Review

Progress of MXene‐Based Materials in the Field of

Rechargeable Batteries
Jianfei Gao, Jing Li, Qian Wang * and Cheng Zou *

Institute for Advanced Materials and Technology, University of Science and Technology Beijing,
Beijing 100083, China; m202411392@xs.ustb.edu.cn (J.G.); m202421618@xs.ustb.edu.cn (J.L.)
* Correspondence: b2286713@ustb.edu.cn (Q.W.); zoucheng@ustb.edu.cn (C.Z.)

Abstract: With the rapid development of electrical energy storage technologies, tradi‐
tional battery systems are limited in practical applications by insufficient energy density
and short cycle life. This review provides a comprehensive and critical summary of
MXene or MXene‐based composites as electrode materials for high‐performance energy
storage devices. By integrating the synthesis techniques of MXenes that have been stud‐
ied, this paper systematically illustrates the physicochemical properties, synthesis strat‐
egies, and mechanisms of MXenes, and analyzes the bottlenecks in their large‐scale
preparation. Meanwhile, it collates the latest research achievements of MXenes in the
field of metal–ion batteries in recent years, focusing on integrating their latest progress
in lithium–ion, sodium–ion, lithium–sulfur, and multivalent ion (Zn2+, Mg2+, Al3+) batter‐
ies, and reveals their action mechanisms in different electrode material cases. Combining
DFT analysis of the effects of surface functional groups on adsorption energy with ex‐
perimental studies clarifies the structure–activity relationships of MXene‐based compo‐
sites. However, the development of energy storage electrode materials using MXenes
and their hybrid compounds remains in its infancy. Future development directions for
MXene‐based batteries should focus on understanding and regulating surface chemistry,
investigating specific energy storage mechanisms in electrodes, and exploring and de‐
veloping electrode materials related to bimetallic MXenes.

Academic Editor: Alessandro

Keywords: transition metal carbides; rechargeable batteries; reversible capacity;
Dell’Era electrode materials; carbide MXene

Received: 10 April 2025

Revised: 10 May 2025
Accepted: 16 May 2025
Published: 20 May 2025 1. Introduction
Citation: Gao, J.; Li, J.; Wang, Q.; Over the past few decades, with rapid technological advances and the constant de‐
Zou, C. Progress of MXene‐Based pletion of fossil fuels, there has been a growing demand for sustainable energy sources
Materials in the Field of [1]. From various portable electronic devices to large‐scale energy storage systems, re‐
Rechargeable Batteries. Materials
chargeable batteries have become the foundation of modern green life and progress [2].
2025, 18, 2386. https://doi.org/
However, current battery technology faces challenges such as low energy density, short
10.3390/ma18102386
cycle life, poor stability, and insufficient safety, which severely limits the application of
Copyright: © 2025 by the authors.
batteries in high‐power scenarios where they have to be charged and discharged quickly
Licensee MDPI, Basel, Switzerland.
[3,4]. Therefore, it is urgent to further improve the performance of the battery, and tradi‐
This article is an open access article
distributed under the terms and
tional anode materials such as graphite are close to their theoretical capacity limits [5,6].
conditions of the Creative Commons Metal–air batteries (zinc–air batteries) and metal–ion batteries (lithium, sodium,
Attribution (CC BY) license zinc plasma batteries) are the two major branches in the field of rechargeable batteries.
(https://creativecommons.org/license Taking the zinc–air battery as an example, it stores energy through the electrochemical
s/by/4.0/).

Materials 2025, 18, 2386 https://doi.org/10.3390/ma18102386

Materials 2025, 18, 2386 2 of 49

reaction between the zinc anode and oxygen in the air, and its theoretical energy density
is much higher than that of a lithium–ion battery (5928 Wh/kg for lithium‐air battery)
[7]. However, its practical application is limited by the design of bifunctional catalysts
(e.g., high cost of noble metal Pt/Ir and carbon carrier corrosion), CO2 sensitivity of the
electrolyte, and cycling decay due to zinc dendrite growth [7]. In contrast, metal–ion
eliminates the need for external oxygen and offers advantages in cycle life, power densi‐
ty, and process maturity.
Since its first report in 2011, MXene, an emerging two‐dimensional material, has
demonstrated remarkable potential in the field of electrochemical energy storage [8].
Characterized by a high specific surface area, excellent electrical conductivity, good me‐
chanical properties, abundant surface functional groups, and a controllable layered
structure, MXene offers higher theoretical capacity, faster ion transport efficiency, and
better stability than traditional battery materials [9,10]. These advantages position
MXene as a promising candidate for advancing next‐generation energy storage technol‐
ogies. However, there are still major challenges for its practical application. First, the
process of large‐scale preparation of MXene is immature, and most of the preparation
methods are restricted to experiments. Second, MXene as an electrode material may
produce accumulation between layers during charging and discharging, which may
even lead to severe oxidative degradation at high current densities, affecting the perfor‐
mance of the battery [11,12]. Enhancing the interfacial compatibility of MXene with oth‐
er active electrode materials to avoid side reactions is also one of the current keys to im‐
prove battery performance. To address these challenges, many strategies have been ana‐
lyzed and proposed, including synthesizing and using a single extremely thin MXene
lamella, extending the MXene lamella spacing to achieve tunability, constructing hetero‐
geneous/composite electrode materials with MXene as the substrate and designing dif‐
ferent electrode structures, and expanding the bridging between active materials and
MXene [13,14]. By modifying and functionalizing MXene to improve its interfacial inter‐
action with electrolytes, or by optimizing its surface functional groups to enable effective
compositing with other high‐capacity electrode materials, the cycling stability and
charge transfer efficiency of MXene‐based batteries can be significantly enhanced [15].
One of the most common applications of MXene is as a conductive substrate for compo‐
site electrodes, where its abundant surface functional groups enable the grafting or
growth of other electrochemically active materials—such as transition metal oxides, sul‐
fides, and other compounds—thereby constructing multidimensional conductive
frameworks [15–17]. These materials are chemically synthesized by physical mixing, in
situ growth, or solvothermal methods, or self‐assembled into strong transition layers
and covalently bonded heterogeneous structures by electrostatic interaction [18,19]. The
special electronic structure and variable valence states of electrochemically active phases
provide high‐capacity storage sites, which effectively promote charge transfer and im‐
prove electrochemical performance [18,20].
In 2011, MXene was discovered and began to be noticed and used as a new material
for metal–ion batteries; in 2014, a breakthrough was made in MXene‐based aluminum–
ion batteries (AIBs), which provided a direction for MXene to be explored in MVIBs; in
2016, preliminary lithium–ion research was launched, and MXene’s material properties
were explored in depth; in 2018, MXene‐based magnesium–ion batteries (MIBs) ap‐
peared and attracted attention; in 2019, the MXene‐based zinc–ion battery (ZIB) was pi‐
oneered as an application of MVIB; in 2021, the multivalent–ion battery (MVIB) was
commercialized, which could not be separated from the success of MXene’s many years
of research accumulated in various ion battery systems. Currently, with the deepening
of research, the performance of MXene combined with ion batteries has been optimized,
and the application prospect is becoming more and more promising. These key points in
Materials 2025, 18, 2386 3 of 49

chronological order clearly show the complete development of MXene and ion batteries
from material discovery, and technological breakthroughs to application expansion and
commercialization, as shown in Figure 1.
This review aims to systematically summarize the latest research advancements of
MXene in the field of metal–ion batteries in recent years, detailing its structural‐
performance characteristics and synthesis methodologies. The synthesis approaches for
MXene are categorized into three types based on fluorine usage: “fluorine‐based etch‐
ing”, “fluorine‐free etching”, and “fluorine‐free synthesis”. A comparative analysis is
conducted to evaluate how different etching methods influence MXene’s surface func‐
tional groups and the number/thickness of its nanosheets. Additionally, the bottlenecks
in large‐scale MXene preparation are systematically analyzed, with a focus on decipher‐
ing the mechanisms of fluorine‐free etching techniques to provide a theoretical founda‐
tion for green synthesis and functional modification. The review integrates the recent
progress of MXene in lithium–ion, sodium–ion, lithium–sulfur, and multivalent ion
(Zn2+, Mg2+, Al3+) batteries, revealing its multifunctional roles in different systems—such
as anchoring polysulfides in lithium–sulfur batteries, regulating ion diffusion pathways,
and inhibiting lithium dendrite growth. By combining density functional theory (DFT)
analysis of surface group effects on adsorption energy with experimental results, the
structure–activity relationships of MXene‐based composites are clarified, highlighting
the interplay between material structure and electrochemical performance. Finally, the
review outlines future development directions for MXene‐based batteries, proposing
critical perspectives and suggestions to inspire research in electrochemical energy stor‐
age systems. These insights aim to guide advancements toward more efficient, sustaina‐
ble, and high‐performance energy storage technologies.

Figure 1. Timeline of representative MXene breakthroughs in MIBs in recent years.

2. Properties of MXene
MXene materials have attracted considerable attention due to their exclusive prop‐
erties, including high electrical conductivity, good mechanical properties, outstanding
thermal stability, and hydrophilicity [21,22]. Moreover, they typically possess abundant
surface functional groups (‐OH, ‐O, ‐F, etc.), providing numerous active sites that endow
them with remarkable surface reactivity and tunability. Coupled with their unique two‐
dimensional layered structure, these characteristics render MXene materials highly
promising for wide applications in energy storage/conversion [23,24], sensors [25], catal‐
ysis [26], and electromagnetic shielding [27], etc.

2.1. Structure of MXene

MXenes are transition metal carbides, nitrides, and carbon–nitrides with an
Mn+1XnTx formula, whose precursors were commonly designated as MAX phases [28]. As
shown in Figure 2a, M represents early transition metal atoms, including any one of Sc,
Ti, V, Cr, Mn, Zr, Nb, Mo, Hf, Ta, and W; A mainly consists of metallic and nonmetallic
elements between the second and the fourth main groups, such as Al, Si, P, S, Ga, Ge,
As, Cd, In, Sn, T, and Pb; X sites can be occupied by carbon, nitrogen, or both; n can vary
Materials 2025, 18, 2386 4 of 49

from 1 to 4, and Tx (where x is variable) indicates surface terminations on the surface of

the outer transition metal layers [29].

Figure 2. (a) Distribution of possible constituent elements of MXene in the periodic table. (b)
Crystal structure of MXene obtained from MAX. Reproduced with permission [30]. Copyright
2013, Wiley‐VCH.

The Mn+1AnX phase is a typical ternary layered ceramic, abbreviated as the MAX
phase. MAX phases are classified into three distinct hexagonal crystal structures (space
group P63/mmc) according to the value of n, as 211, 312, and 413 [30,31]. It is well dis‐
played in Figure 2b that the number of atomic layers between two layers of A atoms var‐
ies, and there is always one less layer of X atoms than M atoms during the periodic ar‐
rangement of M atoms under different structures. The MAX phase exhibits an alternat‐
ing stacking sequence of A atom layers and M(n+1)Xn layers in space, where (n + 1) close‐
packed layers of M atoms form octahedral coordination polyhedra with X atoms filling
the octahedral interstitial sites [30,32]. For example, Ti2AlC is the simplest MAX phase. It
is formed by the alternate stacking of Ti‐Al‐Ti‐C atomic layers in space. The C atoms are
distributed between two adjacent layers of Ti atoms, composing a three‐atomic‐layer‐
arranged Ti‐C‐Ti structural microdomain. These microdomains are periodically interca‐
lated by monolayer Al atomic sheets [33]. Among them, the M‐X bond in the MAX phase
has the mixed characteristics of ionic, covalent, and metallic bonds, while the M‐A bond
is purely metallic in nature. Since the bond energy of the M‐A bond is relatively weaker
than that of the M‐X bond, the M‐X atomic layers can be retained by chemically etching
the M‐A bond, thereby obtaining a two‐dimensional layered structure similar to gra‐
phene. However, unlike graphene, the M‐A bond still belongs to a chemical bond, and
its bond energy is much greater than the van der Waals force between the two‐
dimensional graphene layers, so it is difficult to separate it by mechanical methods [34].
About the predominant approach for MXene synthesis, the A layers with relatively
weak bond energy in the MAX phase can be selectively etched by chemical means and
replaced by active functional groups, resulting in three‐layer or multi‐layer M‐X‐M
nanosheets with various functional groups on the surface, called Mn+1XTx.

2.2. Conductivity
In 2004, Geim and Novoselov first isolated single‐layer graphene, marking the ad‐
vent of the two‐dimensional materials era [35]. Two‐dimensional materials have highly
efficient heat and charge transfer in the in‐plane direction. MXene is not only structural‐
ly similar to two‐dimensional graphene, but its metal layers also possess excellent con‐
ductive properties [35]. MXene surface functional groups have a strong influence on the
electrical conductivity. When electrons are transferred from M‐metal to the surface of
MXene, the Fermi energy level of Mn+1XnTx without surface functional groups will move
Materials 2025, 18, 2386 5 of 49

downward, and the electrical conductivity will be reduced, and all MXenes without sur‐
face groups theoretically exhibit metallic properties. Therefore, the conductivity of
MXenes can be adjusted by adjusting the type and number of surface functional groups
[36,37]. R et al. [38] employed hydrogen plasma treatment to make the ‐OH groups on
the surface of MXene react and neutralize with H atoms, obtaining the surface‐exposed
Ti3C2 MXene without terminal groups. It was found that the resistivity of MXene de‐
creased from 5.64 μ Ω m to 4.62 μ Ω m. Subsequently, O2 plasma treatment was carried
out to form new functional groups (=O) on the surface, and at this time, the resistivity
increased to 5.71 μ Ω m. During the etching process, the M‐A bonds will break, and the
outermost electrons of the surface metal atoms are in an approximately unmatched tran‐
sition state. At this moment, the surfaces of some MXenes will be terminated and trans‐
formed into semiconductors [38,39]. Therefore, the high conductivity of MXene materi‐
als mainly depends on the density of states near the Fermi level of the M‐layer atoms.
When the surface functional groups of MXenes are the same, their electrical conductivity
mainly depends on the type of M atoms in MXene.
Moreover, in addition to the reactive groups with M atoms, X atoms also have a
large effect on the electrical conductivity of MXene materials. Zhang et al. [40] calculated
the DOS of Tin+1CnT2 and Tin+1NnT2 at the Fermi energy level (EF) (T = ‐F, =O, ‐OH; n =
1,2,3). The results show that the Fermi energy levels of the nitride MXenes are higher
than those of the carbide MXenes regardless of the termination groups and that the ni‐
tride MXenes have higher electrical conductivity which can be attributed to the fact that
N possesses more electrons than C [40,41]. This is due to the fact that the M and X atoms
of MXene are covalently bonded, and the electrons within the covalent bond form an en‐
ergy band structure, with the discrete electrons moving through the valence band to
produce electrical conductivity. The N atom has more electrons than the C atom, which
gives the nitride MXene a higher electrical conductivity [42].

2.3. Hydrophilicity
The principal factors defining the hydrophilicity of MXenes are the surface terminal
groups’ hydrophilic capability. Therefore, the rational selection of the etching process is
critical, as the chemical etching of MAX phases generates abundant hydrophilic func‐
tional groups (‐OH, ‐O, and ‐F terminations) that can form a large number of hydrogen
bonds with water molecules [43]. In aqueous ion batteries, these hydrogen bonds inter‐
act with electrolyte solvent molecules, significantly enhancing the electrode material’s
wettability toward the electrolyte, and lead to the reduction of interfacial contact re‐
sistance, which consequently accelerates the transport of hydrated ions [44,45]. Notably,
in multivalent ion batteries (MIBs), the electrostatic screening effect induced by polar
functional groups can effectively suppress the Coulombic repulsion during the intercala‐
tion of high‐valence ions (HVIs). In addition, hydrogen bonding between these hydro‐
philic functional groups reinforces interlayer adhesion to alleviate volume expansion
and structural degradation during cycling, and enables hydration‐mediated interlayer
spacing expansion, which creates diffusion channels for large‐radius ions (K+, Zn2+) and
thereby enhances rate performance [44–46]. It is understood from the mentioned find‐
ings that the pronounced hydrophilicity of MXenes ensures both stable colloidal disper‐
sion and rapid ion transport kinetics in aqueous electrolytes. For non‐aqueous systems,
however, precisely balanced amphiphilicity is required to prevent detrimental water ab‐
sorption that would trigger particle aggregation or parasitic side reactions. Most nano‐
materials exhibit intrinsic hydrophobicity, leading to mutual aggregation driven by van
der Waals forces, which severely restricts their further applications. Consequently,
MXenes emerge as a promising candidate for diverse nanocomposite architectures.
Materials 2025, 18, 2386 6 of 49

2.4. Mechanical Properties

The MXene lamellae themselves exhibit excellent mechanical properties due to their
unique structure [47]. This is because after the A layer atoms are chemically etched
away, the electrons are more concentrated between the M‐phase and the X‐phase. As
mentioned above, the M‐X bond is a chemical bond that is a mixture of multiple bonds
and tends to be metallic, with a high binding strength. Its tensile stiffness ranges from
81.71 to 561.4 N/m, surpassing traditional two‐dimensional materials including gra‐
phene [48]. It is worth noting that after etching, MXene can be transformed from multi‐
layer accordion‐like MXene into single‐layer or few‐layer nanosheets by inserting organ‐
ic molecules or other metal ions between the layers [49]. When the constituent elements
are the same, the number of layers of different MXene lamellae will also affect their me‐
chanical properties. However, due to the extremely small size of MXene nanosheets, the
problem of stacking is highly likely to occur, leading to a decline in mechanical and elec‐
trochemical properties. Adding conductive spacers between MXene lamellae to con‐
struct a special layered structure is one of the effective ways to solve the above problems
and effectively improve the mechanical properties of MXene‐based composites. Jiao et
al. successfully constructed a continuous honeycomb‐like conductive network structure,
a waterborne polyurethane/natural rubber/Ti3C2Tx (WPU/NR/MXene) composite film
with flexibility and certain self‐healing properties, by using electrostatic repulsion inter‐
action and vacuum‐assisted filtration [50]. Although the content of MXene is only 5.48
vol% compared with the WPU/NR film without MXene, the WPU/NR/MXene composite
film has an increase of 10.3 times and 8.8 times in tensile strength and toughness, respec‐
tively. Similarly, Luo et al. employed a double‐crosslinking method. They crosslinked
and modified MXene with dopamine, and then introduced Ca2+ in situ into the obtained
layered composite film to further form ionic bond crosslinking between CNF (Cellulose
Nanofibrils) and MXene [51]. The results showed that this double‐crosslinking compo‐
site film strategy enhanced both the toughness and strength of the film, increasing them
from 72.66 MPa and 3.85 MJ/m3 to 142.2 MPa and 9.48 MJ/m3, respectively, significantly
improving the mechanical stability.

3. Preparation Methods
The preparation of two‐dimensional MXenes is mainly obtained by treating their
precursor MAX phase. As can be seen from the above, in the MAX phase, the metallic
M‐A and M‐X bonding energies are much larger than the van der Waals forces, which
makes it difficult to fabricate MXenes by conventional mechanical stripping techniques;
however, the metallic M‐A bonding is weaker than that of the M‐X bonding, which has a
mixed bonding, and therefore the “A” layer can be selectively removed to form the
Mn+1XnTx phase [30]. In 2011, Professor Gogotsi’s team at Drexel University successfully
obtained an accordion‐shaped Ti3C2Tx MXene through the use of HF etching of the alu‐
minum atomic layer in Ti3AlC2 MAX, thereby paving the way for significant advance‐
ments in MXene materials research and applications [8]. Later, various etching methods
have been used to prepare MXene with different structures, and these different etching
methods can be categorized into two main groups according to whether they contain
fluorine or not. In the early stage, the etchant for preparing MXene mainly involves fluo‐
rine‐containing compounds, such as HF, LiF + HCl, and fluorine‐containing molten salts
[52]. Due to the properties of these compounds, three key surface termination groups of
MXenes were identified, namely ‐F, ‐OH, and ‐O groups. Fluorine‐containing etching
methods appeared the earliest, with high yields suitable for large‐scale production and
various uses, including and not limited to HF etching, in situ generation of HF etching,
fluorine‐containing molten salt etching, and so on; as opposed to the earliest production
of non‐fluorinated MXenes using electrochemical etching as early as in 2017, and with
Materials 2025, 18, 2386 7 of 49

this there has been the emergence of other fluorine‐containing etching such as alkali
etching, non‐fluorine‐containing molten salt etching, and recently emerging alternative
fluorine‐containing etching such as Lewis acid molten salt etching, and other emerging
methods of substituting fluorine‐containing etching [53–55]. In addition to the top‐down
etching methods mentioned above, CVD (chemical vapor deposition) for assembling
MXene nanomaterials tailored to specific properties from atomic or molecular sizes is
considered a special bottom‐up synthesis method [56]. In this paper, MXene synthesis
methods are categorized in detail according to the degree of fluorine usage. And the ef‐
fects of different etching methods on the functional groups on the surface of MXene and
the number/thickness of laminae were compared, as shown in Table 1.

3.1. Etching with HF and F Salts

Naguib et al. first adopted HF to etch Ti3AlC2 [57]. The mechanism is shown in
Figure 3a. Relying on the relatively strong reactivity between F ions and Al ions, the M‐
Al bonds are broken to form AlF3, thereby selectively etching away the aluminum layer.
This process is accompanied by the generation of hydrogen gas at the same time, and fi‐
nally the accordion‐like MXene material is obtained [58]. The layers are mainly connect‐
ed by van der Waals forces and hydrogen bonds of surface active groups. The reaction
equation is shown as follows:
Ti3AlC2 + 3HF = AlF3 + 1.5H2 +Ti3C2 (1)

Ti3C2 + 2HF = Ti3C2(F)2 + H2 (2)

Ti3C2 + 2H2O = Ti3C2(OH)2+ H2 (3)

Ti3C2 + 2H2O = Ti3C2(O)2+ 2H2 (4)

First, the Al layer is selectively removed from the Ti3AlC2 MAX phase containing Al
to generate an unsaturated structure of Ti3C2. After the Al atoms are selectively etched
away by F ions, the Ti atoms with unsaturated charges on the surface of Ti3C2 are highly
prone to bond with atoms such as ‐OH, ‐F, and ‐O, endowing its surface with abundant ‐
OH and ‐F groups, thus generating a rich group of surface functional groups. With the
in‐depth progress of research, people have successfully etched a variety of MAX phases
based on HF, resulting in many new MXene materials, such as Ti3C2Tx [59], Ti2CTx [60],
V2CTx [61], Nb2CTx [62,63], Zr3Al3C5 [64], Ta4C3Tx [64], and Mo2C2Tx [65,66]. As shown in
Figure 3c, the morphologies of several MAX phases (Ti2AlC, Mo2TiAlC2) and several
MXene phases (Ti3C2Tx, Ti2CTx, Mo2TiC2Tx, V2CTx) are presented. It can be observed that
they all exhibit similar accordion‐like morphological characteristics, indicating that the
products after etching with hydrofluoric acid possess a certain universality. Figure 3b
shows the XRD patterns of the sample Ti3AlC2 before and after etching with hydrofluor‐
ic acid [57]. The disappearance of the characteristic peak at 39° is due to the fact that HF
selectively etches away the Al layer in Ti3AlC2, causing the remaining Ti3C2 structure to
be reorganized or deformed, and thus the original characteristics of the crystal structure
disappear. Meanwhile, the diffraction peak of the (002) crystal plane shifts to a lower
angle. According to the Bragg equation (nλ = 2d sinθ), the decrease in the diffraction an‐
gle means an increase in the interlayer spacing d. This increase may be attributed to the
fact that the removal of the Al layer reduces the charge‐balancing force between the lay‐
ers, thereby weakening the force between the Ti3C2 layers and leading to an expansion of
the interlayer spacing in the crystal structure. All these indications prove the generation
of the new two‐dimensional material MXene.
However, it is often difficult to obtain the desired single‐layer MXene by this meth‐
od. The greater the bond energy between M and A, the more and thicker the MAX phase
Materials 2025, 18, 2386 8 of 49

lamellae are, the stricter the etching conditions with HF will be, and the lower the yield
will be [67]. Although the direct use of HF etching has the advantages of simple process
and high yield, the use of highly hazardous, highly polluting, and highly corrosive HF
in the etching process is increasingly inconsistent with the concept of green develop‐
ment. Therefore, greener and safer preparation methods are needed for substitution.

Figure 3. (a) Schematic of the principle of using HF etching or in situ generation of HF etching.
Green, light blue, brown, and red balls represent M, A, X, and T atoms, respectively. XRD images
of Ti3AlC2 before HF treatment (simulated as XRD of Ti3C2F2 and Ti3C2(OH)2) and after HF treat‐
ment and measured by ultrasonic stripping. Reproduced with permission [58]. Copyright 2022,
The Royal Society of Chemistry. (b) XRD images of Ti3AlC2 before HF treatment (simulated as
XRD of Ti3C2F2 and Ti3C2(OH)2 and after HF treatment and measured by ultrasonic stripping. Re‐
produced with permission [57]. Copyright 2011, Wiley‐VCH. (c) SEM images of various MXene
and MAX: (i) Ti2AlC(MAX). Reproduced with permission [60]. Copyright 2023, Springer Nature.
(ii) Mo2TiAlC2(MAX). Reproduced with permission [65]. Copyright 2015, American Chemical So‐
ciety. (iii) Ti3C2Tx. Reproduced with permission [59]. Copyright 2015, American Chemical Society.
(iv) Ti2CTx. Reproduced with permission [68]. Copyright 2013, American Chemical Society. (v)
Mo2TiC2Tx. Reproduced with permission [65]. Copyright 2015, American Chemical Society. (vi)
V2CTx. Reproduced with permission [61]. Copyright 2013, American Chemical Society. (d) Sche‐
matic of the process: etching of the MAX phase in a solution of acid and fluoride salts and washing
with water to adjust the pH to neutrality, the resulting precipitates have a clayey character. (e) (i)
TEM image of a few thin sheets of Ti3C2Tx with transverse dimensions up to a few hundred na‐
Materials 2025, 18, 2386 9 of 49

nometers. Very few defective regions are present. The inset shows the electron diffraction pattern
of the entire selected region (ii,iii) TEM images of single and bilayer flakes in the longitudinal di‐
rection, respectively. (f) Accordion‐like multilayered MXene particles. (d–f) Reproduced with
permission. Reproduced with permission [69]. Copyright 2014, Springer Nature. (g–i) SEM images
of (g) 8 h, (h) 16 h, and (i) 32 h etched Ti3AlC2 MAX phase and corresponding h‐Ti3C2 MXene. (j)
TEM micrograph of h‐Ti3C2 flakes after 16 h etching. (g–j) Reproduced with permission [70]. Cop‐
yright 2022, Elsevier.

Based on the etching mechanism, researchers first came up with the idea of replac‐
ing the direct use of HF acid with the method of generating HF in situ during the etch‐
ing process. Fluoride salts (such as LiF, NaF, KF, NH4F, etc.) are mixed with hydrochlo‐
ric acid or sulfuric acid, etc. Similarly, the F ions are utilized to interact with the A atoms
in the MAX phase to generate fluorides. It is worth noting that the cations in the fluoride
salts will act as mild intercalating agents to insert between the lamellae to reduce the van
der Waals forces, thereby obtaining few‐layer or even single‐layer MXene nanosheets
[69]. However, since these cations act as mild intercalating agents, single‐layer
nanosheets can be efficiently obtained only when the van der Waals forces between the
nanosheet layers are relatively small, that is, when there are only two or a few metal at‐
om transition layers. Ghidiu et al. first used a mixture of HCl and LiF to prepare MXene
[69]. The flowchart is shown in Figure 3d. Ti3AlC2 powder was etched at 40 °C, and then
exfoliated through dimethyl sulfoxide intercalation and ultrasonic vibration, resulting in
single‐layer to multi‐layer Ti3C2Tx MXene flakes (Figure 3e shows the TEM images of
single‐layer and double‐layer nanosheets). Observed under a transmission electron mi‐
croscope (TEM), it was found that the HCl/LiF mixture is similar to HF, and a similar ac‐
cordion structure was also produced during the etching process. Moreover, the lateral
size of the Ti3C2Tx flakes reaches from hundreds of nanometers to several micrometers,
and the thickness is between 1 nm and dozens of nanometers (Figure 3f). Notably, the
etching duration exerts profound influence on the resultant microstructure. When em‐
ploying NaBF4/HCl as the etchant, multi‐layer 2D flakes were obtained after 8 h (Figure
3g), while ultrathin nanosheets formed at 16 h (Figure 3h). Prolonged etching to 32 h
yielded AlF3‐coated agglomerates (Figure 3i), indicating structural degradation and un‐
desirable byproduct formation. TEM characterization revealed transparent Ti3C2
nanosheets with optimal structural integrity after 16 h etching (Figure 3j), demonstrating
this duration represents the processing optimum. Compared with HF etching, this
method is milder, and the obtained MXene flakes have larger sizes and fewer defects,
significantly optimizing the electrochemical properties and application potential of the
material.
To further explore the mechanism of the etching process of Ti3AlC and the interca‐
lation effect of cations, Kim et al. summarized different fluorine‐containing etching
methods such as HF, NH4HF2, and LiF/HCl, and proposed that the etching proceeds step
by step, that is, the etching of Al atoms in the inner layer only occurs when the adjacent
outer layer is exfoliated [71]. As shown in Figure 4a–c, the SEM images of the HF etching
process reveal that with continuous etching, the larger polycrystalline Ti3AlC2 particles
gradually decompose into smaller single‐crystal particles. After etching for 24 h, only
single‐crystal particles remain. By comparing the SEM images of the LiF/HCl etching
process (Figure 4d–f), a phenomenon similar to that of HF etching can be observed,
where the polycrystalline aggregates break down into finer crystals. However, com‐
pared with Ti3C2Tx prepared by HF etching, the interlayer distance of multi‐layer Ti3C2Tx
is significantly increased. Analyzing the XRD patterns of the two methods (Figure 4g,h),
the complete disappearance of the (002) peak of the MAX phase etched by HF indicates
that the exfoliation of the Ti3C2Tx layer has not been triggered. Similarly, NH4HF2 etching
Materials 2025, 18, 2386 10 of 49

has an effect similar to that of HF, but NH4HF2 provides the non‐fluorine cation NH4+ as
an intercalating agent to enter the MXene layer and forms a water‐soluble byproduct
(NH4)3AlF6, and the interlayer distance of its multi‐layer MXene is larger than that of HF.
The same conclusion can be drawn from the analysis of the XRD pattern of Ti3C2Tx [72].
Figure 4i (II) shows the shift of the 000 peak to a lower angle, corresponding to the in‐
crease of the C lattice parameter from 18.6 Å of Ti3AlC2 to 19.8 Å of Ti3C2Tx. In the XRD
pattern of Ti3C2Tx‐IC (III, where IC represents the inserted species, namely NH3 and
NH4+), the C lattice further increases to 24.7 Å. This indicates that the C lattice constant
of Ti3C2Tx etched by NH4HF is 25% larger than that of Ti3C2Tx etched by HF.

Figure 4. (a–c) The SEM images of the samples etched by LiF/HCl for different durations, corre‐
sponding to the samples etched by HF for (d) 3 h, (e) 6 h, and (f) 24 h, respectively. (g) The XRD
patterns of the samples etched by LiF/HCl and (h) those etched by HF. Reproduced with permis‐
sion [71]. Copyright 2021, American Chemical Society. (i) (I) The XRD pattern of the Ti3AlC2 film.
(II) Ti3C2Tx after being etched in 50% HF for 2 h and 40 min. (III) Ti3C2Tx ‐IC after being etched in 1
Materials 2025, 18, 2386 11 of 49

M NH4HF2 for 11 h. Reproduced with permission [72,73]. Copyright 2014, American Chemical So‐
ciety.

It is worth noting that HF etching will attack the grain boundaries, causing the pol‐
ycrystals to break into single crystals, with higher etching efficiency. However, it is diffi‐
cult to obtain single‐layer MXene nanosheets due to the lack of intercalating agents.
When LiF/HCl is used for etching, initially only the surface reacts and most of the inter‐
nal regions remain unetched. Moreover, during the delamination process of Li+ and wa‐
ter molecules embedding into the MXene flakes, incomplete exfoliation or impurity for‐
mation may occur, leaving incompletely etched MXene particles. Therefore, although the
method of generating HF in situ significantly reduces the hazards caused by toxicity and
high corrosiveness, it is only suitable for most MAX phases containing Al as the A atom
layer, and the yield of fluoride ions is lower compared with the direct use of HF, and the
etching range is limited. To completely convert the MAX phase into MXene, the etching
conditions need to be adjusted rigorously. Research shows that the etching conditions
are related to the atomic number of the M atom. Usually, the larger the atomic number,
the higher the corresponding increase in the M‐A bond energy, and the more stringent
the required F ion concentration and etching time will be.

3.2. Alkali Etching

In order to avoid the harm caused by fluorine and improve the etching precision
and the conductivity of MXene, researchers have further investigated the fluorine‐free
etching method known as the alkali etching method. Under a high temperature and
high‐concentration alkaline environment, the A phase containing amphoteric metal at‐
oms, such as Al atoms, will react with OH‐ to generate the corresponding hydroxide,
that is, Al(OH)4‒ ions, which will dissolve in the alkaline solution, thereby being re‐
moved from the MAX phase, and ‐OH functional groups will be formed on the surface
of the transition metal layer by combination [71,72]. This process is endothermic. Ac‐
cording to the principles of thermodynamics, a relatively high reaction temperature is
one of the important factors affecting etching. Li et al. first achieved the synthesis of
high‐purity MXene by using the alkali etching method and explored the two main fac‐
tors affecting hot alkali etching—temperature and alkali concentration [72,74]. They
used a hot NaOH solution with a concentration of 27.5 mol/L at 270 °C to etch Ti3AlC2
and successfully prepared multi‐layer Ti3C2TX without fluorine on the surface. The spe‐
cific chemical reaction equations are as follows:
Ti3AlC2 + OH‒ + 5H2O → Ti3C2(OH)2 + Al(OH)4‒ + 2.5H2 (5)

Ti3AlC2 + OH‒ + 5H2O → Ti3C2O2 + Al(OH)4‒ + 2.5H2 (6)

It was found that as the temperature decreases, the production rate of soluble
Al(OH)4‒ will be greatly reduced, thereby significantly reducing the yield of MXene. It is
even difficult to produce MXene at 220 °C. In addition, according to chemical kinetics,
the concentration of hydroxide ions is another important factor affecting etching. Theo‐
retically, the lower the concentration of hydroxide ions, the correspondingly lower the
etching rate and yield. This is also the case in practice. The lower the concentration of
NaOH and the higher the water content, the easier it is to cause the oxidation of Ti and
generate a series of titanium oxides. Eventually, Li et al. found that by hydrothermal
treatment with 27.5 M NaOH at 270 °C, multi‐layer Ti3C2Tx with a purity close to 92%
could be obtained. As shown in Figure 5a (i), at low temperatures, aluminum hydroxide
is difficult to transform into soluble ions. (ii) At high temperatures but with low OH−
concentrations, the higher water content leads to the oxidation of MXene and the genera‐
Materials 2025, 18, 2386 12 of 49

tion of a large amount of oxide impurities. (iii) According to the Bayer process, the high
temperature and high NaOH concentration of 27.5 M NaOH at 270 °C can most efficient‐
ly convert and dissolve aluminum or its oxides. Observing its surface morphology, as
shown in Figure 5b,c, similar to Ti3C2Tx treated with low‐concentration HF, the prepared
Ti3C2Tx has a compact accordion‐like structure. Besides using strong alkalis, milder and
safer organic alkalis as etchants can also obtain relatively pure products. And due to the
significant intercalation effect of organic cations, the thickness of the obtained
nanosheets can be reduced. Based on the mechanism of hydroxide ions etching alumi‐
num atoms, Xuan et al. used tetramethylammonium hydroxide (TMAOH) as an etchant,
and the process is schematically shown in Figure 5d [75]. TMAOH reacts with the Al at‐
om layer between the layers, causing the hydrolysis and breakage of the Ti‐Al bond. The
generated Al(OH)4‒ will modify the etched surface, and at the same time, the bulky TMA
will be inserted between the layers as an intercalating agent. Looking at the AFM image
in Figure 5e, ultimately, uniformly distributed and highly delaminated ultrathin
nanosheets are obtained. Through X‐ray diffraction analysis (Figure 5f), after the reac‐
tion in the TMAOH solution, new diffraction peaks are observed, indicating that the in‐
terlayer spacing has increased to 1.50 nm, successfully realizing the intercalation of TMA
ions.

Figure 5. (a) The etching process of Ti3AlC2 with NaOH aqueous solution under three different
conditions. (i) Low temperature: at low temperature, insoluble Al oxides/hydroxides are formed.
(ii) High temperature, low carbon: under high temperature and low carbon environment, H₂O is
involved in the reaction, Ti is oxidized to form NTO, OH‐ and ‐O are involved in the reaction pro‐
cess. (iii) High‐temperature, high‐carbon: MXene is finally formed. Through (b) SEM and (c) TEM
for the microscopic structure observation of Ti3C2Tx flakes, where the bright spots in the figures
indicate the positions of Ti. (a–c) Reproduced with permission [74]. Copyright 2018, Wiley‐VCH.
(d) The intercalation and delamination process of organic bases, demonstrating the representative
bright‐field of extremely thin nanosheets. (e) The AFM image after the intercalation and separa‐
Materials 2025, 18, 2386 13 of 49

tion of Al(OH)4−. (f) The XRD patterns of the samples before and after the reaction in aqueous
TMAOH, indicating that the basal plane spacing expands from 0.92 to 1.50 nm (d–f). Reproduced
with permission [75]. Copyright 2016, Wiley‐VCH.

Alkali etching also has considerable disadvantages. When the concentration of the
alkali solution and the reaction temperature are relatively low, the corrosiveness to MAX
is relatively weak, which easily causes the oxidation of the M and X skeletons, greatly
reducing the integrity of the MXene structure, and is accompanied by the problem of in‐
sufficient reaction kinetics, only being able to etch its surface [64]. If the reaction temper‐
ature is too high, it may also bring certain safety hazards.

3.3. Electrochemical Etching Method

The electrochemical etching method is one of the fluorine‐free etching methods. The
principle lies in utilizing the conductivity of the MAX phase to apply a specific voltage
to both ends of the MAX electrode in the electrolyte, thereby selectively etching away
the A atom layer [76].
In 2018, Yang et al. first reported a fluoride‐free electrochemical method. By using a
binary aqueous electrolyte (0.1 M NH4Cl and 0.2 M TMAOH), a voltage was applied to
the surface of the Ti3AlC2 electrode to selectively break the Ti‐Al bonds, and the alumi‐
num layer was successfully etched away [77]. Song and their team also adopted this flu‐
oride‐free electrochemical etching method and successfully synthesized 2D fluoride‐free
Nb2CTx MXene nanosheets in a standard three‐electrode configuration [78]. The specific
schematic diagram of the principle is shown in Figure 6a. It is worth noting that it is
usually considered that the chloride ions in the electrolyte are the key to this method.
When a voltage is applied, the Cl ions at the positive electrode can easily react with the
A atom layer to selectively etch away the A layer and attach ‐OH end groups on the sur‐
face of the transition metal layer, forming Mn+1An(OH)X. However, there must be neces‐
sary catalysts in the electrolyte, so the surface of the produced MXene does not only
have the ‐OH group, but also is related to the types of groups carried by the catalysts,
such as ‐Cl, ‐F, and ‐O, etc. Figure 6c shows the Raman spectra of three MAX phases,
namely Ti3AlC2, Ti3SiC2, and Ti2AlC, which are successfully converted into amorphous
carbon CDCs in different electrolytes. When Ti3AlC2 is etched using dilute electrolytes
such as NaCl, HCl, and HF, both titanium and aluminum atoms may be removed, thus
generating amorphous carbon. While using a medium‐concentration HCl solution will
lead to the selective aluminum extraction on the surface of the bulk Ti3AlC2 and form a
thin protective carbon layer on the surface, preventing the further progress of etching
[79]. Meanwhile, the binary electrolyte TMAOH adopted by Yang et al. [77] was added
as a certain amount of intercalating agent, which enlarged the distance between the la‐
mellae, promoting a larger specific surface area inside the MAX phase to come into con‐
tact with the electrolyte, thereby reducing the differences caused by the inconsistent
etching speeds between the surface and the interior. The XRD pattern in Figure 6b re‐
veals the structural changes during the etching and delamination processes. The (002)
peak of Ti3AlC2 shifts to a lower angle, corresponding to the increase of the C lattice pa‐
rameter from 18.0 to 22.6 Å, indicating that TMAOH can be easily embedded into the in‐
terlayer of the MAX phase, thus increasing the efficiency of the electrolyte in etching the
Al layer. When observing the SEM images (Figure 6d), it is found that after electrochem‐
ical etching, the multi‐layer Ti3C2Tx powder is still tightly stacked, similar to the compact
layered bulk Ti3AlC2, rather than the accordion‐like structure produced by traditional
hydrofluoric acid etching. This is because when a voltage is applied to both ends of the
MAX precursor, and the precursor has a large volume and dense layers, the MAX phase
on the surface layer close to the electrolyte is often preferentially converted into the
Materials 2025, 18, 2386 14 of 49

MXene phase, while the middle part remains the MAX phase, which significantly reduc‐
es the yield.

Figure 6. (a) A schematic illustration of the exfoliation and delamination process of the Nb2AlC
MAX phase via electrochemical etching. The red lightning symbol indicates electrical drive. Re‐
produced with permission [78]. Copyright 2020, Wiley‐VCH. (b) The X‐ray diffraction patterns of
Ti3AlC2, Ti3C2Tx, and Ti3C2Tx thin films. Reproduced with permission [77]. Copyright 2018, Wiley‐
VCH. (c) The Raman spectra of amorphous carbon CDC synthesized by etching the MAX phase
(namely Ti3SiC2, Ti3AlC2 and Ti2AlC) in HCl, NaCl or HF electrolytes. The letters D and G repre‐
sent Raman spectral peaks, the G peak corresponds to the vibration in the sp2 hybridized carbon
plane, and the D peak is the defect‐induced peak. Reproduced with permission [80]. Copyright
2014, Wiley‐VCH. (d) The representative SEM images of Ti3AlC2 and Ti3C2Tx. Reproduced with
permission [77]. Copyright 2018, Wiley‐VCH.

In addition, during the etching process, besides selecting an appropriate electrolyte,

it is also necessary to choose a suitable voltage so as to avoid the possible Ti etching
phenomenon under high polarization and the formation of carbide‐derived carbon
(CDC). Liu and their team treated the prepared TiAlC MAX phase [81]. Through the in
situ molten salt electrochemical etching method under low voltage conditions (1.3 V ver‐
sus ref.), Al atoms were selectively removed from the MAX phase, and Ti2CTx MXene
was successfully prepared. During this process, these Al atoms were oxidized to Al3+ and
deintercalated from the Ti2AlC phase. Meanwhile, the Al3+ ions in the LiCl/KCl molten
salt formed a volatile AlCl3 phase. The free Cl− in the molten salt will fill the vacant posi‐
tions of Ti2C to form surface terminal groups ‐Cl. In addition, the free Li+/K+ ions in the
molten salt will move towards the negative electrode and be reduced at the negative
electrode to form Li/K metal deposits.
Materials 2025, 18, 2386 15 of 49

3.4. Molten Salt Etching

Most methods for obtaining MXene require the etching of Al atoms in aqueous sys‐
tems. However, for MAX precursors without an Al layer or MAX phases containing ni‐
trides, the etching process often needs to overcome a higher energy barrier, which signif‐
icantly limits the types of MXene [82]. Therefore, researchers have explored placing the
MAX phase precursors in molten salts with certain compositions. At this time, the A at‐
om layer will be replaced by the atoms in the molten salts without changing the struc‐
tural frameworks of M and X. Accordingly, it is possible to etch some MAX phases that
are difficult to etch by traditional methods, such as those with the A atom layer com‐
posed of Si and some nitride MAX phases [83,84]. Li et al. [85] reported this preparation
method with a similar mechanism to displacement reactions. Through the reaction be‐
tween molten ZnCl2 and the Al element in the MAX phase precursor (such as Ti3AlC2), a
new Zn‐based MAX phase (such as Ti3ZnC2) was synthesized. As shown in the XRD di‐
agrams of Ti3AlC2 and Ti3ZnC2 in Figure 7b and the EDS diagram of Ti3ZnC2 in Figure
7c, compared with Ti3AlC2, the XRD peaks of Ti3ZnC2 shift to lower angles, indicating
that Zn atoms have successfully replaced Al atoms. Interestingly, at 550 °C, an excessive
amount of molten ZnCl2 salt will react with the MAX phase to synthesize MXene termi‐
nated with ‐Cl or without terminal groups on the surface, pioneering the creation of a
fluorine‐free, green, efficient MXene with only ‐Cl terminal groups. However, according
to the obtained EDS of Ti3C2Cl2 (Figure 7d), it shows that the elemental composition of
Ti3C2Cl2 still contains a small amount of Zn (0.7 atomic%), Al (2.9 atomic%), and O (6.3
atomic%). This is because the ‐Cl terminal group can strongly bond to the MXene sur‐
face, but when there are steps such as the presence of oxygen‐containing compounds or
water washing, the ‐Cl terminal group is less competitive than the ‐O terminal group
and is thus replaced. This is a problem that needs to be noted and avoided when using
Lewis molten salt etching.
Materials 2025, 18, 2386 16 of 49

Figure 7. (a) Schematic diagram of Ti3C2Tx MXene preparation. Reproduced with permission [86].
Copyright 2020, Springer Nature. (b) XRD patterns of Ti3AlC2 and Ti3ZnC2. (c,d) SEM images and
corresponding energy dispersive spectra (EDS) of Ti3ZnC2 and Ti3C2Cl2. Shows the elemental
composition and atomic percentage of the corresponding region. (b–d) Reproduced with permis‐
sion [85]. Copyright 2019, American Chemical Society. (e) Molten salt synthesis method and exfo‐
liation process. (f) X‐ray diffraction (XRD) patterns of MAX phase precursors (black), MXene after
removal from the molten salt bath (red), MXene after washing in APS to remove residual Cu
(blue), and MXene after TBAOH stripping treatment (green). The triangular symbols indicate the
characteristic diffraction positions where Cu2+ is reduced to Cu monomers remaining in the sam‐
ple. (g,h) SEM maps of MS‐Ti3C2Tx MXene treated with DMSO followed by sonication, and MS‐
Ti3C2Tx MXene treated with TBAOH for 24 h and 72 h TEM images of MS‐Ti3C2Tx. (e–h) Repro‐
duced with permission [87]. Copyright 2021, American Chemical Society. (i) Schematic diagram of
a molten salt cell with (Ti, Al, C) pellets as working electrode, glassy carbon as reference electrode,
and graphite crucible as counter electrode and a schematic diagram of the process for the prepara‐
tion of Ti2AlC by using carbon nanotubes and reduced graphene oxide as the carbon source. (j)
Ti2AlC MAX (i,iii) obtained by using graphene oxide and carbon nanotubes as the carbon source
and Ti2CCl2 MXene (ii,iv) TEM images of the Ti2CCl2 MXene. (i,j) Reproduced with permission
[81]. Copyright 2022, Wiley‐VCH.
Materials 2025, 18, 2386 17 of 49

Li et al. further summarized and explored the Lewis molten salt etching method,
and the schematic diagram of its preparation process is shown in Figure 7a [86]. The
principle that the A atom layer can undergo substitution with the molten salt lies in the
difference in their redox potentials. Transition metal halides can act as electron acceptors
to react with the A layer in the molten state. The Lewis acid molten salt has a higher re‐
dox potential compared to the MAX phase, so it can etch the MAX phase. For example,
in the molten CuCl2 salt at 700 °C, the redox potential of Cu/Cu2+ is −0.43 eV, which is
greater than that of Si/Si4+ (−1.38 eV). Therefore, the molten Cu2+ can oxidize the Si atoms
in the MAX phase into Si4+, which then enters the molten salt and combines with Cl− to
form SiCl4, while Cu2+ is reduced to Cu atoms and remains outside the MAX phase.
Then, the Cu element is removed by APS ((NH4)2S2O8). Finally, Cl−, Br−, I−, etc., in the
molten salt combine with the M transition metal atoms, and depending on the type of
molten salt, MXene with corresponding surface terminal groups can be obtained. How‐
ever, the binding ability is generally weak, and subsequent substitution of functional
groups can be carried out to flexibly adjust the surface functional groups, thereby ob‐
taining MXene with other terminal groups or even without terminal groups. However,
affected by the synthesis route and changes in surface groups, it often leads to a signifi‐
cant reduction in the rate of exfoliation and delamination of multi‐layer MXene, making
it difficult to obtain good electrochemical properties. Liu et al. successfully etched
Ti3AlC2 using a mixed molten salt of KCl/CuCl2/NaCl at 680 °C in an argon atmosphere
[87]. Subsequently, by inserting the organic molecule TBAOH (tetrabutylammonium
hydroxide) and performing ultrasonic treatment, they successfully prepared MXene
with fewer layers and improved electrochemical properties through the Lewis molten
salt method. The etching and exfoliation processes of the Lewis acid molten salt method
are illustrated in Figure 7e. The HF‐MXenes obtained by traditional hydrofluoric acid
etching usually use DMSO solvent as an intercalating agent for separation because of the
matching of surface energy between DMSO and HF‐MXene. However, the Ti3C2Tx treat‐
ed with DMSO in the Lewis acid molten salt etching method is thicker and has more
layers (as shown in Figure 7h), while the multi‐layer MXene treated with TBAOH can be
further exfoliated. The SEM images before and after exfoliation are displayed in Figure
7g. The Lewis molten salt etching is safer and more environmentally friendly compared
to traditional etching methods and has the advantage of being able to regulate terminal
functional groups. However, it is often difficult to obtain single‐layer MXene through
this redox reaction, and it is affected by the properties of the Lewis molten salt.
It is worth noting that in the past decade or so, most of the MXenes prepared in re‐
search have been derived from MAX phases. However, this process is time‐consuming
and complex, involving multiple steps such as the preparation of MAX, the etching from
MAX to MXene, and the removal of metal impurities. To optimize this process, research‐
ers have devoted a great deal of effort. Besides the bottom‐up CVD deposition method,
recently, Liu et al. proposed an innovative one‐pot molten salt electrochemical etching
method [81]. The specific process (Figure 7i) is divided into two processes: obtaining the
MAX phase and etching the MAX phase to obtain MXene. First, an electrochemical cell
containing a mixture of LiCl and KCl is heated to a stable molten state. Molten alumi‐
num (melting point 660 °C) will wrap around the metal Ti (melting point 1668 °C) and
form Ti‐Al intermetallic compounds on the surface of Ti. Meanwhile, carbon nanotubes
(CNTs) and reduced graphene oxide (rGO) are used as carbon sources to make TiC grow
on the graphite side. Through the bottom‐up growth mode, TiAlC MAX phase nuclei are
generated on the carbon surface and continue to grow as TiC and Ti‐Al intermetallic
compounds are continuously consumed, and based on the structural framework of car‐
bon as a template, TiAlC particles are obtained in a short time. Immediately after that,
the temperature of the molten salt electrode is changed to 500 °C, and Ti2CCl2 MXene is
Materials 2025, 18, 2386 18 of 49

obtained by electrochemically etching away the aluminum atom layer. The use of differ‐
ent carbon sources also has a significant impact on the morphology of the precursor and
MXene. As shown in Figure 7j, both the Ti2AlC MAX phase and Ti2CCl2 MXene grown
from different carbon sources retain the characteristics of CNT and GO. Compared with
other methods, this method only requires a lower temperature and a shorter reaction
time, greatly simplifying the preparation process.

3.5. Chemical Vapor Deposition (CVD) Method

In the process of preparing MXenes, traditional methods such as the Lewis acid
molten salt method or chemical and electrochemical etching require the use of harmful
HF or energy‐consuming Lewis acid molten salt. Chemical Vapor Deposition (CVD) is a
typical bottom‐up synthesis approach that operates at atomic/molecular scales, enabling
direct growth of large‐area two‐dimensional materials [88]. An investigation has demon‐
strated the CVD synthesis of high‐quality two‐dimensional ultrathin Mo2C crystals, us‐
ing methane as the carbon source at temperatures exceeding 1085 °C on layered Mo/Cu
foil substrates [89]. Halim et al. [73] successfully synthesized Ti3AlC2 thin films via di‐
rect current (DC) magnetron sputtering using elemental Ti, Al, and C targets. Subse‐
quent selective etching of the aluminum layers in aqueous HF or NH4HF2 solutions
yielded Ti3C2 MXene films with a controlled thickness of approximately 19 nm. Howev‐
er, conventional CVD or magnetron sputtering techniques can only synthesize a limited
number of MXene and strictly depend on specific substrates (such as Cu foils), failing to
achieve controllable synthesis of termination‐enriched MXene like Ti2CCl2 and Zr2CBr2.
Wang et al. [90] reported a novel synthetic route by utilizing direct reactions between
metal/metal halides and carbon/nitrogen sources without MAX phase precursors. As a
representative case, Ti2CCl2 MXene was successfully grown on Ti substrates at 950 °C
under an argon atmosphere using CH₄ and TiCl4 as precursor gases, with the detailed
synthesis process illustrated in Figure 8a,b. Through the structural analysis by XRD
(Figure 8c,d) and Raman spectroscopy analysis (Figure 8f), it is revealed that the high‐
purity Ti2CCl2 MXene phase has been successfully prepared. Scanning electron micros‐
copy (SEM) images showed a completely new growth morphology that dramatically di‐
verges from conventionally synthesized counterparts. Wrinkled Ti2CCl2 MXene layers
were observed to coat the substrate (Figure 8e), exhibiting vertically oriented growth to
form carpet‐like or spherical vesicular architectures. These nanosheets could be exfoliat‐
ed into monodisperse colloidal suspensions. Notably, nitride‐based MXenes may under‐
go dissolution in HF solutions due to insufficient chemical stability. In contrast, CVD at
640 °C using TiCl4 and N2 reactants on Ti foils enables the successful synthesis of pure‐
phase Ti2NCl2 MXene that is challenging to obtain through conventional approaches.
Generally, directly synthesized MXenes (DS‐MXenes) exhibit superior structural integri‐
ty with near‐ideal stoichiometric coverage of chlorine terminations. The vertically
aligned architecture achieved through CVD growth facilitates enhanced ion intercalation
kinetics, resulting in exceptional rate capability in electrochemical applications.
Thickness, morphology, and size of MXene is more controllable by this method.
However, two critical challenges persist in the CVD synthesis of MXenes: the nucleation
mechanisms and kinetic competitions remain poorly understood, precluding precise
control over crystal dimensions and defect densities; and the validated precursor combi‐
nations are currently limited to select metal halides (TiCl4, ZrCl4) with carbon/nitrogen
sources (CH4, N2), restricting exploration of alternative transition metals and functional
surface terminations. Future research should focus on expanding the metal repertoire (V,
Nb et al.) and surface functionalization, elucidating nucleation mechanisms and opti‐
mizing synthetic protocols, and achieving wafer‐scale uniform synthesis for industrial‐
scale production. These advancements will facilitate practical applications in high‐power
Materials 2025, 18, 2386 19 of 49

energy storage devices, efficient catalysts, and flexible electronics, enabling transforma‐
tive industrial breakthroughs.

Figure 8. (a,b) Schematic of bottom‐up direct synthesis of Ti2CCl2. (c) XRD patterns of CVD‐
Ti2CCl2 and CVD‐Ti2NCl2. (d) Powder XRD pattern of the product of pure TiCCl MXene annealed
at 950 °C for 1 day under vacuum. MXene partially decomposed into TiCl and TiC. XRD patterns
of the final mixture were similar to that of DS‐Ti2CCl2. (e) Front (i) and cross‐section (ii) SEM im‐
ages of CVD‐Ti2CCl2. (iii) SEM image and (iv) STEM image showing that CVD‐TiNCl exhibits a
braided structure. (f) Raman spectra of CVD‐Ti2CCl2 and CVD‐Ti2NCl2 MXenes. [90]. Copyright
2023, American Association for the Advancement of Science (AAAS).

Table 1. Current methods of preparing MXene and the differences between the different routes.

Synthesis
Characteristics Advantages Disadvantages
Methods
The A layer in the MAX phase was HF is toxic and harmful to the
The process is simple, high
etched using F− with Al3+ to generate environment; difficult to peel
HF Etching yield, low cost, and
MXene containing ‐F/‐OH/‐O end off in a single layer and easy
universally applicable.
groups. to build up.
Fluorine‐containing reagents
Fluorine salts (LiF/NH4F) were mixedMuch gentler than direct HF
In situ generation are still needed, and the yield
with acid to generate HF in situ toetching for large nanosheets
HF etching is lower than that of HF
etch the A layer atoms. (lateral dimensions > 1 μm).
etching.
High‐temperature strong basesFluorine‐free; excellent
(NaOH/TMAOH) dissolve the Alhydrophilicity, layer spacing
Alkali etching Harsh reaction conditions.
layer to produce MXene, which iscan be controlled by cationic
dominated by ‐OH end groups. intercalation.
Applying a voltage selectively etchesFluorine‐free; precise etchComplex equipment; slow
Electrochemical
the A layer to produce MXene with a ‐depth control for low‐layeretching rate; easily over‐
etching
OH dominated surface. MXene preparation; highetched.
Materials 2025, 18, 2386 20 of 49

purity (>95%).
The high‐temperature molten salt
Fluorine‐free; suitable for Si‐High‐temperature conditions;
displaces the A layer in the MAX
Molten salt etching based/nitride MAX phasedifficulty in regulating layer
phase to produce MXene with end
etching; adjustable endbase. spacing.
groups such as ‐Cl on the surface.
Nitride MXene can be
The high cost of equipment
Chemical Direct synthesis of MXene by vaporprepared; precise control of
makes large‐scale production
deposition (CVD) phase deposition without MAX phase.size/thickness and few
difficult.
surface defects.

4. Rechargeable Battery
With the global demand for sustainable and efficient energy systems, the limita‐
tions of traditional electrode materials in terms of energy density, cycle life, cost of use,
and environmental impact are becoming more and more prominent [91]. In recent years,
nanocomposite structures based on carbon materials, transition metal oxides or hydrox‐
ides, and conductive polymers have been extensively investigated with a focus on three
key parameters: surface area, electrical conductivity, and pore structure of the electrode
materials. However, outstanding issues such as limited specific capacitance, low conduc‐
tivity, structural degradation, slow kinetics of redox reactions, and restricted ion and
electron transport remain to be addressed [92]. Therefore, the development of new elec‐
trode materials and the search for efficient, safe, and sustainable electrochemical energy
conversion and storage technologies is one of the hot spots in current research.
MXene materials have a unique two‐dimensional structure, excellent physicochem‐
ical properties, outstanding electrical conductivity, high specific surface area, and high
chemical stability. They are considered as revolutionary materials for batteries, superca‐
pacitors, and various electrocatalytic reactions [93–95]. The larger layer spacing of
MXenes can allow for larger ion embedding/de‐embedding, which can enhance ion dif‐
fusion and storage capacity. At the same time, this layered structure helps maintain
structural stability during cycling, reducing electrode degradation and extending battery
life. In recent years, the electrochemical properties of MXenes have been rapidly studied
and a large amount of related literature has been published, but there is a lack of sys‐
tematic organization of the research results in recent years [96]. Therefore, this review
aims to fill this gap by providing a comprehensive framework to understand and utilize
the potential of MXene materials for electrochemical applications, while revealing key
scientific issues and future research directions.

4.1. Lithium–Ion Batteries

A lithium–ion battery is a high‐performance secondary battery, relying on the
movement of lithium ions between the positive and negative electrodes to achieve ener‐
gy storage and release. Because of its high energy density, long life, and low self‐
discharge rate, it is widely used in the power supply system of all kinds of electronic
equipment and grid energy storage [9,97,98]. This section focuses on summarizing the
composite modes and structures of commonly used active electrode materials other than
graphite‐based anode materials with MXenes.
In order to fully utilize the unique properties of MXene materials and the anode
materials, researchers have explored the use of a variety of composite methods. For ex‐
ample, physical mixing mechanical ball‐milling mixing, wet dispersion freeze‐drying
mixing, the use of chemical methods, through the chemical vapor deposition on the sur‐
face of MXene in situ growth of anode materials, or the solvent thermal method of direct
chemical synthesis of composite structures. Self‐assembly of MXene and anode materials
into multi‐layer composite membranes can be realized by electrostatic interaction or oth‐
Materials 2025, 18, 2386 21 of 49

er intermolecular forces. Alternatively, a specific functional group ligand can be de‐

signed to spontaneously self‐assemble with MXene and the anode material to form a
strong transition layer as well as a heterogeneous structure connected by covalent
bonds.
Graphite is the most commonly used anode material for lithium–ion batteries.
However, due to the relatively low theoretical specific capacity of the graphite anode
(usually 372 mAh gെ1) [99], currently, the development of graphite electrodes has
reached its theoretical limit, but it still cannot meet the requirements of technological
progress for energy storage. Therefore, the search for new electrode materials is immi‐
nent. Studies have shown that in addition to graphite‐based materials, silicon‐based ma‐
terials also have relatively high theoretical capacities [100]. Replacing the graphite anode
with silicon not only effectively addresses the safety issues of the liquid electrolyte in
lithium–ion batteries but also significantly improves the specific capacity of the batteries.
It is regarded as one of the most promising electrode materials for next‐generation high‐
energy lithium–ion batteries [101]. However, silicon electrodes will have a large volume
change during the charge/discharge process, and this change will destroy the inherent
layered structure of the electrodes, or the electrodes may even be crushed and pulver‐
ized, resulting in serious capacity loss. In order to solve the problem of volume change,
the usual method is through the composite of certain conductive materials, and the for‐
mation of a multiple buffer structure or with multi‐component composite, so as to inhib‐
it the volume expansion of the electrode, enhance the mechanical stability and electrical
conductivity, and effectively improve the cycling stability of the material [102]. Luckily,
MXene not only has excellent mechanical properties and excellent electrical conductivi‐
ty, its rich surface functional groups and layered structure can be more easily combined
with the electrode material, so it is widely used as a substrate material and potential an‐
ode material composite [103–105]. Han et al. [106] designed a Si‐N‐MXene composite
anode material through interface nitrogen engineering. They mixed a certain proportion
of micron‐sized Si powder, PAN (polyacrylonitrile), and Ti3C2Tx MXene and then cast
the mixture onto a copper foil substrate followed by heat treatment. During the heat
treatment process, PAN was converted into amorphous carbon that fixed Si and MXene,
as shown in Figure 9a. Moreover, a chemical bond of N was formed to connect them,
creating a solid interface nitrogen layer structure on the surfaces of Si and MXene, which
could effectively enhance the adhesion between Si and MXene, thereby improving the
mechanical properties. The structure of MXene creates a robust volumetric buffer layer
to resist volume expansion of the silicon electrode. Si‐N‐MXene was used as the compo‐
site film electrode, lithium metal as the counter electrode, and 1M LiPF6 as the carbonate
electrolyte to form a full cell. The capacity retention was 80.5% after 200 cycles (Figure
9c). The initial capacity and the capacity after 100 cycles are much larger than that of the
single Si‐C electrode. In solving the problem of the volume expansion phenomenon pro‐
duced by Si during charging and discharging, Du et al. [104] have designed another spe‐
cial core‐shell structure, as shown in Figure 9b. Si particles were confined in TiO2 carbon
fibers by electrostatic spinning to obtain Si‐x/TiO2 carbon fibers (ST‐2), and ST‐2 was
successfully wrapped in Ti3C2Tx MXene under self‐assembly. Then the cobalt and mo‐
lybdenum salts were uniformly adsorbed on the surface of MXene in solution and then
heated, and the hierarchical ST‐2@Ti3C2Tx MXene@Co‐MoS2 (CMS) fibers were success‐
fully obtained, which presented a 3D electrode structure with interleaved composition.
Utilizing titanium dioxide, which has a very low volume expansion rate, and MXene,
which has high electrical conductivity, high specific capacity, and multiple active sites, a
hierarchical and robust volumetric buffer layer was constructed together with CMS,
which improves the volumetric change of Si particles in the core during charging and
discharging. Through electrochemical performance testing, the ST‐2@MXene@CMS elec‐
Materials 2025, 18, 2386 22 of 49

trode exhibited relatively excellent electrochemical performance. As shown in Figure

9d,f, its initial charging and discharging capacities reached 1849.9/2071.8 mAh g−1, and
the initial Coulomb efficiency reached 89.3%, indicating a high effective utilization rate
of the battery during the first charging and discharging. Moreover, at a high current
density of 1.0 A/g, the reversible specific capacity reached 1333.1 mAh g−1 after 100 cy‐
cles. And there was still a reversible specific capacity of 891.3 mAh g−1 after 200 cycles. In
contrast, the initial charging capacity of the pure ST‐2 electrode was only 1518.9 m Ah
g−1. And the reversible specific capacity decreased to 478.7 mAh g−1 after 200 cycles at 1.0
A g−1. This was mainly due to the limited buffering capacity of monolayer ST‐2 and the
structural rupture caused by the expansion of Si particles. The ST‐2@MXene@CMS elec‐
trode was demonstrated to have great potential for high‐energy storage, and the im‐
portant role of MXenes in maintaining structural stability during their long‐term cycling
was also shown.
In addition, the influence of MXene surface functional groups on the energy storage
properties has been extensively studied. Different groups affect the adsorption capacity
by changing the binding energy and bond length of Li+ to MXene. Kim et al. [107] opti‐
mized the structure of M2CTX using density functional theory (DFT) to calculate the lat‐
tice parameters and density of states (DOS), focusing on the effect of surface groups on
lithium adsorption, diffusion barriers, and storage capacity, as shown in Figure 9g. For
small‐sized, highly electronegative groups (‐Cl, Br), which form short bond lengths
(2.21–2.35 Å) and low adsorption energies (−1.31~−0.71 eV) with Li+, the electrons are
highly delocalized and the adsorption stability is strong. Small groups (‐Cl) diffuse fast‐
er due to low spatial site resistance. And the large groups (‐Se, Te) still keep low poten‐
tial barriers through the electron leaving domain effect. However, for the lithium storage
performance, the capacity of the (‐Cl,Br) group system is 190–287 mAh g−1 in monolayer
adsorption, and the ‐Se group system (Cr2CSe2) achieves 391.3 mAh g−1 by bilayer ad‐
sorption. This is due to the fact that, at high concentrations, the ‐Cl, Br groups are sus‐
ceptible to destabilization due to Li+ repulsion, whereas the Se‐ groups maintain stability
by virtue of moderate electron delocalization (adsorption energy −0.033 eV). Overall, the
surface groups are regulated by “adsorption stability‐diffusion efficiency‐storage capaci‐
ty”, which determines the actual performance of MXene as an electrode. Future research
can focus on the optimization of group combination to accelerate the translation of
MXene from theory to practical application.
Materials 2025, 18, 2386 23 of 49

Figure 9. (a) Schematic diagram of the synthesis process for the interfacial nitrogen layer between
Si and MXene. Reproduced with permission [106]. Copyright 2022, Elsevier BV. (b) Schematic il‐
lustration of the cycling process of the ST2@MXene@CMS electrode. Reproduced with permission
[104]. Copyright 2024, Springer Nature. (c) Long‐life cycling performance of the NMC811/Si‐N‐
MXene full battery. Reproduced with permission [106]. Copyright 2022, Elsevier BV. (e) Initial
charge–discharge curves and bar chart of initial Coulombic efficiency for the ST2@MXene@CMS
electrode. (d,f) Cycling performance curves of the electrode at current densities of 0.1 A g−1 and 1.0
A g−1. An arrow pointing in the direction of an increasing number of cycles indicates that the mate‐
rial will continue the current trend in subsequent cycles. (d–f) Reproduced with permission [104].
Copyright 2024, Springer Nature. (g) Trends in lithium adsorption energy with lithium concentra‐
tion on Cr2CCl2, Cr2CBr2, Cr2CSe2, Cr2CTe2, Mn2CCl2, and Mn2CBr2 nanosheets. Reproduced with
permission [107]. Copyright 2024, Elsevier.

Phosphorus also has an excellent theoretical capacity and high electrical conductivi‐
ty. Even the average discharge potential of phosphorus is higher than that of silicon,
making it one of the most promising anode materials for lithium–ion batteries [108].
Materials 2025, 18, 2386 24 of 49

However, similar to silicon, phosphorus electrodes also have relatively large volume
changes and slow kinetics. Research has already shown that through the liquid‐phase
exfoliation method, bulk black phosphorus can be exfoliated into phosphorene or black
phosphorus quantum dots. The two‐dimensional phosphorene has a very small volume
change during the charging and discharging process, which can effectively avoid vol‐
ume changes and form more lithium–ion channels, thereby significantly improving the
electrochemical performance [109]. Based on this, Li et al. [110] developed a corrugated
phosphorene/MXene heteronanocomposite electrode. The preparation process is shown
in Figure 10a. After fully mixing and dispersing urea and Ti3C2Tx MXene, the mixture
was dropped into a diphosphoric acid solution. In this regard, phosphorus is able to
form stable P‐O‐Ti covalent bonds with ‐OH on the surface of Ti3C2Tx MXene, thereby
making a membrane after self‐assembly. The incorporation of polar urea molecules can
avoid the concentration of phosphorus aggregating on the active sites on the MXene sur‐
face and promote a uniform distribution among the MXene lamellae, such as the corru‐
gated protrusions in Figure 10b(i). In addition, the typical accordion‐like lamellar struc‐
ture of MXene is retained (Figure 10b(ii)). Through bridging and crosslinking, phos‐
phene and MXene form stable ionic or charged 2D lamellar corrugated heterostructures.
When electrons transition from the Fermi level of MXene to the Fermi level of phos‐
phorene, a migration of the work function from a higher value to a lower value occurs,
aligning the Fermi levels of the two materials. Moreover, changes in the electron concen‐
tration and vacancy concentration will occur at the heterostructure. These changes can
improve the charge conductivity, reduce the energy barrier for the migration of the solid
electrolyte interface (SEI) film of lithium ions on the electrode surface, and greatly en‐
hance the electrochemical performance. The formed conductive framework can signifi‐
cantly increase the stability of the structure and volume changes. Electrochemical per‐
formance analysis was performed on a half‐cell system consisting of a phos‐
phorene/MXene nanocomposite film as the anode and a 1 M LiPF6‐based carbonate
mixed electrolyte solution, as shown in Figure 10c. At a current density of 100 mA g−1,
the electrode delivers an ideal capacity of 1463.2 mAh g−1 and maintains a favorable re‐
versible capacity of 848.3 mAh g−1 after 100 cycles. This demonstrates excellent cycling
stability, which significantly surpasses that of pure MXene and phosphorene electrodes.
All these data show its great potential as a new anode material for lithium–ion batteries.
Antimony (Sb), similar to phosphorus, also has a unique monolayer two‐dimensional
structure, antimonene. Antimony also has high theoretical capacity with high lithium in‐
sertion potential. However, it has the same problems of large volume change and poor
electronic conductivity during charging and discharging. Bo et al. [111] counted and
synthesized covalently bonded Ti3C2Tx MXene@antimonene (MXene@AME) het‐
eroanodes. Antimonene is self‐assembled with the ‐OH groups on the surface of MXene,
which serves as both a conductive matrix and a stress‐absorbing layer. A strong hetero‐
structure (Ti‐O‐Sb) is formed between the two under electrostatic action, schematically
shown in Figure 10d. Similar to phosphene, it can greatly improve electrochemical per‐
formance. The MXene@AME anode exhibits outstanding cycling performance at both a
lower current density of 0.2 A g−1 and a higher current density of 1 A g−1. As shown in
Figure 10e, after 300 cycles at the low current density, it can still maintain a capacity of
455 mAh g−1, with a retention rate as high as 93.8%. The phenomenon that the capacity
first decreases and then recovers, and is even higher than the initial capacity (447 mAh
g−1), may be due to the formation of an unstable SEI layer in the initial charging and dis‐
charging cycles, the incomplete activation of the electrode material, or the degradation
of the electrode structure. Subsequently, it is because of the stable reconstruction of the
Ti‐O‐Sb bond and the formation of a stable SEI layer. In contrast, the reversible capacity
of pure Ti3C2Tx MXene was only 81.7 mAh g−1 after 100 cycles under the same conditions.
Materials 2025, 18, 2386 25 of 49

This may be attributed to the reduction of active sites due to the stacking of MXene lay‐
ers, resulting in a faster capacity decay during cycling.
In addition, alloy‐based anode materials also have high lithium storage capacity
through alloying and de‐alloying mechanisms [112,113]. But there are also problems
such as poor electrical conductivity during charging and discharging, large volume
changes, and dendrite growth during lithium–ion deposition [114]. Tin‐based materials,
featuring high theoretical specific capacity and energy density, have also attracted wide‐
spread attention. Guan et al. [115] synthesized a Sn2S3@C/Ti3C2Tx composite electrode
material with a laminated leaf‐like structure. Sn2S3 was uniformly dispersed on several
layers of MXene nanosheets after being coated by nanosized C, as shown in Figure 10f.
Interestingly, the mechanical ball‐milling process employed in the preparation introduc‐
es certain defects on the surface of Ti3C2Tx. These defects facilitate the stable anchoring of
Sn2S3@C onto the MXene surface and effectively mitigate the internal stress generated
during charge–discharge cycles, thereby enhancing the overall stability of the composite
structure. When Sn2S3@C/Ti3C2Tx composites were used as an anode for lithium–ion bat‐
teries (Figure 10g), the reversible specific capacity was 989.6 mAh g−1 after 50 cycles at a
current density of 0.1 a g−1. Cheng et al. [116] employed a solvothermal method, adsorb‐
ing tin ions on the MXene surface to induce in situ nucleation and growth, and success‐
fully prepared Sn‐C bonded MXene/SnSe2 composite electrode materials. SnSe2
nanosheets vertically and completely cover the MXene surface, forming a laminar struc‐
ture. However, electrodes of this structure are not stable under the action of high‐
density currents. Scanning electron microscopy (SEM) observations show that after 100
cycles at a current density of 2000 mA g−1, SnSe2 nanosheets undergo in situ fragmenta‐
tion into nanoparticles that disperse between MXene layers. This structural evolution
leads to a notable increase in battery capacity and enhancement in electrochemical per‐
formance. The underlying mechanism involves the fragmented particle structure signifi‐
cantly expanding the specific surface area of the electrode material, which not only ena‐
bles more lithium ions to insert into the material but also provides abundant ion
transport pathways. These pathways accelerate lithium–ion diffusion rates, thereby con‐
tributing to the capacity improvement.
Materials 2025, 18, 2386 26 of 49

Figure 10. (a) Schematic illustration of the preparation process for corrugated phos‐
phorene/Ti3C2Tx nanocomposites. (b) Typical corrugated patterns; (i,ii) SEM images of the surface
and cross‐sectional morphology of the as‐prepared phosphorene/Ti3C2Tx, respectively. (c) Long‐
term cycling stability and corresponding Coulombic efficiency of the phosphorene/MXene elec‐
trode (1—5 cycles: 50 mA g−1; 6—1000 cycles: 500 mA g−1 and 2 A g−1). (a–c) Reproduced with per‐
mission [110]. Copyright 2024, Springer Nature. (d) Schematic diagram of the structural features of
the MXene@AME heterostructure. The circles in the figure indicate titanium Ti‐O‐Sb bonds. (e)
Cycling performance curves of MXene@AME, MXene, and AME at 1 A g−1 over 2000 cycles. (d,e)
Reproduced with permission [111]. Copyright 2024, Elsevier BV. (f) SEM image of
Sn2S3@C/Ti3C2Tx. (g) Cycling performance of Ti3C2Tx, Sn2S3@C, and Sn2S3@C/Ti3C2Tx at 0.1 A g−1.
(f,g) Reproduced with permission [115]. Copyright 2024, Springer Nature. (h) Rate capability of
Ti2NbC2Tx and Ti3C2Tx; (i) Cycling performance of Ti2NbC2Tx and Ti3C2Tx at 0.1 A g−1. (h,i) Repro‐
duced with permission [117]. Copyright 2022, Springer Nature.

In all of the above, a composite electrode is formed from a single‐transition layer of

metal MXene. It has been shown that a variety of M‐metals in MXenes can effectively
improve the stability of the structure during cycling [118,119]. Liu et al. [117] prepared
a double‐transition metal Ti2NbC2Tx MXene and compared its electrochemical perfor‐
mance as an anode with that of the single‐transition metal Ti3C2Tₓ MXene, as shown in
Figure 10h,i. At 0.1 Ag−1 current density, the Ti2NbC2Tx MXene electrode provides a dis‐
Materials 2025, 18, 2386 27 of 49

charge capacity of 305.7 mAhg−1 at the first cycle which is less than that of Ti3C2Tx
MXene. However, Ti2NbC2Tx anodes consistently provide superior multiplication per‐
formance even at different current densities. And after 4000 cycles, the capacity of
Ti2NbC2Tx was 198 mAh g−1 with a retention rate of 81%, which was much higher than
that of Ti3C2Tx anode (47.4%), and the cycling efficiency was always higher. The reason
may be due to the fact that the addition of Nb enlarges the Ti2NbC2Tx MXene interplanar
spacing and provides more active sites, resulting in a lower charge transfer resistance
and a faster Li+ migration rate. Lu et al. [120] used self‐assembly to anchor zero‐
dimensional carbon dots (CDs) on the Ti2NbC2Tx MXene surface via Ti(Nb)‐O‐C cova‐
lent bonds to successfully form a composite anode. After 10,000 cycles at 5 A g−1, its lith‐
ium storage capacity was able to remain stable at 217.3 mAh g−1. Compared with Ti3C2Tx
and Ti2NbC2Tx, the Ti2NbC2Tx@CDs exhibit higher specific capacity and stronger stabil‐
ity. This is attributed to the synergistic effect of dual transition metals in Ti2NbC2Tx,
which expands the interlayer spacing and optimizes the electronic structure, thereby ef‐
fectively enhancing ion diffusion rates and charge transfer efficiency. Additionally, the
double‐transition metal MXene demonstrates significantly superior lithium storage ca‐
pacity, cycle life, and rate performance compared to single‐metal MXenes, highlighting
its greater application potential in electrochemical energy storage systems.
Overall, the current mainstream strategy for constructing high‐performance 2D
MXene‐based electrodes typically involves combining MXene nanosheets with other
electrochemically active phases (such as metal hydroxides, transition metal ox‐
ides/sulfides) to construct diverse 3D architectures. This is because these electrochemi‐
cally active phases, owing to their unique electronic structures and variable valence
states, can undergo reversible transformations during lithium intercalation—for exam‐
ple, titanium‐based and vanadium‐based oxides can reversibly convert to provide high‐
capacity lithium storage sites, thereby enabling efficient charge transfer in electrochemi‐
cal processes. Moreover, constructing 3D MXene electrodes with structures like three‐
dimensional porous structures, three‐dimensional columnar structures, three‐
dimensional stacked structures, and three‐dimensional skeleton structures can effective‐
ly prevent the restacking of two‐dimensional nanosheets due to van der Waals forces.
It is worth noting that the ST‐2@MXene@CMS electrode demonstrated high specific
capacity and cycling stability, but its initial Coulombic efficiency (89.3%) still has room
for improvement. This reflects the fact that the problem of controlling SEI films on sili‐
con surfaces has not yet been fully solved. Combined with the nitrogen interface layer
design by Han et al. [106], it can be speculated that the uniformity of the interface chem‐
ical composition is the breakthrough direction for future electrochemical performance.
The introduction of nitrogen not only enhances the interfacial binding force but may also
suppress the excessive decomposition of the electrolyte by adjusting the electron density
on the silicon surface. With the assistance of machine learning for structural optimiza‐
tion, precise control of the electrode porosity and the distribution of the conductive net‐
work can be achieved, thus overcoming the limitation of “the complexity of ion diffusion
paths within the three‐dimensional structure”. In addition, current research has not fully
utilized the interlayer active sites. The lithium–ion storage capacity between phos‐
phorene layers can be further activated through defect engineering (such as phosphorus
vacancies and antimony doping). Inspired by the corrugated design of Li et al. [110], if
nanoscale support columns or functional molecules like conductive polymers are intro‐
duced between the layers, a dual‐site storage mechanism of surface adsorption and in‐
terlayer insertion can be established while maintaining the interlayer distance, so that
the specific capacity of two‐dimensional materials is no longer limited by the specific
surface area.
Materials 2025, 18, 2386 28 of 49

4.2. Sodium–Ion Batteries

Lithium is a very small element in the earth’s crust, and the cost of using lithium–
ion batteries has increased dramatically in recent years as the scale of development and
use has expanded. As a result, energy storage technologies other than lithium are attract‐
ing much attention [121]. While sodium is extremely abundant in the earth, making it
one of the most promising alternatives to lithium–ion batteries [122]. However, the ionic
radius of sodium is larger than that of lithium, resulting in more difficult intercalation
and deintercalation of sodium ions compared to lithium ions, along with slower kinetics.
As a result, traditional anode materials for lithium ions, such as graphite, are not suita‐
ble for sodium ions [123,124]. Therefore, the development of anode materials with high
sodium storage capacity and long life is the current problem to be solved for sodium–ion
batteries. Density Functional Theory (DFT) calculations show that sodium ions (Na+) can
be smoothly embedded into the lattice structure of Ti3C2Tx MXene with a low diffusion
energy barrier of 0.41 eV [125]. It is shown that Ti3C2Tx MXene is expected to achieve ef‐
ficient charge transfer and storage when used as an anode material for sodium–ion bat‐
teries.
The embedding mechanism of sodium ions in MXene is important for the study of
sodium–ion battery materials. During the charge–discharge processes of MXene elec‐
trodes, the two primary factors contributing the most to metal–ion capacity are solvated
metal ions adsorbed on the MXene surface and completely desolvated metal ions inter‐
calated into the interlayer spaces of MXene sheets [126]. Xie et al. [127] discovered that
surface functional groups and transition metal species significantly influence the capaci‐
ty and voltage of MXenes. Specifically, M2C MXenes (M = Sc, Ti, V, etc.) with ‐O termina‐
tions or no functional groups exhibit better applicability for sodium–ion batteries com‐
pared to those with other terminal groups. DFT calculations also confirm this. Sodium
ions can be efficiently adsorbed by MXene without termination groups or ‐O terminals
through good negative adsorption energy. On Ti2CO2, the adsorption energy of Na+ is
−0.202 eV/atom (as shown in Figure 11i). While on the Ti2C surface, despite the absence
of O atom coordination, Na+ can still form a stable adsorption layer through metal–
carbon bond interactions with an adsorption energy of approximately −0.1 eV/atom, as
depicted in Figure 11j. Meanwhile, terminal‐free and ‐O terminated MXenes exhibit low
diffusion barriers and open‐circuit voltages (OCV) for sodium ions, indicating their
promise as anode materials with high capacity and excellent rate performance. In con‐
trast, ‐F and ‐OH terminated MXenes show weaker adsorption capabilities toward sodi‐
um ions. Beyond serving as electron‐rich terminal groups that enhance adsorption of
metal ions like Na+, oxygen terminations (‐O) also participate in heterojunction for‐
mation through both electrostatic interactions and covalent bonding. For example,
Ti3C2Tx MXene, with abundant ‐O terminations on its surface, forms Ti‐O‐P/Ti‐O‐Sb co‐
valent bonds with phosphorene/antimonene to create heterojunctions. MXene surfaces
obtained by etching Ti3AlC2 with LiF/HCl carry negative charges due to their rich ‐O, ‐
OH, and ‐F terminations. Cationic modification (PEI) of Si/TiO2 carbon fibers enables the
formation of stable composite structures with MXene via electrostatic bonding, leverag‐
ing the charged nature of these terminal groups.
Similar to lithium–ion batteries, the stacking of MXenes nanolayers causes their ac‐
tive surface to shrink, resulting in a decrease in their electrochemical performance.
Moreover, the insertion and extraction of sodium ions will affect the volume changes of
the anode material, causing expansion and contraction, resulting in structural instability
and even cracking and pulverization. Similarly, by rationally constructing MXene‐based
3D porous composite materials and taking advantage of the high electrical conductivity
and good mechanical flexibility of MXene, these problems can be effectively solved.
Zhang et al. [128] utilized amino acid molecules, including L‐aspartic acid, L‐glutamic
Materials 2025, 18, 2386 29 of 49

acid, and L‐2‐aminoadipic acid (abbreviated as LAA, LGA, L2AA, collectively named
LXA), which possess surface ‐COOH groups. These groups form strong amide (HN‐
C=O) bonds with the ‐NH2 groups of amino‐functionalized Ti3CN‐NH2 MXene. This
bonding process creates a stable interlayer tenon–mortise structure in the composite. The
resulting materials are named LAA‐TCN, LGA‐TCN, and L2AA‐TCN, collectively ab‐
breviated as LXA‐TCN, as shown in Figure 11a. This tenon–mortise structure is analo‐
gous to pillars between nanolaminar sheets, effectively enabling controlled expansion of
the interlayer spacing. In the in situ XRD pattern of L2AA‐TCN (Figure 11b), the (002)
diffraction peak exhibits negligible shifts during discharge and charge processes, indi‐
cating that L2AA‐TCN maintains a stable lamellar structure. This pillar effect, combined
with the strain tolerance of the MXene skeleton, enables stable and fast Na+ storage. At a
current density of 1.0 A−1, after 1200 cycles (Figure 11c), the reversible capacities of
L2AA‐TCN, LGA‐TCN, and LAA‐TCN are 121.7, 84.1, and 64.1 mAh g−1, respectively,
with capacity retentions of 68.1%, 63.5%, and 61.2%, significantly higher than that of
pristine Ti3CN MXene (40.5%). Beyond structural tuning of MXene‐based composites,
transition metal oxides/sulfides, owing to their higher mass capacities, have been widely
employed as electrode materials for lithium–ion batteries [129,130]. For instance, upon
simple combination with graphene, MoO3 nanoplates serve as anode materials for sodi‐
um–ion batteries and exhibit outstanding electrochemical performance [131]. But this
type of transition metal oxides/sulfides is also accompanied by the disadvantages of in‐
sufficient electrical conductivity and large volume expansion rate during charging and
discharging. Yu et al. [132] employed vapor sulfidation and NC coating methods to en‐
capsulate an N‐doped carbon layer on the surface of the MoO3/MoS2 heterostructure.
The resulting material was then physically mixed with MXene nanosheets and modified
to form a MoO3/MoS2/NC/MXene composite, as illustrated in the process structure of
Figure 11d. Due to the different electron affinity energies (Efbs) of MoO3 and MoS2, a
built‐in electric field is formed between MoS2 and MoO3 until they reach the same Efb.
This heterogeneous heterostructure acts as an accelerator for electron transport, thereby
enhancing the composite’s ultrafast electron diffusion and sodium–ion transport capa‐
bilities. The introduction of sulfidation, NC coating, and MXene significantly enhances
electrical conductivity and ionic diffusion/transport kinetics. Electrochemical perfor‐
mance analysis (as shown in Figure 11e,f) reveals that the MoO3/MoS2/NC/MXene elec‐
trode delivers a reversible capacity of 464 mAh g−1 at a low current density of 0.1 A g−1,
higher than the MXene‐free MoO3/MoS2/NC electrode (326 mAh g−1). Notably, it retains
a discharge capacity of 202 mAh g−1 even at a high current density of 5 A g−1. Additional‐
ly, at a current density of 1 A g−1, the electrode material retains a high discharge capacity
of 320 mAh g−1 after 2000 cycles, with a capacity retention close to 100%, demonstrating
excellent electrochemical performance. In contrast, the MXene‐undoped MoO3/MoS2/NC
electrode experiences a drastic capacity drop to 141 mAh g−1 after 2000 cycles. Clearly,
without the mechanical support of MXene, the electrode structure is prone to collapse.
By contrast, the introduction of MXene establishes a 2D conductive network that signifi‐
cantly accelerates electron transport. Meanwhile, its flexible nanosheets effectively buff‐
er volume expansion during cycling and optimize ionic diffusion kinetics, thereby
achieving synergistic enhancement of electrochemical performance.
Materials 2025, 18, 2386 30 of 49

Figure 11. (a) Schematic diagrams of three LXA‐TCN structures. (b) Galvanostatic charge–
discharge (GCD) curves and in situ XRD patterns of L2AA‐TCN. (c) Cycling stability of LXA‐TCN
and TCN at 1.0 A g−1. (a–c) Reproduced with permission [128]. Copyright 2024, Elsevier BV. (d)
Synthesis process and structural schematic of the MoO3/MoS2/NC/MXene composite. (e) Specific
capacities of different samples at various current densities. (f) Cycling performance curve of
MoO3/MoS2/NC/MXene at 1 A g−1. (d,f) Reproduced with permission [132]. Copyright 2024, Else‐
vier BV. (g) Specific capacity of different samples at different current densities. (h) Cycling per‐
formance curves of MoO3/MoS2/NC/MXene at 1 A/g. (g,h) Reproduced with permission [133].
Materials 2025, 18, 2386 31 of 49

Copyright 2024, Elsevier BV. (i) Ion adsorption energy on ‐O terminated MXene nanosheets. (j)
Ion adsorption energy on non‐terminated MXene nanosheets. (i,j) Reproduced with permission
[127]. Copyright 2014, American Chemical Society.

In addition to the above‐mentioned tin sulfides and MoS2, other 2D metal sulfides
such as VS2 are regarded as the next generation of anode materials for lithium/sodium–
ion batteries due to their unique layered structure and ultra‐high theoretical specific ca‐
pacity [134,135]. But they still can not avoid the volume expansion and agglomeration
during the cycle process, and their own poor electrical conductivity, resulting in a de‐
cline in electrochemical performance [136]. Vanadium sulfides (e.g., VS2, VS4, and V5S8)
have been used as energy storage materials due to their multivalent properties. In par‐
ticular, VS4 has a quasi‐one‐dimensional chain structure connected by S22− dimers, and
the chains are linked by weak van der Waals forces to form a wide chain spacing (5.83
Å), which facilitates Li+ and Na+ insertion and extraction [137,138]. Similarly, the weak
van der Waals forces between the layers in the two‐dimensional layered structure of
SnS2 facilitate the embedding/de‐embedding of ions and effectively mitigate the volume
expansion of the electrode material. Hou et al. [133] uniformly fixed the VS4/SnS4 het‐
eronanosheets obtained through hydrothermal reaction on the surface of MXenes by
electrostatic self‐assembly, and prepared a heterogeneous‐structured bimetallic sulfide
VS4/SnS2@MXene nanosheet, whose structure is shown in Figure 11g. Similarly, this het‐
erogeneous interface accelerates the transport of ions and electrons during electrode re‐
actions. MXene nanosheets effectively enhance the electrical conductivity of composite
electrodes, suppress volume expansion, and improve the reaction kinetics of the elec‐
trode. Based on this, cycling performance tests were conducted on different electrodes
(as shown in Figure 11h). The results show that after 200 cycles at 0.1 A g−1, the
VS4/SnS2@MXene composite electrode delivers a high capacity of 1565.3 mAh g−1, far ex‐
ceeding that of the SnS2@MXene and VS4@MXene electrodes. Even after 500 cycles, the
VS4/SnS2@MXene composite electrode maintains its original lamellar structure, indicat‐
ing no severe agglomeration or pulverization occurs during charging/discharging pro‐
cesses. Notably, the MXene‐free VS4/SnS2 composite electrode only delivers a capacity of
238 mAh g−1. This is because the 3D structure of MXene increases the electrode’s surface
area, enabling it to accommodate more VS4/SnS2 heterojunctions on its surface. This fea‐
ture thereby creates abundant ion storage sites, ultimately enhancing the electrochemical
performance of the composite electrode.
The ionic radius of Na+ (1.02 Å) is significantly larger than that of Li+ (0.76 Å), lead‐
ing to higher lattice stress during its intercalation. Zhang et al. achieved precise regula‐
tion of interlayer spacing through covalent bonding between amino acid molecules and
MXene layers, providing an adaptive space for Na+ insertion. In the
MoO3/MoS2/NC/MXene system, Yu et al. revealed that the built‐in electric field at the
heterojunction, enabled by Fermi level alignment and defect synergistic effects, signifi‐
cantly optimizes ion migration kinetics. Hou et al. further demonstrated in their three‐
dimensional VS4/SnS2@MXene bimetallic composite system that the combination of na‐
noscale interfacial covalent bonding (Ti‐O‐S bond collaborative anchoring) and mi‐
croscale heterogeneous porous frameworks achieves performance enhancement through
multiscale synergistic regulation. However, the matching between MXene surface
charge density and Na+ adsorption energy remains overlooked. Future research should
integrate theoretical calculations and in situ characterization to precisely tune surface
chemical states, such as through fluorination (‐F) or nitrogen doping, to enhance Na+
binding capability.
Materials 2025, 18, 2386 32 of 49

4.3. Lithium–Sulfur Batteries

Unlike lithium and sodium–ion batteries, the charging and discharging process of
Li–S batteries is carried out by breaking and forming S‐S chemical bonds in the middle
of the S8 molecule. When cathode sulfur is reduced to lithium sulfide (Li2S), it can theo‐
retically provide a specific capacity of 1675 mAh g−1 and an energy density of 2800
Wh/Kg, which is approximately three to five times higher than that of conventional lith‐
ium–ion batteries [139]. However, the research and development of lithium–sulfur bat‐
teries is mainly hindered by three problems: (1) the low conductivity of the sulfur cath‐
ode hinders the redox reaction, resulting in a reduction in the efficiency of the use of el‐
emental sulfur. (2) In the process of charging and discharging, soluble long‐chain sulfide
will be generated and pass through the diaphragm to circulate between the positive and
negative electrodes, resulting in the shuttle effect to make the active sulfur loss and re‐
duce the capacity of the battery. (3) Volume expansion during charging and discharging
[140–142].
MXene, with its abundant surface functional groups or grafted active sites, can ef‐
fectively anchor lithium polysulfides (LiPSs) and promote the formation of metal–sulfur
bonds, thereby inhibiting the aforementioned shuttle effect. In 2017, Nazar’s research
team systematically investigated the polysulfide anchoring mechanism of Ti‐based
MXene materials (including Ti2C, Ti3C2, and Ti3CN systems) for lithium–sulfur battery
systems [143]. Based on density functional theory (DFT) calculations, they revealed a
synergistic anchoring mechanism between the ‐OH terminations on the MXene surface
and Ti active sites: during the electrochemical cycling process, ‐OH groups first form
thiosulfate coordination intermediates with polysulfides, and then the exposed titanium
atoms form Ti‐S covalent bonds with sulfur species through their strong Lewis acidic
properties.
Through density functional theory (DFT) calculations, it was found that Ti2CF2 and
Ti2CO2, as conductive anchoring materials for lithium polysulfides (LiPSs), suppress the
shuttle effect through distinct mechanisms [144]. The F‐functionalized surface of Ti2CF2
inhibits the shuttle effect via strong interactions with LiPSs, with binding energies (1.02–
1.15 eV) higher than those with electrolytes (0.74–0.79 eV), effectively anchoring LiPSs
on the cathode and preventing their dissolution in the electrolyte. In contrast, the O‐
functionalized surface of Ti2CO2 converts soluble high‐order LiPSs (Li2S8, Li2S7, Li2S6) in‐
to insoluble elemental sulfur, thereby suppressing the shuttle effect. This stage‐
dependent mechanism provides a theoretical basis for designing MXene‐based function‐
al separators by efficiently restraining polysulfide shuttling.
In lithium–sulfur batteries, apart from its relatively high conductivity, the catalytic
effect of MXene is also of great importance. MXene is equipped with abundant surface
functional groups or can be grafted with more active sites, which can effectively anchor
LiPSs and promote the formation of metal‐S bonds, thereby suppressing the aforemen‐
tioned shuttle effect. The main strategy in past research was to introduce highly conduc‐
tive porous materials as scaffolds to alleviate volume expansion and enhance the con‐
ductivity of ions/electrons, thus addressing the above‐mentioned problems [145,146].
Optimizing the separator design to block the transport channels of polysulfides through
physical shielding and chemical anchoring is one of the important strategies to improve
the performance of lithium–sulfur batteries. Compared with traditional transition metal
oxides/sulfides, transition metal selenides have a larger atomic radius and lower ioniza‐
tion energy. Their unique d‐electron structures endow them with higher electrocatalytic
performance. In particular, the CoSe catalyst can accelerate the conversion of polysul‐
fides and Li2S. During the solid–solid conversion stage, it exhibits excellent adsorption
energy and free energy [147]. Building on this, Han et al. [26] utilized graphene oxide as
a conductive and assembly framework, and achieved the self‐assembly of 0D CoSe na‐
Materials 2025, 18, 2386 33 of 49

noparticles, 1D carbon nanofibers (CNFs), and 2D MXene via a hydrothermal reaction,

yielding a 3D aerogel functional separator (CCGM), as illustrated in Figure 12a. Trans‐
mission electron microscopy (TEM) observation of CCGM’s microscopic morphology
(Figure 12b) reveals that CoSe nanoparticles (~141 nm) are uniformly anchored within a
three‐dimensional network composed of carbon nanofibers, lamellar MXene, and a gra‐
phene substrate. Nitrogen adsorption–desorption isotherm analysis indicates that the
CCGM aerogel (Figure 12c) possesses a high Brunauer–Emmett–Teller (BET) specific
surface area of approximately 174.94 m2/g, providing abundant active sites for the ad‐
sorption and conversion of polysulfides. Notably, in lithium–sulfur batteries, the reduc‐
tion of Li2S2 to Li2S during discharge determines the battery’s discharge rate. The Gibbs
free energy profile from S8 to Li2S in Figure 12d reveals that the Gibbs free energy of
CoSe (0.84 eV) is lower than that of graphene (0.93 eV) and Ti3C2O2 (1.01 eV). This indi‐
cates that nanosized CoSe catalyst particles dispersed in the 3D conductive network can
effectively accelerate Li2S conversion, enabling fast conversion kinetics.
Within this network, the reticular structure formed by two‐dimensional graphene
and MXene effectively captures polysulfides, mitigating volume expansion and the shut‐
tle effect during charging and discharging processes. When the porous sulfur electrode
integrated with CCGM aerogel serves as the sulfur cathode (Figure 12e,f), it demon‐
strates a high initial discharge specific capacity of 1205 mAh g−1. Even at a high rate of
5C, it achieves reversible conversion of polysulfides. After 300 cycles, it retains a capaci‐
ty of 559.3 mAh g−1 with a decay rate of only 0.055% per cycle, exhibiting excellent elec‐
trochemical stability. By designing such adsorption–catalytic functional separators, the
migration of polysulfides toward the anode can be restricted. Controlling permeability
to enable selective Li+ transport retains dissolved lithium polysulfides (LiPSs) on the
cathode side, effectively alleviating the shuttle effect, improving charge transfer, and in‐
hibiting the nucleation and growth of Li dendrites.
Materials 2025, 18, 2386 34 of 49

Figure 12. (a) Schematic diagram of the synthesis process of the three‐dimensional CCGM aerogel.
(b) Transmission electron microscope image of CCGM. (c) N2 adsorption–desorption isotherms of
CGM and CCGM. (d) Relative Gibbs free energy spectra of reducing LiPSs on CoSe, graphene, and
MXene substrates. (e) Rate performance of S@CGM and S@CCGM cathodes. (f) Long‐term cycling
stability of the S@CCGM electrode at a high current rate of 1C. (a–f) Reproduced with permission
[26]. Copyright 2024, Elsevier BV. (g) Mott–Schottky type contact band diagrams of MXene (work
function Wm = 4.37 eV) and SnO2 (work function Ws = 3.84 eV). (h) Rate performance of batteries
with different separators at current rates from 0.1C to 2C. (i) Cycling performance at a small cur‐
rent rate of 0.05C. (j) Long‐term cycling performance at a high current rate of 2C. (g–j) Repro‐
duced with permission [148]. Copyright 2024, Springer Nature.

In lithium–sulfur batteries, when the electronic structures on both sides of the het‐
erojunction change, it can effectively enhance the strong chemical adsorption and cata‐
lytic effect on LiPSs [149]. Deng et al. [148] first obtained single‐layer Ti3C2Tx MXene
(SnO2@MXene) nanosheets modified by SnO2 nanoparticles through the hydrothermal
method. Then, they mixed them with N‐methyl‐2‐pyrrolidone and dried them in a vac‐
uum on both sides of a polypropylene film to obtain a special heterogeneous structure
interlayer (SnO2@MXene‐modified PP film). The SnO2@MXene heterojunction, as shown
in Figure 12g, exhibits a charge transfer behavior where electrons migrate from SnO2 to
MXene when Ti3C2Tx MXene comes into contact with semiconducting SnO2. This process
Materials 2025, 18, 2386 35 of 49

forms a negatively charged accumulation region near MXene, generating a built‐in elec‐
tric field (BIEF) that promotes electron transfer, thereby enhancing the adsorption and
conversion of lithium polysulfides (LiPSs).
Taking CNT (carbon nanotube)/S as the cathode and using three intermediate dia‐
phragms, namely PP, MXene‐PP (single‐layer MXene without SnO2 modification), and
SnO2@MX‐PP, to assemble coin batteries for different electrochemical performance anal‐
yses, as shown in Figure 12h–j. The SnO2@MXene‐PP separator‐based coin cell delivers a
high initial capacity of 1414 mAh g−1 at 0.05C, and even at a high current rate of 2C, it re‐
tains an initial capacity of 845 mAh g−1. This value is significantly higher than those of
MX‐PP (1230 mAh g−1) and PP (1150 mAh g−1), with a 25.3% capacity increase especially
at the second discharge plateau (Li2S deposition), indicating more efficient conversion of
lithium polysulfides (LiPSs). Ye et al. [150] also designed a selective membrane that
combines diamino crown ether (CE) with two‐dimensional graphene oxide (GO) as an
ion sieve layer. The modified GO‐CE ion sieve layer can also be further combined with
MXene to improve ionic conductivity, and the abundant functional groups brought by
MXene and CE can form supramolecular channels, thereby suppressing the shuttle of
Lps. This intermediate layer with a special structure has been proven to effectively im‐
prove the rate performance and cycling stability of the battery and enhance the electro‐
catalytic efficiency of sulfur in lithium–sulfur batteries.
To address the shuttle–deposition cycle of LiPSs, the heterojunction enhances the
chemical anchoring of LiPSs through charge redistribution, while the built‐in electric
field accelerates the electron migration, providing a kinetic advantage for the catalytic
reaction. By introducing semiconductor/metal compounds to construct heterojunctions
(e.g., transition metal selenides, oxides), the electronic states on the surface of MXene can
be targeted to optimize the adsorption energy and conversion pathway of LiPSs. In the
future, the heterojunction components matching with MXene can be screened in combi‐
nation with density functional theory (DFT) calculations to realize the precise regulation
of interfacial effects.

4.4. Multivalent Ion Batteries

In addition to the combination of MXene as a substrate or catalytic main body with
LIB mentioned above, other types of multivalent ion batteries (MVIBs) are also expected
to have a relatively high theoretical capacity and are expected to become the next‐
generation new batteries [10,127]. The difference from the aforementioned lithium–ion
and sodium–ion batteries lies in that high‐valence ions (such as Zn2+, Mg2+, and even
higher‐valence Al3+, etc.) can carry more charges, thus having the potential for greater
energy density and faster charging and discharging [10,151]. Research on zinc–ion bat‐
teries began as early as the 1970s. However, due to the limitations of materials at that
time, it did not develop significantly. It was not until recently that MXene materials with
excellent energy storage potential were discovered and the research and development of
lithium–ion related batteries reached a bottleneck that the research on multivalent ion
batteries such as zinc–ion batteries was explored again. Nevertheless, the most promi‐
nent problem with multivalent ion batteries lies in their limited specific capacity. Since
their volume is much larger than that of lithium ions, it leads to slow insertion kinetics
in the electrode materials [152]. In addition, due to the uneven zinc deposition, zinc
dendrites are prone to form on the zinc anode during the charging and discharging pro‐
cess, and they may even pierce the electrode separator, resulting in a short circuit, which
will affect the battery structure and safety [153]. Therefore, the electrode structure needs
to be further optimized.
The MXene surface is rich in end groups such as ‐OH, ‐O, and ‐F, which regulate
the adsorption and desorption behavior of ions through electrostatic interactions or hy‐
Materials 2025, 18, 2386 36 of 49

drogen bonding. For example, the ‐OH and ‐O groups enhance the hydrophilicity of
MXene and facilitate ion transport in aqueous electrolytes. And the ‐F group regulates
the electronic structure and optimizes the desolvation process of ions. These embedded
ions are first adsorbed on the surface and then diffuse toward the interlayer of MXene,
forming a double ionic layer within a monolayer sharing the same sites [154]. As em‐
bedding/de‐embedding proceeds, the interlayer spacing widens due to solvent mole‐
cules and trapped cation column support. Notably, in aqueous zinc–ion batteries, Zn2+
binds to water molecules to form the hydrated ion [Zn(H2O)6]2+, whose effective diame‐
ter significantly expands from 0.15 nm for bare ions to 0.86 nm. And it will hinder the
diffusion of ions in the narrow space of MXene, leading to capacity loss. To address the
performance degradation caused by narrow interlayer spacing, Zhao et al. [155] em‐
ployed a 3D macroporous pre‐intercalated pure Mg0.21Ti3C2Tx MXene‐based film as the
cathode for multivalent ion batteries (MIBs). However, pure MXenes are prone to inter‐
layer restacking during use due to van der Waals forces and mechanical stress generated
during cycling. Additionally, they exhibit significant volume changes during ion interca‐
lation, posing challenges to their structural stability. Peng et al. [156] employed diamines
of different sizes as pillars, which were inserted into MXene interlayers via a one‐step
amination reaction and covalently crosslinked with surface (‐OH/‐O) functional groups.
This approach enabled precise regulation of interlayer spacing and formation of three‐
dimensional (3D) porous hydrogel/aerogel structures, simultaneously enhancing specific
capacitance and effectively suppressing structural collapse during long‐term cycling.
Moreover, the surface functional groups of pure MXene batteries and the reversible ca‐
pacity of their double‐layer capacitive structure are lower than those of conventional
zinc–ion batteries. Therefore, the direct use of pure MXenes as electrode materials re‐
mains a challenge. Generally, during crystal nucleation and growth, a large amount of
two‐dimensional (2D) conductive materials such as MXenes are introduced as conduc‐
tive substrates for in situ growth to construct heterostructures [157,158]. Introducing a
certain amount of single‐layer Ti3C2 MXene thin nanosheets to regulate the growth struc‐
ture of vanadium oxide crystals V2O5∙6H2O (HVO) significantly enhances electrochemi‐
cal performance by introducing defects into the cathode material. Scanning electron mi‐
croscopy (SEM) observation (Figure 13a) reveals that HVO is selectively grown at specif‐
ic sites on Ti3C2 MXene, causing its morphology to transition from a multi‐layer self‐
stacked wrinkled structure to a reticular porous structure (T‐HVO). Electrochemical
characterization of the obtained cathode material is shown in Figure 13d. When the cur‐
rent density increases from 0.2 to 30 A g−1, the specific capacity of the T‐HVO‐20 h elec‐
trode at different current densities is higher than that of the pure HVO electrode without
MXene. Additionally, after 1000 cycles, the T‐HVO electrode still maintains a reversible
capacity of 276.9 mAh g−1. In contrast, the pure HVO electrode without MXene has an in‐
itial capacity of 336.9 mAh g−1, but its capacity retention drops to only 48 mAh g−1 after
1000 cycles. In addition, in the Ragone diagram (Figure 13b), the T‐HVO electrode exhib‐
its a remarkable energy density of 309.2 Wh/kg and a power capacity of 17.6 kW/kg,
which are far higher than those of the HVO electrode. The significant improvement in
electrochemical performance can be attributed to the following reasons. The O function‐
al groups with low binding energy on the MXene surface form V‐O‐Ti bonds with the
vanadium oxide crystals, resulting in a strong interfacial interaction between the two
phases. Under the induction of MXene, a large number of bicoordinate oxygen defects
are generated at the lattice interface. Along with the increase in the EPR intensity signal,
the number of unpaired electrons increases, causing more V5+ to be transformed into V4+
through electron transfer. As shown in Figure 13c, with the extension of the induction
growth time, both pairs of oxidation peaks shift to the left (the blue part represents
V5+/V4+, and the red part represents V4+/V3+). However, the area of the first pair of redox
Materials 2025, 18, 2386 37 of 49

peaks corresponding to V4+/V3+ expands significantly, indicating that the generation of

oxygen defects leads to an increase in the proportion of V4+. It should be noted that these
bicoordinate oxygen defects mainly enhance the reactivity of the V4+/V3+ reaction, and
promote the transfer of charges and the adjustment of active sites. Similarly, in the T‐
HVO electrode, the current response in Zone II broadens (Figure 13e), proving that the
redox reaction of V4+/V3+ is significantly improved. It also demonstrates that the exist‐
ence of oxygen defects does improve the reactivity, and increase the solid diffusion rate
of zinc ions and the conductivity of the electrode, which is beneficial for accelerating the
electrochemical intercalation reaction and significantly improving the capacity and rate
performance of the zinc–ion battery.

Figure 13. (a) SEM images of HVO and T‐HVO with different induction growth times. HVO selec‐
tively grows on Ti3C2 MXene (i) as a reticulated porous structure (ii). (b) Ragone diagrams of dif‐
ferent vanadium oxides as cathodes of zinc–ion batteries. (c) Comparison of CV curves of HVO
and T‐HVO electrodes in the fourth cycle. (d) Electrochemical properties of HVO and T‐HVO: (i)
Cycling stability test of HVO and T‐HVO at 10 A/g. (ii) Comparison of rate performance at differ‐
ent current densities. (e) Current density diagrams at different potentials during the battery dis‐
charging process, showing the current response during the battery discharging process and the
changes in the response diffusion coefficient at different potentials. Zone I represents the redox re‐
action of V5+/V4+, and Zone II represents the redox reaction of V4+/V3+. (a–e) Reproduced with per‐
mission [159]. Copyright 2024, Wiley‐VCH. (f) SEM image of mesoporous Mn2O3@TiO2@MXene.
Reproduced with permission [160]. Copyright 2023, Wiley‐VCH. (g) Schematic diagrams of a
standard battery with a Mg metal anode and an anode‐free battery with a MXene film as an anode
current collector, as well as schematic diagrams of the porous Mg deposition on Cu and the hori‐
zontal Mg deposition behavior on Ti3C2Tx MXene film. (h) (i,ii) are the plating/stripping perfor‐
mances of Mg/Cu and Mg/Ti3C2Tx batteries at 1.0 mA/cm2 and 50% DOD, respectively. (i) Cycling
performance test of an anode‐free battery with an activated Ti3C2Tx MXene film. (g–i) Reproduced
Materials 2025, 18, 2386 38 of 49

with permission [161]. Copyright 2023, Wiley‐VCH. (j) Comparison of rate performances of meso‐
porous Mn2O3 and mesoporous Mn2O3@TiO2@MXene. (k) Comparison of rate performances of
mesoporous Mn2O3 and mesoporous Mn2O3@TiO2@MXene. (j,k) Reproduced with permission
[160]. Copyright 2023, Wiley‐VCH. (l) Zeta potentials of different Ti3C2Tx‐based materials. (m) Cy‐
cling performances of different Ti3C2Tx‐based batteries. (l,m) Reproduced with permission [162].
Copyright 2024, Wiley‐VCH.

Magnesium–ion batteries (MIBs), also known as multivalent ion batteries, are con‐
sidered to be one of the next generation of low‐cost, high‐energy energy storage devices
[163]. MIBs have a larger specific capacity than traditional LIB batteries [164]. However,
unlike the SEI film which is beneficial to the performance of lithium–ion batteries, mag‐
nesium–ion batteries mostly use organic or ionic liquid electrolytes, and Mg2+ has strong
electrostatic interaction and low conductivity. The formed solid electrolyte film is not
conducive to the reversible insertion/extraction and interfacial diffusion of ion fluxes on
the cathode, and even causes the inactivation of the electrode surface, resulting in capac‐
ity attenuation [165]. Through chemical adsorption by the oxygen (‐O) and fluorine (‐F)
terminations on the MXene (Ti3C2Tx) surface, the local Mg2+ concentration is significantly
enhanced, addressing the migration barrier caused by the strong Coulombic force of
multivalent ions. Li et al. [160] reported a three‐phase heterogeneous structure of meso‐
porous Mn2O3@TiO2@MXene, and its morphological characterization is shown in Figure
13f. It has an initial capacity as high as 241.5 mAh g−1 at 0.1 A g−1 and exhibits excellent
electrochemical rate performance (Figure 13k). When an aqueous magnesium–ion capac‐
itor composed of mesoporous Mn2O3@TiO2@MXene as the positive electrode material
and activated carbon (AC) as the negative electrode material was subjected to 2400 cy‐
cles of testing at a current density of 1.0 A g−1, its capacity retention rate was still 99.91%
(Figure 13j). The heterogeneous structure formed by MXene and TiO2 particles derived
from Mn2O3 can mitigate the volume expansion of manganese sesquioxide, significantly
solving the problems of interface separation and decline in electrochemical performance
caused by the instability of other heterogeneous structures. Apart from the acceleration
of magnesium–ion diffusion by the inherent electric field generated by the heterojunc‐
tion, the improvement in performance is mainly due to the large number of interfaces
(specific surface area of 37.73 m2/g) generated by the three‐phase heterogeneous struc‐
ture of mesoporous Mn2O3@TiO2@MXene, which can provide abundant active sites for
magnesium ions.
In addition, apart from the problem of the rate of movement, insertion, and extrac‐
tion of magnesium ions in the electrolyte, how to design a reasonable electrode structure
to avoid the waste of active metals caused by using large pieces of active metals as an‐
ode electrodes and to reasonably increase the energy density of the battery is also an im‐
portant issue [166]. Based on this, researchers have designed an anode‐free battery struc‐
ture. For example, in rechargeable magnesium–ion batteries, an inactive material is used
to construct a current collector. During the initial charging and discharging cycles, Mg2+
is deposited on it, and it participates in the electrode reaction as the negative electrode in
subsequent cycles [167]. The cathode rich in magnesium ions is the main source for
magnesium deposition on the anode during charging, thus reducing the volume and
weight of the battery and avoiding the decrease in energy density caused by large anode
materials [168]. However, how to ensure that magnesium can be continuously deposited
during the continuous charging process, maintain a stable electrode structure, and sup‐
press the growth of dendrites during deposition remains an issue to be resolved for cur‐
rent anode‐free magnesium metal batteries.
Li et al. [161] prepared an anode‐free magnesium metal battery by parallel stacking
single‐layer Ti3C2Tx films as current collectors. The schematic diagrams of a standard
Materials 2025, 18, 2386 39 of 49

battery with a Mg metal anode, an anode‐free battery with Ti3C2Tx films as anode cur‐
rent collectors, and the porous Mg deposition behavior on the corresponding traditional
Cu current collector as well as the horizontal Mg deposition on the surface of the Ti3C2Tx
current collector are shown in Figure 13g. Due to the unique two‐dimensional layered
structure and excellent mechanical properties of Ti3C2Tx, it can improve the adhesion of
magnesium metal during the initial deposition and control the volume change of the
electrode. Moreover, the surface of the Ti3C2Tx film is uniformly distributed with func‐
tional groups such as magnesiophilic active oxygen and active fluorine, which attract
magnesium ions and form a dense MgF2‐rich SEI film around the inactive current collec‐
tor anode. In addition, Ti3C2Tx has an approximate lattice matching degree (≈96%) with
Mg, thereby being able to guide the nucleation and growth of Mg on the surface of
MXene sheets. Working together with the uniformly high magnesium–ion concentration
around the SEI film, it results in a uniform and stable horizontal electrodeposition of
Mg. The results show that, as shown in Figure 13h(ii), when the battery is cycled at a
current density of 1.0 mA/cm2 with a fixed capacity of 1.0 mAh/cm2 (QC) until the charg‐
ing voltage reaches the limit of 1 V (QS), the Ti3C2Tx MXene film anode with secondary
deposited magnesium metal after pretreatment can still maintain a Coulomb efficiency
(CE) of 99.4% and a high magnesium utilization rate (depth of discharge, DOD) of 50%
after 364 cycles of testing at a high current density of 5.0 mA/cm2. Compared with the
uneven magnesium deposition produced when the traditional copper foil is used as the
anode current collector (Figure 13h(ii)) (70 cycles, CE = 98.4%), the charging curve of
Ti3C2Tx MXene as an inactive anode is more stable (Figure 13h(i)), achieving unprece‐
dented high efficiency and long‐life magnesium plating/stripping performance. In addi‐
tion, a full battery was composed of Ti3C2Tx MXene as an anode current collector and a
coupled pre‐magnesified Mo6S8 cathode, and its cycling performance was tested at a cur‐
rent density of 0.1 C (1C = 128 mA g−1) (Figure13i). The initial discharge capacity of the
battery was 63.2 mAh g−1, and after 100 cycles, it still had a capacity retention rate of
47.2%, which is much higher than that of the traditional standard magnesium metal an‐
ode battery, showing good cycling stability and relatively high energy density.
In addition to zinc–ion and magnesium–ion batteries, more expensive aluminum–
ion batteries have extremely rich reserves in the earth’s crust, and trivalent aluminum
can carry more electrons, with a higher theoretical capacity (2980mAh g−1) and energy
density [169–171]. But the problems are also very prominent. First, similar to magnesi‐
um–ion batteries, the migration of ions and electrons is hindered by the electrolyte as
well as by stronger electrostatic interactions [172]. Second, the embedding/de‐
embedding process of aluminum ions involves the migration of bulk AlCl4– rather than
Al3+, which leads to a further decrease in the diffusion rate as well as a further increase
in the electrode material requirements. Guan et al. [162] proposed a strategy to regulate
the surface charge of the MXene cathode to overcome the above difficulties. Although
using pure MXene as the cathode material, the insertion of a large number of AlCl4− ions
during the charging and discharging process can expand the layer spacing of the neigh‐
boring MXene layers, which can effectively solve the problems of stacking and volume
expansion between the layers. However, the Ti3C2Tx MXene obtained after etching with
a large number of surface functional groups such as OH and COOH will make it nega‐
tively charged as a whole, which further causes a certain electrostatic repulsion to the
embedding/de‐embedding process of AlCl4−. The zeta potential of Ti3CNTx (13.4 mV)
was found to be much lower than that of Ti3C2Tx (30.4 mV) by doping N with Co atoms,
as shown in Figure 13l. The zeta potential of Ti3CNTx (13.4 mV) was found to be much
lower than that of Ti3C2Tx (30.4 mV) by doping N with Co atoms. It indicates that the
doping of N effectively reduces the surface negative charge density, while the addition
of Co causes the surface charge to finally become positive. This change in surface charge
Materials 2025, 18, 2386 40 of 49

reverses the electrostatic interaction between MXene and active anions from electrostatic
repulsion to electrostatic attraction, allowing more AlCl4− ions to be embedded in the in‐
terlayer of Ti3CNTx@Co, thus increasing its capacity. The results show that the
Ti3CNTx@Co cathode–Al anode cell has an ultra‐high capacity of up to 240 mAh g−1
compared with the graphite cathode used in the past (Figure 13m), and still maintains a
high reversible capacity after 600 cycles.
The application of MXenes in multivalent ion batteries (MVIBs) essentially leverag‐
es their 2D layered structure, tunable surface chemistry, high electrical conductivity, and
other multifunctional properties to construct integrated systems. Existing studies have
effectively alleviated challenges such as slow multivalent ion migration, high interfacial
impedance, and dendrite growth through strategies like interlayer spacing regulation,
heterostructure construction, and surface charge engineering. However, further explora‐
tion is still needed in areas such as interfacial chemistry, multiscale structural design,
and material compatibility. Future efforts could involve combining high‐throughput cal‐
culations to screen optimal functional group combinations or developing MXene‐based
composite electrolytes, aiming to promote MVIBs as complementary and potentially su‐
perior alternatives to lithium–ion batteries.

5. Conclusions and Outlook

MXene is an emerging 2D layered material, which has been widely used in energy
storage in recent years due to its unique properties. This paper systematically introduces
the structure, properties, and general synthesis method of MXene. It focuses on the great
potential of MXene for applications in the field of lithium–ion, sodium–ion, lithium–
sulfur, and multivalent ion batteries. The problems faced by different energy storage
schemes and the efficient and safe solutions proposed for these problems are studied
and outlined. Summarizing the research in recent years, it can be found that the indirect
use of MXene is primarily aimed at enhancing electrode performance through the fol‐
lowing aspects.
1. Utilizing its excellent conductivity and two‐dimensional layering, it is used as a
conductive substrate for composite electrodes. MXene’s rich surface functional groups
grafting/growth of other electrochemically active phases such as transition metal ox‐
ides/sulfides or even a variety of common composite composite composition of different
dimensions of the conductive framework. The linkage between the two is generally
achieved by direct chemical synthesis through physical mixing (mechanical ball‐milling
mixing or wet dispersion freeze‐drying mixing), in situ growth or solvothermal meth‐
ods, or by electrostatic/other forces to realize the self‐assembly of MXene and the anode
material into a solid transition layer or to form heterostructures connected by covalent
bonds. The electrochemically active phase is able to provide higher capacity storage sites
by virtue of its special electronic structure and variable valence state of the chemistry,
thus enabling efficient charge transfer in electrochemistry.
2. Design of the structure of the electrode material. Early studies have shown that
the use of MXene to build three‐dimensional structures such as three‐dimensional skele‐
ton, aerogel, etc., as the cathode framework and grafting composite other materials with
excellent electrochemical properties, not only can retain the characteristics of the electro‐
chemically active phase of the high‐capacity, but also use the high electrical conductivity
and mechanical stability of MXene to avoid the cathode volume expansion brought
about by the problem of pulverization. It is also very important for the stable output of
the battery under long cycle.
3. Utilizing the special layer structure of MXene. How to avoid stacking between
the layers and expand the layer spacing, which can further accommodate larger and
more charged multivalent ions, and also bring larger specific surface area, which are
Materials 2025, 18, 2386 41 of 49

very important for the capacity of the battery, reducing the formation of dendrites, and
enhancing the kinetics of ion embedding/de‐embedding to the cathode.
4. In the above study, it can also be found that the modulation of MXene surface
functional groups into active sites with electrostatic attraction to multivalent ions also
contributes significantly to the battery capacity enhancement.
The charging and discharging process of multivalent ion batteries is very complex,
with both mass transfer problems of ions in specific electrolytes, desolvation at the elec‐
trode interfaces and diffusion problems of reduction and deposition on SEI membranes,
which often lead to slow ion kinetics and are difficult to replicate again by conventional
single methods. However, high‐priced ion batteries have the potential for greater cur‐
rent density, faster impulse discharge, and are currently one of the best alternatives to
replace lithium–ion batteries as a new and efficient energy storage device of the era.
Therefore, the current research needs to fully consider the excellent performance and
special structure of MXene itself for a comprehensive electrode design in order to avoid
material wastage and utilize its best performance. This review aims to consolidate the
past research results and summarize the latest research results in recent years, so as to
catalyze the generation of new MXene‐based electrode materials with even better per‐
formance.
Although MXene‐based electrode materials have been spread in various fields of
rechargeable batteries and have made great progress, there is still a lot of room for de‐
velopment for rechargeable batteries through the advancement of research and the de‐
velopment and innovation of a steady stream of new materials.
1. The complex preparation process is one of the key factors limiting the wide‐
spread development of MXene. Despite the toxicity of hydrofluoric acid (HF) and the
controversies over its environmental hazards, which make large‐scale production out‐
side laboratory settings difficult, alternative etching methods such as alkaline etching,
electrochemical etching, molten salt etching, and chemical vapor deposition (CVD) re‐
main in the early stages of research. These methods involve multiple reaction and etch‐
ing steps, which also increase production costs and reduce efficiency in practical appli‐
cations. Therefore, as the only synthesis method that currently balances high delamina‐
tion efficiency and low defect density, HF etching to prepare Ti3C2Tx MXene remains the
standard for producing high‐quality MXenes at the laboratory stage. In the future, ef‐
forts should be dedicated to developing greener fluoride‐free, simpler, and more effi‐
cient synthesis methods. Such methods should enable precise control over MXene sheet
thickness, tuning of surface functional group types, and adjustable interlayer spacing.
2. The specific mechanism of MXene in electrodes still has a great deal of room for
research, and the effects of the type of MXene, the number of layers, as well as the type
and number of functional groups on the performance of composite anodes are not yet
known. The future should be devoted to the study of the connection between MXenes
and other active phases to explore the physicochemical principles behind the electro‐
chemical performance enhancement.
3. Bimetallic MXenes (such as Ti2NbC2Tx) enable directional regulation of electronic
structure and chemical bond properties by introducing a second transition metal. Stud‐
ies have shown that Nb incorporation significantly expands the interlayer spacing of
Ti2NbC2Tx (from 1.05 nm to 1.25 nm), providing efficient diffusion channels for multiva‐
lent ions like Zn2+ and Mg2+ (with diffusion rates increased by over 50%). This effectively
mitigates the kinetic limitations of ion transport in traditional MXenes caused by narrow
interlayer spacing. Additionally, the compositional tunability of bimetallic MXenes
(Ti/V, Nb/Mo combinations) induces charge redistribution, forming local electron‐rich
regions that activate more ion adsorption sites. Through precise design of transition
metal composition and interfacial chemical states, directional optimization of the mate‐
Materials 2025, 18, 2386 42 of 49

rial’s intrinsic properties is achieved, offering new insights for developing universal en‐
ergy storage materials. However, most current electrode materials still use single‐metal
MXenes. Therefore, future research should further investigate the synthesis, applica‐
tions, and energy storage mechanisms of bimetallic MXenes in batteries.

Funding: This research received no external funding.

Data Availability Statement: No new data were created.

Conflicts of Interest: The authors declare no conflicts of interest.

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