2019Tang-Carbon-metal Compound Composite Electrodes For Capacitive Deionization Synthesis, Development and Applications

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Materials Chemistry A
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Carbon–metal compound composite electrodes

for capacitive deionization: synthesis, development
Published on 15 November 2019. Downloaded by University of Georgia on 1/3/2020 1:07:17 PM.
Cite this: J. Mater. Chem. A, 2019, 7,

26693 and applications
a
Kexin Tang, Terence Zhi Xiang Hong,ab Liming Youab and Kun Zhou *ac
Capacitive deionization (CDI) is an emerging desalination technology that utilizes the capacitive properties
(electrical double-layered capacitance, redox or ion intercalation pseudocapacitance) of electrodes to
remove ions. A key challenge of CDI technology is the development of electrodes for the desalination of
high concentration solutions at low energy levels. This requires electrodes to have a large desalination
capacity, high charge efficiency and long-term stability. However, the development of pristine carbon
materials has hit a bottleneck due to their structural properties (e.g., limited surface area) and adsorption
mechanism (i.e., electrosorption). In contrast, metal compounds (especially transition metal compounds)
have received increasing attention due to their dielectric property, redox activity or ion selectivity. This
study comprehensively reviews the use of carbon–metal composites as electrodes for efficient CDI
desalination, mainly with respect to their design strategies, synthesis, structural and electrochemical
properties and desalination performance, and the roles that the metal compounds play in altering the
Received 8th August 2019
Accepted 13th November 2019
structure and properties of their carbon composites. Some future directions, particularly pertaining to
the use of simulation to accelerate CDI development, as well as the concerns of working with complex
DOI: 10.1039/c9ta08663c
feed solutions, are put forward for attaining the goal of implementing CDI technology for seawater
rsc.li/materials-a desalination.
1. Introduction
With population expansion and urbanization, non-renewable
freshwater resources are facing depletion.1 In fact, many
a
Environmental Process Modelling Centre, Nanyang Environment & Water Research
populous cities, such as Cape Town, Mexico City, Tokyo, Deli
Institute, Nanyang Technological University, 1 CleanTech Loop, Singapore 637141,
Singapore. E-mail: kzhou@ntu.edu.sg
and Beijing are facing water stress.2,3 Furthermore, for almost
b
Interdisciplinary Graduate School, Nanyang Technological University, 50 Nanyang all industries, their energy intensities are strongly related to
Avenue, Singapore 639798, Singapore water usage.4 For example, energy generating industries
c
School of Mechanical and Aerospace Engineering, Nanyang Technological University, (hydroelectric power generation, nuclear power, steam power
50 Nanyang Avenue, Singapore 639798, Singapore
Dr. Kexin Tang received her PhD Terence Zhi Xiang Hong received
degree in chemical engineering his bachelor's degree from the
from Tianjin University under School of Materials Science and
the co-supervision of Prof. Hon- Engineering, Nanyang Techno-
gbin Cao and Prof. Yuping Li in logical University, Singapore in
2018. She currently works as 2018. Presently, he is pursuing
a Postdoctoral Fellow with Prof. PhD study under the supervision
Kun Zhou at the Nanyang Envi- of Prof. Kun Zhou at the
ronment and Water Research Nanyang Environment and
Institute, Singapore. Her Water Research Institute,
research interests include the Nanyang Technological Univer-
synthesis and properties of sity. His research interest lies in
carbon-based materials and the molecular dynamics study of
their applications in energy storage and water treatment. nanocomposites for seawater desalination.
This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 26693–26743 | 26693
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Journal of Materials Chemistry A Review
generation from fossil energy combustion and shale gas devel- scale applications. The trapping of solar latent heat also offers
opment) require large amounts of water to drive and maintain new opportunities. However, these methods are gradually
the systems.4 To address the global water crisis, engineers are replaced by alternative desalination technologies due to their
striving to develop solutions utilizing the abundance of high energy demand and equipment maintenance cost.10
seawater. However, desalination technologies are energy- Pressure-driven desalination technologies, e.g., reverse osmosis
intensive processes (Fig. 1). Therefore, recent research efforts (RO), forward osmosis and ultraltration, enable water trans-
are ongoing to improve the cost-effectiveness of desalination.5–9 port through porous membranes. With breakthroughs in
Overall, increasing freshwater yields and developing energy- membrane technology, pressure energy recovery and module
saving desalination technologies are key priorities for the design, RO has overtaken MSF and MED as the dominant
sustainable development of human activities. technology in the desalination market.11 As evident in Fig. 1,
The current motivation for improving desalination technol- seawater desalination with RO can produce water at a lower
ogies is to search for clean energy alternatives and low energy energy requirement (3–4 kW h m3) as compared to MSF (10
consumption using different driving forces based on heat, kW h m3) and MED (5 kW h m3). However, the main
pressure or electric elds. Thermally driven desalination tech- challenges remaining for RO are controlling membrane fouling
nologies, e.g., multiple-effect distillation (MED) and multi-stage and scaling, enhancing membrane permeation and selectivity,
ash distillation (MSF), have been used extensively for large- and further reducing energy consumption.12
Different from the thermal- and pressure-driven methods for
extracting freshwater from brine, electric eld-driven desalina-
tion removes ions instead, which account for a lower mass
content in saltwater. Therefore, electric eld-driven desalina-
tion technologies can produce freshwater with extremely low
conductivity at a higher rate. Furthermore, electric eld-driven
desalination technologies are more energy efficient and envi-
ronmentally friendly, as electrical energy is typically used in the
desalination process without involving any harmful chemicals.
As summarized in Fig. 2, with advancements in the synthesis
technologies of ion exchanger and electrode materials, the
electric-eld driven desalination processes have evolved into
many forms,13 e.g., electrodialysis, electrodeionization (EDI,
electrodialysis with ion exchanger bed in diluted chamber),
capacitive deionization (CDI), membrane CDI (MCDI, CDI with
ion exchange membrane attached on electrode surface) and
ow-electrode CDI (FCDI).14–19 Based on the similarities of these
devices in terms of conguration, the evolution of these electric
eld-driven desalination technologies is based on the
Fig. 1 Energy consumption and water cost of typical industrial desa- enhancement of the charge/ion transfer in various components
lination processes: multi-stage flash distillation (MSF), multiple-effect (aqueous solution, ion exchange medium and electrode). For
distillation (MED), reverse osmosis for seawater and brackish water
example, the ion exchangers in EDI are ion-conductive, which
desalination (SWRO and BWRO), solar pond powered RO and elec-
trodialysis. Data is summarized from ref. 5–9. enable faster ion transfer compared to the ow of saltwater in
Liming You received his bache- Dr. Kun Zhou is an Associate

lor's degree in physics from Professor at the School of
Nanyang Technological Univer- Mechanical & Aerospace Engi-
sity, Singapore in 2019. He neering, Nanyang Technological
received a PhD scholarship University, Singapore, and
under the Nanyang Environ- Deputy Director of the Environ-
mental and Water Research mental Process Modelling
Institute, Singapore, in the same Centre at the Nanyang Environ-
year to perform research under ment and Water Research Insti-
the supervision of Prof. Kun tute, Singapore. His research
Zhou. His present research interests focus on micro/nano
project focuses on the design on mechanics of materials and
novel two-dimensional nanostructures, and nanomaterial
materials with desirable adsorbent properties for water synthesis and modelling for energy and environmental applica-
purication. tions. He has published over 280 journal articles.
26694 | J. Mater. Chem. A, 2019, 7, 26693–26743 This journal is © The Royal Society of Chemistry 2019
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materials, researchers in the eld of CDI have proposed to

dene the general concept of CDI as a cyclical desalination
process that uses electrodes to adsorb and regenerate ions
under an electric eld, regardless of the electrode material
used.26 Depending on the type of material used, CDI desalina-
tion can be achieved by any of the following mechanisms: (1)
classical electric double-layered capacitance (EDLC) of porous
carbon materials,25 (2) pseudocapacitance of the carbon-redox
active composite, (3) ion intercalation mechanism of the
intercalation host materials (IHCs),27 or (4) hybrid mechanism

of the above mechanisms.28
Owing to the joint development of materials science and
material processing, the desalination performance of carbon-
related materials in CDI applications has been gradually
improved. As shown in Fig. 3a, it was discovered that among
Fig. 2 The evolution of electric field-driven desalination devices: carbon-related materials, activated carbon (AC), graphene and
electrodialysis (Walters et al., 1955),14 CDI (capacitive deionization, Blair
et al. 1960),15 electrodeionization [electrodialysis with ion exchange carbon nanotubes (CNTs) attract the most attention from CDI
resins (IERs) packed in the diluted chambers, Gittens and Gluechauf, researchers due to the low cost of AC and the excellent elec-
1965],16 MCDI [CDI with anion or cation exchange membranes (AEM or tronic and electrical properties of graphene and CNTs.29,30 The
CEM) attached on the surface of electrodes, Lee et al., 2006],17 FCDI general principles for developing carbon-related materials for
(CDI utilizing flow-electrodes, Jeon et al., 2013),18 and FCDI with IERs efficient and rapid CDI desalination are as follows: (1) good
(the combination of electrodeionization and FCDI technologies, which
is currently not reported but is considered a possible approach for
hydrophilicity to ensure direct contact between the ions and
future desalination). electrode surfaces, (2) high conductivity to achieve rapid elec-
tron transfer within the electrodes, (3) suitable pore structure
and high specic surface area to achieve rapid migration of ions
the feed chamber, ion exchange membranes (IEMs) improve ion from the bulk aqueous solution to the electrode surface and
mobility and reduce the effect of co-ion repulsion,20 electrodes provide sufficient space for ion storage, (4) good electrode
with high capacitance in CDI can store more ions and have stability, including chemical and electrochemical stability to
a higher electron-conductivity than the bare electrolytes in ensure consistent cycling performance, and (5) easy electrode
electrodialysis.21 The energy consumption and water cost of preparation and assembly methods to lower the market
electrodialysis and EDI could compete with those of RO. price.31–33
However, the systematic assessment of the energy and cost of Following the above principles, efforts have been made to
CDI produced water has not been performed yet. The energy develop new carbon frameworks using advanced synthesis
consumption of CDI is strongly dependent on the operating methods (e.g., microwave/ultrasound-assisted hydrothermal
conditions, salinity of feed solution and water and energy method,34 electrospinning,35 3D printing36), porous templates
recovery; it dramatically increases accordingly with the applied (e.g., cross-linked polymers,37 metal oxides38 and metal–organic
voltage and salt concentration.21–23 Still, studies have indicated and covalent-organic frameworks),39,40 and surface modica-
that for a feed solution with low salinity, MCDI can be more tions (e.g., nitrogen doping and sulfur doping).41 For more
energy efficient than RO.24 details on the development of carbon materials for CDI appli-
cations, readers are encouraged to refer to the review articles by
Liu et al.32 and Liu et al.33 Even though the desalination
1.1 Developments of CDI electrodes performance of carbon materials has been greatly improved
Compared to the saltwater in the polar chambers (anode and aer these developments (for example, their average desalina-
cathode) of electrodialysis and EDI set-ups, the carbon-based tion capacity has been increased from 5 to 20 mg g1 over
materials in CDI-related processes are more charge conduc- the past two decades),42–47 CDI electrodes made of pure carbon
tive, and therefore can store/remove ions even faster. As a major components have hit bottlenecks, which include limited surface
component in CDI, carbon electrodes have been studied exposure to the solution and ions, inevitable faradaic reactions,
extensively for CDI applications. conning operating conditions (e.g., low applied potential and
The utilization of carbon electrodes for CDI was rst intro- low salt concentration), and dramatically increased energy
duced in 1960 when Blair and Murphy demonstrated the consumption when desalting highly saline water.23,48
demineralization of saline water using a porous carbon elec-
trode with a large surface area (Fig. 2).15 However, CDI did not
receive much attention until the late 1990s. Aer nearly two 1.2 Carbon–metal compound composites for CDI
decades of rapid development, CDI, as a low-energy, environ- An effective approach to further improve the desalination
mentally friendly, energy efficient and easy-to-deploy desalina- performance of CDI is to replace its pure carbon electrodes with
tion technology, has attracted increasing attention.25 Since carbon–metal compound composite electrodes (Fig. 4). As
many new electrode materials have emerged apart from carbon described in Fig. 3b and c, these metal compounds in carbon
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Fig. 3 (a) Number of published articles about capacitive deionization (CDI) using various carbon-related materials (2006–2018). Numbers of
published articles of (b) carbon–TMO composites and (c) carbon–GAMO/2D-IHCs/3D-IHCs nanomaterials (2006–2019).
composite electrodes are categorized into transition metal TMOs. Due to the wide variety of TMOs and their physico-
oxides (TMOs), group A metals or metal oxides (GAMOs), and chemical properties, diverse types of carbon–TMO composites
IHCs. The deposited/inserted metal compound can improve the have been investigated as CDI electrodes, for the purpose of
desalination performance of the composite by either acting as achieving higher salt removal capacities and rates as well as
a protective layer, introducing pseudocapacitance, or domi- more stable cycling performance. As summarized in Fig. 3b,
nating ion removal; this depends on its physical and electro- most of the research has been dedicated to titanium dioxide
chemical properties and the composition of the composite. (TiO2),31,49–55 manganese dioxide (MnO2)56–61 and zinc oxide
Fig. 4 Schematic diagram of the overall review on capacitive deionization using carbon–metal compound composites, including the types of
metal compounds (transition metal oxides, group A metal oxides, and ion intercalation host compounds) and their functions in the composites,
the ion removal mechanisms, and the properties which could impact the desalination performance of the composites.
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(ZnO)62–64 due to their low cost, abundance in nature and envi- IHCs. In addition to TMOs and GAMOs, IHCs, also known as
ronmental friendliness. In addition, some alternative TMOs, battery-like materials, have recently attracted great attention for
including stannic oxide (SnO2),65,66 ferric oxide (FeOx),58,67,68 applications in CDI, due to their large salt removal capacities
copper oxide (CuO),57 ceric oxide (CeO2),68 vanadium pentoxide and low energy consumption even at high salt concentrations.79
(V2O5),28 and zirconium dioxide (ZrO2),69 have also been inves- Different from carbon–TMO and carbon–GAMO electrodes that
tigated as additives for carbon electrodes. Generally, TMOs can store ions on their porous surfaces, IHCs electrodes can store
enhance the desalination performance of pristine carbon elec- more ions in bulk materials through their ion intercalation/
trodes, beneting from their semiconducting properties (acting deintercalation mechanism. Such IHCs include sodium/
as a charge inducer to protect the carbon surface) and their lithium metal oxides79–82 and phosphides,83 hexacyanoferrates
abundant oxygen-containing functional groups (increasing the (or Prussian blue compounds),84–87 and two-dimensional (2D)
hydrophilicity of the composites). intercalation nanomaterials, [e.g., 2D MnO2, transition metal
Some characteristics of TMOs, however, may hinder their nitride, carbide or boride (MXene) and transition metal
applications in CDI. Firstly, most studied TMOs have high dichalcogenides (TMDCs)].88–94
electrical resistance. This is detrimental for CDI electrodes For battery-like electrodes like sodium metal oxides, phos-
since the heat generated from the high resistance would phides and hexacyanoferrates, they absorb ions into their lattice
decrease the charge efficiency or may even destroy the electrode structure under an applied electric eld, and they are only
structure. Secondly, being non-conductive also means that any effective for basic ion adsorption (e.g. Na+, K+, and Li+). There-
charge/ion transport at the interface of TMOs would be rather fore, in CDI applications, when using such battery-like elec-
slow. Although nanosized or porous TMOs can provide larger trodes as cathodes, another kind of electrode should be
contact areas for charges/ions, such qualities may also decrease simultaneously employed for chloride ion adsorption, resulting
the electrode conductivity due to the introduction of more in a hybrid conguration. Depending on the material of the
crystal interfaces. Thirdly, metal ions may be eluted by the anode, there are two proposed hybrid congurations: a carbon
owing solution during the charging and discharging electrode covered with an anion exchange membrane (to limit
processes. The nal product (e.g., freshwater) of CDI desalina- co-ions rejection at anode) or an anion intercalation electrode,
tion is intended for human consumption and some transition such as silver81,95 or BiOCl electrodes.96 Employing ion exchange
metal ions from the composites are highly toxic (e.g., manga- membranes in CDI, however, is known to increase the overall
nese, copper and zinc); even a small number of dissociated ions material cost while the use of expensive silver is also imprac-
can prove fatal.70 tical. Therefore, more research in this area is expected to be
In order to solve these problems, this review aims to provide conducted.
readers with a comprehensive understanding of the desalina- The 2D-IHCs, including MXene, TMDCs and 2D-layered
tion mechanisms of carbon–TMO composites, and ultimately, TMOs (2D-TMOs), refer to nanosheet materials with a thick-
to guide their future design and development. ness of a single or few atomic crystals.97,98 Because of their fully
GAMOs. GAMOs, e.g., Al2O3 and SiO2, are more electro- exposed active sites and their unique electrical, electronic and
chemically stable than TMOs due to their full penultimate photonic properties, 2D nanomaterials have been extensively
shells, which contribute to their wide employment in the elec- developed as the host material for various applications, such as
tronic industry.71 In the eld of CDI, GAMOs can enhance the energy storage, catalysis, sensor technology and hydrogen
desalination process through the following features; namely, (1) evolution, etc.99 Due to their exceptional electrical properties
their stability; instead of introducing pseudocapacitance, and redox activities, 2D nanomaterials have been reported to
GAMOs act as a dielectric coating to protect electrodes from potentially serve as energy storage electrodes.100,101 These 2D
directly reacting with the electrolyte,72 (2) GAMOs like Al2O3 nanomaterials undergo ion intercalation into their layered
(positively charged) and SiO2 (negatively charged) are naturally structures to store energy, resulting in chemical connections
charged within a wide range of pH values,73,74 they can change between the inserted ions and the active surfaces. This mech-
the potential of zero charge of electrodes to balance salt anism endows 2D-IHCs with the following advantages over
adsorption at the anode and cathode,75,76 (3) an ultrathin alkaline intercalation materials: (1) in most cases, they allow the
dielectric coating; GAMOs can improve the capacitance of intercalation of both anions and cations (having no charge
carbon electrodes because of the enhanced electric eld at the selectivity) unlike their alkaline intercalation counterparts; (2)
interface of carbon,77 and (4) the hydrophilicity of GAMOs also compared with storing alkaline ions in the lattice of three-
help carbon to get wet in saline water more easily.78 dimensional bulk IHC (3D-IHC) materials, the charge/ion
However, GAMOs are usually semiconductors (similar to transfer is faster in 2D-IHCs because of their in-plane struc-
TMOs), and excessive loading could reduce the conductivity of ture and more exposed active sites; (3) they generally do not
the composite. Although some attempts have been made to swell during charging and discharging. As a result, researchers
apply carbon–GAMO composites in CDI, their desalination began applying 2D-IHCs in CDI desalination (Fig. 3c).
performance has not met expectations. To better make use of Although the IHC electrode is superior to a pure carbon
the above characteristics of GAMOs, this review aims to nd the electrode in terms of its desalination capacity, some problems
key factors to further optimize the CDI desalination perfor- common with IHC electrodes in batteries may also exist in CDI.
mance of carbon–GAMO composites by establishing their For example, the IHC electrodes in CDI applications are
structural–properties relationships.
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analogous to their roles in batteries,102 although the IHC elec- the electrical conductivities, surface properties, porous struc-
trodes (in CDI) have a high desalination capacity (mirroring tures and electrochemical performances of their composites.
high energy density of the battery electrodes), their low desali- The low resistance of a CDI electrode is extremely essential
nation rates are also comparable to the low analogous power for a high desalination performance. Although most metal
densities of the battery-like electrodes. In addition, although compounds are less conductive than carbon, it is possible to
the cycle efficiency of the battery-like electrode has not yet been improve the desalination performance of a carbon–metal
systematically investigated in CDI, it is not expected to be high compound composite without compromising its electrical
as batteries typically have worse cycling performance than conductivity. The main strategy is to form a continuous
supercapacitors (SCs, 1000 vs. 10 000). Furthermore, due to conductive network within the composite and reduce the
the large number of metal components in CDI electrodes, resistance introduced by the metal compound, including the
battery materials need to be recycled to avoid wastage of use of highly conductive carbon bases (e.g., CNTs and gra-
resources and environmental pollution.102–104 In the eld of phene),28,31,33,125,146 selection of the morphology (e.g., nanorods,
energy storage, scientists try to ll the gap between batteries nanotubes, nanobers, nanowires and micro-
and SCs by using pseudo-capacitive electrodes. By forming sheets),52,62,111,131,152,155 porous and crystal struc-
composite electrodes using carbon and metal compounds (e.g., tures49,52,106,124,127,140 and content of the metal compound (e.g., by
TMOs, GAMOs, 2D-IHCs or 3D-IHCs), there are opportunities to controlling the thickness of the deposited layer),59,61,118 and the
address the problems of the low salt removal capacity of introduction of a third component (e.g., conductive polymers).
a pristine carbon electrode and the low cycling efficiency and A sufficient number of effective ion adsorption sites are
environmental issues of a metal-based electrode. another prerequisite for good desalination performance by
carbon–metal compound composite electrodes. However, the
1.3 Purposes and contents of this review deposition of the metal compound layers reduces the surface
area of the carbon–metal compound composites with carbon-
Although the scientic concepts and methods pertaining to based structure. This phenomenon is predictable since the
carbon materials for CDI applications have been systematically deposited metal compound would partially cover a portion of
reviewed by Presser et al.,25 Pan et al.32 and Huang et al.,156 there the pores of the carbon base and they generally have a lower
was a lack of focus on metal–assisted carbon composites. specic surface area than pristine carbon materials. Addition-
Therefore, this paper specically aims to review and summarize ally, some of the pores may be fully blocked by excessive
the published research utilizing such composite electrodes for deposits and/or a third introduced component. Methods for
CDI. More specically, this paper will focus on the relationships further developing the pore structures of the composites
between the synthesizing approaches, nanoscopic oxide struc- include the activation of the composite under high-temperature
ture, electrochemical properties, desalination performance and annealing and/or reducing gases,119,120,124 as well as pore
ion removal mechanisms. As summarized in Table 1, this paper expansion with the structural transition of the metal
generally reviews four different kinds of carbon–metal compound.57,124 For graphene, however, due to the mutual
compound composites, in which the metal compounds are: attraction between the graphene nanolayers, graphene
TMOs (TiO2, MnOx, ZnO, SnO2, FeOx, CuO, V2O5, CeO2, ZrO2 prepared by conventional methods has a small specic surface
and RuO2), GAMOs (SiO2, Al2O3 and Li2O), 2D-IHCs (MXene, area. But with the incorporation of a metal compound such as
TMDCs and 2D layered TMOs) and 3D-IHCs (metal/metal alloy, nanostructured TiO2, the aggregated graphene layers can be
Prussian blue, phosphates, and sodium/lithium metal oxides expanded and thus its overall surface area increases.52
with 3D structures). Since carbon–TMO composites containing For carbon–metal compound composites with metal-based
TiO2 and MnOx are studied the most among all carbon–TMO structure, the surface area of an IHC also plays a key role in
composites (Fig. 3b), the discussion of carbon–TMO composites determining its salt removal ability in CDI applications. With an
is divided into three sections, i.e., carbon–TiO2, carbon–MnOx expanded structure, the diffusion resistance of ions can be
and other carbon–TMO composites (Sections 3–5). The major reduced as compared to the lattice interiors of condensed IHC
challenges for metal-based CDI electrodes with an outlook on materials. However, taking 2D-IHCs as an example, their adja-
their future development are put forward at the end. cent layers may be restacked as a result of van der Waals
interactions, therefore it is difficult to obtain a 2D-IHC with
2. Roles of nanostructured metal a high specic surface area (typically <30 m2 g1). Accordingly,
effective methods to resolve the issue of restacking should be
compounds in the desalination the primary focus in the synthesis of 2D-IHCs, for example, by
performance of carbon–metal introducing and inserting other components between their
compound composite electrodes layers (e.g., CNTs and conductive polymers) or utilizing freeze-
drying to retain their porous structures. For 3D-IHCs, more
The desalination performance of a carbon–metal compound available ion storage sites can be created by preparing three-
composite electrode is governed by its electronic and electro- dimensional structures that are not easily stacked. For
chemical properties and is particularly affected by its constit- example, a pure Prussian blue (PB) electrode removes salt in
uent metal compounds (Fig. 5), including their synthetic routes, small volumes at a low rate,27 but when PB nanocubes are grown
morphologies, structures and contents, resulting in changes in on the surface of graphene, the salt adsorption capacity (SAC)
Table 1 Processing method, structural and electrochemical properties, and CDI performance of carbon–metal compound composites
Electrode Metal source Processing Metal structure in composite Electrochemical properties Desalination performance
Review
Carbon–TiO2 composites
Ti–ACC105 Titanium(IV) butoxide Chemical reaction at room Amorphous nanoparticles Not available 2.05 mg g1, 1.0 V,
temperature 250 mg L1
Ti(1.05)/ACC69 Titanium(IV) butoxide Chemical reaction at room Amorphous nanoparticles Not available 4.56 mg g1, 1.0 V,
temperature 5.8 mg L1
AC–TiO2 (ref. 106) Titanium(IV) isopropoxide Sol–gel method; 450 C, air Anatase 151 F g1, 1 mV s1, 4 M 5.11 mg g1, 1.2 V,
NaCl 500 mg L1
AC–TiO2 (ref. 49) Titanium(IV) butoxide Sol–gel method; 850 C, Rutile Not available 12.7 mg g1, 1.2 V,
nitrogen 500 mg L1
ISCCEs107 TiO2 nanopowder Mixing; coating Nanoparticles 93 F g1, 5 mV s1, 0.5 M 0.88 mg cm2, 1.2 V,
KCl 200 mg L1
TiO2/AC108 Titanium(IV) isopropoxide Sol–gel reaction; IL-inducing Anatase nanoparticles 51.5 F g1, 10 mV s1, 0.5 M 8.03 mg g1, 1.2 V,
crystallization NaCl 100 mg L1
This journal is © The Royal Society of Chemistry 2019

GA/TiO2 (ref. 31) TiCl3 Ultrasonication; hydrothermal Anatase nanoparticles 142.6 F g1, 5 mV s1, 0.1 M 15.1 mg g1, 1.2 V,
treatment NaCl 500 mg L1
ACTNF50 Titanium(IV) isopropoxide Electrospinning; calcination at Anatase nanobers 380 F g1, 10 mV s1, 1 M 17.7 mg g1, 1.2 V,
700 C, air; NaCl 292 mg L1
TiO2-coated, AC51 Titanium(IV) butoxide Sol–gel spray; 250 C, air Amorphous nanoparticles 104 F g1, 2 mV s1, 1 M 17 mg g1, 1.2 V,
NaCl 584.4 mg L1
RGO/TiO2 nanorod52 TiO2 nanoparticles Alkaline hydrothermal Anatase/rutile nanorods 443 F g1, 10 mV s1, 1 M 16.4 mg g1, 1.2 V,
method; 650 C, argon NaCl 300 mg L1
TiO2/AC109 Titanium(IV) butoxide Sol–gel method; 450 C, Anatase nanoparticles 135 F g1, 5 mV s1, 0.5 M 0.036 mg cm2, 1.6 V,
nitrogen NaCl 200 mg L1
TiO2/AC-p53 Titanium(IV) isopropoxide KOH activation; 900 C, Anatase nanoparticle 64.5 F g1 (EIS capacitance) 11.5 mg g1, 1.2 V,
nitrogen; sol–gel reaction; IL- 100 mg L1
inducing crystallization
TiO2/CNTs110 Titanium(IV) butoxide Sol–gel method; 500 C, Anatase nanoparticles 122 F g1, 1 mV s1, 1 M 4.3 mg g1, 1.2 V,
nitrogen KCl 500 mg L1
TiO2-NTs/HCF/CF111 Titanium sheet Electrochemical reaction; Rutile nanotubes 268.5 F g1, 50 mV s1, 1 M 63.9%, 1.6 V, 100 ms cm1
500 C, oxygen Na2SO4 Na2SO4
AC–TiO2 (15)54 Titanium(IV) isopropoxide Sol–gel method; two-step Amorphous 84 F g1, 0.1 A g1, 1 M 17.4 mg g1, 1.2 V,
hydrolysis; NaCl 292 mg L1
Ti–C-1 (ref. 112) Titanium sheet Anodization; high vacuum Nanotubes 56.2 F g1, 2 mV s1, 0.5 M 9.61 mg g1, 1.4 V,
magnetron sputtering NaCl 50 mg L1
Ti–C-2 (ref. 112) Titanium sheet Anodization; chemical Nanotubes 46.1 F g1, 2 mV s1, 0.5 M 7.11 mg g1, 1.4 V,
deposition NaCl 50 mg L1
THC-A113 Titanium sheet Anodization; 500 C, oxygen; Rutile nanotubes 238.2 F g1, 20 mV s1, 1 M 13.11 mg g1, 1.2 V,
vacuum inducing hydrolysis; Na2SO4 500 mg L1
600 C, air; mild acid
treatment
TNT/MWCNT114 Titanium foil Anodization at 0 C; Anatase nanotubes 34.4 F g1, 20 mV s1, 0.5 M 13.2 mg g1, 2.0 V,
ultrasonication NaCl 50 mg L1
CAs/TiO2 (ref. 68) TiCl3 Hydrothermal method; 550 C, Anatase nanoparticles 158.6 F g1, 5 mV s1, 57.13 mg g1 (Cu2+), 1.2 V,
nitrogen 50 mg L1 CuCl2 50 mg L1 CuCl2
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J. Mater. Chem. A, 2019, 7, 26693–26743 | 26699

Journal of Materials Chemistry A
Table 1 (Contd. )
ACC–TiO2 (ref. 55) TiO2 nanoparticles Coating; spray pyrolysis; Anatase nanoparticles 126.3 F g1, 1 mV s1, 0.5 M 5.3 mg g1, 1.5 V, 1 g L1
titanium(IV) butoxide 350 C, air NaCl
ACP/TiO2/SO3 (ref. TiO2 nanopowder Chemisorption; screen Not applicable 214 F g1, 5 mV s1, 0.5 M 22 mg g1, 1.0 V,
115) printing KCl 500 mg L1
TiO2@PC116 Titanium isopropoxide Hydrothermal treatment; Anatase nanoparticles 261.6 mA g1, 0.1 A g1, 46.73 mg g1, 10 mA g1,
600 C, argon 1 M NaCl 1 g L1
Carbon–MnOx composites
MnO2/NCs117 KMnO4, MnSO4$H2O Chemical reduction; 200 C, a-MnO2 needle-shaped 204.7 F g1, 1 mV s1, 1 M 0.99 mg g1, 1.2 V,
air particles NaCl 25 mg L1
MnO2/PSS/CNTs118 KMnO4, MnSO4$H2O Layer-by-layer deposition; Nanoparticles 77.2 F g1, 10 mV s1, 1 M 4.7 mg g1, 1.2 V,
200 C, air NaCl 128 mg L1
26700 | J. Mater. Chem. A, 2019, 7, 26693–26743

Graphene@MnO2 MnSO4$H2O Two-stage microwave a-MnO2, nanorods 292 F g1, 10 mV s1, 1 M 5.01 mg g1, 1.2 V,
nanorods56 irradiation NaCl 50 mg L1
Graphene@MnO2 MnSO4$H2O Two-stage microwave a-MnO2 nanoparticles 180 F g1, 10 mV s1, 1 M 3.50 mg g1, 1.2 V,
nanoparticles56 irradiation NaCl 50 mg L1
CAGDMnAct119 Mn(NO3)2$6H2O Immersing; supercritical MnO nanoparticles 79 F g1, 0.5 mV s1, 0.1 M 6.4 mg g1, 1.5 V,
drying; 750 C, nitrogen / NaCl 1461 mg L1
CO2
MO/ACF120 MnCl2$4H2O Chemical reaction at room Mn3O4 particles 3.0 F g1, 10 mV s1, 0.1 M 10.5 mg g1 (Cd2+), 1.5 V,
temperature; 700 C, nitrogen Cd(NO3)2 18 mg L1
RGO–PPy–Mn57 KMnO4 Ultrasonication; hydrothermal Nanoscale MnO2 356 F g1, 10 mV s1, 3 M 18.4 mg g1, 2.0 V,
method; freeze drying KCl 500 mg L1
MnO2/CF121 MnSO4 Galvanostatic MnO2 nanosheets 387 F g1, 0.1 A g1, 1 M 145.42 mg g1 (Cu2+),
electrodeposition Na2SO4 0.8 V, 6 mg L1
A-ECNF/MnOx122 KMnO4 Redox reaction at 30 C; Amorphous particles 157 F g1, 1 mV s1, 1 M 8.2 mg g1, 1.2 V,
300 C, air NaCl 500 mg L1
MnO2/MWCNTs123 KMnO4 Redox reaction at 85 C d-MnO2 with poor crystallinity 144 F g1, 1 A g1, 0.5 M 6.65 mg g1, 1.8 V,
NaCl 43 mg L1
MnO2/AC58 (CH3COO)2Mn$4H2O Anodic electrodeposition Amorphous particles 77.6 F g1, 5 mV s1, 1 M 9.26 mg g1, 1.0 V,
NaCl 584.4 mg L1
MRF–MnD–CB124 Mn(NO3)2 Soaking; 750 C, CO2 Amorphous particles 113 F g1, 0.5 mV s1, 0.1 M 6.1 mg g1, 1.5 V,
NaCl 1500 mg L1
MnO2-coated CA59 (CH3COO)2Mn$4H2O Anodic electrodeposition Amorphous MnO2 92.8 F g1, 15 A m2, 0.1 M 22.5 mg g1, 10 A g1,
NaCl 5844 mg L1
HB/CNTs125 KMnO4 Microwave-assisted redox Birnessite Not available 155.6 mg g1 (Zn2+),
reaction, 120 C 158.4 mg g1 (Ni2+), 0 V/
SCE, 50 mg L1
15Mn@C-400 (ref. 126) Mn(NO3)2$4H2O Mixing and vaporization; Tetragonal MnO2 83.9 F g1, 5 mV s1, 1 M 5.4 mg g1, 1.2 V,
400 C, nitrogen NaCl 25 mg L1
a-MnO2/CFP60 KMnO4 Hydrothermal reaction a-MnO2 126.7 F g1, 1 mV s1, 1 M 16.4 mg g1 (Ni2+), 1.5 V,
NaCl 100 mg L1
MnO2/CNT–CS127 (CH3COO)2Mn$4H2O Anodic electrodeposition b-MnO2 42.3 F g1, 5 mV s1, 1 M 10.07 mg g1, 1.6 V,
NaCl 877 mg L1
MnO2/ACCkAg/ACC128 KMnO4 Redox reaction a-MnO2 311 F g1, 5 mA g1, 1 M 17.8 mg g1, 1.6 V,
NaCl 1167 mg L1
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Review
Table 1 (Contd. )
Review
VACNTs–MnO2 (ref. 61) Bis(ethylcyclopentadienyl) CVD growth of VACNTs; Amorphous MnOx 220 F g1, 5 mV s1, 1 M 28.6 mg g1, 1.2 V,
manganese atomic layer deposition NaCl 100 mg L1
Other carbon–TMO composites

ACC:ZnO62 Zn(CH3COO)2$2H2O, Zn Hydrolyzation; seeding on ZnO nanorods 99 F g1, 1 mV s1, 0.5 M 8.5 mg g1, 1.2 V,
(NO3)2$6H2O glass substrates; hydrothermal NaCl 100 mg L1
method; 350 C, air
Z_ACC63 Zn(CH3COO)2$2H2O, Zn Hydrolyzation; seeding on ZnO nanorods 70 F g1, 1 mV s1, 0.5 M 3.6 mg g1, 1.6 V,
(NO3)2$6H2O glass substrates; hydrothermal NaCl 993.5 mg L1
method; 150 C, air
ZnO–ACC composites62 Zn(CH3COO)2$2H2O, Zn Hydrolyzation; seeding on ZnO nanorods (NR), 1 mV s1, 0.5 M NaCl, NR: 1.2 V, 100 mg L1, NR:
(NO3)2$6H2O glass substrates; hydrothermal nanoparticles (NP), 95 F g1, NP: 75F g1, MSH: 8.5 mg g1, NP: 1.0 mg g1,
method; 150 C, air microsheets (MSH), 74 F g1, MSP: 73 F g1 MSH: 8.5 mg g1, MSP:

microspheres (MSP) 2.1 mg g1
ZnO/AC cathode64 ZnO nanoparticles Physical mixing Not available 66 F g1, 2 mV s1, 1 M 9.4 mg g1, 1.2 V,
NaCl 500 mg L1
ZnO NP-coated ACC55 ZnO nanoparticles, Soaking; spraying; 350 C, air Not available 120.8 F g1, 1 mV s1, 0.5 M 5.72 mg g1, 1.5 V,
Zn(CH3COO)2$2H2O NaCl 1000 mg L1
CAGDFeAct119 Fe(NO3)2$9H2O Immersing; supercritical Fe3O4 nanoparticles 72 F g1, 0.5 mV s1, 0.1 M 7.8 mg g1, 1.5 V,
drying; 750 C, nitrogen / NaCl 1461 mg L1
CO2
RGO–PPy0.5–Cu1 (ref. CuSO4 Ultrasonication; hydrothermal Amorphous particles 240 F g1, 10 mV s1, 3 M 15.1 mg g1, 2.0 V,
57)57 method; freeze drying KCl 500 mg L1
RGO@Fe3O4 (ref. 58) Fe(NO3)2$9H2O Hydrothermal method Cubic crystal structure of 155 F g1, 1 mV s1, 1 M 8.33 mg g1, 1.2 V,
Fe3O4 NaCl 250 mg L1
CAs/Fe2O3 (ref. 68) FeCl2 Hydrothermal method; 550 C, Fe2O3 nanoparticles 130 F g1, 5 mV s1, 41.42 mg g1 (Cu2+), 1.2 V,
Fe3O4/rGO67 FeCl3$6H2O Thermal hydrolysis; 850 C, Fe3O4 nanoparticles Not available 4.3 mg g1 (Ca2+), 1.5 V,
nitrogen 35 mg L1 CaCO3
CAs/CeO2 (ref. 68) CeCl3 Hydrothermal method; 550 C, CeO2 nanoparticles 139 F g1, 5 mV s1, 49.28 mg g1 (Cu2+), 1.2 V,
Gr/SnO2 (ref. 65) SnCl2$2H2O Microwave radiation Rutile SnO2 323 F g1, 5 mV s1, 1 M 1.49 mg g1, 1.4 V,
NaCl 30 mg L1
N-AC/SnO2 (ref. 66) SnCl2$2H2O Hydrothermal method Tetragonal SnO2 nanoparticles 408.8 F g1, 10 mV s1, 1 M 3.42 mg g1, 1.2 V,
NaCl 50 mg L1
RGO-SnO2 (ref. 129) SnCl2$2H2O Hydrothermal method Rutile SnO2 142 F g1, 5 mV s1, 0.5 M 17.62 mg g1, 1.2 V,
NaCl 400 mg L1
Ca-alginate-coated CaCl2 Casting; displacement Not available 70 F g1, 2 mV s1, 1 M 15.6 mg g1 (Ca2+), 1.2 V,
AC130 reaction CaCl2 10 mM CaCl2
MWCNT–hV2O5 (ref. 28) VOSO4 Electrochemical deposition Hydrated disordered V2O5 244 F g1, 1 mV s1, 1 M 23.6 mg g1, CCa, 35.064 g
NaCl L1
ZrO2 NFs/AC131 Zirconium(IV) isopropoxide Sol–gel method; ZrO2 nanobers 869.9 F g1, 10 mV s1, 1 M 16.35 mg g1, 1.2 V,
electrospinning; 700 C, air NaCl 104 mg L1
RuO2(20)–AC132 Ruthenium chloride Anodic deposition RuO2 nanoparticles 60.6 F g1, 5 mV s1, 1 M 11.3 mg g1, 1.2 V,
NaCl 292.2 mg L1
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J. Mater. Chem. A, 2019, 7, 26693–26743 | 26701

Table 1 (Contd. )
Zr(0.38)/ACC69 Zirconium(IV)-n-propoxide Chemical reaction at room Not available Not available 2.05 mg g1, 1.0 V,
rGO/Co3O4 (ref. 133) CoCl2$6H2O Sonication; hydrolysis; 450 C, Co3O4 nanoparticles 210 F g1, 5 mV s1, 2 M 20.21 mg g1, 1.6 V,
air NaCl 500 mg L1
Carbon–GAMO composites
Si(0.28)/ACC69 3-Trimethoxypropylsilane Chemical reaction at room Not available Not available 1.46 mg g1, 1.0 V,
Al(0.20)/ACC69 Aluminum isopropoxide Chemical reaction at room Not available Not available 1.75 mg g1, 1.0 V,
MOx-carbon foam134 Alkylsilicate, aluminum tri- Dip-coating; 350 C, air Not available 20 F g1 for SiO2, 18 F g1 3.5 mg g1 (KCl), 2.0 V,
sec-butoxide for Al2O3, 1 mV s1, 0.1 M 745.5 mg L1
26702 | J. Mater. Chem. A, 2019, 7, 26693–26743

KCl
CX–SiO2 (ref. 135) SiO2 nanoparticles Sonication; 200 C, air SiO2 nanoparticles Not available 2.9 mg g1, 1.2 V,
233 mg L1
MOx–carbon felt136 SiO2 nanoparticles Sol–gel method; dip-coating; SiO2 or l-Al2O3 nanoparticles Not available 4.38 mg g1 (CaSO4), 1.2 V,
aluminum tri-sec butoxide 120 C, air 516.5 mg L1
MOx/CNTf137 Tetraethylorthosilicate, Sol–gel method; Co-spraying; SiO2 or l-Al2O3 nanoparticles 66 F g1 for SiO2-coating, 6.5 mg g1, 1.2 V,
aluminum isopropoxide 350 C, air 52 F g1 for Al2O3-coating, 2000 mg L1
50 mA g1, 0.5 M K2SO4
Porous silicon– Silicon wafers HF etching; 850 C, C2H2 and Microchannels Not available 5.2 mg g1, 125 mg
carbon138 H2 gcarbon1, 1.0 V, 35 g L1
Li+/G/CNF139 LiNO3 Electrospinning; 900 C, N2 Li2O and LiC6 nanoparticles Not available 84%b, 1.4 V,
36 300 mg L1
Carbon–IHC composites
K-birnessite LMO94 KMnO4 Chemical reaction Flowerlike MnO2 nanosheets Not available 14.9 mg g1, 1.0 V,
500 mg L1
Na-birnessite LMO93 Mn(NO3)2$6H2O Chemical reaction; Na-birnessite powder Not available 31.5 mg g1, 1.2 V,
hydrothermal treatment 877 mg L1
Mg-buserite LMO93 Mn(NO3)2$6H2O Chemical reaction; Mg-buserite powder Not available 37.5 mg g1, 1.2 V,
hydrothermal treatment; ion- 877 mg L1
exchange process
Ti3C2-MXene88 Elemental titanium Ti3AlC2-MAX phase synthesis Delaminated Ti3C2 layers 176 F g1, 0.1 A g1, 1 M 13.2 mg g1, 0.8 V,
(1550 C, 50 MPa); HF NaCl 292.2 mg L1
exfoliation
Mo1.33C-MXene/CNTs92 Elemental molybdenum (Mo2/3Sc1/3)2AlC MAX phase Mo1.33C-MXene multilayers 150 F g1, 0.1 A g1, 1 M 15 mg g1, 0.8 V, 35.064 g
synthesis (1500 C, argon); HF NaCl L1
exfoliation
Porous Ti3C2Tx- Ti3AlC2 powders HF exfoliation; Ti3C2Tx nanosheets 156 F g1, 5 mV s1, 1 M 45 mg g1, 1.2 V, 10 g L1
MXene140 ultrasonication; freeze-drying NaCl
2D MXene Ti3C2Tx Ti3AlC2 powders HF exfoliation; NaOH Surface: TiO2/carbon, 200 F g1, 2 mV s1, 1 M 26.8 mg g1, 1.4 V,
nanosheets141 exfoliation; Ar plasma interlayer: Ti3C2 nanosheets NaCl 500 mg L1
treatment
MoS2 (ref. 89) Bulk MoS2 powders Chemical exfoliation; ltration Multilayer MoS2 nanosheets 109.7 F g1, 10 mV s1, 1 M 8.81 mg g1, 1.2 V,
& acetone treating NaCl 400 mg L1
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Review
Table 1 (Contd. )
Review
MoS2/CNTs90 MoS2 particles Mixing and tip-sonication; Stacked MoS2 layers 210 F g1, 0.1 A g1, 1 M 25 mg g1, 0.8 V, 29.22 g
ltration; electrochemical NaCl L1
activation
T-MoS2 (ref. 142) (NH4)6Mo7O24$4H2O Hydrothermal treatment; MoS2 nanosheets with surface 221.4 F g1, 5 mV s1, 1 M 24.6 mg g1, 0.8 V,
ultrasonication; freeze-drying; defects NaCl 100 mg L1
300 C, air
TiS2/CNTs91 TiS2 particles Mixing and tip-sonication; Stacked TiS2 layers 68 mA h g1, 0.1 A g1, 1 M 14.5 mg g1, 0.8 V, 35.06 g
ltration NaCl L1
Ag@C143 AgNO3 Ultraviolet radiation and Ag Ag particles 0.23 mA h cm2, 2 mV s1, 16.8 mg g1, 0.7 V,
reduction 2 M NaCl 584 mg L1
Ag–Cu@graphene144 AgNO3, CuCl2$2H2O PVP stabilization; 600 C, air Ag and Cu nanoparticles 128 F g1, 10 mV s1, 1 M 16.8 mg g1, 1.2 V,
NaCl 600 mg L1
NiHCF27 NiCl2, Na4Fe(CN)6 Chemical reaction; Nanoparticles 17.6 mA h NiHCF g1, 2.8 A 12.5 mg g1, 2.8 A m1,

m1, 1.17 g L1 1.17 g L1
PB/rGA145 K3Fe(CN)6 Hydrothermal treatment; Prussian blue nanocubes Not available 130 mg g1, 100 mA g1,
freeze-drying 2.5 g L1
FePO4/RGO146 (NH4)2Fe(SO4)2 Chemical precipitation; Amorphous FePO4 Not available 100 mg g1, 100 mA g1,
chemical oxidation; 400 C, nanoparticles 2.5 g L1
nitrogen
FePO4/RGO147 (NH4)2Fe(SO4)2 Hydrothermal treatment Amorphous FePO4 Not available 85.94 mg g1, 1.8 V, 2.33 g
nanospheres L1
Na3V2(PO4)3@C148 V2O5 powder Hydrothermal treatment, NASICON structure Not available 124 mg g1, 100 mA g1,
750 C, argon 1.0 g L1
Na3V2(PO4)3@C149 NH4VO3 Sol–gel formation; 350 C, air; NASICON structure 100 mF cm2, 5 mA cm2, 137.2 mg g1, 1.0 V, 5.84 g
800 C, argon 1 M Na2SO4 L1
Na3V2(PO4)3/ V2O5 powder Hydrothermal treatment; NASICON structure Not available 107.5 mg g1, 100 mA g1,
graphene150 750 C, argon 1.0 g L1
NaTi2(PO4)3/C151 Tetra-n-butyl titanate Solvothermal treatment; NASICON structure 146 F g1, 10 mV s1, 1 g 167.4 mg g1, 1.8 V, 1.0 g
700 C, nitrogen L1 NaCl L1
AgCl/graphene150 AgNO3 Hydrothermal treatment; AgCl nanoparticle Not available 107.5 mg g1, 100 mA g1,
freeze-drying 1.0 g L1
Graphene@Na4Ti9O20 TiO2 powder Hydrothermal treatment; Na4Ti9O20 nanotubes 125.2 F g1, 1 mV s1, 1 M 41.8 mg g1, 1.4 V,
nanotube152 200 C, oxygen NaCl 250 mg L1
Carbon@Na4Ti9O20 TiO2 powder Hydrothermal treatment; Na4Ti9O20 nanotubes 153.3 F g1, 1 mV s1, 1 M 66.1 mg g1, 1.4 V,
nanotube153 400 C, nitrogen NaCl 1.0 mg L1
Li4Ti5O12@C154 Tetrabutyl titanate Hydrothermal treatment; Li4Ti5O12 nanoake arrays Not available 25.0 mg g1, 5 mA g1, 2.5 g
500 C, air L1
Na2Ti3O7–CNT@rGO155 Tetrabutyl titanate Hydrothermal treatment; Na2Ti3O7 nanowires Not available 129 mg g1, 145 mA g1,
vacuum ltration 3.0 g L1
a
CC: constant current, which in this case is 166 mA g1. b Salt removal efficiency performance.
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J. Mater. Chem. A, 2019, 7, 26693–26743 | 26703

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Fig. 5 Typical synthesis strategies of carbon–metal compound composites. Depending on the main components of the composites, they can
be categorized into carbon-based, metal-based, and other complex structures. For carbon-based structures, nanostructured metal compounds
are deposited onto the carbon surface to alter its surface properties. For metal-based structures, conductive carbon materials are used to
increase the conductivity of the bulk IHCs or prevent restacking of the layered IHCs. Other complex structures can be formed by utilizing the
core–shell (metal compound decorated carbon or carbon protected metal compounds) nanoforms and conductive materials (e.g., graphene,
carbon black and conductive polymers).
and salt removal rate (SRR) of the composite increase 10 and 20 electrode stores charge through both the EDLC (non-faradaic
times respectively.145 way) of carbon and the redox reactions (non-faradaic or fara-
The introduction of a metal compound on the carbon daic way, depending on whether the content of the electrode
surface enhances the hydrophilicity of the composite. Carbon changes or whether redox products are formed outside the
materials are generally hydrophobic due to the weak polarity of electrode) between sodium or chloride ions and the metal
the carbon–hydrogen bonds on their surface. Because of the compound (Table 2). According to the Kim–Yoon plot summa-
abundant nucleophilic atoms (oxygen, sulfur or nitrogen) in rized from the values in Table 1 (Fig. 6), even though the
metal compounds, the ion transfer in the porous electrodes can deposition of TMOs enhances the desalination performance of
be facilitated. For example, aer introducing TiO2 in the pure carbon electrodes, the SAC and SRR values of carbon–TMO
material preparation process, the titanium precursors are composites are still limited by ion adsorption on the carbon
transformed into TiO2 of various crystal forms and morphol- surface. In contrast, for composites with high SAC and SRR
ogies, and they may interact with the surface functional groups values, e.g., FePO4/RGO,146 Na3V2(PO4)3@C,133,148 Na2Ti3O7–
of carbon through Ti–OH or Ti–O–C bonds. The enhanced CNT@rGO155 and PB/rGA,145 the metal compound is the main
hydrophilicity due to Ti–OH bonds can improve the trans- component and dominates ion storage, which involves the
portation of water molecules and ions.50,52 Also, the hydrophilic intercalation/de-intercalation of sodium ions into/out of the
functional group Mn–O–H can be introduced through redox lattices or layers of IHCs.
reactions, high-temperature annealing or electrochemical Symmetric or asymmetric CDI modules can be assembled
deposition, and uniformly depositing and distributing MnOx based on the redox activities and stabilities of metal
nanostructures across on the carbon surface on the atomic level compounds in the anode and cathode (Table 2). Among the
using the atomic layer deposition (ALD) technique.57,61,122,125,127 metal compounds illustrated in Table 1, only carbon–TiO2,
In addition, IHCs are naturally hydrophilic due to their abun- carbon–ZrO2 and carbon–Mo1.33C-Mxene can be assembled
dance of nucleophilic atoms. symmetrically. In most cases, a carbon–metal compound
In addition to altering the surface properties of carbon– composite electrode needs to be asymmetrically assembled with
metal compound composites, pseudocapacitance can be intro- a carbon counter electrode according to the potentials of the
duced by the metal compound. As a result, the composite redox reactions; however, even in these cases, the metal
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Table 2 The ion storage mechanism and metal ion leakage of carbon–metal compound composites
Electrode Composite Ion storage mechanism CDI cell assembly Metal leakage Ref.
Cathode Carbon–TiO2 EDLC Symmetric 7 31, 50–53

Carbon–MnOx MnOx + Na+ + e 4 MnO x Na
+
Asymmetric 3 61 and 127
Carbon–ZnO EDLC Asymmetric 3 62
Carbon–ZrO2 EDLC Symmetric 7 131
Carbon–WO3 WO3 + Na+ + e 4 NaWO3 Asymmetric 3 64
6Na+ + 6e + WO3 4 W + 3Na2O
Carbon–SnO2 4SnO2 + 31Na+ + 31e 4 Na15Sn4 + 8Na2O Asymmetric 3 129
Carbon–FeOx FeOx + 2xNa+ + 2xe 4 Fe + xNa2O Asymmetric 3 58, 67 and 68

Carbon–V2O5 V2O5 + Na+ + e 4 NaV2O5 Asymmetric 3 28
NaV2O5 + Na+ + e 4 Na2V2O5
Carbon–CeO2 CeO2 + Na+ + e 4 CeOONa Asymmetric 3 68
Carbon–RuO2 RuO2 + 4Na+ + 4e 4 Ru + 2Na2O Asymmetric 3 132
Carbon–Co3O4 Co3O4 + xNa+ + xe 4 NaxCo3O4 Asymmetric 3 133
NaxCo3O4 + xNa+ + xe 4 CoxO + xNa2O
Carbon–SiO2 EDLC Asymmetric 7 135–137
Carbon–Ti3C2-Mxene Sodium ion intercalation Asymmetric NAa 88, 140 and 141
Carbon–Mo1.33C-Mxene Sodium ion intercalation Symmetric NA 92
Carbon–MoS2 xNa+ + xe + MoS2 4 NaxMoS2 Asymmetric NA 72 and 90
NaxMoS2 + 4Na+ + 4e 4 Mo + 2Na2S + xNa
Carbon–TiS2 TiS2 + xNa+ + ne 4 NaxTiS2 Asymmetric NA 91 and 142
Carbon–PB FeFe(CN)6 + xNa+ + xe 4 NaxFeFe(CN)6 Asymmetric NA 145
Carbon–FePO4 2FePO4 + Na+ + e 4 2Na0.5FePO4 Asymmetric NA 146 and 147
Carbon–Na3V2(PO4)3 NaV2(PO4)3 + 2Na+ + 2e 4 Na3V2(PO4)3 Asymmetric NA 148–150
Carbon–Na3Ti2(PO4)3 NaTi2(PO4)3 + 2Na+ + 2e 4 Na3Ti2(PO4)3 Asymmetric NA 151
Carbon–Na4Ti9O20 Na4Ti9O20 + 9Na+ + 9e 4 Na13Ti9O20 Asymmetric NA 152–155
Anode Carbon–TiO2 EDLC Symmetric 7 31, 50–53
Carbon–ZrO2 EDLC Symmetric 7 115
Carbon–l–Al2O3 EDLC Asymmetric 7 136 and 137
Carbon–Mo1.33C-Mxene Chloride ion intercalation Symmetric NA 92
Carbon–Ag/AgCl Ag + Cl e 4 AgCl Asymmetric NA 143
Carbon–BiOCl Bi + Cl + H2O 4 BiOCl + 2H+ + 3e Asymmetric NA 96
a
NA: not applicable.
compound may also be dissolved by other redox reactions (i.e.,

transition between the redox couples of the metal compound)
under a high voltage, causing ion leakage and performance
degradation of the composite electrode. Many cases of this issue
have been reported in the usage of carbon–TMO composites as
CDI electrodes,60,64,121 and even if there were no related reports,
the issue on IHC electrodes having a potential ion leakage
problem needs to be further studied.
The above discussion indicates that the type of metal
compound primarily determines the properties and perfor-
mances of its corresponding carbon–metal compound
composite. Therefore, the detailed synthetic routes, develop-
ment and applications of these carbon–metal compound
composites are reviewed and discussed below in accordance
with the type of metal compound utilized.
3. Carbon–TiO2 composites
Fig. 6 Kim–Yoon plot: salt adsorption capacity (SAC) vs. salt removal
rate (SRR) of the reported carbon–metal compound composite CDI Titanium dioxide (TiO2) or titania, an electrochemically stable
electrodes, in which the composite electrodes with both high SAC and and hydrophilic reagent abundant in nature, has been exten-
SRR values are given with their references. The remaining unmarked sively investigated for applications in electronic devices.157 TiO2
data is summarized from the values in Table 1. can be incorporated into the carbon electrode surface through
mechanical (surface coating), chemical (sol, sol–gel or
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hydrothermal reactions) or electrochemical (anodization) higher electrosorption in CDI applications than a pure AC
approaches. By using different titanium sources (e.g., titanium electrode. However, by using the mild chemical approach, there
alkoxides, TiO2 nanopowder, titanium sheet and inorganic may be difficulties in producing ne, uniform-sized particles
salts) and varying heating temperatures and gaseous media, with desirable crystal structures.
different particle sizes (micrometer down to nanosized), shapes Sol–gel method. Compared to its amorphous phase, nano-
(Fig. 7, nanoparticles, nanorods, nanobers and nanotubes) structured crystalline TiO2 (anatase or rutile) possesses better
and crystal phases (amorphous, anatase and rutile) would be electrochemical properties due to its shorter electron transfer
formed in the nal products. Since the properties of TiO2 vary path and larger specic surface area.158,159 To obtain crystalline
with size down to the nanometer scale and change with the TiO2, the sol–gel process has been employed in several studies
morphology of the shrinking nanomaterials, strategies for the to fabricate carbon–TiO2 nanoparticle composites.49,51,53,54,108,160
synthesis of carbon–TiO2 composites are focused on controlling Regarding the conventional sol–gel method, a high temper-
the accumulation of TiO2 on the carbon surface. ature (above 400 C) and long post-calcination time (over 5 h)
are required to obtain TiO2 in crystalline phases. For instance,
Lee et al. prepared an AC–TiO2 composite through the sol–gel
3.1 Carbon–TiO2 (nanoparticle form) composites method before annealing it in air at 450 C for 5 h, wherein the
As shown in Table 1, compared with the other nanostructures of TiO2 possessed an anatase structure but poor crystallinity.106
TiO2 (nanotubes, nanobers and nanorods), TiO2 nanoparticles Nonetheless, the AC–TiO2 composite has a higher EDLC and
are the most common additives for carbon due to the large lower diffusion resistance than pristine AC. Furthermore, the
variety of approaches to control the particle size and crystal composite exhibited a SRR value 39% higher than pristine AC.
structure. To prepare carbon–TiO2 nanoparticle composite The anatase structure of TiO2 can be further enhanced by
electrodes, three commonly employed methods are the mild altering the annealing atmosphere to nitrogen.109,110 For
chemical approach, sol–gel method and hydrothermal treat- instance, the anatase TiO2/CNTs composite electrode annealed
ment. As the techniques for controlling the particle sizes and in nitrogen exhibited a high specic capacitance (122 F g1) and
distributions are rened, these parameters could be more excellent electro-adsorptive capacity (1.0 mg g1) in comparison
effectively adjusted to maximize performance. with pristine CNTs (40 F g1, 0.7 mg g1) under the same
Mild chemical approach. In an earlier attempt, Ryoo et al. conditions.
directly modied AC cloth (ACC) by a chemical reaction An alternative method to enhance the crystallinity of TiO2 is
involving titanium alkoxide, titanium(IV)-butoxide (TNBT), and to increase the annealing temperature. However, at a higher
the hydroxyl groups on the carbon surface at room tempera- temperature, this energy-consuming process must be conduct-
ture,69,105 producing well-distributed amorphous TiO2 particles. ed in an inert or vacuum environment to avoid the oxidation
Since part of the hydroxyl groups on the ACC surface were and structural breakdown of carbon framework. For example,
consumed by the chemical reaction, its polarity was weakened, Chang et al. fabricated a similar AC–TiO2 composite49 following
and thus the effective electric eld strength was increased. the same route as Lee et al.,106 but the annealing temperature
Consequently, due to the small oxidation–reduction potential of was increased to 850 C to obtain rutile TiO2, which exhibited an
titania, the composite exhibited lower physical adsorption and EDLC 2.16 times higher than that of pristine AC. Furthermore,
Fig. 7 Morphology control of TiO2 in carbon–TiO2 composites.
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AC–TiO2 containing rutile TiO2 (better crystallinity) exhibited annealing (>450 C), the microwave-assisted sol–gel method
a better salt removal performance than AC–TiO2 using anatase still requires a large energy input. To achieve green-synthesis,
TiO2 (poor crystallinity) (13.3 mg g1 vs. 5.11 mg g1).49,106 Srimuk et al. prepared an AC–TiO2 composite containing
In addition to obtaining a crystalline structure, in order to amorphous TiO2 via a two-step hydrolysis of TIP on the carbon
avoid the aggregation of particles and reduce the extent of surface.54 In the rst step, TiO2 formation occurs when TIP was
uneven loading, it is desirable for TiO2 to be uniformly hydrolyzed at the oxygen containing surface groups of AC. More
dispersed onto the carbon surface. Therefore, several titania was subsequently adsorbed onto the previously formed
approaches have been employed as pre-, co- or post-treatment titania surface, leading to the continuous thickening of the
for the sol–gel process (i.e., modied sol–gel methods), coating. This two-step hydrolysis process to prepare the AC–
including ultrasonication,106 microwave radiation,108 two steps TiO2 composite is energy-efficient as no high-temperature
hydrolysis,54 and sol–gel spraying.51,55 annealing is required. However, the amorphous AC–TiO2
Liu et al. synthesized an AC–TiO2 composite based on the composite exhibited a lower specic capacitance as compared
microwave radiation assisted sol–gel method using titanium(IV) to the pure AC electrode due to the amorphous structure of its
isopropoxide (TIP) as a titania precursor. The method included TiO2-coating. Nevertheless, the salt removal performances of
a redox reaction step and a crystallization step (Fig. 8a).108 In the the electrodes, especially the cycling performance in oxygen
crystallization step, the ionic liquid plays a role analogous to the saturated aqueous solutions, has signicantly improved by the
hydrothermal method in driving the surface anatase crystalli- addition of titania. For example, a pristine AC electrode shows
zation of amorphous TiO2 nanoparticles formed in the reaction a 50% decrease of its initial SAC value aer 20 cycles, in
step (Fig. 8b). The benets of using microwave radiation are contrast, the amorphous AC–TiO2 composite electrode can
that the reaction can be maintained at an room temperature preserve 80% of its initial SAC value aer 60 cycles.54
and the reacting process facilitated by ionothermal (sol–gel Aside from the microwave and two-step hydrolysis methods
method in the presence of an ionic liquid) synthesis. As a result, of incorporating TiO2 into the carbon microstructure, another
in comparison with pristine AC, anatase nanostructured AC/ approach is to directly coat the bulk carbon material by the sol–
TiO2 composite showed a higher specic capacitance (84.7 F g1 gel method.51,55 The composite coated with a sprayed TiO2 layer
vs. 44.9 F g1) and salt removal capacity (8.05 mg g1 vs. 5.43 mg must be annealed in relatively mild conditions (250–350 C in
g1), as well as a better cycling performance (Fig. 8c). air, 1–2 h) to decompose the organic contents to form an
Although the energy consumption of utilizing microwave is amorphous structure,51 thus no signicant improvement on
considerably lower as compared with high-temperature specic capacitance was observed. Nevertheless, the composite
Fig. 8 Microwave-assisted ionothermal synthesis of the nanostructured anatase TiO2/AC composite: (a) synthesis route, (b) transmission
electron microscopy (TEM) micrograph and the inset shows the crystalline size of anatase TiO2 (at TIP/H2O molar ratio of 1 : 30), and (c) the
adsorption–desorption cycles at [NaCl]0 of 100 mg L1 and applied potential difference of 1.2 V. Reproduced with permission.106 Copyright 2013,
Elsevier.
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displayed a better electrosorption performance due to its oxide (GO) was mixed with TiCl3. Aer stabilizing the mixture
enhanced wetting property introduced by the TiO2 layer, which with NH3$H2O by ultrasonication, it was subjected to hydro-
created more active sites for charged ions. thermal treatment at 180 C for 12 h to generate a GA/TiO2
To combine the advantages of amorphous and crystalline hydrogel. Finally, a monolithic GA/TiO2 hybrid was obtained
TiO2, Laxman et al. deposited two layers of TiO2 (crystalline and aer freeze-drying the as-prepared hydrogel. Note that neither
amorphous) on the carbon surface, where the crystalline layer high-temperature annealing nor post-treatment was conduct-
was introduced by dip-coating with pre-stabilized rutile TiO2 ed. By using TiCl3 as the titanium precursor, the authors
nanoparticles (depositing into the microstructure), before the proposed that TiO2 could be chemically bonded to the GO
amorphous layer was sprayed onto the crystalline layer (coating sheets by the reaction with low-valence ions (Ti3+), and the
onto the bulk surface).55 They also discovered that the localized formed chemical bonds should be stronger than the physical
permittivity-dependent dipole density formed within the nano- bonds introduced by the adsorption of high-valence titanium
particles allowed the dielectric nanosized oxides to improve the ions. The X-ray diffraction (XRD) patterns and high resolution
electric eld strength. Thus, the composite with two-layered TiO2 transmission electron microscopy (HRTEM) images of the
displayed both a better capacitance and salt removal perfor- hybrid suggested that the deposited TiO2 nanoparticles were
mance than a pure carbon electrode. in an anatase phase (Fig. 9). Furthermore, due to its mono-
Compared with the sol–gel synthesis methods and the clas- lithic morphology, the as-obtained product could be used as
sical mild reaction approach, modied sol–gel methods can electrode without binders in energy storage and CDI applica-
improve the capacitances and desalination performances of tions. As shown in Fig. 9c–e, comparing to AC and pure GA, the
carbon–TiO2 composites by distributing the nanoparticles more 3D porous structure with an open pores structure endows the
uniformly and regulating the crystal structure formations of hybrid with an outstanding specic capacitance, salt removal
TiO2. However, to control the crystal structure and the dis- and cycling ability.
persity, sol–gel methods either require great energy input, or Following this work, a 3D exible carbon aerogel/TiO2 (CAs/
need multiple steps to obtain the nal product. TiO2) hybrid was prepared by Li et al. using watermelon peels as
Hydrothermal treatment. Compared to the sol–gel method, the carbon source.68 The hybrid aerogel demonstrated an
hydrothermal synthesis can produce uniform crystals of outstanding decontamination capacity of 57.13 mg g1 for Cu(II)
a smaller particle size on a larger scale.161 Assisted by ultra- removal (1.2 V), which highlighted the possibility of using CDI
sonication, Yin et al. introduced a simple and versatile method for decontamination and the recovery of toxic heavy metals in
to fabricate three-dimensional (3D) graphene aerogel/TiO2 pollution cleanups.
(GA/TiO2) nanoparticle hybrids (Fig. 9).31 Briey, graphene
Fig. 9 Hydrothermal synthesis of anatase TiO2 composite graphene aerogel hybrid (GA/TiO2): (a) formation mechanism, (b) scanning electron
microscopy (SEM) image and XRD pattern (inserted), comparative studies of (c) CV curves (0.1 M NaCl solution, 100 mV s1) and (d) desalination
capacity with different equilibrium concentrations, and (e) electrosorption and regeneration cycles in 500 mg L1 NaCl. Reproduced with
permission.31 Copyright 2013, Wiley-VCH.
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3.2 Carbon–TiO2 (nanorods/nanober form) composites To overcome this challenge, Wei et al. prepared a TiO2-NTs/
HCF/CF (THC) composite electrode using the anodic oxidation
Due to the natural tendency of nanoparticles to aggregate, most
electrochemical method.111,113,163 TiO2 nanotubes (TNTs) were
efforts to synthesize carbon–TiO2 nanoparticle composites
prepared by the anode oxidation of titanium sheets. For the
must focus on the uniform dispersion of nanoparticles. In
synthesis of the carbon bers, precursors composed of glucose
terms of morphology, nanorods and nanobers have relatively
and Ni(CH3COO)2$4H2O were directed into the vacuumed
larger axial ratios, which can prevent the intra-aggregation and
nanochannels of the TNTs. The same precursor was used to
inter-agglomeration of nanoparticles (more ion storage space),
and thus provide more interfacial connection between the form the carbon beads (vacuum-dried at 60 C). The nal
nanoparticles (faster electron transfer). product was obtained aer a two-stage heat treatment (200 C
for 2 h in air, 600 C for 3 h in nitrogen). The electrode has

Studies for carbon–TiO2 nanorod or nanober composites
a unique structure in which hollow carbon bers function as
for CDI were performed by El-Deen et al.50,52 A TiO2 nanober/
a binding layer to attach the carbon spheres to the top of the
AC composite was synthesized by the physical blending of
TNTs. Aer acid activation, the composite electrode (THC-A)
electrospun TiO2 nanobers (TNFs), AC and polyvinylidene
reveals excellent mechanical stability, electrochemical and
uoride (PVDF, binder) using a high-speed mixer. Due to the
electrosorption performances. For instance, comparing
improved hydrophilicity and anatase structure of TiO2, the
optimum electrochemical (380 F g1, 10 mV s1, 1 M NaCl) and a conventional carbon electrode prepared by mixing AC/carbon
desalination performances (17.7 mg g1, 1.2 V, 292 mg L1) black/PTFE (16.3 F g1, 6.99 mg g1) with a THC electrode (THC-
A without acid activation, 135.3 F g1, 9.85 mg g1), the THC-A
were achieved at 10 wt% loading of TNFs.50
electrode possesses a higher specic capacitance (238.2 F g1,
In another attempt, El-Deen et al. prepared a reduced gra-
20 mV s1, 1 M Na2SO4) and salt removal capacity (13.11 mg g1,
phene oxide and TiO2 nanorod composite (RGO/TiO2 nanorod)
1.2 V, 500 mg L1).
by introducing the excellent electronic properties of graphene to
The integration of the current collector and active material
metal oxides.52,162 The RGO/TiO2 nanorod composite was
increased the contact area and enhanced the bonding force
fabricated by sonication (2 h), hydrothermal treatment (10 M
KOH, 120 C, 24 h) and high-temperature sintering (Ar, 650 C, between them, which allowed the electrons in the current
1 h). The scanning electron microscope (SEM) and TEM images collector to quickly travel and be uniformly distributed within
the active material. However, such an electrode is impractical
suggested that TiO2 nanorods were intercalated into the exible
for industrial applications due to its complicated synthesis
and ultrathin wrinkled graphene nanolayers, resulting in
route. Moreover, maintaining the cycling performance of the
a sandwich-like structure. As a result, the agglomerated gra-
electrode presents another challenge and regular electrode
phene was expanded and its specic surface area increased,
replacement is required, which incurs an excessive cost since
which differed from the reduced specic surface areas of other
the entire electrode including the titanium current collector is
carbon–TiO2 composites. Furthermore, due to high-
temperature sintering, anatase TiO2 nanorods were formed discarded. Compared with other monolithic materials31,164 or
with a small fraction of TiO2 transited to the rutile phase. The electrodes using titanium foam (which also provides a larger
contact area) as the current collector, there is still a signicant
RGO/TiO2 nanorods composite demonstrated an astonishing
gap between the experimental stage and practical application
increased specic capacitance (443 F g1, 10 mV s1, 1 M NaCl)
for the THC-A electrode.
when 20 wt% TiO2 nanorods were incorporated, in comparison
Compared to other metal compounds which will be dis-
with the low specic capacitance of pristine graphene electrode
cussed below, TiO2 nanostructures are unique in that they can
(59 F g1) under identical conditions. Due to the improved
improve the cycle performance of the electrode as a protective
hydrophilicity, increased surface area and reduced polarity of
RGO, the composite electrodes displayed an excellent desali- layer.31,54,108 Due to the catalytic role of TiO2 in the reduction of
nation (16.4 mg g1) and cycling performance (almost no oxygen, nanostructured TiO2 can prevent active oxygen from
participating in carbon oxidation reactions, which accounts for
degradation within 25 cycles).52
the poor cycling performances of pure carbon electrodes.
3.3 Carbon–TiO2 (nanotube form) composites

4. Carbon–MnOx composites
A current collector is regarded as one of the main components
of the electrode in a CDI unit which can quickly distribute While manganese oxides (MnOx) are abundant in nature, they
charge evenly to the active materials. A common method to exhibit poor electrical conductivities (s z 106 to 105
prepare an electrode for CDI is to press the carbon slurry con- U1 cm1).165 Nevertheless, they still are of great interest for
taining binders (e.g., PVDF or PTFE, polytetrauoroethylene) applications in electrochemical devices due to their multiple
onto the current collector (e.g., graphite or titanium plate). oxidation states (MnO, Mn3O4, Mn2O3, MnO2), various types of
However, due to the weak interactions between the conductive crystal structure,166–168 fascinating electrochemical properties
substrate and capacitive layer, the contacting resistance may (redox couples of Mn4+/Mn3+ and Mn3+/Mn2+), and outstanding
pose a daunting challenge in practical application. The poten- theoretical specic capacitance (1400 F g1). To compensate for
tial solutions are to increase the contact area and form the poor electrical conductivity of MnOx, several approaches
a stronger connection between the current collector and active have been developed to obtain the desired morphologies and
material. crystal structures: (1) selecting the appropriate manganese
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substrates (e.g., KMnO4, MnSO4$H2O, Mn(NO3)2$6H2O, and pore volume of the electrode. Although the MnO2/NCs
MnCl2$4H2O, NaMnO4, and hydrated manganese(II) acetate composite electrode exhibited better capacitance and desali-
tetrahydrate) and synthetic methods (e.g., redox reaction, sol– nation performances than an AC electrode, the mechanism
gel, microwave radiation, anodic electrodeposition, layer-by- employed by MnO2 for desalination was unclear as comparative
layer deposition and hydrothermal methods) to achieve studies of the pristine and MnO2/NCs carbon composite elec-
various nanoscopic morphologies (nanoparticles, nanorods, trodes were not conducted.
nanosheet and nanobers) and crystal structures (Fig. 10), (2) Based on this method, several carbon–MnOx composites
controlling the thickness of the MnOx layer or the loading were designed for CDI. For example, Cai et al. prepared a MnOx
amount, (3) incorporating other metals into MnOx compounds, covered electrospun carbon nanober composite (ECNF/MnOx)
and (4) compositing these compounds with other conductive for CDI applications.122 Due to the presence of the MnOx layer,
porous architecture, such as carbon and conductive polymers. the composite possessed a hydrophilic and negative charged
surface compared with the hydrophobic and neutrally charged
pure ECNF, where the former could enhance the transportation
4.1 Carbon–MnOx (nanoparticle form) composites
and diffusion of counter ions into the carbon ber electrode,
Compared to MnOx with other morphologies (e.g., nanorods, resulting in a higher charge efficiency as well as desalination
nanosheets and nanolms), MnO2 nanoparticles are promi- performance. Chen et al. prepared a MnO2 covered multi-walled
nently used in carbon–MnO2 composites mainly due to their CNTs composite (MnO2/MWCNTs) using the same method.123
simple and diverse synthetic methods. In most cases shown in Compared with the pristine MnO2 electrode, the MnO2/
Table 1, to deposit the inorganic manganese precursors onto MWCNTs composite electrode exhibited a higher electro-
a carbon matrix (e.g., AC, CA, CNTs, AC bers and graphene), sorption capacity and better cycling performance during the
additional energy must be supplied, which can be provided by CDI process.
redox reactions, high-temperature annealing, the presence of Although both studies indicated that MnOx may enhance
an electric eld or a microwave/ultrasonic energy source. desalination through ion intercalation/deintercalation, several
Redox reaction. Yang et al. rst reported a MnO2 nanoporous issues required further investigation; (1) the contribution to
carbon (MnO2/NCs) composite electrode by the co-precipitation CDI desalination by the ion intercalation/deintercalation
of MnSO4$H2O and KMnO4 onto the surface of the silica- mechanism was not clearly stated, (2) the electrode resis-
templated nanoporous carbon frameworks.117 The nanoporous tances increased aer MnOx loading, (3) none of the studies
structure was determined by the template size, calcination compared the desalination performances of composite and
(850 C, nitrogen) and annealing (200 C, air) conditions. MnOx non-composite electrodes (carbon–MnOx vs. pristine carbon),
layers could also be formed by a simple redox reaction between and (4), the SAC values of these composites were still too low for
the carbon matrix and KMnO4.169 practical usage (<10 mg g1).
Aer loading MnO2, the mesopores developed by the silica To balance the capacitance and resistance of the MnO2
templates in the carbon matrix were partially covered and composite, Li and Park pointed out that a conductive additive is
blocked, resulting in an decrease in the specic surface area
Fig. 10 Polyhedral representation of the eight Mn oxides: (a) b-MnO2, (b) R-MnO2, (c) a-MnO2, (d) d-MnO2, (e) l- MnO2, (f) LiMn2O4, (g) Mn2O3,
and (h) Mn3O4. The light yellow, pink, and dark purple polyhedral represent Mn2+ tetrahedra, Mn3+ and Mn4+ octahedra, and Li+ tetrahedra,
respectively. Black spheres represent K+ ions. Reproduced with permission.167 Copyright 2013, American Chemical Society. (i) Relative values of
the specific capacitance, ionic conductivity, and Brunauer–Emmett–Teller (BET) surface area of various MnO2 forms. Reproduced with
permission.168 Copyright 2009, American Chemical Society.
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necessary for the composite to achieve a high SAC value and performance of modied materials is to select a carbon base of
charge efficiency.128 Therefore, a small amount of SWCNTs was moderate desalination capacity beforehand, or it would be
added as a conductive reagent (0.1 mg cm2) to the composite futile for further modication by MnOx nanoparticles.
aer MnO2 was deposited by the redox reaction between ACC Microware-assisted hydrothermal method. During the
and KMnO4 (MnO2/ACC/SWCNT). In addition, to facilitate Cl synthesis of carbon–MnO2 composites by hydrothermal or
adsorption, a 100 nm-thick Ag layer was deposited onto the standard high-temperature annealing methods, the common
anode (Ag/ACC) via e-beam evaporation. As expected, the procedure is to add a MnO2 precursor to the carbon matrix,
asymmetric unit (MnO2/ACC/SWCNTkAg/ACC) demonstrated resulting in the release of inorganic ceramics on the surface of
a higher capacitance (311 F g1 at 5 mA cm2), SAC value the matrix. The main drawbacks of these methods are the low
(17.8 mg g1 at 0.02 M and 1.2 V) and charge efficiency
residual recyclability, formation of secondary pollutants, long

(85%).128 synthesis time and high energy input. To achieve a facile and
High-temperature annealing. In addition to redox reactions, green-synthesis route, the energy input in the methods above
another facile approach to load MnOx crystals is high- must be replaced with low-power energy sources, e.g., a micro-
temperature annealing (>700 C). In this case, instead of wave source.
using a redox active manganese precursor (e.g., KMnO4), a mild For example, El-Deen et al. prepared a graphene wrapped
precursor (MnSO4$H2O) is employed instead to avoid the MnO2-nanostructure via a two-step microwave-assisted one-pot
decomposition of carbon structure at high temperatures. synthesis.56 Compared to conventional synthesis methods that
During high-temperature annealing, since carbon is an effective would take a few hours, this method only requires 30 min. By
reductant, MnOx particles with lower valences (MnO or Mn3O4) controlling the second irradiation duration, MnO2 nano-
are likely to be formed in the composites. Because of the particles or nanorods could be formed. Another feature of this
interactions between the manganese precursor and carbon one-pot synthesis is that ammonium persulfate can simulta-
matrix, the porous structure of the carbon matrix could be neously oxidize the graphite and manganese precursor, allow-
maintained or even further developed. ing graphite exfoliation and the intercalation of MnO2
Following these approaches, Chen et al. fabricated nanostructure into the graphene sheets to occur simulta-
a manganese oxide/active carbon ber composite (MO2/ACF) by neously. This research also conrmed that as compared to
high-temperature annealing (nitrogen, 700 C).120,170 The MnO2 nanoparticles, the nanorod morphology of MnO2, which has
nanosheets were reduced to Mn3O4 aer high temperature a large axial ration that can prevent the aggregation of graphene
treatment, which conrmed the reduction ability of the carbon. sheets, allowed the composite to achieve higher electrochemical
The as-prepared composite showed a higher adsorption ability (292 F g1 at 10 mV s1 in 1 M NaCl) and desalination perfor-
for Cd2+ ions due to the lower total energy of Mn3O4 compared mances (5.01 mg g1 at 1.2 V in 50 mg L1 NaCl). Despite this,
with pure carbon when Cd2+ ion was adsorbed.120 probably due to the unrened graphene structure (e.g., the
To obtain more uniformly dispersed MnOx particles, Zafra thickness of graphene layer) and poor crystallinity of MnO2, the
et al. combined the carbonization and annealing processes, reported electrosorption capacity of the nanostructure was
specically, the intermediate composite was prepared in undesired.
advance by soaking the carbon aerogel precursor in Although microwave-assisted one-pot synthesis exhibits
Mn(NO3)2$6H2O solution, before thermally treating the inter- facile and eco-friendly features, structural defects on its prod-
mediate composite at a high-temperature (CO2, 750 C).119 MnO ucts undermine its reliability. Instead, hydrothermal synthesis
particles were detected in the composite, which demonstrates could produce more uniformly distributed and better crystal-
a similar pore structure as the pristine electrode, however, the linity MnO2 nanoparticles. For instance, recently, Li et al.
electric resistance of the composite doubled due to the poor synthesized a needle-structured a-MnO2/carbon ber paper (a-
conductivity of MnO crystals. MnO2/CFP) composite using the hydrothermal method (120 C,
Based on this work, Macias et al. conrmed that by adding 3 to 12 h) for nickel and manganese ions removal (Fig. 11).60 It is
several additives (manganese precursor, carbon black and noteworthy that a smaller amount of more porous MnO2 was
diatomite) simultaneously, a composite carbon aerogel (MRF– deposited at a longer time; this was caused by the particles
Mn–D–CB) with a more developed pore structure, enhanced detaching with increasing stress as their porosity increased. In
conductivity and capacitance could be achieved.124 However, terms of nickel removal efficiency and capacity, the prepared
due to the intrinsic low electrosorption ability of carbon aerogel, composite shows great improvements in comparison with the
MRF–Mn–D–CB showed low SAC value (6.1 mg g1) even at original CFP substrates. However, when the composite was used
a higher voltage (1.5 V) and salt concentration (1500 mg L1). as a cathode, manganese ion leakage was observed. This
Another approach is to carbonize the composite at a lower phenomenon was not reected in the other works that used
temperature. For example, Zhao et al. prepared a MnOx-ordered carbon–MnOx composites as cathodes in CDI applica-
mesoporous carbon composite by optimizing the carbonization tions,59,81,128,171 which suggested that the stability of carbon–
temperature (300–400 C) and the loading of the manganese MnOx composites should be subject to more investigation as
precursor (7–35%).126 Even though the composite exhibited both the cathode and anode.
a higher desalination performance than pure carbon (5.4 vs. Despite the simplicity and environmental friendliness of
3.1 mg g1), it was still inadequate for practical application. microwave-assisted synthesis, the crystallinity of the oxide
This work indicated that the key to improving the desalination particles is poor. In addition, although hydrothermal synthesis
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methods.58,121 By adjusting the deposition parameters (e.g.,

current density or scan rate, electrolyte composition, deposition
time and temperature), the morphology, porosity, oxidation
state and crystallinity of MnO2 can be controlled. Additionally,
an enhanced electrochemical performance of MnO2 can be
obtained.175–177 Taking morphology as an example, MnO2 with
columnar structures, discrete oxide clusters, nanosheets, petal
and ower-like morphologies and continuous coatings can be
prepared.178
The formation of MnO2 on an anode substrate depends on

the electro-kinetic phenomena (i.e., nucleation and growth of
crystal grains) during the process, where the accessible elec-
troactive sites and fast charge transfer ability of the substrate
play a key role in determining the physicochemical properties of
MnO2. Since nanostructured carbon materials (e.g., CNTs) are
highly porous and conductive, they are considered suitable
Fig. 11 Morphology, structure and performance of a-MnO2/CFP substrates for the anodic electrodeposition of MnO2 thin lms.
composite: (a) proposed growth mechanism of the a-MnO2 nano- In the eld of SCs, electrodeposited carbon–MnOx composites
needles on carbon fiber paper, (b and c) SEM images of the surfaces of are well-studied and many advancements have been made
the MnO2 deposited onto carbon fiber paper, (d) XRD patterns, and (e)
towards achieving a high capacitance and long cycling life,
nickel ion adsorption–desorption behavior for the MnO2/CFP
composites. Reproduced with permission.60 Copyright 2018, American whereas, studies pertaining to the applications of these
Chemical Society. composites for CDI has just begun.
Hu et al. fabricated a MnO2/carbon ber (MnO2/CF) elec-
trode for copper ion removal using the galvanostatic electro-
could improve particle crystallinity and control the particle size, deposition method in a three-electrode setup containing
the reaction is time-consuming. Therefore, a combination of a MnSO4 precursor.121 Uniform and adhesive deposition was
microwave-assisted and hydrothermal synthesis may achieve achieved by pretreating the carbon bers with a HNO3 solution.
the goal of rapid production and good crystallinity. During the process, the deposition duration was precisely
As an example, Liu et al. fabricated a nanostructured bir- controlled to obtain various loading amounts. The optimal
nessite incorporated CNT composite (HB/CNTs) using the specic capacitance (397 F g1 at 0.1 A g1 in 1 M Na2SO4) and
microwave-assisted hydrothermal method.125,172 Following Cu2+ electrosorption capacity [172.88 mg g1 under 0.8 V in
a typical hydrothermal synthesis route, the holding time at 6 mg L1 Cu(NO3)2] were obtained with a deposition time of
a relatively high temperature and high pressure was only 1000 s. Unfortunately, similar to the a-MnO2/CFP composite
10 min. By optimizing the amount of birnessite in the HB/CNTs, prepared by Li et al.,60 the release of manganese ions of MnO2/
a high electrical conductivity and uniform dispersion of the CF cathode was detected, even though it was relatively insig-
MnO2 were achieved. The composite showed remarkably nicant (0.3 mg L1). However, this suggested that the cycling
enhanced Zn2+ removal performance based on the mechanisms performance of MnO2/CF would be a major issue during long-
of insertion/extraction of Zn2+ into/from birnessite and term application.
reduction/oxidation between Mn(IV) and Mn(III)/Mn(II). Further By using an AC substrate as the working electrode and 0.5 M
studies of the individual contributions from CNTs and birnes- manganese acetate as the manganese precursor, Liu et al.
site indicated that the adsorption capacities of pure CNTs and electrodeposited MnO2 on AC surface through the cyclic vol-
pristine birnessite are much lower than that of the composite. tammetry (CV) method in a three-electrode setup.58 Due to the
This result indicated the existence of a synergistic adsorption increased hydrophilic surface and introduced
effect in combination with the pseudocapacitance of birnessite pseudocapacitance, the composite electrode exhibited
and the EDLC of CNTs. a tremendous improvement in its electrochemical performance
and NaCl electrosorption in comparison with a pure AC
electrode.
4.2 Carbon–MnOx (thin lm) composites Furthermore, Hand et al.59 prepared a MnO2/carbon aerogel
Since MnOx is generally less conductive than carbon, the key to (MnO2/CA) composite using the same protocol as Liu et al.,58
synthesizing a high-performance carbon–MnOx (thin lm) and for comparison, another MnO2/CA composite was fabri-
composite is to control the thickness of the MnOx layer. For cated by redox (electrodeless) method was prepared. The char-
synthesizing the thin lm MnOx, anodic electrodeposition and acterization results indicated the following points: (1)
ALD have been reported to disperse MnOx thin lm effectively compared to the discrete crust morphology of the electro-
and uniformly on the carbon surface. deposited MnO2/CA composite, more uniformly distributed
Anodic electrodeposition. Anodic electrodeposition of MnO2 MnO2 was observed in the electrodeless samples, (2) both CV
thin lms typically involves the oxidation of Mn(II) to MnO2 (ref. and redox deposition increased the Brunauer–Emmett–Teller
173 and 174) through potentiostatic or galvanostatic (BET) surface area and micropore volume, and (3) CV samples
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displayed greater carbon structure disruption because of their electrode demonstrated an excellent cycling behavior due to the
crust morphology. However, despite the difference in their presence of CS.
morphologies, comparable capacitance ranged from 164 to 285 The above studies have shown that anodic electrodeposition
F g-MnO21 were measured for both CV and redox deposited is effective for incorporating MnO2 thin lms onto a carbon
samples. In terms of Na+ removal, electrodes prepared from substrate. However, current results indicate that further
redox reactions exhibits higher removal rates and capacities research is urgently needed to address the following issues: (1)
than those of CV electrodes, suggesting that the elementally the reported SAC values of electrodeposited composites are far
heterogeneous morphology of the electroless samples could from those of competing composites synthesized by other
facilitate charge transfer and ion diffusion. methods, e.g., redox reaction and hydrothermal methods, (2)
Nevertheless, since the electrical conductivity of MnO2 is manganese ions released during the adsorption and desorption
much lower than carbon (105 to 106 vs. 50 S cm1), this cycles may lead to secondary contamination and possibly
proved that the MnO2 coating on the carbon substrate had endanger human health, (3) the effects of electrodeposition
created a resistive barrier between the current collector and methods and parameters on the desalination performance of
carbon. Therefore, the coating amount should be precisely the composite are unclear, and (4) the correlations of the
optimized to reconcile the increase in resistance (decrease in morphologies/structure of the MnO2 lm and the desalting
charge efficiency) and the desalination performance. performances of their corresponding composites should be
To obtain a carbon–MnO2 composite with a higher electrical further studied.
conductivity, Liu et al. prepared a MnO2/CNT–chitosan Atomic layer deposition. ALD is a facile approach for the
composite (MnO2/CNT–CS) based on their previous work, since conformal deposition of redox-active thin lm on carbon
CNTs are generally more conductive compared to other nano- substrates on the atomic level. Typically, the ALD of MnO2 relies
structured carbon.58,127 The incorporation of MnO2 resulted in on the sequential chemical reactions between the pulse-
a signicant surface area decrease but great hydrophilicity introduced manganese precursor and oxidant under a variable
improvement of the composite. In addition, although the elec- temperature. The thickness of the layers can be precisely
trodeposited MnO2 thin lm increased the equivalent series controlled on the Ångstrom level by adjusting the precursor gas
resistance of the CNT–CS by nearly 5 times (37.1 vs. 7.3 U), uxes, heating temperature, exposure and purging time.
MnO2/CNT–CS showed a higher capacitance compared with Furthermore, due to the self-limiting nature of the surface
that of the CNT–CS (Fig. 12). Considering the lower surface area binary reactions, the surface of the ALD lms are extremely
and electrical conductivity of MnO2/CNT–CS composite, the smooth and continuous.
increase in pseudocapacitance could be attributed to the redox With these features of ALD, Silva et al. coated vertically
reactions of the MnO2 thin layer. Thus, a MnO2/CNT–CS aligned CNTs with Mn3O4 to form the composite (VACNTs/
cathode composite exhibited higher Na+ adsorption capacity Mn3O4) by ALD for binder-free capacitors.179,180 During the ALD
with respect to the CNT–CS electrode. The MnO2/CNT–CS process, hundreds of pulse cycles (0.2 to 2.5 s per pulse, 200 C)
Fig. 12 Electrochemical and desalination performances of MnO2/CNT–CS: (a) schematic diagram of the electrodeposition process using CNT
as the carbon substrate and CS as a binder, (b) specific capacitance at various scan rates (1 M NaCl aqueous solution), and (c) cycling performance
of MnO2/CNT–CS composite between 1.2 and 0.0 V (1 mM NaCl aqueous solution). Reproduced with permission.125 Copyright 2017, American
Chemical Society.
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were conducted to achieve a thicker deposition, e.g., with 600 any other reported CNT–MnOx composites, and consequently,
ALD cycles, the thickness of Mn3O4 layer could be 25 nm. The its sodium ion adsorption ability (490 mmol g1) is higher than
deposited thin lm showed poor crystallinity, which is any other reported carbon-based electrodes for CDI applica-
a common feature for ALD metal oxide thin lms. Due to the tions. However, despite its outstanding salt removal perfor-
synergistic effect of the VACNTs and Mn3O4 layer, higher mance in salt removal, some issues should be further
capacitance of the composite was obtained with more ALD considered when using VACNTs/Mn3O4 electrodes for large-
layers. However, the reported capacitance of the composite was scale CDI, e.g., its scalability, cost, long-term stability (the
only 80 mF cm2 which is much lower than that of other release of manganese ions), energy demand of the ALD and the
carbon–MnOx composites due to practical reasons. toxicity of the manganese precursor, etc.
Based on this research, Shi et al. believed that the low

capacitances of VACNTs/Mn3O4 composite may be caused by 4.3 Carbon–MnO2–conductive polymer composites
the inherent properties of the directly grown VACNTs.61 Using
Some of the aforementioned studies have shown that a major
the same method (chemical vapor deposition, CVD) but with
problem of carbon–MnOx binary composite electrodes is the
a different catalyst, Shi et al. attempted to grow VACNTs on
slow release of manganese ions during the adsorption–
a substrate affixed catalyst, where the catalyst was 1 nm-thick Fe
desorption cycles in CDI. This is because MnOx nanoparticles
over 10 nm-thick Al2O3, affixed on prime n-type Si (100) wafers
are deposited onto the carbon surface by van der Waals forces or
prepared by electron beam deposition.181 Aer CVD growth,
weak chemical bonds and are exposed to the electrolyte.
a critical step was to detach the grown VACNTs from the Si
Therefore, a strategy to prevent manganese leakage is to enforce
substrate by H2 etching, then ALD of MnOx was conducted. As
the connection between MnOx and the carbon surface.
shown in Fig. 13a, to ensure the fast electron transport from the
It has been conrmed that the incorporation of conductive
current collector to the active material, VACNTs/Mn3O4 was
polymer, being both a binder and a conductive additive, to
transferred to a titanium sheet and secured by a physical con-
obtain a ternary composite with a complex structure could be
straining method.182 Morphology characterization demon-
a solution to this problem. Conductive polymers are electrically
strated the successful deposition of Mn3O4 layer on VACNTs
conductive based on a conjugated bonding system along the
surface (Fig. 13b–e). The prepared sample exhibited both the
polymer backbone with the insertion of dopant/counter ions
highest mass and areal specic capacitances as compared to
(e.g., Cl).183 The most commonly studied conductive polymers
Fig. 13 Synthesis, characterization and performance of the VACNT/MnOx hybrid: (a) schematic illustration of the MnOx coating on VACNTs via
ALD, cross-sectional SEM images of (b) pristine VACNTs and (c) VACNT/MnOx after 150 ALD cycles, (d and e) TEM images with 75 and 150 ALD
MnOx coating cycles, respectively, (f) sodium ion adsorption performance of VACNT/MnOx. Reproduced with permission.61 Copyright 2018,
American Chemical Society.
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for charge storage are polyaniline (PANI), polypyrrole (PPy) and electrical resistance (4.6 vs. 1.2 U cm). In contrast, the electro-
polystyrene sodium sulfonate (PSS).184 Although they have lower chemical properties of MnO2/PSS/CNTs were enhanced due to
rates of adsorption and desorption of ions as compared to the improved charge transfer inside the bulk material. As
carbon, conductive polymers can improve charge storage of the a result, this ternary composite exhibited a higher and more
composite through redox reactions, i.e., the pseudocapacitive stable desalination performance (e.g., no manganese ion
charge storage. leakage was observed) than MnO2/CNTs (4.7 vs. 3.3 mg g1),
Following the promising performance of these ternary where the latter was prepared by the conventional hydrothermal
composites in SCs and lithium batteries (LIBs) applica- method.
tions,185,186 Yang et al. reported the rst ternary carbon–MnOx– Even though the SAC value of MnO2/PSS/CNTs is not as high
polymer composite electrode (MnO2/PSS/CNTs) for CDI appli- as other reported carbon–MnOx composites (Table 1), the
cations, where layer-by-layer (LBL) deposition was employed to signicance of this study was that it provided a method which
alternatively deposit MnO2 (positively charged) and PSS (nega- guarantees the stability of the composites, thus resolving the
tively charged) layers onto CNTs.118 It is noteworthy that the LBL issue of ion leakage. Subsequent methods of improving the salt
deposition was governed by the electrostatic interactions removal performance of the composite are selecting a carbon
between two oppositely charged species. The LBL deposition of with higher capacitance (e.g., graphene), selecting a conductive
MnO2 and PSS onto CNTs endowed the composite with the polymer with higher conductivity (e.g., PPy) and employing
following advantages during synthesis; (1) the negatively or a more efficient composite preparation method (e.g., ALD
positively charged layers on the CNTs surface enabled the technique).
homogeneous dispersion of CNTs in an aqueous solution, (2) Compared with other carbon allotropes, graphene has
MnO2 was rmly bonded with CNTs through electrostatic unique electronic properties and is considered a promising
interactions, and (3) MnO2 could be uniformly dispersed and material for SCs electrodes, since it is reported that its quantum
deposited onto CNTs. Compared with pristine CNTs, physical specic capacitance could be as high as 550 F g1 when
characterization showed that LBL deposition signicantly assuming a theoretical specic surface area of 2630 m2 g1.187,188
decreased the BET surface area (191.8 vs. 406.6 m2 g1) and total Among the conductive polymers, PPy has relatively high theo-
pore volume (0.297 vs. 0.586 cm3 g1) while increasing the retical (620 F g1) and measured (530 F g1) specic
Fig. 14 Synthesis and desalination performance of the RGO–PPy–Mn composite: (a) schematic illustration for the synthesis procedure, (b) CDI
profiles of as-prepared electrodes under 2.0 V, (c) electrosorption capacity and removal efficiency of the RGO–PPy0.5–Mn0.4 electrode in NaCl
solutions with respect to different initial concentrations, and (d) regenerated electrosorption capacity of RGO–PPy0.5–Mn0.4 electrode.
Reproduced with permission.57 Copyright 2015, The Royal Society of Chemistry.
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capacitances with a moderate conductivity (10–50 S cm1).183 In such as ZnO, SnO2, FeOx, V2O5, CuO, CeO2, RuO2 and ZrO2.
addition, the theoretical capacitance of MnO2 could be as high Through various preparation techniques, the above TMO
as 1400 F g1. Therefore, a composite combining the advan- additives can generally improve the desalination abilities of
tages of graphene, PPy and MnO2 is expected to exhibit excellent carbon–metal compound composites (Table 1). However, due to
electrochemical and desalination performances. the different atomic structures (i.e., different partially lled d-
Following this assumption, Gu et al. prepared a 3D gra- orbitals) and electronic properties (e.g., different dielectric
phene–PPy–Mn composite (RGO–PPy–Mn) by a two-step constant) of the additives, their inclusions result in varied
hydrothermal process.57 As shown in Fig. 14a, GO was effects on the composite properties, desalination mechanisms
prepared in advance via a modied Hummer's method. RGO– and stabilities.
PPy hydrogel was then obtained by simultaneously reducing GO

sheets and polymerizing PPy with KMnO4. Finally, RGO–PPy–
Mn was obtained aer hydrothermal treatment. Expansion of 5.1 Carbon–ZnO composites
the 3D RGO nanostructure with the presence of MnO2 and PPy Nanostructured ZnO materials have attracted immense atten-
was conrmed by its increased surface area and pore volume. tion in many elds of applications due to their rich nanoforms
Because of its enhanced specic capacitance (356 F g1 at and unique properties.189 In the eld of energy storage, ZnO
1 A g1 in 1 M NaCl), the RGO–PPy–Mn composite reached nanomaterials have been well-studied as battery-active mate-
a SAC value of 18.4 mg g1 (2.0 V in 500 mg L1 NaCl solution), rials and additives for SCs. However, because of the dendrite
which is considerably high among the reported carbon–MnOx growth during consecutive cycling, ZnO-based battery elec-
composites (Fig. 14b–d). However, RGO–PPy–Mn lost 45% of its trodes usually have poor cycle lives. When ZnO is mixed with
salt removal capability within 5 cycles, which suggested poor a carbon base, the formation of dendrites (zincates) can be
cycling stability. Unfortunately, no explanation was provided for prevented, thus excellent capacitive properties of the composite
its performance degradation. can be achieved. Taking graphene as an example, the incorpo-
For 3D RGO-based materials, Dey et al. suggested that there ration of ZnO into graphene nanosheets can generally increase
are two major technical challenges when they are used as charge the capacitance and cycling stability of the composite.190–193
storage electrodes:188 (1) the low electrical conductivity and fragile As an additive for CDI electrodes, ZnO is also suitable for
framework due to their extended networks, and (2) the tradeoff carbon property modications since ZnO is naturally hydro-
between decreasing contact resistance and maintaining their 3D philic in the presence of hydroxyl groups (which increase the
structures. Due to the similar mechanisms of charge storage and electrolyte-carbon surface contact) and has semiconductor
ion removal, it is speculated that the aforementioned technical properties (which enhance the electronic properties of
issues also exist for the RGO–PPy–Mn composite, resulting in its composites under an applied potential).194 Based on the excel-
rapid degradation of salt removal capacity. Furthermore, the lent performance of carbon–ZnO composites as SCs electrodes,
authors did not provide any information about the leakage of the effects of the nanostructures and properties of ZnO on the
manganese ions from the RGO–PPy–Mn electrode. Hence, desalination performance of carbon–ZnO composites have been
comprehensive studies on ion leakage in the RGO–PPy–Mn investigated through experimental analysis and numerical
electrodes, as well as new carbon–polymer–Mn composites for calculation studies.
CDI desalination, should be conducted. For example, Dutta et al. systematically investigated the
Due to the redox active MnOx, carbon–MnOx composites effects of ZnO nanostructures forms, quantities and lengths of
generally demonstrate poor cycling performances and have ZnO nanorods, applied electric eld strength and assembly of
a propensity to leak manganese ions. This may not be an issue asymmetric electrodes on the desalination performance of their
in SCs as the released ions would remain in the electrolytes and corresponding carbon composites.55,62,63,195–198
participate in the redox reactions, whereas in CDI, the feed Firstly, they modied an ACC electrode by growing ZnO
solution (or electrolyte) is constantly pumped through the CDI nanorods on its surface via a simple low-temperature two-step
unit causing the continuous loss of manganese ions, which hydrothermal method, which ZnO nanorods were grown using
would permanently impair both the electrode performance and zinc acetate dihydrate as a seeding precursor and zinc nitrate
the quality of the treated water. Note that the effects of the hexahydrate as a crystal growth precursor.195 By precisely
manganese ion leakage have not been systematically assessed controlling the concentrations and pH values of the precursors,
yet, and more efforts towards understanding the leakage the electrosorption efficiency of the composite had doubled
mechanism and proposing control methods should be under- compared with a plain ACC electrode.
taken. Nevertheless, since the manganese ion leakage is more Beside nanorods, the effects of ZnO nano/microstructures
severe when the composite is employed as an anode, an asym- (nanoparticles, microspheres and microsheets) on the desali-
metric conguration using carbon–MnOx as the cathode is nation performance of the electrodes were further investi-
more advantageous for CDI. gated.62,199 Using the same precursors and crystal seeding
method, various ZnO nano/micromaterials were synthesized by
5. Other carbon–TMO composites adjusting the reaction period (3 to 5 hours) in a chemical bath
(50 mM zinc nitrate and 0.5 M urea at 95 C) (Fig. 15a–e). Among
Apart from TiO2 and MnOx, many other TMOs have also been these nano/microstructures, only ZnO nanorods and micro-
used to prepare carbon–TMO electrodes for CDI applications, sheets could enhance the desalination and regeneration
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Fig. 15 (a–c) SEM images of ZnO nano/microstructures decorated ACC composites: (a) nanoparticles; (b) nanorods; (c) microsheets; (d)
microspheres. (e) Schematic representation of hydroxyl groups on the polar facet in ZnO nano/microstructures. Reproduced with permission.62
Copyright 2014, Elsevier. (f) Schematic of electric field distribution on the surface of an ACC electrode coated with ZnO nanorods. Reproduced
with permission.63 Copyright 2014, American Chemical Society. (g) Schematic of enhanced ion adsorption along ZnO nanorods. Variations of
electric field (h) along the c-axis and at the nanorod tips, (i) with changes in nanorod diameter and (j) with comparison of nanorod and nano-
particles. Reproduced with permission.198 Copyright 2015, Elsevier.
performances of their composites. These enhancements arise Previous studies have shown that carbon–MnOx composites
from mainly three aspects of ZnO nanorods: (1) the polar face of may release manganese ions even when used as a cathode
ZnO (0001) tends to be exposed on the composite surface,199 (2) (typically the corrosion reactions are more severe at the
this polar face is rich in hydroxyl groups which increase the anode).60,119 Considering these ion leakage issues, it is also
hydrophilicity of the composites,200 and (3) a coating of ZnO can critical to assess the stability of the ZnO dielectric coating
generate electron–hole pairs under an applied potential due to during charging and discharging. By mechanically mixing
its semiconductor properties.49 In contrast, since ZnO with different TMO nanoparticles (e.g., ZnO, CuO, MnO2 or WO3)
nanoparticle and microsphere morphologies are likely to fully with AC, Liu et al. assembled several asymmetric capacitors
block pores and have fewer polar faces (0001) exposed on the containing carbon–TMO either as anodes or cathodes, and
surface, poorer desalination performance was observed. pristine AC as the opposite electrodes (ACk+TMO/AC and
Using nite element method simulations, they further found TMO/ACkAC).64 These asymmetric capacitors were utilized for
that when ZnO nanorods were deposited on the ACC surface, CDI desalination (at a constant current mode, voltage changes
the interfacial electric elds surrounding the nanorods for between 1.2 V and 0 V, 500 ppm NaCl).
a single ion/charge would be strengthened, and as a result, the The ZnO/ACkAC conguration showed an enhanced and
CDI desalination performance of the composite would improve relatively stable salt removal performance compared with the
(Fig. 15f–j).63,197,198 Specically, as the mean length of ZnO ACkAC (9.4 vs. 4.5 mg g1) conguration (which served as
nanorods increased, the electric eld weakened, even though a benchmark). In contrast, the conductivity prole of the
the electric eld surrounding the tip of the nanorod was still ACk+ZnO/AC conguration became unstable during CDI
much stronger compared with the other regions.201 Moreover, cycling, resulting in Zn ion release, probably due to the disso-
with an increase of the nanorod diameter, a stronger electric lution of ZnO under an acidic condition. Meanwhile, the
eld was observed.202 This result is in accordance with the MnO2/ACkAC and WO3/AC/kAC congurations similarly
assumption that more exposed polar faces of the composite exhibited improved desalination performances compared with
would improve its desalination performance. the ACkAC capacitor, but ACk+MnO2/AC and ACk+WO3/AC
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capacitors did not. This is because MnO2 and WO3 remain in desalination performance (1.49 mg g1) compared with other
the negative charge state independent of their congurations, carbon–TMO composites, probably due to the low concentra-
according to the zeta potential analysis over a wide range of pH tion of treated saltwater (30 mg L1 NaCl) that resulted in the
values (pH ¼ 2–12).64 When MnO2 and WO3 were allocated to low capacitance observed.
the anodes, their negative charge would partially offset the Instead of using the microwave irradiation method, Sami
applied electric eld, thereby inhibiting the adsorption– et al. prepared a similar nanocomposite, i.e., rGO-SnO2, using
desorption of anions. In contrast, when applied to the cathodes, the hydrothermal method (Fig. 16),129 in which the synthesis
they can strengthen their electric elds and improve the method of GO and the tin precursor used were the same as
adsorption–desorption of cations. MnO2 showed better desali- those reported by El-Deen et al.65 Similar to the cases of carbon–
nation performance as a cathode additive than WO3 because of TiO2 and carbon–MnOx composites, even though microwave
its lower dielectric characteristic. For CuO, however, when used irradiation is facile to form nanoparticles, the nanoparticles
as an additive for AC, neither conguration was stable due to generally have poor crystallinity and the adhesion of nano-
the Cu2+ ion release at the anode and the deposition of copper particles to the carbon surface is weak. Therefore, in order to
hydroxide at the cathode. simultaneously establish a strong connection between the SnO2
In the case of the ZnO/ACkAC conguration, the incorpo- and graphene, prevent the aggregation of graphene layers and
ration of ZnO in a carbon-based cathode had improve its enhance the crystallinity of SnO2, GO nanosheets were reduced
desalination ability, but a small amount of Zn ion release at the by sodium borohydride instead of urea, and SnO2 nanoparticles
cathode was still observed (less than 0.5 mg L1 aer a 150 h were deposited via hydrothermal synthesis instead of micro-
operation). The quantity of Zn ions released may be associated wave irradiation. As a result, the rGO-SnO2 nanocomposite
with the applied voltage and the amount of ZnO added to the showed a promising SAC value of 17.62 mg g1 at 1.2 V in
cathode. However, these relationships have not been previously 400 mg L1 NaCl solution, which is about 12 times higher than
explored. Therefore, further research on the long-term stability that of the SnO2/Gr sample reported by El-Deen.65
of carbon–ZnO composites in CDI systems is still required. Furthermore, Yasin et al. attempted to prepare a nitrogen-
doped SnO2 intercalated AC nanocomposite (N-AC/SnO2) by
5.2 Carbon–SnO2 composites one-pot hydrothermal synthesis.66 However, presumably due to
the inherently low desalination performance of AC, the desali-
Tin oxide (SnO2), also known as stannic oxide, is considered nation performance of the N-AC/SnO2 nanocomposite is far
a promising additive for electrochemical applications due to its from satisfactory for practical application (3.42 mg g1, 1.2 V,
low cost, eco-friendliness, chemical stability and high capaci- 50 mg L1). Despite the poor desalination performance, this
tance.203–206 Carbon–SnO2 nanocomposites have been reported research showed that SnO2 deposition would improve the
as high-performance anode (negative) materials for SCs, LIBs hydrophilic properties of the composite. Moreover, a high
and SIBs.207–209 Particularly, SnO2 has received increasing specic capacitance (408.8 F g1) and expanded voltage window
attention for applications in SIBs due to its high theoretical (4 to 3.5 V) of the composite can be achieved by utilizing a low
sodium ion storage capacity (1378 mA h g1).210,211 scan rate (10 mV s1) and high salt concentration (1 M NaCl).
In consideration of this, researchers believe that SnO2 would With progress made in the development of carbon–SnO2
also have promising sodium ion removal capability in CDI composites as negative electrodes for SIBs, it is also expected
applications. For this purpose, El-Deen et al. synthesized a gra- that the desalting abilities of carbon–SnO2 composites for CDI
phene/SnO2 (SnO2/Gr) nanocomposite via a sonication and will be rened. Similarly with carbon–MnOx composites,
microwave irradiation method using SnCl2$2H2O as the tin following issues can be studied in the future: (1) the stability of
precursor.65 Since no high-temperature treatment was SnO2 as a cathode or anode in a carbon–SnO2 composite, since
employed during the synthesis process, the formation of SnO2 the carbon–TMO anodes in CDI tend to experience performance
on the graphene surface accompanied the reduction of GO degradation and metal ion leakage, (2) the effect of the SnO2
nanosheets: morphology on the properties and performances of its
Microwave irradiation composites, and (3) the comparative study of SnO2 relative to
SnCl2 þ GO þ H2 O
! Gr þ SnO2 þ 2HCl
other TMOs.
(1)
SEM and TEM images conrmed the successful deposition 5.3 Carbon–FeOx composites
of SnO2 nanoparticles on the graphene surface. With 15% Due to their abundance in nature, facile synthesis methods,
addition of SnO2 (with respect to dry GO), the SnO2/Gr nano- easy accessibility to different oxidation states and polymorphs,
composite demonstrated a high capacitance (323 F g1 at 5 mV electronic and magnetic properties and low biotoxicity, iron
s1) and stable cycling performance (95.1% of its initial values oxides (FeOx) are ideal materials for a large variety of applica-
aer 50 cycles) in 1 M NaCl solution. The deposition of SnO2, tions, e.g., biomedicine, energy storage devices (ESDs, including
however, may decrease the surface area and increase the LIBs, SIBs and SCs), water splitting and catalysis.212–215
intrinsic resistance of the nanocomposite as well, which may in In terms of sodium ion storage, similar to SnO2, FeOx can
turn impair its electrochemical performance. Under an applied react with sodium by forming Fe nanoparticles dispersed in
voltage of 1.4 V, such a nanocomposite exhibited a relatively low a Na2O matrix, yielding a theoretical capacitance of
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Fig. 16 Structure and performance of a rGO-SnO2 nanocomposite: (a) synthetic strategy, (b) TEM image, (c) CV curves at various scan rates
(0.5 M NaCl), and (d) CDI adsorption/desorption behavior at 1.2 V. Reproduced with permission.127 Copyright 2018, The Royal Society of
Chemistry.
1007 mA h g1.216,217 Because of the poor conductivity of FeOx, capacitances have improved signicantly. In CDI, Fe3O4/rGO
however, the electrochemical redox reactions are rather slow and RGO@Fe3O4 electrodes have a salt removal capacity trice
and as a result, their capacitances are relatively low for indus- and twice that of a pure rGO electrode, respectively.
trial applications. One feasible strategy is to develop hybrid Nevertheless, the SAC values of these reported carbon–FeOx
carbon-based electrode materials. Taking graphene as an composites are still relatively low (not exceeding 10 mg g1)
example, both Fe2O3@graphene nanosheets and Fe2O3-RGO when desalting NaCl solutions, which renders them less desir-
composites demonstrate higher sodium ion storage capacity able than other carbon–TMO electrodes. With control of their
and more stable cycling performances compared with pure morphologies, crystal structures, sizes and dispersion of FeOx,
graphene electrodes when Fe2O3 nanocrystals are incorporated better desalination performance can be expected. However,
into the graphene nanostructure.216,218 same as the other carbon–TMO electrodes, future studies about
Based on the same mechanism, the removal of sodium ions the asymmetric conguration are required to analyze the
from saltwater using carbon–FeOx electrodes has been reported release of ferric ions.
for CDI applications. For example, Zafra et al. synthesized
a Fe3O4 decorated CA (CAGDFeAct) composite via high-
temperature calcination using iron(II) nitrate hydrate as the 5.4 Carbon–other TMO composites
iron precursor.119 Compared with an identical structure modi- Apart from TiO2, MnOx, ZnO, SnO2 and FeOx, carbon hybrids
ed with MnO crystals (CAGDMnAct), the CAGDFeAct with CuO, V2O5, CeO2, ZrO2 and RuO2 have also been studied
composite exhibited a slightly higher capacitance (91 vs. 99 F for water desalination since they are common additives for the
g1) and desalination capacity (6.4 vs. 7.8 mg g1). Fe3O4 electrodes of LIBs, SIBs and SCs. Depending on whether the
embedded rGO composites have been applied for sodium ion metal ion valency changes, these TMOs would invoke different
removal as well. Trinh et al. successfully prepared a uniformly desalination mechanisms.
dispersed Fe3O4/rGO composite by a simple thermal hydrolysis Gu et al. prepared a RGO–PPy–Cu composite by the hydro-
method;67 while Li et al. prepared the RGO@Fe3O4 nano- thermal method using copper sulfate as the copper precursor.57
composite using the hydrothermal method;219 in these two Unlike the RGO–PPy–Mn composite prepared with the same
nanocomposites, Fe3O4 plays a critical role in joining the gra- synthesis route, the addition of Cu did not prevent the aggre-
phene nanosheets, therefore, their wettability and specic gation of graphene nanosheets, which was evident from the
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similar pore structures of RGO–PPy–Cu and pure RGO (e.g., for ESDs. For applications in water desalination, a hydrated
similar specic surface areas, average pore widths and total V2O5 decorated MWCNTs (MWCNT–hV2O5) composite was
pore volumes) and the unchanged valence state of Cu2+ during recently reported by Lee et al., where the composite was
the hydrothermal process, indicating that no redox reactions synthesized by the electrochemical deposition method using
occurred between Cu2+ and GO or Cu2+ and PPy. According to vanadyl sulfate as the vanadium precursor:28
CV characterization, CuO in the RGO–PPy–Cu composite offers
no benets to its capacitive properties. Since RGO–PPy–Cu still 2VO2+ + 3H2O / V2O5 + 6H+ + 2e (2)
demonstrates competitive capacitance and salt removal
capacity (15.1 mg g1, 2.0 V, 500 mg L1) with respect to pristine As shown in Fig. 17, before testing in a CDI unit, a stable
potential window (0.2 to +0.4 V vs. Ag/AgCl) was pre-
RGO, it is possible that the capacitive property of the composite

is mainly due to RGO–PPy. Furthermore, as described by Liu determined by the CV method to avoid the excessive decom-
et al.,64 CuO is unstable as both the anode (dissolved) and position of water and V2O5. The desalination performance of
cathode (deposited as copper hydroxide) for CDI applications. MWCNT–hV2O5 was then assessed in an asymmetric membrane
To limit the high reactivity of copper and extend the opera- pseudocapacitive deionization (MPDI) conguration, where the
tion lifetime of the copper electrode, Alami et al. proposed to composite was used as the cathode and a commercial AC elec-
coat the copper electrode with graphene, which is an electro- trode as the anode. The mass of the AC electrode was twice that
chemically stable and electrically conductive surface layer.220 In of the MWCNT–hV2O5 electrode owing to the approximately
a three-electrode conguration, the trial experiment showed twofold capacitance of MWCNT–hV2O5. In constant current
that the graphene-coated copper electrode was stable for 60 min mode, the MPDI cell exhibited an excellent SAC value (25 mg
and removed 12% of the total dissolved ions compared to the gcell1), cycling performance (about 15% degradation was
instantaneous degradation of the pure copper electrode. observed within 100 cycles) as well as energy efficiency (12.8 kT
Further studies on the cycling performance of graphene-coated per ion in 0.2 M NaCl solution).
copper electrodes should be conducted in an actual CDI device. Despite the excellent performance, several concerns should
Differing from CuO, vanadium oxides have many states (VO, be addressed for any further applications of carbon–vanadium
V2O3, VO2 and V2O5) and are rich in redox couples (VO2+/V3+, oxides composites; (1) the high SAC value of the MWCNT–hV2O5
VO2+/VO2+), which make them promising materials or additives electrode should not only be attributed to its good
Fig. 17 Electrochemical and desalination performance of the MWCNT–hV2O5 composite: CV at 1 mV s1 for the determination of (a) the
reduction potential limit and (b) the oxidation potential limit, (c) time-dependent conductivity profile in MPDI cell and the potential changes (vs.
Ag/AgCl) at the anode and cathode, and (d) normalized cycling performance of the cell [SAC (mg gcell1)] or only one electrode [SAC (mg g1)].
Reproduced with permission.28 Copyright 2017, Wiley-VCH.
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pseudocapacitive properties, but also to the synergistic effect surfaces using ruthenium chloride as the ruthenium precursor.
due to the presence of IEMs and the high salt concentration Compared to other TMOs, RuO2 is the most metallically
solution. According to Tang et al.,23 at 0.2 M NaCl concentration conductive (3 102 U1 cm1) and possesses a high theoretical
using mesoporous carbon as the electrode material, for capacitance even as a hydrate compound (760 F g1 for RuO2-
example, the SAC value of the mesoporous carbon electrode $nH2O). Due to these characteristics, RuO2 and its composites
could reach up to 19.5 mg g1 at 1.2 V, whereas distorted are popular electrode materials for energy storage.223–225
adsorption–desorption kinetics were observed for CDI under Consequently, in CDI applications, the RuO2/AC composite
identical conditions. (2) There is a trade-off between the need to exhibited an enhanced desalination performance as compared
use IEMs and the addition of V2O5. (3) Although as claimed by with a pure AC electrode. However, because RuO2 is both
Lee et al.28 that there was no leakage of vanadium ions during expensive and toxic, it is not practical as a carbon additive for
the desalination of MPDI, a slight potential-dependent redox CDI applications.
reaction at 0.35 V (vs. Ag/AgCl) was still observed during CV According to the properties and desalination performances
characterization, which involved a valency change between VO2+ of the carbon–metal compound composites discussed above
and V3+. This result suggested that some vanadium ions may (CuO, V2O5, CeO2 ZrO2 and RuO2, as summarized in Table 1), it
have dissolved but were trapped in the solution between the is suggested that V2O5 and ZrO2 are more suitable as carbon
anode and anion exchange membrane. Since V2O5 and vana- additives for CDI applications because of their abundance in
dium ions are toxic to humans, IEMs must be deployed to avoid nature, as well as the high theoretical capacitance of V2O5 and
any leakage, in turn raising the total cost for practical the good chemical stability of ZrO2. To further develop their
application. corresponding carbon composites, more research should be
Li et al. synthesized a CAs/CeO2 composite by hydrother- conducted to improve the stability of carbon–V2O5 composites
mally depositing cerium oxide on the CA surfaces for copper(II) and enhance the electroconductivity of carbon–ZrO2
ion removal.68 The CAs/CeO2 composite exhibited a copper(II) composites.
removal performance comparable to that of CAs/TiO2 (49.3 vs.
57.1 mg g1), which is higher than the copper(II) removal
performance of pure CAs electrode (30.4 mg g1) under iden- 6. Carbon–GAMO composites
tical conditions (1.2 V, 50 mg L1 CuCl2). The enhanced To understand the roles GAMOs play in carbon–GAMO elec-
performance of the CAs/CeO2 composite arises from its reduced trodes for CDI, their synthesis methods, structures, electro-
internal resistance, increased capacitance and higher removal chemical and desalination performances are summarized and
rate of high-valence ions by CDI. Since cerium is a rare-earth discussed (Table 1). Reported GAMOs additives include Al2O3,
metal (low in reserve and expensive) and CeO2 does not SiO2, and Li2O. Compared to Li2O, Al2O3 and SiO2 have been
exhibit a superior desalination capacity compared with TiO2, studied more comprehensively due to their dielectric properties
CeO2 may not be a preferred additive for carbon-based CDI and good hydrophilicities. Although the negative effects of
electrodes. combining Al2O3 and SiO2 with carbon have been reported in
Yasin et al. prepared a zirconia nanobers/AC composite the early stages of developing potential CDI electrodes (e.g.
(ZrO2 NFs/AC) by mechanically mixing zirconia nanobers with increasing the series resistance of their carbon composites),
commercial AC, where the zirconia nanobers were synthesized with the development of nanoscience and electrochemical
via sol–gel based electrospinning, high-temperature sintering theories, certain advantages of these insulating coatings were
and subsequent sonication methods.131 The ZrO2 NFs/AC elec- gradually discovered (e.g., increasing the wettability of elec-
trode has increased wettability and specic capacitance trodes, balancing the charge on the anode and the cathode and
compared with a pure AC electrode, and as a result, it demon- protecting the carbon base for extended cycle life).
strated a higher electrosorption capacity (16.35 mg g1, 1.2 V,
104 mg L1 NaCl). According to the quasi-rectangular shape of
the CV curves, it is suggested that the ZrO2 NFs/AC electrode 6.1 Carbon–SiO2/Al2O3 composites
removes ions based on its EDLC mechanism. Although ZrO2 Ryoo et al. pioneered the studies on the effects of chemically
may be a suitable additive for CDI electrodes due to its good incorporating SiO2 and Al2O3 into ACC for CDI applications.
chemical stability and eco-friendliness,221 its high electrical However, these two composites exhibited even worse salt
resistance (3.28 106 U1 cm1) could decrease the charge removal performances as CDI electrodes when compared with
and energy efficiency of its carbon composites.222 Therefore, a pristine ACC electrode.69 They explained that this was due to
seeking solutions to enhance the electrical conductivities of the the applied potential being too weak, which could not reduce or
carbon–ZrO2 composites should be the next step to further oxidize SiO2 and Al2O3, thus the issue of surface polarization of
improve their CDI desalination performances. This could be the ACC could not be resolved. Yang et al. prepared a CA-silica
achieved by reducing the ZrO2 nanoform sizes or the thickness gel composite via a paste-rolling method by using silica gel
of the ZrO2 layers. powder as the silicon precursor.226 With an optimized amount
Recently, Ma et al. reported an enhanced CDI desalination of silica gel (50%), the composite displayed an enhanced
system employing both capacitive and pseudocapacitive ion desalination performance (including its salt removal ability,
storage mechanisms with RuO2/AC electrodes.132 The RuO2 charge efficiency as well as its cycling performance) due to its
nanoparticles were electrochemically deposited onto the AC increased wettability, mechanical hardness and durability.
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Quan et al. achieved a similar enhanced desalination perfor- same synthesizing route used by both Lado et al.228 and Han
mance using an SiO2 sol–gel-coated biomass derived carbon et al.134 The results indicated that the surface properties of
electrode.227 carbon materials contributed more to their ion removal capa-
Furthermore, Im et al. investigated the electrochemical bilities than their specic surface areas, which is speculated by
characteristics of silica-coated AC powder electrodes for CDI the following two reasons: (1) under the same synthesizing
applications.73 Using the sol–gel method to integrate various conditions (e.g., dipping time), different metal oxide loading
amounts of silica into the AC electrodes, they found that the amounts were observed for different carbon materials since the
incorporation of 1 mM SiO2 per gram of carbon could endow loading amount strongly relies on the interactions between the
the AC electrode with some desirable features: (1) SiO2-coated alkoxide sols and carbon. As a result, different surface wetta-
AC electrodes have higher capacitances at negative potentials, bility and surface charge could be obtained. (2) Because of the
(2) the internal diffusion resistance of the electrodes have moderate specic surface areas of SiO2 (780 m2 g1) and l-Al2O3
signicantly decreased, (3) the surface of the composite (340 m2 g1), the SiO2 or l-Al2O3 coating is likely to enhance the
becomes more negatively charged in neutral solutions, and (4) desalination performances of carbon materials with low specic
the specic capacitance of the composite forms a linear rela- surface areas, or dampen the desalination performances of the
tionship with respect to the zeta potential of the electrodes. carbon materials with high specic surface areas. This research
These results suggest that the SiO2-coated AC electrode is more suggested that with SiO2 or l-Al2O3 coatings, a variety of carbon
suitable as a negative electrode and also account for the materials (especially those with poor wettability and low surface
improvements in its CDI desalination performance. areas) could be utilized as CDI electrodes, thereby reducing
Since SiO2 is more suitable as a cathode additive, some material costs in industrial applications.
studies have been conducted for the asymmetrical CDI Another advantage of the above asymmetrical CDI congu-
conguration using a carbon–SiO2 composite as a cathode. For ration is the ability to balance the adsorption of cations and
example, Leonard et al. reported an asymmetrical CDI device anions. Taking carbon xerogel electrodes as an example, Gao
for water soening, in which silica modied carbon and et al. found that the pure carbon xerogel electrodes demonstrate
magnesium doped alumina modied carbon were used as the better Cl adsorption than Na+ adsorption in a 4 mM NaCl
cathode and anode, respectively.74 The composites were solution.135 Aer coating the negative electrode with SiO2 or
prepared in three steps: Firstly, SiO2 nanoparticles and –COOH functional groups, its current density signicantly
magnesium doped AlOOH were synthesized using the sol–gel increased, resulting in enhanced cation adsorption (36% and
method. Secondly, insulating oxides nanoparticles were spray- 50% increment for SiO2 and –COOH-coated carbon xerogel
coated onto conducting carbon-based electrodes. Lastly, the electrodes respectively). A further study indicated that the
composites were calcined in air to sinter the particles onto the potential of zero charge of the negative electrode was altered
carbon surfaces. Due to the inherent surface potentials of the such that it was close to the discharging potential, as evidenced
SiO2 and Mg-doped Al2O3 coatings, the composites could by Avraham et al.,75 which could be responsible for the
provide more accessible sites for ions and increase the improved desalination performance of the asymmetrical CDI
attraction toward counter-ions. Therefore, such an asymmet- cell. Furthermore, with modied carbon surfaces, Lado et al.228
rical CDI device could effectively remove ions of various and Han et al.134 observed better cation adsorption compared to
valence states and hydration radii. chlorine ion adsorption at the anode surface due to the
Asymmetric coatings with SiO2 and Al2O3 nanoporous thin competition between OH and Cl ions. A balanced capacitive
lms are also effective for improving the desalination perfor- performance of the anode and cathode allows for more effective
mances of different carbon substrates. For example, Lado et al. utilization of the electrodes.
coated carbon ber electrodes with SiO2 and l-Al2O3 using The long-term stability of the asymmetrical CDI unit
a simple dipping and sintering method.228 The asymmetrical congured with a SiO2-coated cathode and a l-Al2O3-coated
CDI unit which consisted of a SiO2-coated carbon ber anode was also investigated. With low-cost carbon felt as the
composite as the cathode and a l-Al2O3-coated carbon ber carbon substrate, Lado et al. found that the cycling performance
composite as the anode, exhibited ed a Ca2+ removal perfor- of the electrodes was highly dependent on the ion species in the
mance 5 times higher than that of a CDI cell with pure carbon feed solution and the regeneration method.136,230 For instance,
ber electrodes. In the same asymmetric system using aqueous due to the unique adsorption of SO42 ions by l-Al2O3, the cell
KCl as the electrolyte, Han et al. established that the presence of was unable to regenerate by short-circuiting. Applying a reverse
insulating nanoparticles on the electrodes could modify their potential could enhance cell regeneration, however, re-
isoelectric points and increase the charge efficiency of the adsorption would occur at the end of desorption. Further-
asymmetrical CDI unit.134 more, even with a dielectric coating, electrode degradation was
Wouters et al. further studied the dependence of the desa- inevitable, and the anode exhibited much more severe deteri-
lination performance of an asymmetrical CDI unit on the oration due to surface oxidation. Therefore, the renement of
carbon types in its electrodes.229 Four types of carbon materials anode protection strategies is vital to preserve CDI performance
(foam, nanofoam, cloth and sheet) with different properties in this conguration.
(surface area, wettability, pore size distribution and Although dielectric coatings are effective in improving the
morphology) were used as carbon substrates, with different desalination abilities of low-cost carbon materials, their salt
loading amounts of SiO2- and l-Al2O3-coated onto them via the removal capacities and energy efficiencies are still too low for
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practical usage. To further improve their performances, Santos surface areas and resistance. Consequently, the desalination
et al. introduced a current collector-free CDI architecture performances of carbon electrodes can be improved, and the
(Fig. 18), in which the electrodes were fabricated by simulta- adsorption of cations and anions balanced. Due to the intrinsic
neously spraying CVD grown CNT bers (CNTf) and metal oxide low salt removal abilities of the carbon substrates, however, the
sol nanoparticles (SiO2 for the cathode and l-Al2O3 for the desalination performances of these reported asymmetrical CDI
anode) on a collector before being sintered in air (350 C).137 The devices are undesirable for commercial applications.
overlapped CNTf electrodes were reported to have unique
electrochemical properties due to their consolidated contin- 6.2 Carbon–porous silicon composites
uous network structures, while the co-spraying method allowed
It should be noted that the metal oxides in the above compos-
the metal oxide particles to be more uniformly distributed and

inltrate the interior of the electrodes. Using this current ites were coated onto the carbon surfaces. The large-scale
collector-free CDI device for brackish water desalination (2 g manufacturing of these carbon particulate-based electrodes
L1 NaCl solution), a SAC value of 6.5 mg g1 was obtained at would, however, encounter several issues as described by Metke
1.2 V, as compared to a SAC value of only 4.4 mg g1 for an AC- et al.138 For example, (1) high-performance carbon architecture
based symmetrical CDI device. Moreover, a signicant high (SWCNTs or 3D graphene foams) rely on expensive lab-scale
charge efficiency (86%) was obtained for such a membrane-free, processing, (2) the exfoliated particulate matter could contam-
current collector-free CDI cell, resulting in an extremely low inate the water sources, (3) the porous networks of carbon may
energy consumption (0.26 W h g1). In such asymmetrical be prone to fouling, and (4) it may be necessary to pressure-cast
architecture, however, some pores of the CNTf may not be the particles to resist the water ow.
accessible to ions, because CNTf is continuous (due to their Pertaining to the above issues, Metke et al. prepared a HF
long lengths) and the coating may block the pores of the CNTs. etched porous silicon-based CDI electrode. To prevent oxidation
Therefore, the desalination performances of the CNTf elec- of the silicon surface, a carbon layer was deposited onto porous
trodes are expected to be improved by increasing the surface silicon by the polycondensation and carbonization of C2H2 at
areas of CNTs or optimizing their alignments. a high temperature (850 C).138 This porous silicon-based CDI
The above studies have established that with dielectric electrode demonstrated salt removal ability over a wide range of
coatings of SiO2 and Al2O3, the structures and electrochemical salt concentrations (from freshwater to seawater). The overall
properties of carbon composites can be altered, e.g., increasing SAC values increased from 3.8 to 5.2 mg g1 with the increase of
their wettability and surface potentials, changing their specic salt concentration. However, when normalized to the mass of
the carbon layer, its SAC value could be as high as 125 mg
Fig. 18 Synthesis, morphology and performance of an asymmetrical and current collector-free CDI architecture: (a) composite synthesis via sol
spray on CVD-spun CNTf, (b) SEM image of MOx/CNTf, high-resolution TEM images and EDS elemental maps of (c) SiO2/CNTf and (d) l-Al2O3/
CNTf, (e) desalination stability (1.5 A m2, 2 g L1) of MOx/CNTf electrodes and (f) the corresponding consumed and regenerated energies.
Reproduced with permission.135 Copyright 2018, The Royal Society of Chemistry.
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gcarbon1. It is noteworthy that a high energy efficiency (85%) exchange membranes and capacitive electrodes. In the discus-
and low energy consumption (1.45 W h L1) were achieved sion below, we have summarized and discussed the synthesis
through this porous silicon-based electrode, which exhibited and desalination performances of carbon–2D-IHC electrodes for
signicant advantages over RO desalination (>5 W h L1). CDI desalination, and briey described their properties. As
However, further studies are needed to explore its salt removal a comparison, the properties and desalination performances of
mechanism of the silicon-based electrode and increase its salt pure 2D-IHC electrodes (carbon-free) are also discussed.
removal capacity.
7.1 Carbon–2D-TMO composites

6.3 Carbon–lithium compound composites
2D-TMOs, or layered metal oxides, refer to TMO nanosheets

In addition to SiO2, Al2O3 and porous silicon, lithium oxide
with 2D layered structures, which can exist naturally as layered
(Li2O) has also been used as an additive for CDI carbon elec-
crystals (V2O5, WO3, MoO3 and Ga2O3)232 or be synthesized in
trodes. However, unlike SiO2 and Al2O3 which utilize their
practice through advanced techniques (exfoliation, layer-by-
dielectric properties to alter the carbon surface properties, Li2O
layer deposition, dip-coating, etc.).233,234 Owing to the efficient
likely enhances the desalination performance of the electrode
exposure of their surfaces with abundant redox sites, 2D-TMOs
through a redox reaction between Li2O and sodium ions. For
have attracted considerable attention as potential electrode
example, Zhang et al. prepared a Li-ion doped graphene/CNFs
materials for ESDs, either in their pure forms or as composites
composite (Li+/G/CNF) for CDI applications via electro-
with a conductive carbon material.235–238
spinning and subsequently carbonization using a suspension
Since several 2D-TMOs–assisted carbon composites have
consisting of polyacrylonitrile, graphene oxide and LiNO3.139
already been described and reviewed in Sections 3–5, their
During the carbonization process, LiNO3 decomposed to form
applications in CDI would not be extensively covered here.
Li2O and LiC6 through the pyrolysis of LiNO3 and the reduction
Briey recapitulating, ALD-deposited MnO2 lms on VACNTs
of Li2O, respectively, as described by the following reactions:
signicantly improve the desalination capacity of the composite
4LiNO3 / 2Li2O + 4NO2 + O2 (3) (the VACNTs/MnO2 discussed in Section 4.3).61 In addition, we
previously discussed the effects of ZnO polymorphs on the
Li2O + 13C / 2LiC6 + CO (4) desalination performances of their corresponding carbon
composites (Section 5.1); the results indicated that both thicker
The Li+/G/CNF electrode demonstrated an outstanding salt and shorter rod-like structures and nanosheet structures are
removal efficiency (84%, 1.4 V) at concentrations close to that more conducive for desalination, since the latter can render
of seawater (35 000 ppm), while only 45% for pure CNF a greater surface exposure for the composite, along with an
electrodes under the same conditions. The enhanced desali- increased wettability and stronger electrical elds.62
nation performance was attributed to the phase change of LiC6 Note that the main component in the above composites is
and Li2O lattice in an electric eld.231 For the cathode, the carbon, while the deposition of a small amount of TMOs can
electroconductivity of the composite was greatly enhanced due signicantly improve their capacitive characteristics. Therefore,
to lithium delocalization (electron donor) of LiC6, which the notion of making TMOs the main component to amplify
caused its electroconductivity to exceed that of graphite. Then, their pseudocapacitance characteristics was proposed, with
Na+ ions can be adsorbed and removed faster based on the a synthesis strategy to introduce a small amount of conductive
enhanced EDLC of the composite. On the anode, it is possible intermediary (e.g., graphene and CNTs) into 2D-TMOs which
for the Li+ ions in LiC6 and Li2O to leave the lattice and form has already been applied for the synthesis of 2D-TMOs hybrid
a diffusion layer at the electrode/electrolyte interface, and the electrodes for ESDs.239–241 The usage of such composites for CDI
charged diffusion layer can attract more Cl ions from the desalination, however, have not been reported to the best of our
bulk solution to increase the Cl concentration at this inter- knowledge. Nevertheless, researchers have begun to express
face. Consequently, the composite has a higher electro- a strong interest in the desalination performances of 2D-TMOs
sorption capacity and faster salt removal rate for both the electrodes.
anode and cathode. In a hybrid CDI (HCDI) conguration with an AC cathode,
The study of Zhang et al.139 suggested that other carbon– Wu et al. synthesized a owerlike (2D-layered structure assem-
lithium composite electrodes in LIBs may also exhibit good bled 3D network) K-birnessite-type MnO2 as the anode via
desalination performances. However, it is a top priority to a simple chemical reaction between KMnO4 and HCl.94 The
investigate the potential issue of lithium leakage during desa- hybrid conguration demonstrated an extraordinary desalina-
lination, since it is possible for the deintercalation of anodic tion capacity (14.9 mg g1, 1.4 V, 500 mg L1) and cycling
lithium ions is possible, as described above. stability (95.4% aer 300 cycles, 1.0 V), while a symmetrical AC-
based CDI cell had only 15.7% of its initial capacity le aer 285
7. Carbon–2D-IHC composites cycles. Although the oxidation issue of a carbon anode was
avoided by replacing it with MnO2, the structural evolution of
Inspired by their energy storage mechanisms, 2D-IHCs are ex- MnO2 during the cycle tests remains unclear.
pected to effectively serve as both the cathode and anode in To further investigate the above issue, Byles et al. reported
a symmetrical CDI device, thus circumventing the usage of anion the direct usage of Na-birnessite and Mg-buserite layered
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manganese oxide (LMO) electrodes for HCDI desalination.93 7.2 Carbon-MXene composites
Using sodium or magnesium ions to stabilize the interlayer
MXene is a new member of 2D nanomaterials in the form of
regions of the Na-birnessite and Mg-buserite LMOs, they were
a transition metal carbide, nitride or carbonitride, which is
prepared by a hydrothermal method.242 As shown in Fig. 19,
generally synthesized by selectively extracting element “A” from
the two LMOs both displayed excellent salt removal perfor-
their MAX phases (Mn+1AXn, n ¼ 1, 2, 3), where the letters “M”,
mances in NaCl or MgCl2 solutions, but both underwent
“A” and “X” correspond to a transition metal, an element in the
gradual deterioration within 200 cycles despite that IEMs
main group A and carbon/nitrogen, respectively.243 MXene has
were utilized to protect the electrodes. Due to their different been reported to possess promising lithium or sodium ion
interlayer distances and the charge per hydrated ion, both storage capacities due to its unique properties,243,244 for
LMOs showed different performances in NaCl and MgCl2

example; (1) MXene is generally reported to have good electrical
solutions. For instance, because of the single charge per
conductivity comparable to that of graphene and have excellent
hydrated Na+ ion as compared to the two charges per hydrated
hydrophilicity, (2) it can be made into binder-free electrodes, (3)
Mg2+ ion, Na+ ions tend to diffuse faster than Mg2+ ions in the
it allows for rapid ion intercalation between its layers, and (4) it
interlayer regions of the LMOs. As a result, both materials
can store energy through redox reactions, yet its charge–voltage
exhibited better retention performances in a NaCl solution
prole shows a triangular shape similar to that of a capacitive
than a MgCl2 solution. Moreover, through XRD analysis of the electrode, which is a typical characteristic of pseudo-capacitors.
initial and post-experimental electrodes, ion intercalation Based on the electrochemical energy storage capability of
during the charging and discharging of the electrodes was
MXene, Srimuk et al. pioneered the application of MXene for
observed.
CDI desalination.88 Following the method introduced by Naguib
Although only a few studies have reported the CDI applica-
et al.,245 they synthesized a Ti3C2-MXene electrode by etching
tions of 2D-TMOs, with the increasing focus on 2D nano-
the ternary MAX phase (Ti3AlC2) with HF. To form a binder-free
materials and battery-like electrodes in the eld of CDI, it is
electrode, the MXene ethanol suspension was sonicated in an
expected that pure 2D-TMOs electrodes as well as their nano-
ice bath and then the electrode was formed by direct ltration of
carbon composites are expected to demonstrate compelling the suspension using a porous glass ber spacer. Such a binder-
competitiveness in the near future. free MXene electrode possessed a higher capacitance (176 F g1)
than a YP-80F AC electrode (84 F g1). Meanwhile, in an
Fig. 19 Pure LMO as the negative electrode for HCDI: (a) schematic diagram of the layered structure, (b) XRD characterization of the structural
evolution of Na-birnessite and Mg-buserite LMOs during the CDI cycling test, and cycling performances in 15 mM (c) NaCl and (d) MgCl2
solutions. Reproduced with permission.93 Copyright 2018, American Chemical Society.
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asymmetrical CDI conguration, Ti3C2-MXene demonstrated which Mo1.33C-MXene was synthesized by etching (Mo2/3Sc1/
a stable salt removal ability with an average SAC value of 13 mg 3)2AlC MAX phase with concentrated HF, Mo1.33C-MXene was
g1 (1.2 V, 5 mM NaCl), in comparison with a SAC value of 9 mg then exfoliated into nanosheets using tetrabutylammonium
g1 for AC under identical conditions. Considering the hydroxide. The binder-free Mo1.33C-MXene/CNTs composite
extremely small surface area of Ti3C2-MXene (6 m2 g1), Srimuk was then obtained aer ltering the sonicating-dispersed
et al. suggested that Ti3C2-MXene does not store or remove ions Mo1.33C-MXene and CNTs suspension with a porous spacer.
by electrosorption (the capacitive way), but by an ion interca- The characterization results revealed that the restacking
lation mechanism.88 problem was successfully resolved by inserting CNTs between
Like graphene, the aggregation and restacking problems of the MXene layers (Mo1.33C vs. Mo1.33C/CNTs: 1 vs. 30 m2 g1).
Even though the composite exhibited a low SAC value (5 mg g1,
MXene may hinder its ion storage capacity due to the van der
Waals interactions between its layers. To solve these problems, 5 mM) at a relatively low applied potential of 0.8 V, a higher SAC
studies have shown that the electrochemical performances of value (15 mg g1) could be achieved at seawater concentration
MXene can be improved by inserting another one-dimensional (600 mM), where the energy consumption (17 kT per ion) is
(1D) or 2D nanomaterials between its layers, forming a hetero- comparable to that of carbon-based MCDI (25 kT per ion)
structure. Such 1D or 2D nanomaterials can either be another operating in constant current mode.250 It is noteworthy that for
ion intercalation materials (e.g., SnO2 and MoS2) or a carbon this Mo1.33C-MXene/CNTs composite, CNTs account for only
material (e.g., CNTs (1D) and graphene (2D)).246–249 Taking the a small fraction of the total mass (5 mg CNTs vs. 90 mg Mo1.33C-
carbon material as an example, Xie et al. fabricated porous Ti3C2 MXene), which is distinctive from other carbon–metal
MXene/CNT and Ti3C2 MXene/graphene composites via a self- compound composites discussed in Sections 3–5.
assembly method for sodium ion storage.248 The results The above results have shown that having a large number of
showed that as compared to 2D–2D stacking (Ti3C2 MXene/ active adsorption sites is crucial to attaining a high desalination
graphene composite), the 2D–1D hybridization of MXene and capacity for MXene, similarly to the case of graphene.251,252 In
CNTs is more effective in reducing the restacking of MXene light of this, Bao et al. recently synthesized an aerogel-like
nanosheets, and therefore the Ti3C2 MXene/CNTs composite porous cryo-derived Ti3C2-MXene for CDI by vacuum freeze-
exhibited a higher sodium ion storage capacity and better drying (Fig. 20).140 The synthesis approach of 3D porous
cycling performance. MXene is described as follows: using chloroform as replace-
With this background, Srimuk et al. further prepared ment molecules, the chloroform solvent molecules entered the
a Mo1.33C-MXene/CNTs composite for CDI desalination,92 in MXene nanosheets to displace the smaller ions and further
Fig. 20 Morphology, structure and desalination performances of the porous Ti3C2Tx-Mxene electrode: (a) SEM, (b and c) HRTEM, (d) selected
area electron diffraction, (e) nitrogen sorption isotherms of the porous and non-porous Ti3C2Tx-Mxene architectures; the inserted figure is the
pore size distribution of the porous Ti3C2Tx-Mxene, (f) electrosorption capacity of porous Ti3C2Tx-Mxene, restacked Ti3C2Tx and AC electrode
within a wide range of salt concentrations, and (g) cycling performance of the porous Ti3C2Tx-Mxene electrode in 500 mg L1 NaCl solution.
Reproduced with permission.138 Copyright 2018, Elsevier.
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enlarged their layer spacings. Aerwards, freeze-drying was no signicant changes in its BET surface area. Even so, because
employed to prevent the nanosheets from restacking aer of its enhanced electrical conductivity, the 1T phase MoS2
removal of the solvent molecules. With an expanded porous electrode showed a signicantly higher specic capacitance
structure, 3D porous Ti3C2-MXene exhibited an extremely high (109.7 vs. 17.6 F g1, 5 mV s1, 1 M NaCl) and desalination
SAC value of 45 mg g1 (10 g L1 NaCl at 1.2 V) and an excellent performance (8.81 vs. 2.5 mg g1, 1.2 V, 400 mg L1 NaCl) than
cycling performance of 60 cycles (500 mg L1 NaCl, almost no the bulk MoS2 electrode.
degradation), which far exceeded those of the restacked Ti3C2- Based on its rectangular CV curves, Xing et al. speculated
MXene prepared by Srimuk et al.88 and most carbon-based that MoS2 electrodes mainly rely on electrosorption on their
electrodes. Guo et al. found that by using Ar plasma modica- EDL surfaces to achieve desalination, which differs from the ion
tion instead of toxic wet chemical modications (e.g., applying intercalation mechanism proposed in the application of SIBs.255
chloroform), the mean interlayer distance of 2D MXene Ti3C2Tx Another problem with this study is the use of N-butyllithium to
nanosheets can be extended from 1.11 to 1.23 nm, and as obtain the 1T phase MoS2, which is known to react violently
a result, an improved desalination performance was achieved when exposed to water and air. In view of the dangers this
with a salt removal capacity of 26.8 mg g1 and a SRR value of synthesis method presents and the underwhelming desalina-
9.4 mg g1 min1 (500 mg L1 NaCl at 1.4 V).211 tion capacity of the composite, other safer methods for
Given that over 70 kinds of MAX phases have been reported, promoting the conductivity of MoS2 nanosheets should be
the exploration of CDI-effective MXene electrodes is expected to considered.
continue.249,253 Meanwhile, with the development of other To further study the desalination mechanism of MoS2 and
strategies to counter the aggregation and restacking issues of improve its conductivity without using N-butyllithium, Srimuk
MXene layers (e.g., compositing MXene with new carbon et al. prepared a MoS2/CNTs hybrid electrode,90 which was
materials like graphene and CNTs), the salt removal capability synthesized in three steps. First, a mixture of MoS2 and CNTs
of MXene electrodes is expected to be much higher in the near suspension was dispersed via a simple ice-bath assisted tip-
future. ultrasonic method using commercially available MoS2 powder
(20 mm) as the precursor. Next, a freestanding MoS2/CNTs thin
lm was formed by ltration. Then, the thin lm was electro-
7.3 Carbon–TMDC composites chemically activated (10 V, 4 h, 1 M Na2SO4) to form an extended
TMDCs are compounds with a formula given by TX2, where “T” layer.90 Compared to the chemical exfoliation using N-butyl-
is a transition metal from groups IV B to VII B (Ti, Zr, V, Mo, W, lithium, electrochemical exfoliation is much safer, simpler and
etc.), and “X” is a chalcogen element of the VI A group (S, Se, Te). scalable.259 Characterization results suggested that the multi-
Some bulk TMDC materials exist as mineral forms in nature, layered structure was formed aer 4 h of electrochemical acti-
such as MoS2 which is mostly preserved as molybdenite. vation (Fig. 21). Furthermore, the MoS2/CNTs electrode
Depending on the combination of atoms, number of layers and demonstrated both a high specic capacitance at the anode
doping element, TMDCs can be metallic conductive (similar to (200 F g1) and the cathode (210 F g1), indicating its ability to
graphene with overlapping energy bands) or semi-conductive remove both Na+ and Cl ions. When employing the electro-
(an energy band gap close to 2 eV). Taking MoS2 as an chemically exfoliated MoS2/CNTs electrode as CDI electrodes in
example, single- or multi-layered MoS2 are electrochemically a symmetrical CDI device, it displayed a high SAC value of 25 mg
inactive owning to its semi-conductive property. To enhance the g1 (0.8 V, 0.5 M NaCl). In contrast, the inactivated MoS2/CNTs
electrical conductivity of MoS2, the following approaches have electrode only showed a small SAC value of 0.6 mg g1 under
proved to be effective: (1) forming a hybrid with graphene, CNTs identical conditions.
or conductive polymers,254,255 (2) obtaining the 1T phase of MoS2 Based on the phase transition with an increase of the mean
using a chemical exfoliation method,256 and (3) doping with interlayer distance (i.e., from 2H to 1T-phase) of the electro-
other transition metal atoms (e.g., Nb and Re).257,258 Based on chemically activated MoS2/CNTs composite,260 Srimuk et al.
their tunable electronic and electrical properties, TMDCs have conrmed its ion intercalation mechanism by electrochemical
attracted much attention in the energy storage applications in in situ Raman spectroscopy and XRD methods. When the
ESDs. The similar roles of TMDCs in CDI has been recently magnitude of the applied absolute potential exceeded 0.4 V, the
studied. peaks of the XRD pattern corresponding to the MoS2 structure
A pioneering work using MoS2 electrodes for CDI desalina- in the exfoliated MoS2/CNTs electrode disappeared, indicating
tion was conducted by Xing et al.,89 where the MoS2 electrodes that the intercalation of ions had extended the MoS2 interlayer
were synthesized in two steps. First, MoS2 powder was chemi- spacings.
cally exfoliated into metallic 1T phase nanosheets using N- It was also reported by Jia et al.142 that the defects in the MoS2
butyllithium. Next, the MoS2–Au-PET electrodes were dissolved nanosheets could dramatically increase its desalination
in acetone to obtain disordered structures of MoS2. The capacity from 12.8 to 35 mg g1 (0.8 V, 100 mg L1). The
successfully exfoliated 1T phase MoS2 nanosheet structure was abundant surface defects would signicantly increase the
conrmed to be a layered structure with an average thickness of number of surface negative charges and enhance the electrical
2.2–2.6 nm by SEM, Raman spectroscopy, high-resolution X-ray conductivity of the electrode, thereby enhancing the electro-
photoelectron spectroscopy and atomic force microscopy. static attraction of ions and building a thick EDL at the
However, based on its nitrogen sorption isotherm, there were electrode/electrolyte interface. However, according to Xie
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efficiency (>85%) can be achieved in this membrane-free HCDI

device at high salt concentrations. However, to maintain a good
cycling performance, the applied potential of the TiS2/CNTs
electrode must be conscientiously monitored, as it was found via
electrochemical in situ XRD that these phase transitions inside
the TiS2/CNTs electrode strongly depend on the applied voltage
window. For example, at 0.3 V (vs. Ag/AgCl), the ion intercala-
tion was incomplete; at 0.6 V (vs. Ag/AgCl), TiS2 tended to
catalyze the decomposition of water molecules, thereby lowering
the surface pH of the electrode and causing a phase transition

from TiS2 to TiO2, ultimately resulting in an irreversible volume
expansion of the material. Although a slight expansion of the
material was observed at 0.4 V (vs. Ag/AgCl), sufficient ions
could be intercalated into TiS2 (Table 2). Thus an potential
slightly higher than 0.4 V (vs. Ag/AgCl) could be benecial for
the long-term operation of the TiS2/CNTs electrode.262
By controlling the applied potential, Srimuk et al. further
proved that the TiS2/CNTs electrode is ion selective,263 for
example, the removal capacity of Mg2+ was found to be 31 times
higher than that of Cs+ in the potential range of 396 to
220 mV (vs. Ag/AgCl), while from 219 to +26 mV (vs. Ag/AgCl),
the scenario was reversed where the removal capacity of Cs+ was
1.7 times that of Mg2+. These results suggested that selective
cation removal could be accomplished by simply adjusting the
applied potential. For separation applications, further studies
on the structural stability, cycling selectivity and selectivity at
Fig. 21 The multi-layered structure through electrochemical activa-
a low potential of the TiS2/CNTs composite should be
tion of MoS2/CNTs electrodes evidenced of the by (a) Raman spectra
and (b) XRD. Reproduced with permission.90 Copyright 2017, The Royal conducted.
Society of Chemistry. A series of studies by Srimuk et al. have shown that due to
their substantially different ion removal mechanisms, both
MoS2 and TiS2 are disuldes with layered structures that exhibit
et al.,261 such a structure rich in surface defects could also distinct desalting abilities and long-term stabilities. In addi-
signicantly improve the electrocatalytic performance of the tion, owning to the catalytic properties of TMDC compounds
composite, i.e., by reducing the overpotential of hydrogen- (e.g., decomposition of water), their operating voltages are
evolution reactions. The electrocatalytic effect reduces the limited (typically 0.8 V). With the development of more TMDCs
charge efficiency of desalination as the charge for ion removal is for CDI applications in the future, TMDCs with higher desali-
reduced. Therefore, the amount of surface defects of the nation abilities, better stabilities, and lower catalytic activities
composite should be controlled to balance its electrochemical can be synthesized. By incorporating them into carbon to form
ion removal ability and electrocatalytic activities. composites, their desalination performances can be further
In addition to MoS2, Srimuk et al. further studied the fara- improved.
daic desalination behavior of another TMDC—TiS2.91 Unlike From the above discussion, it was discovered that there are
Ti3C2-MXene and MoS2, TiS2 is more electrically conductive and signicant differences in the compositions, structures and ion
exhibits a battery-like electrochemical behavior. The binder-free removal mechanisms of 2D-IHCs/2D-IHC carbon composites
TiS2/CNTs electrode was synthesized following the steps of from those of other carbon–metal compound (including both
sonication-mixing-sonication-ltration. Similar to MoS2/CNTs, TMOs and GAMOs) composites. Nevertheless, they also share
with the conductive network of CNTs, the TiS2/CNTs electrode some common features in terms of the interactions between the
exhibited a higher energy storage capacity compared with pure ions and electrode surfaces. Such differences and similarities
TiS2 electrodes (68 vs. 40 mA h g1, current density of are summarized below:
100 mA g1). Since TiS2 is only effective for sodium ion inter- 2D-IHCs and their carbon composites remove ions through
calation, a HCDI cell (TiS2/CNTskK20) was assembled for their ion intercalation mechanism. Differing from the carbon-
desalination, wherein a TiS2/CNTs electrode and a carbon based composites, the carbon component in a carbon–2D-IHC
electrode (K20) were used as the cathode and anode respec- composite is used as an additive to improve the conductivity
tively. In such a HCDI cell, the TiS2/CNTs electrode showed and dispersibility of the 2D-IHCs. However, even though the ion
a Na+ removal capacity of 35.8 mg g1 (0.8 V, 600 mM). intercalation mechanism of 2D-IHCs has been veried by the
The distinctive feature of this research is that due to the changes in their structures and compositions during charging
selective sodium-ion intercalation property of TiS2, a high charge and discharging, the exact intercalation reactions have not yet
been established yet.
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2D-IHC electrodes show high charge efficiencies at high conditions. HCDI with the Ag-coated carbon anode even
concentrations. Due to the permselective removal of ions, no co- demonstrated lower energy consumption than an MCDI cell
ion repulsions would occur for 2D-IHCs electrodes as compared with uncoated carbon electrodes. This study highlights the
with carbon-based electrodes. Moreover, thanks to the suppres- potential of using an Ag-coated carbon anode in HCDI for
sion of the effects of co-ion repulsion, 2D-IHC electrodes can improved desalination performance and energy efficiency.
process high salinity solutions with lower energy consumption. Vengatesan et al. synthesized a graphene composite deco-
Due to the catalytic effects of 2D-IHC materials, however, rated with bimetallic nanoparticles (Ag and Cu) as an anode for
they may decompose water during desalination. For example, HCDI application.144 The HCDI unit exhibited a high desalina-
the aforementioned 2D-IHCs materials have been reported to tion capacity (16.81 mg g1, 1.2 V, 600 mg L1 NaCl) and charge
engage in electrocatalytic activities in hydrogen evolution efficiency (90%). However, as discussed in Section 5.4, Cu or
reactions.264–266 Triggering the hydrogen evolution reactions CuO is unstable as both anode and cathode materials. There-
may simultaneously contribute to material wastage and low fore, it is necessary to study the electrochemical stability of the
charge efficiencies of the 2D-IHCs electrodes for desalination. Ag–Cu decorated graphene electrode. Furthermore, according
Therefore, it is necessary to exercise precise control over the to reports by both Yoon et al. and Vengatesan et al.,143,144 since
applied potential across the electrodes, because the effective the amount of metal nanoparticles are small in both the cases of
potential of the 2D-IHCs electrodes is susceptible to changes. the Ag-coated carbon electrode and the Ag–Cu-coated graphene
electrode, the faradaic mechanisms only play a supporting role
in desalination and the dominant desalination mechanisms are
8. Carbon–3D-IHC composites the EDLC of carbon. Therefore, their desalination capacities
3D-IHCs possess super sodium ionic conductivities, which cannot compete with those of typical battery electrodes.
allow sodium ions to smoothly pass through the lattice inter-
stitial sites via ion intercalation/deintercalation without any 8.2 Carbon–Prussian blue composites
signicant nanostructure deformation. Compared to 2D-IHCs
which store ions between their layers, 3D-IHCs typically store Prussian blue, as a low-cost and non-toxic IHC material, has
ions within their lattice structures. However, 3D-IHCs have low a high propensity to engage in redox activities. Combined with
electrical conductivities, which limit their overall electro- a highly conductive carbon matrix, the carbon–Prussian blue
chemical performances. Therefore, many studies have been composite is a promising candidate for CDI desalination.
conducted to improve the electrical conductivities of 3D-IHCs, Ding et al. fabricated a nickel hexacyanoferrate/rGO
mainly by incorporating carbon in them during their struc- composite (NiHCF/rGO) as a HCDI cathode,267 which was
tural reconstruction. There are two strategies for forming such synthesized by a simple reaction between NiHCF and GO, fol-
carbon–3D-IHC composite: by coating the 3D-IHC surface with lowed by reduction of the GO by N2H4 and subsequently
carbon and growing the 3D-IHC on a carbon surface. Depend- a freeze-drying process. The HCDI cell (ACkNiHCF/rGO) ach-
ing on the strategy used and the type of 3D-IHC in question, the ieved both a good desalination capacity (22.8 mg g1) and long-
electric conductivity of a carbon–3D-IHC composite could be term stability (capacity retention of 78% aer 100 cycles) at
greatly increased, and several of such composites have been a low voltage of 0.6 V. However, the desalination capacity of
used as electrodes for electrochemical CDI desalination. NiHCF/rGO is inferior to that of spongy pure rGO,252 probably
due to the rough random stacking of NiHCF and rGO by the
simple reaction.
8.1 Carbon–metal compound /metal alloy composites In view of this, Vafakhah et al. synthesized a freestanding
As an additive for CDI carbon-based electrodes, a metal or metal Prussian blue/graphene aerogel composite (PB/GA)145 by form-
alloy considered must be stable in an aqueous solution, able to ing the graphene aerogel formed by hydrothermal and freeze-
react electrochemically with ions, and improve the electrical drying methods to generate a monolithic structure
conductivity of the composite. A metal that fullls the above (Fig. 22a).252 Subsequently, the Prussian blue nanocubes can be
conditions is silver (Ag), which is expensive and rare. Therefore, easily embedded into the aerogel via the nucleation and growth
a practical way to prepare a carbon–Ag composite is to deposit method during the hydrothermal treatment without compro-
or coat the carbon surface with a small amount of Ag mising its monolithic structure. Even though the embedding of
nanoparticles. Prussian blue nanocubes decreased the specic surface area of
Yoon et al. synthesized an Ag-coated carbon composite the composite, the desalination capacity of PB/GA increased
electrode by the photo induced reduction of AgNO3.143 Since Ag signicantly (15 vs. 130 mg g1) and was consistent within 100
can react with Cl at a specic voltage, the Ag coating can be cycles (Fig. 22b). The desalination mechanism of PB/GA was
considered an anion exchange layer. Hence, the Ag-coated investigated by in situ XRD (Fig. 22c–g). The XRD patterns pre-
carbon could serve as an anode for CDI applications. By using sented a distinct constituent peak shi of Prussian blue, indi-
pristine carbon as the cathode, optimum desalination perfor- cating the movement of the Na+ ions into/out of the Prussian
mance (SAC value ¼ 15.6 mg g1, 0.7 V, 10 mM NaCl; charge blue crystals via intercalation and deintercalation. This study
efficiency ¼ 92.2%) can be achieved when the deposition suggested that a freestanding carbon matrix augmented with
amount of Ag is 1.3 mg cm1. In contrast, an uncoated carbon redox-active IHC materials holds great prospects for high-
anode can only remove 7.6 mg g1 of salt under the same performance desalination.
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Fig. 22 Morphology and desalination performance of PB/GA composite as the anode for HCDI application: (a) TEM image of the embedded
Prussian blue nanocubes in the graphene aerogel matrix, (b) cycling performance at various current densities, (c–e) in situ XRD characterization
during the charging and discharging process, including (c) the 2D-evolution illustration of peaks and (d) the corresponding XRD patterns, and (e)
higher magnification for the indicated oval in (c). Schematic crystal structures of Prussian blue (f) before Na+ intercalation and (g) after Na+
deintercalation. Reproduced with permission.143 Copyright 2019, The American Chemical Society.
8.3 Carbon–phosphate composites FePO4 electrodes (64 mg g1 for FePO4 nanoparticles146 and
50.1 mg g1 for FePO4 nanospheres147). Ma et al. further esti-
Phosphates generally exhibit good electrochemical properties
mated the initial production cost and the energy consumption
and are safer than common metal oxides.268 For example, the
of FePO4@RGO electrode to be $1 and 9.0 104 kW h per
naturally abundant ferric phosphate (FePO4) possesses a high
gram respectively, indicating its potential applications in the
theoretical specic capacity (175 mA h g1), and has been
industry.147
successfully applied as a host material for CDI.
Sodium super ionic conductive (NASICON) materials have
Guo et al. synthesized a FePO4@RGO composite via chemical
precipitation, oxidation and low temperature calcination received great attention as cathode materials for HCDI because
(400 C, nitrogen).146 Material characterization results indicated of the low activation energy of sodium ions in their lattices,
resulting in their high sodium ion conductivities and high
that FePO4 exists in the form of amorphous nanoparticles and is
theoretical specic capacities. Na3V2(PO4)3, as a representative
randomly distributed on the graphene layers. Under a constant
NASICON material, has a high theoretical specic capacity of
current, FePO4@RGO achieved a high SAC value of 100 mg g1
117.6 mA h g1.269 Its carbon composite is reported to exhibit an
(100 mA g1, 2.5 g L1). Ma et al. synthesized a similar
excellent desalination performance when coupled with AgCl or
FePO4@RGO composite with a mesoporous FePO4 nanosphere
AgCl/graphene anodes.148–150
structure using a one-pot hydrothermal method.147 At 1.8 V with
a 40 mM NaCl feed solution, such a mesoporous amorphous Zhao et al. performed carbon coating on various Na3V2(PO4)3
FePO4@RGO composite demonstrated a similar desalination nanostructures (NVP@C) by controlling the hydrothermal
reaction time (0.5 to 24 h) to investigate the effects of NVP
capacity compared to its previously discussed counterpart (86
nanostructures on their desalination performances (Fig. 23a).148
vs. 100 mg g1). In contrast, the FePO4@RGO electrodes in both
These complexes were NVP nanospheres (NVPS@C), NVP
studies exhibited higher desalination capacities than pure
nanoakes (NVPF@C) and NVP nanowires (NVPW@C).
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Fig. 23 Structure and desalination performances of the carbon-coated Na3V2(PO4)3 nanostructures (NVP@C): (a) SEM images of (a1) NVP
nanospheres, (a2) NVP nanoflakes and (a3) NVP nanowires (NVPW@C), (a4) CV curve (1 M NaCl solution with a scan rate of 1 mV s1) of porous
carbon-coated NVP nanowires, and (a5) cycling performance of NVPW@C–AgCl CDI system at a current density of 100 mA g1. Reproduced
with permission.146 Copyright 2018, American Chemical Society. (b1) SEM, (b2) TEM, (b3) CV and (b4) rate capability of the graphene-coated NVP
nanoparticle composite. Reproduced with permission.148 Copyright 2019, Wiley-VCH. (c1) SEM, (c2) TEM, (c3) CV and (c4) desalination
performance of the porous carbon-coated NVP nanocube composite. Reproduced with permission.147 Copyright 2019, American Chemical
Society.
Compared with NVPS@C (65.6 mg g1) and NVPF@C (83.1 mg conductivity of carbon and high theoretical sodium-ion storage
g1), NVPW@C displayed the highest desalination capacity capacity of NaTi2(PO4)3 (133 mA h g1),270 the HCDI system with
(124 mg g1, 100 mA, 1 g L1 NaCl) and best cycling perfor- the NTP/C composite cathode and AC anode exhibited an
mance (76.5% of its initial capacity reserved aer 500 cycles), excellent desalination capacity of 167.4 mg g1 (1.8 V, 1 g L1
probably owing to the synergistic effect of its conductive NaCl) and decent desalination ability (90% of initial capacity
network and surface carbon coating. Following a similar fabri- was retained aer 30 cycles). Note that among all carbon–metal
cation strategy but replacing the polydopamine with GO as the compound composites reported, this was the best desalination
carbon source, Zhao et al. also prepared an NVP@graphene performance reported thus far. The studies of Ding et al.267 and
composite (Fig. 23b) for electrochemical desalination, which Wang et al.151 highlight the vital roles of the porous carbon
achieved a similar desalination capacity (107.5 mg g1, 100 mA, framework and the ionic conductive metal compounds in
1 g L1 NaCl).150 Cao et al. synthesized a similar NVP@C improving the desalination performance of carbon–metal
composite (Fig. 23c) via sol–gel, pre-oxidation and carboniza- compound composites.
tion methods, which likewise exhibited a decent desalination The reported carbon–phosphate composites reported
performance (137.2 mg g1, 1.0 V, 5.84 g L1) as compared with exhibit high SAC values (close to 100 mg g1), stable cycle
the two composites reported by Zhao et al.148–150 performances and low energy consumption, thereby indi-
Wang et al. integrated an ionic conductive NASICON and cating that these materials are suitable as cathode materials
a metal-organic-framework-derived porous carbon to form for CDI. With their present successful applications in SIBs,
a NaTi2(PO4)3/carbon composite (NTP/C) by a two-stage sol- further developments of carbon–phosphate composites for
vothermal treatment and high-temperature annealing (700 C, CDI electrodes are expected.
nitrogen).151 Due to its high specic surface area, good electrical
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8.4 Carbon–3D sodium/lithium metal oxide composites 9. Computational simulation uses for
To improve the electrical conductivity of Na4Ti9O20 nanotubes carbon–metal compound composites
(NTO), which is an alkali-metal titanate and a well-known sodium
ion intercalation material,271 Zhou et al.152 and Yue et al.153 coated in CDI
the surfaces of NTO with graphene (rGO@NTO) and carbon Simulations are utilized to interpret and produce semi-
(C@NTO), respectively. In an asymmetrical conguration with an quantitative estimates of data obtained from actual experi-
AC-anode, both composites exhibited higher desalination ments, represent molecular behavior and obtain both observ-
performances as cathodes compared with pure NTO electrodes. able and non-observable data that are difficult or impossible to
These two studies also suggested that graphene coating is more be obtained using experimental probes.272 To formulate the
effective than core–shell carbon coating in enhancing the desali- governing equations and create models, experiments must be
nation performance of Na4Ti9O20. This can be attributed to two rst conducted to identify the dependent and independent
reasons: rstly, graphene has intrinsically better intrinsic elec- variables.273 In theory, it is possible to produce results without
tronic properties and higher electrical conductivity than other conducting the actual experiment. However, additional equa-
forms of carbon and secondly, its 2D–1D heterostructure can tions are required to account for the different parameters and
simultaneously prevent graphene layers from restacking while improve the reliability of the simulation, which proved more
providing enough space for ion penetration, since the stacking of challenging. With advancements in computer processing, it is
core–shell nanotube structure would lead to less space utilization. currently possible to conduct simulations that could account
Instead of directly coating carbon on the surface of a nano- for many equations on both the macroscale and nanoscale
structured sodium metal oxide, Guo et al. prepared a Li4Ti5- levels.
O12@C composite with a sandwich-like structure by growing
Li4Ti5O12 nanoakes on a carbon cloth surface and subse-
quently coating them with another layer of carbon.154 Although 9.1 Using molecular dynamics simulation for CDI
the desalination capacity of the composite is 300% higher than applications
that of a pristine carbon cloth (25 vs. 8 mg g1), it is still lower
than that of typical battery electrodes. Taking into account of Graphene is the most commonly modelled material for CDI
the research performance by Zhou et al. and Yue et al.,152,153 this electrodes, due to its high electrical conductivity, large surface
study highlights the importance of using a carbon matrix with area, exceptional mechanical stability, and chemical inert-
superior electrical properties when synthesizing metal oxide ness.274 Most importantly, due to its regular single-layer
composite electrodes for CDI. hexagonal carbon pattern and the atomic interactions
between carbon atoms, graphene is simple to model and is
By using both CNTs and graphene as the carbon matrix to
assumed to be the perfect electrode in simulations. Molecular
maximize the performance of carbon and IHC materials, Srir-
amulu et al. synthesized a carbon–sodium metal oxide composite dynamics simulations allow for the simple modeling of gra-
(Na2Ti3O7–CNT@rGO) with a sandwich-like structure.155 Layered phene layers into any patterns, such as a at or corrugated
Na2Ti3O7 was rst deposited onto the CNTs surfaces to form surface, which is useful when attempting to represent a realistic
Na2Ti3O7–CNT nanowires, then the composite nanowires were graphene electrode. According to Fasolino et al.,275 due to
dispersed in a GO solution to form a freestanding nanolm thermal uctuations, graphene sheets tend to form corrugated
composite with a 2D–1D nanostructure. Since layered Na2Ti3O7 or ripple-like surfaces instead of at surfaces.
According to Dahanayaka et al.,276 by having a corrugated
can provide enough storage sites for sodium ions, and CNTs with
graphene surface, the water ux through the CDI channel would
graphene layers increase the electrical conductivity of the
composite, these two advantages can synergistically contribute to be reduced with an improvement in ion removal capacity of the
the high desalination capacity (129 mg g1, 1.4 V, 3.0 g L1 NaCl) CDI unit. This is mainly due to the increased friction between
and excellent cycling performance (83.3% performance retained the water and corrugated surfaces of the graphene electrodes,
aer 80 cycles) of the composite. which hinders water movement and anchors ions onto the
Based on the structure-desalination performance analysis of graphene surfaces, rendering them susceptible to ion accumu-
carbon–3D-IHC composites, it was established that in order to lation.276 Therefore, simulations on a metal oxide-coated gra-
phene electrode can be conducted to study the differences in
achieve a high desalination capacity, the composite and setup
behaviors and performances of CDI units utilizing graphene
must satisfy the following conditions; namely, (1) the carbon
matrix must have a high electrical conductivity and form electrodes with at or corrugated surface.
a conductive network to allow rapid transfer of electrons. (2) To simulate metal deposition onto the graphene surface,
The IHC materials must be sodium super-ionic conductive and Fonseca et al. investigated the interactions between graphene
dominate the removal of sodium ions. (3) The voltage limit and Ti at their interface. The molecular dynamics simulation
must be determined prior to desalination since IHC materials explored different extents of Ti coverage on the graphene
typically store sodium ions at a specic voltage. (4) The IHC surface while evaluating the formation of bonds between the
two materials at different temperatures. It was discovered that
materials must be stable in aqueous solutions. (5) The
the degree of Ti attachment could be greatly improved by
composite must have an interconnected but porous structure
intendent of how the IHCs composites are synthesized. introducing atomic vacancies onto the graphene surface and
promoting electrostatic inuence between the two materials
View Article Online
using a substrate. This is because the bonding of Ti with the and LiMn2O4 (1011 cm2 s1).281 Therefore, this study opened up
dangling carbon atoms found at the vacancies is more ener- opportunities to simulate the diffusivity of ions in graphene–
getically favorable as compared with forming Ti–Ti bonds, and metal compound composites.
using a substrate improves adhesion by increasing the attractive
forces between the non-bonded Ti and graphene. Furthermore,
9.2 DFT studies to understand the electrode properties
Fonseca et al. indicated that since the interface was found to be
thermally stable against the breaking of carbon–carbon sp3 An alternative method to investigate the properties of the elec-
bonds, it was thermodynamically unfavorable to form titanium trodes is the density functional theory (DFT). For example, Chen
carbide.277 However, it is challenging to simulate the deposition et al. investigated the charge storage process of a graphene
of TiO2 onto the graphene electrode instead of pure Ti, due to coupled TiO2 sandwich-like hybrid anode.282 However, differ-
the additional interactions between the Ti atoms and the O ences between the theoretical and experimental voltages were
atoms. found. This is due to the simulation undermining the extent of
In addition, other molecular dynamics simulations utilizing electrode polarization during the actual experiment which
metal atoms/ions for graphene interactions were conducted for resulted in larger current densities produced during the actual
solute removal. To analyze the interactions between Mn2+, Au, experiment as compared to modeling, as well as the discrepancy
Pt, Na+, Li+ and the graphene sheet, Chan et al. used continuous of the dielectric energetic kinetics between the amount of TiO2
approximation and a 6-12 Lennard-Jones potential in his used in actual experiments and the simulation respectively.282
simulation.278 By plotting their electrical potential energy over Furthermore, Chen et al. highlighted that when compared with
the perpendicular distance of the metal atoms/ions above the pure graphene electrodes, the partial hybridization of TiO2
graphene surface, their equilibrium positions could be found by nanocrystals with graphene provides a more suitable channel at
minimizing the potential energy. As noted, the equilibrium the graphene–TiO2 interface for sodium intercalation/
positions for Mn2+, Au, Pt, Na+ and Li+ were found to be 2.25, deintercalation due to a much smaller energy barrier.282
3.30, 3.25, 2.91, and 2.5 A respectively. This method is useful in Jaber-Ansari et al. conducted DFT calculations to investigate
nding the minimum intermolecular spacing between two the phenomena of the improved capacity retention of graphene-
graphene electrodes to ensure that the metal atoms/ions expe- coated spinel-structured LiMn2O4 cathodes relative to pristine
rience no net force from the electrodes when adsorbed.278 LiMn2O4 cathodes.283 The reason is due to the suppression of
Furthermore, research was conducted to simulate the inter- the manganese separated from the cathode by the graphene
actions between metal ions and metal composites. To obtain layer. Firstly, the coated graphene and solid electrolyte inter-
the diffusivity (D) of the Li+ ions in the FeMnO3/graphene phase layer formed entering electrolyte decomposition function
composite at varying temperatures, Bin et al. conducted as a partially permeable barrier to prevent manganese ions from
a molecular dynamics simulation to obtain the displacement moving into the electrolyte while allowing fast lithiation/de-
values of the Li+ ions at specic timings aer allowing the ions lithiation. Secondly, graphene can simultaneously oxidize and
to diffuse for 40 ps at varying temperatures through the FeMnO3 reduce the Mn3+ in the LiMn2O4 cathodes to form Mn4+ and
structure at varying temperature (Fig. 24).279 Using the equation: Mn2+, respectively. Subsequently, only the Mn2+ ions would be
D ¼ [r(t)2]/2t, D can be obtained using a linear tting to plot transferred into the electrolyte.
[r(t)]2 over 2t, where r(t) is the displacement of the Li+ ions at Geng et al. investigated the effects of an external electric eld
simulated time t. Aerwards, the diffusivity D at room temper- on a graphene–ZnO composite by studying its binding energies,
ature is extrapolated from a set of diffusivity values at varying charge function, band structure and work functions (Fig. 25).284
temperatures according to the Arrhenius relationship (Fig. 24c). It was discovered that the binding energies decrease as the
As a result, Bin et al. determined the room temperature diffu- electric eld strength increases with a peak value at zero electric
sion coefficient of Li+ ions through FeMnO3 at 3.9 1012 cm2 eld, while the rate of charge transfer decreases linearly when
s1, which approaches the diffusivities of some well-known the electric eld increases. Also, the magnitude of the work
electrode materials such as graphite (1.12 1010 cm2 s1)280 functions differs based on the constituent components of the
composite. For example, the work function of the ZnO
Fig. 24 (a) FeMnO3 membrane structure used for Li+ ion diffusion. (b) Density of states for FeMnO3. (c) Arrhenius plot of the Li+ ion diffusion
coefficient in FeMnO3. Reproduced with permission.279 Copyright 2016, Elsevier.
View Article Online
In another of their simulated experiment,55 it was discovered

that reducing the diameter of the nanoparticles could result in
a stronger electric eld around them. Similar to the previous
simulation,198 nanoparticles with higher dielectric constants
would result in stronger electric elds. In addition, during the
polarization of TiO2 and ZnO nanoparticles in the direction of
the crystal poling (z-axis) parallel to the applied eld direction,
the applied potential loss slope was steeper for ZnO despite it
having a corresponding electrical eld strength similar TiO2.
This could be explained by the crystal symmetry of both oxides,

which also determines their polarization characteristics and the
dielectric constants. Since ZnO is non-centrosymmetric as
compared to TiO2 (centrosymmetric, Fig. 26c and d), the net
polarization inside its crystal core of ZnO is typically higher due
to a greater uneven charge distribution leading to fewer charge
cancellations, thereby resulting in a stronger electric eld.
By using nite element to analyze the inelastic behavior of
carbon bers in an aluminum matrix, Ismar et al. characterized
the carbon bers by a transversely isotropic elastic material
law.285 In addition, due to the small shear modulus of carbon
ber, the stark contrast between the transverse and longitudinal
thermal expansion coefficients of carbon, and the large differ-
Fig. 25 (a) Binding energies and (b) work functions of the ZnO/P/G, ence in the thermal expansion coefficients of the aluminum
ZnO/V/G, ZnO/O/G composites under the influence of an external matrix and the carbon ber, the composite exhibited a distinct
electric field. Reproduced with permission.284 Copyright 2014, The gradient of equivalent inelastic strain during the thermal
Royal Society of Chemistry. cooling, and small degrees of inelastic strain and damage under
monotonic and cyclic loadings.
component increases with the electric eld strength, while the

graphene exhibits an opposite effect. However, the width of the 9.4 Validating the theoretical results from models
band gap is independent of the electric eld.284 Therefore, it is Regardless of the simulations employed, it is important to
possible to investigate the simulated performance of the gra- validate the theoretical results since they could be utilized in
phene–ZnO composites in an external electric eld. other simulations or literature. Methods to validate the results
Hence, while there may be discrepancies between the actual include cross-referencing with actual data, using small scale
experiment and simulations, these modeling studies assisted representation and selecting the appropriate simulation
in explaining the improved performance of graphene–metal mechanism.
compound composites in the above experimental CDI reports, From the research papers presented above, one of the
and are benecial for the future development of CDI common procedures when running simulations is to cross-
electrodes. reference the theoretical results with actual research data. To
reduce the number of variables and parameters, and improve
the reliability and duration of the simulation, simulations are
9.3 Testing the performance of carbon–metal compound conducted on the nanoscale.272 However, on the atomic level, it
composites in CDI using nite-element simulation can be challenging to compare the results due to limited
To study the reaction of carbon–metal compound composites empirical data.272 Therefore, to improve the reliability of the
under the inuence of heating, loading or an electric eld on simulation results, the qualities of the models has to be
the macroscale, the nite element method is commonly used. considered,272 mainly the modeling theory, and how the simu-
Laxman et al. conducted nite element simulations to lation was conducted. Furthermore, it is important to document
determine the electric eld distribution along an electrode.55,198 the soware, simulation conditions, assumptions made and
They estimated the effects of using different metal oxides such model parameters to allow other researchers to efficiently
as TiO2 and ZnO nanoparticles with varying morphologies and replicate the simulations. This will be useful in reducing the
geometries, with respect to the electric eld distribution. degrees of approximation, uncertainty and compromises made
According to the simulation results,198 by thickening the in future research endeavors.286
dielectric coating (1 mm, 3 mm to 7 mm) of strong dielectric Depending on the property being investigated, the relevance
materials (TiO2), their external electric eld strengths is of the modeling theory and its level of simplicity, some models
reduced. However, the electric elds would be strengthened are favored over others. For example, molecular dynamics
instead for weaker dielectric materials (ZnO) due to their simulations are commonly used to investigate ion interactions
reduced resistance to polarization (Fig. 26a and b). with the electrodes, the ion removal performances and the
View Article Online

Fig. 26 The influences of external electric field on ZnO and TiO2. Electric field distribution around the (a) ZnO- and (b) TiO2-coated electrode
being submerged in NaCl solution. The orientation and size of the arrows represent the electric field direction and magnitude. Reproduced with
permission.198 Copyright 2015, Elsevier. Schematic crystal structures of (c) noncentrosymmetric ZnO and (d) centrosymmetric TiO2 with different
charge distributions. Reproduced with permission.55 Copyright 2018, American Chemical Society. https://pubs.acs.org/doi/10.1021/
acsami.7b16540
water ux through a CDI channel.287 With a wide range of metal compounds and incorporating a small amounts of highly
models to choose from, researchers could select the most conductive carbon materials (graphene or CNTs) into ultrathin
appropriate modeling mechanism pertaining to their research layered or ultra-porous metal compounds to obtain electro-
interests. When choosing models, it is important to evaluate chemically stable extended structures.
their validity by examining the practicality of the set-up. Therefore, the dominant desalination mechanisms in these
Considering that it is virtually impossible for a single model two kinds of electrodes are different. For a carbon-based elec-
to fully represent an actual experiment, assumptions must be trode using a metal compound as an additive, ion adsorption
established. Such an assumption was mentioned previously in mainly depends on the EDLC of the porous carbon substrate,
the case of CDI graphene electrodes, which the graphene was while the coated TMO improves the desalination performance of
assumed to be a perfect electrode.55 the composite by either altering the surface properties (wetta-
bility, surface potential and specic surface area, etc.) of the
carbon substrate (e.g., TiO2, ZnO, ZrO2, SiO2 and Al2O3) or
10. Conclusion and perspectives introducing pseudocapacitance to store more ions (e.g., MnOx,
SnO2, FeOx, V2O5 and RuO2). In contrast, for a battery electrode
The development of electrodes with high desalination capac-
utilizing nanostructured carbon as an additive, ions are stored in
ities and long-term stabilities is particularly crucial for efficient
a fully exfoliated surface lattice (2D-IHC) or in the lattice inter-
CDI desalination. By merging the advantages of pure carbon
stitial sites (3D-IHC) where they reach through ion intercalation/
and pure metal compound, this review highlights the recent
deintercalation. Meanwhile, the carbon nanostructure increases
advancements in the synthesis and development of carbon–
the rate of electron transfer in these composites.
metal compound composites as effective electrodes for CDI
For both strategies, the ultrathin layered structure of metal
desalination. According to the preparation methods for elec-
compounds and the porous framework of carbon are vital for
trodes with high desalination performances (e.g., SAC > 15 mg
high performance desalination of the composite. The ultrathin
g1 and SRR > 1 mg g1 min1) in Table 1 and Fig. 6, there are
layered structure provides a low electrode resistance to enhance
two strategies for achieving a high desalination performance:
electron transfer between the carbon and metal compound, and
depositing or coating the surface of highly conductive and
it also enhances the capacitance of the composite because of the
porous carbon substrates with uniformly dispersed ultrathin
View Article Online
increased electric eld strength across the ultrathin layers. regarded as a primary focus in the development of new carbon–
Furthermore, the ultrathin layered structure can provide more metal compound composites.
accessible active sites and reduce the negative effects of exces- Secondly, the electrical conductivities of composites need to
sive deposition (which may partially cover/block the pores of the be further enhanced. Generally, the theoretical capacitance of
carbon material), and thus the utilization of the metal a metal compound (e.g., RuO2, spinel MnO2 and Ti3C2) is highly
compound can be improved. dependent on its electrical conductivity. However, the capaci-
To understand the interactions between ions and elec- tive performances of metal compounds are compromised
trodes in CDI, various simulations were reviewed depending because of their poor crystallinity or thick layers. As a result, the
on the relevance of their governing theories. Molecular key to improving their electrical conductivities is to reconstruct
dynamics simulations were used to evaluate the interactions them into ultrathin structure. Furthermore, the electrical
between the graphene surface and metal atoms/ions to obtain conductivities of metal compounds also depend signicantly on
the ion adsorption capacity of the graphene and diffusivity of their nanostructures, the size of nanosheets, the continuities of
the atoms/ions, while DFT was employed to investigate the surface deposits and the connections between the nano-
charge storage and capacity retention of the electrodes, as well particles. Consequently, it is paramount to synthesize
as the interactions between the electrodes and the external composites with large ultrathin nanosheets or ultrathin and
electric eld. Other mechanism such as nite element simu- continuous deposits. Another method to increase the conduc-
lation was also utilized to evaluate the electric eld distribu- tivity of a carbon–metal compound composite is to incorporate
tion and adsorption energy of the electrodes. Finally, the into a third conductive component, e.g., conductive polymers.
reliability of the theoretical results can be improved by cross- In particular, in situ deposited conductive polymers not only
referencing them with experimental data for small scale improve the electrical conductivity of the material, but also
representations and selecting the appropriate simulation prevent the restacking of 2D nanomaterials (graphene, or 2D-
theories. IHCs), and disperse the deposited metal compound nano-
particles more uniformly onto the carbon surface.
Thirdly, it is vital to form ultrathin-layered heterostructures
10.1 Perspectives on the development of new carbon–metal in the composites. Since some of the metal compounds previ-
compound composites for CDI ously discussed are harmful, to avoid any toxic ion leakage, it
This review emphasizes the importance of the development of would be feasible to form heterostructures (such as layer-by-
novel carbon–metal compound composites to address the low layer or core–shell structure) in the composites, along with
salt removal capacities of pure carbon electrodes and the low a redox-active component inside and non-toxic ultrathin
adsorption rates and cycling abilities of metal-based electrodes, coating on their surface. Furthermore, the 2D heterostructured
which are analogous to the low energy densities of SCs and the architecture can enhance the electrochemical performances of
low power densities of batteries. Since carbon–ultrathin metal composites by mitigating the restacking issue of their
composites have been extensively studied and applied as elec- condensed layers.246 Compared to the 2D–2D heterostructure,
trodes for ESDs, following the footsteps of these research, the the 2D–1D stacking strategy is more effective in creating an
development of new carbon–metal compound composites for expanded 2D layered structure and providing sufficient space
CDI would be relatively simply. However, when utilizing ESD for electrolyte penetration. For example, as shown in Table 1,
electrodes in CDI desalination, in addition to salt removal samples like the RGO/TiO2 nanorods, graphene@MnO2 nano-
capacities and rates, other factors such as the preparation cost, rods, MoS2/CNTs, Na3V2(PO4)3@C and Na2Ti3O7–CNT@rGO
environmental compatibility, biological toxicity, etc., should generally demonstrate higher desalination performances than
also be considered. Based on the above discussions, a few metal compounds in other forms (nanoparticles, dense bulk
possible research directions are proposed as follows. materials). Therefore, exploring other 2D–1D heterostructured
Firstly, more facile and greener synthesis methods to obtain nanomaterials would be a salient approach to further enhance
the ultrathin metal layers of the composites need to be devel- the desalination performances of carbon–metal compound
oped. For the EDLC-dominated carbon–metal compound composites.
composites, the microwave-assisted hydrothermal method is Fourthly, carbon–metal compound composites can be
considered the most energy-efficient and facile approach as utilized as redox-active ow-electrodes for continuous CDI
compared to other methods (e.g., sol–gel, conventional hydro- desalination. The above-mentioned composite electrodes are
thermal method, high-temperature annealing, electrodeposi- stationary and require regeneration for next-step adsorption,
tion, CVD or ALD). However, these methods encounter which determines their intermittent operational functionality.
challenges when obtaining an ultrathin deposition with By utilizing a ow-electrode, regeneration can be conducted in
complete coverage and generally resorts to utilizing the highly an external module isolated from the CDI module (self-colliding
toxic HF is used to exfoliate the bulk material and form 2D or discharging in another CDI unit) and thus the system can
nanosheets for IHC electrodes. Differing from the practice of operate continuously.18,288 As reported by Ma et al.289 and Xu
using ESD electrodes in micro/nano-devices, CDI electrodes are et al.,290 redox-active components can improve charge/ion
relatively larger in size. Therefore, the efficiency and environ- transfer in the ow-electrodes. Since this research direction is
mental compatibility of the preparation methods for CDI elec- rather revolutionary, the simulation development of new
trodes are essential. These research directions should be carbon–metal compound composite materials and
View Article Online
investigation of their electrochemical characteristics as ow- synthesis, desalination mechanism, theoretical model estab-
electrodes should be conducted. lishment, process condition optimization, etc. Until now, the
commercial applications of CDI technology are still limited in
10.2 Perspectives on the computational modeling and a RO-dominated desalination market. But for the past two
simulating potential of CDI using carbon–metal compound decades, with the rapid development of battery electrodes, new
composites opportunities arose for industrial applications of CDI for
desalination.291 However, several issues mentioned below
Although there have been modeling studies conducted, they are
should be considered for future research endeavors:
few compared to those of physical experiments. Despite the
Firstly, to establish a reliable correlation between the
discrepancies between the simulation and experimental data,
capacitance and salt removal capacity of an electrode, its elec-

the main reason behind the lack of published research in
trochemical behavior should be evaluated in accordance with
modeling studies is the issue of reliability should there be no
the actual conditions in CDI, where the parameters, such as the
existing physical data for referential purposes, unless it does
unit conguration, electrolyte concentration, potential window
not exist in the rst place. However, researchers can still utilize
and electrode state (stationary or owable), should correspond
simulations for various purposes, as described below.
to appropriate value.
Firstly, simulations can be conducted to replicate the
Secondly, to systematically compare the diverse CDI elec-
synthesis of graphene–metal oxide composite electrodes. While
trodes with different salt removal mechanisms (e.g., EDLC,
there is a plethora of research papers describing the different
pseudocapacitance and ion intercalation charge storage), it is
routes of fabricating the electrodes, such as the sol–gel method
strongly recommended that researchers report the performance
and hydrothermal treatment, hitherto a few studies have
matrices suggested by Suss et al.22 In particular, the CDI Ragone
attempted to simulate the different steps of the fabrication
plot or Kim–Yoon plot can simultaneously provide information
processes until now. In addition, it is possible to vary certain
about the SAC values and salt remove rates of the electrodes.292
fabrication conditions in the simulations to uncover potential
Such reports serve as databases and thus allow future
optimal fabrication route. It is also possible to conveniently
researchers to systematically compare the desalination proper-
validate the simulation by cross-referencing their results with
ties of different electrodes.
the actual fabrication methods.
Thirdly, following the breakthroughs in the development of
Secondly, the graphene–metal oxide interface of the
SCs, LIBs and SIBs, it is foreseeable that the application of these
composite electrodes can be studied through employing simu-
novel materials for CDI will become prevalent. However, for
lations. As most of physical experiments characterize the
practical applications in CDI, relatively large electrodes should
composite electrodes either as a whole or separately as the
be used during tests, and a CDI unit with small electrodes (e.g.,
graphene and the metal oxide, it is difficult to observe in detail
weighing a few micrograms) should not be utilized to obtain an
how the graphene–metal oxide interface contributes to the
accurate evaluation of its desalination performance.
desalination performance of the composite. As simulations can
Finally, another consideration for CDI applications is that no
be conducted on the atomic level, it is possible to model such an
by-products should be generated. This indicates that the
interface and simulate the interfacial metal atom/ion interac-
composite electrode containing TMOs, GAMOs or IHCs must be
tions under different conditions.
chemically stable in a constant electric eld. Therefore, for
Thirdly, simulations can be utilized to determine the
a battery-like electrode, its long-term cycling stability must be
optimal the operating conditions of the composite electrodes.
tested, and the dissolved ion species must be monitored in
Since the extent of physical experiments are limited by cost,
between cycles. To avoid potential health hazards, even greater
time and the presently available technology, the range of oper-
precaution must be taken when the incorporated metals or
ating conditions (e.g., applied voltage, salt concentration,
metal compounds are toxic in nature.
distance between electrodes, etc.) experimented on to evaluate
the electrode performance cannot reach the levels of versatility
and multiplicity of simulations. Furthermore, it is possible to Conflicts of interest
quickly identify issues in the parameter values during simula-
tions to allow for quick mitigations, which is not the case in There are no conicts to declare.
physical experiments. Furthermore, when the same electrode
has been used for different tests, its deterioration must to be
accounted for unless the electrode is replaced. In contrast, these
Acknowledgements
is not required of simulations, which provide consistency and The authors acknowledge nancial support from Nanyang
save cost by allowing the same model to be repeatedly employed Environment and Water Research Institute (Core Funding),
for different tests. Nanyang Technological University, Singapore.
10.3 Perspectives on the concerns of the practical CDI

applications of carbon–metal compound composites References
With the development of CDI technology for nearly two decades, 1 T. Oki and S. Kanae, Science, 2006, 313, 1068–1072.
much progress has been made in the areas of material 2 A. Maxmen, Nature, 2018, 554, 13–14.
View Article Online
3 C. Tortajada and V. Fernandez, in Global Water Security: 28 J. Lee, P. Srimuk, K. Aristizabal, C. Kim, S. Choudhury,
Lessons Learnt and Long-Term Implications, Springer Y. C. Nah, F. Mucklich and V. Presser, ChemSusChem,
Singapore, Singapore, 2018, pp. 1–19, DOI: 10.1007/978- 2017, 10, 3611–3623.
981-10-7913-9_1. 29 B. Marinho, M. Ghislandi, E. Tkalya, C. E. Koning and G. de
4 E. Metzger, P. Reig, W. H. Wen, R. S. Young and B. Owens, With, Powder Technol., 2012, 221, 351–358.
Water-Energy Nexus: Business Risks and Rewards, World 30 E. Bekyarova, S. Sarkar, F. Wang, M. E. Itkis, I. Kalinina,
Resources Institute, 2016. X. Tian and R. C. Haddon, Acc. Chem. Res., 2013, 46, 65–76.
5 I. Dincer and C. Acar, Int. J. Energy Res., 2015, 39, 585–606. 31 H. Yin, S. Zhao, J. Wan, H. Tang, L. Chang, L. He, H. Zhao,
6 I. C. Karagiannis and P. G. Soldatos, Desalination, 2008, 223, Y. Gao and Z. Tang, Adv. Mater., 2013, 25, 6270–6276.
448–456. 32 Y. Liu, C. Y. Nie, X. J. Liu, X. T. Xu, Z. Sun and L. K. Pan, RSC

7 N. Ghaffour, T. M. Missimer and G. L. Amy, Desalination, Adv., 2015, 5, 15205–15225.
2013, 309, 197–207. 33 P. Y. Liu, T. T. Yan, L. Y. Shi, H. S. Park, X. C. Chen,
8 R. K. McGovern, A. M. Weiner, L. G. Sun, C. G. Chambers, Z. G. Zhao and D. S. Zhang, J. Mater. Chem. A, 2017, 5,
S. M. Zubair and J. H. Lienhard, Appl. Energy, 2014, 136, 13907–13943.
649–661. 34 Y. Liu, L. Pan, T. Chen, X. Xu, T. Lu, Z. Sun and
9 M. Papapetrou, A. Cipollina, U. La Commare, G. Micale, D. H. C. Chua, Electrochim. Acta, 2015, 151, 489–496.
G. Zaragoza and G. Kosmadakis, Desalination, 2017, 419, 35 G. Wang, Q. Dong, Z. Ling, C. Pan, C. Yu and J. Qiu, J. Mater.
8–19. Chem., 2012, 22, 21819–21823.
10 M. Al-Shammiri and M. Safar, Desalination, 1999, 126, 45– 36 S. H. Roelofs, B. Kim, J. C. T. Eijkel, J. Han, A. van den Berg
59. and M. Odijk, Lab Chip, 2015, 15, 1458–1464.
11 N. Misdan, W. J. Lau and A. F. Ismail, Desalination, 2012, 37 X. Xu, H. Tan, Z. Wang, C. Wang, L. Pan, Y. V. Kaneti,
287, 228–237. T. Yang and Y. Yamauchi, Environ. Sci.: Nano, 2019, 6,
12 I. G. Wenten and K. Khoiruddin, Desalination, 2016, 391, 981–989.
112–125. 38 C. Tsouris, R. Mayes, J. Kiggans, K. Sharma, S. Yiacoumi,
13 H. Strathmann, Desalination, 2010, 264, 268–288. D. DePaoli and S. Dai, Environ. Sci. Technol., 2011, 45,
14 W. R. Walters, D. W. Weiser and L. J. Marek, Ind. Eng. 10243–10249.
Chem., 1955, 47, 61–67. 39 Y. Liu, X. Xu, M. Wang, T. Lu, Z. Sun and L. Pan, Chem.
15 J. W. Blair and G. W. Murphy, in Saline Water Conversion, Commun., 2015, 51, 12020–12023.
American Chemical Society, 1960, vol. 27, ch. 20, pp. 206– 40 Y. Li, X. Xu, S. Hou, J. Ma, T. Lu, J. Wang, Y. Yao and L. Pan,
223. Chem. Commun., 2018, 54, 14009–14012.
16 G. J. Gittens and E. Glueckguf, AIChE-IChemE symposium 41 S. Porada, F. Schipper, M. Aslan, M. Antonietti, V. Presser
series, 1965, vol. 9, pp. 79–83. and T.-P. Fellinger, ChemSusChem, 2015, 8, 1867–1874.
17 J. B. Lee, K. K. Park, H. M. Eum and C. W. Lee, Desalination, 42 J. Biener, M. Stadermann, M. Suss, M. A. Worsley,
2006, 196, 125–134. M. M. Biener, K. A. Rose and T. F. Baumann, Energy
18 S. I. Jeon, H. R. Park, J. G. Yeo, S. Yang, C. H. Cho, M. H. Han Environ. Sci., 2011, 4, 656–667.
and D. K. Kim, Energy Environ. Sci., 2013, 6, 1471–1475. 43 J. C. Farmer, D. V. Fix, G. V. Mack, R. W. Pekala and
19 W. Tang, J. Liang, D. He, J. Gong, L. Tang, Z. Liu, D. Wang J. F. Poco, J. Electrochem. Soc., 1996, 143, 159–169.
and G. Zeng, Water Res., 2019, 150, 225–251. 44 R. Kumar, S. Sen Gupta, S. Katiyar, V. K. Raman,
20 L. Alvarado and A. C. Chen, Electrochim. Acta, 2014, 132, S. K. Varigala, T. Pradeep and A. Sharma, Carbon, 2016,
583–597. 99, 375–383.
21 M. A. Anderson, A. L. Cudero and J. Palma, Electrochim. 45 H. B. Li, L. D. Zou, L. K. Pan and Z. Sun, Environ. Sci.
Acta, 2010, 55, 3845–3856. Technol., 2010, 44, 8692–8697.
22 M. E. Suss, S. Porada, X. Sun, P. M. Biesheuvel, J. Yoon and 46 L. J. Liu, X. R. Guo, R. Tallon, X. K. Huang and J. H. Chen,
V. Presser, Energy Environ. Sci., 2015, 8, 2296–2319. Chem. Commun., 2017, 53, 881–884.
23 K. X. Tang, Y. H. Kim, J. J. Chang, R. T. Mayes, J. Gabitto, 47 Z. Y. Yang, L. J. Jin, G. Q. Lu, Q. Q. Xiao, Y. X. Zhang, L. Jing,
S. Yiacoumi and C. Tsouris, Chem. Eng. J., 2019, 357, 103– X. X. Zhang, Y. M. Yan and K. N. Sun, Adv. Funct. Mater.,
111. 2014, 24, 3917–3925.
24 R. Zhao, S. Porada, P. M. Biesheuvel and A. van der Wal, 48 C. Zhang, D. He, J. Ma, W. Tang and T. D. Waite, Water Res.,
Desalination, 2013, 330, 35–41. 2018, 128, 314–330.
25 S. Porada, R. Zhao, A. van der Wal, V. Presser and 49 L. M. Chang, X. Y. Duan and W. Liu, Desalination, 2011, 270,
P. M. Biesheuvel, Prog. Mater. Sci., 2013, 58, 1388–1442. 285–290.
26 P. M. Biesheuvel, M. Z. Bazant, R. D. Cusick, T. A. Hatton, 50 A. G. El-Deen, J.-H. Choi, K. A. Khalil, A. A. Almajid and
K. B. Hatzell, M. C. Hatzell, P. Liang, S. Lin, S. Porada N. A. Barakat, RSC Adv., 2014, 4, 64634–64642.
and J. G. Santiago, arXiv:1709.05925, 2017. 51 C. Kim, J. Lee, S. Kim and J. Yoon, Desalination, 2014, 342,
27 S. Porada, A. Shrivastava, P. Bukowska, P. M. Biesheuvel 70–74.
and K. C. Smith, Electrochim. Acta, 2017, 255, 369–378.
View Article Online
52 A. G. El-Deen, J.-H. Choi, C. S. Kim, K. A. Khalil, 77 J. J. Wouters, J. J. Lado, M. I. Tejedor-Tejedor and

A. A. Almajid and N. A. Barakat, Desalination, 2015, 361, M. A. Anderson, J. Electrochem. Soc., 2012, 159, A1374–
53–64. A1382.
53 P. I. Liu, L. C. Chung, C. H. Ho, H. Shao, T. M. Liang, 78 A. Soleimani Dorcheh and M. H. Abbasi, J. Mater. Process.
R. Y. Horng, M. C. Chang and C. C. Ma, J. Colloid Technol., 2008, 199, 10–26.
Interface Sci., 2015, 446, 352–358. 79 J. Lee, S. Kim, C. Kim and J. Yoon, Energy Environ. Sci., 2014,
54 P. Srimuk, M. Zeiger, N. Jackel, A. Tolosa, B. Kruner, 7, 3683–3689.
S. Fleischmann, I. Grobelsek, M. Aslan, B. Shvartsev, 80 S. Kim, J. Lee, C. Kim and J. Yoon, Electrochim. Acta, 2016,
M. E. Suss and V. Presser, Electrochim. Acta, 2017, 224, 203, 265–271.
314–328. 81 S. Kim, H. Yoon, D. Shin, J. Lee and J. Yoon, J. Colloid

55 K. Laxman, D. Kimoto, A. Sahakyan and J. Dutta, ACS Appl. Interface Sci., 2017, 506, 644–648.
Mater. Interfaces, 2018, 10, 5941–5948. 82 B. Shapira, I. Cohen, T. R. Penki, E. Avraham and
56 A. G. El-Deen, N. A. M. Barakat and H. Y. Kim, Desalination, D. Aurbach, J. Power Sources, 2018, 378, 146–152.
2014, 344, 289–298. 83 S. Shanbhag, Y. Bootwala, J. F. Whitacre and M. S. Mauter,
57 X. Gu, Y. Yang, Y. Hu, M. Hu, J. Huang and C. Wang, J. Langmuir, 2017, 33, 12580–12591.
Mater. Chem. A, 2015, 3, 5866–5874. 84 L. Guo, R. Mo, W. Shi, Y. Huang, Z. Y. Leong, M. Ding,
58 Y. H. Liu, H. C. Hsi, K. C. Li and C. H. Hou, ACS Sustainable F. Chen and H. Y. Yang, Nanoscale, 2017, 9, 13305–13312.
Chem. Eng., 2016, 4, 4762–4770. 85 S. Choi, B. Chang, S. Kim, J. Lee, J. Yoon and J. W. Choi, Adv.
59 S. Hand and R. D. Cusick, Environ. Sci. Technol., 2017, 51, Funct. Mater., 2018, 28, 1802665.
12027–12034. 86 S. Z. Liu and K. C. Smith, Electrochim. Acta, 2018, 271, 652–
60 P. Li, Y. Gui and D. J. Blackwood, ACS Appl. Mater. Interfaces, 665.
2018, 10, 19615–19625. 87 A. Shrivastava and K. C. Smith, J. Electrochem. Soc., 2018,
61 W. Shi, X. Zhou, J. Li, E. R. Meshot, A. D. Taylor, S. Hu, 165, A1777–A1787.
J.-H. Kim, M. Elimelech and D. L. Plata, Environ. Sci. 88 P. Srimuk, F. Kaasik, B. Kruner, A. Tolosa, S. Fleischmann,
Technol. Lett., 2018, 5, 692–700. N. Jackel, M. C. Tekeli, M. Aslan, M. E. Suss and V. Presser,
62 M. T. Z. Myint, S. H. Al-Harthi and J. Dutta, Desalination, J. Mater. Chem. A, 2016, 4, 18265–18271.
2014, 344, 236–242. 89 F. Xing, T. Li, J. Y. Li, H. R. Zhu, N. Wang and X. Cao, Nano
63 K. Laxman, M. T. Myint, H. Bourdoucen and J. Dutta, ACS Energy, 2017, 31, 590–595.
Appl. Mater. Interfaces, 2014, 6, 10113–10120. 90 P. Srimuk, J. Lee, S. Fleischmann, S. Choudhury, N. Jackel,
64 J. Y. Liu, M. Lu, J. M. Yang, J. Cheng and W. S. Cai, M. Zeiger, C. Kim, M. Aslan and V. Presser, J. Mater. Chem.
Electrochim. Acta, 2015, 151, 312–318. A, 2017, 5, 15640–15649.
65 A. G. El-Deen, N. A. M. Barakat, K. A. Khalil, M. Motlak and 91 P. Srimuk, J. Lee, A. Tolosa, C. Kim, M. Aslan and V. Presser,
H. Y. Kim, Ceram. Int., 2014, 40, 14627–14634. Chem. Mater., 2017, 29, 9964–9973.
66 A. S. Yasin, J. Jeong, I. M. A. Mohamed, C. H. Park and 92 P. Srimuk, J. Halim, J. Lee, Q. Z. Tao, J. Rosen and
C. S. Kim, J. Alloys Compd., 2017, 729, 764–775. V. Presser, ACS Sustainable Chem. Eng., 2018, 6, 3739–3747.
67 N. T. Trinh, S. Chung, J. K. Lee and J. Lee, J. Energy Chem., 93 B. W. Byles, B. Hayes-Oberst and E. Pomerantseva, ACS
2016, 25, 354–360. Appl. Mater. Interfaces, 2018, 10, 32313–32322.
68 J. Li, X. X. Wang, H. Q. Wang, S. H. Wang, T. Hayat, 94 T. T. Wu, G. Wang, S. Y. Wang, F. Zhan, Y. Fu, H. Y. Qiao
A. Alsaedi and X. K. Wang, Environ. Sci.: Nano, 2017, 4, and J. S. Qiu, Environ. Sci. Technol. Lett., 2018, 5, 98–102.
1114–1123. 95 F. Chen, Y. Huang, L. Guo, M. Ding and H. Y. Yang,
69 M. W. Ryoo and G. Seo, Water Res., 2003, 37, 1527–1534. Nanoscale, 2017, 9, 10101–10108.
70 R. K. Gautam, S. K. Sharma, S. Mahiya and 96 F. Chen, Y. Huang, L. Guo, L. Sun, Y. Wang and H. Y. Yang,
M. C. Chattopadhyaya, in Heavy Metals in Water: Presence, Energy Environ. Sci., 2017, 10, 2081–2089.
Removal and Safety, The Royal Society of Chemistry, 2015, 97 M. Xu, T. Liang, M. Shi and H. Chen, Chem. Rev., 2013, 113,
pp. 1–24, DOI: 10.1039/9781782620174-00001. 3766–3798.
71 L. Venema, Nature, 2011, 479, 309. 98 G. R. Bhimanapati, Z. Lin, V. Meunier, Y. Jung, J. Cha,
72 B. Liu, X. Wang, Q. Zhao and L. Li, J. Am. Ceram. Soc., 2015, S. Das, D. Xiao, Y. Son, M. S. Strano, V. R. Cooper,
98, 2641–2646. L. Liang, S. G. Louie, E. Ringe, W. Zhou, S. S. Kim,
73 E. S. Im, J. H. Choi and K. Y. Jung, J. Electrochem. Soc., 2012, R. R. Naik, B. G. Sumpter, H. Terrones, F. Xia, Y. Wang,
159, E198–E203. J. Zhu, D. Akinwande, N. Alem, J. A. Schuller,
74 K. C. Leonard, J. R. Genthe, J. L. Sanlippo, W. A. Zeltner R. E. Schaak, M. Terrones and J. A. Robinson, ACS Nano,
and M. A. Anderson, Electrochim. Acta, 2009, 54, 5286–5291. 2015, 9, 11509–11539.
75 E. Avraham, M. Noked, I. Cohen, A. Soffer and D. Aurbach, 99 S. Z. Butler, S. M. Hollen, L. Cao, Y. Cui, J. A. Gupta,
J. Electrochem. Soc., 2011, 158, P168–P173. H. R. Gutiérrez, T. F. Heinz, S. S. Hong, J. Huang,
76 X. Gao, A. Omosebi, J. Landon and K. Liu, J. Electrochem. A. F. Ismach, E. Johnston-Halperin, M. Kuno,
Soc., 2014, 161, E159–E166. V. V. Plashnitsa, R. D. Robinson, R. S. Ruoff,
S. Salahuddin, J. Shan, L. Shi, M. G. Spencer,
View Article Online
M. Terrones, W. Windl and J. E. Goldberger, ACS Nano, 126 C. X. Zhao, X. Y. Lv, J. S. Li, T. Xie, Y. Y. Qi and W. Chen, J.
2013, 7, 2898–2926. Electrochem. Soc., 2017, 164, E505–E511.
100 B. Mendoza-Sanchez and Y. Gogotsi, Adv. Mater., 2016, 28, 127 Y. H. Liu, T. C. Yu, Y. W. Chen and C. H. Hou, ACS
6104–6135. Sustainable Chem. Eng., 2018, 6, 3196–3205.
101 L. L. Peng, Y. Zhu, D. H. Chen, R. S. Ruoff and G. H. Yu, Adv. 128 M. Li and H. G. Park, ACS Appl. Mater. Interfaces, 2018, 10,
Energy Mater., 2016, 6, 1600025. 2442–2450.
102 P. Simon, Y. Gogotsi and B. Dunn, Science, 2014, 343, 1210– 129 S. K. Sami, J. Y. Seo, S. E. Hyeon, M. S. A. Shershah, P. J. Yoo
1211. and C. H. Chung, RSC Adv., 2018, 8, 4182–4190.
103 A. M. Bernardes, D. C. R. Espinosa and J. A. S. Tenorio, J. 130 H. Yoon, J. Lee, S. R. Kim, J. Kang, S. Kim, C. Kim and
Power Sources, 2004, 130, 291–298. J. Yoon, Desalination, 2016, 392, 46–53.
104 D. Larcher and J. M. Tarascon, Nat. Chem., 2015, 7, 19–29. 131 A. S. Yasin, M. Obaid, I. M. A. Mohamed, A. Yousef and
105 M. W. Ryoo, J. H. Kim and G. Seo, J. Colloid Interface Sci., N. A. M. Barakat, RSC Adv., 2017, 7, 4616–4626.
2003, 264, 414–419. 132 X. Ma, Y.-A. Chen, K. Zhou, P.-C. Wu and C.-H. Hou,
106 J.-W. Lee, H.-I. Kim, H.-J. Kim and S.-G. Park, Appl. Chem. Electrochim. Acta, 2019, 295, 769–777.
Eng., 2010, 21, 265–271. 133 G. Divyapriya, K. K. Vijayakumar and I. Nambi,
107 J. H. Lee and J. H. Choi, Desalin. Water Treat., 2013, 51, 503– Desalination, 2019, 451, 102–110.
510. 134 L. C. Han, K. G. Karthikeyan, M. A. Anderson, J. J. Wouters
108 P. I. Liu, L. C. Chung, H. Shao, T. M. Liang, R. Y. Horng, and K. B. Gregory, Electrochim. Acta, 2013, 90, 573–581.
C. C. M. Ma and M. C. Chang, Electrochim. Acta, 2013, 96, 135 X. Gao, J. Landon, J. K. Neathery and K. L. Liu, J.
173–179. Electrochem. Soc., 2013, 160, E106–E112.
109 H. H. Li, J. Yang, C. Zhang, H. Y. Li and P. P. Pei, J. Porous 136 J. J. Lado, R. E. Perez-Roa, J. J. Wouters, M. I. Tejedor-
Mater., 2015, 22, 887–895. Tejedor and M. A. Anderson, Sep. Purif. Technol., 2014,
110 H. Li, Y. Ma and R. Niu, Sep. Purif. Technol., 2016, 171, 93– 133, 236–245.
100. 137 C. Santos, J. J. Lado, E. Garcia-Quismondo, I. V. Rodriguez,
111 K. J. Wei, Y. Wang, W. Q. Han, J. S. Li, X. Y. Sun, J. Y. Shen D. Hospital-Benito, J. Palma, M. A. Anderson and
and L. J. Wang, J. Power Sources, 2016, 318, 57–65. J. J. Vilatela, J. Mater. Chem. A, 2018, 6, 10898–10908.
112 A. Omosebi, X. Gao, N. Holubowitch, Z. Li, J. Landon and 138 T. Metke, A. S. Westover, R. Carter, L. Oakes, A. Douglas and
K. Liu, J. Electrochem. Soc., 2017, 164, E242–E247. C. L. Pint, Sci. Rep., 2016, 6, 24680.
113 K. J. Wei, Y. H. Zhang, W. Q. Han, J. S. Li, X. Y. Sun, 139 T. Zhang, H. Zhao, X. X. Huang and G. Wen, Desalination,
J. Y. Shen and L. J. Wang, Desalination, 2017, 420, 70–78. 2016, 379, 118–125.
114 M. Ramadan, H. M. A. Hassan, A. Shahat, 140 W. Z. Bao, X. Tang, X. Guo, S. Choi, C. Y. Wang, Y. Gogotsi
R. F. M. Elshaarawy and N. K. Allam, New J. Chem., 2018, and G. X. Wang, Joule, 2018, 2, 778–787.
42, 3560–3567. 141 L. Guo, X. Wang, Z. Y. Leong, R. Mo, L. Sun and H. Y. Yang,
115 B. H. Min, J.-H. Choi and K. Y. Jung, Korean J. Chem. Eng., FlatChem, 2018, 8, 17–24.
2018, 35, 272–282. 142 F. Jia, K. Sun, B. Yang, X. Zhang, Q. Wang and S. Song,
116 M. Ding, S. Fan, S. Huang, M. E. Pam, L. Guo, Y. Shi and Desalination, 2018, 446, 21–30.
H. Y. Yang, ACS Appl. Energy Mater., 2019, 2, 1812–1822. 143 H. Yoon, J. Lee, S. Kim and J. Yoon, Desalination, 2017, 422,
117 J. Yang, L. D. Zou, H. H. Song and Z. P. Hao, Desalination, 42–48.
2011, 276, 199–206. 144 M. R. Vengatesan, I. F. Fahmi Darawsheh, B. Govindan,
118 J. Yang, L. Zou and H. Song, Desalination, 2012, 286, 108– E. Alhseinat and F. Banat, Electrochim. Acta, 2019, 297,
114. 1052–1062.
119 M. C. Zafra, P. Lavela, G. Rasines, C. Macias, J. L. Tirado 145 S. Vafakhah, L. Guo, D. Sriramulu, S. Huang,
and C. O. Ania, Electrochim. Acta, 2014, 135, 208–216. M. Saeedikhani and H. Y. Yang, ACS Appl. Mater.
120 Y. P. Chen, L. Peng, Q. R. Zeng, Y. Yang, M. Lei, H. J. Song, Interfaces, 2019, 11, 5989–5998.
L. Y. Chai and J. D. Gu, Clean Technol. Environ. Policy, 2015, 146 L. Guo, Y. Huang, M. Ding, Z. Y. Leong, S. Vafakhah and
17, 49–57. H. Y. Yang, J. Mater. Chem. A, 2018, 6, 8901–8908.
121 C. Hu, F. Liu, H. Lan, H. Liu and J. Qu, J. Colloid Interface 147 J. Ma, L. Wang, F. Yu and X. Dai, Chem. Eng. J., 2019, 370,
Sci., 2015, 446, 359–365. 938–943.
122 W. S. Cai, Z. B. Xiong, T. Hussain, J. M. Yang, Y. B. Wang 148 W. Zhao, L. Guo, M. Ding, Y. Huang and H. Y. Yang, ACS
and J. Liu, J. Electrochem. Soc., 2016, 163, A2515–A2523. Appl. Mater. Interfaces, 2018, 10, 40540–40548.
123 B. Chen, Y. Wang, Z. Chang, X. Wang, M. Li, X. Liu, 149 J. Cao, Y. Wang, L. Wang, F. Yu and J. Ma, Nano Lett., 2019,
L. Zhang and Y. Wu, RSC Adv., 2016, 6, 6730–6736. 19, 823–828.
124 C. Macias, G. Rasines, P. Lavela, M. C. Zafra, J. L. Tirado 150 W. Zhao, M. Ding, L. Guo and H. Y. Yang, Small, 2019, 15,
and C. O. Ania, ACS Sustainable Chem. Eng., 2016, 4, 1805505.
2487–2494. 151 K. Wang, Y. Liu, Z. Ding, Y. Li, T. Lu and L. Pan, J. Mater.
125 L. H. Liu, G. H. Qiu, S. L. Suib, F. Liu, L. R. Zheng, W. F. Tan Chem. A, 2019, 7, 12126–12133.
and L. H. Qin, Chem. Eng. J., 2017, 328, 464–473.
View Article Online
152 F. Zhou, T. Gao, M. Luo and H. Li, Chem. Eng. J., 2018, 343, 178 W. Wei, X. Cui, X. Mao, W. Chen and D. G. Ivey, Electrochim.
8–15. Acta, 2011, 56, 1619–1628.
153 Z. Yue, T. Gao and H. Li, Desalination, 2019, 449, 69–77. 179 R. M. Silva, G. Clavel, Y. F. Fan, P. Amsalem, N. Koch,
154 L. Guo, D. Kong, M. E. Pam, S. Huang, M. Ding, Y. Shang, R. F. Silva and N. Pinna, Adv. Mater. Interfaces, 2016, 3,
C. Gu, Y. Huang and H. Y. Yang, J. Mater. Chem. A, 2019, 1600313.
7, 8912–8921. 180 R. M. Silva, A. C. Bastos, F. J. Oliveira, D. E. Conte, Y. Fan,
155 D. Sriramulu and H. Y. Yang, Nanoscale, 2019, 11, 5896– N. Pinna and R. F. Silva, J. Mater. Chem. A, 2015, 3, 17804–
5908. 17810.
156 Z. H. Huang, Z. Y. Yang, F. Y. Kang and M. Inagaki, J. Mater. 181 A. J. Hart and A. H. Slocum, J. Phys. Chem. B, 2006, 110,
Chem. A, 2017, 5, 470–496. 8250–8257.

157 X. Chen and S. S. Mao, Chem. Rev., 2007, 107, 2891–2959. 182 H. K. Mutha, PhD thesis, Massachusetts Institute of
158 L. Kavan, Chem. Rec., 2012, 12, 131–142. Technology, 2017.
159 K. X. Tang, Y. P. Li, H. B. Cao, C. L. Su, Z. S. Zhang and 183 G. A. Snook, P. Kao and A. S. Best, J. Power Sources, 2011,
Y. Zhang, Electrochim. Acta, 2016, 190, 678–688. 196, 1–12.
160 M. K. Seo and S. J. Park, Curr. Appl. Phys., 2010, 10, 391–394. 184 S. R. Sivakkumar and R. Saraswathi, J. Power Sources, 2004,
161 C.-C. Wang and J. Y. Ying, Chem. Mater., 1999, 11, 3113– 137, 322–328.
3120. 185 Y. Hou, Y. Cheng, T. Hobson and J. Liu, Nano Lett., 2010, 10,
162 Y. V. Kolen'ko, K. A. Kovnir, A. I. Gavrilov, A. V. Garshev, 2727–2733.
J. Frantti, O. I. Lebedev, B. R. Churagulov, G. Van 186 R. K. Sharma, A. Karakoti, S. Seal and L. Zhai, J. Power
Tendeloo and M. Yoshimura, J. Phys. Chem. B, 2006, 110, Sources, 2010, 195, 1256–1262.
4030–4038. 187 J. Xia, F. Chen, J. Li and N. Tao, Nat. Nanotechnol., 2009, 4,
163 D. Gong, C. A. Grimes, O. K. Varghese, W. C. Hu, 505–509.
R. S. Singh, Z. Chen and E. C. Dickey, J. Mater. Res., 2001, 188 R. S. Dey, H. A. Hjuler and Q. J. Chi, J. Mater. Chem. A, 2015,
16, 3331–3334. 3, 6324–6329.
164 L. Wang, M. Wang, Z. H. Huang, T. X. Cui, X. C. Gui, 189 W. Zhong Lin, J. Phys.: Condens. Matter, 2004, 16, R829–
F. Y. Kang, K. L. Wang and D. H. Wu, J. Mater. Chem., R858.
2011, 21, 18295–18299. 190 Y. L. Chen, Z. A. Hu, Y. Q. Chang, H. W. Wang, Z. Y. Zhang,
165 W. T. Deng, X. B. Ji, Q. Y. Chen and C. E. Banks, RSC Adv., Y. Y. Yang and H. Y. Wu, J. Phys. Chem. C, 2011, 115, 2563–
2011, 1, 1171–1178. 2571.
166 S. Devaraj and N. Munichandraiah, J. Phys. Chem. C, 2008, 191 X. C. Dong, Y. F. Cao, J. Wang, M. B. Chan-Park, L. H. Wang,
112, 4406–4417. W. Huang and P. Chen, RSC Adv., 2012, 2, 4364–4369.
167 D. M. Robinson, Y. B. Go, M. Mui, G. Gardner, Z. Zhang, 192 M. Saranya, R. Ramachandran and F. Wang, Journal of
D. Mastrogiovanni, E. Garfunkel, J. Li, M. Greenblatt and Science: Advanced Materials and Devices, 2016, 1, 454–460.
G. C. Dismukes, J. Am. Chem. Soc., 2013, 135, 3494–3501. 193 Y. Z. Guo, B. B. Chang, T. Wen, C. M. Zhao, H. Yin,
168 O. Ghodbane, J. L. Pascal and F. Favier, ACS Appl. Mater. Y. N. Zhou, Y. G. Wang, B. C. Yang and S. R. Zhang, RSC
Interfaces, 2009, 1, 1130–1139. Adv., 2016, 6, 19394–19403.
169 S. W. Lee, J. Kim, S. Chen, P. T. Hammond and Y. Shao- 194 X. Zhou, X. Guo, W. Ding and Y. Chen, Appl. Surf. Sci., 2008,
Horn, ACS Nano, 2010, 4, 3889–3896. 255, 3371–3374.
170 K. Kai, Y. Yoshida, H. Kageyama, G. Saito, T. Ishigaki, 195 M. T. Z. Myint and J. Dutta, Desalination, 2012, 305, 24–30.
Y. Furukawa and J. Kawamata, J. Am. Chem. Soc., 2008, 196 K. Laxman, L. Al Gharibi and J. Dutta, Electrochim. Acta,
130, 15938–15943. 2015, 176, 420–425.
171 B. W. Byles, D. A. Cullen, K. L. More and E. Pomerantseva, 197 K. Laxman, M. T. Z. Myint, R. Khan, T. Pervez and J. Dutta,
Nano Energy, 2018, 44, 476–488. Desalination, 2015, 359, 64–70.
172 J. Yan, Z. J. Fan, T. Wei, J. Cheng, B. Shao, K. Wang, 198 K. Laxman, M. T. Z. Myint, R. Khan, T. Pervez and J. Dutta,
L. P. Song and M. L. Zhang, J. Power Sources, 2009, 194, Electrochim. Acta, 2015, 166, 329–337.
1202–1207. 199 S. Baruah and J. Dutta, Sci. Technol. Adv. Mater., 2009, 10,
173 S.-C. Pang, M. A. Anderson and T. W. Chapman, J. 013001.
Electrochem. Soc., 2000, 147, 444–450. 200 M. T. Myint, R. Kitsomboonloha, S. Baruah and J. Dutta, J.
174 W. Wei, X. Cui, W. Chen and D. G. Ivey, Chem. Soc. Rev., Colloid Interface Sci., 2011, 354, 810–815.
2011, 40, 1697–1721. 201 P. Nan, X. Haizhou, Y. Minghui, C. Xuefeng, W. Xiaoping,
175 T. Shinomiya, V. Gupta and N. Miura, Electrochim. Acta, J. G. Hou, H. Jianxing and S. Z. Deng, Nanotechnology,
2006, 51, 4412–4419. 2010, 21, 225707.
176 H. Zhang, G. Cao, Z. Wang, Y. Yang, Z. Shi and Z. Gu, Nano 202 Y. Yang, W. Guo, X. Wang, Z. Wang, J. Qi and Y. Zhang,
Lett., 2008, 8, 2664–2668. Nano Lett., 2012, 12, 1919–1922.
177 B. Babakhani and D. G. Ivey, J. Power Sources, 2011, 196, 203 Y. Sun, F. Lei, S. Gao, B. Pan, J. Zhou and Y. Xie, Angew.
10762–10774. Chem., Int. Ed. Engl., 2013, 52, 10569–10572.
View Article Online
204 X. W. Lou, C. M. Li and L. A. Archer, Adv. Mater., 2009, 21, 230 J. J. Lado, R. E. Perez-Roa, J. J. Wouters, M. I. Tejedor-
2536–2539. Tejedor, C. Federspill and M. A. Anderson, J. Environ.
205 Y. Idota, T. Kubota, A. Matsufuji, Y. Maekawa and Chem. Eng., 2015, 3, 2358–2367.
T. Miyasaka, Science, 1997, 276, 1395–1397. 231 K. R. Kganyago and P. E. Ngoepe, Phys. Rev. B: Condens.
206 X. W. Guo, X. P. Fang, Y. Sun, L. Y. Shen, Z. X. Wang and Matter Mater. Phys., 2003, 68, 205111.
L. Q. Chen, J. Power Sources, 2013, 226, 75–81. 232 K. Kalantar-zadeh, J. Z. Ou, T. Daeneke, A. Mitchell,
207 J. Mu, B. Chen, Z. Guo, M. Zhang, Z. Zhang, C. Shao and T. Sasaki and M. S. Fuhrer, Appl. Mater. Today, 2016, 5,
Y. Liu, J. Colloid Interface Sci., 2011, 356, 706–712. 73–89.
208 X. Yang, R. Y. Zhang, J. Zhao, Z. X. Wei, D. X. Wang, 233 Z. Sun, T. Liao, Y. Dou, S. M. Hwang, M. S. Park, L. Jiang,
X. F. Bie, Y. Gao, J. Wang, F. Du and G. Chen, Adv. Energy J. H. Kim and S. X. Dou, Nat. Commun., 2014, 5, 3813.
Mater., 2018, 8, 1701827. 234 X. Xiao, H. Song, S. Lin, Y. Zhou, X. Zhan, Z. Hu, Q. Zhang,
209 B. Liu, Z. P. Guo, G. D. Du, Y. Nuli, M. F. Hassan and J. Sun, B. Yang, T. Li, L. Jiao, J. Zhou, J. Tang and Y. Gogotsi,
D. Z. Jia, J. Power Sources, 2010, 195, 5382–5386. Nat. Commun., 2016, 7, 11296.
210 Y. Wang, D. W. Su, C. Y. Wang and G. X. Wang, Electrochem. 235 A. P. Yu, H. W. Park, A. Davies, D. C. Higgins, Z. W. Chen
Commun., 2013, 29, 8–11. and X. C. Xiao, J. Phys. Chem. Lett., 2011, 2, 1855–1860.
211 L. Li, Y. Zheng, S. L. Zhang, J. P. Yang, Z. P. Shao and 236 Z. S. Wu, G. M. Zhou, L. C. Yin, W. Ren, F. Li and
Z. P. Guo, Energy Environ. Sci., 2018, 11, 2310–2340. H. M. Cheng, Nano Energy, 2012, 1, 107–131.
212 P. Tartaj, M. P. Morales, T. Gonzalez-Carreno, 237 J. Mei, T. Liao and Z. Q. Sun, J. Energy Chem., 2018, 27, 117–
S. Veintemillas-Verdaguer and C. J. Serna, Adv. Mater., 127.
2011, 23, 5243–5249. 238 L. Peng, X. Peng, B. Liu, C. Wu, Y. Xie and G. Yu, Nano Lett.,
213 L. Zhang, H. B. Wu and X. W. D. Lou, Adv. Energy Mater., 2013, 13, 2151–2157.
2014, 4, 1300958. 239 D. Guo, X. Z. Yu, W. Shi, Y. Z. Luo, Q. H. Li and T. H. Wang,
214 G. M. Zhou, D. W. Wang, F. Li, L. L. Zhang, N. Li, Z. S. Wu, J. Mater. Chem. A, 2014, 2, 8833–8838.
L. Wen, G. Q. Lu and H. M. Cheng, Chem. Mater., 2010, 22, 240 S. J. He, C. X. Hu, H. Q. Hou and W. Chen, J. Power Sources,
5306–5313. 2014, 246, 754–761.
215 L. S. Zhong, J. S. Hu, H. P. Liang, A. M. Cao, W. G. Song and 241 T. M. Higgins, D. McAteer, J. C. Coelho, B. Mendoza
L. J. Wan, Adv. Mater., 2006, 18, 2426–2431. Sanchez, Z. Gholamvand, G. Moriarty, N. McEvoy,
216 X. J. Liu, T. Q. Chen, H. P. Chu, L. Y. Niu, Z. Sun, L. K. Pan N. C. Berner, G. S. Duesberg, V. Nicolosi and
and C. Q. Sun, Electrochim. Acta, 2015, 166, 12–16. J. N. Coleman, ACS Nano, 2014, 8, 9567–9579.
217 M. Valvo, F. Lindgren, U. Lafont, F. Bjorefors and 242 Q. Feng, L. Liu and K. Yanagisawa, J. Mater. Sci. Lett., 2000,
K. Edstrom, J. Power Sources, 2014, 245, 967–978. 19, 1567–1570.
218 Z. Jian, B. Zhao, P. Liu, F. Li, M. Zheng, M. Chen, Y. Shi and 243 B. Anasori, M. R. Lukatskaya and Y. Gogotsi, Nat. Rev.
H. Zhou, Chem. Commun., 2014, 50, 1215–1217. Mater., 2017, 2, 16098.
219 H. B. Li, Z. Y. Leong, W. H. Shi, J. Zhang, T. P. Chen and 244 M. Naguib, J. Come, B. Dyatkin, V. Presser, P. L. Taberna,
H. Y. Yang, RSC Adv., 2016, 6, 11967–11972. P. Simon, M. W. Barsoum and Y. Gogotsi, Electrochem.
220 A. H. Alami, K. Aokal, A. A. Hawili, R. Hasan and Commun., 2012, 16, 61–64.
H. Alawadhi, Desalination, 2018, 446, 51–58. 245 M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon,
221 R. H. Nielsen and G. Wilng, in Ullmann's Encyclopedia of L. Hultman, Y. Gogotsi and M. W. Barsoum, Adv. Mater.,
Industrial Chemistry, 2010, pp. 767–768, DOI: 10.1002/ 2011, 23, 4248–4253.
14356007.a28_543.pub2. 246 E. Pomerantseva and Y. Gogotsi, Nat. Energy, 2017, 2,
222 S. Ikeda, O. Sakurai, K. Uematsu, N. Mizutani and M. Kato, 17089.
J. Mater. Sci., 1985, 20, 4593–4600. 247 M. Q. Zhao, C. E. Ren, Z. Ling, M. R. Lukatskaya, C. Zhang,
223 R. R. Bi, X. L. Wu, F. F. Cao, L. Y. Jiang, Y. G. Guo and K. L. Van Aken, M. W. Barsoum and Y. Gogotsi, Adv. Mater.,
L. J. Wan, J. Phys. Chem. C, 2010, 114, 2448–2451. 2015, 27, 339–345.
224 H. Xia, Y. S. Meng, G. L. Yuan, C. Cui and L. Luc, 248 X. Q. Xie, M. Q. Zhao, B. Anasori, K. Maleski, C. E. Ren,
Electrochem. Solid-State Lett., 2012, 15, A60–A63. J. W. Li, B. W. Byles, E. Pomerantseva, G. X. Wang and
225 Y. Zhang and S. J. Park, Carbon, 2017, 122, 287–297. Y. Gogotsi, Nano Energy, 2016, 26, 513–523.
226 C.-M. Yang, W.-H. Choi, B.-K. Na, B. W. Cho and W. I. Cho, 249 X. Zhang, Z. H. Zhang and Z. Zhou, J. Energy Chem., 2018,
Desalination, 2005, 174, 125–133. 27, 73–85.
227 G. X. Quan, H. Wang, F. Zhu and J. L. Yan, Bioresources, 250 R. Zhao, P. M. Biesheuvel and A. van der Wal, Energy
2018, 13, 437–449. Environ. Sci., 2012, 5, 9520–9527.
228 J. J. Lado, J. J. Wouters, M. I. Tejedor-Tejedor, 251 H. Wang, D. S. Zhang, T. T. Yan, X. R. Wen, J. P. Zhang,
M. A. Anderson and E. Garcia-Calvo, J. Electrochem. Soc., L. Y. Shi and Q. D. Zhong, J. Mater. Chem. A, 2013, 1,
2013, 160, E71–E78. 11778–11789.
229 J. J. Wouters, M. I. Tejedor-Tejedor, J. J. Lado, R. Perez-Roa 252 X. Xu, L. Pan, Y. Liu, T. Lu, Z. Sun and D. H. Chua, Sci. Rep.,
and M. A. Anderson, J. Electrochem. Soc., 2018, 165, E148– 2015, 5, 8458.
E161.
View Article Online
253 M. W. Barsoum, in MAX Phases, 2013, pp. 1–12, DOI: 273 J.-H. Ryu, T.-J. Kim, T.-Y. Lee and I.-B. Lee, J. Taiwan Inst.
10.1002/9783527654581.ch1. Chem. Eng., 2010, 41, 506–511.
254 H. Tang, J. Wang, H. Yin, H. Zhao, D. Wang and Z. Tang, 274 F. Schedin, A. Geim, S. Morozov, E. Hill, P. Blake,
Adv. Mater., 2015, 27, 1117–1123. M. Katsnelson and K. Novoselov, Nat. Mater., 2007, 6, 652.
255 L. David, R. Bhandavat and G. Singh, ACS Nano, 2014, 8, 275 A. Fasolino, J. Los and M. I. Katsnelson, Nat. Mater., 2007,
1759–1770. 6, 858.
256 M. Acerce, D. Voiry and M. Chhowalla, Nat. Nanotechnol., 276 M. Dahanayaka, B. Liu, Z. Hu, Z. Chen, A. W.-K. Law and
2015, 10, 313–318. K. Zhou, Phys. Chem. Chem. Phys., 2017, 19, 8552–8562.
257 M. R. Laskar, D. N. Nath, L. Ma, E. W. Lee, C. H. Lee, 277 A. F. Fonseca, T. Liang, D. Zhang, K. Choudhary,
T. Kent, Z. Yang, R. Mishra, M. A. Roldan, J.-C. Idrobo, S. R. Phillpot and S. B. Sinnott, ACS Appl. Mater.
S. T. Pantelides, S. J. Pennycook, R. C. Myers, Y. Wu and Interfaces, 2017, 9, 33288–33297.
S. Rajan, Appl. Phys. Lett., 2014, 104, 092104. 278 Y. Chan and J. Hill, Micro Nano Lett., 2010, 5, 247–250.
258 S. H. Woo, L. Yadgarov, R. Rosentsveig, Y. Park, D. Song, 279 H. Bin, Z. Yao, S. Zhu, C. Zhu, H. Pan, Z. Chen, C. Wolverton
R. Tenne and S. Y. Hong, Isr. J. Chem., 2015, 55, 599–603. and D. Zhang, J. Alloys Compd., 2017, 695, 1223–1230.
259 N. Liu, P. Kim, J. H. Kim, J. H. Ye, S. Kim and C. J. Lee, ACS 280 M. Park, X. Zhang, M. Chung, G. B. Less and A. M. Sastry, J.
Nano, 2014, 8, 6902–6910. Power Sources, 2010, 195, 7904–7929.
260 M. Azhagurajan, T. Kajita, T. Itoh, Y. G. Kim and K. Itaya, J. 281 P. Yu, B. N. Popov, J. A. Ritter and R. E. White, J.
Am. Chem. Soc., 2016, 138, 3355–3361. Electrochem. Soc., 1999, 146, 8–14.
261 J. Xie, H. Zhang, S. Li, R. Wang, X. Sun, M. Zhou, J. Zhou, 282 C. Chen, Y. Wen, X. Hu, X. Ji, M. Yan, L. Mai, P. Hu, B. Shan
X. W. Lou and Y. Xie, Adv. Mater., 2013, 25, 5807–5813. and Y. Huang, Nat. Commun., 2015, 6, 6929.
262 A. S. Nagelberg and W. L. Worrell, J. Solid State Chem., 1979, 283 L. Jaber-Ansari, K. P. Puntambekar, S. Kim, M. Aykol,
29, 345–354. L. Luo, J. Wu, B. D. Myers, H. Iddir, J. T. Russell,
263 P. Srimuk, J. Lee, S. Fleischmann, M. Aslan, C. Kim and S. J. Saldaña, R. Kumar, M. M. Thackeray, L. A. Curtiss,
V. Presser, ChemSusChem, 2018, 11, 2091–2100. V. P. Dravid, C. Wolverton and M. C. Hersam, Adv. Energy
264 Y. Li, H. Wang, L. Xie, Y. Liang, G. Hong and H. Dai, J. Am. Mater., 2015, 5, 1500646.
Chem. Soc., 2011, 133, 7296–7299. 284 W. Geng, X. Zhao, W. Zan, H. Liu and X. Yao, Phys. Chem.
265 M. Wiechen, M. M. Najafpour, S. I. Allakhverdiev and Chem. Phys., 2014, 16, 3542–3548.
L. Spiccia, Energy Environ. Sci., 2014, 7, 2203–2212. 285 H. Ismar, F. Schröter and F. Streicher, Compos. Sci. Technol.,
266 Z. W. Seh, K. D. Fredrickson, B. Anasori, J. Kibsgaard, 2000, 60, 2129–2136.
A. L. Strickler, M. R. Lukatskaya, Y. Gogotsi, 286 H. J. Berendsen, Simulating the physical world: hierarchical
T. F. Jaramillo and A. Vojvodic, ACS Energy Lett., 2016, 1, modeling from quantum mechanics to uid dynamics,
589–594. Cambridge University Press, 2007.
267 Z. Ding, X. Xu, Y. Li, K. Wang, T. Lu and L. Pan, 287 H. Zhang, B. Liu, M.-S. Wu, K. Zhou and A. W.-K. Law,
Desalination, 2019, 468, 114078. Comput. Mater. Sci., 2017, 131, 100–107.
268 B. L. Ellis, W. R. M. Makahnouk, Y. Makimura, K. Toghill 288 A. Rommerskirchen, B. Ohs, K. A. Hepp, R. Femmer and
and L. F. Nazar, Nat. Mater., 2007, 6, 749. M. Wessling, J. Membr. Sci., 2018, 546, 188–196.
269 S. Li, Y. Dong, L. Xu, X. Xu, L. He and L. Mai, Adv. Mater., 289 J. Ma, D. He, W. Tang, P. Kovalsky, C. He, C. Zhang and
2014, 26, 3545–3553. T. D. Waite, Energy Environ. Sci., 2016, 50, 13495–13501.
270 X. Li, X. Zhu, J. Liang, Z. Hou, Y. Wang, N. Lin, Y. Zhu and 290 X. Xu, M. Wang, Y. Liu, T. Lu and L. Pan, ACS Sustainable
Y. Qian, J. Electrochem. Soc., 2014, 161, A1181–A1187. Chem. Eng., 2016, 5, 189–195.
271 R. Ma, T. Sasaki and Y. Bando, Chem. Commun., 2005, 948– 291 M. E. Suss and V. Presser, Joule, 2018, 2, 10–15.
950, DOI: 10.1039/B415983G. 292 T. Kim and J. Yoon, RSC Adv., 2015, 5, 1456–1461.
272 W. F. van Gunsteren, X. Daura, N. Hansen, A. E. Mark,
C. Oostenbrink, S. Riniker and L. J. Smith, Angew. Chem.,
Int. Ed., 2018, 57, 884–902.

2019Tang-Carbon-metal Compound Composite Electrodes For Capacitive Deionization Synthesis, Development and Applications

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2019Tang-Carbon-metal Compound Composite Electrodes For Capacitive Deionization Synthesis, Development and Applications

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Carbon–metal compound composite electrodes

Cite this: J. Mater. Chem. A, 2019, 7,

Journal of Materials Chemistry A Review

Liming You received his bache- Dr. Kun Zhou is an Associate

Review Journal of Materials Chemistry A

materials, researchers in the eld of CDI have proposed to

intercalation host materials (IHCs),27 or (4) hybrid mechanism

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

This journal is © The Royal Society of Chemistry 2019

J. Mater. Chem. A, 2019, 7, 26693–26743 | 26699

26700 | J. Mater. Chem. A, 2019, 7, 26693–26743

This journal is © The Royal Society of Chemistry 2019

Other carbon–TMO composites

This journal is © The Royal Society of Chemistry 2019

J. Mater. Chem. A, 2019, 7, 26693–26743 | 26701

26702 | J. Mater. Chem. A, 2019, 7, 26693–26743

This journal is © The Royal Society of Chemistry 2019

This journal is © The Royal Society of Chemistry 2019

J. Mater. Chem. A, 2019, 7, 26693–26743 | 26703

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Cathode Carbon–TiO2 EDLC Symmetric 7 31, 50–53

Carbon–FeOx FeOx + 2xNa+ + 2xe 4 Fe + xNa2O Asymmetric 3 58, 67 and 68

compound may also be dissolved by other redox reactions (i.e.,

Journal of Materials Chemistry A Review

Fig. 7 Morphology control of TiO2 in carbon–TiO2 composites.

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

for 2 h in air, 600 C for 3 h in nitrogen). The electrode has

3.3 Carbon–TiO2 (nanotube form) composites

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

residual recyclability, formation of secondary pollutants, long

Journal of Materials Chemistry A Review

methods.58,121 By adjusting the deposition parameters (e.g.,

The formation of MnO2 on an anode substrate depends on

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Based on this research, Shi et al. believed that the low

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

PPy hydrogel was then obtained by simultaneously reducing GO

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

RGO, it is possible that the capacitive property of the composite

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

the metal oxide particles to be more uniformly distributed and

Journal of Materials Chemistry A Review

7.1 Carbon–2D-TMO composites

2D-TMOs, or layered metal oxides, refer to TMO nanosheets

Review Journal of Materials Chemistry A

LMOs showed diﬀerent performances in NaCl and MgCl2

Journal of Materials Chemistry A Review

Review Journal of Materials Chemistry A

Journal of Materials Chemistry A Review