JPH11102845A - Electric double layer capacitor and method of manufacturing the same - Google Patents
Electric double layer capacitor and method of manufacturing the sameInfo
- Publication number
- JPH11102845A JPH11102845A JP9264252A JP26425297A JPH11102845A JP H11102845 A JPH11102845 A JP H11102845A JP 9264252 A JP9264252 A JP 9264252A JP 26425297 A JP26425297 A JP 26425297A JP H11102845 A JPH11102845 A JP H11102845A
- Authority
- JP
- Japan
- Prior art keywords
- double layer
- electric double
- layer capacitor
- resin
- electrode body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
(57)【要約】
【課題】容量が大きく、充放電サイクル耐久性に優れる
電気二重層キャパシタを提供する。
【解決手段】炭素質粉末と結合材とを含む混合物を集電
体と一体化してなる分極性電極を正極体及び負極体と
し、かつ、非水系電解液を有する電気二重層キャパシタ
において、前記結合材が、ポリイミド樹脂及び／又はポ
リアミドイミド樹脂である電気二重層キャパシタ。(57) [Problem] To provide an electric double layer capacitor having a large capacity and excellent charge / discharge cycle durability. An electric double layer capacitor having a polarizable electrode obtained by integrating a mixture containing a carbonaceous powder and a binder with a current collector as a positive electrode body and a negative electrode body and having a non-aqueous electrolyte solution. An electric double layer capacitor in which the material is a polyimide resin and / or a polyamideimide resin.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気二重層キャパシ
タ、特に作動信頼性に優れた電気二重層キャパシタに関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric double layer capacitor, and more particularly to an electric double layer capacitor excellent in operation reliability.
【０００２】[0002]
【従来の技術】電気二重層キャパシタは、分極性電極と
電解液との界面に形成される電気二重層に電荷を蓄積す
ることを原理としており、電気二重層キャパシタの容量
密度を向上させるため、分極性電極には高比表面積の活
性炭、カーボンブラック等の炭素材料、金属又は導電性
金属酸化物の微粒子等が用いられている。これらの高比
表面積の分極性電極は、効率よく充電及び放電するた
め、集電体と呼ばれる金属や黒鉛等の抵抗の小さい層又
は箔と接合されている。集電体としては、通常電気化学
的に耐食性の高いアルミウム等のバルブ金属、ＳＵＳ３
０４、ＳＵＳ３１６Ｌ等のステンレス鋼等が使用され
る。2. Description of the Related Art An electric double layer capacitor is based on the principle that electric charges are accumulated in an electric double layer formed at an interface between a polarizable electrode and an electrolytic solution. In order to improve the capacitance density of the electric double layer capacitor, Activated carbon having a high specific surface area, a carbon material such as carbon black, fine particles of a metal or a conductive metal oxide, or the like is used for the polarizable electrode. These polarizable electrodes having a high specific surface area are bonded to a low-resistance layer or foil such as a metal or graphite, which is called a current collector, in order to charge and discharge efficiently. As a current collector, a valve metal such as aluminum, which has high electrochemical corrosion resistance, SUS3
04, stainless steel such as SUS316L or the like is used.
【０００３】電気二重層キャパシタの電解液としては有
機電解液と水電解液があるが、作動電圧が高く、充電状
態のエネルギ密度を大きくできることから、有機電解液
を用いた電気二重層キャパシタが注目されている。有機
電解液を用いる場合、電気二重層キャパシタセルの内部
に水分が存在すると、水分の電気分解により性能が劣化
するため、分極性電極を充分に脱水する必要があり、通
常、減圧下で加熱する乾燥処理が施される。[0003] Electrolyte for an electric double layer capacitor includes an organic electrolytic solution and a water electrolytic solution. However, an electric double layer capacitor using an organic electrolytic solution attracts attention because its operating voltage is high and the energy density in a charged state can be increased. Have been. When an organic electrolytic solution is used, if water is present inside the electric double layer capacitor cell, the performance is degraded due to the electrolysis of the water, so the polarizable electrode needs to be sufficiently dehydrated, and is usually heated under reduced pressure. A drying process is performed.
【０００４】分極性電極としては、主に活性炭が主成分
として使用されるが、活性炭は通常粉末状であり、例え
ばポリテトラフルオロエチレン等の含フッ素樹脂を含む
結合材と混合してあらかじめシート状に成形し、これを
集電体と電気的に接続させて電極体として用いる。この
際、活性炭を含む電極シートと集電体との接合強度が強
く、かつ電気的な接触抵抗が小さくなるように、例えば
導電性接着層を電極シートと集電体の間に介在させる。
しかし、電極自体の抵抗の低減には電極層の厚さを薄く
することが有効であるのに対し、上記の方法で連続的に
工業的に例えば１００μｍ程度の電極シートに成形する
ことは困難である。Activated carbon is mainly used as the main component for the polarizable electrode. Activated carbon is usually in the form of powder, and is mixed with a binder containing a fluorine-containing resin such as polytetrafluoroethylene to form a sheet beforehand. 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 low.
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 continuously and industrially form an electrode sheet of, for example, about 100 μm by the above method. is there.
【０００５】また、例えばカルボキシメチルセルロース
等の炭化水素系結合材を水に溶解し、これに活性炭を分
散させてスラリとなし、このスラリを集電体に塗布し乾
燥して電極体とする方法もある。しかし、こうして得た
電極体は、電極と集電体との接合強度が弱く、またカル
ボキシセルロース等のセルロースは耐熱性が乏しく、高
温加熱や真空加熱により電極内の水分等の不純物を充分
に除去できない。Also, a method of dissolving a hydrocarbon binder such as carboxymethylcellulose in water, dispersing activated carbon into the slurry to form a slurry, applying the slurry to a current collector, and drying to form an electrode body is known. is there. However, the electrode body thus obtained has a low 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】カルボキシセルロースのかわりにポリフッ
化ビニリデン等の含フッ素樹脂を結合材とし、これを有
機溶媒に溶解した溶液に活性炭を分散させてスラリとな
し、このスラリを集電体に塗布し乾燥して電極体とする
方法もある。しかし、特定の有機溶媒に可溶なポリフッ
化ビニリデン等の含フッ素樹脂からなる結合材では電極
と集電体との接合強度が弱く、大きな接合強度は得られ
ない。さらに耐熱性も充分ではなく、高温加熱や真空加
熱により電極内の水分等の不純物を充分に除去できない
ため充分な充放電サイクル特性が得られず、さらなる充
放電サイクル信頼性を向上させる必要があった。Instead of carboxycellulose, a fluorocarbon resin such as polyvinylidene fluoride is used as a binder, and activated carbon is dispersed in a solution obtained by dissolving the binder in an organic solvent to form a slurry. The slurry is applied to a current collector and dried. There is also a method of forming an electrode body. However, with a binder made of a fluorine-containing resin such as polyvinylidene fluoride soluble in a specific organic solvent, the bonding strength between the electrode and the current collector is weak, and a large bonding strength cannot be obtained. Furthermore, 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 it is necessary to further improve charge / discharge cycle reliability. Was.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、集電体と分
極性電極との接合強度が強く、容量が大きく、充放電サ
イクル耐久性に優れる電気二重層キャパシタ及びその製
造方法を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide an electric double layer capacitor having a high junction strength between a current collector and a polarizable electrode, a large capacity, and excellent charge / discharge cycle durability, and a method of manufacturing the same. With the goal.
【０００８】[0008]
【課題を解決するための手段】本発明は、炭素質粉末と
結合材とを含む混合物を集電体と一体化してなる分極性
電極を正極体及び負極体とし、かつ、非水系電解液を有
する電気二重層キャパシタにおいて、前記結合材が、ポ
リイミド樹脂及び／又はポリアミドイミド樹脂であるこ
とを特徴とする電気二重層キャパシタ及びその製造方法
を提供する。SUMMARY OF THE INVENTION According to the present invention, a polarizable electrode obtained by integrating a mixture containing a carbonaceous powder and a binder with a current collector is used as a positive electrode body and a negative electrode body, and a nonaqueous electrolytic solution is used. The present invention provides an electric double layer capacitor and a method for manufacturing the same, wherein the binder is a polyimide resin and / or a polyamideimide resin.
【０００９】本明細書において、炭素質粉末と結合材と
を含む分極性電極を集電体と一体化させたものを電極体
という。そして、この電極体を正極側に用いる場合は正
極体、負極側に用いる場合は負極体という。In the present specification, a polarizable electrode including a carbonaceous powder and a binder is integrated with a current collector to form an 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】本発明の電気二重層キャパシタにおいて、
分極性電極に含まれる結合材は、ポリイミド樹脂又はポ
リアミドイミド樹脂であり、これら樹脂の耐熱温度は通
常２００〜４００℃の範囲にあり耐熱性が高い。ポリイ
ミド樹脂はその主鎖の繰り返し単位中にイミド結合を有
する樹脂の総称であり、耐薬品性、機械的性質、寸法安
定性、電気的特性において優れている。In the electric double layer capacitor of the present invention,
The binder contained in the polarizable electrode is a polyimide resin or a polyamideimide resin, and the heat resistance of these resins is usually in the range of 200 to 400 ° C., and the heat resistance is 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 properties.
【００１１】ポリイミド樹脂は、線状ポリイミド樹脂と
硬化型ポリイミド樹脂に大別できる。線状ポリイミド樹
脂には熱可塑性樹脂と非熱可塑性樹脂があり、硬化型樹
脂には熱硬化性樹脂と光硬化性樹脂が含まれるが、いず
れのタイプのポリイミド樹脂も、樹脂を溶剤に溶かした
ワニスを結合材として使用するのが好ましい。[0011] Polyimide resins can be broadly classified into linear polyimide resins and curable polyimide resins. The linear polyimide resin has a thermoplastic resin and a non-thermoplastic resin, and the curable resin includes a thermosetting resin and a photocurable resin, but any type of polyimide resin also has a resin dissolved in a solvent. Preferably, a varnish is used as the binder.
【００１２】ポリアミドイミド樹脂は、その主鎖の繰り
返し単位中にイミド結合とアミド結合とを有する樹脂の
総称であり、ポリイミド樹脂に比べ耐熱性は少し劣るが
可撓性に富み耐磨耗性が優れる。ポリアミドイミド樹脂
も、樹脂を溶剤に溶かしたワニスを結合材として使用す
るのが好ましい。Polyamide imide resin is a general term for resins having an imide bond and an amide bond in the main chain repeating unit. The polyamide imide resin is slightly inferior to polyimide resin in heat resistance, but has high flexibility and abrasion resistance. Excellent. As for the polyamideimide resin, it is preferable to use a varnish obtained by dissolving the resin in a solvent as a binder.
【００１３】ポリイミド樹脂又はポリアミドイミド樹脂
のワニスには、溶剤に可溶なポリイミド樹脂又はポリア
ミドイミド樹脂を溶剤に溶解したものと、ポリアミック
酸等のポリイミド樹脂前駆体又はポリアミドイミド樹脂
前駆体を溶剤に溶解したものであって、高温の熱処理に
よりポリイミド樹脂又はポリアミドイミド樹脂になるも
のとがあるが、いずれも同様に使用できる。A varnish of a polyimide resin or a polyamideimide resin is prepared by dissolving a polyimide resin or a polyamideimide resin soluble in a solvent in a solvent, and adding a polyimide resin precursor such as polyamic acid or a polyamideimide resin precursor to the solvent. Some are dissolved and become polyimide resin or polyamide-imide resin by high-temperature heat treatment, but any of them can be used similarly.
【００１４】ポリイミド樹脂のワニスの商品を具体的に
例示すると、宇部興産社の「Ｕ−ワニス」（ポリアミッ
ク酸を溶剤に溶解したもの）、新日本理化社の「リカコ
ート」（溶剤に可溶なポリイミド樹脂を溶剤に溶解した
もの）、デュポン社の「パイヤーＭＬ」、日立化成社の
「ＰＩＱ」、東レ社の「トレニース」、旭化成工業社の
「パイメル」がある。また、溶剤に可溶なポリアミドイ
ミド樹脂を溶剤に溶解したワニスとしては、東洋紡社の
「Ｎ７５２５」や「ＮＡ−１１」等がある。Specific examples of polyimide resin varnish products include "U-Varnish" (a product obtained by dissolving polyamic acid in a solvent) from Ube Industries, Ltd. and "Likacoat" (a solvent soluble in a solvent) from Shin Nippon Rika Co., Ltd. Polyimide resin dissolved in a solvent), DuPont's "Pier ML", Hitachi Chemical's "PIQ", Toray's "Trenice", and Asahi Kasei's "Pimmel". Examples of varnishes prepared by dissolving a polyamideimide resin soluble in a solvent include “N7525” and “NA-11” manufactured by Toyobo.
【００１５】本発明における分極性電極は、抵抗を低く
するためにカーボンブラックや黒鉛等の導電材を含んで
もよい。本発明における電極体は例えば以下のようにし
て作製できる。The polarizable electrode according to 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】結合材として使用する樹脂は、粉末又はワ
ニスとして使用することが好ましく、これらの形態の樹
脂をＮ−メチル−２−ピロリドン（以下、ＮＭＰとい
う）等の溶剤に溶解し、この溶液に例えば活性炭粉末、
導電材としてカーボンブラック粉末や黒鉛微粒子を分散
させてスラリとする。このスラリを集電体の表面にダイ
コータ、ドクターブレード、アプリケータ等によって塗
工し、予備乾燥後、２００℃以上、好ましくは２５０℃
以上の高温中、さらに好ましくは減圧下で加熱乾燥し、
集電体上に分極性電極を形成する。このようにして得ら
れた電極体は、集電体箔と電極とが強固に接合されてい
る。The resin used as the binder is preferably used as a powder or a varnish. These forms of the resin are dissolved in a solvent such as N-methyl-2-pyrrolidone (hereinafter referred to as NMP). For example, activated carbon powder,
A slurry is prepared by dispersing carbon black powder or graphite fine particles as a conductive material. This slurry is applied to the surface of the current collector by a die coater, a doctor blade, an applicator, or the like, and after predrying, at least 200 ° C., preferably 250 ° C.
In the above high temperature, more preferably heat drying under reduced pressure,
A polarizable electrode is formed on the current collector. In the electrode body thus obtained, the current collector foil and the electrode are firmly joined.
【００１７】本発明において、分極性電極中に結合材は
３〜３０重量％含まれることが好ましい。結合材は分極
性電極層中に３重量％以上含まれることによって実用性
のある接合強度が得られる。しかし、あまり多く含まれ
ると分極性電極の電気抵抗が大きくなるので３０重量％
以下とするのが好ましい。より好ましくは５〜１５重量
％である。In the present invention, the polarizable electrode preferably contains 3 to 30% by weight of a binder. When the binder is contained in the polarizable electrode layer in an amount of 3% by weight or more, practical bonding strength can be obtained. However, if it is contained too much, the electric resistance of the polarizable electrode increases, so that 30% by weight
It is preferable to set the following. More preferably, it is 5 to 15% by weight.
【００１８】本発明の電気二重層キャパシタに使用され
る有機電解液は特に限定されず、公知の有機溶媒にイオ
ン解離性の塩類を含む有機電解液を使用できる。なかで
もＲ1 Ｒ2 Ｒ3 Ｒ4 Ｎ+ 、Ｒ1 Ｒ2 Ｒ3 Ｒ4 Ｐ+ （ただ
し、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4はアルキル基で、それぞれ
同じでも異なっていてもよい）等で表される第４級オニ
ウムカチオンと、ＢＦ4 -、ＰＦ6 -、ＣｌＯ4 -、ＣＦ3 Ｓ
Ｏ3 -等のアニオンとからなる塩を有機溶媒に溶解させた
有機電解液を使用するのが好ましい。The organic electrolyte used for the electric double layer capacitor of the present invention is not particularly limited, and any known organic solvent containing an ion dissociable salt in an 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. ), BF 4 − , PF 6 − , ClO 4 − , CF 3 S
O 3 - is preferable to use salts of organic electrolyte dissolved in an organic solvent consisting of an anion such as.
【００１９】上記有機溶媒としては、プロピレンカーボ
ネート、ブチレンカーボネート、ジエチルカーボネート
等のカーボネート類、γ−ブチロラクトン等のラクトン
類、スルホラン又はこれらの混合溶媒が好ましく使用で
きる。As the organic solvent, carbonates such as propylene carbonate, butylene carbonate and diethyl carbonate, lactones such as γ-butyrolactone, sulfolane and a mixed solvent thereof can be preferably used.
【００２０】本発明の電気二重層キャパシタの分極性電
極は、電気化学的に不活性な高比表面積の材料であれば
使用できるが、比表面積が大きい活性炭粉末を主成分と
するのが好ましい。また、活性炭粉末以外の、カーボン
ブラック、ポリアセン、金属微粒子、導電性金属酸化物
微粒子等の大比表面積の材料も好ましく使用できる。The polarizable electrode of the electric double layer capacitor of the present invention can be used as long as it is an electrochemically inactive material having a high specific surface area. However, it is preferable to use activated carbon powder having a large specific surface area as a main component. In addition, materials having a large specific surface area, such as carbon black, polyacene, metal fine particles, and conductive metal oxide fine particles, other than activated carbon powder, can also be preferably used.
【００２１】上記の分極性電極を電気的に接続するため
の集電体は、導電性に優れ、かつ電気化学的に耐久性の
ある材料であればよく、アルミニウム、チタン、タンタ
ル等のバルブ金属、ステンレス鋼、金、白金等の貴金
属、黒鉛、グラッシーカーボン、カーボンブラックを含
む導電性ゴム等の炭素系材料等、いずれも好ましく使用
できる。The current collector for electrically connecting the above-mentioned polarizable electrodes may be a material having excellent conductivity and being electrochemically durable, and may be a valve metal such as aluminum, titanium or tantalum. And noble metals such as stainless steel, gold, and platinum; and carbon-based materials such as graphite, glassy carbon, and conductive rubber containing carbon black.
【００２２】[0022]
［例１］活性炭粉末４５重量部、カーボンブラック５重
量部、ポリイミド樹脂（新日本理化社製、商品名：リカ
コート）２０重量％を含有するＮＭＰ溶液５０重量部、
及びＮＭＰ１００重量部をボールミルで湿式混合し、こ
の混合物に、コロイド状黒鉛１４．４重量％と熱硬化性
ポリアミドイミド樹脂３．６重量％とを含有するＮＭＰ
溶液１００重量部を加えてさらにボールミルにて混合し
て、固形分濃度２６重量％のスラリを調製した。幅１０
ｃｍ、厚さ３０μｍのアルミニウムエッチング箔の片面
にこのスラリを塗布して電極層を形成し、１２０℃で３
０分乾燥後プレス圧延し、さらに２７０℃で３０分熱硬
化させ、プレス圧延して厚さ１００μｍの電極体を作製
した。[Example 1] 50 parts by weight of an NMP solution containing 45 parts by weight of activated carbon powder, 5 parts by weight of carbon black, and 20% by weight of a polyimide resin (trade name: Ricacoat, manufactured by Shin Nippon Rika Co., Ltd.)
And 100 parts by weight of NMP in a ball mill, and NMP containing 14.4% by weight of colloidal graphite and 3.6% by weight of a thermosetting polyamideimide resin is added to the mixture.
100 parts by weight of the solution was added and further mixed by a ball mill to prepare a slurry having a solid content concentration of 26% by weight. Width 10
This slurry was applied to one side of an aluminum etched foil having a thickness of 30 μm and a thickness of 30 μm to form an electrode layer.
After drying for 0 minutes, press rolling was performed, followed by thermosetting at 270 ° C. for 30 minutes, and press rolling to prepare an electrode body having a thickness of 100 μm.
【００２３】上記の電極体から有効電極面積４ｃｍ×６
ｃｍの２枚の電極体を得てこれを正極体及び負極体と
し、厚さ１６０μｍのガラス繊維マットからなるセパレ
ータを介して電極層が対面するように対向させた。その
後、２３０℃で５時間真空乾燥して不純物を除去した。
次いで、１．５ｍｏｌ／ｌの（Ｃ2 Ｈ5 ）3 （ＣＨ3 ）
ＮＰＦ6 のプロピレンカーボネート溶液を電解液として
真空含浸させて、電解液含浸素子を作製し電気二重層キ
ャパシタとした。From the above electrode body, an effective electrode area of 4 cm × 6
cm of the electrode body was obtained, and these were used as a positive electrode body and a negative electrode body, and were made to face each other via a separator made of a glass fiber mat having a thickness of 160 μm so that the electrode layers faced each other. Thereafter, vacuum drying was performed at 230 ° C. for 5 hours to remove impurities.
Then, 1.5 mol / l of (C 2 H 5 ) 3 (CH 3 )
The propylene carbonate solution of NPF 6 was vacuum impregnated with an electrolytic solution to produce an electrolytic solution impregnated element, thereby obtaining an electric double layer capacitor.
【００２４】得られた電気二重層キャパシタの初期の放
電容量及び内部抵抗を測定した後、４０℃の恒温槽中で
０〜２．８Ｖの間で１Ａの定電流による充放電を３００
０サイクル繰り返し、３０００サイクル後の放電容量及
び内部抵抗を測定し、前後の性能変化を観察することに
より、電気二重層キャパシタの長期的な作動信頼性を加
速的に評価した。初期容量は６．５Ｆ、初期内部抵抗は
０．２５Ωであり、サイクル試験後の容量は６．２Ｆ、
内部抵抗は０．３０Ωであった。After measuring the initial discharge capacity and internal resistance of the obtained electric double layer capacitor, charge and discharge with a constant current of 1 A was performed in a constant temperature bath at 40 ° C. between 0 and 2.8 V.
By repeating the 0 cycle, the discharge capacity and internal resistance after 3000 cycles were measured, and by observing the performance change before and after, the long-term operation reliability of the electric double layer capacitor was acceleratedly evaluated. The initial capacity was 6.5F, the initial internal resistance was 0.25Ω, and the capacity after the cycle test was 6.2F.
The internal resistance was 0.30Ω.
【００２５】［例２］ポリイミド樹脂を使用せず、ポリ
アミドイミド樹脂（東洋紡社製、商品名：Ｎ７５２５）
が電極層中に８重量％含まれるように調製した以外は例
１と同様にして電気二重層キャパシタ素子を作製し、例
１と同様に性能を評価した。初期容量は６．１Ｆ、初期
内部抵抗は０．２５Ωであり、サイクル試験後の容量は
５．８Ｆ、内部抵抗は１．１０Ωであった。Example 2 Polyamide-imide resin (manufactured by Toyobo Co., Ltd., trade name: N7525) without using a polyimide resin
Was prepared in the same manner as in Example 1 except that 8% by weight was contained in the electrode layer, and the performance was evaluated in the same manner as in Example 1. The initial capacity was 6.1 F, the initial internal resistance was 0.25 Ω, the capacity after the cycle test was 5.8 F, and the internal resistance was 1.10 Ω.
【００２６】［例３］ポリイミド樹脂のかわりにポリフ
ッ化ビニリデンを使用し、かつ熱硬化させる温度を１８
０℃、真空乾燥する温度を１５０℃とした以外は例２と
同様にして電気二重層キャパシタ素子を作製し、例１と
同様に性能を評価した。初期容量は４．２Ｆ、初期内部
抵抗は０．２５Ωであり、サイクル試験後の容量は２
Ｆ、内部抵抗は４．１Ωであった。[Example 3] Polyvinylidene fluoride was used in place of the polyimide resin, and the temperature for thermosetting was 18
An electric double layer capacitor element was produced in the same manner as in Example 2 except that the temperature at 0 ° C. and the temperature for vacuum drying were 150 ° C., and the performance was evaluated in the same manner as in Example 1. The initial capacity was 4.2F, the initial internal resistance was 0.25Ω, and the capacity after the cycle test was 2F.
F, the internal resistance was 4.1Ω.
【００２７】[0027]
【発明の効果】本発明の電気二重層キャパシタにおい
て、分極性電極に含まれる結合材であるポリイミド樹脂
又はポリアミドイミド樹脂は耐熱性が高いため、分極性
電極を高温で加熱処理したり減圧下で加熱処理したりで
きる。そのため、活性炭中にある水分を高度に乾燥除去
できる。According to 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, has high heat resistance, the polarizable electrode is subjected to heat treatment at high temperature or reduced pressure. It can be heat treated. Therefore, the moisture in the activated carbon can be highly dried and removed.
【００２８】また、ポリイミド樹脂及びポリアミドイミ
ド樹脂は有機電解液に対する耐性があり、金属等の集電
体への接着強度もきわめて優れる。このため、ポリイミ
ド樹脂及び／又はポリアミドイミド樹脂を結合材として
有する分極性電極を正極及び負極とする電気二重層キャ
パシタは、大電流密度で充放電サイクルを繰り返して
も、長期間にわたって電圧を印加しても、作動性能が安
定しており、電極自体の内部抵抗の増加も少ない。The polyimide resin and the polyamide imide resin have resistance to an organic electrolytic solution, and have extremely excellent adhesive strength to a current collector such as a metal. For this reason, an electric double layer capacitor using a polarizable electrode having a polyimide resin and / or a polyamideimide resin as a binder as a positive electrode and a negative electrode can apply a voltage for a long period even if 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.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 河里 健 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ken Ken Kawari 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside the Central Research Laboratory of Asahi Glass Co., Ltd.
Claims (3)
体と一体化してなる分極性電極を正極体及び負極体と
し、かつ、非水系電解液を有する電気二重層キャパシタ
において、前記結合材が、ポリイミド樹脂及び／又はポ
リアミドイミド樹脂であることを特徴とする電気二重層
キャパシタ。An electric double layer capacitor comprising a positive electrode body and a negative electrode body, wherein a polarizable electrode obtained by integrating a mixture containing a carbonaceous powder and a binder with a current collector, and comprising a non-aqueous electrolyte. An electric double layer capacitor, wherein the binder is a polyimide resin and / or a polyamideimide resin.
含まれる請求項１記載の電気二重層キャパシタ。2. The method according to claim 1, wherein the binder is 3 to 30% by weight in the polarizable electrode.
The electric double layer capacitor according to claim 1, which is included.
リアミドイミド樹脂、ポリイミド樹脂前駆体及びポリア
ミドイミド樹脂前駆体からなる群から選ばれる１種を有
機溶媒に溶解させたワニスに炭素質粉末を分散させて塗
工液とし、該塗工液を集電体に塗工し、加熱硬化させる
ことを特徴とする電気二重層キャパシタの製造方法。3. A varnish obtained by dissolving one kind selected from the group consisting of a polyimide resin, a polyamide imide resin, a polyimide resin precursor and a polyamide imide resin precursor in an organic solvent, wherein the carbonaceous powder is prepared by dissolving a carbonaceous powder in a positive electrode body and a negative electrode body. A method for producing an electric double layer capacitor, comprising: dispersing a coating liquid; applying the coating liquid to a current collector; and curing by heating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26425297A JP3791149B2 (en) | 1997-09-29 | 1997-09-29 | Electric double layer capacitor and manufacturing method thereof |
Applications Claiming Priority (1)
| 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)
| Publication Number | Publication Date |
|---|---|
| JPH11102845A true JPH11102845A (en) | 1999-04-13 |
| JP3791149B2 JP3791149B2 (en) | 2006-06-28 |
Family
ID=17400602
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26425297A Expired - Fee Related JP3791149B2 (en) | 1997-09-29 | 1997-09-29 | Electric double layer capacitor and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3791149B2 (en) |
Cited By (10)
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|---|---|---|---|---|
| US6709560B2 (en) | 2001-04-18 | 2004-03-23 | Biosource, Inc. | Charge barrier flow-through capacitor |
| JP2006100163A (en) * | 2004-09-30 | 2006-04-13 | Kri Inc | Electrode material and secondary power source using the same |
| JP2006253450A (en) * | 2005-03-11 | 2006-09-21 | Nisshinbo Ind Inc | Electrode composition, electrode for electricity storage device, and electricity storage device |
| US7368191B2 (en) | 2001-07-25 | 2008-05-06 | Biosource, Inc. | Electrode array for use in electrochemical cells |
| US7554792B2 (en) * | 2007-03-20 | 2009-06-30 | Avx Corporation | Cathode coating for a wet electrolytic capacitor |
| 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 |
| US9293268B2 (en) | 2013-11-22 | 2016-03-22 | Corning Incorporated | Ultracapacitor vacuum assembly |
| JP2016219426A (en) * | 2011-03-09 | 2016-12-22 | アクイオン エナジー インコーポレイテッド | Aqueous electrolyte energy storage device |
| JPWO2014119157A1 (en) * | 2013-02-04 | 2017-01-26 | 住友電気工業株式会社 | Sodium molten salt battery electrode and sodium molten salt battery |
| US9960397B2 (en) | 2011-03-09 | 2018-05-01 | Aquion Energy, Inc. | Aqueous electrolyte energy storage device |
-
1997
- 1997-09-29 JP JP26425297A patent/JP3791149B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6709560B2 (en) | 2001-04-18 | 2004-03-23 | Biosource, Inc. | Charge barrier flow-through capacitor |
| US7833400B2 (en) | 2001-04-18 | 2010-11-16 | Biosource, Inc. | Method of making a flow through capacitor |
| US8002963B2 (en) | 2001-04-18 | 2011-08-23 | Biosource, Incorporated | Charge barrier flow-through capacitor-based method of deionizing a fluid |
| US7368191B2 (en) | 2001-07-25 | 2008-05-06 | Biosource, Inc. | Electrode array for use in electrochemical cells |
| JP2006100163A (en) * | 2004-09-30 | 2006-04-13 | Kri Inc | Electrode material and secondary power source using the same |
| JP2006253450A (en) * | 2005-03-11 | 2006-09-21 | Nisshinbo Ind Inc | Electrode composition, electrode for electricity storage device, and electricity storage device |
| US7554792B2 (en) * | 2007-03-20 | 2009-06-30 | Avx Corporation | Cathode coating for a wet electrolytic capacitor |
| JP2016219426A (en) * | 2011-03-09 | 2016-12-22 | アクイオン エナジー インコーポレイテッド | Aqueous electrolyte energy storage device |
| US9960397B2 (en) | 2011-03-09 | 2018-05-01 | Aquion Energy, Inc. | 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 |
| JPWO2014119157A1 (en) * | 2013-02-04 | 2017-01-26 | 住友電気工業株式会社 | Sodium molten salt battery electrode and sodium molten salt battery |
| US9293268B2 (en) | 2013-11-22 | 2016-03-22 | Corning Incorporated | Ultracapacitor vacuum assembly |
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|---|---|
| JP3791149B2 (en) | 2006-06-28 |
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