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A first-principles roadmap and limits to design

efficient supercapacitor electrode materials
Cite this: DOI: 10.1039/c9cp02614b
Basant A. Ali and Nageh K. Allam *

Our life is turning into an electronic world where we need our devices charged all the time. Although
batteries have been doing the job so far, we need devices that charge way faster with longer cycling
Published on 16 July 2019. Downloaded on 8/3/2019 6:48:00 PM.

Received 8th May 2019,
Accepted 16th July 2019
DOI: 10.1039/c9cp02614b
rsc.li/pccp
stability. The answer could be supercapacitors; however, electrode materials that maintain both high
energy density and high power density are yet to be discovered. Currently, researchers base their work
on guess and check methods to modify electrode materials with limited organized work that targets the
prediction of the properties of materials at an earlier stage. To this end, density functional theory (DFT)
could be a realistic tool for early prediction of the properties of supercapacitor electrode materials. The
targeted supercapacitor electrodes should exhibit multiple properties, which can be calculated using
different DFT routes. Herein, a roadmap to predict the desired supercapacitive properties of materials
using different levels of DFT is presented. Our target is to let researchers decide which property of the
material they wish to predict or develop and choose the appropriate DFT route to do so.

I. Introduction are based on guess and check selection of electrode materials and
electrolytes, while materials design and material–electrolyte
Joseph MacDouall once said, ‘‘Chemistry is a game that electrons interface design are not widely used.3 The limited use of
play’’.1 If one were able to know the roles, they could control the computational prediction in designing materials for supercapacitor
game and uncover the mysteries of materials, which are the devices could be due to the wide variety of computational tools,
backbone of our modern civilization. To this end, energy making it hard to choose the appropriate method in each case. Even
storage platforms are the bottleneck hindering the efficient DFT is divided into many versions. While classical DFT is usually
use of electronic devices. Although Li-ion batteries seem to used to predict the properties of porous carbon materials, electronic
provide an ultimate solution for mobile phones and laptops, DFT is usually used to predict the electronic properties of the
they are not sufficient for larger devices such as electric cars materials. In this regard, the materials used in supercapacitors
and stationary energy storage. For electric cars, they need to be can be divided into capacitive materials and faradaic materials, each
charged and rework efficiently very rapidly, which is controlled with their own charge storage mechanisms and hence their own
by the power density of the energy storage device. In this
regard, supercapacitor devices may provide a solution to the Nageh Allam received his PhD degree
power density problem provided that electrode materials can be in Materials Science and Engineering
tuned to provide such energy density values. For this to happen, from Pennsylvania State University.
both the operating potential window and the resulting maximum He joined the Georgia Institute of
current density need to be maximized.2 However, reports so far Technology as a postdoctoral fellow,
then the Massachusetts Institute of
Energy Materials Laboratory, School of Sciences and Engineering, The American Technology as a research scholar. He
University in Cairo, New Cairo 11835, Egypt. E-mail: nageh.allam@aucegypt.edu moved to The American University in
Cairo in September 2011, where he is
Basant Ali received both her BSc in Chemistry and MSc in now a professor of Materials Science
Computational Chemistry from Alexandria University. She joined and Engineering. His research
The American University in Cairo as a PhD student in Fall 2018. focuses on the fabrication of well-
Her research focuses on applying state-of-the-art computational Nageh K. Allam designed nanostructured materials
methods to study nanostructured systems for use in supercapacitors. with composition, size and shape
Her work also comprises the development of efficient materials for control for use in energy conversion and storage, sensor applications,
high-performance supercapacitor devices. She is a recipient of the and biomedical applications, among others. The research comprises both
Allehedan Endowed Scholarship. experimental and theoretical activities.

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properties. The variations between the energy storage mechanisms,
the electrolyte material, and the computational methods used in
materials design made it hard for researchers to decide where to
start and how to find the way in designing good materials for use as
supercapacitor electrodes.
For supercapacitor research, it seems that more than one
version of DFT should be combined to investigate the char-
acteristics of the entire system. While electronic density func-
tional theory (eDFT) can be used to estimate the conductivity
and quantum capacitance of electrode materials, classical
density functional theory (cDFT) can provide information about
the electrode/electrolyte interface by estimating the electrical
double layer (EDL) capacitance. Therefore, DFT, either electro-
nic or classical, is a good tool for predicting the energy storage
characteristics of a wide range of potential materials. In this
regard, cDFT was found to be as accurate as molecular dynamics
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with the calculation time 3 times lower.4 Consequently, cDFT has
been used to predict the capacitive behavior of many carbon
materials.3,5,6 However, cDFT is determined to be unsuitable to
accurately predict the capacitance of pseudocapacitive materials,
battery-like materials, and hybrid materials. On the other hand,
eDFT is a good tool for predicting the band gap energy, electronic
properties, and quantum capacitance from the density of states
(DOS) of the materials of interest.7 Therefore, the combination
of eDFT and cDFT should be a perfect tool for predicting the
capacitance of a plethora of electrode materials. New tools are
aimed at combining both eDFT and cDFT to estimate the overall
capacitance for electrode materials.8–10 Note that different
morphologies will result in different charge storage mechanisms
and hence will need different computational treatments. Herein, a
thorough analysis of the available literature is provided and used to
propose a roadmap for researchers to guide them to select the best
DFT descriptors to screen materials for use as supercapacitor
electrodes. We hope that this roadmap will help in designing better
supercapacitor devices. It is noteworthy that cDFT and eDFT may
have other terms in the literature due to their wide range of
applications. cDFT is sometimes referred to as fluid DFT and eDFT
usually referred to as DFT without the (e), or quantum DFT (qDFT).
II. Charge storage mechanisms in
supercapacitor electrodes
Materials store electrical charges via different storage mechanisms.
The electrostatic attraction between the charged surface of a
material and electrolyte ions is called electrical double layer (EDL)
capacitance, which is usually observed in carbon-based materials2,11
EDL capacitance depends on the surface area, pore size, electrolyte
ionic size, mobility of the electrolyte ions and material/electrolyte
interface resistance.12 However, if the material exhibits a faradaic
behavior such as the diffusion of electrolyte ions into/out of the
material in terms of fast intercalation or surface redox reaction, this
will result in pseudocapacitance.2,11,13 Pseudocapacitive materials,
such as MoS2 electrodes, mainly have a layered structure that
facilitates the intercalation of electrolyte ions. If there are no
empty orbitals for bonding with the electrolyte ions, the
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intercalation will be hard. Similarly, if the material is a solid
crystal with no layered structure, the diffusion of ions will be
slow, and the power density will be minimal. The third charge
storage mechanism is known as a battery-like mechanism in
which the electrode material undergoes a faradaic process in
terms of redox reaction(s).14–16 The reversibility and the nature of
the redox reaction in battery-like materials will give insights into
the cycling stability of the electrode material. Moreover, hybrid
materials (faradaic and non-faradaic) have also been investigated
to design better electrodes.13,17 Due to their high electrical break-
down rates and high dielectric potentials, polymer-based capaci-
tors have recently gained extensive attention. Electronic DFT has
been widely used to screen and model new polymers for polymer-
based supercapacitors.18,19
Although the nature of the material itself is important to identify
the charge storage mechanism, the nature of the electrolyte is
equally important as it controls the operational potential window,
which controls the resulting power density of the supercapacitor.12,20
As aqueous electrolytes usually undergo splitting in low potential
windows, they are not favorable and are usually replaced with ionic
liquids. However, ionic liquids have large ionic radii, hindering the
diffusion of ions into the internal pores of the electrode material.12,21
The pH of the aqueous electrolyte affects the charge storage
mechanism. For example, while Na2SO4 does not usually react with
NiOOH and results in EDL capacitance only, the use of H2SO4 leads
to the formation of Ni(OH)2 and results in a battery-like behavior.22
The electrolytes used in supercapacitors can also be in the form of
solid materials such as reactive polymers, gel polymers, or dry solid
polymers.12 The material/electrolyte interaction in terms of the
electrostatic attraction between the material and ions, the possibility
of diffusion of electrolyte ions into the pores or layers of the
materials, the reaction between the material and the electrolyte,
and the mobility of ions in the electrolyte will give insights into the
overall capacitance of the electrode material.12,20,21,23,24 In this
regard, DFT can be used to uncover the material/electrolyte
interactions and to provide a solution for the possible charge
storage mechanism and capacitance value.3
The electrochemical capacitance of an electrode material
can be calculated from cyclic voltammetry, charge–discharge
time, and electrochemical impedance spectroscopy graphs.2,13
The shape of a cyclic voltammogram can be an indication of the
charge storage mechanism (Fig. 1), where the cyclic voltammo-
gram tends to be perfectly rectangular in shape for pure EDL
capacitive materials and distortedly rectangular in shape when
diffusion is predominant (pseudocapacitive materials), and
clear redox peaks appear when it is a battery-like material.14 It
is noteworthy that DFT can predict the electrochemical behavior
and can be related to the Nernst equation to give insights into
the electrochemical properties of the electrode material.25,26
III. Classical density functional theory
(cDFT)
Some parameters do not need expensive electronic calculations
to be accurately determined and it is enough to treat the system
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Fig. 1 The cyclic voltammograms of the different charge storage mechanisms.
classically to obtain accurate results. cDFT is considered to be
an analog to eDFT and can be successfully applied to classical
systems.27,28 In cDFT, the classical solvent density function r(r)
can be acted upon by another functional (function of a function),
which is the Helmholtz free energy (F). With minimization of F,
the equilibrium solvent density req(r) can be reached. The
equilibrium solvent density can be defined as the number of
solvent molecules per unit surface area (represented by r) of the
solute or the interface.4 The functional F can be divided into
three terms as presented in eqn (1). While the first term (Fid)
represents the non-interacting solvent molecules, the second
term (Fext) represents the external potential due to the inter-
action at the solvent–solute interface, and the third term (Fexc) is
the solvent–solvent interaction term, which resembles the
exchange–correlation term in DFT and it is the only unknown
term that needs an approximation to be determined.4 Note that m
is the chemical potential.
ð it assumes a homogeneous smooth surface model.35 This is
F½rðrÞ ¼ Fid ½rðrÞ þ Fext ½rðrÞ þ Fexc ½rðrÞ  m rðrÞdr (1)
A. Predicting the characteristics of porous structures
As the EDL capacitance results from the electrostatic adsorption
of electrolyte ions at the surface of the electrode material, the
surface area of the material is crucial to decide whether the
material will be suitable for the supercapacitor application. In
this regard, porous materials are commonly used due to their
high surface area.29,30 However, if pores are not compatible in
size with electrolyte ions, the porous structure will be
useless.21,30,31 Therefore, studying porous structures and pore
size distribution is necessary to model and screen materials for use
in supercapacitors. Evans et al. illustrated a cDFT-based model to
predict the characteristics of porous structures from theoretical
adsorption isotherms, where specific surface area, pore volume,
pore size, and pore size distribution can be estimated by
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adsorption fitting.32–34 The gas–solid adsorption process occurs
at a given temperature and pressure until the system reaches
equilibrium, which corresponds to the minimum grand potential of
the system that is a function of the density of the adsorbed gas and
the Helmholtz free energy.35 One of the approximations used to
calculate the theoretical adsorption isotherm is the non-local DFT
(NLDFT), which treats the solid surface as inert particles and models
the adsorption process with an adsorbent–adsorbate distributed
potential.35 NLDFT gives the minimized grand potential as a
function of the equilibrium adsorption state subjected to the
external potential at a specific potential of the fluid.35 The
Helmholtz free energy second term is usually treated using
the smooth density approximation (SDA)36 or fundamental
measure theory (FMT),37 while the third term is usually treated
using the Lennard-Jones intermolecular potential in both gas–
gas and gas–solid interactions. Although NLDFT is, to some
extent, good in estimating the characteristics of porous structures,
problematic when modeling microporous carbon materials that
usually have a broad pore size distribution.35 Another commonly
used method is the quenched solid DFT (QSDFT), which considers
the grand potential of the adsorbent and adsorbate, giving a two-
component DFT, where the adsorbent is modeled as a hard core
interacting with the adsorbate around it through a pairwise
attractive potential.35 Once the DFT model is applied to the system,
a pore shape must be defined since both NLDFT and QSDFT are
affected by the pore shape, which greatly affects the results.38
However, other methods can work with more than one shape.30
The DFT method can then be used to predict the isotherm and the
pore properties. The usually used gases in the pore structure
analysis for materials in supercapacitors are N2 and CO2. However,
CO2 gas provides more accurate results for carbon materials with
pores of sizes 1 nm or lower. NLDFT shows good estimation for
porous supercapacitor electrode materials.31,39–41 For hetero-
geneous unsmooth surfaces, QSDFT is most probably used to
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model the isotherm.42–44 Usually both NLDFT and QSDFT are
used to give accurate results over the whole range of pore sizes
and porous structures.29,45–47 However, the NLDFT usually
overestimates the pore volume and specific surface area in
comparison with the QSDFT and the experimental results.30
Other pore description models were used to account for the
curvature of pores for nanopores such as the electric double-
cylinder capacitor (EDCC) for mesopores and the electric wire
in cylinder capacitor (EWCC) for micropores.48,49
B. Predicting the characteristics of electrode/electrolyte
interfaces
The suitability of a porous structure for supercapacitor applications
depends on its compatibility with electrolyte ions, making it
necessary to model the electrode/electrolyte interface.50,51 To
this end, Coarse-Grained Classical DFT (CGDFT) is a good
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structures modeled by CGDFT can be planar surfaces such as
flat surfaces, slit pores, spherical surfaces, or concave/convex
cylindrical pores.3 Research studies have proved that a porous
structure can greatly affect the real EDL capacitance of the material
as well as the accuracy of the computational calculations. Thus, it
is better to model the right pore structure and ensure that the best
pore structure is chosen for the intended application. The
minimization of the grand potential of cDFT can be achieved
by considering the oppositely charged, tangentially connected
hard spheres taken into consideration the temperature, pore
size, pore structure, and the surface chemical potential.3,6 The
EDL capacitance can be calculated as the derivative of the
surface charge density in terms of surface potentials. Although
ionic liquid and organic electrolytes have wide potential windows,
they have limitations due to their incompatible ionic radii to the
pore size of most of the materials. CGDFT was used to provide

model that considers ions in the electrolyte as charged hard
spheres and the solvent molecules as hard sphere dimers.3,6 The
pair potential between the ionic species (i) and the solvent
molecules ( j) can be represented by eqn (2).6 Therefore, CGDFT
can be used to model electrode/electrolyte interactions represented
by the EDL considering the different pore structures. The pore
insights into the dependence of EDL capacitance on pore size.52,53
It was found that an organic electrolyte is relatively not dependent
on pore size compared to an ionic liquid electrolyte. The capaci-
tance was constant at pore sizes beyond twice the ion diameter as
an EDL is formed due to the presence of both counter ions and the
organized solvent molecules as presented in Fig. 2(A and B).53,54

Fig. 2 (A) EDL capacitance of slit nanopores as a function of pore size: (a) ionic liquid electrolyte and (b) organic electrolyte,54 with permission from the
American Chemical Society, copyright 2013. (B) EDL capacitance in terms of the electrostatic potential of the pore (u), R is the pore radius, 2a is the lattice
constant, w is the energy of transfer of one cation or one anion, and the differential capacitance is symmetric about u = 0,55 with permission from the
American Physical Society, copyright 2014. (C) The distribution of ions near the positive electrode, x is the mole fraction of ‘‘1-ethyl-3-methylimidazolium
tetrafluoroborate (EMI-BF4)’’,56 with permission from the American Chemical Society, copyright 2016. (D) EDL capacitance of nanopores as a function of
pore size,58 with permission from the American Chemical Society, copyright 2018. (E) Schematic representation of the ionic interaction in the ionic
mixture electrolyte; black arrows represent the following – I: the TMA+–BF4 interaction, II: the EMIM+–BF4 interaction, III: the steric effect, IV: the
EMIM+–EMIM+ interaction, and V: the TMA+–EMIM+ interaction, and red arrows represent the ion diffusion,59 with permission from the American
Chemical Society, copyright 2017. (F) Ion distribution on the negatively charged walls (EMIM+: 1-ethyl-3-methylimidazolium, TMA+: tetramethylammo-
nium, BF4: tetrafluoroborate),59 with permission from the American Chemical Society, copyright 2017.

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CGDFT can provide a good tool for modeling the pore size in the
range from ionic radii to microscopic structures.54 The mechanism
of the charge storage mechanism in a tubular shaped pore
structure was studied as illustrated in Fig. 2(B).55 The charging
process occurs due to the swapping of cations with anions when
the cation–anion attraction is surpassed by the cation-applied
potential interaction. It was found that decreasing the cylindrical
pore size enhances the electrostatic interaction, and the opposite
charges were unbound, while the same charges were packed.55 The
mixed ionic liquid effect on capacitance was also studied using
CGDFT.56,57 The results showed that the mixed liquid has the best
capacitance due to the best ionic distribution on the positive
electrode as illustrated in Fig. 2(C).56 The curvature effect, such
as convex and concave EDLs, was also studied, Fig. 2(D). Upon
increasing the inner radius, the pore becomes slit-like instead of
spherical and the capacitance decreases dramatically.58 The weak
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ion–ion interaction in the electrolyte can enhance the power
density of the supercapacitor while decreasing its energy density
due to the increased distance between the ions at the electrode
surface.59 The modeling of ionic liquid mixtures allowed research-
ers to find electrolytes with different ionic interactions that allowed
enhancement of both power density and energy density.59 Fig. 2(E)
shows that the mesopores attract the cations with strong ion–ion
interactions, which are packed in a dense arrangement, while the
micropores attract the cations with weak ion–ion interactions to
provide high power density.59 Fig. 2(F) presents the ionic distribution
of the charged ions on the surface of the porous electrode.59 CGDFT
research helped in proving that the micropores prefer smaller
ions60,61 and the importance of impurity ions in the electrolytes.62
Although charged nanopores prefer small ions, the CGDFT proved
that the cylindrical large porous structure can prefer large counter
ions if the ionic size was compatible with the large pore size.63
8 potential couple and Ex is the exchange–correlation term (energy).69
> si þ sj
>
< 1;
> ro
2
Uij ðrÞ ¼ (2)
>
> ZZe 2
s þ sj
>
: i j ; r i
4pe0 er 2 energy. The Ex is also divided into two terms: the exchange energy
where r is the center-to-center distance, e0 is the permittivity of free
space, s is the diameter of the spheres, Z is the valence (+1 and 0 for
the two spheres in the dimer cation and 1 for the spherical anion),
and e = 1 is the local dielectric constant of vacuum.
As the electrochemical capacitance is also controlled by the
ionic diffusion of the electrolyte ions near the electrode, the
inclusion of thermodynamic treatment in terms of time-
dependent DFT (TDDFT) can be beneficial for the calculation
of the dynamics of ions during the charging process in porous
structures.3 The local density ri(r,t) varies with time according
to eqn (3).64 The kinetics of the charging process was modeled
using classical TDDFT by studying the response of the charging
density and ionic density profile to the variation of the electrode
voltage.65 The van der Waals effect on the charging process and the
change in surface charge upon application of the electrode voltage
over time were successfully studied using classical TDDFT.66
@ri ðr; tÞ
¼ rfDi ri ðr; tÞr½bmi ðr; tÞ þ bVi ðrÞg (3)
@t
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where Di is the self-diffusivity of ion i, ri(r,t) can be obtained from
1
the derivative of the Helmholtz functional (F), b ¼ , kB is the
kB T
Boltzmann constant, T is the temperature, and Vi(r) denotes the
external potential from the electrodes.
IV. Electronic density functional theory
(eDFT)
In 1998, Kohn won the Nobel Prize in chemistry for simplifying
one of the most watchful chemistry problems; the Schrödinger
equation.67 Instead of solving the Schrödinger equation
through the exact wave functions of electrons, Kohn and Sham
showed that electrons can be treated implicitly and the wave
function can be replaced by electronic density.68 By minimizing
the electronic density energy, the equation can be simplified
into a functional (function of a function). The new functional is
divided into two parts: the first treats the density through
minimization through all the wave functions, then the densities
are minimized as well.69,70 Kohn and Hohenberg proved that
the properties of a given electronic system can all be driven
through the electronic density.67 However, multi-electron systems
showed inaccurate results. Kohn and Sham also provided
another solution to this problem through the introduction of
electrons in terms of non-interacting particles that have the same
density of the interacting ones.68 The KS orbitals were presented
by a wave function of a Slater determinant of the product of all
electrons of all spins. As the KS kinetic energy was also considered
as the contribution of all electrons, the energy equation was
simplified as E = Ts + U + V + Ex, where Ts is the kinetic energy, U
is the interelectron repulsion (Hartree energy), V is the one-body
Since DFT depends on the approximation that electrons are not
interacting, a term representing those interactions should be used
to correct the result, which is named the exchange–correlation
and the correlation energy. While the exchange energy is the
electron–electron repulsion minus Hartree energy, the correlation
energy is the hard part to solve. This led researchers to come up
with approximations for the exchange–correlation function. One of
the approximations is the local density approximation (LDA), where
only the local density is used to approximate the exchange–correla-
tion functional.71 Another approximation is the generalized gradient
approximation (GGA), in which the functional is defined by both the
local electron density and gradient in the electron density. Although
the physical terms used in the GGA are more than those used in the
LDA, the way by which the gradient of electron density included in
the functional is the key point to define its accuracy. One of the
most commonly used approximated functionals is the Perdew–
Burke–Ernzerhof (PBE) functional.71 The functionals differ in
accuracy according to the properties, structures, and chemical
formulae of the studied systems. Strongly correlated systems, as
in solid state materials, need some extra treatment such as
hybrid functionals or the Hubbard correction.72 Some functionals
are hybrid, which combine the exact exchange calculated from the
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Hartree–Fock calculation with the GGA and/or LDA exchange–
correlation, such as the Becke, three-parameter, Lee–Yang–Parr
(B3LYP) functionals.73 In order to solve the wave function, the
equation should be expressed in terms of basis sets. The basis sets
can be either a plane wave or Gaussian orbital basis set. Atomic
(Gaussian) orbital basis sets are more computationally cheap, but
they are non-orthogonal that depend on the atomic positions and
having superposition errors when atoms are close to each other.
On the other hand, the plane wave function is orthogonal, does
not depend on the atomic position, and does not have basis set
superposition errors. However, it needs many functions to be
solved. Thus, the previous knowledge of the electronic structure
and the needed properties will make it easier to decide which
functional to use. Although electronic DFT is considered to be
computationally expensive, it has been used during the past
decades to model molecules and solid-state materials for energy
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applications18,72,74–76 due to its high accuracy and cost efficiency
compared to experimental methods. It is important to notice that
some software packages use Gaussian orbitals in calculations (e.g.
6-31G and ccPVDZ), such as the Gaussian, Dalton and GAMESS
packages, while others such as VASP, Materials Studio and
Quantum espresso packages use a plane wave basis set. There-
fore, it is important to determine whether the system can be
modeled using Gaussian orbitals or a plane wave basis set.
Details of the basic science behind eDFT and the manipulation of
using its methods were previously discussed in the literature.77–80
For layered structures, such as layered metal oxides or layered
carbon materials, it is important to determine the van der Waals
(vdW) forces as they control the diffusion of ions into the layered
structure during the charge/discharge process. To this end, eDFT
has been a very successful tool for identifying vdW forces in
layered structures of electroactive materials.81–83 However, DFT
cannot be used in its plain form. Thus, modifications to the
theory were made to allow the successful modeling of the vdW
forces with the inserted ions. Grimme84,85 and Hasegawa et al.86
proposed an insertion of an empirical correction into eDFT (e.g.
GGA, LDA, hybrid functionals, meta-GGA) to describe the vdW
forces between layers in a model known as vdW-D. On the other
hand, non-local functionals such as the Rydberg functional87 and
the vdW-DF88 were used to model graphite and carbon layered
structures.89 Other modifications were applied to the models in
recent years to include the exchange–correlation functionals and
to allow modeling of hydrogen bonding and other types of
bonding.82 Some of the new models were implemented in software
packages to be used directly, such as VASP, with many vdW models
such as vdW-revPBE, vdW-DF, and vdW-optPBE.81,82
The capacitive and pseudocapacitive behaviors depend
greatly on the interaction between the electrode and the elec-
trolyte. Thus, in-depth study of the electrified interface between
the charged electrode and the oppositely charged electrolyte
ions is mandatory to understand the nature of capacitance.
When an electrode is in contact with electrolyte ions without
having a net charge, there will be a potential of zero charge
(PZC). At the PZC, the electrolyte ions do not have a preference
of accumulation near the electrode and an applied voltage will
be needed to form the aggregates of ions on the surface of the
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electrode (EDL). The electrode/electrolyte interface can be
explained by the classical Helmholtz model where two parallel
plates represent the electrode surface and the electrolyte ions
spaced by a distance d. The two parallel plates are oppositely
charged and the electrostatic potential between them drops
linearly and is independent of the distance of the outer charges.
However, the Helmholtz model is not accurate for some
systems.5 On the other hand, another model, ‘‘Gouy–Chapman
model’’, is more accurate since it depends on the application of
Maxwell–Boltzmann statistics to the electrolyte charges in
which the countercharges are distributed along the diffuse
layer and decrease with distance from the electrode so that
the electrostatic potential decreases with increasing distance
from the electrode. The Helmholtz model and the Gouy–Chapman
model were combined into a new model, ‘‘Stern model’’, in which
the electrolyte ions form a parallel plane of countercharges to the
electrode but do not completely neutralize the electrode charge,
instead a diffuse layer of the net countercharges exists beyond the
ionic plane. However, the previous classical models do not provide
a clue about the atomic distribution, chemical interactions or
interfacial structure of the electrode/electrolyte interface.5 On the
other hand, DFT can provide a solution to uncover the exact
electrode/electrolyte interaction through solvation models that
model the separation between the electrode charge and the
electrolyte countercharge.90–92 The DFT calculations of the
electronic structure of the electrode can be combined with
the continuum models representing the electrolyte to give the
overall interaction.90,91 Continuum solvation models treat the
electrode material quantum mechanically using DFT and place
it into a cavity within a dielectric continuum. Electrolyte ions
contribute to the continuum through a Debye screening
response.90 Solvation models differ in many terms such as the
construction of the cavity. The cavity can be easily determined
through a few parameters from the solute-electron iso-density or
the electrostatic potential. Another method to determine the
cavity is by using atom-centered spheres, which is a complex but
more flexible method.90 The ionic continuum regions and the
dielectric can be treated linearly or non-linearly with the applied
potential. The distance between the dielectric and ionic cavities
can have a value of x or both the dielectric and ionic cavities are
shared in the same cavity with no distance between them (shared
ionic cavity). Some solvation models such as the LinearPCM,93–95
CANDLE96 and SCCS97 have an iso-density model for cavity
determination, a linear treatment for fluid dielectric, ionic
responses and shared ionic cavity, while the Non-linearPCM95
treats both fluid dielectric and ionic responses non-linearly. On
the other hand, the Anderson and Jinnouchi model98 and
the Debo et al. model99 have an iso-density model for cavity
determination, a linear treatment for fluid dielectric, a non-
linear treatment for ionic response, and separate ionic cavities.
The soft-sphere model100 uses atom-centered spheres to deter-
mine the cavity and linear treatment for the fluid dielectric with
no inclusion of the ionic response and shared cavity model. A
new developed solvation model for supercapacitor metallic
electrodes named the nonlinear electrochemical soft sphere
(NESS)90 uses atom-centered spheres to determine the cavity
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Fig. 3 The electrode/electrolyte modeling techniques.
and treats both fluid dielectric and ionic responses nonlinearly
with separate ionic cavities. The solvation model represents the
method of treatments of the relationship between the electrode
and electrolyte, while the electronic structure of the electrode
should have another method of treatment that will result in the
quantum capacitance value. There are two main methods to
estimate the electronic information about the electrode in an EDL
system: the effective screening medium (ESM)101 and joint density
functional theory (JDFT) methods.102,103 The electrode/electrolyte
modeling techniques can be summarized as presented in Fig. 3.
A. Predicting the electrochemical performance
Supercapacitors are electrochemical energy storage devices. Hence,
it is important to predict and identify the factors controlling their
electrochemical performance upon their use in such devices.
1. Resistance calculations. Supercapacitor electrodes need
to have fast electron transfer during the charge/discharge
processes. However, if the material is not conductive enough
or cannot perform a redox reaction within the applied potential
window, the electrode will not function as needed. To this end,
DFT can be a good tool for predicting the band diagram of the
electrode material and giving insights into its electrochemical
performance.104 For EDL-based supercapacitors, the capacitance
of the material can be estimated via the permittivity of the
material, which can be calculated from the dielectric constant
of the material. Sharma et al.19 performed a screening of the
capacitive performance of 267 polymers using DFT with the
generalized gradient approximation (GGA) and the band gap
correction Heyd–Scuseria–Ernzerhof (HSE06) functional. They
were able to calculate the dielectric constants, the band gap
values, the dielectric losses, and the dielectric breakdown of the
studied polymers. The results showed a good agreement with
experimentally reported values, highlighting the reliability of
DFT in predicting the electronic properties of polymers.19 As the
band diagram and charge density distribution at the electrode
material and/or the interface between two different materials
are crucial to evaluating the performance of supercapacitors,105,106
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Xiong et al.105 performed DFT calculations to investigate the
origin of the high capacitive performance of MnO2/graphite
petals on a carbon nanotube substrate using the GGA and the
plane-wave self-consistent field (PWSCF). The charge/discharge
process was simulated by applying stress pressure and calculating
the relaxation/compression of the MnO2 crystal on the graphite
surface. The researchers were able to calculate the density of
states (DOS), the electronic structure, and the charge density
distribution of the MnO2/graphite interface, indicating that the
charge transfer at the MnO2/graphite interface was facilitated by
the oxygen atoms in the MnO2 without which the resistance of
the material would have made it impossible for supercapacitor
applications.105 On the other hand, the defect states and vacancy
formation energy of Co3O4 showed a great enhancement in
conductivity and electrochemical performance over other metal
oxides.107 Thus, DFT is a promising tool for estimating the
resistance of electrode materials and their promising performance
as either EDL or diffusion-based supercapacitors.
2. Predicting the binding energy of ions at the electrode
surface. The binding energy between the electrolyte ion and the
surface of the electrode material affects the adsorption/desorption
of ions during the charge/discharge process. In this regard, DFT
can predict the binding energy and the effect of the adsorption of
electrolyte ions on the capacitive performance and conductivity of
the electrode material. For example, to simulate the adsorption of
ions from KOH electrolyte, the DOS of the adsorption of K+ and
OH ions on reduced graphene oxide (RGO) was calculated using
DFT (GGA).108 The DOS was found to vary with the type of ion and
the adsorption position, giving insights into the origin of the
capacitance performance of RGO in KOH.108 The binding energies
between K+ ions and different configurations of nitrogen-doped
graphene oxide (N-GO) were also calculated using DFT (GGA)109 as:
BE = Ebare surface + Eisolated ion  Esystem with adsorbed ions (4)
The results revealed the nature and strength of the bonding
between the electrolyte ions and the electrode material relative
to the positions of the N atoms.109
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3. Predicting the potential window. Predicting the working
potential window of the electrodes is crucial in determining the
expected power density of a supercapacitor, where the higher
the potential window, the larger the power density. One of the
main factors affecting the potential window of a supercapacitor
is the type of the electrolyte used. In this regard, DFT can be
used to predict the potential window of the electrolyte, enabling
the screening of a variety of electrolytes to identify the best
performing electrolyte. As aqueous electrolytes, such as diluted
acids, diluted bases, and salts, are limited by the water splitting
process occurring at 1.23 V,110 ionic liquids (ILs) have been
emerged as alternatives as the reduction of the cation represents
the cathodic limit and the oxidation of the anion represents the
anodic limit.111 To this end, DFT, with either simple basis set
models or the plane wave, can accurately predict the highest
occupied molecular orbital (HOMO) and the lowest unoccupied
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molecular orbital (LUMO). The HOMO represents the anodic
limit and the ionization energy of the molecule, while the LUMO
represents the cathodic limit and the electron affinity of the
molecule. The cathodic and anodic potential limits of each ion
can then be calculated as:111
eLUMO
Vcathodic ¼ 
e
(5)
eHOMO
Vanodic ¼ 
e
where eLUMO and eHOMO are the LUMO and HOMO energies,
respectively, and e is the electron charge. The cathodic limit and
the anodic limit of the IL can then be estimated as the
maximum of the cathodic limits of two ions and the minimum
of the anodic limits of two ions, respectively.111 As ILs are
liquids, insertion of solvation parameters into the calculation is
necessary. Thus, the use of solvation models such as the PCM will
add a reality to the calculations. In this regard, Ong et al.111 studied
the potential windows of six ILs using different levels of theory and
it was found that the use of molecular dynamics combined with
DFT (GGA) resulted in the best prediction results, while DFT with
the B3LYP/PCM model overestimated the potential window. Lian
et al.112 used DFT with the long range corrected hybrid functional
oB97XD and the atomic basis set 6-311++G** to model a newly
mixed IL and to estimate its potential window.112
4. Predicting the charge storage mechanism. As explained
above, the shape of a cyclic voltammogram can give insights
into the charge storage mechanism of supercapacitor electro-
des, see Fig. 1. While the pseudocapacitive behavior is believed
to be due to the delocalized valence electron transfer, the
battery-like behavior is due to the localized valence electron
transfer.25 In this regard, DFT (GGA) was used to identify the
charge storage mechanism of graphene oxide (GO).25 The DOS
of the partially oxidized GO with different degrees of delocalization
were calculated. It was found that the partially oxidized GO
exhibited extra energy states around the Fermi level and those
states increase with increasing energy delocalization and allow a
wider potential window. Those new energy states can accept or
donate electrons, providing a better pseudocapacitive behaviour.25
Although the study included only the DOS calculations using
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simple DFT, it was very promising to uncover the secrets behind
the pseudocapacitive behavior of materials. However, eDFT is
not only used to identify the charge storage mechanism in
carbon materials, but can also be extended to other materials
such as oxides113,114 and hydroxides.115 It was found that DFT
can relate the charge storage mechanism and ion intercalation
to the crystal structure of the metal oxide/hydroxide.113–115 Deng
et al. studied the charge storage mechanism in Co(OH)2 and
CoOOH crystals using DFT (GGA+U). It was found that Co(OH)2
exhibits a battery-like behaviour with a minimum shift in the
crystal structure, which explains the high stability of the Co(OH)2
after 8000 cycles, highlighting the promising application of this
battery-like behaviour.115
5. Proton intercalation. Acidic electrolytes, such as H2SO4,
may be used with d-orbital metal oxide or sulfide electrodes for
possible intercalation of protons into electrode materials,
resulting in pseudocapacitive behavior. Therefore, the prediction
of the possible proton intercalation should help in the design of
efficient pseudocapacitive electrode materials. As the most com-
monly used pseudocapacitive materials are RuO28,116,117 and
MXenes,26,118 they were the focus of the DFT studies in the
literature. The in-depth understanding of the pseudocapacitive
nature of the hydrous RuO2 explaining the proton diffusion was
presented by Ozolins et al.116 The DFT (GGA) model was used to
give insights into the electronic properties of RuO2 and the
electron–proton double insertion (RuOOH). From the DOS
calculations, it was found that the added electron was confined
around the hydroxyl group. The voltage corresponding to the
proton intercalation was calculated using eqn (6)–(8). It was
found that the proton intercalation voltage of bulk RuO2 is low,
suggesting that the charge storage mechanism is due to the bulk
intercalation and one-dimensional diffusion along RuO2. At
a higher voltage, the charge storage mechanism involves reversible
proton adsorption at the surface oxygen to form hydroxyl groups
and water molecules.116
DGðn þ 1Þ  DGðnÞ
Vn ¼  (6)
e
n 
DGðnÞ ¼ G½RuO2 ; n  G½RuO2   G ½H2  (7)
2
 7   
G ½H2  ¼ E0 þ EZPE þ kB T  T S (8)
2
where n is the number of intercalated protons, e is the electronic
charge, DG(n) is the free energy with respect to gas-phase hydrogen
molecules, G[RuO2, n] is the total free energy of RuO2 with n doubly-
inserted protons and electrons, G[RuO2] is the free energy of RuO2
before intercalation, G1[H2] is the standard state free energy of
hydrogen gas, E0 is the calculated static energy of a hydrogen
molecule, EZPE is the zero-point vibrational energy of H2 (0.27 eV),
and S1 is the entropy of gaseous hydrogen (130.68 J (mol K)1).116
Although the previous method was able to shed light on the
performance of RuO2, it did not account for the electrode/electrolyte
interaction, resulting in non-accurate results for the intercalation
voltage. Thus, more modifications were needed to include the EDL
behavior and the electrode/electrolyte interaction.116
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B. Capacitance calculations
One of the simplest DFT methods to estimate the theoretical
capacitance of a material is the one presented by Kansara
et al.,119 where the DFT (GGA) calculations on the H-phase of
bilayer aluminum and the T-phase of bilayer antimony revealed
the accurate capacitance performance of the two materials. The
van der Waals force (EvdW), which represents the interlayer
binding energy, was calculated as
Ebilayer  Elower layer  Eupper layer
EvdW ¼ (9)
N
where N is the number of atoms in the system. The dipole
moment (P) and the interlayer distance (d) can be calculated via DFT
calculations to estimate the stored charge (Qs) using eqn (10). Also,
the energy density (Ed) can be calculated through the difference
between the system energy before and after applying the voltage
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using eqn (11). The energy density can be used to estimate the
capacitance (Cs) using eqn (12). Electric fields of different values
were computationally applied to the electrode material to elucidate
the electrochemical behavior of the electrode material as presented
in Fig. 4(A–D).119 The results showed the promising performance of
the studied materials as supercapacitor electrodes.119 However, this
method was not compared to experimental values and lacks
accuracy due to the absence of the electrolyte effect.
Qs = P/d (10)
Ed = Eafter(E a 0)  Ebefore(E = 0) (11)
Qs2
Cs ¼ (12)
2Ed
Fig. 4 DFT calculated electrochemical performance of the H-phase of bilayer Al and the T-phase of bilayer Sb vs. the change in the electric field:
(A) dipole moment, (B) charge stored, (C) energy storage, and (D) capacitance,119 with permission from the American Chemical Society, copyright 2018.
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1. Quantum capacitance of an EDL capacitor. While the
EDL capacitance of a material is usually controlled by the
surface area, pore size, and pore structure, the quantum
capacitance (CQ) is controlled by the electronic structure of
the electrode material. Quantum capacitance represents the
contribution of the electrode material to the capacitance of the
Helmholtz layer at the EDL interface resulting from the electro-
nic response of the electrode. Both CQ and the EDL capacitance
are important to achieve an overall high capacitance. The total
surface capacitance (CT) can be calculated according to eqn (13)
without the inclusion of the battery-like or pseudocapacitance
effect:120
1 1 1
¼ þ (13)
CT CQ CDL
where CDL is the double layer capacitance, which includes the
Helmholtz layer and diffuse layer. The electronic structure of
the electrode material in an EDL capacitor can be described
using the DOS, following two proposed models, to estimate the
CQ.120,121 For materials with high DOS such as metals, the
electrode chemical potential (me) and the electrode potential do
not change greatly by adding or removing few electrons, where
the total capacitance is a function of the EDL capacitance only
(not taking the battery-like and pseudocapacitive behaviors into
account). However, for materials with low DOS such as semi-
conductor materials, any addition or removal of electrons may
greatly affect the electrode potential.3 Hence, the quantum
capacitance has a special importance for non-metals such as
graphene-based electrodes. The quantum capacitance can be
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calculated as the ratio between the variations of charge (dQ) the Fermi level, affected the DOS, and improved the quantum
and electrode potential (dV) known as the differential electrode capacitance. Quantum capacitance calculations showed that
potential.120–122 Eqn (14) is the commonly used relation between graphene oxide with epoxy groups performs symmetrically in
Cdiff
Q and DOS assuming an uncharged electrode:
120,121,123,124
positive and negative applied potential windows, while the gra-
dQ phene oxide with hydroxyl groups showed asymmetric behavior
diff
CQ ¼ ¼ e2 DOSðVeÞ (14) with better performance in the positive potential window as shown
dV
in Fig. 5(B and C).121 The DOS and quantum capacitance of
where e is the elementary charge, DOS is the electronic density of graphene can be enhanced as well via N-doping, vacancy defects,
states and (Ve) represents the relative electronic density with and adsorption of transition metal atoms as discussed by Yang
respect to the Fermi level. However, for 2D materials, Cdiff
Q can be et al.122 As presented in Fig. 5(D–F), the increase in defect
calculated according to:122,125–128 concentration increased the defect states and enhanced the
ð þ1 quantum capacitance of graphene.122 The Si, S and P-doped
diff dQ
CQ ¼ ¼ e2 DOSFT ðE  mÞdE (15) graphene along with the Si–N, S–N, P–N co-doped graphene
dV 1
were also investigated126 using DFT to estimate their quantum
  capacitance. Fig. 5(G and H) shows the enhancement in the
1 2 E
FT ðE Þ ¼ ð4kB T Þ sech (16) quantum capacitance upon doping graphene with foreign
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2kB T
atoms. While the co-doped graphene showed a better enhancement
where FT(E) is the thermal broadening function, E is the relative over a wider range of applied potentials, single atom-doped
energy with respect to the Fermi level, and m is the electrochemical graphene showed enhancement for limited parts of the applied
potential. For pristine graphene, while ignoring temperature, potential, depending on the type of the doped atom.126
Cdiff
Q can be calculated as:
120,122

diff dQ gs gv V. Combined classical & electronic

CQ ¼ ¼ e2 jmj (17)
dV 2pðhVF Þ2
where gs is the spin degeneration (=2), gv is the valley degeneration
(=2), and VF is the Fermi velocity of carriers (B108 cm s1). One the
other hand, the most important parameter for supercapacitor
applications is the total energy storage capacity, which represents
the effective storage capacity per unit of applied potential.
The energy storage capacity relies on the integrated quantum
capacitance (Cint
Q ) instead of the differential quantum capacitance
(Cdiff
Q ), which is the differential quantum capacitance integrated over
the charge/discharge cycle using eqn (18), assuming equilibrium in
the slow charge/discharge process.120,121,126 Calculations of the
quantum capacitance are considered with respect to the Fermi level
of the working electrode material instead of a reference electrode,
which can be considered as the potential at the point of zero charge
(PZC). The total charge storage capacity of an electrode at a given
charging potential can be calculated as the Cint
Q multiplied by that
given potential.120
ð
Q 1 V
int
CQ ¼ ¼ CQ ðV 0 ÞdV 0 (18)
V Ve 0
Quantum capacitance calculations have been widely used to
guide researchers to enhance the performance of graphene-
based electrodes.120,122,128 Wood et al.120 used the DFT (GGA)
method to design highly performing graphene-based electrodes
with high capacitance. The study focused on calculating the
integrated quantum capacitance while applying different types
of defects, local strains, and curvatures on graphene as pre-
sented in Fig. 5(A). It was shown that defects can improve the
capacitance if provided above certain concentrations.120 The
quantum capacitance of graphene oxide that has epoxy and
hydroxyl groups on its basal plane was studied by Song et al.121
to show the possible enhancement in graphene capacitance.
The study showed that the oxygen-containing groups shifted
DFT
Although quantum capacitance calculated using DFT models
can be used to screen different materials, it is not enough to
predict the total interfacial capacitance. The interfacial capacitance
depends on both the EDL capacitance and the quantum capaci-
tance as presented by eqn (13), where the electrolyte effect should
also be considered. Therefore, researchers have been using
separate methods to calculate the EDL capacitance and the
quantum capacitance, adding the two together to get the total
capacitance.7,125,129 A new model, known as joint density
functional theory (JDFT), has recently been developed130 to
self-consistently account for the electrode/electrolyte interface.
JDFT treats the electrode material electronically while treating
the electrolyte classically. The equilibrium state can be achieved
through minimization of the total free energy:3
AJDFT[n,{Na},V(r)] = AHK[n] + Alq[{Na}] + DA[n,{Na},V(r)] (19)
where AHK is the electronic energy functional from the Hohenberg–
Kohn theorems, Alq is the classical density functional of the liquid
free energy, and DA is the coupling energy related to the interaction
between the electrode and the electrolyte.
A. Predicting the total capacitance of an EDL capacitor
The capacitance of graphene in an electrochemical cell
was modeled using JDFT in different electrolytes at different
concentrations.131 The total capacitance of the electrochemical
cell (CJDFT
T ) was computed using eqn (20). The JDFT showed a
great demonstration of the Dirac shift in graphene with the
applied potential and proved to give good insights into the
capacitance performance of graphene.
q=s
CTJDFT ¼ (20)
e  ePZC

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Fig. 5 (A) Calculated integrated quantum capacitances of graphene and defected graphene upon addition of different point defects at a defect concentration
of one defect per 54 carbon atoms,120 with permission from the American Chemical Society, copyright 2014. (B) Calculated quantum capacitances of graphene
(Gr), epoxy functionalized graphene (–O–) and hydroxyl functionalized graphene (–OH),121 with permission from John Wiley & Sons, copyright 2018.
(C) Calculated stored charges of graphene (Gr), epoxy functionalized graphene (–O–) and hydroxyl functionalized graphene (–OH),121 with permission from
John Wiley & Sons, copyright 2018. (D) DOS (spin up, spin down and total) of the dangling bond C of graphene with different single-vacancy concentrations:
(a) 1.4%, cell (6  6), (b) 3.1%, cell (4  4), (c) 5.6%, cell (3  3), and (d) 12.5%, cell (2  2),122 with permission from the American Chemical Society, copyright 2016.
(E) Calculated quantum capacitances of defected graphene with different single-vacancy concentrations,122 with permission from the American Chemical
Society, copyright 2016. (F) Trend chart of the maximum of CQ for different vacancy concentrations,122 with permission from the American Chemical Society,
copyright 2016. (G) Calculated quantum capacitances for doped graphene,126 with permission from the American Chemical Society, copyright 2015. (H)
Calculated quantum capacitances for N-co-doped graphene,126 with permission from the American Chemical Society, copyright 2015.

where q is the amount of excess electrons, s is the area of
graphene in the cell, e is the applied potential, and ePZC is the
potential of zero charge.131 The quantum capacitance and the
total capacitance were calculated with respect to the number of
graphene layers to show the nature of graphene capacitance.132
While the quantum capacitance was calculated using the JDFT
method with the PCM solvation model, the EDL capacitance
was calculated using the CGDFT model with the ionic liquid
modeled as a mixture of charged hard spheres. The resulting
quantum capacitance with respect to the applied potential in a
vacuum is presented in Fig. 6(A) and in 1 M NaF electrolyte in
Fig. 6(B). The results show that the higher the number of
graphene layers, the higher the quantum capacitance. Fig. 6(C)
shows the change in surface charge density (the EDL charge, the
quantum charge, and the total charge) over the applied voltage
for single layer graphene. It was found that the total charge is
more affected by the quantum charge than by the EDL charge.
The calculated differential capacitance of total charge in 1 M NaF
(Fig. 6(D)) shows a symmetric behavior in both positive and negative
potentials. The study showed that by increasing the number of
graphene layers, the quantum capacitance contributes less towards
the total capacitance than the EDL capacitance as shown in Fig. 6(E).

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Fig. 6 Computed capacitance performance of layered graphene using the JDFT model. (A) Quantum capacitances of different numbers of layers of
graphene in a vacuum. (B) Quantum capacitances of different numbers of layers of graphene in 1 M NaF electrolyte. (C) Calculated surface charge
densities for single layer graphene in 1 M NaF electrolyte. (D) Calculated total differential capacitance over the applied voltage for single layer graphene in
1 M NaF electrolyte. (E) Comparative chart of the origin of capacitance relative to the number of layers of graphene. (F) Calculated capacitance in an
aqueous electrolyte vs. that in an ionic liquid,132 with permission from the American Chemical Society, copyright 2015.

The study also compared the ionic liquid effect with that of an
aqueous electrolyte (Fig. 6(F)), revealing the preference of the aqu-
eous electrolyte especially for higher layered graphene.132
Although the total capacitance calculated for single layer
graphene matches the experimental values, few layered gra-
phene modeling was not very accurate.9 JDFT also allows the
study of the contribution of the dielectric screening of the
electric field of the layered material named the dielectric
capacitance (CDielec).9,133 Zahan et al. used JDFT with the LPCM
solvation model to investigate the origin of the deviation in the
total capacitance values of the few layered graphene.9 The study
of the CQ and CDL of few-layered graphene and multi-layered Pt
revealed the presence of a third term dissident from the EDL
term due to the dielectric response of the electrode. Thus, the
total capacitance based on the three terms can be presented as:
1 1 1 1
¼ þ þ (21)
CT CQ CDL CDielec
The results showed that by increasing the number of layers,
the quantum contribution decreases, and the contribution of

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the dielectric effect increases with the EDL remaining constant. This
explains the minor change in real capacitance for a larger number of
layers.9 JDFT is not only useful for graphene modeling, but was also
successfully used to model 2D boron sheets as a promising super-
capacitor material.10 The boron sheets were modeled in a potential
window from 1 V to 1 V using the CANDLE solvation model. The
results showed that the calculated specific capacitance is three to
four times higher than that of graphene due to the metallic nature
and high DOS of boron, suggesting its promising performance as a
supercapacitor electrode.10 The JDFT was also used to shed light on
the possibility of modeling bare metal electrodes.134 The study used
JDFT with the non-linear continuum solvation model to calculate the
capacitance of a bare Pt electrode and a Pt with adsorbed carbon
monoxide (Pt–CO) electrode. The results showed that the Pt–CO
electrode has its capacitance divided into the capacitance of the
metal region (Cm), the capacitance of the diffuse region of the
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electrolyte (Cd), the gap capacitance (Cg) which resulted from a gap
formed between the electrolyte ions and the terminal O, and the
adlayer capacitance (Ca) between the metal region and the gap
region. The capacitance of a metallic electrode thus follows
eqn (22).134 The results unveiled the reasons behind the decrease
of capacitance of the metal with the adsorbed oxygenated group.
1 1 1 1 1
¼ þ þ þ (22)
CT Cm Cd Cg Ca
B. Predicting the total capacitance of a pseudocapacitor
Quantum capacitance does not take pseudocapacitance into
account, resulting in inaccurate results especially for materials
with high pseudocapacitive behavior. JDFT was used by Zahan
et al. to investigate the origin of the capacitance of hydrated RuO2.8
One of the mysteries of RuO2 electrochemical performance is the
appearance of redox peaks at slow scan rates in the potential
window 0.1–0.4 V, which completely disappear at high scan rates.
Although the pseudocapacitance of RuO2 was studied using DFT,
the calculations did not take the adsorption and intercalation with
electrolyte molecules into account. The study used JDFT with the
LPCM solvation model to quantify the pseudocapacitance of RuO2
in acidic medium.8 The study suggested competitive mechanisms
between the low scan behavior and the high scan behavior. At low
scan rates, the study suggests a thermodynamic equilibrium where
the charge storage mechanism is thermodynamically dominated.
To predict the capacitive behavior, the authors suggested that
during the charging process there would be an EDL energy (EEDL)
and a hydrogen adsorption energy (EH). The EEDL was defined as
the energy drop occurring due to the formation of an EDL
neutralizing the surface charge as in eqn (23):8
ð V2
EEDL ¼  CDL VdV (23)
V1
where V1 and V2 are the chemical potential shifts. The EH is
defined as the hydrogen adsorption energy of one hydrogen atom
and given by:8
1 calculations, one can obtain the parameters in eqn (32) and
EH ¼ ESubþH  ESub  EH2 þ DZPE (24)
2 hence the other terms in eqn (27), giving insights into the charge
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where ESub+H is the total energy of H adsorbed and the substrate,
ESub is the total energy of the bare substrate, and DZPE is the
difference in the zero-point energy of hydrogen on the substrate
and that of the H2 molecule. For nH atoms adsorbed, the H
adsorption energy EH(n) is defined by:8
1
EH ðnÞ ¼ ESubþðnþ1ÞH  ESubþnH  EH2 þ DZPE (25)
2
comparing the nH adsorption energy and the EDL energy,
the charge storage mechanism can be unveiled.
For the non-linear faradaic process, such as in MXene
electrodes, where there is non-equal proton and electron transfer
in the electrochemical system, some modifications should be
applied to model the system using JDFT.26,118 In acidic electro-
lytes, MXenes exhibit a pseudocapacitive behavior; however, the
mechanism was not well understood. JDFT was successfully used
to explain the origin of the charge storage mechanism of MXenes
in acidic medium.26 Zhan et al. provided a modified model to
give insights into the EDL and pseudocapacitive mechanisms
occurring on Ti3C2O2 in H2SO4 following the chemical equation:
0
Ti3C2O2q + 2H+(aq) - Ti3C2O22x(OH)2xq + 2(1  x)H+(aq)
(26)
where x represents the surface H coverage that is between 0
and 1, while q and q 0 are the net charges on the electrode. The
applied voltage usually controls both the x and q values since at
a fixed potential the partially protonated MXene surface can
obtain a net charge when the electrode potential (j) is different
from the PZC. Thus, the free energy of the electrode can be
expressed by:26
G(x,j) = E(x) + xEZPE + Q(V(x,j)) + EEDL(V(x,j)) + (1  x)mH+
(27)
V(x,j) = j  jPZC(x) (28)
ð V¼jjPZC ðxÞ
Qðx; jÞ ¼ CDL dV (29)
V¼0
ð V¼jjPZC ðxÞ
EEDL ðx; jÞ ¼ Qðx; jÞdV (30)
V¼0
1
mHþ ¼ G½H2  þ efSHE  0:059pH (31)
2
7
G½H2  ¼ E ½H2  þ ZPE½H2  þ kB T  TSH2 (32)
2
where E(x) is the total electronic energy of the electrode with the
H coverage of x in zero surface charge, EZPE is the zero-point energy
(ZPE) difference between x = 0 and 1 states, V(x,j) is the relative
potential with respect to the PZC at coverage x and electrode
potential j, Qj is the electrical work to move the charge Q (the
electrode charge) from zero potential to the potential j, EEDL is the
energy of the EDL generated by the electrode charge Q, mH+ is the
chemical potential of a solvated proton in the electrolyte, and fSHE
is the standard hydrogen electrode potential.26 Employing DFT
Phys. Chem. Chem. Phys.

Perspective
Fig. 7 (A) Charge density change of the Ti3C2Tx electrode after charging from a neutral surface at 0.44 H coverage,26 with permission from the American
Chemical Society, copyright 2018, and (B) calculated charge stored on the Ti3C2Tx surface at different electrode potentials; faradaic charge (balance
proton transfer), EDL charge (balance the surface net charge), and total charge (net electron transfer number),26 with permission from the American
Published on 16 July 2019. Downloaded on 8/3/2019 6:48:00 PM.
Chemical Society, copyright 2018.
transferred due to the EDL and due to the redox reaction. The
study assumed two extreme cases, full or no coverage of H atoms
on surfaces with x = 1 and 0, respectively. Fig. 7(A) presents the
charge density of the 0.44 coverage of H on the surface of the
studied MXene. The total charge was calculated to investigate
the origin of the charge stored when compared with the surface
net charge as presented in Fig. 7(B). The study showed that in
the potential window between 0.5 V and 1 V vs. SHE, the
proton transfer from H2SO4 to the MXene was 0.6e, while the
electron transfer to the MXene from the applied voltage was
0.4e, resulting in a net charge of 0.2e on the surface per unit formula
of MXene. Thus, the dominated charge storage mechanism is
the redox process, while the EDL mechanism works against the
redox process.26
VI. Summary & outlook
In this review, the different charge storage mechanisms in
supercapacitor electrodes were summarized. Also, the use of
DFT to predict the origin of the charge storage mechanism and
calculate the capacitive properties of the electrode material was
explained. The review discussed the modelling of electrode
materials in terms of classical DFT (cDFT) and electronic DFT
(eDFT). For porous 3D or 2D carbon materials, it is important to
identify the porous structure, the pore size, and the pore volume.21,31
cDFT was shown to give insights into porous structure from the
predicted isotherm using QSDFT and NSDFT.45–47 While NSDFT was
shown to give accurate results for microporous and smooth surfaces,
QSDFT is more efficient for mesoporous and microporous
structures.35 The combination of the two methods is better used
for materials with inhomogeneous pores. For carbon materials with
nanopores with sizes 1 nm or lower, it is better to use CO2 gas for the
isotherm calculation. However, the pore shape of the carbon
material should also be considered to indicate the accurate results
of the material. While the double slit can be used for microporous
materials, for mesoporous or microporous structures the curvature
Phys. Chem. Chem. Phys.
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PCCP
should be considered and other pore structures should be used.38,48
The EDL capacitance can be estimated through the consideration of
the electrode/electrolyte interaction using CGDFT to model the
surface charge. The CGDFT was able to model the capacitance
of the OLC electrode in EMI-BF4/EMI-TFSI electrolyte to give
5–8 mF cm2 device capacitance, which is in a good agreement
with the experimental value of 6 mF cm2.56 By applying
thermodynamics to DFT (TD-DFT), it is possible to predict
the ion dynamics at the electrode/electrolyte interface and the
charging kinetics, which reflects the power density of the
electrode material.64–66 In cDFT, the usual solvation models
are the classical Helmholtz model, the classical Gouy–Chapman
model, and the classical Stern model. The latter is considered to
be the more accurate model for supercapacitor applications.5
However, for cDFT, the correct pore structure should be used in
the calculations and the accuracy of the calculations will be poor
for aqueous electrolytes as the EDL will not depend on the pore
structure anymore. Besides, for low conductivity materials, the
quantum effect will have a major role in controlling the EDL
capacitance and better models that account for the electronic
distribution should be used.
cDFT is limited to predicting the capacitance of EDL-based
materials and it does not include any electronic treatment,
hence ignoring the faradaic behavior of the electrode material.
However, eDFT can give some insights into the faradaic properties
along with the EDL properties of the electrode material. One of the
most important characteristics of the electrode material is its
conductivity, which can be easily and accurately predicted using
eDFT, and it can be calculated for both faradaic and non-faradaic
materials.105–107 Also, the permittivity of the electrode material can
be estimated through eDFT, giving an indication of the distinction
of some materials over others for electronic applications.19 The
binding energy between the electrolyte ions and the electrode
material can also be predicted, indicating the possibility of inter-
calation or an EDL. eDFT can accurately estimate the electrode
atom–electrolyte ion binding energy.109 Moreover, DFT can be
used to calculate the electrical potential window beyond which
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Fig. 8 Roadmap to the use of DFT to unveil the supercapacitor electrode performance.
the electrolyte will dissociate and gives insights into the stability
of the electrode material itself upon exposure to the applied
potential.111,112 The defect states and extra states available for
occupation by electrons are always an indication of possible
intercalation, and hence a pseudocapacitive behavior.25 Thus,
using eDFT to predict the DOS could help in predicting the
charge storage mechanism. In addition, the thermodynamic
treatment of the eDFT results can be a good tool for predicting
the origin of the pseudocapacitive behavior as well.116
The prediction of the capacitance value can also be achieved
using eDFT only or using a combination of both eDFT and
cDFT. eDFT can predict the quantum capacitance based on the
DOS of the electrode material.120,121 The quantum capacitance
can be accurately calculated for 2D single layered or multi-
layered materials that do not undergo faradaic processes, with
results close to experimental values.121,122,135 The quantum
capacitance can be used to predict the doping effect and the
defect effect in graphene-based electrodes. However, for materials
that undergo faradaic processes, such as MnWO4, the quantum
capacitance is poor to predict the real capacitance. The Cq of
MnWO4 was predicted to be 762 mF cm2, while the experimental
value was 256 F g1 at 0.4 A g1. This overestimation may be due to
the resistance of the other components in the supercapacitor cell
or due to the inaccuracy of the eDFT due to the inclusion of the d
orbitals in the DOS calculations.136 The combination of the
continuum solvation models with the eDFT and the inclusion of
the EDL capacitance in the total capacitance calculations have
been the target for the ultimate prediction of the capacitive
performance of electrode materials. The JDFT model can give
information about the quantum capacitance by treating the elec-
trode material using eDFT and give information about the EDL
capacitance by treating the electrode material using cDFT.3 JDFT
showed a good capacitance prediction for layered graphene
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Perspective
electrode materials.132,133 However, for metals with adsorbed
molecules, some modifications should be made to the calculations.
JDFT was used to model both Pt and Pt–CO after adding the
metal region capacitance, the gap capacitance and the adlayer
region capacitance to the calculations. The results showed the
same trend as the experimental ones, with the calculated
capacitances (27 and 9 mF cm2 for Pt and Pt–CO, respectively)
shifted from the experimental values (70 and 11 mF cm2), with
the shift being larger for the bare metal.134 JDFT depends on
the combination of quantum capacitance and EDL capacitance.
However, the quantum capacitance ignores the faradaic effect.
Thus, modifications have been applied to model and under-
stand the pseudocapacitive effect of electrode materials.8,26
However, there is no universal model for identifying the charge
storage mechanism for all materials, which should be the target
in the near future. Fig. 8 summarizes the possible properties
that can be predicted using DFT calculations. In summary,
DFT (cDFT, eDFT or JDFT) can give a good prediction of the
distinction of the electrode material. However, more modifications
should be applied to predict the pseudocapacitive behavior and the
battery-like behavior of electrode materials. Moreover, the road-
map can be extended to other applications such as catalysis137
and fuel cells.138
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Support for this work by The American University in Cairo
is gratefully acknowledged. Basant Ali is supported by an
Allehedan Endowed Scholarship.
Phys. Chem. Chem. Phys.

Perspective
References
1 J. J. W. McDouall, Computational Quantum Chemistry:
Molecular Structure and Properties In Silico. RSC Theoretical
and Computational Chemistry Series, Royal Society of Chem-
istry, 2013.
2 Y. Wang, Y. Song and Y. Xia, Chem. Soc. Rev., 2016, 45,
5925–5950.
3 C. Zhan, C. Lian, Y. Zhang, M. W. Thompson, Y. Xie, J. Wu,
P. R. C. Kent, P. T. Cummings, D. E. Jiang and D. J.
Wesolowski, Adv. Sci., 2017, 4, 1700059.
4 G. Jeanmairet, N. Levy, M. Levesque and D. Borgis, J. Chem.
Educ., 2014, 91, 2112–2115.
5 S. Maheshwari, Y. Li, N. Agrawal and M. J. Janik, Density
Functional Theory Models for Electrocatalytic Reactions, Elsevier
Inc., 2018.
Published on 16 July 2019. Downloaded on 8/3/2019 6:48:00 PM.
6 C. Lian and H. Liu, Classical Density Functional Theory
Insights for Supercapacitors, Supercapacitors – Theoretical and
Practical Solutions, Lionginas Liudvinavičius, IntechOpen,
2018, DOI: 10.5772/intechopen.76339.
7 E. Paek, A. J. Pak and G. S. Hwang, J. Electrochem. Soc.,
2013, 160, A1–A10.
8 C. Zhan and D. E. Jiang, J. Phys.: Condens. Matter, 2016,
28, 464004.
9 C. Zhan and D. E. Jiang, J. Phys. Chem. Lett., 2016, 7,
789–794.
10 C. Zhan, P. Zhang, S. Dai and D. E. Jiang, ACS Energy Lett.,
2016, 1, 1241–1246.
11 S. Zhang and N. Pan, Adv. Energy Mater., 2015, 5, 1–19.
12 C. Zhong, Y. Deng, W. Hu, J. Qiao, L. Zhang and J. Zhang,
Chem. Soc. Rev., 2015, 44, 7484–7539.
13 B. A. Ali, O. I. Metwalli, A. S. G. Khalil and N. K. Allam, ACS
Omega, 2018, 3, 16301–16308.
14 Y. Gogotsi and R. M. Penner, ACS Nano, 2018, 12, 2081–2083.
15 F. M. Ismail, M. Ramadan, A. M. Abdellah, I. Ismail and
N. K. Allam, J. Electroanal. Chem., 2018, 817, 111–117.
16 N. Ahmed, B. A. Ali, M. Ramadan and N. K. Allam, ACS
Appl. Energy Mater., 2019, 25, 3717–3725.
17 M. Ramadan, A. M. Abdellah, S. G. Mohamed and N. K.
Allam, Sci. Rep., 2018, 8, 7988.
18 A. Jain, Y. Shin and K. A. Persson, Nat. Rev. Mater., 2016, 1, 1–13.
19 V. Sharma, C. Wang, R. G. Lorenzini, R. Ma, Q. Zhu, D. W.
Sinkovits, G. Pilania, A. R. Oganov, S. Kumar and G. A. Sotzing,
et al., Nat. Commun., 2014, 5, 4845.
20 Y. Chen, X. Zhang, D. Zhang, P. Yu and Y. Ma, Carbon,
2011, 49, 573–580.
21 R. Lin, P. Huang, J. Ségalini, C. Largeot, P. L. Taberna,
J. Chmiola, Y. Gogotsi and P. Simon, Electrochim. Acta,
2009, 54, 7025–7032.
22 T. Brousse, D. Belanger and J. W. Long, J. Electrochem. Soc.,
2015, 162, A5185–A5189.
23 R. Lin, P.-L. Taberna, S. Fantini, V. Presser, C. R. Pérez,
F. Malbosc, N. L. Rupesinghe, K. B. K. Teo, Y. Gogotsi and
P. Simon, J. Phys. Chem. Lett., 2011, 2, 2396–2401.
24 X. Wang, Y. Li, F. Lou, M. E. Melandsø Buan, E. Sheridan
and D. Chen, RSC Adv., 2017, 7, 23859–23865.
Phys. Chem. Chem. Phys.
View Article Online
PCCP
25 J. Li, J. O’Shea, X. Hou and G. Z. Chen, Chem. Commun.,
2017, 53, 10414–10417.
26 C. Zhan, M. Naguib, M. Lukatskaya, P. R. C. Kent,
Y. Gogotsi and D. E. Jiang, J. Phys. Chem. Lett., 2018, 9,
1223–1228.
27 N. D. Mermin, Phys. Rev., 1965, 137, A1441–A1443.
28 R. Evans, Adv. Phys., 1979, 28, 143–200.
29 M. Oschatz, S. Boukhalfa, W. Nickel, J. P. Hofmann, C. Fischer,
G. Yushin and S. Kaskel, Carbon, 2017, 113, 283–291.
30 J. N. Caguiat, D. W. Kirk and C. Q. Jia, Carbon, 2014, 72,
47–56.
31 C. Lu, D. Wang, J. Zhao, S. Han and W. Chen, Adv. Funct.
Mater., 2017, 27, DOI: 10.1002/adfm.201606219.
32 R. Evans, U. M. B. Marconi and P. Tarazona, J. Chem. Phys.,
1986, 84, 2376–2399.
33 R. Evans, U. M. B. Marconi and P. Tarazona, J. Chem. Soc.,
Faraday Trans. 2, 1986, 82, 1763–1787.
34 R. Evans and P. Tarazona, Phys. Rev. Lett., 1984, 52, 557–560.
35 J. Landers, G. Y. Gor and A. V. Neimark, Colloids Surf., A,
2013, 437, 3–32.
36 P. Tarazona, Phys. Rev. A: At., Mol., Opt. Phys., 1985, 31,
2672–2679.
37 Y. Rosenfeld, Phys. Rev. Lett., 1989, 63, 980–983.
38 M. Rose, Y. Korenblit, E. Kockrick, L. Borchardt, M. Oschatz,
S. Kaskel and G. Yushin, Small, 2011, 7, 1108–1117.
39 D.-W. Wang, F. Li, M. Liu, G. Q. Lu and H.-M. Cheng,
Angew. Chem., Int. Ed., 2008, 120, 379–382.
40 A. Jänes, H. Kurig and E. Lust, Carbon, 2007, 45, 1226–1233.
41 L. Sun, C. Tian, M. Li, X. Meng, L. Wang, R. Wang, J. Yin
and H. Fu, J. Mater. Chem. A, 2013, 1, 6462–6470.
42 J. K. McDonough, A. I. Frolov, V. Presser, J. Niu,
C. H. Miller, T. Ubieto, M. V. Fedorov and Y. Gogotsi,
Carbon, 2012, 50, 3298–3309.
43 W. Y. Tsai, R. Lin, S. Murali, L. Li Zhang, J. K. McDonough,
R. S. Ruoff, P. L. Taberna, Y. Gogotsi and P. Simon, Nano
Energy, 2013, 2, 403–411.
44 S. Kondrat, C. R. Pérez, V. Presser, Y. Gogotsi and
A. A. Kornyshev, Energy Environ. Sci., 2012, 5, 6474–6479.
45 Y. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. Cai,
P. J. Ferreira, A. Pirkle, R. M. Wallace, K. A. Cychosz and
M. Thommes, et al., Science, 2011, 332, 1537–1541.
46 J. E. Zuliani, S. Tong, C. Q. Jia and D. W. Kirk, J. Power
Sources, 2018, 395, 271–279.
47 R. Yan, M. Antonietti and M. Oschatz, Adv. Energy Mater.,
2018, 8, 1–12.
48 J. Huang, B. G. Sumpter and V. Meunier, Chem. – Eur. J.,
2008, 14, 6614–6626.
49 J. Huang, B. G. Sumpter and V. Meunier, Angew. Chem., Int.
Ed., 2008, 47, 520–524.
50 C. Largeot, C. Portet, J. Chmiola, P. L. Taberna, Y. Gogotsi
and P. Simon, J. Am. Chem. Soc., 2008, 130, 2730–2731.
51 J. Chmiola, G. Yushin, Y. Gogotsi, C. Portet, P. Simon and
P. L. Taberna, Science, 2006, 313, 1760–1763.
52 D. E. Jiang, Z. Jin and J. Wu, Nano Lett., 2011, 11, 5373–5377.
53 D. E. Jiang, Z. Jin, D. Henderson and J. Wu, J. Phys. Chem.
Lett., 2012, 3, 1727–1731.
This journal is © the Owner Societies 2019

PCCP
54 D. E. Jiang and J. Wu, J. Phys. Chem. Lett., 2013, 4, 1260–1267.
55 A. A. Lee, S. Kondrat and A. A. Kornyshev, Phys. Rev. Lett.,
2014, 113, 5151–5160.
56 C. Lian, K. Liu, K. L. Van Aken, Y. Gogotsi, D. J.
Wesolowski, H. L. Liu, D. E. Jiang and J. Z. Wu, ACS Energy
Lett., 2016, 1, 21–26.
57 N. C. Osti, A. Gallegos, B. Dyatkin, J. Wu, Y. Gogotsi and
E. Mamontov, J. Phys. Chem. C, 2018, 122, 10476–10481.
58 C. Lian, D. E. Jiang, H. Liu and J. Wu, J. Phys. Chem. C,
2016, 120, 8704–8710.
59 X. Wang, A. Y. Mehandzhiyski, B. Arstad, K. L. Van Aken,
T. S. Mathis, A. Gallegos, Z. Tian, D. Ren, E. Sheridan and
B. A. Grimes, et al., J. Am. Chem. Soc., 2017, 139, 18681–18687.
60 J. N. Neal, D. J. Wesolowski, D. Henderson and J. Wu,
J. Chem. Phys., 2017, 146, 174701.
61 J. N. Neal, D. J. Wesolowski, D. Henderson and J. Wu,
Published on 16 July 2019. Downloaded on 8/3/2019 6:48:00 PM.
J. Mol. Liq., 2018, 270, 145–150.
62 C. Lian, K. Liu, H. Liu and J. Wu, J. Phys. Chem. C, 2017,
121, 14066–14072.
63 Y. Qiao, C. Lian, B. Lu and J. Wu, Chem. Phys. Lett., 2018,
709, 116–124.
64 J. Jiang, D. Cao, D. E. Jiang and J. Wu, J. Phys.: Condens.
Matter, 2014, 26, 284102.
65 J. Jiang, D. Cao, D. E. Jiang and J. Wu, J. Phys. Chem. Lett.,
2014, 5, 2195–2200.
66 C. Lian, S. Zhao, H. Liu and J. Wu, J. Chem. Phys., 2016,
145, DOI: 10.1063/1.4968037.
67 P. Hohenberg and W. Kohn, Phys. Rev., 1964, 136, B864–B871.
68 W. Kohn and L. J. Sham, Phys. Rev., 1965, 140, A1133–A1138.
69 K. Burke and L. O. Wagner, Int. J. Quantum Chem., 2013,
113, 96–101.
70 N. Mardirossian and M. Head-Gordon, Mol. Phys., 2017,
115, 2315–2372.
71 D. S. Sholl and J. A. Steckel, Density Functional Theory; a
Practical Introduction, John Wiley & Sons, Inc., Wiley,
Canada, 2009.
72 S. A. Tolba, K. M. Gameel, B. A. Ali, H. A. Almossalami and
N. K. Allam, Density Functional Calculations – Recent Progresses
of Theory and Application, InTech, 2018, pp. 3–30.
73 K. Kim and K. D. Jordan, J. Phys. Chem., 1994, 98, 10089–10094.
74 B. A. Ali and N. K. Allam, Spectrochim. Acta, Part A, 2018,
188, 237–243.
75 W. Sharmoukh, Z. M. Hassan, B. A. Ali, M. M. Elnagar,
R. M. Abdo and N. K. Allam, J. Photochem. Photobiol., A,
2018, 367, 128–136.
76 B. A. Ali, W. Sharmoukh, M. M. Elnagar, Z. M. Hassan and
N. K. Allam, Appl. Organomet. Chem., 2018, e4677.
77 G. R. Schleder, A. C. M. Padilha, C. M. Acosta, M. Costa and
A. Fazzio, J. Phys. Mater., 2019, 2, 032001.
78 J. Klimeš and A. Michaelides, J. Chem. Phys., 2012, 137, 120901.
79 A. D. Becke, J. Chem. Phys., 2014, 140, 18–301.
80 R. O. Jones, Rev. Mod. Phys., 2015, 87, DOI: 10.1103/
RevModPhys.87.897.
81 J. Carrasco, J. Phys. Chem. C, 2014, 118, 19599–19607.
82 Z. Wang, S. M. Selbach and T. Grande, RSC Adv., 2014, 4,
4069–4079.
This journal is © the Owner Societies 2019
View Article Online
Perspective
83 A. Lozano, B. Escribano, E. Akhmatskaya and J. Carrasco,
Phys. Chem. Chem. Phys., 2017, 19, 10133–10139.
84 S. Grimme, J. Comput. Chem., 2004, 25, 1463–1473.
85 S. Grimme, J. Comput. Chem., 2006, 27, 1787–1799.
86 M. Hasegawa and K. Nishidate, Phys. Rev. B: Condens.
Matter Mater. Phys., 2004, 70, 205431.
87 H. Rydberg, M. Dion, N. Jacobson, E. Schröder, P. Hyldgaard,
S. I. Simak, D. C. Langreth and B. I. Lundqvist, Phys. Rev. Lett.,
2003, 91, 126402.
88 H. Rydberg, B. I. Lundqvist, D. C. Langreth and M. Dion, Phys.
Rev. B: Condens. Matter Mater. Phys., 2000, 62, 6997–7006.
89 D. C. Langreth, M. Dion, H. Rydberg, E. Schröder, P. Hyldgaard
and B. I. Lundqvist, Int. J. Quantum Chem., 2005, 101, 599–610.
90 R. Sundararaman, K. Letchworth-Weaver and K. A. Schwarz,
J. Chem. Phys., 2018, 148, DOI: 10.1063/1.5024219.
91 R. Sundararaman and K. Schwarz, J. Chem. Phys., 2017,
146, DOI: 10.1063/1.4976971.
92 N. Keilbart, Y. Okada, A. Feehan, S. Higai and I. Dabo,
Phys. Rev. B: Condens. Matter Mater. Phys., 2017, 95, 1–8.
93 K. Mathew, R. Sundararaman, K. Letchworth-Weaver, T. A.
Arias and R. G. Hennig, J. Chem. Phys., 2014, 140, 084106.
94 K. Letchworth-Weaver and T. A. Arias, Phys. Rev. B: Con-
dens. Matter Mater. Phys., 2012, 86, 1–16.
95 K. Letchworth-Weaver, T. A. Arias, K. A. Schwarz,
R. Sundararaman and D. Gunceler, Model. Simul. Mater.
Sci. Eng., 2013, 21, 074005.
96 R. Sundararaman and W. A. Goddard, J. Chem. Phys., 2015,
142, 064107.
97 O. Andreussi, I. Dabo and N. Marzari, J. Chem. Phys.,
American Institute of Physics, 2012, p. 064102.
98 R. Jinnouchi and A. B. Anderson, Phys. Rev. B: Condens.
Matter Mater. Phys., 2008, 77, 245417.
99 J. N. Andrzej Wieckowski, Fuel Cell Science: Theory, Funda-
mentals, and Biocatalysis, Google Books, Wiley, 2010.
100 G. Fisicaro, L. Genovese, O. Andreussi, S. Mandal, N. N.
Nair, N. Marzari and S. Goedecker, J. Chem. Theory Comput.,
2017, 13, 3829–3845.
101 M. Otani and O. Sugino, Phys. Rev. B: Condens. Matter
Mater. Phys., 2006, 73, 115407.
102 S. A. Petrosyan, A. A. Rigos and T. A. Arias, J. Phys. Chem. B,
2005, 109, 15436–15444.
103 S. A. Petrosyan, J. F. Briere, D. Roundy and T. A. Arias, Phys.
Rev. B: Condens. Matter Mater. Phys., 2007, 75, 205105.
104 M. J. Young, A. M. Holder and C. B. Musgrave, Adv. Funct.
Mater., 2018, 28, 1–19.
105 G. Xiong, K. P. S. S. Hembram, R. G. Reifenberger and
T. S. Fisher, J. Power Sources, 2013, 227, 254–259.
106 B. Song, J. Zhao, M. Wang, J. Mullavey, Y. Zhu, Z. Geng,
D. Chen, Y. Ding, K. Sik Moon and M. Liu, et al., Nano
Energy, 2017, 31, 183–193.
107 S. Yang, Y. Liu, Y. Hao, X. Yang, W. A. Goddard III,
X. L. Zhang and B. Cao, Adv. Sci., 2018, 5, 1700659.
108 J. Yoo, S. Byun, C. W. Lee, C. Y. Yoo and J. Yu, Chem.
Mater., 2017, 30, 3979–3990.
109 F. M. Hassan, V. Chabot, J. Li, B. K. Kim, L. Ricardez-
Sandoval and A. Yu, J. Mater. Chem. A, 2013, 1, 2904–2912.
Phys. Chem. Chem. Phys.

Perspective
110 B. S. Shaheen, A. M. Hafez, B. Murali, A. R. Kirmani,
A. Amassian, O. F. Mohammed and N. K. Allam, Sol. Energy
Mater. Sol. Cells, 2016, 151, 149–153.
111 S. P. Ong, O. Andreussi, Y. Wu, N. Marzari and G. Ceder,
Chem. Mater., 2014, 23, 1–28.
112 C. Lian, H. Liu and J. Wu, J. Phys. Chem. C, 2018, 122,
18304–18310.
113 X. Yang, Z. Qiao, F. Liu, S. Yang, L. Zhang and B. Cao,
Electrochim. Acta, 2018, 280, 77–85.
114 Z. Yin, Y. Bu, J. Ren, S. Chen, D. Zhao, Y. Zou, S. Shen and
D. Yang, Chem. Eng. J., 2018, 345, 165–173.
115 T. Deng, W. Zhang, O. Arcelus, J. G. Kim, J. Carrasco,
S. J. Yoo, W. Zheng, J. Wang, H. Tian and H. Zhang, et al.,
Nat. Commun., 2017, 8, DOI: 10.1038/ncomms15194.
116 V. Ozolin- š, F. Zhou and M. Asta, Acc. Chem. Res., 2013, 46,
1084–1093.
Published on 16 July 2019. Downloaded on 8/3/2019 6:48:00 PM.
117 H. A. Zakaryan, A. G. Kvashnin and A. R. Oganov, Sci. Rep.,
2017, 7, 1–9.
118 C. Zhan, W. Sun, P. R. C. Kent, M. Naguib, Y. Gogotsi and
D. Jiang, J. Phys. Chem. C, 2019, 123(1), 315–321.
119 S. Kansara, S. K. Gupta, Y. Sonvane, T. Hussain and
R. Ahuja, ACS Appl. Energy Mater., 2018, 1, 3428–3433.
120 B. C. Wood, T. Ogitsu, M. Otani and J. Biener, J. Phys.
Chem. C, 2014, 118, 4–15.
121 C. Song, J. Wang, Z. Meng, F. Hu and X. Jian, Chem-
PhysChem, 2018, 19, 1579–1583.
122 G. M. Yang, H. Z. Zhang, X. F. Fan and W. T. Zheng, J. Phys.
Chem. C, 2015, 119, 6464–6470.
123 Y. Xin and Y. X. Yu, Mater. Des., 2017, 130, 512–520.
124 S. M. Mousavi-Khoshdel and E. Targholi, Carbon, 2015, 89,
148–160.
Phys. Chem. Chem. Phys.
View Article Online
PCCP
125 E. Paek, A. J. Pak, K. E. Kweon and G. S. Hwang, J. Phys.
Chem. C, 2013, 117, 5610–5616.
126 M. Mousavi-Khoshdel, E. Targholi and M. J. Momeni,
J. Phys. Chem. C, 2015, 119, 26290–26295.
127 A. Pathak, A. S. Gangan, S. Ratha, B. Chakraborty and
C. S. Rout, J. Phys. Chem. C, 2017, 121, 18992–19001.
128 A. J. Pak, E. Paek and G. S. Hwang, Carbon, 2014, 68,
734–741.
129 C. Zhan, T. A. Pham, M. R. Cerón, P. G. Campbell,
V. Vedharathinam, M. Otani, D. E. Jiang, J. Biener, B. C.
Wood and M. Biener, ACS Appl. Mater. Interfaces, 2018, 10,
36860–36865.
130 K. Letchworth-Weaver and T. A. Arias, Phys. Rev. B:
Condens. Matter Mater. Phys., 2012, 86, 075140.
131 S. Sun, Y. Qi and T. Y. Zhang, Electrochim. Acta, 2015, 163,
296–302.
132 C. Zhan, J. Neal, J. Wu and D. E. Jiang, J. Phys. Chem. C,
2015, 119, 22297–22303.
133 C. Zhan, Y. Zhang, P. T. Cummings and D.-E. Jiang,
Carbon, 2017, 116, 278–285.
134 R. Sundararaman, M. C. Figueiredo, M. T. M. Koper and
K. A. Schwarz, J. Phys. Chem. Lett., 2017, 8, 5344–5348.
135 A. Srivastava and B. SanthiBhushan, Appl. Nanosci., 2018,
8, 637–644.
136 K. K. Naik, A. S. Gangan, A. Pathak, B. Chakraborty,
S. K. Nayak and C. S. Rout, ChemistrySelect, 2017, 2,
5707–5715.
137 S. A. Tolba and N. K. Allam, Sci. Rep., 2019, 9, 10159.
138 K. M. Gameel, I. M. Sharafeldin, A. U. Abourayya, A. H.
Biby and N. K. Allam, Phys. Chem. Chem. Phys., 2018, 20,
25892–25900.
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