JPH05304048A - Polarized electrode and manufacture thereof - Google Patents
Polarized electrode and manufacture thereofInfo
- Publication number
- JPH05304048A JPH05304048A JP4109878A JP10987892A JPH05304048A JP H05304048 A JPH05304048 A JP H05304048A JP 4109878 A JP4109878 A JP 4109878A JP 10987892 A JP10987892 A JP 10987892A JP H05304048 A JPH05304048 A JP H05304048A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- polarizable electrode
- activated carbon
- inorganic binder
- carbon fine
- 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
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気二重層キャパシタ
やエレクトロクロミックディスプレイ等の分野に用いら
れる分極性電極およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polarizable electrode used in the fields of electric double layer capacitors, electrochromic displays and the like, and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】従来の分極性電極に関する技術を電気二
重層キャパシタを例にとり説明する。 （Ａ）活性炭粉末を分極性電極に用いるものは、例えば
特開昭５０−４４４６２号公報に示されているように活
性炭粉末と有機結合剤を金属ネット集電体に圧延して形
成していた。この場合、有機結合剤を用いないと強度の
高い分極性電極が得られない。2. Description of the Related Art A conventional polarizable electrode technology will be described by taking an electric double layer capacitor as an example. (A) The one using activated carbon powder for a polarizable electrode is formed by rolling activated carbon powder and an organic binder into a metal net current collector as disclosed in JP-A-50-44462. .. In this case, a polarizable electrode having high strength cannot be obtained unless an organic binder is used.
【０００３】（Ｂ）活性炭繊維布を分極性電極に用いる
ものは例えば特開昭５９−４８９１７号公報に示されて
いるものがある。その電気二重層キャパシタの構成は、
活性炭素繊維の分極性電極の片面にアルミニウム、ニッ
ケル等の導電層（集電体）を形成し、セパレ−タを介し
相対向させ、これらを電解液とともに金属ケ−スと封口
板および両者を絶縁するガスケットによって密封したも
のである。この分極性電極の導電層（集電体）は溶射法
を用いて形成されている。しかしながら活性炭繊維布
は、密度が小さく単位体積当りの容量を増大させること
が困難であり、また、繊維一本一本の接触が少なく、接
触抵抗が大きくなる。An example of using (B) activated carbon fiber cloth as a polarizable electrode is disclosed in JP-A-59-48917. The structure of the electric double layer capacitor is
A conductive layer (current collector) of aluminum, nickel, etc. is formed on one surface of the polarizable electrode of activated carbon fiber, and they are made to face each other through a separator, and these are put together with an electrolytic solution into a metal case, a sealing plate and both. It is sealed with an insulating gasket. The conductive layer (collector) of this polarizable electrode is formed by using a thermal spraying method. However, the activated carbon fiber cloth has a small density, and it is difficult to increase the capacity per unit volume. Further, the contact of each fiber is small and the contact resistance is large.
【０００４】[0004]
【発明が解決しようとする課題】上記のような構成の分
極性電極では、（Ａ）活性炭粉末を用いた場合には多量
の有機結合剤を用いないと強度の高い分極性電極が得ら
れない。しかしながら、有機結合剤を用いると化学的耐
久性が十分ではなく、電気抵抗が大きくなり、放電特性
の優れた分極性電極を得ることが困難であると言った問
題がある。In the polarizable electrode having the above-mentioned structure, when (A) activated carbon powder is used, a polarizable electrode having high strength cannot be obtained unless a large amount of organic binder is used. .. However, when an organic binder is used, there is a problem that the chemical durability is insufficient, the electric resistance increases, and it is difficult to obtain a polarizable electrode having excellent discharge characteristics.
【０００５】（Ｂ）また、活性炭繊維を分極性電極に用
いた場合は活性炭繊維布の密度が小さく単位体積当たり
の容量を大きくすることが困難である。また、活性炭繊
維表面のみに集電体層が形成され、活性炭繊維間での集
電は十分ではなく接触抵抗の大きな、従って内部抵抗値
の小さな電気二重層キャパシタを得ることができないと
言った問題がある。(B) When activated carbon fibers are used for the polarizable electrode, the activated carbon fiber cloth has a low density and it is difficult to increase the capacity per unit volume. In addition, a current collector layer is formed only on the surface of activated carbon fibers, current collection between activated carbon fibers is not sufficient, and a contact resistance is large, so that an electric double layer capacitor with a small internal resistance value cannot be obtained. There is.
【０００６】本発明は前記課題を解決し、必要な強度を
有しかつ従来より内部抵抗の小さい、信頼性の高い分極
性電極およびその製造方法を提供することを目的とす
る。An object of the present invention is to solve the above problems and to provide a highly reliable polarizable electrode having required strength and smaller internal resistance than ever before, and a manufacturing method thereof.
【０００７】[0007]
【課題を解決するための手段】上記従来技術の課題を解
決するため、（１）本発明の分極性電極は、活性炭微粒
子が無機結合剤で結合されてなる分極性電極から成る。In order to solve the above-mentioned problems of the prior art, (1) the polarizable electrode of the present invention comprises a polarizable electrode in which fine particles of activated carbon are bound by an inorganic binder.
【０００８】（２）また、本発明の分極性電極は、活性
炭微粒子と黒鉛微粒子が無機結合剤で結合されてなる分
極性電極であることが好ましい。 （３）本発明の前記（１）に記載の分極性電極において
は、無機結合剤が導電性を有する無機結合剤である事が
好ましい。(2) Further, the polarizable electrode of the present invention is preferably a polarizable electrode in which activated carbon fine particles and graphite fine particles are bound by an inorganic binder. (3) In the polarizable electrode according to the above (1) of the present invention, it is preferable that the inorganic binder is a conductive inorganic binder.
【０００９】（４）本発明の前記（２）に記載の分極性
電極においては、無機結合剤が導電性を有する無機結合
剤である事が好ましい。 （５）本発明の前記（１）または（２）のいずれかに記
載の分極性電極においては、無機結合剤がシリカガラス
またはアルミナである事が好ましい。(4) In the polarizable electrode according to (2) of the present invention, it is preferable that the inorganic binder is a conductive inorganic binder. (5) In the polarizable electrode according to (1) or (2) of the present invention, the inorganic binder is preferably silica glass or alumina.
【００１０】（６）本発明の前記（３）または（４）の
いずれかに記載の分極性電極においては、導電性を有す
る無機結合剤が酸化インジウムまたは酸化インジウムと
酸化錫との混合物である事が好ましい。(6) In the polarizable electrode according to the above (3) or (4) of the present invention, the conductive inorganic binder is indium oxide or a mixture of indium oxide and tin oxide. Things are preferred.
【００１１】（７）本発明の前記（１）に記載の分極性
電極においては、無機結合剤の量が活性炭微粒子に対し
１〜３０重量％である事が好ましい。 （８）本発明の前記（２）に記載の分極性電極において
は、活性炭微粒子に対し無機結合剤が１〜３０重量％、
黒鉛微粒子が５〜３０重量％である事が好ましい。(7) In the polarizable electrode according to the above (1) of the present invention, the amount of the inorganic binder is preferably 1 to 30% by weight based on the activated carbon fine particles. (8) In the polarizable electrode according to (2) of the present invention, the inorganic binder is 1 to 30% by weight with respect to the activated carbon fine particles,
It is preferable that the graphite fine particles be 5 to 30% by weight.
【００１２】（９）本発明の前記（３）に記載の分極性
電極においては、導電性を有する無機結合剤の量が活性
炭微粒子に対し１〜５０重量％である事が好ましい。 （１０）本発明の前記（４）に記載の分極性電極におい
ては、活性炭微粒子に対し導電性を有する無機結合剤が
１〜５０重量％、黒鉛微粒子が５〜３０重量％である事
が好ましい。(9) In the polarizable electrode according to the above (3) of the present invention, the amount of the electrically conductive inorganic binder is preferably 1 to 50% by weight based on the activated carbon fine particles. (10) In the polarizable electrode according to (4) of the present invention, it is preferable that the conductive inorganic binder is 1 to 50% by weight and the graphite fine particles is 5 to 30% by weight with respect to the activated carbon fine particles. ..
【００１３】（１１）また、本発明の前記（１）または
（３）のいずれかに記載の分極性電極の製造方法は、無
機結合剤となる金属アルコキシド溶液と活性炭微粒子と
の混合溶液をゲル化し、加熱することを特徴とする。(11) Further, in the method for producing a polarizable electrode according to the above (1) or (3) of the present invention, a mixed solution of a metal alkoxide solution as an inorganic binder and activated carbon fine particles is gelled. And is heated.
【００１４】（１２）また、本発明の前記（２）または
（４）のいずれかに記載の分極性電極の製造方法は、無
機結合剤となる金属アルコキシド溶液と活性炭微粒子お
よび黒鉛微粒子との混合溶液をゲル化し、加熱すること
を特徴とする。(12) Further, in the method for producing a polarizable electrode according to the above (2) or (4) of the present invention, a metal alkoxide solution as an inorganic binder is mixed with activated carbon fine particles and graphite fine particles. The solution is characterized by gelling and heating.
【００１５】[0015]
【作用】（１）本発明の分極性電極は、活性炭微粒子が
無機結合剤で結合されてなる分極性電極から成るので、
二重層容量密度が高く、必要な機械的強度を有しかつ従
来より内部抵抗の小さい、信頼性の高い分極性電極が提
供できる。(1) Since the polarizable electrode of the present invention comprises a polarizable electrode in which activated carbon fine particles are bound by an inorganic binder,
It is possible to provide a highly reliable polarizable electrode having high double-layer capacity density, required mechanical strength, and lower internal resistance than ever before.
【００１６】（２）また、活性炭微粒子と黒鉛微粒子が
無機結合剤で結合されてなる分極性電極である本発明の
好ましい態様とすることによって、さらに電気抵抗を低
減することができ好ましい。(2) In addition, the preferred embodiment of the present invention, which is a polarizable electrode in which fine particles of activated carbon and fine particles of graphite are bonded with an inorganic binder, is preferable because the electrical resistance can be further reduced.
【００１７】（３）本発明の前記（１）に記載の分極性
電極において、無機結合剤が導電性を有する無機結合剤
である好ましい態様とすることによって、さらに電気抵
抗を低減することができ好ましい。(3) In the polarizable electrode according to the above (1) of the present invention, when the inorganic binder is a conductive inorganic binder, the electrical resistance can be further reduced. preferable.
【００１８】（４）本発明の前記（２）に記載の分極性
電極において、無機結合剤が導電性を有する無機結合剤
である好ましい態様とすることによって、さらに電気抵
抗を低減することができ好ましい。(4) In the polarizable electrode according to the above (2) of the present invention, when the inorganic binder is a conductive inorganic binder, the electrical resistance can be further reduced. preferable.
【００１９】（５）本発明の前記（１）または（２）の
いずれかに記載の分極性電極において、無機結合剤がシ
リカガラスまたはアルミナである好ましい態様とするこ
とによって、これらの無機結合剤は金属アルコキシドの
アルコール溶液などを原料とし、これをゲル化して活性
炭微粒子を結合することができるので、むら無く活性炭
微粒子にまぶすことができ、均一に活性炭微粒子同志を
結合することができる。またこれらの無機結合剤は化学
的に安定であり、電極寿命の低下の懸念がないので好ま
しい。(5) In the polarizable electrode according to (1) or (2) of the present invention, the inorganic binder is silica glass or alumina. Since a metal alkoxide alcohol solution or the like is used as a raw material and can be gelled to bind the activated carbon fine particles, the activated carbon fine particles can be evenly sprinkled, and the activated carbon fine particles can be evenly bound to each other. Further, these inorganic binders are preferable because they are chemically stable and there is no fear of shortening the electrode life.
【００２０】（６）本発明の前記（３）または（４）の
いずれかに記載の分極性電極において、導電性を有する
無機結合剤が酸化インジウムまたは酸化インジウムと酸
化錫との混合物である好ましい態様とすることによっ
て、これらの導電性無機結合剤は金属アルコキシドのア
ルコール溶液などを原料とし、これをゲル化して活性炭
微粒子を結合することができるので、むら無く活性炭微
粒子にまぶすことができ、均一に活性炭微粒子同志を結
合することができるので好ましい。(6) In the polarizable electrode according to (3) or (4) of the present invention, the conductive inorganic binder is indium oxide or a mixture of indium oxide and tin oxide. By adopting an embodiment, these conductive inorganic binders can be made by using an alcohol solution of a metal alkoxide as a raw material and gelling this to bind the activated carbon fine particles, so that the activated carbon fine particles can be evenly sprinkled and uniformly dispersed. Since activated carbon fine particles can be bonded to each other, it is preferable.
【００２１】（７）本発明の前記（１）に記載の分極性
電極において、無機結合剤の量が活性炭微粒子に対し１
〜３０重量％である好ましい態様とすることによって、
電気抵抗を余り上昇させずに必要な機械的強度を満足さ
せることができ好ましい。(7) In the polarizable electrode according to the above (1) of the present invention, the amount of the inorganic binder is 1 with respect to the activated carbon fine particles.
By making it a preferable embodiment that is ˜30 wt%,
It is preferable because the required mechanical strength can be satisfied without increasing the electric resistance so much.
【００２２】（８）本発明の前記（２）に記載の分極性
電極において、活性炭微粒子に対し無機結合剤が１〜３
０重量％、黒鉛微粒子が５〜３０重量％である好ましい
態様とすることによって、電荷保持面積を余り低減する
こと無く電気抵抗を低減でき、且つ、必要な機械的強度
を満足させることができ好ましい。(8) In the polarizable electrode according to the above (2) of the present invention, the inorganic binder is 1 to 3 with respect to the activated carbon fine particles.
By adopting a preferable mode in which 0% by weight and graphite fine particles are 5 to 30% by weight, it is possible to reduce the electric resistance without significantly reducing the charge holding area and to satisfy the required mechanical strength, which is preferable. ..
【００２３】（９）本発明の前記（３）に記載の分極性
電極において、導電性を有する無機結合剤の量が活性炭
微粒子に対し１〜５０重量％である好ましい態様とする
ことによって、電気抵抗を上昇させずに必要な機械的強
度を満足させることができ好ましい。(9) In the polarizable electrode according to the above (3) of the present invention, the amount of the electrically conductive inorganic binder is set to 1 to 50% by weight based on the activated carbon fine particles, whereby the electrical conductivity is improved. It is preferable because the required mechanical strength can be satisfied without increasing the resistance.
【００２４】（１０）本発明の前記（４）に記載の分極
性電極において、活性炭微粒子に対し導電性を有する無
機結合剤が１〜５０重量％、黒鉛微粒子が５〜３０重量
％であるである好ましい態様とすることによって、電荷
保持面積を余り低減すること無く電気抵抗を低減でき、
且つ、必要な機械的強度を満足させることができ好まし
い。(10) In the polarizable electrode according to the above (4) of the present invention, the inorganic binder having conductivity with respect to the activated carbon fine particles is 1 to 50% by weight, and the graphite fine particles is 5 to 30% by weight. By adopting a preferred embodiment, the electric resistance can be reduced without significantly reducing the charge holding area,
In addition, it is preferable because the required mechanical strength can be satisfied.
【００２５】（１１）また、本発明の分極性電極の製造
方法においては、本発明の前記（１）または（３）のい
ずれかに記載の分極性電極は、無機結合剤となる金属ア
ルコキシド溶液と活性炭微粒子との混合溶液をゲル化
し、加熱することによって製造されるので、二重層容量
密度が高く、必要な機械的強度を有しかつ従来より内部
抵抗の小さい、信頼性の高い分極性電極を容易に製造す
ることができる。(11) Further, in the method for producing a polarizable electrode of the present invention, the polarizable electrode according to any one of the above (1) and (3) of the present invention is a metal alkoxide solution as an inorganic binder. It is produced by gelling a mixed solution of activated carbon and activated carbon fine particles and heating it, so it has a high double-layer capacity density, has the required mechanical strength, and has a smaller internal resistance than before, and a highly reliable polarizable electrode. Can be easily manufactured.
【００２６】（１２）また、本発明の分極性電極の製造
方法において、本発明の前記（２）または（４）のいず
れかに記載の分極性電極の製造方法は、無機結合剤とな
る金属アルコキシド溶液と活性炭微粒子および黒鉛微粒
子との混合溶液をゲル化し、加熱することによって製造
されるので、二重層容量密度が高く、必要な機械的強度
を有しかつ更に従来より内部抵抗の小さい、信頼性の高
い分極性電極を容易に製造することができる。(12) Further, in the method for producing a polarizable electrode according to the present invention, the method for producing a polarizable electrode according to any one of the above (2) and (4) of the present invention is a metal as an inorganic binder. Since it is manufactured by gelling a mixed solution of alkoxide solution and activated carbon fine particles and graphite fine particles and heating it, it has a high double-layer capacity density, has the required mechanical strength, and has a smaller internal resistance than before, and is reliable. A highly polarizable electrode can be easily manufactured.
【００２７】[0027]
【実施例】本発明で用いる活性炭微粒子としては、特に
限定するものではなく、各種の活性炭微粒子を用いるこ
とができる。通常これらの活性炭微粒子の粒子径は、特
に限定するものではないが、５〜１００μｍ程度のもの
が好ましい。EXAMPLES The activated carbon fine particles used in the present invention are not particularly limited, and various activated carbon fine particles can be used. Usually, the particle diameter of these activated carbon fine particles is not particularly limited, but is preferably about 5 to 100 μm.
【００２８】本発明で無機結合剤となるセラミックス
は、化学的に安定なＳｉＯ2 、Ａｌ2Ｏ3 が好ましい。
このような無機結合剤を作製するのに用いられる原料は
金属アルコキシドが好ましく用いられる。金属アルコキ
シドとしては、シリコンのメトオキシドやエトオキシド
等のシリコンの低級アルコキシド類あるいはアルミニウ
ムのメトオキシド、エトオキシドないしはプロポキシド
等のアルミニウムの低級アルコキシドが好ましい。The ceramics used as the inorganic binder in the present invention are preferably chemically stable SiO 2 and Al 2 O 3 .
A metal alkoxide is preferably used as a raw material used for producing such an inorganic binder. As the metal alkoxide, preferred are lower alkoxides of silicon such as silicon methoxide and ethoxide, or lower alkoxides of aluminum such as aluminum methoxide, ethoxide and propoxide.
【００２９】また、導電性を有する無機結合剤として
は、Ｉｎ2 Ｏ3 やＩＴＯ（Ｉｎ2 Ｏ3とＳｎＯ2 の混合
物）等の金属酸化物が好ましく用いられる。このような
導電性を有する無機結合剤を作製するのに用いられる原
料は金属アルコキシドが好ましく用いられる。用いる金
属アルコキシドは、インジウムのメトオキシドやエトオ
キシドないしはプロポキシド等のインジウムの低級アル
コキシド類、あるいは錫のメトオキシド、エトオキシド
ないしはプロポキシド等の錫の低級アルコキシドが好ま
しい。As the conductive inorganic binder, metal oxides such as In 2 O 3 and ITO (mixture of In 2 O 3 and SnO 2 ) are preferably used. A metal alkoxide is preferably used as a raw material used for producing such an inorganic binder having conductivity. The metal alkoxide used is preferably an indium lower alkoxide such as indium methoxide or ethoxide or propoxide, or a tin lower alkoxide such as tin methoxide, ethoxide or propoxide.
【００３０】さらに、主に無機結合剤に導電性を付与す
るために用いられる黒鉛微粒子は、サブミクロンの粒径
を有するのが好ましく用いられ、より具体的には、０．
２〜２μｍ程度の粒径の黒鉛微粒子が好ましく用いられ
る。Further, the fine graphite particles mainly used for imparting conductivity to the inorganic binder preferably have a particle size of submicron, and more specifically, the graphite fine particles having a particle size of 0.
Graphite fine particles having a particle size of about 2 to 2 μm are preferably used.
【００３１】前記において、無機結合剤の量は活性炭微
粒子に対し１〜３０重量％程度であることが、電気抵抗
を余り上昇させずに必要な機械的強度を満足させること
ができ好ましい。In the above, it is preferable that the amount of the inorganic binder is about 1 to 30% by weight based on the activated carbon fine particles because the required mechanical strength can be satisfied without increasing the electric resistance.
【００３２】また、前記において、活性炭微粒子と無機
結合剤と黒鉛微粒子とを併用する場合には、活性炭微粒
子に対し無機結合剤が１〜３０重量％、黒鉛微粒子が５
〜３０重量％程度である事が好ましい。この範囲にする
ことによって、電荷保持面積を余り低減させること無く
電気抵抗を低減でき、且つ、必要な機械的強度を満足さ
せることができ好ましい。Further, in the above, when the activated carbon fine particles, the inorganic binder and the graphite fine particles are used in combination, the inorganic binder is 1 to 30% by weight and the graphite fine particles are 5% with respect to the activated carbon fine particles.
It is preferably about 30% by weight. Within this range, the electric resistance can be reduced without significantly reducing the charge holding area, and the necessary mechanical strength can be satisfied, which is preferable.
【００３３】また、前記において、導電性を有する無機
結合剤を用いる場合には、その量は好ましくは、活性炭
微粒子に対し１〜５０重量％程度である。この範囲の好
ましい態様とにすることによって、電気抵抗を上昇させ
ずに必要な機械的強度を満足させることができ好まし
い。Further, in the above case, when the conductive inorganic binder is used, its amount is preferably about 1 to 50% by weight based on the activated carbon fine particles. The preferred embodiment in this range is preferable because the required mechanical strength can be satisfied without increasing the electric resistance.
【００３４】更にまた、活性炭微粒子と導電性を有する
無機結合剤と黒鉛微粒子とを併用する場合には、活性炭
微粒子に対し導電性を有する無機結合剤が１〜５０重量
％、黒鉛微粒子が５〜３０重量％程度の範囲にすること
が好ましく、この範囲とすることより、電荷保持面積を
余り低減すること無く電気抵抗を低減でき、且つ、必要
な機械的強度を満足させることができるので好ましい。Furthermore, when the activated carbon fine particles, the inorganic binder having conductivity and the graphite fine particles are used in combination, the conductive inorganic binder is 1 to 50% by weight and the graphite fine particles are 5 to 5% by weight based on the activated carbon fine particles. It is preferably in the range of about 30% by weight, and in this range, the electric resistance can be reduced without significantly reducing the charge holding area, and the required mechanical strength can be satisfied, which is preferable.
【００３５】尚、前述した如く、無機結合剤または導電
性を有する無機結合剤の原料として、金属アルコキシド
を用いる場合には、その作製工程としては、特に限定す
るものではないか、例えば、金属アルコキシド、アルコ
ール、水、触媒とを１０：１０〜２０：５〜３０：０．
０１〜０．５程度の重量比で混合した溶液を作成する。
この場合、最初に金属アルコキシドにアルコールを加え
撹拌した後、水と触媒を少しづつ混合し攪拌する。ゲル
化をさせて活性炭微粒子や黒鉛微粒子どうしを結合させ
るには、更にこの溶液をおよそ４０〜６０℃で加熱し、
ゲル化を進める。更に残留水分の除去とゲル化を進行さ
せるため約１５０〜２００℃で加熱する。次に有機物を
除去するため約４００〜４５０℃で加熱する。As described above, when a metal alkoxide is used as a raw material for the inorganic binder or the inorganic binder having conductivity, the manufacturing process is not particularly limited. For example, metal alkoxide is used. , Alcohol, water, catalyst 10:10 to 20: 5 to 30: 0.
A solution mixed at a weight ratio of about 01 to 0.5 is prepared.
In this case, alcohol is first added to the metal alkoxide and stirred, and then water and the catalyst are mixed little by little and stirred. In order to gelate and bond the activated carbon fine particles and the graphite fine particles together, this solution is further heated at about 40 to 60 ° C.,
Advance gelation. Further, in order to remove residual water and promote gelation, heating is performed at about 150 to 200 ° C. Next, it heats at about 400-450 degreeC in order to remove an organic substance.
【００３６】ここでアルコールとしては通常低級アルコ
ールが好ましく用いられ、特にメタノール、エタノール
などが好ましい。また、触媒としては、金属アルコキシ
ドの加水分解触媒が用いられ、たとえば、酸またはアル
カリ触媒が用いられる。具体例としては、ＨＣｌ、ＨＮ
Ｏ3 、ＮａＯＨ、ＮＨ4 ＯＨなどが挙げられる。As the alcohol, lower alcohols are usually preferably used, and methanol, ethanol and the like are particularly preferable. Further, as the catalyst, a metal alkoxide hydrolysis catalyst is used, and for example, an acid or alkali catalyst is used. As a specific example, HCl, HN
O 3 , NaOH, NH 4 OH and the like can be mentioned.
【００３７】以下本発明の具体的実施例について説明す
る。 実施例１ シリコンのメトオキシド、メタノ−ル、加水分解触媒と
しての塩酸を重量比で１０：１０：０．２の割合で混合
した溶液に比表面積１８００ｍ2 ｇ-1のフェノ−ル系活
性炭（平均粒径；１０μｍ）を混合後、室温で１時間撹
拌しさらに６０℃で５０時間加熱することによりこの混
合液をゲル化する。このゲルを、直径６ｍｍ、厚さ０．
５ｍｍのタブレット状に加工した後、２００℃でさらに
１時間加熱した。この活性炭微粒子とＳｉＯ2 とから構
成された分極性電極の、ＳｉＯ2の含有量は４ｗｔ％で
あった。無機結合剤であるＳｉＯ2 の含有量は、電気抵
抗値を増大させるので、機械的な強度を維持できるに必
要な４ｗｔ％程度が好ましい。このようにして作製した
タブレットの片面に、１００μｍのアルミニウム層から
なる集電体をプラズマ溶射法により形成した。Specific examples of the present invention will be described below. Example 1 A phenol-based activated carbon having a specific surface area of 1800 m 2 g -1 (average) was added to a solution in which silicon oxide, methanol, and hydrochloric acid as a hydrolysis catalyst were mixed at a weight ratio of 10: 10: 0.2. Particle size; 10 μm) are mixed, then stirred at room temperature for 1 hour and further heated at 60 ° C. for 50 hours to gelate the mixed solution. This gel has a diameter of 6 mm and a thickness of 0.
After processing into a tablet shape of 5 mm, it was further heated at 200 ° C. for 1 hour. The polarizable electrode composed of the activated carbon fine particles and SiO 2 had a SiO 2 content of 4 wt%. The content of SiO 2 which is an inorganic binder increases the electric resistance value, and is therefore preferably about 4 wt% necessary for maintaining the mechanical strength. A current collector made of an aluminum layer having a thickness of 100 μm was formed on one surface of the tablet thus manufactured by a plasma spraying method.
【００３８】このようにして作製した分極性電極を用い
て、コイン型電気二重層キャパシタを構成した。その概
略断面図を図１に示す。図１において、１、２は分極性
電極、３、４は集電体を示す。セパレ−タ５には、直径
１０ｍｍのポリプロピレン製多孔膜を用いた。このセパ
レータ５を介し上記分極性電極１、２を相対向させた
後、テトラエチルアンモニウムのホウフッ化塩（Ｅｔ4
ＮＢＦ4 ）を電解質とした１モル／ｌのプロピレンカ−
ボネ−ト有機電解液として注入後封口ケ−シングし、コ
イン型キャパシタを作製した。ケ−シングの上部部材６
（コイン型封口板、正極）、下部部材７（陰極）はこの
例ではステンレスを用いた。またケ−シングの上部部材
６と下部部材７の封口部８は、ポリプロピレンを用い
た。A coin type electric double layer capacitor was constructed by using the polarizable electrode thus manufactured. The schematic sectional view is shown in FIG. In FIG. 1, 1 and 2 are polarizable electrodes and 3 and 4 are current collectors. For the separator 5, a polypropylene porous membrane having a diameter of 10 mm was used. After the polarizable electrodes 1 and 2 are opposed to each other through the separator 5, tetraethylammonium borofluoride (Et 4
NBF 4 ) as electrolyte and 1 mol / l propylene car
A coin type capacitor was manufactured by injecting as a Bonnet organic electrolyte and then sealing the case. Upper member 6 of casing
(Coin type sealing plate, positive electrode) and lower member 7 (cathode) were made of stainless steel in this example. Polypropylene was used for the sealing member 8 of the upper member 6 and lower member 7 of the casing.
【００３９】このキャパシタを２．４Ｖで充電後、１ｍ
Ａで定電流放電し容量０．２２Ｆ、インピ−ダンス１２
オ−ムを得た。また７０℃の雰囲気下で常時２．４Ｖを
印加したところ初期容量に対する１０００時間後の容量
減少率は１０％であり、二重層容量が大きく、内部抵抗
の小さいキャパシターとすることができた。After charging this capacitor at 2.4 V, 1 m
Constant current discharge at A, capacity 0.22F, impedance 12
I got an om. Further, when 2.4 V was constantly applied in an atmosphere of 70 ° C., the capacity reduction rate after 1000 hours was 10% with respect to the initial capacity, and a capacitor having a large double layer capacity and a low internal resistance could be obtained.
【００４０】従来の活性炭繊維布にプラズマ溶射法を用
いて集電体を形成した分極性電極を用いたキャパシタの
特性は容量が０．１６Ｆ，インピ−ダンス（１ＫＨｚ）
が２１オ−ムであった。 実施例２ 実施例１と同様な方法を用いて、アルミニウムのメトオ
キシド、メタノ−ル、加水分解触媒としての塩酸を重量
比で１０：１０：０．２の割合で混合した溶液に比表面
積１８００ｍ2 ｇ-1のフェノ−ル系活性炭（平均粒径；
１０μｍ）を混合後、室温で１時間撹拌しさらに６０℃
で５０時間加熱することによりこの混合液をゲル化す
る。このゲルを、直径６ｍｍ、厚さ０．５ｍｍのタブレ
ット状に加工した後、２００℃でさらに１時間加熱し
た。この活性炭微粒子とＡｌ2 Ｏ3 とから構成された分
極性電極の、Ａｌ2 Ｏ3 の含有量は６ｗｔ％であった。
無機結合剤であるＡｌ2 Ｏ3 の含有量は、電気抵抗値を
増大させるので、機械的な強度を維持できる６ｗｔ％が
好ましい。このようにして作製したタブレットの片面
に、１００μｍのアルミニウム層からなる集電体をプラ
ズマ溶射法により形成した。このようにして作製した分
極性電極を用いて、図１と同様の断面構造を有するコイ
ン型電気二重層キャパシタを構成した。セパレ−タに
は、直径１０ｍｍのポリプロピレン製多孔膜を用いた。
このセパレータを介し上記分極性電極を相対向させた
後、テトラエチルアンモニウムのホウフッ化塩（Ｅｔ4
ＮＢＦ4 ）を電解質とした１モル／ｌのプロピレンカ−
ボネ−ト有機電解液として注入後封口ケ−シングし、コ
イン型キャパシタを作製した。このキャパシタを２．４
Ｖで充電後、１ｍＡで定電流放電し容量０．２１Ｆ、イ
ンピ−ダンス１４オ−ムを得た。また７０℃の雰囲気下
で常時２．４Ｖを印加したところ初期容量に対する１０
００時間後の容量減少率は１２％であり、二重層容量が
大きく、内部抵抗の小さいキャパシターとすることがで
きた。The characteristics of a conventional capacitor using a polarizable electrode in which a current collector is formed by using a plasma spraying method on activated carbon fiber cloth have a capacitance of 0.16 F and an impedance (1 KHz).
Was 21 ohms. Example 2 Using the same method as in Example 1, a solution in which aluminum oxide, methanol and hydrochloric acid as a hydrolysis catalyst were mixed at a weight ratio of 10: 10: 0.2 had a specific surface area of 1800 m 2. g -1 phenolic activated carbon (average particle size;
10 μm) and then stirred at room temperature for 1 hour and further 60 ° C.
The mixture is gelled by heating at 50 ° C. for 50 hours. The gel was processed into a tablet having a diameter of 6 mm and a thickness of 0.5 mm, and then heated at 200 ° C. for another hour. The content of Al 2 O 3 in the polarizable electrode composed of the activated carbon fine particles and Al 2 O 3 was 6 wt%.
The content of Al 2 O 3 which is an inorganic binder increases the electric resistance value, and is therefore preferably 6 wt% which can maintain the mechanical strength. A current collector made of an aluminum layer having a thickness of 100 μm was formed on one surface of the tablet thus manufactured by a plasma spraying method. A coin-type electric double layer capacitor having a cross-sectional structure similar to that of FIG. 1 was constructed using the polarizable electrode thus manufactured. A polypropylene porous membrane having a diameter of 10 mm was used as the separator.
After allowing the polarizable electrodes to face each other through this separator, tetraethylammonium borofluoride (Et 4
NBF 4 ) as electrolyte and 1 mol / l propylene car
A coin type capacitor was manufactured by injecting as a Bonnet organic electrolyte and then sealing the case. This capacitor is 2.4
After charging with V, constant current discharge was carried out at 1 mA to obtain a capacity of 0.21 F and an impedance of 14 ohms. Moreover, when 2.4 V was constantly applied in an atmosphere of 70 ° C., 10 V relative to the initial capacity was obtained.
The capacity reduction rate after 00 hours was 12%, and a capacitor having a large double-layer capacity and a small internal resistance could be obtained.
【００４１】従来の活性炭繊維布にプラズマ溶射法を用
いて集電体を形成した分極性電極を用いたキャパシタの
特性は容量が０．１６Ｆ，インピ−ダンス（１ＫＨｚ）
が２１オ−ムであった。 実施例３ シリコンのメトオキシド、メタノ−ル、加水分解触媒と
しての塩酸を重量比で１０：１０：０．２の割合で混合
した溶液に比表面積１８００ｍ2 ｇ-1のフェノ−ル系活
性炭（平均粒径；１０μｍ）と無機結合剤に導電性を付
与する０．２〜０．７μｍの粒径を有するコロイド状の
黒鉛微粒子を混合後、室温で１時間撹拌し、さらに６０
℃で５０時間加熱することによりこの混合液をゲル化す
る。このゲルを、直径６ｍｍ、厚さ０．５ｍｍのタブレ
ット状に加工した後、２００℃でさらに１時間加熱し
た。この活性炭微粒子とＳｉＯ2 と黒鉛微粒子から構成
された分極性電極の、ＳｉＯ2 の含有量は４ｗｔ％、黒
鉛微粒子の含有量は２０ｗｔ％であった。黒鉛微粒子の
含有量を６０ｗｔ％以上にすると黒鉛微粒子のタブレッ
トからの脱離が見られた。本実施例では、黒鉛微粒子の
含有量は、特に１０〜３０ｗｔ％が好ましい。このよう
にして作製したタブレットの片面に、１００μｍのアル
ミニウム層からなる集電体をプラズマ溶射法により形成
した。このようにして作製した分極性電極を用いて、図
１とほぼ同様の断面構造を有するコイン型電気二重層キ
ャパシタを構成した。セパレ−タには、直径１０ｍｍの
ポリプロピレン製多孔膜を用いた。このセパレータを介
し上記分極性電極を相対向させた後、テトラエチルアン
モニウムのホウフッ化塩（Ｅｔ4 ＮＢＦ4 ）を電解質と
した１モル／ｌのプロピレンカ−ボネ−ト有機電解液と
して注入後封口ケ−シングし、コイン型キャパシタを作
製した。このキャパシタを２．４Ｖで充電後、１ｍＡで
定電流放電し容量０．２６Ｆ、インピ−ダンス７オ−ム
を得た。また７０℃の雰囲気下で常時２．４Ｖを印加し
たところ初期容量に対する１０００時間後の容量減少率
は８％であり、二重層容量が大きく、内部抵抗の小さい
キャパシターとすることができた。The characteristics of a conventional capacitor using a polarizable electrode in which a current collector is formed on an activated carbon fiber cloth by plasma spraying have a capacitance of 0.16 F and an impedance (1 KHz).
Was 21 ohms. Example 3 A phenol-based activated carbon having a specific surface area of 1800 m 2 g -1 (average) was added to a solution in which silicon oxide, methanol, and hydrochloric acid as a hydrolysis catalyst were mixed at a weight ratio of 10: 10: 0.2. (Particle size: 10 μm) and colloidal graphite fine particles having a particle size of 0.2 to 0.7 μm for imparting conductivity to the inorganic binder are mixed and then stirred at room temperature for 1 hour, and further 60
The mixture is gelled by heating at 0 ° C for 50 hours. The gel was processed into a tablet having a diameter of 6 mm and a thickness of 0.5 mm, and then heated at 200 ° C. for another hour. The polarizable electrode composed of the activated carbon fine particles, SiO 2 and graphite fine particles had a SiO 2 content of 4 wt% and a graphite fine particle content of 20 wt%. When the content of the graphite fine particles was 60 wt% or more, desorption of the graphite fine particles from the tablets was observed. In this example, the content of the fine graphite particles is particularly preferably 10 to 30 wt%. A current collector made of an aluminum layer having a thickness of 100 μm was formed on one surface of the tablet thus manufactured by a plasma spraying method. A coin-type electric double layer capacitor having a cross-sectional structure substantially similar to that shown in FIG. 1 was constructed using the polarizable electrode thus manufactured. A polypropylene porous membrane having a diameter of 10 mm was used as the separator. After the polarizable electrodes were opposed to each other via this separator, a 1 mol / l propylene carbonate organic electrolytic solution containing tetraethylammonium borofluoride salt (Et 4 NBF 4 ) as an electrolyte was added and then sealed. -Thing was performed to produce a coin-type capacitor. This capacitor was charged at 2.4 V and then discharged at a constant current of 1 mA to obtain a capacity of 0.26 F and an impedance of 7 ohm. Further, when 2.4 V was constantly applied in the atmosphere of 70 ° C., the capacity reduction rate after 1000 hours was 8% with respect to the initial capacity, and a capacitor having a large double layer capacity and a low internal resistance could be obtained.
【００４２】従来の活性炭繊維布にプラズマ溶射法を用
いて集電体を形成した分極性電極を用いたキャパシタの
特性は容量が０．１６Ｆ，インピ−ダンス（１ＫＨｚ）
が２１オ−ムであった。The characteristics of a conventional capacitor using a polarizable electrode in which a current collector is formed by using a plasma spraying method on activated carbon fiber cloth have a capacitance of 0.16 F and an impedance (1 KHz).
Was 21 ohms.
【００４３】シリコンのメトオキシドの替わりに、アル
ミニウムのメトオキシドを用いても同様な効果を有する
分極性電極を作製できた。 実施例４ インジウムのメトオキシド、メタノ−ル、加水分解触媒
としての塩酸を重量比で１０：１０：０．２の割合で混
合した溶液に比表面積１８００ｍ2 ｇ-1のフェノ−ル系
活性炭（平均粒径；１０μｍ）を混合後、室温で１時間
撹拌しさらに６０℃で５０時間加熱することによりこの
混合液をゲル化する。このゲルを、直径６ｍｍ、厚さ
０．５ｍｍのタブレット状に加工した後、２００℃でさ
らに１時間加熱した。この活性炭微粒子とＩｎ2 Ｏ3 と
から構成された分極性電極の、Ｉｎ 2 Ｏ3 の含有量は１
０ｗｔ％であり、機械的に強く、電気抵抗値の低い分極
性電極で得られた。このようにして作製したタブレット
の片面に、１００μｍのアルミニウム層からなる集電体
をプラズマ溶射法により形成した。このようにして作製
した分極性電極を用いて、図１とほぼ同様の断面構造を
有するコイン型電気二重層キャパシタを構成した。セパ
レ−タには、直径１０ｍｍのポリプロピレン製多孔膜を
用いた。このセパレータを介し上記分極性電極を相対向
させた後、テトラエチルアンモニウムのホウフッ化塩
（Ｅｔ4 ＮＢＦ4 ）を電解質とした１モル／ｌのプロピ
レンカ−ボネ−ト有機電解液として注入後封口ケ−シン
グし、コイン型キャパシタを作製した。このキャパシタ
を２．４Ｖで充電後、１ｍＡで定電流放電し容量０．２
５Ｆ、インピ−ダンス８オ−ムを得た。また７０℃の雰
囲気下で常時２．４Ｖを印加したところ初期容量に対す
る１０００時間後の容量減少率は８％であり、二重層容
量が大きく、内部抵抗の小さいキャパシターとすること
ができた。Instead of silicon methotoxide,
Similar effect can be obtained by using minium methoxide
A polarizable electrode could be produced. Example 4 Indium methoxide, methanol, hydrolysis catalyst
Hydrochloric acid as a mixture in a weight ratio of 10: 10: 0.2
Specific surface area of the combined solution is 1800m2g-1Phenolic system
1 hour at room temperature after mixing with activated carbon (average particle size; 10 μm)
This is done by stirring and heating at 60 ° C. for 50 hours.
Gel the mixture. This gel has a diameter of 6 mm and a thickness of
After processing into a 0.5 mm tablet,
And heated for 1 hour. Fine particles of this activated carbon and In2O3When
Of a polarizable electrode composed of 2O3Content of 1
0 wt%, mechanically strong and low electric resistance polarization
Obtained with a sex electrode. Tablet made in this way
Current collector consisting of 100 μm aluminum layer on one side
Was formed by plasma spraying. Made in this way
Using the polarizable electrode, a cross-sectional structure similar to that shown in Fig. 1 was obtained.
A coin type electric double layer capacitor having the same was constructed. Sepa
A polypropylene porous film with a diameter of 10 mm is used for the data.
Using. The polarizable electrodes face each other through this separator
After that, tetraethylammonium borofluoride salt
(EtFourNBFFour) As an electrolyte,
Lenker-bonate After injection as an organic electrolyte, sealing case
To produce a coin-type capacitor. This capacitor
Is charged at 2.4 V and discharged at a constant current of 1 mA to a capacity of 0.2
5F, impedance 8 ohms were obtained. Also, the atmosphere at 70 ° C
When 2.4V is constantly applied in the atmosphere, the initial capacity is changed.
The capacity reduction rate after 1000 hours is 8%,
Use a capacitor with a large amount and low internal resistance
I was able to.
【００４４】従来の活性炭繊維布にプラズマ溶射法を用
いて集電体を形成した分極性電極を用いたキャパシタの
特性は容量が０．１６Ｆ，インピ−ダンス（１ＫＨｚ）
が２１オ−ムであった。 実施例５ インジウムと錫のメトオキシド（モル比で９５：５）、
メタノ−ル、加水分解触媒としての塩酸を重量比で１
０：１０：０．２の割合で混合した溶液に比表面積１８
００ｍ2 ｇ-1のフェノ−ル系活性炭（平均粒径；１０μ
ｍ）を混合後、室温で１時間撹拌しさらに６０℃で５０
時間加熱することによりこの混合液をゲル化する。この
ゲルを、直径６ｍｍ、厚さ０．５ｍｍのタブレット状に
加工した後、２００℃でさらに１時間加熱した。この活
性炭微粒子とＩＴＯ（Ｉｎ2 Ｏ3 ＋ＳｎＯ2 ）とから構
成された分極性電極の、ＩＴＯの含有量は１０ｗｔ％で
あり、機械的に強く、電気抵抗値の低い分極性電極が得
られた。このようにして作製したタブレットの片面に、
１００μｍのアルミニウム層からなる集電体をプラズマ
溶射法により形成した。このようにして作製した分極性
電極を用いて、図１とほぼ同様の断面構造を有するコイ
ン型電気二重層キャパシタを構成した。セパレ−タに
は、直径１０ｍｍのポリプロピレン製多孔膜を用いた。
このセパレータを介し上記分極性電極を相対向させた
後、テトラエチルアンモニウムのホウフッ化塩（Ｅｔ4
ＮＢＦ4 ）を電解質とした１モル／ｌのプロピレンカ−
ボネ−ト有機電解液として注入後封口ケ−シングし、コ
イン型キャパシタを作製した。このキャパシタを２．４
Ｖで充電後、１ｍＡで定電流放電し容量０．２７Ｆ、イ
ンピ−ダンス６オ−ムを得た。また７０℃の雰囲気下で
常時２．４Ｖを印加したところ初期容量に対する１００
０時間後の容量減少率は６％であり、二重層容量が大き
く、内部抵抗の小さいキャパシターとすることができ
た。The characteristics of a conventional capacitor using a polarizable electrode having a collector formed by plasma spraying on activated carbon fiber cloth have a capacitance of 0.16 F and an impedance (1 KHz).
Was 21 ohms. Example 5 Indium and tin metoxide (molar ratio 95: 5),
The weight ratio of methanol and hydrochloric acid as a hydrolysis catalyst is 1
The specific surface area of the mixed solution of 0: 10: 0.2 was 18
00m 2 g -1 phenol-based activated carbon (average particle size: 10μ
m) were mixed and then stirred at room temperature for 1 hour and further at 60 ° C. for 50
This mixture is gelled by heating for a time. The gel was processed into a tablet having a diameter of 6 mm and a thickness of 0.5 mm, and then heated at 200 ° C. for another hour. The polarizable electrode composed of the activated carbon fine particles and ITO (In 2 O 3 + SnO 2 ) had ITO content of 10 wt%, and a polarizable electrode having mechanical strength and low electric resistance value was obtained. .. On one side of the tablet made in this way,
A current collector made of a 100 μm aluminum layer was formed by plasma spraying. A coin-type electric double layer capacitor having a cross-sectional structure substantially similar to that shown in FIG. 1 was constructed using the polarizable electrode thus manufactured. A polypropylene porous membrane having a diameter of 10 mm was used as the separator.
After allowing the polarizable electrodes to face each other through this separator, tetraethylammonium borofluoride (Et 4
NBF 4 ) as electrolyte and 1 mol / l propylene car
A coin type capacitor was manufactured by injecting as a Bonnet organic electrolyte and then sealing the case. This capacitor is 2.4
After charging with V, constant current discharge was performed at 1 mA to obtain a capacity of 0.27 F and an impedance of 6 ohms. Moreover, when 2.4 V was constantly applied in an atmosphere of 70 ° C., 100% of the initial capacity was applied.
The capacity reduction rate after 0 hours was 6%, and the capacitor having a large double layer capacity and a small internal resistance could be obtained.
【００４５】従来の活性炭繊維布にプラズマ溶射法を用
いて集電体を形成した分極性電極を用いたキャパシタの
特性は容量が０．１６Ｆ，インピ−ダンス（１ＫＨｚ）
が２１オ−ムであった。 実施例６ インジウムと錫のメトオキシド（モル比で９５：５）、
メタノ−ル、加水分解触媒としての塩酸を重量比で１
０：１０：０．２の割合で混合した溶液に比表面積１８
００ｍ2 ｇ-1のフェノ−ル系活性炭（平均粒径；１０μ
ｍ）とさらに導電性を向上させるサブミクロンの粒径を
有するコロイド状の黒鉛微粒子を混合後、室温で１時間
撹を混合後、室温で１時間撹拌しさらに６０℃で５０時
間加熱することによりこの混合液をゲル化する。このゲ
ルを、直径６ｍｍ、厚さ０．５ｍｍのタブレット状に加
工した後、２００℃でさらに１時間加熱した。この活性
炭微粒子とＩＴＯ（Ｉｎ2 Ｏ3 ＋ＳｎＯ2 ）とから構成
された分極性電極の、ＩＴＯの含有量は１０ｗｔ％であ
り、電気抵抗値の低く、機械的に強い分極性電極で得ら
れた。また、黒鉛微粒子の含有量は、１５ｗｔ％であっ
た。このようにして作製したタブレットの片面に、１０
０μｍのアルミニウム層からなる集電体をプラズマ溶射
法により形成した。このようにして作製した分極性電極
を用いて、図１とほぼ同様の断面構造を有するコイン型
電気二重層キャパシタを構成した。セパレ−タには、直
径１０ｍｍのポリプロピレン製多孔膜を用いた。このセ
パレータを介し上記分極性電極を相対向させた後、テト
ラエチルアンモニウムのホウフッ化塩（Ｅｔ4 ＮＢ
Ｆ4 ）を電解質とした１モル／ｌのプロピレンカ−ボネ
−ト有機電解液として注入後封口ケ−シングし、コイン
型キャパシタを作製した。このキャパシタを２．４Ｖで
充電後、１ｍＡで定電流放電し容量０．２９Ｆ、インピ
−ダンス３オ−ムを得た。また７０℃の雰囲気下で常時
２．４Ｖを印加したところ初期容量に対する１０００時
間後の容量減少率は４％であり、二重層容量が大きく、
内部抵抗の小さいキャパシターとすることができた。The characteristics of a conventional capacitor using a polarizable electrode in which a collector is formed by using a plasma spraying method on activated carbon fiber cloth have a capacitance of 0.16 F and an impedance (1 KHz).
Was 21 ohms. Example 6 Indium and tin methoxide (molar ratio 95: 5),
The weight ratio of methanol and hydrochloric acid as a hydrolysis catalyst is 1
The specific surface area of the mixed solution of 0: 10: 0.2 was 18
00m 2 g -1 phenol-based activated carbon (average particle size: 10μ
m) and colloidal graphite fine particles having a submicron particle size for further improving conductivity, mixed by stirring at room temperature for 1 hour, then stirred at room temperature for 1 hour and further heated at 60 ° C. for 50 hours. The mixture is gelled. The gel was processed into a tablet having a diameter of 6 mm and a thickness of 0.5 mm, and then heated at 200 ° C. for another hour. The polarizable electrode composed of the activated carbon fine particles and ITO (In 2 O 3 + SnO 2 ) had an ITO content of 10 wt%, and was obtained with a mechanically strong polarizable electrode having a low electric resistance value. .. Further, the content of the graphite fine particles was 15 wt%. On one side of the tablet produced in this way, 10
A current collector made of a 0 μm aluminum layer was formed by plasma spraying. A coin-type electric double layer capacitor having a cross-sectional structure substantially similar to that shown in FIG. 1 was constructed using the polarizable electrode thus manufactured. A polypropylene porous membrane having a diameter of 10 mm was used as the separator. After allowing the polarizable electrodes to face each other through this separator, tetraethylammonium borofluoride (Et 4 NB)
A coin-type capacitor was produced by injecting a 1 mol / l propylene carbonate organic electrolytic solution using F 4 ) as an electrolyte and then sealing the case. This capacitor was charged at 2.4 V and then discharged at a constant current of 1 mA to obtain a capacity of 0.29 F and an impedance of 3 ohm. When 2.4 V was constantly applied in an atmosphere of 70 ° C., the capacity reduction rate after 1000 hours was 4% with respect to the initial capacity, and the double layer capacity was large.
It was possible to use a capacitor with a small internal resistance.
【００４６】従来の活性炭繊維布にプラズマ溶射法を用
いて集電体を形成した分極性電極を用いたキャパシタの
特性は容量が０．１６Ｆ，インピ−ダンス（１ＫＨｚ）
が２１オ−ムであった。 実施例７ 正極側分極性電極として実施例６と同様な分極性電極を
用い、負極としてＳｎとＣｄの比が８５：１５の合金
（ウッド合金）にリチウムを吸蔵させた非分極性電極を
用いて電気二重層キャパシタを作製した。本実施例にお
いても他の構成材料は実施例１と同様である。このキャ
パシタは３Ｖの電圧、０．５８Ｆの容量を示した。The characteristics of the conventional capacitor using the polarizable electrode in which the current collector is formed on the activated carbon fiber cloth by the plasma spraying method have a capacitance of 0.16 F and an impedance (1 KHz).
Was 21 ohms. Example 7 A polarizable electrode similar to that of Example 6 was used as the positive electrode side polarizable electrode, and a non-polarizable electrode obtained by occluding lithium in an alloy (Wood alloy) having a Sn: Cd ratio of 85:15 was used as the negative electrode. To produce an electric double layer capacitor. Also in this embodiment, the other constituent materials are the same as in the first embodiment. This capacitor showed a voltage of 3V and a capacitance of 0.58F.
【００４７】本発明の分極性電極は、上記のような電気
二重層キャパシタのみならず電池やエレクトロクロミッ
クディスプレイ等に広く使用できる。The polarizable electrode of the present invention can be widely used not only in the electric double layer capacitor as described above but also in batteries, electrochromic displays and the like.
【００４８】[0048]
【発明の効果】本発明の分極性電極は、二重層容量密度
が高く、必要な機械的強度を有しかつ従来より内部抵抗
の小さい、信頼性の高い分極性電極が提供できる。EFFECT OF THE INVENTION The polarizable electrode of the present invention can provide a highly reliable polarizable electrode having a high double-layer capacitance density, a required mechanical strength, and a smaller internal resistance than ever before.
【００４９】また、活性炭微粒子と黒鉛微粒子が無機結
合剤で結合されてなる分極性電極である本発明の好まし
い態様とすることによって、さらに電気抵抗を低減する
ことができる。Further, by adopting a preferred embodiment of the present invention which is a polarizable electrode in which fine particles of activated carbon and fine particles of graphite are bonded with an inorganic binder, the electric resistance can be further reduced.
【００５０】本発明の前記（１）に記載の分極性電極に
おいて、無機結合剤が導電性を有する無機結合剤である
好ましい態様とすることによって、さらに電気抵抗を低
減することができる。In the polarizable electrode according to the above (1) of the present invention, the electrical resistance can be further reduced by adopting a preferable mode in which the inorganic binder is an inorganic binder having conductivity.
【００５１】また、本発明の前記（２）に記載の分極性
電極において、無機結合剤が導電性を有する無機結合剤
であるである好ましい態様とすることによって、さらに
電気抵抗を低減することができる。Further, in the polarizable electrode according to the above (2) of the present invention, by adopting a preferable mode in which the inorganic binder is an inorganic binder having conductivity, the electric resistance can be further reduced. it can.
【００５２】さらに、本発明の分極性電極において、無
機結合剤がシリカガラスまたはアルミナである好ましい
態様とすることによって、これらの無機結合剤は金属ア
ルコキシドのアルコール溶液などを原料とし、これをゲ
ル化して活性炭微粒子を結合することができるので、む
ら無く活性炭微粒子にまぶすことができ、均一に活性炭
微粒子同志を結合することができる。またこれらの無機
結合剤は化学的に安定であり、電極寿命の長期化を達成
できる。Furthermore, in the polarizable electrode of the present invention, by adopting a preferred embodiment in which the inorganic binder is silica glass or alumina, these inorganic binders are made from an alcohol solution of a metal alkoxide as a raw material and are gelled. Since the activated carbon fine particles can be combined with each other, the activated carbon fine particles can be evenly sprinkled, and the activated carbon fine particles can be uniformly combined. Further, these inorganic binders are chemically stable and can prolong the life of the electrode.
【００５３】本発明の分極性電極において、導電性を有
する無機結合剤が酸化インジウムまたは酸化インジウム
と酸化錫との混合物である好ましい態様とすることによ
って、これらの導電性無機結合剤は金属アルコキシドの
アルコール溶液などを原料とし、これをゲル化して活性
炭微粒子を結合することができるので、むら無く活性炭
微粒子にまぶすことができ、均一に活性炭微粒子同志を
結合することができまた、電気抵抗の低減を達成でき
る。In the polarizable electrode of the present invention, when the inorganic binder having conductivity is indium oxide or a mixture of indium oxide and tin oxide, the conductive inorganic binder is a metal alkoxide. Alcohol solution is used as a raw material, and it can be gelled to bind the activated carbon fine particles, so it can be evenly sprinkled on the activated carbon fine particles, and the activated carbon fine particles can be evenly bound to each other, and the electrical resistance can be reduced. Can be achieved.
【００５４】本発明の分極性電極において、無機結合剤
の量が活性炭微粒子に対し１〜３０重量％である好まし
い態様とすることによって、電気抵抗を余り上昇させず
に必要な機械的強度を満足させることができる。In the polarizable electrode of the present invention, the amount of the inorganic binder is 1 to 30% by weight based on the activated carbon fine particles, so that the required mechanical strength can be satisfied without increasing the electric resistance. Can be made
【００５５】本発明の前記（２）に記載の分極性電極に
おいて、活性炭微粒子に対し無機結合剤が１〜３０重量
％、黒鉛微粒子が５〜３０重量％である好ましい態様と
することによって、電荷保持面積を余り低減すること無
く電気抵抗を低減でき、且つ、必要な機械的強度を満足
させることができる。In the polarizable electrode according to the above (2) of the present invention, the inorganic binder is 1 to 30% by weight and the graphite fine particles are 5 to 30% by weight with respect to the activated carbon fine particles. The electric resistance can be reduced without reducing the holding area so much, and the required mechanical strength can be satisfied.
【００５６】本発明の前記（３）に記載の分極性電極に
おいて、導電性を有する無機結合剤の量が活性炭微粒子
に対し１〜５０重量％である好ましい態様とすることに
よって、電気抵抗を上昇させずに必要な機械的強度を満
足させることができる。In the polarizable electrode according to the above (3) of the present invention, the electrical resistance is increased by adopting a preferred embodiment in which the amount of the conductive inorganic binder is 1 to 50% by weight based on the activated carbon fine particles. It is possible to satisfy the required mechanical strength without doing so.
【００５７】本発明の前記（４）に記載の分極性電極に
おいて、活性炭微粒子に対し導電性を有する無機結合剤
が１〜５０重量％、黒鉛微粒子が５〜３０重量％である
である好ましい態様とすることによって、電荷保持面積
を余り低減することなく電気抵抗を低減でき、且つ、必
要な機械的強度を満足させることができる。In the polarizable electrode according to the above (4) of the present invention, a preferable embodiment is that the conductive inorganic binder is 1 to 50% by weight and the graphite fine particles is 5 to 30% by weight with respect to the activated carbon fine particles. By so doing, it is possible to reduce the electric resistance without significantly reducing the charge holding area, and it is possible to satisfy the required mechanical strength.
【００５８】また、本発明の分極性電極の製造方法にお
いては、二重層容量密度が高く、必要な機械的強度を有
しかつ従来より内部抵抗の小さい、信頼性の高い分極性
電極を容易に製造することができる。Further, in the method of manufacturing a polarizable electrode of the present invention, a highly reliable polarizable electrode having a high double-layer capacitance density, a required mechanical strength and a smaller internal resistance than the conventional one can be easily prepared. It can be manufactured.
【００５９】また、本発明の分極性電極の製造方法にお
いて、さらに黒鉛微粒子を併用する好ましい態様によれ
ば、二重層容量密度が高く、必要な機械的強度を有しか
つ更に従来より内部抵抗の小さい、信頼性の高い分極性
電極を容易に製造することができる。Further, in the method for producing a polarizable electrode of the present invention, according to a preferred embodiment in which graphite fine particles are used in combination, the double-layer capacity density is high, the required mechanical strength is obtained, and the internal resistance is higher than that in the prior art. A small and highly reliable polarizable electrode can be easily manufactured.
【図１】本発明の一実施例の分極性電極を用いたコイン
型電気二重層キャパシタの概略断面図。FIG. 1 is a schematic sectional view of a coin-type electric double layer capacitor using a polarizable electrode according to an embodiment of the present invention.
１、２ 分極性電極 ３、４ 集電体 ５ セパレ−タ ６ ケ−シングの上部部材 ７ ケ−シングの下部部材 ８ 封口部 1, 2 polarizable electrodes 3, 4 current collector 5 separator 6 casing upper member 7 casing lower member 8 sealing portion
Claims (12)
なる分極性電極。1. A polarizable electrode comprising activated carbon fine particles bound with an inorganic binder.
で結合されてなる分極性電極。2. A polarizable electrode comprising activated carbon fine particles and graphite fine particles bonded by an inorganic binder.
である請求項１に記載の分極性電極。3. The polarizable electrode according to claim 1, wherein the inorganic binder is a conductive inorganic binder.
である請求項２に記載の分極性電極。4. The polarizable electrode according to claim 2, wherein the inorganic binder is a conductive inorganic binder.
ナである請求項１または２に記載の分極性電極。5. The polarizable electrode according to claim 1, wherein the inorganic binder is silica glass or alumina.
ウムまたは酸化インジウムと酸化錫との混合物である請
求項３または４に記載の分極性電極。6. The polarizable electrode according to claim 3, wherein the inorganic binder having conductivity is indium oxide or a mixture of indium oxide and tin oxide.
〜３０重量％である請求項１に記載の分極性電極。7. The amount of the inorganic binder is 1 with respect to the activated carbon fine particles.
The polarizable electrode according to claim 1, wherein the polarizable electrode is about 30% by weight.
０重量％、黒鉛微粒子が５〜３０重量％である請求項２
に記載の分極性電極。8. The activated carbon fine particles contain 1 to 3 inorganic binders.
0% by weight and 5 to 30% by weight of fine graphite particles.
The polarizable electrode according to.
微粒子に対し１〜５０重量％である請求項３に記載の分
極性電極。9. The polarizable electrode according to claim 3, wherein the amount of the inorganic binder having conductivity is 1 to 50% by weight based on the activated carbon fine particles.
機結合剤が１〜５０重量％、黒鉛微粒子が５〜３０重量
％である請求項４に記載の分極性電極。10. The polarizable electrode according to claim 4, wherein the inorganic binder having conductivity with respect to the activated carbon fine particles is 1 to 50% by weight and the graphite fine particles is 5 to 30% by weight.
液と活性炭微粒子との混合溶液をゲル化し、加熱するこ
とを特徴とする活性炭微粒子が無機結合剤で結合されて
なる請求項１または３のいずれかに記載の分極性電極の
製造方法。11. The activated carbon fine particles are bound by an inorganic binder, characterized in that a mixed solution of a metal alkoxide solution as an inorganic binder and activated carbon fine particles is gelled and heated. A method of manufacturing a polarizable electrode according to item 1.
液と活性炭微粒子および黒鉛微粒子との混合溶液をゲル
化し、加熱することを特徴とする活性炭微粒子と黒鉛微
粒子が無機結合剤で結合されてなる請求項２または４の
いずれかに記載の分極性電極の製造方法。12. The activated carbon fine particles and the graphite fine particles, which are characterized in that a mixed solution of a metal alkoxide solution serving as an inorganic binder, activated carbon fine particles and graphite fine particles is gelled and heated, and the activated carbon fine particles and the graphite fine particles are bound by the inorganic binder. 5. The method for producing a polarizable electrode according to either 2 or 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10987892A JP3161626B2 (en) | 1992-04-28 | 1992-04-28 | Manufacturing method of polarized electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10987892A JP3161626B2 (en) | 1992-04-28 | 1992-04-28 | Manufacturing method of polarized electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05304048A true JPH05304048A (en) | 1993-11-16 |
| JP3161626B2 JP3161626B2 (en) | 2001-04-25 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10987892A Expired - Fee Related JP3161626B2 (en) | 1992-04-28 | 1992-04-28 | Manufacturing method of polarized electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3161626B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0851271A2 (en) * | 1996-12-24 | 1998-07-01 | Nippon Oil Co. Ltd. | Electrode for electrochromic device and electrochromic device |
| WO2004051680A1 (en) * | 2002-11-29 | 2004-06-17 | Honda Motor Co., Ltd. | Polarizable electrode for electric double-layer capacitor, process for producing the polarizable electrode and process for producing the electric double-layer capacitor |
| EP2088604A1 (en) * | 2006-11-02 | 2009-08-12 | Sumitomo Chemical Company, Limited | Electrode membrane, electrode and method for producing the same, and electric double layer capacitor |
-
1992
- 1992-04-28 JP JP10987892A patent/JP3161626B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0851271A2 (en) * | 1996-12-24 | 1998-07-01 | Nippon Oil Co. Ltd. | Electrode for electrochromic device and electrochromic device |
| EP0851271A3 (en) * | 1996-12-24 | 1999-01-27 | Nippon Oil Co. Ltd. | Electrode for electrochromic device and electrochromic device |
| WO2004051680A1 (en) * | 2002-11-29 | 2004-06-17 | Honda Motor Co., Ltd. | Polarizable electrode for electric double-layer capacitor, process for producing the polarizable electrode and process for producing the electric double-layer capacitor |
| US7057879B2 (en) | 2002-11-29 | 2006-06-06 | Honda Motor Co., Ltd. | Polarizable electrode for electric double-layer capacitor, process for producing the polarizable electrode and process for producing the electric double-layer capacitor |
| KR100694786B1 (en) * | 2002-11-29 | 2007-03-14 | 혼다 기켄 고교 가부시키가이샤 | Polarized electrode for electric double layer capacitor, producing process thereof, and process for producing electric double layer capacitor |
| CN100446138C (en) * | 2002-11-29 | 2008-12-24 | 本田技研工业株式会社 | Polarizable electrode for electric double-layer capacitor, process for producing the polarizable electrode and process for producing the electric double-layer capacitor |
| EP2088604A1 (en) * | 2006-11-02 | 2009-08-12 | Sumitomo Chemical Company, Limited | Electrode membrane, electrode and method for producing the same, and electric double layer capacitor |
| EP2088604A4 (en) * | 2006-11-02 | 2009-12-02 | Sumitomo Chemical Co | Electrode membrane, electrode and method for producing the same, and electric double layer capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3161626B2 (en) | 2001-04-25 |
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Legal Events
| Date | Code | Title | Description |
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| LAPS | Cancellation because of no payment of annual fees |