JPH1197317A - Electric double layer capacitor, electrode and manufacturing method thereof - Google Patents
Electric double layer capacitor, electrode and manufacturing method thereofInfo
- Publication number
- JPH1197317A JPH1197317A JP9253547A JP25354797A JPH1197317A JP H1197317 A JPH1197317 A JP H1197317A JP 9253547 A JP9253547 A JP 9253547A JP 25354797 A JP25354797 A JP 25354797A JP H1197317 A JPH1197317 A JP H1197317A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- double layer
- layer capacitor
- electric double
- powder
- 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
- 239000003990 capacitor Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 32
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 239000008151 electrolyte solution Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 239000005539 carbonized material Substances 0.000 abstract 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000005245 sintering Methods 0.000 description 10
- 238000007033 dehydrochlorination reaction Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電気二重層コンデ
ンサ、電極及びそれらの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric double layer capacitor, an electrode, and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】電気二重層コンデンサは、活性炭の粉末
に電解液をしみこませ、活性炭と電解液の界面にできる
電気二重層の静電容量を利用したコンデンサである。耐
電圧、最高使用温度は、電解液の分解電圧・温度に依存
しており、定格電圧は数Ｖと低いが、ファラッドオーダ
の静電容量が容易に得られることから、電池の代わりに
半導体メモリ（Ｄ−ＲＡＭ）のバックアップ用等の低電
流密度の用途に多く用いられるようになっており、最近
では、もっと電流密度の高い用途、例えば車載鉛蓄電池
の代わり、にも使用することが研究されている。2. Description of the Related Art An electric double layer capacitor is a capacitor utilizing an electrostatic solution of an activated carbon powder and an electrolytic solution impregnated in an activated carbon powder. The withstand voltage and the maximum operating temperature depend on the decomposition voltage and temperature of the electrolytic solution, and the rated voltage is as low as several volts. However, since the Farad order capacitance can be easily obtained, the semiconductor memory is used instead of the battery. It has been widely used for low current density applications such as backup of (D-RAM), and has recently been studied for use in applications having higher current densities, for example, in place of in-vehicle lead-acid batteries. ing.
【０００３】従来、電気二重層コンデンサ用電極とし
て、活性炭にバインダを混入させ焼結したものや焼結後
に腑活処理（酸化による不純物除去処理）したものを用
いていた。しかし、これらの電極を使用すると、次のよ
うな問題点が生じていた。 ａ）活性炭はマクロポアが多く細孔体積比率が高いた
め、密度が低い。 ｂ）比表面積は大きいが細孔径の分布が広いため、電気
二重層コンデンサ用電極として働く実効的な細孔は少な
い。 ｃ）焼結を促進する目的で比較的高温で焼結するため、
電気二重層コンデンサ用電極として働く実効的な細孔は
少ない。 ｄ）低温（８５０℃以下）で焼結すると、グラファイト
化が進まないため、粒子間焼結強度がなく、そして、抵
抗値が高い。Heretofore, as an electrode for an electric double layer capacitor, a material obtained by mixing a binder with activated carbon and sintering or a material subjected to an activation treatment (impurity removal treatment by oxidation) after sintering has been used. However, the use of these electrodes has caused the following problems. a) Activated carbon has a low density because it has many macropores and a high pore volume ratio. b) Although the specific surface area is large, the distribution of the pore diameter is wide, so that there are few effective pores acting as electrodes for electric double layer capacitors. c) sintering at a relatively high temperature to promote sintering,
There are few effective pores acting as electrodes for electric double layer capacitors. d) When sintering at a low temperature (850 ° C. or lower), graphitization does not proceed, so there is no intergranular sintering strength and the resistance value is high.
【０００４】これらの問題点を解決するため、ＰＶＤＣ
（ポリ塩化ビニリデン）樹脂炭化物を使用することが提
案されている（特開平７−２４９５５１号公報参照）。
ＰＶＤＣ樹脂（あるいは塩化ビニリデン系共重合体）炭
化物を使用すると、他の活性炭と比較して長所を有して
おり、その理由として、次のことによるといわれてい
る。ＰＶＤＣ樹脂は、２つの脱塩酸反応温度を有してい
る。第一点は１８０℃から２５０℃で自己分子鎖内での
脱塩酸反応であり、第二点は４５０℃から５５０℃での
分子鎖間の脱塩酸反応で、その際分子間結合が生じてい
る。第一点の温度範囲で加熱すると脱塩酸反応により細
孔が形成され、その細孔は、３６Å以下のマイクロポア
とよばれるものであって、これが電気二重層コンデンサ
用電極として使用されると電解液との界面として有効に
働く。このため、電極としての腑活処理は不必要であ
る。また、第二点の温度範囲以上で加熱すると、脱塩酸
反応により有効マイクロポアを保持しつつ比較的低温で
も焼結を進行させることができる。このため、電気二重
層コンデンサ用電極には不要である大きな径のメソポア
やマクロポアの発生を抑えることができる。このため、
ＰＶＤＣ樹脂炭化物は、比表面積は活性炭に比べて少な
いが、焼結密度が活性炭に比べて大きくなり、体積あた
りの容量は大きくなる。[0004] To solve these problems, PVDC
It has been proposed to use (polyvinylidene chloride) resin carbide (see JP-A-7-249551).
The use of PVDC resin (or vinylidene chloride-based copolymer) carbide has advantages over other activated carbons because of the following. PVDC resins have two dehydrochlorination reaction temperatures. The first point is the dehydrochlorination reaction in the self-molecular chain at 180 ° C to 250 ° C, and the second point is the dehydrochlorination reaction between the molecular chains at 450 ° C to 550 ° C. I have. When heated in the temperature range of the first point, pores are formed by the dehydrochlorination reaction, and the pores are called micropores having a diameter of 36 ° or less. It works effectively as an interface with the liquid. For this reason, activation treatment as an electrode is unnecessary. Further, when the heating is performed at a temperature not lower than the temperature range of the second point, sintering can be advanced even at a relatively low temperature while maintaining effective micropores by the dehydrochlorination reaction. For this reason, generation of mesopores or macropores having a large diameter, which is unnecessary for the electrode for an electric double layer capacitor, can be suppressed. For this reason,
The PVDC resin carbide has a smaller specific surface area than activated carbon, but has a higher sintering density than activated carbon and a larger capacity per volume.
【０００５】しかし、ＰＶＤＣ樹脂炭化物は、次のよう
な問題点を有している。 ａ）バインダレスであるため、成形しにくい。 ｂ）低温（８５０℃以下）での焼結ではグラファイトが
進まないため、オーミックな抵抗が高い。そのため高電
流密度においてはＩＲドロップが大きく容量が取り出せ
ない。 ｃ）ＰＶＤＣ樹脂炭化物は高密度に焼結できるが、粒子
間の空隙やマクロポアが少ないため拡散抵抗が高い。However, the PVDC resin carbide has the following problems. a) It is difficult to mold because it is binderless. b) Ohmic resistance is high because graphite does not advance during sintering at low temperature (850 ° C. or lower). Therefore, at a high current density, the IR drop is large and the capacity cannot be taken out. c) The PVDC resin carbide can be sintered at a high density, but has a high diffusion resistance due to few voids and macropores between particles.
【０００６】また、ＰＶＤＣ樹脂を１８０〜６００℃で
炭化させたものを成形した後、６００〜９５０℃で焼結
して電極とすることも提案されているが、特に薄く成形
すると、強度が弱く、製造段階で割れなどが発生しやす
かった。また、液状の電解質溶液に含浸して用いるた
め、電解液の漏れやドライアップの問題が有った。[0006] It has also been proposed to form a PVDC resin carbonized at 180 to 600 ° C and then sinter it at 600 to 950 ° C to form an electrode. , Cracks and the like were likely to occur in the manufacturing stage. In addition, since it is used after being impregnated with a liquid electrolyte solution, there are problems of leakage of electrolyte solution and dry-up.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、電極の拡散
抵抗を下げ、そして、電極を薄く成形しても強度が弱く
ならず、また、電解液の漏れやドライアップの問題が生
じない電気二重層コンデンサ及び電極を提供するもので
ある。DISCLOSURE OF THE INVENTION The present invention reduces the diffusion resistance of an electrode, and does not reduce the strength even if the electrode is formed thin, and does not cause problems of electrolyte leakage or dry-up. A double layer capacitor and electrodes are provided.
【０００８】[0008]
【課題を解決するための手段】本発明は、ＰＶＤＣ樹脂
炭化物からなる電気二重層コンデンサ用電極において、
前記ＰＶＤＣ樹脂炭化物は径２２μｍ以下の粉末であ
り、そして、該粉末は電解質ゲルと混合したものである
電気二重層コンデンサ用電極である。SUMMARY OF THE INVENTION The present invention relates to an electrode for an electric double layer capacitor comprising a PVDC resin carbide.
The PVDC resin carbide is a powder having a diameter of 22 μm or less, and the powder is an electrode for an electric double layer capacitor which is mixed with an electrolyte gel.
【０００９】また、本発明は、上記電解質ゲルは、希硫
酸に分子量２０万〜４００万のポリエチレングリコール
を添加したものである電気二重層コンデンサ用電極であ
る。Further, the present invention is an electrode for an electric double layer capacitor, wherein said electrolyte gel is obtained by adding polyethylene glycol having a molecular weight of 200,000 to 4,000,000 to dilute sulfuric acid.
【００１０】そして、本発明は、ＰＶＤＣ樹脂炭化物か
らなる電極を具備する電気二重層コンデンサにおいて、
前記電極は径２２μｍ以下のＰＶＤＣ樹脂炭化物粉末か
らなり、そして、該粉末は電解質ゲルと混合したもので
ある電気二重層コンデンサである。The present invention provides an electric double layer capacitor having an electrode made of PVDC resin carbide,
The electrode is a PVDC resin carbide powder having a diameter of 22 μm or less, and the powder is an electric double layer capacitor mixed with an electrolyte gel.
【００１１】更に、本発明は、ＰＶＤＣ樹脂を６００〜
９５０℃で炭化させ、得られた炭化物を粉砕して径２２
μｍ以下の粉末とし、該粉末を電解質ゲルと混合する電
気二重層コンデンサ用電極の製造方法である。[0011] Further, the present invention provides a PVDC resin of 600 to
Carbonized at 950 ° C., and the resulting carbide is pulverized to a diameter of 22
This is a method for producing an electrode for an electric double layer capacitor in which powder having a size of not more than μm is mixed and the powder is mixed with an electrolyte gel.
【００１２】また、本発明は、上記電解質ゲルは、希硫
酸に分子量２０万〜４００万のポリエチレングリコール
を添加したものである電気二重層コンデンサ用電極の製
造方法である。The present invention is also a method for producing an electrode for an electric double layer capacitor, wherein the electrolyte gel is obtained by adding polyethylene glycol having a molecular weight of 200,000 to 4,000,000 to dilute sulfuric acid.
【００１３】そして、本発明は、ＰＶＤＣ樹脂炭化物粉
末を希硫酸に含浸してスラリ化したものに２０万〜４０
０万のポリエチレングリコールを添加する電気二重層コ
ンデンサ用電極の製造方法である。[0013] The present invention provides a slurry obtained by impregnating PVDC resin carbide powder with dilute sulfuric acid to form a slurry.
This is a method for manufacturing an electrode for an electric double layer capacitor to which 100,000 polyethylene glycol is added.
【００１４】更に、本発明は、ＰＶＤＣ樹脂炭化物粉末
を希硫酸に含浸した後、希硫酸をろ過した粉末を電解質
ゲルに混合する電気二重層コンデンサ用電極の製造方法
である。Further, the present invention is a method for producing an electrode for an electric double layer capacitor, wherein a powder obtained by impregnating a PVDC resin carbide powder with dilute sulfuric acid and then filtering the diluted sulfuric acid is mixed with an electrolyte gel.
【００１５】また、本発明は、ＰＶＤＣ樹脂炭化物粉末
と電解質ゲルとの混合物を集電板上に塗布する電気二重
層コンデンサ用電極の製造方法である。The present invention is also a method for producing an electrode for an electric double layer capacitor, in which a mixture of a PVDC resin carbide powder and an electrolyte gel is applied on a current collector.
【００１６】そして、本発明は、ＰＶＤＣ樹脂を６００
〜９５０℃で炭化し、粉砕して得られた径２２μｍ以下
の粉末で電極を作製した後、該電極を電気二重層コンデ
ンサに組込み、次に、電解質ゲルを添加して前記電極に
しみこませる電気二重層コンデンサの製造方法である。Further, the present invention relates to a PVDC resin of 600
After producing an electrode with powder having a diameter of 22 μm or less obtained by carbonizing at −950 ° C. and pulverizing, the electrode is incorporated into an electric double-layer capacitor, and then an electrolyte gel is added to impregnate the electrode. This is a method for manufacturing a double-layer capacitor.
【００１７】[0017]
【発明の実施の形態】本発明の発明の実施の形態を説明
する。本発明の電気二重層コンデンサ、電極及びそれら
の製造方法について、実施例を用いて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described. The electric double layer capacitor, the electrode, and the method of manufacturing the same according to the present invention will be described with reference to examples.
【００１８】本発明の電気二重層コンデンサの製造方法
の実施例１を説明する。まず、３５ｗｔ％硫酸に分子量
４００万のポリエチレングリコール（ＰＥＧ）を２ｗｔ
％添加し、１日放置して硫酸ゲルを作製した。次に、Ｐ
ＶＤＣ樹脂を８５０℃で炭化した後、２２μｍ以下の粒
子サイズに粉砕し、３５ｗｔ％の硫酸に投入し、煮沸含
浸した後、硫酸をろ過して取り除き、ＰＶＤＣ樹脂炭化
物粉末を得た。次に、このＰＶＤＣ樹脂炭化物粉末を上
記硫酸ゲルに入れて混合し、１日放置したものを、集電
板上にドクターブレードを用いて２５ｍｍ□の面積で厚
さ５００μｍになるよう均一に塗布して、電極２を作製
した。この電極２枚で２００μｍ厚のガラス不織繊維の
セパレータ３を挾んでセルを組んだ。セパレータ２には
あらかじめ希硫酸を含浸させたものを用いた。（図１参
照）Embodiment 1 of the method for manufacturing an electric double layer capacitor according to the present invention will be described. First, 2 wt% of polyethylene glycol (PEG) having a molecular weight of 4 million was added to 35 wt% sulfuric acid.
% And left for 1 day to produce a sulfuric acid gel. Next, P
The VDC resin was carbonized at 850 ° C., pulverized to a particle size of 22 μm or less, poured into 35% by weight sulfuric acid, boiled and impregnated, and filtered to remove the sulfuric acid to obtain a PVDC resin carbide powder. Next, this PVDC resin carbide powder was put into the above-mentioned sulfuric acid gel, mixed, and allowed to stand for 1 day. The resulting mixture was uniformly coated on a current collector plate using a doctor blade in an area of 25 mm square to a thickness of 500 μm. Thus, an electrode 2 was produced. A cell was assembled with the two electrodes sandwiching a 200 μm thick nonwoven glass separator 3. The separator 2 was previously impregnated with diluted sulfuric acid. (See Fig. 1)
【００１９】実施例２を説明する。ＰＶＤＣ樹脂を８５
０℃で炭化した後、２２μｍ以下の粒子サイズに粉砕し
て、３５ｗｔ％の硫酸に含浸しスラリ化した粉末を、集
電板上にドクターブレードを用いて２５ｍｍ□の面積に
５００μｍの厚さになるよう均一に塗布した。次に、３
５ｗｔ％硫酸に分子量２０万のポリエチレングリコール
（ＰＥＧ）を２ｗｔ％添加して１日放置して作製した硫
酸ゲルを２００μｍ厚のガラスセパレータに塗布し、ス
ラリ化した粉末を塗布した電極２で該セパレータ３を挾
んでセルを組んだ。電解質ゲルをセルに添加すると電極
２にしみこんだセルが得られた。（図１参照）Embodiment 2 will be described. 85 PVDC resin
After carbonization at 0 ° C., pulverized to a particle size of 22 μm or less, impregnated with 35 wt% sulfuric acid, and slurried the powder, using a doctor blade on a current collector plate to an area of 25 mm □ to a thickness of 500 μm. It was evenly applied. Next, 3
Sulfuric acid gel prepared by adding 2 wt% of polyethylene glycol (PEG) having a molecular weight of 200,000 to 5 wt% sulfuric acid and allowed to stand for 1 day is applied to a 200 μm-thick glass separator, and the separator 2 is coated with the slurry powder by the electrode 2. I made a cell across 3 When the electrolyte gel was added to the cell, a cell soaked into the electrode 2 was obtained. (See Fig. 1)
【００２０】比較例を説明する。ＰＶＤＣ樹脂を１８０
〜６００℃で脱塩酸したものを２２μｍ以下に振動ミリ
ング機で粉砕した粉をふるいわけた後、２５ｍｍ□のカ
ーボン製型につめて、２０〜２５０ｋｇ／ｃｍ2の圧力
で成形しながら温度８５０℃になるまで通電焼結した電
極を５００μｍの厚さに研磨し、３５ｗｔ％硫酸に浸漬
し、減圧含浸を２４時間行い、２００μｍ厚のガラス不
織繊維のセパレータ３を挾んで対向させ、更にその外側
にＰｔ板を配置し集電板とし、更にその外側からテフロ
ン板で挾み込んで固定した（図１参照）。A comparative example will be described. 180 PVDC resin
After dehydrochlorination at ~ 600 ° C, the powder obtained by crushing with a vibration milling machine to 22 µm or less is sieved, packed in a 25 mm square carbon mold, and molded at a pressure of 20 to 250 kg / cm 2 at a temperature of 850 ° C. The electrode sintered by electro-sintering is polished to a thickness of 500 μm, immersed in 35 wt% sulfuric acid, impregnated under reduced pressure for 24 hours, and opposed to each other with a 200 μm-thick glass non-woven fiber separator 3 interposed therebetween. Then, a Pt plate was disposed to form a current collecting plate, and the current collecting plate was sandwiched and fixed from the outside by a Teflon plate (see FIG. 1).
【００２１】実施例１、２及び比較例のセルを大気中で
保持し、容量の経時変化を観察した測定結果を表１に示
す。Table 1 shows the measurement results obtained by observing the time-dependent changes in the capacity of the cells of Examples 1 and 2 and the comparative example while keeping them in the air.
【表１】 [Table 1]
【００２２】表１に示すように、実施例１、２の硫酸ゲ
ルを電解質としたコンデンサセルは、初期容量は小さい
が、大気中での放置によっても経時変化は少ない。一
方、比較例のものでは、１０００時間で半分以下の容量
になっていた。試験終了後、各セルを解体すると、比較
例のものでは電解液がドライアップしていたが、ゲル電
解質を用いたセルでは電極がゲルで覆われており、初期
状態とほとんど変わらない状態であった。As shown in Table 1, the capacitor cells of Examples 1 and 2 using sulfuric acid gel as an electrolyte have a small initial capacity, but have little change with time even when left in the air. On the other hand, in the case of the comparative example, the capacity was reduced to half or less in 1000 hours. When the cells were disassembled after the test, the electrolyte solution was dried up in the comparative example, but in the cell using the gel electrolyte, the electrodes were covered with gel, which was almost the same as the initial state. Was.
【００２３】なお、実際の製品とするときは、セルを樹
脂等で封止してドライアップ防止手段を併用すれば、更
なる長期安定化が見込まれる。In the case of an actual product, further long-term stabilization can be expected by sealing the cell with a resin or the like and using dry-up prevention means in combination.
【００２４】また、本発明は、細かい粉末を使用するた
め、粒子界面とバルクの電解液との接触面積の増大し拡
散抵抗を下げることができる。また、炭化粉を集電板上
に噴霧式や印刷法により薄く成形することも可能であ
る。In the present invention, since a fine powder is used, the contact area between the particle interface and the bulk electrolyte can be increased and the diffusion resistance can be reduced. It is also possible to form the carbonized powder thinly on the current collector plate by spraying or printing.
【００２５】[0025]
【発明の効果】本発明によれば、電極の拡散抵抗を下げ
ることができ、そして、電極を薄く成形しても強度が弱
くならず、また、電解液の漏れやドライアップの問題が
生じない電気二重層コンデンサ及び電極を得ることが可
能となる。According to the present invention, the diffusion resistance of the electrode can be reduced, and the strength does not decrease even if the electrode is formed thin, and the problem of electrolyte leakage and dry-up does not occur. It becomes possible to obtain an electric double layer capacitor and an electrode.
【図１】作製した電極の特性の測定方法の説明図。FIG. 1 is an explanatory diagram of a method for measuring characteristics of a manufactured electrode.
１ セパレータ ２ 電極 ３ 集電板 ４ 固定板 DESCRIPTION OF SYMBOLS 1 Separator 2 Electrode 3 Current collector 4 Fixing plate
Claims (9)
コンデンサ用電極において、 前記ＰＶＤＣ樹脂炭化物は径２２μｍ以下の粉末であ
り、そして、該粉末は電解質ゲルと混合したものである
ことを特徴とする電気二重層コンデンサ用電極。1. An electrode for an electric double layer capacitor comprising a PVDC resin carbide, wherein the PVDC resin carbide is a powder having a diameter of 22 μm or less, and the powder is mixed with an electrolyte gel. Electrode for double layer capacitor.
電極において、 上記電解質ゲルは、希硫酸に分子量２０万〜４００万の
ポリエチレングリコールを添加したものであることを特
徴とする電気二重層コンデンサ用電極。2. The electric double layer capacitor according to claim 1, wherein said electrolyte gel is obtained by adding polyethylene glycol having a molecular weight of 200,000 to 4,000,000 to dilute sulfuric acid. Electrodes.
する電気二重層コンデンサにおいて、 前記電極は径２２μｍ以下のＰＶＤＣ樹脂炭化物粉末か
らなり、そして、該粉末は電解質ゲルと混合したもので
あることを特徴とする電気二重層コンデンサ。3. An electric double layer capacitor provided with an electrode made of a PVDC resin carbide, wherein the electrode is made of a PVDC resin carbide powder having a diameter of 22 μm or less, and the powder is mixed with an electrolyte gel. And electric double layer capacitor.
させ、得られた炭化物を粉砕して径２２μｍ以下の粉末
とし、該粉末を電解質ゲルと混合することを特徴とする
電気二重層コンデンサ用電極の製造方法。4. An electrode for an electric double layer capacitor, wherein a PVDC resin is carbonized at 600 to 950 ° C., and the obtained carbide is pulverized into a powder having a diameter of 22 μm or less, and the powder is mixed with an electrolyte gel. Manufacturing method.
電極の製造方法において、 上記電解質ゲルは、希硫酸に分子量２０万〜４００万の
ポリエチレングリコールを添加したものであることを特
徴とする電気二重層コンデンサ用電極の製造方法。5. The method for manufacturing an electrode for an electric double layer capacitor according to claim 4, wherein the electrolyte gel is obtained by adding polyethylene glycol having a molecular weight of 200,000 to 4,000,000 to dilute sulfuric acid. Manufacturing method of electrode for double layer capacitor.
デンサ用電極の製造方法において、 ＰＶＤＣ樹脂炭化物粉末を希硫酸に含浸してスラリ化し
たものに２０万〜４００万のポリエチレングリコールを
添加することを特徴とする電気二重層コンデンサ用電極
の製造方法。6. The method for producing an electrode for an electric double layer capacitor according to claim 4, wherein 200,000 to 4,000,000 polyethylene glycol is added to a slurry obtained by impregnating a PVDC resin carbide powder with dilute sulfuric acid. A method of manufacturing an electrode for an electric double layer capacitor.
気二重層コンデンサ用電極の製造方法において、 ＰＶＤＣ樹脂炭化物粉末を希硫酸に含浸した後、希硫酸
をろ過した粉末を電解質ゲルに混合することを特徴とす
る電気二重層コンデンサ用電極の製造方法。7. The method for producing an electrode for an electric double layer capacitor according to claim 4, wherein the powder obtained by impregnating the PVDC resin carbide powder with dilute sulfuric acid and then filtering the diluted sulfuric acid is used as an electrolyte gel. A method for producing an electrode for an electric double layer capacitor, characterized in that:
気二重層コンデンサ用電極の製造方法において、 ＰＶＤＣ樹脂炭化物粉末と電解質ゲルとの混合物を集電
板上に塗布することを特徴とする電気二重層コンデンサ
用電極の製造方法。8. The method for manufacturing an electrode for an electric double layer capacitor according to claim 4, wherein a mixture of a PVDC resin carbide powder and an electrolyte gel is applied on a current collector plate. A method for producing an electrode for an electric double layer capacitor.
し、粉砕して得られた径２２μｍ以下の粉末で電極を作
製した後、該電極を電気二重層コンデンサに組込み、次
に、電解質ゲルを添加して前記電極にしみこませること
を特徴とする電気二重層コンデンサの製造方法。9. An electrode is produced from a powder having a diameter of 22 μm or less obtained by carbonizing a PVDC resin at 600 to 950 ° C., and then incorporating the electrode into an electric double layer capacitor. A method for manufacturing an electric double layer capacitor, wherein the method further comprises adding and infiltrating the electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9253547A JPH1197317A (en) | 1997-09-18 | 1997-09-18 | Electric double layer capacitor, electrode and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9253547A JPH1197317A (en) | 1997-09-18 | 1997-09-18 | Electric double layer capacitor, electrode and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1197317A true JPH1197317A (en) | 1999-04-09 |
Family
ID=17252894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9253547A Pending JPH1197317A (en) | 1997-09-18 | 1997-09-18 | Electric double layer capacitor, electrode and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1197317A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2735008A4 (en) * | 2011-07-18 | 2015-08-19 | Indian Inst Scient | An energy storage device, an inorganic gelled electrolyte and methods thereof |
-
1997
- 1997-09-18 JP JP9253547A patent/JPH1197317A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2735008A4 (en) * | 2011-07-18 | 2015-08-19 | Indian Inst Scient | An energy storage device, an inorganic gelled electrolyte and methods thereof |
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