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Twin-graphene as a Promising Anode Material for Na-Ion Rechargeable

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 www.acsanm.org Article

Twin-graphene as a Promising Anode Material for Na-Ion

Rechargeable Batteries
Harkishan Dua, Jyotirmoy Deb, Debolina Paul, and Utpal Sarkar*
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ABSTRACT: In this work, using density functional theory, a twin-graphene-based anode

material is investigated for the use in rechargeable ion batteries with sodium as the
intercalating ion. The pristine twin-graphene structure yielded two best adsorption sites of
its surface where the Na atoms are adsorbed in a layer-wise fashion. We report a theoretical
capacitance of 496.2 mAh/g for Na-adsorbed twin-graphene, which is significantly higher
Downloaded via Utpal Sarkar on April 27, 2021 at 14:41:37 (UTC).

than those of many other carbon allotropies. From NEB calculations, a low diffusion
barrier in twin-graphene suggests good diffusivity, and with a moderate value of open-
circuit voltage, twin-graphene is a good choice for applications as an anode material in Na-
ion rechargeable batteries.
KEYWORDS: density functional theory, twin-graphene, Na-ion battery, adsorption of Na, theoretical capacity, open-circuit voltage,
diffusion of Na

■ INTRODUCTION
With the advent of portable electronics and communication
cost. Owing to its high energy density and long life cycle,
sodium appears as a promising alternative to lithium in
systems, a portable source of energy has become a necessity. rechargeable cells. However, unlike lithium that can readily be
With many aspects of our lives depending on such devices, adsorbed by graphite, sodium faces this challenge that has
efforts to bring forth efficient energy storage systems, which at prevented its usage in commercially available batteries. This
the same time are preferred to be smaller in size, have been also suggests exploring newer materials for anode materials
sought extensively. Rechargeable ion batteries offer themselves that can serve as a host for Na ions.
Anodes based on two-dimensional (2D) materials have
as a clean source of energy, and Li-ion batteries owing to their
gained a great deal of attention as they offer a larger surface
high storage capacity, longer cycle life, and excellent reversible
area for intercalation of ions and faster ion diffusion rates.21,22
capacity1−4 have proven themselves as a formidable candidate
In the recent past, several 2D materials have been predicted
in this area. These batteries work by a cyclic de-extraction/
and synthesized consisting of single elements as well as multi-
intercalation process of lithium ions in the cathode/anode
element and doped structures, among which many find
(electrodes) during discharging/charging. In this regard, the
possible applications in the realm of anode materials. Single-
characteristics of the electrode materials play a fundamental
layer graphene-based anode materials have shown a high
role in the overall performance of such systems. 5−8
theoretical capacitance of 744 mA h/g for Li intercalation on
Commercially available Li-ion batteries use graphite as the
both surfaces, which is twice the value as seen for graphite.11,23
anode material owing to its robust stability, low cost, high
Carbon is a flexible element when it comes to form
conductivity, and excellent cycling ability.9,10 However,
allotropes. Several carbon-based 2D structures have been
graphite as an anode material has a low ion storage capacity
predicted theoretically,24−30 and some of them are already
(372 mA h/g) and a small interlayer spacing (0.335 nm) which
synthesized experimentally.31,32 Out of them, some of the
prevents the overall system from having a satisfactory charge
carbon allotropes such as graphyne,33−37 graphdiyne,38−40
density and fast chargability.11
pentagraphene,41 and T-graphene 42 have shown their
In the development of next-generation batteries, lithium has
potentiality as an anode material in batteries. Most recently,
been in the limelight for quite some time owing to its smaller
a new allotrope of carbon, known as twin-graphene, is
size, low density in solid, and high electrochemical potential.
However, the usage of lithium needs one to endure high costs
with certain drawbacks therein such as heating and safety Received: February 13, 2021
concerns in the usage of these batteries. However, the usage of Accepted: April 14, 2021
alternate elements such as Na,12−17 Mg,18 Al,19 and Ca20 as the
adsorbed ions has become a hot topic in the current research
for rechargeable ion batteries. Sodium, unlike lithium, is an
abundant element that is readily available and at a very low

© XXXX American Chemical Society https://doi.org/10.1021/acsanm.1c00460

A ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
Figure 1. Schematic diagram of the different adsorption sites on the twin-graphene supercell; (a) top view and (b) side view of the two most stable
sites.
predicted by Jiang et al., which is a planar direct-semi-
conducting 2D material.30 The structure of twin-graphene is
like bilayer graphene where the two layers are organically
conjoined by replacing one-third of the parallel aromatic bonds
with carbon dimers. This material is predicted to possess good
electronic properties in pristine as well as doped43,44 forms
with a tunable band gap on application of strain. This has
gained the attention of many toward its application in gas
sensors,45 cancer detection,46 etc., to name a few. To the best
of our knowledge, no work on twin-graphene as an anode
material for the battery has been done. In this paper, we have
explored the possibility of a twin-graphene-based anode
material, and studies have been done on it using sodium as
the intercalated ion. The study commences with finding the
most stable sodiation sites on the twin-graphene surface. These
sites are then used to explore the layer-wise intercalation of
ions and their adsorption energy profiles to predict the
theoretical capacitance. Climbing image NEB calculations
show the diffusion processes in the anode material.
■ COMPUTATIONAL METHODS
Here, the first-principles calculations are carried out within the
framework of density functional theory (DFT) as implemented in the
QuantumATK software.47 For optimizing the structures, the LCAO
method with generalized gradient approximation (GGA) and the
Perdew−Burke−Ernzerhof (PBE) exchange−correlation functional is
used with a PseudoDojo pseudopotential.48,49 Brillouin zone sampling
is done using a 10 × 10 × 1 Monkhorst-Pack k-point grid for
optimization, and the cutoff energy is set to 75 hartree. All the atoms
are relaxed until the residual forces on each atom are less than 0.001
eV/Å, while the residual stress on each atom is set to be less than
0.0001 eV/Å3. The periodic boundary condition is imposed by
keeping a vacuum space of 15 Å between consecutive layers along the
Z-direction to prevent any superficial interactions between these
layers. Adsorption energy is further calculated by incorporating the
Grimme van der Waals (vdW) correction (DFT-D2) scheme.50
Thermodynamic stability is confirmed using ab initio molecular
dynamics (AIMD) simulations performed for 5 ps with a time step of
1 fs at a temperature of 300 K controlled using a Nose−Hoover
thermostat. The nature of adsorption of Na on twin-graphene is
analyzed using Bader charge analysis. Diffusion behavior of Na atoms
on twin-graphene is studied using the climbing-image nudged elastic
band (CI-NEB)51,52 calculations, which are done using the image-
dependent pair potential method.
B https://doi.org/10.1021/acsanm.1c00460
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■ RESULTS AND DISCUSSION
First, the adsorption of a single Na atom on the twin-graphene
surface is studied to find the most stable site for Na adsorption.
For this, a 2 × 2 × 1 supercell (coordinates provided in the
Supporting Information) structure was taken and six different
adsorption sites (A−F) are chosen, as shown in Figure 1.
To find the most preferable sites for single Na adsorption on
the twin-graphene surface, the adsorption energy (Eads) at
different adsorption sites have been calculated using the
relation
Eads = E Na − C − (EC + E Na) (1)
where ENa−C is the total energy of single Na adsorbed on the
twin-graphene system, EC is the total energy of the pristine
twin-graphene, and ENa is the energy of the single Na atom in
the bulk. A lower value of Eads represents energetically
preferable adsorption, while a negative value of Eads shows
the intercalation process is an exothermic one.53,54 The
adsorption energies for a single Na adsorption the at A- and
B-sites are −1.72 and −1.20 eV, respectively. Thus, the A-site
is found to be the most stable site for Na adsorption on twin-
graphene, while the B-site being the next stable one. The A-site
adsorbs the Na atom at a distance of 2.67 Å from the triangular
plane, while the B-site adsorbs the Na atom at a distance of
2.32 Å from the plane of the hexagonal site. The remaining
sites optimize and relax themselves to accommodate Na at the
same A- or B-sites, thus rendering them to be the two most
stable sites for Na adsorption. Further calculations done by
incorporating vdW correction along with GGA−PBE ex-
change−correlation functional yield adsorption energies for Na
adsorbed at the A- and B-sites to be −2.06 and −1.565 eV,
respectively, which again confirms the A-site as the most stable
site. Interestingly, the adsorption energy becomes more
negative, indicating higher stability compared to that without
vdW correction. From AIMD simulation of the same 2 × 2 × 1
supercell, the thermodynamic stability of the single Na atom
for A-site intercalation is confirmed with no significant
structural distortion. At room temperature, only slight
fluctuation around a constant value is seen in the potential
energy profile of the simulation (Figure 2).
The electron localization function (ELF),55 when visualized,
gives us an idea about the nature of the chemical bond
between the adatom and the substrate from an electron
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
Figure 2. Potential energy fluctuation profile during molecular
dynamics simulation at 300 K.
distribution perspective. An electron localization of 1 indicates
the perfect localization state of electrons, while values of 0.5
and 0.0 indicate the fully delocalized electron state and low
electron density regions, respectively. Here, the red regions in
the ELF plot with an electron localization of 1.0 depict regions
with a shared electron interaction, while the blue regions with
an electron localization of 0.0 represent regions with unshared
electron interactions. It is observed from the ELF plot (Figure
3) that a shared electron interaction, that is, covalent-type
bonding, exists between C−C atoms in the substrate as
depicted by red regions around these bonds, while an unshared
electron or ionic bond exists between the adatom and the
carbon substrate. The regions between the carbon and adatom
as shown in green represent areas where free electron gas
behavior with excellent electronic conductivity is observed.
From Bader charge analysis, a charge transfer of 0.89 e from
the sodium atom placed at the A-site to the twin-graphene
substrate is observed, while for the sodium atom placed at the
B-site, a charge transfer of 0.91 e is noticed. To get a deeper
insight into the bonding nature, the charge density difference
for the adsorption of the Na atom on the twin-graphene
surface has been calculated using the relation given in eq 2 and
the corresponding charge density difference plot is shown in
Figure 4
Δρ = ρtotal − ρNa − ρtwin ‐ graphene (2)
where ρtotal, ρtwin‑graphene, and ρNa represent the charge densities
of the overall system with Na-adsorbed twin-graphene, twin-
graphene, and the Na atom, respectively. Interestingly,
electrons are mainly accumulated around the C atoms due to
the higher electronegativity of C atoms compared to the Na
atom. Bader charge analysis as well as charge density difference
suggests that the Na atom is physically adsorbed on twin-
graphene and this process corresponds to redox reaction for
electrode materials.
Twin-graphene is a direct band gap semiconductor with a
band gap of 0.737 eV.28,40 On adsorption of a single Na atom
at the A- or B-site, it is seen that the Fermi level is well within
the conduction band with two bands crossing the Fermi level
(left panel of Figure 5a,b). This implies a metallic character of
the systems and a transition from semiconducting to metallic
Figure 3. Top view of ELF for Na adsorbed on twin-graphene with the cut plane at the level of (a) hexagonal rings, (b) trigonal-like por chains, and
(c) Na atom.
C https://doi.org/10.1021/acsanm.1c00460
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Figure 4. (a) Top view and (b) side view of the charge density
difference plot for Na adsorbed on twin-graphene. Blue regions
indicate electron loss, while the pink regions indicate electron gain.
nature of the material upon Na adsorption. This metallic
nature of the system is an essential requirement for ion
diffusion on the anode material which facilitates fast charging
and discharging activity. This metallic character originates due
to the high value of charge transfer between the Na atom and
twin-graphene surface. The density of states (DOS) profiles
(right panel of Figure 5a,b) also confirm the metallic nature as
the conduction band’s s and p orbitals of the C-atom cross the
Fermi level and enter into the valence band after Na
adsorption. The total DOSs in Na-adsorbed twin-graphene
systems are mainly dominated by the pz orbital of the C-atom.
Theoretical Capacity of Na-Adsorbed Twin-gra-
phene. The maximum number of ions that can be adsorbed
onto the anode material is an important parameter that
indicates the efficiency of the anode material in rechargeable
ion batteries. The maximum ion capacity of an anode material
can be found by adsorption of ions onto the anode material in
a layer-wise fashion and noting the corresponding average
adsorption energy for that layer. The average adsorption
energy (Eave) is given by the expression
E NaXnC − E NaX(n−1)C − XE Na
Eave =
X (3)
where ENaXnC and ENaX(n−1)C are the total energies corresponding
to structures with n and (n − 1) layers of Na accommodated
on twin-graphene. Here, X represents the number of Na atoms
accommodated on each layer. To study the adsorption energies
in the present work, the same 2 × 2 × 1 supercell is employed
and Na atoms are adsorbed on it. With the A-site being the
most stable one for Na adsorption, the first and second layers
are adsorbed by placing Na atoms on each of the A-sites on
both sides of the twin-graphene substrate. For the first layer, all
the eight A-sites are accommodated with Na atoms. On
adsorption, the first layer gives the value of Eave to be equal to
−1.083 eV. This negative value of Eave suggested further
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
Figure 5. Band structure and DOS plot for the single Na atom adsorbed on twin-graphene (a) on the A-site and (b) on the B-site.
increasing the number of Na layers. The adsorption of a
second layer on the other side of the substrate yielded a value
of −1.110 eV for Eave. The magnitude of adsorption energy for
the first layer and second layer increases upon the
incorporation of the vdW functional and is found to be
−1.594 and −1.604 eV, respectively. Unless a positive value of
Eave is obtained, further layers should be adsorbed on the
material to get the maximum ion capacity. Twin-graphene has
a buckled structure with the B-sites situated at a certain
elevation from the A-sites. These B-sites being the next stable
position for adsorption should be used for inserting the third
and fourth ion layers onto the substrate. The optimized
structure of the double layer of Na adsorbed on twin-graphene
is shown in Figure 6, while the same for the single layer, triple
layer, and fourth layer is provided in Figure S1. These B-sites
would absorb four Na atoms on each side giving average
adsorption energies Eave of 0.230 and 0.257 eV for the third
and fourth layers, respectively. The positive values of Eave for
the third and fourth layers imply that more than the double
layer cannot be accommodated on the twin-graphene
Figure 6. (a) Top view and (b) side view of the optimized geometry
for two layers of Na adsorbed on twin-graphene.
D https://doi.org/10.1021/acsanm.1c00460
www.acsanm.org Article
substrate. Furthermore, the effect of strong repulsion between
the adjacent adatoms has been considered based on the
differential adsorption energy calculated using the expression56
Ediff − ads = E Na nC − E Na(n−1)C − E Na (4)
Here, ENanC is the energy of the system with n number of Na
atoms, ENa(n−1)C is the energy of the system with (n − 1)
number of Na atoms, and ENa is the energy of a single sodium
atom. The differential adsorption energies are provided in the
Supporting Information (Table S1), which indicates the
corresponding energy released when a Na atom is introduced
into the system. It can also be inferred that the magnitude of
differential adsorption energy decreases with an increase in Na
concentration until sodium filled up the first layer, except n = 5
and 7. Interestingly, the magnitude of Ediff−ads increases
significantly on adding one more Na atoms in the second
layer, and it again decreases gradually until the second layer is
filled by Na atoms with an exception noted for n = 16. The
adsorption energy of Na-adsorbed twin-graphene systems is
lower than the sodium clustering energy (−1.13 eV),37
confirming that the sodium atoms are adsorbed on the twin-
graphene surface without clustering. Moreover, the adsorption
energy calculated using two different methods follows the same
trend, that is, the first layer has a higher adsorption energy than
the second layer. The negative adsorption energy confirms that
the formation of the double layer adsorbed on twin-graphene is
thermodynamically favourable.
Accordingly, a maximum of sixteen Na atoms can be
accommodated on the 2 × 2 × 1 supercell of twin-graphene
containing seventy two carbon atoms that give a stoichiometric
chemical formula of Na16C72. For a better understanding of
structural stability of the system with increasing sodium
concentration, cohesive energy of the system is calculated
using the expression
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
Figure 7. (a) Schematic diagram showing different paths for diffusion of the single Na atom on twin-graphene. (b) Energy barriers for different
diffusion paths.
Ecoh = E NaxCy − xE Na − yEC
where ENaxCy is the energy of the system containing x number
of Na atoms and y number of C atoms, ENa is the energy of the
single sodium atom, and EC is the energy of the single carbon
atom in the system and is listed in Table S1. All the systems
possess a negative cohesive energy, confirming their structural
stability. However, with an increase in Na concentration, the
magnitude of cohesive energy decreases, and as a result,
stability decreases. Thermodynamic stability of the maximum
Na-ion-accommodated twin-graphene system has been verified
using AIMD simulation. The structure retains its stable
configuration without any deformation. Potential energy
oscillates slightly around a mean value (Figure S2), thus
confirming twin-graphene’s efficient battery performance
toward the sodium-ion rechargeable battery.
Next, we have calculated the electronic band structure at
different Na concentrations, and the associated band gap is
listed in Table S1. Incorporation of a single sodium atom leads
to a transition from semiconducting to metallic character, and
the system retains its metallic character up to six Na atoms
adsorption. Interestingly, the system again transforms into
semiconducting character in addition of seven and eight
sodium atoms on the twin-graphene surface. Seven Na atoms
adsorbed on the twin-graphene surface has a band gap of 0.156
eV, and the band gap increases to 0.190 eV upon adsorption of
eight sodium atoms. On further increasing the concentration of
Na atoms, the system again transforms into metallic nature and
it continues until fourteen Na atoms, which then again shows a
transition to semiconducting character, thereby giving the
double layer-adsorbed system to be a semiconductor. In order
to explain this interesting transition (semiconductor−metal-
lic−semiconductor−metallic−semiconductor) mechanism,
DOS spectra have been analyzed. DOS plots (Figure S3)
also confirm the transition from metallic to a semiconductor
on increasing the number of Na atoms from six to seven and
again from a semiconductor to metallic on increasing the
number of Na atoms from eight to nine.
The theoretical capacitance can be calculated from the
equation
xmF
C=
MC
where xm is the number of ions accommodated on the twin-
graphene supercell, F is the Faraday constant (=26.8
Ahmol−1), and MC is the mass of the twin-graphene supercell.
This gives us the theoretical capacitance of the twin-graphene
anode material to be 496.2 mAh/g. This value of capacitance
www.acsanm.org Article
(5) of twin-graphene as the anode material for Na-ion batteries
(NIBs) is much higher than that of other well-known anode
materials used for NIBs such as single-layer graphene (308
mAh/g)57 and its S-, P-, F-, and B-doped counterparts with
capacities of 296, 332, 340, and 345 mAh/g, respectively,57
graphyne with a capacity of 372 mAh/g,36,58 tetragonal C24
(232.65 mAh/g),59 phosphorene (433 mAh/g),60 MoC2
(446.90 mAh/g),61 SnP3 (253.31 mAh/g),62 and so forth.
Next, the open-circuit voltage (OCV), which is an important
parameter describing the performance of an electrode, can be
calculated using the relation
EC + xE Na − E Na − C
OCV =
xz (7)
where EC is the energy of the pristine twin-graphene supercell,
ENa is the energy of the single Na atom in the bulk, and ENa−C
is the energy of the Na-adsorbed twin-graphene. x is the
number of intercalated ions, and z = 1 for Na ions. The
calculated OCV for different layers of Na ions intercalated on
the anode material gives an average OCV of 1.090 V (the
deposition of a single layer gives an OCV of 1.083 V, while a
second layer gives 1.096 V). This value of OCV is well below
1.5 V and can be considered as a moderate value for
applications in anode materials.63
Diffusion of the Single Na Atom on Twin-graphene.
The ion mobility of Na on twin-graphene is an important
determining factor for the charging/discharging rate and thus
indicates its feasibility as a suitable anode material. In this
regard, the diffusion barriers considering two different
pathways for Na atoms on the twin-graphene substrate have
been investigated here. With the A-site being the most stable
among all sites, we have considered two diffusion pathways
connecting two neighboring A-sites (path 1: connecting two
neighboring A-sites sharing the same boundary and path 2:
connecting two A-sites via a B-site).
CI-NEB calculations suggest a higher diffusion barrier for
path 2 as compared to path 1. As shown in Figure 7, the
calculated diffusion barriers for the Na ion along paths 1 and 2
are 0.198 and 0.52 eV, respectively. Na diffusion on twin-
graphene is lower than that on many other reported 2D
materials such as T-graphene (0.41 eV),42 graphyne (0.40
eV),58 SnP3 (0.38 eV),62 and so forth. This low value of
(6) diffusion barrier indicates faster diffusion of Na ions on the
twin-graphene anode material and a high charging rate.
■
CONCLUSIONS
Using DFT, here, we have investigated a twin-graphene-based
anode material on which Na ions are adsorbed. We have
E https://doi.org/10.1021/acsanm.1c00460
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
shown that Na-adsorbed twin-graphene is thermodynamically
stable and Na is physically adsorbed on the twin-graphene
substrate. From the comparison of adsorption energies at
different sites on twin-graphene, it is seen that the triangular
sites (A-sites) are the most stable ones for adsorption. It is also
observed that a transition from the semiconducting to metallic
nature of the system occurs on adsorption of Na on twin-
graphene. The layer-wise intercalation of these ions on the
twin-graphene substrate revealed a maximum of two layers that
can be adsorbed which yielded a maximum theoretical
capacitance of 496.2 mAh/g. An average OCV of 1.090 V is
reported, which is considered a moderate value for anode
materials along with a low diffusion barrier and further suggests
faster diffusion and higher charging rates in twin-graphene
anode-based Na-ion rechargeable batteries.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsanm.1c00460.
Optimized structure of the single layer, triple layer, and
fourth layer of Na adsorbed on twin-graphene;
adsorption energy and cohesive energy of the system
with increasing Na concentration; potential energy
fluctuation profile during molecular dynamics simulation
at 300 K for double-layer Na-adsorbed twin-graphene;
and structural coordinates of pristine twin-graphene
(PDF)
■ AUTHOR INFORMATION
Corresponding Author
Utpal Sarkar − Department of Physics, Assam University,
Silchar 788011, India; orcid.org/0000-0002-7677-7479;
Email: utpalchemiitkgp@yahoo.com
Authors
Harkishan Dua − Department of Physics, Assam University,
Silchar 788011, India; orcid.org/0000-0002-8483-1340
Jyotirmoy Deb − Department of Physics, Assam University,
Silchar 788011, India; orcid.org/0000-0002-1428-5137
Debolina Paul − Department of Physics, Assam University,
Silchar 788011, India; orcid.org/0000-0002-4106-6685
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.1c00460
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
H.D. thanks DST SERB for his fellowship. J.D. thanks the
Department of Science and Technology (DST), New Delhi,
India, for providing him DST-INSPIRE Fellowship. D.P.
thanks the Council of Scientific and Industrial Research
(CSIR), India, for her CSIR SRF. U.S. would like to thank
DST, New Delhi, India, for the SERB project (file no. EMR/
2016/006764) for financial assistance.
■
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