A292

Journal of The Electrochemical Society, 150 3 A292-A300 2003

0013-4651/2003/150 3 /A292/9/$7.00 The Electrochemical Society, Inc.

Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors

P. L. Taberna, P. Simon,*,a,z and J. F. Fauvarque
Conservatoire National des Arts et Metiers, Laboratoire dElectrochimie Industrielle, 75003 Paris, France This paper presents the results obtained on the electrochemical behavior of electrochemical capacitors assembled in nonaqueous electrolyte. The rst part is devoted to the electrochemical characterization of carbon-carbon 4 cm2 cells systems in terms of capacitance, resistance, and cyclability. The second part is focused on the electrochemical impedance spectroscopy study of the cells. Nyquist plots are presented and the impedance of the supercapacitors is discussed in terms of complex capacitance and complex power. This allows the determination of a relaxation time constant of the systems, and the real and the imaginary part of the complex power vs. the frequency plots give information on the supercapacitor cells frequency behavior. The complex impedance plots for both a supercapacitor and a tantalum dielectric capacitor cells are compared. 2003 The Electrochemical Society. DOI: 10.1149/1.1543948 All rights reserved. Manuscript submitted February 19, 2002; revised manuscript received August 31, 2002. Available electronically January 31, 2003.

Much work has been done for the last ten years on supercapacitors, as their electrochemical properties make these systems act as intermediate power and energy sources between electrochemical batteries and dielectric capacitors.1-3 As compared to dielectric capacitors, supercapacitors can supply high power during several seconds. These characteristics, associated with good cyclability, make them useful in power electronic systems and promising systems in many applications in which supercapacitors are or could be used: automotive, spatial, military, etc. Three different types of supercapacitors are described in the literature: carbon-carbon,4,5 metal oxide,6,7 and electronically conducting polymers.8-10 Carbon-carbon supercapacitors use the cheapest technology due to the low price of activated carbon. These systems function on the basis of the Gouy-Chapmann and Stern-Geary electrochemical double-layer theory.11 The charge is stored through the adsorption of the electrolyte ions on large-surface-area activated carbon 2300 m2/g . There is no charge-transfer reaction occurring during the charge-discharge process. Cyclability of these supercapacitors is then very high 100,000 cycles . Both nonaqueous and aqueous electrolyte can be used. Organic electrolyte leads to a larger electrochemical window than the aqueous one: it is then possible to increase the voltage up to 3 V. Supercapacitor voltage is limited to 1 V with aqueous electrolyte-based supercapacitors.12 This paper rst describes the electrochemical characteristics of supercapacitor cells and presents the results obtained from the galvanostatic charge-discharge plots in terms of specic capacitance and specic resistance evolution during cycling tests. The second part of this paper is devoted to the frequency behavior study of supercapacitor cells. Electrochemical impedance spectroscopy plots of a tantalum dielectric capacitor are also presented and discussed. Experimental Electrochemical apparatus.Galvanostatic cycling tests were carried out with a VMP potentiostat Biologic Technologies , able to record one point every 20 ms. Electrochemical impedance spectroscopy EIS measurements were carried out with a Schlumberger Solartron 1255 frequency response analyzer and a potentiostat Schlumberger Solartron 1286 controlled by a computer with the software ZPlot. The frequency range studied was 10 kHz to 10 mHz. All the measurements were made at the rest potential of the cell. The V signal amplitude applied was 5 mV. Electrodes.Electrodes are constituted by expanded aluminum 5005 current collectors laminated to 150 m thick and active mate-

rial is an activated carbon-based paste. The collectors are mechanically polished with 180-grade glass paper. A conducting paint is applied on the aluminum current collectors using the spray technique. The conducting paint is polyurethane-based containing 7.6% tri-isocyanate hardener and 2.4% polyalcohol base, charged with 30 wt % acetylene black. Current collectors are dried several days under vacuum after painting. Active material is a mixture of 95% activated carbon PICACTIF SC with high specic surface area 2300 m2/g and 5% organic binder carboxy-methylcellulose and poly tetrauoroethylene .13,14 After drying, active material is laminated onto 4 cm2 treated aluminum current collectors. 4 cm2 supercapacitors cells.Two-electrode supercapacitors cells were built by assembling two 4 cm2 electrodes between polytetrauoroethylene PTFE plates. Two 25 m thick PTFE sheets were used as the separator. The system was kept under pressure with stainless steel clamps 16 kg/cm2 . Two-electrode cells were set in a sealed plexiglass box to ensure air tightness for the cells to be tested outside the glove box. This assembly ensures a relative tightness for about 2 weeks, the water content becoming then too high to keep constant the characteristics of the cells. Results and Discussion Cycling performances.The test cells were galvanostatically cycled at 20 mA/cm2 between 0 and 2.3 V for long cycling over 10,000 cycles and between 0 and 3 V for short cycling about 2000 cycles . The electrolyte used was acetonitrile AN with 1.5 M tetraethylammonium tetrauoroborate dried salt. The interest in ANbased electrolytes is due to their high conductivity 55 mS/cm with NEt4 BF4 1.5 M .15 Figure 1 presents a galvanostatic cycle between 0 and 2.3 V for a two-electrode 4 cm2 cell containing 15 mg/cm2 of active material for each electrode. The cell capacitance is deduced from the slope of the discharge curve with C I dV dt 1

where C is the capacitance of the cell in farads, I the discharge current in amperes A , and dV/dt the slope in volts per second V s 1. In a symmetrical system, the specic capacitance C mAC in farads per gram of activated carbon F g 1 is related to the capacitance of the cell C by C mAC 2C m AC 2

* Electrochemical Society Active Member.

a z

Present address: Centre Interuniversitaire de Recherche et dIngenierie des Materiaux, LCMIE, 31400 Toulouse, France. E-mail: simon@chimie.ups-tlse.fr

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Journal of The Electrochemical Society, 150 3 A292-A300 2003

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Figure 1. Charge-discharge curve for 4 cm2 cell assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon between 0 and 2.3 V with cycling current density of 20 mA/cm2.

Figure 3. Evolution of the ESR for 4 cm2 cell assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon between 0 and 2.3 V with cycling current density of 20 mA/cm2.

where m AC is the weight g per electrode of activated carbon. Figure 2 presents the specic capacitance change with the cycle number at I 20 mA cm 2 . The activated carbon specic capacitance was about 100 F/g in this supercapacitor. This value is close to the one previously reported in the literature for this carbon.13 In Fig. 2 it can be seen that the specic capacitance was constant at 95 F/g after a small decrease during the rst 1000 cycles. The pore accessibility of the active material was then not modied by electrochemical redox reactions involving, for example, functional surface groups, impurities, or electrolyte redox couples. The dependence of the equivalent series resistance ESR of the cell on the cycling number is presented in Fig. 3. The VMP Biologics cycling potentiostat used records one point every 20 ms 50 Hz . The ESR measured is then ESR50
Hz

but at the same time, ESR slowly increases during cycling, as can be seen in Fig. 5. This can be attributed to slow kinetics faradaic reactions linked to the positive current collector corrosion and/or to the electrolyte oxidation. Maximum specic energy and power can be estimated at 2.3 V from the previous characteristics using Eq. 4 and 5, respectively. V2 ESR 1 C V2 2 m AM

P max

m AM

E max

V/ I

where V is the voltage drop at beginning of the discharge in volt V , and I I charge I discharge in amperes A . Figure 3 conrms the absence of faradaic reactions. ESR was found to be stable over the cycling test at around 1 cm2. Cycling experiments were also carried out between 0 and 3 V in order to characterize the electrochemical behavior of the cells at higher voltage. Figure 4 presents the cell voltage change vs. time during cycling at 20 mA cm 2. The time dependence of the potential is linear, traducing the absence of major faradaic processes,

where m AM is the total active material weight on the two electrodes 30 mg cm 2 . Calculations give P max 44 kW/kg and E max 17 Wh/kg of active material for the cell. Electrochemical impedance spectroscopy measurements.The impedance of an electrochemical system is measured by applying a low-amplitude alternative voltage V to a steady-state potential V s , with V( ) V maxe j t, where is the pulsation and V max the signal amplitude. This input signal leads to a sinusoidal output current I, with I( ) I maxe j( t ) , where is the phase angle of the current vs. the voltage and I max the signal amplitude. The electrochemical impedance Z( ) is dened asb Z( ) V/ I Z( ) e j Z jZ , where Z and Z are the real part and the imaginary part of the impedance, respectively, dened as Z 2 Z 2 Z( ) 2 .

Scheme 1.

Figure 2. Evolution of the activated carbon specic capacitance for 4 cm2 cell assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon between 0 and 2.3 V with cycling current density of 20 mA/cm2.

One of the simplest ways to describe the supercapacitor frequency behavior is to associate a serial resistance R s and a capacitance C, as presented in Scheme 1. It is then possible to dene the impedance of the circuit as
b In the following equations, the function F of the variable F( ).

will be noted as

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Journal of The Electrochemical Society, 150 3 A292-A300 2003

Scheme 2.

The impedance of this equivalent circuit is then Z R 1 jC 9

Figure 4. Charge-discharge curve for 4 cm2 cell assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon between 0 and 3 V with cycling current density of 20 mA/cm2.

The whole system can be identied as a supercapacitance K, that by analogy with a capacitance, leads to Z and R 1 jC 1 jK 10

Rs

1 jC

K K

C 1 1 R2 iC 2 1 R2 jR C C2 R C2
2

11

leading to 1 jR sC jC

12

The admittance is dened as A Eq. 7

1/Z and can be calculated from

Equation 12 denes a real part and an imaginary part for the supercapacitance K. It is then possible to write Eq. 12 in the complex form K C jC 13

jC

1 1

jR sC
2 Rs C2 2

where C C C 1 R2 C2 R C2
2

The expression of the admittance clearly shows that when 0 then A jC , i.e., A tends to the admittance of a capacity. More complex models are described in the literature, as for example, the transmission line model TLM .16 Some authors take into account the size and shape of the pores pore size distribution to t the Nyquist plot TLM-PSD model .17,18 An alternative approach is to describe the supercapacitor by using resistance and capacitance that are functions of the pulsation and noted as R( ) and C( )

14 15

C2 1 R2

From Eq. 14 and 15, it can be seen that C is the capacitance of the supercapacitor, varying with frequency, and C is the imaginary part of the supercapacitance, where the resistance R appears. It then describes the losses in the supercapacitor, by analogy with the work published earlier.19-21 An alternative approach is to consider the supercapacitor as a whole by using the impedance data Z j 1 C 16

The impedance Z( ) can be written under its complex form Z Z jZ 17

Equations 16 and 17 lead to Eq. 18 C 1 jZ Z Z Z jZ

2

18 It is then possible to dene

Figure 5. Evolution of the ESR for 4 cm cell assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon between 0 and 3 V with cycling current density of 20 mA/cm2.
2

C leading to

jC

18a

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Journal of The Electrochemical Society, 150 3 A292-A300 2003 Z Z Z Z

A295

19

20

where C ( ) is the real part of the capacitance C( ). The lowfrequency value of C ( ) corresponds to the capacitance of the cell that is measured during constant-current discharge, for example. C ( ) is the imaginary part of the capacitance C( ). It corresponds to an energy dissipation by an irreversible process that can lead to a hysteresis, e.g., the dielectric losses in water occuring during the rotation or the movement of the molecules are the reason for food and drink getting hot in a microwave oven.22 These relations are discussed later in this paper. Complex power.Complex writing of the impedance equations has simplied the understanding from the electrical point of view. Complex power has been dened to have similar equations S 1 2 V I 21

where S( ) is the apparent power in volt-amperes VA , I * ( ) the conjugated form of the intensity I( j ) A , and V( j ) the complex voltage V , the latter two varying according to j . Equation 21 leads to the following expression S V rms I rmse
j

22 V max and

Figure 6. Nyquist plots for 4 cm2 cells assembled with two electrodes containing PICACTIF SC activated carbon in AN with 1.5 M NET4 BF4 . Frequency range studied: 10 kHz to 13 mHz.

V max /& and I rms I max /&, and where V rms I max are the maximal amplitude of the electric signal. The complex power also has another classical form S P jQ

S 23 or else S

jQ

2 j V rms

30

This equation comes directly from the denition of a complex number. P is called the active power watt and Q the reactive power volt-ampere-reactive, VAR . The impedance data can be used to apply the denition of the complex power. Equations 22 and 24 are used to establish the relation 25 Z V rms I rms 24

2 j C V rms

31

Ideal resistance has no imaginary part as this component only dissipates energy. The complex power takes the well-known form S
2 V rms

32

and the complex power S( j ) can be written S leading to Eq. 26 and 27 P Q

2 V rms/ Z 2 V rms/ Z 2 V rms/ Z

25

cos sin

W VAR

26 27

Equations 26 and 27 can also be written with complex capacitance from Eq. 19 and 20 that leads to the following expressions P Q C C V rms
2 2

28 29

V rms

The interest of these equations is to work directly with power values. It is generally easier to understand the physical sense, especially when the system studied supercapacitor is a power source. Applications to electrochemical impedance measurements.Ideal capacitance has no real part as there is only a reactive contribution to the power. Equations 23 and 25 have then the following forms

R. S decreases when R increases. with Z Supercapacitors oscillate between two states: resistance at high frequencies and capacitance at low frequencies. Between these two states it behaves like a resistance-capacitance RC transmission line circuit.16,17,18 Figure 6 presents the Nyquist plot of a two-electrode supercapacitor cell assembled with AN 1.5 M Net4 BF4 electrolyte. At high frequencies 10 kHz , supercapacitors behave like a resistance R. At low frequency, the imaginary part of the impedance sharply increases and the plot tends to a vertical line characteristic of capacitive behavior. In the middle frequency range, the inuence of electrode porosity and thickness on the migration rate of the ions from the electrolyte inside the electrode can be seen.23 This shifts the low-frequency capacitive behavior along the real axis toward more resistive values. The thicker the electrodes, the larger the shift. The plot is quite linear in this frequency range. The crossing of this line with the low-frequency vertical line denes the knee frequency: below this frequency, the whole capacitance is reached. For higher values, the capacitance strongly depends on the frequency.19 Figure 7a presents the real part of capacitance (C ) change vs. frequency, according to Eq. 19. The capacitance change is the one commonly described in the literature,21 according to our previous comments: when the frequency decreases, C sharply increases,

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Journal of The Electrochemical Society, 150 3 A292-A300 2003

Figure 8. Normalized reactive power Q / S and reactive power P / S vs. frequency plots for 4 cm2 cells assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon in AN with 1.5 M NET4 BF4 .

capacitive behavior. These representations can be useful to characterize the supercapacitor cells from an electrical point of view. Equations 19, 20, 26, and 27 are used to characterize the inuence of various parameters on the time constant, namely, the nature of the electrolyte solvent and the active material weight in the electrodes. The last example compares the carbon-carbon supercapacitor with a tantalum dielectric capacitor. Inuence of the solvent.Figure 9 presents the Nyquist plot for two supercapacitor cells assembled with two different electrolytes: NEt4 BF4 in AN and in propylene carbonate PC . As expected, Nyquist plots are very different from one system to another. The resistance of the cells at high frequency traduces the high conductivity of the AN-based electrolyte 55 compared to 13 mS cm 1 for 1 M NEt4 BF4 in PC .15 At low frequency, each capacitor behaves like a pure capacitance, characterized by the vertical line parallel to the imaginary axis. A huge difference can be seen at medium frequencies, where the low-frequency capacitive behavior is largely shifted

Figure 7. Evolution of the a real part and b imaginary capacitance vs. frequency for 4 cm2 cells assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon in AN with NET4 BF4 1.5 M.

then tends to be less frequency dependent. This is characteristic of the electrode structure and the electrode/electrolyte interface. Figure 7b presents the evolution of C vs. frequency, accord to Eq. 20. The imaginary part of the capacitance goes through a maximum at a frequency f 0 , dening a time constant as 0 1/f 0 10 s. This time constant has earlier been described as a dielectric relaxation time24 characteristic of the whole system. It can be seen in Fig. 6 that half of the low-frequency capacitance (C LF) is reached at 0 . For shorter times, C C LF/2, and C C LF/2 for longer times. This relaxation time corresponds to what Miller explained as the supercapacitor factor of merit.25 A more explicit presentation of this time constant can be given. Figure 8 presents the normalized imaginary part Q / S and real part P / S of the complex power vs. frequency. The normalized active power corresponds to the power dissipated into the system. The impedance behavior of a supercapacitor varies from a pure resistance at high frequency to a pure capacitance at low frequency, as shown in Fig. 6. All the power is dissipated ( P 100%) at high frequency, when the supercapacitor behaves like a pure resistance R, as can be seen in Fig. 8. From Eq. 26, the real part of the complex power P dissipated in a pure capacitance is zero ( 90). This is what is observed in Fig. 8, where P / S decreases when f decreases. The normalized imaginary part of the power Q / S increases when the frequency is decreased. It was a predictable behavior because Eq. 30 shows that pure capacitance exhibits only reactive power Q. The maximum of Q / S is then reached at low frequency when the supercapacitor behaves like a pure capacitance. The crossing of the two plots appears when P Q , i.e., when 45 and P / S Q/S 1/&, corresponding to the time constant 0 , dening the frontier between the resistive and the

Figure 9. Nyquist plots for 4 cm2 cells assembled with two electrodes containing 15 mg/cm2 PICACTIF SC activated carbon in AN and PC with 1.5 and 1.0 M NET4 BF4 , respectively.

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Journal of The Electrochemical Society, 150 3 A292-A300 2003

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Figure 10. Evolution of the a real part and b imaginary capacitance vs. frequency for 4 cm2 cells assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon in AN and PC with 1.5 and 1.0 M NET4 BF4 , respectively.

along the real axis toward more resistive values for the cell assembled with PC-based electrolyte. This is obviously linked to the huge difference in the viscosity and in the dielectric constant existing between the two solvents,26 leading to a difference in the electrolyte penetration inside the porous structure of the electrode. Best results are then obtained in AN-based electrolyte. Figure 10a presents the real part of the capacitance (C ) for the

Figure 12. a Nyquist plots for 4 cm2 cells assembled with two electrodes containing 15.0 and 11.3 mg/cm2 PICACTIF SC activated carbon in AN 1.5 M NET4 BF4 and b, bottom high-frequency range enhancement.

Figure 11. Normalized reactive power Q / S and active power P / S vs. frequency plots for 4 cm2 cells assembled with two electrodes containing 15 mg/cm2 of PICACTIF SC activated carbon in AN and PC with 1.5 and 1.0 M NET4 BF4 , respectively.

two cells. The low-frequency value of the capacitance is roughly the same around 2 F , as the active material weight in the cells was kept constant. The huge frequency dependence of the capacitance indicates that the whole electrode porosity was not reached in both cases. The time constants are very different, as can be seen in Fig. 10b: 10 and 48 s, respectively, when using AN and PC. The cell using AN is able to deliver its stored energy ve times faster, meaning at higher power. Figure 11 presents the evolution of both the normalized imaginary part Q / S and real part P / S of the complex power vs. frequency. That conrms previous observations: the pure capacitive behavior ( Q 95% S ) is reached at higher frequency for the AN-based cell 25 mHz as compared to the PC-based cell 6 mHz , traducing the great inuence of the solvent on the performances of the cell.

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Journal of The Electrochemical Society, 150 3 A292-A300 2003

Figure 14. Normalized reactive power Q / S and active power P / S vs. frequency plots for 4 cm2 cells assembled with two electrodes containing 15.0 and 11.3 mg/cm2 PICACTIF SC activated carbon in AN with 1.5 M NEt4 BF4 .

electrode porosity. The low-frequency capacitance values are 2 and 1.4 F for the cells containing 120 and 90 mg, respectively, of activated carbon. Figure 13b plots the C dependence on frequency. The plot gives the time constant of the cells, 10 s for the high activated carbon content and 4.8 s for the lowest one. Faster discharge time can then be reached with the low-carbon cell, meaning that discharged power is more important in this case. Figure 14 presents normalized imaginary part Q / S and real part P / S of the complex power vs. frequency for the two cells. The similar shape for the two plots shows that the two systems have close electrochemical properties, as they only differ in the amount of activated carbon. The change in active material weight from 15.0 to 11.3 mg/cm2 has a less pronounced inuence on the complex power behavior as compared to the nature of the solvent cf. Fig. 11 . Comparison between tantalum capacitor and carbon-carbon supercapacitor.The last part of this paper compares two different systems, a tantalum dielectric capacitor Ta and a 4 cm2 supercapacitor cell. The Ta capacitor was composed of three capacitors assembled in parallel. Each capacitor was 68 F, 16 V; the stack was then 204 F, 16 V.
Figure 13. Evolution of the a real part and b imaginary capacitance vs. frequency for 4 cm2 cells assembled with two electrodes containing 15.0 and 11.3 mg/cm2 PICACTIF SC activated carbon in AN with 1.5 M NEt4 BF4 .

Inuence of the active material content.Figure 12a presents the Nyquist plot for two supercapacitors assembled with different active material weight, 120 and 90 mg, respectively. Figure 12b is the high-frequency zoom of the plot. The difference in the active material amount in the cells leads to a difference in the electrode thickness from one cell to the other. The high-frequency resistance is slightly decreased when less active material is used. That was an expected result, as the electrode thickness is less in this case. The most important difference occurs in the middle frequency range, i.e., where the electrode thickness and porosity effects can be seen. When the electrode thickness increases with higher active material amount , the shift toward more positive resistance values increases. This is in agreement with our previous observations. Figure 13a presents the change in the real part of the capacitance C vs. frequency. C sharply increases between 1 Hz and 50 mHz and tends to be less frequency dependent for the cell containing 90 mg of activated carbon. The capacitance is around 1.5 F for this cell. The whole capacitance is not reached at 12 mHz, even for the cell using less active material. This is due to the increase of the electrode thickness: the ions from the electrolyte have not reached the whole

Figure 15. Nyquist plots of a 4 cm2 cell carbon-carbon supercapacitor in AN with 1.5 M NEt4 BF4 electrolyte and with a Ta dielectric capacitor.

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Journal of The Electrochemical Society, 150 3 A292-A300 2003

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Figure 17. Normalized reactive power Q / S and active power P / S vs. frequency plots for 4 cm2 cell carbon-carbon supercapacitor in AN with 1.5 M NEt4 BF4 and with a Ta dielectric capacitor.

Conclusions This paper presents the results obtained with carbon-carbon supercapacitors 4 cm2 cells in organic electrolyte. The rst part of the paper is devoted to basic performance and cycling results. The specic capacitance of the activated carbon used in this work PICACTIF SC from the Pica Company was found to be 95 F g 1 at 20 mA cm 2 constant current cycling. The series resistance was 1 cm2. The use of treated-aluminum current collectors allowed a nominal voltage of 2.3 V to be reached during cycling. The characteristics of the cell were very stable during galvanostatic cycling, up to 10,000 cycles at 20 mA cm 2. The frequency behavior of the cells was then studied by using complex capacitance and complex power equations. It was then possible to dene a relaxation time constant 0 . This time constant corresponds to the value of 45 for the phase angle . It represents a transition for the supercapacitor between a resistive behavior for frequency higher than 1/ 0 and a capacitive behavior for frequency lower than 1/ 0 . The time constant 0 was found to be 10 s for a standard 4 cm2 cell assembled with 15.0 mg/cm2 of activated carbon symmetrical cell . Complex power normalized imaginary part Q / S and real part P / S vs. frequency plots were proposed as a complementary presentation of the impedance response of the supercapacitor cells Z f (Z ). These plots allow an overview of the whole frequency behavior of the supercapacitors, ranging from a pure resistance at high frequency to a pure capacitance at low frequency. The inuence of several parameters on the time constant 0 values was characterized. 0 increases from 10 to 48 s when the solvent was changed from AN to PC, leading to a sharp decrease of the cell power. On the contrary, and as it was expected, the decrease of the activated carbon weight in the electrodes led to a decrease of 0 from 10 to 4.8 s, increasing the cell power. These plots were also used to compare two different systems, a dielectric Ta capacitor 204 F, 16 V and a standard 4 cm2 cell carbon-carbon supercapacitor 2 F, 2.3 V . The 0 time constants were found equal to 50 s and 10 s, respectively, for the Ta and the carbon-carbon systems. Finally, the complex power plot revealed the huge difference in the time needed for the Ta capacitor to pass from pure resistive ( Q 0) to pure capacitive behavior ( P 0) as compared to the carboncarbon supercapacitor. Acknowledgments The authors thank the Delegation Generale pour lArmement for nancial support of this work.
CNAM assisted in meeting the publication costs of this article.

Figure 16. Evolution of the a real part and b imaginary capacitance vs. frequency for 4 cm2 cell carbon-carbon supercapacitor in AN with 1.5 M NEt4 BF4 and with a Ta dielectric capacitor.

Figure 15 presents the Nyquist plot for the two systems. The pure capacitive behavior of the Ta capacitor can be seen as its plot consists of a vertical line. ESR is very low, around 0.1 . The Nyquist plot of the supercapacitor was the same as the one previously observed. Figure 16a gives the capacitance C evolution with frequency. The difference is important from one system to the other. The capacitance of the Ta capacitor was constant at 210 F at high frequency, i.e., 1000 Hz, while at the same time the capacitance of the carbon-carbon system was rst very low and then strongly frequency dependent. This is obviously linked to the basic difference in the capacitors nature. Figure 16b presents the evolution of the imaginary part of the capacitance C vs. frequency. The two time constants were found to be very different, from 50 s to 10 s, respectively, for the Ta and carbon-carbon systems. The minimum discharge time is 2 105 higher for the Ta system, leading to a power capacitor, as compared to the carbon-carbon system. This huge difference can be again explained by the difference in the nature of the two systems. Figure 17 presents the normalized imaginary part Q / S and real part P / S of the complex power vs. frequency plots for both the Ta capacitor and carbon-carbon supercapacitor. This plot provides information regarding the difference in the way to change from resistive to capacitive behavior for the two systems: the change occurs roughly from 20 kHz resistive down to 2 kHz capacitive , i.e., over one order of magnitude. For the carbon supercapacitor, it is visible from 10 Hz resistive to lower than 10 mHz: it spreads over three orders of magnitude. The use of a Ta capacitor can be achieved with high efciency at frequencies as high as 6 103 Hz ( Q 0.95 S ), while the carbon-carbon supercapacitor assembled with 15.0 mg cm 2 of active material is not able to work at the same efciency before 20 mHz.

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A300

Journal of The Electrochemical Society, 150 3 A292-A300 2003 References

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