Review Materials Science
Heteroatom-doped graphene for electrochemical energy storage
Yangyang Wen • Congcong Huang •
Lianzhou Wang • Denisa Hulicova-Jurcakova
Received: 13 September 2013 / Accepted: 20 November 2013 / Published online: 26 March 2014
� Science China Press and Springer-Verlag Berlin Heidelberg 2014
Abstract The increasing energy consumption and envi-
ronmental concerns due to burning fossil fuel are key drivers
for the development of effective energy storage systems based
on innovative materials. Among these materials, graphene has
emerged as one of the most promising due to its chemical,
electrical, and mechanical properties. Heteroatom doping has
been proven as an effective way to tailor the properties of
graphene and render its potential use for energy storage
devices. In this view, we review the recent developments in
the synthesis and applications of heteroatom-doped graphene
in supercapacitors and lithium ion batteries.
Keywords Graphene � Graphene oxide �Heteroatom � Doping or doped � Supercapacitors �Lithium ion batteries
1 Introduction
There is no doubt that the development of low-cost, high-
performance, and environmentally friendly energy storage
systems is a great challenge to fully utilise potential of
renewable energy, such as solar, wind, and tide.
Supercapacitors (SCs) and lithium ion batteries (LIBs) have
been considered as the most promising energy storage systems
for these applications [1, 2]. It has been generally agreed that
the performance of an energy storage device is primarily
dependent on the properties of the electrode materials. Highly
porous carbon materials have been traditionally used as
electrode materials of SCs providing high surface area for ion
electrosorption thus leading to large specific capacitance [1].
On the other hand, graphite has been utilized as commercial
anode material of LIBs since their commercialization.
In the last decade, graphene, a single layer of sp2
hybridized carbon atoms arranged in a hexagonal lattice
has emerged as one of the most attractive carbon allotropes
for energy storage applications due to its unique structure
and properties [3–6], including high theoretical surface
area (2,630 m2 g-1) [7], excellent thermal conductivity
(*5,000 W m-1 K-1) [8], high intrinsic carrier mobility
(2 9 105 cm2 V-1 s-1) [8], high optical transmittance
(*97.7 %) [9], and superior mechanical strength [10].
Various morphologies of graphene have been reported to
date, such as zero-dimensional graphene quantum dots [11,
12], one-dimensional graphene nanoribbons [13, 14], two-
dimensional graphene nanosheets, and three-dimensional
(3D) graphene macroscopic structures (like fibers [15, 16],
foams [17], and hydrogels [18, 19] ). Graphene can be
prepared by various approaches, including mechanical
cleavage of graphite with a Scotch tape [3], epitaxial
growth on single-crystal SiC [20], chemical vapor deposi-
tion [21], exfoliation of graphite powder via solution oxi-
dation [22], or high energy ball milling [23].
Like for most materials, it is very rare for a graphene-
based material with desirable bulk properties to also pos-
sess the surface characteristics required for energy storage
applications [2]. Therefore, three main approaches have
been used to improve the energy storage properties for
SPECIAL ISSUE: Advanced Materials for Clean Energy
Y. Wen � C. Huang � L. Wang � D. Hulicova-Jurcakova (&)
ARC Centre of Excellence for Functional Nanomaterials, School
of Chemical Engineering and Australian Institute for
Bioengineering and Nanotechnology, The University of
Queensland, Queensland 4072, Australia
e-mail: [email protected]
C. Huang
Department of Chemistry, College of Science, Northeastern
University, Shenyang 110819, China
123
Chin. Sci. Bull. (2014) 59(18):2102–2121 csb.scichina.com
DOI 10.1007/s11434-014-0266-x www.springer.com/scp
graphene: (1) development of porosity in graphene.
Improving the specific surface area of graphene materials
without decreasing their electrical properties is an effective
way to enhance the energy storage properties in SCs [24].
This has been achieved by constructing 3D graphene
architectures with open porous structure and high specific
surface area [25], chemical activation [26], and light
treatment [27]; (2) development of heteroatom-doped
graphene (heteroatoms include N, B, P, S). Introduction of
heteroatoms can significantly improve the performance of
the SCs as well as LIBs via altering the electronic prop-
erties of doped graphene [6, 28–30]; (3) development of
graphene-based composites. Combining the high surface
area and electrical conductivity of graphene with the high
electrochemical activity of the second phase (such as
transition metal oxides/hydroxides and conducting poly-
mers) has been reported as an effective way to increase
energy storage capacity of SCs [31, 32].
As mentioned above, chemical doping is an important
approach to tailor the properties of graphene. The hetero-
atom-doped graphene shows different properties compared
with the pristine graphene [24, 33]. For instance, the spin
density and the charge distribution of carbon atoms are
influenced by the neighboring heteroatoms, which increase
the ‘‘activation region’’ on graphene surface thus improving
the energy storage [6, 33, 34]. To date, heteroatom-doped
graphene has been investigated as electrode materials in
numerous applications, including SCs, LIBs, fuel cells, and
field-effect transistors to name a few [28–30, 34–36].
In this review, we focus on the energy storage applica-
tion of heteroatom-doped graphene and review the recent
development in the synthesis approaches and applications
of heteroatom-doped graphene in SCs and LIBs.
2 Synthesis of heteroatom-doped graphene
Heteroatom-doped graphene can be obtained by two dif-
ferent ways: a direct synthesis and a post-treatment [6].
Different methods provide doped graphene with different
levels of doping and distribution of doped atoms.
Direct synthesis includes chemical vapor deposition
(CVD), solvothermal method, segregation growth, and arc-
discharge method [6]. CVD is a common method to produce
heteroatom-doped nanocarbons in which carbon source gas
is mixed with heteroatom-containing precursor at elevated
temperatures [6]. Doped graphene can also be directly grown
on the current collectors used as substrates in the CVD
process as reported by Reddy and colleagues who demon-
strated a controlled growth of nitrogen-doped (N-doped)
graphene layers using acetonitrile as a carbon source. The
N-doped graphene grew directly on copper current collectors
and contained 9 % of nitrogen [37]. By using this method,
active electrode materials can be attached on the current
collectors without any binder which makes the process for
manufacture technology more feasible and efficient.
Solvothermal method was first employed in gram-scale
production of graphene [38]. It is a method with simple
operation, mild synthesis conditions and capability to
deliver relatively large quantities [39]. Deng et al. [39]
prepared N-doped graphene using this method by mixing
lithium nitride and tetrachloromethane with or without
cyanuric chloride, reaching a high nitrogen content of
16.4 %. Another report described the synthesis of N-doped
graphene hydrogel using hydroxylamine hydrochloride and
hydroxylamine through a solvothermal reaction with a
relatively low heteroatom doping (4.32 %) [40].
Compared with direct synthesis, post-treatment approa-
ches seem to attract more attention as an effective way to
introduce heteroatoms into the graphene structure. These
include thermal treatment [28, 30, 41], hydrothermal
method [17, 19, 29], plasma process [42], mechanical ex-
foliation [43], and anodic polarization [44].
For thermal treatment, doped graphene can be prepared by
annealing graphene oxide (GO) in heteroatom-containing gas
at high temperature [41] or carbonizing heteroatom-contain-
ing precursors at high temperature [30]. Wu et al. [41] pre-
pared N-doped or boron-doped (B-doped) graphene through
thermal treatment at 600 or 800 �C using NH3 or BCl3 gas,
showing a small amount of N (3.06 %) and B element
(0.88 %). The phosphorus-doped (P-doped) graphene was
also prepared by a similar approach in which the mixture of
graphene oxide, and triphenylphosphine was heat treated at
elevated temperature, providing phosphorus doping of
1.81 at.% [30]. Thermal treatment as the most frequently used
method shows some advantages like it can control the tem-
perature as well as the flow of the treatment gases easily.
Hydrothermal method is another interesting approach to
prepare doped graphene with desired porous structure and
controlled doping levels. Zhao et al. [17] prepared N-doped
graphene framework with N/C atomic ratio of 4.2 % by
hydrothermal treatment of GO with pyrrole, and the
resulting material showed an ultralow density and high
porosity. Applying the same method, certain reducing
agents were chosen to realize one-step facile process of
doping and reducing the GO. In this way, N-doped
graphene hydrogels were prepared with GO as a raw
material and urea as a reducing-doping agent, obtaining the
controlled nitrogen contents from 3.95 at.% to 6.61 at.%
by controlling GO concentration [19].
3 Heteroatom-doped graphene for supercapacitors
SCs are devices that store and release energy rapidly
and reversibly, providing moderate energy density
Chin. Sci. Bull. (2014) 59(18):2102–2121 2103
123
(1–10 Wh kg-1), high power density (103–106 W kg-1) and
ultralong cycling life ([105 cycles) [24]. SCs have been
applied in electronics, electric vehicles, ac-line filtering, air-
crafts, and so on. Based on the energy storage mechanisms,
SCs can be divided into two types: (1) electrochemical double
layer capacitors (EDLCs) which store energy by charge sep-
aration at the electrolyte/electrode interface and (2) pseud-
ocapacitors that store energy through redox Faradaic
reactions. For EDLCs, porous carbon materials have been
investigated as the electrode materials, while in pseudoca-
pacitors, electrode materials include transition metal oxides/
hydroxides, conducting polymers and carbons containing
oxygen and nitrogen surface functional groups [45].
It has been shown that heteroatom-doped porous car-
bons involve both the EDLCs and pseudocapacitive energy
storage mechanism thus providing high capacitance and
often extended potential window [46]. Understandably, the
heteroatom-doped graphene, as a result of its distinct
electric charge distribution, chemical and electrical prop-
erties, has been increasingly investigated in energy storage
field, particularly in SCs and the next section reviews
recent developments in the synthesis and applications of
heteroatom-doped graphene in SCs.
3.1 N-doped graphene for supercapacitors
Doping of graphene with nitrogen atom that has an extra
valence electron modifies the electronic band structure of
graphene by introducing new energy levels in the lower part of
the conduction band of sp2-bonded carbon atoms [6, 33]. These
new energy levels have been shown to be electrochemically
and catalytically active in energy storage/conversion devices
such as SCs, batteries and fuel cells [6, 33]. Doping with
nitrogen generally results in three common bonding configu-
rations within the carbon lattice, including quaternary N, py-
ridinic N, and pyrrolic N (Fig. 1) [6]. Among these nitrogen
types, pyridinic N and quaternary N are sp2 hybridized, and
pyrrolic N is sp3 hybridized and thus has different charges that
also affect charge of the surrounding carbon atoms.
Thermal treatment, hydrothermal method and plasma
treatment have been the main methods to obtain N-doped
graphene for applications as SCs electrodes and these are
reviewed herein.
3.1.1 N-doped graphene synthesized by thermal treatment
for supercapacitors
Thermal treatment refers to the method which uses high
temperature to produce materials. Using this method,
N-doped graphene was synthesized by treating GO or
graphene with ammonia gas at high temperature.
Following this approach Zhang et al. [47] synthesized
N-doped activated graphene with an ultrahigh specific
surface area of *2,000 m2 g-1 via a microwave exfoliated
process and KOH activation following the annealing in
ammonia gas at 700 �C. The area-normalized capacitance
of the N-doped graphene with similar porous structure
increased from 6 lF cm-2 (160 F g-1) to 22 lF cm-2
(420 F g-1) with 0 at.% and 2.3 at.% N-doping, respec-
tively, at 0.2 A g-1 in 6 mol L-1 KOH electrolyte.
In other report, N-doped graphene with 5.2 at.% of
nitrogen by annealing GO at 550 �C under NH3 gas flow
provided a capacitance of *40 F g-1 at 2 mV s-1 in
1 mol L-1 H2SO4. In addition, the effect of graphene
surface functionalization on supercapacitive performance
was also systematically investigated, including GO,
chemically reduced GO (RG), N-doped RG (NG), and
amine-modified RG (NH2-G) [48]. NG loaded with poly-
pyrrole (PPy) provided higher capacitance (as high as
393 F g-1) than the other GO/PPy, RG/PPy, and NH2-G/
PPy composites [49].
Electrospinning combined with thermal treatment in
ammonia gas was used in preparation of carbon nanofibers
with radially grown graphene. This carbon nanofibers/
graphene material was doped with a small amount of
nitrogen and oxygen with different concentrations (N:
1.1 at.%–3.4 at %, O: 2.6 at.%–3.6 at.%) depending on the
annealing temperature. SCs capable of operating at high
voltage of 1.8 V provided energy density of 29.1 Wh kg-1
in a neutral Na2SO4 electrolyte. The SCs also exhibited
excellent cycling performance with the capacity retention
over 93 % after 5,000 charge–discharge cycles [50].
Hierarchically aminated graphene honeycombs with an
N-doping level of 2.79 at.%–3.91 at.% were reported
through vacuum assisted thermal expansion of GO fol-
lowed by amination in NH3 gas. The functional 3D
assemblies of graphene were micrometer-sized curved
flakes with a high transparency chiffon-like texture,
exhibiting high capacitance of 207 F g-1, and long cycle
life in 6 mol L-1 KOH electrolyte. In addition, the surface
chemistry of the aminated graphene treated at different
temperatures (200–600 �C) was studied using X-ray pho-
toelectron spectroscopy (XPS). It was concluded that at
low amination temperature NH3 reacted with the carbox-
ylic acid species to form mainly intermediate amide or
amine like species through nucleophilic substitution. When
the amination temperature increased, the intramolecular
Fig. 1 Bonding configurations of nitrogen atoms in N-doped graph-
ene [6]. Reprinted with permission from Ref. [6], Copyright (2012),
American Chemical Society
2104 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
dehydration or decarbonylation took place to generate
thermally stable heterocyclic aromatic moieties such as
pyridine, pyrrole, and quaternary type N sites [51].
In another study, N-doped graphene with ultrahigh
electrical conductivity (1,000–3,000 S m-1) was synthe-
sized through pre-reduction with hydrazine followed by
thermal nitridation. Even without adding carbon additives
into the electrodes, the doped graphene-based SCs could
deliver high capacitance of 144.9 F g-1 (0.5 A g-1) in
1 mol L-1 Et4NBF4 organic electrolyte and remarkable
energy and power densities (55.3–80.5 Wh kg-1,
0.558–16.68 kW kg-1) at high operating voltage of 4 V
[52]. The resulting curved doped graphene also displayed
high thermal stability and was highly porous when
assembled into a film. These properties resulted from the
restoration of the graphene network by the formation of
C–N bonded groups and N-doping, which are highly
desirable for SCs.
As mentioned above, the advantage of this method is
that the N-doping level of the graphene can be controlled
by varying the flow rate of ammonia gas and further
influence the electrochemical performance, whereas the
disadvantage is the relatively low N content in graphene
materials. Apart from using ammonia atmosphere, N-doped
graphene can be also synthesized by annealing GO in the
presence of various nitrogen-containing reagents at high
temperature, introducing high N contents in graphene
nanosheets.
Highly crumpled N-doped graphene nanosheets with a
high pore volume of 3.42 cm3 g-1 and relative high
nitrogen contents of 5.21 at.%–11.24 at.% were synthe-
sized by thermal annealing cyanamide and GO. The sup-
ercapacitive properties of the crumpled doped graphene
were studied in both organic and aqueous electrolytes,
achieving impressive 248 F g-1 (1 mol L-1 [Bu4N]BF4)
and 302 F g-1 (6 mol L-1 KOH) at 5 mV s-1, respec-
tively. Excellent electrochemical stability was also
observed with 96.1 % capacitance retention after 5,000
cycles [28].
Zheng et al. [53] obtained the KOH-activated N-doped
graphene (aNG) with a specific surface area of up to
555 m2 g-1 through a two-step process, as shown in Fig. 2.
First, GO was activated by KOH followed by the thermal
annealing with melamine that resulted in a very high
nitrogen content of 20.51 %. Electrochemical results
showed that the aNG yielded a capacitance of 132.4 F g-1
at the current density of 0.1 A g-1, which was consider-
ably higher than that without KOH treatment. The work
demonstrated that KOH activation of thermally annealed
N-doped graphene was a promising method for enhancing
the capacitance of the N-doped graphene.
Another approach involved preparation of graphene/N-
doped porous carbon composite by carbonization of the
mixture of GO and ionic liquids (1-ethyl-3-methylimida-
zolium dicyanamide). Electrochemical evaluation showed
that the composite with a high nitrogen content of
13.51 wt% manifested a significantly enhanced capacitive
performance (206 F g-1 at a current density of 0.1 A g-1)
compared with sample with a low nitrogen content
(7.15 wt%, 161 F g-1) and non-doping graphene/porous
carbon composite (69 F g-1) in 1 mol L-1 H2SO4 elec-
trolyte [54]. It is explained that the improved capacitive
performance was attributed to the Faradaic redox reactions
on the nitrogen functional groups as well as enhanced
surface wettability.
3.1.2 N-doped graphene synthesized by hydrothermal
treatment for supercapacitors
Hydrothermal treatment is an important technique for the
synthesis of various kinds of materials [55]. In case of
N-doped graphene synthesized by hydrothermal synthesis,
GO solution and the nitrogen-containing precursors are
typically put into a steel pressure vessel (autoclave) and
treated at a relatively low temperature (generally\200 �C).
During this process, GO can be reduced and doped simul-
taneously by using appropriate reducing nitrogen-containing
agents.
Ammonia and urea are the most common nitrogen-con-
taining agents reported in hydrothermal method. Hassan
prepared N-doped graphene using ammonia and hydrazine,
and systematically studied the hydrothermal temperature
impact on the nitrogen configuration and electrochemical
performance. The result confirmed that N-doped graphene
prepared at 130 �C exhibited the maximum capacitance of
194 F g-1 at 10 mV s-1 and 6.7 Wh kg-1/3.7 kW kg-1 for
the energy density/power density, respectively, in
1 mol L-1 KCl electrolyte [56].
Fig. 2 (Color online) Illustration of the forming process of KOH
activation of N-doped graphene [53]. Reprinted with permission from
Ref. [53], Copyright (2013), Springer
Chin. Sci. Bull. (2014) 59(18):2102–2121 2105
123
In another report, concentrated ammonia-assisted
hydrothermal method was used to obtain N-doped graph-
ene by simultaneous N-doping and reduction of GO. The
effects of different hydrothermal temperatures on the sur-
face chemistry and the structure of N-doped graphene were
also investigated. The results revealed that specimens
prepared at higher hydrothermal temperature had higher N
doping level (up to 7.2 at.%) and possessed high specific
capacitance of 144.6 F g-1 at 0.2 A g-1 in 6 mol L-1
KOH electrolyte [57].
Bai et al. [58] prepared three kinds of graphene through
a hydrothermal reduction under different pH values. The
N-doped graphene was obtained under basic medium using
ammonia solution, giving a specific capacitance of
185 F g-1 at a current density of 1 A g-1 and the energy
density/power density of 17.1 Wh kg-1/20 kW kg-1 in
30 wt% KOH electrolyte.
N-doped graphene nanosheets with a high nitrogen level
of 10.13 at.% were prepared via simple hydrothermal
reaction of GO and urea. It was shown that during the
hydrothermal process, urea released NH3 in a sustained
manner which reacted with the oxygen functional groups of
the GO thus forming nitrogen doping in graphene. Corre-
sponding N-doped graphene had a large surface area of
593 m2 g-1 and exhibited high gravimetric capacitance of
326 F g-1 at low current load in 6 mol L-1 KOH elec-
trolyte, very good cycling stability and coulombic effi-
ciency (99.58 %) after 2,000 cycles. The energy density of
25.02 Wh kg-1 was achieved at power density of
7.98 kW kg-1 by using a two-electrode symmetric capac-
itor [59]. The results also demonstrated that the pyridinic N
and pyrrolic N played a critical role in improving pseudo-
capacitance by the redox reaction, while quaternary N
enhanced the electronic conductivity during the charge/
discharge process.
Using a similar hydrothermal process with urea, doped
graphene with 5.47 at.%–7.56 at.% of nitrogen was
obtained, showing 184.5 F g-1 at 3 A g-1 and 12.4 %
capacitance loss after 1,200 cycles in an aqueous electro-
lyte of 6 mol L-1 KOH [60]. In addition, microwave-
assisted hydrothermal method with GO and urea was used
to synthesize doped graphene, showing that the positive
effect of N-doped groups on capacitance was more pro-
nounced in acidic than in alkaline media [61].
Besides urea, there are numerous other nitrogen-con-
taining agents used in the synthesis of N-doped graphene.
One such example includes hexamethylenetetramine,
which plays double-role, both as the reducing agent for GO
and the nitrogen source. Using hydrothermal conditions
with hexamethylenetetramine and GO, N-doped graphene
with 8.62 at.% of nitrogen doping was reported. The
material provided capacitance of 161 F g-1 at a current
density of 0.5 A g-1 in 6 mol L-1 KOH electrolyte, and
exhibited good cycling stability after 5,000 consecutive
cycles [62].
A pressure-promoted hydrothermal process with
NH4HCO3 as nitrogen-containing agent was used to pre-
pare N-doped graphene, reaching a high N doping level of
9.76 at.%–13.51 at.%. The product exhibited a specific
capacitance of 170 F g-1 at 0.5 A g-1 in 5 mol L-1 KOH,
and a high retention rate of 96.4 % of its initial capacitance
after 10,000 charge/discharge cycles [63].
It has been also demonstrated that by controlling
hydrothermal conditions, N-doped graphene with porous,
or 3D structure can be easily obtained. In this fashion, You
et al. [64] reported a 3D N-doped graphene-carbon nano-
tube (CNT) networks obtained by hydrothermal treatment,
freeze-drying and subsequent carbonization of GO-dis-
persed pristine CNT in the presence of pyrrole. Such
N-doped graphene-CNT used as electrode in alkaline SCs
showed a capacitance of 180 F g-1 at 0.5 A g-1 current
load and approximately 96 % of the initial capacitance
after 3,000 cycles.
Graphene hydrogels were also successfully prepared
using hydrothermal conditions. N-doped graphene hydro-
gels were synthesized via a hydrothermal method using
urea as the reducing/doping agent. The hydrogels contained
*97.6 wt% of water and had a large specific surface area
of [1,300 m2 g-1 in the wet state, showing a high capac-
itance of 326 F g-1 at 1 A g-1 in 6 mol L-1 KOH elec-
trolyte [19]. Using this approach, N contents in hydrogels
can be controlled by several synthesis parameters, such as
the GO concentration, different N-precursors as well as
their concentrations, hydrothermal temperatures, and so on.
Another example includes macroscopic 3D N-doped
graphene hydrogels prepared from organic amines and GO
as precursors, as shown in Fig. 3. The results showed that
such hydrogels exhibited excellent supercapacitive perfor-
mance. Even at an ultrafast charge/discharge rate of
185 A g-1, a specific capacitance of 113.8 F g-1, and a
high power density of 205.0 kW kg-1 were obtained in
5 mol L-1 KOH electrolyte. In addition, at a considerably
high current density of 100 A g-1, 95.2 % capacitance was
retained after 4,000 cycles [18]. In this work, organic
amines did not only act as nitrogen precursors but also
controlled assembly of the graphene nanosheets in the 3D
structures. The inner structure of the hydrogels and the
content of nitrogen in the graphene were adjusted by
organic amine.
The highest capacitance for N-doped graphene was
obtained using this method. Zhao et al. [17] prepared 3D
N-doped graphene framework with an ultralow density of
(2.1 ± 0.3) mg cm-3 and a high conductivity of
(1.2 ± 0.2) 9 103 S m-1, as shown in Fig. 4. The
N-doped graphene framework with N/C atomic ratio of
4.2 % was prepared by hydrothermal treatment of aqueous
2106 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
GO suspension with pyrrole to form an N-containing
hydrogel, followed by annealing the freeze-dried hydrogel
at 1,050 �C under argon atmosphere. Such framework
presented high-performance capacitive behaviors due to
the combination of heteroatom doping and 3D porous
structure providing an ultrahigh capacitance of
415–484 F g-1 at the current densities of 1–100 A g-1 in
1 mol L-1 LiClO4 aqueous electrolyte.
Compared with other methods, hydrothermal method is a
facile and one-step method of preparing N-doped graphene.
Using this method, 3D graphene architecture with porous
structure could be easily obtained and the graphene synthe-
sized by this approach is more enriched with nitrogen.
3.1.3 N-doped graphene synthesized by plasma treatment
and other methods for supercapacitors
Choi and co-workers [42] paved way toward improving the
capacitance of graphene-based SCs by using N-doped
graphene. N-doped graphene with nitrogen doping between
1.68 at.% and 2.51 at.% was prepared by nitrogen plasma
process. The results showed that the capacitance of
N-doped graphene (282 F g-1) was about 4 times that of
its pristine graphene-based counterpart (69 F g-1) in
6 mol L-1 KOH electrolyte without sacrificing excellent
cycle life ([2 9 105) and high power capability
(*800 kW kg-1). A possible mechanism of the energy
storage in N-doped graphene was proposed on the basis of
XPS analysis as well as the first principles density func-
tional theory calculation of the ionic binding energy
(Fig. 5). It was concluded that the introduction of hetero-
atom nitrogen manipulated the local electronic structures of
graphene sheets, resulting in increased number of adsorbed
ions to store more energy. The enhanced accommodation
of ions on the electrode surface, especially on the N-doped
sites at the basal planes of graphene sheets through elec-
trostatic interaction, was believed to be the reason for the
high capacitance of N-doped graphene.
A solvothermal method was used in the preparation of
N-doped graphene hydrogel using hydroxylamine
hydrochloride (HACl) and hydroxylamine (HA) as the
chemical dopant and reductant. The N-doped hydrogel
prepared from HA contained more nitrogen (4.32 at.%)
while the N-doped hydrogel prepared from HACl pro-
vided higher capacitance (205 F g-1 at scan rate of
1 mV s-1) and energy density/power density
(3.65 Wh kg-1/20.5 kW kg-1) in 25 wt% KOH electro-
lyte, along with good capacitance retention of 92.6 %
after 3,000 cycles [40].
Fig. 3 Photographs and SEM image of the hydrogel synthesized from GO (G-GH) and N-doped graphene hydrogels (GN-GHs). (a) G-GH and
GN-GHs after hydrothermal process at 180 �C for 12 h using ethylenediamine (1, 2.5 lL; 2, 5.0 lL; 3, 10.0 lL; 4, 20.0 lL); (b) GN-GHs after
hydrothermal process at 180 �C for 12 h using ammonia and different organic amine (5, ammonia; 6, diethylenetriamine; 7, tetraethylene-
pentamine; 8, n-propylamine; 9, n-butylamine); (c) SEM image of the typical GN-GH microstructures [18]. Reprinted with permission from Ref.
[18], Copyright (2013), Elsevier
Fig. 4 a, b Photographs of the N-doped graphene framework and one
with a piece of framework size of 1.8 cm 9 1.1 cm 9 1.2 cm
standing on a dandelion. c, d SEM images of the sample in (a).
Scale bars (c) 10 lm, (d) 100 nm [17]. Reprinted with permission
from Ref. [17], Copyright (2012), WILEY–VCH Verlag GmbH &
Co. KGaA, Weinheim
Chin. Sci. Bull. (2014) 59(18):2102–2121 2107
123
An interesting approach has been reported to prepare
N-modified graphene directly from graphite flakes. With the
aid of melamine, graphite flakes were directly ultrasonicated
into few-layer graphene in acetone solution. The subsequent
annealing process further transformed the melamine absorbed
on the graphene sheets into melon (C6N9H3)x and simulta-
neously doped graphene with nitrogen. When tested in 6 mol
L-1 KOH electrolyte, the sample showed a much higher
specific capacitance (227 F g-1 or 155 F cm-3 at 1 A g-1)
than that of undoped graphene (133 F g-1 at 1 A g-1) [43].
3.2 Other heteroatom-doped graphene
for supercapacitors
Boron has been another atom of choice in an attempt of
altering the electronic structure of graphene and thus
improving the energy storage capacity of SCs made from
corresponding B-doped graphene.
B-doped graphene nanoplatelets with the boron doping
of 0.7 at.%–1.1 at.% were produced via the reduction of
GO by a borane-tetrahydrofuran under refluxing (Fig. 6).
This has been the first report on the production of B-doped
graphene from a solution process and on application of
B-doped graphene in SCs. The B-doped graphene had a
high specific surface area of 466 m2 g-1 and showed good
supercapacitive performance including a high specific
capacitance of 200 F g-1 (43 lF cm-2) at 0.1 A g-1 in
Fig. 5 (Color online) a Gravimetric capacitances of SCs built on nickel and paper substrates measured at a series of current densities. (inset) A photograph
showing that a wearable capacitor wrapped around a human arm could store the electrical energy to light up a LED; b the schematic illustration of the plasma
doping process. By the plasma process with physical momentum, nitrogen atoms replaced the existing carbon atoms. (inset) Possible nitrogen configurations
by the doping treatment; c galvanostatic charging/discharging curves at a current density of 1 A g-1 with the IR drops denoted; d cyclic voltammetric curves
measured at a scan rate of 20 mV g-1. Reprinted with permission from Ref. [42], Copyright (2011), American Chemical Society
Fig. 6 a A borane-tetrahydrofuran (THF) adduct, b a reaction
scheme of the reduction of GO with the borane-THF adduct,
c SEM images of B-doped graphene powder at different magnifica-
tions. Reprinted with permission from Ref. [65], Copyright (2013),
American Chemical Society
2108 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
6 mol L-1 KOH aqueous electrolyte and a good stability
after 4,500 cycles [65].
P-doped graphene was reported from graphene nano-
sheets by the activation with phosphoric acid. When
applies as the electrodes of SCs, a high specific capacitance
of 367 F g-1 at 5 mV s-1 and a high energy/power den-
sities of 59 Wh kg-1/9 kW kg-1 were derived in
1 mol L-1 H2SO4 aqueous electrolyte [66]. However, the
content of the phosphorous in doped graphene was not
reported and the effect of phosphorus doping on the
capacitance was not discussed.
3.3 Co-doped graphene for supercapacitors
3D boron and nitrogen co-doped (B,N-doped) monolithic
graphene aerogels (BN-GAs) were synthesized by com-
bined hydrothermal process and freeze-drying process and
used to fabricate an all-solid-state SCs, as illustrated in
Fig. 7. The nitrogen (3.0 at.%) and boron (0.6 at.%) dop-
ing in carbon networks facilitated charge transfer between
neighboring carbon atoms and thus enhanced the electro-
chemical performance of carbon-based materials. The BN-
GAs based all-solid-state SCs exhibited high specific
capacitance (PVA/H2SO4 gel as the solid electrolyte,
62 F g-1 at 5 mV s-1) and enhanced energy and power
density (8.7 Wh kg-1/1.65 kW kg-1) with respect to
undoped, N-doped, B-doped GAs, or layer-structured
graphene paper. The monolith was also tested in 1 mol L-1
H2SO4 aqueous electrolyte providing capacitance as high
as 239 F g-1 at 1 mV s-1 [29].
In a different approach ammmonia borane was used as
both the reducing and doping agent to synthesize the B,N-
doped graphene by refluxing ammmonia borane and GO.
Concurrently the reduction of GO was studied in aqueous
solution and tetrahydrofuran. The result showed that the
reduction of GO in tetrahydrofuran led to a higher boron-
(1.81 at.%) and nitrogen- (1.57 at.%) content in B,N-doped
graphene and such materials exhibited superior superca-
pacitive performance, with a specific capacitance of
130 F g-1 at 1 A g-1 in organic electrolyte of 1 mol L-1
TEABF4 compared with the sample reduced in aqueous
solution [67].
In another work, anodic polarization was applied in
synthesis of oxygen, nitrogen and chlorine co-doped
reduced graphene oxide films in a neutral nitrogen-deaer-
ated KCl electrolyte. The doped graphene showed a Cl
doping of 0.38 at.% and a N doping of 7.25 at.%, along
with the enhanced capacitance in 1 mol L-1 H2SO4
aqueous electrolyte for the doped film (182 F g-1 at
10 mV s-1 for the doped graphene and 75 F g-1 for the
undoped graphene) [44].
Table 1 summarizes the above described synthesis
methods of heteroatom-doped graphene and their sup-
ercapacitive properties. As one can clearly see, various
methods have been utilised in synthesis of heteroatom-
doped graphene materials for SCs. Clear enhancement in
specific capacitance has been demonstrated in aqueous as
well as organic electrolytes that confirms positive effect of
heteroatom doping on the energy storage capacity of SCs.
However, a caution should be taken when comparing the
energy (E) and power (P) densities of SCs constructed
from different electrode materials since on some occasions
E and P were calculated from the capacitance values
obtained from 3-electrode while other correspond to the
capacitance obtained from 2-electrode tests. In addition,
majority of electrochemical tests have been performed in
very strong alkaline solutions, which are not commercially
and environmentally plausible. More investigation on the
heteroatom doping in graphene on the energy storage
capacity in SCs with commercial organic electrolyte seems
urgent in order to transform research and development of
heteroatom-doped graphene in practical application.
It also can be seen that even though a wide investigation
has been performed in N-doped graphene materials, a
fundamental understanding of energy storage mechanism
for introduced N atoms is still lacking. Besides, most work
has focused on the N-doped graphene materials whereas
few works on other heteroatoms doped graphene have been
reported. The energy storage mechanism for heteroatom-
doped graphene is still needed.
4 Heteroatom-doped graphene for LIBs
In comparison with SCs, LIBs have the advantage of high
specific energy density [68]. LIBs typically consist of a
metal oxide-based positive electrode (cathode), graphite-
based negative electrode (anode), a porous membrane
separating the two electrodes, and an electrolyte (typically
LiPF6 or LiClO4 organic electrolytes). The energy storage
mechanism is that lithium ions deintercalate from the sites
between layers of the cathode into electrolytes and inter-
calate into the carbonaceous anode during the charging
process while lithium ions are deintercalated from the
anode and intercalate back to the empty sites between
layers of the cathode during the discharging process [69].
LIBs are irreplaceable in many practical applications
including mobile phones, digital cameras and laptop
computers. However, to extend the application of LIBs into
more wide scale, such as renewable energy, an improve-
ment in cycling life and power density is critically needed.
Extensive research has been performed on the devel-
opment of new and more efficient cathode materials based
on metal oxide materials. At the same time, carbon-based
Chin. Sci. Bull. (2014) 59(18):2102–2121 2109
123
anodes have been investigated with same enthusiasm and
graphene-based anode materials have been attracting
steady interest in past years [69]. Similarly, to the positive
effect of heteroatom doping in graphene on the energy
storage capacity in SCs, heteroatoms can effectively
improve the reversibility and rate performance of anodes of
LIBs [37]. The reason for performance boost is provoked
by doped atoms with different electronegativity (e.g., N:
3.04, B: 2.04, S: 2.58) that can break the electroneutrality
of graphene thus creating the charged sites which improve
the discharge and charge capacity of graphene in LIBs
[30]. Besides, heteroatoms can also induce a large number
of defects onto the graphene surface, which leads to the
formation of a disordered carbon structure that further
enhances the lithium insertion properties [30, 41]. Corre-
spondingly, heteroatom-doped graphene materials
(including N, B, P, and S) have been synthesized as anodes
of LIBs and these are reviewed in the following section.
4.1 N-doped graphene as anode materials for LIBs
In N-doped graphene, the well-bonded nitrogen atom can
drastically alter the electronic properties, provide more
active sites, and enhance the interaction between carbon
Fig. 7 (Color online) a Fabrication illustration of all-solid-state SCs (ASSSs) based on BN-GAs that were involved by a combined hydrothermal
process and freeze-drying process. The as-fabricated SCs with a diameter of 7 mm indicated by the dotted green ring and a simplified schematic
of ASSSs based on aerogels were shown (below left). b Atomic force microscope (AFM) image and c corresponding height profile of the GO
used, with thickness of 1 nm. d Digital images of two pairs of GO solutions with different volumes in the vials and B,N-doped graphene
hydrogels before and after hydrothermal self-assembly. Inset: digital images of the BN-GAs obtained after freeze-drying. e, f) Low- and high-
magnification SEM images of the as-prepared BN-GAs. g, h Low and high-magnification SEM images of the as-prepared BN-GAs as binder/
additive-free electrode upon physical pressing. Reprinted with permission from Ref. [29], Copyright (2012), WILEY–VCH Verlag GmbH & Co.
KGaA, Weinheim
2110 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
Ta
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[63]
Chin. Sci. Bull. (2014) 59(18):2102–2121 2111
123
Ta
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nu
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mo
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ran
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1
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–1
mo
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N
13
0(1
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]
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rap
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eA
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po
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Vs-
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)[4
4]
2112 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
structure and lithium thus also leading to improved kinetics
of lithium diffusion and transfer. Therefore, N-doped
graphene is believed as an potentially promising anode
material for LIBs [70].
Generally, thermal treatment and hydrothermal
approach are the foremost methods used in the preparation
of N-doped graphene for LIBs.
In early 2010, Reddy et al. [37] demonstrated a controlled
growth of N-doped graphene layers grown directly on copper
current collectors by a liquid precursor (acetonitrile) based
CVD method and studied its reversible Li-ion intercalation
properties as an anode material of LIBs. The N-doped
graphene with 9 at.% of nitrogen provided high discharge
capacity of 0.25 mAh cm-2 in the first cycle and remained at
0.05 mAh cm-2 for the reversible discharge capacity, which
was almost double compared to the undoped pristine
graphene. The performance improvement was concluded
due to induced surface defects and the presence of pyridinic
N atoms in the graphene structure. Besides, such feasible and
efficient process of direct growth of an active electrode
material on the current collector is very adaptable to the
battery manufacturing technology.
In another work, thermal treatment of pristine graphene
at 600 �C under ammonia atmosphere was introduced in
the preparation of N-doped graphene with 3.06 at.% of
nitrogen (Fig. 8). The N-doped graphene used as the anode
material exhibited a high initial capacity of 1,043 mAh g-1
and a reversible capacity of 872 mAh g-1 at low current
density of 50 mA g-1. More interestingly, it could be
quickly charged and discharged in a very short time toge-
ther with high-rate capability and excellent long-term
cyclability [41]. N-doped graphene nanosheets with a rel-
atively low doping of 2 %–2.8 % were also synthesized by
a similar thermal treatment and showed high reversible
capacities [34, 70].
Thermal annealing of graphene nanosheets and mela-
mine resulted in a highly N-doped graphene with 7.04 at.%
of nitrogen. Such material exhibited high reversible
capacity of 1,136 mAh g-1 at the current density of
50 mA g-1 and highly stable capacity of 241 mAh g-1 at
an extremely high current density of 20 A g-1 [71]. The
superior electrochemical performance was attributed to the
high nitrogen-doping level and the existence of pyridinic
nitrogen atoms.
Solvothermally reduced and simultaneously functional-
ized N-doped graphene was prepared by refluxing GO in
dimethyl formamide, exhibiting reversible capacity of
180.1 mAh g-1 at the current density of 50 mA g-1 [72].
The evolution of structural changes with different refluxing
time was also investigated, indicating that the removal of
oxygen-containing functional groups left dangling bonds
during the solvothermal reduction, which was responsible
for the N-doping at longer refluxing time.
4.2 N-doped graphene-based composites as anode
materials for LIBs
Hybridizing heteroatom-doped graphene with high capacity
second-phase materials leads into significantly improved
performance of corresponding composites when studied as
anode materials of LIBs [73–83].
SnO2 is regarded as one of the most promising anode
materials with high theoretical capacity (782 mAh g-1)
and low intercalation potential for lithium ions. However, it
suffers from a severe volume change during lithiation and
delithiation process, which leads to extremely poor cycling
stability [69]. Introducing of N-doped graphene to SnO2
can efficiently solve this problem.
In this fashion, SnO2/N-doped graphene sandwich papers
were fabricated by the pyrolysis of the mixture of graphene
and SnCl2, in which 7,7,8,8-tetracyanoquinodimethane
anion acting as both the nitrogen source and the complexing
agent. The composite with a nitrogen doping of 8 at.%
exhibited a high reversible capacity of 910 mAh g-1 at
50 mA g-1 and good cycling stability [74]. The improved
electrochemical performance was attributed to the structural
features that provided large number of surface defects
induced onto the graphene by N-doping, excellent electronic
conductivity, short transportation length for both lithium
ions, and electrons, and enough elastomeric space to
accommodate volume changes upon Li insertion/extraction,
as depicted in Fig. 9.
A hydrothermal process was used in preparation of
ultrathin SnO2 nanorods/N-doped graphene composite with
4.6 at.% of nitrogen. The composite showed high revers-
ible specific capacity of 803 mAh g-1 even after 100
cycles, superior rate capability and outstanding cycling
stability as anode materials of LIBs [75]. The synergistic
Fig. 8 (Color online) a SEM image of the N-doped graphene. b N1 s
XPS spectrum of the N-doped graphene. Inset schematic structure of
the binding conditions of N in a graphene lattice showing the
pyridinic N (N1) and pyrrolic N (N2), indicated by magenta dotted
rings. Reprinted with permission from Ref. [41], Copyright (2011),
American Chemical Society
Chin. Sci. Bull. (2014) 59(18):2102–2121 2113
123
effect between N-doped graphene nanosheets and SnO2,
which greatly decreased the energy barrier for Li penetra-
tion, the structural defects on the sites of pyridinic nitrogen
atoms and improved electronic properties were concluded
as key reasons for such enhanced performance.
In a different approach, hybrid SnO2 nanocrystals/N-
doped graphene composite with 3 at.% of nitrogen doping
was fabricated from a homogeneous aqueous suspension of
SnO2 nanocrystals and GO by in situ hydrazine monohy-
drate vapor reduction. The very high and stable capacity of
1,021 mAh g-1 for the composite material benefited from
the nano-sized SnO2 particles, the highly conductive
graphene, and the Sn-N bond formed between graphene
and SnO2 nanocrystals [83].
SnO2 nanoparticles/N-doped graphene with high nitro-
gen doping of 7.5 at.% was carried out by a modified
polyol reduction method. The composite was used as an
anode material in LIBs, displaying a superior reversible
capacity (1,220 mAh g-1 after 100th cycle at 90 mA g-1).
In addition, impedance measurements also revealed that N
doping significantly reduced the charge transfer resistance
of graphene-based electrodes [81].
Fig. 9 (Color online) Charge/discharge curves of a SnO2/N-doped graphene papers and b commercial SnO2 nanoparticles (20–50 nm) at various
current densities. c, d Cycling performance of SnO2/N-doped graphene paper (c) and SnO2 nanoparticles (d) at a current density of 50 mA g-1.
e Schematic representation showing paths for lithium ions and electrons in the SnO2/N-doped graphene paper, respectively. Reprinted with
permission from Ref. [74], Copyright (2012), WILEY–VCH Verlag GmbH & Co. KGaA, Weinheim
2114 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
Besides SnO2, other hybrid materials are also performed
as the anodes of LIBs. One example is represented by MnO/
N-doped graphene nanosheets with the nitrogen doping of
1.13 wt% and was prepared by a hydrothermal method fol-
lowed by the thermal treatment in ammonia gas as illustrated
in Fig. 10. MnO nanoparticles were homogenously anchored
on the layers of N-doped graphene to form an efficient
electronic/ionic mixed conducting network, exhibiting a
reversible electrochemical lithium storage capacity as high
as 772 mAh g-1 at 100 mA g-1 after 90 cycles [76].
A hydrothermal condition was applied in the preparation of
Fe2O3/N-doped graphene composite with 2.2 wt% of nitro-
gen. The composite showed improved cycling performance
than those of Fe2O3/pristine graphene composite and pure
Fe2O3, delivering a reversible capacity of 1,012 mAh g-1
after 100 cycles at 100 mA g-1 and a superior rate capability
[73]. The small particle size of Fe2O3, the synergistic effect
between Fe2O3 particles and N-doped graphene, and the good
electronic conductivity by introducing N-doped graphene to
the composite were concluded as main factors for high per-
formance of this anodic LIBs material.
In another work, Fe2O3/N-doped graphene composite
with a higher nitrogen doping of 7 % was produced by an
annealing process and delivered a reversible capacity of
1,100 mAh g-1 after 50 cycles [82].
Co3O4/N-doped graphene was reported by a hydrother-
mal reaction with GO, cobalt acetate and ammonia solu-
tion. Such composite delivered high initial capacity of
1,413 mAh g-1 at 400 mA g-1 and a reversible capacity
of 775.2 mAh g-1 after 50 charge/discharge cycles as the
anode material [78]. In this composite, graphene nano-
sheets buffered the volume change of Co3O4 upon lithium
insertion/extraction thus improving the cycling perfor-
mance of LIBs. Moreover, nitrogen doping not only
improved the conductivity of graphene nanosheets, but also
introduced defects to store lithium and enhanced the con-
nection of the Co3O4 nanocrystals to the graphene nano-
sheets, leading to better distribution of Co3O4 on graphene
nanosheets and enhanced rate performance.
TiO2/N-doped graphene composite with 1.75 wt% N
doping was synthesized by the combination of the ammo-
nia thermal treatment and a gas/liquid interface. The results
revealed that such composite showed a much better elec-
trochemical performance than the TiO2/graphene compos-
ite and the bare TiO2 nanoparticles. Importantly, a high
reversible capacity of 109 mAh g-1 was still obtained even
at a super high current density of 5,000 mA g-1 [77].
Another report describes preparation of anatase TiO2
nanoparticles/N-doped graphene via hydrothermal method.
When applied as anode material of LIBs, such composites
exhibited reversible capacity of 226 mAh g-1 at 0.2 C.
The introduction of nitrogen in graphene was proven to
increase the conductivity of graphene as well as providing
more structural defects on N-doped graphene where more
lithium ions could be accommodated thus leading to the
good electrochemical performance [79].
VO2 nanoparticles/N-doped graphene synthesized by a
hydrothermal method also showed an improved LIBs per-
formance, with an enhanced reversible capacity of
251 mAh g-1 (50 mA g-1) compared to the pure VO2 [80].
Apart from metal oxides, other anode materials with
N-doped graphene have also been studied. N-doped
graphene frame supported silicon@graphitic carbon gran-
ules with a nitrogen doping of 3.35 % was synthesized by
one-step solid-state reaction using iron phthalocyanine
(FePc) and silicon nanoparticles (Si NPs) as the precursors.
The self-assembled granules realized a high reversible
capacity up to 1,065 mAh g-1 after 200 cycles at
0.28 A g-1 when applied as anode material in LIBs [84].
VN/N-doped graphene hybrid composites were synthe-
sized by a sol–gel method followed by thermal treatment at
ammonia atmosphere (800 �C). In the composites, VN
nanoparticles were adhered to the surface of N-doped
graphene nanosheets providing efficient electronic and
ionic conducting network and exhibited a capacity of 983
mAh g-1 at 42 mA g-1 [85].
Phase-controlled Ni3S4/N-doped graphene composite
with nitrogen of 6.05 at % was prepared during the hydro-
thermal process. The composite with a high content of the
electrochemically favorable pyridinic nitrogen (up to
81.93 %) showed high discharge capacity of 558.2 mAh g-1
at high discharge rate of 4 C and excellent capacity retention
of 95.19 % after 100 cycles [86].
A fast microwave-assisted route was employed using
ethylenediamne as the nitrogen source to produce the
Zn2GeO4/N-doped graphene nanocomposites. GO sheets
transformed in situ into N-doped graphene through the
Fig. 10 (Color online) Schematic illustration for the preparation of
N-doped MnO (N-MnO)/N-doped graphene hybrid material [76].
Reprinted with permission from reference 76, Copyright (2012),
American Chemical Society
Chin. Sci. Bull. (2014) 59(18):2102–2121 2115
123
reduction and doping of N atoms by the resulting amine
under microwave irradiation. The as-formed nanocom-
posite with nitrogen doping of 1.98 wt% exhibited high
capacity of 1,463 mAh g-1 for the initial discharge
capacity and 1,044 mAh g-1 after 100 cycles at a current
density of 100 mA g-1 and stable rate performance [87].
4.3 Other heteroatom-doped graphene as anode
materials for LIBs
B-doped graphene with a small amount of boron ele-
ment (0.88 at.%) was synthesized by thermal treatment
of GO with BCl3 gas (Fig. 11). When tested as anode
in LIB, this material exhibited an ultrahigh initial
capacity of 1,549 mAh g-1 and high reversible capacity
of 1,227 mAh g-1 at low current density of 50 mA g-1.
More importantly, as-produced B-doped graphene could
be quickly charged and discharged in a very short time
together with high-rate capability and excellent long-
term cycleability. A high capacity of 235 mAh g-1 was
obtained even at high current density of 25 A g-1 with
just 30 s to the full charge [41]. The superior electro-
chemical performance of this B-doped graphene was
attributed to the increased conductivity and electro-
chemical activity, increased disordered surface mor-
phology, produced topological defects by doping and
higher hydrophobicity as well as better wettability
toward organic electrolytes than the pristine graphene,
all of which were favorable for Li storage and conse-
quently improved the reversible capacity of this anodic
material.
In another report, P-doped graphene was synthesized
and for the first time applied as the anode materials in
LIBs. The disordered carbon structure upon doping with
phosphorus was concluded as beneficial to the Li storage.
P-doped graphene with 1.81 at.% of phosphorous was
synthesized after thermal annealing of GO and triphenyl-
phosphine. Enhanced reversible capacity and rate perfor-
mance reaching a capacity of 460 mAh g-1 at 0.1 A g-1
with almost no loss over 80 cycles were observed com-
pared with that of the un-doped graphene (280 mAh g-1)
[30].
Hierarchically porous nitrogen (4.2 %) and sulfur
(0.94 %) co-doped graphene was fabricated through a
facile in situ constructing strategy via nickel foam tem-
plating and using GO, sulfonated polystyrene spheres, and
poly(vinyl pyrrolidone) as precursors. Benefitting from the
synergistic effect of hierarchically porous structure and
nitrogen and sulfur co-doping, the novel electrodes deliv-
ered reversible capacities of 1,137 and 957 mAh g-1 at
first and tenth cycles, respectively, and high-power density
and energy density of 116 kW kg-1 of 322 Wh kg-1 at
80 A g-1, respectively [88].
Table 2 lists all the above mentioned heteroatom-doped
graphene materials applied as anode materials of LIBs.
Similar to SCs, heteroatom doping clearly affects the
performance of graphene in LIBs and improved electro-
chemical properties including capacity, rate performance
and cycling stability are demonstrated. Particularly.
promising is attempt of combining heteroatom-doped
graphene with high capacity inorganic anodic materials
such as SnO2 and Si where doped graphene not only
prevents mechanical deterioration of inorganic phase
during charge/discharge but also improved electronic and
conductivity properties of such composite electrode
materials.
Fig. 11 (Color online) a STEM image of B-doped graphene and b C- and c B-elemental mapping of the square region in (a). d B1 s XPS
spectrum of B-doped graphene. Inset: schematic structure of the binding conditions of B in a graphene lattice showing BC3 (B1) and BC2O (B2),
indicated by magenta dotted rings. Reprinted with permission from Ref. [41], Copyright (2011), American Chemical Society
2116 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
Ta
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O3/N
-do
ped
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Fe(
NH
4) 2
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Chin. Sci. Bull. (2014) 59(18):2102–2121 2117
123
Ta
ble
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nu
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Item
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op
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/met
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0]
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hk
g-
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1
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[88
]
2118 Chin. Sci. Bull. (2014) 59(18):2102–2121
123
5 Conclusion and future prospects
In this paper, we aimed to summarize recent developments
in the synthesis of heteroatom-doped graphene materials
and their application as electrode materials for the energy
storage systems including SCs and LIBs.
Since graphene discovery a large number of methods
have been explored and successfully applied in preparation
of the heteroatom-doped graphene including direct syn-
thesis and post-synthesis treatments. Graphene-based
materials with different levels of doping have been
obtained but the process for a large-scale production of
doped graphene is still lacking thus providing an oppor-
tunity for further exploration and development. Another
important aspect is the ability to control the level of doping
as well as the type of introduced functionalities to the
graphene materials. It is the feeling of authors that the
strategy in most reported researches is to randomly select
precursors and the synthesis methods to produce graphene
materials with some sort of doping. The systematic studies
on the mechanism of heteroatom doping in graphene from
model precursors (such as urea or melamine in case of
N-doped graphene production for instance) and at the
conditions of standard synthesis routes (such as hydro-
thermal or thermal methods for instance) could be very
enriching in terms of good fundamental understanding of
the formation of the heteroatom-doped graphene thus
providing more standardized routes for doped graphene
with desired level and type of doping.
This is particularly important for the application of
heteroatom-doped graphene and its derivatives as electrode
materials of SCs and LIBs. As the studies clearly show,
heteroatom doping greatly enhances the energy storage
capacity and rate performance of graphene materials. Par-
ticularly, the N-doped graphene has been extensively
investigated as the electrode material of SCs and improved
performance has been reported each time. The variations in
graphene electronegativity upon doping, different charge
on doped heteroatoms and surrounding carbon atoms as
well as changes in physical and chemical properties of
graphene have been found as key reasons for improved
energy storage capacity of doped graphene in SCs. How-
ever, a profound fundamental understanding of the effect of
nitrogen doping on the energy storage mechanics is still
somehow lacking, especially the effect of various types of
nitrogen functionalities. It is our opinion that computa-
tional chemistry combined with the state of the art ana-
lytical methods will play a critical role in clarifying the
fundamentals lying behind the energy storage capacity in
N-doped graphene and will lay foundation fordesigning
synthesis methods for specifically enriched N-doped
graphene.
With regards to application of heteroatom-doped
graphene in LIBs, a great amount of interest has been
devoted to N-doped graphene and its composites as anode
materials. The greatly enhanced performance is often
attributed to the alteration of the electronic properties of
graphene upon doping, formation of defects and thus
improved storage capacity for lithium ions and enhanced
bonding capabilities between N-doped graphene and
composite counterparts. Similar to the SCs, the LIBs
research and development would also benefit from better
understanding of the mechanism of the Li ion energy
storage in N-doped graphene and its composites that would
consequently allow designing anode materials with supe-
rior Li ion storage capacity.
The majority of the work has been focused on N-doped
graphene and its application in SCs and LIBs, however,
some reports also show that other heteroatoms including
boron and phosphorus as well as co-doping of nitrogen and
boron have positive effect on the energy storage capacity of
corresponding doped graphene in both the supercapacitors
and Li-ion batteries. While the mechanism of the energy
storage capacity in such graphene materials is yet to be
clarified, results clearly indicate that doping of graphene
with nitrogen, boron, phosphorus, or their mixtures is an
effective way for increasing the specific energy storage
capacities and rate performance, both of which are criti-
cally important in designing effective energy storage sys-
tems for large-scale applications including renewable
energy. Therefore, once the fundamentals behind energy
storage mechanism in heteroatom-doped graphene are
better understood, the new large-scale synthesis routes can
be developed, and the heteroatom-doped-based graphene
materials will play major role as commercial electrode
materials of SCs and LIBs in the future.
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