JP3332980B2 - Manufacturing method of polarizable electrode material - Google Patents
Manufacturing method of polarizable electrode materialInfo
- Publication number
- JP3332980B2 JP3332980B2 JP5250593A JP5250593A JP3332980B2 JP 3332980 B2 JP3332980 B2 JP 3332980B2 JP 5250593 A JP5250593 A JP 5250593A JP 5250593 A JP5250593 A JP 5250593A JP 3332980 B2 JP3332980 B2 JP 3332980B2
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- electrode
- activated carbon
- carbon powder
- resin
- 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方法
に関するものであり、更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分
極性電極材の製造方法に関する。この電極は電気二重層
コンデンサ、二次電池、エレクトロクロミックディスプ
レイなどに使用されるものである。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 a method for producing a polarizable electrode material using an electric double layer formed at an interface between an electrode surface and an electrolyte. It relates to a manufacturing method. This electrode is used for an electric double layer capacitor, a secondary battery, an electrochromic display, and the like.
【０００２】[0002]
【従来の技術】電気二重層コンデンサを例にとり、その
基本構成を図２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イオン透
過性につくられたセパレータ２で仕切られている。そし
て分極性電極１の周辺は封止材３で密閉され、また分極
性電極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。2. Description of the Related Art The basic configuration of an electric double layer capacitor is shown in FIG. In the figure, reference numeral 1 denotes a polarizable electrode containing an electrolytic solution, and the center of the electrode is separated by a separator 2 made of an electric insulating material and made permeable to ions. The periphery of the polarizable electrode 1 is sealed with a sealing material 3, and a conductive sheet 4 serving as a collecting electrode is arranged outside the polarizable electrode 1.
【０００３】分極性電極（以下単に「電極」と云う）は
静電容量を大きくするために表面積が大きい必要がある
ことから活性炭粉末や活性炭素繊維などが多く使用され
ている。電極の形態としては（１）硫酸水溶液等の電解
液で活性炭素粉末をペースト状としたペースト状電極
（特開昭６２−１３０５０６、同６３−２４４６０９、
特開平２−１７４２１０）、（２）多孔質の炭素成形体
に電解液を含浸して使用するもので、この炭素成形体と
してフェノール樹脂成形体を発泡、炭化、賦活した多孔
質電極（特開平２−２９７９１５）、メソピッチを賦活
し、成形、炭化した多孔質電極（特開平２−１８５００
８）、（３）活性炭素繊維の織布等を用い、電解液を含
浸する炭素繊維電極（特開昭６４−８２５１４）などが
ある。Activated carbon powder, activated carbon fiber, and the like are often used for a polarizable electrode (hereinafter simply referred to as an "electrode") because it requires a large surface area in order to increase the capacitance. Examples of the form of the electrode include (1) a paste-like electrode in which activated carbon powder is made into a paste with an electrolytic solution such as an aqueous solution of sulfuric acid (JP-A-62-130506 and JP-A-63-244609;
JP-A-2-174210), (2) A porous carbon molded article which is used by impregnating an electrolytic solution with a porous electrode obtained by foaming, carbonizing and activating a phenol resin molded article as the carbon molded article. 2-297915), a meso pitch activated, molded and carbonized porous electrode (JP-A-2-18500)
8), (3) A carbon fiber electrode using a woven fabric of activated carbon fibers or the like and impregnating with an electrolytic solution (JP-A-64-82514).
【０００４】[0004]
【発明が解決しようとする課題】電極は静電容量を大き
くするため表面積が大きいことの他に、電気抵抗が小さ
いこと、耐食性がよいこと、耐電圧が大きいことなどが
要求される。前記したペースト状電極（１）では活性炭
粉末の大きな比表面積がそのまま電極の表面積に生かさ
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。成形体に
した多孔質電極（２）は炭素が骨格を成して連続的に連
なっているので、電気抵抗は低いが、成形体の賦活で表
面積を大きくすることが難しい。また活性炭素繊維はそ
れ自体が高価であり、これを使用する電極（３）はコス
ト高となるばかりでなく、電気抵抗や表面積についても
十分なものではない。したがって本発明は表面積が大き
く従って静電容量を大きくでき、また電気抵抗、耐食性
や強度に優れ、さらに製造、取扱いも容易な電極を製造
する方法を提供することを目的とする。In order to increase the capacitance, the electrode is required not only to have a large surface area but also to have low electric resistance, good corrosion resistance, high withstand voltage and the like. The above-mentioned paste-like electrode (1) has the advantage that the large specific surface area of the activated carbon powder is utilized as it is in the surface area of the electrode as it is, but has a large electric resistance, and the assembly work of the capacitor is troublesome. The porous electrode (2) formed into a compact has a low electrical resistance since carbon forms a skeleton and is continuously connected, but it is difficult to increase the surface area by activating the compact. Activated carbon fiber is expensive in itself, and the electrode (3) using it is not only expensive but also has insufficient electric resistance and surface area. Accordingly, an object of the present invention is to provide a method for producing an electrode which has a large surface area and therefore a large capacitance, is excellent in electric resistance, corrosion resistance and strength, and is easy to produce and handle.
【０００５】[0005]
【課題を解決するための手段】本発明は上記の目的を達
成するため案出されたものであり、その要旨は活性炭粉
末とパルプ等のセルロース質繊維とフェノール樹脂とか
ら主としてなるシートを硬化、焼成後、水蒸気賦活する
ことを特徴とする分極性電極材の製造法である。SUMMARY OF THE INVENTION The present invention has been devised to achieve the above object, and its gist is to cure a sheet mainly composed of activated carbon powder, cellulosic fibers such as pulp, and a phenol resin. This is a method for producing a polarizable electrode material, characterized by activating steam after firing.
【０００６】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
て使用することが好ましい。As the activated carbon, ordinary activated carbon such as carbonized and activated charcoal, sawdust, coal, phenolic resin and the like is used. It is preferable to use this activated carbon after being ground to about 50 μm or less.
【０００７】 セルロース質繊維としては通常紙に使用
されるパルプが好適であるが、その他レーヨン、綿等セ
ルロース繊維を短くしたものが使用できる。繊維は活性
炭粉末、フェノール樹脂とともにシートにされるが、そ
の際抄紙法が製造上容易であり、そのまま抄紙される繊
維の長さは５ｍｍ以下が好ましい。フェノール樹脂はレ
ゾ−ル型のものが好ましい。未硬化液状のフェノール樹
脂はセルロール質繊維シートに均一含浸が可能であり、
この方法が最も有利な樹脂含浸法である。この際含浸を
容易にするためにフェノール樹脂にアセトン等の有機溶
剤を加え粘度を調整することもできる。[0007] As the cellulosic fiber, pulp usually used for paper is suitable, but other shortened cellulose fibers such as rayon and cotton can be used. The fiber is made into a sheet together with activated carbon powder and phenolic resin. At that time, the papermaking method is easy in production, and the length of the fiber to be made as it is is preferably 5 mm or less. The phenol resin is preferably of the resol type. Uncured liquid phenolic resin can be uniformly impregnated into the cellulosic fiber sheet,
This method is the most advantageous resin impregnation method. At this time, in order to facilitate the impregnation, an organic solvent such as acetone can be added to the phenol resin to adjust the viscosity.
【０００８】本発明に係る電極の出発材料であるシート
の成分としての活性炭粉末は電極の表面積を大きくする
ため３０重量％（以下％は「重量」％を表わす）以上が
好ましい。上限は他の成分に量を確保する制約から５０
％以下が好ましい。[0008] The activated carbon powder as a component of the sheet as a starting material of the electrode according to the present invention is preferably at least 30% by weight (hereinafter,% represents "% by weight") in order to increase the surface area of the electrode. The upper limit is 50 due to restrictions on the amount of other components.
% Or less is preferable.
【０００９】セルロース質繊維は抄紙を容易とし、シー
ト及び電極の強度を保つため３０％以上が好ましく、他
の成分を含有させる制約から７０％位までとするのがよ
い。The cellulosic fiber is preferably at least 30% in order to facilitate papermaking and maintain the strength of the sheet and the electrode, and is preferably up to about 70% due to the restriction of containing other components.
【００１０】フェノール樹脂は、シート及び電極の強度
を保つため１０％以上が好ましく、また多すぎると活性
炭粉末の細孔を塞ぐので３０％以下がよい。この場合の
樹脂の量は溶媒、水分等を除く固形分換算である。The content of the phenolic resin is preferably at least 10% in order to maintain the strength of the sheet and the electrode. If the amount is too large, the pores of the activated carbon powder are blocked, so the content is preferably at most 30%. The amount of the resin in this case is a solid content excluding the solvent, water and the like.
【００１１】シートは以上の成分を主成分とするが、こ
れにポリアクリロニトリル、ポリビニルアルコール等の
繊維や導電性をよくするため黒鉛微粉等を総計２０％以
下程度加えることもできる。The sheet contains the above components as main components, and fibers such as polyacrylonitrile and polyvinyl alcohol and graphite fine powder or the like for improving conductivity can be added to the sheet in a total amount of about 20% or less.
【００１２】抄紙したセルロース繊維にフェノール樹脂
（以下「樹脂」と略称する）を含浸する場合、活性炭粉
末は抄紙の際パルプ等に含有させるのが好ましいが、特
に細粉活性炭粉末の場合はフェノール樹脂に混合し、樹
脂の含浸と同時にシートに含有させることも可能であ
る。また濾紙のように市販されている紙を用いこれに活
性炭粉末及び樹脂を含有させてもよく、本発明における
シートにはこのような紙も含まれる。樹脂の含浸シート
を樹脂の溶液中に浸漬して行い、次いで引上げ、必要に
よりロール間を通すなどにより含浸量を調整する。また
含浸量は溶剤により樹脂固形分の濃度を変えることによ
っても調整することができる。When impregnating phenolic resin (hereinafter abbreviated as "resin") into the paper-made cellulose fiber, the activated carbon powder is preferably contained in pulp or the like at the time of paper-making. And it can be contained in the sheet simultaneously with the impregnation of the resin. Further, a commercially available paper such as a filter paper may be used, and the activated carbon powder and the resin may be contained therein. The sheet in the present invention includes such a paper. The impregnated sheet of the resin is immersed in a solution of the resin, then pulled up, and if necessary, the amount of impregnation is adjusted by passing between rolls. The amount of impregnation can also be adjusted by changing the concentration of the resin solid content with a solvent.
【００１３】樹脂及び活性炭粉末を含むシートは次に好
ましくは１２０〜１８０℃程度で乾燥し、プリプレグシ
ートとする。プリプレグシートは厚い場合はそのまま硬
化、焼成し、製品とすることもできるが、薄いシートを
複数枚積層して圧着し、硬化、焼成することが望まし
い。シートが厚いと抄紙しにくく、また樹脂や活性炭粉
末を均一に含浸させるのが難しいので０．１〜１ｍｍの
厚さが好ましい。Next, the sheet containing the resin and the activated carbon powder is dried preferably at about 120 to 180 ° C. to obtain a prepreg sheet. When the prepreg sheet is thick, it can be cured and fired as it is to produce a product. However, it is desirable to laminate a plurality of thin sheets, press-bond, cure and fire. If the sheet is thick, it is difficult to make paper, and it is difficult to uniformly impregnate the resin or activated carbon powder, so the thickness is preferably 0.1 to 1 mm.
【００１４】 プリプレグシートは好ましくは１５０〜
２００℃程度である樹脂の硬化温度に加熱し、硬化させ
る。この際黒鉛板等でプリプレグシートを挟んで０．５
〜１０ｋｇ／ｃｍ2程度に圧縮すると、大きな気孔の発
生が防止され、また積層の場合は各シート間の密着性が
良くなり、電極材の密着度が大きくなることにより表面
積が大きくなるので好ましい性能をもつ電極材を作るこ
とができる。The prepreg sheet is preferably 150 to
The resin is heated to a curing temperature of about 200 ° C. to be cured. At this time, the prepreg sheet is sandwiched between graphite plates, etc.
When compressed to about 10 kg / cm 2 , the generation of large pores is prevented, and in the case of lamination, the adhesion between the sheets is improved, and the surface area is increased by increasing the degree of adhesion of the electrode material. Electrode material having the following characteristics.
【００１５】硬化したシートは次に不活性雰囲気下で焼
成する。焼成はシートが反らないよう例えば黒鉛板の間
に挟んで行なうのがよい。この際加圧して気孔率を調整
することもできる。焼成の昇温は早すぎると樹脂や繊維
の分解、揮散が急激となり、大きな気孔が発生するの
で、８００℃程度までを２０〜１００時間かけるのが好
ましい。焼成の最終温度は特に制限なく、通常の炭素の
黒鉛化と同様３０００℃近い温度まで可能である。特に
高温で焼成すると不純物が揮散除去され、電極として好
ましい。The cured sheet is then fired under an inert atmosphere. The firing is preferably performed, for example, by sandwiching the sheet between graphite plates so as not to warp. At this time, the porosity can be adjusted by applying pressure. If the temperature of the firing is too high, the decomposition and volatilization of the resin and the fiber become rapid, and large pores are generated. Therefore, it is preferable to apply the temperature up to about 800 ° C. for 20 to 100 hours. The final temperature of the calcination is not particularly limited, and can be a temperature close to 3000 ° C. as in the case of normal graphitization of carbon. In particular, when firing at a high temperature, impurities are volatilized and removed, which is preferable as an electrode.
【００１６】焼成したシートは次に賦活処理する。賦活
方法は紫外線照射賦活、グロー放電賦活フッ素賦活、水
蒸気賦活等種々方法があるが、水蒸気賦活のみが好まし
い電極特性を示す方法である。水蒸気賦活の条件は温
度：７５０〜１０００℃、時間：２０分〜１８０分が好
ましい。温度が７５０℃以下時間が２０分以下の場合は
処理時間が長過ぎて実用的でなく、温度が１０００℃以
上時間が１８０分以上の場合は不均一性及び強度、電気
比抵抗等の物性低下が発現する。The fired sheet is then activated. There are various activation methods, such as UV irradiation activation, glow discharge activation fluorine activation, and water vapor activation, but only water vapor activation is a method showing preferable electrode characteristics. The conditions for steam activation are preferably as follows: temperature: 750 to 1000 ° C., time: 20 minutes to 180 minutes. When the temperature is 750 ° C. or less and the time is 20 minutes or less, the treatment time is too long to be practical, and when the temperature is 1000 ° C. or more and the time is 180 minutes or more, the physical properties such as non-uniformity, strength, and electrical resistivity decrease. Is expressed.
【００１７】[0017]
【作用】本発明のシートには、活性炭粉末がフェノール
樹脂に混合されるが、セルロース粉末の量だけ樹脂が少
なくなるので、活性炭粉末の細孔が樹脂で塞がれること
が少ない。更に、焼成後水蒸気賦活することにより新た
に細孔が造成され、従って表面積の大きな電極材を容易
に製作することができる。セルロース質繊維は炭化前に
シートを補強することによりその取扱い性を高める。セ
ルロース質繊維は炭化過程で一部分解するが、かなりの
部分は炭化した繊維の形として残る。繊維の一部分解揮
散に伴って微細な気孔が発生し、表面積の増加につなが
る。また炭化した繊維は強度の向上にも役立つ。以上の
ように各原料成分の炭化により得られた炭素のうち特定
の炭素が水蒸気により選択的に賦活されると考えられる
が、詳細は明らかでない。In the sheet of the present invention, the activated carbon powder is mixed with the phenol resin. However, since the amount of the resin is reduced by the amount of the cellulose powder, the pores of the activated carbon powder are less likely to be blocked by the resin. Further, by activating the steam after firing, new pores are formed, and therefore, an electrode material having a large surface area can be easily manufactured. Cellulosic fibers enhance their handling by reinforcing the sheet prior to carbonization. Cellulosic fibers are partially degraded during the carbonization process, but a significant portion remains in the form of carbonized fibers. Fine pores are generated along with partial decomposition and volatilization of the fiber, which leads to an increase in surface area. The carbonized fibers also help improve strength. As described above, it is considered that specific carbon among carbons obtained by carbonization of each raw material component is selectively activated by steam, but the details are not clear.
【００１８】[0018]
【実施例】叩解した木材パルプ（カナディアンフリーネ
ス）４０％、ＰＶＡ繊維（クラレ（株）製、ＶＰＢ１０
５、１デニール、長さ４mm）１０％、活性炭粉末（武田
薬品工業（株）製、ＬＰＫ−４３６、平均粒度８μｍ）
５０％を混合したスラリー水溶液を丸網抄紙機（（株）
東洋精機製作所製、ＴＳＳ式シートマシン）により抄紙
し、混抄シートを得た。シートは厚さ０．２５mmで重量
は１１０g であった。Example: Beated wood pulp (Canadian freeness) 40%, PVA fiber (Kuraray Co., Ltd., VPB10)
5, 1 denier, length 4 mm) 10%, activated carbon powder (LPK-436, manufactured by Takeda Pharmaceutical Co., Ltd., average particle size 8 μm)
A 50% slurry aqueous solution was mixed with a circular mesh paper machine (Ltd.)
Papermaking was performed using a TSS sheet machine (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a mixed sheet. The sheet was 0.25 mm thick and weighed 110 g.
【００１９】 このシートをフェノール樹脂（昭和高分
子（株）製、ＢＲＬ−１２０Ｚ）に浸漬後、１３０℃で
１分間乾燥し、プリプレグシートとした。樹脂含浸量
（固形分）２４％であった。これを６枚積層し、黒鉛板
に挟み、５ｋｇ／ｃｍ2で加圧して２６０℃、１０分間
加熱硬化した。生成したシートは肉眼で観察したところ
一体に接合していた。これを４枚重ねて黒鉛板に挟み、
非酸化性雰囲気下、４日間で１０００℃に昇温した。次
に自然放冷後黒鉛板から取り出した炭素板４枚は接着す
ることなく、独立し、夫々良好な外観を有していた。The sheet was immersed in a phenol resin (BRL-120Z, manufactured by Showa Polymer Co., Ltd.) and dried at 130 ° C. for 1 minute to obtain a prepreg sheet. The resin impregnation amount (solid content) was 24%. Six of these were laminated, sandwiched between graphite plates, pressurized at 5 kg / cm 2 , and heat-cured at 260 ° C. for 10 minutes. When the resulting sheet was observed with the naked eye, it was found that the sheet was integrally joined. Four of these are stacked and sandwiched between graphite plates,
The temperature was raised to 1000 ° C. for 4 days in a non-oxidizing atmosphere. Next, the four carbon plates taken out of the graphite plate after natural cooling were independent and had good appearances without bonding.
【００２０】 Ｎ2ガスでバブリングした４０℃飽和水
蒸気を８５０℃に温度調節された炉内に導入し、上記４
枚のうち２枚を２０分間、水蒸気賦活処理した。残りの
２枚の焼成板は比較材である。以上の炭素板の物性を表
１に示す。The saturated steam at 40 ° C. bubbled with N 2 gas is introduced into a furnace temperature-controlled at 850 ° C.
Two of the sheets were subjected to a steam activation treatment for 20 minutes. The remaining two fired plates are comparative materials. Table 1 shows the physical properties of the carbon plate described above.
【００２１】[0021]
【表１】 [Table 1]
【００２２】 比表面積：ＢＥＴ法、Ｎ2ガス 電気比抵抗：四端子法、電流１Ａｍｐ 曲げ強さ：３点曲げ法、荷重速度０．５mm／分 圧縮強度：１０mm角サンプルを５枚積層し、上下より全
体を 加圧し破壊時の強度を測定。荷重速度０．５ｍｍ／分 腐食電流：１００％硫酸中測定。水素標準電極使用 灰分：８５０℃、５時間、空気中で燃焼し残渣を測定Specific surface area: BET method, N 2 gas Electric resistivity: Four-terminal method, current: 1 Amp Flexural strength: 3-point bending method, load speed: 0.5 mm / min Compressive strength: 5 samples of 10 mm square are laminated, Measure the strength at the time of destruction by pressing the whole from above and below. Load speed 0.5 mm / min Corrosion current: measured in 100% sulfuric acid. Using a standard hydrogen electrode Ash content: Combustion in air at 850 ° C for 5 hours and measurement of residue
【００２３】コンデンサとしての性能を調べるため、図
１に示すように基本構成（１、２、４）のものを５個重
ね、上端及び下端にＡｌ板５を配し、導電端子とした。
ここで炭素板は直径１８mm、厚さ０．４mmの円形板に加
工し、これに４０％硫酸を含浸し電極１としたものであ
る。集電極となる導電シート４は緻密なガラス状炭素
（昭和電工（株）製、ＳＧカーボン、厚さ０．４mm）の
直径２３mmの円板に加工し使用した。電極の中央部を仕
切るイオン透過性で電気絶縁材からなるシート２にはポ
リエチレン製不織布（日本バイリーン（株）製）で空孔
率１８％（面積比）のものを直径２０mm、厚み０．１１
mmにて使用した。In order to examine the performance as a capacitor, five basic components (1, 2, 4) were stacked as shown in FIG. 1, and Al plates 5 were disposed at the upper and lower ends to serve as conductive terminals.
Here, the carbon plate was processed into a circular plate having a diameter of 18 mm and a thickness of 0.4 mm, which was impregnated with 40% sulfuric acid to form an electrode 1. The conductive sheet 4 serving as a collecting electrode was processed into a disk having a diameter of 23 mm made of dense glassy carbon (SG carbon, manufactured by Showa Denko KK) and having a thickness of 0.4 mm. A sheet 2 made of polyethylene non-woven fabric (manufactured by Nippon Vilene Co., Ltd.) having a porosity of 18% (area ratio) having a diameter of 20 mm and a thickness of 0.11 is used as a sheet 2 made of an electrically insulating material that partitions the central portion of the electrode.
mm.
【００２４】電極の周囲の封止はテフロン製パッキンシ
ート３（ダイキン工業（株）製、ＰＦＡ）を外径２３m
m、内径１８mmに加工して使用した。The outer periphery of the electrode is sealed with a packing sheet 3 made of Teflon (PFA, manufactured by Daikin Industries, Ltd.) having an outer diameter of 23 m.
m, and processed to an inner diameter of 18 mm.
【００２５】このようにして組み立てた電気二重層コン
デンサの上下にベークライト板６を配置に、上下より２
０kg／cm2 の荷重をかけた状態で性能を調べた。電極１
に含浸する硫酸の代わりに、真空下でプロピレンカーボ
ネイト（Ｐ．Ｃ）を含浸し電極１とし、その他の構成は
同様として性能を調べた。結果を表２に示す。The bakelite plates 6 are arranged above and below the electric double layer capacitor assembled in this manner,
The performance was examined under a load of 0 kg / cm2. Electrode 1
The electrode 1 was impregnated with propylene carbonate (PC) under vacuum in place of the sulfuric acid impregnated into the electrode 1, and the performance was examined in the same manner as for the other components. Table 2 shows the results.
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【発明の効果】本発明によれば、焼成後水蒸気賦活を施
すだけで比表面積が大きく静電容量の大きな電極が得ら
れる。またこの電極は電気抵抗が小さく、耐食性が大き
い。しかも炭化した繊維で補強されているので、強度が
大きいなど優れた効果を有している。そしてその製法は
抄紙法を利用しているのでシートは薄いにも拘らず取扱
容易であり、かつ生産性がよい。According to the present invention, an electrode having a large specific surface area and a large capacitance can be obtained only by activating steam after firing. This electrode has low electric resistance and high corrosion resistance. Moreover, since it is reinforced with carbonized fibers, it has excellent effects such as high strength. And since the manufacturing method uses a papermaking method, the sheet is easy to handle even though it is thin, and the productivity is good.
【図１】図２のコンデンサを積層した状態を示す断面図
である。FIG. 1 is a sectional view showing a state in which the capacitors of FIG. 2 are stacked.
【図２】本発明における電気二重層コンデンサの基本構
成を示す断面図である。FIG. 2 is a sectional view showing a basic configuration of an electric double layer capacitor according to the present invention.
１ 電解液を含浸した電極 ２ 多孔性の電気絶縁性セパレータ ３ 封止材 ４ 導電シート ５ アルミニウム板 ６ ベークライト板 DESCRIPTION OF SYMBOLS 1 Electrolyte impregnated electrode 2 Porous electrically insulating separator 3 Sealing material 4 Conductive sheet 5 Aluminum plate 6 Bakelite plate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 笹林 敬吾 長野県大町市大字大町6850 昭和電工株 式会社大町工場内 (72)発明者 篠原 久臣 長野県長野市稲里町中氷鉋1080 川中島 寮内 (72)発明者 小林 茂 長野県長野市妻科町151−１ 審査官 竹井 文雄 (56)参考文献 特開 平４−288361（ＪＰ，Ａ) 特開 昭62−292612（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01G 9/058 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keigo Sasabayashi 6850 Omachi Omachi, Omachi City, Nagano Prefecture Showa Denko KK Omachi Plant (72) Inventor Hisaomi Shinohara 1080 Nakai Plane, Inari Town, Nagano City, Nagano Prefecture Dormitory Kawanakajima ( 72) Inventor Shigeru Kobayashi Examiner, 151-1, Tsushina-machi, Nagano City, Nagano Prefecture Fumio Takei (56) References JP-A-4-288361 (JP, A) JP-A-62-292612 (JP, A) (58) Field surveyed (Int.Cl. 7 , DB name) H01G 9/058
Claims (3)
ール樹脂とから主としてなるシートを硬化、焼成後、水
蒸気賦活することを特徴とする分極性電極材の製造法。1. A method for producing a polarizable electrode material, comprising curing a sheet mainly composed of activated carbon powder, cellulosic fiber, and phenol resin, firing the sheet, and then activating steam.
量％，セルロース質繊維を３０〜７０重量％、フェノー
ル樹脂を固形分として１０〜３０重量％とする請求項１
記載の分極性電極材の製造法。2. The sheet according to claim 1, wherein the activated carbon powder is 30 to 50% by weight, the cellulosic fiber is 30 to 70% by weight, and the phenolic resin is 10 to 30% by weight as a solid content.
A method for producing the polarizable electrode material according to the above.
着し、硬化焼成してなる請求項１又は２記載の分極性電
極材の製造法。3. The method for producing a polarizable electrode material according to claim 1, wherein a plurality of the laminated sheets are pressure-bonded and cured and fired.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5250593A JP3332980B2 (en) | 1993-03-12 | 1993-03-12 | Manufacturing method of polarizable electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5250593A JP3332980B2 (en) | 1993-03-12 | 1993-03-12 | Manufacturing method of polarizable electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06267794A JPH06267794A (en) | 1994-09-22 |
| JP3332980B2 true JP3332980B2 (en) | 2002-10-07 |
Family
ID=12916593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5250593A Expired - Fee Related JP3332980B2 (en) | 1993-03-12 | 1993-03-12 | Manufacturing method of polarizable electrode material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3332980B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3527789B2 (en) * | 1994-12-29 | 2004-05-17 | 旭化成ケミカルズ株式会社 | Electrode for electric double layer capacitor and its manufacturing method |
| DE69735858T2 (en) * | 1996-12-12 | 2006-12-28 | Corning Inc. | ACTIVE CARBON ELECTRODES FOR ELECTRIC DOUBLE-LAYER CAPACITORS |
| JP4035275B2 (en) * | 2000-04-04 | 2008-01-16 | 関西熱化学株式会社 | Method for producing polarizable electrode for electric double layer capacitor |
| EP1426334A4 (en) | 2001-09-11 | 2009-07-29 | Showa Denko Kk | Activated carbon, method for production thereof and use thereof |
| KR101135417B1 (en) | 2004-08-18 | 2012-04-17 | 제이엑스 닛코닛세키에너지주식회사 | Raw material carbon composition for carbon material for electrode of electric double layer capacitor |
| US7933114B2 (en) * | 2007-08-31 | 2011-04-26 | Corning Incorporated | Composite carbon electrodes useful in electric double layer capacitors and capacitive deionization and methods of making the same |
| TWI479717B (en) * | 2013-11-28 | 2015-04-01 | Csb Battery Co Ltd | Lead-acid capacitor batteries and the preparation of lead-acid battery method |
| WO2016002930A1 (en) * | 2014-07-04 | 2016-01-07 | 株式会社佐藤工務所 | Method for producing polarizable electrode for electric double layer capacitors, polarizable electrode for electric double layer capacitors, and electric double layer capacitor |
| JP6558725B2 (en) * | 2014-07-04 | 2019-08-14 | 島根県 | Method for producing polarizable electrode for electric double layer capacitor and electric double layer capacitor |
-
1993
- 1993-03-12 JP JP5250593A patent/JP3332980B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06267794A (en) | 1994-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3356534B2 (en) | Electrolyte holding plate and method for manufacturing the same | |
| JP3332980B2 (en) | Manufacturing method of polarizable electrode material | |
| JP2001040548A (en) | Active carbon fiber, active carbon fiber cloth and its production | |
| JPH11340103A (en) | Manufacture of activated carbon material | |
| JP3132098B2 (en) | Manufacturing method of polarizable electrode material | |
| JP3330235B2 (en) | Carbon material for electric double layer capacitor and method for producing the same | |
| JPH0258369B2 (en) | ||
| JP3159754B2 (en) | Electric double layer capacitor | |
| JPH0559867B2 (en) | ||
| JPH09278558A (en) | Carbonaceous porous body and its production | |
| JP2013063862A (en) | Porous carbon base material and capacitor using the same | |
| JPH0660884A (en) | Manufacture of porous carbon sheet for phosphoric acid fuel cell | |
| JP2820492B2 (en) | Carbon plate and method for producing the same | |
| JP2013043785A (en) | Porous carbon substrate, and capacitor using the same | |
| JPH06671B2 (en) | Highly graphitized porous carbon fiber sheet and method for producing the same | |
| JP2013239681A (en) | Electrode and manufacturing method of the same | |
| JPH0360478A (en) | Production of porous carbon sheet | |
| JP3152990B2 (en) | Manufacturing method of polarized electrode | |
| JPH02184510A (en) | Production of carbon plate | |
| JPH07220732A (en) | Manufacture of porous carbon plate for phosphoric acid fuel cell | |
| JP4080095B2 (en) | Manufacturing method of thick porous carbon material | |
| JP2006169058A (en) | Method of manufacturing porous vitreous carbon sheet and polarizing electrode material for electric double layer capacitor comprising the sheet | |
| JP2000143225A (en) | Activatated carbon material and its production | |
| JPH05155672A (en) | Porous carbon plate and its production | |
| JPH07135127A (en) | Electric double layer capacitor and its manufacture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |