Journal of Science: Advanced Materials and Devices 4 (2019) 341e352

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Journal of Science: Advanced Materials and Devices

journal homepage: www.elsevier.com/locate/jsamd

Review Article

Heteroatom doped high porosity carbon nanomaterials as electrodes

for energy storage in electrochemical capacitors: A review
Qaisar Abbas a, *, Rizwan Raza b, Imran Shabbir c, A.G. Olabi d, e
a
School of Engineering, Computing and Physical Sciences, University of the West of Scotland, Paisley, PA1 2BE, United Kingdom
b
Department of Physics, COMSATS Institute of Information Technology, Lahore, Pakistan
c
Energy Optimisation-Energy Department Tata Steel, Port Talbot, UK
d
Department of Sustainable and Renewable Energy Engineering, University of Sharjah, Sharjah, United Arab Emirates
e
Mechanical Engineering and Design, School of Engineering and Applied Science, Aston University, Aston Triangle, Birmingham, B4 7ET, UK

a r t i c l e i n f o a b s t r a c t

Article history: At present it is indispensable to develop and implement new/state-of-the-art carbon nanomaterials as
Received 24 April 2019 electrodes in electrochemical capacitors, since conventional activated carbon based supercapacitor cells
Received in revised form cannot fulfil the growing demand of high energy and power densities of electronic devices of the present
23 July 2019
era, as a result of the rapid developments in this field. Functionalized carbon nanomaterials symbolize
Accepted 26 July 2019
the type of materials with huge potential for their use in energy related applications in general and as an
Available online 20 August 2019
electrode active material for electrochemical capacitors in particular. Nitrogen doping of carbons has
shown promising results in the field of energy storage in electrochemical capacitors, gaining attention of
Keywords:
Environmental concerns
researchers to evaluate the performance of new heteroatoms functionalised materials such as sulphur,
Energy crisis phosphorus and boron lately. Literature is widely available on nitrogen doped materials research for
Electrical energy storage energy storage applications; however, there has been a limited number of review works on other
Heteroatom doped carbon nanomaterials functional materials beyond nitrogen. This review article thus aims to provide important insights and an
Electrochemical energy storage systems up-to-date analysis of the most recent developments, the directions of future research, and the tech-
niques used for the synthesis of these functional materials. A critical review of the electrochemical
performance including specific capacitance and energy/power densities is made, when these single
doped or co-doped active materials are used as electrodes in electrochemical capacitors.
© 2019 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

1. Introduction distributed and intermittent supply base to the consumer. Among

different electrical energy storage systems, electrochemical batte-
Energy landscape is expected to go through significant trans- ries and electrochemical capacitors (ECs) play a key role in this
formation attributed to the crisis instigated by the imbalance in respect. ECs are devices that can fill the gaps between electro-
world's energy supply and demand. Environmental concerns and chemical batteries and electrostatic capacitors in terms of energy
expanding gap between supply and demand of energy signify the and power densities as shown in Fig. 1.
implementation of renewable energy technologies such as solar, Electrochemical capacitors, also known as supercapacitors or
wind and tidal towards diversification of energy generation in or- ultra-capacitors (UCs), are high power electrical energy storage
der to maintain un-interrupted supply of energy at relatively lower devices retaining inimitable properties such as exceptionally high
cost combined with numerous environmental benefits. Due to the power densities (approx. 5 kWkg
1) [2], rapid charge discharge
intermittent nature of these renewable sources of energy, appro- (millisecond), excellent cycle-ability (>half a million cycles) [3] and
priate electrical energy storage systems are required for ensuring high charge retention (>90% capacitive retention) [4]. Depending
security and continuity in the supply of energy from a more on their charge storage mechanism, ECs can be classified into two
categories; electric double layer capacitors (EDLCs) and pseudo-
capacitors (PCs). In EDLCs, capacitance arises from purely physical
phenomenon involving separation of charge at polarized electrode/
* Corresponding author. electrolyte interface where as in PCs electrical energy is stored
E-mail address: [email protected] (Q. Abbas).
through fast and fully reversible faradic reaction coupled with the
Peer review under responsibility of Vietnam National University, Hanoi.

https://doi.org/10.1016/j.jsamd.2019.07.007
2468-2179/© 2019 The Authors. Publishing services by Elsevier B.V. on behalf of Vietnam National University, Hanoi. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
342 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352

Electrode / Electrolyte Interface

+ Electrode Separator - Electrode

Carbon Electrode

Carbon Electrode
Fig. 1. Ragone plot of energy density vs power density for various electrical energy
storage and conversion devices [1].

electronic transfer at the electrode/electrolyte interface [5], a

schematic diagram of the charge storage mechanism of both elec-
tric double layer capacitor and pseudo-capacitor is shown in Fig. 2,
followed by a detailed discussion on the charge storage mechanism
in the electric double layer capacitors (EDLCs) and pseudocapaci-
tors (PCs).

1.1. Energy storage mechanism of electrochemical capacitors " "

As discussed in the previous section, there are two types of
charge storage phenomenon i.e. surface charge storage (physical
Fig. 3. Schematic of the charge storage mechanism of an electrical double layer
storage of charge) and bulk charge storage (electrochemical storage capacitor.
of charge), also known as electric double layer capacitance and
pseudocapacitance, respectively. Carbon based materials such as
activated carbons [7], graphene [8], carbon nano-tubes [9,10], car- purely a physical phenomenon without any electronic transfer
bide derived carbons [11] and carbon fibres [12] are the key elec- which makes EDLCs an ideal candidate for high power application
trode materials used as electrodes in electric double layer capacitors. since it can be fully charged or discharged in a very short span of
EDLCs store electrical charge on the same principle as in electro- time [20,21] and retains an exceptionally long cycle life [22,23].
static capacitors, however, in case of the electric double layer Energy storage in pseudocapacitors is realized through fast and
capacitor two separate layers of electrical charges are formed be- fully reversible Faradic charge transfer, which is an electrochemical
tween positively/negatively charged carbon electrodes and elec- phenomenon where an electronic transfer occurs at the electrode/
trolyte ions, respectively [13,14] as illustrated in Fig. 3. Specific electrolyte interface [24e26] as shown in Fig. 4. Ruthenium oxide
capacitance of a capacitor can be calculated using equation (1). [27], manganese oxide [10], iron oxide [28] and nickel oxide [29]
are the most commonly used metal oxides whereas polyacetylene
A
C ¼ ε0 εr (1) [30], polypyrrole [31], poly(3,4-ethylenedioxythiophene) [32] and
d polyaniline [33] are frequently used conducting polymers as elec-
EDLCs maintains specific capacitance six to nine orders of trode materials in pseudocapacitors.
magnitude higher when compared with conventional capacitors PCs have much higher energy densities as compared to EDLCs
[15] since charge separation ‘d’ is much smaller during the forma- since the specific capacitances of pseudocapacitive devices are also
tion of an electric double layer, and the specific surface area ‘A’ of an much higher which can have a positive impact on energy density of
active material is much higher (up to 3000 m2g-1) [16e19] when the device according to Equation (2). However, the pseudocapaci-
compared with electrostatic capacitors. Charge storage in EDLCs is tive devices have lower cycle life [34] and cyclic efficiency [35] in

Fig. 2. Schematic diagrams of A) an electric double layer capacitor [EDLC] and B) a pseudo-capacitor [PC] [6].
 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352 343

+ Electrode Separator - Electrode

Interface Interface

Electrode Electrode

Carbon Electrode

Carbon Electrode
e e

Electroly
Electroly
C+ C+

Fig. 4. Schematic of the charge storage mechanism of a pseudocapacitor.

comparison to EDLCs since charge is stored within bulk of the active and PC is due to the dopant such as metal oxides/conducting
material where long term cycle-ability can have an adverse effect polymers or heteroatoms. However, the use of metal oxides based
on the integrity of the active material. dopants in practical applications is limited due to its higher cost,
lower conductivity (with the exception of ruthenium oxide) and
limited cycle stability [39]. Heteroatoms doped carbons have dis-
1.2. Energy and power merits of electrochemical capacitors played an improved capacitive performance due to the pseudo-
capacitive contribution through a fast and fully reversible Faradic
Despite maintaining high power densities, ECs suffer from reaction without forfeiting the excellent power density and long
inferior energy densities as compared to other electrochemical cycle life [40].
energy storage and conversion devices such as electrochemical Numerous research studies have been performed to evaluate the
batteries and fuel cell respectively, limiting their engineering ap- contribution made by nitrogen [41] boron [42], phosphorus [43]
plications requiring high power/energy capabilities. To overcome and sulphur [44] based functional groups in the field of energy
this challenge, extensive research has been undertaken to improve storage especially when incorporated in carbon based electrode
the energy densities of ECs, in order to broaden their scope of ap- active materials for supercapacitor applications. Nitrogen is by far
plications [36,37]. Since the energy density (E) of an electro- the most extensively investigated heteroatom whereas other het-
chemical capacitor is directly proportional to its capacitance (C) and eroatoms are considered for investigation more recently.
square of the operating voltage (V) as defined by Equation (2).

1 2. Functionalized nano-carbons
E ¼ CV2 (2)
2
2.1. Nitrogen [N] functionalized carbons
where the operation voltage V is limited by the type of electrolyte
used.
A diverse range of synthesis techniques has been adopted to
Either by increasing the specific capacitance or the operating
produce N-doped carbons however; some of the most frequently
voltage is considered an effective way to enhance the energy
used techniques are deliberated below. One of the most frequently
density of the EC cell. However, using electrolytes with higher
used methods to synthesise nitrogen doped carbon is through heat-
working voltages such as organic or ionic liquids results in higher
treatment of un-doped (crude) carbons with nitrogen containing
equivalent series resistance (ESR) which results in the poorer po-
material such as urea [CH4N2O] [45], nitric acid [HNO3] [46] and
wer density; the power density of EC is given by Equation (3).
ammonia [NH3] [47] where nitrogen is introduced on the surface of
an active material. Another simple approach of producing N-doped
1 ðDVÞ2
P¼ (3) carbons is through carbonization of nitrogen containing precursors
2 R such as melamine [C3H6N6], polyacrylonitrile [C3H3N] and poly-
Alternative approach to enhance the energy density of an vinylpyridine, [C6H9NO]n where nitrogen can be introduced inside
electrochemical capacitor cell is by increasing the specific capaci- carbon structure. Finally, an alternative technique, which is a
tance of ECs. The improved specific capacitance is attainable by comparatively cost-effective way of producing N-doped carbons, is
introducing the pseudo-capacitive entities such as metal oxides/ through thermal treatment of nitrogen containing biomass such as
conducting polymers [38] or heteroatoms (nitrogen, sulphur, boron glucosamine [C6H13NO5] [48,49]. These nitrogen doped carbons
and phosphorous) on the surface or within the structure of a carbon produced through a variety of synthesis techniques are widely used
based active material where the total capacitance is the sum of both for electrical energy storage in supercapacitors, since N-doping
EDLC and PC. EDLC is exhibited by a carbon based active material results in superior performance of the electrochemical capacitor
344 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352

cell where the specific capacitance of a nitrogen doped active ma-

terial is the sum of EDLC due to the physical phenomenon occurring
at the electrode/electrolyte interface and PC due to the fast and fully
revisable Faradic reaction coupled with electronic transfer owing to
the electron donor properties of nitrogen [50] as represented by
Equations (4) and (5).

C ¼ NH þ 2e
4
CH
NH2 (4)

C
NHOH þ 2e
þ 2Hþ 4
C
NH2 þ H2 O (5)

Specific capacitance of an electrochemical capacitor can be
improved substantially by the mean of nitrogen doping in one
such study, Han et al. prepared the pueraria-based carbon (PC)
followed by nitrogen doping achieved by a simple thermal
treatment of pueraria powder and melamine (NPC). It was
observed that nitrogen doped carbon exhibited a remarkably
superior capacitance of 250 Fg-1 as compared to 44 Fg-1 for un-
doped carbon at the current density of 0.5 Ag-1 using 6M KOH as
an electrolyte with its capacitance retention over 92% [51].
Another study by Mao et al. showed that N-doping resulted in Fig. 5. Images showing the wettability of the un-doped (RF) and nitrogen doped (NRF)
the improved electrochemical performance where N-doped car- carbons samples [55].

bon displayed an excellent areal capacitance with the attained

specific capacitance of more than twice (683 mF cm
2 at
2 mA cm
2) after nitrogen doping as compared to 330 mF cm
2 2.2. Phosphorus [P] functionalized carbons
for an un-doped carbon when used as an electrode in the
supercapacitor cell with an excellent long term cyclic stability of Phosphorus displays analogous chemical properties as nitrogen
more than 96% after 10000 cycles [52]. Inferior energy densities since it has the same number of valence electrons; however, the
of supercapacitors limit their practical applications, and nitrogen higher electron-donating capability and larger atomic radius makes
doping can be adopted as a favourable technique to improve it the preferred choice for its adoptions as a dopant in carbon
their energy densities for their wider adoption in practical use. materials.
The improved energy density of 6.7 Whkg
1 as compared to A commonly used method to produce phosphorus doped car-
5.9 Whkg
1 was attained after the introduction of nitrogen bons is through thermal treatment of carbon with phosphorus
functionalities which provides a clear evidence that N-doping is containing regents both at carbonization and activation stages
an efficient way of improving the energy densities of the [66e68], which results in introducing phosphorous on to the car-
supercapacitor cells and the enhancement in energy densities bon surface whereas phosphorous species can be doped inside the
will lead to their commercial applications [53]. An exceptionally carbon matrix when phosphorous containing precursor is carbon-
high energy density of 55 Wh kg
1 (one of the highest values ized at elevated temperatures [69,70]. It is more convenient to
ever reported in the literature for this type of active material) at prepare P-doped carbons through the first procedure; however by
a power density of 1800 W kg
1 with an excellent cycling effi- adopting the latter process P-doped carbon materials can be syn-
ciency of over 96% was achieved when Dai and co-workers used thesised by precisely controlling the P content.
the nitrogen doped porous graphene as an electrode and n Adoption of phosphorus-doped carbons for their application in
BMIMBF4 electrolyte to benefit from the higher operating po- the broad field of energy storage such as electrochemistry generally
tential of around 3.5 V [54]. Nitrogen doping also improves the and as an electrode material in electrochemical capacitors particu-
wetting behaviour of the electrolyte which improves the elec- larly is a highly promising concept. However, the use of phosphorous
trode/electrolyte contact at the interface along with reduction in doped carbon as an electrode in electrochemical capacitors has been
solution resistance. A study by Candelaria et al. showed that the limited, resulting in the limited understanding of its effect on physio-
wettability improved after nitrogen doping with the drop in chemical properties ultimately restricting its potential to be used as
contact angle from 102.3 to zero as shown in Fig. 5. The ni- an active material and hence on the overall performance of a
trogen doped carbon attained capacitive value of twice higher supercapacitor cell [71]. Phosphorous doping results in an improved
than that of an un-doped carbon [55]. Further examples of ni- charge storage due to the additional pseudo-capacitive component
trogen carbons when used as an active material in super- alongside electric double layer since phosphorus also possesses
capacitors with a comprehensive evaluation of their physical and electron-donor characteristics and also an enhanced transport
electrochemical properties presented in the literature is shown capability due to its exceptionally high electrical conductivity when
in Table 1. Table 1 shows various physical and electrochemical used as an active material [72]. Yi et al. synthesised the cellulose-
properties of different types of nitrogen doped carbon based derived both un-doped carbon (CC) and phosphorous doped car-
materials when used as electroactive materials. bon (P-CC) showing an excellent capacitive performance along with
It can be established from the above discussions that nitrogen the improved conductivity. A specific capacitance of 133 Fg-1 at a
doping is the most favourable routes to synthesise functional high current density of 10 Ag-1 and the excellent capacitance
electrode-active materials for supercapacitor applications. N- retention of nearly 98% after 10000 cycles were achieved. A
doping is advantageous to improve both physical and electro- momentous drop from 128.1 to 0.6 U in charge transfer resistance
chemical properties such as wettability, capacitive performance alongside drop in contact angle from 128.3 to 19.2 after phos-
and energy/power densities respectively which can have a positive phorus doping was witnessed [66] as shown in Fig. 6, where Fig. 6a)
impact on the overall performance of the system. shows the drop in contact angle with an improved wetting behaviour
 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352 345

Table 1
Physical and electrochemical characteristics of various nitrogen doped carbons used as active materials in supercapacitors.

Electrode materials Specific surface area (m2 g
1) Capacitance (Fg
1) Energy density (Wh kg
1) Power density (kW kg
1) Reference

Carbon nano-cages 2407 313 6 22 [56]

Activated carbon 1580 855 39 23 [57]
zeolite-templated carbon 3600 273 8 98000 [53]
Graphene nano-sheets 380 480 83 426 [58]
Activated Carbon 2905 351 39 1.0 [45]
Activated Carbon 1459 451 11 125 [59]
Activated carbon 2255 258 5 10 [60]
Graphene 203 390 55 1800 [54]
Activated biomass 2650 200 6 8 [61]
Activated carbon 2723 221 5 2500 [62]
Graphene aerogels 446 318 60 900 [63]
Activated carbon 1848 261 4 10 [64]
Template derived carbon 2506 337 10 14.4 [65]

Fig. 6. a) Contact angle of 6M KOH on the surface; b) Nyquist plots of the doped and un-doped carbons [66].

and Fig. 6b) represents the Nyquist plots of various carbons charac- electrode materials with their physical and electrochemical proper-
terizing the resistive behaviour of various carbon samples. ties is given in Table 2.
In another study, phosphorus doped graphene was synthesised Phosphorus-doping can assist in achieving higher capacitive
by the activation of graphene with sulphuric acid, which resulted in performance alongside other supplementary benefits such as
P-doping of 1.30%. It was established that P-doping not only improved conductivity and reduced charge transfer resistance
improved the capacitive performance it also widened an operating (owing to improve wettability). However, immense research is
voltage window of the cell which resulted in the enhanced energy mandatory in order to understand the underlying reasons for these
density as given by Equation (1). An exceptionally high energy improvements to adopt phosphorus doped active materials for use
density of 1.64 Whkg
1 at a high power density of 831 Wkg-1 was as electrode for electrochemical capacitors commercially.
realised due to the higher operating potential of 1.7 V rather than
1.2 V for an aqueous electrolyte (1M H2SO4) [73]. It has also been 2.3. Sulphur [S] functionalized carbons
reported that oxygen surface functionalities such as chemisorbed
oxygen (carboxylic groups) and quinones of an active material are When compared with nitrogen, oxygen or boron, sulphur
electrochemically active and can contribute towards the overall doping of carbon materials is still very rare which signifies an
performance of the cell [40]. However, these surface functional excellent research opportunity in the field of carbon materials for
groups are unstable in nature and can cause deterioration in capac- energy storage applications in general and electrochemical capac-
itive performance [74]. Phosphorous can also be used as an oxidation itors in particular. Very little has been known until very recently
protector when introduced within the carbon structure preventing about the effect sulphur functional groups on the performance of
the combustion of oxygen species which contributes toward the these materials when adopted in applications related to field of
enhancement in the cell performance accompanied by the obstruc- energy storage. Electronic reactivity of active material can be
tion in formation of electrophilic oxygen species [75,76]. A recent improved by incorporating sulphur functional groups within the
study by Ma et al. has shown that phosphorous doping not only carbon scaffold or on the surface, since sulphur modifies the charge
enhances the capacitive performance due to the additional capaci- distribution within the carbon structure or on the surface respec-
tance arising from the reversible redox reaction, but also prevents tively due to its electron donor properties which results in an
the formation of unstable quinone and carboxylic groups, resulting in increased electrode polarization and specific capacitance via fast
a higher operating voltage of 3.0 V much when used in conjunction and fully reversible faradaic process [84,85]. Sulphur functionalized
with pure carbon (around 2.5 V) leading to the delivery of an active carbon nanomaterials have been prepared using various
exceptionally high energy density of 38.65 Wh kg
1at a power methods which include the direct thermal treatment of sulphur
density of 1500 W kg
1 when used with the organic electrolyte (1 M containing compounds or by co-carbonization of carbon with
Et4NBF4/PC) [68]. A wide range of phosphorus doped carbon based elemental sulphur [86e89]. Improved conductive performance and
346 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352

Table 2
Physical and electrochemical characteristics of various phosphorus doped carbons used as active materials in supercapacitors.

Electrode materials Specific surface area (m2 g
1) Capacitance (Fg
1) Energy density (Wh kg
1) Power density (kW kg
1) Reference

Activated carbon 940 367 8.5 10 [69]

Activated carbon 1535 133 4.7 0.83 [66]
Activated carbon 2133 121 39 1500 [68]
Carbon aerogels 1618 406 17 200 [77]
Activated carbon 2055 210 e e [78]
Mesoporous carbon 1122 228 e e [79]
Activated carbon 2133 121 39 1500 [68]
Carbon aerogel 1450 110 17 170 [80]
Graphene 221 115 11.6 0.83 [73]
Graphene e 367 59 9 [81]
Nano-tubes e 2080 42 750 [82]
Carbon nano-fibre 586 336 e e [83]

electrode/electrolyte wettability can be achieved by doping the Sulphur doping can be considered as an efficient way to improve
carbon based electrode material with both nitrogen and sulphur the active material performance including enhanced specific
functional groups however, recent work by X Ma and co-workers capacitance, conductivity and wettability whereas drop in charge
has shown that sulphur functionalities results in superior conduc- transfer resistance and solution resistance of the active material
tive performance as compared to nitrogen doping [90]. Since can also be achieved. By Improving these performance parameters,
sulphur doping improves electronic conductivity, so higher specific energy density can be improved without scarifying their superior
capacitance achieved due to pseudo-capacitive contribution along power densities which is the major hurdle towards the commer-
with electric double layer capacitance (EDCL) coming from sulphur cialisation of electrochemical capacitor technology. However, still
functionalities and the porous parameters respectively of the active very little research work has been performed to study the effect of
material. Sulphur functionalizing improves the energy density of sulphur doping and under lying reasons for these improvements.
the cell without any drop in its excellent power density due to its
superior conductivity. Highly porous Sulphur doped carbon with 2.4. Boron [B] functionalized carbons
specific surface area of 1592 m2g-1 and pore structure ranging from
micro to macro was synthesised by carbonizing sodium lignosul- The electronic structure of a carbon based active material can be
fonate. Sample with high sulphur weight percentage of up to 5.2 wt modified by introducing boron into the carbon framework. It is
% was prepared which exhibited the highest specific capacitance of easier to dope carbon based nanomaterials either with nitrogen or
320 Fg-1 with high energy density of up to 8.2 Wh kg
1 at power boron since nitrogen and boron possess analogous electronic
density of 50 W kg
1 [91]. In another study capacitive performance configuration and sizes when compared with carbon atom
improvement from 145 Fg-1 to 160 Fg-1 was attained at the scan rate [104,105]. Charge transfer between neighbouring carbon atoms can
of 10 mVs
1 for un-doped and sulphur doped graphene respec- be facilitated by introducing boron into carbon lattice since it has
tively. High energy density of 160 Whkg
1 at a power density of three valence electrons and act as an electron acceptor which re-
5161 Wkg-1 was reached using 6M KOH electrolyte for doped car- sults in the uneven distribution of charges. This charge transfer
bon. Improved wetting behaviour and capacitive performance was results in an improved electrochemical performance due to the
realized when sulphur-decorated nano-mesh graphene was used as pseudo-capacitive contribution originated from this electronic
an electro-active material. Sulphur decorated nano-mesh graphene transfer (Faradic reaction) [106]. Boron functionalizing can be
was synthesised by thermal treatment of elemental sulphur with accomplished using a diverse range of synthesis techniques such as
nano-mesh at 155  C. Specific capacitance of 257 Fg-1 was attained laser ablation [107], arc discharge method [108,109], by means of
which was 23.5% higher than un-doped graphene for the doping hydrothermal reaction [110], by substitutional reaction of boron
level 5 wt% of sulphur alongside drop in contact angle from 88.2 to oxide (B2O3) [111e113] or by adopting chemical vapour deposition
69.8 after doping as shown in Fig. 7 [92]. Some further explaes of technique [114e116]. Hydrothermal reaction is the most commonly
sulphur doped active materials are provided in Table 3. used technique to produce boron doped active materials, and the

Fig. 7. a) Contact angle of a water droplet on doped and un-doped samples. b) Specific capacitances of electrodes at different current densities.
 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352 347

Table 3
Physical and electrochemical characteristics of various sulphur doped carbons used as active materials in supercapacitors.

Electrode materials Specific surface area (m2 g
1) Capacitance (Fg
1) Energy density (Wh kg
1) Power density (kW kg
1) Reference

Carbon nano-sheets 2005 312 7 21.6 [93]

Carbon sphere 3357 405 54 0.074 [94]
Graphene 187 150 124 2. [95]
Activated carbon 1952 325 37 274 [96]
Activated carbon 1592 320 8 0.05 [91]
Activated carbon 2225 162 e e [97]
Graphene 288 270 e e [98]
Activated carbon 1730 283 e e [99]
Activated carbon 1057 332 e e [100]
Bio-carbon 660 225 e e [101]
Graphene 497 21 20 624 [102]
Graphene oxide 1500 65 e e [103]
Activated carbons e 325 22 7393 [96]

Fig. 8. Schematic presentation of the preparation of BT-rGO.

improved specific capacitance of 173 Fg-1 was achieved when boron performance of the electrochemical cell. Boron doping not only
doped graphene was synthesised through a thermal reaction. An improves capacitive performance it also enhances electrode/elec-
atomic percentage of 4.7% of boron was found to be the optimum trolyte wettability, resulting in reduction in solution resistance. A
level of boron doping when introduced into the bulk of graphene, study by Gao and co-workers, where boron doped controlled
with the achieved capacitance of nearly 80% higher than that of an porosity meso-porous carbon was prepared using a hard template
un-doped active material. The electrochemical capacitor cell approach, showed that the specific capacitance of 268 Fg-1 was
delivered a superior energy density of 3.86 Wh kg
1 at a power attained after boron doping, which is considerably higher than
density of 125 W kg
1, and managed to retain the energy density of 221 Fg-1 for an un-doped carbon at 5 mVs-1. The exceptionally low
2.92 W h kg
1 at a much higher power density of 5006 kW kg
1 solution resistance RS of 1.05U was also obtained due to the
with an excellent cycling stability of nearly 97% after 5000 charge/ improved wettability after the incorporation of boron functional
discharge cycles as shown in Fig. 9(a,b) [117]. Among other syn- groups [118,119]. Improving the surface chemistry of an electrode
thesis techniques, template or nanocasting method (hard or soft active material after boron doping can have other benefits such as
template) is also considered as a useful procedure which assists in superior conductivity. Boron doped graphene oxide was syn-
controlling the porous structure (specific surface area, pore size and thesised through a simple thermal annealing of GO/B2O3 as shown
pore shape) in a precise manner resulting in a positive effect on the in Fig. 8. The exceptionally high specific capacitance of 448 Fg-1 was

Fig. 9. a) Cycling stability and coulombic efficiency of Boron doped electrode; b) Ragone plot of a symmetric cell [117].
348 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352

Table 4
Physical and electrochemical characteristics of various boron doped carbons used as active materials in supercapacitors.

Electrode materials Specific surface area (m2 g
1) Capacitance (Fg
1) Energy density (Wh kg
1) Power density (kW kg
1) Reference

Graphene e 308 10 2.02 [121]

Activated carbon 1257 268 e e [118]
Graphene nano-sheets e 53 5 1 [122]
Meso porous carbon 1258 222 6.5 5 [119]
Graphene nano-platelets 466 200 e e [123]
Graphene oxide e 113 1.25 6 [122]
Activated carbon 670 197 e e [124]
Graphene Nano-platelets 466 200 e e [123]
Activated carbon 1657 196 e e [125]
Graphene e 173 4 125 [117]
Graphene e 491 80 221 [126]
Graphene 1102 336 e e [127]
Graphene e 270 40 e [128]
Graphene 170 268 21 5 [129]
Carbon nanofiber 641 180 22 400 [130]

reached after boron doping without using any conductivity desired manner for superior performance of energy storage devices
enhancer such as carbon black since boron doping resulted in the when used as electrodes [135e137].
improved conductivity of the active material [120]. A study by Wang et al. [138] showed that the capacitive per-
More examples of boron doped carbon when used as active formance of nitrogen and sulphur co-doped carbon samples out-
materials in supercapacitors are presented in Table 4. performed the capacitive performance of carbons using either
We have discussed various functional materials including ni- nitrogen or sulphur as dopant due to the synergetic pseudo-
trogen, sulphur, phosphorus and boron which have been widely capacitive contribution made by nitrogen and sulphur hetero-
used by researchers to improve the performance of electrochemical atoms. Specific capacitance values of 371 Fg-1, 282 Fg-1 and 566 Fg-1
capacitors. However, there is still an enormous scope to enhance were achieved for nitrogen, sulphur and nitrogen/sulphur co-
the capacitive-ability of these electrochemical devices further doped samples respectively when used in supercapacitor cells
which is achievable though co-doping of these carbon based elec- with 6M KOH as an electrolyte [138]. The maximum specific ca-
trodes. Co-doping of an active material using different combina- pacitances of 240 Fg-1 and 149 Fg-1 were achieved for aqueous and
tions such as nitrogen/boron, nitrogen/sulphur or in some cases ionic liquid electrolytes respectively at a high current density of
introducing more than two functional groups on the surface or 10 Ag-1 using nitrogen and sulphur co-doped hollow cellular carbon
inside the carbon matrix has been adopted, and its impact on the nano-capsules, which are much the higher capacitive values for this
physical and electrochemical properties will be discussed in type of electrode material reported in the literature [139]. Nitrogen
detail in the following section. and sulphur co-doped graphene aerogel offered a high energy
density of 101 Wh kg
1 when used as an electrode, which is one of
2.5. Functionalized carbons through co-doping the highest values ever achieved for this type of material. The
electrode materials also offered a large specific capacitance of
Efforts have been made to understand the impact of co-doping 203 F g
1 at a current density of 1 A g
1 when used alongside ionic
on the performance of energy storage materials recently liquid (1-ethyl-3-methylimidazolium tetra-fluoroborate,
[58,131e133]. Overall performance of energy storage devices can be EMIMBF4) as an electrolyte [140]. Similarly, a recent study by
improved further due to the synergetic effect of co-doping. Intro- Chen et al. showed that nitrogen and phosphorus co-doping results
duction of more than a single heteroatom can enhance the capac- in a very high specific capacitance of 337 F g
1 at 0.5 A g
1 which
itive performance of the carbon when used as an electrode material can deliver the energy density of 23.1 W h kg
1 to 12.4 W h kg
1 at
by tailoring its properties such as by improving the wetting power densities of 720.4 W kg
1 to 13950 W kg
1, respectively
behaviour toward the electrolyte, by introducing pseudo-capacitive [141]. Boron and nitrogen is considered as an excellent combination
species and decreasing its charge transfer resistance [134]. Het- of heteroatoms which is used by researchers to elevate the per-
eroatoms such as nitrogen, boron, phosphorus and sulphur are formance of an electrode active material through the synergistic
incorporated in various combinations to tune carbon materials in a effects of more than a single dopant; nitrogen and boron co-doped

Table 5
Physical and electrochemical characteristics of various co-doped carbons used as active materials in supercapacitors.

Electrode materials Dopant SSA (m2 g
1) Capacitance (Fg
1) Energy density (Wh kg
1) Power density (W kg
1) Reference

Activated carbon N&S 1047 298 21 180 [147]

Activated carbon N&S 748 362 11 4 [148]
Carbon spheres N&P 232 232 8 601 [149]
Carbon nanowires B&N 1022 504 23 200 [144]
Activated carbon N&S 453 247 34 4220 [150]
Activated carbon N&S 1093 272 12 8 [151]
Carbon nano-sheets N&S 1147 280 7 487 [152]
Hierarchical carbon N&P 1431 337 23 14 [141]
Graphene aerogels N&S 217 203 100 0.94 [140]
Activated carbon O,N &S 2650 576 107 900 [146]
Carbon sphere P,N&O 890 157 10 750 [153]
Hierarchical carbon O,N&S 1307 245 9 100 [154]
 Q. Abbas et al. / Journal of Science: Advanced Materials and Devices 4 (2019) 341e352 349

materials have demonstrated an excellent electrochemical perfor- is till needed to explore other functional materials since this field
mance recently [142e145]. Very recently, researchers have been is still very young with very little deliberation.
trying to evaluate the impact of trinary doping where more than Already these functional materials have shown an immense
two functional groups are introduced and the overall electro- potential however, it will be extremely fascinating for researchers
chemical performance is a sum of the electric double layer capac- in the field of energy storage to follow further improvements in
itance coming from the porous parameters of the active materials advanced functionalized carbon materials, and to witness how such
and the pseudo-capacitance of heteroatoms. A very recent study by materials will start to transform the field of materials for energy
Zhao and co-workers has shown that the excellent electrochemical applications in general and for their suitability in supercapacitors in
performance can be attained when more than two functional particular.
groups are introduced in a highly porous carbon. The specific
capacitance of 576 Fg-1 together with an extraordinary energy
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