Renewable and Sustainable Energy Reviews 52 (2015) 12821293

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Recent development in the production of activated carbon electrodes

from agricultural waste biomass for supercapacitors: A review
Adekunle Moshood Abioye, Farid Nasir Ani n
Faculty of Mechanical Engineering, Universiti Teknologi Malaysia, UTM, Skudai 81310, Johor Bahru, Malaysia

art ic l e i nf o a b s t r a c t

Article history: An overview of the recent development in the production of activated carbon electrodes from
Received 8 March 2015 agricultural waste biomass for application in supercapacitors is presented. The use of agricultural waste
Received in revised form biomass as precursor for the production of activated carbons has been on the increase lately because it is
24 May 2015
cheap, readily available and also viewed as a veritable way of combating waste disposal problem in the
Accepted 27 July 2015
agricultural industries. The effects of activating methods (physical, chemical and microwave-induced)
and conditions on the properties of activated carbons are reviewed. The survey of articles published in
Keywords: the last decade indicates the viability of biomass active carbons being used as electrodes in super-
Activated carbon electrodes capacitors. Under optimum process conditions, active carbons with specic capacitance as high as
Supercapacitors
374 F g
1 and high-rate long-cycle stability at 4 A g
1 have been produced. In this review, the inuence
Microwave-induced activation
of surface modication on activated carbon properties is also discussed. From the survey literature, it can
Surface modication
be seen that the changes in surface chemistry and the introduction of specic surface functionalities on
the surface of activated carbons impacted more on the electrochemical properties than the physio-
chemical properties of the activated carbons.
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Biomass: Sources and composition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Experimental conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1. Preparation of activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3.1.1. Physical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1.2. Chemical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1.3. Microwave induced/assisted activation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Surface modication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4. Characterization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.1. Physiochemical characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.1.1. Effects of convention heating conditions on the physical and chemical properties of activated carbons . . . . . . . . . . . . . . . . . . . . 4
4.1.2. Effects of microwave heating conditions on the physical and chemical properties of activated carbons . . . . . . . . . . . . . . . . . . . . 6
4.2. Electrochemical characterization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.3. Effects of surface modication on capacitive performance of active carbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5. Future outlooks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

n
Corresponding author. Tel.: 60 7 553 4715; fax: 60 7 556 6159.
E-mail addresses: kunleabioye@yahoo.com (A.M. Abioye), farid@fkm.utm.my (F.N. Ani).

http://dx.doi.org/10.1016/j.rser.2015.07.129
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293 1283

1. Introduction Table 1
Lignocellulosic constituent of some agricultural residuals and wastes.
High energy cost, continuous depletion of fossil fuel reserves
Lignocellulosic Hemicellulose Cellulose Lignin (%) Reference
and climate change due to excessive greenhouse gases lead to the materials (%) (%)
society turning towards renewable and sustainable energy
sources. As a result, there has been an increase in the production Banana waste 14.8 13.2 14 [22]
of green and clean energy from sources such as solar and wind and Sugarcane bagasse 2732 3244 1924 [22]
Cocoa pod husks 37 35.4 14.7 [24]
also the development of low CO2 emission electric vehicles/hybrid Oil palm empty fruit 16.818.9 38.142.0 10.511.7 [25]
electric vehicles. A major requirement in harnessing the inter- bunch
mittent electricity being generated from these renewable sources Palm kernel shell 22.7 20.8 50.7 [26]
is an efcient energy storage system. Batteries and electrochemical Oil palm bre 2270 4250 1425 [27]
Oil palm trunks 34.3 41.2 N/A [28]
capacitors are the leading energy storage devices, but both have
Oil Palm frond 40.40 30.40 21.70 [26]
their shortcomings. Though, electrochemical capacitors can be Hardwood stems 2440 4050 1825 [22]
chargeddischarged in a matter of seconds but they have lower Softwood stems 2535 4550 2535 [22]
energy densities than batteries (about 5 Wh kg
1), however, much Bamboo 1526 2643 2131 [22]
higher power densities (10 kW kg
1) [1] can be achieved within Sunower shell 34.6 48.4 17 [22]
Cassava peels 23.9 37.9 7.5 [24]
the same period than batteries. Thus, supercapacitors lying Kola nut pods 40.41 70.11 38.727 0.17 21.29 7 0.27 [29]
between electrochemical batteries and conventional capacitors Coconut husk 23.7070.62 0.52 7 0.01 3.54 70.01 [29]
are seeing as a promising replacement for batteries especially in Plantain peels (ripe) 15.077 0.09 13.87 7 0.02 1.63 7 0.02 [29]
the areas of load levelling and electrical energy storage devices; Plantain peels (unripe) 11.38 7 0.03 10.157 0.04 1.75 7 0.02 [29]
Soybean oil cake 52.51 21.58 2.80 [30]
and also for applications that required maximum power, long cycle
life, operational stability, fast chargedischarge time, low level of
heating, appropriate dimension/weight and low cost [1,2]. How-
ever, meeting the higher requirements of the future systems such fertilizers (after burning) while the remaining are burnt and left in
as portable electronics, hybrid electric vehicles and large scale open place. This review presents the analysis of the experimental
industrial equipment required substantial performance improve- data obtained for different agricultural biomass wastes as a
ment of the supercapacitors through the development of new precursor for activated carbon electrodes for supercapacitor appli-
materials and increase in our understanding of the electrochemi- cation as reported in the literature. The process of surface
cal interfaces at the nanoscale [1]. modication and its effects on the activated carbons were also
Electrode material being one of the major factors that deter- investigated in this review.
mine supercapacitors performance has continued to attract a lot
of research interests. Carbon-based materials (such as carbon
black, carbon nanotubes, glassy carbon and activated carbon), 2. Biomass: Sources and composition
transition metals (such as NiO, RuO2, MnO2 and IrO2) and
conducting polymers are some of the commonly used electrode Biomass, sometimes referred to as stored energy, is renewable
materials [3]. In the last decade, research interests have been organic materials derived from plants and animals that can serve
focused on the search and development of green carbon materials as sources of energy. Biomass is made up of carbohydrate and has
with special attention being paid to those that has the potential for less energy storage problems when compared with other renew-
agro-industrial waste mitigation. Activated carbon being a carbo- able sources such as solar and wind [22]. Wastes such as
naceous material is predominantly amorphous in nature and has agricultural/agro-industries wastes and municipal wastes and
high porosity due primarily to the production process and treat- purposely-grown energy crops such as sugarcane, corn, wheat,
ment [4]. Based on numerous studies already carried out in the etc. are the main sources of biomass.
area of preparation and physiochemical properties of activated Woody biomass contains in varying proportion hemicellulose,
carbon, it could be established that the memory, high surface area, cellulose and lignin that are referred to as lignocellulosic materials,
pore structure and chemical polarity of activated carbon depend and small amounts of simple sugar, protein, starches and lipids
largely on the precursor material and activation process [4,5]. Most [23]. The constituents of lignocelluloses are strongly intermeshed
of the commercial activated carbons are produced from fossil fuel and are chemically bonded by either non-covalent forces or
based precursor (petroleum and coal) which made them to be covalent linkage [22], and their composition varies from one plant
expensive and environmentally non-friendly hence the increasing species to another (Table 1). From the ultimate and proximate
focus on biomass precursors which are cheaper, readily available, analyses reported by Saidur et al. [22] it can be seen that biomass
renewable, structurally porous and environmentally friendly [2]. is chemically composed of carbon, hydrogen, oxygen, nitrogen and
In recent years the use of agricultural waste biomass, such as traces of sulphur and chlorine.
waste coffee beans [6], cassava peel waste [7], apricot shell [8],
sugarcane bagasse [911], rice husk [9,12,13], sunower seed shell
[14], coffee endocarp [15], rubber wood sawdust [16], oil palm 3. Experimental conditions
empty fruit bunch [2,17], camellia oleifera shell [18], poplar wood
[19], argan seed shell [20], bamboo species [5], peanut shell [13], 3.1. Preparation of activated carbon
palm kernel shell [4,21] as precursor materials to prepare porous
carbons for EDLCs have gained much attention due to their The preparation and production of activated carbon usually
abundant availability and low cost. The amount of agricultural consist of carbonization and activation that can be done either
waste biomass being generated across the globe has been on the separately in two-stage process or combined in a single stage
increase with the increase in agricultural activities in various process. The carbonization of a precursor takes place at a low
countries. Efforts at diversifying their utilization have, therefore, temperature usually between 400 1C and 850 1C and in the
been a great challenge since the direct discharge of some of these absence of oxygen. Activation is a process of converting carbonac-
wastes causes environmental problems. Some of these bio-wastes eous materials into activated carbon by thermal decomposition in
are used as feedstock for boilers, mulching for oil palm plantation, a furnace (convectional heating) or a microwave using a controlled
1284 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293

Table 2
Activation methods for preparation of activated carbon.

Activation method Activating Lignocellulosic materials Reference

agent

Chemical KOH Bamboo species, distillers dried grains with soluble, waste tea-leaves, oil palm empty fruit bunches, [2,4,5,7,14,15,20,30
argan seed shells, sunower seed shell, coffee endocarp, cassava peel waste, soybean oil cake 36]
ZnCl2 Date stones, waste coffee beans, sugarcane bagasse, waste camellia oleifera [6,10,18,3537]
NaOH Apricot shell [8]
K2CO3 Cocoa pod husk, straw pulping [34,36]
FeCl3 Date stones [37]
Physical Steam, Corncob, bagasse bottom ash, macadamia nut-shell, rice husk y ash, sawdust y ash [38]
CO2
CO2 Coffee endocarp [15,32,39]
Steam Date stones, bean pods, coconut shells, apple pulp, olive stones [4042]
Combined chemical and KOH/CO2 Oil palm empty fruit bunches, cassava peel waste [2,7]
physical (Physiochemical)
Microwave induced/assisted ZnCl2 Cotton stalk, white pine wood, sugarcane bagasse, peanut shell, rice husk [11,13,43,44]
KOH Date stone, oil palm empty fruit bunch, oil palm ber, cotton stalk, oil palm shell [17,21,4547]
K2CO3 Cotton stalk, tobacco stems, wood sawdust [45,48,49]
NaOH Langsat empty fruit bunch waste [50]
H3PO4 Waste tea, cotton stalk, bamboo [5153]
Steam Jatropha hull, coconut shells [5456]

atmosphere and heat. Physical activation, chemical activation, H3PO4 and FeCl3, which doubled as dehydrating agents and
combined chemical and physical (Physiochemical) activation and oxidants. Chemical activation is a step process in which the
microwave-induced activation are the methods being employed carbonisation and activation are carried out simultaneously and
for the preparation of activated carbon (Table 2). usually in the temperature range of 300950 1C thus inuencing
the pyrolytic decomposition and, therefore, resulting in the
development of a better porous structure and increased carbon
3.1.1. Physical activation
yield. Potassium hydroxide (KOH) and zinc chloride (ZnCl2) are the
Physical or thermal activation consists of carbonization of
most commonly used activating agents as can be seen in Table 2.
carbonaceous raw material at temperature between 400 1C and
The chemical activation process has the advantage of producing
850 1C and activation of the resulting carbon char by controlled
activated carbons with high surface area. But the post-activation
gasication using oxidising gases such as carbon dioxide, air or
washing of the carbons that is required to remove the residuals of
steam or a mixture of these gases at a temperature range of
reactants and inorganic residue (ash) that originates from the
600 1C900 1C. CO2 being a clean, easy to handle activating agent
precursor or is introduced during activation makes the process
is usually preferred as it facilitates the control of the activation
tedious, time and energy consuming and expensive.
process due to the slow reaction rate at temperature around
Zhang et al. [18] prepared activated carbon via ZnCl2 activation
800 1C [57]. However, the choice of activating agent also depends
of camellia oliefera shell (COS) and found out that the surface area
on the precursor material because different materials required a
and pore structure of the prepared activated carbons are inu-
different activating agent to obtain high surface area as reported
enced by both the activation temperature and ZnCl2/COS impreg-
by Aworn et al. [38]. The development of porosity (that is, to
nation ratio. From the available literature, carbon material with
increase the surface area and the pore volume) is the major
the highest specic surface area of 2959 m2 g
1 and high pore
function of the activating agent during the activation process,
volume of 1.65 cm3 g
1 was prepared by Jin et al. [31] via KOH
and this is usually accomplished through a controlled carbon
activation of biochar generated from the pyrolysis of distillers
burn-off and elimination of volatile matters. The level of carbon
dried grains with soluble (DDGS) at 950 1C. This result shows that
burn-off greatly depends on the temperature and duration of
biochar preparation and ash content of the biochar have signi-
activation as well as other experimental parameters such as gas
cant inuence on the microstructure of the activated carbon.
ow and furnace type and ultimately determine the quality of the
activated carbon. Some of the materials studied by this method are
coffee endocarp, macadamia nut shell, corncob, bagasse bottom
3.1.3. Microwave induced/assisted activation
ash, and sawdust y ash [15,32,38,39].
Microwave heating is a heating process in which the carbon
Nabais et al. [39] performed physical activation of coffee
bed is supplied with energy directly through the conversion of
endocarp using both CO2 and steam as activating agents at a
microwave energy by dipole rotation and ionic conduction inside
temperature of 700 1C. They were able to establish that the surface
the particles [45]. Microwave induced/assisted activation was
chemistry of the activated carbon is independent of the activation
developed in order to avoid the obvious problems of the conven-
process used. And that while the steam activation has higher
tional heating process during physical and chemical activation.
activation rate than CO2 activation, the CO2 activation produced
One of such problems is the thermal gradient. Since the heat
activated carbons with high BET surface area and pore volume
source in conventional heating process is outside the carbon bed,
when compared with samples produced by steam activation. Also,
there is a temperature gradient from the hot surface to the interior
the activated carbons were considered suitable for application as
of each char particle, thus leading to distortion and inhomoge-
supercapacitor electrodes since the cylindrical shape of the pre-
neous microstructure in the prepared activated carbon [58]. In
cursor were maintained during the activation process.
microwave heating the thermal gradient is in the reverse order
from the interior of the char to the cool surface leading to more
3.1.2. Chemical activation effective and fast microwave-induced reaction resulting in shorter
In the chemical activation process, the precursor material is processing time and high energy savings [59]. Internal and volu-
mixed with activating agents such as KOH, ZnCl2, NaOH, K2CO3, metric heating, energy transfer instead of heat transfer, instant
 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293
start-up and shutdown, fast heating, selective heating, higher level
of safety and automation, quick and smaller setup and improved
efciency are other benets offered by microwave heating as
reported in the literatures [46,58,60,61]. Due to the advantages
enumerated above the use of microwave heating for the prepara-
tion of activated carbons for various applications such as liquid
purication e.g. [17,43,46,47] and supercapacitor electrodes e.g.
[11,13,62] has been on the increase recently.
3.2. Surface modication
Texture and surface chemistry are twin factors that determine
the electrochemical performance of carbon materials. Whereas the
texture of activated carbons may be tailored for a particular
application through proper choice of activation conditions and
procedure that make preparation of activated carbon with varying
proportions of micro, meso and macropores possible; the nature
and concentration of surface functional group may be modied
using appropriate thermal and chemical post-treatments [63].
Modication of surface functional groups of carbon materials
usually leads to changes in the double-layer properties such as
wettability, capacitance, electrical conductivity, point of zero
charge and self-discharge characteristics of the carbon [64]. Sur-
face chemical heterogeneity that is related to the presence of
heteroatoms determines the chemical characteristics of activated
carbon. The heteroatoms are primarily oxygen and hydrogen and
to some extent nitrogen, sulphur, halogens and phosphorous.
These heteroatoms are either derived from the starting materials
and become part of the chemical structure due to incomplete
carbonization or introduced during the activation process [6466].
The surface oxygen functional groups mainly carboxylic, lactone,
phenol, carbonyl, pyrome, chromene, quinone and ether groups
can be classied into acidic, basic and neutral depending on their
chemical properties. The formation of these surface oxides
depends not only on the method of preparation of the carbon
but also on the temperature at which the carbon was rst exposed
to oxygen [64]. Acidic surface groups such as carboxylic, lactonic,
and phenolic functionalities which are considered to be unstable
are normally formed either by exposing carbons to oxygen at a
temperature between 200 1C and 700 1C or when carbons react
with oxidizing solutions at room temperature [64]. On the other
hand, formation of basic and neutral surface oxides which are
considered to be more stable occurs at low temperature when
carbon surface that is free from all surface compounds due to heat
treatment is in contact with oxygen [64].
As mentioned above, thermal and chemical treatments are the
methods being employed in surface modication. Thermal treat-
ments are carried out using either conventional heating method or
microwave heating, and it involves heat treatment of activated
carbon at high temperature (700 1Co r1000 1C) under hydro-
gen or inert atmosphere (nitrogen or helium) resulting in selective
removal of some surface acidic functionalities [63]. Hydrogen is
proposed to be more effective for removing oxygen functionalities
and also for stabilizing the activated carbon surface through
effective deactivation of active sites hence its preference over
inert atmosphere by researchers [65]. Modication of activated
carbon via microwave heating was carried out by Liu et al. [67],
Menndez et al. [68], Valente Nabais et al. [69] and Zhang et al.
[70]. It was observed by Liu et al. [67] and Zhang et al. [70] that
there was a gradual decrease in the surface acidic groups during
modication, while the surface basic groups increase slightly.
Several authors have studied chemical surface modication of
activated carbon using HNO3, H2O2, H2SO4 [7,19,31,63,71], ammo-
nium peroxydisulfate [20] and ammonia water [72]. Bakhmatyuk
et al. [73] carried out chemical modication of activated carbon
surface by Mn2 ions in a mixture of aqueous solutions of 5%
1285
KMnO4, 5% nitric acid with 6% ethyl alcohol added at a tempera-
ture of 80 1C, and observed that the modication lead to a shift in
Fermi level location of the material to the negative side by 0.14 V
and considerable increase in intensity I(EF) on Fermi level.
4. Characterization
4.1. Physiochemical characterization
Physiochemical characterization of carbons is done to provide
clues as to the commercial viability of the experimental carbons
[74]. Characterization of activated carbons by N2 and CO2 sorption
analyses are normally carried out to gain understanding of the
inuence of production conditions on the pore structure develop-
ment in carbons [10]. The International Union of Pure and Applied
Chemistry (IUPAC) adopted the classication of pores in porous
materials into micropores (o2 nm), mesopores (250 nm) and
macropores (450 nm) [75]. Each of these pore structure has their
adsorption purpose; while microporous structure of activated
carbon is usually desired for adsorption, the presence of meso-
pores in activated carbons are helpful in the adsorption of large
molecules and where faster adsorption rate is required [52,76]. In
order to compare the coffee ground carbon (CGC) produced with
Maxsorba reference material commonly use in supercapacitor
research [77], Rufford et al. [6] have calculated the pore size
distribution in CGC and Maxsorb from CO2 at 273 K and N2 at 77 K
adsorption isotherms (Fig. 1). Rufford and his team found out that
CGC displays a Type I isotherm characteristic of a microporous
material just like commercial Maxsorb but has a greater ratio of
narrow micropores (o1 nm) to total pore volume than Maxsorb
despite having less total pore volume than Maxsorb.
Summary of the surface area and pore structure parameters of
the activated carbons produced at optimum conditions via the
conventional heating method and microwave-induced method
reported in the literature are presented in Tables 3 and 4,
respectively. From the two tables, it can be seen that the devel-
opment of porosity in activated carbons highly depends on the
precursor and the production method.
4.1.1. Effects of convention heating conditions on the physical and
chemical properties of activated carbons
Jin et al. [31] used biochar from distillers dried grains with
solubles (DDGS) with ash content higher than 45% wt to produce
hierarchical carbon with the highest BET surface area of
2959 m2 g
1 and observed a structure of micro-layered graphene
or graphite in the TEM images (Fig. 2). Jin et al. [31], therefore,
proposed that the observed nano-layered graphene or graphite
structure might have been formed due to the protein rich
precursor and high ash content in DDGS biochar. Further investi-
gation is, therefore, suggested since it is not clear how protein rich
precursors formed carbon nanosheets.
Among activating agents, KOH is widely used due to higher
surface area and improved electrochemical performance usually
associated with it. According to Deng et al. [45], the gasication
reaction during KOH activation was responsible for the develop-
ment of porosity of activated carbon. It was proposed that at
activation temperature above 700 1C KOH was reduced to metallic
potassium during the carbonization process [33,45]. Lillo-Rdenas
et al. [87] in their study of the gasication of graphite by alkali
metal proposed the chemical reaction:
6KOH 2C-2K 3H2 2K2CO3 (1)
and subsequent decomposition of K2CO3 in inert atmosphere by
carbon as follows:
1286 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293

Fig. 1. Cumulative pore size distribution in coffee ground carbon (CGC) and Maxsorb calculated from CO2 at 273 K (left) and N2 at 77 K (right) [6].

Table 3
Characteristics of activated carbons produced by chemical activation at optimum condition.

Material Agent SBET Smicro Smeso Vtotal Vmicro Vmeso dAve. Yield Ref.
(m2 g
1) (m2 g
1) (m2 g
1) (cm2 g
1) (cm2 g
1) (cm2 g
1) (nm) (%)

Cassava peel waste KOH/ 1352 876 0.579 0.356 [7]

CO2
Sugarcane bagasse ZnCl2 1788 1.74 0.19 1.55 34.2 [10]
Oil palm empty fruit bunch KOH/ 1704 539 0.89 0.62 2.24 [2]
CO2
Palm kernel shell KOH 217 0.12 0.11 0.01 [4]
Camellia oleifera ZnCl2 2080 265 1815 1.18 0.12 1.06 2.3 [18]
Argan seed shells KOH 2132 2.18 0.96 1.22 [20]
Apricot shell NaOH 2335 0.984 0.797 0.187 [8]
Waste coffee beans ZnCl2 1019 0.48 0.21 [6]
ZnCl2 1021 1.30 0.35 0.95 [78]
Bamboo species KOH 2555 1044 10 1.25 0.94 [5]
Sunower seed shell KOH 1235 1153 82 0.67 0.59 0.08 2.2 [14]
KOH/ 2585 1760 825 1.41 0.83 0.58 2.1
CO2
Waste tea leaves KOH 2841 1.366 2.67 [33]
Distillers dried grains with soluble KOH 2959 1.65 0.83 0.42 [31]
(DDGS)
Coffee endocarp CO2 1038 0.46 0.44 [15]
KOH 361 0.17 0.11
Soybean oil cake K2CO3 1352.8 760.1 0.68 0.4 0.28 11.56 [30]
KOH 618.54 273.7 0.291 0.143 0.148 4.11
Cocoa pod husk KOH 490 0.24 2.0 13.5 [36]
K2CO3 615 0.31 2.0 24.2
ZnCl2 780 0.58 2.9 37.3
Straw pulping KOH 917 686 18.7 [34]
K2CO3 1104 687 19.8

K2CO3 2C-2K 3CO
K2CO3-K2OCO2
As a result, more pores were formed when K2CO3 was reduced
by carbons to form K, K2O, CO and CO2. Also, there is an increase in
total pore volume due to the interaction of metallic potassium in
the carbon matrix which widens the space between carbon atomic
layers [2]. Farma et al. [2], Ismanto et al. [7] and Li et al. [14] have
prepared activated carbons via combined chemical activation (KOH)
and physical activation (CO2) from oil palm empty fruit bunches,
(2) cassava peel wastes and sunower seed shells respectively and
found out that the combination of chemical activation with physical
(3) activation produces activated carbon with higher SBET values than
chemical activation (KOH) alone. The result obtained at optimum
activating conditions by Li et al. [14] shows that combined activa-
tion approach has improved activation by 67.67%. Similar results
were obtained by Farma et al. [2] and Ismanto et al. [7]. According
to Farma et al. [2], the observed improvement can be explained by
KOH activation mechanism discussed above. Also, the extension of
the activation time due to the combination of the processes allowed
the sample to benet from the effect of CO2 activation.
 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293 1287

Table 4
Characteristics of activated carbons produced by microwave-induced chemical activation at optimum conditions.

Material Agent SBET Smicro Sexternal Vtot Vmicro Vmeso Ave. Pore size () Yield Ref.
(m2 g
1) (m2 g
1) (m2 g
1) (cm3 g
1) (cm3 g
1) (cm3 g
1) (%)

Sugarcane bagasse ZnCl2 1489 229 1.3 0.33 0.85 [11]

Pineapple peels KOH 1006 521 485 0.59 0.28 0.31 23.44 [79]
K2CO3 680 538 142 0.45 0.28 0.17 25.97
Rice husks KOH 752 346 406 0.64 0.26 0.38 34.14 [12]
K2CO3 1165 607 558 0.78 0.33 0.45 26.89
Cotton stalks KOH 729.33 529.46 199.88 0.38 0.26 0.12 [45]
K2CO3 621.47 384.67 236.8 0.38 0.11 0.27
Orange peels K2CO3 1104.45 420.09 684.36 0.615 0.247 0.368 22.27 80.99 [80]
Pistachio nut shells KOH 700.53 0.375 [81]
Oil palm (Elaeis) EFB KOH 807.54 0.45 21.93 [17]
Oil palm bers KOH 1223 796 427 0.72 0.42 0.3 23.57 32.09 [47]
Oil palm residues KOH 1372 821 551 0.76 0.44 0.32 22.06 73.78 [82]
Bamboo H3PO4 1432 1112 0.696 0.503 0.1903 47.8 [52]
Cotton stalks H3PO4 652.82 127.18 525.64 0.476 0.057 0.419 [51]
Lotus stalks H3PO4 1434 453.93 928.39 1.337 0.307 1.03 40.1 [76]
Waste tea H3PO4 1157 1623 687.3 0.829 0.573 0.256 35 [53]
Grapevine rhytidome H3PO4 1607 617 990 1.42 0.48 0.94 25 [83]
Cotton stalks ZnCl2 794.84 156.69 0.63 0.083 0.547 32 37.92 [43]
Pine wood powder ZnCl2 1459 0.7 [44]
Industrial waste lignin ZnCl2 1172.7 1002 162.4 0.64 0.457 0.174 20.82 60.73 [84]
Pomelo skins NaOH 1355 524 811 0.77 0.29 0.48 23.09 [85]
Peanut shell ZnCl2 1552 1.75 0.02 1.73 37.7 [13]
Rice Husks ZnCl2 1527 1.96 0.02 1.94 32.4 [13]
Oil palm shell KOH 895 0.491 21.91 [21]
Wood sawdust K2CO3 1496.1 892.79 603.26 0.864 0.47 0.394 23.06 80.74 [48]
Date stones KOH 856 0.468 21.82 [46]
Langsat empty fruit bunch NaOH 1293.3 839.38 453.88 0.752 0.449 0.303 23.23 81.31 [50]
Tobacco stems K2CO3 2557 1.647 16.65 [49]
Sunower seed oil K2CO3 1411.55 0.836 23.6 [86]
residues

temperature (say 700 1C), the increase in impregnation ratio

Fig. 2. TEM images of the hierarchical carbon [31].
Xu et al. [8] prepared activated carbons from apricot shell via
NaOH chemical activation and got activated carbon with BET
surface area of 2335 m2 g
1 at a carbonization temperature of
400 1C. It was observed that further increase in carbonization
temperature beyond 400 1C brought about substantial decrease in
both BET surface area and pore volume which is an indication of
the negative effect of increased carbonization temperature on the
development of porosity by the NaOH activated carbon. The result
of the study by Li et al. [14] on KOH activation of sunower seed
shell shows a linear relationship between the activation tempera-
ture and BET surface area and pore volume. They observed that
there was a corresponding increase in both BET surface area and
pore volume as the activation temperature increased from 600 to
800 1C, which according to them is due to the fact that activating
reactions occur faster at high temperature and more pores
channels developed accordingly. The result, therefore, indicates
that the activating temperature is a leading factor for pore
structure development. Li et al. [14] also observed that at high
brought about increase in BET surface area and total pore volume.
Thus, the results show that the activation temperature and the
impregnation ratio are two important factors for the development
of pore structure by activated carbon. These results correlated with
the results of the study conducted by Rufford et al. [10] using ZnCl2
and studies of Ahmadpour and Do [88] and Molina-Sabio and
Rodrguez-Reinoso [89] on the effect of impregnation ratio on the
surface area. However, the results differ on the effect of activation
temperature on the surface area. Ismanto et al. [7] prepared
activated carbon having surface area of 1352 m2 g
1 from cassava
peel waste via combined chemical activation (KOH) and physical
activation (CO2). After modication, a slight change was observed
on the activated carbon surface. From the surface morphology of
modied activated carbons from cassava peel shown in Fig. 3, it is
obvious that all the activated carbon studied have similar surface
morphology.
4.1.2. Effects of microwave heating conditions on the physical and
chemical properties of activated carbons
As stated earlier in this review, microwave heating has some
advantages over the conventional method. The most prominent is
the reduction in treatment time that translates to a reduction in
energy consumption. As the number of researchers using micro-
wave heating to prepare activated carbon in recent times
increases, more results are coming out on the inuence of
operational parameters such as precursor, activation agent,
impregnation ratio in chemical activation, agent ow rate in
physical activation, radiation power and radiation time on the
yield and adsorption capacities of activated carbon. In addition to
higher surface area which may be ascribed to the difference in the
heating generation mechanism, the microwave assisted activated
carbons showed diverse features from activated carbons prepared
1288 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293
Fig. 3. Surface morphology of modied activated carbon from cassava peel waste [7].
by conventional method [76]. Microwave activated carbon has
signicant adsorption properties which depend not only on the
surface area, the pore size distribution, but also on its chemical
structure [58,76]. Thus, the existence of carboxylic groups and
higher charge density on the surface of adsorbent and micropore
structure have been identied as the factors responsible for the
increase in adsorption capacity in microwave heating method [90].
Foo and Hameed investigated the effects of chemical agent on
the adsorption capacity of rice husks-based activated carbon [12]
and pineapple peel-based activated carbon [79] prepared by
microwave activation with KOH and K2CO3 as chemical agents.
The result obtained using rice husks as precursor shows that
K2CO3activated sample have better pore structures, good adsorp-
tion capacity and higher yield. The result obtained using pineapple
peel as precursor, however, indicated that the KOH-activated
sample has superior pore structure and adsorption capacity. The
above results clearly show that precursor has signicant inuence
on the pore structures and adsorption capacity of microwave
assisted chemical activated carbons. In addition, as can be seen
in Table 4, the use of pineapple peel as precursor instead of rice
husks resulted in reversed results for same set of chemical agent.
The results obtained by Foo and Hameed [79] with pineapple peel
as precursor, however, correlated with the earlier study of Deng
et al. [45] in which they used cotton stalks (CS) as feedstock to
prepared activated carbon by microwave-induced KOH and K2CO3
activation. For the two chemical agents Deng et al. [45] posited
that at optimum preparation conditions and a slight variations in
the parameters, the effects of impregnation ratio, radiation power
and radiation time follow the same pattern.
Biomass is a poor microwave absorber as noticed by researchers
such as Wang et al. [44] and Liu et al. [52] in their study. They found
out that the precursor needs to be impregnated with the agent for
pyrolysis to commence after which the activated carbon could
receive microwave energy by itself followed by the development of
the pore structure. They, therefore, proposed that the chemical
agents serve not only as activating agents but also as the main
microwave absorber at the initial stage. Using activated carbon
obtained from bamboo by microwave-induced phosphoric acid
activation Liu et al. [52] reported that the pore structure was not
adequately developed at low microwave power but improves with
increase in microwave power. According to Deng et al. [43], as the
microwave power increases more energy is being made available to
the sample leading to the development of more pores and active sites
on the sample. Foo and Hameed [50] investigated the effects of
microwave power on the adsorption capacity of activated carbon
prepared by microwave-induced NaOH chemical activation from
langsat empty fruit bunch waste and found that the adsorption
uptake and carbon yield greatly depend on the microwave power.
Thus, when microwave power was increased from 90 to 600 W a
drastic increase in the adsorption uptake caused by increase in
expansion of the carbon structure. The expansion of carbon structure
was due to the combined effects of internal and volumetric heating.
 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293 1289

Table 5
Specic capacitance of porous carbons reported in literature.

Material Activating method SBET (m2 g
1) Specic capacitance (F g
1) Electrolyte Cell conguration Ref.

Sugarcane bagasse MW-ZnCl2 1416 138 EMImBF4 2E [11]

Peanut shell MW-ZnCl2 1552 199 1 M Et4NBF4/PC 2E [13]
Rice husks MW-ZnCl2 1527 194 1 M Et4NBF4/PC 2E [13]
Argan seed shells KOH 2062 355 1 M H2SO4 3E [20]
Waste tea leaves KOH 2841 330 2 M KOH 3E [33]
Oil palm EFB KOH CO2 1704 149 1 M H2SO4 2E [2]
Waste coffee beans ZnCl2 1019 368 1 M H2SO4 2E, 3E [6]
ZnCl2 1021 100 TEABF4/AN 3E [78]
Coffee endocarp CO2 1038 167 1 M H2SO4 3E [15]
KOH 361 69 1 M H2SO4 3E
DDGS KOH 2959 260 6 M KOH 2E [31]
Sunower seed shell KOH 1162 244 30 wt% KOH 2E [14]
CO2 KOH 2509 311 30 wt% KOH 2E
Apricot shell NaOH 2335 339 6 M NaOH 2E [8]
Sugarcane bagasse ZnCl2 1788 300 1 M H2SO4 2E, 3E [10]
Cassava peel waste KOH CO2 1352 153 0.5 M H2SO4 3E [7]
Camellia oleifera shell ZnCl2 1935 374 1 M H2SO4 3E [18]
1935 266 6 M KOH 3E
Corn grains KOH 3199 257 6 M KOH 2E [91]

Fig. 4. CV curves for chestnut shell activated carbons at scan rate of (A) 50 mV s
1 and (B) 200 mV s
1 [92].

Though rapid and uniform heating rate which allowed samples
to acquire more active sites in a shorter time is one of the
advantages of microwave heating method, prolong exposure of
activated carbon to microwave radiation might lead to destruction
and loss of micropores as observed by Liu et al. [52]. To demon-
strate the effects of radiation time on the activation Liu et al. [52]
had prepared activated carbons from bamboo by microwave using
phosphoric acid as the agent. The phosphoric acid/carbon ratio
was kept at 1:1 and microwave power at 350 W while the
radiation time was varied from 5 min to 30 min. They observed a
signicant increase in both micropores and mesopores at the
initial stage indicating simultaneous formation and enlargement
of pores at this stage. However, as the activation progresses,
increase in micropores slowdown is observed, with a drop at
30 min while mesopore surface and volume continue to increase
throughout the activation. Liu et al. [52] further observed a gradual
decrease in carbon yield from 58.6% at 5 min to 45.3% at 30 min; a
trend similar to what was observed by Li et al. [49] and Deng et al.
[43] when they prepared activated carbons from tobacco stems
and cotton stalk respectively under microwave radiation. This
phenomenon is attributed to the continuous loss of weight with
prolong radiation time. At the experimental conditions of 700 W
(microwave power) and 1.5 (K2CO3/C) ratio Li et al. [49] evaluated
the effects of microwave radiation time on the yield and the
adsorption capacity of activated carbons prepared from tobacco
stems. The results obtained show that methylene blue adsorption
and iodine number of activated carbon increased from 290 to
519 mg g
1 and 1320 to 1834 mg g
1 respectively with increase in
microwave radiation time from 20 to 30 min and decreased from
517 to 360 mg g
1 and 1834 to 1490 mg g
1, respectively, with
further increase in microwave radiation time from 30 to 40 min. It
was noted, that beyond optimum microwave radiation time of
30 min, there is burn off of carbon pores resulting in lower
adsorption capacity and yield of carbon. A similar result was
obtained by Foo and Hameed [48] when they evaluated the effect
of microwave radiation time at impregnation ratio of 1.5 and
microwave input power of 600 W on the mesoporous activated
carbon prepared from wood sawdust by K2CO3 activation.
4.2. Electrochemical characterization
Estimation of the electrochemical properties of activated carbon
is usually done using cyclic voltammetry (CV), galvanostatic charge/
discharge (GCD) and electrochemical impedance spectroscopy (EIS).
While cyclic voltammetry measurements are commonly used to
test the EDLC performances of the activated carbons, the galvano-
static charge/discharge measurements are conducted to test the
capacitors performance [14]. The equivalent series resistance (ESR)
1290 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293
of the activated carbons are commonly obtained from the electro-
chemical impedance spectroscopy measurements.
Specic capacitance of porous carbons reported in the surveyed
literature is presented in Table 5. Because different experimental
methods were used by various authors to determine the specic
capacitance, the values reported are sometimes not consistent.
Furthermore, the calculation of specic capacitance also differs
depending on the cell used (3 or 2 electrodes). For a single
electrode, the specic capacitance (C) can be calculated using the
following equation [14]:
4It
C sin
gle
V  m
where I is discharge current (mA); t is total discharge time (s); m is
total mass of active material in both electrodes (g); V is potential
difference during discharge (V) and C single is specic capacitance
(F g
1)
For a three-electrode cell conguration, cyclic voltammetry,
electrochemical impedance spectroscopy and galvanostatic chron-
opotentiometry (GCP) are commonly used to evaluate the electrode
performance. Typical CV curve for electric double-layer (EDL)
capacitance in which the supercapacitive behaviour is based purely
on the electrostatic mechanism is rectangular. Fig. 4 shows the CV
curves at scan rates of 50 mV s
1 and 200 mV s
1 obtained by [92].
As can be seen from Fig. 4, the CV curves of all the electrodes
present a more typical rectangular shape at a lower scan rate than
those obtained at higher scan rate. A higher scan rate normally
stimulates large ohmic resistance which causes distortion in the CV
loop resulting in a narrower loop with an oblique angle [93]. A
broader voltammogram area indicates higher capacitance and a
better cyclic reversibility [94]. The capacitance given by C I=r is
estimated from the current density, I (at the middle point of the
measured potential range) and the potential scan rate, r; the
potential range,V, depends on the electrolyte solution. At constant
current density, the potential of chronopotentiogram, V, varies
linearly with time, t, for capacitance originated purely from EDL.
The capacitance is then given by the slope,dV=dt, of the linear
relationship, that is, C I=dV=dt. On the other hand if the super-
capacitive behaviour includes redox reactions, the CV curve is not
rectangular. Therefore, the point of potential to be used for
capacitance calculation should be carefully chosen for each case.
In the case of two-electrode cell conguration, the electrode
performance is evaluated by galvanostatic charge/discharge (GCD).
A two-electrode cell represents a real supercapacitor device, there-
fore, the value of capacitance, C, normally obtained in the same way
as GCP is for the full cell. In two-electrode cell, the electrode
materials are sometimes damaged by high potentials; attention
should be paid not only to electrolytes and solvents but also to the
collector and counter electrode when setting the potential range,
V. For better evaluation of the electrode performance it is
recommended to carry out both three-electrode cell and two-
electrode cell measurements on the same electrode material.
Cheng et al. [92] prepared hierarchical porous carbons from
chestnut shell by ZnCl2 activation. On employing as electrodes for
supercapacitors containing 6 M KOH solutions, specic capacitance of
105 F g
1 at a current density of 0.1 A g
1 and 92.0 F g
1 at current
density up to 10 A g
1 was exhibited by the porous carbon prepared
at 700 1C. The authors suggested that the electrocapacitive perfor-
mance of the porous carbon-based supercapacitor could be attributed
to the surface area, pore structure, surface functional groups and the
graphitic degree of the carbons. Xu et al. [8] prepared activated
carbons from apricot shell via NaOH chemical activation. The as-
prepared activated carbon when used as an electrode in a 6 M KOH
aqueous electrolyte, gives a high double layer capacitance of
339 F g
1, apparent electrode density of 0.504 g cm
3 and a volu-
metric capacitance of 171 F cm
3. They noted that while specic
surface area and gravimetric capacitance decrease with the increase
in carbonization temperature, the apparent electrode density
increases with the increase in carbonization temperature. Rufford
et al. [10] conducted preparation of activated carbons by ZnCl2
activation of sugarcane bagasse. Specic capacitance of  300 F g
1
and specic energy of  10 W h kg
1 was observed when the
sugarcane bagasse carbon was used in a two-electrode, sandwich-
type supercapacitor conguration containing 1 M H2SO4 electrolyte.
The result obtained clearly demonstrates the benet of mesopores to
double layer capacitance at fast charge/discharge rate; between 77%
and 83% of the initial capacitance were retained after 5000 cycles at
4 current density above 2 A g
1. In their earlier studies Rufford et al.
[6,78] prepared activated carbons from waste coffee grounds via ZnCl2
activation and evaluated the electrochemical performance of the CGC
electrodes in 1 M H2SO4 aqueous solution electrolyte and TEABF4/AN
electrolyte, respectively. The CGC electrode exhibits high specic
capacitance up to 368 F g
1 and energy densities up to 20 Wh kg
1
in the inorganic electrolyte while, in the organic electrolyte, the
specic capacitance and energy densities are lower; just above
100 F g
1 and 16.5 Wh kg
1, respectively, at a fast chargedischarge
rate. Valente Nabais et al. [15] prepared activated carbons from coffee
endocarp via both physical (CO2) activation and KOH activation. The
activated carbons were compared with the activated carbon prepared
from commercial acrylic bre via physical (CO2) activation. The results
obtained show that the physically activated samples from coffee
endocarp have higher specic capacitance values which range from
149 to 176 F g
1 compared with the chemically activated samples of
16 to 69 F g
1 and the activated carbon bre of 2 to 85 F g
1. Based
on the observed results, Valente Nabais et al. conclude that the
electrochemical properties of activated carbons are governed by a set
of factors with overlapping inuence. Employing two different
activation strategies Li et al. [14] utilized sunower seed shell (SSS)
to prepared series of nanoporous carbons. The pore structures of the
carbons were found to be highly dependent on the activation
temperature and SSS/KOH impregnation ratio. And when used as
electrode material for electrochemical double layer capacitor contain-
ing 30% wt KOH electrolyte it performed better than ordered
mesoporous and commercial wood-based active carbons. Zhang
et al. [18] investigated in the electric double-layer capacitor the active
electrode material prepared by ZnCl2 activation from camellia oleifera
shell. The surface area and pore structure were found to be dependent
on two factors, namely activation temperature and COS/ZnCl2 impreg-
nation ratio which in turn affect the electrochemical performance of
the active carbon. At optimum conditions of 600 1C activation
temperature and impregnation ratio of 3, the specic capacitance
obtained were 374 and 266 F g
1 in 1 M H2SO4 and 6 M KOH
electrolyte at current density of 0.2 A g
1, respectively. In their study
Peng et al. [33] prepared highly porous active carbons with high
surface area in the range between 2245 m2 g
1 and 2841 m2 g
1
from waste tea leaves by KOH activation. At current density of
1 A g
1, specic capacitance as high as 330 F g
1 was obtained in
supercapacitor application in aqueous KOH electrolyte; all the elec-
trodes show good cycle stability up to 2000 cycles with about 92% of
the initial capacitance still retained at current density of 5 A g
1. A
combined chemical (KOH) and physical (CO2) activation process was
adopted by Farma et al. [2] in preparing highly porous binderless
activated carbon electrode from oil palm empty fruit bunches. The
authors noted that in addition to producing porous carbon with well-
developed pore structure and good electrochemical performance
the combined approach also has economic advantage since a small
quantity of chemical agent is required resulting in reduced activation
time. At optimum activation time of 3 h, the values of specic
capacitance, specic energy density and specic power density
obtained from the electrochemical measurements of the supercapa-
citor cells fabricated using these electrodes are 150 F g
1, 4.297
Wh kg
1 and 173 W kg
1, respectively.
 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293
To prepare nanoporous carbon from sugarcane bagasse Si et al.
[11] had employed a facile microwave-induced ZnCl2 activation.
When the sample carbon was used as electrode material in ionic
liquid supercapacitor it exhibits good capacitive performance and
high capacitance retention which, according to the authors, are
closely related to the pore size. The authors noted that the large
pore size benets the good capacitance of porous carbon in ionic
liquid electrolyte. Peanut shell and rice husk were used as pre-
cursors by He et al. [13] to prepare mesoporous carbons having high
surface area of 15271634 m2 g
1 for supercapacitors via
microwave-induced ZnCl2 activation. An energy density of
19.3 Wh kg
1 at a power density of 1007 W kg
1 was obtained
when the mesoporous carbon was used as capacitor electrode in
1 M Et4NBF4/PC electrolyte at high current density. The authors
attributed these values to the bigger average pore size and unique
mesopore structure of the microwave assisted mesoporous carbons.
To investigate the source of high capacitance observed in carbons
with low surface area derived from seaweed, Wu et al. [95]
prepared activated carbon from dried laver. When the activated
carbon with surface area of about 2 m2 g
1 was used as electrode in
6 M KOH solution a capacitance of 116.9 F g
1 was observed. The
authors attributed the value to the presence of ultrasmall micro-
pores which contributed immensely to the development of capaci-
tance of such carbons, as against the generally accepted view that
the capacitance is largely derived from heteroatoms undergoing
Faradaic reactions. According to the authors, these ultrasmall
micropores could not be probe by adsorbates such as N2 and Ar,
hence they suggested that CO2 adsorption should be implemented
rst especially in the case of heteroatom-rich materials.
4.3. Effects of surface modication on capacitive performance of
active carbons
To study the effects of surface modication, Ismanto et al. [7]
prepared activated carbons from cassava peel waste by combined
chemical (KOH) and physical (CO2) activation. The surface of as-
prepared activated carbons was subsequently modied using hydro-
gen peroxide (H2O2), nitric acid (HNO3) and sulphuric acid (H2SO4)
solutions. The authors observed no considerable effect of surface
modication on the specic surface area of the activated carbons but
noted that there was a signicant inuence on the surface chemistry
of the carbons as a result of the increase or introduction in the
surface functional groups on the surface of the activated carbons. The
specic capacitance of HNO3-treated activated carbon was reported
to reach 264.08 F g
1 which is 72.6% above 153.00 F g
1 reported for
non-treated activated carbon. Elmouwahidi et al. [20] treated acti-
vated carbons prepared by KOH-activation from argan seed shells
(ASS) so as to introduce oxygen and nitrogen functionalities on the
surface of the activated carbons. The results show that N2-rich
activated carbons have the highest capacitance and retention of
355 F g
1 at 125 mA g
1 and 93% at 1 A g
1, respectively, compared
to the O2-rich activated carbons. The authors explained that while
the surface carboxyl groups on the surface of O2-rich activated
carbons hindered electrolyte diffusion into the pores, the presence
of nitrogen functionalities, on the other hand, lead to a well-
developed micro-mesoporosity and a good pseudocapacitance
effects. Liu et al. [19] investigated the modied porous wood carbon
monolith (m-WCM) prepared by pyrolysis of poplar wood and
subsequently modied with HNO3 solution. The results show that
there is a signicant increase in specic capacitance after surface
modication indicating the importance of surface treatment in
improving the electrochemical capacitive behaviour of the carbon
materials. However, the authors observed that there was a substan-
tial decrease in the specic capacitance with increase in modication
conditions. This phenomenon is attributed to the harsh modication
conditions due to increase in temperature thereby resulting in
1291
surface and structure destruction. Jin et al. [31] utilized biochar
generated from the pyrolysis of distillers dried grains with solubles
(DDGS) to prepared hierarchical carbon having high specic surface
area of 2959 m2 g
1 and high pore volume of 1.65 cm3 g
1 by KOH
catalytic activation. The hierarchical carbon was further treated with
4 M HNO3 at 150 1C. A pronounced increase in oxygen content in the
hierarchical carbon was noticed by the authors. When the hierarch-
ical carbon was used as supercapacitor electrode in 6 M KOH
electrolyte and evaluated after 2000 constant current charge/dis-
charge cycles, it showed a stable reversible capacitance of 260 F g
1
at a constant current of 0.6 A g
1 compared to specic capacitance of
200 F g
1 obtained with non-treated hierarchical carbon at a higher
current of 0.5 A g
1 after 2000 cycles.
Balathanigaimani et al. [91] prepared novel activated carbons
from corn grains (CG) by varying the activation time from 30 min
to 240 min. They observed quinone to be the dominant surface
functional group. When the CG-ACs was employed as electrodes in
electrical double layer capacitor (EDLC), they found out that the
relationship between the surface area and the specic capacitance
is non-linear whereas the relationship between the surface area
and activation time was observed to be linear. It was also observed
by the authors that the activated carbon with the highest quinone
fraction value shows a better EDLC performance. This can be
explained by the fact that quinone is an electron capacitor that
increases capacitance through the pseudocapacitance via redox
mechanism [96].
5. Future outlooks
In recent time, the use of microwave heating technology for the
preparation of activated carbon electrodes from agricultural waste
biomass has been on the increase owing to the advantages of this
technology over the conventional heating method. However, there
are limiting issues for industrialization and scale-up of microwave-
assisted activated carbon [97]. Currently, there are few published
works; however, the results obtained so far are promising, and
therefore to improve the performance of the activated carbon
electrodes further research is needed.
Furthermore, a good understanding of the interrelationship
between pore size, surface area, surface chemistry and the
performance of electrochemical capacitor is necessary so as to be
able to design nanostructured materials that could bring about
impressive improvements on the existing energy and power
capabilities of the electric double layer capacitors.
In addition, a good knowledge of the inuence of electrolytes
on the physical properties, molecular interactions and supercapa-
citor performance is needed so as to come up with electrolyte
systems that have higher conductivity at room temperature and
can operate at higher voltages which are crucially needed for
future generation of supercapacitors.
6. Conclusion
The variations in the performance of agricultural waste-based
activated carbons produced under the same conditions but from
different precursors have brought into fore the inuences of the
preparation procedures and conditions as well as the effects of the
structure and composition of the agricultural waste precursors.
Capacitive performances of the electrodes have been found to
depend not only on surface area of the activated carbons but also
on other factors such as the pore structure and distribution,
electrical conductivity and surface functionalities. In addition, ultra-
small micropores present in the low surface area active carbons have
been found to contribute immensely to the capacitance observed in
1292 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293
those carbons. Overall, electrochemical performance of the energy
cells was also found to be dependent on the electrolyte system used.
Microwave heating is presently enjoying wider acceptability
and use for the synthesis of porous materials because of a number
of advantages it has over the conventional heating method in
addition to shorter treatment time. These include among other
uniform and volumetric heating leading to a more homogeneous
nucleation, energy-efciency, simple and inexpensive.
Currently, enormous research efforts are being channelled
towards the development of low cost active carbon electrodes
that will give high capacitance at low resistance with the ultimate
goal of enhancing the specic energy of the carbon-based super-
capacitors without compromising its high level specic power.
Acknowledgements
The authors are grateful to Ministry of Higher Education,
Malaysia and UTM for Research University Grant Vot no 05H25
funding in carrying out the research activity.
References
[1] Simon P, Gogotsi Y. Materials for electrochemical capacitors. Nat Mater
2008;7:84554.
[2] Farma R, Deraman M, Awitdrus A, Talib IA, Taer E, Basri NH, et al. Preparation
of highly porous binderless activated carbon electrodes from bres of oil palm
empty fruit bunches for application in supercapacitors. Bioresour Technol
2013;132:25461.
[3] Kavaliauskas Z, Marcinauskas L, Valetkevicius P. Formation and characteriza-
tion of carbon and nickel oxide/carbon composites for supercapacitors. Acta
Phys Pol A 2011;119:2535.
[4] Abechi SE, Gimba CE, Uzairu A, Dallatu YA. Preparation and characterization of
activated carbon from palm kernel shell by chemical activation. Res J Chem Sci
2013;3:5461.
[5] Gonzlez-Garca P, Centeno TA, Urones-Garrote E, vila-Brande D, Otero-Daz
LC. Microstructure and surface properties of lignocellulosic-based activated
carbons. Appl Surf Sci 2013;265:7317.
[6] Rufford TE, Hulicova-Jurcakova D, Zhu Z, Lu GQ. Nanoporous carbon electrode
from waste coffee beans for high performance supercapacitors. Electrochem
Commun 2008;10:15947.
[7] Ismanto AE, Wang S, Soetaredjo FE, Ismadji S. Preparation of capacitors
electrode from cassava peel waste. Bioresour Technol 2010;101:353440.
[8] Xu B, Chen Y, Wei G, Cao G, Zhang H, Yang Y. Activated carbon with high
capacitance prepared by NaOH activation for supercapacitors. Mater Chem
Phys 2010;124:5049.
[9] Kalderis D, Bethanis S, Paraskeva P, Diamadopoulos E. Production of activated
carbon from bagasse and rice husk by a single-stage chemical activation
method at low retention times. Bioresour Technol 2008;99:680916.
[10] Rufford TE, Hulicova-Jurcakova D, Khosla K, Zhu Z, Lu GQ. Microstructure and
electrochemical double-layer capacitance of carbon electrodes prepared by
zinc chloride activation of sugar cane bagasse. J Power Sources
2010;195:9128.
[11] Si WJ, Wu XZ, Xing W, Zhou J, Zhuo SP. Bagasse-based nanoporous carbon for
supercapacitor application. J Inorg Mater 2011;26:10712.
[12] Foo KY, Hameed BH. Utilization of rice husks as a feedstock for preparation of
activated carbon by microwave induced KOH and K2CO3 activation. Bioresour
Technol 2011;102:98147.
[13] He X, Ling P, Qiu J, Yu M, Zhang X, Yu C, et al. Efcient preparation of biomass-
based mesoporous carbons for supercapacitors with both high energy density
and high power density. J Power Sources 2013;240:10913.
[14] Li X, Xing W, Zhuo S, Zhou J, Li F, Qiao SZ, et al. Preparation of capacitors
electrode from sunower seed shell. Bioresour Technol 2011;102:111823.
[15] Valente Nabais JM, Teixeira JG, Almeida I. Development of easy made low cost
bindless monolithic electrodes from biomass with controlled properties to be
used as electrochemical capacitors. Bioresour Technol 2011;102:27817.
[16] Taer E, Deraman M, Talib IA, Awitdrus A, Hashmi SA, Umar AA. Preparation of a
highly porous binderless activated carbon monolith from rubber wood
sawdust by a multi-step activation process for application in supercapacitors.
Int J Electrochem Sci 2011;6:330115.
[17] Foo KY, Hameed BH. Preparation of oil palm (Elaeis) empty fruit bunch
activated carbon by microwave-assisted KOH activation for the adsorption of
methylene blue. Desalination 2011;275:3025.
[18] Zhang J, Gong L, Sun K, Jiang J, Zhang X. Preparation of activated carbon from
waste Camellia oleifera shell for supercapacitor application. J Solid State
Electrochem 2012;16:217986.
[19] Liu MC, Kong LB, Zhang P, Luo YC, Kang L. Porous wood carbon monolith for
high-performance supercapacitors. Electrochim Acta 2012;60:4438.
[20] Elmouwahidi A, Zapata-Benabithe Z, Carrasco-Marin F, Moreno-Castilla C.
Activated carbons from KOH-activation of argan (Argania spinosa) seed shells
as supercapacitor electrodes. Bioresour Technol 2012;111:18590.
[21] Foo KY, Hameed BH. Utilization of oil palm biodiesel solid residue as renew-
able sources for preparation of granular activated carbon by microwave
induced KOH activation. Bioresour Technol 2013;130:696702.
[22] Saidur R, Abdelaziz EA, Demirbas A, Hossain MS, Mekhilef S. A review on
biomass as a fuel for boilers. Renewable Sustainable Energy Rev
2011;15:226289.
[23] Zhang L, Xu C, Champagne P. Overview of recent advances in thermo-chemical
conversion of biomass. Energy Convers Manage 2010;51:96982.
[24] Daud Z, Kassim ASM, Aripin AM, Awang H, Hatta MZM. Chemical composition
and morphological of cocoa pod husks and cassava peels for pulp and paper
production. Aust J Basic Appl Sci 2013;7:40611.
[25] Abdullah N, Gerhauser H. Bio-oil derived from empty fruit bunches. Fuel
2008;87:260613.
[26] Abdullah SS, Yusup S, Ahmad MM, Ramli A, Ismail L. Thermogravimetry study
on pyrolysis of various lignocellulosic biomass for potential hydrogen produc-
tion. Int J Chem Biol Eng 2010;3:13741.
[27] Hassan A, Salema AA, Ani FN, Bakar AA. A review on oil palm empty fruit
bunch ber-reinforced polymer composite materials. Polym Compos
2010:2079101.
[28] Demirbas A. Relationships between lignin contents and xed carbon contents
of biomass samples. Energy Convers Manage 2003;44:14816.
[29] Adeyi O. Proximate composition of some agricultural wastes in Nigeria and
their potential use in activated carbon production. J Appl Sci Environ Manage,
14; 2010. p. 558.
[30] Tay T, Ucar S, Karagoz S. Preparation and characterization of activated carbon
from waste biomass. J Hazard Mater 2009;165:4815.
[31] Jin H, Wang X, Gu Z, Polin J. Carbon materials from high ash biochar for
supercapacitor and improvement of capacitance with HNO3 surface oxidation.
J Power Sources 2013;236:28592.
[32] Nabais JV, Carrott P, Ribeiro Carrott MM, Luz V, Ortiz AL. Inuence of
preparation conditions in the textural and chemical properties of activated
carbons from a novel biomass precursor: the coffee endocarp. Bioresour
Technol 2008;99:722431.
[33] Peng C, Yan X b, Wang R t, Lang J w, Ou Y j, Xue Q j. Promising activated
carbons derived from waste tea-leaves and their application in high perfor-
mance supercapacitors electrodes. Electrochim Acta 2013;87:4018.
[34] Jin XJ, Yu ZM, Wu Y. Preparation of activated carbon from lignin obtained by
straw pulping by KOH and K2CO3 chemical activation. Cellul Chem Technol
2012;46:7985.
[35] Rahim YA, Aqmar SN, Dewi DRS. ESR study of electron trapped on activated
carbon by KOH and ZnCl2 activation. J Mater Sci Eng 2010;4:226.
[36] Cruz G, Piril M, Huuhtanen M, Carrin L, Alvarenga E, Keiski RL. Production of
activated carbon from cocoa (Theobroma cacao) pod husk. J Civil Environ Eng
2012;2:10915.
[37] Theydan SK, Ahmed MJ. Optimization of preparation conditions for activated
carbons from date stones using response surface methodology. Powder
Technol 2012;224:1018.
[38] Aworn A, Thiravetyan P, Nakbanpote W. Preparation and characteristics of
agricultural waste activated carbon by physical activation having micro- and
mesopores. J Anal Appl Pyrolysis 2008;82:27985.
[39] Nabais JMV, Nunes P, Carrott PJM, Ribeiro Carrott MML, Garca AM, Daz-Dez
MA. Production of activated carbons from coffee endocarp by CO2 and steam
activation. Fuel Process Technol 2008;89:2628.
[40] Bouchelta C, Medjram MS, Bertrand O, Bellat JP. Preparation and characteriza-
tion of activated carbon from date stones by physical activation with steam.
J Anal Appl Pyrolysis 2008;82:707.
[41] Cabal B, Budinova T, Ania CO, Tsyntsarski B, Parra JB, Petrova B. Adsorption of
naphthalene from aqueous solution on activated carbons obtained from bean
pods. J Hazard Mater 2009;161:11506.
[42] Cagnon B, Py X, Guillot A, Stoeckli F, Chambat G. Contributions of hemi-
cellulose, cellulose and lignin to the mass and the porous properties of chars
and steam activated carbons from various lignocellulosic precursors. Bioresour
Technol 2009;100:2928.
[43] Deng H, Yang L, Tao G, Dai J. Preparation and characterization of activated
carbon from cotton stalk by microwave assisted chemical activationapplica-
tion in methylene blue adsorption from aqueous solution. J Hazard Mater
2009;166:151421.
[44] Wang T, Tan S, Liang C. Preparation and characterization of activated carbon
from wood via microwave-induced ZnCl2 activation. Carbon 2009;47:18803.
[45] Deng H, Li G, Yang H, Tang J, Tang J. Preparation of activated carbons from
cotton stalk by microwave assisted KOH and K2CO3 activation. Chem Eng J
2010;163:37381.
[46] Foo KY, Hameed BH. Preparation of activated carbon from date stones by
microwave induced chemical activation: application for methylene blue
adsorption. Chem Eng J 2011;170:33841.
[47] Foo KY, Hameed BH. Adsorption characteristics of industrial solid waste
derived activated carbon prepared by microwave heating for methylene blue.
Fuel Process Technol 2012;99:1039.
[48] Foo KY, Hameed BH. Mesoporous activated carbon from wood sawdust
by K2CO3 activation using microwave heating. Bioresour Technol
2012;111:42532.
 A.M. Abioye, F.N. Ani / Renewable and Sustainable Energy Reviews 52 (2015) 12821293
[49] Li W, Zhang L b, Peng J h, Li N, Zhu X y. Preparation of high surface area
activated carbons from tobacco stems with K2CO3 activation using microwave
radiation. Ind Crops Prod 2008;27:3417.
[50] Foo KY, Hameed BH. Preparation of activated carbon by microwave heating of
langsat (Lansium domesticum) empty fruit bunch waste. Bioresour Technol
2012;116:5225.
[51] Deng H, Zhang G, Xu X, Tao G, Dai J. Optimization of preparation of activated
carbon from cotton stalk by microwave assisted phosphoric acid-chemical
activation. J Hazard Mater 2010;182:21724.
[52] Liu Q-S, Zheng T, Wang P, Guo L. Preparation and characterization of activated
carbon from bamboo by microwave-induced phosphoric acid activation. Ind
Crops Prod 2010;31:2338.
[53] Yagmur E, Ozmak M, Aktas Z. A novel method for production of activated
carbon from waste tea by chemical activation with microwave energy. Fuel
2008;87:327885.
[54] Xin-hui D, Srinivasakannan C, Jin-hui P, Li-bo Z, Zheng-yong Z. Preparation of
activated carbon from Jatropha hull with microwave heating: optimization
using response surface methodology. Fuel Process Technol 2011;92:394400.
[55] Xin-hui D, Srinivasakannan C, Jin-hui P, Li-bo Z, Zheng-yong Z. Comparison of
activated carbon prepared from Jatropha hull by conventional heating and
microwave heating. Biomass Bioenergy 2011;35:39206.
[56] Yang K, Peng J, Srinivasakannan C, Zhang L, Xia H, Duan X. Preparation of high
surface area activated carbon from coconut shells using microwave heating.
Bioresour Technol 2010;101:61639.
[57] Ioannidou O, Zabaniotou A. Agricultural residues as precursors for activated
carbon productiona review. Renewable Sustainable Energy Rev
2007;11:19662005.
[58] Hesas RH, Wan Daud WMA, Sahu JN, Arami-Niya A. The effects of a microwave
heating method on the production of activated carbon from agricultural
waste: a review. J Anal Appl Pyrolysis 2013;100:111.
[59] Yuen FK, Hameed BH. Recent developments in the preparation and regenera-
tion of activated carbons by microwaves. Adv Colloid Interface Sci
2009;149:1927.
[60] Menndez JA, Arenillas A, Fidalgo B, Fernndez Y, Zubizarreta L, Calvo EG, et al.
Microwave heating processes involving carbon materials. Fuel Process Technol
2010;91:18.
[61] Oghbaei M, Mirzaee O. Microwave versus conventional sintering: a review of
fundamentals, advantages and applications. J Alloys Compd 2010;494:17589.
[62] He X, Geng Y, Qiu J, Zheng M, Long S, Zhang X. Effect of activation time on the
properties of activated carbons prepared by microwave-assisted activation for
electric double layer capacitors. Carbon 2010;48:16629.
[63] Figueiredo JL, Pereira MFR, Freitas MMA, Orfao JJM. Modication of the surface
chemistry of activated carbons. Carbon 1999;37:137989.
[64] Pandolfo AG, Hollenkamp AF. Carbon properties and their role in super-
capacitors. J Power Sources 2006;157:1127.
[65] Shafeeyan MS, Daud WMAW, Houshmand A, Shamiri A. A review on surface
modication of activated carbon for carbon dioxide adsorption. J Anal Appl
Pyrolysis 2010;89:14351.
[66] El-Sayed Y, Bandosz TJ. Adsorption of valeric acid from aqueous solution onto
activated carbons: role of surface basic sites. J Colloid Interface Sci
2004;273:6472.
[67] Liu QS, Zheng T, Li N, Wang P, Abulikemu G. Modication of bamboo-based
activated carbon using microwave radiation and its effects on the adsorption
of methylene blue. Appl Surf Sci 2010;256:330915.
[68] Menndez JA, Menndez EM, Iglesias MJ, Garcia A, Pis JJ. Modication of the
surface chemistry of active carbons by means of microwave-induced treat-
ments. Carbon 1999;37:111521.
[69] Valente Nabais JM, Carrott PJM, Ribeiro Carrott MML, Menndez JA. Prepara-
tion and modication of activated carbon bres by microwave heating. Carbon
2004;42:131520.
[70] Zhang L, Mi M, Li B, Dong Y. Modication of activated carbon by means of
microwave heating and its effects on the pore texture and surface chemistry,
Res J Appl Sci Eng Technol 2013;5:17915.
[71] Li H, Xi HA, Zhu S, Wen Z, Wang R. Preparation, structural characterization,
and electrochemical properties of chemically modied mesoporous carbon.
Microporous Mesoporous Mater 2006;96:35762.
[72] Wang R, Deng M. Surface modication of carbon electrodes for supercapacitor
using ammonia water. Adv Mater Res 2012;396-398:12658.
[73] Bakhmatyuk BP, Venhryn BY, Grygorchak II, Micov MM. Inuence of chemical
modication of activated carbon surface on characteristics of supercapacitors.
J Power Sources 2008;180:8905.
1293
[74] Ng C, Losso JN, Marshall WE, Rao RM. Physical and chemical properties of
selected agricultural byproduct-based activated carbons and their ability to
adsorb geosmin. Bioresour Technol 2002;84:17785.
[75] Guo J, Lua AC. Preparation of activated carbons from oil-palm-stone chars by
microwave-induced carbon dioxide activation. Carbon 2000;38:198593.
[76] Huang L, Sun Y, Wang W, Yue Q, Yang T. Comparative study on characteriza-
tion of activated carbons prepared by microwave and conventional heating
methods and application in removal of oxytetracycline (OTC). Chem Eng J
2011;171:144653.
[77] Raymundo-Piero E, Leroux F, Bguin F. A high-performance carbon for
supercapacitors obtained by carbonization of a seaweed biopolymer. Adv
Mater 2006;18:187782.
[78] Rufford TE, Hulicova-Jurcakova D, Fiset E, Zhu Z, Lu GQ. Double-layer
capacitance of waste coffee ground activated carbons in an organic electrolyte.
Electrochem Commun 2009;11:9747.
[79] Foo KY, Hameed BH. Porous structure and adsorptive properties of pineapple
peel based activated carbons prepared via microwave assisted KOH and K2CO3
activation. Microporous Mesoporous Mater 2012;148:1915.
[80] Foo KY, Hameed BH. Preparation, characterization and evaluation of adsorp-
tive properties of orange peel based activated carbon via microwave induced
K2CO3 activation. Bioresour Technol 2012;104:67986.
[81] Foo KY, Hameed BH. Preparation and characterization of activated carbon
from pistachio nut shells via microwave-induced chemical activation. Biomass
Bioenergy 2011;35:325761.
[82] Foo KY, Hameed BH. Microwave-assisted preparation and adsorption perfor-
mance of activated carbon from biodiesel industry solid reside: inuence of
operational parameters. Bioresour Technol 2012;103:398404.
[83] Hejazifar M, Azizian S, Sarikhani H, Li Q, Zhao D. Microwave assisted
preparation of efcient activated carbon from grapevine rhytidome for the
removal of methyl violet from aqueous solution. J Anal Appl Pyrolysis
2011;92:25866.
[84] Maldhure AV, Ekhe JD. Preparation and characterizations of microwave
assisted activated carbons from industrial waste lignin for Cu(II) sorption.
Chem Eng J 2011;168:110311.
[85] Foo KY, Hameed BH. Microwave assisted preparation of activated carbon from
pomelo skin for the removal of anionic and cationic dyes. Chem Eng J
2011;173:38590.
[86] Foo KY, Hameed BH. Preparation and characterization of activated carbon
from sunower seed oil residue via microwave assisted K2CO3 activation.
Bioresour Technol 2011;102:97949.
[87] Lillo-Rdenas MA, Juan-Juan J, Cazorla-Amors D, Linares-Solano A. About
reactions occurring during chemical activation with hydroxides. Carbon
2004;42:13715.
[88] Ahmadpour A, Do DD. The preparation of activated carbon from macadamia
nutshell by chemical activation. Carbon 1997;35:172332.
[89] Molina-Sabio M, Rodrguez-Reinoso F. Role of chemical activation in the
development of carbon porosity. Colloids Surf A: Physicochem Eng Aspects
2004;241:1525.
[90] Franca AS, Oliveira LS, Nunes AA, Alves CC. Microwave assisted thermal
treatment of defective coffee beans press cake for the production of adsor-
bents. Bioresour Technol 2010;101:106874.
[91] Balathanigaimani MS, Shim WG, Lee MJ, Kim C, Lee JW, Moon H. Highly
porous electrodes from novel corn grains-based activated carbons for elec-
trical double layer capacitors. Electrochem Commun 2008;10:86871.
[92] Cheng L, Guo P, Wang R, Ming L, Leng F, Li H, et al. Electrocapacitive
properties of supercapacitors based on hierarchical porous carbons from
chestnut shell. Colloids Surf A: Physicochem Eng Aspects 2014;446:12733.
[93] Cheng Q, Tang J, Ma J, Zhang H, Shinya N, Qin LC. Graphene and carbon
nanotube composite electrodes for supercapacitors with ultra-high energy
density. Phys Chem Chem Phys 2011;13:1761524.
[94] Farma R, Deraman M, Awitdrus IA, Talib R, Omar JG, Manjunatha MM, et al.
Physical and electrochemical properties of supercapacitor electrodes derived
from carbon nanotube and biomass carbon. Int J Electrochem Sci
2013;8:25773.
[95] Wu X, Xing W, Florek J, Zhou J, Wang G, Zhuo S, et al. On the origin of the high
capacitance of carbon derived from seaweed with an apparently low surface
area. J Mater Chem A 2014;2:189989004.
[96] Hsieh CT, Teng H. Inuence of oxygen treatment on electric double-layer
capacitance of activated carbon fabrics. Carbon 2002;40:66774.
[97] Waheed ul Hasan S, Ani FN. Review of limiting issues in industrialization and
scale-up of microwave-assisted activated carbon production. Ind Eng Chem
2014;53:1218591.