JP3791149B2 - Electric double layer capacitor and manufacturing method thereof - Google Patents

Electric double layer capacitor and manufacturing method thereof Download PDF

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Publication number
JP3791149B2
JP3791149B2 JP26425297A JP26425297A JP3791149B2 JP 3791149 B2 JP3791149 B2 JP 3791149B2 JP 26425297 A JP26425297 A JP 26425297A JP 26425297 A JP26425297 A JP 26425297A JP 3791149 B2 JP3791149 B2 JP 3791149B2
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Japan
Prior art keywords
electrode
electric double
double layer
layer capacitor
polyimide resin
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Expired - Fee Related
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JP26425297A
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Japanese (ja)
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JPH11102845A (en
Inventor
和也 平塚
学 数原
克治 池田
健 河里
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旭硝子株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method of manufacturing an electric double layer capacitor, particularly an electric double layer capacitor excellent in operation reliability.
[0002]
[Prior art]
The electric double layer capacitor is based on the principle that electric charges are accumulated in the electric double layer formed at the interface between the polarizable electrode and the electrolyte. In order to improve the capacity density of the electric double layer capacitor, Carbon materials such as activated carbon and carbon black having a high specific surface area, fine particles of metal or conductive metal oxide, and the like are used. These polarizable electrodes having a high specific surface area are joined to a low-resistance layer or foil, such as a metal or graphite, called a current collector, in order to charge and discharge efficiently. As the current collector, valve metals such as aluminum having high electrochemical corrosion resistance, stainless steel such as SUS304 and SUS316L, and the like are usually used.
[0003]
There are two types of electrolytes for electric double layer capacitors: organic electrolytes and water electrolytes. However, since the operating voltage is high and the energy density of the charged state can be increased, electric double layer capacitors using organic electrolytes are attracting attention. . When using an organic electrolyte, if water is present inside the electric double layer capacitor cell, the performance deteriorates due to the electrolysis of the water. Therefore, the polarizable electrode needs to be sufficiently dehydrated and is usually heated under reduced pressure. A drying process is performed.
[0004]
As a polarizable electrode, activated carbon is mainly used as a main component. However, activated carbon is usually in the form of a powder, for example, mixed with a binder containing a fluorine-containing resin such as polytetrafluoroethylene and formed into a sheet in advance. This is electrically connected to a current collector and used as an electrode body. At this time, for example, a conductive adhesive layer is interposed between the electrode sheet and the current collector so that the bonding strength between the electrode sheet containing activated carbon and the current collector is high and the electrical contact resistance is reduced. However, while it is effective to reduce the thickness of the electrode layer to reduce the resistance of the electrode itself, it is difficult to industrially form an electrode sheet of, for example, about 100 μm continuously by the above method. is there.
[0005]
There is also a method in which a hydrocarbon-based binder such as carboxymethyl cellulose is dissolved in water, activated carbon is dispersed therein to form a slurry, and this slurry is applied to a current collector and dried to form an electrode body. However, the electrode body obtained in this way has a weak bonding strength between the electrode and the current collector, and cellulose such as carboxycellulose has poor heat resistance, and sufficiently removes impurities such as moisture in the electrode by high-temperature heating or vacuum heating. Can not.
[0006]
Instead of carboxycellulose, a fluorine-containing resin such as polyvinylidene fluoride is used as a binder, and activated carbon is dispersed in a solution in which this is dissolved in an organic solvent to form a slurry. This slurry is applied to a current collector and dried to form an electrode body. There is also a method. However, a bonding material made of a fluorine-containing resin such as polyvinylidene fluoride that is soluble in a specific organic solvent has a low bonding strength between the electrode and the current collector, and a large bonding strength cannot be obtained. Furthermore, the heat resistance is not sufficient, and impurities such as moisture in the electrode cannot be sufficiently removed by high temperature heating or vacuum heating, so that sufficient charge / discharge cycle characteristics cannot be obtained, and further charge / discharge cycle reliability needs to be improved. It was.
[0007]
[Problems to be solved by the invention]
The present invention, bonding strength between the collector and the polarizable electrode layer is strong, has large capacity, and an object thereof is to provide an electric double layer Capacity data producing method which is excellent in charge-discharge cycle durability.
[0008]
[Means for Solving the Problems]
The present invention provides a slurry by dispersing carbonaceous powder in a varnish obtained by dissolving one or more selected from the group consisting of polyimide resin, polyamideimide resin, polyimide resin precursor and polyamideimide resin precursor in an organic solvent, The slurry is applied to the surface of the current collector, heated and dried at 200 ° C. or higher under reduced pressure, and an electrode layer containing a binder that is a polyimide resin and / or a polyamide-imide resin and a carbonaceous powder is obtained. to produce an integrated electrode and provides an electrical double layer Capacity data producing method characterized that you use as positive electrode and negative electrode element of the electric double layer capacitor having a non-aqueous electrolyte said electrode.
[0009]
In this specification, a binder and carbonaceous powder including conductive electrode layer (hereinafter, polarizable referred electrode layer) is called a current collector that is integrated with the electrode body. When this electrode body is used on the positive electrode side, it is called a positive electrode body, and when it is used on the negative electrode side, it is called a negative electrode body.
[0010]
In the method for producing an electric double layer capacitor of the present invention, the binder contained in the polarizable electrode layer is a polyimide resin or a polyamideimide resin, and the heat resistance temperature of these resins is usually in the range of 200 to 400 ° C. and has heat resistance. high. Polyimide resin is a general term for resins having an imide bond in the repeating unit of the main chain, and is excellent in chemical resistance, mechanical properties, dimensional stability, and electrical characteristics.
[0011]
Polyimide resins can be broadly classified into linear polyimide resins and curable polyimide resins. Linear polyimide resins include thermoplastic resins and non-thermoplastic resins, and curable resins include thermosetting resins and photo-curing resins. Both types of polyimide resins dissolve the resin in a solvent. It is preferred to use varnish as a binder.
[0012]
Polyamideimide resin is a general term for resins having an imide bond and an amide bond in the repeating unit of the main chain, and is slightly inferior in heat resistance to polyimide resin but rich in flexibility and excellent in wear resistance. As for the polyamide-imide resin, a varnish obtained by dissolving the resin in a solvent is preferably used as the binder.
[0013]
In the varnish of polyimide resin or polyamideimide resin, a polyimide resin or polyamideimide resin soluble in a solvent is dissolved in a solvent, and a polyimide resin precursor such as polyamic acid or a polyamideimide resin precursor is dissolved in a solvent. However, there are some which become a polyimide resin or a polyamide-imide resin by high-temperature heat treatment, and any of them can be used similarly.
[0014]
Specific examples of polyimide resin varnish products include Ube Industries' “U-Varnish” (polyamic acid dissolved in a solvent), Shin Nippon Rika Co., Ltd.'s “Rika Coat” (a solvent-soluble polyimide resin. Solvent dissolved in a solvent), Du Pont's "Pier ML", Hitachi Chemical's "PIQ", Toray's "Trenice", and Asahi Kasei's "Paimel". Examples of varnishes obtained by dissolving a polyamideimide resin soluble in a solvent in a solvent include “N7525” and “NA-11” manufactured by Toyobo.
[0015]
The polarizable electrode in the present invention may contain a conductive material such as carbon black or graphite in order to reduce the resistance. The electrode body in the present invention can be produced, for example, as follows.
[0016]
The resin used as the binder is preferably used as a powder or varnish, and these forms of resin are dissolved in a solvent such as N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and activated carbon powder is added to this solution. Then, carbon black powder or graphite fine particles are dispersed as a conductive material to form a slurry. This slurry is applied to the surface of the current collector by a die coater, doctor blade, applicator, etc., and after preliminary drying, it is dried by heating at a high temperature of 200 ° C. or higher, preferably 250 ° C. or higher, more preferably under reduced pressure. A polarizable electrode layer is formed on the electric body. In the electrode body thus obtained, the current collector foil and the electrode layer are firmly bonded.
[0017]
In the present invention, the polarizable electrode layer preferably contains 3 to 30% by weight of the binder. When the binder is contained in the polarizable electrode layer by 3% by weight or more, practical bonding strength can be obtained. However, if too much is included, the electric resistance of the polarizable electrode increases, so it is preferable to make it 30% by weight or less. More preferably, it is 5 to 15% by weight.
[0018]
The organic electrolyte used for the electric double layer capacitor of the present invention is not particularly limited, and an organic electrolyte containing ion-dissociable salts in a known organic solvent can be used. Among them, R 1 R 2 R 3 R 4 N + , R 1 R 2 R 3 R 4 P + (where R 1 , R 2 , R 3 and R 4 are alkyl groups, which may be the same or different. ) And the like, and an organic electrolytic solution in which a salt made of an anion such as BF 4 , PF 6 , ClO 4 , CF 3 SO 3 is dissolved in an organic solvent. Is preferred.
[0019]
As the organic solvent, carbonates such as propylene carbonate, butylene carbonate, and diethyl carbonate, lactones such as γ-butyrolactone, sulfolane, or a mixed solvent thereof can be preferably used.
[0020]
For the polarizable electrode layer of the electric double layer capacitor of the present invention, any material that is electrochemically inert and has a high specific surface area can be used, but it is preferable that the activated carbon powder having a large specific surface area be the main component. Further, materials having a large specific surface area such as carbon black, polyacene, metal fine particles, and conductive metal oxide fine particles other than the activated carbon powder can be preferably used.
[0021]
The current collector for electrically connecting the polarizable electrode layers may be any material that has excellent conductivity and is electrochemically durable, such as valve metals such as aluminum, titanium, and tantalum, and stainless steel. Any precious metal such as steel, gold or platinum, carbon-based material such as graphite, glassy carbon, or conductive rubber containing carbon black can be preferably used.
[0022]
【Example】
[Example 1]
45 parts by weight of activated carbon powder, 5 parts by weight of carbon black, 50 parts by weight of NMP solution containing 20% by weight of polyimide resin (manufactured by Shin Nippon Chemical Co., Ltd., trade name: Rika Coat), and 100 parts by weight of NMP are wet-mixed with a ball mill. To the mixture, 100 parts by weight of an NMP solution containing 14.4% by weight of colloidal graphite and 3.6% by weight of thermosetting polyamide-imide resin was added and further mixed by a ball mill to obtain a solid content of 26% by weight. A slurry was prepared. This slurry is applied to one side of an aluminum etching foil having a width of 10 cm and a thickness of 30 μm to form an electrode layer, dried at 120 ° C. for 30 minutes, press-rolled, further thermally cured at 270 ° C. for 30 minutes, and press-rolled. An electrode body with a thickness of 100 μm was produced.
[0023]
Two electrode bodies having an effective electrode area of 4 cm × 6 cm are obtained from the above electrode bodies, which are used as a positive electrode body and a negative electrode body, and are opposed so that the electrode layers face each other through a separator made of a glass fiber mat having a thickness of 160 μm. I let you. Thereafter, impurities were removed by vacuum drying at 230 ° C. for 5 hours. Next, 1.5 mol / l of a propylene carbonate solution of (C 2 H 5 ) 3 (CH 3 ) NPF 6 was vacuum impregnated as an electrolytic solution to produce an electrolytic solution impregnated element to obtain an electric double layer capacitor.
[0024]
After measuring the initial discharge capacity and internal resistance of the obtained electric double layer capacitor, it was charged and discharged with a constant current of 1 A between 0 and 2.8 V in a constant temperature bath at 40 ° C. for 3000 cycles, and after 3000 cycles The long-term operation reliability of the electric double layer capacitor was acceleratedly evaluated by measuring the discharge capacity and the internal resistance of the capacitor and observing the change in performance before and after. The initial capacity was 6.5F, the initial internal resistance was 0.25Ω, the capacity after the cycle test was 6.2F, and the internal resistance was 0.30Ω.
[0025]
[Example 2]
An electric double layer capacitor element was produced in the same manner as in Example 1 except that the polyimide resin was not used and the polyamide imide resin (trade name: N7525, manufactured by Toyobo Co., Ltd.) was prepared so as to be contained by 8 wt% in the electrode layer. The performance was evaluated in the same manner as in Example 1. The initial capacity was 6.1F, the initial internal resistance was 0.25Ω, the capacity after the cycle test was 5.8F, and the internal resistance was 1.10Ω.
[0026]
[Example 3]
An electric double layer capacitor element was prepared in the same manner as in Example 2 except that polyvinylidene fluoride was used instead of polyimide resin, the temperature for thermosetting was 180 ° C., and the temperature for vacuum drying was 150 ° C. Similarly, the performance was evaluated. The initial capacity was 4.2F, the initial internal resistance was 0.25Ω, the capacity after the cycle test was 2F, and the internal resistance was 4.1Ω.
[0027]
【The invention's effect】
In the manufacturing method of the electric double layer capacitor of the present invention, since the polyimide resin or the polyamideimide resin, which is a binder contained in the polarizable electrode layer, has high heat resistance, the polarizable electrode is heat-treated at high temperature or heated under reduced pressure. Can be processed. Therefore, the water in the activated carbon can be highly dried and removed.
[0028]
Further, the polyimide resin and the polyamideimide resin are resistant to an organic electrolytic solution, and have extremely excellent adhesion strength to a current collector such as a metal. For this reason, an electric double layer capacitor having a polarizable electrode having a polyimide resin and / or a polyamideimide resin as a binder as a positive electrode and a negative electrode applies a voltage over a long period of time even when charge / discharge cycles are repeated at a large current density. However, the operation performance is stable, and the increase in the internal resistance of the electrode itself is small.

Claims (2)

  1. Polyimide resin, polyamideimide resin, by dispersing the carbonaceous powder of one or more varnish dissolved in an organic solvent selected from the group consisting of polyimide resin precursor and polyamide-imide resin precursor and slurry, collector and the slurry The electrode layer containing the binder and the carbonaceous powder, which is a polyimide resin and / or polyamide-imide resin, is integrated with the current collector by coating on the surface of the body and drying by heating under reduced pressure at 200 ° C. or higher. A method for producing an electric double layer capacitor, comprising: producing an electrode, and using the electrode as a positive electrode body and a negative electrode body of an electric double layer capacitor having a non-aqueous electrolyte solution .
  2. The process according to claim 1, wherein said binder is contained 3 to 30 wt% in the electrodeposition electrode layer.
JP26425297A 1997-09-29 1997-09-29 Electric double layer capacitor and manufacturing method thereof Expired - Fee Related JP3791149B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
JP26425297A JP3791149B2 (en) 1997-09-29 1997-09-29 Electric double layer capacitor and manufacturing method thereof

Publications (2)

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JP3791149B2 true JP3791149B2 (en) 2006-06-28

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6709560B2 (en) 2001-04-18 2004-03-23 Biosource, Inc. Charge barrier flow-through capacitor
WO2003009920A1 (en) 2001-07-25 2003-02-06 Biosource, Inc. Electrode array for use in electrochemical cells
JP2006100163A (en) * 2004-09-30 2006-04-13 Kri Inc Electrode material and secondary power supply using it
JP2006253450A (en) * 2005-03-11 2006-09-21 Nisshinbo Ind Inc Composition for electrode, accumulation device and electrode therefor
US7554792B2 (en) * 2007-03-20 2009-06-30 Avx Corporation Cathode coating for a wet electrolytic capacitor
US8298701B2 (en) 2011-03-09 2012-10-30 Aquion Energy Inc. Aqueous electrolyte energy storage device
KR101823873B1 (en) * 2011-03-09 2018-01-31 아퀴온 에너지 인코포레이티드 Metal-free aqueous electrolyte energy storage device
KR101166701B1 (en) 2011-03-21 2012-07-19 비나텍주식회사 Composite for electrode of supercapacitor, method for manufacturing supercapacitor electrode using the composite, and supercapacitor using the method
CN105027331A (en) * 2013-02-04 2015-11-04 住友电气工业株式会社 Electrode for sodium molten salt batteries, and sodium molten salt battery
US9293268B2 (en) 2013-11-22 2016-03-22 Corning Incorporated Ultracapacitor vacuum assembly

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