JPH0851045A - Electric double-layer capacitor carbon material - Google Patents
Electric double-layer capacitor carbon materialInfo
- Publication number
- JPH0851045A JPH0851045A JP6204409A JP20440994A JPH0851045A JP H0851045 A JPH0851045 A JP H0851045A JP 6204409 A JP6204409 A JP 6204409A JP 20440994 A JP20440994 A JP 20440994A JP H0851045 A JPH0851045 A JP H0851045A
- Authority
- JP
- Japan
- Prior art keywords
- carbon material
- electric double
- layer capacitor
- paper
- carbon
- 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 OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- 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、静電容量の大きい電気
二重層キャパシタを製造するための炭素材に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon material for manufacturing an electric double layer capacitor having a large capacitance.
【０００２】[0002]
【従来の技術】電気二重層キャパシタ（コンデンサ）の
分極性電極材として、フェノール樹脂から取得した活性
炭を用いる方法が知られている。2. Description of the Related Art There is known a method of using activated carbon obtained from phenol resin as a polarizable electrode material of an electric double layer capacitor.
【０００３】たとえば、国際公開ＷＯ９１／１２２０３
号には、活性炭原料をアルカリ金属の水酸化物浴中７０
０℃未満で熱処理して得られる高静電容量炭素質素材に
つき開示がある。ここで活性炭原料としては、一般に活
性炭を製造するための炭素質原料であればいかなるもの
でもよく、その例としてはたとえばヤシ殻、木粉、石
炭、樹脂などがあげられるとしてあり、実施例では、ヤ
シ殻、ヤシ殻炭化物、木粉炭化物、石炭炭化物、フェノ
ール樹脂炭化物を用いている。アルカリ金属の水酸化物
としては、ナトリウム、カリウム、セシウム、リチウム
などの水酸化物が用いられるとしてあるが、実施例では
専ら水酸化ナトリウムを用いている。For example, International Publication WO91 / 12203
No. 70, activated carbon raw material in alkali metal hydroxide bath 70
There is a disclosure of a high capacitance carbonaceous material obtained by heat treatment at a temperature of less than 0 ° C. Here, the activated carbon raw material may be generally any carbonaceous raw material for producing activated carbon, and examples thereof include coconut shell, wood flour, coal, resin, etc., and in Examples, Coconut husks, coconut shell charcoal, wood powder charcoal, coal charcoal, and phenol resin charcoal are used. As the alkali metal hydroxide, hydroxides of sodium, potassium, cesium, lithium and the like are used, but sodium hydroxide is used exclusively in the examples.
【０００４】特開昭６３−２１３９１３号公報には、不
純物としてFe 500ppm 以下、Cr 50ppm以下、Ni 200ppm
以下、Na 50ppm以下、Ｋ 50ppm以下、Ｓ 1000ppm以下お
よびCl 100ppm 以下を含有する活性炭よりなる分極性電
極を用いた電気二重層コンデンサが示されている。活性
炭原料としては、石油コークス、石炭コークス、フェノ
ール系樹脂、ピッチ系樹脂、セルロース系樹脂、ヤシガ
ラなどが好適に用いられ、これらの中では石油コーク
ス、ヤシガラ、フェノール系樹脂の粉末が、比表面積が
大きく不純物含有量の少ない活性炭を得る上で特に好ま
しいとしてある。なお活性炭の製造法については、通常
の炭化・賦活方法によって得られるとあるのみである。In Japanese Patent Laid-Open No. 63-2113913, Fe 500 ppm or less, Cr 50 ppm or less, Ni 200 ppm as impurities.
Hereinafter, an electric double layer capacitor using a polarizable electrode made of activated carbon containing Na of 50 ppm or less, K of 50 ppm or less, S of 1000 ppm or less and Cl of 100 ppm or less is shown. As the activated carbon raw material, petroleum coke, coal coke, phenolic resin, pitch resin, cellulose resin, coconut husk, etc. are preferably used. It is said to be particularly preferable in order to obtain activated carbon having a large content of impurities. It should be noted that the method for producing activated carbon is only said to be obtained by a usual carbonization / activation method.
【０００５】特開昭６３−１８７６１４号公報には、比
表面積が１８００〜３５００m2/gであり、平均細孔径が
５〜１５オングストロームで、かつ全細孔容積に対する
内径２０オングストローム以上の細孔の占める容積の比
率が２０〜４０％である炭素系材料よりなる分極性電極
を用いた電気二重層コンデンサが示されている。ここで
炭素系材料としては、石油コークス、ヤシガラ、フェノ
ール系樹脂を炭化・賦活してなる活性炭が好適に用いら
れるとしてあり、実施例では活性炭原料として、ヤシガ
ラ、フェノール樹脂粉末、石油コークス、フェノール系
活性炭繊維を用いている。なお、活性炭の製造法につい
ては特に記載はない。Japanese Unexamined Patent Publication (Kokai) No. 63-187614 discloses that pores having a specific surface area of 1800 to 3500 m 2 / g, an average pore diameter of 5 to 15 angstroms, and an inner diameter of 20 angstroms or more with respect to the total pore volume. An electric double layer capacitor using a polarizable electrode made of a carbon-based material having a volume ratio of 20 to 40% is shown. Here, as the carbonaceous material, petroleum coke, coconut husk, activated carbon obtained by carbonizing and activating a phenolic resin is said to be preferably used, and in the examples, coconut husk, phenol resin powder, petroleum coke, phenolic as the activated carbon raw material. Activated carbon fiber is used. There is no particular description about the method for producing activated carbon.
【０００６】特公平５−５２０４９号公報（特開平１−
１０２９１４号公報）には、粉末活性炭と電解質溶液と
の混合物を両電極とする電気二重層コンデンサ用カーボ
ンペースト電極において、前記電解質が硫酸であり、前
記粉末活性炭がフェノール樹脂系であって、かつ前記粉
末活性炭の比表面積が１１００〜１５００m2/gの範囲に
あると共に前記粉末活性炭の平均粒子径が 1.5〜 4.0μ
m の範囲にあるカーボンペースト電極が示されている。
ただし、フェノール樹脂系粉末活性炭の製造法について
は特に記載はない。Japanese Patent Publication No. 5-52049 (JP-A-1-520)
No. 102914), in a carbon paste electrode for an electric double layer capacitor having a mixture of powdered activated carbon and an electrolyte solution as both electrodes, the electrolyte is sulfuric acid, the powdered activated carbon is a phenol resin system, and The specific surface area of the powdered activated carbon is in the range of 1100 to 1500 m 2 / g and the average particle diameter of the powdered activated carbon is 1.5 to 4.0 μm.
Carbon paste electrodes in the m range are shown.
However, there is no particular description about a method for producing the phenol resin-based powder activated carbon.
【０００７】特開平５−１２１２７１号公報には、活性
炭粉末と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、焼成した分極性電極材の製造法
が示されている。各成分の割合は、活性炭粉末が３０〜
５０重量％、セルロース質繊維が３０〜７０重量％、フ
ェノール樹脂が固形分として１０〜３０重量％である。
ここで活性炭は、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を５
０μm 以下程度に粉砕したものが用いられ、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、フェノール樹脂は、レゾール型のもの
が好ましく、未硬化液状で繊維シートに含浸するのが最
も有利な製法であるとしている。Japanese Unexamined Patent Publication (Kokai) No. 5-121271 discloses a method for producing a polarizable electrode material by curing and firing a sheet mainly composed of activated carbon powder, a cellulosic fiber and a phenol resin. Activated carbon powder is 30 ~
50% by weight, cellulosic fiber 30 to 70% by weight, and phenol resin as solid content 10 to 30% by weight.
Here, the activated carbon is a conventional activated carbon such as activated charcoal obtained by carbonizing coconut wood, sawdust, coal, phenol resin, etc.
Pulp that is crushed to a size of 0 μm or less is used. As the cellulosic fiber, pulp normally used for paper is suitable, but rayon, cotton, or other short cellulose fibers can be used. Phenolic resin is a resole. The mold is preferable, and the most advantageous manufacturing method is to impregnate a fibrous sheet with an uncured liquid.
【０００８】該公報においては、シートを製造する好ま
しい方法はパルプ等で紙をつくるのと同じように抄紙
し、これに未硬化で液状になっているフェノール樹脂を
含浸すること、活性炭粉末はパルプ等と一緒に抄紙の際
含有させるのが好ましいが、特に細粉の場合はフェノー
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こと、樹脂および活性炭粉末を含む
シートは次に１２０〜１８０℃程度で乾燥してプリプレ
グシートとすること、プリプレグシートは厚い場合はそ
のまま硬化、焼成して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
望ましいこと、プリプレグシートは１５０〜２００℃程
度に加熱し、硬化させること、この際黒鉛板等で挟んで
0.5〜１０kg/cm2程度に圧縮することが好ましいこと、
圧縮によって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よくなり、電極材の嵩密度
が大きくなることにより表面積が大きくなることなども
記載されている。In this publication, a preferred method for producing a sheet is to make paper in the same manner as paper is made from pulp or the like, and impregnate it with an uncured, liquid phenol resin. It is preferable to include it in the papermaking together with, etc., but especially in the case of fine powder, it is possible to mix it with a phenol resin and to include it in the sheet at the same time as impregnation of the resin, and the sheet containing the resin and activated carbon powder is Next, it can be dried at about 120 to 180 ° C. to form a prepreg sheet. When the prepreg sheet is thick, it can be cured and baked as it is to be a product, but a plurality of thin sheets are laminated, pressure-bonded and cured, It is desirable to bake, the prepreg sheet is heated to about 150 to 200 ° C. to be cured, and at this time, sandwiched by a graphite plate or the like.
It is preferable to compress to about 0.5 to 10 kg / cm 2 ,
It is also described that the generation of large pores is prevented by the compression, the adhesion between the sheets is improved in the case of lamination, and the bulk density of the electrode material is increased to increase the surface area.
【０００９】特開平５−１２９１５７号公報には、炭素
繊維、繊維状活性炭、微粉末活性炭、パルプおよび分散
剤にポリフロン（ポリテトラフルオロエチレンの商品
名）を加えて構成した抄紙を分極性電極として使用した
電気二重層コンデンサが示されている。実施例において
は、繊維状活性炭としてはフェノール樹脂繊維を出発原
料としたもの、微粉末活性炭としてはヤシがらを出発原
料としたものを用いている。In Japanese Patent Laid-Open No. 5-129157, carbon paper, fibrous activated carbon, finely powdered activated carbon, pulp, and a paper made by adding polyflon (trade name of polytetrafluoroethylene) to a dispersant are used as polarizable electrodes. The electric double layer capacitor used is shown. In the examples, phenolic resin fibers are used as a starting material for the fibrous activated carbon, and coconut shell is used as a starting material for the finely powdered activated carbon.
【００１０】[0010]
【発明が解決しようとする課題】しかしながら、フェノ
ール樹脂から取得した活性炭は、電気二重層キャパシタ
（コンデンサ）の分極性電極材として用いた場合、単位
容積当りの静電容量が低目であり、内部抵抗は高目であ
るなど、性能の点で改良の余地がある。However, activated carbon obtained from phenol resin has a low electrostatic capacity per unit volume when used as a polarizable electrode material of an electric double layer capacitor (capacitor), There is room for improvement in terms of performance, such as high resistance.
【００１１】本発明者らは、パルプ等のセルロースを炭
化・賦活した活性炭についても電気二重層キャパシタ用
炭素材としての性能を調べたが、上記フェノール樹脂か
ら取得した活性炭に比しむしろ劣る結果しか得られなか
った。The present inventors have also investigated the performance of activated carbon obtained by carbonizing and activating cellulose such as pulp, as a carbon material for electric double layer capacitors, but the result is rather inferior to the activated carbon obtained from the above phenol resin. I couldn't get it.
【００１２】また従来の活性炭は原料自体のコストが高
く、そのため製品活性炭の製造コストも高くなるという
問題点があった。Further, the conventional activated carbon has a problem in that the cost of the raw material itself is high, and therefore the production cost of the product activated carbon is also high.
【００１３】本発明は、このような背景下において、静
電容量が高い上、内部抵抗は低く、しかもコスト的にも
有利な電気二重層キャパシタ用炭素材を提供することを
目的とするものである。Under such circumstances, the present invention has an object to provide a carbon material for an electric double layer capacitor, which has a high electrostatic capacity, a low internal resistance and is advantageous in terms of cost. is there.
【００１４】[0014]
【課題を解決するための手段】本発明の電気二重層キャ
パシタ用炭素材は、紙基材フェノール樹脂積層板の使用
済み品を粉砕して炭化処理した後、アルカリ金属水酸化
物で賦活処理して得た炭素材からなることを特徴とする
ものである。The carbon material for an electric double layer capacitor of the present invention is obtained by crushing a used paper-based phenolic resin laminate to carbonize it and then activating it with an alkali metal hydroxide. It is characterized by comprising the carbon material obtained by the above.
【００１５】以下本発明を詳細に説明する。The present invention will be described in detail below.
【００１６】紙基材フェノール樹脂積層板は、紙基材に
フェノール樹脂を含浸したものを所定枚数積層して加熱
加圧することにより一体化したものである。The paper base phenolic resin laminate is a paper base impregnated with a phenol resin, which is integrated by laminating a predetermined number of sheets and heating and pressing.
【００１７】紙基材フェノール樹脂積層板は、プリント
配線板のドリル穴あけ加工用治具板として多量に使用さ
れている。紙基材フェノール樹脂積層板を治具板として
用いるとプリント配線板に対するドリルの喰いつきが良
く、高い孔精度が得られるからである。Paper-based phenolic resin laminates are widely used as jig plates for drilling holes in printed wiring boards. This is because when the paper-based phenolic resin laminated plate is used as the jig plate, the bite of the drill with respect to the printed wiring board is good and high hole accuracy is obtained.
【００１８】ここで紙基材としては、クラフト紙、リン
ター紙、再生紙などが用いられる。Here, as the paper substrate, kraft paper, linter paper, recycled paper, etc. are used.
【００１９】フェノール樹脂としては、フェノール類
（フェノール、クレゾール、アルキルフェノール等）、
アルデヒド類（ホルマリン、パラホルムアルデヒド
等）、可塑剤（桐油、脱水ヒマシ油、オイチシカ油、フ
ェノール化油等）を配合した変性フェノール樹脂が用い
られる。アルデヒド類の使用量は、フェノール類１モル
に対し 1.2〜 1.8モル程度とすることが多い。As the phenol resin, phenols (phenol, cresol, alkylphenol, etc.),
A modified phenol resin containing aldehydes (formalin, paraformaldehyde, etc.) and a plasticizer (tung oil, dehydrated castor oil, deer oil, phenolized oil, etc.) is used. The amount of aldehyde used is often 1.2 to 1.8 mol per mol of phenol.
【００２０】フェノール樹脂を紙基材に含有させるに
は、フェノール樹脂の溶液を塗布または含浸させる方
法、レジトール（Ｂステージ）やプレポリマーなどの反
応中間物をパルプに混抄して抄紙する方法などが採用さ
れる。In order to incorporate the phenol resin into the paper base material, a method of coating or impregnating a solution of the phenol resin, a method of mixing reaction intermediates such as resistol (B stage) and a prepolymer with pulp and making a paper, etc. Adopted.
【００２１】加熱加圧による一体化は、通常は多段式油
圧プレス機を用いて行われる。加熱加圧条件は、たとえ
ば、温度１３０〜１７０℃、圧力５０〜１００kgf/cm
2 、時間４０〜１２０分程度である。これにより、紙基
材フェノール樹脂積層板が製造される。The integration by heating and pressurization is usually performed by using a multistage hydraulic press machine. The heating and pressurizing conditions are, for example, a temperature of 130 to 170 ° C. and a pressure of 50 to 100 kgf / cm.
2. The time is about 40 to 120 minutes. This produces a paper-based phenolic resin laminate.
【００２２】紙基材フェノール樹脂積層板は、先に述べ
たようにプリント配線板用のドリル穴あけ加工用治具板
として多量に使用されているが、本発明においてはそれ
を炭素材の原料として用いる。この場合、その使用済み
品を原料として用いると、コスト的にも産業廃棄物の有
効利用の点でも有利となる。As described above, the paper-based phenolic resin laminated plate is used in large amounts as a jig plate for drilling holes for printed wiring boards. In the present invention, it is used as a raw material for carbon materials. To use. In this case, using the used product as a raw material is advantageous in terms of cost and effective utilization of industrial waste.
【００２３】すなわち、紙基材フェノール樹脂積層板を
適当な大きさに粉砕してから不活性ガス雰囲気下に炭化
処理した後、さらに不活性ガス雰囲気下にアルカリ金属
水酸化物で賦活処理することにより、目的の炭素材を得
る。That is, the paper-based phenolic resin laminate is crushed to an appropriate size, carbonized in an inert gas atmosphere, and then activated with an alkali metal hydroxide in an inert gas atmosphere. Thus, the target carbon material is obtained.
【００２４】炭化処理時の温度は５００〜９００℃、好
ましくは５５０〜８５０℃、さらに好ましくは６００〜
８００℃が適当であり、温度が余りに低いときあるいは
温度が余りに高いときには静電容量の大きな炭素材が得
られない。The temperature during the carbonization treatment is 500 to 900 ° C, preferably 550 to 850 ° C, more preferably 600 to 900 ° C.
800 ° C. is suitable, and when the temperature is too low or the temperature is too high, a carbon material having a large capacitance cannot be obtained.
【００２５】賦活処理は、アルカリ金属水酸化物を用い
て行われる。アルカリ金属水酸化物としては、水酸化カ
リウムが特に好適であり、そのほか、水酸化ナトリウ
ム、水酸化リチウム、水酸化セシウムなどを用いること
もできる。The activation treatment is carried out using an alkali metal hydroxide. As the alkali metal hydroxide, potassium hydroxide is particularly preferable, and sodium hydroxide, lithium hydroxide, cesium hydroxide and the like can also be used.
【００２６】炭化物とアルカリ金属水酸化物との混合割
合は、炭化前の上記使用済み品粉砕物基準で、１：0.5
〜１：１０（重量比）とすることが多い。アルカリ金属
水酸化物の過少は賦活不足を招き、その過多は得られる
炭素材（活性炭）の脆化を招く。The mixing ratio of the carbide and the alkali metal hydroxide is 1: 0.5 on the basis of the used pulverized product before carbonization.
It is often set to 1:10 (weight ratio). If the amount of alkali metal hydroxide is too small, the activation will be insufficient, and if it is too large, the carbon material (activated carbon) obtained will be brittle.
【００２７】賦活処理に際しては、アルカリ金属水酸化
物を水と共存させて用いる。水の共存量は、アルカリ金
属水酸化物に対し0.05〜１０重量倍程度とするのが適当
であり、そのような範囲内となるようにアルカリ金属水
酸化物−水混合物中のアルカリ金属水酸化物の濃度を設
定する。水の共存量が余りに少ないときはアルカリ金属
水酸化物の溶融温度が高いため操作性が悪くなり、一方
水の共存量が余りに大きときはアルカリ金属水酸化物に
よる賦活機能が低下する。In the activation treatment, an alkali metal hydroxide is used together with water. It is appropriate that the coexisting amount of water is about 0.05 to 10 times the weight of the alkali metal hydroxide, and the alkali metal hydroxide in the alkali metal hydroxide-water mixture is adjusted so as to fall within such a range. Set the concentration of the object. When the amount of coexisting water is too small, the melting temperature of the alkali metal hydroxide is high, so that the operability becomes poor, while when the amount of water coexisting is too large, the activation function of the alkali metal hydroxide deteriorates.
【００２８】賦活処理時の温度は４００〜９００℃程
度、好ましくは４５０〜８００℃程度が適当であり、温
度が余りに低いときあるいは温度が余りに高いときには
静電容量の大きな炭素材が得られない。The temperature at the time of activation treatment is about 400 to 900 ° C., preferably about 450 to 800 ° C. When the temperature is too low or the temperature is too high, a carbon material having a large capacitance cannot be obtained.
【００２９】賦活処理後は、アルカリ洗浄、酸洗浄、脱
水、粉砕、造粒などの精製工程や二次加工工程に供す
る。After the activation treatment, it is subjected to a purification step such as alkali washing, acid washing, dehydration, pulverization and granulation and a secondary processing step.
【００３０】このようにして得た炭素材は、ＢＥＴ比表
面積が５００〜３０００m2/g程度であり、電気二重層キ
ャパシタ用炭素材として用いられる。The carbon material thus obtained has a BET specific surface area of about 500 to 3000 m 2 / g and is used as a carbon material for electric double layer capacitors.
【００３１】電気二重層キャパシタは、たとえば、(a)
上記で得た炭素材の粉末品、導電材料、バインダーおよ
び溶媒を混合してペースト状の混合物を調製してからシ
ート状に成形して電極材料となし、該シート２枚をセパ
レータを介して重ねて外装容器に収容し、この中に電解
液を注入する方法、(b) 上記で得た炭素材の粉末品と電
解液との混合物を調製してペースト状となし、これをセ
パレータを介在させた状態で外装容器に収容する方法、
(c) 上記で得た炭素材の粉末品に樹脂系粉末品（たとえ
ばフェノール樹脂）を混合した後、高温（６００〜１０
００℃）で熱処理して炭素成形体を作り、電解液を含浸
させて、これをセパレータを介在させた状態で外装容器
に収容する方法をはじめ、従来採用されている各種の方
法により作製される。電解液としては、水溶液系電解液
や非水溶媒系電解液が用いられる。The electric double layer capacitor is, for example, (a)
A powdery product of the carbon material obtained above, a conductive material, a binder and a solvent are mixed to prepare a paste-like mixture, which is then molded into a sheet to form an electrode material, and the two sheets are stacked with a separator interposed therebetween. And then injecting the electrolytic solution into it, (b) preparing a mixture of the powdered carbon material obtained above and the electrolytic solution into a paste, and interposing this with a separator. To store in the outer container in the closed state,
(c) After mixing the powdered carbon material obtained above with a resin-based powdered product (for example, a phenol resin), a high temperature (600-10)
It is manufactured by various methods conventionally used, including a method of heat-treating at 00 ° C.) to form a carbon molded body, impregnating an electrolytic solution, and housing this in an outer container with a separator interposed. . As the electrolytic solution, an aqueous solution-based electrolytic solution or a non-aqueous solvent-based electrolytic solution is used.
【００３２】[0032]
【作用】本発明の電気二重層キャパシタ用炭素材は、紙
基材フェノール樹脂積層板を粉砕して炭化処理した後、
アルカリ金属水酸化物で賦活処理して得た炭素材からな
る。The carbon material for electric double layer capacitors of the present invention is obtained by pulverizing a paper-based phenolic resin laminated plate and carbonizing it.
It is composed of a carbon material obtained by activation treatment with an alkali metal hydroxide.
【００３３】この炭素材は、静電容量が高くかつ内部抵
抗が低いという電気二重層キャパシタ用炭素材として最
適の性質を有している。本発明の炭素材がそのような特
質を有する理由は、単にパルプやフェノール樹脂を炭化
・賦活して得た炭素材（活性炭）ではそのようなすぐれ
た性質が得られないことから、原料が紙とフェノール樹
脂との混合物からなる上、高圧プレスを伴なう圧縮成形
工程を経ているためと思われる。This carbon material has the optimum properties as a carbon material for an electric double layer capacitor that it has a high electrostatic capacity and a low internal resistance. The reason why the carbon material of the present invention has such characteristics is that the carbon material (activated carbon) obtained by simply carbonizing and activating pulp or phenol resin cannot obtain such excellent properties. This is probably because it is composed of a mixture of ethylene glycol and phenol resin, and has undergone a compression molding process involving a high pressure press.
【００３４】[0034]
【実施例】次に実施例をあげて本発明をさらに説明す
る。以下「部」、「％」とあるのは重量基準で表わした
ものである。EXAMPLES The present invention will be further described with reference to examples. Hereinafter, "part" and "%" are expressed on a weight basis.
【００３５】炭素材の製造 実施例１ 〈紙基材フェノール樹脂積層板の製造〉水溶性またはア
ルコール溶性のレゾール樹脂からなるフェノール樹脂ワ
ニスを調製した後、塗布樹脂量が紙基材７０部に対し３
０部となるようにクラフト紙（坪量２００g/m2）に塗
布、含浸させ、ついで温度約１６０℃で乾燥してプリプ
レグを作製した。このプリプレグの多数枚を積層し、積
層物の上下をステンレススチール製の鏡面板で挟むと共
に、その両外側にクッション材を重ね、多段式油圧プレ
ス機の熱盤間にセットした。この状態で、温度１４０
℃、圧力７０kgf/cm2、時間９０分の条件で熱プレスし
た後、解板、耳切りを行って、厚さ 1.5mm、寸法１０２
０mm×１０２０mmの紙基材フェノール樹脂積層板を得
た。 Production of Carbon Material Example 1 <Production of Paper-Based Phenolic Resin Laminate> A phenol resin varnish made of a water-soluble or alcohol-soluble resole resin was prepared, and then the amount of the applied resin was 70 parts of the paper substrate. Three
Kraft paper (basis weight: 200 g / m 2 ) was applied and impregnated so that the content became 0 part, and then dried at a temperature of about 160 ° C. to prepare a prepreg. A large number of these prepregs were laminated, and the top and bottom of the laminate were sandwiched by stainless steel mirror plates, and cushioning materials were placed on both outer sides of the laminate, and the cushion plates were set between the hot plates of a multi-stage hydraulic press machine. In this state, the temperature 140
After hot pressing under the conditions of ℃, pressure 70kgf / cm 2 and time 90 minutes, the plate is delaminated and the edges are trimmed to a thickness of 1.5mm and a size of 102.
A 0 mm × 1020 mm paper-based phenolic resin laminate was obtained.
【００３６】〈炭素材の製造〉この紙基材フェノール樹
脂積層板をプリント配線板のドリル穴あけ加工用治具板
として使用した後、その使用済み品をおおよそ 2.5mm角
に粗粉砕してから、窒素ガス雰囲気下に温度７００℃で
２時間炭化処理した。用いた積層板使用済み品の重量を
１００部とするとき、炭化物の量は３０部であった。つ
いで、炭化処理後の炭化物１００部、水酸化カリウム
（ＫＯＨ）２５０部および水２５０部の混合物を調製
し、窒素ガス雰囲気下に温度５００℃で２時間賦活反応
を行った。<Manufacture of carbon material> After using this paper-based phenolic resin laminate as a jig plate for drilling a printed wiring board, the used product is roughly crushed into about 2.5 mm square, Carbonization treatment was carried out at a temperature of 700 ° C. for 2 hours in a nitrogen gas atmosphere. When the weight of the used laminated plate used was 100 parts, the amount of carbide was 30 parts. Then, a mixture of 100 parts of carbonized carbonized product, 250 parts of potassium hydroxide (KOH) and 250 parts of water was prepared, and an activation reaction was carried out at a temperature of 500 ° C. for 2 hours under a nitrogen gas atmosphere.
【００３７】次に、賦活反応により得られた炭素材（活
性炭）をアルカリ洗浄および酸洗浄して、該炭素材に含
まれる金属を充分に除去し、ついで乾燥した。Next, the carbon material (activated carbon) obtained by the activation reaction was washed with an alkali and an acid to sufficiently remove the metal contained in the carbon material, and then dried.
【００３８】〈電気二重層キャパシタ用炭素材としての
性能〉上記で得た炭素材を平均粒径１０〜１５μm に粉
砕して測定用試料とし、この試料に３０％濃度の硫酸液
を添加して、適度の流動性を有するカーボンペーストを
調製した。このカーボンペーストを、絶縁性ブチルゴム
シートで作った４０mm×４０mm×３mmの容積の中に詰め
（２個作成）、セパレータを挟んで重ね、さらに集電極
としてのカーボン板を両側に置き、２０kg/cm2の圧力を
かけた。<Performance as Carbon Material for Electric Double Layer Capacitor> The carbon material obtained above was ground into an average particle size of 10 to 15 μm to prepare a sample for measurement, and a sulfuric acid solution of 30% concentration was added to this sample. A carbon paste having appropriate fluidity was prepared. This carbon paste is packed in a volume of 40 mm × 40 mm × 3 mm made of insulating butyl rubber sheet (two pieces are made), stacked with a separator sandwiched between them, and carbon plates as collector electrodes are placed on both sides, 20 kg / cm A pressure of 2 was applied.
【００３９】図１に電気二重層キャパシタの要部のモデ
ル図を示したように配線を行い、１ボルトで１時間充電
した後、１００mAで定電流放電させた後、 0.4ボルトか
ら 0.2ボルトまでの電位低下時間を測定して、静電容量
を算出した。Wiring was performed as shown in the model diagram of the main part of the electric double layer capacitor in FIG. 1, charging was performed for 1 hour at 1 volt, and constant current discharge was performed at 100 mA, and then 0.4 to 0.2 volt. The potential decrease time was measured and the capacitance was calculated.
【００４０】比較例１ 紙基材フェノール樹脂積層板の使用済み品を粗粉砕した
ものに代えて、市販のフェノール樹脂粉末を用いたほか
は、実施例１と同様にして炭化処理、ＫＯＨによる賦活
処理、さらには洗浄処理を行い、炭素材を得た。この炭
素材を用いて、実施例１と同様にして電気二重層キャパ
シタ用炭素材としての性能を調べた。Comparative Example 1 Carbonization treatment and activation with KOH were carried out in the same manner as in Example 1 except that a commercially available phenol resin powder was used instead of coarsely crushing the used paper-based phenol resin laminate. A carbon material was obtained by performing treatment and further washing treatment. Using this carbon material, the performance as a carbon material for an electric double layer capacitor was examined in the same manner as in Example 1.
【００４１】比較例２ 紙基材フェノール樹脂積層板の使用済み品を粗粉砕した
ものに代えて、パルプ（クラフト紙）を用いたほかは、
実施例１と同様にして炭化処理、ＫＯＨによる賦活処
理、さらには洗浄処理を行い、炭素材を得た。この炭素
材を用いて、実施例１と同様にして電気二重層キャパシ
タ用炭素材としての性能を調べた。Comparative Example 2 Except that pulp (kraft paper) was used in place of coarsely crushed used paper-based phenolic resin laminates,
In the same manner as in Example 1, carbonization treatment, KOH activation treatment, and further washing treatment were performed to obtain a carbon material. Using this carbon material, the performance as a carbon material for an electric double layer capacitor was examined in the same manner as in Example 1.
【００４２】炭素材の性能評価 〈条件および結果〉実施例１、比較例１〜２の条件およ
び結果を表１に示す。原料の項中、Ａは紙基材フェノー
ル樹脂積層板の使用済み品、Ｂはフェノール樹脂粉末、
Ｃはパルプ（クラフト紙）である。 Performance Evaluation of Carbon Material <Conditions and Results> Table 1 shows the conditions and results of Example 1 and Comparative Examples 1 and 2. In the section of raw materials, A is a used paper-based phenol resin laminate, B is phenol resin powder,
C is pulp (kraft paper).
【００４３】[0043]
【表１】 実施例１ 比較例１ 比較例２ 原料 A B C 炭化温度 (℃) 700 700 700 ＫＯＨ量 (倍) 2.5 2.5 2.5 賦活温度 (℃) 500 500 500 BET 比表面積 (m2/g) 920 930 940 ペースト密度 (g/cm3) 0.86 0.81 0.70 静電容量 (F/cm3) 106 95 69 [Table 1] Example 1 Comparative Example 1 Comparative Example 2 Raw material ABC Carbonization temperature (℃) 700 700 700 KOH amount (times) 2.5 2.5 2.5 Activation temperature (℃) 500 500 500 BET Specific surface area (m 2 / g) 920 930 940 Paste density ( g / cm 3 ) 0.86 0.81 0.70 Capacitance (F / cm 3 ) 106 95 69
【００４４】表１から、紙基材フェノール樹脂積層板を
原料として用いて製造した炭素材は、フェノール樹脂粉
末またはパルプ（クラフト紙）を原料として用いて製造
した炭素材に比し、電気二重層キャパシタ用炭素材とし
て用いたときの静電容量が高いことがわかる。From Table 1, the carbon material produced using the paper-based phenolic resin laminate as a raw material has an electric double layer as compared with the carbon material produced using phenolic resin powder or pulp (kraft paper) as a raw material. It can be seen that the electrostatic capacity when used as a carbon material for capacitors is high.
【００４５】炭素材の表面積とペースト濃度との関係 実施例１、比較例１〜２において、賦活条件を変更する
ことにより種々のＢＥＴ比表面積を持つ炭素材を製造し
て測定用試料を作成し、これらの試料に３０％濃度の硫
酸液を添加して、適度の流動性を有するカーボンペース
トを調製した。このときの炭素材の表面積とペースト密
度との関係を図２に示す。 Relationship between Surface Area of Carbon Material and Paste Concentration In Example 1 and Comparative Examples 1 and 2, carbon materials having various BET specific surface areas were manufactured by changing activation conditions to prepare samples for measurement. A 30% sulfuric acid solution was added to these samples to prepare a carbon paste having an appropriate fluidity. The relationship between the surface area of the carbon material and the paste density at this time is shown in FIG.
【００４６】図２から、紙基材フェノール樹脂積層板を
原料として用いて製造した炭素材は、フェノール樹脂粉
末またはパルプ（クラフト紙）を原料として用いて製造
した炭素材に比し、ペースト密度が高く、その結果充填
密度が高くなり、電気二重層キャパシタ用炭素材として
用いたときに高静電容量をもたらすものと判明した。From FIG. 2, the carbon material produced using the paper-based phenol resin laminate as a raw material has a paste density higher than that of the carbon material produced using phenol resin powder or pulp (kraft paper) as a raw material. It was found to be high, resulting in a high packing density, resulting in a high capacitance when used as a carbon material for electric double layer capacitors.
【００４７】その理由は、紙基材フェノール樹脂積層板
はフェノール樹脂をパルプに含浸させた後、圧縮成形し
て製造するものであるため、フェノール樹脂およびパル
プよりも緻密となり、その結果特に賦活工程において、
表面積では表現できない粒子の亀裂や大きな細孔がフェ
ノール樹脂およびパルプよりも少なくなるためと推察さ
れる。The reason for this is that the paper-based phenolic resin laminate is manufactured by impregnating the pulp with the phenolic resin and then compression-molding it, so that it is denser than the phenolic resin and the pulp, and as a result, particularly in the activation step. At
It is inferred that the number of cracks and large pores that cannot be expressed by the surface area is smaller than that of phenol resin and pulp.
【００４８】他の炭素材との比較 石油コークス、ヤシ殻チャーおよび石炭につき、実施例
１と同じ条件でＫＯＨによる賦活を行った。 Comparison with other carbon materials Petroleum coke, coconut shell char and coal were activated with KOH under the same conditions as in Example 1.
【００４９】得られた炭素材を用いて、実施例１と同様
にして電気二重層キャパシタ用炭素材としての性能を調
べた。また内部抵抗についても測定した。条件および結
果を表２に示す。なお実施例１の場合についても表２に
示した。原料の項中、Ａは紙基材フェノール樹脂積層
板、Ｄは石油コークス、Ｅはヤシ殻チャー、Ｆは石炭で
ある。Using the obtained carbon material, the performance as a carbon material for an electric double layer capacitor was examined in the same manner as in Example 1. The internal resistance was also measured. The conditions and results are shown in Table 2. The case of Example 1 is also shown in Table 2. In the raw material section, A is a paper-based phenol resin laminate, D is petroleum coke, E is coconut shell char, and F is coal.
【００５０】[0050]
【表２】 実施例１ 比較例３ 比較例４ 比較例５ 原料 A D E F 炭化温度 (℃) 700 - - - ＫＯＨ量 (倍) 2.5 2.5 2.5 2.5 賦活温度 (℃) 500 500 500 500 静電容量 (F/cm3) 106 69 60 71 内部抵抗 (Ω) 3.0 4.4 5.4 4.0 [Table 2] Example 1 Comparative Example 3 Comparative Example 4 Comparative Example 5 Raw material ADEF Carbonization temperature (° C) 700---KOH amount (times) 2.5 2.5 2.5 2.5 Activation temperature (° C) 500 500 500 500 Capacitance (F / cm 3 ) 106 69 60 71 Internal resistance (Ω) 3.0 4.4 5.4 4.0
【００５１】上記において内部抵抗は次の方法により測
定した。すなわち、所定時間充電後、定電流放電する
と、図３に電気二重層コンデンサの定電流放電曲線を示
したように、初期に電圧降下を示し、その後直線的に減
少していく。ここでは、 0.4Ｖ〜 0.2Ｖまでの電圧が降
下する範囲を直線とみなし、その延長線がｔ＝０をきる
点Ｖ2 と初期電圧降下Ｖ0 との差をＩＲドロップによる
電圧降下として、次式により抵抗Ｒを算出した。 Ｒ＝（Ｖ2 −Ｖ0 ）／Ａ Ａ: 0.1 (Amp)In the above, the internal resistance was measured by the following method. That is, when a constant current is discharged after charging for a predetermined time, a voltage drop is initially shown and then linearly decreases as shown in the constant current discharge curve of the electric double layer capacitor in FIG. Here, the range in which the voltage drops from 0.4 V to 0.2 V is regarded as a straight line, and the difference between the point V 2 at which the extension line cuts t = 0 and the initial voltage drop V 0 is taken as the voltage drop due to IR drop. The resistance R was calculated by the formula. R = (V 2 −V 0 ) / A A: 0.1 (Amp)
【００５２】表２から、紙基材フェノール樹脂積層板を
原料として用いて製造した炭素材は、石油コークス、ヤ
シ殻チャー、石炭をＫＯＨ賦活して製造した従来の炭素
材に比し、電気二重層キャパシタ用炭素材として用いた
ときの静電容量が高く、内部抵抗は低く、性能がすぐれ
ていることがわかる。From Table 2, the carbon material produced by using the paper-based phenolic resin laminate as a raw material has a higher electric conductivity than the conventional carbon material produced by activating KOH of petroleum coke, coconut shell char and coal. It can be seen that when used as a carbon material for a multilayer capacitor, the electrostatic capacity is high, the internal resistance is low, and the performance is excellent.
【００５３】[0053]
【発明の効果】本発明の電気二重層キャパシタ用炭素材
は、静電容量が高くかつ内部抵抗が低いという電気二重
層キャパシタ用炭素材として最適の性質を有している。The carbon material for an electric double layer capacitor of the present invention has optimum properties as a carbon material for an electric double layer capacitor that has a high electrostatic capacity and a low internal resistance.
【００５４】現在、紙基材フェノール樹脂積層板の使用
済み品は廃棄処分されるなどその処置に窮していたが、
これを電気二重層キャパシタ用炭素材の原料として用い
ると、その有効利用が図られる上、コストの点でも一段
と有利になる。At present, the used products of the paper-based phenolic resin laminated plate are disposed of, such as being discarded,
When this is used as a raw material of a carbon material for electric double layer capacitors, it can be effectively used and further advantageous in terms of cost.
【図１】炭素材の評価に供した電気二重層キャパシタの
要部のモデル図である。FIG. 1 is a model diagram of a main part of an electric double layer capacitor used for evaluation of a carbon material.
【図２】炭素材の表面積とペースト密度との関係を示し
たグラフである。FIG. 2 is a graph showing the relationship between the surface area of carbon material and the paste density.
【図３】内部抵抗を求めるための電気二重層コンデンサ
の定電流放電曲線を示したグラフである。FIG. 3 is a graph showing a constant current discharge curve of an electric double layer capacitor for obtaining internal resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松田 嘉宗 兵庫県尼崎市南塚口町４丁目２番37号 利 昌工業株式会社尼崎工場内 (72)発明者 佐伯 美香子 兵庫県尼崎市南塚口町４丁目２番37号 利 昌工業株式会社尼崎工場内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshimune Matsuda 4-37, Minamitsukaguchi-cho, Amagasaki-shi, Hyogo Prefecture Amagasaki factory, Risho Industry Co., Ltd. (72) Mikako Saeki Minamitsukaguchi-machi, Amagasaki-shi, Hyogo 4-chome 2-37 Risama Industry Co., Ltd. Amagasaki factory
Claims (2)
化処理した後、アルカリ金属水酸化物で賦活処理して得
た炭素材からなることを特徴とする電気二重層キャパシ
タ用炭素材。1. A carbon material for an electric double layer capacitor, which comprises a carbon material obtained by crushing a paper-based phenolic resin laminate, carbonizing it, and then activating it with an alkali metal hydroxide.
度５００〜９００℃で炭化処理した後、アルカリ金属水
酸化物にて温度４００〜９００℃で賦活処理して得た炭
素材からなることを特徴とする請求項１記載の電気二重
層キャパシタ用炭素材。2. A carbon material obtained by crushing a paper-based phenolic resin laminate, carbonizing it at a temperature of 500 to 900 ° C., and then activating it at a temperature of 400 to 900 ° C. with an alkali metal hydroxide. The carbon material for an electric double layer capacitor according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP20440994A JP3330235B2 (en) | 1994-08-04 | 1994-08-04 | Carbon material for electric double layer capacitor and method for producing the same |
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| JP20440994A JP3330235B2 (en) | 1994-08-04 | 1994-08-04 | Carbon material for electric double layer capacitor and method for producing the same |
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| Publication Number | Publication Date |
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| JPH0851045A true JPH0851045A (en) | 1996-02-20 |
| JP3330235B2 JP3330235B2 (en) | 2002-09-30 |
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| JP20440994A Expired - Fee Related JP3330235B2 (en) | 1994-08-04 | 1994-08-04 | Carbon material for electric double layer capacitor and method for producing the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001319837A (en) * | 2000-05-09 | 2001-11-16 | Mitsubishi Chemicals Corp | Activated carbon for electric double-layer capacitor |
| US6592838B1 (en) | 1999-10-21 | 2003-07-15 | Matsushita Electric Industrial Co., Ltd. | Activated carbon for use in electric double layer capacitor and method of producing the same |
| JP2008050258A (en) * | 2007-09-12 | 2008-03-06 | Mitsubishi Chemicals Corp | Carbonaceous substance and electrical double layer capacitor using the same |
| JP2016157836A (en) * | 2015-02-25 | 2016-09-01 | 株式会社サンエイト | Polarizable electrode for electric double layer capacitor and electric double layer capacitor using the same |
| JP2020132488A (en) * | 2019-02-21 | 2020-08-31 | 関西熱化学株式会社 | Production method of activated carbon |
| JP2020142967A (en) * | 2019-03-07 | 2020-09-10 | 関西熱化学株式会社 | Method for producing activated carbon |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5208160B2 (en) * | 2003-01-14 | 2013-06-12 | 関西熱化学株式会社 | Method for producing porous carbon for electric double layer capacitor, porous carbon for electric double layer capacitor obtained by the production method, and electric double layer capacitor using porous carbon for electric double layer capacitor |
-
1994
- 1994-08-04 JP JP20440994A patent/JP3330235B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6592838B1 (en) | 1999-10-21 | 2003-07-15 | Matsushita Electric Industrial Co., Ltd. | Activated carbon for use in electric double layer capacitor and method of producing the same |
| JP2001319837A (en) * | 2000-05-09 | 2001-11-16 | Mitsubishi Chemicals Corp | Activated carbon for electric double-layer capacitor |
| JP4503134B2 (en) * | 2000-05-09 | 2010-07-14 | 三菱化学株式会社 | Activated carbon for electric double layer capacitors |
| JP2008050258A (en) * | 2007-09-12 | 2008-03-06 | Mitsubishi Chemicals Corp | Carbonaceous substance and electrical double layer capacitor using the same |
| JP2016157836A (en) * | 2015-02-25 | 2016-09-01 | 株式会社サンエイト | Polarizable electrode for electric double layer capacitor and electric double layer capacitor using the same |
| JP2020132488A (en) * | 2019-02-21 | 2020-08-31 | 関西熱化学株式会社 | Production method of activated carbon |
| JP2020142967A (en) * | 2019-03-07 | 2020-09-10 | 関西熱化学株式会社 | Method for producing activated carbon |
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| JP3330235B2 (en) | 2002-09-30 |
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