JP3152990B2 - Manufacturing method of polarized electrode - Google Patents
Manufacturing method of polarized electrodeInfo
- Publication number
- JP3152990B2 JP3152990B2 JP9020492A JP9020492A JP3152990B2 JP 3152990 B2 JP3152990 B2 JP 3152990B2 JP 9020492 A JP9020492 A JP 9020492A JP 9020492 A JP9020492 A JP 9020492A JP 3152990 B2 JP3152990 B2 JP 3152990B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- activated carbon
- sheet
- polarizable electrode
- fiber
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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】[0001]
【産業上の利用分野】本発明は、分極性電極材の製造法
に関するものであり、さらに詳しく述べるならば、電極
表面と電解液との界面に形成される電気二重層を利用し
た電気二重層キャパシタ、電池、及びエレクトロミック
ディスプレイ等に用いる分極性電極の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polarizable electrode material, and more particularly, to an electric double layer utilizing an electric double layer formed at an interface between an electrode surface and an electrolyte. The present invention relates to a method for manufacturing a polarizable electrode used for a capacitor, a battery, an electro-mic display, and the like.
【０００２】電気二重層コンデンサーの基本構造を図１
に示す。図において、１は電解液を含む分極性電極であ
り、電極の中央部は電気絶縁材でかつイオン透過性につ
くられたセパレータで仕切られている。そして周辺は封
止材３で密閉される。電極１の外側には集電極となる導
電性シート４が配置される。FIG. 1 shows the basic structure of an electric double layer capacitor.
Shown in In the figure, reference numeral 1 denotes a polarizable electrode containing an electrolytic solution, and the center of the electrode is partitioned by an electrically insulating material and a separator made to be ion-permeable. The periphery is sealed with a sealing material 3. A conductive sheet 4 serving as a collecting electrode is disposed outside the electrode 1.
【０００３】[0003]
【従来の技術】分極性電極（以下単に「電極」という）
は表面積が大きいことが必要であるところから、活性炭
粉末や活性炭素粉末などが多く使用されている。従来の
電極製造技術を電気二重層キャパシタを例にとり説明す
る。2. Description of the Related Art Polarizable electrodes (hereinafter simply referred to as "electrodes")
Activated carbon powder, activated carbon powder and the like are often used because they require a large surface area. A conventional electrode manufacturing technique will be described using an electric double layer capacitor as an example.
【０００４】（１）硫酸水溶液などの電解液と活性炭素
粉末をペースト状にしたもの（特開昭６２−１３０５０
６号、同６３−２４４６０８号、同２−１７４２１０
号） （２）フェノール樹脂成形体を発泡、炭化、賦活した多
孔質炭素成形体（特開平２−２９７９１５号）又はメソ
ピッチを発泡、炭化、賦活した多孔質炭素成形体（特開
平２−２９７９１５号）に電解を含浸したもの （３）カーボンブラックをホモプロピレン重合体、エチ
レン・プロピレン共重合体などのカーボンブラック分散
させる樹脂に分散させた基材層と、その表面にエチレン
樹脂とカーボンブラックからなる導電層を接着したもの
（特開昭６３−１８１４１２号） （４）炭素を電極材とするもので、活性炭、活性炭素繊
維、炭素繊維又は粉末炭素を高温で酸化処理した布帛状
のもの（特開昭６４−８２５１４号）、粉末活性炭素の
表面にグラファイトウィスカ−を成長させたもの（特開
平２−２８１６０８号）あるいはフェノール樹脂を炭化
した炭素多孔体であるもの（特開平２−２９７９１５
号）(1) An electrolytic solution such as an aqueous sulfuric acid solution and activated carbon powder in the form of a paste (Japanese Patent Laid-Open No. Sho 62-13050)
No. 6, No. 63-244608, No. 2-174210
(2) A porous carbon molded article obtained by foaming, carbonizing and activating a phenolic resin molded article (JP-A-2-297915) or a porous carbon molded article obtained by foaming, carbonizing and activating a meso pitch (JP-A-2-297915) ) With electrolytically impregnated (3) A base layer in which carbon black is dispersed in a resin for dispersing carbon black, such as a homopropylene polymer or an ethylene / propylene copolymer, and the surface thereof is composed of an ethylene resin and carbon black. Adhesion of conductive layer (Japanese Patent Application Laid-Open No. 63-181412) (4) Fabric using carbon as an electrode material and oxidizing activated carbon, activated carbon fiber, carbon fiber or powdered carbon at high temperature (Japanese Patent Laid-Open No. 64-82514), those obtained by growing graphite whiskers on the surface of powdered activated carbon (JP-A-2-281608), or phenol. Those resins are carbon porous body was carbonized (JP 2-297915
issue)
【０００５】前記従来技術（１）のペースト状電極では
活性炭粉末がそのまま導体として活かされるので表面積
が大きい利点はあるが、電気抵抗が大きく、またコンデ
ンサの組立作業が面倒である。また従来技術（２）の成
形体電極では炭素が骨格をなして連続的に連なっている
ので、電気抵抗は低いが、成形体賦活で表面積を大にす
ることが難しい。また活性炭素は高価であり、これを使
用することはコスト高になるばかりでなく、表面積及び
電気抵抗についても充分な性能が得られない。さらに、
従来技術（３）はペースト状電極（２）と同様に電気抵
抗が大きく、従来技術（４）はウィスカ成長工程により
コスト高になる。また、フェノールを樹脂を炭化させた
ものは十分に大きな表面積（１０００m2／g ）とする
と、圧縮強度が低下する等の難点があった。[0005] The paste-like electrode of the prior art (1) has the advantage that the activated carbon powder is used as a conductor as it is, and therefore has a large surface area. However, the electric resistance is large and the assembling work of the capacitor is troublesome. Further, in the molded body electrode of the prior art (2), since carbon forms a skeleton and is continuously connected, the electric resistance is low, but it is difficult to increase the surface area by activating the molded body. Activated carbon is expensive, and its use not only increases the cost but also does not provide sufficient performance in terms of surface area and electrical resistance. further,
The prior art (3) has a large electric resistance like the paste-like electrode (2), and the prior art (4) increases the cost due to the whisker growth step. Further, when phenol is obtained by carbonizing a resin, if the surface area is sufficiently large (1000 m 2 / g), there is a problem that the compressive strength is reduced.
【０００６】これら従来技術とは異なり、抄紙してシー
ト状の分極性電極を製造する方法としては下記のものが
あり、繊維の特性を生かして表面積を大きくとることが
可能になる。 （５）特開昭６４−５４７２１号公報に示されているよ
うに、黒鉛微粉、活性炭素繊維、パルプを混抄し、混抄
シートをコロイダルカーボン溶液、フッ素樹脂溶液に浸
漬した後乾燥（２００℃以下）する製造法。 （６）本出願人が特願平３−２８１４２６号において提
案した、活性炭粉末、セルロース繊維を混抄した抄紙シ
ートをフェノール樹脂に浸漬したのち加熱成形後、焼成
する製造法。[0006] Unlike these prior arts, there are the following methods for producing a sheet-shaped polarizable electrode by making paper, and it is possible to increase the surface area by utilizing the properties of the fiber. (5) As described in JP-A-64-54221, graphite fine powder, activated carbon fiber, and pulp are mixed, and the mixed sheet is immersed in a colloidal carbon solution or a fluororesin solution and then dried (200 ° C. or lower). A) manufacturing method. (6) A production method proposed by the present applicant in Japanese Patent Application No. 3-281426, in which a papermaking sheet in which activated carbon powder and cellulose fibers are mixed is immersed in a phenol resin, heated, and then fired.
【０００７】[0007]
【発明が解決しようとする課題】上記（５）、（６）の
方法による抄紙シートを溶液に浸漬し乾燥して電極を製
造する方法は、浸漬・乾燥工程を経るために工程が複雑
になる。また（６）の方法によるとフェトル樹脂の浸
漬、乾燥、硬化工程を伴ない面倒である。したがって本
発明は抄紙段階においてポリアクリロニトリル系繊維を
混抄することによりする抄紙シートの浸漬・乾燥工程を
経ずに電気抵抗が安定しかつ低い分極性電極を製造する
ことを目的とする。The method of manufacturing an electrode by immersing a papermaking sheet in a solution according to the above-mentioned methods (5) and (6) and then drying the sheet makes the process complicated because of the immersion and drying processes. . Further, according to the method (6), the steps of dipping, drying and curing the fettle resin are troublesome. Accordingly, an object of the present invention is to produce a polarizable electrode having a stable electric resistance and a low electric resistance without going through a dipping / drying step of a papermaking sheet by mixing polyacrylonitrile fibers in a papermaking stage.
【０００８】[0008]
【課題を解決するための手段】本発明は、上記問題点を
解決するために抄紙の際、活性炭、セルロース質繊維の
他にバインダーとして活性炭を担持させるためにポリア
クリロニトリル系繊維を好ましくは黒鉛微粉混を加えて
混抄させて得たシートを焼成することを特徴とする分極
製電極の製造法である。焼成前に加熱加圧成形を行いポ
リアクリルニトリル系繊維を溶融させてもよい。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention relates to a method of forming a polyacrylonitrile fiber, preferably a graphite fine powder, in order to carry activated carbon as a binder in addition to activated carbon and cellulosic fiber during papermaking. This is a method for producing a polarized electrode, comprising baking a sheet obtained by mixing and mixing. Before sintering, heat and pressure molding may be performed to melt the polyacrylonitrile-based fibers.
【０００９】ポリアクリロニトリル系繊維の割合は、上
記のことを実現するために２０ー４０重量％とすること
が好ましい。２０重量％未満では、活性炭を担持し、ま
た溶融しバインダーとして活性炭を担持させるための絶
対量が少なく加熱加圧積層時に積層面の剥離等が発生す
る。また、次工程の焼成処理を経た時点で活性炭の粉落
ち等が生じる。一方、ポリアクリロニトリル系繊維の割
合が４０重量％を超えると、溶融したポリアクリルニト
リルがバインダーとして活性炭を担時するとき同時にシ
ートの空隙を埋め空隙率を低下させるため分極性電極の
特性が低下する。The ratio of the polyacrylonitrile fiber is preferably 20 to 40% by weight in order to realize the above. If the amount is less than 20% by weight, the absolute amount for supporting the activated carbon and melting and supporting the activated carbon as a binder is small, and peeling of the lamination surface occurs during lamination under heating and pressing. In addition, at the point of time when the firing process in the next step is performed, powder fall of the activated carbon occurs. On the other hand, when the proportion of the polyacrylonitrile-based fiber exceeds 40% by weight, the properties of the polarizable electrode are degraded because the molten polyacrylonitrile simultaneously serves as a binder and fills the voids of the sheet and reduces the voidage. .
【００１０】ポリアクリロニトリル系繊維は長さが２〜
７ｍｍで径が１〜５デニールのものが好ましい。またア
クリルニトリルはアクリルニトリルの単量体、共重合体
などを使用することができる。The polyacrylonitrile fiber has a length of 2 to 2.
Those having a diameter of 7 mm and a diameter of 1 to 5 deniers are preferred. As acrylonitrile, acrylonitrile monomers, copolymers and the like can be used.
【００１１】使用する活性炭はやしがら、おが屑、石
炭、フェノール樹脂などを炭化し、賦活したものなど通
常の活性炭が用いられる。この活性炭を５０μｍ以下程
度に粉砕して使用する。活性炭の割合は、表面積を大き
くするために３０重量％以上が好ましい。上限はほかの
成分による制約から５０重量％以下が好ましい。パルプ
の割合は、抄紙を容易とし、シート及び分極性電極の強
度を保つ事により３０重量％以上が好ましく、他の成分
の制約から５０重量％以下が好ましい。As the activated carbon to be used, ordinary activated carbon such as carbonized and activated charcoal, sawdust, coal, phenol resin and the like is used. This activated carbon is used after being ground to about 50 μm or less. The ratio of the activated carbon is preferably 30% by weight or more in order to increase the surface area. The upper limit is preferably 50% by weight or less due to restrictions by other components. The proportion of pulp is preferably 30% by weight or more for facilitating papermaking and maintaining the strength of the sheet and the polarizable electrode, and is preferably 50% by weight or less due to restrictions on other components.
【００１２】セルロース質繊維には通常紙に使用される
パルプや、その他のセルロース質繊維であるレーヨン、
線等などが使用可能である。その際抄紙製造を容易なら
しめるには、繊維の長さは５ｍｍ以下が好ましい。The cellulosic fibers include pulp which is usually used for paper, rayon which is another cellulosic fiber,
Lines and the like can be used. In that case, the length of the fiber is preferably 5 mm or less in order to facilitate papermaking.
【００１３】黒鉛微粉は分極性電極の電気抵抗を低減す
るために使用される。通常の黒鉛微粉は比表面積が数ｍ
2 ／ｇと小さく、使用割合が大きくなると分極性電極の
表面積が小さくなり、また、使用割合が小さくなると電
気抵抗低減の効果が出ない。したがってその使用割合は
２〜１０重量％が好ましい。この場合の全体の組成は、
活性炭、セルロース質繊維、黒鉛微粉及びポリアクリロ
ニトリル系繊維の使用割合がそれぞれ３０〜４８重量
％、３０〜４８重量％、２〜１０重量％及び２０〜４０
重量％となる。[0013] Graphite fine powder is used to reduce the electric resistance of the polarizable electrode. Normal graphite fine powder has a specific surface area of several meters
2 / g, the surface area of the polarizable electrode is reduced when the usage ratio is increased, and the effect of reducing the electric resistance is not obtained when the usage ratio is reduced. Therefore, the use ratio is preferably 2 to 10% by weight. The overall composition in this case is
The usage ratio of activated carbon, cellulosic fiber, graphite fine powder and polyacrylonitrile fiber is 30 to 48% by weight, 30 to 48% by weight, 2 to 10% by weight and 20 to 40%, respectively.
% By weight.
【００１４】また「固体活性炭電極を用いた大容量電気
二層コンデンサ、田渕順次他日本電気（株）基礎研、’
９１年電気化学秋季大会講演要旨集」等の文献にある如
く、分極性電極は熱処理温度により、分極性電極性能が
大きく左右される。分極性電極が熱処理温度の低い場
合、黒鉛微粉の使用が有効であり、電極の容量を高め
る。[0014] Also, "Large-capacity electric double-layer capacitor using solid activated carbon electrode, Jun Tabuchi, etc.
As described in the literature such as "Abstracts of Lectures for Electrochemical Fall 1991," the performance of polarizable electrodes is greatly affected by the heat treatment temperature. When the polarizable electrode has a low heat treatment temperature, the use of graphite fine powder is effective and increases the capacity of the electrode.
【００１５】以上説明した活性炭、パルプ及びポリアク
リルニトリル径繊維は紙を作るのと同様に抄紙される。
抄紙されたシートは１枚が厚みが０．２〜２ｍｍでかつ
１００〜２５０ｇ／ｍ2 の単重をもつものが好ましい。
このシートを好ましくは１〜５枚積層して、窒素、アル
ゴンなどの不活性雰囲気で焼成する。焼成はシートが反
らないよう例えば黒鉛板の間に挟んで行うのがよい。焼
成の昇温は８００℃程度までを５〜１００時間かけるの
が好ましい。焼成の最終温度は各成分を炭化できるなら
ば特に制限がない。The activated carbon, pulp and polyacrylonitrile diameter fibers described above are made in the same manner as paper.
It is preferable that one sheet of the paper made has a thickness of 0.2 to 2 mm and a single weight of 100 to 250 g / m 2 .
Preferably, one to five such sheets are stacked and fired in an inert atmosphere such as nitrogen or argon. The firing is preferably performed, for example, by sandwiching between sheets of graphite so as not to warp the sheet. It is preferable to raise the temperature of firing to about 800 ° C. for 5 to 100 hours. The final temperature of firing is not particularly limited as long as each component can be carbonized.
【００１６】上記したシートを、焼成する前に加熱加圧
成形することが好ましい。加熱加圧成形においては、ポ
リアクリロニトリル系繊維が溶融しバインダーの機能を
果たして活性炭などを焼成が完了するまで保持する。こ
のような作用を果たすために、加熱温度は２００℃〜３
００℃であることが好ましい。加熱温度が２００℃未満
の場合は、ポリアクリロニトリル系繊維が一部分溶融す
るために加熱加圧積層成形後、積層面の剥離等が生じ、
一方３００℃を超える場合は、ポリアクリロニトリル系
繊維が不融化（酸化）され溶融せず繊維状態のままであ
り、バインダーの機能を果たさないので、いずれの場合
も好ましくない。It is preferable that the above-mentioned sheet is heated and pressed before firing. In the heat and pressure molding, the polyacrylonitrile fiber melts and functions as a binder to hold activated carbon or the like until firing is completed. To achieve such an effect, the heating temperature should be 200 ° C. to 3 ° C.
Preferably it is 00 ° C. When the heating temperature is less than 200 ° C., the polyacrylonitrile-based fiber partially melts, and after heating and pressure lamination molding, peeling of the lamination surface occurs,
On the other hand, when the temperature exceeds 300 ° C., the polyacrylonitrile fiber is infusibilized (oxidized) and does not melt and remains in a fiber state, and does not fulfill the function of the binder.
【００１７】また、加熱加圧成形時の圧力は１〜１０Ｋ
ｇ／ｃｍ2 が好ましい。圧力が１Ｋｇ／ｃｍ2 未満の場
合、積層面の密着性が低下し、一方圧力１０Ｋｇ／ｃｍ
2 を超えても、成形後の密度上昇がほとんど変化ない。The pressure at the time of heating and pressing is 1 to 10K.
g / cm 2 is preferred. When the pressure is less than 1 kg / cm 2 , the adhesion of the laminated surface is reduced, while the pressure is 10 kg / cm 2.
Even if it exceeds 2 , the increase in density after molding hardly changes.
【００１８】[0018]
【作用】上記の方法で製造することにより浸漬工程を行
わずに電極を製造できるため、工程が簡略化されるのみ
ならず、抄紙により空隙率のバラツキが少ないシートが
得られるので、これを焼成した電極でも空隙率のバラツ
キを少なくすることができる。また焼成した電極は微細
構造は使用中にも電解液に対して安定している。According to the above-mentioned method, since the electrode can be manufactured without performing the immersion step, not only the process is simplified, but also a sheet having a small variation in the porosity is obtained by papermaking, and the sheet is fired. Even with the electrode as described above, the variation in the porosity can be reduced. The fired electrode has a fine structure that is stable with respect to the electrolyte even during use.
【００１９】上記の方法で製造した分極性電極の代表的
特性は嵩密度０．３〜１．０ｇ／ｃｍ3 、曲げ強度５０
〜１５０ｇ／ｃｍ2 、電気比抵抗５０００μ〜２０００
０Ωｃｍ、比表面積５００〜１５００ｍ2 ／ｇである。
またこの電気比抵抗は電極使用中にもほとんど変動せず
安定している。Typical characteristics of the polarizable electrode manufactured by the above method are a bulk density of 0.3 to 1.0 g / cm 3 and a bending strength of 50.
１５０150 g / cm 2 , electrical resistivity 5000 μ〜2000
0 Ωcm and specific surface area of 500 to 1500 m 2 / g.
The electrical resistivity is stable with almost no change during use of the electrode.
【００２０】さらに請求項３の方法によると、加熱・加
圧成形の際、ポリアクリロニトリル系が溶融しバインダ
ーとして活性炭を担持するので、最終焼成体中における
活性炭の分布を均一にすることができる。According to the third aspect of the present invention, the polyacrylonitrile-based material is melted and supports activated carbon as a binder at the time of heating and pressure molding, so that the distribution of activated carbon in the final fired body can be made uniform.
【００２１】以下、実施例により本発明を詳しく説明す
る。Hereinafter, the present invention will be described in detail with reference to examples.
実施例１ 活性炭（武田薬品製、ＬＰＫ−４３６，平均粒度６μ
ｍ）、パルプ（セルロース繊維）、人造黒鉛微粉（昭和
電工製ＵＨＧ−３０，平均粒度１０μｍ）及びポリアク
リロニトリル系繊維（旭化成（株）製品：平均長さ３ｍ
ｍ，径３デニール）をそれぞれ３０重量％、４０重量
％、５重量％及び２５重量％の割合で抄紙した。シート
の寸法は１２０ｍｍ×１２０ｍｍ×０．３ｍｍ、重さが
１．６ｇであった。このシートを４枚積層し、黒鉛板に
挟み温度２６０℃で圧力３Ｋｇ／ｃｍ2 、保持３０分の
条件で加熱加圧成形をすることで、厚さ０．８ｍｍの積
層板を得た。この積層板を黒鉛板に挟み不活性化雰囲気
で焼成し厚さ０．７６ｍｍの分極性電極を作製した。Example 1 Activated carbon (LPK-436, manufactured by Takeda Pharmaceutical Co., Ltd., average particle size 6 μm)
m), pulp (cellulose fiber), artificial graphite fine powder (UHG-30 manufactured by Showa Denko, average particle size 10 μm) and polyacrylonitrile fiber (Asahi Kasei Corporation product: average length 3 m)
m, diameter 3 denier) at 30% by weight, 40% by weight, 5% by weight and 25% by weight, respectively. The dimensions of the sheet were 120 mm x 120 mm x 0.3 mm, and the weight was 1.6 g. Four sheets were laminated, sandwiched between graphite plates, and heated and pressed under the conditions of a temperature of 260 ° C., a pressure of 3 kg / cm 2 , and a holding time of 30 minutes to obtain a laminated plate having a thickness of 0.8 mm. The laminate was sandwiched between graphite plates and fired in an inert atmosphere to produce a 0.76 mm thick polarizable electrode.
【００２２】この分極性電極の物性を測定したところ嵩
密度０．５５ｇ／ｃｍ3 、曲げ強度８０Ｋｇ／ｃｍ2 及
び電気比抵抗０．００５Ωｃｍであった。また、成形圧
力を６ｋｇ／ｃｍ2 とした場合、崇密度が若干上昇する
ものの物性はほとんど変化なかった。後述の実施例２〜
４の場合も、成形圧力を高くすると嵩密度が若干上昇す
るものの物性はほとんど変化なかった。When the physical properties of the polarizable electrode were measured, the bulk density was 0.55 g / cm 3 , the bending strength was 80 kg / cm 2, and the electrical resistivity was 0.005 Ωcm. When the molding pressure was 6 kg / cm 2 , the physical properties hardly changed although the density increased slightly. Example 2 to be described later
Also in the case of No. 4, although the bulk density slightly increased when the molding pressure was increased, the physical properties hardly changed.
【００２３】実施例２ 実施例１と同じ活性炭、パルプ及びポリアクリロニトリ
ル系繊維の割合をそれぞれ４０重量％、３０重量％及び
３０重量％として抄紙し、実施例１と同一寸法及び重さ
のシートを得た。続いて実施例１と同様に加熱加圧成形
して厚さ０．８５ｍｍの積層板を得た。この積層板を実
施例１と同様に焼成し、厚さ０．８８ｍｍの分極性電極
を得た。この物性を測定したところ嵩密度０．４５ｇ／
ｃｍ3 、曲げ強度８０Ｋｇ／ｃｍ2 及び電気比抵抗０．
０１Ωｃｍであった。Example 2 The same activated carbon, pulp and polyacrylonitrile fiber as in Example 1 were used in a ratio of 40% by weight, 30% by weight and 30% by weight, respectively, to make a sheet, and a sheet having the same dimensions and weight as in Example 1 was obtained. Obtained. Subsequently, it was heated and pressed in the same manner as in Example 1 to obtain a laminate having a thickness of 0.85 mm. This laminated plate was fired in the same manner as in Example 1 to obtain a polarizable electrode having a thickness of 0.88 mm. When the physical properties were measured, the bulk density was 0.45 g /
cm 3 , bending strength 80 Kg / cm 2 and electrical resistivity 0.
It was 01 Ωcm.
【００２４】実施例３ 実施例１と同じ活性炭、パルプ及びアクリアクリロニト
リル系繊維の割合を３０重量％、３０重量％及び４０重
量％として、抄紙した。実施例１と同様に加熱加圧成形
して厚さ０．８４ｍｍの積層板を得た。この積層板を実
施例１と同様に焼成し、厚さ０．７３ｍｍの分極性電極
を得た。この物性を測定したところ嵩密度０．４８ｇ／
ｃｍ3 、曲げ強度９０Ｋｇ／ｃｍ2 及び電気比抵抗０．
００９Ωｃｍであった。Example 3 Papermaking was conducted with the same proportions of activated carbon, pulp and acrylacrylonitrile fibers as in Example 1, but 30% by weight, 30% by weight and 40% by weight. It was heated and pressed in the same manner as in Example 1 to obtain a laminate having a thickness of 0.84 mm. This laminate was fired in the same manner as in Example 1 to obtain a 0.73 mm-thick polarizable electrode. When the physical properties were measured, the bulk density was 0.48 g /
cm 3 , bending strength 90 Kg / cm 2 and electrical resistivity 0.
009 Ωcm.
【００２５】実施例４ 実施例１と同様な割合で抄紙し、加熱加圧成形の圧力を
６Ｋｇ／ｃｍ2 で成形し、焼成したところ嵩密度０．５
８ｇ／ｃｍ3 が得られた。そのほかの物性については、
実施例１とほぼ同様であった。Example 4 A paper was made at the same ratio as in Example 1, molded at a pressure of 6 kg / cm 2 under heat and pressure, and calcined.
8 g / cm 3 was obtained. For other physical properties,
It was almost the same as Example 1.
【００２６】[0026]
【発明の効果】以上説明したように、本発明法によると
樹脂の浸漬工程を行わずに、安定した低電気比抵抗の分
極性電極が容易に得られ、これを電気二重層キャパシタ
等に使用することにより電気比抵抗の低減及び信頼性の
向上を図ることができる。As described above, according to the method of the present invention, a stable low electric resistivity polarizable electrode can be easily obtained without performing the resin immersion step, and this is used for an electric double layer capacitor or the like. By doing so, it is possible to reduce the electric resistivity and improve the reliability.
【図１】分極性電極の概念図である。FIG. 1 is a conceptual diagram of a polarizable electrode.
１ 分極性電極 ２ セパレータ ３ 封止材 ４ 導電性シート 1 minute polarity electrode 2 separator 3 sealing material 4 conductive sheet
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−190318（ＪＰ，Ａ) 特開 昭63−226019（ＪＰ，Ａ) 特開 平３−85711（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01G 9/058 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-190318 (JP, A) JP-A-63-226019 (JP, A) JP-A-3-85711 (JP, A) (58) Field (Int.Cl. 7 , DB name) H01G 9/058
Claims (4)
リロニトリル系繊維を抄紙してシートとした後焼成する
ことを特徴とする分極性電極の製造法。1. A method for producing a polarizable electrode, comprising activating carbon, cellulosic fiber, and polyacrylonitrile-based fiber to form a sheet, followed by firing.
びポリアクリロニトリル系繊維を抄紙してシートとした
後焼成することを特徴とする分極性電極の製造法。2. A method for producing a polarizable electrode, comprising: activating activated carbon, cellulosic fibers, graphite fine powder, and polyacrylonitrile-based fibers to form a sheet and firing the sheet.
・加圧成形することを特徴とする請求項１又は２記載の
分極性電極の製造法。3. The method for producing a polarizable electrode according to claim 1, wherein a plurality of the sheets are heated and pressed before the firing.
粉及びポリアクリロニトリル系繊維の使用割合がそれぞ
れ３０〜４８重量％、３０〜４８重量％、２〜１０重量
％及び２０〜４０重量％であることを特徴とする請求項
２記載の分極性電極の製造法。4. The use ratio of said activated carbon, cellulosic fiber, graphite fine powder and polyacrylonitrile-based fiber is 30 to 48% by weight, 30 to 48% by weight, 2 to 10% by weight and 20 to 40% by weight, respectively. Claims characterized by the following:
3. The method for producing a polarizable electrode according to item 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9020492A JP3152990B2 (en) | 1992-03-16 | 1992-03-16 | Manufacturing method of polarized electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9020492A JP3152990B2 (en) | 1992-03-16 | 1992-03-16 | Manufacturing method of polarized electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05258997A JPH05258997A (en) | 1993-10-08 |
| JP3152990B2 true JP3152990B2 (en) | 2001-04-03 |
Family
ID=13991963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9020492A Expired - Fee Related JP3152990B2 (en) | 1992-03-16 | 1992-03-16 | Manufacturing method of polarized electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3152990B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006332625A (en) * | 2005-04-25 | 2006-12-07 | Power System:Kk | Positive electrode for electric double layer capacitor and manufacturing method thereof |
| CN105655153B (en) * | 2016-01-06 | 2018-02-16 | 东北师范大学 | A kind of preparation method of self-supporting capacitor electrode material |
-
1992
- 1992-03-16 JP JP9020492A patent/JP3152990B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05258997A (en) | 1993-10-08 |
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