Applied Nanoscience

https://doi.org/10.1007/s13204-018-0643-x

ORIGINAL ARTICLE

Trade‑off between quantum capacitance and thermodynamic stability

of defected graphene: an implication for supercapacitor electrodes
Anurag Srivastava1 · Boddepalli SanthiBhushan1

Received: 13 November 2017 / Accepted: 4 January 2018

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
Defects are inevitable most of the times either at the synthesis, handling or processing stage of graphene, causes significant
deviation of properties. The present work discusses the influence of vacancy defects on the quantum capacitance as well as
thermodynamic stability of graphene, and the nitrogen doping pattern needs to be followed to attain a trade-off between these
two. Density Functional Theory (DFT) calculations have been performed to analyze various vacancy defects and different
possible nitrogen doping patterns at the vacancy site of graphene, with an implication for supercapacitor electrodes. The
results signify that vacancy defect improves the quantum capacitance of graphene at the cost of thermodynamic stability,
while the nitrogen functionalization at the vacancy improves thermodynamic stability and quantum capacitance both. It has
been observed that functionalizing all the dangling carbons at the defect site with nitrogen is the key to attain high thermo-
dynamic stability as well as quantum capacitance. Furthermore, the results signify the suitability of these functionalized
graphenes for anode electrode of high energy density asymmetric supercapacitors.

Keywords Supercapacitor · Graphene · Quantum capacitance · Thermodynamic stability · Defects

Introduction Supercapacitor is an energy storage device with extremely

Graphene, the wonder material is been widely analysed for
enormous applications ranging from electronics, energy stor-
age, and aerospace to radioactive isotope filters. The struc-
tural defects, classified broadly into intrinsic and extrinsic,
are most likely to occur either at synthesis, handling or pro-
cessing stages of graphene, and can have remarkable influ-
ence on its electronic and chemical properties (Banhart et al.
2010; Liu et al. 2015). The present work reports both the
intrinsic vacancy defects and extrinsic nitrogen functionali-
zation to observe the influence on quantum capacitance and
thermodynamic stability of graphene, with implication for
supercapacitor devices.
fast charging/discharging (high power density) and
extremely high life time of > 10,000 cycles (life time of Li-
ion battery is ~ 500 cycles only). Nevertheless, it lags behind
the Li-ion battery in terms of energy storage capacity
(energy density) (Zhan et al. 2017; Paek et al. 2013a). Gra-
phene is the most promising electrode material for develop-
ing high energy density supercapacitors, owing to its
extremely large surface area, high conductivity, mechanical
robustness and stability. In general, the energy density
( E = 21 CV2) is a function of total capacitance (C) offered by
the supercapacitor, while the latter is a series combination
of quantum (C Q) and double layer (C DL) capacitances
(C1 = C1 + C1 ). Hence, it is important to use electrode mate-
Q DL

Electronic supplementary material The online version of this
article (https​://doi.org/10.1007/s1320​4-018-0643-x) contains
supplementary material, which is available to authorized users.
Boddepalli SanthiBhushan is the first author.
* Anurag Srivastava
profanurag@gmail.com
1
Advanced Materials Research Group, CNT Lab, ABV-Indian
Institute of Information Technology and Management,
Gwalior, MP 474015, India
rials having significant quantum capacitance for obtaining
high total capacitance, thereby high energy density. Defects
and doping have been extensively studied by various
researchers for improving the total capacitance of graphene
(El-Gendy et al. 2017; Mousavi-Khoshdel et al. 2015;
Hirunsit et al. 2016; Yang et al. 2015; Wood et al. 2013). In
particular, nitrogen as a functionalized dopant has exten-
sively been examined owing to its rich chemistry with car-
bon (Jeong et al. 2011; Zhu et al. 2016; Paek et al. 2013b;

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 Applied Nanoscience

Zhang et al. 2017; Li et al. 2014; Luo et al. 2013). In several density (Q) of graphene for the applied external potential (𝜑),
cases, though the doping enhances capacitance of graphene, i.e., CQ = dQ
d𝜑
. The excess charge density (Q) on graphene,
it severely compromises the thermodynamic stability and
when the chemical potential is shifted by applying 𝜑∕e, is
thereby the lifetime of electrode. There lack reports that
given by (Zhan et al. 2015),
illustrate the doping pattern needs to be followed to achieve
a trade-off between the two important quantities, quantum ∞

∫
capacitance and thermodynamic stability. In this work, we Q=e D(E)[f (E) − f (E − 𝜑)]dE (1)
have introduced various vacancy defects in graphene viz. −∞
Single Vacancy (SV), Double Vacancy (DV), Triple Vacancy
(TV), and Quadruple Vacancy (QV) to have a constructive Here, D(E) is the DOS, f (E) is Fermi–Dirac distribution
idea of vacancy defect influence on the quantum capacitance function, E refers to Energy with respect to Fermi level, and
and thermodynamic stability. Further, the SV, DV and TV e is elementary charge (1.6 × 10−19 Coulombs).By differen-
defects are functionalized with nitrogen to produce SV Mon- tiating Q with respect to 𝜑, one can obtain the expression for
omerized (SVM), SV Dimerized (SVD), SV Trimerized quantum capacitance as,
(SVT), DV Monomerized (DVM), DV Dimerized (DVD), ∞
DV Trimerized (DVT), DV Tetramerized (DVTtr or Porphy-
∫
dQ
= e2 (2)
[ ]
CQ = D(E) FT (E − 𝜑) dE
rin-type), TV Monomerized (TVM), TV Dimerized (TVD), d𝜑
−∞
TV Trimerized (TVT), TV Tetramerized (TVTtr), and TV
pentamerized (TVP) defect configurations as shown in Here, FT (E) is the thermal broadening function, given by,
Fig. 1, to analyze the influence of doping pattern.
1 E
( )
FT (E) = sec h2 (3)
4KT 2KT
Methodology The CQ expression for maintaining the charge/discharge syn-
chronization between quantum capacitance and DOS profile
The analysis has been performed under the banner of Den- is given by (Zhan et al. 2016),
sity Functional Theory (DFT) based first principles code, ∞
Atomistix Toolkit (2016). Atomistix ToolKit is a further e2
( )

4KT ∫
E+𝜑
development of TranSIESTA-C, which in turn is based on CQ = D(E) sec h2 dE (4)
2KT
the technology, models, and algorithms developed in the −∞
academic codes TranSIESTA (Brandbyge et al. 2002) and
However, the energy density of supercapacitor doesn’t
McDCal (Taylor et al. 2001), employing localized basis
exactly rely on the differential quantum capacitance given
sets as developed in SIESTA (Soler et al. 2002). Norm-
by eq-(4), but rather on the integrated quantum capacitance
conserving Troullier-Martins pseudopotentials (Troullier
(Cqint ). The Cqint can be obtained by integrating the differen-
and Martins 1991) have been used in the present work to
tial quantum capacitance over the entire charge/discharge
describe the interactions between nuclei and electrons. The
cycle assuming equilibrium conditions (i.e., slow charge/
exchange–correlation interaction energy of electrons has
discharge) (Wood et al. 2013). The Cqint reported in this work
been described through Perdew–Burke–Ernzerhof (PBE)
is given by,
functional (Perdew et al. 1996) within the Generalized Gra-
dient Approximation (GGA) method. A large density mesh V

Ve ∫ Q
cutoff of 130 Hartree has been considered for accuracy of 1
Cqint = C (V � )dV � (5)
calculations. All the vacancy defects and nitrogen function- 0
alized configurations are realized on a periodic 4 × 4 hex-
agonal supercell (32 atoms) of graphene. A Monkhorst–Pack For all the graphene configurations, the integrated quantum
grid of 12 × 12 × 1 k-points utilized to sample the Brillouin capacitance is calculated over the potential range − 0.6 to
zone, while the Density of State (DOS) profiles extracted 0.6 V, which is the electrochemical range of aqueous elec-
with 27 × 27 × 1 k-points. Furthermore, spin polarized cal- trolyte of a supercapacitor.
culations have been performed for graphene configurations
having odd number of electrons.
The quantum capacitance (CQ) of graphene configurations
has been extracted from their respective electronic DOS pro-
files assuming the fixed band approximation, i.e., the DOS
profile is assumed to be not affected by charging/discharging.
The CQ can be defined as variation caused in excessive charge

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Applied Nanoscience
Fig. 1  Pristine graphene and its different vacancy defected configura-
tions, a Pristine, b Single vacancy (SV), c Double vacancy (DV), d
Triple Vacancy (TV), e Quadruple Vacancy (QV). Nitrogen function-
alized configurations of SV (f–h), f SV Monomerized (SVM), g SV
Dimerized (SVD), h SV Trimerized (SVT). Nitrogen functionalized
Results and discussion
The Projected DOS (PDOS) profiles for pristine graphene
have been plotted in Fig. 2a, where the pristine graphene
exhibits perfect zero band gap at Dirac point. In addition, the
states around fermi level are solely due to p-orbitals of car-
bon, which can be attributed to the well-known aromaticity
configurations of DV (i–l), i DVM, j DVD, k DVT, l DV Tetramer-
ized (DVTtr or porphyrin-type). Nitrogen functionalized configura-
tions of TV (m-q), m TVM, n TVD, o TVT, p TVTtr, q TV Pen-
tamerized (TVP). (In the images, the grey and blue balls indicate
carbon and nitrogen atoms, respectively)
or conjugation of graphene due to the delocalized π-cloud
originated from residual p-orbital of carbon.
Before proceeding to the calculation of integrated quan-
tum capacitance (Cqint ) for defected and functionalized gra-
phene configurations, the accuracy of our DFT based Cqint
for pristine graphene has been evaluated with respect to that
of experiment by Ponomarenko et al. (Ponomarenko et al.
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 Applied Nanoscience

Fig. 2  a Projected DOS (PDOS) of pristine graphene, the plot shows integrated quantum capacitance (Cqint ) of pristine graphene plotted
Total DOS (TDOS), s-states, and p-states of carbon (from top to bot- over the potential range − 0.6 to 0.6 V from DFT (this work) and
tom), here Fermi level is shifted to energy zero. b Comparison of experiment (Ponomarenko et al. 2010)

2010). The experimental data that is actually available for
the energy range − 0.4 to 0.4 eV has been extrapolated to
match with our bias window − 0.6 to 0.6 V. As seen from
Fig. 2b, our DFT based Cqint for pristine graphene is in excel-
lent agreement with the experimental Cqint . Furthermore, it
is also in excellent agreement with the previous theoretical
reports (Paek et al. 2013a; Yang et al. 2015; Wood et al.
2013; Paek et al. 2013b).
L is the length of the sheets considered (9.85 Å approxi-
mately). The calculated formation energies for different
vacancy defects and their functionalized configurations
are listed in Table 1, where the configurations having
low formation energy are considered more stable than
their counterparts. Here, all the formation energies listed
in Table 1 are positive indicating the endothermic nature

Table 1  Formation energy and peak integrated quantum capacitance

Vacancy defects for different graphene configurations

Graphene configuration Formation energy Peak Cqint (uF/cm2)

The pristine graphene has been subjected to vacancy defects (eV/Å)
viz. SV, DV, TV and QV having defect concentrations 3.12,
6.25, 9.37 and 12.5%, respectively, and analyzed for thermo- Pristine – 10.72
dynamic stability and Cqint . The thermodynamic stability is SV 0.84 107.61
an important factor that can give a comparative idea about DV 0.80 39.16
the life times of defected configurations as supercapacitor TV 1.23 160.29
electrodes. The electrode materials need to have good ther- QV 1.42 119.6
modynamic stability to maintain high life times. The ther- SVM 0.66 92.21
modynamic stability of our defected configurations has been SVD 0.44 68.77
assessed through calculation of formation energies per unit SVT 0.25 260.68
length of sheet ( EFL ) using the expression below, DVM 0.76 62.04
DVD 0.71 53.65
DVT 0.45 97.79
[ EN
]
ED − xEC − y 2 2
EFL = (6) DVTtr (porphyrin-type) 0.25 65.27
L TVM 1.07 79.02
TVD 0.79 72.81
Here, ED, EC and EN2 refer to the energies of defected
TVT 0.72 103.46
sheet, carbon atom of pristine graphene, and nitrogen
TVTtr 0.53 56.05
gas, respectively. x and y indicate the number of car-
TVP 0.32 135.12
bons and nitrogens present in the defect configuration.

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Applied Nanoscience
of the defect creation. The thermodynamic stability of
the vacancy defected configurations follow the trend
DV > SV > TV > QV, portraying DV as the most stable
vacancy defect owing to its least formation energy and
QV as the least stable vacancy defect owing to its highest
formation energy. Apparently, the thermodynamic stabil-
ity decreases with increasing defect size.
Figure 3a depicts the computed electronic DOS pro-
files for different vacancy defects. A close inspection of
the DOS profiles articulate the shift of Fermi level into
valence band for the vacancy defected configurations in
comparison to the pristine case. This shift can be attrib-
uted to the induced p-type behavior due to electron defi-
ciency caused by the vacancy defect. Moreover, several
defect induced peaks can be witnessed in the DOS pro-
files. The estimated Cqint for vacancy defected configura-
tions are depicted in Fig. 3b and the corresponding peak
values are listed in Table 1. All the vacancy defects have
caused significant rise in the quantum capacitance of
graphene. The peak Cqint measured for pristine graphene
is only 10.72 uF/cm2 at − 0.6 V, while it is 107.61 uF/
cm 2 at − 0.04 V for SV, 39.16 uF/cm2 at 0.6 V for DV,
160.29 uF/cm 2 at 0.02 V for TV, and 119.6 uF/cm 2 at
− 0.06 V for QV defect configurations. Here, TV and DV
offer the highest and lowest peak Cqint , respectively. The
enormous Cqint observed for SV, QV, and TV in Fig. 3b are
a result of defect induced DOS peaks at the Fermi level
as seen from Fig. 3a.
Fig. 3  a DOS profiles of pristine graphene and its vacancy defects SV, DV, TV and QV defects (from bottom to top). b integrated quantum
capacitances for different vacancy defects
Influence of nitrogen functionalization
Though the vacancy defects results enhanced Cqint , but
severely diminishes the thermodynamic stability of gra-
phene, as reported in previous section. In this section, the
vacancy defects have been functionalized with nitrogen in
search of trade-off between Cqint and thermodynamic stabil-
ity. For the same, the SV, DV and TV defects have been
functionalized with nitrogen to produce SVM, SVD, SVT,
DVM, DVD, DVT, DVTtr (Porphyrin-type), TVM, TVD,
TVT, TVTtr, and TVP configurations.
As seen from Table 1, nitrogen functionalization on SV,
DV and TV defects have resulted in significant improve-
ment in thermodynamic stability. The thermodynamic
stability follows the trend SVT > SVD > SVM > SV,
DVTtr > DVT > DVD > DVM > DV, and TVP > TVTtr
> TVT > TVD > TVM > TV. Here, it is worth mentioning
that the thermodynamic stability increases with increasing
nitrogen functionalization at the vacancy defect site, and in
each vacancy case the maximum stability has been attained
when all the dangling carbons at the vacancy defect site are
replaced by nitrogen.
As seen from the DOS profiles depicted in Fig. 4a, c and e,
the Fermi level of SV, DV and TV functionalized configura-
tions remain in the valance band in comparison to pristine
graphene. This is due to the fact that incorporated functional
nitrogens are still not enough to fill the electron deficiency cre-
ated by carbon vacancy. To observe the influence of function-
alized nitrogens on the DOS profiles of defected graphenes,
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 Applied Nanoscience

Fig. 4  a DOS profiles for SV,

SVM, SVD, and SVT configu-
ration (from bottom to top). b
Integrated quantum capaci-
tance for different SV nitrogen
functionalized configurations.
c DOS profiles for DV, DVM,
DVD, DVT, and DVTtr con-
figuration (from bottom to top).
d Integrated quantum capaci-
tances for different DV nitrogen
functionalized configurations.
e DOS profiles for TV, TVM,
TVD, TVT, TVTtr and TVP
configuration (from bottom
to top). f Integrated quantum
capacitances for different TV
nitrogen functionalized configu-
rations

the PDOS profiles have been plotted for SVT configuration s-states at the Fermi level as seen from the PDOS profile. In
in fig. S1 of supporting information. Unlike carbon of pris- fact, not just the SVT but all the functionalized configurations
tine graphene, the functionalized nitrogen induces both p and show both p and s-states of nitrogen at the Fermi level, reason

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Applied Nanoscience
being the presence of a lone pair in the leftover p-orbital of
nitrogen that induces p-states, and an unbonded s­ p2 hybrid
orbital at the dangling site that induces both p and s-states.
The presence of lone pair on these functionalized nitrogens
has been confirmed in an earlier report (Taluja et al. 2016).
The spin polarized DOS profiles for functionalized configura-
tions having odd number electrons SVM, SVT, DVM, DVT,
TVM, TVT, TVP are plotted in Fig. S2 of supporting informa-
tion. The spin up and spin down components of DOS for all
these configurations found to be anti-symmetric near the Fermi
level, implying magnetic behavior. The integrated quantum
capacitances for different functionalized configurations have
been presented in Fig. 4b, d and f. The peak Cqint for SVM,
SVD and SVT configurations are measured as 92.21 uF/cm2
at − 0.08 V, 68.77 uF/cm2 at − 0.22 V and 260.68 uF/cm2
at 0.04 V, respectively. While, it is 62.04 uF/cm2 at 0.32 V,
53.65 uF/cm2 at 0.32 V, 97.79 uF/cm2 at 0.6 V and 65.27 uF/
cm2 at 0.6 V for DVM, DVD, DVT and DVTtr (Porphyrin-
type) configurations, respectively, and 79.02 uF/cm2 at 0.48 V,
72.81 uF/cm2 at − 0.06 V, 103.46 uF/cm2 at 0.1 V, 56.05 uF/
cm2 at − 0.3 V and 135.12 uF/cm2 at 0.44 V for TVM, TVD,
TVT, TVTtr and TVP, respectively. The peak Cqint follows the
trend SVT > SVM > SVD, DVT > DVTtr > DVM > DVD,
and TVP > TVT > TVM > TVD > TVTtr. Among the SV
functionalized configurations, SVT which has no dangling
carbons offer the highest Cqint . Among the DV functional-
ized configurations, DVTtr with no dangling carbons offer
the second highest Cqint and DVT with one dangling carbon
offer the highest Cqint. Among the TV functionalized configura-
tions, TVP with no dangling carbons offer the highest Cqint. It
is worth noting that functionalizing all the dangling carbons
of vacancy defect site with nitrogen is the key to attain high
thermodynamic stability (as seen from previous section) and
quantum capacitance. The SVT configuration has no dangling
carbons unlike its close counterparts SVM and SVD, and
hence offers an impressive 3.36 times higher thermodynamic
stability and 2.42 times higher Cqint than SV defect. DVTtr
(porphyrin-type) configuration too has no dangling carbons,
thus offers an impressive 3.2 times higher thermodynamic sta-
bility and 1.66 times higher Cqint than DV defect. Likewise, the
TVP configuration too has no dangling carbons, thus offers a
remarkable 3.84 times higher thermodynamic stability than
TV defect and significant Cqint. Furthermore, the functionalized
configurations mostly offer the quantum capacitance peaks on
the positive side of the bias window, thus implying their best
suitability for anode electrode of high energy density asym-
metric supercapacitors.
Conclusion
The impact of vacancy defects on the quantum capacitance
as well as thermodynamic stability of pristine graphene,
and the influence of nitrogen doping pattern at the vacancy
defect site have been examined through DFT calculations.
The results signify that vacancy defects improve the quan-
tum capacitance of graphene at the cost of thermodynamic
stability. However, this challenge can be overcome by
nitrogen functionalization of the vacancy defect site with
specific pattern. The key to obtain high thermodynamic
stability and quantum capacitance is to functionalize all
the dangling carbons of vacancy defect site with nitro-
gen. Such a move has resulted in remarkable 3.36 times
enhancement in thermodynamic stability and 2.42 times
enhancement in Cqint for SV defect, 3.2 times enhancement
in thermodynamic stability and 1.66 times enhancement
in Cqint for DV defect, and 3.84 times enhancement in ther-
modynamic stability and significant Cqint for TV defect.
The results imply that the functionalized configurations
are extremely useful for anode electrodes of high energy
density asymmetric supercapacitors owing to their impres-
sive quantum capacitances and thermodynamic stability.
Acknowledgements The authors would like to thank Atal Bihari Vaj-
payee—Indian Institute of Information Technology and Management,
Gwalior for providing the infrastructural support for carrying out this
research work. They would also like to thank Prof. De-en Jiang and
Cheng Zhan of University of California, Riverside, and Brandon C.
Wood of Lawrence Livermore National Laboratory, Livermore for the
valuable scientific discussions.
References
Atomistix ToolKit—version 2016.4, QuantumWise A/S (www.quant​
umwis​e.com)
Banhart F, Kotakoski J, Krasheninnikov AV (2010) Structural defects
in graphene. ACS Nano 5(1):26–41
Brandbyge M, Mozos J-L, Ordejon P, Taylor J, Stokbro K (2002)
Density-functional method for nonequilibrium electron trans-
port. Phys Rev B 65(16):165401
El-Gendy DM, Ghany NAA, El Sherbini EF, Allam NK (2017)
Adenine-functionalized Spongy Graphene for green and high-
performance supercapacitors. Sci Rep 7:43104
Hirunsit P, Liangruksa M, Khanchaitit P (2016) Electronic struc-
tures and quantum capacitance of monolayer and multilayer gra-
phenes influenced by Al, B, N and P doping, and monovacancy:
theoretical study. Carbon 108:7–20
Jeong HM, Lee JW, Shin WH, Choi YJ, Shin HJ, Kang JK et al
(2011) Nitrogen-doped graphene for high-performance ultra-
capacitors and the importance of nitrogen-doped sites at basal
planes. Nano Lett 11(6):2472–2477
Li D, Yu C, Wang M, Zhang Y, Pan C (2014) Synthesis of nitro-
gen doped graphene from graphene oxide within an ammo-
nia flame for high performance supercapacitors. RSC Adv
4(98):55394–55399
13

Liu L, Qing M, Wang Y, Chen S (2015) Defects in graphene: genera-
tion, healing, and their effects on the properties of graphene: a
review. J Mater Sci Tech 31(6):599–606
Luo G, Liu L, Zhang J, Li G, Wang B, Zhao J (2013) Hole defects and
nitrogen doping in graphene: implication for supercapacitor appli-
cations. ACS Appl Mater Interfaces 5(21):11184–11193
Mousavi-Khoshdel M, Targholi E, Momeni MJ (2015) First-princi-
ples calculation of quantum capacitance of codoped graphenes as
supercapacitor electrodes. J Phys Chem C 119(47):26290–26295
Paek E, Pak AJ, Hwang GS (2013a) A computational study of the
interfacial structure and capacitance of graphene in [BMIM][PF6]
ionic liquid. J Electrochem Soc 160(1):A1–A10
Paek E, Pak AJ, Kweon KE, Hwang GS (2013b) On the origin of
the enhanced supercapacitor performance of nitrogen-doped gra-
phene. J Phys Chem C 117(11):5610–5616
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approx-
imation made simple. Phys Rev Lett 77(18):3865
Ponomarenko LA, Yang R, Gorbachev RV, Blake P, Mayorov AS,
Novoselov KS et al (2010) Density of states and zero Landau
level probed through capacitance of graphene. Phys Rev Lett
105(13):136801
Soler JM, Artacho E, Gale JD, Garcia A, Junquera J, Ordejon P et al
(2002) The SIESTA method for ab initio order-N materials simu-
lation. J Phys Condens Matter 14(11):2745
Taluja Y, SanthiBhushan B, Yadav S, Srivastava A (2016) Defect and
functionalized graphene for supercapacitor electrodes. Superlat-
tices Microstruct 98:306–315
Taylor J, Guo H, Wang J (2001) Ab initio modeling of quantum trans-
port properties of molecular electronic devices. Phys Rev B
63(24):245407
Troullier N, Martins JL (1991) Efficient pseudopotentials for plane-
wave calculations. Phys Rev B 43(3):1993
13
Applied Nanoscience
Wood BC, Ogitsu T, Otani M, Biener J (2013) First-principles-inspired
design strategies for graphene-based supercapacitor electrodes. J
Phys Chem C 118(1):4–15
Yang GM, Zhang HZ, Fan XF, Zheng WT (2015) Density func-
tional theory calculations for the quantum capacitance perfor-
mance of graphene-based electrode material. J Phys Chem C
119(12):6464–6470
Zhan C, Neal J, Wu J, Jiang DE (2015) Quantum effects on the
capacitance of graphene-based electrodes. J Phys Chem C
119(39):22297–22303
Zhan C, Zhang Y, Cummings PT, Jiang DE (2016) Enhancing graphene
capacitance by nitrogen: effects of doping configuration and con-
centration. Phys Chem Chem Phys 18(6):4668–4674
Zhan C, Lian C, Zhang Y, Thompson MW, Xie Y, Wu J et al (2017)
Computational insights into materials and interfaces for capacitive
energy storage. Adv Sci. https​://doi.org/10.1002/advs.20170​0059
Zhang Y, Wang F, Zhu H, Zhou L, Zheng X, Li X et al (2017) Prepara-
tion of nitrogen-doped biomass-derived carbon nanofibers/gra-
phene aerogel as a binder-free electrode for high performance
supercapacitors. Appl Surf Sci 426:99–106
Zhu J, Childress AS, Karakaya M, Dandeliya S, Srivastava A, Lin
Y et al (2016) Defect-engineered graphene for high-energy-
and high-power-density supercapacitor devices. Adv Mater
28(33):7185–7192
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