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2D V2B As A Promising Anode
2D V2B As A Promising Anode
2D V2B As A Promising Anode
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
Received 23rd November 2022, operation would be ensured for V2BS2 as electrode materials because of the low open circuit voltage
Accepted 22nd December 2022 with 0.37 V. The high charge/discharge rate for LIBs is also achievable owing to the high mobility of
DOI: 10.1039/d2cp05477a 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
rsc.li/pccp materials for rechargeable metal ion batteries.
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surface of MBenes/MXenes is inevitable during the process of More importantly, the low open circuit voltage (OCV) and diffu-
chemical synthesis.18 The essential role of terminal atoms on sion barrier for LIBs enable battery safety and fast kinetics for
MXenes/MBenes in the electronic and electrochemical properties charge/discharge process of V2BS2 as an anode material for LIBs.
has been well studied. Taking functionalized Ti2C as an example, It provides guidance for the experimental synthesis of function-
Ti2CO2 shows semiconductor properties (band gap: 0.3 eV), alized V2B. Our work found that choosing functionalized
whereas Ti2CF2 is a conductor.19,20 It is reported that some MBenes with terminals with moderate electronegativity and
functional atoms may affect the adsorption of metal ions, e.g., F larger electronic capacity and lowering the lattice mismatch
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functionalized Ti3CN could weaken the adsorption ability towards between adsorbed metal layers and substrate are two major
Na.21 In contrast, when Zr2C and Zr3C2 were terminated by suggestions for designing high performance electrode materials
O atoms, the adsorption energy of a single Na atom varied from for rechargeable ion batteries.
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 2. Computational details
materials. Sulfur (S), with an electronic configuration of 3s2 3p4
All the calculations based on density functional theory (DFT)
that contains two empty electronic orbitals and moderate electro-
were performed by using Vienna ab initio simulation package
negativity (2.54), is considered as a potential surface termination
(VASP).30,31 To consider the ion–electron interactions, the pro-
tuning the adsorption ability of metal ions, thus achieving high
jector augmented wave (PAW) method32 was employed. The
theoretical specific capacity.23,24 In particular, S functionalized
generalized gradient approximation (GGA) of Perdew–Burke–
Ti2B has exhibited good structural stability and shown excellent
Ernzerhof (PBE) functional33,34 was used to describe the
electrochemical performance for SIBs.25 Moreover, S-function-
exchange and correlation interaction. Spin-polarized calcula-
alized Cr2C and Mo2C were revealed with competitive electro-
tions were performed by tuning ISPIN = 2 in this work. The
chemical properties using as anode materials for LIBs.26 Another
geometry optimization and electronic properties for unit cells
fundamental principle in the design of novel electrode materials
were carried out based on a G-centered 12 12 1 and 25
is to lower the lattice mismatch between adsorbed metal ion
25 1 Monkhorst–Pack k-mesh,35 respectively. Additionally, a
layers and negative electrode materials. Three major advantages
G-centered 4 4 1 Monkhorst–Pack k-mesh was taken into
of smaller lattice misfit between adsorbed metal ions layer and
account for structural optimization with a supercell of 3 3 1
electrode materials can be concluded from the previous studies.
and a vacuum layer of 30 Å in the z direction. The cut-off energy
Firstly, a smaller interfacial disordered cation layer can avoid pore
of plane wave expansion was set to 520 eV. The van der Waals
formation and increase the morphology stability during metal ion
interaction was adopted according to the DFT-D3 dispersion
cycling.27 Secondly, a smaller misfit will contribute to less lattice
correction strategy to take the effect of nonbonding forces into
expansion or contraction28 and reduce the local strain, prevent the
account.36 The convergence criteria for energy and force were
formation of vacancies and maintain good mobility of cations.29
set to 105 eV and 0.02 eV Å1, respectively. Phonon dispersion
Most importantly, a smaller mismatch ensures the suitable dis-
calculations with cell size of 1 1 1 were performed based on
tance between the adatoms and is beneficial for the balance of the
the finite displacement method37,38 embedded in the PHO-
attraction and repulsion of adsorbed atoms, thereby favoring the
NOPY package.39 Ab initio molecular dynamics (AIMD) simula-
multilayer adsorption ability and increasing the energy density of
tions was carried out at 300/500 K for 10 ps with a time step of
the anode materials.22 Thus, lowering the lattice mismatch is an
2 fs using the NVT ensemble.40 The diffusion properties of
important strategy for ensuring battery safety and increasing
cations were identified using the climbing image nudged
capacity for developing high performance electrode materials.
elastic band (CI-NEB) method.41
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 3. Results and discussion
layer in rechargeable batteries deserves further study.
As reported by Ma et al., V2B has a lattice constant of 2.958 Å, 3.1. Structural properties of V2BS2
which shows a similar lattice constant to layered Li (2.95 Å),17 The initial V2B monolayer (space group: P3% m1) is composed of a
while a low theoretical capacity of 476 mA h g1 for V2B as anode sandwich like V–B–V layered structure with B atoms embedded
for LIBs.16 Motivated by the importance of surface functional in the middle of V layers. The side view and the top view of the
groups and lattice mismatch, we systematically investigated the V2B monolayer are displayed in Fig. S1a and b (ESI†). To
suitability of S-functionalized V2B as a potential anode material determine the most energetic favorable site for functional
for LIBs/SIBs/KIBs, especially for LIBs, using density functional atoms on the surface of V2B, the energy minimization principle
theory. This study firstly proved that V2BS2 exhibits excellent was used. Based on the symmetry properties of V2B surface
conductivity via the band structure and density of states calcula- (presented in Fig. S1c–e, ESI†), three possible sites were
tions. Secondly, the S-functionalized V2B shows good dynamic considered, that is I (B top), II (V1 top), and III (V2 top). The
and thermal stability. Thirdly, the adsorption for the second optimized configuration of S-functionalized V2B with the lowest
layer of Li atoms on V2BS2 is energetically favorable, energy is shown in Fig. 1a, where S atoms prefer to locate at
thus ensuring the high specific capacity (up to 606 mA h g1). 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 carriers during charge transfer is ensured. Therefore, V2BS2 is
Ti2CS2,44 and Ti2NS2.45 Additionally, the lattice constant, bond determined as having metallic properties and superior to
length, and layer thickness of V2BS2 are summarized and com- the other electrode materials, such as Na2Ti3O7 (band gap:
pared with other similar MXene/MBene-based materials in Table 2.99 eV).47 The finding is in line with the band structure
S1 (ESI†). To be specific, the optimized lattice constant (3.05 Å), analysis that V2BS2 is an excellent conductor. Moreover, the
bond length (V–B: 2.13 Å, V–S: 2.34 Å) and layer thickness (5.47 Å) partial DOS is also calculated to understand the orbital con-
for V2BS2 is almost the same as that of V2CS2 (lattice constant: tribution of various atoms, which indicates that the electrons
3.06 Å; V–C: 2.08 Å, V–S: 2.37 Å; thickness: 5.43 Å)42 and V2NS2 from the d orbital of V are critical for the conductivity of the
(lattice constant: 3.09 Å; V–N: 2.06 Å, V–S: 2.35 Å)43 due to their V2BS2 monolayer (Fig. S2, ESI†). To avoid the underestimation
similar structural features. More importantly, the lattice constant of the band gap caused by PBE functionals, band structure
of V2BS2 is shorter than those obtained in the previous study of calculation using HSE06 functional was carried out. As shown
Ti-based S-functionalized MXenes/MBenes, such as Ti2NS2 in Fig. S3 (ESI†), V2BS2 exhibits good conductivity due to the
(3.17 Å), Ti2CS2 (3.17 Å), and Ti2BS2 (3.50 Å), indicating the presence of energy bands crossing the Fermi energy level. To be
suitability of the anode materials for LIBs from the perspective noted, because of the similar results obtained from different
of lattice matching. 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
3.2. Electronic properties of V2BS2
material with excellent battery conductivity.
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 3.3. Stability of V2BS2
materials. Therefore, the band structure and density of states The dynamic and thermal stability are major prerequisites for
(DOS) calculations were performed to evaluate the conductivity V2BS2 serving as electrode materials for metal ion batteries.
of V2BS2. On the one hand, as shown in Fig. 1b, there exist Firstly, we investigated its dynamic stability via phonon disper-
energy bands crossing the Fermi level of the S-functionalized sion calculation. As presented in Fig. 1d, no imaginary frequen-
V2B, manifesting the good metallicity of V2BS2. On the other cies are observed in the whole Brillouin zone, conveying that
hand, the energy band for spin up and spin down overlap S-terminated V2B is dynamically stable. Alongside this, the
completely, suggesting the non-magnetic properties of V2BS2. existence of quadratic dispersion of the out-of-plane acoustic
DOS results show that there are a large number of states in the mode inside the Brillouin zone further proves the characteristics
vicinity of the Fermi energy level (Fig. 1c), thereby implying a of two-dimensional materials of V2BS2.48 Next, the thermal
high carrier density. Besides, the metallic properties are mainly stability of V2BS2 is evaluated through AIMD simulation at
contributed by V atoms. Similar to the other anode materials, 500 K and the result is displayed in Fig. 1e. The free energy of
like the VS2 monolayer,46 and accordingly, the supplement 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 between adatoms and surface functional atoms and high coor-
maintains a stable structural characteristic. The snapshot inset dination binding environment when metal ions are adsorbed on
in Fig. 1e is the corresponding side view and top view of V2BS2 at the b site. The results of the optimal binding sites are consistent
the end of the simulation. Though some small shifts of the with previous reports of metal ions adsorbed on the Ti2BS2
atomic position are detected at this temperature, there is no monolayer.25 What should be noted is that, compared with bare
bond reconstruction and phase transformation for V2BS2, con- V2B MBenes with Ead for Li/Na are B0.73/0.45 eV,16 the highest
firming that V2BS2 possesses excellent thermal stability. In Ead for Li/Na on S-functionalized V2B are greatly promoted,
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summary, the structure of V2BS2 is stable dynamically and indicating the success of choosing S as functional atoms.
thermally. This finding indicates that it has the potential to Understanding reasons of the Ead difference for different
work at relatively high temperatures, which greatly encouraged adatoms will help us get a deep insight into the adsorption
our follow-up research. process for V2BS2 as an electrode material. Thus, we compared
Ead for M at the most stable site. As found, though alkali metals
3.4. Potential suitability for V2BS2 as anode materials have similar chemical and physical properties, the Ead varies
irregularly. Compared with different adatoms, the adsorption
3.4.1. Adsorption properties of a single Li/Na/K atom on
energy follows the order of K (2.120 eV) 4 Li (1.683 eV) 4
V2BS2. The adsorption ability of anode materials with regard to
Na (1.613 eV). With the decrease of the atomic electronega-
metal ions is a crucial parameter for evaluating the performance of
tivity (Li: 0.98; Na: 0.93; K: 0.82) and atomic number, the charge
electrode materials. Thereby, the adsorption energy for a single
transferred increased from 0.594 to 0.776 |e|, the bond length
metal ion was explored. According to the symmetry of the surface
changed from 2.321 to 3.013 Å. However, to fully comprehend
active site, three possible sites are considered and displayed in
the variance of Ead for M, we need to analyze their relative
Fig. 1a (side view), that is a (on the top of the B atom), b (on the top
changes. The adsorption energy is majorly contributed by
of the V1 atom), g (on the top of the V2 atom). The pre-adsorption
electrostatic interaction, that is the charge transfer between
model is shown in Fig. S4 (ESI†). The adsorption energy for single
M and S and the bond length of M–S (dM–S). Specifically, an
atom (Ead) on V2BS2 was computed as given below:
elongated M–S bond will weaken the interaction, while
Ead = EV2BS2+M – EV2BS2 – EM (1) increased charge transfer will promote attraction. As shown
in Table 1, with Li adsorption as the reference state, the DdNa/d0
where EV2BS2+M, EV2BS2, and EM are the total energies of V2BS2 + is 16.1%, surpassing the charge transfer change rate (DeNa/
M, V2BS2, and single metal ion (M = Li, Na, and K and the same e0 : 13.4%), suggesting an overall negative contribution for
implication for M is used in the following sections. The energy adsorption of Na. Therefore, Ead for Na is slightly lower than
of the single metal ion is obtained from their bulk structure). Ead for Li. For the adsorption of K, DdK/d0 (29.8%) is less than
The more negative the Ead, the stronger the interaction between DeNa/e0 (30.6%), demonstrating a positive contribution to the
adatoms and V2BS2 monolayer. The adsorption energy are electrostatic interaction. Unlike the small value of EDNa–Li
summarised in Fig. 2. (0.05), EDK–Li is 0.16, which will result in a larger ED in M–S.
The adsorption energy for single Li/Na/K is negative at The larger ED generally leads to a stronger M–S interaction.
different sites, suggesting that the adsorption of metal ion on Consequently, Ead for K is stronger than Ead for Li by 0.437 eV.
the substrate is energetically favorable. Specifically, adsorption Next, to explore the adsorption processes of alkali metal on
at the b site is more preferred, as Ead for M follows the order of MBenes from a deeper perspective, charge density difference
b o a o g. This can be attributed to the suitable distance (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.
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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
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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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Similarly, for the adsorption of the second layer of Li, NEC is still after lithiation/sodiation maintains good metallicity because
observable around the outer two layers of Li atoms, thus the there are states across Fermi energy level. For that reason, we
repulsive interaction between the nearby Li atoms is well reduced. can conclude that V2BS2 has superb properties in the electro-
In contrast to Fig. 6b, though a certain amount of NEC is formed chemical cycle.
around the second layer of Na atoms, the electrons become more The thermal stability of V2BS2 after metal layer adsorption is
localized as the existence of areas with an ELF value above 0.5. essential for the safety of battery operation. Since high concen-
Considering the larger size of Na radius compared with that of the tration adsorption of Li atoms (up to two layers) is seen on the
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Li atom, there is an increased repulsive potential when a large surface of V2BS2, AIMD simulation at different temperatures
amount of Na atoms are adsorbed on the surface of V2BS2, the were conducted for V2BS2Li4. Additionally, AIMD for V2BS2Na/K2
NEC is not strong enough to weaken the repulsion between were also performed as comparison. The results are displayed in
positively charged Na atoms, thereby resulting a weaker inter- Fig. 7 and Fig. S7 (ESI†). First, we evaluated the thermal stability of
action between outer Na layers and V2BS2 monolayer. Further- V2BS2Li4 at 300 K. There is no sharp drop or rise for the free energy
more, the third layer adsorption of Li is provided as a comparison. of V2BS2Li4 during the simulation (Fig. 7a) and the structures are
The ELF map for V2BS2Li6 displays that a relatively larger area of well maintained as can be seen from the top and side view of
covalent bond character (ELF value between 0.5 and 1) and a V2BS2Li4 (Fig. 7b), demonstrating the stability of lithiated V2BS2.
smaller amount of metallic bond feature (ELF value around 0.5) is High temperature stability operation is also another serious pro-
formed around the third layer of Li, suggesting the decreased blem facing currently.56,57 Next, we elevated the temperature up to
amount of NFC. Therefore, the third layer of Li atoms’ interaction 500 K. As displayed in Fig. 7a, the free energy of V2BS2Li4 fluctuates
with the substrates is less stable, which is consistent with the around a stable value around 417 eV, and no structural recon-
adsorption energy result (E3rd ad for Li is 0.030 eV). In total, ELF struction for V2BS2Li4 was observed. However, the sharp decrease of
analysis supports the significance of NEC in promoting the the free energy of V2BS2Na/K2 was observed (Fig. S7a and b (ESI†)),
stability of multilayer alkali metal adsorption. indicating the instability of the V2BS2 with the adsorbed Na/K layer.
To gain a deeper insight into the physical mechanism of the From the final configuration of V2BS2Na/K2 we can see that several
metal layer and substrate interaction, Bader charge analysis Na/K atoms tend to move away from the V2BS2 surface (Fig. S7c
was carried out to quantify the charge transfer during the and d (ESI†)). This can be attributed to the larger lattice mismatch
monolayer adsorption of different metal atoms. The average between Na/K layer and V2BS2 leading to a compact arrangement of
charge transferred from adatoms to V2BS2 monolayer is mea- Na/K atoms. As a consequence, to maintain a suitable interatomic
sured to be 0.256, 0.233, and 0.301 |e| for Li, Na, and K, spacing, several adatoms will be forced off the surface. In short,
respectively, confirming the presence of coulombic interaction high concentration Li covered V2BS2 shows excellent thermal
between the adsorbed metal layer and the substrate. Our stability even at a high temperature of 500 K, conveying that
finding proves that S-atoms with moderate electronegativity V2BS2 are outstanding candidate electrode materials for LIBs.
and dual empty electron orbitals are potential functional 3.4.4. Theoretical capacity and working potential of the
groups for V2B as electrode materials. Additionally, the electronic V2BS2 monolayer. High metal ion storage capacity is one of the
properties of V2BS2 covered by one layer of Li/Na were analyzed most important indicators for high performance electrode
to estimate its suitability as anode materials by calculating the materials for rechargeable metal ion batteries. Based on the
DOS of V2BS2Li2 and V2BS2Na2. As shown in Fig. S6 (ESI†), V2BS2 adsorption ability of metal ions, the maximum capacity (Cm) of
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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metal ion batteries can be estimated as follows58: operation via reducing the probability of dendrite formation.67
xmax i F From a holistic perspective, V2BS2 with an intrinsic high density
Cm ¼ (5) of charge carriers, low diffusion barriers, outstanding specific
MV2 BS2
capacity, and moderate OCV makes it a competitive candidate
where xmax stands for the maximum concentration of adsorbed for LIBs among others high performance electrode materials,
metal ions, i is the valence number of adsorbed cations, F represents such as 2D holey carbon nitride68 and bilayer covalent triazine
the Faraday constant along with a value of 26 801 mA h mol1, framework.69 In this regard, V2BS2 exhibits excellent electro-
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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.
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47 X. Zhang, Z. Zhang, S. Yao, A. Chen, X. Zhao and Z. Zhou, 59 Y. Aierken, C. Sevik, O. Gülseren, F. M. Peeters and D. Çakr,
npj Comput. Mater., 2018, 4, 1–6. J. Mater. Chem. A, 2018, 6, 2337–2345.
48 H. Tornatzky, R. Gillen, H. Uchiyama and J. Maultzsch, 60 S.-F. Wang, B.-T. Wang, T. Bo, J.-R. Zhang and F.-W. Wang,
Phys. Rev. B, 2019, 99, 144309. Appl. Surf. Sci., 2021, 538, 148048.
49 J. Zhao, N. Ma, T. Wang, N. Li, Y. Wang and J. Fan, J. Mater. 61 J. Wang, T.-N. Ye, Y. Gong, J. Wu, N. Miao, T. Tada and
Chem. A, 2022, 10, 21611–21621. H. Hosono, Nat. Commun., 2019, 10, 1–8.
50 Y. Wang, W. Tian, H. Zhang and Y. Wang, Phys. Chem. 62 M. Manju, S. Thomas, S. U. Lee and A. K. Madam, Appl. Surf.
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