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S-functionalized 2D V2B as a promising anode

material for rechargeable lithium ion batteries†
Cite this: Phys. Chem. Chem. Phys.,
2023, 25, 4015
Yuhang Wang,a Ninggui Ma,a Yaqin Zhang, a
Bochun Liang,a Jun Zhaoa and
Jun Fan *ab

Received 23rd November 2022,
Accepted 22nd December 2022
DOI: 10.1039/d2cp05477a
rsc.li/pccp
The development of novel high specific capacity anode materials is urgently needed for rechargeable
metal ion batteries. Herein, S-functionalized V2B as the electrode material for Li/Na/K ion batteries are
comprehensively investigated using first-principles calculations. Specifically, V2BS2 was verified with
good electrical conductivity via band structure and density of states calculations. Phonon dispersion and
ab initio molecular dynamic simulations were performed and confirmed the dynamic and thermal
stability of V2BS2. The use of V2BS2 with a high theoretical specific capacity of 606 mA h g1 for lithium
ion batteries (LIBs) due to the bilayer adsorption of Li atoms is encouraging, which is attributed to the
double empty orbitals of the S atoms and small lattice mismatch (1.5%) between the Li layers and
substrate. Furthermore, dendrite formation would be well prohibited and safety issues for battery
operation would be ensured for V2BS2 as electrode materials because of the low open circuit voltage
with 0.37 V. The high charge/discharge rate for LIBs is also achievable owing to the high mobility of
adatoms on the surface of V2BS2. Our work not only finds use as a promising material for the field of
energy storage, but also provides constructive design strategies for developing high performance anode
materials for rechargeable metal ion batteries.

1. Introduction Two-dimensional (2D) transition metal borides (MBenes),

Environmental and energy issues have attracted widespread
attention in recent years.1,2 The development of rechargeable
metal ion batteries is of vital importance for electrochemical
energy storage, especially for using renewable energy sources
effectively and building a sustainable society.3 Of all the alter-
native electronic devices available in daily life, lithium ion
batteries (LIBs) have been widely used for several decades.4 As
yet, the development of high-performance LIBs with higher
energy density and increased battery safety continues to be
motivated by the increasing demand for energy storage.5
Research studies on improving theoretical capacity and battery
safety have never ceased. On the other hand, alternative metal
ion batteries, including sodium ion batteries (SIBs)6–8 and
potassium ion batteries (KIBs) have attracted extensive interest.
Until now, the search for suitable electrode materials, particu-
larly anode materials, is one of the most urgent issues in the
development of rechargeable ion batteries.
a
Department of Materials Science and Engineering, City University of Hong Kong,
83 Tat Chee Avenue, Kowloon, Hong Kong, China. E-mail: junfan@cityu.edu.hk
b
Center for Advance Nuclear Safety and Sustainable Department, City University of
Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, China
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/
10.1039/d2cp05477a
analogous to MXenes with larger specific areas and adjustable
chemical properties, have attracted more and more attention
fro both theoretical and experimental researchers in the fields
of energy storage and electrocatalysis.9–12 MB (or M2B2) type
MBenes is a commonly investigated one. For example, Guo
et al. found that Mo2B2 MBene was a potential candidate for
LIBs owning to the small diffusion barrier and high storage
capacity of B444 mA h g1 for Li atoms.13 V2B2, Cr2B2, and
Mn2B2 were also predicted to be potential candidates for LIBs/
SIBs.14 Apart from this, M2B is another phase of the MBenes.
There are also some research studies about their application in
energy storage. For instance, Mo2B was found to have high
theoretical volumetric capacity and low migration energy bar-
rier for LIBs.15 Sc2B was predicted with an ultra-high specific
capacity for magnesium ion batteries.16 Recently, N functiona-
lized Ti2B was found to exhibit promising application for SIBs,
with a storage capacity of 797 mA h g1.17 In short, MBenes are
promising candidates for battery materials and are worthy of
further study. Limited by the short discovery time, the under-
standing of V2B-based MBenes is still in its infancy.
Suitable surface functional groups for MBenes/MXenes are
one of the key factors for high performance electrode materials.
Generally, the exposed metal atoms of bare MBenes/MXenes
are chemically active because of the large amount of dangling
bonds. As a result, the introduction of functional groups on the

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surface of MBenes/MXenes is inevitable during the process of
chemical synthesis.18 The essential role of terminal atoms on
MXenes/MBenes in the electronic and electrochemical properties
has been well studied. Taking functionalized Ti2C as an example,
Ti2CO2 shows semiconductor properties (band gap: 0.3 eV),
whereas Ti2CF2 is a conductor.19,20 It is reported that some
functional atoms may affect the adsorption of metal ions, e.g., F
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functionalized Ti3CN could weaken the adsorption ability towards
Na.21 In contrast, when Zr2C and Zr3C2 were terminated by
O atoms, the adsorption energy of a single Na atom varied from
positive to negative, indicating the enhancement of Na affinity.22
As has been stated, selective functionalization of MBenes/MXenes
is crucial for the development of high-performance electrode
materials. Sulfur (S), with an electronic configuration of 3s2 3p4
that contains two empty electronic orbitals and moderate electro-
negativity (2.54), is considered as a potential surface termination
tuning the adsorption ability of metal ions, thus achieving high
theoretical specific capacity.23,24 In particular, S functionalized
Ti2B has exhibited good structural stability and shown excellent
electrochemical performance for SIBs.25 Moreover, S-function-
alized Cr2C and Mo2C were revealed with competitive electro-
chemical properties using as anode materials for LIBs.26 Another
fundamental principle in the design of novel electrode materials
is to lower the lattice mismatch between adsorbed metal ion
layers and negative electrode materials. Three major advantages
of smaller lattice misfit between adsorbed metal ions layer and
electrode materials can be concluded from the previous studies.
Firstly, a smaller interfacial disordered cation layer can avoid pore
formation and increase the morphology stability during metal ion
cycling.27 Secondly, a smaller misfit will contribute to less lattice
expansion or contraction28 and reduce the local strain, prevent the
formation of vacancies and maintain good mobility of cations.29
Most importantly, a smaller mismatch ensures the suitable dis-
tance between the adatoms and is beneficial for the balance of the
attraction and repulsion of adsorbed atoms, thereby favoring the
multilayer adsorption ability and increasing the energy density of
the anode materials.22 Thus, lowering the lattice mismatch is an
important strategy for ensuring battery safety and increasing
capacity for developing high performance electrode materials.
Therefore, the application of substrate materials that can simulta-
neously combine the functionalization of S atoms and the for-
mation of small lattice mismatch with the adsorbed metal ion
layer in rechargeable batteries deserves further study.
As reported by Ma et al., V2B has a lattice constant of 2.958 Å,
which shows a similar lattice constant to layered Li (2.95 Å),17
while a low theoretical capacity of 476 mA h g1 for V2B as anode
for LIBs.16 Motivated by the importance of surface functional
groups and lattice mismatch, we systematically investigated the
suitability of S-functionalized V2B as a potential anode material
for LIBs/SIBs/KIBs, especially for LIBs, using density functional
theory. This study firstly proved that V2BS2 exhibits excellent
conductivity via the band structure and density of states calcula-
tions. Secondly, the S-functionalized V2B shows good dynamic
and thermal stability. Thirdly, the adsorption for the second
layer of Li atoms on V2BS2 is energetically favorable,
thus ensuring the high specific capacity (up to 606 mA h g1).
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More importantly, the low open circuit voltage (OCV) and diffu-
sion barrier for LIBs enable battery safety and fast kinetics for
charge/discharge process of V2BS2 as an anode material for LIBs.
It provides guidance for the experimental synthesis of function-
alized V2B. Our work found that choosing functionalized
MBenes with terminals with moderate electronegativity and
larger electronic capacity and lowering the lattice mismatch
between adsorbed metal layers and substrate are two major
suggestions for designing high performance electrode materials
for rechargeable ion batteries.
2. Computational details
All the calculations based on density functional theory (DFT)
were performed by using Vienna ab initio simulation package
(VASP).30,31 To consider the ion–electron interactions, the pro-
jector augmented wave (PAW) method32 was employed. The
generalized gradient approximation (GGA) of Perdew–Burke–
Ernzerhof (PBE) functional33,34 was used to describe the
exchange and correlation interaction. Spin-polarized calcula-
tions were performed by tuning ISPIN = 2 in this work. The
geometry optimization and electronic properties for unit cells
were carried out based on a G-centered 12  12  1 and 25 
25  1 Monkhorst–Pack k-mesh,35 respectively. Additionally, a
G-centered 4  4  1 Monkhorst–Pack k-mesh was taken into
account for structural optimization with a supercell of 3  3  1
and a vacuum layer of 30 Å in the z direction. The cut-off energy
of plane wave expansion was set to 520 eV. The van der Waals
interaction was adopted according to the DFT-D3 dispersion
correction strategy to take the effect of nonbonding forces into
account.36 The convergence criteria for energy and force were
set to 105 eV and 0.02 eV Å1, respectively. Phonon dispersion
calculations with cell size of 1  1  1 were performed based on
the finite displacement method37,38 embedded in the PHO-
NOPY package.39 Ab initio molecular dynamics (AIMD) simula-
tions was carried out at 300/500 K for 10 ps with a time step of
2 fs using the NVT ensemble.40 The diffusion properties of
cations were identified using the climbing image nudged
elastic band (CI-NEB) method.41
3. Results and discussion
3.1. Structural properties of V2BS2
The initial V2B monolayer (space group: P3% m1) is composed of a
sandwich like V–B–V layered structure with B atoms embedded
in the middle of V layers. The side view and the top view of the
V2B monolayer are displayed in Fig. S1a and b (ESI†). To
determine the most energetic favorable site for functional
atoms on the surface of V2B, the energy minimization principle
was used. Based on the symmetry properties of V2B surface
(presented in Fig. S1c–e, ESI†), three possible sites were
considered, that is I (B top), II (V1 top), and III (V2 top). The
optimized configuration of S-functionalized V2B with the lowest
energy is shown in Fig. 1a, where S atoms prefer to locate at
the III site. The optimized configuration is similar to other
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Fig. 1 Optimized configuration of (a) S-functionalized V2B, (b) band structure, (c) total and partial density of states, (d) phonon dispersion calculations of
V2BS2, and (e) the variation of the free energy and the structure in the AIMD simulations at 500 K during the time period of 10 ps for V2BS2.
MXene-based S-functionalized monolayers, e.g., V2CS2,42 V2NS2,43
Ti2CS2,44 and Ti2NS2.45 Additionally, the lattice constant, bond
length, and layer thickness of V2BS2 are summarized and com-
pared with other similar MXene/MBene-based materials in Table
S1 (ESI†). To be specific, the optimized lattice constant (3.05 Å),
bond length (V–B: 2.13 Å, V–S: 2.34 Å) and layer thickness (5.47 Å)
for V2BS2 is almost the same as that of V2CS2 (lattice constant:
3.06 Å; V–C: 2.08 Å, V–S: 2.37 Å; thickness: 5.43 Å)42 and V2NS2
(lattice constant: 3.09 Å; V–N: 2.06 Å, V–S: 2.35 Å)43 due to their
similar structural features. More importantly, the lattice constant
of V2BS2 is shorter than those obtained in the previous study of
Ti-based S-functionalized MXenes/MBenes, such as Ti2NS2
(3.17 Å), Ti2CS2 (3.17 Å), and Ti2BS2 (3.50 Å), indicating the
suitability of the anode materials for LIBs from the perspective
of lattice matching.
3.2. Electronic properties of V2BS2
The cyclability, rate capability performance, and conductivity
are important parameters for rechargeable metal ion batteries,
which are highly related to the electronic properties of anode
materials. Therefore, the band structure and density of states
(DOS) calculations were performed to evaluate the conductivity
of V2BS2. On the one hand, as shown in Fig. 1b, there exist
energy bands crossing the Fermi level of the S-functionalized
V2B, manifesting the good metallicity of V2BS2. On the other
hand, the energy band for spin up and spin down overlap
completely, suggesting the non-magnetic properties of V2BS2.
DOS results show that there are a large number of states in the
vicinity of the Fermi energy level (Fig. 1c), thereby implying a
high carrier density. Besides, the metallic properties are mainly
contributed by V atoms. Similar to the other anode materials,
like the VS2 monolayer,46 and accordingly, the supplement of
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carriers during charge transfer is ensured. Therefore, V2BS2 is
determined as having metallic properties and superior to
the other electrode materials, such as Na2Ti3O7 (band gap:
2.99 eV).47 The finding is in line with the band structure
analysis that V2BS2 is an excellent conductor. Moreover, the
partial DOS is also calculated to understand the orbital con-
tribution of various atoms, which indicates that the electrons
from the d orbital of V are critical for the conductivity of the
V2BS2 monolayer (Fig. S2, ESI†). To avoid the underestimation
of the band gap caused by PBE functionals, band structure
calculation using HSE06 functional was carried out. As shown
in Fig. S3 (ESI†), V2BS2 exhibits good conductivity due to the
presence of energy bands crossing the Fermi energy level. To be
noted, because of the similar results obtained from different
functionals for V2BS2, PBE functionals were used for the following
calculations. Overall, the metallic nature of V2BS2 guarantees its
good electrical conductivity and suggests its potential as electrode
material with excellent battery conductivity.
3.3. Stability of V2BS2
The dynamic and thermal stability are major prerequisites for
V2BS2 serving as electrode materials for metal ion batteries.
Firstly, we investigated its dynamic stability via phonon disper-
sion calculation. As presented in Fig. 1d, no imaginary frequen-
cies are observed in the whole Brillouin zone, conveying that
S-terminated V2B is dynamically stable. Alongside this, the
existence of quadratic dispersion of the out-of-plane acoustic
mode inside the Brillouin zone further proves the characteristics
of two-dimensional materials of V2BS2.48 Next, the thermal
stability of V2BS2 is evaluated through AIMD simulation at
500 K and the result is displayed in Fig. 1e. The free energy of
the system fluctuates near a stable value around 334 eV at
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500 K during the simulation period of 10 ps, suggesting V2BS2
maintains a stable structural characteristic. The snapshot inset
in Fig. 1e is the corresponding side view and top view of V2BS2 at
the end of the simulation. Though some small shifts of the
atomic position are detected at this temperature, there is no
bond reconstruction and phase transformation for V2BS2, con-
firming that V2BS2 possesses excellent thermal stability. In
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summary, the structure of V2BS2 is stable dynamically and
thermally. This finding indicates that it has the potential to
work at relatively high temperatures, which greatly encouraged
our follow-up research.
3.4. Potential suitability for V2BS2 as anode materials
3.4.1. Adsorption properties of a single Li/Na/K atom on
V2BS2. The adsorption ability of anode materials with regard to
metal ions is a crucial parameter for evaluating the performance of
electrode materials. Thereby, the adsorption energy for a single
metal ion was explored. According to the symmetry of the surface
active site, three possible sites are considered and displayed in
Fig. 1a (side view), that is a (on the top of the B atom), b (on the top
of the V1 atom), g (on the top of the V2 atom). The pre-adsorption
model is shown in Fig. S4 (ESI†). The adsorption energy for single
atom (Ead) on V2BS2 was computed as given below:
Ead = EV2BS2+M – EV2BS2 – EM (1)
where EV2BS2+M, EV2BS2, and EM are the total energies of V2BS2 +
M, V2BS2, and single metal ion (M = Li, Na, and K and the same
implication for M is used in the following sections. The energy
of the single metal ion is obtained from their bulk structure).
The more negative the Ead, the stronger the interaction between
adatoms and V2BS2 monolayer. The adsorption energy are
summarised in Fig. 2.
The adsorption energy for single Li/Na/K is negative at
different sites, suggesting that the adsorption of metal ion on
the substrate is energetically favorable. Specifically, adsorption
at the b site is more preferred, as Ead for M follows the order of
b o a o g. This can be attributed to the suitable distance
Fig. 2 Adsorption energy (eV) of Li/Na/K at different sites on the surface
of V2BS2.
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between adatoms and surface functional atoms and high coor-
dination binding environment when metal ions are adsorbed on
the b site. The results of the optimal binding sites are consistent
with previous reports of metal ions adsorbed on the Ti2BS2
monolayer.25 What should be noted is that, compared with bare
V2B MBenes with Ead for Li/Na are B0.73/0.45 eV,16 the highest
Ead for Li/Na on S-functionalized V2B are greatly promoted,
indicating the success of choosing S as functional atoms.
Understanding reasons of the Ead difference for different
adatoms will help us get a deep insight into the adsorption
process for V2BS2 as an electrode material. Thus, we compared
Ead for M at the most stable site. As found, though alkali metals
have similar chemical and physical properties, the Ead varies
irregularly. Compared with different adatoms, the adsorption
energy follows the order of K (2.120 eV) 4 Li (1.683 eV) 4
Na (1.613 eV). With the decrease of the atomic electronega-
tivity (Li: 0.98; Na: 0.93; K: 0.82) and atomic number, the charge
transferred increased from 0.594 to 0.776 |e|, the bond length
changed from 2.321 to 3.013 Å. However, to fully comprehend
the variance of Ead for M, we need to analyze their relative
changes. The adsorption energy is majorly contributed by
electrostatic interaction, that is the charge transfer between
M and S and the bond length of M–S (dM–S). Specifically, an
elongated M–S bond will weaken the interaction, while
increased charge transfer will promote attraction. As shown
in Table 1, with Li adsorption as the reference state, the DdNa/d0
is 16.1%, surpassing the charge transfer change rate (DeNa/
e0 : 13.4%), suggesting an overall negative contribution for
adsorption of Na. Therefore, Ead for Na is slightly lower than
Ead for Li. For the adsorption of K, DdK/d0 (29.8%) is less than
DeNa/e0 (30.6%), demonstrating a positive contribution to the
electrostatic interaction. Unlike the small value of EDNa–Li
(0.05), EDK–Li is 0.16, which will result in a larger ED in M–S.
The larger ED generally leads to a stronger M–S interaction.
Consequently, Ead for K is stronger than Ead for Li by 0.437 eV.
Next, to explore the adsorption processes of alkali metal on
MBenes from a deeper perspective, charge density difference
(CDD) was obtained to visualize the charge redistribution
between the adatoms and the V2BS2 monolayer. Charge dis-
tribution is differentiated by color difference (Fig. 3). Clearly,
the region of charge accumulation is observed between ada-
toms and nearby three S atoms. Conversely, there is a signifi-
cant electron depletion around the adsorbed metal atoms,
suggesting that the alkali metal is bonded via electrostatic
interaction spontaneously.
Table 1 Comparison of charge transfer from metal ion to substrates (|e|),
bond length, change rate of bond length (DdM/d0 (%)) and charge transfer
(DeM/e0 (%)) with reference to Li adsorption, and the electronegativity
difference (ED) between Na/K and Li
Charge Bond length DdM/d0 DeM/e0 Electronegativity
Adatoms transfer (|e|) (M–S) (Å) (%) (%) difference (ED)
Li 0.594 2.321 0 0 0
Na 0.677 2.694 16.1 13.4 0.05
K 0.776 3.013 29.8 30.6 0.16
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Fig. 3 Charge density difference of metal ion adsorbed on V2BS2: (a) Li,
(b) Na, and (c) K. The charge accumulation and depletion regions are
colored yellow and cyan, respectively. The isosurface level is set to
0.0015 e Å3.
By and large, the adsorption of a single atom on V2BS2 is
energetically favorable, suggesting that S-functionalized V2B
MBene is desirable.
3.4.2. Diffusion properties of V2BS2. The mobility of the
adatoms on the surface of anode, which is considered as the
contributing factor affecting the charge/discharge rate during
battery operation, is another important indicator for the elec-
trode materials. Thus, the diffusion properties of alkali metal
were studied. As mentioned above, the alkali atoms prefer to be
adsorbed on the b site. Three possible pathways are considered
for the ion diffusion (Fig. 4a): b site–b site (path-1), b site–a
site–b site (path-2), and b site–g site–b site (path-3). The results
show that path-1 will be converted to path-2 after the calcula-
tion of the diffusion of Li/Na/K, which is consistent with
previous reports.49,50 Thus, we only discuss path-2 and path-3
in the following section. As displayed in Fig. 4b–d, path-2 is
identified as the optimal path for alkali metal diffusing on the
surface of V2BS2, accompanied by the energy barrier of 0.223 eV
for Li, 0.084 eV for Na, and 0.053 eV for K, respectively.
Obviously, the diffusion barrier for path-3 is much higher than
the process going through path-2. This can be attributed to the
fact that path-2 goes through a site and the Ead difference
Fig. 4 Designed diffusion path for Li/Na/K (a) and the diffusion barriers for
alkali metal on the surface of V2BS2 (b–d).
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between the a site and the b site is far lower than the Ead
difference between the g site and the b site. Besides, the
diffusion barrier for Na/K is smaller than that of the Li atom,
suggesting that Na/K can migrate easily on the V2BS2 monolayer
as compared with Li. Similar trends are also observed on other
MXene-related anodes materials, e.g., Nb2N50 and V3C2.51 Most
importantly, we notice that the theoretical diffusion barrier for
adatoms is relatively lower than that of other 2D materials, such
as Ti3C2S2 (0.25 for Li),24 MoS2 (0.28 for Na),52 graphene (0.39/
0.27/0.14 for Li/Na/K),53 and MoN2 (0.78/0.56/0.49 for Li/Na/
K).54 Overall, the lower adsorption energy difference between a
site and b site ensures the low diffusion energy barrier of Li/Na/
K, implying the outstanding rate capability it would have and
signifying the great potential of S-functionalized V2B as energy
storage materials.
3.4.3. Layer-by-layer adsorption properties of Li/Na/K on
V2BS2. The ability of multilayer adsorption for alkali metal is
the key to achieving a high theoretical specific capacity. Thus,
we further investigated layer-by-layer adsorption behavior of Li/
Na/K on V2BS2 monolayer. The average adsorption energy for
the 1st, 2nd, and 3rd layer of M was calculated using the
following equations:
E1st
ad = (EV2BS2M2  EV2BS2  18  EM)/18 (2)
E2nd
ad = (EV2BS2M4  EV2BS2M2  18  EM)/18 (3)
E3rd
ad = (EV2BS2M6  EV2BS2M4  18  EM)/18 (4)
where EV2BS2M2, EV2BS2M4, EV2BS2M6, and EV2BS2, are the total energy
of V2BS2M2, V2BS2M4, V2BS2M6, and V2BS2, respectively. EM is
the energy of single M in its bulk phase. Similar to the single
atom adsorption of Li/Na/K, three possible adsorption sites,
namely a (on the top of B atom), b (on the top of V1 atom), g (on
the top of V2 atom), were considered. The initial configurations
for the adsorption of the first metal layer on different sites are
demonstrated in Fig. S5 (ESI†). The negative value indicates the
adsorption of metal ion can occur spontaneously, while the
positive value manifests that the adsorption of Li/Na/K is
unfavorable energetically. The results are summarised in Table S2
(ESI†). First, the energetically favorable site for the first layer
alkali metal adsorption is the b site, which is in line with the
single atom adsorption. To be specific, E1stad for Li, Na, and K are
0.702 eV, 0.327 eV, and 0.426 eV, correspondingly, indicat-
ing that Li and Na adsorption is exothermic. Side views for
Li/Na are displayed in Fig. 5a and c. It may be noted that, the
adsorption ability for the whole layer follows the sequence of
K o Na o Li, which is consistent with atomic radius changes.
Generally, a larger atomic radius will require a larger atomic
spacing to balance the attractive and repulsive forces between
atoms. Therefore, the major reason for E1st ad for M is that the
smaller lattice mismatch between adatoms and substrate pro-
vides a suitable distance of adsorbed atoms (lattice mismatch
between the metal layer and V2BS2: Li–V2BS2 (1.5%), Na–V2BS2
(16.6%), and K–V2BS2 (49.8%)), thus favoring the minimization
of the repulsive potential of adjacent to adatoms and resulting
in higher adsorption energy. Calculation details of the lattice
mismatch can be found in our previous report.17
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Fig. 5 Side view of optimized configuration of (a) V2BS2Li2, (b) V2BS2Li4,
(c) V2BS2Na2, and (d) V2BS2Na4.
Next, we studied the second layer adsorption of Li/Na
because of their negative E1stad . Analogous to the consideration
of the first layer adsorption, three potential anchored sites were
taken into account. In this case, g site adsorption is more
favorable, followed by the results that the E2nd ad for Li and Na
are 0.044 eV and 0.112 eV, respectively. Encouragingly, the
adsorption of the 2nd layer of Li is still feasible and side view of
the optimized configuration is shown in Fig. 5b. In contrast to
the positive value of E2nd
ad for unfunctionalized V2B,
16 2nd
Ead for
Li on V2BS2 is greatly improved. This strongly demonstrates
the influence of surface functional groups on the adsorption
capacity of metal ions. In contrast, the adsorption energy for Na
decreased from negative to positive. On the one hand, the
increase of Na ions leads to the increase of the repulsion
between metal ions. On the other hand, the distance between
Na ions in the second layer and the substrate increases
(the distance of the second Li/Na atoms to the substrate is
3.94/5.35 Å (Fig. 5b and d)), and the attraction between the
Fig. 6 Electron localization function (ELF) maps of multilayer adsorption of Li, Na, K: (a) V2BS2Li2, (b) V2BS2Li4, (c) V2BS2Li6, (d) V2BS2Na2, (e) V2BS2Na4,
and (f) V2BS2K2.
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substrate and metal atoms decreases. Two reasons jointly lead
to the difficulty of the adsorption of the second layer Na atoms.
To explore the maximum capacity of Li adsorption on the V2BS2
monolayer, the adsorption energy for the 3rd layer of Li was
calculated. The result suggests that Li can’t be adsorbed up to
three layers as a positive value of E3rd
ad is obtained. To sum up,
V2BS2 show excellent multilayer adsorption affinity for Li ions
with lower lattice mismatch and suitable surface terminations,
confirming our designing strategy that V2BS2 could be utilized
as a promising anode material for metal ion batteries, particu-
larly for LIBs. The anode materials for LIBs we designed break
through the limitation of Li ion adsorption monolayer on
MXenes/MBenes. Compared with other two-dimensional mate-
rials, it has obvious progress.
To better comprehend the binding characters between metal
layer adsorbed and V2BS2 and the multilayer adsorption beha-
vior, the electron localization function (ELF)55 was performed
and ELF maps projected onto the (110) plane for the stoichio-
metries of V2BS2Li2, V2BS2Li4, V2BS2Li6, V2BS2Na2, V2BS2Na4,
and V2BS2K2 are shown in Fig. 6. Specifically, the ELF value
indicates the probability of finding an electron near the refer-
ence electron with the same spin and thus the value of ELF
varies from 0 to 1. The higher value of ELF corresponds to the
increased localization of the electrons. ELF = 1 denotes that the
electrons are fully localized. ELF = 0.5 is attributed to uniform
electron gas with metallic bond features, and the value near
zero represents a low electron density area. As shown in Fig. 6,
the negative electron cloud (NEC) was formed after the metal
ion adsorption. Typically, NEC with the characteristic of anions
plays a significant part in ensuring the stability of the adsorbed
metal layers. Obviously, the area of NEC formed after the first
layer adsorption of Li and Na (Fig. 6a and d) is larger than the
adsorption of K (Fig. 6f), indicating a stronger stabilization
ability. This finding is in agreement with adsorption energy
results that E1st 1st
ad for Li/Na is negative, while Ead for K is positive.
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PCCP
Similarly, for the adsorption of the second layer of Li, NEC is still
observable around the outer two layers of Li atoms, thus the
repulsive interaction between the nearby Li atoms is well reduced.
In contrast to Fig. 6b, though a certain amount of NEC is formed
around the second layer of Na atoms, the electrons become more
localized as the existence of areas with an ELF value above 0.5.
Considering the larger size of Na radius compared with that of the
Published on 27 December 2022. Downloaded by SHANDONG UNIVERSITY on 4/14/2023 4:03:24 AM.
Li atom, there is an increased repulsive potential when a large
amount of Na atoms are adsorbed on the surface of V2BS2, the
NEC is not strong enough to weaken the repulsion between
positively charged Na atoms, thereby resulting a weaker inter-
action between outer Na layers and V2BS2 monolayer. Further-
more, the third layer adsorption of Li is provided as a comparison.
The ELF map for V2BS2Li6 displays that a relatively larger area of
covalent bond character (ELF value between 0.5 and 1) and a
smaller amount of metallic bond feature (ELF value around 0.5) is
formed around the third layer of Li, suggesting the decreased
amount of NFC. Therefore, the third layer of Li atoms’ interaction
with the substrates is less stable, which is consistent with the
adsorption energy result (E3rd ad for Li is 0.030 eV). In total, ELF
analysis supports the significance of NEC in promoting the
stability of multilayer alkali metal adsorption.
To gain a deeper insight into the physical mechanism of the
metal layer and substrate interaction, Bader charge analysis
was carried out to quantify the charge transfer during the
monolayer adsorption of different metal atoms. The average
charge transferred from adatoms to V2BS2 monolayer is mea-
sured to be 0.256, 0.233, and 0.301 |e| for Li, Na, and K,
respectively, confirming the presence of coulombic interaction
between the adsorbed metal layer and the substrate. Our
finding proves that S-atoms with moderate electronegativity
and dual empty electron orbitals are potential functional
groups for V2B as electrode materials. Additionally, the electronic
properties of V2BS2 covered by one layer of Li/Na were analyzed
to estimate its suitability as anode materials by calculating the
DOS of V2BS2Li2 and V2BS2Na2. As shown in Fig. S6 (ESI†), V2BS2
Fig. 7 The variation of the free energy in the AIMD simulations during the time period of 10 ps for V2BS2Li4 (a), top view (upper layer) and side view (lower
layer) of V2BS2Li4 after AIMD simulations at 300 K (b) and 500 K (c).
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after lithiation/sodiation maintains good metallicity because
there are states across Fermi energy level. For that reason, we
can conclude that V2BS2 has superb properties in the electro-
chemical cycle.
The thermal stability of V2BS2 after metal layer adsorption is
essential for the safety of battery operation. Since high concen-
tration adsorption of Li atoms (up to two layers) is seen on the
surface of V2BS2, AIMD simulation at different temperatures
were conducted for V2BS2Li4. Additionally, AIMD for V2BS2Na/K2
were also performed as comparison. The results are displayed in
Fig. 7 and Fig. S7 (ESI†). First, we evaluated the thermal stability of
V2BS2Li4 at 300 K. There is no sharp drop or rise for the free energy
of V2BS2Li4 during the simulation (Fig. 7a) and the structures are
well maintained as can be seen from the top and side view of
V2BS2Li4 (Fig. 7b), demonstrating the stability of lithiated V2BS2.
High temperature stability operation is also another serious pro-
blem facing currently.56,57 Next, we elevated the temperature up to
500 K. As displayed in Fig. 7a, the free energy of V2BS2Li4 fluctuates
around a stable value around 417 eV, and no structural recon-
struction for V2BS2Li4 was observed. However, the sharp decrease of
the free energy of V2BS2Na/K2 was observed (Fig. S7a and b (ESI†)),
indicating the instability of the V2BS2 with the adsorbed Na/K layer.
From the final configuration of V2BS2Na/K2 we can see that several
Na/K atoms tend to move away from the V2BS2 surface (Fig. S7c
and d (ESI†)). This can be attributed to the larger lattice mismatch
between Na/K layer and V2BS2 leading to a compact arrangement of
Na/K atoms. As a consequence, to maintain a suitable interatomic
spacing, several adatoms will be forced off the surface. In short,
high concentration Li covered V2BS2 shows excellent thermal
stability even at a high temperature of 500 K, conveying that
V2BS2 are outstanding candidate electrode materials for LIBs.
3.4.4. Theoretical capacity and working potential of the
V2BS2 monolayer. High metal ion storage capacity is one of the
most important indicators for high performance electrode
materials for rechargeable metal ion batteries. Based on the
adsorption ability of metal ions, the maximum capacity (Cm) of
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metal ion batteries can be estimated as follows58:
xmax  i  F
Cm ¼ (5)
MV2 BS2
where xmax stands for the maximum concentration of adsorbed
metal ions, i is the valence number of adsorbed cations, F represents
the Faraday constant along with a value of 26 801 mA h mol1,
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operation via reducing the probability of dendrite formation.67
From a holistic perspective, V2BS2 with an intrinsic high density
of charge carriers, low diffusion barriers, outstanding specific
capacity, and moderate OCV makes it a competitive candidate
for LIBs among others high performance electrode materials,
such as 2D holey carbon nitride68 and bilayer covalent triazine
framework.69 In this regard, V2BS2 exhibits excellent electro-

MV2BS2 is the molar weight of V2BS2. The multilayer adsorption ability chemical properties as an anode material for LIBs, and is
is indispensable for achieving high capacity, while K can’t be awaiting experimental confirmation.
adsorbed up to at least one layer, thus we only calculated the Cm
for Li and Na. It should be noted that xmax = 2 and 4 for monolayer
and bilayer adsorption. Cm for LIBs is calculated as 606 mA h g1
due to the bilayer adsorption behaviour. Encouragingly, the 4. Conclusions
theoretical specific capacity of V2BS2 for LIBs is larger than that
In summary, the suitability of S-functionalized V2B as an anode
of many other 2D electrode materials, such as 288.52 mA h g1
material for metal (Li/Na/K) ion batteries was systematically
for V2NS2,42 335.495/348.926 mA h g1 for V2CO2/Ti2CO2,59
investigated through DFT calculations. Initially, the band struc-
311.86 mA h g1 for Ti2CS2,44 308.28 mA h g1 for
ture and DOS calculations show the metallic properties of
Ti2NS2,43 401 mA h g1 for Mo2CS2,23 503.1 mA h g1 for
V2BS2. The stability of V2BS2 was verified dynamically and
Ti2B,60 480 mA h g1 for TiB,61 268.53/462.61/329.22 mA h g1
thermally via phonon dispersion calculation and AIMD simula-
for Ti3C2O/S/Se2,23 501 mA h g1 for SiC,62 and 372 mA h g1 for
tion, respectively. Additionally, bilayer adsorption of Li atoms
graphite.63 In sharp contrast, Cm based on the maximum
on V2BS2 endows it with a good storage capacity and high
adsorption ability for SIBs is calculated to be 303 mA h g1,
theoretical specific capacity of 606 mA h g1. The low diffusion
which is much lower than the value for LIBs because of the
barrier of the Li atom (0.223 eV) shows an excellent rate
monolayer adsorption ability caused by larger lattice mismatch.
capacity for V2BS2 serving as an anode material for LIBs. Most
This result is not as competitive as other 2D anode materials, for
importantly, a lower value of OCV (0.37 V) for LIBs further
instance, Ti3C2S2 (463 mA h g1),64 TiB3 (667.52 mA h g1),7 TiB
guarantees the safety of battery operation.
(480 mA h g1).61 On the other hand, although a layer of Na can
Overall, the advantage of S as a functional atom for V2B-
be spontaneously adsorbed on the surface of V2BS2, AIMD for
based MBenes for use as promising electrodes for LIBs with
V2BS2Na2 results show that it is relatively unstable due to the
high theoretical specific capacity can be concluded due to two
large lattice mismatch. Therefore, V2BS2 is not a suitable electrode
reasons: (1) S has larger electron acceptance because of its
material for SIBs. On the whole, inspirational high capacity for
higher electronegativity and two electronic empty orbitals,
LIBs further confirms our assumption that V2B functionalized by
which will not only provide stronger adsorption ability for
S with moderate electronegativity and double empty outer shell
single Li atoms but also promote the adsorption affinity for
electronic orbitals as well as the perfectly matched lattice constant
the layer-by-layer adsorption of Li atoms. (2) Selecting V atoms
between the anode materials and the adatoms are effective
as the major components for MBenes and adjusting the lattice
strategies for metal ion batteries.
parameter of MBenes can achieve an extremely low lattice
The OCV is another important descriptor for evaluating the
mismatch (B1.5%) between the lattice constant of layered Li
potential suitability of novel anode materials. Given that V2BS2
atoms and the substrate. A well matched lattice parameter
is not suitable for SIBs due to the low theoretical specific
ensures a suitable distance for adatoms to balance attraction
capacity, we only consider the OCV value for LIBs. The
and repulsion potential between absorbed metal layers. This
charge–discharge process of V2BS2 can be described as folows:
work not only shows the application prospects of V2BS2 in
V2BS2 + xe + xLi+ 2 V2BS2Lix. The difference in the total
energy storage, but also provides theoretical guidance for the
energy before and after Li adsorption is generally used to
design of high-performance electrode materials.
determine the OCV of the batteries. Here, the change of
internal energy is approximately equal to the change of the
Gibbs free energy since PDV and entropy term (TDS) are
negligible.65 Thus, OCV is expressed by Author contributions
V E (EV2BS2 + nt  ELi  EV2BS2+ntLi)/ntxe (6)
Yuhang Wang: conceptualization, methodology, software,
where EV2BS2, ELi, and EV2BS2+ntLi are the total energy of V2BS2, investigation, formal analysis, writing – original draft. Ninggui
single Li atom from the bulk phase and the total energy of Ma: validation, formal analysis, writing – review & editing.
V2BS2 + nt Li. nt is the total number of adatoms (nt = 18 for Yaqin Zhang: validation, formal analysis, writing – review &
monolayer adsorption, 36 for bilayer adsorption), and x is the editing. Bochun Liang: validation, formal analysis, writing –
charge on Li ion in the electrolyte.66 The calculation result review & editing. Jun Zhao: validation, formal analysis, writing –
shows that the OCV value for Li adsorption on V2BS2 is 0.37 V. review & editing. Jun Fan: resources, supervision, writing –
Generally, lower OCV (o1 V) will ensure the safety of battery review & editing, funding acquisition.

4022 | Phys. Chem. Chem. Phys., 2023, 25, 4015–4024 This journal is © the Owner Societies 2023

PCCP
Conflicts of interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to have influenced the work reported in this paper.
Acknowledgements
Published on 27 December 2022. Downloaded by SHANDONG UNIVERSITY on 4/14/2023 4:03:24 AM.
This work was supported by the Research Grants Council of
Hong Kong (CityU 11306517, 11305919, and 11308620) and
NSFC/RGC Joint Research Scheme N CityU104/19. This research
made use of the computing resources of the X-GPU cluster
supported by the Hong Kong Research Grant Council Colla-
borative Research Fund: C6021-19EF.
Notes and references
1 I. Hussain, S. Sahoo, C. Lamiel, T. T. Nguyen, M. Ahmed,
C. Xi, S. Iqbal, A. Ali, N. Abbas and M. S. Javed, et al., Energy
Storage Mater., 2022, 13–43.
2 M. Hu, K. Zhou, T. Zhao, Z. Li, X. Zeng, D. Yu, X. Yu,
M. Zhao, Z. Shao and Q. Xu, et al., Green Energy Environ.,
2022, DOI: 10.1016/j.gee.2022.08.006.
3 Z. Liu, Y. Huang, Y. Huang, Q. Yang, X. Li, Z. Huang and
C. Zhi, Chem. Soc. Rev., 2020, 49, 180–232.
4 B. Scrosati, J. Hassoun and Y.-K. Sun, Energy Environ. Sci.,
2011, 4, 3287–3295.
5 J.-Y. Hwang, S.-T. Myung and Y.-K. Sun, Adv. Funct. Mater.,
2018, 28, 1802938.
6 M. Zhou, Y. Shen, J. Liu, L. Lv, X. Gao, Y. Zhang, X. Meng,
X. Yang, Y. Zheng and Z. Zhou, Vacuum, 2022, 200, 111054.
7 R. Li, Y. Wang, L.-C. Xu, J. Shen, W. Zhao, Z. Yang, R. Liu,
J.-L. Shao, C. Guo and X. Li, Phys. Chem. Chem. Phys., 2020,
22, 22236–22243.
8 M. Zhou, Y. Shen, J. Liu, L. Lv, X. Gao, X. Wang, X. Meng,
X. Yang, Y. Zheng and Z. Zhou, Solid State Ionics, 2022,
378, 115898.
9 F. Li and Q. Tang, ACS Appl. Nano Mater., 2019, 2,
7220–7229.
10 B. Zhang, J. Zhou, Z. Guo, Q. Peng and Z. Sun, Appl. Surf.
Sci., 2020, 500, 144248.
11 X. Liu, X. Ge, Y. Dong, K. Fu, F. Meng, R. Si, M. Zhang and
X. Xu, Mater. Chem. Phys., 2020, 253, 123334.
12 B. Zhang, J. Zhou and Z. Sun, J. Mater. Chem. A, 2022,
15865–15880.
13 Z. Guo, J. Zhou and Z. Sun, J. Mater. Chem. A, 2017, 5,
23530–23535.
14 J. Jia, B. Li, S. Duan, Z. Cui and H. Gao, Nanoscale, 2019, 11,
20307–20314.
15 X.-H. Zha, P. Xu, Q. Huang, S. Du and R.-Q. Zhang, Nano-
scale Adv., 2020, 2, 347–355.
16 N. Ma, T. Wang, N. Li, Y. Li and J. Fan, Appl. Surf. Sci., 2022,
571, 151275.
17 B. Liang, N. Ma, Y. Wang, T. Wang and J. Fan, Appl. Surf.
Sci., 2022, 153927.
This journal is © the Owner Societies 2023
View Article Online
Paper
18 J. Zhou, J. Palisaitis, J. Halim, M. Dahlqvist, Q. Tao,
I. Persson, L. Hultman, P. O. Persson and J. Rosen, Science,
2021, 373, 801–805.
19 X.-F. Yu, J.-B. Cheng, Z.-B. Liu, Q.-Z. Li, W.-Z. Li, X. Yang and
B. Xiao, RSC Adv., 2015, 5, 30438–30444.
20 E. S. Sim, G. S. Yi, M. Je, Y. Lee and Y.-C. Chung, J. Power
Sources, 2017, 342, 64–69.
21 W. Guo, Z. She, H. Xue and X. Zhang, Appl. Surf. Sci., 2020,
529, 147180.
22 Q. Meng, J. Ma, Y. Zhang, Z. Li, A. Hu, J.-J. Kai and J. Fan,
J. Mater. Chem. A, 2018, 6, 13652–13660.
23 V. Mehta, H. S. Saini, S. Srivastava, M. K. Kashyap and
K. Tankeshwar, J. Phys. Chem. C, 2019, 123, 25052–25060.
24 D. Li, X. Chen, P. Xiang, H. Du and B. Xiao, Appl. Surf. Sci.,
2020, 501, 144221.
25 Y. Wang, N. Ma, B. Liang and J. Fan, Appl. Surf. Sci., 2022,
153619.
26 Z. Chen, S. Huang, X. Yuan, X. Gan and N. Zhou, Appl. Surf.
Sci., 2021, 544, 148861.
27 M. Yang and Y. Mo, Angew. Chem., 2021, 133, 21664–21671.
28 C. Xu, K. Märker, J. Lee, A. Mahadevegowda, P. J. Reeves,
S. J. Day, M. F. Groh, S. P. Emge, C. Ducati and B. Layla
Mehdi, et al., Nat. Mater., 2021, 20, 84–92.
29 I. T. Røe and S. K. Schnell, J. Mater. Chem. A, 2021, 9,
11042–11048.
30 G. Kresse and J. Furthmüller, Phys. Rev. B: Condens. Matter
Mater. Phys., 1996, 54, 11169.
31 G. Kresse and J. Furthmüller, Comput. Mater. Sci., 1996, 6,
15–50.
32 G. Kresse and D. Joubert, Phys. Rev. B: Condens. Matter
Mater. Phys., 1999, 59, 1758.
33 J. P. Perdew, K. Burke and M. Ernzerhof, Phys. Rev. Lett.,
1996, 77, 3865.
34 P. E. Blöchl, Phys. Rev. B: Condens. Matter Mater. Phys., 1994,
50, 17953.
35 H. J. Monkhorst and J. D. Pack, Phys. Rev. B: Solid State,
1976, 13, 5188.
36 S. Grimme, J. Comput. Chem., 2006, 27, 1787–1799.
37 G. Kresse, J. Furthmüller and J. Hafner, EPL, 1995, 32, 729.
38 K. Parlinski, Z. Li and Y. Kawazoe, Phys. Rev. Lett., 1997,
78, 4063.
39 A. Togo and I. Tanaka, Scr. Mater., 2015, 108, 1–5.
40 G. J. Martyna, M. L. Klein and M. Tuckerman, J. Chem. Phys.,
1992, 97, 2635–2643.
41 G. Henkelman, B. P. Uberuaga and H. Jónsson, J. Chem.
Phys., 2000, 113, 9901–9904.
42 B. Yan, C. Lu, P. Zhang, J. Chen, W. He, W. Tian, W. Zhang
and Z. Sun, Mater. Today Commun., 2020, 22, 100713.
43 V. Shukla, N. K. Jena, S. R. Naqvi, W. Luo and R. Ahuja, Nano
Energy, 2019, 58, 877–885.
44 Y. Wang, M. Zhou, L.-C. Xu, W. Zhao, R. Li, Z. Yang, R. Liu
and X. Li, J. Power Sources, 2020, 451, 227791.
45 C. Yao, W. Li, K. Duan, C. Zhu, J. Li, Q. Ren and G. Bai,
Nanomaterials, 2021, 11, 2478.
46 Y. Jing, Z. Zhou, C. R. Cabrera and Z. Chen, J. Phys. Chem. C,
2013, 117, 25409–25413.
Phys. Chem. Chem. Phys., 2023, 25, 4015–4024 | 4023

Paper
47 X. Zhang, Z. Zhang, S. Yao, A. Chen, X. Zhao and Z. Zhou,
npj Comput. Mater., 2018, 4, 1–6.
48 H. Tornatzky, R. Gillen, H. Uchiyama and J. Maultzsch,
Phys. Rev. B, 2019, 99, 144309.
49 J. Zhao, N. Ma, T. Wang, N. Li, Y. Wang and J. Fan, J. Mater.
Chem. A, 2022, 10, 21611–21621.
50 Y. Wang, W. Tian, H. Zhang and Y. Wang, Phys. Chem.
Published on 27 December 2022. Downloaded by SHANDONG UNIVERSITY on 4/14/2023 4:03:24 AM.
Chem. Phys., 2021, 23, 12288–12295.
51 K. Fan, Y. Ying, X. Li, X. Luo and H. Huang, J. Phys. Chem. C,
2019, 123, 18207–18214.
52 M. Mortazavi, C. Wang, J. Deng, V. B. Shenoy and
N. V. Medhekar, J. Power Sources, 2014, 268, 279–286.
53 S. Wang, Y. Si, B. Yang, E. Ruckenstein and H. Chen, J. Phys.
Chem. Lett., 2019, 10, 3269–3275.
54 X. Zhang, Z. Yu, S.-S. Wang, S. Guan, H. Y. Yang, Y. Yao and
S. A. Yang, J. Mater. Chem. A, 2016, 4, 15224–15231.
55 A. D. Becke and K. E. Edgecombe, J. Chem. Phys., 1990, 92,
5397–5403.
56 M. M. Rahman, S. Mateti, Q. Cai, I. Sultana, Y. Fan, X. Wang,
C. Hou and Y. Chen, Energy Storage Mater., 2019, 19, 352–359.
57 F. Leng, C. M. Tan and M. Pecht, Sci. Rep., 2015, 5, 1–12.
58 A. Urban, D.-H. Seo and G. Ceder, npj Comput. Mater., 2016, 2, 1–13.
4024 | Phys. Chem. Chem. Phys., 2023, 25, 4015–4024
View Article Online
PCCP
59 Y. Aierken, C. Sevik, O. Gülseren, F. M. Peeters and D. Çakr,
J. Mater. Chem. A, 2018, 6, 2337–2345.
60 S.-F. Wang, B.-T. Wang, T. Bo, J.-R. Zhang and F.-W. Wang,
Appl. Surf. Sci., 2021, 538, 148048.
61 J. Wang, T.-N. Ye, Y. Gong, J. Wu, N. Miao, T. Tada and
H. Hosono, Nat. Commun., 2019, 10, 1–8.
62 M. Manju, S. Thomas, S. U. Lee and A. K. Madam, Appl. Surf.
Sci., 2021, 541, 148417.
63 J. R. Dahn, T. Zheng, Y. Liu and J. Xue, Science, 1995, 270,
590–593.
64 Q. Meng, J. Ma, Y. Zhang, Z. Li, C. Zhi, A. Hu and J. Fan,
Nanoscale, 2018, 10, 3385–3392.
65 M. Aydinol, A. Kohan, G. Ceder, K. Cho and J. Joannopoulos,
Phys. Rev. B: Solid State, 1997, 56, 1354.
66 M. Aydinol, A. Kohan and G. Ceder, J. Power Sources, 1997,
68, 664–668.
67 T. Yu, Z. Zhao, L. Liu, S. Zhang, H. Xu and G. Yang, J. Am.
Chem. Soc., 2018, 140, 5962–5968.
68 A. Ghosh, S. Mandal and P. Sarkar, ChemPhysChem, 2022,
23, e202200182.
69 B. Ball, C. Chakravarty and P. Sarkar, J. Phys. Chem. C, 2019,
123, 30155–30164.
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