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 Journal of Physics: Condensed Matter

J. Phys.: Condens. Matter 33 (2021) 175001 (9pp) https://doi.org/10.1088/1361-648X/abe267

A V3C2 MXene/graphene heterostructure as

a sustainable electrode material for metal
ion batteries
Partha Pratim Dinda1 and Shweta Meena2,∗
1
School of VLSI and Embedded Systems, National Institute of Technology Kurukshetra, Kurukshetra
136119, Haryana, India
2
Department of Electronics and Communication Engineering, National Institute of Technology
Kurukshetra, Kurukshetra 136119, Haryana, India

E-mail: mail2shwetameena@nitkkr.ac.in

Received 4 September 2020, revised 17 January 2021

Accepted for publication 2 February 2021
Published 21 April 2021

Abstract
Individually, MXene and graphene based frameworks have been recognized as promising 2D
electrode materials for metal ion batteries. Herein, we have engineered a heterostructure of
V3 C2 MXene and graphene using computational design. A comprehensive investigation of
designed heterostructure has been reported in this work. Simulated heterostructure has been
evaluated for various functionalities such as high performance of thermal stability, metal ion
intercalation, diffusion energy using density functional theory method. Interestingly,
simulation examinations and obtained calculations demonstrate the high storage capacity of Li
and Ca (598.63 mAh g−1), and Na (555.87 mAh g−1 ) with the designed V3 C2 /graphene
model. Promising diffusion energy barriers for Li (0.11 eV), Na (0.17 eV) and Ca (0.15 eV)
ions are also investigated and have explained systematically in the present work. Moreover, we
have achieved high capacity and fast charge/discharge rates of V3 C2 /graphene heterostructure
indicating its promising electrode potential efficiency for ion batteries especially for Na ion
battery. Thus, our investigation demonstrate the advantages of newly designed V3 C2 MXene
and graphene heterostructure for advance metal ion batteries.
Keywords: density functional theory, Mxene, metal-ion batteries, heterostructure
(Some figures may appear in colour only in the online journal)

1. Introduction of electric vehicles based on LIBs as a result of high cost [8].

Recently, MXenes and graphene both have been recognized
as newest class of two-dimensional (2D) materials for energy
storage, sensors and electronic devices [1, 2]. Among them,
metal ion batteries have gained promising attention and huge
interest owing to their applications varying from portable elec-
tronic device to power grid systems [1–3]. So far, high capacity
ion batteries particularly lithium ion battery (lithium ion bat-
tery) have received great attention in the area of electric vehi-
cles and electronic systems due to their outstanding lifecycle,
large power density and high storage capacity [4–7]. However,
scarcity of lithium resources limits the large-scale utilization
∗ NIBs and CIBs are currently insufficient for next generation
Author to whom any correspondence should be addressed.
Therefore, a lot of attempts are being made to develop novel
energy materials for improving LIBs efficiency. More likely,
sodium ion battery (NIBs) is anticipated to be an effective
replacement to LIBs in near future due to cost effective and
easily available as compared to lithium [9]. Additionally, other
abundantly available alkali atoms like calcium, potassium, zinc
and magnesium can be also potential choices [9, 10]. Sodium
ion batteries (NIBs) and calcium ion batteries (CIBs) exhibit
promising results in terms of high energy storage capacity for
portable electronic devices [11–13].
In spite of comprehensive investigation, it is surprisingly
noticed that the storage capacity and charging rate of LIBs,

1361-648X/21/175001+9$33.00 1 © 2021 IOP Publishing Ltd Printed in the UK

J. Phys.: Condens. Matter 33 (2021) 175001
Figure 1. Schematic showing the (a) rational design of V3 C2 MXene/graphene heterostructure as anode with metal ion intercalation and (b)
next generation design of proposed metal ion battery using MXene/graphene heterostructure as anode material.
Figure 2. Simulated V3 C2 MXene/graphene heterostructure; (a) top view and (b) side view.
of ion batteries [11, 14]. To overcome these major concerns,
2D materials have been proposed as encouraging materials for
anode because of their improved volumetric and gravimetric
capacity resulting in large charging rate and surface area [8].
For instance, Mo2 C has been studied with enhanced electro-
chemical property in LIBs [6]. Further, the electrochemical
performance of FeS2 as anode for alkali-ion (lithium ion bat-
teries, sodium ion batteries and potassium ion batteries) have
been reported [15]. On the other hand, various 2D materials
such as black phosphorus, transition metal dichalcogenides,
vertically aligned nanosheet (VANS), MXenes nanostructures
etc have also been extensively studied for energy storage appli-
cations [16–28]. However, single/mono layered sheets of these
2D materials are limited with poor rate performance and rapid
capacity fading. The experimental investigations demonstrate
the easy restack of these layers during the cycling process
[19, 21, 28]. In addition, these observations must be corrob-
orated with simulation studies for better understanding and
advancements of metal ion batteries. So far, monolayers of
V3 C2 MXene has been reported for ion battery application [9].
Importantly, experimental and theoretical studies reveal
that the device performance of above discussed 2D sheets
fades gradually with passage of time and results in the restack-
ing of 2D sheets during the time of cycling process causing
shortening of the life span. To the best of our knowledge,
2
P P Dinda and S Meena
the heterostructures of 2D material could be a viable alter-
nate to overcome the above-mentioned critical limitation. The
heterostructures of 2D sheets are more beneficial for rapid
electron transport and accelerated cation transport in elec-
trodes that increase in electric performance [29–31]. Also,
these heterostructures having variable interlayer distance can
intercalate multivalent ion (i.e., Ca2+ ) and larger ion (i.e.,
Na+ ), hence are an encouraging prospect for replacing Li
in the existing ion battery. Recently, MXene/graphene het-
erostructures have been proposed for electrochemical perfor-
mance [8, 32]. However, these structures are limited with
low storage capacity (236.69 mAh g−1 for Na ion with
V2 CO2 /graphene heterostructure and 416.39 mAh g−1 for Ca
ion with Ti2 CO2 /graphene heterostructure) of metal ion (Na,
Li and Ca) and poor diffusion energy barriers (0.34 eV for Na
ion with V2 CO2 /graphene and Ti2 CO2 /graphene heterostruc-
ture) [8].
Herein, we have designed a novel heterostructure based on
V3 C2 MXene and graphene and surprisingly obtained high
storage capacity of Li and Ca (598.63 mAh g−1 ), and Na
(555.87 mAh g−1 ) ions compared to previously reported het-
erostructure based systems. Additionally, we have observed
promising diffusion energy barriers for Li (0.11 eV), Na
(0.17 eV) and Ca (0.15 eV) ions that are systematically
explained in the present work (figure 1 shows the proposed het-
J. Phys.: Condens. Matter 33 (2021) 175001 P P Dinda and S Meena

Figure 3. Simulated V3 C2 /graphene heterostructure with single alkali atom; (a) side view and (b) top view, and V3 C2 /graphene
heterostructure with 100% concentration; (c) top view and (d) side view.

erostructure of V3 C2 MXene and graphene and its energy stor-

age capability). Moreover, this work demonstrates interfacing
exceptional property of MXene (V3 C2 ) with superior electri-
cal conductivity of graphene for its (V3 C2 /graphene) possible
utilization in ion battery application. Overall, the high stor-
age capacity of our designed V3 C2 MXene and graphene het-
erostructure make it a potential anode material for metal-ion
batteries, especially for Li and Na ion batteries.

2. Computational details

Density functional theory (DFT) calculation for

V3 C2 /graphene heterostructure were performed by
using atomistic tool kit. To optimize the heterostructure
(MXene/graphene), generalized gradient approximation with
Perdew–Burke–Ernzerhofer was used [33, 34]. The opti-
mization method was LBFGS and the optimization procedure
ended when the inter-atomic forces were below 0.01 eV Å−1 .
The van der Waals correction used was Grimme (DFT-D2)
[35], to describe the interaction between heterostructure
and atoms. The mesh cut-off of 2000 eV was applied. The
Brillouin zone was sampled using a Monkhorst–Pack k-point
mesh scheme, and the meshes of gamma-centered 3 × 3 × 1
k-points were used for geometry optimization and 5 × 5 × 1
were used for the electronic structure optimization of the
heterostructure. The vacuum distance of 25 Å was used
to avoid interlayer interaction. A 0.01 eV Å−1 force con-
vergence was used to achieve ground state energy. The
climbing image nudged elastic band (CI-NEB) [36] method
was applied to calculate minimum diffusion energy barrier
and diffusion path of metal ions on the V3 C2 /graphene
heterostructure.
Figure 4. Adsorption energies for Li, Na and Ca on V3 C2 /graphene
heterostructure system.
3. Results and discussion
Rational design and stability of V 3 C2 MXene/gra phene
heterostructure. To build MXene/graphene heterostructure,
we have optimized supercells with minimum lattice mis-
match between the layers that avoid interlayer interac-
tion. Further, 3 × 3 heterostructure of V3 C2 MXene and
graphene has been optimized and demonstrated in the present
work. The V3 C2 /graphene heterostructure [figure 2(a)] is
built up by interfacing V3 C2 and graphene monolayers.
Lattice parameters of V3 C2 /graphene heterostructure are
a = b = 2.95 Å and 25 Å of vacuum distance was assumed to
circumvent factitious periodic interaction. In V3 C2 , the bond
length between V1–C is 2.06 Å, V2–C is 1.90 Å and C–C

3
J. Phys.: Condens. Matter 33 (2021) 175001
in graphene is 1.42 Å in V3 C2 /graphene heterostructure. Lat-
tice mismatch of V3 C2 /graphene heterostructure is 2.39%. The
interlayer distance between V3 C2 and graphene in the het-
erostructure is 3.17481 Å [see figure 2(b)]. The binding energy
of heterostructure is calculated as Eb = [Eh − Em − Eg ] [37],
where Em , Eg and Eh are the total energies calculated for
MXene, graphene and heterostructure, respectively. The cal-
culated binding energy of the considered heterostructure is
−1.1992 eV. Negative binding energy signifies stable het-
erostructure. This result signifies that the interfacial interac-
tion between the individual monolayers is weak, which is also
reported for MoS2 /graphene and MnO2 /graphene heterostruc-
tures [38, 39]. This confirms that graphene is effective in
separating MXene layer and circumvent restacking effect.
Single alkali metal atom intercalation and binding energy
of V 3 C2 /gra phene heterostructure. Li intercalation has been
demonstrated with the optimized geometry of V3 C2 /graphene
heterostructure. Additionally, intercalation of larger ion (i.e.,
Na+ ) and multivalent ion (i.e., Ca2+ ) have also been investi-
gated with the V3 C2 /graphene heterostructure that is essential
to design advance battery. Strong binding of Li atoms with
heterostructures has been documented in the previous reports
[40–42]. Here in the present work we have investigated the
intercalation of single alkali atoms (Li, Na and Ca) between
V3 C2 and graphene as shown in figures 3(a) and (b). It has
been well documented in the literature that the intercalated
Li atoms are more favourable and closer to the MXene layer
in the heterostructure of MXene/graphene [27]. Intercalated
alkali atoms (Li, Na, and Ca) reside between three V atoms.
Therefore, every molecular unit of V3 C2 in heterostructure can
accommodate one alkali atom (Li, Na and Ca). In addition,
alkali atoms reside in the same position in the other unit cells
that are presented in figures 3(c) and (d).
Strong binding between alkali atoms (Li, Na and Ca) and
the MXene/graphene heterostructure is important so as to
circumvent the creation of metallic sodium, lithium or cal-
cium, which enhances the reversibility and safety of ion bat-
tery. Hence, it is necessary to ensure large binding energy of
alkali atoms. The binding energy, Eb (Li, Na and Ca) for Li, Na
and Ca intercalated in the heterostructure is defined by the
equation (1):
1
Eb = [E − E(V3 C2 /Gr ) − xEM ]. (1)
x (V3 C2 /Gr +xM)
Here, M = Li, Na and Ca, E(V3 C2 /Gr +xM) and E(V3 C2 /Gr ) are
the total energies with alkali atoms and without alkali atoms,
respectively of the heterostructure. EM is the total energy of
an alkali atom in its most stable bulk structure and x is the
number of alkali atom. Here, we used BCC bulk structure
for Li, BCC bulk structure for Na and FCC bulk structure
for Ca. van der Walls interaction are also included in the Li,
Na and Ca bulk energy calculations. Alkali metal ions (Li,
Na and Ca) adsorption on V3 C2 /graphene heterostructure pro-
duces negative adsorption energy (Ead ) for a single adatom.
The adsorption energy (see figure 4) for all three alkali atoms
intercalation.
The results obtained so far can be summed up as: (1) No dis-
tortion in the structure was reported during single alkali atom
4
P P Dinda and S Meena
(Li, Na and Ca) intercalation on V3 C2 /graphene heterostruc-
ture system. Hence, this signifies stability of the system. (2)
The values of binding energy are found to be negative for the
considered heterostructure, which implies that intercalation of
Li, Na and Ca in the considered heterostructure system is sta-
ble. (3) The interlayer spacing between MXene and graphene
layer should not exceed 1.5 Å, as it may give rise to vol-
ume expansion issue [43] in case of rechargeable ion battery.
However, this work reports the increase in interlayer spacing
between V3 C2 and graphene to be for Li (∼0.8 Å), Na (∼1.3 Å)
and Ca (∼1.3 Å) for single atom intercalation. This value of
separation of interlayer distance give rise to approximately up
to 0%–12% expansion in volume along the z-axis as the con-
centration increases from single atom to full concentration,
which is close to 7% for conventional graphite anodes [44].
(4) The considered V3 C2 /graphene system displays strongest
binding for alkali atom (Na, Li and Ca). The binding energy
(Eb ) calculated for single atom of Ca, Na and Li are found to be
−1.21 eV, −1.24 eV and −1.81 eV, respectively. Lithium has
the strongest binding energy on V3 C2 /graphene heterostruc-
ture system as compared to Ca and Na atom in the same con-
sidered heterostructure system. Another important factor that
decides the value of the binding energy (Eb ) is the amount of
charge transfer from alkali atom to the heterostructure system.
For example, Li atom binds strongly to the V3 C2 /graphene het-
erostructure, whereas Na atom and Ca atom are not strongly
bonded to the heterostructure system as compared to the Li
atom in the same system, since there is a larger charge transfer
in case of Li atom in the heterostructure, which shows stronger
ionic interaction in V3 C2 /graphene based heterostructure sys-
tem. Hence, in case of Li atom intercalation, there is a high
tendency to get electrons from Li atom as compared to Na
atom and Ca atom intercalation [45]. Since, the source of bind-
ing between the heterostructure system and the metal ion (Li,
Na and Ca) is primarily ionic, the distance of alkali atom from
the two layers is one of the significant factors. (5) The ground
state energy is taken into consideration during the calculation
of binding energy (Eb ).
E f fect of alkali atom (Li, Na and Ca) concentration
in V 3 C2 /gra phene heterostructure. Here, we investigate the
effect of alkali atom (Li, Na and Ca) concentration on the
physical properties of V3 C2 /graphene heterostructure. Here,
the concentration of alkali atoms is denoted as the ratio of
the number of alkali atoms to the number of formula units
of V3 C2 /graphene heterostructure (here, 100% corresponds to
three alkali atoms (Li, Na and Ca) for each formula unit).
Figure 5 shows the variation of the binding energy (Eb ) as a
function of the concentration of alkali ions. As the number of
intercalated alkali ions increases, the average binding energy
(Eb ) decreases gradually. The lowering of binding energy (Eb )
is due to two main reasons: (1) due to weak electrostatic attrac-
tion between V3 C2 /graphene host and alkali cations (Li+ , Na+
and Ca2+ ). (2) Increasing metal atom repulsion (i.e. Li–Li,
Na–Na and Ca–Ca) at high concentrations of alkali atoms
and also due to the decreasing of interatomic spacing between
positively charged metal ions (Li+ , Na+ and Ca2+ ). At a par-
ticular concentration value, nearly 70%, the binding energy of
calcium atom (EbCa ) becomes positive for the V3 C2 /graphene
J. Phys.: Condens. Matter 33 (2021) 175001
Figure 5. Binding energy of V3 C2 /graphene heterostructure as a
function of alkali atom concentration.
Figure 6. The voltage profile of V3 C2 /graphene heterostructure
with different alkali atom concentration.
heterostructure system, and due to this the system turns into
energetically unstable for further Ca intercalation.
 The binding
energy of lithium atom (EbLi ) and sodium atom EbNa is always
negative for V3 C2 /graphene heterostructure system, signifying
that the V3 C2 /graphene heterostructure is stable for Li and Na
intercalation. Even for higher concentration of lithium (Li) and
sodium (Na), the heterostructure shows stability. Our results
establish that V3 C2 /graphene heterostructure can be used for
high capacity ion batteries.
Another key point is how the stability of V3 C2 /graphene
heterostructure is affected when alkali ion (Li+ , Na+ and
Ca2+ ) concentration is increased. We found that interlayer
spacing expands as the number of alkali atoms increases
in the heterostructure. The calculated interlayer spacing of
V3 C2 /graphene expansion for Li intercalation from zero to
full coverage is 0.56 Å along the z-axis. At the same time,
5
P P Dinda and S Meena
Figure 7. Maximum capacity of different alkali atoms in the
V3 C2 /graphene heterostructure.
Table 1. Result of different alkali atoms in V3 C2 /graphene
heterostructure system as investigated in the present work. d is the
interlayer distance between layers after optimization. E b is the
binding energy of intercalating different alkali atoms and h is the
adatom height from graphene layer. Only the largest binding energy
value is provided here for single alkali atom intercalation in
V3 C2 /graphene heterostructure system.
Single alkali atom
System d (Å) E b (eV) h (Å)
V3 C2 /Gr + Li 4.0 −1.81 1.43
V3 C2 /Gr + Na 4.47 −1.24 1.61
V3 C2 /Gr + Ca 4.5 −1.21 1.87
during Na intercalation and Ca intercalation, the interlayer
spacing expanded to 1.68 Å and 1.71 Å, respectively. However,
V3 C2 /graphene heterostructure is unstable against Ca interca-
lation at higher concentrations. Stability of the heterostructure
system is also one of the most significant part while exploring
new 2D materials. However, when two individual stable 2D
materials which are bonded by van der Waals interaction form
a heterostructure, it is expected that the stability of the entire
heterostructure system shall not be affected much.
Theoretical OCV and stora ge ca pacitycalculations. From
practical application point of view, the storage capacity of ion
battery is a significant factor for the electrode material per-
formance. To investigate the maximum storage capacity for
alkali metal atoms (Li, Na and Ca), we carried out the adsorp-
tion at the interlayer and at the top and bottom surface of
the V3 C2 /graphene heterostructure with an increase in num-
ber of adsorbed metal atoms. The open-circuit voltage (OCV)
value gives the idea about the performance of ion battery. The
charge/discharge process of V3 C2 /graphene heterostructure is
represented by the half-cell reaction [8] shown in equation (2):
 
(x 2 − x 1 ) M + + (x 2 − x 1 ) e− + V3 C2 /Gr + x 1 M
 
↔ V3 C2 /Gr + x 1 M , (2)
J. Phys.: Condens. Matter 33 (2021) 175001
Figure 8. Diffusion barrier of V3 C2 /graphene with (a) Li, (b) Na and (c) Ca intercalation.
where, x is the alkali atom concentration and x 1  x  x 2 .
The OCV values were calculated at different coverage of
V3 C2 /graphene heterostructure using the equation (3):
EV3 C2 /Gr +X1 M − EV3 C2 /Gr +x2 M + (x 2 − x 1 ) EM
V≈
(x 2 − x 1 ) e
where, EV3 C2 /Gr +x1 M and EV3 C2 /Gr +x2 M are the total energies of
the V3 C2 /graphene heterostructure with x1 and x2 alkali atom
(Li, Na and Ca) intercalated, respectively. EM is the total
energy of corresponding alkali atom (Li, Na and Ca). Our
calculations reveal that the calculated OCV for alkali atom
intercalation decreases gradually with increasing metal ion
concentration (see figure 6). As the alkali atom concentration
increases from x = 66.67%–100%, the OCV decreases from
0.69 V to 0.36 V for V3 C2 /graphene heterostructure with Na
atom intercalation. For Li atom and Ca atom intercalation in
the same heterostructure, the OCV value decreases to a nega-
tive value. The binding energy (Eb ) change with the alkali ion
concentration correlate with the calculated voltage value. As
V3 C2 /graphene + Li has the largest binding energy, the cal-
culated OCV value is also larger than Na and Ca OCV in the
same heterostructure system.
P P Dinda and S Meena
Also, the maximum storage capacity can be calculated by
the equation (4) [3, 46]:
C ≈ zx max F/MV3 C2 /Gr , (4)
, (3) where, z denotes the valence number, xmax denotes the
maximum adatom content, F represents the Faraday con-
stant (26.8 Ahmol−1) and MV3 C2 /Gr represents the relative
molecular mass of V3 C2 /graphene heterostructure. The
relative molecular mass of V3 C2 /graphene is 208.92 g mol−1.
The calculated maximum capacities for V3 C2 /graphene
is 598.63 mAh g−1 (xmax = 4.67) for Li and goes into
saturation with Li2 /V3 C2 /Li1.33 /C2.67 /Li1.33 configuration,
598.63 mAh g−1 (xmax = 2.33) for Ca with saturation config-
uration Ca/V3 C2 /Ca0.67 /C2.67 /Ca0.67 and 555.87 mAh g−1
(xmax = 4.33) for Na with saturation configuration
Na2 /V3 C2 /Na/C2.67 /Na1.33 . These results confirm that
V3 C2 /graphene heterostructure is a promising anode material
for metal-ion batteries with high capacity. Figure 7 shows
the theoretical gravimetric capacities. As compared to other
MXene/graphene heterostructures reported previously in
literature [8, 29, 37], our result possesses higher capacity
which signifies the advantage of the present system over the
previous ones. V3 C2 /graphene heterostructure with Li and
6
J. Phys.: Condens. Matter 33 (2021) 175001 P P Dinda and S Meena

Table 2. Comparison of different heterostructure and MXene bilayer systems.

System Interlayer distance (Å) Binding energy (eV) Capacity (mAh g−1 ) Diffusion barrier (eV) Reference
Ti2 CF2 /Gr + Li 3.07 −1.64 339 0.35 [37]
Ti2 CO2 /Gr + Li 3.11 −2.34 426 0.47 [37]
V2 CO2 /Gr + Li 2.779 −2.537 234.123 0.6 [29]
bi-V2 CO2 + Li 2.5 −3.573 175.365 0.6 [29]
bi-Ti2 CO2 + Li 2.480 −2.308 182.717 0.4 [29]
Sc2 C(OH)2 /Gr + Li 2.278 −0.941 227.876 0.56 [29]
bi-Sc2 C(OH)2 + Li 0.548 −0.309 187.577 0.5 [29]
V2 CO2 /Gr + Ca 3.19 −5.75 411.31 0.5 [8]
bi-V2 CO2 + Ca 2.79 −4.01 288.23 1.5 [8]
V2 CO2 /Gr + Na 3.12 −2.05 236.69 0.3 [8]
bi-V2 CO2 + Na 2.70 −2.78 158.70 1.3 [8]
Ti2 CO2 /Gr + Ca 3.37 −2.55 416.39 0.5 [8]
bi-Ti2 CO2 + Ca 3.07 −3.56 298.04 1.6 [8]
Ti2 CO2 /Gr + Na 3.27 −1.11 240.07 0.3 [8]
V3 C2 /Gr + Li 4.0 −1.81 598.63 0.11 Present work
V3 C2 /Gr + Na 4.47 −1.24 555.87 0.17 Present work
V3 C2 /Gr + Ca 4.5 −1.21 598.63 0.15 Present work

Table 3. Comparison of the capacity performance of anode from
MXene materials for experimental studies and the present work.
Material sample Experimental capacity Simulation capacity
V2 C + Li 254 mAh g−1 [48] 472 mAh g−1 [49]
Ti3 C2 + Li 264.5 mAh g−1 [50] 320 mAh g−1 [51]
Ti3 C2 F2 + Li 123.6 mAh g−1 [50] 130 mAh g−1 [51]
Ca intercalation have the largest gravimetric capacity due to
smaller atomic size of alkali atom table 1.
Metal ion di f fusion on V 3 C2 /gra phene heterostructure.
A diffusion barrier with low energy and high mobility are
important factor for efficient electrode material. Specifically,
the mobility of an alkali metal atom on an electrode material is
the main requirement to determine the performance rate dur-
ing charging and discharging of an ion battery. In our study,
we investigated single Li, single Na and single Ca kinetics
on V3 C2 /graphene heterostructure, by calculating the lowest
energy metal atom (Li, Na and Ca) diffusion path joining
two adjacent binding sites by using the CI-NEB method [see
figures 8(a)–(c)].
Compared to monolayer V3 C2 systems [9], Li, Na and
Ca atom displays comparatively higher diffusion barriers for
V3 C2 /graphene heterostructure system. This is because of the
existence of geometric constraint in heterostructure systems
so that the alkali atom must traverse between the two mono-
layer surfaces rather than moving on the top of single layer
surface as in monolayer systems. In one of the studies [8],
the authors have reported diffusion energy barrier of 0.34 eV
for Na, with MXene/graphene heterostructure. In yet another
study [29], diffusion energy barrier of 0.6 eV has been reported
for Li with MXene/graphene heterostructure. The diffusion
energy barrier calculated for mono-V3C2 + Li, V3 C2 + Na
and V3 C2 + Ca is reported to be 0.04 eV, 0.02 eV and 0.04 eV,
respectively [9], while it is found to be 0.11 eV, 0.17 eV and
0.15 eV for V3 C2 /graphene + Li, V3 C2 /graphene + Na and
V3 C2 /graphene + Ca heterostructure, respectively in this study
which are better compared to the above reported work on het-
erostructures (see table 2). As the bilayer structures have the
benefit of high capacity for a given volume as compared to
monolayer structures, it is believed that monolayer systems
denote lower limit for energy barrier. But, to achieve prac-
tical kinetic property, one should take into account the dif-
fusion of metal ions between two individual layers and not
only on individual layer surface. The huge difference in energy
barrier can be correlated with binding energy values, separa-
tion between interlayer and alkali atom (Li, Na and Ca) to
host distances. Diffusion energy barriers for V3 C2 /graphene
based system for different intercalation alkali atoms are less
as compared to graphite system (0.5 eV) [47] and high capac-
ity Si anode material which has energy barrier of 0.57 eV. This
suggests that V3 C2 /graphene heterostructure is an encourag-
ing and promising candidate for anode material in ion-battery
application.
Table 3 shows the comparison of the capacity performance
of anode from MXene materials for experimental studies and
the present work.
4. Conclusions
In summary, by making use of first-principles calculations,
the present study investigates Li, Na and Ca atom adsorption
properties of typical MXene/graphene heterostructure for pos-
sible use as electrodes in ion-battery. Since, the interfacial con-
tact is found to be weak, to circumvent restacking of MXene
layers graphene is incorporated which facilitates rapid trans-
port of ions for faster charging/discharging. The results show
that heterostructures give superior electric conductivity and
metal atom (Li, Na and Ca) adsorption strength. The result
suggest that V3 C2 /graphene based heterostructure is an
encouraging prospect as electrode material for MXene based
Na ion-battery owing to its high Na specific capacity. It has
been found from charge transfer computations that alkali

7
J. Phys.: Condens. Matter 33 (2021) 175001
atoms that are intercalated turn positively charged by donat-
ing an electron to V3 C2 /graphene host, which is important in
battery applications. There is decrease in charge transfer in
case of Li and Ca atoms with the increase in concentration,
however, for Na atom nearly 1 e is transferred for all concentra-
tions. The average voltage calculated for Ca ion concentration
becomes negative after 33.3% and 66.6% for Li ion concentra-
tion, however, it remains positive in case of Na till 100%. The
diffusion energy barriers obtained for Na and Li systems are
low, signifying higher charge/discharge rates for battery appli-
cations. Even though Li ions have the lowest energy barriers,
there is significant increase in interlayer distance, which might
give rise to the problem of volumetric expansion for battery
applications.
Data availability
Supporting data for the present study are available within this
article as the supplementary information file.
Supporting information
Comparative table of different Mxene based heterostructure
and MXene bilayer systems.
Notes
Authors declare no competing financial interest and no con-
flicts of interest for this work.
Acknowledgments
Authors would like to thank the National Institute of Technol-
ogy, Kurukshetra, and the Department of Electronics & Com-
munication Engineering for providing the computational tools
and other resources for carrying out this research work.
ORCID iDs
Partha Pratim Dinda https://orcid.org/0000-0001-9596-
8441
Shweta Meena https://orcid.org/0000-0002-7283-4560
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