JPH0897102A - Electrical double-layer capacitor, polarizable electrode for secondary battery and its manufacture, and electrical double-layer capacitor or secondary battery using the polarizable electrode - Google Patents
Electrical double-layer capacitor, polarizable electrode for secondary battery and its manufacture, and electrical double-layer capacitor or secondary battery using the polarizable electrodeInfo
- Publication number
- JPH0897102A JPH0897102A JP6261513A JP26151394A JPH0897102A JP H0897102 A JPH0897102 A JP H0897102A JP 6261513 A JP6261513 A JP 6261513A JP 26151394 A JP26151394 A JP 26151394A JP H0897102 A JPH0897102 A JP H0897102A
- Authority
- JP
- Japan
- Prior art keywords
- layer capacitor
- secondary battery
- electrode
- polarizable electrode
- double layer
- 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.)
- Pending
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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (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
及び二次電池用の分極性電極、その製造方法及びこの分
極性電極を使用した電気二重層キャパシタ或いは二次電
池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric double layer capacitor and a polarizable electrode for a secondary battery, a method for producing the polarizable electrode, and an electric double layer capacitor or a secondary battery using the polarizable electrode.
【０００２】[0002]
【従来の技術】分極性電極は、電気二重層キャパシタ及
び二次電池等の電極に用いられており、近年のコードレ
ス化の波に乗り、より容量が大きく、高性能の電気二重
層キャパシタ及び二次電池が必要とされ、これらの電気
二重層キャパシタ及び二次電池に不可欠の分極性電極へ
の要求が高まっている。2. Description of the Related Art Polarizable electrodes have been used in electrodes of electric double layer capacitors and secondary batteries, and have taken advantage of the recent wave of cordless technology, and have higher capacity and higher performance. Secondary batteries are required, and demands for polarizable electrodes, which are essential for these electric double layer capacitors and secondary batteries, are increasing.
【０００３】従来、電気二重層キャパシタ及び二次電池
に用いられている分極性電極については、さまざまな提
案がなされており、例えば、活性炭粉末と電解液と混合
してペースト状にしたもの（特開平１−１０２９１４号
公報参照）や、活性炭素繊維を用いたもの（特開平３−
１４１６２９号公報参照）、或いは、バインダとしてポ
リエチレンやポリプロピレンを用いたもの（特開平４−
２２０６２号公報参照）、或いは、バインダにポリアセ
ン系高分子を用いた固体分極性電極（特開平４−２８８
３６１号公報参照）を挙げることができる。Various proposals have heretofore been made for polarizable electrodes used in electric double layer capacitors and secondary batteries, for example, those prepared by mixing activated carbon powder and an electrolytic solution into a paste (special feature: (Kaihei 1-102914) and those using activated carbon fiber (Japanese Patent Laid-Open No. 3-102914).
No. 141629), or one using polyethylene or polypropylene as a binder (Japanese Patent Laid-Open No. Hei 4-
22062) or a solid polarizable electrode using a polyacene polymer as a binder (Japanese Patent Laid-Open No. 4-288).
361).
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記活性炭を
電解液と混合してペースト状にした方法や活性炭素繊維
を用いた方法やバインダを用いた分極性電極では、電解
液を真空含浸する際に粉落ちや繊維の脱落が発生してし
まい、その結果、電気二重層キャパシタ及び二次電池の
容量が経時的に低下するという欠点がある。However, in the method of forming a paste by mixing the activated carbon with the electrolytic solution, the method of using the activated carbon fiber, and the polarizable electrode using the binder, when impregnating the electrolytic solution in vacuum, However, there is a drawback in that powder and fibers are dropped off, and as a result, the capacities of the electric double layer capacitor and the secondary battery decrease over time.
【０００５】本発明は、上記従来技術の欠点を克服し、
炭素電極からの粉落ち或いは繊維の脱落を抑制すること
のできる電気二重層キャパシタ及び二次電池用分極性電
極、その製造方法及びこの分極性電極を使用した電気二
重層キャパシタ或いは二次電池を提供するためになされ
たものである。The present invention overcomes the above drawbacks of the prior art,
Provided are an electric double layer capacitor and a polarizable electrode for a secondary battery, which are capable of suppressing powder drop or fiber drop from a carbon electrode, a manufacturing method thereof, and an electric double layer capacitor or a secondary battery using the polarizable electrode. It was made to do.
【０００６】[0006]
【課題を解決するための手段】上記目的を解決するため
に本発明が採用した電気二重層キャパシタ及び二次電池
用分極性電極の構成は、賦活されている炭素電極上にガ
ラス状カーボンを０．２７μｇ／ｃｍ2〜４．３ｍｇ／
ｃｍ2の範囲で付着させてなることを特徴とするもので
あり、同様に本発明が採用した分極性電極の製造方法の
構成は、賦活されている炭素電極上にポリカルボジイミ
ド樹脂を０．５μｇ／ｃｍ2〜５ｍｇ／ｃｍ2の範囲で適
用し、非酸化性雰囲気下で焼成することを特徴とするも
のであり、同様に本発明が採用した電気二重層キャパシ
タ或いは二次電池の構成は、前記本発明の電気二重層キ
ャパシタ及び二次電池用分極性電極を、集電体に接合し
てなることを特徴とするものである。The structure of the electric double layer capacitor and the polarizable electrode for a secondary battery adopted by the present invention in order to solve the above-mentioned object is such that the glassy carbon is eliminated on the activated carbon electrode. 0.27 μg / cm 2 to 4.3 mg /
It is characterized in that it is adhered in a range of cm 2 , and similarly, the constitution of the method for producing a polarizable electrode adopted by the present invention is such that 0.5 μg of polycarbodiimide resin is added on an activated carbon electrode. / Cm 2 to 5 mg / cm 2 and is fired in a non-oxidizing atmosphere. Similarly, the structure of the electric double layer capacitor or secondary battery adopted by the present invention is The electric double layer capacitor and the polarizable electrode for a secondary battery of the present invention are joined to a current collector.
【０００７】即ち、本発明の発明者らは、ガラス状炭素
は、優れた耐薬品性を有し、且つ、層間化合物を作りに
くいという特性、及び、基材上に付着させた場合に基材
からの粉落ち等の発塵を抑制するという特性を有してい
るので、賦活されている炭素電極上にガラス状カーボン
を付着させることにより、電極の成分、例えば活性炭間
を強固に結合させ、粉落ち、繊維の脱落による電気二重
層キャパシタ及び二次電池の容量の経時的低下を抑制で
きるのではないかという着想を得、更に研究を続けた結
果、本研究を完成させたものである。That is, the inventors of the present invention have found that glassy carbon has excellent chemical resistance and is difficult to form an intercalation compound, and when it is adhered onto a substrate, it is a substrate. Since it has a property of suppressing dust generation such as powder falling from, by adhering glassy carbon on the activated carbon electrode, the components of the electrode, for example, strongly bond between activated carbon, This research was completed as a result of continuing the research with the idea that it is possible to suppress the decrease in the capacity of the electric double layer capacitor and the secondary battery due to the falling of powder and the dropping of fibers.
【０００８】以下に本発明を具体的に説明する。The present invention will be specifically described below.
【０００９】本発明で用いられる賦活されている炭素電
極としては、粒状、繊維状、粉末状の活性炭がバイン
ダ、電気、熱及び圧力の少なくとも１種類の方法によっ
て結合されたものを挙げることができ、その形状として
は、板状、棒状、筒状、繊維状等で特に限定されず、
又、その比表面積は５００ｍ2／ｇ以上であるものが望
ましい。The activated carbon electrode used in the present invention may be one in which granular, fibrous or powdered activated carbon is bound by at least one method of binder, electricity, heat and pressure. The shape is not particularly limited and may be plate-shaped, rod-shaped, tubular, fibrous, or the like.
Further, it is desirable that its specific surface area is 500 m 2 / g or more.
【００１０】一方、本発明で用いられるガラス状カーボ
ンとしては、例えば、ポリカルボジイミド樹脂を原料
に、非酸化性雰囲気下で焼成して得られるガラス状カー
ボン（例えば特開平４−２０９７１２号公報参照）を挙
げることができるが、一般にガラス状カーボンと称され
ているものであれば、制限なく使用することができる。On the other hand, as the glassy carbon used in the present invention, for example, a glassy carbon obtained by firing a polycarbodiimide resin as a raw material in a non-oxidizing atmosphere (see, for example, JP-A-4-209712). As long as they are generally called glassy carbon, they can be used without limitation.
【００１１】上記ポリカルボジイミド樹脂それ自体は周
知ものか、或いは、周知のものと同様にして製造するこ
とができるものであって｛米国特許第２，９４ｌ，９５
６号明細書；特公昭４７−３３２７９号公報；Ｊ．Ｏｒ
ｇ．Ｃｈｅｍ．，２８，２０６９〜２０７５（１９６
３）Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗ ｌ９８ｌ，ｖｏ
ｌ．８ｌ．Ｎｏ．４，６ｌ９〜６２ｌ等参照｝、例えば
有機ジイソシアネートの脱二酸化炭素を伴う縮合反応に
より容易に製造することができる。The above-mentioned polycarbodiimide resin itself is well known, or can be produced in the same manner as well known. {US Pat. No. 2,941,95
6, Japanese Patent Publication No. 47-33279, J. Or
g. Chem. , 28 , 2069-2075 (196
3) Chemical Review l98l, vo
l. 8l. No. 4, 619 to 62l, etc.}, for example, it can be easily produced by a condensation reaction involving decarbonization of an organic diisocyanate.
【００１２】このポリカルポジイミド樹脂の製造に使用
される有機ジイソシアネートは、脂肪族系、脂環式系、
芳香族系、芳香−脂肪族系等のいずれのタイプものであ
ってもよく、これらは単独で用いても、或いは、２種以
上を組み合わせて共重合体として用いてもよい。The organic diisocyanate used in the production of this polycarbodiimide resin is an aliphatic type, alicyclic type,
It may be of any type such as aromatic type and aromatic-aliphatic type, and these may be used alone or in combination of two or more kinds as a copolymer.
【００１３】本発明において使用されるポリカルボジイ
ミド樹脂には、下記式 −Ｒ−Ｎ＝Ｃ＝Ｎ− （但し、式中のＲは有機ジイソシアネート残基を表す）
で示される少なくとも１種の繰り返し単位からなる単独
重合体又は共重合体が含包される。The polycarbodiimide resin used in the present invention has the following formula: -RN = C = N- (wherein R represents an organic diisocyanate residue).
A homopolymer or copolymer composed of at least one repeating unit represented by
【００１４】上記式における有機ジイソシアネート残基
Ｒとしては、中でも芳香族ジイソシアネート残基が好適
である。（ここで有機ジイソシアネート残基とは、有機
ジイソシアネート分子から２つのイソシアネート基（Ｎ
ＣＯ）を除いた残りの部分である）。このようなポリカ
ルボジイミド樹脂の具体例としては、以下のものを挙げ
ることができる。As the organic diisocyanate residue R in the above formula, an aromatic diisocyanate residue is particularly preferable. (Here, the organic diisocyanate residue means two isocyanate groups (N
(CO) and the rest). The following can be mentioned as specific examples of such a polycarbodiimide resin.
【００１５】[0015]
【化１】 [Chemical 1]
【００１６】上記各式中において、ｎは１０〜１０，０
００の範囲内、好ましくは５０〜５，０００の範囲内で
ある。尚、ポリカルボジイミド樹脂の末端はモノイソシ
アネート等を用いて封止されていてもよい。In each of the above formulas, n is 10 to 10,0.
It is in the range of 00, preferably in the range of 50 to 5,000. The end of the polycarbodiimide resin may be sealed with monoisocyanate or the like.
【００１７】本発明の電気二重層キャパシタ及び二次電
池用分極性電極を製造するには、まず、ガラス状カーボ
ンを与えることのできる例えば上記ポリカルボジイミド
樹脂により炭素電極を被覆するのであるが、この工程で
は、通常の工業的な被覆方法を用いることができる。即
ち、例えばポリカルボジイミド樹脂溶液又はポリカルボ
ジイミド樹脂粉末分散液に含浸する方法、或いはこれら
の溶液や分散液を刷毛やブラシにより塗布する方法、ス
プレーにより散布する方法を用いることにより、前記溶
液や分散液により炭素電極表面の全部或いは一部を被覆
した後、そのまま焼成工程へ進むか、必要であれば乾燥
機又は熱プレスで溶媒や分散媒を除去し、析出するポリ
カルボジイミド樹脂を溶着させればよいのである。In order to manufacture the electric double layer capacitor and the polarizable electrode for a secondary battery of the present invention, first, the carbon electrode is coated with, for example, the above polycarbodiimide resin capable of providing glassy carbon. In the process, a usual industrial coating method can be used. That is, for example, by using a method of impregnating a polycarbodiimide resin solution or a polycarbodiimide resin powder dispersion, or a method of applying these solutions or dispersions with a brush or a brush, or a method of spraying them, the solution or dispersion After coating all or a part of the carbon electrode surface with, the process proceeds to the firing step as it is, or if necessary, the solvent or dispersion medium may be removed by a dryer or heat press, and the polycarbodiimide resin to be deposited may be welded. Of.
【００１８】上記ポリカルボジイミド樹脂溶液又は分散
液を使用する場合の濃度は、目的とする分極性電極の物
性等により適宜に決定すればよいが、例えば、溶媒又は
分散媒１００重量部に対してポリカルボジイミド樹脂
０．０１〜１５重量部という範囲を挙げることができ
る。The concentration in the case of using the above polycarbodiimide resin solution or dispersion may be appropriately determined depending on the physical properties of the target polarizable electrode and the like. The range of 0.01 to 15 parts by weight of carbodiimide resin can be mentioned.
【００１９】又、ポリカルボジイミド樹脂溶液又は分散
液を使用する場合の樹脂分の目付量は、０．５μｇ／ｃ
ｍ2〜５ｍｇ／ｃｍ2が好ましく、この場合の塗布厚みは
１ｎｍ〜７５０μｍとなるが、この範囲より樹脂溶液が
少ない場合には、炭素電極からの粉落ち、或いは繊維の
脱落を抑制することができないという欠点が生じ、この
範囲より樹脂が多い場合には電極表面上の樹脂層が厚く
なり、その結果、樹脂層が電極表面の穴をつぶし、電極
表層から電解液が電極内に浸透できなくなり、その結果
静電容量が低下するという問題が生じる。When the polycarbodiimide resin solution or dispersion is used, the basis weight of the resin component is 0.5 μg / c.
m 2 to 5 mg / cm 2 is preferable, and the coating thickness in this case is 1 nm to 750 μm, but when the resin solution is less than this range, it is possible to suppress powder falling off from the carbon electrode or fiber falling off. If there is more resin than this range, the resin layer on the electrode surface will become thicker, and as a result, the resin layer will crush the holes on the electrode surface and electrolyte will not be able to penetrate into the electrode from the electrode surface layer. As a result, there arises a problem that the capacitance decreases.
【００２０】上記のようにして得られた、例えばポリカ
ルボジイミド樹脂により被覆された炭素電極を次に焼成
する。この焼成工程は、従来公知のいずれの方法によっ
てもよく、例えば、真空、或いは窒素、アルゴン、水素
等の非酸化性雰囲気下で行うことができる。尚、この工
程での焼成温度に上限はないが、５００℃〜２０００
℃、好ましくは、７００℃〜１５００℃という範囲を挙
げることができる。この焼成工程では、５００℃より低
い温度では電気抵抗が大きくなり、静電容量が低下して
しまうという欠点があり、２０００℃より高い温度で
は、炭素電極の表面積を減少させ、その結果、静電容量
を低下させてしまうという欠点が生じる。The carbon electrode coated with, for example, a polycarbodiimide resin, obtained as described above, is then fired. This firing step may be performed by any conventionally known method, and can be performed, for example, in a vacuum or in a non-oxidizing atmosphere such as nitrogen, argon or hydrogen. There is no upper limit to the firing temperature in this step, but 500 ° C to 2000 ° C.
C., preferably 700.degree. C. to 1500.degree. C. can be mentioned. In this firing process, there is a drawback that the electric resistance becomes large at a temperature lower than 500 ° C. and the electrostatic capacity lowers, and at a temperature higher than 2000 ° C., the surface area of the carbon electrode is reduced, resulting in electrostatic discharge. The drawback is that the capacity is reduced.
【００２１】上記の焼成工程を経ることにより、賦活さ
れている炭素電極上にガラス状カーボンを付着させた本
発明の電気二重層キャパシタ及び二次電池用分極性電極
を得ることができる。尚、ガラス状カーボンの付着量
は、使用したガラス状カーボンの原料物質を５００℃〜
２０００℃で焼成した際の炭素収率によって決定され、
ポリカルボジイミド樹脂の場合、炭素収率は５５乃至８
５％であるから、前記のような目付量であれば、０．２
７μｇ／ｃｍ2〜４．３ｍｇ／ｃｍ2という範囲となる。By passing through the above firing step, it is possible to obtain the electric double layer capacitor and the polarizable electrode for a secondary battery of the present invention in which glassy carbon is adhered on the activated carbon electrode. In addition, the adhesion amount of glassy carbon is 500 ° C.
Determined by the carbon yield when calcined at 2000 ° C.,
In the case of polycarbodiimide resin, carbon yield is 55 to 8
Since it is 5%, if the above basis weight is 0.2
The range is 7 μg / cm 2 to 4.3 mg / cm 2 .
【００２２】又、ガラス状カーボンの厚みは、０．５〜
６９０ｎｍとなる。The glassy carbon has a thickness of 0.5 to
It becomes 690 nm.
【００２３】このようにして得られた本発明のガラス状
カーボンが付着した賦活されている炭素電極は、そのま
ま、或いは適宜に切断することにより、電気二重層キャ
パシタ及び二次電池用の分極性電極として使用すること
ができ、電気二重層キャパシタ及び二次電池とするに
は、例えばガラス状カーボン若しくはアルミニウムやス
テンレスなどの金属板又は金属箔若しくは導電性ゴム等
による集電体に、適宜の導電性接着剤により固着し、更
に適宜の電解液を含浸すればよい。The activated carbon electrode to which the glassy carbon of the present invention thus obtained is attached, as it is, or by cutting it appropriately, a polarizable electrode for an electric double layer capacitor and a secondary battery. The electric double layer capacitor and the secondary battery can be used as, for example, a metal plate such as glassy carbon or aluminum or stainless steel, a metal foil, or a current collector made of conductive rubber, and an appropriate conductive property. It may be fixed with an adhesive and further impregnated with an appropriate electrolytic solution.
【００２４】[0024]
【実施例】次に本発明を実施例により具体的に説明す
る。EXAMPLES Next, the present invention will be specifically described by way of examples.
【００２５】ポリカルボジイミド樹脂溶液又は粉末分散
液の製造方法 ２、４−トリレジンジイソシアネート／２、６−トリレ
ンジジイソシアネート（８０／２０）の混合物５４ｇ
を、テトラクロロエチレン５００ｍｌ中でカルボジイミ
ド化触媒（３−メチル−１−フェニル−２−ホスホレン
−１−オキシド）０．１２ｇと共に、１２０℃で４時間
反応させ、ポリカルボジイミド樹脂溶液を得た。この溶
液をスプレードライヤーで乾燥し、固形分を粉砕して、
得られたポリカルボジイミド樹脂粉末をエタノール中に
分散した。Method for producing polycarbodiimide resin solution or powder dispersion 54 g of a mixture of 2,4-triresin diisocyanate / 2,6-tolylene diisocyanate (80/20)
Was reacted with 0.12 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholen-1-oxide) in 500 ml of tetrachloroethylene at 120 ° C. for 4 hours to obtain a polycarbodiimide resin solution. This solution is dried with a spray dryer, the solid content is crushed,
The obtained polycarbodiimide resin powder was dispersed in ethanol.
【００２６】実施例１乃至実施例６ 活性炭粉末（平均粒径１０μｍ、比表面積１５００ｍ2
／ｇ）８０重量部とフェノール樹脂（平均粒径１０μ
ｍ）２０重量部とを混合し、１５０℃、１００ｋｇ／ｃ
ｍ2の圧力で１５分間熱プレスした。この熱プレス品を
アルゴンガス中で９００℃で熱処理して炭素電極を得
た。この炭素電極を３０ｍｍφ×１ｍｍｔに切り出し
て、その表面に表１に示す組成のポリカルボジイミド樹
脂溶液を塗布して、アルゴンガス雰囲気下で表１に示す
焼成温度で焼成し、分極性電極を得た。次に、この分極
性電極２枚を３０ｗｔ％硫酸に浸漬し、真空含浸する際
の粉落ちの有無を確認した。結果を表１に示す。Examples 1 to 6 Activated carbon powder (average particle size 10 μm, specific surface area 1500 m 2
/ G) 80 parts by weight and phenol resin (average particle size 10μ
m) mixed with 20 parts by weight, 150 ° C, 100 kg / c
It was hot pressed at a pressure of m 2 for 15 minutes. This hot-pressed product was heat-treated in argon gas at 900 ° C. to obtain a carbon electrode. This carbon electrode was cut into a size of 30 mmφ × 1 mmt, and a polycarbodiimide resin solution having a composition shown in Table 1 was applied to the surface of the carbon electrode and baked at an baking temperature shown in Table 1 under an argon gas atmosphere to obtain a polarizable electrode. . Next, the two polarizable electrodes were dipped in 30 wt% sulfuric acid, and the presence or absence of powder drop during vacuum impregnation was confirmed. The results are shown in Table 1.
【００２７】真空含浸後、１組の分極性電極を、ポリカ
ルボジイミドフィルムを焼成することによって得られる
ガラス状炭素（日清紡製）による集電体へ、熱硬化性樹
脂と膨張黒煙粉末からなる導電性接着剤を介して接合
し、簡易電気二重層キャパシタとした。この簡易電気二
重層キャパシタの両端に０．９Ｖを印加し、１時間定電
圧充電を行った。その後１０ｍＡで定電流放電し、電圧
が０．５４Ｖから０．４５Ｖに降下する時間から、この
電気二重層キャパシタの静電容量を測定した。又、上記
充放電条件で５０００回充放電を行い、１回目の容量を
１００％とした場合の容量変化を測定した。結果を表１
に示す。After the vacuum impregnation, a set of polarizable electrodes was made into a current collector made of glassy carbon (manufactured by Nisshinbo Co., Ltd.) obtained by firing a polycarbodiimide film, and a conductive material composed of a thermosetting resin and expanded black smoke powder was used. A simple electric double layer capacitor was obtained by bonding with a conductive adhesive. 0.9 V was applied to both ends of this simple electric double layer capacitor, and constant voltage charging was performed for 1 hour. After that, constant-current discharge was performed at 10 mA, and the capacitance of this electric double layer capacitor was measured from the time when the voltage dropped from 0.54 V to 0.45 V. Further, the charging / discharging was performed 5000 times under the above charging / discharging conditions, and the capacity change was measured when the capacity of the first charging was 100%. The results are shown in Table 1.
Shown in.
【００２８】実施例７乃至実施例１２ 実施例１乃至６で作成した炭素電極に、表１に示すよう
にポリカルボジイミド粉末分散液を塗布し、実施例１と
同様にして分極性電極を得た。次に、実施例１と同様に
して、この分極性電極２枚を３０ｗｔ％硫酸に浸漬して
真空含浸し、更に簡易電気二重層キャパシタとした。粉
落ちの有無と静電容量及び容量変化を表１に示す。Examples 7 to 12 The carbon electrodes prepared in Examples 1 to 6 were coated with a polycarbodiimide powder dispersion as shown in Table 1, and polarizable electrodes were obtained in the same manner as in Example 1. . Next, in the same manner as in Example 1, two polarizable electrodes were immersed in 30 wt% sulfuric acid and vacuum impregnated to obtain a simple electric double layer capacitor. Table 1 shows the presence / absence of powder drop, the electrostatic capacity and the capacity change.
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例１３乃至実施例１８ 実施例１乃至６で作製した分電極性電極を用い、この分
極性電極にテトラエチルアンモニウムのホウフッ化塩
（Ｅｔ4ＮＢＦ4）を電解質とした１モル／ｌのプロピレ
ンカーボネート電解液を真空含浸し、このときの粉落ち
の有無を調べた。結果を表２に示す。Examples 13 to 18 The split electrode prepared in Examples 1 to 6 was used, and 1 mol / l of tetraethylammonium borofluoride (Et 4 NBF 4 ) was used as an electrolyte for the polarizable electrode. The above propylene carbonate electrolyte solution was vacuum impregnated, and the presence or absence of powder drop at this time was examined. The results are shown in Table 2.
【００３１】この分極性電極とガラス状炭素（日清紡
製）の集電体とを導電性接着剤を介して接合し、実施例
１乃至６と同様に電気二重層キャパシタを組み上げ、こ
の簡易電気二重層キャパシタの両端に１．８Ｖを印加
し、１時間定電圧充電を行った。その後１０ｍＡで定電
流放電し、電圧が１．０８Ｖから０．９Ｖ降下する時間
から、この電気二重層キャパシタの静電容量を測定し
た。又、上記放電条件で、実施例１乃至６と同様に５０
００回充放電した際の容量の変化を測定した。結果を表
２に示す。This polarizable electrode and a glassy carbon (Nisshinbo Co., Ltd.) current collector were joined via a conductive adhesive, and an electric double layer capacitor was assembled in the same manner as in Examples 1 to 6, and this simple electric capacitor was used. 1.8 V was applied to both ends of the multilayer capacitor, and constant voltage charging was performed for 1 hour. After that, constant current discharge was performed at 10 mA, and the capacitance of this electric double layer capacitor was measured from the time when the voltage dropped from 1.08 V to 0.9 V. Further, under the above discharge conditions, as in Examples 1 to 6, 50
The change in capacity when charged and discharged 100 times was measured. The results are shown in Table 2.
【００３２】[0032]
【表２】 [Table 2]
【００３３】比較例１乃至比較例８ 実施例１乃至６で作製した炭素電極に、表３に示す組成
のポリカルボジイミド樹脂溶液を塗布し、表３に示す焼
成温度でアルゴンガス中で焼成し分極性電極を得た。こ
の分極性電極に３０ｗｔ％硫酸水溶液を真空含浸して粉
落ちの有無を調べた。結果を表３に示す。続いて実施例
１乃至６と同様に簡易電気二重層キャパシタを組み上
げ、実施例１乃至６と同様の条件で性電容量と５０００
回充放電した際の容量の変化を測定した。結果を表３に
示す。Comparative Examples 1 to 8 The polycarbodiimide resin solutions having the compositions shown in Table 3 were applied to the carbon electrodes prepared in Examples 1 to 6 and baked in argon gas at the baking temperature shown in Table 3 to A polar electrode was obtained. The polarizable electrode was vacuum-impregnated with a 30 wt% sulfuric acid aqueous solution and examined for powder falling. The results are shown in Table 3. Subsequently, a simple electric double layer capacitor was assembled in the same manner as in Examples 1 to 6, and a simple electric double layer capacitor and a static capacitance of 5000 were obtained under the same conditions as in Examples 1 to 6.
The change in capacity after repeated charge and discharge was measured. The results are shown in Table 3.
【００３４】比較例９ 活性炭素繊維（比表面積１５００ｍ2／ｇ）を１００ｋ
ｇ／ｃｍ2でプレスして３０ｍｍφ×１ｍｍｔの大きさ
に切断し、３０ｗｔ％硫酸水溶液を真空含浸した。この
ときの粉落ちの有無を調べた。結果を表３に示す。この
分極性電極をガラス状炭素（日清紡製）に導電性接着剤
を介して接合し、実施例１乃至６と同様に電気二重層キ
ャパシタを組み上げ、実施例１乃至６と同様の条件で静
電容量と５０００回充放電した際の容量の変化を測定し
た。結果を表３に示す。Comparative Example 9 100 k of activated carbon fiber (specific surface area 1500 m 2 / g)
It was pressed at g / cm 2 and cut into a size of 30 mmφ × 1 mmt, which was vacuum impregnated with a 30 wt% sulfuric acid aqueous solution. The presence or absence of powder drop at this time was examined. The results are shown in Table 3. This polarizable electrode was bonded to glassy carbon (manufactured by Nisshinbo Co., Ltd.) via a conductive adhesive to assemble an electric double layer capacitor in the same manner as in Examples 1 to 6, and electrostatically charged under the same conditions as in Examples 1 to 6. The change in the capacity and the capacity after charging and discharging 5000 times were measured. The results are shown in Table 3.
【００３５】比較例１０ 実施例１乃至６で作製した炭素電極を分極性電極として
３０ｗｔ％硫酸水溶液を真空含浸した。このときの粉落
ちの有無を調べた。結果を表３に示す。この分極性電極
をガラス状炭素（日清紡社製）に導電性接着剤を介して
接合し、実施例１乃至６と同様に電気二重層キャパシタ
を組み上げ、実施例１乃至６と同様の条件で静電容量、
５０００回充放電した際の容量の変化を測定した。結果
を表３に示す。Comparative Example 10 The carbon electrodes prepared in Examples 1 to 6 were used as polarizable electrodes and vacuum impregnated with a 30 wt% sulfuric acid aqueous solution. The presence or absence of powder drop at this time was examined. The results are shown in Table 3. This polarizable electrode was bonded to glassy carbon (manufactured by Nisshinbo Co., Ltd.) via a conductive adhesive, and an electric double layer capacitor was assembled in the same manner as in Examples 1 to 6, and static electricity was applied under the same conditions as in Examples 1 to 6. Capacitance,
The change in capacity after charging and discharging 5000 times was measured. The results are shown in Table 3.
【００３６】[0036]
【表３】 [Table 3]
【００３７】[0037]
【発明の効果】上記実施例から明らかなように、本発明
は、炭素電極からの粉落ち或いは繊維の脱落を抑制する
ことのできる電気二重層キャパシタ及び二次電池用分極
性電極、その製造方法及びこの分極性電極を使用した電
気二重層キャパシタ或いは二次電池を提供することがで
きるものである。As is apparent from the above-described embodiments, the present invention is directed to an electric double layer capacitor and a polarizable electrode for a secondary battery, which are capable of suppressing powder drop or fiber drop from a carbon electrode, and a method for manufacturing the same. It is also possible to provide an electric double layer capacitor or a secondary battery using this polarizable electrode.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｍ 10/40 Ｚ (72)発明者 濱田 一寿 東京都足立区西新井栄町１−18−１ 日清 紡績株式会社東京研究センター内 (72)発明者 弘中 孝志 東京都足立区西新井栄町１−18−１ 日清 紡績株式会社東京研究センター内 (72)発明者 寺田 剛 東京都足立区西新井栄町１−18−１ 日清 紡績株式会社東京研究センター内 (72)発明者 松林 克征 東京都足立区西新井栄町１−18−１ 日清 紡績株式会社東京研究センター内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Internal reference number FI Technical indication location H01M 10/40 Z (72) Inventor Kazutoshi Hamada 1-18-1 Nishiarai-cho, Adachi-ku, Tokyo Seishin Spinning Co., Ltd.Tokyo Research Center (72) Inventor Takashi Hironaka 1-18-1 Nishiarai Sakaecho, Adachi-ku, Tokyo Nisshin Spinning Co., Ltd. Tokyo Research Center (72) Inventor Go Terada 1 Nishiarai Sakae, Adachi-ku, Tokyo 18-1 Nisshin Spinning Co., Ltd. Tokyo Research Center (72) Inventor Katsushi Matsubayashi 1-18-1 Nishiaraieicho, Adachi-ku, Tokyo Nisshin Spinning Co., Ltd. Tokyo Research Center
Claims (8)
ーボンを０．２７μｇ／ｃｍ2〜４．３ｍｇ／ｃｍ2の範
囲で付着させてなることを特徴とする電気二重層キャパ
シタ及び二次電池用分極性電極。1. An electric double layer capacitor and a secondary battery comprising glassy carbon deposited on an activated carbon electrode in a range of 0.27 μg / cm 2 to 4.3 mg / cm 2. Polarizable electrodes.
とも一部を覆う皮膜として付着されている請求項１に記
載の電気二重層キャパシタ及び二次電池用分極性電極。2. The polarizable electrode for an electric double layer capacitor and a secondary battery according to claim 1, wherein glassy carbon is attached as a coating covering at least a part of the carbon electrode.
ド樹脂を原料とし、非酸化性雰囲気下で焼成したもので
ある請求項１に記載の電気二重層キャパシタ及び二次電
池用分極性電極。3. The polarizable electrode for an electric double layer capacitor and a secondary battery according to claim 1, wherein the glassy carbon is obtained by firing a polycarbodiimide resin as a raw material in a non-oxidizing atmosphere.
ｍの厚みで炭素電極上に付着されている請求項１に記載
の電気二重層キャパシタ及び二次電池用分極性電極。4. The glassy carbon is 0.5 to 690 n
The polarizable electrode for an electric double layer capacitor and a secondary battery according to claim 1, wherein the polarizable electrode has a thickness of m and is deposited on a carbon electrode.
ジイミド樹脂を０．５μｇ／ｃｍ2〜５ｍｇ／ｃｍ2の範
囲で適用し、非酸化性雰囲気下で焼成することを特徴と
する電気二重層キャパシタ及び二次電池用分極性電極の
製造方法。5. An electric double layer characterized by applying a polycarbodiimide resin on an activated carbon electrode in the range of 0.5 μg / cm 2 to 5 mg / cm 2 and firing in a non-oxidizing atmosphere. A method for manufacturing a capacitor and a polarizable electrode for a secondary battery.
して適用される請求項５に記載の電気二重層キャパシタ
及び二次電池用分極性電極の製造方法。6. The method for producing a polarizable electrode for an electric double layer capacitor and a secondary battery according to claim 5, wherein the polycarbodiimide resin is applied as a solution thereof.
分が、溶媒１００重量部に対して０．０１重量部から１
５重量部である請求項６に記載の電気二重層キャパシタ
及び二次電池用分極性電極の製造方法。7. The resin component in the polycarbodiimide resin solution is from 0.01 to 1 part by weight based on 100 parts by weight of the solvent.
It is 5 parts by weight, and the method for producing a polarizable electrode for an electric double layer capacitor and a secondary battery according to claim 6.
二重層キャパシタ及び二次電池用分極性電極を、集電体
に接合してなることを特徴とする電気二重層キャパシタ
及び二次電池。8. An electric double layer capacitor and a secondary, comprising the electric double layer capacitor according to any one of claims 1 to 4 and a polarizable electrode for a secondary battery bonded to a current collector. battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6261513A JPH0897102A (en) | 1994-09-29 | 1994-09-29 | Electrical double-layer capacitor, polarizable electrode for secondary battery and its manufacture, and electrical double-layer capacitor or secondary battery using the polarizable electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6261513A JPH0897102A (en) | 1994-09-29 | 1994-09-29 | Electrical double-layer capacitor, polarizable electrode for secondary battery and its manufacture, and electrical double-layer capacitor or secondary battery using the polarizable electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0897102A true JPH0897102A (en) | 1996-04-12 |
Family
ID=17362954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6261513A Pending JPH0897102A (en) | 1994-09-29 | 1994-09-29 | Electrical double-layer capacitor, polarizable electrode for secondary battery and its manufacture, and electrical double-layer capacitor or secondary battery using the polarizable electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0897102A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6198621B1 (en) | 1998-02-05 | 2001-03-06 | Nec Corporation | Electric double layer capacitor using polarizable electrode of single particle layer |
| US6320740B1 (en) | 1999-02-03 | 2001-11-20 | Nec Corporation | Method for manufacturing a polarized electrode for an electric double-layer capacitor |
| WO2005113844A1 (en) * | 2004-05-14 | 2005-12-01 | Sgl Carbon Ag | Gas impervious electrodes for carbothermic reduction furnace |
| US20080055819A1 (en) * | 2006-09-04 | 2008-03-06 | Fuji Jukogyo Kabushiki Kaisha | Lithium-ion capacitor |
| WO2010110153A1 (en) * | 2009-03-27 | 2010-09-30 | 独立行政法人科学技術振興機構 | Method for producing graphene film, method for manufacturing electronic element, and method for transferring graphene film to substrate |
-
1994
- 1994-09-29 JP JP6261513A patent/JPH0897102A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6198621B1 (en) | 1998-02-05 | 2001-03-06 | Nec Corporation | Electric double layer capacitor using polarizable electrode of single particle layer |
| US6320740B1 (en) | 1999-02-03 | 2001-11-20 | Nec Corporation | Method for manufacturing a polarized electrode for an electric double-layer capacitor |
| WO2005113844A1 (en) * | 2004-05-14 | 2005-12-01 | Sgl Carbon Ag | Gas impervious electrodes for carbothermic reduction furnace |
| US20080055819A1 (en) * | 2006-09-04 | 2008-03-06 | Fuji Jukogyo Kabushiki Kaisha | Lithium-ion capacitor |
| US8724292B2 (en) * | 2006-09-04 | 2014-05-13 | Fuji Jukogyo Kabushiki Kaisha | Lithium-ion capacitor |
| WO2010110153A1 (en) * | 2009-03-27 | 2010-09-30 | 独立行政法人科学技術振興機構 | Method for producing graphene film, method for manufacturing electronic element, and method for transferring graphene film to substrate |
| CN102438944A (en) * | 2009-03-27 | 2012-05-02 | 独立行政法人科学技术振兴机构 | Method for producing graphene film, method for manufacturing electronic element, and method for transferring graphene film to substrate |
| JP4970619B2 (en) * | 2009-03-27 | 2012-07-11 | 独立行政法人科学技術振興機構 | Method for producing graphene film, method for producing electronic device, and method for transferring graphene film to substrate |
| KR101357060B1 (en) * | 2009-03-27 | 2014-02-03 | 도꾸리쯔교세이호징 가가꾸 기쥬쯔 신꼬 기꼬 | Method for producing graphene film, method for manufacturing electronic element, and method for transferring graphene film to substrate |
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