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Environmental Science
Cite this: Energy Environ. Sci., 2012, 5, 9611
www.rsc.org/ees PAPER
Exploring the large voltage range of carbon/carbon supercapacitors in
aqueous lithium sulfate electrolyte
Qiang Gao,a Laurent Demarconnay,a Encarnaci
on Raymundo-Pi~neroa and François B
eguin*ab
Received 20th May 2012, Accepted 31st August 2012
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A

DOI: 10.1039/c2ee22284a

This study investigates the large voltage range of symmetric carbon/carbon capacitors in
environmentally friendly aqueous lithium sulfate electrolyte. A high over-potential related to the
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hydrogen sorption mechanism at the negative electrode contributes usefully to enhance the operating
voltage up to 1.9 V with an excellent stability during 10 000 charge/discharge cycles. Such a voltage
value is two times higher than the values generally demonstrated with symmetric carbon/carbon
capacitors in conventional aqueous media, while avoiding the disadvantages of the corrosive properties
of acidic and basic electrolytes. Temperature programmed desorption analysis of the electrodes after
long-term cycling gives the evidence that the maximum voltage is essentially limited by an irreversible
electro-oxidation process at the positive electrode. If the potential of the positive electrode goes beyond
a given value during cell operation, a massive electro-oxidation of carbon leads to a further deleterious
increase of the maximum potential of the electrode and an increase of electrode resistance resulting in a
decrease of capacitance. Inconvenience can be sidestepped by performing a controlled chemical
oxidation of the carbon surface using hydrogen peroxide. As a consequence, the maximum potential of
the electrode remains stable during operation of the cell at 1.9 V, and the system can be charged/
discharged during 10 000 cycles with very moderate loss of capacitance or increase of resistance.

1. Introduction rapidly, requiring the development of highly reliable energy

storage solutions.
Burning of fossil fuels with large anthropogenic CO2 emissions Among the various storage systems, electrical double-layer
outpaces nature’s recycling capability, resulting in significant capacitors (EDLCs – also called supercapacitors) based on
environmental harm, such as global warming and oceans acidi- porous carbons have recently attracted considerable attention.2
fication.1 As a result, low-carbon technologies, such as solar and They are able to operate at high charge and discharge rates over
wind energy as well as hybrid electric vehicles (HEVs), grow almost unlimited cycle life, being highly desirable and competi-
tive for applications in HEVs.3,4 Such devices demonstrate higher
power than most batteries, though their energy density (5 W h
kg
1 for commercial supercapacitors) remains lower than for
a
Centre de Recherche sur la Matiere Divis

ee, CNRS/University, 1b Rue de
la F
erollerie, 45071 Orl

eans, France
b
lithium-ion batteries (70–100 W h kg
1).4 Hence, intensive
Faculty of Chemical Technology, Poznan University of Technology,
Piotrowo 3, 60-965 Poznan, Poland. E-mail: francois.beguin@put. research efforts as described, e.g., by US Department of Energy,
poznan.pl; Fax: +48 616652571; Tel: +48 616653632

Broader context
Enhancing the energy density, while keeping environmentally friendly systems, remains the primary challenge for supercapacitor
developers. This enhancement can be essentially realized by improving voltage, e.g., by using electrolytes with a large stability
potential range. In this context promising voltage values have been obtained with alkali sulfate solutions, in particular Li2SO4 based
electrolytes. We have found that the voltage is essentially limited by the destructive oxidation of the positive carbon electrode when
its potential becomes too high. Due to this carbon degradation, the system thus exhibits continuous power decay during cycling. By
controlling chemically the oxidation of carbon before its introduction in the positive electrode, we could successfully reduce its
maximum potential to relatively lower values and consequently sidestep its destructive electro-oxidation during long-term cycling up
to an operating voltage of 1.9 V. Hence, it becomes realistic to forecast the production of high energy and power supercapacitors
with environmentally friendly, cost-effective and safe components.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 9611–9617 | 9611

focus on boosting the energy density of supercapacitors while
keeping high specific power and cycle life.5
Generally, the mechanisms of energy storage in super-
capacitors involve two modes: the charge accumulation in the
double-layer formed at the electrode/electrolyte interface (EDL)
and a pseudo-capacitive contribution related to faradic reac-
tions.6 Nowadays, carbons are the most studied electrode
materials for supercapacitors, owing to their high specific surface
area, good electrical conductivity and low cost.7–9 The high
accessible surface area of carbons is particularly applicable for
more charge being stored at the electrode/electrolyte interfaces.
In addition, the EDL capacitance of activated carbon depends
strongly on the relative sizes of pores and ions. Carbons with
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
subnanometric pores, e.g. 0.7–0.9 nm, satisfy mostly the
requirements for ions electro-sorption.10–12 Apart from porosity,
in protic electrolytes, the introduction of surface groups on
carbons may enhance the total capacitance by pseudo-faradic
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contributions,7 while rendering the carbon surfaces more acces-
sible for the electrolyte. It is generally accepted that the CO-type
groups have a positive effect on the total capacitance.13 Overall,
the porosity and surface functionality of carbon influence obvi-
ously the performance of supercapacitors.
Since the energy density of supercapacitors is proportional to
the capacitance and the square of voltage,14 currently extensive
research aims at increasing the operating voltage of super-
capacitors. Actually, the voltage is limited by the stability
potential window of the electrolytes. In aqueous medium, the
practical working voltage is usually less than 1.0 V, whereas it is
in the range of 2.5–2.7 V for organic electrolytes.3 Unfortunately,
the latter presents serious disadvantages, such as low conduc-
tivity and moisture isolated building atmosphere, and they are
environmentally unfriendly. Thus, aqueous electrolytes seem to
be more acceptable from an industrial point of view in the long-
term. Generally, H2SO4 and KOH are the most commonly
studied aqueous electrolytes for supercapacitors. To enhance
voltage in these media, Khomenko et al. have suggested a novel
concept of asymmetric supercapacitors in 1 mol L
1 H2SO4 with
carbons for both electrodes; the system exhibits a high stability
over 10 000 cycles at 1.6 V.14 The high over-potential for di-
hydrogen evolution has been utilized effectively to improve the
working voltage in the concept, though the corrosive property of
H2SO4 impedes the large-scale applications.
Lately, it has been observed that the di-hydrogen over-potential
is higher in neutral aqueous electrolytes than in KOH or H2SO4.
For instance, a stability potential window of 2.0 V, and even more,
could be achieved with a carbon based three-electrode cell in 0.5
mol L
1 Na2SO4.15,16 Consequently, a practical voltage of 1.6 V
during 10 000 charge/discharge cycles has been obtained with a
symmetric carbon/carbon capacitor in Na2SO4.15 An even higher
voltage of 2.2 V has been recently claimed when using 1 mol L
1
Li2SO4;17 such a high voltage has been attributed to the important
dehydration energy of ions and to the comparable concentrations
of protons and hydroxyl groups at neutral pH which do not favor
hydrogen or oxygen evolution.
In this work, we are particularly interested in studying the
behavior of the carbon electrodes close to the voltage limits. We
selected Li2SO4 because it apparently allows reaching a high
voltage, but also because its high solubility extends the temper-
ature operating range to lower values, being an interesting option
9612 | Energy Environ. Sci., 2012, 5, 9611–9617
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from the industrial point of view. Actually, the solubility of
Li2SO4 can reach 2.7 mol L
1 compared with 1.97 mol L
1 for
Na2SO4 at 25  C, and 3 mol L
1 compared to 0.34 mol L
1 at
0  C.18,19 By including a reference electrode in a symmetric cell,
the potential evolution, capacitance and resistance are separately
studied for both electrodes during galvanostatic charge–
discharge cycling. Furthermore, the surface functionalities of
both carbon electrodes are monitored after long-term operation
of the cell at different values of maximum voltage. After coupling
the results of both kinds of analyses, it will be possible to clarify
the role of the positive and negative electrodes and the influence
of surface groups in such systems during long-term cycling.
Especially, it will be shown that after deactivation of the surface
active sites by controlled chemical oxidation, the positive carbon
electrode can be protected from electro-oxidation during cell
operation at high voltage.
2. Experimental
2.1. Materials
The activated carbon for the study was a commercial sample
(AC, MeadWestvaco, USA). A carbon ACH was prepared
through oxidation of AC (1 g) with 40 mL of 35 wt% H2O2
solution under stirring for 1 h at room temperature. The resul-
tant material was extensively rinsed with distilled water.
2.2. Textural properties
The porous texture of the materials was analyzed by N2 and CO2
adsorption (Autosorb-1, Quantachrome, USA) at 77 K and
273 K, respectively. Before the measurements, the samples were
outgassed at 200  C overnight under vacuum. The specific
surface area was evaluated from the N2 adsorption isotherm
using the Brunauer–Emmett–Teller (BET) equation. The
micropore and ultra-micropore (pores in the range of 0.4–0.8
nm) volumes were obtained by application of the Dubinin–
Radushkevich equation to N2 and CO2 adsorption data,
respectively. The mesopore volume was determined by applying
the non-linear differential functional theory (NL-DFT) equation
to N2 adsorption data.
2.3. Surface functionality analysis
The surface functionality of carbons was analyzed by tempera-
ture-programmed desorption (TPD) under an inert atmosphere
(He). The sample (20 mg) was placed in an STA 449C Thermo-
balance (Netzsch, Germany) and kept at room temperature for
1 h under a helium flow of 150 mL min
1. Then, the temperature
was increased to 1100  C at a rate of 10  C min
1. The decom-
position products were detected by on-line mass spectrometry
(QMS 403C, Aeolos, Netzsch, Germany). To investigate the
evolution of surface chemistry during charge–discharge cycling,
positive electrodes were taken out from supercapacitors after five
thousand galvanostatic cycles and washed carefully with distilled
water to remove the electrolyte ions. Fresh electrodes were also
subjected to the same treatment for a comparison with the cycled
ones.
X-ray photo-electron spectra (XPS) on carbon powder were
recorded with a VG ESCALAB 250 spectrometer using an Al Ka
This journal is ª The Royal Society of Chemistry 2012

Table 1 Porous texture of as-received and surface-modified carbons
Vultramicroa/cm3 g
1
Sample SBET(N2)/m2 g
1 (d < 0.7–0.8 nm)
AC 2224 0.83
ACH 2214 0.90
a
Obtained by applying the Dubinin–Radushkevich equation to the CO2 adsorption data. b Obtained by applying the Dubinin–Radushkevich equation
to the N2 adsorption data. c Obtained by applying the NLDFT method to the N2 adsorption data.
monochromatic source (15 kV, 15 mA) and a multi-detection
analyzer, under 10
8 Pa residual pressure.
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
2.4. Electrochemical characterization
Electrodes (1 cm diameter, 300 mm  50 mm thickness) were
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pressed from a mixture of the studied carbons (80 wt%), PTFE
(10 wt%), carbon black (10 wt%, Pure Black, Superior Graphite
Co.). Two-electrode cells were built using a Teflon Swagelok
construction with a glass fiber separator and gold current
collectors; three-electrode cells with Hg/Hg2SO4 as a reference
electrode comprised the studied carbon and a graphite rod as
working and counter electrodes, respectively. For investigations
in three-electrode cells, the activated carbon was stuck onto the
gold current collector with a graphite conductive adhesive 502
(13 wt%, Electron Microscopy Sciences Company, UK).
Cyclic voltammetry and galvanostatic charge/discharge
cycling were implemented in oxygen-free 2 mol L
1 Li2SO4
aqueous solution (pH z 6) using a VMP potentiostat-galvano-
stat (Biologic, France). All potentials are reported vs. the normal
hydrogen electrode (NHE).
3. Results and discussion
3.1. Electrochemical performance of AC carbon and AC/AC
supercapacitors in 2 mol L
1 Li2SO4
The activated carbon AC with a high specific surface area and a
small amount of oxygen-containing surface functionalities (see
Tables 1 and 2) has been firstly studied in a three-electrode cell
using 2 mol L
1 Li2SO4 as electrolyte.
Cyclic voltammograms (CVs, Fig. 1) were recorded at a scan
rate of 2 mV s
1 with a gradual decrease of negative potential
cut-off, i.e., towards di-hydrogen evolution (the theoretical value
in 2 mol L
1 Li2SO4 is
0.35 V vs. NHE). The maximum positive
potential has been set at a value slightly lower than the theo-
retical one allowing water oxidation, i.e. 0.88 V vs. NHE. If the
negative potential cut-off is higher than the value for water
reduction, a rectangular shaped voltammogram, typical of the
double-layer charging, is obtained. When it becomes lower than

0.35 V vs. NHE, water is reduced, and the double-layer
Table 2 Accumulated CO2 and CO amounts, and O evolved from the
studied carbons during TPD measurements
CO2 evolution/ CO evolution/ Total O evolution/
Sample mmol g
1 mmol g
1 wt%
AC 159 461 1.5
ACH 805 1946 6.6
This journal is ª The Royal Society of Chemistry 2012
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Vmicrob/cm3 g
1 Vmesoc/cm3 g
1
(d < 2 nm) (2 < d < 50 nm)
0.83 0.45
0.80 0.48
formation takes place together with a pseudo-capacitive contri-
bution related to reversible sorption of nascent hydrogen inside
the pores of activated carbon.20 A noticeable hump appears
around 0.4 V vs. NHE during the anodic sweep, owing to the
electro-oxidation process of the stored hydrogen.21 Pseudo-
capacitance due to reversible hydrogen storage might contribute
effectively to the total capacitance in addition to the EDL
capacitance. The negative current increases sharply from
potentials below
1.0 V vs. NHE, indicating H2 gas evolution
and the plausible limit for negative polarization. Finally, we can
estimate that the stability potential window of the AC carbon in
2 mol L
1 Li2SO4 is around 2.0 V. These results confirm the
previous findings obtained in 0.5 mol L
1 Na2SO4,15,16 i.e. the
stability potential window in alkali sulfate aqueous electrolytes is
larger than that in acidic or basic ones. However, this value is
smaller than recently claimed, e.g., 2.2 V for another carbon in
less concentrated Li2SO4 electrolyte,17 indicating that the nature
of the carbon material may influence its electrochemical stability.
The galvanostatic charge/discharge characteristics of a
symmetric AC/AC capacitor in 2 mol L
1 Li2SO4 (Fig. 2)
demonstrate a pure capacitive behavior, with straight lines, up to
1.2 V. For cell voltages higher than 1.2 V, there is a distortion of
the linearity associated with pseudo-capacitive effects related to
the above-mentioned hydrogen storage mechanism.
In order to confirm that the cell operates properly, the discharge
capacitance evolution has been studied during long-term galva-
nostatic (1 A g
1) charge/discharge cycling at different values of
maximum voltage (Fig. 3). Whatever the value up to 1.8 V, a small
but fast decrease of discharge capacitance (e.g. 11% for AC at 1.8
V) is observed during the initial 1000 cycles and then capacitance
stabilizes up to 10 000 cycles for voltages of 1.6 V and 1.8 V. The
Fig. 1 Three-electrode cyclic voltammograms (CVs, 2 mV s
1) of AC in
2 mol L
1 Li2SO4. The loops are obtained by stepwise shifting of
the negative potential limit to more negative values. The vertical line
at
0.35 V vs. NHE corresponds to the thermodynamic potential for
water reduction.
Energy Environ. Sci., 2012, 5, 9611–9617 | 9613

Fig. 2 Galvanostatic charge–discharge characteristics (200 mA g
1) of a
symmetric AC/AC supercapacitor in 2 mol L
1 Li2SO4.
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
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Fig. 3 Evolution of the discharge capacitance during the galvanostatic
(1 A g
1) cycling of symmetric AC/AC supercapacitors in 2 mol L
1
Li2SO4.
enhancement of capacitance observed when the voltage increases
from 1.6 to 1.8 V is typical of a pseudo-capacitive contribution
involving hydrogen sorption. For a maximum voltage of 1.9 V, the
capacitance continuously decays with a loss of 30% after 10 000
cycles. Hence, a practical voltage of 1.8 V can be achieved with the
symmetric AC/AC capacitor in 2 mol L
1 Li2SO4. Such a practical
value is two times higher than the values generally obtained with
symmetric carbon based capacitors in acidic or basic aqueous
electrolytes22 and even higher than the value of 1.6 V reported for
the same carbon in 0.5 mol L
1 Na2SO4.15
However, the stability potential window of 2.0 V for the AC
carbon is not completely used. In order to understand the reason,
the real working potential range of each electrode, during charge/
discharge of the two-electrode cell, has been separately measured
by adding a Hg/Hg2SO4 reference electrode. Fig. 4 represents the
maximum potential (E+) reached by the positive electrode and
the minimum potential (E
) reached by the negative one, for a
given maximum voltage applied to the capacitor. The E0V values
represent the electrode potential when the voltage is set to 0 V
between two successive cycles at different values of maximum
voltage. For maximum voltages of 1.8 and 1.9 V, the positive
electrode potentials reach 0.99 and 1.06 V vs. NHE, respectively.
Such values are beyond the thermodynamic potential for di-
oxygen evolution, e.g., 0.88 V. Furthermore, the negative
potentials reach
0.81 and
0.84 V vs. NHE for voltages of 1.8 V
and 1.9 V, respectively. These potential values are lower than the
thermodynamic limit for water reduction (
0.35 vs. NHE) but
they are still much higher than the practical negative potential
limit of ca.
1 V vs. NHE estimated in Fig. 1. Hence, the
9614 | Energy Environ. Sci., 2012, 5, 9611–9617
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Fig. 4 Potential limits of positive (E+) and negative (E
) electrodes
during the galvanostatic (200 mA g
1) cycling of a symmetric AC/AC
supercapacitor up to different values of maximum voltage. The E0V
values correspond to the electrodes potential when the working voltage is
shifted to 0 V before each change of maximum voltage. The lower
horizontal line represents the negative potential limit related to a
noticeable H2 evolution estimated in a three-electrode cell. The upper
horizontal one corresponds to the thermodynamic limit for water
oxidation. Electrolyte: 2 mol L
1 Li2SO4.
maximum voltage of the system seems to be limited by the
positive electrode, though the potential of the former may
slightly exceed the thermodynamic limit without detrimental
effect on the system cycle life.
In order to detect possible changes of electrodes surface
functionality during cell operation, the carbon materials from
negative and positive electrodes have been analyzed by TPD after
charging/discharging the system during 5000 cycles at maximum
voltages of 1.6 V, 1.8 V and 1.9 V. Fig. 5 displays the amount of
CO2 and CO evolved from the fresh electrodes and from the
cycled ones. CO2 evolves at relatively low temperature (around
300  C) and can be attributed to the decomposition of carboxylic
type acidic functionalities. CO evolves at higher temperatures,
around 700  C, and is originated from the decomposition of basic
functionalities such as quinones, phenols.22 At the negative
electrode (Fig. 5a), the amount of surface functionalities does not
change significantly even at high cell voltages. By contrast, for
the positive electrode, Fig. 5b shows a clear electro-oxidation of
AC at 1.6 V. Compared to the fresh electrode, the amount of
acidic (evolving as CO2) and basic (evolving as CO)23 surface
functionalities increases from 2-fold to 4-fold and 1.5-fold to
2-fold, respectively, when the maximum voltage increases from
1.6 V to 1.8 V. This change of functionality may explain the slight
capacitance decay during the first thousand cycles, but it does not
further affect the performance of the AC/AC capacitor during
long-term cycling up to 1.8 V.
Considering the higher potential reached by the positive elec-
trode at a maximum voltage of 1.9 V after a few cycles (see
Fig. 4), one could expect a more serious surface oxidation of
carbons after long-term cycling.24 In fact, Fig. 5b shows that after
5000 cycles the amount of CO2-type groups is smaller than at
1.8 V, whereas the CO-type groups only slightly increase. This
behavior fits well with the mechanism suggested for the electro-
chemical oxidation of carbon at potentials higher than the value
for water oxidation.25 At high over-potentials, the acidic groups
generated by electro-oxidation can be further oxidized leading to
CO2 evolution. As a consequence, the capacitance decay
observed in Fig. 3 for 1.9 V may be originated from: (i) a mass
This journal is ª The Royal Society of Chemistry 2012

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Fig. 5 Evolved CO2 and CO amounts measured by TPD on the fresh
AC or ACH electrodes (values at 0 V) and on (a) negative and (b) positive
electrodes of a symmetric capacitor after 5000 charge/discharge cycles at
different values of maximum voltage. Electrolyte: 2 mol L
1 Li2SO4.
loss of the positive electrode; (ii) a reduction of electrode integrity
and contact with the current collector due to evolution of gases.
The latter is certainly related to the continuous resistance
increase observed when the cell operates at 1.9 V (Fig. 6a),
whereas at lower voltage (1.8 V), the resistance remains almost
constant. The progressive increase of maximum potential for the
positive electrode (E+) recorded during the operation of the cell
at 1.9 V (Fig. 6) leads to a more extensive electro-oxidation of
carbon and, as exposed above, the evolution of CO2 and a
continuous decrease of capacitance during cycling. By contrast
when the voltage is such that capacitance is almost stabilized
after a few thousand cycles, e.g., at 1.6 and 1.8 V, the maximum
potential of the positive electrode slightly decreases during the
first thousand cycles and further remains unchanged during the
next thousand cycles (Fig. 6b).
Of the above, it is now clearly established that the capacitance
decay occurring during cycling above a limit voltage is correlated
with an increase of maximum potential of the positive electrode
and its destructive oxidation.
3.2. Electrochemical performance of the oxidized AC carbon
(ACH) and of ACH/ACH supercapacitors in 2 mol L
1 Li2SO4
The uncontrolled electrochemical oxidation of the positive elec-
trode gives an explanation for obtaining a cell voltage smaller
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Fig. 6 Capacitance retention ratio (Cn/C1  100, where Cn is the
capacitance at the nth cycle and C1 at the 1st cycle) and (a) resistance
variation ratio (Rn/R1  100, where Rn is the resistance at the nth cycle
and R1 at the 1st cycle) or (b) maximum potential (E+) of the positive
electrode vs. NHE during galvanostatic (200 mA g
1) cycling of a
symmetric AC/AC supercapacitor. Electrolyte: 2 mol L
1 Li2SO4.
than the stability potential window of the AC electrode. In order
to explore the possibility of protecting the AC surface from a
further serious electro-oxidation process, it has been chemically
oxidized in a controlled manner by H2O2 giving the carbon
ACH.
In comparison with the pristine AC carbon, Table 1 shows that
the porous texture of ACH presents almost no differences. By
contrast, the TPD data demonstrate an increase of surface
functionalities evolving as CO and CO2 (Table 2). More CO-type
groups (phenols, quinones and carbonyl groups) were formed
than CO2-type groups (carboxylic groups).
Table 3 summarizes the results obtained from the deconvolu-
tion of the XPS C1s peak. After the mild oxidation of AC to give
ACH, the surface functionality is enriched from 0.54 to 1.21 at%
of carboxylic groups (–O–C]O, B.E. ¼ 289.0  0.2 eV),
from 0.09 to 0.65 at% of keto and quinone groups (C]O, B.E. ¼
287.5  0.2 eV) and 1.22 to 1.84 at% of phenol and ether groups
Table 3 Amount of surface groups on the AC and ACH carbons
determined from the C1s X-ray photoelectron spectra
C–OR/at% C]O/at% –O–C]O/at%
Sample 286.3  0.2 eV 287.5  0.2 eV 289.0  0.2 eV O/at%
AC 1.22 0.09 0.54 3.2
ACH 1.84 0.65 1.21 6.3
Energy Environ. Sci., 2012, 5, 9611–9617 | 9615
 View Online

Fig. 9 Potential limits of positive (E+) and negative (E
) electrodes

1
Fig. 7 Three-electrode cyclic voltammograms (CVs, 2 mV s ) of ACH during the galvanostatic (200 mA g
1) cycling of a symmetric ACH/ACH
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A

in 2 mol L
1 Li2SO4. The loops are obtained by stepwise shifting of
the negative potential limit to more negative values. The vertical line
at
0.35 V vs. NHE corresponds to the thermodynamic potential for
water reduction.
Downloaded by Politechnika Poznanska on 20 November 2012
supercapacitor up to different values of maximum voltage. The E0V
values correspond to the electrodes potential when the working voltage is
shifted to 0 V before each change of maximum voltage. The lower
horizontal line represents the negative potential limit related to a

noticeable H2 evolution estimated in a three-electrode cell. The upper

horizontal one corresponds to the thermodynamic limit for water
(C]O, B.E. ¼ 286.3  0.2 eV).26 In good agreement with TPD
oxidation. Electrolyte: 2 mol L
1 Li2SO4.
analysis, it is noticeable that the content of C–O or C]O groups
leading to CO evolution is higher than the amount of –O–C]O
groups.
From the electrochemical point of view, the three-electrode
cyclic voltammograms of ACH (Fig. 7) and AC (Fig. 1) are very
comparable. Similarly, the galvanostatic charge/discharge
profiles of ACH/ACH (Fig. 8) and AC/AC (Fig. 2) capacitors are
quite similar, demonstrating that the values of specific capaci-
tance are not much affected by the presence of oxygenated
surface functionalities in 2 mol L
1 Li2SO4 medium, as is also the
case in Na2SO4.15 However, Fig. 9 shows that the maximum
potential values for the ACH positive electrode, at whatever the
cell voltage, are higher than for the AC based supercapacitors
(compare with Fig. 4). Despite these high values of maximum E+,
the ACH/ACH capacitor can be reversibly cycled at 1.9 V instead Fig. 10 Evolution of the discharge capacitance during the galvanostatic
of 1.8 V for AC/AC (see Fig. 10). (1 A g
1) cycling of symmetric ACH/ACH supercapacitors in 2 mol L
1
Actually, after 5000 charge/discharge cycles of the ACH/ACH Li2SO4.
capacitor at 1.9 V, the amount of CO2-type and CO-type func-
tionalities generated on the surface of the negative (Fig. 5a) and
positive (Fig. 5b) electrodes does not exceed 1.3 times the amount
found on the fresh electrode. At the same voltage, the electro-
oxidation of the positive electrode is noticeably less important
than for the AC electrodes (see Fig. 5b). This result confirms that,
after chemical oxidation, there are less active sites available for
electro-oxidation than in the pristine AC.27 Furthermore, Fig. 11
shows that the maximum potential of the positive electrode

Fig. 11 Capacitance retention ratio (Cn/C1  100, where Cn is the

Fig. 8 Galvanostatic charge–discharge characteristics (200 mA g
1) of a
symmetric ACH/ACH supercapacitor in 2 mol L
1 Li2SO4.
capacitance at the nth cycle and C1 at the 1st cycle) or maximum potential
(E+) of the positive electrode vs. NHE during galvanostatic (200 mA g
1)
cycling of a symmetric ACH/ACH supercapacitor. Electrolyte: 2 mol L
1
Li2SO4. Inset: resistance variation ratio (Rn/R1  100, where Rn is the
resistance at the nth cycle and R1 at the 1st cycle).

9616 | Energy Environ. Sci., 2012, 5, 9611–9617 This journal is ª The Royal Society of Chemistry 2012

slightly decreases during the first 1000 cycles and remains almost
constant up to 5000 cycles. At 1.9 V maximum voltage, the
maximum value of E+ for the ACH/ACH capacitor stabilizes at
1.08 V between 1000 and 5000 cycles (Fig. 11), while it reaches
1.18 V for the AC/AC capacitor after 5000 cycles (see Fig. 6b).
During galvanostatic cycling of the ACH/ACH supercapacitor
up to 1.9 V, there is a very moderate loss of capacitance and the
series resistance is constant (see inset in Fig. 11). It is therefore
anticipated that the controlled chemical oxidation of AC by
H2O2 ‘‘neutralizes’’ most of the available active sites, allowing the
system to be protected from deleterious electro-oxidation up to a
voltage of 1.9 V.
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
4. Conclusions
An operating voltage as high as 1.9 V, with excellent cycle life
over 10 000 cycles, has been demonstrated for the symmetric
Downloaded by Politechnika Poznanska on 20 November 2012
carbon/carbon capacitor in 2 mol L
1 Li2SO4. This voltage is two
times higher than the values generally observed in acidic and
basic aqueous electrolytes. Such a good performance is attrib-
uted to the high over-potential related to the hydrogen storage
mechanism. The maximum cell voltage is essentially limited by
the positive electrode. When the maximum potential of the
positive electrode (E+) is too high, it leads to an irreversible
electro-oxidation on the active sites of carbon and the evolution
of CO2. Due to this partial destruction of the positive electrode,
the resistance continuously increases during cycling and the
capacitance decreases. The carbon electrode can be to some
extent stabilized by controlled chemical oxidation with hydrogen
peroxide. The reaction occurs on the active sites of carbon
contributing to its deactivation when the system operates at high
voltage. Interestingly, after this treatment, the maximum
potential of the positive electrode is pushed to slightly lower
values. Therefore, it might be anticipated that the high voltage
value claimed by Fic et al. in ref. 17 might be as well related to a
specific surface functionality of the carbon electrodes.
Taking into account that the lithium sulfate electrolyte elimi-
nates the disadvantages related to the corrosive properties of
acidic and basic electrolytes, it becomes realistic to forecast the
production of high energy density supercapacitors with envi-
ronmentally friendly, cost-effective and safe components.
Acknowledgements
The authors thank the French Agency for Research (ANR -
ABHYS project) for contributing to the financial support of this
work. Q.G. acknowledges the Ministry of Education of PRC and
This journal is ª The Royal Society of Chemistry 2012
View Online
the China Scholarship Council for allotting a PhD grant. F.B.
acknowledges the support of the Foundation for Polish Science
within the WELCOME program (ECOLCAP project).
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