JP4627096B2 - Method for producing polarizable electrode for electric double layer capacitor - Google Patents
Method for producing polarizable electrode for electric double layer capacitor Download PDFInfo
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- JP4627096B2 JP4627096B2 JP35243598A JP35243598A JP4627096B2 JP 4627096 B2 JP4627096 B2 JP 4627096B2 JP 35243598 A JP35243598 A JP 35243598A JP 35243598 A JP35243598 A JP 35243598A JP 4627096 B2 JP4627096 B2 JP 4627096B2
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- electric double
- double layer
- layer capacitor
- polarizable electrode
- mixture
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- 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
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、炭素微粉及び含フッ素樹脂からなる混和物をシート状に加工する電気二重層コンデンサ用分極性電極の製造方法に関する。
【0002】
【従来の技術】
分極性電極と電解質界面で形成される電気二重層を利用した電気二重層コンデンサ(キャパシタ)は、小型大容量のコンデンサとして、大容量化、長寿命化の為、種々の改良がなされ、近年急速に需要が伸びている。この改良方法としては、耐亀裂性や破壊性を改良するために、活性炭とペーストの粘調度を与えるのに十分な量の電解質及び必要に応じてポリテトラフルオロエチレンのバインダーとの混合物よりなるカーボンペースト電極が提案されている(特公昭53−7025号公報)。かかるカーボンペースト電極は、可撓性であり、耐亀裂性や耐破壊性は有するものの、形状保持性が小さく、その使用には強度を補うための特別な構造のセルを必要とし、電極の製造には複雑な工程を要した。
【0003】
更に炭素質として、活性炭繊維を使用した機械的強度が大きい電極が知られている(特公昭60−15138号公報、特公昭61−26207号公報、特公昭61−26208号公報)。しかし、繊維状のものを扱うため、これも工程が複雑であった。
【0004】
また、炭素微粉、含フッ素重合体樹脂及び液状潤滑剤からなる混和物をシート状の電極形状に成型した後、液状潤滑剤を除去し、次いで成型物を一軸又は多軸方向に延伸処理することを特徴とする方法によって製造する電極も提案されている(特公平7−105316号公報)。これも液状潤滑剤を除去したり、延伸をしたりとする工程が複雑であった。
【0005】
【発明が解決しようとする課題】
上述したように、従来から知られている製造方法は工程が複雑であり、また、十分な強度を有する薄いカーボンペースト電極は実現されていない。
【0006】
本発明は、前述した従来の問題を解決したもので、厚さを薄くしても十分な強度を有し、可撓性である電気二重層コンデンサ用分極性電極を、簡単な工程により、製造する方法を提供することを課題とする。
【0007】
【課題を解決するための手段】
上述した課題を解決する本発明は、炭素微粉及び含フッ素樹脂からなる混和物をシート状に加工する電気二重層コンデンサ用分極性電極の製造方法において、炭素微粉と、この炭素微粉に対して1〜20重量%の含フッ素樹脂とを混合して混和物とする工程と、前記混和物を圧縮成型し、焼成して固形物とする工程と、この固形物を削り出し、スカイビング、又はスライス加工してシート状に加工する工程とを有することを特徴とする電気二重層コンデンサ用分極性電極の製造方法にある。
【0008】
ここで、前記混和物の圧縮成型は、例えば、20MPa以上の圧力で行うのがよい。
【0009】
また、例えば、前記固形物を円柱状とし、これをスカイビング加工してシート状に加工するのがよい。
【0010】
本発明において、圧縮成型に使用するプレス機は、成型に必要な圧力を加えられる物であれば、特にプレスの機器の種類を限定する物ではない。また、焼成はプレス機に加熱装置が備え付けられていれば、そのままプレス機で行っても良いし、又は、成型された固形物を型から脱型し、あらためて加熱炉で焼成しても良い。また、後の削り出し及びスカイビング加工に支障が生じなければ、芯体を含んだ状態で円柱状に成形してもよい。
【0011】
一方、固形物をシート状に加工する方法は特に限定されないが、削り出し及びスカイビング、又は、スライス加工で行えばよい。かかる加工に使用する機器も特に限定されないが、固形物に芯体を含んでいる場合には、円柱状の中心にある芯体を軸として回転させながらスカイビング加工するのがよい。ここで、スカイビング加工とは、切削工具の強い剪断力又はすべり力で個体物を薄層に削り取ることをいう。
【0012】
本発明この方法で製造された電気二重層コンデンサ用分極性電極は、柔軟性、強度、加工精度、コスト等の数々の面で極めて優れた特長を有することが認められた。
【0013】
【発明の実施の形態】
以下、実施例および比較例をあげて本発明を更に詳しく説明するが、これらによって本発明の範囲が何ら限定されるものではない。
【0014】
[実施例1]
炭素微粉として粉末ヤシガラ炭(325メッシュ)70重量%、カーボンブラック(粒径40〜80μm、表面積60〜100m2/g)20重量%、含フッ素樹脂としてポリテトラフルオロエチレン粉末(粒径0.2μm)10重量%をV形ブレンダーに投入し混合した。得られた混和物を内径10cm、高さ10cmの円柱が作成できる型に充填し100MPaの圧力を加えて円柱状の固形物を作成し、360℃の電気炉で12時間焼成後、徐冷した。この円柱状の固形物から0.5mmのシートを削りだした。
【0015】
このシートを使用して以下の方法により強度、電極単位体積当たりの容量の高温下での長期信頼性を評価した。この結果は、下記表1に示す。
【0016】
なお、強度は、次のように測定した。シートから幅1cmの短冊の試料片を打ち抜き、引っ張り試験機にて強度を測定した。引っ張り速度は1cm/分とした。
【0017】
また、長期信頼性は、コイン型の電気二重層コンデンサを作製し評価した。直径2cmの円盤をシートから2枚打ち抜いたこれをポリプロピレン製のセパレーターを介して対向させ、ステンレス鋼製キャップ及びステンレス鋼製缶から成る外装容器中にポリプロピレン製絶縁パッキングを介して一体化後、かしめ封口した。なお、封口に際し、テトラエチルアンモニウムパークロレートの1モルプロピレンカーボネート溶液を注入した。このように作製した電気二重層コンデンサを用いて、70℃の高温における1000時間1V連続印加時の容量変化を測定した。
【0018】
[比較例1]
実施例1において、V形ブレンダーから得られた混和物をシート化する際、ロールを使用して、混和物を圧延し、シートを得る以外は実施例1と同様に行った。この結果も併せて表1に示す。
【0019】
【表1】
*70℃、1V印加、1000時間経過後
【0020】
【発明の効果】
本発明による電気二重層コンデンサ用分極性電極の製造方法で製造されたシート状電極を用いることで、機械的特性に優れ、かつ大容量、長寿命の電気二重層コンデンサを作製することが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polarizable electrode for an electric double layer capacitor, in which a mixture comprising carbon fine powder and a fluorine-containing resin is processed into a sheet shape.
[0002]
[Prior art]
Electric double layer capacitors (capacitors) using an electric double layer formed at the polarizable electrode and electrolyte interface have been improved in various ways to increase capacity and extend the life of small capacitors with large capacity. Demand is growing. In order to improve crack resistance and fracture resistance, this improvement method includes carbon comprising a mixture of activated carbon and a sufficient amount of electrolyte to give the viscosity of the paste and, if necessary, a binder of polytetrafluoroethylene. A paste electrode has been proposed (Japanese Patent Publication No. 53-7025). Such a carbon paste electrode is flexible and has crack resistance and fracture resistance, but has low shape retention, and its use requires a specially structured cell to supplement the strength, It took a complicated process.
[0003]
Further, electrodes having high mechanical strength using activated carbon fibers as carbonaceous materials are known (Japanese Patent Publication Nos. 60-15138, 61-26207, 61-26208). However, the process is complicated because it deals with fibrous materials.
[0004]
Also, after molding an admixture of carbon fine powder, fluoropolymer resin and liquid lubricant into a sheet-like electrode shape, the liquid lubricant is removed, and then the molded product is stretched in a uniaxial or multiaxial direction. An electrode manufactured by a method characterized by the above has also been proposed (Japanese Patent Publication No. 7-105316). This also involved a complicated process for removing the liquid lubricant and stretching.
[0005]
[Problems to be solved by the invention]
As described above, the conventionally known manufacturing method has a complicated process, and a thin carbon paste electrode having sufficient strength has not been realized.
[0006]
The present invention solves the above-mentioned conventional problems, and produces a polarizable electrode for an electric double layer capacitor that has sufficient strength even when the thickness is reduced and is flexible by a simple process. It is an object of the present invention to provide a method for performing the above.
[0007]
[Means for Solving the Problems]
This invention which solves the subject mentioned above is a carbon fine powder in the manufacturing method of the polarizable electrode for electric double layer capacitors which processes the mixture which consists of carbon fine powder and a fluorine-containing resin into a sheet form, and 1 with respect to this carbon fine powder. A step of mixing -20% by weight of a fluorine-containing resin to form an admixture, a step of compression-molding the admixture and baking to form a solid, and scraping, skiving, or slicing the solid A method of manufacturing a polarizable electrode for an electric double layer capacitor.
[0008]
Here, the compression molding of the mixture is preferably performed at a pressure of 20 MPa or more, for example.
[0009]
Further, for example, the solid material may be formed into a columnar shape, which is skived to be processed into a sheet shape .
[0010]
In the present invention, the press machine used for compression molding is not particularly limited as long as it can apply pressure necessary for molding. Further, if the heating device is provided in the press machine, the firing may be performed with the press machine as it is, or the molded solid may be removed from the mold and fired again in the heating furnace. Further, if there is no hindrance to the subsequent cutting and skiving processing, it may be formed into a cylindrical shape including the core.
[0011]
On the other hand, the method for processing a solid material into a sheet is not particularly limited, but may be performed by cutting and skiving or slicing. The equipment used for such processing is not particularly limited, but when the solid body includes a core, it is preferable to skiving while rotating about the core at the center of the columnar shape. Here, skiving processing means that an individual object is cut into a thin layer by a strong shearing force or sliding force of a cutting tool.
[0012]
The polarizable electrode for an electric double layer capacitor produced by this method of the present invention was found to have extremely excellent features in many aspects such as flexibility, strength, processing accuracy, and cost.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, the scope of the present invention is not limited at all by these.
[0014]
[Example 1]
70% by weight of powdered coconut charcoal (325 mesh) as carbon fine powder, 20% by weight of carbon black (particle size 40-80 μm, surface area 60-100 m 2 / g), polytetrafluoroethylene powder (particle size 0.2 μm as fluororesin) ) 10 wt% was put into a V-shaped blender and mixed. The obtained mixture was filled in a mold capable of producing a cylinder having an inner diameter of 10 cm and a height of 10 cm, and a pressure of 100 MPa was applied to form a cylindrical solid, which was baked in an electric furnace at 360 ° C. for 12 hours and then gradually cooled. . A 0.5 mm sheet was cut out from the cylindrical solid.
[0015]
Using this sheet, the strength and the long-term reliability of the capacity per electrode unit volume at high temperatures were evaluated by the following methods. The results are shown in Table 1 below.
[0016]
The strength was measured as follows. A strip of 1 cm wide strip was punched from the sheet, and the strength was measured with a tensile tester. The pulling speed was 1 cm / min.
[0017]
The long-term reliability was evaluated by producing a coin-type electric double layer capacitor. Two discs with a diameter of 2 cm are punched out of the sheet, facing each other via a polypropylene separator, and integrated into an outer container composed of a stainless steel cap and a stainless steel can via a polypropylene insulating packing, and then caulked. Sealed. At the time of sealing, a 1 mol propylene carbonate solution of tetraethylammonium perchlorate was injected. Using the thus produced electric double layer capacitor, the change in capacitance at the time of continuous application of 1 V for 1 hour at a high temperature of 70 ° C. was measured.
[0018]
[Comparative Example 1]
In Example 1, when forming the mixture obtained from the V-shaped blender into a sheet, the same procedure as in Example 1 was performed except that the mixture was rolled using a roll to obtain a sheet. The results are also shown in Table 1.
[0019]
[Table 1]
* 70 ° C, 1V applied, after 1000 hours. [0020]
【The invention's effect】
By using the sheet-like electrode produced by the method for producing a polarizable electrode for an electric double layer capacitor according to the present invention, an electric double layer capacitor having excellent mechanical properties and a large capacity and a long life can be produced.
Claims (3)
Priority Applications (1)
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JP35243598A JP4627096B2 (en) | 1998-12-11 | 1998-12-11 | Method for producing polarizable electrode for electric double layer capacitor |
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JP35243598A JP4627096B2 (en) | 1998-12-11 | 1998-12-11 | Method for producing polarizable electrode for electric double layer capacitor |
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JP4627096B2 true JP4627096B2 (en) | 2011-02-09 |
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JP4176417B2 (en) | 2002-08-23 | 2008-11-05 | 日本バルカー工業株式会社 | Functional sheet with reinforcement |
WO2019142511A1 (en) | 2018-01-16 | 2019-07-25 | 株式会社村田製作所 | Electricity storage device and method for manufacturing electricity storage device |
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