Title of Invention	AN ELECTROCHEMICAL SUPERCAPACITOR AND A PROCESS FOR PREPARING THE SAME
Abstract	The present investigation is directed to fabricate and demonstrate high performance electrochemicalo redox supercapacitors,which employ conducting polymers such as polyaniline (PANI)as active material.The conducting polymer is deposited potentiodynamically on inexpensive stainless steel(SS)or non noble metal substrates from an electrolyte solution of 0.5M H2SO4 CONSISTING OF 0.5 M of the monomer.

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FIELD OF INVENTION The present invention relates generally to electrochemical supercapacitors, and, more precisely electrochemical redox supercapacitors employing potentiodynamically deposited polyaniline on a stainless steel substrate. Applications of capacitors Research and development of electrochemical supercapacitors have gained importance in recent years. The use of a capacitor in conjuncture with a battery leads to functioning of a hybrid power source. While the battery can supply the energy for the normal functioning of an appliance, the capacitor, which is in parallel with the battery, can supply energy at higher power levels for short duration pulses. A potential application is in hybrid electric vehicles, where the energy of the capacitor is used for short periods during acceleration, climbing up of gradients, etc. The pulse duration may vary from milliseconds as in the case of telecommunication devices to a few minutes as in the case of electric vehicles. Although the specific energy of a capacitor is lower than that of a battery, its specific power is much higher. PRESENT STATE OF ART Electrochemical capacitors, also called as supercapacitors or ultracapacitors, are charge storage devices, which store higher charge than the conventional capacitors. The discharge and discharge processes of a supercapacitor proceeds at a higher rate than in rechargeable batteries. In addition, the cycle-life of an electrochemical capacitor is several times higher than that of a battery system. Supercapacitors are attractive for potential applications in emerging technology areas that require electrical energy in the form of high power pulses. Examples of such applications include digital communication devices that require power pulses in the millisecond range, and traction power systems in an electric vehicle where the high power demand can last from seconds up to minutes. A capacitor-battery combination has been proposed where the capacitor handles the peak power and the battery provides the sustained load between pulses. Such a hybrid power system can apparently improve the overall power performance and extend battery cycle- life without increase in size or weight of the system. Charge storage in supercapacitors are much higher than mat in conventional capacitors. Compared to batteries, higher power densities and longer cycle life of supercapacitors have been either demonstrated or projected. These advantages of supercapacitors over batteries are achievable because no rate-determining and life-liiniting phase transformations take place at the electrode/electrolyte interface. The dominant supercapacitors technology has been based on double-layer charging at high surface area carbon electrodes. A capacitor is formed at the carbon/electrolyte interface by electronic charging of the carbon surface with counter-ions in the solution phase. At the interface, a separation of ionic charges arises giving rise to the formation of a double-layer. The double-layer capacitance (Cdi) is given by Cdi = dq/dE where dq is the accumulated charge and dE is the potential difference across the interface. Capacitance that arises due to accumulation of charges in the course of an electron-transfer process or in a ionic doping-undoping process is known as pseudocapacitance (C(p). Hydrated RuO2 is one of the examples of this category of capacitor materials9. The role and utilization of pseodocapacitance for energy storage in electrochemical supercapacitors are discussed by Conway et al. In the materials which possess capacitance due to both the above phenomena, the total capacitance (Q) is due to Cdi and Cq>. Thus, The relative contribution of Cdi and Ccp depends on the chemical and physical nature of the material. Conducting polymers also have been investigated as active materials for supercapacitors. When a conducting polymer is p-doped (positively charged), electrons leave the polymer backbone to generate an excess positive charge; anions migrate from the electrolyte solution into the polymer matrixes to balance the positive charge. In the case of n-doping of conducting polymers, the polymer backbone becomes negatively charged by the addition of electrons from the external circuit; cations enter the polymer matrixes from the electrolyte solution to balance the negative charge. As disclosed in the U.S. Pat. No. 5,527,640 and described elsewhere, at least three different types of supercapacitors can be constructed, using conducting polymers as electrode active materials. A Type I capacitor is based on a symmetric configuration, with the same p-dopable conducting polymer active material on both electrodes of a cell. A Type II capacitor has an asymmetric configuration, with two different p-dopable active materials on the two electrodes. Relatively simple conducting polymers, such as polyaniline, polypyrrole and polythiophene, can be efficiently p-doped and can easily be synthesized from inexpensive commercially available monomers. However, the voltage window of a single cell device is limited in the range of 1 V to 1.5 V. In type EH supercapacitors, conducting polymer can be charged both positively (p-doped) and negatively (n-doped). When this capacitor is fully charged, one electrode is in a fully p-doped state and the other is in a fully n-doped state. When the capacitor is discharged, both electrodes will return to their undoped state. As a result, the cell voltage is increased to about 3 V and the complete charge is released on discharge. Studies on PANI in bom aqueous and non-aqueous electrolytes have been reported in the literature for electrochemical capacitor application. PANI has been deposited electrochemically on platinized tantalum substrates by passing a galvanostatic current in HC1 supporting electrolyte containing dissolved aniline monomer. The optimized electrodes have been prepared with 20 C cm"2 of deposition charge. Among several aqueous electrolytes used for characterization of PANI, the electrolyte of 3 M NaC104 + 1 M HCIO4 has been found superior in view of constancy of a high discharge capacity over a large number of charge/discharge cycles. A discharge T A capacity value of 0.8 C cm" has been reported over about 2 x 10 charge/discharge cycles. The discharge capacity per unit mass of PANI has been reported to be less than 100 F/g, and it decreases with an increase in thickness of the PANI. LIMITATIONS Conducting polymers have an advantage of being relatively inexpensive as well as easy to fabricate. However, supercapacitors have hitherto been fabricated only on costly noble metal substrates, such as Pt or Au. Electrochemical deposition of some polymers onto non-noble metals and alloys have been accomplished through the use of initiators such as CuCh, M0CI5, IrCk, and PtCl6. Each of these methods have substantial drawbacks. First, the high cost of noble metals makes the fabrication of such devices economically unattractive. Secondly, researchers have found that the initiators explored heretofore have resulted in deposition processes which are very difficult to control, and which yield poor coating quality, i.e., poor adhesion and high resistance. Accordingly, there is a need for an electrochemical capacitor device which is fabricated of a conductive polymer deposited on an inexpensive substrate, and which demonstrates acceptable device performance. There is a concomitant need for a method for fabricating such devices in an inexpensive, repeatable, manner. Moreover, the values of specific capacitance reported for the capacitors assembled with PANI is Accordingly, it is an object of the present invention to provide an electrochemical supercapacitor in which a polymer is deposited on an inexpensive substrate. It is a further object of the present invention to provide a method of fabricating such supercapacitors economically. The polymer used in the supercapacitors of the present invention is polyaniline, referred to hereinafter as PANI and the inexpensive substrates are selected from stainless steel, copper, nickel, aluminium and lead. BRIEF DESCRIPTION OF THE TABLES AND DRAWINGS: TABLE 1 details the electrical parameters of PANI capacitor obtained at several charge/discharge currents. FIG. 1. The variation of the potential of positive electrode (O), the potential of negative electrode (A) and the voltage of the capacitor ( • ) during a 0.75 A charge/discharge cycle of a PANI capacitor. The electrode potentials are measured with respect to a saturated calomel electrode. FIG. 2. Ragone plots of PANI capacitor based on mass of the PANI. Charge/discharge current values are indicated at each data point. FIG. 3. Cycle-life of a PANI capacitor. Specific capacitance (F g"1) based on mass of PANI (O) and capacitance (F) of the capacitor ( • ) versus cycle number are shown. Charge/discharge curves of the first and 1000th cycles are shown in the inset. Charge/discharge current is 0.75 A. FIG. 4. Specific capacitance based on the mass of PANI as a function of temperature at several values of charge/discharge currents. FIG. 5. Variation of voltage of a Zn-MnO2 cell during 1 min pulse current and 5 min open-circuit in the absence (solid line) and in the presence (dashed line) of two series PANI capacitors in parallel to the cell. Pulse current values are indicated. FIG. 6. A photograph showing running of a toy tan by three charged PANI capacitors in series. SUMMARY OF THE INVENTION In the present study, redox supercapacitors using polyaniline (PANI) coated stainless steel (SS) electrodes have been assembled and characterized. PANI has been deposited on SS substrate by a potentiodynamic method from an acidic electrolyte containing aniline monomer. By employing stacks of electrodes, with a geometrical area of 24 cm each, in acidic perchlorate electrolyte, a capacitance value of about 450 F has been obtained over a long cycle-life. Characterization studies have been carried out by galvanostatic charge/discharge cycling of the capacitors singly as well as in series and parallel configurations. Various electrical parameters have been evaluated. Use of the capacitors in parallel to a battery for pulse power loads, and also working of a toy fan connected to the charged capacitors have been demonstrated. A specific capacitance value of about 1300 F g"1 of PANI has been obtained. This value is several times higher than the values reported in the literature for PANI, perhaps, the highest value known for a capacitor material. An explanation for achieving higher capacitance is as follows: The nature of an electro deposit generally depends on the surface morphology of the substrate. In the present study, the surface of SS was polished to a mild rough finish before using for PANI deposition. Accordingly, the growth of PANI could have taken place microscopically uneven. Additionally, in the potentio-dynamic method, the electrode is continuously cycled between -0.2 and 1.2 V vs. SCE and the oxidation of aniline occurs only when the potential is between 0.9 and 1.2 V vs. SCE. In the potential range between 0 and 0.9 V vs. SCE, PANI deposition does not take place. This is in contrast to the galvanostatic and potentiostatic methods, where the deposition occurs continuously. Thus in the potentio-dynamic method employed in the present study, there is a break in deposition in between two consecutive potential sweeps. As a result of this, the nucleation of PANI occurs during each sweep after the potential reaches > 0.9 V vs. SCE. Since continuous growth of PANI does not take place, a fresh nucleation in each cycle is likely to produce a discontinuous phase. This phenomenon results in a porous deposit. Furthermore, at higher scan rates, the residence time of the electrode between 0.9 and 1.2 V vs. SCE is smaller resulting in lower rates of electro deposition of PANI per cycle. This means, the quantity of the polymer grown is extremely small in a potential sweep before the nucleation occurs in the subsequent sweep at higher scan rates. This is supported by the fact that it requires about 1000 potential sweeps to prepare a PANI7SS electrode. By a combination of the effects of potential cycling and high scan rate, it is likely that the PANI deposited on SS is nanostructured, thus, possessing high porosity and large specific surface. The inexpensive SS substrate and the high capacitance PANI are the favorable factors for a commercial exploitation. The following examples illustrate the invention but is not limited thereto: Example 1: In all the present examples, analar grade chemicals and doubly distilled water were used for preparation of solutions. Aniline was vacuum distilled at about 120 °C. A solution of 0.5 M aniline in 0.5 M H2SO4 was used for polymerization. Stainless steel (SS) (3 cm x 4 cm) substrates with suitable tags for electrical connections were sectioned out of a sheet (thickness = 0.2 mm) of commercial grade 304. The SS current collectors were polished with successive grades of emery papers to a mildly rough finish, copiously washed with a detergent, rinsed with double distilled water and air-dried. The geometric area of each electrode on both the sides is about 24 cm . A saturated calomel electrode (SCE) was used as the reference electrode. The electrochemical deposition of PANI was carried out potentio-dynamically at a sweep rate of 200 mV s-1 in the potential range of- 0.2 to 1.2 V vs. SCE. The deposition was continued by repeated cycling till the mass of PANI became 90 mg on each electrode. As the rate of deposition decreases with increase of sweep rate, about 1000 sweeps were required to achieve this mass of PANI at 200 mV s'1 sweep rate. After the deposition, the PANI/SS electrodes were washed in 0.5 M H2S04 thrice and in 1 M HC104 + 3 M NaC104 once followed by storing in the latter solution. A PANI capacitor was assembled in a polypropylene container by stacking seven electrodes using micro-porous polypropylene separator sheets of 1.2 mm thickness. This separator, which was used in commercial lead-acid batteries, was acid resistant. The separators were soaked for several hours in the acidic electrolyte used for fabrication of the capacitor in order to leach out any soluble impurities. Alternate electrodes were tagged together. The tag consisting of three electrodes was used as the positive terminal and the tag of the rest four electrodes was used as the negative terminal. The electrolyte was an aqueous solution of 1 M HC104 + 3 M NaC104. A computer controlled Eco Chemie galvanostat/potentiostat model Autolab 30 was used for the deposition of PANI and also for galvanostatic charge/discharge cycling. The charge/discharge cycling with various currents was performed for the capacitors singly, as well as in their series and parallel combinations. The voltage range per capacitor was maintained between 0 and 0.75 V. The capacitors were charged in series and connected to a toy fan as a device demonstration. The capacitor voltage and current during working of the fan were recorded manually. Ac impedance measurements were performed by using EG&G PARC impedance analyzer model 6310 in the frequency range 100 kHz- 10m Hz with an excitation signal of 5 mV. Ambient temperature measurements were carried out in an air-conditioned room at 20±1° C. For the purpose of measurements in the temperature range 0 to 40° C, a refrigerator cum heater Julabo model F25 with ethylene glycol and water mixture as the thermal medium was employed. Example 2; Referring to the FIG. 1, the open-circuit potential of a PANI/SS electrode is about 0.4 V vs. SCE, suggesting that PANI is in emeraldine (EM) state. The open-circuit voltage of the capacitor, which consists of PANI as the active material for both the positive and negative electrode materials, is 0 V in the discharged state. During galvanostatic charging, there is a shift in the electrode potential values as shown. The potential of the positive electrode shifts in the positive direction and the negative electrode potential in the negative direction. At the end of charging, the positive electrode potential reaches 0.75 V vs. SCE and the negative electrode potential becomes 0 V vs. SCE. It is known that the conductivity of PANI decreases at potentials less than 0 V. Thus, it is important to maintain the mass balance of PANI on the electrodes in such a way that the negative electrode potential would not polarize below 0 V. This is accomplished in the present study by using 4 negative electrodes and 3 positive electrodes. During discharge of the capacitor to 0 V, the potentials of both the positive and negative electrodes approach the open-circuit value (FIG. 1). The variation of the capacitor voltage during a 0.75 A charge/discharge cycle between 0 and 0.75 V is shown. The voltage variation is nearly linear during both charging and discharging, which is typical for an electrochemical capacitor and is distinguishable from the behavior of a battery. The electrical parameters of the capacitor, namely, specific capacitance (C), specific energy (E) and specific power (P) are calculated using Eqs. (1) - (3), respectively. where I is the discharge current and t is the discharge time. The letters m stand for the mass of PANI present on all electrodes. The values of C, E and P obtained from FIG. 1, respectively, are 720 Fg-1, 113 Wh g-1and 1.0 kW kg"1 based on m. Different electrical parameters calculated based on m are given in TABLE 1. Example 3: Referring to FIG. 2, the data of specific energy versus specific power that are calculated based on m are shown as Ragone plots. At a specific power of 240 W kg"1 of PANI, a specific energy of about 240 Wh kg"1 is obtained. However, the specific energy decreases to 110 Wh kg"1 at a specific power of 1000 W kg'1 of PANI. Nevertheless, this value is several times higher than 2.7 Wh kg-1 at 1000 W kg-1 recently reported for galvanostatically deposited PANI on platinized titanium electrodes. It may be noted from FIG. 2 that the PANI capacitors can be employed as high power as well as a high-energy device. The combined effect of high power and high energy is an attractive characteristic of these capacitors. Example 4: Referring to FIG. 3, a capacitor was subjected to a continuous charge/discharge cycling with 750 mA current. The cycle-life data obtained over about 1000 cycles are shown in FIG. 3 together with specific capacitance of PANI. Charge/discharge curves of the first and the last cycles are shown in the inset. A capacitance value of 450 F is obtained for the first cycle. It gradually decreased to about 440 F during the first 100 cycles and thereafter it is fairly constant. At the end of 1000 cycles, the discharge capacitance obtained is 420 F. The charge/discharge curves (FIG. 3 inset) recorded at the teginning and ending of cycle-life test are almost identical. These data suggest that the PANI/SS electrodes are stable over a large number of cycles. These data support the stability and electrochemical activity of the PANI/SS electrodes over a long cycle life of the capacitors. Example 5: Referring to FIG. 4, the PANI capacitors were evaluated for their performance at several temperatures between 0 and 40 °C. The specific capacitance values measured at several currents are shown in FIG. 4. The capacitance decreases with an increase of discharge current at all temperatures. At a given current value, the discharge capacitance increases with temperature, rapidly from 0 to 20 °C, and marginally from 20 to 40 °C. The intrinsic redox reactions of the PANI are perhaps slower at lower temperatures, thus, affecting the specific capacitance. Example 6: Referring to FIG. 5, the use of the PANI/SS capacitor was demonstrated by connecting two capacitors in series across a D-size Zn/Mn02 cell and passing pulse currents. Since the voltage of the cell is about 1.55 V, the voltage of the capacitors in series closely matches with the cell voltage. The combined unit of the cell and capacitors was connected to a galvano-static circuit consisting of a regulated power source, a high resistance and an ammeter is series. The voltage of the device was measured, while different magnitudes of current were passed for pulse discharge. Current values of different magnitudes were passed for 1 min at 5 min intervals. The experiment was performed in the absence of capacitors also, and the data are shown in FIG. 5. At a pulse current of 0.1 A, the voltage decreases by about 80 mV in the absence of the capacitors. On the other had, the decrease is negligibly small when the capacitors are connected in parallel to the cell. The difference in the voltage dip increases with increase in pulse current and the influence of the capacitors is distinctly evident at high current values. At 0.75 A, for instance, the voltage dip is about 600 mV and 100 mV, respectively, in the absence and presence of the capacitors. Additionally, the open-circuit voltage value in between the successive pulses is much higher in presence of the capacitors in relation to their absence. Example 7: Referring to FIG. 6, another demonstration of functioning of the PANI capacitors was performed by connecting three capacitors in series and charging to 2.25 V. After disconnecting from the charging circuit, a toy fan was connected to the charged capacitors. The fan was seen running for more than 4 h as shown in the photograph (FIG. 6). However, the speed of the fan, according to the visual observation, decreased with time. The variation in voltage and current with time during running of the fan were recorded. The voltage of the capacitors decreased to about 0.5 V at the end of the experiment, and the current was in the range from 10 to 5 mA. TABLE 1. Electrical parameters of PANI capacitor obtained at several charge/discharge currents. The following are the advantages of the supercapacitor of the present invention: 1. The cycle life of the said capacitors is long. 2. The decrease in specific capacitance of the said capacitors of the present invention after a large number charge/discharge is very less. 3 The specific capacitance value obtained is 1300 F g"1 of PANI at a discharge power density of 400 W kg'1 for the said capacitors. 4. By increasing charge/discharge current, a power density of 1 kW kg-1 obtained for the said capacitor and the specific capacitance at this power density is 830 Fg-1. 5. The capacitance values given hereinabove is very much higher than the values reported in the literature for PAN! 6. The capacitance values given hereinabove is very much higher than the values reported in the literature for any capacitor material. 7. The said capacitors are characterized by connecting them in parallel and series. 8. The application of the said capacitors is demonstrated by connecting them in parallel to a battery and passing pulse currents. 9. Running of a toy fan with the said capacitor is demonstrated. 10. Temperature dependence of the capacitance of the said capacitors are evaluated. References Cited: 1. B.E. Conway, "Electrochemical Supercapacitors", Kluwer Academic / Plenum Publishers, New York (1999) pp. 1. 2. A.F. Burke and T.C. Murphy, in "Materials for Electrochemical Energy Storage and Conversion: Batteries, Capacitors and Fuel Cells", D.H. Doughty, B. Vyas, T. Takamura and J.R. Huff (Editors), Materials Research Society, Pittsburg (1995) pp.375. 3. S. Sarangapani, B.V. Tilak and C.P. Chen, J. Electrochem. Soc. 143(1996)3791. 4. D. Belanger, X. Ren, J. Davey, F. Uribe and S. Gottesfeld, J. Electrochem. Soc. 147 (2000)2923. 5. F. Fusalba, P. Gouerec, D. Villers and D. Belanger, J. Electrochem. Soc. 148 (2001) Al. 6. K.S. Ryu, K.M. Kim, N.G. Park, Y.J. Park and S.H. Chang, J. Power Sources 103 (2002) 305. 7. J.P. Cheng and T.R. Jow, J. Power Sources 62 (1996) 155. 8. B.E. Conway, J. Electrochem. Soc. 138 (1991) 1539. 9. K. Rajendra Prasad and N. Munichandraiah, J. Electrochem. Soc. (2002) submitted. 10. S.M. Park in "Handbook of Organic Conductive Molecules and Polymers", Vol. 3, H.S. Nalwa (Editor), John Wiley and Sons, New York (1997) pp. 428. WE CLAIM: 1. An electrochemical supercapacitor comprising the necessary electrodes characterized in that polyaniline is used as active material which is deposited potentiodynamically (by sweeping the electrode potential) on stainless steel (SS), or other non-noble metals such as copper, nickel, aluminium, lead. 2. An electrochemical supercapacitor as claimed in Claim 1, wherein the geometrical area of each electrode used is 24 cm . 3. An electrochemical supercapacitor as claimed in Claim 1, wherein Polyaniline (PANI) is deposited potentiodynamically (by sweeping the electrode potential) on stainless steel (SS) substrate to prepare the necessary electrode, and the geometrical area of each electrode used is 24 cm2. 4. A process of preparing electrochemical supercapacitor as claimed in claim 1, comprising the steps of :- (a) Preparing a polymerization solution containing 0.5M polymer in 0.5M H2SO4 ; (b) Preparing the substrates made of stainless steel or non-noble metals such as copper, nickel, aluminium, and lead with suitable tags for electrical connections, me geometric area of each electrode on both the sides being 24 cm2; (c) Polishing the substrate current collectors so as to have a mildly rough finish followed by washing, rinsing and drying by known methods; (d) Depositing the polymer potentiodynamically by electrochemical method, at a sweep rate of 200 mV s"1 in the Potential range of - 0.2 to 1.2 V vs. the known reference electrode, continuously by repeated cycling till the mass of the polymer became 90 mg on the electrode; (e) Washing the polymer/substrate electrodes in 0.5 M H2SO4 thrice and in 1M HCIO4 +3M NaCI04 once, followed by storing the electrodes in the second solution; (f) Assembling the polymer capacitor in a polypropylene container by stacking a number of electrodes obtained from step (d) using micro porous polypropylene separator sheets of 1.2 mm thickness; (g) Soaking the separators for several hours in the acidic electrolyte used for fabrication of the capacitor in order to leach out any soluble impurities; and (h) Tagging the alternate electrodes together so as to form the positive and negative terminals. 5. A process as claimed in claim 4, wherein the reference electrode used is saturated calomel electrode (SCE). 6. A process as claimed in claims 4 or 5, wherein the number of electrodes used in step (f) are seven. 7. A process as claimed in any one of claims 4 to 5, wherein the electrolyte used is an aqueous solution of 1M HCIO4 + 3 M NaCIO4. 8. A process of preparing electrochemical supercapacitor as claimed in claim 1, comprising the steps of :- (a) Preparing a polymerization solution containing vacuum distilled 0.5M aniline in 0.5M H2S04 ; (b) Preparing the substrates made of stainless steel with suitable tags for electrical connections, the geometric area of each electrode on both the sides being 24 cm2 ; (c) Polishing the stainless steel current collectors so as to have a mildly rough finish followed by washing, rinsing and drying by known methods; (d) depositing the polymer potentiodynamically by electrochemical method, at a sweep rate of 200 mV s"1 in the Potential range of - 0.2 to 1.2 V vs saturated colomel reference electrode, continuously by repeated cycling till the mass of the polymer became 90 mg on the electrode; (e) Washing the PAN1/SS electrodes in 0.5 M H2SO4 thrice and in 1M HCIO4 + 3 M NaCIO4 once, followed by storing the electrodes in the later solution; (f) Assembling the PANI capacitor in a polypropylene container by stacking a number of electrodes obtained from step (d) using micro porous polypropylene separator sheets of 1.2 mm thickness; (g) Soaking the separators for seven hours in the acidic electrolyte consisting of an aqueous solution of 1M HCIO4 + 3 M NaCIO4 used for fabrication of the capacitor in order to leach out any soluble impurities; and (h) Tagging the alternate electrodes together so as to form the positive and negative terminals. 9. The use of the electrochemical capacitors in conjunction with a battery in a hybrid power supply apparatus.

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