Journal of Energy Chemistry 69 (2022) 132–149

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Journal of Energy Chemistry

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

Review

The roles of MXenes in developing advanced lithium metal anodes

Nicolas Lucero a, Dayannara Vilcarino a,b, Dibakar Datta c, Meng-Qiang Zhao a,⇑
a
Department of Chemical and Materials Engineering, Newark College of Engineering, New Jersey Institute of Technology, Newark, NJ 07103, USA
b
Jose Marti Stem Academy, Union City, NJ 07087, USA
c
Department of Mechanical and Industrial Engineering, Newark College of Engineering, New Jersey Institute of Technology, Newark, NJ 07103, USA

a r t i c l e i n f o a b s t r a c t

Article history: Lithium (Li) metal has emerged as the most promising anode for rechargeable Li batteries owing to its
Received 17 August 2021 high theoretical specific capacities, low negative electrochemical potential, and superior electrical con-
Revised 4 January 2022 ductivity. Replacing the conventional graphite anodes with Li metal anodes (LMAs) provides great poten-
Accepted 7 January 2022
tial to exceed the theoretical limitations of current commercial Li-ion batteries, leading to next-
Available online 19 January 2022
generation high-energy–density rechargeable Li metal batteries (LMBs). However, further development
of LMAs is hindered by several inherent issues, such as dangerous dendrite growth, infinite volume
Keywords:
change, low Coulombic efficiency, and interfacial side reactions. MXenes, a family of two-dimensional
MXenes
2D materials
(2D) transition metal carbides and/or nitrides, have recently attracted much attention to address these
Lithium dendrites issues due to their 2D structure, lithiophilic surface terminations, excellent electrical and ionic conduc-
Lithium metal anodes tivity, and superior mechanical properties. Herein, an overview of recent advances in the roles of
Stability MXenes for stabilizing LMAs is presented. In particular, strategies of utilizing MXenes as the Li hosts, arti-
ficial protection layers, electrolyte additives, and for separator modifications to develop stable and
dendrite-free LMAs are discussed. Moreover, a perspective on the current challenges and potential out-
looks on MXenes for advanced LMAs is provided.
Ó 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by ELSEVIER B.V. and Science Press. All rights reserved.

Nicolas Lucero is a currently rising chemical engi-
neering senior student in the Department of Chemical
and Materials Engineering at New Jersey Institute of
Technology. As part of the BS/MS program at New
Jersey Institute of Technology (NJIT), he is also working
towards a master’s in Materials Science & Engineering
and is doing research under the supervision of Prof.
Meng-Qiang Zhao. His current research interests
mainly focus on the use of 2D materials in energy
storage and conversion applications, including the
lithium dendrite suppression for Li metal anodes.
Dayannara Vilcarino is a rising junior at Jose Marti
Stem Academy. She is currently working as a visiting
student in the Department of Chemical and Materials
Engineering at New Jersey Institute of Technology
under the supervision of Prof. Meng-Qiang Zhao. Her
current research interests mainly focus on the inter-
face between Li and liquid electrolyte, dendrite sup-
pression of Li metal anodes and advanced energy
storage/conversion.

⇑ Corresponding author.
E-mail address: mz24@njit.edu (M.-Q. Zhao).

https://doi.org/10.1016/j.jechem.2022.01.011
2095-4956/Ó 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.
N. Lucero, D. Vilcarino, D. Datta et al.
Dibakar Datta is an assistant professor of Mechan-
ical Engineering at the NJIT. He earned his Ph.D.
from Brown University in 2015 (Major: solid
mechanics, Minors: physics and chemistry). He was
a postdoc at Stanford University (2015–2016). His
primary research interest is the computational
modeling of nanomaterials for energy storage
applications.
Meng-Qiang Zhao is an Assistant Professor in the
Department of Chemical and Materials Engineering
at New Jersey Institute of Technology. He obtained
his Ph.D. degree in chemical engineering from
Tsinghua University. After graduation, he worked as
a postdoctoral researcher in Prof. Yury Gogotis’
group at Drexel University and Prof. A.T. Charlie
Johnson’s group at the University of Pennsylvania.
His research interests focus on the development of
low-dimensional materials for energy, environ-
mental, and health applications.
1. Introduction
MXenes, a large family of two-dimensional (2D) transition
metal carbides and/or nitrides, are attracting increasing attention
since their discovery in 2011 [1–3]. MXenes have a hexagonal lat-
tice with sixfold symmetry. They are composed of atomic layers of
transition metal (M) and carbon and/or nitrogen (X) atoms, where
X atoms occupy the center of ‘‘XM6” octahedrons [3]. Generally,
MXenes are produced by selectively removing the A-layer atoms
(e.g., Al, Si, Ga) from their parent MAX phases, a group of layered
transition metal ternary carbides and/or nitrides, followed by
delamination into single-layer flakes [4]. The term ‘‘MXene” was
used aiming at emphasizing the removal of A- layer atoms from
the MAX phases as well as its 2D morphology that is analogous
to ‘‘graphene”. The general formula of MXenes is denoted as Mn+1-
XnTx, where M represents the early transition metals (e.g., Ti, Nb, V,
Mo, Ta), X represents carbon and/or nitrogen, n can vary from 1 to
4, and Tx represents the surface termination groups such as –OH, –
F, –O, and –Cl [3].
To date, more than 30 different stoichiometric MXenes have
been experimentally synthesized, and over 100 more are theoreti-
cally predicted with distinct physical and chemical properties [3,5].
The list is still expanding rapidly. Considering the solid solution on
the M and X sites and the possibility of different surface termina-
tions, MXenes represent a large and diverse family of 2D materials.
The most common synthesis method for MXenes is to etch the
MAX phases in a hydrofluoric (HF)-containing solution to remove
the A-layer atoms. Initially, aqueous solution of HF was widely
used to produce a variety of MXenes [2,6]. Later on, the etchant
was expanded to LiF/HCl and NH4HF2, in which HF was in-situ
formed [7,8]. In addition to aqueous solution, water-free polar
organic solvents such as propylene carbonate (PC) and N-methyl-
2-pyrrolidone (NMP) were also explored to produce Ti3C2Tx MXene
from the Ti3AlC2 MAX phase using NH4HF2 as the etchant [9]. So
far, most of the synthesized MXenes are derived from Al-
containing MAX phases due to the low reduction potential of Al
compared to other A elements. To synthesize MXenes from Si-
containing precursors, Alhabeb et al. particularly used HNO3/HF
mixture as the etchant to achieve the oxidant-assisted selective
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Journal of Energy Chemistry 69 (2022) 132–149
etching of Si from Ti3SiC2 [10]. Although the HF-containing solu-
tion has been demonstrated as the most powerful method for the
synthesis of numerous kinds of MXenes, the high toxicity of HF
remains a serious issue and concern for the environmental and
health considerations. Therefore, approaches towards the HF-free
synthesis process are attracting increasing attention recently. In
2016, Urbankowski et al., for the first time, reported the synthesis
of 2D Ti4N3 MXene from Ti4AlN3 in a molten fluoride salt, without
using HF [11]. Later on, Li et al. developed a general Lewis molten
salt etching route to produce a variety of MXenes [12,13]. The mol-
ten salt etching method shows the remarkable capability of pre-
cisely controlling the surface termination of MXene materials
[14]. Several other HF-free routes, such as the electrochemical
etching [15–17], alkali-assisted hydrothermal process [18], ther-
mal reduction method [19], and halogen etching [20], are also pro-
posed and demonstrated for MXene synthesis. In addition to the
top-down synthesis strategies mentioned above, bottom-up syn-
thesis strategies, such as the salt-templated topochemical method
[21,22] and chemical vapor deposition [23], have also been applied
for MXene synthesis. However, the MXenes produced by the
bottom-up methods exhibit distinct atomic structures with those
derived from the MAX phases and, thus, leading to differed physi-
cal and chemical properties.
The first MXene that was discovered is Ti3C2Tx [2]. Its demon-
strated high metallic conductivity, hydrophilic surface, and the
ability to intercalate cations and store charge initially led to an
extensive interest in using MXenes for energy storage, such as
supercapacitors and lithium (Li)-ion batteries (LIBs) [24–26]. Dur-
ing the past decade, numerous exciting applications of MXenes
have emerged, including energy storage and conversion, electro-
magnetic interface shielding, sensors, separation membranes,
catalysis, transparent conducting films, electronics and optoelec-
tronics, and multi-functional nanocomposites [1,3]. Among these,
the use of MXenes for electrochemical energy storage and conver-
sion is of great interest, aiming to provide clean and renewable
energy strategies to address the current energy shortage issues
[5,24,27]. The extraordinary electrical conductivity, high
hydrophilicity, large and tunable interlayer spaces, compositional
diversity, and abundant surface chemistries make MXenes promis-
ing not only as electrode materials but also other components in
next-generation rechargeable batteries. For example, MXenes have
been widely used as anode materials, binders, and conductive
additives to improve the energy and power density of LIBs
[24,27]. When used as anode materials, the high density of MXenes
(4.0–5.0 g cm 3) is particularly promising to give rise to a high vol-
umetric energy density [3,24]. In recent years, the study and inves-
tigation on MXenes for rechargeable batteries beyond LIBs,
including lithium-sulfur, alkali-ion (e.g., Na+, K+), multivalent-ion
(e.g., Mg2+, Zn2+, and Al3+), and metal batteries are rapidly develop-
ing and have achieved great progress [5,28,29]. In particular, there
is an emerging interest in the utilization of MXenes to develop
stable and dendrite-free Li-metal anodes (LMAs) for advanced Li-
metal batteries (LMBs) [28].
LMBs are lithium batteries with an anode from lithium metal.
To improve the energy densities of next-generation lithium batter-
ies, efforts are mainly devoted to the innovation of advanced bat-
tery materials, including both cathode and anode. Among high-
capacity anodes, Li metal is a perfect candidate due to its high the-
oretical specific capacities (3860 mAh g 1 and 2061 mAh cm 3)
and the lowest negative electrochemcial potential ( 3.04 V vs.
the standard hydrogen electrode) [30–32]. LMBs provide great
potentials to exceed the theoretical limitations of current commer-
cial LIBs, which may realize longer driving mileage of at least 400
miles per single charge for electric vehicles and solve the current
dilemma faced by LIBs [31–33]. One of the most pressing chal-
lenges for LMBs is the aggressive Li metal chemistry that leads to
N. Lucero, D. Vilcarino, D. Datta et al.
the formation of Li dendrites [30,31]. The growth of Li dendrites
can penetrate the separator and cause short circuit in the battery,
leading to high current discharge and even explosions. Besides, the
aggressive Li metal chemistry also leads to the formation of ‘‘dead
Li”, serious consumption of electrolyte, and thick solid-electrolyte
interphase (SEI) layer, which results in the poor electrochemical
performance of LMBs, such as low Coulombic efficiency, short
cycling life, and safety hazard. To solve these issues, multiple
strategies have been developed to achieve stable and dendrite-
free LMAs, including fabrication of Li host matrix [34,35], forma-
tion of artificial protection layer [36–39], modification of the elec-
trolyte [40,41] or separator [42,43], and binder design [44].
Numerous nanomaterials, such as carbon nanotubes (CNTs), gra-
phene, nanodiamonds, SiO2, MoS2, and metal–organic frameworks
(MOFs), have played important roles in the abovementioned
strategies [44–47]. In comparison, MXenes shows the advantages
of high electrical conductivity, rapid ion diffusion, excellent
Fig. 1. A timeline showing the historical development of using MXenes for LMAs
with four different roles.
Fig. 2. (a) Schematic illustration of the MXene (Mn+1XnTx) structure with n = 2. (b) Schematic illustration of the ordered and solid-solution double transition metal MXenes
with n = 2. (c) Band structures of Ti2CT2 and related MXenes and MAX phases, reproduced from Ref. [51] with permission of American Physical Society.
134
Journal of Energy Chemistry 69 (2022) 132–149
mechanical stability, tunable surface chemistry, and easy-
assembly feature due to the 2D morphology [3]. All these merits
give MXenes exciting potentials in the development of advanced
LMAs.
There have been several excellent reviews on the synthesis of
MXenes and their applications in energy storage and conversion,
including LIBs, supercapacitors, and battery technologies beyond
LIBs [5,27,28,48]. However, a more specific summary focuses on
the use of MXene to develop stable and dendrite-free LMAs is
required. In the present review, a detailed summary of the
advances in the synthesis strategies of MXenes will not be covered
since it has been extensively summarized. We will start with a
brief introduction to the properties of MXenes that make them
suitable for the applications in LMBs. Next, we will highlight recent
advances in the roles of MXenes for the development of advanced
LMAs. A brief timeline showing the historical development of using
MXenes for LMAs with four different roles is presented in Fig. 1.
Finally, we will present our perspective on the current challenges
and outlooks for promising future research directions.
2. Properties of MXenes
2.1. Structural properties
The MXene monolayers consist of alternating layers of M and X
atoms, which have a hexagonal close-packed (hcp) crystal struc-
ture with the X atoms occupying the octahedral sites in the
close-packed M atoms (Fig. 2a) [3]. So far, MXenes with Ti, Mo,
Nb, V, Cr, Zr, Hf, Sc, Ta, W, and Y in the M site have been reported
[3,5]. In most cases, the M sites are occupied by one single metal
element. However, MXenes with two different metals as M layers
also exist and thermodynamically stable. These binary metals can
either be randomly distributed in the M layers to form a solid solu-
tion or have the long-range ordering to form ordered double
transition-metal MXenes (Fig. 2b) [49,50]. The discovery of binary
transition-metal MXenes largely expanded the family of MXene
materials with differed properties. The X sites can be occupied by
carbon, nitrogen, or both. For the carbonitride MXenes, it is
believed that the C and N atoms randomly occupy the center of
N. Lucero, D. Vilcarino, D. Datta et al.
‘‘XM6” octahedrons, independent of carbonitride stoichiometry
[3,24].
During the synthesis of MXenes, the exposed metal elements of
MXenes are always terminated with surface functional groups
(e.g., –O, –OH, –F, and –Cl), which could significantly affect their
properties. For instance, the band structure of Ti2CTx changes obvi-
ously based on the types of its surface functional groups (Fig. 2c)
[51]. The types of MXene surface terminations depend on the syn-
thesis process and MXene composition, and they can be altered or
completely removed by post-processing methods. For example,
Ti3C2Tx synthesized by 48–51 wt.% HF showed the terminations
of 8 at.% OH, 55 at.% F, and 37 at.% O, while the LiF-HCl etching
led to 5 at.% OH, 22 at.% F, and 73 at.% O [52]. For the HF etching
method, increasing the HF concentration led to an increase in the
F termination and a decrease in the OH termination [53]. Using a
similar etching method, Mo2CTx and Nb2CTx MXenes contained sig-
nificantly lower amount of F termination but more O-containing
terminations [54]. Pure Cl and Br terminated MXenes can be pro-
duced by the chloride and bromide based Lewis acid molten salt
etching methods, respectively [12–14]. Several post-treatment
strategies have been proposed to alternate and control the MXene
surface terminations after synthesis. Thermal treatment is an effec-
tive process to control the surface functionality of MXenes. Sere-
dych et al. investigated the change of MXene surface
terminations by performing thermal gravimetric with mass spec-
trometry analysis up to 1500 °C under a He atmosphere [54]. It
was observed that OH terminations on Ti3C2Tx can be effectively
removed by annealing around 320 °C. A significant release of O
and F terminations occurred at 830–850 °C, accompanied with a
structural conversion from hexagonal MXenes to cubic TiC form.
The reactive O- and F-containing groups provide great potential
for the modification of MXene surface terminations by chemical
treatment. Alkalis, such as NaOH and KOH, have been widely used
to remove or reduce the amount of F terminations while increase
the O-containing terminations [55]. Grafting of alkylphosphonic
acid ligands on the hydroxyl terminal groups was achieved by
reactions between Ti3C2Tx MXene flakes and alkyl phosphonic acid,
leading to the surface chemistry migration from hydrophilic to
hydrophobic, which significantly improve the dispersion of Ti3C2Tx
MXene in nonpolar organic solvents [56]. Similar transformation
was also achieved by treating the MXenes with tetrabutylammo-
nium hydroxide (TBAOH) as an intercalant and surface modifier
[57]. The obtained TBA-modified MXenes showed excellent dis-
persibility in many organic solvents. Recently, a general strategy
to install and remove surface groups of MXenes was achieved by
substitution and elimination reactions in molten inorganic salts
[14]. MXenes with O, NH, S, Cl, Se, Br, and Te, as well as bare
MXenes were successfully synthesized, which showed distinctive
structural and electronic properties. This work shed lights on the
precise control over the surface termination of MXenes and conse-
quently, their physical and chemical properties.
The interlayer spacing, or c-lattice parameter, is another impor-
tant structure property of MXene, which is also tunable, depending
on the MXene composition and the size of intercalants. For most
MXenes, the interlayer spacing increases with increasing n value
(Mn+1XnTx). For example, Ti3C2Tx shows a c-lattice parameter of
20.51 Å, larger than that of Ti2CTx (15.04 Å) [6]. MXenes exhibit
extraordinary intercalation capability for water, numerous organic
molecules and cations [3,26]. As a result, adjusting the intercalant
species has become the mostly used method to tune the interlayer
spacing of MXenes. MXenes produced in aqueous solutions contain
two types of intercalated water, physisorbed and chemisorbed. The
physisorbed water can be removed at temperatures below 200 °C,
while the removal of chemisorbed water requires vacuum anneal-
ing at temperatures above 500 °C [54,58,59]. Therefore, aging in a
high humidity environment and thermal treatment are simple yet
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Journal of Energy Chemistry 69 (2022) 132–149
effective methods to control the interlayer spacing of MXenes. Ghi-
diu et al. noticed that the c-lattice parameter of Ti3C2Tx MXene
increased from 25.0 to 30.0 Å after pressing the sample in a high
humidity environment to 300 MPa, which reverted back to
25.0 Å after drying over a P2O5 desiccant for a few days [60]. This
indicated the effect of water intercalant on the interlayer spacing
of MXenes. Mashtalir et al. treated Ti3C2Tx MXene in hydrazine
and observed the increasing of c-lattice parameter from 20.2 to
25.4 Å due to the replacement of water by hydrazine with a larger
size [61]. Natu et al. demonstrated a significant increase in the c-
lattice parameter of MXenes from 24.6 to 42–101 Å when the
water intercalant was replaced by polar organic solvents such as
acetonitrile (ACN), dioxane (DXN), N,N-dimethylformamide
(DMF), and N-methyl-2-pyrrolidone (NMP) [9]. MXenes with ultra-
large interlayer spacing were obtained by the intercalation of
cetyltrimethylammonium bromide (CTAB) and Sn4+ between Ti3-
C2Tx layers to form a pillared structure, which led to much
improved electrochemical performance in lithium-ion capacitors
[62]. It should be noted that most of the intercalant exchange pro-
cesses are reversible, either chemically or electrochemically, lead-
ing to the reversible change of the interlayer spacing of MXenes.
Through post-processing, many polymer macromolecules and
nanomaterials, such as poly(vinyl alcohol) [63], polyaniline (PANI)
[64], Si nanoparticles [65], carbon nanotubes [66,67], and graphene
[68,69], can also be intercalated into MXene layers to change their
interlayer spacing and prevent the restacking of MXene flakes. The
fabrication of such MXene-based nanocomposites or hybrids has
been attracting much attention to improve the performance of
MXenes during their applications and to explore unexpected prop-
erties [70–72]. The easily tunable interlayer spacing of MXenes
makes them promising candidates for applications where the
interlayer spacing matters, such as electrochemical energy storage
and separations.
2.2. Electronic properties
All bare MXenes, without surface terminations, are predicted to
be metallic conductors due to their metal-like free-electron density
and the high degree of coplanar alignment of individual MXene
flakes [73–75]. After adding surface terminations, most MXenes
still exhibit a high electrical conductivity. For example, the conduc-
tivity of individual Ti3C2Tx MXene flake was measured to be
4600 ± 1100 S cm 1 and a field-effect electron mobility of 2.6 ± 0.
7 cm2 V 1 s 1 [76]. The conductivity of transparent Ti3C2Tx MXene
films obtained by spin coating increased from 5736 to 9880 S cm 1
when the film thickness increased from 4 to 88 nm, superior to
other solution processed 2D materials [77]. The electrical conduc-
tivity of MXenes is affected by the flake size, stoichiometry, surface
chemistry, intercalants, and point defects. For example, Kayali et al.
reported that the conductivity of a 5-mm-thick Ti3C2Tx film
increased from 1000 to 2100 S cm 1 when the flake size
increased from 0.18 to 3.05 mm [78]. The intercalation of large
organic cations, such as TBA+, between MXene flakes results in a
large interlayer spacing and smaller electrical conductivity
[79,80]. In contrast, the intercalation of small alkali cations tends
to preserve a small interlayer spacing and high electrical conduc-
tivity of MXene films [81]. Thermal annealing of MXenes to remove
the intercalated water and some surface termination groups usu-
ally leads to an increase in the electrical conductivity [8,82]. In
general, larger MXene flakes with fewer defects, less surface termi-
nations, and smaller intercalants lead to a higher electrical conduc-
tivity. Zhang et al. synthesized single-layer large Ti3C2Tx flakes with
average lateral size of 10 ± 2.1 lm using a modified minimally
intensive layer delamination (MILD) method. Pure MXene films
containing such large MXene flakes exhibited a high electrical con-
ductivity of 15100 S cm 1 [83]. Zeraati et al. synthesized the Ti3-
N. Lucero, D. Vilcarino, D. Datta et al.
C2Tx MXene under the protection of N2 atmosphere during the
selective etching to minimize the point defects for the obtained
MXene flakes. MXene films fabricated by these high-quality and
large-size flakes showed an exceptional electrical conductivity up
to 2.4  104 S cm 1 [84]. High-quality and large-size Ti3C2Tx flakes
with few defects were also obtained by the selective etching of
modified Ti3AlC2 MAX phase (excess Al during synthesis), which
led to the fabrication of MXene films with the electrical conductiv-
ity up to 2.0  104 S cm 1 [85]. Not just high electrical conductiv-
ity, MXenes have also been demonstrated with high ionic
conductivity during their application in a variety of electrochemi-
cal energy storage devices. Density-functional theory (DFT) calcu-
lations show that Ti3C2 MXene has a low Li+ diffusion barrier of
0.07 eV, much lower than anatase TiO2 (0.35–0.65 eV) and even
lower than graphite (0.3 eV) [86]. The high ionic conductivity
together with low Li+ diffusion barrier makes MXenes promising
candidates for applications in lithium batteries.
The addition of surface functional groups on bare MXenes leads
to the shift of Fermi level down to lower energy due to the interac-
tion between transition metal atoms and terminations, which gives
the possibility to make some MXenes semiconductors [51,87]. For
example, the metallic Sc2C becomes semiconductor when its sur-
face is terminated by OH or F [73]. The electronic properties of
MXenes are greatly influenced by the types of surface terminations
and transition metal M elements, which has been widely investi-
gated by both theoretical studies and experimental characteriza-
tions. Sc2C(OH)2 exhibits a direct semiconducting characteristic,
while Sc2CF2 has an indirect bandgap [73]. Ti2CF2 and Ti3C2O2 are
metallic materials, while Ti2CO2 and Hf3C2O2 are all predicted to
be semiconductors [87]. Superconductivity has been observed in
Nb2CTx (Tx = Se, S, or NH), whereas nonterminated or O-
terminated multilayer Nb2C did not show a superconducting tran-
sition [14]. The transition metal M has also been widely used to
regulate the electronic properties of MXenes. Alternating the outer
Ti layers of Ti3C2 and Ti4C3 with Mo atoms leads to the transition
from metallic to semiconducting behavior [50,88]. Similar semi-
conducting behavior, a negative temperature dependence of resis-
tivity, was also observed for Mo2CTx MXenes [89]. It is interesting
to note that some O-terminated M2C and ordered double transition
metal MXenes, such as Mo2C, Mo2TiC2, and Mo2HfC2, are predicted
to be topological insulators [90,91].
2.3. Mechanical properties
Similar to many metal carbides, the high elastic modulus of
MXenes was predicted in early studies. Initial investigations in
the mechanical properties of MXenes are mainly based on compu-
tations methods. The Young’s moduli of the pristine MXenes were
calculated as 597, 502, and 534 GPa for Ti2C, Ti3C2, and Ti4C3,
Fig. 3. The roles of MXenes in the development of stable and dendrite free LMAs.
136
Journal of Energy Chemistry 69 (2022) 132–149
respectively [92]. Experimental study of the fundamental mechan-
ical properties of single-layer Ti3C2Tx MXene was carried out
recently using atomic force microscopy (AFM) nanoindentation
[93]. The outstanding Young’s modulus of 330 GPa and tensile
strength of 17.3 GPa were demonstrated. A higher Young’s mod-
ulus of 390 GPa and higher tensile strength of 26 ± 1.6 GPa were
demonstrated for Nb4C3Tx by a similar testing method [94]. The
tested Young’s moduli are smaller than the theoretical predictions,
which can be ascribed to the presence of surface terminations and
point defects. The high mechanical strength of MXenes suggests
their great potentials as building blocks for fabricating strong films
and as nanofillers in strong nanocomposites. Chen et al. processed
the Ti3C2Tx dispersions with 0.1 M HCl solution and obtained Ti3C2-
Tx films with a high tensile strength of 112 MPa [95]. Ti3C2Tx films
with highly aligned large MXene flakes manufactured by a blade
coating technique showed a tensile strength of 560 MPa, exceed-
ing that of Al foil [83]. A wide range of materials, including PVA
[63], cellulose nanofibers [96], and graphene oxide [97], have been
used to improve the tensile strength of MXene-based films. A 10%
PVA mass ratio in the MXene/PVA nanocomposite film provides a
tensile strength 1.5 times of the pure MXene film [63]. The tensile
strength and Young’s modulus of a MXene/cellulose nanofibrils
composite film reached 341 MPa and 41.9 GPa, respectively, much
higher than pure MXene films fabricated by a similar method [96].
However, enhancement of tensile strength using these binders
often accompanied with a significant decrease in the electrical con-
ductivities due to the electron transport is hindered by the insulat-
ing intercalants between MXene flakes.
3. MXenes for Li metal anodes
To develop stable and dendrite-free LMAs, the main direction is
to achieve a uniform Li deposition during the Li plating and strip-
ping process [31]. As discussed above, several strategies have been
successfully developed to achieve high-performance LMAs, in
which the electronic/ionic conductive nanomaterials (e.g., CNTs,
graphene, porous carbon, conductive polymers) occupy an impor-
tant position. In comparison, MXenes exhibit impressive metallic
conductivity, rapid ion diffusion coefficient, multifunctional sur-
face terminations that act as nucleation sites to induce good lithio-
philicity, excellent mechanical strength and chemical stability
against Li metal, and easy-assembly feature due to the 2D mor-
phology. All these merits give MXenes great potentials for applica-
tions in advanced LMAs. As illustrated in Fig. 3, so far, MXenes have
been widely used to fabricate three-dimensional (3D) Li hosts and
ultrathin artificial protection layers to suppress the growth of Li
dendrites. Besides, MXenes are also used to modify the separators
and electrolytes to develop high-performance LMBs.
N. Lucero, D. Vilcarino, D. Datta et al. Journal of Energy Chemistry 69 (2022) 132–149

3.1. Li hosts overpotential after 200 cycles at 1.0 mA cm 2, demonstrating the

During the repeated Li plating/stripping process, the LMAs per-
form significant and infinite volume change that results in the
damage of SEI layer, Li dendrite formation, electrolytes consump-
tion, and low Coulombic efficiency. To address these issues, a
proper Li host matrix with uniform Li nucleation sites is needed,
which can mitigate the obvious volume change of Li metal and
suppress the growth of Li dendrites. Extensive efforts have been
devoted to use MXene-based materials to fabricate the 3D Li host,
not just using pure MXenes, but also their derivatives and
hybrids/nanocomposites.
3.1.1. MXene frameworks as Li hosts
The first report on using MXenes as the Li hosts was published
in 2017 by Yang’s group [98]. Based on the unique ductility of Li
metals and the lubricity of MXene nanosheets, flexible Ti3C2Tx
MXene-Li metal film with a lamellar structure was fabricated by
a repeated roll-to-roll mechanical pressing method (Fig. 4a). Dur-
ing the tests in a symmetric cell, the lamellar Ti3C2Tx-Li film exhib-
ited excellent cycling stability with only 1.5% increase in the
good stability of the obtained LMAs (Fig. 4b and c). No obvious
growth of Li dendrites was observed after 200 cycles. The electro-
chemical of Ti3C2Tx-Li film was superior to that of graphene/Li and
BN/Li films fabricated by a similar method, which was ascribed to
the high electrical conductivity, uniform distribution of Li nucle-
ation cites, and good mechanical strength of MXenes. To improve
the high-rate performance of LMAs, the same group developed per-
pendicular Ti3C2Tx MXene-Li arrays with alternating MXene walls
and interior Li metal layers through a simple rolling-cutting pro-
cess (Fig. 4d) [99]. Such well-designed structure enabled both fast
transfer of Li ions and homogenization of the electric field, leading
to homogeneous deposition of Li metals between the perpendicu-
lar MXene arrays with a high-rate capability up to 20 mA cm 2
(Fig. 4e and f). The perpendicular Ti3C2Tx-Li arrays gave rise to a
dendrite-free LMA with a low potential of 25 mV, a high capacity
of 2056 mAh g 1, and good cycle stability up to 1700 h, superior
to that of rGO-Li arrays with a similar structure.
Detailed investigation in the Li metal nucleation and growth
behavior on MXenes was carried out by Ha et al. (Fig. 5a and b)
[100]. Using microporous 3D Ti3C2Tx MXene frameworks sup-

Fig. 4. (a) Schematic illustration of the fabrication of flexible lamellar Ti3C2Tx-Li films by a repeated roll-to-roll mechanical pressing method. Schematic showing (b) the
numerous transfer channels for Li ions in the lamellar Ti3C2Tx-Li film and (c) the growing process of Li dendrite in the presence of MXene layers, which possess good inhibiting
effect for the vertical growth of Li dendrites; Reproduced from Ref. [98] with permission of Elsevier. (d) Schematic illustration of the fabrication procedure of perpendicular
MXene-Li arrays. (e) Top view scanning electron microscopy (SEM) image of perpendicular MXene-Li arrays after initial stripping for 20 mAh cm 2 and subsequent plating for
1 mAh cm 2. (f) Schematic illustration of the stripping and plating states of perpendicular MXene-Li and rGO-Li arrays with corresponding SEM images. Reproduced from Ref.
[99] with permission of WILEY-VCH.

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N. Lucero, D. Vilcarino, D. Datta et al. Journal of Energy Chemistry 69 (2022) 132–149

Fig. 5. (a) Schematic image showing the mechanism of Li growth on MXene layers. (b) SEM images showing the surface of MXene electrodes after Li metal deposition at a
current density of 0.5 mA cm 2 with different capacities; Reproduced from Ref. [100] with permission of WILEY-VCH. (c) Scheme of 3D printing MXene arrays and lattices to
guide the nucleation and growth of lithium; Reproduced from Ref. [101] with permission of Elsevier.

ported by DFT calculations, the authors demonstrated that both O-
and F-containing functional groups on MXene surface could serve
as the nuclei sites for Li metals. The high density of these surface
functional groups over the entire MXene surface guided the uni-
form deposition of Li metal nuclei, which coalesced and agglomer-
ated into larger secondary particles during the continuing Li
plating process. Finally, they formed a dense Li metal layer com-
posed of close-packed particle-by-particle microstructures without
dendrite growth. This unique lithium metal deposition behavior
led to high average Coulombic efficiencies of >99.0% and stable
long-term cycle life over 1000 cycles.
For the adoption of 2D materials in energy storage applications,
a rational design of the 3D electrode strucutres using the 2D build-
ing blocks is usually required to maximize their performance [102].
Similar, 3D MXene-based architectures have also been designed to
serve as Li hosts. Due to the relative weak interactions between
MXene flakes, it has been a challenge to fabricate mechanically
stable 3D MXene frameworks. To solve this issue, extrusion-type
3D printing was employed to build 3D Ti3C2Tx MXene arrays and
lattices, which enabled the uniform and dendrite-free deposition
of Li metals and provided enough interspaces to accommodate
the large amount of plating Li metals (Fig. 5c) [101]. The 3D printed
MXene-based anode provided a very low overpotential of 10 mV,
long cycle life stability up to 1200 h, and high-rate capabilities up
to 20 mA cm 2. 3D Ti3C2Tx MXene Li host was also fabricated by
femtosecond laser treatment on a vacuum-assisted filtered MXene
membrane to cut microchannels on it [103]. The laser treatment
was accompanied with the formation of high-density lithiophilic
TiO2 nanoparticles on the microchannel walls, which served as
the nucleation site for Li metals with a low nucleation overpoten-
tial of 10 mV. Besides, the F terminations on MXenes induced the
formation of LiF-reinforced SEI layer, which could suppress the Li
dendrite growth. As a result, a long cycle life of 750 cycles
(1500 h) with a Coulombic efficiency of 98.8% was achieved at
1 mA cm 2.
Not just Ti3C2Tx, MXene with other stoichiometry, such as Nb2-
CTx, has also been used to fabricate 3D conductive Li host. Sulfur (S)
and nitrogen (N) were codoped into the Nb2CTx MXene lattice to
provide extrinsic defects and active sites for Li nucleation and
growth and enhance the electrical conductivity [104]. As a result,
the S and N codoped Nb2CTx MXene exhibited great ability to inhi-
bit Li dendrite growth and reduce side reaction, giving the as-
developed LMA excellent electrochemical performance. In another
report, interconnected 2D arrays of niobium nitride (NbN)
nanocrystals synthesized by the topochemical method (ammonia-
tion of 2D niobium oxide flakes) was used as Li hosts to develop
stable LMAs [105]. Theoretical and experimental analysis revealed
that the 2D arrays of NbN nanocrystals possessed the merits of

138
N. Lucero, D. Vilcarino, D. Datta et al.
high Li affinity, fast Li+ migration and transport, and good thermo-
dynamic stability against Li metal. Consequently, the as-fabricated
LMAs exhibited a high Coulombic efficiency of >99% after 500
cycles at 1 mA cm 2.
3.1.2. MXene derivatives as Li hosts
To improve the electrochemical performance of MXenes as Li
hosts, several post-treatment approaches were developed to con-
vert MXenes into metal oxides/carbon hybrids. The obtained
MXene derivatives showed to improve the lithiophilicity and
increased the porosity, which facilitate the Li infusion and uniform
deposition. Tian et al. constructed ultrafine TiO2 nanoparticles con-
fined in 3D freestanding carbon paper by one-step in-situ oxida-
tion of Ti3C2Tx MXene paper with CO2 (Fig. 6a) [106]. The in-situ
formed TiO2 nanoparticles effectively improve the wettability of
Li metal into the host and serve as Li nucleation seeds to guide
more uniform Li deposition and growth. On the other hand, the
derivated 3D freestanding conductive carbon matrix provides an
effective support for Li deposition and buffers the volume change
during the cycling processes. These two synergistic effects con-
tribute to the achievement of stable and dendrite-free LMAs
(Fig. 6b–e). Instead of using CO2, Yao et al. converted the Ti3C2Tx
MXene film into sandwich-like TiS2-TiO2/MXene hierarchical
structure by in-situ vulcanization [107]. Electrochemical tests in
symmetric cells revealed a lower overpotential of 75 mV after
1000 h at the current density of 5 mA cm 2 for the TiS2-TiO2/
MXene structure, showing better performance compared with
MXene films. It is ascribed to the introduction of lithiophilic TiS2
and TiO2 particles. Wang et al. utilized NH3/Ar to convert Ti3C2Tx
MXene papers into TiO2/N-doped C hybrids, which were trans-
formed into 3D LiTiO2-Li3N-C hybrid frameworks during the fol-
Fig. 6. Schematic illustration of (a) the fabrication of flexible freestanding C/TiO2 paper derived from MXene paper and (b) its Li metal deposition behavior; SEM images
showing the morphology evolution during Li plating processes after Li deposition for (c) 0, (d) 2, and (e) 10 h at 0.2 mA cm 2 on the freestanding C/TiO2 paper. Reproduced
from Ref. [106] with permission of Elsevier.
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Journal of Energy Chemistry 69 (2022) 132–149
lowed lithiation process [108]. When used as the Li hosts, the 3D
LiTiO2-Li3N-C hybrids achieved nearly zero volume expansion dur-
ing the Li stripping/plating process, delivering an extended cycling
life of 2000 h in symmetric cells at a current density of 1 mA cm 2
at 25 °C. Even at a high current density of 10 mA cm 2, the sym-
metric cells can be cycled for 34 h at 10 °C and 500 h at 50 °C,
respectively. In a control experiment, it was demonstrated that
the 3D LiTiO2-Li3N-C hybrids performed much better than the
LiTiO2-C hybrids, in which N was not dopped into the carbon
matrix during the MXene conversion process. This indicated that
Li3N formed during the lithiation process served as a superlithio-
philic interphase to guide uniform Li deposition and suppress the
Li dendrite growth.
3.1.3. MXene-based hybrids/nanocomposites as Li hosts
The abundant surface functional groups and 2D morphology
provide MXenes great potential to hybridize with other nanomate-
rials and polymer molecules. The fabrication of MXene-based
hybrids/nanocomposites has attracted much attention and become
the most effective method to improve the electrochemical perfor-
mance of MXenes as Li hosts for LMAs. This performance enhance-
ment is contributed either by the improved lithiophilicity or by the
improved mechanical stability of the 3D hosts, or both.
During an initial effort, graphene oxide (GO) was used to help
the assembly of Ti3C2Tx MXene flakes into aerogel (Fig. 7a) [109].
To prepare the aerogel, the mixed aqueous dispersion of Ti3C2Tx
and GO was cross-linked through hydrogel iodine (HI) reduction
of GO nanosheets. The reduced GO (rGO) was self-assembled into
a porous aerogel, in which Ti3C2Tx flakes were uniformly dis-
tributed on the rGO skeleton, forming the Ti3C2Tx/rGO hybrid aero-
gel. The interconnected voids in the aerogel can serve as stable host
N. Lucero, D. Vilcarino, D. Datta et al. Journal of Energy Chemistry 69 (2022) 132–149

Fig. 7. (a) SEM image of the Ti3C2Tx/rGO aerogel, showing obvious 3D porous structure. Inset: a photograph of the aerogel. (b) Voltage profiles of the symmetric cells with rGO
and M/G-70 aerogel scaffolds at current density of 10 mA cm 2 under deposition capacity of 1 mAh cm 2; Reproduced from Ref. [109] with permission of WILEY-VCH. (c)
Schematic diagram of Li-Ti3C2Tx-rGO preparation and (d) the wettability process of Ti3C2Tx-rGO hybrid; (e) SEM cross-sectional images of Ti3C2Tx-rGO and (g) Li-Ti3C2Tx-rGO
films; SEM images showing the surface of bare Li and Li-Ti3C2Tx-rGO at 1.0 mA
cm 2 after 200 h. Reproduced from Ref. [110] with permission of American Chemical Society.

for high Li loading with mitigated volume fluctuation. The Ti3C2Tx
contributed high electrical conductivity, fast Li ion transport capa-
bility, and abundant Li nucleation sites. As a result, the Ti3C2Tx/rGO
hybrid aerogels delivered high cycling stability and low over-
potential at current density up to 10 mA cm 2 as Li hosts
(Fig. 7b). With increasing mass fraction of Ti3C2Tx up to 70%, the
hybrid (M/G-70) aerogel showed improved electrochemical perfor-
mance. However, too much Ti3C2Tx (e.g., 90%) would destroy the
3D porous structure due to aggregation, resulting in worse
Coulombic efficiency. In another approach, freeze-drying method
was used to fabricate 3D Ti3C2Tx MXene/GO aerogels directly from
the aqueous dispersion of Ti3C2Tx and GO nanosheets (the ratio of
GO to Ti3C2Tx was 3:1), which was mechanically pressed to prepare
layer-stacked Ti3C2Tx/GO hybrid films [111]. A lithiation spark
reaction was carried out to reduce GO into rGO, producing a 3D Ti3-
C2Tx/rGO nanoporous film, which provided abundant nanoporous
channels for the infusion of molten Li metal. The as-fabricated Ti3-
C2Tx/rGO hybrid films showed strong capability to suppress the
growth of Li dendrites, achieving an ultrahigh Li loading of 92%,
high Coulombic efficiency of 99%, and an excellent cycle life stabil-
ity up to 2700 h at a high capacity of 5 mAh cm 2. The Ti3C2Tx/rGO
hybrid (Ti@G) films were also prepared by the direct filtration of
Ti3C2Tx and GO dispersions, followed by a spark reaction for GO
reduction (Fig. 7c) [110]. These filtered Ti3C2Tx/rGO films have
been demonstrated as excellent Li hosts (Li-Ti@G) for stable and
dendrite-free LMAs too (Fig. 7d–g).
140
In addition to graphene materials, polymers are another choice
to improve the mechanical stability of MXene frameworks. By
soaking the commercial melamine foam (MF) in a Ti3C2Tx MXene
solution, Shi et al. obtained 3D flexible, conductive, and recyclable
Ti3C2Tx/melamine foams [112]. The MF provides the excellent
mechanical toughness and microporous network, while the coated
Ti3C2Tx MXene contributes the lithiophilicity based on its surface
terminations and high electrical conductivity. Consequently, the
Ti3C2Tx/melamine foam achieved a high Coulombic efficiency of
99% and an exceptional cycle life stability of 3800 h at a high cur-
rent density of 50 mA cm 2 and high areal capacity of 50 mAh
cm 2. Ti3C2Tx MXenes were also coated on the surface of 3D Cu
foam using CTAB as the linker [113]. Compared with bare Cu foam,
the MXene@Cu foam significantly suppressed the Li dendrite
growth during Li plating/stripping, leading to much improved
Coulombic efficiency and cycling stability. The mechanical stability
of MXene-based scaffold can be significantly enhanced by cross-
linking the Ti3C2Tx MXene flakes with polysiloxane via hydrolysis,
polycondensation, and silylation reactions [114]. Silver nanowires
(AgNW) were added into the cross-linked MXene scaffold to fur-
ther improve the electrical conductivity and lithiphilicity. The
obtained covalently cross-linked MXene/AgNW scaffold showed
excellent mechanical strength and resilience even during large
continuous stress fluctuations caused by the rapid and deep Li plat-
ing/stripping process. As a result, the hybrid was capable of cycling
for over 3000 h at a current density of 20 mA cm 2 and an areal
N. Lucero, D. Vilcarino, D. Datta et al.
capacity of 10 mAh cm 2. Poly(vinyl alcohol) (PVA) was used to
cross-linking Ti3C2Tx MXene flakes directly through hydrogen
bonding, giving highly robust and ultralight MXene/PVA (ULRMA)
aerogels after a free-drying process (Fig. 8a) [115]. The MXene/
PVA aerogels exhibited exceptional mechanical strength with less
sacrifice of intrinsic properties of MXenes at an ultralow density
below 10 mg cm 3, which allowed for maximizing the gravimetric
energy density of Li metal (Fig. 8b–d). When serving as the Li host,
a stable LMA with long lifetime of 1600 h at 1.0 mA cm 2 with a
high Coulombic efficiency of 98.8% was obtained. No Li dendrite
growth on the MXene/PVA aerogel was observed after 90 min of
Li deposition at a current density of 1.0 mA cm 2. Under the same
condition, Li dendrites were observed on Cu foil and MXene aero-
gels (Fig. 8e–g). Effect of MXene contents in the aerogels for their
performance as LMAs was investigated. The optimal performance
was achieved with 70 wt.% MXene, while lower MXene content
suffered from reduced lithiophilic sites and conductivity and
higher MXene content resulted in reduced mechanical stability. A
trace of cellulose nanofibers (CNFs) were added into the Ti3C2Tx
MXene frameworks to achieve a topological design of strong
MXene paper by a spin steaming technology-induced assembly
process [116]. The CNFs induced the generation of microspheres
with MXene flakes via intermolecular hydrogen bonding. The
interlocks between MXene sheets and microspheres contributed
to the improved mechanical strength and flexibility of the resulted
hybrid films while avoiding the re-stacking of MXene flakes, which
led to expanded interspaces, a high areal capacity for Li plating,
and superior rate capability. Finally, the ultrathin (25 mm)
Fig. 8. (a) Schematic illustration of the fabrication strategy of the Ti3C2Tx MXene/PVA aerogel. (b) Optical images of the MXene/PVA aerogel standing on a dandelion-flower.
(c) SEM images of the MXene/PVA aerogel with hierarchically porous 3D architecture. (d) Optical image of a MXene/PVA aerogel pressed under a weight of 100 g. Optical
images showing the evolution of electrode interface for 90 min of Li deposition on (e) Cu, (f) MXene aerogel, and (g) MXene/PVA aerogel at a current density of 1.0 mA cm 2.
Reproduced from Ref. [115] with permission of WILEY-VCH.
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Journal of Energy Chemistry 69 (2022) 132–149
MXene/CNF hybrid film anodes displayed stable Coulombic effi-
ciency of 98.9% for over 250 cycles at 1 mA cm 2 and good cycling
stability for over 1300 h at 0.5 mA cm 2.
The electrochemical performance of MXenes as Li hosts for
LMAs can be further improved by the introduction of external
lithiophilic agents into the MXene architectures. For example, Zn
metal was electrodeposited onto the surface of Ti3C2Tx MXene
flakes in a filtered MXene paper [117]. The obtained Ti3C2Tx
MXene/Zn layered structure was used as an effective Li host for a
dendrite-free LMAs, in which metallic Zn homogeneously grown
on Ti3C2Tx paper served as nucleation seeds to guide the Li nucle-
ation and uniform deposition. The Ti3C2Tx/Zn/Li anodes delivered
an average Coulombic efficiency of 97.7% over 600 cycles at a cur-
rent density of 1 mA cm 2 with an areal capacity of 1 mAh cm 2.
Similar concept was employed to other lithiophilic nanomaterials,
such as 2D Si nanosheets [118], nanoporous Si@C [119], and layer-
by-layer-assembled Si/C nanostructures [120], by the same group.
These lithiophilic nanomaterials were introduced into the MXene
frameworks through the vacuum-assisted filtration of their disper-
sions in MXene solutions (Fig. 9a–c). When the obtained MXene-
based hybrids were used as Li hosts, dendrite-free LMAs with a
high Coulombic efficiency of >97% and a cycle life stability over
1000 h (600 cycles) were obtained at a current density of
2 mA cm 2, superior to that of Cu foils (Fig. 9d–f). Several other
lithiophilic agents were also introduced into the MXene frame-
works to improve their electrochemical performance as advanced
Li hosts. Wei et al. added covalent organic framework (COF)-
LZU1 microspheres into a filtered Ti3C2Tx MXene paper and
N. Lucero, D. Vilcarino, D. Datta et al.
Fig. 9. (a) Schematic of fabrication for 2D Si@MXene hybrid films. (b) Digital photograph of a 2D Si@MXene hybrid film showing its flexibility. (c) SEM image showing the
cross section of a 2D Si@MXene film. (d) Schematic and SEM images showing the Li deposition morphology on (e) a Cu foil and (f) 2D Si@MXene film at 20th cycles of Li
plating. Reproduced from Ref. [120] with permission of American Chemical Society.
demonstrated its superior performance for dense and dendrite-free
Li deposition compared to pure MXene papers [121]. Direct growth
of the same COFs on Ti3C2Tx MXene flakes was achieved via a cova-
lent assembly process, which involved Ti3C2Tx amination with NH2
moieties followed by in-situ COF deposition [122]. Covalently
assembled 2D-2D MXene/COF heterostructures were obtained,
yielding 3D scaffolds with high crystallinity, well-defined pore
structures, and chemically stable frameworks. When used as the
Li host, dendrite-free Li deposition was achieved on the hierarchi-
cal MXene/COF monolith with improved Coulombic efficiency
(99%) and long cycling stability (800 h) under high current densi-
ties up to 20 mA cm 2, superior to both MXene and COF architec-
tures with a similar structure. Zhao et al. designed a multi-storey
corridor structure of Ti3C2Tx MXene/Li7B6 hybrids through a
repeated rolling and folding strategy [123]. This multi-storey corri-
dor structure was composed of lamellar Ti3C2Tx MXene flakes and
vertically aligned Li7B6 nanofibers. The interlayer lithiophilic Li7B6
nanofibers served as pillars to prevent the collapse of the 3D struc-
ture during the depth plating process and worked as nucleation
sites to induce uniform deposition of Li metal. Consequently, the
obtained hybrid LMA delivered dendrite-free Li deposition with a
low overpotential of 24 mV at 1.0 mA cm 2 and long cycling stabil-
ity over 1000 h, as well as high-rate capability up to 20 mA cm 2
and large area capacity of 10 mAh cm 2.
It should be noted that, in most cases, the vacuum-assisted fil-
tered MXene films are not used as the Li hosts directly to develop
due to the compact stacking of MXene flakes and the resulting lim-
ited Li infusion/plating interspaces. Therefore, the fabrication of
MXene-based hybrids/nanocomposites through introducing exter-
nal agents not only improves the mechanical strength or lithio-
philicity, but also provides necessary porous channels for Li
plating/infusion. This has become the most promising strategy to
develop MXene-based architectures for advanced stable and
dendrite-free LMAs.
3.2. Artificial protection layers
It is widely recognized that the stability and cycle performance
of lithium batteries are largely determined by the electrode/elec-
trolyte interfaces [124–126]. These interfaces are intrinsic instable
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Journal of Energy Chemistry 69 (2022) 132–149
in both chemical and mechanical. Therefore, several regulation
strategies have been proposed to improve their stability, towards
the development of stable lithium battery electrodes, including
LMAs [125,127]. Among them, the fabrication of artificial protec-
tion layer is one of the most effective strategies because it can
straightforwardly alleviate the undesirable electrolyte decomposi-
tion, enhance the interfacial attachment in spite of the volume
change, and therefore greatly boost the cyclability of Li metal
anodes [125,127]. In particular, an artificial protection layer on Li
metal can guide the uniform Li deposition and inhabit the growth
of Li dendrites [31,36]. This artificial protection layer could be a
thin and dense layer of ion conductor that can prevent the elec-
trolyte penetration and Li dendrite formation. It can also be a
layer/matrix of electron conductor with well-distributed Li nucle-
ation sites that offer uniform Li deposition. As discussed above,
most MXenes are metallic electron conductors with low Li ion dif-
fusion barriers with excellent mechanical strength and abundant
surface terminations that can serve as Li nucleation sites. These
merits make MXenes an ideal building block for the fabrication
of artificial protection layer towards stable and dendrite-free LMAs
through both physical and chemical means [127].
Initial efforts indicate that the alignment or orientation of
MXene flakes plays an important role in their performance as
LMA protection layers. Parallelly aligned Ti3C2Tx MXene layers
were produced via a simple self-assembly procedure at a water/
air interface, which can be picked up by a Cu foil directly [128].
Thickness of the parallelly aligned MXene layers can be controlled
by the pick-up times (350 nm for each time). Through a rolling pro-
cess, the continuous and tightly adhered MXene layers can be
transferred onto a Li foil, which could protect the active Li metal
from oxidation and give rise to good stability even when exposed
in air for 2 days. Upon Li plating, Li metal was inclined to nucleate
at the edges of MXene flakes first, followed by horizontally growth
along the nanosheets, leading to the formation of smooth and
dense Li cobblestones finally. No Li dendrite growth was observed
during the >100 cycles of repeating Li plating and stripping pro-
cess. It was demonstrated that the parallelly aligned MXene layers
not only enabled the unform Li nucleation and growth, but also led
to the formation of a dense and uniform SEI layer due to the pres-
ence of large amount of LiF, which was derived from the abundant
N. Lucero, D. Vilcarino, D. Datta et al.
F terminations on MXenes. The parallelly aligned MXene layer pro-
tected LMAs delivered a long cycle life up to 900 h and excellent
deep stripping/plating capabilities up to 35 mAh cm 2. In a control
experiment, the vacuum-assisted MXene films were used as the
artificial protection layer, delivering a short cycle life of 120 h
due to their numerous lifting edges. The results indicated the
importance of parallel alignment of MXene flakes. In an alternative
approach, nondelaminated multi-layer Ti3C2Tx MXene particles
were coated on Li metal through a similar rolling-transfer process
and served as the protection layer [129]. Rather than parallelly
aligned MXene layers, here, the multi-layer MXene particles were
randomly dispersed with each one displayed plenty of interlayer
spacings, which provided sufficient room to store Li. The MXene
coatings on Li metal provided a fast electron and Li ion transport
while the interlayer limited the Li growth along the perpendicular
direction, which largely mitigated the dendrite growth and gave
rise to a good cycle life over 1050 cycles at 10 mA cm 2 and 10
mAh cm 2.
The growth mechanism of Li metal on Ti3C2Tx MXene layers was
further investigated by combined ab initio calculations and exper-
imental observations, which showed a differed Li metal growth
mode compared to the one mentioned above (Fig. 10) [130]. The
Ti3C2Tx MXene layer with a thickness of 14 mm and flat surface
was obtained by casting a delaminated Ti3C2Tx slurry onto a Cu foil
by doctor blade. Ex-situ scanning electron microscopy observa-
tions revealed that the Li deposition on the MXene layers occurred
in two stages. First, heterogeneous Li nucleation started with Li
nucleates with a diameter of 0.5 mm (Fig. 10g), which grew hor-
izontally and formed smooth plates with a diameter of 5.0 mm
Fig. 10. (a) Schematic illustration of Li deposition on Cu foils. SEM images showing the morphological evolution the Li–Cu electrodes with a capacity of (b) 0.2, (c) 2.0, and (d)
5.0 mAh cm 2. (e) Top-view SEM image of a Li-Cu electrode after 300 cycles. (f) Schematic illustration of Li deposition on MXene films. SEM images showing the
morphological evolution the Li-Ti3C2Tx electrodes with a capacity of (g) 0.2, (h) 2.0, and (i) 5.0 mAh cm 2. (j) Top-view SEM image of a Li-Ti3C2Tx electrode after 300 cycles.
Reproduced from Ref. [130] with permission of WILEY-VCH.
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Journal of Energy Chemistry 69 (2022) 132–149
(Fig. 10h). After that, homogeneous Li deposition took place on
the Li plates, forming a uniform and continuous Li film on the
MXene layers (Fig. 10i and j). No dendrite formation was observed
after 300 cycles of repeating Li plating and stripping process. Ab
initio calculations indicated that for all three termination groups
on MXenes, only O can stay stable during Li deposition, while F will
be quickly consumed to form LiF during initial Li deposition and
OH did not allow Li deposition. During Li plating, nanometers-
thick transition layer of hcp-Li was deposited on the Ti3C2Tx MXene
layers first via ionic bonding, followed by the continuous deposi-
tion of body-centered cubic (bcc) Li via metallic bonding. The
growth of Li metal was preferentially along the (110) facet due
to the lattice matching between Ti3C2Tx and hcp-Li and then with
bcc-Li. The planar and dendrite-free growth mode of Li metal was
explained by the preferred thermodynamic factors including the
large dendrite formation energy and small Li migration barrier.
The blade-coated MXene layers delivered a stable cycle life over
500 h at 1.0 mA cm 2 and a wide working current density range
from 0.5 to 10.0 mA cm 2. The Li metal growth mechanism pro-
posed here is in good agreement with the observations on paral-
lelly aligned MXene films discussed above.
It has been mentioned that introducing superlithiophilic agents
on MXenes becomes an efficient strategy to further regulate the Li
plating/stripping behaviors to produce advanced LMAs. Using the
Lewis acidic molten salt ZnCl2 etching method, single Zn atoms
were successfully immobilized on Ti3C2Clx MXenes with a Zn con-
tent of 0.87% [131]. The large presence of Zn atoms guided the
homogeneous nucleation and plating of Li metal on the obtained
Zn-MXene layers. With continuing plating, the deposited Li grew
N. Lucero, D. Vilcarino, D. Datta et al.
vertically along the nucleated sites due to the strong electric field
at the Zn-MXene edges, affording bowl-like and even blocky Li,
but without Li dendrites. In comparison, many Li spheres with
sizes of 20 nm were grown at the edges of Ti3C2Tx MXene flakes,
which transformed into thick and flat Li layer with increasing Li
plating levels. When used for LMAs, the spray-coated Zn-MXene
films achieved a low overpotential of 11.3 ± 0.1 mV, deep strip-
ping/plating levels up to 40 mAh cm 2, and a long cycle life stabil-
ity over 1200 h at 1 mA cm 2 and 1 mAh cm 2, which was superior
to the Ti3C2Tx MXenes films under the same test conditions. Qian
et al. sputtered ultrafine and robust Au nanoparticles on filtered
Ti3C2Tx MXene papers, in which the Au layer acted as lithiophilic
nucleation agent to improve the homogeneous Li deposition
[132]. Compared to the MXene paper, the Au coated MXene (MXe-
ne@Au) paper achieved a more uniform deposition of Li metal and
a significantly lower nucleation overpotential from 42.7 mV to
nearly zero. As a result, the MXene@Au paper delivered a high
cycling stability over 650 h at 1.0 mA cm 2 and 1.0 mAh cm 2,
superior to that of >300 h for the MXene paper. The same group
also utilizes amorphous liquid metal (3 °C GaInSnZn) as coatings
on the Ti3C2Tx MXene paper to induce isotropic and more uniform
deposition of Li metal [133]. The Coulombic efficiency and perfor-
mance of symmetric cells are obviously improved both in ether-
based and carbonate-based electrolytes. A recent result indicated
that the lithiophilicity of MXene surface can be improved by tuning
the MXene composition from Ti3C2Tx to V2CTx [134]. DFT calcula-
tions showed that the Li ion diffusion barriers on V2CTx are smaller
than those on Ti3C2Tx. As a result, filtered V2CTx films were used as
the artificial protection layer for LMAs directly. In a Li/V2CTx-Cu
half cell, a high Coulombic efficiency of 96.3% after 180 cycles at
4 mAh cm 2 and 4 mA cm 2 and good rate capability with a
Coulombic efficiency of 96.9% up to 250 cycles at 10 mA cm 2.
The cell also showed a long cycling stability for over 1200 h at
1 mA cm 2 and 1 mAh cm 2. The work suggests that tuning the
stoichiometric composition of MXenes is also an effective method
to improve their electrochemical performance for LMAs.
3.3. Modification of separators
As an important component in rechargeable batteries, porous
separators are used to separate the cathode and anode, avoiding
the internal short circuit while allowing the repeated ion transport
through their pores. In LMBs, the uneven distribution of Li ion flux
through the separators is an important inducement for Li dendrite
growth, which may penetrate the separators, leading to internal
short circuit and even explosion. To solve these issues, methods
of modifying the separators using polymers or nanomaterials to
homogenizing Li ion flux, has become an effective strategy for
the development of stable and dendrite-free LMAs. In addition,
modification of the separators can lead to improved mechanical
and thermal transport properties, which makes the separators
more rigid to prevent the Li dendrite penetration and will be able
to withstand the thermal runaway caused by the internal short
circuit.
MXenes shows great potentials for application in separator
modification to stabilize the LMAs due to their advantages of
high-density lithiophilic surface terminations, high electrical and
ionic conductivity, as well as excellent mechanical strength against
Li metal. Besides, the 2D structure and applicability for solution
process of MXenes make them to be easily coated on separators.
However, compact stacking of MXene flakes will result in limited
pathways for Li ion diffusion and electrolyte infiltration. As a
result, when using MXenes to modify the separators, spacers
between MXene layers are usually introduced to prevent their
compact stacking and provide nanoporous channels for ion trans-
port. For example, negatively charged Ti3C2Tx MXenes were cou-
144
Journal of Energy Chemistry 69 (2022) 132–149
pled with positively charged polyethyleneimine (PEI)
functionalized CNTs in an aqueous solution, which was then fil-
tered on a commercial glass fiber (GF) separator as the functional
coatings [136]. The coated MXene/PEI/CNT hybrid layer exhibited
a uniform assembly with PEI/CNT intercalated between MXene
flakes as conductive linkers and lithiophilic pillars, creating a
nano-sandwich motif and accessible channels. The resulting
MXene/PEI/CNT modified GF separator showed a much smaller
contact angle compared to that modified by pure MXene layers,
indicating better electrolyte affinity and accessibility. Besides, the
specific surface area (SSA) of the MXene-based coatings was
increased from 25.8 m2 g 1 from pure MXene film to 268 m2 g 1
for the MXene/PEI/CNT hybrid layer, with a broad pore size distri-
bution in the range of 10–80 nm. During the tests in Li/Li symmet-
ric cells, the MXene/PEI/CNT modified separators delivered much
lower overpotential and better cycling stability compared to non-
modified GF separators, without obvious Li dendrite formation
for over 400 cycles when the current densities step-increased from
0.5 to 5 mA cm 2. It is interesting to note that the bare MXene
modified separators exhibited much higher overpotential com-
pared to the non-modified ones due to the high barrier for Li diffu-
sion. This confirmed that the 3D channels in the MXene/PEI/CNT
hybrids and lithiophilic PEI pillars can effectively guide the homo-
geneous Li ion flux and Li plating.
Porous carbon nanoparticles were also incorporated into the
Ti3C2Tx MXene layers for separator modification [137]. First, ZIF-
67 metal–organic framework (MOF) nanoparticles were in-situ
decorated on Ti3C2Tx MXene flakes, which was then transformed
into a porous carbon-decorated and N-doped MXene hybrids after
an in-situ nucleation and pyrolysis process. During the pyrolysis of
ZIF-67, the coordinated 2-methylimidazole acted as nitrogen
source to dope N atoms into the MXene nanosheets. The N-
Ti3C2Tx/C hybrids were coated on a commercial polypropylene
(PP) separator using the slurry-casting method, yielding the N-
Ti3C2Tx/C@PP separator. SSA of the N-Ti3C2Tx/C hybrid coating
was measured as 62.7 cm2 g 1, higher than that of pure Ti3C2Tx
films, indicating a more open structure for electrolyte infiltration.
During the tests in a Li-S battery with Li metal as the anode, the
cells with N-Ti3C2Tx/C@PP separator exhibited much better cycling
stability and high-rate capability compared to those using Ti3C2-
Tx@PP and PP separators. No Li dendrite growth was observed after
100 cycles at 0.1 C when using the N-Ti3C2Tx/C@PP separator. How-
ever, obvious growths of Li dendrites were observed when suing
Ti3C2Tx@PP and PP separators. The dendrite-free Li plating function
of the N-Ti3C2Tx/C@PP separator was further confirmed by tests in
Li/Cu cells, which was ascribed to the synergistic effects of N dop-
ing and porous carbon nanoparticle decoration on MXenes. The
homogeneous N heteroatoms performed as lithiophilic sites to reg-
ulate the Li ion flux through the separator, and the decorated car-
bon reduced the local current density during Li plating, further
suppress the growth of Li dendrites. In another work, Han et al.
modified the commercial PP separator by the hybrids of Ti3C2Tx
MXene and solid-state electrolyte Li1.3Al0.3Ge1.7(PO4)3 (LAGP). A
slurry of 80 wt.% LAGP nanoparticles, 10 wt.% Ti3C2Tx MXene, and
10 wt.% polyvinylidene fluoride (PVDF) binder was coated on the
PP separators with a doctor blade and dried in vacuum, yielding
the LAGP/MXene hybrid film modified separators (PP/
LAGP + MXene) with a coating thickness below 10 mm [135]. In
the hybrids, the MXene layers provided fast electron transport,
while the LAGP nanoparticles served both as the Li ion conductors
and spacers to prevent the compact stacking of MXene flakes. This
synergistic effect gave rise to the homogeneous Li ion flux through
the separator and led to uniform and dendrite-free Li plating
(Fig. 11). In addition, the LAGP can react with Li metal to form
stable SEI layer comprising Li3PO4, LiF, and Ge, which served as a
protection layer on the LMA. As a result, the symmetric Li/Li cell
N. Lucero, D. Vilcarino, D. Datta et al.
Fig. 11. (a) Schematic showing the dendritic Li deposition using a traditional porous PP separator and uniform planar-like Li deposition using the the LAGP/MXene-modified
PP separator. Cross-sectional and surface SEM images of the deposited Li metal with the (b) PP and (c) PP/LAGP + MXene separators. Reproduced from Ref. [135] with
permission of Elsevier.
with the PP/LAGP + MXene separator showed stable cycling for
over 1000 h at 1 and 2 mAh cm 2, exceeding that with the PP sep-
arator, which showed obvious voltage hysteresis increase after
250 h.
3.4. Electrolyte additives
In LMBs, the reaction between Li metal and the electrolyte will
induce the formation of the thin SEI layers. Since the formation of
SEI is mainly determined by electrolytes, the composition of elec-
trolytes plays an important role in forming a thin, stable, dense,
and elastic SEI layer to protect the LMAs. Therefore, the modifica-
tions of electrolytes, in terms of solvents, salts, and additives, have
been considered as the most effective strategy to stabilize the
LMAs [40,41]. In particular, inspired by the industrial electroplat-
ing technique, inorganic nanoparticles (e.g., nanodiamonds [138],
SiO2 [139], and TiN [140]) have been widely used as the additives
in LMB electrolytes to induce the uniform deposition of Li metals
based on the nanocomposite plating mechanism. As mentioned
above, MXene flakes showed great capability to be dispersed in
numerous aqueous and organic solvents to form stable colloidal
solution. Besides, considering their high lithiophilicity, low Li ion
diffusion barrier, good chemical stability against Li metal, and
excellent mechanical properties, MXenes possess huge potentials
as additives for LMB electrolytes to suppress the Li dendrite growth
for stable LMAs. One recent report demonstrates the excellent per-
formance of MXenes as additives in aqueous Zn-ion battery elec-
trolytes for stable and dendrite-free Zn-metal electrodes [141].
However, due to the presence of abundant hydrophilic surface ter-
minations, the dispersion of MXenes in conventional liquid LMB
electrolytes to form stable colloidal solution is still a great chal-
lenge. As a result, no report has been published on using MXene
additives in liquid electrolyte for LMBs so far.
145
Journal of Energy Chemistry 69 (2022) 132–149
On the other hand, the enriched surface terminations accompa-
nied with excellent electrical conductivity and multiple composi-
tions with differed properties give MXenes unlimited potentials,
exceeding other 2D materials, for the development of multi-
functional polymer nanocomposites. In this consideration, MXenes
have recently emerged as promising additives in polymer-based
solid electrolytes to fabricate advanced composite polymer elec-
trolytes (CPEs) for the development of advanced solid-state LMBs.
Pan et al. added a small amount of Ti3C2Tx into a poly(ethylene
oxide) (PEO)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)
complex to fabricate MXene-based CPEs [143]. The MXene addi-
tives inhibited the crystallization of PEO electrolyte, promoted its
segmental motion, and thus enhanced the ionic conductivity. A
small loading of 3.6 wt.% of MXenes led to the increase of ionic con-
ductivity from 9.47  10 6 S cm 1 for the MXene-free electrolyte
to 2.2  10 5 S cm 1 at 28 °C. The achieved conductivity was com-
parable to many other CPEs, but the required additive loading
amount was much smaller, indicating that Ti3C2Tx MXene was
more effective in enhancing the ionic conductivities of CPEs. Such
a low MXene loading also led to the negligible electrical conductiv-
ity, which is essential for solid electrolytes. A Li/Li symmetric cell
using MXene/PEO/LITFSI as the electrolyte and separator exhibited
a good cycling stability for over 100 h at 0.3 mA cm 2 at 60 °C, indi-
cating a stable CPE/Li interface. The full-cell all-solid-state LMB
fabricated with the ob obtained CPE also showed superior rate
capability and cycling stability, with a capacity of 92 mAh g 1 at
1C, 91.4% capacity retention after 100 cycles at C/3, and a high
Coulombic efficiency of >97%.
To reduce the electrical conductivity of MXene layers and
improve their dispersibility in the polymer electrolyte matrix,
mesoporous SiO2 (mSiO2) layer was directly grown on Ti3C2Tx
flakes via hydrolysis of tetraethyl orthosilicate (TEOS) under the
direction of CTAB, giving rise to monodispersed MXene based
N. Lucero, D. Vilcarino, D. Datta et al.
Fig. 12. (a) Schematic illustration of fabricating sandwich-like MXene-mSiO2 nanosheets. (b) Schematic illustrating the fabrication of the MXene-mSiO2 containing ePPO solid
polymer electrolyte. (c) Digital pictures of the MXene-mSiO2/ePPO composite electrolyte withstanding poking, twisting, and stretching. (d) Cycling stabilities of lithium
symmetric cells using the MXene-mSiO2 containing, mSiO2 containing, and ePPO solid polymer electrolytes at room temperature under 0.05 mA cm 2 and 0.05 mAh cm 2.
Reproduced from Ref. [142] with permission of WILEY-VCH.
mesoporous SiO2 nanosheets with sandwich structure (MXene-
mSiO2) (Fig. 12a). MXene-mSiO2 based CPEs were prepared by dis-
persing the MXene-mSiO2 nanosheets in liquid poly(propylene
oxide) elastomer (ePPO) at 150 °C, followed by swelling LiTFSI salt
and propylene carbonate (PC) (Fig. 12b) [142]. The obtained CPEs
had a maximum 210% stain at a tensile stress of 0.34 MPa and a
high Young’s modulus of 10.5 MPa, superior to that of pure ePPO
and Si/ePPO electrolytes. The obtained solid electrolyte also
showed good mechanical flexibility and robustness (Fig. 12c). The
much improved mechanical properties of the MXene-mSiO2 based
CPEs were attributed to the strong hydrogen-bonding interaction
between the MXene/mSiO2 nanosheets and ePPO polymer. A high
ionic conductivity of 4.6  10 4 S cm 1 at room temperature was
achieved with 30 wt.% of LiTFSI and 2 wt.% of MXene-mSiO2. This
can be attributed to numerous Lewis acid-base interactions
between MXene-mSiO2 nanosheets and LiTFSI with the large pres-
ence of F from Ti3C2Tx MXene and OH from mSiO2, leading to the
construction of highways of Li ion transport at the MXene-
mSiO2/ePPO interfaces. Electrochemical tests of Li/Li symmetric
cells with the MXene/mSiO2 based CPEs revealed an ultralong
and stable cycling stability up to 2000 h at 0.05 mA cm 2 with
an initial overpotential of 19.2 mV, much superior to that of pure
ePPO and mSiO2 containing electrolytes (Fig. 12d). This demon-
strated the successful suppression of Li dendrite growth upon
ultralong Li plating/stripping cycling, which was ascribed to the
high Young’s modulus, good electrochemical stability, and high
ionic conductivity of the MXene-mSiO2 based CPEs. The stable
LMAs induced by the MXene-mSiO2 based CPEs were further
demonstrated by the excellent cycling stability of the full-cell
146
Journal of Energy Chemistry 69 (2022) 132–149
LMBs, which showed 92% capacity retention after 250 cycles
under 0.5 C at room temperature. Furthermore, safety of the
MXene/mSiO2 based CPEs for LMBs was demonstrated by hammer,
bending, and cutting tests on the corresponding all-solid-state
pouch cells. Progresses on using Ti3C2Tx MXene as the additive to
develop advanced CPEs for stable LMBs can be extended to a family
of MXenes with differed stoichiometry and plentiful while tunable
surface function groups towards various high Li+-conducting solid
polymer electrolytes.
4. Conclusions and perspectives
In the past several years, MXenes have been widely used and
showed great potential to stabilize LMAs and suppress the growth
of Li dendrites. Not only MXenes, but also their derivatives and
MXene-based hybrids/nanocomposites, have been served as effec-
tive Li hosts with a large Li loading. As the Li hosts, the mechanical
stability of MXene-based 3D frameworks can be significantly
improved by inducing cross-linking polymers or graphene-based
materials. The dense and thin MXene layers could serve as promis-
ing artificial protection layers on LMAs due to their lithiophilic sur-
face, high electrical conductivity, and excellent mechanical
stability again Li metal. The thin MXene layers can also be used
to modify the separators to regulate and homogenize the Li ion flux
to enable the uniform deposition of Li metals. However, lithiophilic
nanoparticles should be introduced between the MXenes layers to
create electrolyte and ion diffusion pathways first. As a strong and
conductive 2D material with abundant surface functional groups,
N. Lucero, D. Vilcarino, D. Datta et al.
MXenes are promising to be filled in solid polymer electrolytes to
enhance the ionic conductivity and mechanical strength. The uti-
lization of MXenes has obviously relieved the inherent issues of
LMAs, generating stable and dendrite-free LMAs with significantly
improved electrochemical performance in both symmetric Li/Li
cells and full-cell LMBs. For all the MXene-modified LMAs, lithio-
philic atoms or nanoparticles (e.g., N atoms, Zn atoms, Zn nanopar-
ticles, Si, porous carbon) can always be incorporated into the
MXene frameworks to further improve their electrochemical
performance.
Many challenges still exist. First, most of the reported efforts
mainly focused on a single composition, Ti3C2Tx MXene, with only
two exceptions. Further investigations on the effects of other stoi-
chiometric MXenes for the development of advanced LMAs are
desired. Second, as discussed above, the surface terminations of
MXenes play a dominating role in the electronic properties of
MXenes. Consequently, they will also show a significant influence
on the Li nucleation and deposition behavior. It has been reported
that OH termination does not allow Li deposition, while O stays
stable and acts as lithiophilic sites for Li nucleation and growth
and F termination would induce the formation of LiF-reinforced
SEI layer. Further understanding of the effects of multiple surface
functional groups on Li nucleation and deposition is still needed.
Moreover, investigations on controlling the MXene surface termi-
nation to achieve a better regulation of Li deposition are suggested,
for the purpose of optimizing the electrochemical performance of
modified LMAs. Third, the effect of MXene content in the MXene/
Li composite anodes on their Li-ion storage capacity and the
resulted battery energy density is still unknown. Considering the
relatively lower capacity of MXenes compared to Li metal [24],
there should be an optimized MXene fractions in the composite
anodes. Finally, it is known that most MXenes are easy to be oxi-
dized in an oxidizing environment, which leads to a significant
change in their electron/ion transport and surface properties,
greatly affecting the Li deposition behavior. More attention should
be paid to this issue.
Currently, liquid electrolyte modification has become one of the
most promising strategies for advanced LMAs due to their lowest
obstacle for commercialization. However, application of MXenes
in this aspect is seriously hindered by their limited solubility in
LMB electrolytes. Modification of MXene surface terminations to
enable their stable dispersion in LMB electrolytes for stable and
dendrite-free LMAs based on the nanocomposite electroplating
mechanism will be an interesting direction. With the initial pro-
gress, the use of MXenes as additives to develop advanced solid-
state electrolytes for next-generation solid-state LMBs deserves
more efforts. However, due to the high electrical conductivity of
MXenes, the concentration of MXene additives in the electrolyte
cannot be too high to avoid the cell shorting.
Among the four strategies discussed, the use of MXenes as elec-
trolyte additives should show the greatest potential towards the
practical application of MXene-modified LMAs, since it will intro-
duce few changes in the current battery fabrication process. How-
ever, as mentioned above, the stable dispersion of MXenes in LMB
electrolytes is an obvious obstacle and needs to be resolved first.
Consequently, the use of MXenes for artificial protection layers
shows better practical potential currently due to their easy, yet
effective, and scalable fabrication process. Besides, electrochemical
tests in more realistic battery systems, such as pouch cells rather
than the laboratory coin cells, are highly suggested to achieve a
better reflection of the practical application ability. For the large-
scale operation of LMBs, the thermal safety is an important issue
to concern. It has been demonstrated that the MXene-based LIB
anodes showed reduced heat generation with electrolyte and
improved onset temperature of thermal runaway in LIB full cells
compared to graphite anodes [144]. Analysis on the roles of
147
Journal of Energy Chemistry 69 (2022) 132–149
MXenes, particularly the MXene modification layer for separators,
for blocking cell thermal runaway in LMBs is highly desired and yet
to be carried out. Furthermore, considering the high reactivity of Li
metal, the use of MXenes to stabilize and isolate LMAs from water
and air should also be a promising research topic, which would
benefit the handling of LMAs and their use in electric vehicles. In
general, the applications of MXenes in the development of stable
and dendrite-free LMAs are still in the infant stage and the poten-
tial is truly enormous.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This work was supported by the NJIT Start-Up Funds and Fac-
ulty Seed Grant. The authors acknowledge the help from Dr. Bing
Hao with editing the figures.
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