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Materials Chemistry
Cite this: DOI: 10.1039/c2jm34066f
www.rsc.org/materials FEATURE ARTICLE
KOH activation of carbon-based materials for energy storage
Jiacheng Wang* and Stefan Kaskel*
Received 22nd June 2012, Accepted 8th August 2012
DOI: 10.1039/c2jm34066f
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F

Because of their availability, adjustable microstructure, varieties of forms, and large specific surface area,
porous carbon materials are of increasing interest for use in hydrogen storage adsorbents and electrode
materials in supercapacitors and lithium–sulfur cells from the viewpoint of social sustainability and
environmental friendliness. Therefore, much effort has been made to synthesize and tailor the
microstructures of porous carbon materials via various activation procedures (physical and chemical
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activation). In particular, the chemical activation of various carbon sources using KOH as the activating
reagent is very promising because of its lower activation temperature and higher yields, and well-defined
micropore size distribution and ultrahigh specific surface area up to 3000 m2 g
1 of the resulting porous
carbons. In this feature article, we will cover recent research progress since 2007 on the synthesis of
KOH-activated carbons for hydrogen and electrical energy storage (supercapacitors and lithium–sulfur
batteries). The textural properties and surface chemistry of KOH-activated carbons depend on not only
the synthesis parameters, but also different carbon sources employed including fossil/biomass-derived
materials, synthetic organic polymers, and various nanostructured carbons (e.g. carbon nanotubes,
carbon nanofibers, carbon aerogels, carbide-derived carbons, graphene, etc.). Following the
introduction to KOH activation mechanisms and processing technologies, the characteristics and
performance of KOH-activated carbons as well as their relationships are summarized and discussed
through the extensive analysis of the literature based on different energy storage systems.

Department of Inorganic Chemistry, Dresden University of Technology, chemie.tu-dresden.de; stefan.kaskel@chemie.tu-dresden.de; Fax: +49
Bergstrabe 66, D-01069 Dresden, Germany. E-mail: jiacheng.wang@ 351 463 37287; Tel: +49 351 463 33632

Jiacheng Wang received his From 1990 to 1995, Prof. Dr

PhD in materials physics and
chemistry from Shanghai Insti-
tute of Ceramics, Chinese
Academy of Sciences in 2007
under the supervision of Prof.
Qian Liu. After three and a half
years of postdoctoral research
as a project researcher and then
a JSPS postdoctoral fellow at
the University of Tokyo, he
joined the research group of
Prof. Dr Stefan Kaskel at
Jiacheng Wang Dresden University of Tech-
nology as an Alexander von
Humboldt research fellow in
April 2011. As a Marie Curie Intra-European Fellow, he will join
the group of Prof. Graham Hutchings at Cardiff University in
September 2012. His research interests cover inorganic porous
materials for energy storage, CO2 capture, and heterogeneous
catalysis.
Stefan Kaskel studied chemistry
in T€
ubingen. In 1997, he obtained
his PhD degree from Eberhard-
Karls-Universit€at T€
ubingen
working on in situ powder
diffraction. After a post-doctoral
stay as a Feodor Lynen fellow of
the Alexander von Humboldt
foundation in the working group
of J. D. Corbett, Ames Labora-
tory (DOE) and Iowa State
University, Ames, Iowa, he
Stefan Kaskel obtained his habilitation degree
in 2003 at Bochum University on
the design and functionality of
new porous materials and he also worked as a group leader at the
Max Planck Institute for Coal Research from 2002 to 2004. Since
June 2004, he has been a Professor of Inorganic Chemistry at
Dresden University of Technology and, from 2008 on, has also been
head of the department of thin-film technology at the Fraunhofer
Institute for Material and Beam Technology (IWS), Dresden.

This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem.


1. Introduction
Energy consumption/production relying on the combustion of
traditional, non-renewable, limited fossil fuels not only is a
requisite for the rapid development of world economies, but also
leads to increasing environmental pollution, global climate
warming, and energy crisis. Environmental pollution and energy
supply have become two of the most important topics, especially
for rapidly developing economies. Both areas are closely linked,
and a clean solution is to replace fossil fuels by efficient,
sustainable, and environmentally friendly technologies, such as
hydrogen (H2) and electrochemical energy systems including
supercapacitors (SCs), batteries, etc. However, the latter carrier
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F
technologies can only lead to sustainable energy supply if
renewable resources such as solar or wind energy are used for
electricity or hydrogen production.
Carbon-based materials, ranging from activated carbons
(ACs) and one-dimensional (1D) carbon nanotubes (CNTs) to
the subject of the 2010 Nobel Prize in Physics, two-dimensional
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(2D) graphene nanosheets,1 hold great technological promise for
a variety of sustainable energy applications including H2 on-
board storage and electrochemical electrodes, because carbon
materials possess various desirable advantages, such as low-cost,
light weight, adjustable porosity, many varieties of forms, ease of
processability, and controllable heteroatom doping. In general,
the increasing specific surface area (SSA) and pore volume (PV)/
micropore volume (MV), as well as well-defined pore size
distribution (PSD) of porous carbons, are key to not only
enhancing H2 storage capacity, but also achieving a better elec-
trochemical capacitance performance in terms of both power
delivery rate and energy storage capacity.
In order to develop the pore network in carbon materials, the
application of physical or chemical activation is often required.2
Physical activation is done by carbonization of carbon precursors
in an inert atmosphere to remove non-carbon elements, followed
by the activation in the presence of suitable oxidizing gasifying
agents (O2, CO2 or steam) to develop the porosity, usually in the
temperature range of 600–1200  C. Chemical activation is
generally made by mixing carbonaceous materials with chemical
activating agents (KOH, H3PO4, ZnCl2, etc.), followed by the
carbonization at 400–900  C. This process gives rise to porous
carbons with a high SSA of over 2000 m2 g
1 and large PV mainly
made up of micropores and some small mesopores. Compared to
physical activation, chemical activation has superior advantages
such as lower activation temperatures, higher yields, less activa-
tion time, and higher SSA and PV/MV, although it has disad-
vantages including the corrosiveness of the chemical agents and
the necessary washing process to remove the chemical agents.
Among various chemical reagents, KOH is widely used since it
can result in ACs with defined micropore size distribution, high
MV, and a very high SSA of up to 3000 m2 g
1.3 KOH activation
has been known since 1978, when famous commercially available
ACs, AX21 and Maxsorb, were prepared using fossil-based
carbon sources.4 The pore microstructures as well as elemental
composition of the ACs evidently depend on the activation
parameters (mass ratio of KOH–carbon, activation temperature
and time, etc.) and carbon sources used. Thus, various activation
parameters have been investigated by using different carbon
sources (e.g. coals, pitches, natural biomass, synthetic organic
J. Mater. Chem.
View Online
polymers) to prepare the ACs. Moreover, KOH activation is also
efficient for generating micropores and small mesopores into the
framework of various structured carbons, such as carbon fibers
(CFs), carbon nanofibers (CNFs), CNTs, templated porous
carbons (TPCs), carbide-derived carbons (CDCs), carbon aero-
gels (CAs), and graphene. These KOH-activated carbons with
increased SSA and PV/MV have been applied in H2 storage, SCs,
and batteries in order to find the optimal porous carbons for
high-power energy applications. At present, a wide variety of
KOH-activated carbonaceous materials is available and it is
worthwhile reviewing the impact for energy storage applications,
since the activation parameters and the microstructures are
essential for the performance of KOH-activated carbons direct-
ing the research towards new fields in the future.
In this feature article, we briefly summarize recent progress
since 2007 on KOH activation of various carbonaceous mate-
rials, varying from coals, cokes, pitches, and synthetic organic
polymers, and natural biomass as well as the derivatives to
various structured carbons (CNFs, CFs, CNTs, TPCs, CAs,
CDCs, graphene, etc.), and their applications toward H2 and
electrical energy storage. The literature focusing on the synthesis
of the ACs by KOH activation and/or other applications except
for H2 and electrical energy storage are not included because of
the topic of this feature article. This feature article is expected to
be a modest spur to induce other researchers to come forward
with the valuable contributions to the fields of material, envi-
ronment, and energy science.
2. Mechanism of KOH activation
Although the KOH activation is a well-known method to
generate the pore network in carbons, the activation mechanism
has not been well understood because of the complexity due to
the large number of variables in both the experimental parame-
ters and the reactivity of different precursors used. In a general
view, the reaction of carbon and KOH starts with solid–solid
reactions and then proceeds via solid–liquid reactions including
the reduction of potassium (K) compound to form metallic K,4,5
the oxidation of carbon to carbon oxide and carbonate, and
other reactions among various active intermediates.
Otowa et al.4 proposed that the main products were H2, H2O,
CO, CO2, potassium oxide (K2O), and potassium carbonate
(K2CO3), in KOH activation of petroleum coke below 700  C.
This process consists of several simultaneous/consecutive reac-
tions, some of which are shown in eqn (1)–(4). KOH dehydrates
to transform into K2O at 400  C (eqn (1)). Then carbon is
consumed by the reaction of carbon and H2O with the emission
of H2 (eqn (2)). K2CO3 is formed (eqn (4)) by the reaction of K2O
and CO2 which is produced in the reaction in eqn (3).
2KOH / K2O + H2O (1)
C + H2O / CO + H2 (2)
CO + H2O / CO2 + H2 (3)
CO2 + K2O / K2CO3 (4)
Linares-Solano and co-workers5 studied KOH activation of
anthracite in which the evolution of CO2, CO, and H2 was
This journal is ª The Royal Society of Chemistry 2012

observed by temperature-programmed reaction (TPR) experi-
ments. Combining the experimental data and theoretical calcu-
lations, the prominent global reaction stoichiometrically
occurring between carbon and KOH is proposed as shown in eqn
(5). The standard Gibbs free energy change (DG ) of this reaction
is positive at room temperature and becomes negative at ca.
570  C. In fact, since the partial pressure of H2 is much less than
1 atm due to the dilution with the flow of inert gas, the actual
temperature when DG becomes negative should be lower than
570  C. Although the activation starts with the reaction in
eqn (5), it further proceeds via the reaction of metallic K with
KOH to K2O.6
6KOH + 2C / 2K + 3H2 + 2K2CO3
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F
(5)
During KOH activation, previous results4–6 indicate that
K2CO3 forms at about 400  C. At about 600  C, KOH is
completely consumed. The as-formed K2CO3 in eqn (4) and (5),
significantly decomposing into CO2 and K2O at temperatures
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higher than 700  C (eqn (6)), completely disappears at 800  C.
Moreover, the resulting CO2 can be further reduced by carbon to
form CO at high temperature (eqn (7)). The K compounds (K2O
and K2CO3) also can be reduced by carbon to produce metallic K
at temperatures over 700  C (eqn (8) and (9)).
K2CO3 / K2O + CO2 (6)
CO2 + C / 2CO (7)
K2CO3 + 2C / 2K + 3CO (8)
C + K2O / 2K + CO (9)
Based on the above observations and discussions, three main
activation mechanisms for KOH activation of carbon are
concluded which have been widely accepted:4–8 (a) Etching the
carbon framework by the redox reactions between various
potassium compounds as chemical activating reagents with
carbon as shown in eqn (5), (8) and (9), called chemical activa-
tion, is responsible for generating the pore network; (b) the
formation of H2O (eqn (1)) and CO2 (eqn (3) and (6)) in the
activation system positively contributes to the further develop-
ment of the porosity through the gasification of carbon, namely
physical activation (eqn (2) and (7));9 (c) the as-prepared metallic
K (eqn (5), (8) and (9)), efficiently intercalating into the carbon
lattices of the carbon matrix during the activation, results in the
expansion of the carbon lattices in Fig. 1.10 After the removal of
the intercalated metallic K and other K compounds by washing,
the expanded carbon lattices cannot return to their previous non-
porous structure and thus the high microporosity that is neces-
sary for large SSA and PV/MV is created.
The development of large SSA and high porosity in KOH-
activated carbons is the result of the synergistic, comprehensive
actions including chemical activation, physical activation, and
carbon lattice expansion by the metallic K intercalation.
However, the real reaction processes and activation mechanisms
are variable depending not only on the activation parameters (i.e.
amount of KOH, activation temperature, etc.), but also on the
reactivity of various carbon sources. Both the activation
parameters and carbon sources also have significant influence on
This journal is ª The Royal Society of Chemistry 2012
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Fig. 1 Activation mechanism by the penetration of metallic K into the
carbon lattices, the expansion of the lattices by the intercalated metallic
K, and the removal of the intercalated K from the carbon matrix.
Reprinted with kind permission from ref. 10. Copyright 2012, Institute of
Physics.
the pore microstructure and surface chemistry, which further
affects the performance of KOH-activated carbons in many
applications from gas storage to the electrodes. Thus, it is
impossible to preview both which activation procedure will yield
the ACs with the desirable structure and property, and which
reactions and activation mechanisms will be involved. However
all these limitations do not reduce the popularity and effective-
ness of KOH activation in developing the highly porous
networks in carbon materials.
3. Production of KOH-activated carbons
In laboratory scale, KOH activation is normally performed in a
horizontal stainless tube furnace under an inert gas flow. Before
activation, various biomass materials to be used as carbon
sources are pre-treated with processes such as hydrothermal
carbonization and pre-calcination to form chars. Then KOH is
mixed with these chars, coals, cokes, or various structured
carbons either just physically or by impregnation with KOH
aqueous solution. Normally the KOH–carbon mass ratio ranges
from 2 to 5. An extra step for evaporation of water at low
temperature is necessary when the impregnation method is
adopted. The resulting mixture is put into a crucible and
carbonized at high temperatures, e.g. 650–950  C. After cooling,
the product is thoroughly washed with either aqueous acid
solution or just water to remove any soluble impurities, and then
dried to obtain the ACs and various activated structured carbons
with enhanced SSA and PV.
In pilot scale, versatile rotary kilns are the most widely used for
chemically preparing ACs in a wide range of sizes.9 The choice of
carbon sources mainly depends on cost, availability, and quality
(high carbon content, and low inorganic and volatile contents).
And various raw materials rich in carbon, such as cokes, coal,
peat, pitches, lignite, wood, and nut shells, are used in the
industrial production of the ACs by chemical activation with
H3PO4 or ZnCl2 as the activating reagent.9 At present, the
production of KOH-activated carbons (Brand: Maxsorb) from
coal, coke or a combination is operated by Kansai Coke and
Chemical Ltd., Japan.4 The carbonaceous feeds are preferably
utilized in a pulverized form.3 The mass ratio of KOH to carbon
is preferably between 2.5 and 3.5. The activation proceeds with
agitation in an indirectly fired rotary kiln and the process consists
of a two-stage heat treatment. The first step is the dehydration at
370–400  C for 0.5 to 1.5 h. The second stage is the activation at
750–900  C for 0.5 to 2 h. The remaining KOH, salts and K
formed during the activation are removed by washing thor-
oughly and the products are recovered and dried. From the
J. Mater. Chem.

viewpoint of cost, sustainability, and environmental friendliness,
further consideration of wood and nut shells as carbon sources
for ACs with ultrahigh SSA prepared by KOH activation can be
made in industry.
4. KOH-activated carbons for supercapacitor (SC)
electrodes
One of the most important applications of KOH-activated
carbons in the field of energy storage is the SCs, in which the
charge accumulates at the electrode/electrolyte interface, sche-
matically represented in Fig. 2a.11–15 SCs have a lower specific
energy but high specific power compared to other energy storage
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F
systems (Fig. 2b). Significant advantages for the SCs include the
operation in extended temperature range, high specific power of
10 kW kg
1, long cycle life of 100 000 times, and rapid charge–
discharge. Typical examples are the use of the SCs for memory
back-up systems, industrial power and energy management, and
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as a temporary energy storage device for elevators and regener-
ative braking in electric and hybrid cars.
Among various available candidates for the SC electrodes,
porous carbons are investigated most intensively because of their
well-developed microstructure, good conductivity, excellent
stability, high SSA, low cost, and accessibility. The capacitance
of carbon-based SCs not only is usually proportional to the SSA
of porous carbons,12 but also can be enhanced through pseudo-
capacitive effect by the incorporation of heteroatoms (e.g.
oxygen, nitrogen, etc.) into the carbon framework.13 As
mentioned in the Introduction, KOH activation of carbonaceous
materials can result in ACs with dramatically increased SSA and
PV/MV, uniform PSD, and controllable surface functional
groups, depending on the activation parameters and carbon
sources used. These ACs are ideally suitable for the SC elec-
trodes. For carbon-based SCs, both the gravimetric capacitance
and volumetric capacitance are of great importance in practical
applications.17 It is worth noting that excess activation can cause
Fig. 2 (a) Representation of a supercapacitor (SC) based on porous
electrodes.11 Reprinted with kind permission. Copyright 2006, Elsevier.
(b) A Ragone plot showing the specific power against specific energy for
various electrical energy storage systems. If a supercapacitor (SC) is used
in an electric vehicle, the specific power shows how fast one can go, and
the specific energy shows how far one can go on a single charge. Times
shown are the time constants of the devices, obtained by dividing the
energy density by the power.16 Reprinted with kind permission. Copy-
right 2008, Nature Publishing Group.
J. Mater. Chem.
View Online
larger PV, which further makes the density and conductivity of
the ACs decrease. Thus a lower volumetric energy density and
loss of power capability are obtained. So finely tailoring the
porous microstructure and surface chemistry of porous carbons
by KOH activation is crucial for obtaining high performance SCs
while balancing the gravimetric and volumetric capacitances.
4.1. Fossil-based carbon sources
Since the earliest report for the activation of coal and coke by
KOH,3 fossil-based carbon sources, such as coals, pitches,18–21
and cokes,22–25 have attracted much attention in the search for
novel ACs with high SSA as the electrode materials.
Kang and co-authors investigated the effect of pre-carbon-
ization of mesophase pitch-based ACs on the textural properties
and electrochemical performance of the SCs.18,19 Pre-carboniza-
tion was beneficial for growing graphitic microcrystallites and
hindered the crystallites from the intersection during KOH
activation, and thus the SSA and the pore size range of 1.5–
2.4 nm of the ACs decreased with increasing pre-carbonization
temperature.18 This is consistent with the theory that the KOH
activating agent has a higher possibility of penetrating and
etching the carbon structures that have less order. The maximum
specific capacitance of 145 F g
1 in organic electrolytes was
obtained for the ACs with 2258 m2 g
1 which was applied in the
SCs having high energy density (31 W h kg
1) and power density
(12 kW kg
1).19 Wang et al. studied the effects of the softening
point of pitches on the textural properties of the ACs.20 With the
same SSA, higher softening point pitch-based ACs showed a
higher MV (0.51 cm3 g
1) and a better specific capacitance of
256 F g
1 in KOH electrolytes than lower softening point pitch-
based ACs (0.45 cm3 g
1 and 191 F g
1), indicating the MV
contributed more to the specific capacitance. Blanco activated a
mesophase-derived pitch with a KOH–pitch mass ratio ¼ 3 to
produce the ACs with the SSA of up to 2000 m2 g
1 and average
PSD of 0.97 nm.21 The good specific capacitances obtained
were 242, 208, and 145 F g
1 in 1 M H2SO4, KOH and LiCl
electrolytes, respectively. The total loss of capacitance after 7000
cycles in H2SO4 media was 8% at 0.6 V and 16% at 1 V, whereas
in KOH electrolytes the reduction in the capacitance was 72%,
even at a very small operating voltage (0.6 V). This behaviour is
associated with the strong oxidation of the positive electrode
caused by the progressive shift of the working potential towards
very positive potential values during cycling.21
By rapid microwave heating, He et al. prepared a series of the
ACs derived from cokes22–25 and investigated the effects of acti-
vation time (27–37 min), KOH–coke mass ratio, and microwave
power on the pore structures of the ACs. The results indicated
that the effect orders of the experimental parameters on the SSA
of the ACs were the following: microwave power > activation
time > KOH–coke mass ratio. The ACs with the SSA of up to
2312 m2 g
1 as the SC electrode demonstrated a specific capac-
itance of 343 F g
1 and remained at 246 F g
1 even after 800
cycles with an energy density at 8.0 W h kg
1.
4.2. Natural biomass-based carbon sources
Fossil-based carbon sources are limited and non-renewable, and
thus it is urgent to develop various renewable, abundant, natural
This journal is ª The Royal Society of Chemistry 2012
 View Online

biomass as well as the derivatives and waste products as the Table 1 Properties and characteristics of some KOH-activated carbons
economic, environmentally friendly carbon sources for preparing as the SC electrodes derived from natural biomass-based materials
the ACs. Starting SSA PV Specific
Various natural biomass-based materials, derived from plants materials (m2 g
1) (cm3 g
1) Electrolyte capacitance (F g
1) Ref.
and animals, have been transformed into the ACs via the pre-
treatment (hydrothermal carbonization or pre-calcination), fol- Cherry stones 1273 — H2SO4 232 26
Organic 120
lowed by KOH activation as shown in Fig. 3. The textural Fish scale 2273 2.74 KOH 168 27
properties and specific capacitances of several ACs are presented Pig bone 2157 2.26 KOH 185 28
in Table 1, indicating that the natural biomass-derived materials SSSa 2585 1.41 KOH 311 31
are promising candidates to prepare low-cost, high-performance Waste paper 526 — KOH 180 29
Wood 2967 1.35 Organic 236 33
ACs as the SC electrodes. sawdust
Various waste materials,26–33 such as cherry stones,26 fish Cellulose 2457 1.08 Organic 220 33
scales,27 pig bone,28 waste paper,29 banana fibres,30 sunflower Wheat straw 2316 1.50 Organic 251 32
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F

Potato starch 2342 1.24 KOH 335 37

seed shells (SSS),31 wheat straw,32 and wood sawdust,33 have been Starch 1510 1.01 KOH 194 38
used for synthesizing the ACs. KOH activation of cherry stone Glucose-d 2970 — Na2SO4 186 39
wastes resulted in microporous ACs with the SSA of 1100– a
Sunflower seed shell.
1300 m2 g
1, uniform PSD of 0.9–1.3 nm, and large capacitances
of 232 and 120 F g
1 in H2SO4 and organic electrolytes,
respectively. And the volumetric capacitance in the H2SO4 elec-
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trode was as high as 87 F cm
3.26 Novel fish scale based 3D
hierarchical lamellar porous carbon (FHLC) demonstrated very
high SSA (2273 m2 g
1) and PV (2.74 cm3 g
1).27 The capacitance
of FHLC was 168 F g
1 at 0.05 A g
1, and it was still as high as
130 F g
1 at a high current density of 40 A g
1, while the specific
capacitances of commercial AC YP17 (Kuraray Chemical) were
158 F g
1 at 0.05 A g
1 and only 109 F g
1 at 10 A g
1.27
Hierarchical porous carbons derived from pig bone possessed a
specific capacitance of 185 F g
1 at 0.05 A g
1, which still
maintained 130 F g
1 even at 100 A g
1.28 Lee et al. reported that
waste paper-derived ACs demonstrated the SSA of 526 m2 g
1
and the specific capacitance of 180 F g
1 in KOH electrolytes.29
Banana fibre-based ACs showed an enhancement of the SSA
(686 m2 g
1) up to 30 times that of the original one and the
specific capacitance was 66 F g
1 in organic electrolytes.30 SSS-
based ACs31 with the SSA of 619–2585 m2 g
1 were obtained by
KOH activation, which had the specific capacitance of up to
311 F g
1 in KOH electrolytes. The micropores in the texture of
SSS-based ACs contributed more to the capacitance than the
mesopores.31 Wheat straw-based ACs, prepared at 700  C using a
KOH–char weight ratio of 3.5,32 had the SSA of up to 2316 m2
g
1 and PV of up to 1.50 cm3 g
1 as well as uniform pores below
4 nm. The specific capacitance reached 251 F g
1 in organic
electrolytes.32 Wood sawdust-based AC, developed by hydro-
thermal carbonization, followed by KOH activation, had high
SSA (2968 m2 g
1) and PV (1.35 cm3 g
1), mainly derived from
pores with pore size lower than 3 nm. The specific capacitance of
AC-W800 exceeded that of commercial YP-17D optimized for
SC applications by 100% in Fig. 4a.33
Natural fungi have been transformed into the ACs with SSA of
up to 2264 m2 g
1 by KOH activation.34 Fungi-based char shows
bulky morphology (Fig. 5a), whereas AC-4, prepared with a
KOH–char mass ratio of 4, has large cavities with pore sizes of
1 to 10 mm (Fig. 5b), implying a significant morphological
change during the activation. The ACs demonstrate type I
isotherms (Fig. 5c), typical of microporous materials, and the
ACs exhibited narrow PSD mainly centred at 0.8 nm. The
increase of the mass ratio of KOH–char evidently makes the
micropores broaden, and the formation of larger micropores
(1.3–1.9 nm) is observed for ACs prepared with KOH–char mass
ratio $1/4 (Fig. 5d). The resulting fungi-based carbons show an
excellent specific capacitance of 240 F g
1 in an organic elec-
trolyte and a high adsorption capacity for CO2.34,35 Direct
pyrolysis of starch-based gels resulted in the low SSA (<600 m2
g
1) of porous carbons,36 while the SSA over 2000 m2 g
1 of the
ACs were obtained by KOH activation of starch-based
chars.33,37,38 Potato starch-based activated carbon spheres
(PACS) with high SSA (1605–2342 m2 g
1), PV (0.74–1.24 cm3
g
1), and good specific capacitances of up to 335 F g
1 in KOH

Fig. 4 Electrochemical characterization of various carbon materials in

Fig. 3 Transformation of various natural biomass-derived materials
into the ACs via (a) pre-treatment followed by (b) KOH activation.
1 M tetraethylammonium tetrafluoroborate (TEABF4) solution in
acetonitrile (AN) at room temperature: (a) capacitance retention with
current density, (b) specific capacitance as a function of the SSA of
micropores. Reprinted with kind permission from ref. 33. Copyright
2012, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

This journal is ª The Royal Society of Chemistry 2012 J. Mater. Chem.

 View Online

1.17 cm3 g
1).41 RF-based ACs presented a high specific capac-

itance of 500 F g
1,40 and the capacitance of PF-based ACs
reached 234 F g
1 in the aqueous electrolyte and 137 F g
1 in the
organic electrolyte.41 The ACs produced by KOH activation of
polyfurfuryl alcohol (PFA) with a KOH–PFA mass ratio
ranging from 1 to 3 at 700  C for 1 h exhibited a very fine PSD
(below 3 nm), high SSA of 1070–2600 m2 g
1, and good electrical
conductivities (up to 130 S cm
1).43 Such ACs showed high
capacitances (over 147 F g
1) in organic electrolytes at 2.5 V. A
linear relationship between the SSA vs. capacitance is found,
implying that the capacitance values are primarily controlled by
the SSA of the ACs.43 Very recently, Yushin and co-workers
adopted the same procedure for the activation of polypyrrole,
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F

which allowed us to produce ACs with an ultrahigh SSA of up to

3432 m2 g
1 and a PV of 0.5–4 nm pores up to 2.39 cm3 g
1.42
Activation at higher temperatures led to the increase in the SSA
and the broadening of PSD through the formation of additional
volumes of 1–4 nm pores. The highest specific capacitance of
these ACs was as high as 300 F g
1 in ionic liquid electrolytes at
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Fig. 5 SEM images of (a) the fungi-based char and (b) AC-4, and N2
adsorption isotherms (c) and PSD (d) of the ACs prepared using different
KOH–char ratios (1, 2, 4, and 5). The inset in (a) is the photograph of
Agaricus.
60  C, which is unprecedented for carbon materials. Very good
rate performance at high scan rates and current densities suggests
a great promise of the proposed ACs for safe and high-energy SC
applications.42

electrolytes were prepared by stabilization and carbonization, 4.4. Various structured carbons as carbon sources
followed by KOH activation.37 A series of ACs with the PSD
Except for the ACs prepared from fossil/natural biomass/poly-
distributed in the range of 1–3 and 4–5 nm were fabricated with a
mer based carbon sources, various structured carbons have been
similar preparation method, using various starches as the
etched by KOH activation to introduce the additional micro-
precursors.38 The specific capacitances for these starch-based
pores and small mesopores into the framework under the
ACs were between 170 and 200 F g
1 in KOH aqueous solu-
maintenance of the intrinsic shapes and properties of the original
tion.38 Large SSA (up to 2425 m2 g
1) and PV (up to 1.08 cm3
carbons, thus greatly improving the SSA and MV/PV as well as
g
1) were obtained for starch- and cellulose-based ACs prepared
the capacitive performance. The textural properties and specific
by hydrothermal carbonization, followed by KOH activation.33
capacitances of several activated nanostructured carbons are
Higher activation temperature led to lower specific capacitance
listed in Table 2.
but better rate performance and faster frequency response of the
fabricated devices. All ACs have higher specific capacitances
Templated porous carbons (TPCs). TPCs, synthesized using a
than YP-17D as shown in Fig. 4a. The specific capacitance
‘hard template’ or ‘soft template’ method, possess well-
measured at 0.1 A g
1 was found to exhibit a good correlation
controlled PSD, and an interconnected pore structure, and thus
with the SSA of micropores (Fig. 4b). Whitacre and co-workers
TPCs are promising candidates for the SC electrodes. KOH
investigated the relationship of precursor pre-carbonization
activation can significantly improve the SSA and PV of TPCs by
conditions vs. the porosity and capacitive energy storage prop-
adding micropores into the carbon framework,44–47 thus causing
erties for the ACs derived from glucose-d.39 KOH activation of
the char pyrolyzed at lower temperature considerably augmented
both the SSA and specific capacitance of the ACs via effective Table 2 Properties and characteristics of KOH-activated carbons as the
pore formation. The specific capacitance of the ACs with the SC electrodes derived from several nanostructured carbons
highest SSA (2970 m2 g
1) in a neutral Na2SO4 electrolyte was
Starting SSA PV Specific
186 F g
1, dozens of times that of the carbon pre-carbonized at materials (m2 g
1) (cm3 g
1) Electrolyte capacitance (F g
1) Ref.
500  C without activation.39
FDU-15 1410 0.73 KOH 200 46
MOF-5 2222 1.14 KOH 271 47
4.3. Synthetic organic polymer-based carbon sources Organic 156
CNTs 644 0.89 KOH 57 51
Different from the ACs from natural biomass, a one-step CNFs 1520 0.71 H2SO4 255 56
carbonization and activation of polymers has been employed for KOH 202
preparing the ACs with high SSA.40–43 The excess small meso- Organic 87
CDCs 1650 0.82a Organic 180 62
pores are found in the polymer-based ACs, which can shorten the MEGO 3100 2.14 Organic 200 66
diffusion route of electrolyte ions. Phenol–formaldehyde (PF) 2400 — Ionic liquid 166
and resorcinol–formaldehyde (RF) resins were activated by CAs 1468 — KOH 245 71
KOH to form the ACs with well-defined micropore size distri- a
Micropore volume (MV).
bution, and large SSA (up to 2445 m2 g
1) and PV (up to

J. Mater. Chem. This journal is ª The Royal Society of Chemistry 2012


the better capacitance for activated TPCs (a-TPCs) than that for
original TPCs.
Activation of ordered mesoporous carbons (OMPCs) gener-
ated large numbers of micropores into the mesopore walls, and
meantime it retained the main mesoporous channels, although
the mesostructural ordering for activated OMPCs (a-OMPCs)
evidently decreased.44,45 The SSA and PV of a-OMPCs went up
when increasing the KOH–OMPCs weight ratio and/or acti-
vating temperature and the maximum SSA of 2060 m2 g
1 and a
PV of 1.91 cm3 g
1 were obtained. a-OMPCs showed superior
capacitances over OMPCs both in aqueous and organic elec-
trolytes. Very recently, Zhao et al. prepared KOH-activated
FDU-15 (KF) having high SSA (up to 1410 m2 g
1) and PV (up
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F
to 0.73 cm3 g
1), about twice those of FDU-15. Activation at
high temperatures resulted in the shrinkage of the mesoporous
framework evidenced in Fig. 6a–f, also indicating that the
ordered mesostructures were still well maintained. Typical cyclic
voltammograms (CVs) for the activated carbons presented a
quasi-rectangular voltammogram shape in Fig. 6g, indicative of
Downloaded by Duke University on 06 October 2012
their being excellent candidates as the electrodes. The activated
carbons exhibited an improved gravimetric capacitance of 200 F
g
1, excellent rate performance, and good cycling stability with a
capacitance retention of 98% over 300 cycles,46 implying that
the hierarchical micro-, mesopore structures are beneficial for
fast ionic transport within the mesopores and diffusion from
mesopores to micropores. Tuning the pore structures and
textures of metal–organic framework (MOF-5) based porous
carbons by KOH activation resulted in the excellent capacitances
of 271 and 156 F g
1 as well as the high energy densities on a
gravimetric basis of 9.4 and 31.2 W h kg
1 in aqueous and
Fig. 6 TEM images of FDU-15 (a and b), and KOH-activated FDU-15
(FK): KF1-90 (c and d), and KF6-90 (e and f), viewed from [11] (a, c and
e) and [01] (b, d and f) directions, and (g) the CV curves at a scan rate of
5 mV S
1 of FDU-15 and activated samples with a KOH–carbon ratio of
1.0 for 45, 60, 90 min, respectively.46
This journal is ª The Royal Society of Chemistry 2012
View Online
organic electrolytes, respectively.47 Due to the high packing
density of 0.93 g cm
3, the related volumetric specific energy
densities of up to 8.8 and 29.0 W h L
1 were obtained in aqueous
and organic electrolytes, respectively.
Carbon nanotubes (CNTs) and their composites. Due to their
unique tubular morphology, superior electronic conductivity,
and good mechanical/thermal stability, CNTs with a graphitic
structure have attracted much attention for use in SC elec-
trodes.48–50 Generally, the SSA of CNTs is below 200 m2 g
1, so
their specific capacitance is far lower than that of the ACs with a
general SSA of 2000 m2 g
1. KOH activation is an efficient
method for etching CNTs to create lots of defects and thus
significantly enhance the porosity of CNTs. Xu et al.51,52 per-
formed KOH activation of CNTs at 800  C for 1 h, leading to the
dramatic increase in the SSA and PV from 166 m2 g
1 and
0.45 cm3 g
1 for original CNTs to 644 m2 g
1 and 0.98 cm3 g
1
for activated CNTs (a-CNTs). a-CNTs became short and dis-
torted, and their surface was very rough. The specific capaci-
tances of a-CNTs were linearly proportional to the SSA and the
maximum specific capacitance was 54 F g
1, far higher than
19 F g
1 for original CNTs.51
A good alternative for enhancing the specific capacitance is to
design high SSA AC–CNTs composites. An interesting AC–
CNTs nanocomposite with significantly increased SSA of up to
2462 m2 g
1 was prepared by the activation of mesocarbon
microbeads (MCMBs) with a KOH–MCMBs weight ratio ¼ 5 at
900  C for 2 h. CNTs were in situ formed by iron catalysis during
the activation. KOH activation of the polyacrylonitrile (PAN)–
carbon nanotubes (CNTs) composites53,54 formed the AC–CNTs
composites with pore size predominantly ranging from 1–5 nm
and excellent SSA (2266 m2 g
1), evidently higher than that of
CO2-activated ones (358 m2 g
1).53 Various AC–CNTs nano-
composites showed very good gravimetric capacitances in 6 M
KOH electrolytes of up to 243, 250, and 303 F g
1, respec-
tively.53–55 These values are higher than those of a-CNTs and
commercially available ACs.
Carbon nanofibres (CNFs), carbon fibres (CFs), and carbide
derived carbons (CDCs). CNFs56,57 are cylindrical carbon mate-
rials like CNTs but with structural and textural characteristics
different from CNTs. Activated CNFs (a-CNFs) with larger SSA
(up to 1520 m2 g
1) were obtained with the retention of the
shape, surface roughness, diameter, graphene sheet size, and
electrical conductivity of starting CNFs.56 The specific capaci-
tance of a-CNFs increased linearly as the SSA and the attainable
values were as high as 255, 202, and 87 F g
1 for H2SO4, KOH,
and organic electrolytes, respectively, while the as-prepared
CNFs showed very low specific capacitance because of low SSA
(448 m2 g
1) and the anomalous small size of micropores. A good
cycle life, with a capacitance retention of 92% after 10 000
charge–discharge cycles, was achievable for a-CNFs.56 Lee et al.
activated vanadium-containing CNFs to obtain a-CNFs with
enhanced SSA of up to 2800 m2 g
1, higher than that of a-CNFs
derived from vanadium-free CNFs, indicating the presence of the
catalytic activation by V2O5.57 a-CNFs demonstrated the supe-
rior specific capacitance of 127 F g
1 to 25 F g
1 of the original
CNFs in organic electrolytes. Compared with the SSA of PF
resin-based CFs without activation,58 the SSA increased with the
J. Mater. Chem.

Fig. 7 (a) Evolution of the gravimetric capacitance with the chlorination
temperature for as-produced and KOH-activated CDCs, and (b) varia-
tion of the normalized capacitance vs. the average pore size of CDCs
before and after activation, and other activated microporous carbons.62
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F
activation by CO2 and KOH to 939 and 1893 m2 g
1, respec-
tively. Compared to specific capacitances (136 and 63 F g
1) of
CFs treated by CO2, CFs treated by KOH exhibited higher
capacitances (214 and 116 F g
1) in aqueous and organic elec-
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trolytes, respectively, and good rate capability due to the higher
SSA and well-adapted PSD of CFs activated by KOH.58
CDCs represent a new kind of porous carbons produced by
selective thermo-chemical etching of the carbide-forming element
from metal carbide. Nanoporous CDCs have promising poten-
tial in H2 storage, catalysis, separation/purification, etc.59–62
Gogotsi et al. undertook KOH activation of CDCs and found
that the lower the chlorination temperature was, the more effi-
cient the activation was due to different microstructural ordering
of starting CDCs. It is in agreement with the results obtained for
the activation of other carbons pre-carbonized at different
temperatures. In Fig. 7a, activated CDCs (a-CDCs) demon-
strated good gravimetric capacitances, 30% larger than those of
as-produced CDCs.62 The maximum capacitance of 180 F g
1
was obtained for CDC prepared at 600  C after KOH activation
due to the maximum fraction of pores below 0.7 nm for those
samples. In Fig. 7b, the pore filling seems to be optimal when the
pore size is close to 0.7–0.8 nm and the normalized capacitance
decreases with the increase of pore size, confirming the mecha-
nism of charge storage of the ions in the double layers of carbon-
based SCs.
Graphene-based materials. Following the earlier discovery of
well-known zero-dimensional (0D) buckyballs and 1D CNTs,
the emergence of 2D graphene1 has attracted much attention due
to its unique nanosheet structure, superior electrical properties,
good mechanical, thermal and chemical stabilities, and a high
theoretical SSA of 2630 m2 g
1.63–65 However the SSA values of
graphene-based materials, normally several hundreds of square
meters per gram,63 are much lower than 2630 m2 g
1, resulting in
low capacitive performances of graphene-based SCs.
In 2011, Zhu et al. performed KOH activation of microwave
exfoliated graphite oxide (MEGO) to generate pores (Fig. 8A).66
The large SSA (up to 3100 m2 g
1) and PV (up to 2.14 cm3 g
1) of
activated MEGO (a-MEGO) are far higher than the previously
reported values of other graphene-based materials. The
morphology of a typical graphene piece was maintained in a-
MEGO (Fig. 8B). High resolution electron images (Fig. 8C–F)
indicated the formation of a continuous 3D pore network, the
sizes of which range from 1 to 10 nm. N2 adsorption and CO2
J. Mater. Chem.
View Online
Fig. 8 (A) Schematic showing the microwave exfoliation/reduction of
GO and the following chemical activation of MEGO with KOH that
creates pores. (B) Low-magnification SEM image of a 3D a-MEGO
piece. (C) High-resolution SEM image of a-MEGO that demonstrates the
porous morphology. (D) Annular dark field scanning transmission elec-
tron microscopy (ADF-STEM) image of the same area as (C), acquired
simultaneously. As seen, a-MEGO contains micro- and mesopores with a
distribution of sizes between 1 and 10 nm. (E) High-resolution phase
contrast electron micrograph of the thin edge of an a-MEGO chunk,
taken at 80 kV. (F) Exit wave reconstructed high resolution transmission
electron microscopy (HR-TEM) image from the edge of a-MEGO. The
in-plane carbon atoms are clearly resolved, and various n-membered
carbon rings can be seen. Substantial curvature of the single-carbon
sheets is visible, with the in-plane crystallinity being preserved. Reprinted
with kind permission from ref. 66. Copyright 2011, American Association
for the Advancement of Science (AAAS).
adsorption experiments also revealed that a-MEGO contained
micropores of 1 nm size, and mesopores centred at 4 nm in size.
Various characterizations imply that a-MEGO is comprised of
almost entirely single sheets of sp2-bonded carbon.
Two-electrode SC cells constructed with a-MEGO (2400 m2
g ) exhibited a specific capacitance of 166 F g
1 in a 1-butyl-3-

1
methyl-imidazolium tetrafluoroborate (BMIM BF4)/AN elec-
trolyte at a constant current of 5.7 A g
1 and a working voltage
of 3.5 V. The corresponding volumetric capacitance was 60 F
cm
3. The energy density and power density for a-MEGO in the
cell are 70 W h kg
1, and 250 kW kg
1, respectively. Consid-
ering a weight ratio of 30% for a-MEGO in a packaged SC
device, a practical energy density of over 20 W h kg
1 for a
packaged device is expected, four times higher than the existing
AC-based SCs. A practical power density of 75 kW kg
1 is one
order higher than the values from commercial carbon-based SCs
that have an energy density between 4 and 5 W h kg
1.67 After
10 000 constant current charge–discharge cycles, 97% of the
capacitance is retained. The specific capacitance of a-MEGO
(3100 m2 g
1) at 3.5 V and 0.7 A g
1 is 200 F g
1 in organic
electrolytes, the highest gravimetric capacitance reported to date
amongst any carbons derived from graphene-based materials.
KOH activation of thermally exfoliated graphite oxide (TEGO),
already being synthesized in tons,68 is also successfully per-
formed. Therefore, the feasibility for producing a-MEGO and a-
TEGO in large-scale allows for constructing low-cost, high-
performance SCs in the near future.
This journal is ª The Royal Society of Chemistry 2012

Zhao and co-workers reported the AC–graphene composites
were prepared by KOH activation of homogeneous composites
containing RF resin and graphene oxide (GO) at 800  C.69 In the
AC–graphene composites, the graphene sheet is surrounded by
thin layers of porous ACs. Hierarchical pores with diameters
ranging from one to hundreds of nanometres are observed and
the textural properties are found to depend on the GO content of
starting composites. This kind of novel AC–graphene composites
shows a high specific capacitance of up to 397 F g
1 in KOH
electrolytes. In ionic liquid electrolytes, the maximum specific
capacitance is 287 F g
1 at 90  C.69
Carbon aerogels (CAs) and commercial activated carbons
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F
(ACs). CAs,70,71 having a unique three-dimensional nano-
network, were subjected to KOH activation for optimizing their
pore structures and improving specific capacitances. Decreasing
the pre-carbonization temperature of CAs’ precursor can help to
increase the SSA and PV of activated CAs (a-CAs).70,71 For
example, the SSA of a-CAs, prepared by pre-carbonization at
Downloaded by Duke University on 06 October 2012
900  C, followed by activation, was 997 m2 g
1, while it increased
by 47% to 1468 m2 g
1 of a-CAs, synthesized by pre-carbon-
ization at 500  C, followed by activation.71 a-CAs possessed
three-level micro-, meso-, and macropore systems with yields of
up to 68% and SSAs of up to 3247 m2 g
1. There is a linear
relationship between specific capacitance and the SSA for a-CAs
with similar pore systems. The highest specific capacitance of a-
CAs reached 245 F g
1 in KOH electrolytes, 2.3 times that of
CAs. Furthermore, this capacitance was still as high as 201 F g
1
when increasing the current density to 100 mA cm
2, indicating
that a-CAs have a high-rate charge–discharge performance.71
The commercial ACs were further activated by KOH to improve
the SSA (up to 2800 m2 g
1) and MV (up to 1.03 cm3 g
1) for
resulting activated ACs (a-ACs) with good yields of 50–73% and
enhanced purity.72 Values of 200 F g
1 in aqueous electrolytes
and 150 F g
1 in organic electrolytes were obtained for a-ACs,
three times those of original ACs.72
4.5. KOH-activated carbons with heteroatoms within their
structures
The ACs prepared by KOH activation normally contain a vari-
able amount of the heteroatoms (e.g. oxygen, nitrogen, sulfur,
hydrogen), depending on the synthesis procedures and carbon
sources. The presence of the heteroatoms on the surface of the
ACs can enhance the capacitance through the pseudo-capaci-
tance effect derived from Faradaic redox reactions. Thus the
introduction of the heteroatoms has been regarded as an efficient
method to enhance the specific capacitance of the ACs, instead of
improving the porosity of the ACs. Among the heteroatoms,
nitrogen is widely studied as a foreign atom entering the carbon
framework to provide the pseudo-capacitance effect.73–81
Different nitrogen-containing functional groups in a carbon
matrix are presented in Fig. 9A. For the ACs with similar
nanotextural properties and MV, their specific capacitances in
aqueous solutions linearly increase with nitrogen content, and
show no significant enhancement in the organic electrolyte in
Fig. 9B.12
By employing carbon sources rich in nitrogen, a series of
nitrogen-enriching ACs were prepared by KOH activation of
This journal is ª The Royal Society of Chemistry 2012
View Online
Fig. 9 (A) Schematic drawing of various nitrogen-containing functional
groups in a carbon matrix and (B) the capacitances for several ACs with a
similar nanotexture and SSA but various nitrogen contents.12
polyaniline,73,74 silk fibroin,75 ammoxidised coal,76 and novolac
resin.77 The nitrogen-containing ACs derived from polyaniline
possessed high SSA up to 2287 m2 g
1. The nitrogen atoms
existed in the form pyridinic, pyrrolic, quaternary, and oxidized
nitrogen groups.73,74 The obtained ACs exhibited a high specific
capacitance of 455 F g
1 in KOH electrolytes. The specific
capacitance per unit surface area was 23 mF cm
2, three times
higher than that of the commercial carbon Maxsorb (6 mF cm
2).
Kim et al. performed KOH activation of silk fibroin-based chars
to provide nitrogen-containing ACs, showing higher, both
gravimetric and volumetric, capacitances compared with a
typical phenolic resin-based AC.75 Nitrogen-doped coal-based
ACs, developed by combining ammoxidisation, carbonization,
and activation in various sequences,76 had well-developed SSA
reaching from 1577 to 2510 m2 g
1, and 1.0 to 8.5 wt% of
nitrogen. Increased capacity and charge exchange were observed
due to the nitrogen heteroatoms introduced. The pyrrolic, pyr-
idonic, and oxidized nitrogen species are the most effective
configurations. Nitrogen-decorated PCs with a SSA of over
2900 m2 g
1 and MV of over 1.2 cm3 g
1 were prepared by KOH
activation of novolac resin, and the gravimetric and volumetric
capacitances in organic electrolytes were 180 F g
1 and 106 F
cm
3 at 1 mA cm
2, respectively, higher than the values of
coconut shell- and PF resin-based PCs.77
One-step activation of carbon source/nitrogen source blends is
another good choice for obtaining nitrogen-incorporated ACs.78
Jurewicz and Babel produced a series of ACs with a high SSA of
over 3000 m2 g
1, a PV of over 2 cm3 g
1, an additional PSD in
the mesopore region (2–3.5 nm), and a high nitrogen content of
up to 5.9 atom% by employing a coconut shell–melamine
mixture.78 The entire lack of pyridinic nitrogen and the consid-
erable amount of oxygen groups are very helpful to obtaining
high-capacitance properties. The ACs with the highest level of
nitrogen doping demonstrated excellent capacitances of 307 and
293 F g
1 for the negative and positive electrodes, respectively, in
an acidic capacitor, and 368 F g
1 for the negative electrode in an
alkaline capacitor. The nitrogen-enriched ACs derived from coal/
urea precursors showed different nitrogen contents (0.2–5.6 wt%)
and a high SSA of 2209–3268 m2 g
1.79 The presence of nitrogen
heteroatoms considerably increases the capacitance, especially if
they work as the negative electrode in an alkaline capacitor.
Gao and colleagues reported the synthesis of a series of highly
porous nitrogen-containing carbons by KOH activation of
nitrogen-doped TPCs (NTPCs) which were synthesized by
nanocasting zeolite 13X (ref. 80) or SBA-15 (ref. 81) using
ethylene diamine and carbon tetrachloride as the nitrogen and
J. Mater. Chem.
 View Online

carbon sources, respectively. When increasing the mass ratio of

KOH–C, the SSA and MV/PV of activated NTPCs (a-NTPCs)
increased gradually and the nitrogen content decreased to low
levels. a-NTPCs from the zeolite 13X template with a large SSA
of up to 2970 m2 g
1 and a MV of 1.04 cm3 g
1 exhibited good
gravimetric capacitances of 259 and 176 F g
1 in KOH and
organic electrolytes, respectively.80 The corresponding volu-
metric capacitances were 101 and 69 F cm
3, respectively.3 After
KOH activation of the NTPCs from SBA-15 as the hard
template,81 the capacity (240 F g
1) of a-NTPCs with a narrow
micropore size of 0.61–0.68 nm was much higher than 109 F g
1
for the activated nitrogen-free CMK-3. Both porous carbons had
similar textural properties, implying that nitrogen in a-NTPCs
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F

greatly improves the electrochemical properties.81

Furthermore, KOH-activated carbons inevitably contain the
surface oxygen groups, making a positive contribution to the
capacitance.82–84 Ling et al. adopted a quick KOH activation of
coal to prepare oxygen-rich ACs (OACs) with the SSA of
1950 m2 g
1, good conductivity, and high oxygen content of up
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to 12 wt%.82 Compared to high SSA ACs prepared by the

conventional KOH activation, OACs presented a higher specific
capacitance of 370 F g
1 in KOH electrolytes. Blanco and
co-authors studied the effect of thermal treatment on the
performance of carbon-based SCs.83 By thermal treatment of
pitch-derived AC, rich in oxygen functional groups, at 1000  C,
the modified AC (AC-1000) was formed in which most of the
oxygen functionalities were removed. The AC, rich in oxygen
groups, had a higher specific capacitance of 240 F g
1 in H2SO4
electrolytes than AC-1000 (170 F g
1). Both materials showed an
excellent life cycle and only 5% loss was observed after 10 000
cycles.83 Santamarıa activated coke by KOH and NaOH,
respectively, and found large differences in capacitive behaviour
between KOH-activated and NaOH-activated carbons.84 The
CO-type surface oxygen groups positively contributed to the
capacitance, with a good linear correlation being found between
specific capacitance and CO-type oxygen groups.
5. KOH-activated carbons for Li–S cell electrodes
Because of their good theoretical capacity (1675 mA h g
1),
nearly one magnitude higher than that (176 mA h g
1) of
LiFePO4, and the low cost of sulfur (S), Li–S cells may succeed
lithium-ion cells in high power hybrid electrical vehicles.85,86
Fig. 10a schematically represents a rechargeable Li–S battery. In
a typical discharge process (Fig. 10b), the reduction of S
produces various soluble long-chain polysulfides which further
combine with Li to form insulated Li2S. However, mass
commercialization of the Li–S batteries used in electrical vehicles
has still not been realized because there are two most important
obstacles for the Li–S batteries that are not completely solved: (i)
the poor electrical conductivity of elemental S leading to low
utilization of active materials; (ii) the intrinsic polysulfide shuttle
due to the solubility of polysulfides in both discharge and charge
processes. Recently, strategies have been explored to develop
cathodes made of S on KOH-activated hierarchical porous
carbons to improve the cyclability and utilization of S in the
Li–S cells.87,88
Liang and colleagues reported a bimodal micro-, meso-porous
carbon with high SSA used as a cathode material for the Li–S
Fig. 10 (a) Schematic representation and (b) load curve of a Li–S
battery. Reprinted with kind permission from ref. 86. Copyright 2012,
Nature Publishing Group.
batteries, as shown in Fig. 11a.87 KOH activation of mesoporous
carbon (MPC) with an uniform PSD of 7.3 nm, prepared
through a soft-template procedure, resulted in a bimodal porous
carbon with the formation of micropores into the mesoporous
framework of MPC while maintaining the original mesopores.
The SSA increases from 369 m2 g
1 for MPC to 1566 m2 g
1 for
activated MPC (a-MPC); the contribution from the micropores
is 962 m2 g
1. Elemental S is loaded to a-MPC through a solution
infiltration method to form a series of hierarchically structured
S–C composites (S_C0107) with increased S content. As shown
in Fig. 11b, the initial discharge capacity decreased with the
increase in S loading: when the S loading was 11.7 wt% in S_C01,
the specific capacity of the initial discharge was 1584.56 mA h
g
1, which was about 94.6% of S utilization based on the theo-
retical maximum 1675 mA h g
1; when the S loading was
51.5 wt% in S_C07, the initial discharge capacity decreased to
818 mA h g
1. The specific capacities of S_C01 at a high current
density of 2.5 A g
1 were far higher than those of both S_MPC
and S_WVA-1500 cathodes, implying that the presence of both
micropores and mesopores accounts for the high discharge
capacity.
Recently, Huang et al. prepared hierarchical porous carbons
by KOH activation of pig bone-based chars that are renewable,
cheap and environmentally friendly.88 Pig bone is a kind of
natural organic–inorganic composite. During the activation, the
organic component acts as the carbon source, while the inorganic
component plays the role of a natural template for the formation
of hierarchical pores. Pores with sizes ranging from micropores
(0.6–2.0 nm), mesopores (2–10 nm) to macropores (100 nm) are
found in pig bone based hierarchical porous carbons (BHPCs),

J. Mater. Chem. This journal is ª The Royal Society of Chemistry 2012


Fig. 11 (a) Illustration of the C–S composite cathode material by using a
bimodal porous a-MPC as the support, and (b) specific discharge
capacity of the C–S composites that cycled in 1.0 M bis(trifluoromethane)
sulfonimide lithium (LiTFSI) in 1,3-dioxolane–dimethoxyethane
Published on 08 August 2012 on http://pubs.rsc.org | doi:10.1039/C2JM34066F
(55 : 40) at 298 K. The calculation of specific discharge capacities is based
on the mass of S. WVA-1500 with 1760 m2 g
1 is microporous carbon
purchased from MeadWestvaco. Reprinted with kind permission from
ref. 87. Copyright 2009, American Chemical Society.
determined by SEM and HRTEM images (Fig. 12a and b) as well
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as nitrogen adsorption measurements at 77 K. The SSA (703–
2157 m2 g
1) and PV (0.57–2.26 cm3 g
1) of the BHPCs vary
depending on the activation temperature. The hierarchical
BHPC–S composite (Fig. 12c–d) in the Li–S batteries has a high
initial capacity of 1265 mA h g
1 and retains 643 mA h g
1 after
50 cycles, which is higher than that of the normal cathode.
The application of hierarchical porous carbons prepared by
KOH activation (a-MPC and BHPCs) effectively enhances the
performance of the C–S composite electrodes.87,88 The excellent
capacities obtained are possibly ascribed to the synergetic effect
of the hierarchical pores. Hierarchical pores with high SSA
loading S not only enable sufficient contact to the insulating S
and a high electrical conductivity of the C–S composite, but also
can adsorb and store the polysulfides on the cathode areas
during the discharge process, which can prevent polysulfide
dissolving in the electrolyte. Moreover, the appropriate meso-,
macro-pores are beneficial for fast transport and diffusion of
ions to micropores during the electrochemical cycle, and
significantly stopping the aggregation of S. Thus hierarchical
porous carbons as the S cathodes in the Li–S cells demonstrate
their superior capacitive performance to that of normal porous
carbons.
Fig. 12 SEM (a) and HRTEM images (b) of BHPC-850; illustration (c
and d) of the BHPC–S composite cathode. AB and G represent acetylene
black and gelation, respectively.88
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6. KOH-activated carbons for H2 storage
H2 is regarded as a next-generation energy carrier because of its
high chemical energy (39 kW h kg
1) and pollution-free
combustion. Safe and efficient storage of a sufficient quantity of
H2 is one of the main challenges for realizing on-board applica-
tion using H2 as a transportation fuel. The target energy densities
for the development of H2 on-board storage systems, set by the
US Department of Energy (DOE), are 5.5 wt% by year 2015 and
7.5 wt% ultimately.89 Porous carbons have attracted much
attention in the physiadsorbent for H2 storage due to their
simplicity, light weight, low cost, fast kinetics, and high SSA.
Generally, the H2 storage capacity of porous carbons is propor-
tional to the SSA and MV. Thus, higher SSA and MV, and well-
defined micropore size distribution of KOH-activated carbons
used as the physisorbents are highly advantageous for increasing
H2 adsorption capacity. There are two physical procedures for
enhancing the adsorption capacity: (i) increasing storage pres-
sure, and (ii) decreasing adsorption temperature to 77 K. This
part of the article about H2 storage in KOH-activated carbons,
derived from a wide range of carbonaceous materials, is divided
into two sections based on the storage temperatures: ambient
temperature (293–303 K) and cryogenic temperature (77 K).
6.1. H2 storage at ambient temperature (293–303 K)
A high number of investigations of KOH-activated carbons for
H2 adsorption are found in the past several years. Some
researchers prepared the ACs with different porosities by KOH
activation of anthracite90,91 and pitch.92 The maximum H2
uptakes (1.1–1.2 wt%) of these ACs, compared to those of AX21
and Maxsorb-3000, were reported at 298 K and 100–200 bar. At
pressure up to 500 bar, the H2 uptake increased to 2.7 wt%.91
Natural raw materials93–96 such as coffee bean waste,93 wood,94,95
and corncobs96 have been recently used as low-cost starting
materials for preparing the ACs with a variable SSA of 780–
3012 m2 g
1 and a MV of 0.25–1.70 cm3 g
1 by adjusting the
amount of KOH. Webley and Sun also confirmed that KOH was
the best activation reagent for generating high SSA ACs from
corncobs.96 The highest H2 uptakes for these natural raw
biomass-based carbons were reported ranging from 0.4–0.8 wt%
at 298–303 K and 20–120 bar. The hydrogen adsorption capacity
of the ACs was suppressed when significantly increasing the
amounts of surface acidic groups.95 Park and co-workers
measured the H2 uptake of 0.81 wt% at 298 K and 100 bar for the
ACs prepared from polystyrene (PSI)-based ion-exchangeable
resins by KOH activation at 700  C.97 Liu and co-authors
reported that the amount of H2 adsorption reached 0.62 wt% at
293 K and 75 bar for the activated polyaniline-based carbon tube
with high SSA up to 2415 m2 g
1 and PV up to 1.55 cm3 g
1.98
Various structured carbons91,99–105 such as TPCs,101,102
MWCNTs,103 CFs,104,105 and CNFs91,99,100 were also activated
with KOH to enhance the SSA and MV, as well as the H2 uptake.
The SSA and MV of activated CMK-8 (a-CMK-8), greatly
increased from 833 m2 g
1 and 0.31 cm3 g
1 to 2700 m2 g
1 and
1.0 cm3 g
1, respectively. The H2 uptake significantly went up to
0.75 wt% for a-CMK-8, 2.5 times higher than that for CMK-8.101
Gao et al. reported that KOH-activated nitrogen-doped ordered
mesoporous carbon had enhanced SSA of over 2700 m2 g
1 and
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MV of over 1.0 cm3 g
1, as well as good H2 uptake (0.88 wt%) at
298 K and 80 bar, much higher than those of the original
sample.102 Pristine MWCNTs stored 0.2 wt% of H2 which
increased to 0.32 wt% upon KOH activation, corresponding to
an enhancement of 60% at 298 K and 19 bar.103 Linares-Solano
and co-workers activated CFs in lab-scale and scale-up to form
a-CFs in 34–83% yields with enhanced SSA (683–2888 m2 g
1)
and MV (0.31–1.23 cm3 g
1) depending on the amounts of KOH.
The highest H2 uptake was 1.1 wt% at 298 K and 200 bar.105
Vanadium embedded activated CFs with high SSA (up to
2780 m2 g
1) and MV (up to 1.52 cm3 g
1) demonstrated
excellent H2 uptake (2.5 wt%) at 298 K and 100 bar possibly due
to the key role of a vanadium catalyst improving H2 storage.104
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Cazorla-Amor os et al.91 and Jimenez et al.99 activated commer-
cially available CNFs, resulting in enhanced SSA (265–570 m2
g
1) and H2 uptake (0.22–0.40 wt%) at ambient temperature
compared with those of original CNFs. Lee et al.100 investigated
the effect of pore size on electrospun CNFs activated by KOH,
and found the PV in the range of pore size from 0.6 to 0.7 nm
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contributed more to H2 storage at ambient temperature.
The H2 adsorption capacities for KOH-activated carbons at
ambient temperatures are also collected in Fig. 13, showing the
relationship of the H2 uptake at 293–303 K and 19–500 bar vs.
the SSA for AX21, Maxsorb-3000, and KOH-activated carbons.
It has been reported that the H2 uptake in porous carbons,
prepared from a single carbon source, linearly increases with the
pressure at ambient temperature and no saturation adsorption
occurs in the tested pressure ranges at ambient temperature. It is
evident that both the SSA and H2 uptake spread widely in
Fig. 13, possibly because a wide range of carbon sources and
variable activation parameters employed result in the different
microstructures (pore shape, pore size, etc.), and surface func-
tional groups affecting the H2 uptake. However, there is a clear
trend that the H2 uptakes of KOH-activated carbons increase
with the SSA. Moreover, the isosteric enthalpy for H2 adsorption
in KOH-activated carbons mainly ranges from 6–8 kJ
mol
1,96,106 which is too low for significant adsorption of H2 at
ambient temperature and pressure. Even under an ultrahigh
pressure of 500 bar, only 2.7 wt% of H2 is adsorbed. Most KOH-
activated carbons including AX21 and Maxsorb-3000 only
Fig. 13 The relationship of the H2 uptake at 293–303 K and 19–500 bar
with the SSA for AX21,91 Maxsorb-3000,91 and KOH-activated carbons
from different carbonaceous materials: anthracites,90,91 pitch,92 natural
raw materials,93–96 synthetic organic polymers,97,98 and various structured
carbons (CNFs,91,99,100 TPCs,101,102 MWCNTs,103 and CFs104,105).
J. Mater. Chem.
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demonstrate the H2 uptake to be no more than 1.2 wt% at
pressure #200 bar. These adsorption values are still far below the
DOE target of 5.5 wt% by year 2015.
6.2. H2 storage at cryogenic temperature (77 K)
The H2 storage capacity of porous carbons can be significantly
enhanced by decreasing the adsorption temperature to 77 K. As
an example, AX21 adsorbs 2.4 wt% of H2 at 77 K and 1 bar,107
while the amount of H2 adsorbed at 298 K and pressure up to
200 bar is only 1.2 wt%.91 Thus large numbers of studies focused
on various KOH-activated carbons for H2 storage at 77 K.
Linares-Solano et al.91 and Fierro et al.90,108 optimized the
activation of anthracite by controlling the KOH–anthracite
weight ratio and activation temperature to synthesize a set of the
ACs with different porosities. The excellent H2 uptake (5.6–
6.0 wt%) for these ACs was obtained, higher than that (5.3 wt%)
of Maxsorb-3000 at 77 K and 40 bar.108 An advanced AC
monolith with the SSA of 2374 m2 g
1 and MV of 1.04 cm3 g
1,
prepared from the ACs by pressing, adsorbs 4.9 wt% of H2, at
77 K and 40 bar.109 And the volumetric capacity was 29.7 g H2
per L. At 77 K and 1 bar, the ACs from the mesophase pitch
demonstrated a very good H2 adsorption capacity of 2.8 wt%.92
Various natural raw materials and the derivatives were trans-
formed into the ACs by pre-treatment, followed by KOH acti-
vation93,95,96,104,106,110–113 and the highest H2 uptakes reported
were 2.0 wt%, 2.6 wt%, and 2.7 wt% for corncob-,96 wood-,95 and
Quercus agrifolia-based ACs,110 respectively, at 77 K and 1 bar.
Aguilar-Elguezabal found that the amount of H2 adsorbed was
independent of the N2 flow rate during KOH activation, while it
depended on the N2 flow rate during the NaOH activation.110
Coffee bean waste-based ACs had the H2 adsorption ability of
4.0 wt% at 77 K and 40 bar.93 Gao et al. realized excellent H2
adsorption capacity (6.24 wt%) at 77 K and 20 bar of the ACs
with the SSA of 2930 m2 g
1 and MV of 1.0 cm3 g
1 prepared by
the activation of citric acid-based gel containing nickel.111
Sucrose as the carbon precursor is more expensive, but it allows
for obtaining highly microporous ACs without undesired
impurities, e.g. sulphur and heavy metals. Adsorption of H2 at
0.93 bar showed the H2 uptake (2.5 wt%) for the sucrose based
ACs with the highest SSA (1825 m2 g
1).113 In 2011, Sevilla
et al.106 employed the hydro-chars derived from glucose, starch,
cellulose, and eucalyptus sawdust for synthesizing the ACs with
high SSA (up to 2700 m2 g
1) and narrow micropore size
distribution (0.7–2.0 nm), exhibiting high hydrogen uptake up to
6.4 wt% at 77 K and 20 bar.
Polyaniline-based carbon tubes, activated by KOH, adsorbed
5.2 wt% H2 at 77 K and 50 bar.98 Activation of polythiophene
formed the sulfur-containing ACs with the highest H2 storage
capacity of 5.71 wt% at 77 K and 20 bar.115 Polypyrrole-based ACs
had two bimodal pore systems (micropore: 1.2 nm and small
mesopores: 2.2–3.4 nm) with ultrahigh SSA (3000–3500 m2 g
1)
and large PV (up to 2.6 cm3 g
1) depending on the activation
temperature and the amount of KOH. The ACs achieved a
maximum H2 uptake of 7.03 wt% at 20 bar and 77 K, one of the best
H2 adsorption capacities for porous solid adsorbents. An attractive
volumetric density was calculated to be up to 37 g H2 per L.116
The enhancement of the SSA and MV in various structured
carbons was achieved by KOH activation to increase the H2
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adsorption capacity. Activation of various TPCs,102,117–119
synthesized by the hard template method, greatly increased their
porosities by between 60% and 550% to obtain a high SSA of up
to 3188 m2 g
1 and a MV of up to 1.16 cm3 g
1, causing an
evident exaltation in the H2 uptake (at 77 K and 20 bar) of
between 35% and 440% from 1.27–3.5 wt% for TPCs to between
3.9 and 6.84 wt% for a-TPCs. A very significant increase in the
SSA of MWCNTs and their composites by more than 12 times
was observed after KOH activation.91,120 a-MWCNTs and a-
CNFs adsorbed 2.2 wt% and 1.0 wt% H2, respectively, at 77 K
and 40 bar.91 The activation of polyaniline-based CNFs resulted
in an increase of H2 uptake from 1.26 to 2.38 wt% at 77 K and
1.1 bar.121 At 77 K and 4 MPa, the gravimetric and volumetric H2
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storage capacity was 3.45 wt% and 25.4 g L
1, respectively. A
saturated H2 adsorption of 5.0 wt% was reported for a-CFs
with the SSA up to 2888 m2 g
1.105 The activation of zirconium
carbide-derived carbon (ZrC-CDC) resulted in a 50% increase in
porosity, 80% of which arose from micropores in Fig. 14.61,114
Increase of the activation temperature caused the broadening of
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micropores and the formation of large micropores. The activated
ZrC-CDC exhibited an enhancement of 63% in H2 uptake at
77 K and 20 bar from 3.8 wt% for Zr-CDC to 6.2 wt% for the
activated one, which could store 2.7 wt% of H2 at 1 bar. Gao and
co-workers proposed KOH activation of the commercial ACs.8
These superactivated carbons with high SSA of up to 3180 m2
g
1 exhibited the H2 uptake of up to 7.08 wt% at 77 K and 20 bar,
and the corresponding volumetric H2 storage was 43.2 g L
1, the
highest values for porous carbons ever reported.
By investigating the relationship of H2 uptake at 77 K and
0.93–1.1 bar vs. the SSA of KOH-activated carbons shown in
Fig. 15a, it is concluded that the larger the SSA is, the higher the
H2 uptake is for the ACs with the SSA below 1850 m2 g
1,
although there is an evident scattered nature of the uptake vs. the
SSA. For the SSA higher than 1850 m2 g
1, the amount of H2
adsorbed fluctuates between 2.0 and 2.8 wt%. Such a fluctuation
should be ascribed to the broadening of micropores. The
previous literature confirms that the pore size below 0.7 nm is
most active for H2 storage.107,122 The high SSA of the ACs can be
obtained by increasing the activation temperature and/or the
KOH amount, accompanied by concomitant micropore broad-
ening (one example for activating ZrC-CDC in Fig. 14). Thus the
micropore broadening counteracts the increase of the SSA
contributing to H2 storage, so no improvement for the H2 uptake
Fig. 14 Nitrogen adsorption isotherms (a) and PSD curves (b) of the
ACs prepared at a KOH–ZrC-CDC weight ratio of 4 and activation
temperature in the range of 600–900  C.114
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Fig. 15 The relationship of the H2 uptake at 77 K and 0.93–1.1 bar with
(a) the SSA and (b) MV for AX21 (ref. 107) ( ) and KOH-activated
carbons derived from anthracite,91 pitch,92 natural raw mate-
rials,95,96,104,106,110,111 synthetic organic polymers,115,116 and various struc-
tured carbons (commercial ACs,8 TPCs,102,118 ZrC-CDC,114 CNFs,91,121
and MWCNT–graphite composite120).
is observed for KOH-activated carbons with the SSA above
1850 m2 g
1. A similar trend for the relationship of the H2 uptake
vs. the MV of KOH-activated carbons is also evidenced in
Fig. 15b. The H2 uptake goes up for those with the MV lower
than 0.74 cm3 g
1, while it holds between 2.0 and 2.8 wt% for
those with the MV higher than 0.74 cm3 g
1.
Fig. 16 shows a good correlation between the H2 uptake at
77 K and high pressure (10–50 bar) vs. the SSA (a) and MV (b)
for KOH-activated carbons, irrespective of carbon sources and
activation parameters. In Fig. 16a, except for those including
AX21 with H2 uptake obeying the Chahine rule (the dotted line,
slope ¼ 2.0  10
2 mg H2 per m2),124 most of the KOH-activated
carbons with SSAs below 3000 m2 g
1 clearly outperform the
Chahine rule, while most of the KOH-activated carbons with
SSAs higher than 3000 m2 g
1 evidently underperform the
Chahine rule. Furthermore, the differential increase in H2
adsorption capacity of KOH-activated carbons including Max-
sorb-3000 with the SSA over 3000 m2 g
1 is significantly smaller
than expected, represented by the solid line (slope ¼ 2.2 
10
2 mg H2 per m2) in Fig. 16a, likely due to the broadening of
micropores in these porous carbons with ultrahigh SSA. For
those carbons with the same SSA, e.g. 2000 m2 g
1, the H2
uptake at 20 bar is clearly higher than those at higher pressure
(30–50 bar), indicating that except for the SSA, other textural
properties depending on the activation conditions and carbon
sources significantly affect the H2 uptake. Including the esti-
mated maximum H2 uptake (4.5–8.7 wt%) of several ACs102,115,116
in Fig. 16a, all H2 uptakes are well consistent with the expected
values (the solid line). Similar results are also observed in the
relationship of the H2 uptake at 77 K and high pressure (10–
50 bar) vs. the MV for KOH-activated carbons, as shown in
Fig. 16b. A quasi-linear relationship (the expected solid line,
slope ¼ 60 mg H2 per cm3) is found between the H2 uptake vs.
MV of KOH-activated carbons with the MV lower than
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Fig. 16 The relationship of H2 uptake at 77 K and 10–50 bar and esti-
mated maximum H2 uptake102,115,116 at 77 K with (a) the SSA and (b) MV
for commercial ACs91,107,123 (AX21 and Maxsorb-3000) and KOH-acti-
vated carbons from coal,90,91,108,109 natural biomass,93,106,111,112 synthetic
organic polymers,98,115,116 and structured carbons (commercial ACs,8
MWCNTs,91 TPCs,102,117–119 CNFs,91,99,121 CFs,105 and ZrC-CDC114). The
dashed line in (a) corresponds to the Chahine rule (slope ¼ 2.0  10
2 mg
H2 per m2).
1.1 cm3 g
1 in spite of a strong scattered nature. Most of the
porous carbons with MVs higher than 1.1 cm3 g
1 as well as
commercial AX21 and Maxsorb-3000 clearly outperform the
expected line, which also can be due to the broadening of
micropores. By comparing the results in Fig. 15b and 16b, it is
found that the large micropores should greatly contribute to the
H2 uptake at 77 K and high pressures.
7. Conclusion and outlook
Considerable efforts have been devoted, in the past five years, to
the development of the ACs with ultrahigh SSA (over 3000 m2
g
1) and PV (over 2 cm3 g
1) by KOH activation of fossil-based
materials, synthetic organic polymers, and low-price natural
biomass including various biowastes. Generally, the increase of
the activation temperature and mass ratio of KOH–carbon can
enhance the porosity, while the higher pre-carbonization
temperature results in the lower SSA and PV. The micropore
widening of the ACs proceeds when increasing the activation
temperature and mass ratio of KOH–carbon. The integration of
micropores and small mesopores into the framework of various
nanostructured carbons (e.g. CNTs, CNFs, TPCs, CAs, gra-
phene, etc.) by KOH activation dramatically increases the
interconnected pore networks and porosity, while maintaining
the original textural properties (morphology, pore size, etc.).
KOH-activated carbons with enhanced porosity, widely
available in various forms (powders, fibres, aerogels, nanotubes,
graphene, etc.), represent very attractive materials for the
J. Mater. Chem.
View Online
electrodes. They demonstrate superior capacitance performances
of the SCs to the commercial ACs. The SC performance can be
affected by the carbon structure, pore size, and surface func-
tionality. For example, the normalized capacitance decreases
with the increase of micropore size. The incorporation of the
heteroatoms by employing nitrogen/oxygen-enriched precursors
can improve the specific capacitance through the pseudo-
capacitance effect. Also, KOH-activated carbons with hierar-
chical pores and high SSA efficiently enhance the performance of
the C–S composite electrodes in the Li–S batteries by improving
the electrical conductivity, preventing both the aggregation of S
and the dissolution of polysulfide, and shortening the diffusion
route of the electrolyte ions.
Because of low enthalpy of H2 adsorption, the amounts of H2
adsorbed in most KOH-activated carbons at ambient tempera-
ture are no more than 1.2 wt% under 200 bar or below. At 77 K
and ambient pressure, the larger the SSA/MV is, the higher the
H2 uptake is for KOH-activated carbons with the SSA or MV
below 1850 m2 g
1 or 0.74 cm3 g
1, respectively. For those with
higher SSA or MV, the amounts of H2 adsorbed fluctuate
between 2.0 and 2.8 wt%. Such a fluctuation should be ascribed
to the broadening of micropores. At 77 K and high pressure,
KOH-activated carbons with the SSA of above 3000 m2 g
1 or
the MV of above 1.1 cm3 g
1 evidently outperform the expected
values. The highest H2 uptakes obtained by the experimental
observation and from the Langmuir simulations are as high as
7.08 and 8.7 wt%, respectively, implying the high potential of
KOH-activated carbons in H2 storage.
Carbon materials play a key role in developing environmen-
tally friendly energy sources (on-board H2 storage, electrical
energy storage, etc.) for substituting the fossil energy to meet a
sustainable society. Considering the advantages of KOH-acti-
vated carbons, they are regarded as promising candidate mate-
rials for future energy storage devices and other applications (e.g.
catalytic supports, adsorbents for organic pollutants and heavy
metal cations, etc.). Therefore, to further increase the H2 uptakes
of porous carbons, improve the performance of carbon-based
SCs and Li–S cells, and optimize porous carbons for other
applications, tremendous research and attention on new combi-
nations of KOH activation and various carbon sources to enable
the development of porous carbons with desirable structure and
performance are indispensable in the future.
Acknowledgements
J.W. thanks the Alexander von Humboldt Foundation for
granting him a research fellowship.
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