JP2009016722A - Capacitor and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a capacitor which has a small voltage drop by suppressing a self-discharge phenomenon with respect to the capacitor to be used for various electronic devices. <P>SOLUTION: The capacitor includes a capacitor element 1 constituted by opposing a pair of positive and negative electrodes 2 and 3, each having a carbon-based electrode layer 6 formed on a surface of a current collector 5 made of metal foil, to each other with a separator 4 interposed therebetween, and a metal case 9 which stores the capacitor element 1 together with a driving electrolytic solution, and insulating resin is charged in the gap between separators 4 coming into contact with ends of at least the electrodes 2 and 3 of the capacitor element 1. Consequently, surfaces of cellulose fibers forming the separators 4 are covered with the insulating resin to suppress reaction (dehydration, hydrolysis reaction) of the separators 4 with the driving electrolytic solution, and consequently the self-discharge phenomenon is suppressed to maintain a higher voltage than before. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a capacitor excellent in long-term reliability, among capacitors used for regeneration of various electronic devices and hybrid vehicles, or for power storage.

  FIG. 4 is a partially cutaway perspective view showing the configuration of an electric double layer capacitor as an example of this type of conventional capacitor. In FIG. 4, 21 indicates a capacitor element, and the capacitor element 21 is a positive electrode 22. And the negative electrode 23 are wound with a separator 24 interposed therebetween.

  The positive electrode 22 and the negative electrode 23 are configured by forming carbon-based electrode layers 26 (the back side is not shown) on both surfaces of a current collector 25 made of an aluminum foil. A positive electrode lead wire 27 and a negative electrode lead wire 28 are connected to the positive electrode 22 and the negative electrode 23, respectively.

  The capacitor element 21 thus configured is inserted into a bottomed cylindrical metal case 29 after impregnating a driving electrolyte solution (not shown), and a hole through which the positive electrode lead wire 27 and the negative electrode lead wire 28 are inserted. After the rubber sealing member 30 having the above is disposed in the opening of the metal case 29, the outer periphery of the opening of the metal case 29 is drawn inward and the opening end of the metal case 29 is curled. Sealing is performed.

  In addition, as the driving electrolytic solution, one using mainly propylene carbonate (PC) as a solvent and tetraethylammonium salt or the like as an electrolyte is used.

  5 (a) and 5 (b) are cross-sectional views showing the main part of the capacitor element 21, and FIG. 5 (a) is a positive electrode in which a carbon-based electrode layer 26 is formed on the entire surface of the current collector 25. FIG. 5 (b) shows that the positive electrode 22 and the negative electrode 23 in which the carbon-based electrode layer non-formed portion is formed at one end are positioned in opposite directions. FIG. 3 shows a structure in which the carbon-based electrode layer-unformed portions of the positive electrode 22 and the negative electrode 23 protrude in opposite directions by being overlapped and wound.

As prior art document information related to the invention of this application, for example, Patent Document 1 is known.
JP-A-9-17698

  However, in the above conventional capacitor, if the external electrode terminals are left open after being charged, there is a problem that the voltage gradually decreases due to the self-discharge phenomenon inherent to the capacitor. In general, there is no problem at all. However, for example, when it is used for starting an engine of an automobile, there is a problem that the engine cannot be started due to a voltage drop.

  Thus, when the mechanism of the voltage drop due to such a self-discharge phenomenon is estimated, it is considered that the reaction shown in FIG. 6 occurs between the positive and negative electrodes.

  That is, when electrons are supplied into the electrode by charging on the negative electrode side, as shown in (Equation 1), at the interface between the negative electrode and the driving electrolyte, electrons act in the presence of a small amount of water and oxygen to cause hydroxylation. Product ions are generated. For example, in the case where aluminum is used as the metal foil of the current collector, as shown in (Formula 2), aluminum and hydroxide ions generated in (Formula 1) react, and as a result, aluminate Generate. At this time, it seems that aluminum hydroxide is also generated. However, since hydroxide ions are present near the negative electrode, the atmosphere in the liquid is alkaline. It seems to exist as an acid.

  On the other hand, on the positive electrode side, as shown in (Equation 4), hydrogen ions and aluminum oxide are generated and emitted electrons at the interface between the positive electrode and the driving electrolyte in the presence of a small amount of water and aluminum foil. In addition, when the tetrafluoroborate anion melted in the solvent reacts with water molecules attracted in the vicinity of the positive electrode, hydrofluoric acid is generated as shown in (Expression 5), (Expression 6), and (Expression 7). Furthermore, this hydrofluoric acid is considered to exist in the form of hydronium ions and fluorine ions as shown in (Formula 8).

  As described above, at the interface between the electrode and the driving electrolyte, electrons are exchanged mainly in the reaction process of (Equation 1) and (Equation 4), thereby increasing or decreasing the number of electrons inside the electrode and increasing the voltage. It seems to gradually decrease.

  Based on this estimation, after applying various loads to the conventional capacitor, the product was disassembled and investigated, and the following three phenomena were mainly confirmed.

  As the first phenomenon, precipitation of aluminum hydroxide was confirmed in the exposed section of the negative electrode aluminum foil. This is presumably because the aluminate produced in the vicinity of the negative electrode reacted with hydrogen ions attracted in the vicinity of the negative electrode to produce aluminum hydroxide and water, as shown in (Equation 3).

  As a second phenomenon, the presence of aluminum fluoride was confirmed on the front and back surfaces of the separator at the portion sandwiched between the negative electrode end of the separator and the positive electrode surface. This is probably because the aluminate produced at the negative electrode reacted with hydrofluoric acid during migration to the positive electrode, as shown in (Equation 9).

  As a third phenomenon, the presence of aluminum fluoride was confirmed in the exposed portion of the positive electrode aluminum foil. This seems to be because the fluorine ions generated at the positive electrode through the reaction process of (Formula 5), (Formula 6), (Formula 7), and (Formula 8) reacted with aluminum as shown in (Formula 10). .

  In particular, the aluminum fluoride production sites that infer the reaction of (Equation 9) are concentrated on the front and back surfaces of the separator sandwiched between the negative electrode end and the positive electrode surface of the separator. This is particularly because aluminate is generated from the cross-section exposed part of the aluminum foil of the negative electrode and migrates to the positive electrode side, suggesting that the reaction initiation part of the aluminate is the cross-section exposed part of the aluminum foil. It seems that there is.

  Among such reactions, the dehydration reaction of the carbon electrode layer (carboxymethyl cellulose as a binder material) is referred to (Reference: “Heart Fundamental Organic Chemistry”, pages 249-251, Baifukan, issued April 30, 1986). This will be described in detail with reference to (Chemical Formula 1) showing the Fischer esterification reaction in which an ester and water are produced by reacting an acid with a carboxylic acid and an alcohol.

  In (Chemical Formula 1), the reaction process is explained step by step in the order of (1) to (6). Step (1) shows acid catalysis, and the carbonyl group of carboxylic acid is protonated. Occur. This protonation increases the positive charge on the carbon atom of the carboxyl group and facilitates nucleophilic attack on the carbon.

  Step (2) is a reaction in which the alcohol to the protonated acid undergoes a nucleophilic attack. In this step, a new carbon-oxygen bond (ester bond) is formed, and the process of formation of the reaction acid ortho acid hemiester Via. Steps (3) and (4) are equilibrium reactions in which protons are added to or removed from three oxygens. This equilibrium reaction is reversible and occurs very quickly, and is an equilibrium that always occurs in acidic solutions of compounds containing oxygen. In step (4), the two hydroxy groups are equivalent and may be protonated to either.

  In the step (5), the carbon-oxygen bond is cleaved and water is eliminated. This stage corresponds to the reverse reaction of the second stage (2), and in order for this to occur, it is necessary to protonate the hydroxy group to enhance the elimination ability. In the step (6), protons are eliminated from the protonated ester.

  These series of reactions are dehydration condensation reactions classified as addition / elimination reactions. Fischer's esterification reaction process is composed entirely of reversible reactions, and there is also a hydrolysis that is a reverse reaction. For example, when water generated in the reaction process is removed from the reaction system, the reaction is on the right side. Proceed to.

  In the reaction process shown in FIG. 6, the reaction is expected to progress because water is consumed by charging the capacitor.

  As an electrode binder, carboxymethyl cellulose ammonium or the like shown in (Chemical Formula 2) is mainly used. Carboxymethyl cellulose ammonium has a site having a structure in which hydrogen of a carboxyl group is substituted with ammonium in the molecule and a hydroxy group. It is possible that the acid generated in the reaction process shown in FIG. 6 acts to cause the Fischer esterification reaction as shown in (Chemical Formula 3).

  Further, the dehydration reaction of the separator (cellulose) is also described in detail using (Chemical Formula 4) according to the same reference (“Heart Fundamental Organic Chemistry”, pages 176 to 177, issued by Baifukan, April 30, 1986). Then, intramolecular dehydration is known as a dehydration reaction that proceeds by desorption of water molecules within the molecule. For example, when concentrated sulfuric acid is added to ethanol as a dehydrating agent and heated to 160 to 180 ° C., water is eliminated to produce ethylene having a double bond. Further, any hydrogen on the carbon adjacent to the carbon attached to the hydroxy group can be eliminated in principle. For example, 2-methyl-2-butanol produces two types of alkenes.

  The dehydration reaction tends to occur in the order of third> second> primary alcohol. As the separator constituting the capacitor element, cellulose or the like shown in (Chemical Formula 5) is mainly used, but the acid generated in the reaction process shown in FIG. 6 acts, and cellulose is shown in (Chemical Formula 6). In this way, the hydroxy group is protonated and dehydrated, and a double bond may be generated in the molecule.

  It is highly likely that water is generated by the action of acid on the cellulose-based material and the like used for the capacitor element by the mechanism as described above.

  Further, when the capacitor element 21 is inserted into the metal case 29, as shown in FIG. 7A (corresponding to the capacitor element 21 shown in FIG. When the protruding separators 24 are bent and as shown in FIG. 7B (corresponding to the capacitor element 21 shown in FIG. 5B), the current collectors protruded from both end faces of the capacitor element 21, respectively. 25 and the separator 24 are bent, and as shown in FIG. 7C, the current collector 25 is bent and the carbon-based electrode layer 26 bites into the separator 24 as shown in FIG. In such a case, there is a problem that the above-described reaction is further accelerated because current concentration occurs in a bent portion or a broken portion of the separator 24.

  The present invention solves such a conventional problem, suppresses the self-discharge phenomenon by suppressing the reaction occurring between the positive and negative electrodes, and can leave the external electrode terminals open for a long time after charging. An object of the present invention is to provide a capacitor that has a small voltage drop and can maintain a higher voltage than conventional ones.

  In order to solve the above-mentioned problems, the present invention comprises an element configured by facing a pair of positive and negative electrodes in which a carbon-based electrode layer is formed on the surface of a current collector made of metal foil with a separator interposed therebetween, In a capacitor formed of an exterior member containing this element together with a driving electrolyte, the separator is in contact with at least the electrode end portion of the element and is filled with an insulating resin.

  As described above, the capacitor according to the present invention has a structure in which the surface of the cellulose fiber constituting the separator is covered with the insulating resin due to the structure in which the insulating resin is filled in the gap of the separator that is in contact with at least the electrode end portion of the element. And the drive electrolyte reaction (dehydration reaction) can be suppressed, which suppresses the self-discharge phenomenon and causes a voltage drop even if the external electrode terminals are left open for a long time after charging. There is little effect that the voltage higher than the conventional voltage can be maintained.

(Embodiment 1)
Hereinafter, the first aspect of the present invention will be described with reference to the first embodiment.

  FIG. 1 is a partially cutaway perspective view showing a configuration of an electric double layer capacitor as an example of a capacitor according to Embodiment 1 of the present invention, and FIG. 2 is a schematic diagram showing a capacitor element used in the electric double layer capacitor. 1 and FIG. 2, reference numeral 1 denotes a capacitor element. The capacitor element 1 is wound with a positive electrode 2 and a negative electrode 3 overlapped at the same position, with a separator 4 interposed therebetween. The positive electrode 2 and the negative electrode 3 are formed by forming carbon-based electrode layers 6 on both surfaces of a current collector 5 made of an aluminum foil, respectively. Further, a positive electrode lead wire 7 and a negative electrode lead wire 8 are connected to the positive electrode 2 and the negative electrode 3, respectively.

  The capacitor element 1 configured in this manner is inserted into the bottomed cylindrical metal case 9 after impregnating a driving electrolyte solution (not shown), and the hole through which the positive electrode lead wire 7 and the negative electrode lead wire 8 are inserted. After the rubber sealing member 10 having the above is disposed in the opening of the metal case 9, the outer periphery of the opening of the metal case 9 is drawn inward and the opening end of the metal case 9 is curled. Sealing is performed.

  Reference numeral 11 denotes a resin-filled portion in which a part of the separator 4 constituting the capacitor element 1 is filled with an insulating resin. The resin-filled portion 11 is a separator in contact with at least the end portions of the positive electrode 2 and the negative electrode 3. 4 is provided so that the gap between the separators 4 is filled with an insulating resin.

  The insulating resin constituting the resin-filled portion 11 includes polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polyphenylene sulfide (PPS), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer ( PFA), fluorinated ethylene propylene copolymer (FEP), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), or a composite material thereof Can be used.

  Also, these are all resins that are stable with respect to the driving electrolyte. For example, when PP is filled, the PP modified with a terminal hydroxyl group is dispersed in an organic solvent, and this dispersion is used as a separator. After being applied to the surface of the substrate, the voids in the vicinity of the separator surface can be filled by heating this to evaporate the organic solvent and weld the resin particles. Since the organic solvent is a high-boiling solvent and the separator is allowed to stand in a vacuum or a reduced-pressure atmosphere after being applied to the separator surface, PP can enter the separator void together with the solvent. Can be more closely packed with PP.

  The capacitor according to the present embodiment thus configured suppresses the reaction (dehydration reaction) between the separator 4 and the driving electrolyte by covering the surface of the cellulose fiber constituting the separator 4 with an insulating resin. As a result, the self-discharge phenomenon is suppressed, and even after leaving the external electrode terminals open for a long period of time, the voltage drop is small and a higher voltage than before can be maintained. It plays.

  FIG. 3 shows another example of the capacitor according to the present embodiment. In FIG. 3, 12 is a positive electrode, 13 is a negative electrode, and the positive electrode 12 and the negative electrode 13 are made of aluminum foil. The positive electrode 12 and the negative electrode 13 are formed by forming a carbon-based electrode layer 16 on both surfaces of a current collector 15 made of a carbon-based electrode layer 16 and forming a carbon-based electrode layer-unformed portion at the one end. Are stacked with their positions shifted in opposite directions and wound with a separator 14 interposed therebetween, so that the carbon-based electrode layer-unformed portions of the positive electrode 12 and the negative electrode 13 protrude in opposite directions. Thus, a capacitor element is configured.

Reference numeral 11 denotes a resin filling portion, which is formed in the same manner as the resin filling portion 11 shown in FIG.

  In addition to the effects obtained by the capacitor shown in FIG. 2, the capacitor configured as described above is provided with a carbon-based electrode layer non-formed portion at one end of the current collector 15 so that the carbon-based electrode layers of the positive and negative electrodes are not formed. With the configuration in which the forming portions protrude in opposite directions, the positive electrode and the negative electrode can be taken out from both end faces of the capacitor element, respectively, so that not only the lead wires for external lead are unnecessary, This brings about an exceptional effect that the connection resistance can be reduced.

  In the present embodiment, the capacitor element 1 has been described by taking a winding type as an example, but the present invention is not limited to this, and a multilayer capacitor element is used. In this case, the same effect can be obtained.

(Embodiment 2)
Hereinafter, the second and fifth aspects of the present invention will be described with reference to the second embodiment.

  In this embodiment, instead of the resin filling portion 11 provided in the capacitor element of the capacitor described in Embodiment 1 with reference to FIGS. 1 to 3, the hydroxyl group of cellulose constituting the separator 4 (14) is fluorine. This is the structure of (Chemical Formula 7) substituted with

  As a method for fluorinating cellulose, a separator is disposed between an anode electrode and a cathode electrode disposed in a decompression tank, and at least one of argon, argon fluoride, fluorine, carbon fluoride, and hydrocarbon is decompressed in the decompression tank. By injecting into the electrode and applying a high frequency voltage to the electrode, the injected gas is ionized in a plasma state, and then a high voltage pulse is applied to the electrode to replace the hydroxyl group of the separator with fluorine. Is.

  Since the capacitor according to the present embodiment configured as described above can suppress the reaction (dehydration reaction) between the separator and the driving electrolyte, similarly to the capacitor according to the first embodiment, the self-discharge Even if the phenomenon is suppressed and the external electrode terminals are left in an open state after charging for a long period of time after charging, the voltage drop is small, and an exceptional effect is achieved in that a higher voltage can be maintained than before.

(Embodiment 3)
In the following, the third aspect of the present invention will be described with reference to the third and sixth aspects of the present invention.

  In the present embodiment, instead of the resin filling portion 11 provided in the capacitor element of the capacitor described with reference to FIGS. 1 to 3 in the first embodiment, the current collector 5 (15) constituting the capacitor element is used. The carbon electrode layer 6 (16) contains a polysaccharide, and the hydroxyl group of the polysaccharide is partially substituted with fluorine (Chemical Formula 8).

  As a method for fluorinating the polysaccharide of the carbon-based electrode layer formed on the current collector, an anode and a cathode are disposed in a vacuum chamber, and the cathode and the current collector are connected to each other with argon, argon fluoride. Injecting at least one of fluorine, fluorocarbon, and hydrocarbon into a decompression tank and applying a high frequency voltage to the electrode to ionize the injected gas into a plasma state, and then applying a high voltage to the electrode By applying a pulse, the hydroxyl group of the polysaccharide can be substituted with fluorine.

  The capacitor according to the present embodiment configured as described above can suppress the reaction between the polysaccharide and the driving electrolyte (dehydration reaction, esterification reaction), thereby suppressing the self-discharge phenomenon and charging. Even if the external electrode terminals are left in an open state for a long period of time later, the voltage drop is small, and it is possible to maintain a higher voltage than before.

(Embodiment 4)
The fourth embodiment of the present invention will be described below with reference to the fourth embodiment.

  In this embodiment, instead of the resin filling portion 11 provided in the capacitor element of the capacitor described in the first embodiment with reference to FIGS. 1 to 3, a collection of the negative electrode 3 (13) constituting the capacitor element is used. The carbon-based electrode layer 6 (16) of the current collector 5 (15) contains a polysaccharide, and the carbon-based electrode layer 6 (16) of the current collector 5 (15) of the positive electrode 2 (12) does not contain a polysaccharide. , A structure containing latex.

  The capacitor according to the present embodiment configured as described above can suppress the reaction between the polysaccharide and the driving electrolyte (dehydration reaction, esterification reaction), thereby suppressing the self-discharge phenomenon and charging. Even if the external electrode terminals are left in an open state for a long period of time later, the voltage drop is small, and it is possible to maintain a higher voltage than before.

(Embodiment 5)
Hereinafter, the invention according to the seventh aspect of the present invention will be described with reference to the fifth embodiment.

  In the present embodiment, the separator 4 (14) provided in the capacitor element of the capacitor described in Embodiment 1 with reference to FIGS. 1 to 3 before the capacitor element is manufactured with a pair of positive and negative electrodes facing each other. In this case, the separator is immersed in an acidic solution heated in advance, thereby generating the dehydration reaction shown in (Chemical Formula 6), thereby reducing the number of functional groups associated with this reaction, and then washing with water to remove the acid. This makes it possible to suppress the dehydration reaction during the use of the capacitor, so that the self-discharge phenomenon is suppressed, and even if the external electrode terminals are left open for a long time after charging, the voltage drop is small and higher than before. There is a special effect that the voltage can be maintained.

  The capacitor according to the present invention suppresses the self-discharge phenomenon, and has an effect that the voltage drop is small even if the external electrode terminals are left in an open state after charging for a long time, and a higher voltage than the conventional one can be maintained. In particular, it is useful as a field for starting an engine of an automobile.

1 is a partially cutaway perspective view showing a configuration of an electric double layer capacitor as an example of a capacitor according to Embodiment 1 of the present invention. Cross-sectional view of the main part showing a capacitor element (a positive / negative electrode overlapped and wound at the same position) used in the electric double layer capacitor Capacitor element used in the same electric double layer capacitor (positive / negative by winding a positive / negative electrode with a carbon-based electrode layer non-formed part formed on one end while shifting the positions in opposite directions and winding them. The main part sectional view showing each carbon-based electrode layer non-formed part of the electrode of (1) projecting in opposite directions) Partially cutaway perspective view showing the configuration of an electric double layer capacitor as an example of a conventional capacitor (A) Main part sectional view showing a capacitor element (a positive / negative electrode overlapped and wound at the same position) used in the electric double layer capacitor, (b) The capacitor element (carbon at one end) The positive / negative electrodes on which the system electrode layer non-formed part is formed are overlapped with each other while being shifted in opposite directions, and the carbon-based electrode layer non-formed parts of the positive / negative electrode are in conflict with each other. The main part sectional view showing what protruded in the direction) Schematic diagram estimating the mechanism of voltage drop due to the self-discharge phenomenon (A) Main part sectional view showing the bent state of the separator, (b) Main part sectional view showing the current collector and the bent state of the separator, (c) The bent current collector bites into the separator. Cross-sectional view of the relevant part showing a state in which the separator is torn

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Capacitor element 2,12 Positive electrode 3,13 Negative electrode 4,14 Separator 5,15 Current collector 6,16 Carbon-type electrode layer 7 Positive electrode lead wire 8 Negative electrode lead wire 9 Metal case 10 Sealing member 11 Resin filling part

Claims (7)

An element configured by facing a pair of positive and negative electrodes having a carbon-based electrode layer formed on the surface of a current collector made of metal foil with a separator interposed therebetween, and an exterior housing the element together with a driving electrolyte A capacitor comprising a member, wherein a separator gap in contact with at least an electrode end of the element is filled with an insulating resin. An element configured by facing a pair of positive and negative electrodes having a carbon-based electrode layer formed on the surface of a current collector made of metal foil with a cellulose-containing separator interposed therebetween, and the element together with a driving electrolyte A capacitor comprising a packaged outer member, wherein the hydroxyl group of cellulose in the separator in contact with at least the electrode end of the element is partially substituted with fluorine. An element configured by facing a pair of positive and negative electrodes having a carbon-based electrode layer formed on the surface of a current collector made of metal foil with a cellulose-containing separator interposed therebetween, and the element together with a driving electrolyte In the capacitor composed of the packaged exterior member, the carbon-based electrode layer of the current collector constituting the element contains a polysaccharide, and at least the hydroxyl groups of the polysaccharide in the carbon-based electrode layer of the positive electrode current collector are partially made of fluorine. Replaced capacitor. An element configured by facing a pair of positive and negative electrodes having a carbon-based electrode layer formed on the surface of a current collector made of metal foil with a cellulose-containing separator interposed therebetween, and the element together with a driving electrolyte In the capacitor formed of the housed exterior member, the carbon-based electrode layer of the negative electrode current collector constituting the element includes a polysaccharide, and the carbon-based electrode layer of the positive electrode current collector does not include a polysaccharide and includes latex. Capacitor assumed. A device is manufactured by facing a pair of positive and negative electrodes, each having a carbon-based electrode layer formed on the surface of a current collector made of metal foil, with a separator containing cellulose interposed therebetween, and the device is packaged together with a driving electrolyte. In the manufacturing method for producing a capacitor housed in a member, a separator constituting the element is disposed between an anode electrode and a cathode electrode previously disposed in a decompression tank, and argon, argon fluoride, fluorine, carbon fluoride, At least one type of hydrocarbon is injected into the vacuum chamber, a high-frequency voltage is applied to the electrode, and then a high voltage pulse is applied to partially replace the hydroxyl group of the separator with fluorine. A method for manufacturing a capacitor. A device is manufactured by facing a pair of positive and negative electrodes, each having a carbon-based electrode layer formed on the surface of a current collector made of metal foil, with a separator containing cellulose interposed therebetween, and the device is packaged together with a driving electrolyte. In a manufacturing method for producing a capacitor housed in a member, at least a positive electrode constituting the element is disposed between an anode and a cathode arranged in advance in a decompression tank, and a current collector of the cathode and the positive electrode With at least one selected from the group consisting of argon, argon fluoride, fluorine, carbon fluoride, and hydrocarbon injected into the vacuum chamber, a high frequency voltage is applied to the positive electrode, and then a high voltage pulse is applied. A method of manufacturing a capacitor that performs the processing. A device is manufactured by facing a pair of positive and negative electrodes, each having a carbon-based electrode layer formed on the surface of a current collector made of metal foil, with a separator containing cellulose interposed therebetween, and the device is packaged together with a driving electrolyte. A method for manufacturing a capacitor in which a separator constituting the element is immersed in a preheated acidic solution and then washed with water in a method for manufacturing a capacitor housed in a member.

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