Energy Storage Materials 55 (2023) 498–516

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Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm

Ion-selective covalent organic frameworks boosting electrochemical energy

storage and conversion: A review
Ce Wang a, Jiadong Tang a, Zengyun Chen a, Yuhong Jin a, *, Jingbing Liu a, Hong Xu b, *,
Hao Wang a, *, Xiangming He b, *, Qianqian Zhang a, *
a
Key Laboratory for New Functional Materials of Ministry of Education, Faculty of Materials and Manufacturing, Beijing University of Technology, Beijing, 100124, P.
R. China
b
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China

A R T I C L E I N F O A B S T R A C T

Keywords: Controlling selective ion transport is highly desirable for high-efficiency energy related applications. Covalent
Covalent organic frameworks organic frameworks (COFs) are emerging porous materials with tunable aperture sizes and diverse functional
Ion selective transport groups with charge densities similar to those of biomimetic ion channels. These merits endow COFs with
Size confinement
excellent ion selectivity. Currently, the development of ion-selective COFs has become a focus in energy related
Electrostatic interactions
applications; however, it faces some severe challenges. This review article systematically summarizes recent
Energy storage and conversion
progress in the development of ion-selective COF-based materials related to the energy field. First, the structure
and processes of the skeletons, linkages, and physical/chemical properties of ion-selective COFs are introduced.
Second, the ion-selective mechanisms of COF-based materials are clarified based on size confinement and
electrostatic interactions. Third, recent progress in the application of COFs, including lithium-ion batteries, zinc-
ion batteries, and salinity gradient energy generators, is discussed. Finally, major existing challenges and po­
tential future directions for ion-selective COF research and application are identified. This review provides a
theoretical basis for the design of novel COFs with superior ion selectivity for next-generation energy related
devices.

1. Introduction
The excessive consumption of non-sustainable fossil fuels coupled
with industrialization has caused serious energy deficiencies. Mean­
while, the by-products of fossil fuel usage, including greenhouse gasses
and other pollutants, have triggered severe environmental issues
worldwide [1–4]. Therefore, the exploration of clean and renewable
energy sources is of great significance for alleviating energy and envi­
ronmental crises. Moreover, there is an urgent need to transform the
global energy system from nonrenewable and heavily polluting to sus­
tainable and low-carbon [5].
Recently, energy conversion and storage technologies have attracted
increasing interest and have significantly improved energy systems. For
example, secondary batteries (mainly lithium-ion batteries) and salinity
gradient energy generators dominate the clean energy field and are
expected to substitute fossil fuel energy sources. However, their fragile
operating life and poor cyclic stability hinder the development of energy
conversion and storage technologies owing to the severe side effects
caused by excessive and unwanted ion transport. These challenges can
be overcome by introducing new materials for secondary batteries and
salinity gradient energy generators [6–8].
Porous materials are promising candidates for improving energy
conversion and storage technologies. Porous organic polymers (POPs)
and metal-organic frameworks (MOFs) are attractive energy systems
because of their abundant porous channels and tunable chemistry [9,
10]. Moreover, these compounds can be grafted by active functional
groups to facilitate ion transport and improve electrochemical perfor­
mance [11]. However, POPs and MOFs do not meet the requirements of
high energy demands because of some inherent drawbacks. For
example, POPs have amorphous and disordered pore architectures,
which weaken ion-selective transport. In addition, the large pore sizes
and instability of MOFs in solvents impair ion selectivity and impede
their widespread application in energy conversion and storage [12].
Therefore, materials with ordered pore structures, good

* Corresponding author: H. Xu, X. He, Institute of Nuclear and New Energy Technology, Tsinghua University, 100084, Beijing, P. R. China.
E-mail addresses: jinyh@bjut.edu.cn (Y. Jin), hongxu@tsinghua.edu.cn (H. Xu), haowang@bjut.edu.cn (H. Wang), hexm@tsinghua.edu.cn, hexiangming@
tsinghua.org.cn (X. He), zhangqianqian@bjut.edu.cn (Q. Zhang).

https://doi.org/10.1016/j.ensm.2022.12.015
Received 23 September 2022; Received in revised form 19 November 2022; Accepted 10 December 2022
Available online 11 December 2022
2405-8297/© 2022 Elsevier B.V. All rights reserved.
C. Wang et al. Energy Storage Materials 55 (2023) 498–516

Fig. 1. Structure and design of ion-selective COFs for energy storage and conversion applications, including lithium-ion batteries, zinc-ion batteries, and salinity
gradient energy generators.

chemical-mechanical stability, and superior ion selectivity could assist
in overcoming the energy bottleneck.
As emerging porous materials, covalent organic frameworks (COFs)
have attracted significant attention because they address the drawbacks
of POPs and MOFs [13]. COFs are a class of crystalline porous materials
connected by covalent bonds that contain lightweight elements (C, H, O,
and N), thus reducing the mass density for applications in energy con­
version/storage devices [14]. Moreover, the abundant rigid nano­
channels and easily grafted functional groups endow COFs with rapid
ion transport properties and excellent electrolyte wettability.
Furthermore, COFs exhibit outstanding solvent stability owing to their
long-chain molecular structure. Finally, tunable pore sizes (0.52–6.5
nm) and exquisite decoration on the pore walls are expected to yield
outstanding ion selectivity. Therefore, COFs are ideal platforms for en­
ergy related applications. For example, Fig. 1 shows a schematic dia­
gram of the structure and design of ion-selective COFs for energy storage
and conversion applications, including lithium-ion batteries, zinc-ion
batteries, and salinity gradient energy generators. Benefiting from the
advantages of COFs, the inherent problems of energy conversion and
storage have been successfully alleviated, and electrochemical

Fig. 2. Structure (skeleton and linkage types) of COFs. The skeleton types include star-pore, trigonal, rhombic, tetragonal, and hexagonal types. Linkage types
comprise boroxine, boronic ester, imide, hydrazone, azine, and β-ketoenamine.

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Fig. 3. Timeline of the main developments in COFs with different properties and application potentials.
performance has been significantly improved.
Although the structural design and energy applications of COFs have
been reviewed [15–18], a detailed and systematic summary of
ion-selective COFs concerning energy applications is still lacking. In this
review, we specifically examine COFs for the energy sector and provide
recommendations for their development and application. Moreover, the
interactions and mechanisms of COF structures and ion selectivity for
energy conversion and storage are described. Finally, applications in
secondary batteries and salinity gradient energy generators are pre­
sented. Our review serves as a useful guide for designing functional
ion-selective COFs for energy systems.
2. Structure and development of COFs
2.1. Structure of COFs: skeletons and linkage types
The structure of the COFs is determined by their skeleton and linkage
types. Similar to the design and synthesis of MOFs, preselected building
blocks are joined to form COF materials [19]. Hence, the skeleton
characteristics of COF materials can be determined by the type of
connection between the reaction monomers. Fig. 2 shows several
different skeleton structures, namely star-pore, trigonal, rhombic,
tetragonal, and hexagonal. Geometric topology diagrams can help in
designing COF skeletons, where the inherent geometry of the building
units is connected in specific ways [15]. For example, the combination
of C2-symmetric blocks (C2+C2) generates COFs with star pores [20,21]
or rhombic COFs [22,23]; the C2+C6 topology scheme leads to trian­
gular skeletons [24,25]; tetragonal COFs have been designed using the
C2+C4 topology scheme [26]; and the self-condensation of C2-symmetric
[27,28] or C3-symmetric blocks [29,30] creates hexagonal skeletons. A
combination of C2-symmetric and C3-symmetric blocks can be devel­
oped to form hexagonal COFs [31,32]. The pore shapes and pore sizes of
COFs can, therefore, be adjusted based on geometric topography and
molecular design strategies to meet the demands of different fields.
In addition to their skeleton structure, the linkage type of COFs is
crucial for their crystallinity, stability, and application [17]. The first
COFs were generated by boronic acid self-polymerization and boronic
ester condensation reactions, connected by B-O bonds [27]. Although
this type of COF has excellent crystallinity and thermal stability owing to
the high reversibility of the reaction [33, 34], it cannot exist stably in
water, acid, and alcohol environments [15]. Therefore, it is difficult to
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realize the application of this type of COF beyond the pre-development
stage. To improve chemical stability, aldehyde and amine groups are
used in condensation reactions to generate COFs with linked C = N
bonds, which generally require acetic acid as a catalyst [35]. However,
the crystallinity of his type of COF is slightly lower than that of boronic
ester-linked COFs. The synthesis of hydrazone-linked COFs involves the
interaction of a hydrogen bond between the alkoxyl chains (oxygen
atoms) and -CONH- units (hydrogens) [36]. A series of azine-linked
COFs can be generated through the condensation reactions of alde­
hyde and hydrazine, which usually have excellent chemical stability and
small micropores [37]. Imide-linked COFs with highly porous structures
can be obtained by a condensation reaction between anhydrides and
amines at high temperatures [31]. The synthesis of β-ketoenamine in­
volves two reaction processes: first, the reactive monomer undergoes a
reversible Schiff base reaction to form an enol; second, an enol-keto
isomer is used to synthesize the β-ketoenamine COFs. Despite the
excellent chemical stability of β-ketoenamine COFs, their crystallinity is
reduced owing to irreversible reactions during the synthesis process [8].
Generally, the selection of different building blocks allows the type
of COF linkage to be adjusted. This strategy can be an efficient approach
for regulating the pore size, crystallinity, and chemical stability, all of
which substantially affect the ion selectivity of COFs for applications in
energy storage and conversion devices.
2.2. Development of COFs
As a relatively new type of organic porous material, COFs have been
developed for over a decade. A study of their development can help
summarize the experiences of designing multifunctional ion-selective
COFs (Fig. 3). In 2005, COF-1 and COF-5, as the start of the COF fam­
ily, were synthesized through a reversible condensation reaction of
phenyl diboronic acid and hexahydroxytriphenylene [C18H6(OH)6] by
Yaghi’s team [27]. The products of the reaction were highly crystalline,
and their architectures were completely controlled by strong covalent
bonds between the C, O, and B atoms. Moreover, the developed COFs
had the advantages of adjustable pore size (7–27 Å), high thermal sta­
bility (500–600 ◦ C), and specific surface area (COF-1: 711 m2 g − 1;
COF-5: 1590 m2 g − 1). This study laid the foundation for subsequent
studies on COFs. Generally, three-dimensional (3D) COFs are very
difficult to crystallize because of kinetic and thermodynamic con­
straints. In addition, the insolubility of the 3D structure rules out the
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Fig. 4. Mechanism of ion-selective COFs with respect to (a) the size-confinement effect and (b) electrostatic interactions. (c) COF-1 and COF-5 with different pore
sizes[60]. (copyright 2016, American Chemical Society). (d) Schematic illustrations of the lithium-ion hopping pathways in TpPa-SO3Li nanochannels[61].
(copyright 2021, American Chemical Society). (e) Schematic illustrations of ion-selective transport based on the electric double layer.

possibility of stepwise synthesis or crystal isolation. Furthermore, the
essentially infinite structures generated by the reaction of the monomer
into 3D extended structures make the synthesis of 3D COFs even more
complicated. However, Yaghi [38] overcame these challenges in 2007
based on the principles of reticulation chemistry. Specifically, 3D COFs
connected by covalent bonds (C–C, C-B, C–O, and B-O) were synthe­
sized by condensation reactions of the tetrahedral building unit tetra
(4-dihydroxyborylphenyl)methane, or by co-condensation with a
triangular building unit (2,3,6,7,10,11-hexahydroxytriphenylene). In
addition to boronic acid or borate ester, the synthesis of new types of
COFs using different reaction monomers has also been actively explored.
In 2008, Thomas [39] synthesized the first covalent triazine-based
framework (CTF-1) via trimerization condensation. Notably, this was
synthesized with molten ZnCl2 at 400 ◦ C, thus exhibiting excellent
thermal stability, although the crystallinity of CTF-1 was poor. Yaghi
[35] prepared and characterized the first 3D COF-300 linked solely from
C–C and C–N bonds, which exhibited good crystallinity and thermal
stability.
Whilst great progress has been made in the variety of COFs produced,
their application still faces serious impediments. In 2011, Wang et al.
[40]. synthesized imine-linked COF-LZU-1 via the condensation of 1,3,
5-Triformylbenzene and 1,4-diaminobenzene. Remarkably, COF-LZU-1
was applied to catalyze the Suzuki-Miyaura coupling reaction for the
first time, and promoted the application of COFs in heterogeneous
catalysis. After several years of development, researchers have also
explored different reaction monomers to synthesize a variety of COFs for
specific fields. In 2013, Jiang et al. [41]. developed a new reaction for
the preparation of CuP-SQ COF based on squaraine chemistry, which has
great potential in photocatalytic systems. Two years later, the same
group successfully synthesized the first TPB-DMTP-COF that was stable
in strong acids and bases, as well as in boiling water, which could be
used as an efficient catalyst after post-modification [42]. Compared with
amine COFs, carbon-carbon double bond 2DPPV COF is more stable and
shows great potential in photovoltaics because of the high proportion of
carbon-carbon double bonds with π–π conjugation [43].
The development of the chemistry of COFs and their applications
depends on the characterization and in-depth understanding of their
structures. Currently, structural characterization is limited to theoretical
calculations coupled with powder X-ray diffraction (PXRD) or electron
diffraction [44–49]. Yaghi et al. [50]. synthesized 3D large single-crystal

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Fig. 5. Designing COFs with functional groups to improve ion selectivity. The approaches for introducing functional groups involve (a) bottom-up synthetic and (b)
postsynthetic modifications. (c) Bottom-up method for the synthesis of COF-TpBD and COF-COOH[70]. (copyright 2022, Wiley-VCH) (d) Chemical lithiation of
TpPa-SO3H to obtain TpPa-SO3Li[61]. (copyright 2021, American Chemical Society).

imine-based COFs and collected single-crystal X-ray diffraction data
with a resolution of 0.83 Å, yielding a straightforward solution for COF
atomic-level structures as well as detailed framework information such
as interpenetration, guest molecular arrangement, and linker disorders,
which greatly promote the application and development of COFs. As
research on COFs continues, understanding is continually improving
[51]. For example, COFs with specific functional groups have been
synthesized to regulate ion transport, and are widely used in
photocatalysis and energy conversion and storage [52–54].
3. Mechanisms of ion selectivity in COFs
The merits of high surface area, abundant ordered nanochannels, and
diverse structural designs endow COFs with excellent ion-transport
performance. Furthermore, ion-selective transport is significant for
COFs in terms of energy storage and conversion. Therefore, an in-depth

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discussion of ion-selective COFs is urgently required to further improve
the electrochemical performance of energy systems. Recent research has
shown that size confinement and electrostatic interactions play key roles
in regulating ion selectivity [55,56]. Figs. 4a and 4b show schematics of
ion-selective COFs in terms of size confinement and electrostatic in­
teractions, respectively.
3.1. Size confinement
The size confinement effect is the most crucial physical feature of
nanochannels that enables the validation of ion-selective transport
[57–59]. Furthermore, the pore sizes of COFs can be designed within
wide ranges (from angstroms to nanometers), which can be used to
easily implement the effect of size confinement. Notably, the precisely
controllable pore sizes of COFs give the potential for application in
secondary batteries. Taking lithium-sulfur (Li-S) batteries as an
example, the shuttle effect of polysulfides (with a wide range of mo­
lecular dimensions, 1.36–2.50 nm) still hinders commercial progress.
Hence, alleviating the polysulfide shuttle via the size-confinement effect
of COFs is an ideal strategy. Lee et al. [60] fabricated COF-1 and COF-5
(with the actual pore sizes of 0.7 and 2.7 nm, respectively) on a carbon
nanotube and modified separators (COF-1 NN and COF-5 NN) for Li-S
batteries (Fig. 4c). Compared to COF-5, which has a larger pore size,
the COF-1 NN interlayer with microporous features allows for
ion-selective transport. Moreover, the COF-1 NN interlayer suppresses
the shuttling of the polysulfide polyanion and is favorable for Li+ (dy­
namic diameter ~ 1.52 Å) ion diffusion. Consequently, the developed
Li-S battery exhibited excellent rate performance and cyclic stability.
3.2. Electrostatic interaction
Electrostatic interactions are another effective approach for
achieving ion-selective transport in COFs. Generally, grafting polar
groups is considered a promising way to enhance the function and
application of COFs. Moreover, ion-selective transport can be achieved
via the electrostatic interactions of charged groups on the pore walls of
COFs. Notably, compared to size confinement, electrostatic interactions
can obtain high ion selectivity by regulating the charge density of COF
functional groups. If fast transportation of the anion ion is needed, a
positively charged functional group can be grafted on the surface of the
COF to boost anion diffusion and vice versa. In particular, excessive
anion transport is the main reason for the deterioration in the electro­
chemical performance of cation insertion-type batteries. The electro­
static repulsion of COFs can effectively suppress anion transport and
promote Li+ diffusion.
Sun et al. [61]. fabricated an ion-selective TpPa-SO3Li COF film on a
commercial separator, and the charged groups (-SO3Li) block the
diffusion of polysulfides. Moreover, as shown in Fig. 4d, the ordered
TpPa-SO3Li sites provide Li+-ion hopping paths owing to the
cation-dipole interactions. Therefore, the TpPa-SO3Li/Celgard separator
exhibits a high Li+-ion transference number (0.88). Benefiting from the
strong electrostatic repulsion of COFs with anions, the Li-S battery with
a COF-modified separator developed by this team displayed excellent
cycling performance, even under high sulfur-loading conditions. In
addition to electrostatic repulsion, the electric double layer (EDL) also
plays a critical role in ion-selective transport. The EDL is generated by
the excess surface charge adsorption of counterions in the electrolyte
[62,63]. As shown in Fig. 4e, the EDL overlaps the entire nanochannel
and only allows unidirectional diffusion of ions with opposite charges
[64,65]. Driven by the electrostatic force of the charged groups in the
nanochannels, the ions can diffuse selectively and rapidly, thus
improving the electrochemical properties.
4. Design of ion-selective COFs
In addition to their physical properties (i.e., dimension, pore size,
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Energy Storage Materials 55 (2023) 498–516
and surface area), the physicochemical environment of COF pores plays
an important role in ion selectivity. Crucially, the introduction of
functionalized groups in COFs can enhance ion selectivity. For example,
the introduction of negatively charged sulfonate groups in neutral COF
can effectively inhibit anion transport and promote Li+ diffusion, thus
improving the electrochemical performance [66]. As shown in Figs. 5a
and 5b, bottom-up synthetic [67,68] and post-synthetic modifications
[42] are the two most common approaches for introducing functional
groups into COF pores to enhance ion selectivity [69].
4.1. Bottom-up approach
The bottom-up approach is a simple and effective method for intro­
ducing functional moieties into the COF skeleton. In this case, the target
COFs are obtained by selecting building blocks or pre-designed building
blocks for polymerization reactions. The functional group content can be
precisely tuned and uniformly distributed in the COF pores. Further­
more, the bottom-up approach successfully constructs functional ion-
selective COFs for lithium-ion batteries. As shown in Fig. 5c, Guo
et al. [70]. synthesized COF-TpBD and COF-COOH to construct func­
tional separators for lithium-metal batteries. Compared to COF-TpBD,
the COF-COOH type effectively promoted the diffusion of Li+ and
inhibited anion transport. Moreover, apart from monofunctional groups,
bifunctional groups can be achieved via the bottom-up method. Wang
et al. [71]. constructed a TB-COF containing triazine (lithiophilic
interaction) and boroxine units (sulfiphilic interaction) for Li-S batte­
ries, which greatly improved ion selectivity transport. Nevertheless, the
limited availability of building blocks can impair the diversity of COFs,
whereas the modification groups within the COF pores may reduce
crystallinity [66].
4.2. Postsynthetic modification
The functional groups introduced by the bottom-up approach may
affect the crystallinity of COFs, and some ion-selective COFs cannot be
synthesized in a single step. Therefore, postsynthetic modification is an
effective complementary approach. Zang et al. [72]. combined a
cationic monomer (ethidium bromide, EB) with 1,3,5-triformylphloro­
glucinol (TFP) via a bottom-up approach to form the cationic COF
EB-COF:Br. They then prepared a series of ionic COFs (EB-COF:X, X = F,
Cl, Br, or I) via post-synthesis (ion exchange), and the proton conduction
of the ionic COF-based material was greatly improved. As shown in
Fig. 5d, COFs for Li-ion batteries are often chemically lithiated based on
both the bottom-up approach and postsynthetic modification to improve
Li+ ion selectivity.
5. Applications of ion-selective COFs for energy storage and
conversion
COFs with excellent physical and chemical properties can effectively
modulate ion transport inside the electrochemical environment. Firstly,
the pore size of COFs can be tunable from 0.52 to 6.50 nm so that the
anions with larger ionic radii can be separated from the cations with
smaller ionic radii. Secondly, COFs with abundant functional groups can
transport specific ions by electrostatic interactions. Finally, the electric
double layer (EDL, formed by excess charge adsorption of the pores) on
the nanochannels of COFs overlaps the pathways of ions transport and
only specific ions are allowed to pass through. Thus, COFs are expected
to achieve both anion and cation diffusion regulation to boost energy
storage and conversion, such as metal ion batteries and osmotic energy
generators.
5.1. Lithium secondary batteries
Lithium-ion batteries continue to develop and have been successfully
used in many applications; however, they still face challenges. First,
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Fig. 6. COF-based separators of lithium-ion batteries. (a) Electrochemical behavior of electrolyte in a TPB-BD(OH)2–COF/PVDF separator (i) and conventional
separator (ii). (b) Performance of Li-symmetrical cells with different separators at 5 mA cm− 2. Performance of Li-LNMO full batteries under different current
densities: (c) 0.5C and (d) 1C[98]. (copyright 2022, American Chemical Society). (e) Synthesis of SCOF-2, selective transport of Li+, and blocking polysulfides. (f)
Graphic comparison of Li-S batteries using Celgard and SCOF-2 modified separators. (g) Cycling performance of Li-symmetric cells with Celgard and SCOF-2 modified
separators. (h) Long-term cycling of Li-S asymmetric cells at 1 C over 800 cycles with Celgard and SCOF-2 modified separators[66]. (copyright 2022, Wiley-VCH).

excessive anion transport impairs the diffusion of lithium ions, leading
to severe polarization. This aggravates the decline of the internal
chemical environment of the battery, resulting in the rapid deterioration
of electrochemical performance [73,74]. In addition, excessive anion
transport forms a nonhomogeneous solid electrolyte interphase (SEI)
layer on the surface of the anode, leading to electrochemical perfor­
mance degradation and, potentially, dendrites piercing the separator,
giving rise to safety concerns [75–79]. Fortunately, ion-selective COFs
are promising for solving the problems of polarization and Li dendrites
in lithium-ion batteries. COFs are often used to modify separators,
solid-state electrolytes, artificial SEI films, and hosts of Li-S battery
cathode materials to regulate ion transport in Li-ion batteries.
5.1.1. Separators
The separator is a necessary path for ion transport between the
cathode and anode, and its performance significantly affects the ion-
conducting kinetics and structural stability of the interface [56,65,
80-82]. Moreover, conventional separators face challenges such as low
lithium-ion conductivity and poor lithium-ion selectivity, which lead to
several safety issues. However, some important research progress has
been made on functional separators to enhance the electrochemical
performance of lithium-ion batteries. Nevertheless, it is difficult to
simultaneously enhance the ionic conductivity and lithium-ion trans­
ference number of conventional separators, meaning that the problems
of polarization and lithium dendrites still need to be overcome [83–89].
COFs are composed of lightweight elements, and the low density of
COFs used as functional separators has little effect on the mass-energy
density of batteries. Moreover, abundant and ordered nanochannels
with functional moieties in the pores can promote Li+ transport and
suppress excessive anion transport. In addition, porous COFs facilitate
electrolyte infiltration, thus accelerating Li+ diffusion. In the electrolyte,
the charged groups on the surface of the nanochannel adsorb counter­
ions and form an electrical double layer (EDL) that exhibits efficient ion
selectivity [62,90-95]. Moreover, nanochannels can interact with the
solvent sheath to achieve salt dissociation, thus facilitating Li+ transport
[96,97]. Finally, the electrolyte insolubility of COFs ensures safe battery
operation. Thus, COF-based separators can regulate the ionic conduction
and enhance the electrochemical performance of batteries.
COF-based self-supporting separators would be of great significance
for batteries. For example, Liu et al. [98]. synthesized a self-supporting
TPB-BD(OH)2–COF separator for lithium-ion batteries. In this case, the
hydrogen bond network was formed via the reaction of the hydroxyl
group (-OH) of TPB-BD(OH)2–COF with the electrolyte, which resulted
in the desolvation of Li+ (Fig. 6a). Moreover, the desolvated electrolyte
formed a LiF-rich SEI layer on the Li metal surface, and the Li//Li
symmetric cell and LNMO//Li full cell exhibited excellent cycle stabil­
ities (Fig. 6b-6d). Although the self-supporting TPB-BD(OH)2–COF
membrane showed a certain mechanical strength, it required an auxil­
iary PVDF separator in lithium batteries. In addition, the synthesis of
COF membranes limits the range of building blocks and functional
groups, meaning that the modification of the functionalization of con­
ventional separators by COFs is more prevalent.
Acid groups grafted onto COFs are often used to modify separators
and modulate ion-selective transport. Wang et al. [66]. synthesized
sulfonate-rich SCOF-2 and modified the separators of Li-S batteries
(Figs. 6e and 6f). In this case, the sulfonate functional groups not only

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Fig. 7. (a) Schematic of COFs with and without fillers. (b) Two-step synthesis of the stable and oriented Q-COF SSE. (c) Ionic conductivity of Q-COF SSE films
prepared at room temperature and 150 ◦ C. (d) Cycling performance of symmetrical Li//Li cells of Q-COF SSE. (e) Cycling performance of Li//NMC811 cells with Q-
COF SSE prepared at room temperature (black) and high temperature (pink)[106]. (copyright 2021, Wiley-VCH). (f) Illustration of a Li-COF filled with DMA@LiTFSI
and Li+ transport in DLC and (g) a comparison of its properties. (h) Enlarged view of voltage curves. (i) Cycling performance of Li///LFP pouch cell[109]. (copyright
2022, Wiley-VCH).

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Fig. 8. (a) Schematic of a COF-5 layer fabricated on Li in situ. (b) Voltage profiles of Li-symmetric cells with COF-5 or bare Li. (c) Long-term cycling life and
corresponding Coulombic efficiency of Li-S symmetric cells cell with COF-5[127]. (copyright 2022, Wiley-VCH). (d) Schematic diagrams of COF film ionic selectivity;
the COF is Li+ permeability and TFSI− blocking[128]. (copyright 2020, Wiley-VCH). (e) Schematic diagrams of the in situ synthesis of COF-coated siloxane[133].
(copyright 2022, Wiley-VCH).

enhanced the electronegativity but also enlarged the layer-spacing of the batteries exhibited excellent cycle stability (Figs. 6g and 6h). In another
COFs. Moreover, theoretical calculations showed that the sulfonates example, Sun et al. [61]. prepared a TpPa-SO3Li modified Celgard
narrowed the bandgap and had stronger interactions with sulfur species, separator for Li-S batteries. The capacity retention was 78% after 100
inhibiting the polysulfide shuttle effect. Consequently, the modified cycles at 0.2 C, and the Li+ transfer number was as high as 0.88. The

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excellent performance resulted from the abundant nanochannels of the
COF (suppressing the polysulfide shuttle effect) and a large number of
sulfonic acid sites with negative electrical properties (promoting rapid
Li+ conduction along the COF pore wall and repelling polysulfide ions).
Carboxy-group-modified COF-based separators are also capable of
regulating ion-selective transport. For example, Guo et al. [99]. syn­
thesized COF-COOH, which was coated on the surface of PP as a
modified lithium battery separator. The rigid nanochannels and anion
frameworks of COF-COOH were favorable for Li+ transport (tLi+ = 0.7),
and the Li-Li symmetric battery was stable during cycling (over 1000 h)
with a low voltage hysteresis. In addition, DFT calculations showed that
COF-COOH can promote the desolvation of Li+ solvates and accelerate
the diffusion of Li+.
Except for acid groups, the localized groups of COFs can regulate Li+
transport. Li et al. [100]. fabricated a PS@COF separator and found that
the COF provided a partially negatively charged group (–OCH3) for Li+
transport, thereby increasing the Li+ transference number (tLi+). More­
over, polar groups (–C = N–) can chelate the lone pair of electrons of
transition metal ions (TM), enhancing the connection between COF-TM
and TM, and improving the battery’s rate and cycling performance. Sun
et al. [101]. designed a Li-CON@GN/Celgard composite membrane with
ordered lithiation sites for Li-S batteries. In their study, the triazole
group of Li-CON impeded the polysulfide shuttle effect, and the lithiated
sites (O-Li-N) not only achieved Li+-selected conduction but also pro­
moted the dissociation of Li2S. Overall, COF-based functional separators
can inhibit anion transport and promote Li+ ion transport, thereby
greatly alleviating problems associated with side reactions and lithium
dendrites.
5.1.2. Solid electrolyte
The development of solid-state electrolyte-based rechargeable bat­
teries has made significant progress in recent decades. However,
intrinsically low ionic conductivity and high resistance result in severe
performance degradation [102–104]. Fortunately, crystalline porous
COFs with ordered permanent nanochannels and rapid ionic conducting
pathways have demonstrated a promising strategy for solid-state elec­
trolytes [105]. As shown in Fig. 7a, COF-based solid-state electrolytes
with or without fillers are a practical strategy for conducting Li+ ions.
5.1.2.1. Components. The pore size and crystallographic orientation of
COFs are key factors in the regulation of Li+ transport in solid-state
electrolytes. Xu et al. [106]. synthesized imine-linked COFs (I-COFs,
pore size = 3.2 nm) and further converted quinolyl linkage COFs
(Q-COFs, pore size = 2.6 nm) through the Povarov reaction. Moreover,
the Q-COF powders were mechanically processed and heat-pretreated to
obtain flexible Q-COF solid-state electrolyte (SSE) films with a holistic
crystallographic orientation (Fig. 7b). The Q-COF SSE film exhibited an
ultralow HOMO value (− 6.2 eV), high decomposition voltage (5.6 V),
and remarkable ionic conductivity (1.5 × 10− 4 S cm− 1), as shown in
Fig. 7c. Symmetrical Li//Li cells and asymmetrical Li//NMC811 cells
with Q-COF SSE exhibited excellent cycle stability owing to the direc­
tional hopping pathways (Figs. 7d and 7e). Functional groups grafted
onto the pore walls of the COFs are also favorable for ion-selective
conduction. Han [107] introduced imidazolium functional groups into
defective COFs (dCOF-ImTFSI-60) as SSEs for lithium-ion conduction.
This yielded a high Li+ conductivity of 7.05 × 10− 3 S cm− 1 at 423 K,
which was the highest of crystalline porous materials based on
all-solid-state electrolytes.
In addition to self-supporting COF-based solid-state electrolytes, COF
composite SSE films are also candidates for solid-state electrolytes. For
example, Chen et al. [108]. synthesized a composite membrane of ara­
mid/COF with a thickness of 7.1 μm using a layer-by-layer spin
approach. The membrane exhibited low resistance and high ionic con­
ductivity (1.62 × 10− 4 S cm− 1 at 30 ◦ C and 4.6 × 10− 4 S cm− 1 at 70 ◦ C),
and was stably cycled 500 times for Li-Li symmetric batteries.
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Energy Storage Materials 55 (2023) 498–516
5.1.2.2. Hosts. Encapsulating conductive polymers into the porous
skeletons of COFs is another solution for conducting Li+ ions, which
enables directional transport of Li+ ions. Manthiram et al. [109]. re­
ported the in situ solidification of the liquid electrolyte DMA@LiTFSI in
COF channels to boost the charge-carrier concentration. Moreover, the
decoupling of Li+ ions from the COFs walls and molecular chains
directionally activated the motion of Li+ ions (Fig. 7f). The Li+ con­
ductivity and transference number were also significantly enhanced
(Fig. 7g). Furthermore, as the COF SSE film was fabricated in Li//Li
symmetrical cells and Li//LFP pouch cells, owing to their fortified me­
chanical toughness, they exhibited excellent electrochemical properties
(Figs. 7h and 7i).
Polyethylene glycol (PEG) is regarded as an outstanding filler for
porous skeletons because of its incombustibility, stability, and excellent
interface affinity [110]. Zhang [111,112] confined PEG into the nano­
channels of COFs, effectively diminishing the crystalline phase and
dynamically promoting the ion-coupled chain. As a result, ionic con­
ductivity was enhanced and activation energy decreased.
5.1.3. Artificial SEI films
An unstable electrolyte-electrode interface is a prominent problem
that hinders the development of lithium-ion batteries. Crucially, the
structure, chemical composition, and mechanical properties of the
interface have a significant influence on overall electrochemical per­
formance. A large interfacial impedance can retard the kinetic transport
of Li+ ions and increase the cell polarization, and the electrolyte may
erode the electrode surface, causing side reactions and consuming active
lithium and electrolyte, leading to the generation of a non-homogeneous
SEI film. Moreover, an unstable interface causes Li+ nonhomogeneous
deposition, and dendrites may seriously threaten the safety of the cell
[113,114]. Therefore, electrolyte modification is always used to stabi­
lize the electrolyte–electrode interface [115–122]; however, electrolyte
modification has problems, such as high costs and low ion transport
rates [123,124]. Constructing an artificial interphase can provide a more
stable surface structure and, consequently, may be beneficial to the
long-term cycling life of lithium-ion batteries [125,126].
COFs are regarded as ideal ion-transport artificial interphases owing
to their rigid nanochannels, abundant lithophilic sites, and stable
physicochemistry. Manthiram et al. [127]. fabricated a dense COF-5
protective layer on a Li metal anode for Li-S batteries in situ (Fig. 8a).
The Li//Li symmetric cells were stable at a high current density of 10 mA
cm− 2 for 13,200 h, and the Li-S asymmetric cells were stable for 600
cycles at 1 C (Figs. 8b and 8c). The COF-5 layer inhibited S deposition
and improved the utilization of active materials. Moreover, the nano­
channels of the COF-5 layer facilitated the selective conduction of Li+
ions and inhibited Li dendrite growth on the anode surface. In addition
to the abundant nanochannels, the excellent mechanical properties of
COFs also suppress Li-dendrite growth. For example, Huang et al. [128].
prepared an in situ rigid COF thin film on Li metal (Fig. 8d), and the
inherently abundant nanochannels contributed to the selective diffusion
of ions. Furthermore, the COF film favored Li+ diffusion and suppressed
the transport of TFSI− anions. Consequently, the Li-S cells with the COF
film exhibited stable cycle life performance.
The in situ construction of a COF protective layer on Li metal surfaces
is difficult because of the chemically active nature of the metal. Hence,
the ex situ construction of COF artificial interphases on metal anode
surfaces is a more common approach. Qiao [129] synthesized a
TpTG-COF nanomesh, and transferred this to a Li metal surface. The
experimental results combined with theoretical calculations showed
that the active sites (N, O) and coordinated Cl− of TpTG were favorable
for Li+ ion diffusion, reduced the nucleation overpotential, and
enhanced the stability of the electrode–electrolyte interface. Lai [130]
synthesized and coated an anode with a robust MXene@COF hetero­
structure with conductive frameworks. The C = N reactive groups of the
COF were lithiated during discharge, which improved the lithophilicity
of the nanosheets and greatly reduced the Li+ nucleation overpotential.
C. Wang et al. Energy Storage Materials 55 (2023) 498–516

Fig. 9. COFs as the host material for sulfur cathodes. (a) Morphology of COF-MF and COF-CS. (b) Cycling performance of S-loaded COF-MF, COF-CS, and carbon
black cathodes[162]. (copyright 2019, Elsevier). (c) Schematic illustration for TB-COF synthesis. (d) Cycling performance of TB-COF at 1 C and 2 C[71]. (copyright
2018, Elsevier). (e) Schematic illustration of 2D PI-COF, PI-CONs, and PI-CONs/S construction. (f) Cycle performance of PI-COF/S and PI-CONs/S up to 500 cycles at
1.0 C[164]. (copyright 2021, American Chemical Society). (g) Sulfurization of the DUT-177 COF to obtain S-DUT-177 for Li-S batteries. (h) Cycle stability of
S-DUT-177 at a current density of 500 mA g − 1[54]. (copyright 2022, American Chemical Society).

Moreover, the high electronic conductivity of Mxene improved the Li+
deposition kinetics and effectively prevented local charge accumulation.
Hence, the MXene@COF/Li anode exhibited long cycling stability.
Notably, some COFs may interact with the electrolyte and generate LiF
to enhance the mechanical strength of the SEI. Consequently, the growth
of Li dendrites and the change in anode volume during cycling are
inhibited [131].
In addition to Li-metal anodes, the application of COFs has expanded
to other anodes, having an enhancing effect on commercial Si anodes
[132]. Feng et al. [133]. obtained a Tf-TAPA COF layer and coated this
on a siloxene anode (Fig. 8e). The porous Tf-TAPA COF layer increased
the ionic conductivity and electrolyte compliance, and the Tf-TAPA
COF@siloxene anode exhibited long-term cycling stability.
COFs feature ordered nanochannels, abundant active sites, and
tunable functional groups with excellent ion selectivity and conductiv­
ity. Hence, most COFs can regulate ion-selective transport and improve
the stability of the electrolyte–electrode interface, guaranteeing a long
battery life-cycle.
5.1.4. Cathode materials
The development of electric vehicles has increased the requirements
for battery electrode materials in terms of cost, energy density, and
environmental friendliness [134–143]. Researchers have shown great
interest in organic compounds as electrode materials because of their
low cost and lack of heavy metals [144–148]. Despite some achieve­
ments in the design of organic electrode materials, disadvantages such as
poor electrical conductivity, large polarization, and severe structural
degradation still hinder their development [149–151]. Fortunately, as
an emerging organic material, COFs feature abundant pores, high sur­
face areas, diverse structures, low densities, and excellent chemical
stability [14,152,153], making them highly suitable as electrode mate­
rials for specific performance requirements [96,154,155]. Furthermore,
COFs provide many active sites for Li+ intercalation/deintercalation,
and their abundant pore channels and π–π conjugated layers facilitate
Li+ transport [156,157].
Li-S batteries have attracted significant attention because of their
advantages in terms of energy density and cost; however, the dissolution
of lithium polysulfides impedes practical application [158,159]. COFs
with abundant and ordered pore structures and precisely designed

508
C. Wang et al.
Fig. 10. Ion-selective COFs for zinc-ion batteries. (a) Schematic illustration of the deposition behavior of Zn on bare Zn and 3D-COOH–COF@Zn. (b) Cycling
performance of Zn-symmetrical cells of different samples. (c) Coulomb efficiency in Zn-Cu asymmetrical cells of different samples and (d) corresponding voltage
profiles of 3D-COOH–COF@Zn[169]. (copyright 2022, Elsevier). (e) Deposition mechanism of FCOF@Zn and bare Zn surfaces. (f) Cycling performance of
Zn-symmetrical cells using FCOF film. (g) Coulomb efficiency of Zn plating/stripping for FCOF-coated Ti and bare Ti, and (h) corresponding voltage profiles of
FCOF-coated Ti[175]. (copyright 2021, Springer Nature).
functional groups can regulate lithium polysulfide transport, making
them suitable for accommodating sulfur cathodes [160,161]. Yu et al.
[162]. synthesized a porphyrin 3D COF-MF with a flower-like
morphology and multilevel pore channels, which consisted of ultra­
thin conjugated COF nanosheets. Compared with conventional bulk
COFs, the COF-MF had more accessible sites and could accommodate
higher sulfur loading (Fig. 9a). Moreover, the porphyrin unit in the COF
skeleton showed strong electrostatic interactions with polysulfides and
effectively improved ion-selective transport. Hence, COF-MF@S
exhibited excellent cycling performance with a capacity retention of
53% after 1000 cycles at 1 C (Fig. 9b).
Importantly, the units of COF construction have a significant impact
on the performance of sulfur cathodes via electrostatic interactions.
Wang et al. [71]. constructed a TB-COF containing triazine (lithiophilic
interaction) and boroxine (sulfiphilic interaction) building units, which
significantly improved the electrochemical performance of Li-S batteries
(Fig. 9c). Consequently, the TB-COF@S exhibited excellent cycling
performance with a capacity retention of 81.6% after 800 cycles at 1 C
(Fig. 9d). Tang et al. [163]. also prepared COF-1/S composites for Li-S
batteries that delivered initial discharge capacities of 1628 and 929
mAh g − 1 after 100 cycles. This improved performance was attributed to
the homogeneous coexistence of electron-rich O atoms and
electron-deficient B atoms of COF-1, which simultaneously increase the
electrochemical interactions with Li+ and Sx2− .
In addition to the construction of functional groups, the nanosheet
exfoliation of COFs significantly improves the performance of sulfur
cathode materials. For example, Li et al. [164]. synthesized a polyamide
PI-COF using a solvothermal method, and PI-CON nanosheets were
synthesized by liquid exfoliation. Moreover, they loaded sulfur into
PI-CONs as a host material to enhance the electrochemical performance
of Li-S batteries. The PI-CONs/S delivered a discharge capacity of 1330
mAh g − 1 at 0.1 C, and showed excellent rate capabilities (620 mAh g − 1
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Energy Storage Materials 55 (2023) 498–516
at 4C) and superior cycling stability (85% capacity retention at 1 C),
which is among the best reported for all materials. This exceptional
performance was attributed to the synergy between the stable and
conjugated porous framework of CON and the strong oxygen-lithium
interaction brought about by the carbonyl group (Figs. 9e and 9f).
The thianthrene-based two-dimensional (2D) DUT-177 COF was first
synthesized by Kaskel et al. [54]. In this case, the high-temperature
sulfidation of DUT-177 and sulfur was accompanied by the substitu­
tion reaction of sulfur chains with nitrile and the insertion reaction of
sulfur atoms into the thiamethylene ring, yielding S-DUT-177 with
excellent sulfur ion selectivity. As a Li-S battery cathode, S-DUT-177
delivered a capacity of 720 mAh g − 1 under a current density of 100 mA
g − 1, and the capacity retention was 76.6% after 500 cycles at a current
density of 500 mA g − 1 (Figs. 9g and 9h).
5.2. Zinc-ion batteries
Zinc-ion batteries are promising candidates for next-generation
batteries because of their high safety, low cost, and nontoxicity. How­
ever, chaotic ion transport induces dendrite growth and adverse side
reactions inside these batteries. Indeed, the disorderly growth of Zn
dendrites may penetrate the separator and cause a short circuit, which
seriously hinders the commercialization of zinc-ion batteries [165,166].
Hence, the regulation of ion transport is vital for the further develop­
ment of this technology, for which COFs are well-suited [167,168].
COFs with acid groups can regulate ion-diffusion behavior because of
their electrostatic interactions with anions. Wu et al. [169]. synthesized
a 3D-COOH–COF film as the protective layer of the Zn anode, as shown
in Fig. 10a. The abundant negative functional groups on the nano­
channels of the film suppressed the diffusion of SO2−
4 and promoted Zn
2+
transport. Consequently, batteries with 3D-COOH–COF exhibited
excellent cycling performance for Zn plating/stripping for more than
C. Wang et al. Energy Storage Materials 55 (2023) 498–516

Fig. 11. Self-supporting COFs for salinity gradient energy conversion. (a) Schematic diagram of ion transport using a BDA-TAM COF self-supporting membrane and
(b) the corresponding power density and current densities[64]. (copyright 2022, Wiley-VCH). (c) Illustration of salinity gradient conversion with a TpPa-SO3H
self-supporting COF and (d) the corresponding current and power densities[187]. (copyright 2022, Wiley-VCH). (e) Scheme of ion transport through a COF
monolayer membrane under a salinity gradient and (f) the output power densities of different COF monolayer membranes. (g) Electrostatic potential illustrating the
effect of interpore distance on the pore-pore coupling effect of COFs[188]. (Copyright 2022, Springer Nature).

1000 h (Fig. 10b–d). Zhao et al. [170]. constructed a TpPa-SO3H film on via COFs, which can help resolve the safety issues of zinc-ion batteries
Zn metal that could regulate Zn2+ ion deposition and suppress the and promote their rapid development.
growth of Zn dendrites. In addition to acidic groups, other functional
groups can regulate ion transport [171]. For example, Liu et al. [172].
5.3. Salinity gradient energy generators
fabricated a CTF as the coating layer to regulate Zn2+ deposition kinetics
and address adverse side reactions, thus enhancing electrochemical
As a core component of salinity gradient energy conversion, perm­
performance [172].
selective membranes suffer from large pore sizes, low pore densities,
The electrodeposition behavior of Zn is closely related to its crys­
high impedance, and poor ion selectivity. These problems seriously limit
tallography and morphology. Therefore, controlling the deposition of
the output power and efficiency of salinity gradient energy conversion
planar Zn is promising for achieving long cycle life in Zn batteries [173,
[176–180]. In this context, COFs have developed rapidly in recent years,
174]. Lu et al. [175] developed a fluorinated covalent organic frame­
and their richly ordered pore channels, easily tunable pore size, and pore
work (FCOF) coated on the surface of a Zn anode (Fig. 10e). Unlike other
environment endow them with unique advantages [181–186]. So far,
traditional protective layer materials, FCOF films have several advan­
both self-supporting and composite COF membranes have been applied
tages, including excellent mechanical properties with robust adhesion to
in salinity gradient energy conversion, as outlined in the following
the Zn surface, which affords durability during the battery operation.
sections.
Furthermore, the F atoms of the FCOF films exhibit strong electroneg­
ativity interactions with the underlying Zn atoms, resulting in a lower
5.3.1. Self-supporting COF membranes
surface energy of the Zn (002) plane than that of the Zn (101) plane.
COF self-supporting membranes cannot be easily synthesized using
Consequently, Zn is preferentially deposited along the (002) crystal
the solvothermal method, while interfacial polymerization provides a
plane, which inhibits dendrite growth. The study showed that the
promising means of preparation. Our group [64] prepared a
FCOF@Zn symmetric and asymmetric cells achieved long-term stable
self-supported ultrathin (1.5 μm) BDA-TAM COF membrane with
cycling (Fig. 10f-h). Furthermore, ion-selective transport is modulated
nano-confined channels (1.4 nm) by interfacial polymerization. The

510
C. Wang et al. Energy Storage Materials 55 (2023) 498–516

Fig. 12. COF-based composite membranes for salinity gradient energy conversion. (a) Schematic of the osmotic energy conversion process. (b) MD simulations
showing a 3D view of ion diffusion across a PyPa-SO3H/SANF membrane, and the corresponding (c) power output and (d) current-time curve[53]. (copyright 2021,
American Chemical Society). (e) Schematic representation of the experiment. (f) Output power density of a COF-BTAxBTHy/PAN composite membrane with (g)
transference number (t-) versus various KCl concentration gradients[191]. (copyright 2022, Wiley-VCH). (h) Schematic of the experimental analysis of a COF-(SO3Na)
x/PAN membrane with corresponding (i) linear fits of ΔVoc - ΔT used to analyze thermo-sensation sensitivity, and (j) variations in Voc and Isc with corresponding
power densities (black numbers) at different temperatures[192]. (copyright 2022, Wiley-VCH).

output power of the salinity gradient energy conversion was up to 5.31
W m − 2 owing to the excellent cation selectivity and high ion conduc­
tance of the BDA-TAM COF membrane (Figs. 11a and 11b). Further­
more, the BDA-TAM COF membrane exhibited excellent chemical
stability and a long cycle life. Although ultrathin COF membranes
reduce impedance, their performance must be improved owing to low
surface charge densities. Wen et al. [187]. prepared TaPa-SO3H
self-supported membranes using interfacial polymerization, and the
abundant one-dimensional (1D) nanochannels and high charge density
achieved high ionic conductivity and selectivity (Figs. 11c and 11d) and
delivered a power density of 5.9 W m − 2, although the thicker mem­
brane (10.7 μm) increased ion transport impedance.
The thickness of permselective membranes has a significant impact
on their power output performance. For example, Tang et al. [188].
prepared COF monolayer membranes using a pre-assembled interfacial
polymerization method for salinity gradient energy conversion. They
reported an increase in output power density, to 135 W m − 2 and even
300 W m − 2, by changing the metal centers of the porphyrin molecules
in the COF. This improvement in performance was attributed to the
significantly reduced impedance of the COF monolayer membranes.

511
C. Wang et al.
Fig. 13. Perspectives and research opportunities for ion-selective COFs for energy storage and conversion.
Furthermore, the novel pore-pore coupling effect caused by the high
pore density and low pore spacing effectively suppressed concentration
polarization. This work not only expands the application of COFs but
also provides new directions for the design of novel salinity differential
energy conversion materials (Figs. 11e and 11f). Except for surface
charge and membrane thickness, high ionic selectivity and permeability
can be achieved owing to the ability to closely control the channel
orientation of these materials [189].
5.3.2. Composite COF membranes
Self-supporting COF membranes have excellent power output per­
formance yet their mechanical properties still need to be improved. The
synthesis of COF-based composite membranes provides a viable alter­
native. For example, Jiang et al. [53]. prepared a composite PyPa-­
SO3H/SANF COF membrane (with abundant and ordered nanochannels)
and anion-grafted aramid nanofibers (ANFS, with high mechanical
strength). When applied in reverse electrodialysis (RED) as a permse­
lective membrane, a power density of 9.6 W m − 2 was obtained in a
natural seawater system alongside long-life performance and
high-power generation. The excellent performance of the system was
due to the synergistic effect of COFs and ANFs, which not only improved
water wettability but also ion diffusion/rectification and trans­
membrane flux (Figs. 12a–d). Zhai et al. [190]. prepared an asymmetric
COF-LZU1@CNT-CNF membrane via COF spin-coating for salinity
gradient energy conversion The ordered, high-density pores of the COF
provided excellent ion selectivity, and the CNT-CNF membrane pro­
vided 3D charged space that delivered a power density of 4.26 W m − 2 in
seawater.
Functional group modification of COFs can effectively increase sur­
face charge and, thus, improve power output performance. However, the
effect of the charge distribution in a membrane on the diffusive transport
of ions requires further investigation. Sun et al. [191]. prepared a series
of COF-BTAxBTHy/PAN composite membranes to investigate the effect
of charge distribution on output power, and found that excessive ionic
strength compressed the electric double layer (EDL), leading to poor ion
selectivity and reduced ion-transport performance. Thus, by optimizing
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Energy Storage Materials 55 (2023) 498–516
the COF-BTA1BTH1/PAN membrane, a power density of 51.9 W m − 2
was achieved (Figs. 12e–g). Furthermore, the same authors optimized
the number of ionic sites in a COF-(SO3Na)x/PAN membrane and
increased the power by applying thermal gradients (Figs. 12h–j); a
power density of 231 W m − 2 was reached with a temperature difference
of 60 K [192]. These studies demonstrate the great potential of COF
membranes for energy conversion applications, including the harvesting
of osmotic energy between seawater and freshwater.
6. Conclusions and outlook
The versatility of COFs has attracted significant attention since their
first discovery. Here, the structure, design, and ion-selectivity mecha­
nisms of COFs were reviewed with the aim of promoting their wider
application. In this review, we outlined the structure (skeletons and
linkage types) and physical properties (pore size and specific surface
areas) of a diverse range of COFs, and described their ion-selectivity
mechanisms based on their foundational physicochemical properties.
Finally, we summarized the applications of ion-selective-based COFs in
secondary ion batteries and salinity gradient energy generators.
Compared to other porous materials (e.g., POPs and MOFs), COFs
have many advantages. Given their composition of light elements (C, N,
H, O, etc.), low-density COFs have almost no impact on the mass energy
density of energy production devices. Moreover, the abundant and or­
dered nanochannels of COFs can improve electrolyte penetration,
thereby increasing the abundance of ions and favoring specific ion
diffusion. At the same time, the tunable nanochannel size and various
functional groups decorated on the walls of COFs yield excellent ion-
selectivity properties.
Although significant improvements in performance have been ach­
ieved by employing ion-selective COFs in energy storage and conver­
sion, several persistent problems need to be addressed to further
enhance ion selectivity. In particular, we recommend that the following
strategies should be further explored in the design of ion-selective COFs:
C. Wang et al.
1) The abundant and rigid-ordered nanochannels of COFs form the
basis for ion-selective transport; however, the relationships between
pore properties (size and density) and ion transport are ambiguous
during the operation of electrochemical devices. Notably, the range
of the covered electrical double layer decreases as the nanochannel
size increases, impairing ion-selective transport, while a pore size
that is too small will limit ionic conductivity and even cause polar­
ization. Therefore, dynamic electrochemical models are required to
fully investigate the ion-transport behavior in nanochannels.
2) Charge density plays a vital role in the ion-selective transport of
COFs, and ion selectivity may deteriorate owing to the compression
of the electric double layer when the charge density is too high.
Moreover, excessive functional group grafting impairs the nano­
channel structure and crystallinity, which damages the ion selec­
tivity of COFs. Theoretical calculations and experimental simulations
should help us gain further insight into the interactions between the
pore sizes, pore densities, and charge densities of COFs.
3) Structural stability is very important for the durable operation of
energy devices; however, the favorable crystallinity of COFs has
typically declined during electrochemical cycling, and the evolved
amorphous structures limit ongoing efficiency. Therefore, the inter­
nal pore structures and structural evolution of COFs need to be
characterized using various advanced structural testing tools. By
fine-tuning the pore structure and density of COFs, the development
of suitable charge density distributions and stable structures should
be possible. This will improve ion-selective transport in energy
storage and conversion.
4) As an emerging porous material, the crystal-chemical environment
and aperture structure of COFs need to be precisely investigated.
Neutron diffraction (ND) is highly penetrating and sensitive to light
atoms, which can analyze the structural characteristics and the dis­
tribution of light atoms of COFs. High-resolution transmission elec­
tron microscopy (HRTEM) can provide microscopic morphology and
crystallinity, and even visualize pore structure. Grazing incidence
small-angle X-ray scattering (GISAXS) is an ideal analytical tool to
probe COFs membrane structure, which can study samples that
cannot be observed by HRTEM. Transmission X-ray microscopy
(TXM) with a high elemental resolution is sensitive to light elements,
which can investigate the changes in the chemical environment and
elemental distribution of COFs materials during electrochemical
processes. A precise study of the morphologic and structural evolu­
tion of COFs by advanced analysis techniques is beneficial for us to
further unveil the mechanism of ion selectivity in nanoporous ma­
terials to boost their energy conversion and storage applications.
By addressing these highlighted research needs, structurally stable
COFs with excellent ion selectivity could be designed and applied to a
wider range of energy applications, as summarized in Fig. 13.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by Natural Science Foundation of Beijing
Municipality (2212001), Beijing Nova Program (Z201100006820112)
and National Natural Science Foundation of China (62075002 and
U21A20170) and the Ministry of Science and Technology of China
(2019YFE0100200).
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Energy Storage Materials 55 (2023) 498–516
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