Professional Documents
Culture Documents
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
Downloaded by Politechnika Poznanska on 20 November 2012
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.
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
View Online
focus on boosting the energy density of supercapacitors while from the industrial point of view. Actually, the solubility of
keeping high specific power and cycle life.5 Li2SO4 can reach 2.7 mol L1 compared with 1.97 mol L1 for
Generally, the mechanisms of energy storage in super- Na2SO4 at 25 C, and 3 mol L1 compared to 0.34 mol L1 at
capacitors involve two modes: the charge accumulation in the 0 C.18,19 By including a reference electrode in a symmetric cell,
double-layer formed at the electrode/electrolyte interface (EDL) the potential evolution, capacitance and resistance are separately
and a pseudo-capacitive contribution related to faradic reac- studied for both electrodes during galvanostatic charge–
tions.6 Nowadays, carbons are the most studied electrode discharge cycling. Furthermore, the surface functionalities of
materials for supercapacitors, owing to their high specific surface both carbon electrodes are monitored after long-term operation
area, good electrical conductivity and low cost.7–9 The high of the cell at different values of maximum voltage. After coupling
accessible surface area of carbons is particularly applicable for the results of both kinds of analyses, it will be possible to clarify
more charge being stored at the electrode/electrolyte interfaces. the role of the positive and negative electrodes and the influence
In addition, the EDL capacitance of activated carbon depends of surface groups in such systems during long-term cycling.
strongly on the relative sizes of pores and ions. Carbons with Especially, it will be shown that after deactivation of the surface
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 active sites by controlled chemical oxidation, the positive carbon
requirements for ions electro-sorption.10–12 Apart from porosity, electrode can be protected from electro-oxidation during cell
in protic electrolytes, the introduction of surface groups on operation at high voltage.
carbons may enhance the total capacitance by pseudo-faradic
Downloaded by Politechnika Poznanska on 20 November 2012
9612 | Energy Environ. Sci., 2012, 5, 9611–9617 This journal is ª The Royal Society of Chemistry 2012
View Online
Sample SBET(N2)/m2 g1 (d < 0.7–0.8 nm) (d < 2 nm) (2 < d < 50 nm)
monochromatic source (15 kV, 15 mA) and a multi-detection formation takes place together with a pseudo-capacitive contri-
analyzer, under 108 Pa residual pressure. bution related to reversible sorption of nascent hydrogen inside
the pores of activated carbon.20 A noticeable hump appears
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
around 0.4 V vs. NHE during the anodic sweep, owing to the
2.4. Electrochemical characterization
electro-oxidation process of the stored hydrogen.21 Pseudo-
Electrodes (1 cm diameter, 300 mm 50 mm thickness) were capacitance due to reversible hydrogen storage might contribute
Downloaded by Politechnika Poznanska on 20 November 2012
pressed from a mixture of the studied carbons (80 wt%), PTFE effectively to the total capacitance in addition to the EDL
(10 wt%), carbon black (10 wt%, Pure Black, Superior Graphite capacitance. The negative current increases sharply from
Co.). Two-electrode cells were built using a Teflon Swagelok potentials below 1.0 V vs. NHE, indicating H2 gas evolution
construction with a glass fiber separator and gold current and the plausible limit for negative polarization. Finally, we can
collectors; three-electrode cells with Hg/Hg2SO4 as a reference estimate that the stability potential window of the AC carbon in
electrode comprised the studied carbon and a graphite rod as 2 mol L1 Li2SO4 is around 2.0 V. These results confirm the
working and counter electrodes, respectively. For investigations previous findings obtained in 0.5 mol L1 Na2SO4,15,16 i.e. the
in three-electrode cells, the activated carbon was stuck onto the stability potential window in alkali sulfate aqueous electrolytes is
gold current collector with a graphite conductive adhesive 502 larger than that in acidic or basic ones. However, this value is
(13 wt%, Electron Microscopy Sciences Company, UK). smaller than recently claimed, e.g., 2.2 V for another carbon in
Cyclic voltammetry and galvanostatic charge/discharge less concentrated Li2SO4 electrolyte,17 indicating that the nature
cycling were implemented in oxygen-free 2 mol L1 Li2SO4 of the carbon material may influence its electrochemical stability.
aqueous solution (pH z 6) using a VMP potentiostat-galvano- The galvanostatic charge/discharge characteristics of a
stat (Biologic, France). All potentials are reported vs. the normal symmetric AC/AC capacitor in 2 mol L1 Li2SO4 (Fig. 2)
hydrogen electrode (NHE). 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
3. Results and discussion
the above-mentioned hydrogen storage mechanism.
3.1. Electrochemical performance of AC carbon and AC/AC In order to confirm that the cell operates properly, the discharge
supercapacitors in 2 mol L1 Li2SO4 capacitance evolution has been studied during long-term galva-
nostatic (1 A g1) charge/discharge cycling at different values of
The activated carbon AC with a high specific surface area and a
maximum voltage (Fig. 3). Whatever the value up to 1.8 V, a small
small amount of oxygen-containing surface functionalities (see
but fast decrease of discharge capacitance (e.g. 11% for AC at 1.8
Tables 1 and 2) has been firstly studied in a three-electrode cell
V) is observed during the initial 1000 cycles and then capacitance
using 2 mol L1 Li2SO4 as electrolyte.
stabilizes up to 10 000 cycles for voltages of 1.6 V and 1.8 V. The
Cyclic voltammograms (CVs, Fig. 1) were recorded at a scan
rate of 2 mV s1 with a gradual decrease of negative potential
cut-off, i.e., towards di-hydrogen evolution (the theoretical value
in 2 mol L1 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
CO2 evolution/ CO evolution/ Total O evolution/ Fig. 1 Three-electrode cyclic voltammograms (CVs, 2 mV s1) of AC in
Sample mmol g1 mmol g1 wt%
2 mol L1 Li2SO4. The loops are obtained by stepwise shifting of
the negative potential limit to more negative values. The vertical line
AC 159 461 1.5
ACH 805 1946 6.6 at 0.35 V vs. NHE corresponds to the thermodynamic potential for
water reduction.
This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 9611–9617 | 9613
View Online
Fig. 2 Galvanostatic charge–discharge characteristics (200 mA g1) of a Fig. 4 Potential limits of positive (E+) and negative (E) electrodes
symmetric AC/AC supercapacitor in 2 mol L1 Li2SO4. during the galvanostatic (200 mA g1) cycling of a symmetric AC/AC
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
9614 | Energy Environ. Sci., 2012, 5, 9611–9617 This journal is ª The Royal Society of Chemistry 2012
View Online
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
Downloaded by Politechnika Poznanska on 20 November 2012
This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 9611–9617 | 9615
View Online
in 2 mol L1 Li2SO4. The loops are obtained by stepwise shifting of supercapacitor up to different values of maximum voltage. The E0V
the negative potential limit to more negative values. The vertical line values correspond to the electrodes potential when the working voltage is
at 0.35 V vs. NHE corresponds to the thermodynamic potential for shifted to 0 V before each change of maximum voltage. The lower
water reduction. horizontal line represents the negative potential limit related to a
Downloaded by Politechnika Poznanska on 20 November 2012
9616 | Energy Environ. Sci., 2012, 5, 9611–9617 This journal is ª The Royal Society of Chemistry 2012
View Online
slightly decreases during the first 1000 cycles and remains almost the China Scholarship Council for allotting a PhD grant. F.B.
constant up to 5000 cycles. At 1.9 V maximum voltage, the acknowledges the support of the Foundation for Polish Science
maximum value of E+ for the ACH/ACH capacitor stabilizes at within the WELCOME program (ECOLCAP project).
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 References
up to 1.9 V, there is a very moderate loss of capacitance and the 1 A. Goeppert, M. Czaun, G. K. Surya Prakash and G. A. Olah, Energy
series resistance is constant (see inset in Fig. 11). It is therefore Environ. Sci., 2012, 5, 7833–7853.
anticipated that the controlled chemical oxidation of AC by 2 J. R. Miller and P. Simon, Science, 2010, 321, 651–652.
3 R. K€ otz and M. Carlen, Electrochim. Acta, 2000, 45, 2483–2498.
H2O2 ‘‘neutralizes’’ most of the available active sites, allowing the 4 J. R. Miller and A. F. Burke, Electrochem. Soc. Interface, 2008, 17,
system to be protected from deleterious electro-oxidation up to a 53–57.
voltage of 1.9 V. 5 A. Burke, Electrochim. Acta, 2007, 53, 1083–1091.
6 B. E. Conway, Electrochemical Supercapacitors: Scientific
Published on 31 August 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22284A
carbon/carbon capacitor in 2 mol L1 Li2SO4. This voltage is two 9 E. Frackowiak, Phys. Chem. Chem. Phys., 2007, 9, 1774–1785.
10 C. Vix-Guterl, E. Frackowiak, K. Jurewicz, M. Friebe, J. Parmentier
times higher than the values generally observed in acidic and and F. Beguin, Carbon, 2005, 43, 1293–1302.
basic aqueous electrolytes. Such a good performance is attrib- 11 E. Raymundo-Pi~ nero, K. Kierzek, J. Machnikowski and F. Beguin,
uted to the high over-potential related to the hydrogen storage Carbon, 2006, 44, 2498–2507.
12 C. Largeot, C. Portet, J. Chmiola, P.-L. Taberna, Y. Gogotsi and
mechanism. The maximum cell voltage is essentially limited by
P. Simon, J. Am. Chem. Soc., 2008, 130, 2730–2731.
the positive electrode. When the maximum potential of the 13 M. J. Bleda-Martınez, J. A. Macia-Agull o, D. Lozano-Castello,
positive electrode (E+) is too high, it leads to an irreversible E. Morall on, D. Cazorla-Amor os and A. Linares-Solano, Carbon,
electro-oxidation on the active sites of carbon and the evolution 2005, 43, 2677–2684.
14 V. Khomenko, E. Raymundo-Pi~ nero and F. Beguin, J. Power
of CO2. Due to this partial destruction of the positive electrode, Sources, 2010, 195, 4234–4241.
the resistance continuously increases during cycling and the 15 L. Demarconnay, E. Raymundo-Pi~ nero and F. Beguin, Electrochem.
capacitance decreases. The carbon electrode can be to some Commun., 2010, 12, 1275–1278.
extent stabilized by controlled chemical oxidation with hydrogen 16 M. P. Bichat, E. Raymundo-Pi~ nero and F. Beguin, Carbon, 2010, 48,
4351–4361.
peroxide. The reaction occurs on the active sites of carbon 17 K. Fic, G. Lota, M. Meller and E. Frackowiak, Energy Environ. Sci.,
contributing to its deactivation when the system operates at high 2012, 5, 5842–5850.
voltage. Interestingly, after this treatment, the maximum 18 D. Linde, CRC Handbook of Chemistry and Physics, CRC press,
Florida, 88th edn, 2007–2008.
potential of the positive electrode is pushed to slightly lower 19 W. F. Linke and A. Seidell, Solubilities: Inorganic and Metal-Organic
values. Therefore, it might be anticipated that the high voltage Compounds, D. van Nostrand, New York, 4th edn, 1965.
value claimed by Fic et al. in ref. 17 might be as well related to a 20 K. Jurewicz, E. Frackowiak and F. Beguin, Appl. Phys. A: Mater. Sci.
specific surface functionality of the carbon electrodes. Process., 2004, 78, 981–987.
21 F. Beguin, K. Kierzek, M. Friebe, A. Jankowska, J. Machnikowski,
Taking into account that the lithium sulfate electrolyte elimi- K. Jurewicz and E. Frackowiak, Electrochim. Acta, 2006, 51, 2161–
nates the disadvantages related to the corrosive properties of 2167.
acidic and basic electrolytes, it becomes realistic to forecast the 22 M. J. Bleda-Martınez, D. Lozano-Castell o, E. Morall
on, D. Cazorla-
production of high energy density supercapacitors with envi- Amor os and A. Linares-Solano, Carbon, 2006, 44, 2642–2651.
23 R. Berenguer, J. P. Marco-Lozar, C. Quijada, D. Cazorla-Amor os
ronmentally friendly, cost-effective and safe components. and E. Morall on, Carbon, 2009, 47, 1018–1027.
24 Y. Yang and Z. G. Lin, J. Appl. Electrochem., 1995, 25, 259–266.
25 Z. R. Yue, W. Jiang, L. Wang, S. D. Gardner and C. U. Pittman Jr,
Acknowledgements Carbon, 1999, 37, 1785–1796.
The authors thank the French Agency for Research (ANR - 26 E. Raymundo-Pi~ nero, M. Cadek and F. Beguin, Adv. Funct. Mater.,
2009, 19, 1032–1039.
ABHYS project) for contributing to the financial support of this 27 S. S. Barton, M. J. B. Evans, E. Halliop and J. A. F. MacDonald,
work. Q.G. acknowledges the Ministry of Education of PRC and Carbon, 1997, 35, 1361–1366.
This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 9611–9617 | 9617