Applied Surface Science 652 (2024) 159301

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Applied Surface Science

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Full Length Article

A novel two-dimensional whorled CrB4 and MoB4 as high-performance

anode material for metal ion batteries
M. Kashif Masood a, Jing Wang a, *, Juntao Song a, Ying Liu a, b
a
Department of Physics and Hebei Advanced Thin Film Laboratory, Hebei Normal University, Shijiazhuang 050024, China
b
National Key Laboratory for Materials Simulation and Design, Beijing 100083, China

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

Keywords: Finding high-storage-capacity anode materials has been a focus of ion-battery research. Two-dimensional (2D)
Anode materials materials have shown promise as high-performance electrode-materials as they have developed gradually. Here
DFT we examined the viability of 2D CrB4 and MoB4 monolayers as optimal anode-materials for Li/Na/K ion batteries
MBene
using first-principles DFT calculations. Preliminary investigations showed that both materials exhibited ther­
Ultrahigh storage capacity
modynamic, structural, and mechanical stability. We found that a strongly negative adsorption energy can help
Metal-ion batteries
in stabilizing the adsorption of metal-ions on materials surface instead of clustering, that ensures metal-ion-
batteries stability. The maximum theoretical storage capacities of Li, Na, and K ions adsorbed on the CrB4
monolayer surface were 1689,1126 and 750 mA h g− 1, respectively, while those on the surface of MoB4 were
1155,770 and 513 mA h g− 1, respectively. Additionally, calculated open-circuit voltages for Li-ions (0.84,0.82
V), Na-ions (0.25,0.32 V), and K-ions (0.85,0.81 V) for CrB4 and MoB4 monolayers, respectively. Electronic
properties showed that increasing the metal ions concentration enhanced both materials’ electrical conductivity
and remained the metallic in nature after adsorption. However, Li/Na/K energy barriers are nevertheless
consistent with various typical 2D anode materials. The light shaded on 2D MoB4 and CrB4 is anticipated to
identify new anode materials for LIBs, NIBs, and KIBs.

1. Introduction
Rechargeable metal-ion battery (MIB) research is crucial to max­
imizing the use of renewable energy sources and increasing develop­
ment of sustainable societies, as environmental and energy-related
concerns have recently gained significant traction [1]. Development of
alkali metal ion batteries with properties including a light weight,
sizable reversible capacity, flexibility, and great cycling stability to suit
efficient energy storage applications requirements [2].Performance of
alkali-ion battery is influenced by electrode materials characteristics
[3]. Scientists are looking for new technological methods that can
enhance electrochemical reactions because of the demand for more
energy growth [4]. With its low-price, high-energy density, and mod­
erate voltage, among many methods, lithium-ion batteries are a type of
energy storage that is growing in prominence. Nevertheless, Lithium, a
key component in lithium-ion batteries (LIBs), is scarce on earth, and its
high preparation cost seriously restricts further LIBs application [5,6].
Additionally, even though portable, tiny gadgets usually use recharge­
able Li-ion batteries, greater developments in terms of power density
and rate capabilities will be required. Li is being replaced by metal ions
like Na and K to boost power density and lower LIB costs. Due to the
similar operating system just like LIBs, sodium- and potassium-ion bat­
teries have recently been investigated and proposed as the upcoming
generation of potential rechargeable batteries [7,8]. Current MIBs per­
formance is no longer enough to fulfill growing large-scale energy
storage need, and to develop new battery materials is an urgent need,
particularly MIBs with high power and energy densities, as people
depend totally on energy storage devices [9–11].
Materials of anode in NIBs and KIBs have been subject of a lot of
research, and the procedure of the investigation is similar to that of LIBs
[12–14]. By theoretical and experimental investigations, a wide range of
2D anode materials have been described, such as 2D transition metal
oxides and nitrides, MXenes, MBenes, and graphene-like structures
(silicene, germanene, phosphazene, etc.), and others as well. These
materials are used in areas such as optoelectronics and catalysis, and
operate well in metal-ion batteries because of their distinctive nano­
structures and superior electrical properties. For instance, the excep­
tionally large specific surface area offers more possible places for metal

* Corresponding author.
E-mail address: jwang@hebtu.edu.cn (J. Wang).

https://doi.org/10.1016/j.apsusc.2024.159301
Received 28 October 2023; Received in revised form 28 December 2023; Accepted 3 January 2024
Available online 8 January 2024
0169-4332/© 2024 Elsevier B.V. All rights reserved.
M. Kashif Masood et al.
Fig. 1. Optimized geometries, three stable sites (H, T, and B sites), and phonon Curve of the MB4 monolayer view. (a, b) for CrB4 (c, d) for MoB4.
ions to interact, and exceptional mechanical properties can withstand
structural deformation during charge and discharge processes [15–21].
MXenes have gained interest due to their unique potential use in flexible
electronic devices, spintronics, catalysis, hybrid electrochemical ca­
pacitors, and Li/Na/K-ion batteries. Researchers have attempted to
extend X to other components in response to the success of MXene.
Interestingly, boron, which is next to carbon on the periodic table, may
also create a structure like that of graphene. The valence diversity of
boron allows for the development of a wide variety of complex struc­
tures, some of which may contain novel electrode materials. As a result,
a new class of 2D materials known as MBenes, which are MXene-based
analogues of boron-based MBenes, has emerged [22–25]. For conversion
and energy storage applications these materials are highly desirable
because of their outstanding properties, which include enormous spe­
cific surface area, remarkable electrical conductivity, and a variety of
crystalline shapes [26,27]. Gao et al. reported firstly in 2017 that Mo2B2
and Fe2B2 has an exceptional storage capacity of 444 mA h g− 1 and 665
mA h g− 1 respectively, for Li-ion batteries [28]. The performance of
boron-based monolayers for alkali metal ion batteries (AMIBs) as anode
materials has been thoroughly investigated. Li et al. described a new
TiB3 monolayer with exposed B atoms on the surface has 1335.4 mA h
g− 1 of theoretical capacity is achieved by a large unit cell area and more
adsorption sites [29]. Monolayer TiB4 shows promising capacities for Li,
Na and K are 510.53 mA h g− 1, 390.99 mA h g− 1 and 316.59 mA h g− 1
respectively [30]. In 2023, Shihao et al. also studied TiB4 for Li/Na ion
batteries and calculated storage capacity of 2353.2 mA h g− 1 and
1764.9 mA h g− 1, with low diffusion barrier of 0.24 eV and 0.09 eV
respectively [31]. To best of our knowledge, MBene monolayer MB4(X
= Cr,Mo) is still lacking for LIBs, NIBs, and KIBs as an anode material.
In this study, we selected first two transition metal elements of group
VI and designed MB4 monolayers (M = Cr, Mo) using the structural
prediction and element replacement methods. We explored the potential
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Applied Surface Science 652 (2024) 159301
of electrochemical properties of MB4(M = Cr,Mo) monolayer sheets for
alkali metal ion batteries as anode materials. We investigated in detail
alkali metal (Li, Na, and K) adsorption and diffusion in CrB4 and MoB4,
which are significantly lower than those of some 2D electrode materials.
The process involved figuring out alkali ion adsorption energies at
different monolayer positions. Anode materials’ path and energy barrier
were ascertained using nudged elastic band (NEB) method. It was noted
that these materials had notable ion storage capacities and maintained
their metallic behavior even after being adhering to alkali metal atoms.
We highlight stability and performance of these materials. We computed
storage capacities, average open-circuit voltages and alkali atom
adsorption formation energies at various Li/Na/K contents. As a result,
we conclude that CrB4 and MoBr4 monolayers in alkali metal-ion bat­
teries are better choices for anode materials.
2. Computational details
For all density functional theory (DFT) computations, plane-wave
approach of Vienna ab initio simulation package (VASP) version 5.4.4
was used [32,33]. Using projected augmented wave (PAW) approach
interactions between the ions and electrons were represented. A 480 eV
cutoff energy was used with a plane-wave basis. Exchange correlation
energy is described by Perdew, Burke, and Ernzerhof (PBE) functional
[34,35]. Geometry optimization of CrB4 and MoB4 monolayer unit cells
and 3 × 3 × 1 supercells based on Γ-centered 12 × 12 × 1 and 4 × 4 × 1
Monkhorst-Pack k-meshes, respectively were carried out. DFT-D3
method was used for long-range van der Waals (vdW) interactions be­
tween CrB4/MoB4 monolayer and adsorbed alkali metal ions [36,37].
Using PHONOPY Code, phonon calculations were performed [38] to
demonstrate dynamic stability, which is based on density functional
perturbation theory (DFPT). A vacuum space of 20 Å perpendicular to
layers was presented for interactions between the adjacent layers.
M. Kashif Masood et al.
Fig. 2. (I) Strain-energy curves for calculation of in-plane stiffness constants for CrB4. CrB4 total energy is plotted as a function of strain along different amounts (a) x-
axis, (b) y-axis, and (c) equibiaxial strain along x and y axis, which are necessary for in-plane stiffness constants calculation (II) Strain–energy curves for the
calculation of in-plane stiffness constants for MoB4. Total energy of MoB4 is plotted as a function of strain along amount (a) x-axis, (b) y-axis, and (c) equibiaxial
strain along x- and y-axis.
Convergence thresholds were set at a total energy value of 10-8 eV and a
Hellmann-Feynman force of − 0.02 eV/Å to ensure results accuracy and
reliability. To analyze charge transfer, Bader charge analysis was used
for Li/Na/K and Cr/Mo borides. To investigate structural stability and
adsorption of Li/Na/K-ion on CrB4/MoB4 anode materials, an ab initio
molecular dynamics (AIMD) simulation was performed and the simu­
lation for duration of 5 ps was carried out, with a 1 fs time step, under
the canonical ensemble (NVT) and microcanonical ensemble (NVE) at a
room temperature (300 K) [39,40]. Using this simulation, it was possible
to evaluate the structural stability of CrB4 and MoB4 monolayers for both
the pristine and adsorbed ions. Data post-processing was performed
using the VASPKIT code [41]. The direct supercell approach was used to
calculate the phonon frequencies. This method makes use of the forces
derived from the optimized supercell using the Hellmann-Feynaman
theorem [42]. The stress tensor-generated small strain was evaluate to
determine the elastic constants, and the Voigt-Reuss-Hill approximation
was used to calculate Young’s modulus and Poisson’s ratio [43].
3. Results and discussion
3.1. MB4 Monolayer structure
A comparable structure of crystal, with five atoms per unit cell and
space group P6/mmm, has been shared to optimized structures of 2D
CrB4 and MoB4, as seen in Fig. 1(a, c). An intermediate triangular sheet
of Cr/Mo atoms was sandwiched among two hexagonal honeycomb
sheets of boron atoms. Our calculations show that the lattice parameters
for unit cell are a = b = 2.89 Å and thickness d = 3.02 Å for CrB4; and a
= b = 2.96 Å and thickness d = 3.28 Å for MoB4, and for supercell are
8.67 Å (CrB4) and 8.87 Å (MoB4) which is compatible with previous
studies [44–46]. The Cr/Mo composition and B atoms in our system
suggests a 1:4 ratio. A single Boron atoms sheet is unstable, and to fully
3
Applied Surface Science 652 (2024) 159301
fill honeycomb π-bond, one more electron needed to each boron atom to
achieve the s2sp2 configuration. More, boron atoms should have a
valence of − 1 and MoS2 2D crystals discovery indicates that in a 2D
system Mo metal is in good compliance. Boron sheet structure can be
stabilized by integrating a Cr/Mo atom between two B-sheets. Four
electrons can be donated by each Cr/Mo atom and have an electronic
configuration of 2s2sp2, making the B − anion similar to the configura­
tion of the carbon atom in graphene. B atoms with pz orbitals formed a
hexagonal lattice, whereas Cr/Mo atoms with 5d orbitals formed a
triangular lattice. To stabilize each B honeycomb, σ-bonds are formed by
sp2 hybrid orbitals, and π-bonds are formed by pz orbitals. Within these
monolayers, through strong vdW interactions two boron sheets interact
with each other, and bonding properties make this material exhibit high
charge mobility and form double Dirac cones [44–46]. From Fig.S1(a-b),
at energy window close to the Fermi level, two Dirac cones emerge. One
symmetry cone located at K (cone I) is just above Fermi level and
another symmetry cone located along the site Γ to K (cone II) below the
Fermi level, and these two cones have same electronic Fermi velocity of
5.31 × 105 ms− 1, approximately half of that with graphene, which is
consistent with a previous study [46–48]. Clearly represent some of
energy bands across Fermi level in energy band structures of both CrB4
and MoB4. This indicates that the MB4 material is best for electrode
material in metal ion batteries and has metallic conductivity.
3.2. Kinetic, mechanical, thermal and thermodynamic stability of MB4
monolayer
For evaluating the materials’ stability, we calculated the kinetic,
thermal, and thermodynamic stabilities for the dynamic stability of MB4.
Fig. 1(b) and (d) represent phonon dispersion curve and projected
vibrational density of states (PVDOS) for both CrB4 and MoB4 mono­
layers, respectively, indicating that neither material has imaginary
M. Kashif Masood et al. Applied Surface Science 652 (2024) 159301

Table 1
Calculted elastic constants (N/m), Young’s Modulus (N/m) and Poisson’s Ratio
of CrB4 and MoB4.
Material C11 C12 C66 Young’s Modulus Poisson’s Ratio
(Y) (ϑ)
CrB4 358.15 83.40 137.37 338.73 0.23
MoB4 401.05 59.94 170.55 392.09 0.14
frequencies.We also performed the phonon calculations to check the
further dynamical stabilities of both materials under the strain of + 2.5
% and − 2.5 % and find no imaginary frequencies as shown in Fig.S2(a-
d). which means that the dynamic stability of both materials is favor­
able. When developing high-capacity anode materials, it is imperative to
take into account the mechanical stability of that materials. Robust
mechanical properties are needed to withstand volume expansion
resulting from a battery’s charge–discharge cycle. Because 2-Dimen­
sional materials are able to resist large amounts of stress and strain
without collapse, they can be utilized as mechanical support networks
for high-performance anode materials [49,50]. As a result, we computed
in-plane stiffness constants of anode materials to investigate their me­
chanical stability. For a 2D material under strain, by using Voigt [51]
notation: i.e., 1-xx,2-yy,6-xy, total potential energy U(Ɛ) can be pre­
sented as [52].
1 1
U(ε) = C11 ε2xx + C22 ε2yy + C12 εxx εyy + 2C66 ε2xy
2 2
Where C11, C22,C12, and C66 present dimensional elastic tensors, and
εxx and εyy denote uniaxial strain along x- and y directions, respectivly.
When uniaxial strain is applied along x and y directions, material stiff­
ness is indicated by in-plan stiffness constants C11 and C12 . Material’s
capacity to withstand biaxial strain is represented by C12 and resistance
to deformation brought on by share strain is represented by C66 . We
applied a strain in vicinity of − 2.5 % to + 2.5 % with a small gap of 0.5
% like the Gayatree et al [53,54]. The strain-energy data with uniaxial
deformation along the x-axis and y-axis are fitted with a second-order
polynomial to determine the value of C11 and C22 . Similaryly, bi-axial
planner deformation along xy-plane gives C12 value as shown in
Fig. 2. For hexagonal system, C11 and C22 are same and additional relation
C66 = 12(C11 − C12 ) exists. Elastic constant can be calculated using
following equation:
1 ∂Es2
Cij =
S0 ∂εi ∂εj
Where i,j = xx,yy, or xy,and S0 is supercell equilibrium area. From value
of elastic constants in-plane Young’s Modulus (Y)and Poisson’s ratio (ϑ)
are directly determined [55].
2 2
C11 − C12
Young ′s Modulus (Y ) = (3)
C11
C12
Poisson ′s ratio (ϑ ) = (4)
C11
Elastic instability is related to the elastic constants of a material,
which describe its response to mechanical deformations. An elastic
instability occurs when one or more elastic constants become negative.
This implies that the crystal is no longer stable against small de­
formations, indicating a potential phase transition or structural insta­
bility. Calculated values of elastic constants are
C11 = 358.15 N/m, C12 = 83.40 N/m and C66 = 137.37 N/m for CrB4 and
C11 = 401.05 N/m, C12 = 59.94 N/m and C66 = 170.55 N/m for MoB4.
There is no elastic constant is negative and also satisfy the Born-Huang
[53,56] criteria for mechanical stablility i.e C11 C12 > 0 and C11 > C12 ,
which indicate both monolayers are mechanically stable. Both materials
appear to have considerable mechanical flexibility based on Poisson’s
ratio (0.23 and 0.14) and Young’s modulus (338.73 N/m and 392.09 N/
m) values respectivly as shown in Table 1, As compared to the other 2D
materials, these results are significant greater than the [57]o-B2N2 ,2D-
SnB [58] and SiP3 [59] and less than 2D α-CN [60]which is extremely
advantageous for the production of flexible anode materials.
We estimate the thermal stability for the pristine and alkali metal
ions (Li/Na/K) adsorbed-MB4 by using the AIMD simulation with NVT
(1) and NVE ensembles for a supercell of 3 × 3 × 1.For alkali metal ions
adsorption, the top/bottom sites of MB4 were chosen, and the simulation
ran for 5 ps(5000 fs). Large-scale AIMD computations that access all of
alkali metal ion trajectories and movement at 300 K are sufficient to
show the structural stability because the lack of computational re­
sources. Fig. 3(a, b) represent the pristine CrB4/MoB4 and S3-4 (a-f)
represent the energy fluctuations versus time steps of full Li/Na/K
adsorbed CrB4/MoB4 for NVT and NVE ensembles respectively, and we
find that CrB4 and MoB4 structures do not change, and for adsorption of
alkali metal layers, some substrate deformation and total energy fluc­
tuate shortly with time. It was also observed that the K atoms’ equilib­
rium positions were slightly deviate from the actual position due to its
large atomic size but no bonds broken. With the K atoms eliminate, these
somewhat deformed MB4 sheets soon regained their planar structure.
Despite slight distortions caused by the oscillation of the atoms in some
configurations, the structural stabilities are maintained. The free energy
fluctuating around a stationary center at 300 K, confirms that no
(2) structural reorganization occurred during the simulations. This suggests
that the MB4 monolayers have considerable heat stability during Li/Na/
K ion interaction and extraction. Notably, compared to graphite, the
volume of the Li/Na/K-ions adsorbed-MB4 monolayer was less altered
during the adsorption and desorption processes [61,62]. This result is

Fig. 3. Energy fluctuation vs time steps for pure CrB4 and MoB4 monolayer.

4
M. Kashif Masood et al. Applied Surface Science 652 (2024) 159301

Table 2 potassiation of this material.

Calculated adsorption energy, Bader charge and structural parameters of For thermodynamic stability of MB4 determination, we calculated
different alkali atoms on both sides of CrB4 and MoB4. the formation energy of metal-ion-adsorbed MB4 using the following
Adsorption energy (eV) Bader charge (e) equation [69]:
Top Bridge Hollow Top Bridge Hollow Ef = (EMB4 +nLi/Na/K − EMB4 − nELi/Na/K ) /n + 1 (5)
Li0.11CrB4 2.01 2.04 2.55 0.77 0.77 0.76
here EMB4 +nLi/Na/K and EMB4 represent total energy vales of Li, Na and
− − −
Na0.11CrB4 − 2.04 − 2.06 − 2.29 0.73 0.74 0.77
K0.11CrB4 − 2.67 − 2.68 − 2.84 0.75 0.78 0.79 K-ions adsorbed and pristine MB4 monolayer, respectively. ELi/Na/K
Li0.11MoB4 − 2.06 − 2.09 − 2.63 0.73 0.71 0.71 represent total energy values of Li, Na and K-ion in the bulk, and “n” is
Na0.11MoB4 − 1.79 − 1.81 − 2.08 0.72 0.72 0.75 total number of Li, Na and K-ions adsorbed. Calculated formation energy
K0.11MoB4 2.75 2.76 2.93 0.76 0.77 0.79
is shown in Fig.S5(a-f), and convex hulls are formed by solid lines
− − −
Height (hs-s) of CrB4 3.02 Å
Height (hs-s) of 3.28 Å connecting lowest forming energies. The structure located on convex
MoB4 hulls represent stable structure and we noted that Ef curves of Li/Na/K
Lattice constants (a, 2.89 Å adsorbed-MB4 (x = 1,2,3,4,5 and 6) demonstrate the stability, resem­
b) of CrB4 bling prior 2D materials.
Lattice constants (a, 2.96 Å
b) of MoB4

3.3. Adsorption Li, Na and K on surface of MB4

consistent with previous reports on 2D materials [63–65] and moreover,
prior research confirms that 2D materials are stable at 300 K for at least
5 ps [64,66,67]. In the practical application of anode materials, it is well
known that significant volume expansion upon alkali metal ion
adsorption usually impairs the service life of the electrode materials and
we studied the significant parameter of volume change that occurs
during the process of lithiation/de-lithiation, sodiation/de-sodiation,
and potassiation/de-potassiation of the monolayer. Lattice mismatch is
also a parameter for ion adsorption [68]. For maximum concentration,
small lattice mismatches for CrB4 are found be Li(3.34 %), Na (3.46 %),
and K (3.92 %) and for MoB4 are Li(2.53 %), Na (2.65 %), and K (2.82
%). The slightly larger expansion with Na/K addition is due to its higher
van der Waals radius. These outcomes confirm that lattice mismatch is
not a worrying issue and suggest the robust lithiation, sodiation, and
Strong Li/Na/K bonding on the surface controls the electrochemical
efficiency of 2D materials in LIBs, NIBs, and KIBs. For a material to be
suitable as an alkali-ion battery negative electrode, there must be strong
alkali metal adsorption on the host surface. Li/Na/K adsorption energies
on CrB4 and MoB4 surfaces were therefore computed. According to
geometrical symmetry, we took into account all conceivable adsorption
sites as H-site (top of Cr/Mo atom), T-site (top of B atom) and B-site
(bridge site on B-B) for ions, as illustrated in Fig. 1(a,c).To determine
most suitable adsorption site for each ion, we compared alkali metal
atoms (X) adsorption energy, which can be expressed by the following
equation [70]:
Eads = (EX− − EMB4 − EX ) (6)
MB4

Fig. 4. Adsorption energies (Eads) for CrB4 and MoB4 (a) Stable Li/Na/K sites with their respective adsorption energies and (b-d) Average adsorption energies (Ead)
with increasing Li/Na/K adsorbed layers (x = 1,2,3,4,5,6).

5
M. Kashif Masood et al. Applied Surface Science 652 (2024) 159301

Table 3 here EMB4 +X and EMB4 present total energy of MB4 monolayer values
Calculated average adsorption energy of alkali metal atoms adsorbed on CrB4 with X and without X adsorption, respectively. EX presents total energy
and MoB4. values of X in bulk phase, and “n” is total number of alkali X atoms
Layer LinCrB4 NanCrB4 KnCrB4 LinMoB4 NanMoB4 KnMoB4 adsorbed. Table 3 lists average adsorption energies of metals adsorbed
n1 − 1.31 − 0.39 − 1.37 − 1.29 − 0.44 − 1.31
on MB4 monolayers at various concentrations and shown in Fig. 4(b-d).
n2 − 1.25 − 0.33 − 1.28 − 1.28 − 0.38 − 1.26 Li and Na ions were adsorbed with 9 atoms in each layer, whereas K was
n3 − 0.86 − 0.16 − 0.88 − 0.84 − 0.27 − 0.88 only adsorbed with 4 atoms in each layer due to the larger atomic size of
n4 − 0.63 − 0.10 − 0.72 − 0.62 − 0.18 − 0.71 K. Fig. S6(a-e) shows the top and side view of adsorption of Li atoms
n5 0.51 0.55 0.50 0.48
− − − −
layer on CrB4 from L1 to L6. The fact that all alkali adsorptions exhibit
n6 − 0.48 − 0.29 − 0.40 − 0.23
negative adsorption energies in a variety of configurations suggests that
the energetics of metal ion adsorption on a substrate are favorable.
Adsorption energy decreased as concentration of Li/Na/K increased.
here EX− MB4 and EMB4 represent the total energy vales of MB4 monolayer
This happens because of weaker attractive interactions between host
with X and without X adsorption, respectively. EX represents single X
and the Li, Na, and K ions and higher repulsive interactions between
atom total energy values. All the computed Eads values derived from
adsorbed Li, Na, and K ions. In a 3 × 3 × 1 supercell of the MB4
equation (6) have a negative sign, indicating exothermic adsorption that
monolayer, there were 54Li ions (six layers), 36Na ions (four layers),
most often forms metallic clusters. From the Table.2 and Fig. 4(a) it can
and 24 K ions (six layers). The adsorption energy changes to a positive
be seen that H-site is more stable as compared to T, B-Sites for Li/Na/K
value when we attempt to adsorb one more layer, indicating that we
on both CrB4 and MoB4 surfaces. Calculated values adsorption energy of
cannot add any more layers. As the number of adsorption layers in­
more stable H-site for Li0.11CrB4, Na0.11CrB4 and K0.11 are − 2.55 eV,
creases, the distance between the atoms of the first layer of adsorption
− 2.29 eV and − 2.84 eV, respectively. Similarly, values for Li0.11MoB4,
and the substrate gradually increases, and it is almost unchanged when
Na0.11MoB4, and K0.11MoB4 are − 2.63 eV, − 2.08 and − 2.93, respec­
the third layer is adsorbed, which indicates that the interaction influence
tively. Therefore, the H-site was selected for further alkali metal ions
between the substrate and the adatoms of the second and third layers
adsorption. The capability of multilayer alkali metal adsorption is key to
becomes smaller which is shown in Fig.S(7,8).
achieving large theoretical specific capacities. As a result, we examined
In case of single layer adsorption of metal ions which is the evidence
layer-by-layer adsorption of alkali ions on CrB4 and MoB4 monolayers.
of high adsorption energy and when we increase the number of layers up
For various X-layers average adsorption energy (Ead) was calculated
to triple layers the Coulomb interaction (repulsion) increase due to
using following equation:
which adsorption energy decreases. From Fig.S.7(a-f), the small
Ead = (EMB4 +nX − EMB4 − nEX )/n (7) adsorption energy, and the large distance of the outermost Li layer from

Fig. 5. Electron localization functions (ELFs) of the (1 0 0) section on the CrB4 and MoB4 monolayer: (a) Li6CrB4, (b) Na4CrB4, (c) K6CrB4, (d) Li6MoB4, (e) Na4MoB4
and (f) K6CrB4.

6
M. Kashif Masood et al.
Fig. 6. Difference between charge density with isosurface value of 0.001 e/Å3 for (a) Li0.11CrB4 (b) Na0.11CrB4 (c) K0.11CrB4 (d) L0.11MoB4 (e) Na0.11MoB4
(f) K0.11MoB4.
the substrate for CrB4 and MoB4 are 7.44 Å and 6.88 Å which indicated
that the interaction of the adsorbed atoms with the substrate was rela­
tively weak. Usually, with the accumulation of adsorbed cations on the
CrB4/MoB4 surface, the adsorption energy will gradually decrease and
similar patterns are followed for Na/K as shown in Fig.S8(a-d). When the
repulsive electrostatic force between cations completely balances the
attractive force between cations and CrB4/MoB4 the adsorption con­
centration of the cations reaches its peak. So, we did not consider the
more layer of metal adsorbed on the substrate. The adsorption energy of
metal ion on 2D substate not only depends on the energy needed for
charge transfer from the metal atom to the substrate, but also depends
on the ion-substrate coulomb interaction (contributed by both charges
and ion- substrate distance) [71]. We firstly look at the charge transfer,
charges transfer from K to the substrate are more than that of Na and Li.
This is consistent with the sequence of metallicity strength [68] How­
ever, when we turn to the metal-N distance, which reflects the ion-
substrate distance, we can find that Li distance is lower than Na/K,
which induces a higher ion substrate coulomb interaction in the Li case
which is due to the shorter atomic radius of Li.
In multilayer adsorption studies, the negative electron cloud (NEC)
around anions plays a crucial role in stabilizing ion intercalation. The
ELF map sliced in the (1 0 0) direction of the maximum alkali-metal atom
adsorption on the CrB4/MoB4 monolayer surface is plotted in Fig. 5 (a)–
(f). For the substrate, many electrons gather around the B atoms,
whereas the electrons of the Cr/Mo atoms are lost and the B atom forms
an ionic bond with Cr/Mo. For the adsorption of Li/Na/K atoms, it was
found that a large number of negative electron clouds accumulated
between the first layer of the adsorbed atoms. The localization between
the outermost adsorbed atoms gradually increases with an increase in
the number of adsorption layers. The presence of NEC between the Li/
Na/K layers significantly weakens the repulsion between the atoms and
plays a key role in improving the stability of multilayer adsorption
[60,72–74]. Next, we find the charge density difference of XMB4
monolayer to envisage chemical reactivity of Li/Na/K adsorbed CrB4/
MoB4. Charge density difference of ions adsorbed-MB4 monolayer was
determined using the following formula [75].
Δρ(r) = ρX− MB4 (r) − ρMB4 (r) − ρX (r) (8)
7
Applied Surface Science 652 (2024) 159301
Here, ρX− MB4 , ρMB4 specifies the charge density of X atom-adsorbed and
bare MB4, and ρX specify the charge density of isolated alkali X-ion.
Determined the charge densities of more stable site (H-site) are given in
Fig. 6. This analysis indicates that the green area in the figures denotes
electron depletion, while the yellow area denotes electron accumula­
tion, which proves electrochemical reaction between the CrB4/MoB4
monolayer and X ions. Furthermore, charge transported from X to ions
to CrB4/MoB4 was calculated by Badar charge analysis, and it was found
that the X-ions work as a charge donor to the CrB4/MoB4 monolayers.
The higher values of charge transferred for H-site for Li0.11CrB4,
Na0.11CrB4 and K0.11 are 0.76 e, 0.77e and 0.79e, respectively. Similarly,
for Li0.11MoB4, Na0.11MoB4, and K0.11MoB4 are 0.71e, 0.75e and 0.79e,
respectively. The calculated charge transfer values for all sites are given
in Table 2. Higher values of charge transfer from alkali metal ion X to
CrB4/MoB4 monolayers confirm that these materials have the best Ead
and storage capacity, which is useful for battery applications.
3.4. Theoretical storage capacity (TSC) and open circuit voltage (OCV)
For rechargeable alkali ion batteries, high ion storage capacity, low
open-circuit voltage (OCV), and a stable voltage profile are essential
characteristics of high-performance electrode materials. We explored
lithiation, sodiation, and potassiation processes using computational
modelling and increasing Li, Na, and K ions concentration on top and
bottom sides of host material. Adatom contents were applied for
adsorption to the most stable H-site. The maximum capacity (Cm) of the
MB4 can be calculated with Li/Na/K (X) adsorbed by this equation [76]
i × Xmax × F
Cm = (9)
WMB4
where i and Xmax represent valence electrons of cations (i = 1 for Li/Na/
K) and highest concentration of metal ions, respectively. F is Faraday
constant having value of 26,801 mAhmol− 1. WMB4 is molar weight of
MB4 (CrB4 and MoB4) monolayers. As multilayer adsorption is necessary
to obtain high capacity, we decrease K-atoms number that can be
adsorbed in one layer to 4 atoms because K cannot be adsorbed up to 9
atoms in one layer because of atomic size just like Li and Na can.
 M. Kashif Masood et al.
Fig. 7. Average open circuit voltage (OCV) and theoretical storage capacity (TSC) of CrB4/MoB4 as a function of (a, d) Li (b, e) Na and (c-f) K content.
Corresponding ions theoretical storage capacities on CrB4 monolayer
were 1689, 1126, and 750 mA h g− 1 for Li, Na, and K ions, respectively.
Similarly, TSC of ions on MoB4 was 1155, 770 and 513 mA h g− 1 for Li,
Na, and K ions, respectively. TSC with increasing ions contents are
shown in Fig. 7.With other 2D materials comparison, CrB4 and MoB4
monolayers could accommodate an even larger Li/Na/K ion capacity
than TiB4(511,391 and 317 mA h g− 1 for Li, Na and K) [30], TiB (408
and 328 mA h g− 1 for Li and Na ions) [18],Ti2N (484 and 242 mA h g− 1
for Li and K ions) and Ti2C (439,348 and 141 mA h g− 1 for Li, Na, and K
ions) monolayers [77]. Whereas a little smaller Li (2353 mA h g− 1) and
Na (1765 mA h g− 1) ions capacity than TiB4 [31]. Specifically, these
substances exhibit significantly greater storage capabilities than
graphite, the conventional anode material (372 mA h g− 1 for LIBs) [78].
To further investigate the electrochemical properties of CrB4 and MoB4
as Li/Na/K host materials for LIBs/NIBs/KIBs, the voltage profile was
Fig. 8. Migration path1 and path2 for alkali ion on MB4 monolayer.
8
­
Applied Surface Science 652 (2024) 159301
determined. For an effective rechargeable battery with exceptional
performance to be certified, Low- and high-voltage profiles need to be
used for the anode and cathode, respectively. Open-circuit voltage
(OCV) was evaluated for each XnMB4 concentration using the following
equation equation [74,79,80]:
Vave = ( nEX + EMB4 − EMB4 +nX )/nze (10)
here EMB4 +X and EMB4 represent total energy vales of MB4 monolayer
with and without X adsorption, respectively. EX represents total energy
values of X in bulk phase, and “n” is total number of alkali X atoms
adsorbed and “z” is charge on X atom. Therefore, to determine the
voltage, Li/Na/K ions are added in stepwise mode onto CrB4 and MoB4
surfaces and voltage profiles are calculated by using eq (10) which is
depicted in Fig. 7. As the ion’s concentration increased, calculated OCVs
values gradually decreased. Calculated OCVs for LixCrB4, NaxCrB4 and
KxCrB4 are 0.84 V, 0.25 V and 0.85 V, respectively. Similarly, for Lix
MoB4, NaxMoB4, and KxMoB4, the OCVs values are 0.82, 0.32 V and 0.81
V, respectively, which are lower than previously reported monolayers
such as NaxMoN2 (0.96 V), KxMoN2 (1.11 V), NaxVS2 (1.3 V/1.4 V for
1H/1T phase), LixMo4/3O2 (1.83 V) NaxMo4/3B2(0.89 V), KxMo4/
3B2(1.49 V), LixMo4/3B2O2 (1.83 V), NaxMo4/3B2O2 (0.94 V) KxMo4/
3B2O2 (1.18 V) [81–84]. It is noteworthy that these average OCV values
fall within desired range of 0–1.0 V for commercially available in AMIBs
as anode materials. [85].
3.5. Diffusion barrier
On the MB4 monolayer, the X atoms diffusion energy barriers were
examined using climbing image-nudged elastic band (Cl-NEB) method.
We also calculated the D (diffusion coefficient) of alkali atoms on MB4 as
a temperature function with the Arrhenius equation as follows [86]
M. Kashif Masood et al.
Fig. 9. NEB path diffusion barrier energy of metal ion diffusion on CrB4 and MoB4 monolayer for (a) Li diffusion, (a,b) Li diffusion, (b,c) Na diffusion, and (e,f)
K diffusion.
D(T) = a2 v0 e−bBE/kT
Here, a represents the distance of alkali X atom migration at the
adsorption sites of the MB4 monolayer. vo = 1013 Hz is vibrational fre­
quency and Eb is diffusion barrier. Boltzmann constant and absolute
temperature are represented by kB and T. In addition, also CI-NEB
technique was applied to investigate charging/discharging process,
which determines the transition state, minimum energy paths (MEPs),
and surface barrier for ion migration in the MB4 monolayer. Lithiation/
delithiation, sodiation/desodiation, and potassiation/depotassiation
mechanisms for metal-ion batteries have been justified by this method
[86].To study a single X atom adsorption behavior on the MB4 mono­
layers, a 3 × 3 × 1 supercell was selected, and two (H and T) atomic
positions were considered after full symmetry was achieved, as in Fig. 1
(a). Their respective adsorption energies are listed in Table 2. Based on
these two most stable sites, we chose two paths path-1 and path-2. To
migrate the X-atom content, Path-1 follows the H1-T-H2 direction,
whereas Path-2 follows the H1-H2 direction, as depicted in Fig. 8. These
paths were selected because H-site is most stable, and the T-site is also
stable and advantageous for all the alkali metals evaluated. One X metal
ion was deposited on the supercell of monolayer MB4 for X-ion migra­
tion. Three intermediate images of both diffusion paths were introduced
to show the advancement of the diffusion process between the starting
and final sites. These additional images help to clarify the process and
provide diffusion mechanism for better understanding. We can observe
Applied Surface Science 652 (2024) 159301
(11) entire diffusion process and examine the energy barriers at each stage by
incorporating these intermediate images.
As presented in Fig. 9(a-f), Our calculated energy barriers for
Li0.11CrB4 are 0.55 eV and 0.52 eV, for NaxCrB4 are 0.29 eV and 0.26 eV,
and for KxCrB4 are 0.18 eV and 0.17 eV for path-1 and path-2 respec­
tively. Similarly, for LixMoB4 are 0.57 eV and 0.54 eV, for NaxMoB4 are
0.29 eV and 0.27 eV, and for KxMoB4 are 0.18 eV and 0.17 eV for path-1
and path-2 respectively. As a result, path-2 (H1-H2) indicating easy
diffusion and the calculated lowest diffusion barrier on CrB4 surface is
0.52 eV for Li ions, 0.26 eV for Na ions and 0.17 eV for K ions. Similarly,
lowest diffusion barrier on MoB4 surface is 0.54 eV for Li ions, 0.27 eV
for Na ions and 0.17 eV for K ions. We note that Li diffusion barriers on
both CrB4 and MoB4 is higher than typical 2D materials including gra­
phene ~0.37 eV,MoS2 ~0.21 eV [87] and most MXenes (0.05–0.15 eV)
[66,88,89]. However, Li/Na/K energy barriers remains comparable to
some well-known anode materials such as β12 borophene is 0.66 eV for
Li, 0.33 eV for Na ions. χ3 borophene with a value of 0.60 eV for Li ions
and 0.34 eV for Na ions [90],TiO2-based polymorphs (0.3–0.65 eV)
[91,92], silicon (0.57 eV [93,94], and phosphorene categories
(0.13–0.76 eV [95,96]. Energy barriers comparison to previous data is
depicted in Table 4.
9
M. Kashif Masood et al. Applied Surface Science 652 (2024) 159301

Table 4 between valence band maximum (VBM) and conduction band minimum
Comparison of voltage, diffusion barrier, and capacity of MB4 with those of other (CBM) for both materials results in metallic character. Assessing elec­
materials. tronic characteristics of materials before and after adsorption of alkali
Material Voltage Diffusion Barrier Capacity (mA Refs metals is crucial. Therefore, we conducted Density of States (DOS) cal­
(V) (eV) h/g) culations for the pristine state, as well as after lithiation, sodiation, and
LixCrB4 0.84 0.52 1689 this potassiation and it was observed that the metal atoms transfer electrons.
work Both materials were metallic in their pristine form. Fig.S9 depict the
NaxCrB4 0.25 0.26 1126 this PDOS for the pristine CrB4 and MoB4 exhibits metallic characteristics
work
and main contribution coming from the conduction band’s Cr-d, Mo-
KxCrB4 0.85 0.17 750 this
work d and B-p states. It is important to note that although other states
LixMoB4 0.82 0.54 1155 this contribute tangentially to the electrical conductivity, their influence is
work negligible in comparison to these states. According to the TDOS shown
NaxMoB4 0.32 0.27 770 this in Fig. 10, when alkali concentration increases, electronic states at Fermi
work
KxMoB4 0.81 0.17 513 this
level increase, indicating that system has more accessible active elec­
work trons. The PDOS for the CrB4 and MoB4 monolayers with the lowest and
Lixβ12 borophene 0.93 0.66 1984 [90] highest loadings of Li/Na/K ions on supercell are examined in Fig.S10-
Naxβ12 borophene 0.65 0.33 1984 [90] S11. It was observed that even with Li/Na/K adsorption, the material
Lixχ3 borophene 1.09 0.60 1240 [90]
maintained its metallic character, as indicated by the presence of peaks
Naxχ3 borophene 0.78 0.30 1240 [90]
NaxWB4 0.73 0.21 472 [97] corresponding to Li-s, Na-s, or K-s states. During lithiation, sodiation,
LixMoN2 3.64 0.78 432 [81] and potassiation, the metallic nature is retained, ensuring improved
KxMoN2 1.11 0.49 260 [81] electrical conductivity. This indicates that an increase in electronic
KxSnSe 0.45 0.16 271 [66] conductivity is anticipated because of transfer of charge carriers to the
KxTiS2 1.32 0.44 282 [98]
CB. The higher electronic conductivity suggests that each material has
LixALC 1.38 0.78 740 [99]
NaxSiP 2.14 0.16 734 [100] the potential to be a good host for LIBs, NIBs, and KIBs.
LixCP 1.99 0.11 1108 [60]
4. Conclusions

3.6. Electronic states

In this work, storage, adsorption,geometric structure, stability,
diffusivity,mechanical and electronic properties of CrB4 and MoB4
Another crucial factor that significantly influences the anode per­
monolayers were investigated using DFT method for anode material in
formance is electrical conductivity. It plays a pivotal role in determining
metal ion batteries. The computed adsorption energies were negative,
effectiveness of anode functions. Materials with narrower bandgaps
indicating that formation of CrB4 and MoB4 monolayers was exothermic
exhibit superior conductivity. To comprehend the electronic character­
and thermodynamically stable. AIMD simulation of low and high Li/Na/
istics of monolayers of CrB4 and MoB4, we analyzed the density of states
K ion contents show thermal stability of chosen host materials for alkali
(DOS) and projected density of states (PDOS). Fermi level overlap
ion batteries. Young’s modulus is 338.73 and 392.09 N/m for CrB4 and

Fig. 10. Total density of states for alkali adsorption at different contents, (a) LxWB4 (b) NaxCrB4 (c) KxCrB4 (d) LxMoB4 (e) NaxMoB4 (c) KxMoB4 where x
= 0.11,1,2,3,4,5,6.

10
M. Kashif Masood et al.
MoB4 respectively and calculated poison’s ratio values are 0.23 and 0.14
for CrB4 and MoB4 respectively. This suggests that mechanically flexible
anode materials can accommodate large volume expansions during the
lithiation/de-lithiation, sodiation/de-sodiation, and potassiation/de-
potassiation processes. Both monolayers feature stable ion-intercalated
structures and good capability for capturing metal ions. The charge
density difference shows net charge transfer from metal ions (Li, Na, and
K) to monolayers (CrB4 and MoB4). The higher charge transfer values for
Li0.11CrB4, Na0.11CrB4, and K0.11 are 0.76 e, 0.77 e and 0.79 e, respec­
tively. Similarly, for Li0.11MoB4, Na0.11MoB4, and K0.11MoB4 are 0.71 e,
0.75 e and 0.79 e, respectively. Maximum theoretical capacities of Li,
Na, and K ions adsorbed on CrB4 monolayer surface were 1689, 1126
and mA h/g, respectively. Similarly, on the surface of MoB4 are 1155,
770 and 513 mA h g− 1 respectively. Moreover, the calculated lowest
diffusion barrier on the surface of CrB4 is 0.52 eV (Li ions), 0.26 eV (Na
ions) and 0.17 eV (K ions); similarly, lowest diffusion barrier on MoB4 is
0.54 eV (Li ions) surface, 0.27 eV (Na ions) and 0.17 eV (K ions). Our
findings demonstrate that CrB4 and MoB4 monolayers can be used as
reliable electrode materials for high-performance LIBs, NIBs, and KIBs,
encouraging additional in modern electronic devices applications.
CRediT authorship contribution statement
M. Kashif Masood: Investigation, Methodology, Formal analysis,
Visualization, Writing – original draft. Jing Wang: Resources, Project
administration, Funding acquisition, Conceptualization. Juntao Song:
Writing – review & editing, Supervision. Ying Liu: Resources, Project
administration, Funding acquisition, Conceptualization.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This research is funded by The National Natural Science Foundation
of China (Grant No.12174084), Science Research Project of Hebei Ed­
ucation Department (Grant No. ZD2021065), and The Key Program of
Natural Science Foundation of Hebei Province (Grant No.
A2021205024).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.apsusc.2024.159301.
References
[1] Z. Liu, et al., Voltage issue of aqueous rechargeable metal-ion batteries, Chem.
Soc. Rev. 49 (1) (2020) 180–232.
[2] J.-M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium
batteries, Nature 414 (6861) (2001) 359–367.
[3] M.N. Obrovac, V.L. Chevrier, Alloy negative electrodes for Li-ion batteries, Chem.
Rev. 114 (23) (2014) 11444–11502.
[4] N. Oyama, et al., Dimercaptan–polyaniline composite electrodes for lithium
batteries with high energy density, Nature 373 (6515) (1995) 598–600.
[5] K. Belasfar, et al., First-principles study of BC3 monolayer as anodes for lithium-
ion and sodium-ion batteries applications, J. Phys. Chem. Solid 139 (2020)
109319.
[6] L. Pan, et al., Recent advances in atomic-scale storage mechanism studies of two-
dimensional nanomaterials for rechargeable batteries beyond Li-ion, Chem. Res.
Chin. Univ. 36 (2020) 560–583.
11
Applied Surface Science 652 (2024) 159301
[7] E. Olsson, et al., Adsorption and migration of alkali metals (Li, Na, and K) on
pristine and defective graphene surfaces, Nanoscale 11 (12) (2019) 5274–5284.
[8] R. Hu, et al., Synthesis of SnS 2 ultrathin nanosheets as anode materials for
potassium ion batteries, Chem. Res. Chin. Univ. 37 (2021) 311–317.
[9] A. Samad, A. Shafique, Y.-H. Shin, Adsorption and diffusion of mono, di, and
trivalent ions on two-dimensional TiS2, Nanotechnology 28 (17) (2017) 175401.
[10] M. Armand, J.-M. Tarascon, Building better batteries, Nature 451 (7179) (2008)
652–657.
[11] S. Kansara, et al., 2D BeP 2 monolayer: investigation of electronic and optical
properties by driven modulated strain, RSC Adv. 10 (45) (2020) 26804–26812.
[12] Y. Jin, et al., Low-solvation electrolytes for high-voltage sodium-ion batteries,
Nat. Energy 7 (8) (2022) 718–725.
[13] M.K. Butt, et al., Storage of Na in 2D SnS for Na ion batteries: a DFT prediction,
PCCP 24 (48) (2022) 29609–29615.
[14] J. Rehman, X. Fan, W. Zheng, Computational insight of monolayer SnS2 as anode
material for potassium ion batteries, Appl. Surf. Sci. 496 (2019) 143625.
[15] J. Zhu, A. Chroneos, U. Schwingenschlögl, Silicene/germanene on MgX 2 (X= Cl,
Br, and I) for Li-ion battery applications, Nanoscale 8 (13) (2016) 7272–7277.
[16] T. Zhu, et al., A facile immobilization strategy for soluble phosphazene to
actualize stable and safe lithium-sulfur batteries, Small 18 (38) (2022) 2203693.
[17] M. Sun, U. Schwingenschlögl, Structure prototype outperforming MXenes in
stability and performance in metal-ion batteries: a high throughput study, Adv.
Energy Mater. 11 (14) (2021) 2003633.
[18] Y. Li, et al., Computational evaluation of ScB and TiB MBenes as promising anode
materials for high-performance metal-ion batteries, Phys. Rev. Mater. 6 (4)
(2022) 045801.
[19] Y. Zhang, et al., Two-dimensional transition metal chalcogenides for alkali metal
ions storage, ChemSusChem 13 (6) (2020) 1114–1154.
[20] Y. Yu, J. Zhou, Z. Sun, Modulation engineering of 2D MXene-based compounds
for metal-ion batteries, Nanoscale 11 (48) (2019) 23092–23104.
[21] N. Shekh, D. Chodvadiya, P.K. Jha, Rational design of h-AlC monolayer as anode
material for Mg-ion battery: A DFT study, Energy Storage 5 (3) (2023) e415.
[22] Y. Xie, et al., Prediction and characterization of MXene nanosheet anodes for non-
lithium-ion batteries, ACS Nano 8 (9) (2014) 9606–9615.
[23] Z. Yang, et al., Tuning the electrochemical performance of Ti 3 C 2 and Hf 3 C 2
monolayer by functional groups for metal-ion battery applications, Nanoscale 13
(26) (2021) 11534–11543.
[24] Q. Peng, et al., Vanadium carbide (V4C3) MXene as an efficient anode for Li-ion
and Na-ion batteries, Nanomaterials 12 (16) (2022) 2825.
[25] K. Rajput, et al., Ca2C MXene monolayer as a superior anode for metal-ion
batteries, 2D Materials 8 (3) (2021) 035015.
[26] S. Anantharaj, et al., Recent trends and perspectives in electrochemical water
splitting with an emphasis on sulfide, selenide, and phosphide catalysts of Fe Co,
and Ni: a review, ACS Catal. 6 (12) (2016) 8069–8097.
[27] V.G. Nair, et al., 2D MBenes: a novel member in the flatland, Adv. Mater. 34 (23)
(2022) 2108840.
[28] Z. Guo, J. Zhou, Z. Sun, New two-dimensional transition metal borides for Li ion
batteries and electrocatalysis, J. Mater. Chem. A 5 (45) (2017) 23530–23535.
[29] R. Li, et al., A boron-exposed TiB 3 monolayer with a lower electrostatic-potential
surface as a higher-performance anode material for Li-ion and Na-ion batteries,
PCCP 22 (39) (2020) 22236–22243.
[30] Y. Li, et al., Computational determination of a graphene-like TiB 4 monolayer for
metal-ion batteries and a nitrogen reduction electrocatalyst, PCCP 25 (10) (2023)
7436–7444.
[31] S. Ma, et al., A novel two-dimensional whorled TiB4 as a high-performance anode
material for Li-ion and Na-ion batteries, Appl. Surf. Sci. 639 (2023) 158083.
[32] G. Kresse, J. Furthmüller, Phys. Rev. B: Condens. Matter Mater. Phys. (1996).
[33] G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector
augmented-wave method, Phys. Rev. B 59 (3) (1999) 1758.
[34] M. Benhamida, N. Baadji, K. Bouamama, Computational Study of Mechanical and
Electronic Properties of Transition Metal Carbides Ti x M1–x C with M= Nb, V
and Zr, J. Nanoelectron. Optoelectron. 14 (5) (2019) 622–625.
[35] J. Perdew, Y. Wang, Phys. Rev. B: Condens. Matter Mater. Phys. (1986).
[36] Y.-S. Lin, et al., Long-range corrected hybrid density functionals with improved
dispersion corrections, J. Chem. Theory Comput. 9 (1) (2013) 263–272.
[37] S. Kumari, et al., Synergistic plasma-assisted electrochemical reduction of
nitrogen to ammonia, Chem. Commun. 54 (95) (2018) 13347–13350.
[38] A. Togo, I. Tanaka, First principles phonon calculations in materials science,
Scripta Comput. Sci. Appl. Math. Materialia 108 (2015) 1–5.
[39] X. Wang, et al., Density functional theory based molecular dynamics study of
solution composition effects on the solvation shell of metal ions, PCCP 22 (28)
(2020) 16301–16313.
[40] N. Humphrey, S. Bac, S. Mallikarjun Sharada, Ab initio molecular dynamics
reveals new metal-binding sites in atomically dispersed Pt1/TiO2 catalysts,
J. Phys. Chem. C 124 (44) (2020) 24187–24195.
[41] V. Wang, et al., VASPKIT: A user-friendly interface facilitating high-throughput
computing and analysis using VASP code, Comput. Phys. Commun. 267 (2021)
108033.
[42] K. Parlinski, Z. Li, Y. Kawazoe, First-principles determination of the soft mode in
cubic ZrO 2, Phys. Rev. Lett. 78 (21) (1997) 4063.
[43] R. Hill, The elastic behaviour of a crystalline aggregate, Proc. Phys. Soc. London,
Sect. A 65 (5) (1952) 349.
[44] X. Liu, et al., Lattice thermal conductivity of two-dimensional CrB4 and MoB4
monolayers against Slack’s guideline, Results Phys. 51 (2023) 106696.
M. Kashif Masood et al.
[45] J. Wang, et al., Electric field manipulation of multiple nonequivalent Dirac cones
in the electronic structures of hexagonal CrB4 sheet, Chin. Phys. B 27 (9) (2018)
097304.
[46] S.-Y. Xie, et al., First-principles calculations of a robust two-dimensional boron
honeycomb sandwiching a triangular molybdenum layer, Phys. Rev. B 90 (3)
(2014) 035447.
[47] Y. Li, et al., Dirac fermions in strongly bound graphene systems, Phys. Rev. Lett.
109 (20) (2012) 206802.
[48] A. Lopez-Bezanilla, Interplay between p− and d− orbitals yields multiple Dirac
states in one-and two-dimensional CrB4, 2D Materials 5 (3) (2018) 035041.
[49] C. Zhang, et al., High capacity silicon anodes enabled by MXene viscous aqueous
ink, Nat. Commun. 10 (1) (2019) 849.
[50] C. Wang, et al., Slurryless Li2S/reduced graphene oxide cathode paper for high-
performance lithium sulfur battery, Nano Lett. 15 (3) (2015) 1796–1802.
[51] R.C. Andrew, et al., Mechanical properties of graphene and boronitrene, Phys.
Rev. B 85 (12) (2012) 125428.
[52] Y. Ding, Y. Wang, Density functional theory study of the silicene-like SiX and XSi3
(X= B, C, N, Al, P) honeycomb lattices: the various buckled structures and
versatile electronic properties, J. Phys. Chem. C 117 (35) (2013) 18266–18278.
[53] G. Barik, S. Pal, Monolayer Molybdenum Diborides containing Flat and Buckled
Boride Layers as Anode Materials for Lithium-Ion Batteries, PCCP (2023).
[54] G. Barik, S. Pal, 2D MoS2-MoSe2 and MoS2-NbS2 lateral heterostructures as
anode materials for LIBs/SIBs, Appl. Surf. Sci. 596 (2022) 153529.
[55] S. Thomas, E.B. Nam, S.U. Lee, Atomistic dynamics investigation of the
thermomechanical properties and Li diffusion kinetics in ψ-graphene for LIB
anode material, ACS Appl. Mater. Interfaces 10 (42) (2018) 36240–36248.
[56] M. Born, K. Huang, M. Lax, Dynamical theory of crystal lattices, Am. J. Phys. 23
(7) (1955) 474.
[57] N. Khossossi, et al., Revealing the superlative electrochemical properties of o-
B2N2 monolayer in Lithium/Sodium-ion batteries, Nano Energy 96 (2022)
107066.
[58] Y. Kuai, et al., A two-dimensional metallic SnB monolayer as an anode material
for non-lithium-ion batteries, PCCP 24 (38) (2022) 23737–23748.
[59] Y. Kuai, et al., Two-dimensional SiP3 monolayer as promising anode with Record-
high capacity and fast diffusion for Alkali-ion battery, Appl. Surf. Sci. 586 (2022)
152510.
[60] P. Patel, et al., A density functional theory study on the assessment of α-CN and
α-CP monolayers as anode material in Li-ion batteries, J. Storage Mater. 71
(2023) 108074.
[61] J. Vetter, et al., Ageing mechanisms in lithium-ion batteries, J. Power Sources 147
(1–2) (2005) 269–281.
[62] X. Lv, et al., Metallic FeSe monolayer as an anode material for Li and non-Li ion
batteries: a DFT study, PCCP 22 (16) (2020) 8902–8912.
[63] B. Akgenc, New predicted two-dimensional MXenes and their structural,
electronic and lattice dynamical properties, Solid State Commun. 303 (2019)
113739.
[64] M. Li, et al., A novel hyperbolic two-dimensional carbon material with an in-
plane negative Poisson’s ratio behavior and low-gap semiconductor
characteristics, ACS Omega 5 (26) (2020) 15783–15790.
[65] C. Lundgren, A. Kakanakova-Georgieva, G.K. Gueorguiev, A perspective on
thermal stability and mechanical properties of 2D Indium Bismide from ab initio
molecular dynamics, Nanotechnology 33 (33) (2022) 335706.
[66] Q. Peng, et al., Two-dimensional SnS and SnSe as Hosts of K-Ion storage: A first-
principles prediction, J. Phys. Chem. C 127 (32) (2023) 15730–15737.
[67] S. Lu, et al., Perfect planar tetra-coordinated MC 6 monolayer: superior anode
material for Li-ion battery, PCCP 21 (27) (2019) 15187–15194.
[68] Q. Meng, et al., Theoretical investigation of zirconium carbide MXenes as
prospective high capacity anode materials for Na-ion batteries, J. Mater. Chem. A
6 (28) (2018) 13652–13660.
[69] Y.-Y. Wu, et al., Two-dimensional tetragonal Ti2BN: A novel potential anode
material for Li-ion batteries, Appl. Surf. Sci. 513 (2020) 145821.
[70] J. Tao, L. Guan, Tailoring the electronic and magnetic properties of monolayer
SnO by B, C, N O and F Adatoms, Sci. Rep. 7 (1) (2017) 1–7.
[71] G. Chaney, et al., Comprehensive study of lithium adsorption and diffusion on
Janus Mo/WXY (X, Y= S, Se, Te) using first-principles and machine learning
approaches, ACS Appl. Mater. Interfaces 13 (30) (2021) 36388–36406.
[72] AR, M.Y.E.M.O. and Y. Xie, Trojan I. Medvedev S. Lyakhov AO Valle M. Prakapenka
V. Nature, 2009. 458: p. 182–185.
12
Applied Surface Science 652 (2024) 159301
[73] T. Yu, et al., TiC3 monolayer with high specific capacity for sodium-ion batteries,
JACS 140 (18) (2018) 5962–5968.
[74] S. Luo, et al., First-Principles Study of FeB2 Monolayers as High-Capacity
Electrode Materials for Mg-Ion Batteries, J. Phys. Chem. C (2023).
[75] W. Tang, E. Sanville, G. Henkelman, A grid-based Bader analysis algorithm
without lattice bias, J. Phys. Condens. Matter 21 (8) (2009) 084204.
[76] A. Urban, D.-H. Seo, G. Ceder, Computational understanding of Li-ion batteries,
npj Comput. Mater. 2 (1) (2016) 1–13.
[77] D. Wang, et al., First-principles calculations of Ti2N and Ti2NT2 (T= O, F, OH)
monolayers as potential anode materials for lithium-ion batteries and beyond,
J. Phys. Chem. C 121 (24) (2017) 13025–13034.
[78] K. Toyoura, et al., Effects of off-stoichiometry of LiC6 on the lithium diffusion
mechanism and diffusivity by first principles calculations, J. Phys. Chem. C 114
(5) (2010) 2375–2379.
[79] Q.-H. Qiu, et al., First-principles studies of the two-dimensional 1H-BeP2 as an
electrode material for rechargeable metal ion (Li+, Na+, K+) batteries, Comput.
Mater. Sci 216 (2023) 111868.
[80] Y. Xiao, W. Zhang, Adsorption mechanisms of Mo2CrC2 MXenes as potential
anode materials for metal-ion batteries: a first-principles investigation, Appl. Surf.
Sci. 513 (2020) 145883.
[81] X. Zhang, et al., Theoretical prediction of MoN 2 monolayer as a high capacity
electrode material for metal ion batteries, J. Mater. Chem. A 4 (39) (2016)
15224–15231.
[82] D.B. Putungan, S.-H. Lin, J.-L. Kuo, Metallic VS2 monolayer polytypes as potential
sodium-ion battery anode via ab initio random structure searching, ACS Appl.
Mater. Interfaces 8 (29) (2016) 18754–18762.
[83] B. Chen, et al., Prediction of boridenes as high-performance anodes for alkaline
metal and alkaline Earth metal ion batteries, Nanoscale 14 (48) (2022)
17955–17975.
[84] Z. Zhang, et al., Computational screening of layered materials for multivalent ion
batteries, ACS Omega 4 (4) (2019) 7822–7828.
[85] A. Samad, U. Schwingenschlögl, M 2 X Monolayers as Anode Materials for Li Ion
Batteries, Phys. Rev. Appl 15 (3) (2021) 034025.
[86] G. Henkelman, B.P. Uberuaga, H. Jónsson, A climbing image nudged elastic band
method for finding saddle points and minimum energy paths, J. Chem. Phys. 113
(22) (2000) 9901–9904.
[87] E. Pollak, et al., The interaction of Li+ with single-layer and few-layer graphene,
Nano Lett. 10 (9) (2010) 3386–3388.
[88] L. David, R. Bhandavat, G. Singh, MoS2/graphene composite paper for sodium-
ion battery electrodes, ACS Nano 8 (2) (2014) 1759–1770.
[89] D. Er, et al., Ti3C2 MXene as a high capacity electrode material for metal (Li, Na,
K, Ca) ion batteries, ACS Appl. Mater. Interfaces 6 (14) (2014) 11173–11179.
[90] X. Zhang, et al., Borophene as an extremely high capacity electrode material for
Li-ion and Na-ion batteries, Nanoscale 8 (33) (2016) 15340–15347.
[91] M.V. Koudriachova, N.M. Harrison, S.W. de Leeuw, Effect of diffusion on lithium
intercalation in titanium dioxide, Phys. Rev. Lett. 86 (7) (2001) 1275.
[92] M. Wagemaker, et al., Two phase morphology limits lithium diffusion in TiO2
(anatase): A 7Li MAS NMR study, JACS 123 (46) (2001) 11454–11461.
[93] O.I. Malyi, T.L. Tan, S. Manzhos, A comparative computational study of
structures, diffusion, and dopant interactions between Li and Na insertion into Si,
Appl. Phys Express 6 (2) (2013) 027301.
[94] V.V. Kulish, et al., Enhanced Li adsorption and diffusion in silicon nanosheets
based on first principles calculations, RSC Adv. 3 (13) (2013) 4231–4236.
[95] G.-C. Guo, et al., Pristine and defect-containing phosphorene as promising anode
materials for rechargeable Li batteries, J. Mater. Chem. A 3 (21) (2015)
11246–11252.
[96] S. Zhao, W. Kang, J. Xue, The potential application of phosphorene as an anode
material in Li-ion batteries, J. Mater. Chem. A 2 (44) (2014) 19046–19052.
[97] M.K. Masood, et al., Theoretical prediction of stable WB4 monolayer as a high-
capacity anode material for alkali-metal ion batteries, J. Phys. Chem. Solid (2023)
111814.
[98] Z. Zhang, et al., Two-dimensional transition metal dichalcogenides as promising
anodes for potassium ion batteries from first-principles prediction, PCCP 21 (42)
(2019) 23441–23446.
[99] D. Chodvadiya, et al., Potential anodic application of 2D h-AlC for Li and Na-ions
batteries, Appl. Surf. Sci. 593 (2022) 153424.
[100] P. Patel, et al., Two-Dimensional α-SiX (X= N, P) Monolayers as Efficient Anode
Material for Li-Ion Batteries: A First-Principles Study, ACS Appl. Nano Mater. 6
(3) (2023) 2103–2115.