JPH04142724A - Electric double-layer capacitor - Google Patents
Electric double-layer capacitorInfo
- Publication number
- JPH04142724A JPH04142724A JP26525790A JP26525790A JPH04142724A JP H04142724 A JPH04142724 A JP H04142724A JP 26525790 A JP26525790 A JP 26525790A JP 26525790 A JP26525790 A JP 26525790A JP H04142724 A JPH04142724 A JP H04142724A
- Authority
- JP
- Japan
- Prior art keywords
- conductive film
- electric double
- layer capacitor
- conductive
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims description 19
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 16
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002367 Polyisobutene Polymers 0.000 claims abstract description 10
- 239000006258 conductive agent Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000006230 acetylene black Substances 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 238000005096 rolling process Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、電気二重層コンデンサーに関し、特に分極
性電極に対する電極板の接触抵抗を低減し、安定した接
触状態を得るための集電体の改良に関する。Detailed Description of the Invention (Industrial Application Field) This invention relates to electric double layer capacitors, and in particular to a current collector for reducing the contact resistance of an electrode plate to a polarizable electrode and obtaining a stable contact state. Regarding improvements.
（従来の技術）
電気二重層コンデンサーの基本的構成は、封口材をかね
た枠体の内側にセパレータを介して一対の分極性電極を
配置し、各分極性電極の表面を集電体を兼用した金属電
極板で被覆密封した構造である。(Prior technology) The basic structure of an electric double layer capacitor is that a pair of polarizable electrodes are placed inside a frame that also serves as a sealing material with a separator in between, and the surface of each polarizable electrode also serves as a current collector. The structure is covered with a sealed metal electrode plate.
しかしながら、この構造の場合に、分極性電極と電極板
とが単に接触しているだけでは、部分的に不十分な接触
状態となり、内部抵抗が増加する欠点が生ずる。However, in the case of this structure, if the polarizable electrode and the electrode plate are simply in contact with each other, the contact state is partially insufficient, resulting in a disadvantage that the internal resistance increases.
したがって、この種の問題を解決するために、分極性電
極と金属電極板との間に黒鉛系導電接着剤を用いて接着
すること、あるいは特開平２−６５１１４号公報に示す
ように、集電体を構成する導電性フィルムを介して両者
を熱圧着によって接着することも提案されている。Therefore, in order to solve this kind of problem, it is necessary to bond the polarizable electrode and the metal electrode plate using a graphite-based conductive adhesive, or as shown in Japanese Patent Application Laid-Open No. 2-65114, It has also been proposed to bond the two together by thermocompression bonding via a conductive film that constitutes the body.
しかしながら、これらの構造では、以下に述べる欠点が
あった。However, these structures have the following drawbacks.
（発明が解決しようとする課題）
すなわち、前者の導電性接着剤を用いた場合には、接着
剤中に含まれる溶剤の揮散状態によっては不均一な導電
性を示したり、溶剤が一部に偏在してこの部分の導電性
が著しく阻害されるほか、接触抵抗も大きく、大電流を
取り出すことができなかった。(Problems to be Solved by the Invention) In other words, when the former type of conductive adhesive is used, it may exhibit uneven conductivity depending on the volatilization state of the solvent contained in the adhesive, or the solvent may partially evaporate. The uneven distribution significantly impeded the conductivity of this area, and the contact resistance was also large, making it impossible to extract a large current.
また、後者の導電性フィルムを介在させる方法にあって
は、それ自体の抵抗が大きいため、電気抵抗を小さくす
るためには、厚さを薄くする必要があった。また分極性
電極との密着性も悪く、しかも抵抗を小さくするために
厚さを薄くしであるので、熱圧着時にフィルムに穴が開
いたり、切れてしまうなどの欠点があった。In addition, in the latter method of interposing a conductive film, since the resistance itself is high, it was necessary to reduce the thickness in order to reduce the electrical resistance. In addition, the adhesion to the polarizable electrode is poor, and since the film is made thin to reduce resistance, there are drawbacks such as holes or cuts in the film during thermocompression bonding.
つまり、従来の導電性フィルムは、ポリプロピレン、ポ
リエチレン、ポリ塩化ビニル、ポリスチレン、ポリウレ
タン、ポリイミドなどの樹脂に、導電材としてカーボン
ブラックを分散させ、フィルム状に成形したものである
ため、樹脂含有量が少なくなると成形性に影響を与え、
破れ易くなり、逆に樹脂含有量が増すと導電性に影響を
与え、抵抗が大きくなる。In other words, conventional conductive films are made by dispersing carbon black as a conductive material in resins such as polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyurethane, polyimide, etc. and forming them into a film, so the resin content is low. If the amount decreases, it will affect the formability,
It becomes easier to tear, and conversely, as the resin content increases, it affects the conductivity and increases the resistance.
したがって、従来では、樹脂含有量を２０〜４０ ｗ
ｔ％程度とした場合に、その厚みは抵抗を考慮して精々
２０〜８０μｍ程度の厚みにしか出来ず、また、この程
度の厚みとするとホットブレ′スによって破れや切れが
生し易くなり、製品歩留まりが低下する原因となってい
た。Therefore, in the past, the resin content was reduced to 20 to 40 w.
If the thickness is about t%, the thickness can only be about 20 to 80 μm at most considering resistance, and if the thickness is made to this extent, it will be easy to tear or cut due to hot bracing, and the product will be damaged. This caused a decrease in yield.
この発明は後者の導電性フィルムを集電体として用いる
電気二重層コンデンサーにおいて、前記導電性フィルム
の材料１組成を工夫することで、フィルム厚みが厚い場
合であっても固有抵抗値が小さく、ホットプレス時の破
れや切れを未然に防止できるとともに、分極性電極に対
する接着性を向上できるようにした電気二重層コンデン
サーを提供することを目的としている。This invention is an electric double layer capacitor that uses the latter conductive film as a current collector.By devising the composition of the material 1 of the conductive film, the specific resistance value is small even when the film thickness is large, and the The object of the present invention is to provide an electric double layer capacitor which can prevent tearing and cutting during pressing and can improve adhesion to polarizable electrodes.
すなわちこの発明は、前記導電性フィルムの樹脂成分と
して、ポリイソブチレンとポリビニルイソブチルエーテ
ルとを混合した二成分系樹脂を用いることにより、従来
の樹脂を用いた場合に比べて固有抵抗値が極めて小さく
なり、かつ十分な量の導電剤を混合分散することのでき
る導電性フィルムを得られることを知見し、本発明を完
成するに至った。That is, this invention uses a two-component resin that is a mixture of polyisobutylene and polyvinyl isobutyl ether as the resin component of the conductive film, so that the specific resistance value is extremely small compared to when conventional resins are used. The present inventors have discovered that it is possible to obtain a conductive film in which a sufficient amount of a conductive agent can be mixed and dispersed, and have completed the present invention.
（課題を解決するための手段）
前記目的を達成するため、この発明は、導電性フィルム
からなる集電体に固形分極性電極を密着させた電気二重
層コンデンサーにおいて、前記導電性フィルムの樹脂成
分は、ポリイソブチレンとポリビニルイソブチルエーテ
ルとからなる二成分系樹脂であることを特徴とするもの
である。(Means for Solving the Problems) In order to achieve the above object, the present invention provides an electric double layer capacitor in which a solid polarizable electrode is closely attached to a current collector made of a conductive film, in which a resin component of the conductive film is is characterized by being a two-component resin consisting of polyisobutylene and polyvinyl isobutyl ether.
前記導電性フィルムを構成する樹脂の組成比は、全重量
に対して１０〜５０ｗｔ％とし、残部を導電剤とするこ
とができる。The composition ratio of the resin constituting the conductive film may be 10 to 50 wt% based on the total weight, and the remainder may be a conductive agent.
さらに、前記導電性フィルムの中に分散される導電剤は
、アセチレンブラックと黒鉛の混合物が用いられる。Furthermore, the conductive agent dispersed in the conductive film is a mixture of acetylene black and graphite.
前記ポリイソブチレン（Ｐ Ｉ Ｂ）は、粘度平均分子
量２，１００．０００である。The polyisobutylene (P I B) has a viscosity average molecular weight of 2,100.000.
前ｇ己ポリビニルイソブチルエーテル は、平均に値（粘度）は、１００〜１３０である。Polyvinyl isobutyl ether The average value (viscosity) is 100 to 130.
また両者の組成比は、Ｐ ＩＢ ： Ｐ ＩＢＥ−１
：１〜４コ１程度の組成比が好ましい範囲である。Moreover, the composition ratio of both is P IB: P IBE-1
: A preferred range is a composition ratio of about 1 to 4 parts to 1 part.
また、以上の組成比の樹脂を全量に対し、１０〜５０ｗ
ｔ％（残部導電剤）としたのは、１０ｗｔ％を下回った
場合には、フィルムへの成形性が阻害され、また５Ｑｗ
ｔ％を越えると導電剤の含有量が急速に低下し、第２図
に示すように、体積固有抵抗値が増すためであり、いず
れの場合であっても好ましい結果を与えないからである
。In addition, 10 to 50 w of resin with the above composition ratio is added to the total amount.
t% (remaining conductive agent) is because if it is less than 10wt%, the formability into a film will be inhibited, and 5Qw
This is because if the content exceeds t%, the content of the conductive agent rapidly decreases, and as shown in FIG. 2, the volume resistivity value increases, and in either case, favorable results will not be obtained.
また、用いられる導電剤としては、アセチレンブラック
と黒鉛の混合物が分散性，導電性などのの面で好ましく
、その粒径は均一分散性の面で５μｍ程度が好ましい。Further, as the conductive agent used, a mixture of acetylene black and graphite is preferable in terms of dispersibility and conductivity, and the particle size is preferably about 5 μm in terms of uniform dispersibility.
以上の組成の導電性フィルムの成形方法としては、ロー
ル圧延により成形することによって所定厚みに連続的に
形成される。As a method for forming the conductive film having the above composition, it is continuously formed to a predetermined thickness by forming by roll rolling.
なお、得られる導電性フィルムの厚みは固有抵抗値やホ
ットメルト時の接着性を考慮して０．１〜１■ｍが好ま
しい。Note that the thickness of the conductive film obtained is preferably 0.1 to 1 μm in consideration of specific resistance value and adhesiveness during hot melting.
第１図は以上の導電性フィルムを用いた電気二重層コン
デンサーを示すものである。FIG. 1 shows an electric double layer capacitor using the above conductive film.
また−１導電性フイルムに固形分極性電極のみを密着さ
せた電極板を用いて積層構造にした電気二重層コンデン
サーを第３図に示す。FIG. 3 shows an electric double layer capacitor having a laminated structure using an electrode plate in which only a solid polarizable electrode is adhered to a -1 conductive film.
図において、１は封口材を兼ねた樹脂製の枠体、２は枠
体１の内側に配置されたセパレータ、３はセパレータ２
上下面に配置された固形分極性電極であり、枠体１の内
部には電解液が充填されている。In the figure, 1 is a resin frame that also serves as a sealing material, 2 is a separator placed inside the frame 1, and 3 is a separator 2.
It is a solid polarizable electrode arranged on the upper and lower surfaces, and the inside of the frame 1 is filled with an electrolytic solution.
また各分極性電極３の表面には、前記導電性フィルムか
らなる集電体４を介して金属電極板５が接着され、内部
を被覆密封している。Further, a metal electrode plate 5 is adhered to the surface of each polarizable electrode 3 via a current collector 4 made of the conductive film, and the inside is covered and sealed.
この接着方法としては、前記分極性電極３を内部に設置
した枠体１上に前記集電体４を設置し、次いでこの集電
体４の上面に金属電極板５を設置した状態でこの表面を
前記集電体の軟化点以上、融点以下に加熱加圧すること
によって、前記集電体４は一旦軟化し、両面が前記分極
性電極３．枠体１及び金属電極板５の表面に融着し、冷
却によって固化し、各部を一体に接着する。In this bonding method, the current collector 4 is installed on the frame 1 in which the polarizable electrode 3 is installed, and then the metal electrode plate 5 is installed on the top surface of the current collector 4, and the surface of the current collector 4 is placed on the frame 1. By heating and pressurizing the current collector 4 to a temperature above the softening point and below the melting point, the current collector 4 is once softened, and both surfaces are covered with the polarizable electrode 3. It is fused to the surfaces of the frame body 1 and the metal electrode plate 5, solidified by cooling, and each part is bonded together.
（実 施 例）
次にこの発明の詳細な説明する。但し以下の実施例に限
定されるものではない。(Example) Next, the present invention will be explained in detail. However, the present invention is not limited to the following examples.
実施例
ＰＩＢ：ＰＩＢＥ−２：１に調整された樹脂２５ ｗ
ｔ％にアセチレンブラックと黒船の混合物７５ｗｔ％を
混合分散したマスターバッチをロール圧延により、厚さ
０．４ｍ＋ｍの導電性フィルムとした。Example PIB: PIBE-2:1 adjusted resin 25w
A masterbatch in which 75 wt % of a mixture of acetylene black and Kurofune was mixed and dispersed in t % was rolled into a conductive film with a thickness of 0.4 m + m.
次いでこの導電性フィルムを所定の寸法に裁断し第１図
に示す集電体４として用い、１４０℃で加熱加圧による
接着により、第１図に示す電気二重層コンデンサーを組
み立てた。Next, this conductive film was cut to a predetermined size and used as the current collector 4 shown in FIG. 1, and the electric double layer capacitor shown in FIG. 1 was assembled by adhesion by heating and pressing at 140°C.
比較例
従来例と同一仕様で、ポリエチレンを樹脂として用い、
これにカーボンブラックを組成比２５ニア５ｗｔ％の割
合で混合分散したマスターバッチを、溶融押し出し成形
し、厚さ０．０６ｍｎの導電性フィルムを得られ、これ
を集電体として用い、第１図の構造の電気二重層コンデ
ンサーを得られた。Comparative example Same specifications as the conventional example, using polyethylene as the resin,
A masterbatch in which carbon black was mixed and dispersed at a composition ratio of 25 nia and 5 wt% was melt-extruded to obtain a conductive film with a thickness of 0.06 mm, which was used as a current collector. An electric double layer capacitor with the structure was obtained.
次に以上の実施例と比較例の物性を比較測定したところ
、以下の表に示す結果を得られた。Next, the physical properties of the above Examples and Comparative Examples were comparatively measured, and the results shown in the table below were obtained.
（発明の効果）
以上の表からも明らかなように、この発明の導電性フィ
ルムを集電体として用いた電気二重層コンデンサーにあ
っては、従来のフィルム厚みに比べて１０倍程度の厚み
であっても固有抵抗値が低く、ホットメルト作業性が良
好であり、分極性電極に対する接着性も良好である。(Effects of the invention) As is clear from the above table, the electric double layer capacitor using the conductive film of the present invention as a current collector has a thickness that is approximately 10 times that of the conventional film. Even if it is present, it has a low specific resistance value, good hot-melt workability, and good adhesion to polarizable electrodes.
したがって、本発明の電気二重層コンデンサーにあって
は、分極性電極に対する電極板の接触抵抗が従来の導電
性フィルムを用いたものよりもさらに低減することがで
き、初期の及び経時後の内部抵抗を低くでき、性能向上
を図ることができる。Therefore, in the electric double layer capacitor of the present invention, the contact resistance of the electrode plate to the polarizable electrode can be further reduced than that using a conventional conductive film, and the internal resistance at the initial stage and after aging can be reduced. can be lowered and performance can be improved.
また、集電体のホットメルト接着時の破れや切れがなく
、製品歩留まりも向上する。Furthermore, there is no tearing or cutting during hot-melt bonding of the current collector, and product yield is improved.
第１図は電気二重層コンデンサーの説明用断面図、第２
図は樹脂分割合と体積固有抵抗値との関係を示すグラフ
、第３図は電気二重層コンデンサーの他の例を示す断面
図である。
１・・・枠体
２・・・セパレータ
３・・・固形分極性電極
４・・・導電性フィルムからなる集電体５・・・金属電
極板Figure 1 is an explanatory cross-sectional view of an electric double layer capacitor, Figure 2
The figure is a graph showing the relationship between the resin content ratio and the volume resistivity value, and FIG. 3 is a sectional view showing another example of an electric double layer capacitor. 1... Frame 2... Separator 3... Solid polarizable electrode 4... Current collector made of conductive film 5... Metal electrode plate
Claims (4)
を密着させた電気二重層コンデンサーにおいて： 前記導電性フィルムの樹脂成分は、ポリイソブチレンと
ポリビニルイソブチルエーテルとからなる二成分系樹脂
であることを特徴とする電気二重層コンデンサー。(1) In an electric double layer capacitor in which a solid polarizable electrode is closely attached to a current collector made of a conductive film: The resin component of the conductive film is a two-component resin made of polyisobutylene and polyvinyl isobutyl ether. An electric double layer capacitor characterized by:
重量に対して１０〜５０ｗｔ％であり、残部が導電剤で
あることを特徴とする請求項１記載の電気二重層コンデ
ンサー。(2) The electric double layer capacitor according to claim 1, wherein the composition ratio of the resin constituting the conductive film is 10 to 50 wt% based on the total weight, and the remainder is a conductive agent.
セチレンブラックと黒鉛からなることを特徴とする請求
項１または２記載の電気二重層コンデンサー。(3) The electric double layer capacitor according to claim 1 or 2, wherein the conductive agent dispersed in the conductive film comprises acetylene black and graphite.
チレンとポリビニルイソブチルエーテルとの組成比が１
：１〜４：１であることを特徴とする請求項１記載の電
気二重層コンデンサー。(4) The composition ratio of polyisobutylene and polyvinyl isobutyl ether of the resin constituting the conductive film is 1
2. The electric double layer capacitor according to claim 1, wherein the ratio is 1 to 4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26525790A JP2559163B2 (en) | 1990-10-04 | 1990-10-04 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26525790A JP2559163B2 (en) | 1990-10-04 | 1990-10-04 | Electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04142724A true JPH04142724A (en) | 1992-05-15 |
| JP2559163B2 JP2559163B2 (en) | 1996-12-04 |
Family
ID=17414717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26525790A Expired - Lifetime JP2559163B2 (en) | 1990-10-04 | 1990-10-04 | Electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2559163B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1107267A1 (en) * | 1999-03-23 | 2001-06-13 | Nisshinbo Industries, Inc. | Electrolyte composition for electric double layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacitor |
-
1990
- 1990-10-04 JP JP26525790A patent/JP2559163B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1107267A1 (en) * | 1999-03-23 | 2001-06-13 | Nisshinbo Industries, Inc. | Electrolyte composition for electric double layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacitor |
| EP1107267A4 (en) * | 1999-03-23 | 2006-05-10 | Nisshin Spinning | Electrolyte composition for electric double layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2559163B2 (en) | 1996-12-04 |
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