JPS58197669A - Electrode for layer-built cell - Google Patents
Electrode for layer-built cellInfo
- Publication number
- JPS58197669A JPS58197669A JP57077443A JP7744382A JPS58197669A JP S58197669 A JPS58197669 A JP S58197669A JP 57077443 A JP57077443 A JP 57077443A JP 7744382 A JP7744382 A JP 7744382A JP S58197669 A JPS58197669 A JP S58197669A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- sheet
- phlorocarbon
- plastic material
- carbon plastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/365—Zinc-halogen accumulators
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、金属（例えばＺｎ）−・・ロゲン（例えばＢ
ｒ）１１％！ｉｌ液循積型積層二次電池に用いられる電
極に関するものでおる。更に詳しくは、本発明は、導電
性樹脂素材を用いて形成されるｗＬＪｒＩＩＡ部分と、
この電極部分を保持する電極枠とを一体に成型して構成
される積層電池の電極に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides metal (e.g. Zn)...rogen (e.g. B
r) 11%! This invention relates to an electrode used in an IL liquid circulation type stacked secondary battery. More specifically, the present invention includes a wLJrIIA portion formed using a conductive resin material,
This invention relates to an electrode for a laminated battery constructed by integrally molding an electrode frame that holds this electrode portion.
第１図は、本発明に係る電極が使用される電池のひとつ
である電解液循壜型積・層二次電池の基本構成図である
。この電池は、陰極１と陽極６とをセパレータ５を挾ん
で両ＩＩに設置し、陰極１とセパレータ５との間の陰極
室２に、陰極液貯蔵槽６から陰極液を供給、循環させる
とともに、陽極６とセパレータ５との間の陽極室４に、
陽極液貯蔵槽７から陽極液を供給、循環させるように構
成されている。なお、９ｍ、９ｂは液傭壌用のポンプ、
１０ｍ、１０ｂは充放電時に開くバルブである。FIG. 1 is a basic configuration diagram of an electrolyte circulating bottle type multilayer secondary battery, which is one of the batteries in which the electrode according to the present invention is used. In this battery, a cathode 1 and an anode 6 are placed in both IIs with a separator 5 in between, and catholyte is supplied and circulated from a catholyte storage tank 6 to a cathode chamber 2 between the cathode 1 and separator 5. , in the anode chamber 4 between the anode 6 and the separator 5,
It is configured to supply and circulate the anolyte from the anolyte storage tank 7. In addition, 9m and 9b are liquid pumps,
10m and 10b are valves that open during charging and discharging.
第２図は、このような電池を積層構成とした場合の一例
を示す分解斜視図である。この図におい′τ、１１はア
ルミ締付端板、１２は樹脂締付端板、１６はパツキン、
１４は電極端板、１５は金網尋で構成された端子、であ
る。各電極１及びセパレータ５は、図示するように積層
され、アルミ締付端板１１によって両側から挾まれ、締
付ボルト１６、締付ナツト１７で全体が一体に構成され
る。電解液ハ、マニホールド１８からチャンネル１９及
びマイクロチャンネル２０を通って、電極部の表向に供
給され、また循環するようになっているところで、この
ような積層電池に用いられる電極１は、インジェクショ
ンモールド方式６るいｅよヒートプレスモールド方式婢
によって成形して構成される。一方、成型して構成され
る電極に要求される主な性能は、化学的には耐薬品性、
電％ｓ敵の不浸透性等であり、また電気的には低抵抗で
ある事等である。それ故に、従来より電極材料として、
ポリオレフイ／（例えばボリエナレ／）系樹脂で、特に
高分子量かつ高＠嵐であるものｔペース・ポリマーとし
、これに、わる割合でカーボンブラックを混練させた、
所稍カーボン・プラスチックが使用されている。FIG. 2 is an exploded perspective view showing an example of such a battery having a stacked structure. In this figure, ′τ, 11 is an aluminum clamping end plate, 12 is a resin clamping end plate, 16 is a packing,
14 is an electrode end plate, and 15 is a terminal made of wire mesh. Each electrode 1 and separator 5 are stacked as shown in the figure, sandwiched from both sides by aluminum fastening end plates 11, and are integrally formed with a fastening bolt 16 and a fastening nut 17. The electrolyte C is supplied from the manifold 18 to the surface of the electrode section through the channels 19 and the microchannels 20, and is circulated therein. It is constructed by molding using the heat press mold method. On the other hand, the main properties required for molded electrodes are chemical resistance,
It is impervious to electricity and has low electrical resistance. Therefore, as an electrode material,
A polyolefin/(for example, Boliennale/) based resin with a particularly high molecular weight and high @arashi t-pace polymer is kneaded with carbon black in a different proportion.
Some carbon plastic is used.
しかしながら、実際の検層電池を運転する場合、カーボ
ンプラスチック表面は、成型の段階で金型面が。転写さ
れておし、外観は艷のある元沢圓となり、陽極表面では
Ｚｎの電着、陽極表面ではＢｒｌ二Ｂｒ−イオンの反応
が生ずるが、カーボンプラスチックを成型して構成され
る電極は、電着したＺｎの密着性が不足したり、特に陽
極における反応表面積が不足するために、電池効率が低
下するという問題点があった。However, when actually operating a logging battery, the carbon plastic surface is exposed to the mold surface during the molding stage. It has been transferred, and the appearance is Motozawa round with a barb. Zn is electrodeposited on the anode surface, and a reaction of Br12Br- ions occurs on the anode surface, but the electrode is made by molding carbon plastic. There has been a problem in that battery efficiency is lowered due to insufficient adhesion of electrodeposited Zn and especially insufficient reaction surface area at the anode.
ここにおいて、本発明は、このような問題点を解決する
ことを目的としてなされたものである。Here, the present invention has been made for the purpose of solving such problems.
本発明に係る電極は、四フッ化（又は三７ツ化、ニフツ
化）エチレンをペースボリマートシタフロロカーボンシ
ートをカーボンプラスチック表面に重ね合わせ、両者を
一体成型し七構成した点に特徴がある。The electrode according to the present invention is characterized in that a tetrafluorinated (or trifluorinated, or niffused) ethylene-paced polyfluorocarbon sheet is superimposed on a carbon plastic surface, and both are integrally molded.
第６図は本発明に係る電極の一例を示す分解斜視図でお
る。図において、１０は電極部を構成するカーボンプラ
スチック材、１０１はカーボンプラス？：、／り材１０
の表面を榎う７０ロカーボンシー）、１０ｍ、１０ｂは
マイクロチャンネル成型枠、１０ｃ、ｉＱ４は外枠素材
である。カーボンプラスチック材１０は、その表ｔｈｌ
（この例では一方の表向）にフロロカーボンシート１０
１が重ね合すれて密着し、これをマイクロチャンネル成
型枠１０ａ１１０ｂが両側から挾み、更にこれらを枠素
材１０ｅ、１０ｄが両側から挾むようにして一体に成型
される。FIG. 6 is an exploded perspective view showing an example of an electrode according to the present invention. In the figure, 10 is the carbon plastic material that constitutes the electrode part, and 101 is carbon plus? :, / material 10
10m and 10b are microchannel molding frames, and 10c and iQ4 are outer frame materials. The carbon plastic material 10 has a surface thl
Fluorocarbon sheet 10 (one side in this example)
1 are superimposed and in close contact with each other, microchannel molding frames 10a110b sandwich this from both sides, and these are further sandwiched by frame materials 10e and 10d from both sides, so that they are integrally molded.
ここで、フロロカーボンシート１０１は、例えば厚さが
０．３−以下の多孔質の７−トであって、カーボンプラ
スチック材１００表面に熱圧着によって密着させると、
見掛は上電極部の表面積が増加（数倍〜数十倍に増加）
したことと−じになる。Here, the fluorocarbon sheet 101 is, for example, a porous sheet with a thickness of 0.3 mm or less, and when it is closely attached to the surface of the carbon plastic material 100 by thermocompression bonding,
The apparent surface area of the upper electrode increases (several to tens of times more)
It's the same as what I did.
このため、このように構成される電極を積層して電池を
構成した場合、陰極側では、Ｚｎ電着性が向上し、陽極
側ではＢｒｌの反応が十分に行なわれるようになる。ま
た、７Ｉｊロカーボノ／−ト１０１は、その電気伝導性
がカーボンプラスチックの倍近く高いという特性を備え
ていること等から、全体として電池効率を上げることが
できる。Therefore, when a battery is constructed by stacking electrodes configured in this manner, the Zn electrodeposition property is improved on the cathode side, and the Brl reaction is sufficiently carried out on the anode side. In addition, the 7Ij locarbonate 101 has a characteristic that its electrical conductivity is nearly twice as high as that of carbon plastic, and therefore the battery efficiency can be improved as a whole.
なお、電極の成型は、カーボンプラスチック材１０に重
ね合せる７０ロカーボンプ−トの厚みが薄いため、体積
的に試料の増加は少なく、従って、カーボンプラスチッ
ク材１０と同一形状に切断したフロロカーボンシートラ
単に追加、重ね合せて行なえばよく、成型温度等の成型
条件は、フロロ力−ボンシートのないときとはソ同じで
あるっ第４図は、本発明に係る電極と、従来の電極（フ
ロロカーボンシートを密着しないで構成した電極）の電
極特性を比較して示した線図である。この実験では、電
解液に５Ｍ／−１３ＺｎＢｒ１ ＋Ｂｒｌ溶液を用い、
４０ｍＡ／ｄで放電したときの種々の電解液臭素＃度に
おける電極電位を、銀−塩化銀参照基準でプロットした
もので、実線は７本発明に係る電極、破線は従来の電極
の特性をそれぞれ示している。In addition, when molding the electrode, since the thickness of the fluorocarbon plate overlaid on the carbon plastic material 10 is thin, the increase in the volume of the sample is small. The molding conditions, such as molding temperature, are the same as those without the fluorocarbon sheet. FIG. In this experiment, a 5M/-13ZnBr1 +Brl solution was used as the electrolyte,
The electrode potential at various electrolyte bromine degrees when discharged at 40 mA/d is plotted using a silver-silver chloride reference standard, where the solid line shows the characteristics of the electrode according to the present invention, and the broken line shows the characteristics of the conventional electrode. It shows.
この実験結果から明らかなように、本発明に係る電極は
、従来の電極に比べ、各電解液臭素濃度において放電時
の分極が小さく、全体的に高い電位を維持しており、電
圧効率及びクーロン効率が高くなっていることが認めら
れる。As is clear from the experimental results, the electrode according to the present invention has smaller polarization during discharge at each electrolyte bromine concentration than conventional electrodes, maintains a high overall potential, and has improved voltage efficiency and coulomb It is recognized that the efficiency is high.
なお、上記の実施例では、カーボンプラスチック材の一
方の表面に７０ロカーボンシートを密着させた場合につ
いて説明したが、両方の表面に密層させてもよい。また
、このフロロカーボンシートに代えて、テフロン（商標
）中にカーボンブランクを分散したテフロン多孔膜シー
トを用い、これを熱圧着によってカーボンツーラスチッ
ク材の表面に密着させるようにしてもよい。In the above embodiment, the case where the 70 carbon sheet was closely attached to one surface of the carbon plastic material was explained, but it may be closely layered on both surfaces. Moreover, instead of this fluorocarbon sheet, a Teflon porous membrane sheet in which carbon blanks are dispersed in Teflon (trademark) may be used, and this may be adhered to the surface of the carbon toolastic material by thermocompression bonding.
第１表は、テフロン多孔膜シートを用いた場合、その多
孔度と、電着亜鉛の密着性について調べた結果である。Table 1 shows the results of investigating the porosity and adhesion of electrodeposited zinc when a Teflon porous membrane sheet was used.
第 １ 表
（成型温度 １２５１：” １分、加圧 １００ｋ）
７ｃｍ ）この実験結果から、テフロン多孔膜７−トの
多孔度としては・５０〜７０％、望ましくは、６０チが
良いことがわかった。また、加熱温度としては１２５Ｃ
前後、加圧は８０〜１００に、７ｍ、保持時間は１分が
適当であつ友。Table 1 (Molding temperature 1251: 1 minute, pressure 100k)
7 cm) From the results of this experiment, it was found that the porosity of the Teflon porous membrane 7 is preferably 50 to 70%, preferably 60 cm. In addition, the heating temperature is 125C.
Appropriate pressure is 80 to 100, 7 m, and holding time is 1 minute.
以上説明したように、本発明によれば、次に列挙するよ
うな楕々の特長を令する電極が実現できる。As explained above, according to the present invention, it is possible to realize an electrode having various features as listed below.
（１） 反応有効面積が増大し、陽極側ではＢｒｌの
反応性が良くなり、また陰極側では電着Ｚｎの密着性が
良くなる。(1) The effective reaction area increases, the reactivity of Brl improves on the anode side, and the adhesion of electrodeposited Zn improves on the cathode side.
（ＩＩ） 電極表面の電気抵抗が改善され、電流密度
分布状態が良くなり、内部ロスを減少できる。この結果
、電池効率を大巾に増加できる。(II) The electrical resistance of the electrode surface is improved, the current density distribution is improved, and internal loss can be reduced. As a result, battery efficiency can be greatly increased.
（ｌｉｔ） 臭素極として放電時の分極特性が良くな
り、その結果、電圧効率及びクーロン効率を増加できる
。(lit) As a bromine electrode, the polarization characteristics during discharge are improved, and as a result, voltage efficiency and Coulombic efficiency can be increased.
第１図は本発明に係る電極が使用される電池の一例を示
す積層二次電池の基本構成図、第２図は第１図に示す電
池を積層構成とした場合の一例を示す分解斜視図、第６
図は本発明に係る電極の一例を示す分解斜視図、第４図
は本発明に係る電極と従来の電極の電極特性を比較して
示す特性線図である。
１０・・・カーボンプラスチック材、１０１・・・フロ
ロカーボ／シート、１０ｍ 、 １０ｂ・・・マイクロ
チャンネル成型枠、１０＠、 １０ｄ・・・外枠素材代
理人弁理士 木 村 三 朗FIG. 1 is a basic configuration diagram of a laminated secondary battery showing an example of a battery in which the electrode according to the present invention is used, and FIG. 2 is an exploded perspective view showing an example of a laminated structure of the battery shown in FIG. 1. , 6th
The figure is an exploded perspective view showing an example of the electrode according to the present invention, and FIG. 4 is a characteristic diagram showing a comparison of the electrode characteristics of the electrode according to the present invention and a conventional electrode. 10...Carbon plastic material, 101...Fluorocarbo/sheet, 10m, 10b...Micro channel molding frame, 10@, 10d...Outer frame material agent Mitsuro Kimura
Claims (1)
くとも一方の表面に、四フッ化（父は三７ツ化、二ツノ
化）エチレン全ベースポリマーとしたフロロカーボンシ
ート又ハチフロン多孔膜ンーーを重ね合せて密着し、一
体成型して構成したことを特徴とする積層電池の電極。 （２） テフシン多孔膜シートの多孔度を５０〜７０
優、望ましくは６０チとした特許請求の範囲第１ＪＪ記
載の積層電池のｌｔ極。[Claims] (11) On at least one surface of the carbon plastic material constituting the electrode section, there is a fluorocarbon sheet or Hachifluorocarbon porous polymer made entirely of tetrafluoride (or trifluoride or difluoride) ethylene. An electrode for a laminated battery, characterized in that it is constructed by overlapping and adhering membranes and integrally molding them. (2) The porosity of the Tefcin porous membrane sheet is 50 to 70.
The lt pole of the laminated battery according to claim 1 JJ, which is excellent, preferably 60 inches.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57077443A JPS58197669A (en) | 1982-05-11 | 1982-05-11 | Electrode for layer-built cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57077443A JPS58197669A (en) | 1982-05-11 | 1982-05-11 | Electrode for layer-built cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58197669A true JPS58197669A (en) | 1983-11-17 |
| JPH0139635B2 JPH0139635B2 (en) | 1989-08-22 |
Family
ID=13634159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57077443A Granted JPS58197669A (en) | 1982-05-11 | 1982-05-11 | Electrode for layer-built cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58197669A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62154585A (en) * | 1985-12-27 | 1987-07-09 | Tanaka Kikinzoku Kogyo Kk | Halogen battery |
| JPS62184775A (en) * | 1986-02-06 | 1987-08-13 | Tanaka Kikinzoku Kogyo Kk | Halogen battery |
| JPH01134879A (en) * | 1987-11-19 | 1989-05-26 | Meidensha Corp | Electrode for secondary battery |
| JPH02135672A (en) * | 1988-11-17 | 1990-05-24 | Meidensha Corp | End plate electrode of liquid circulation type stacked cell |
-
1982
- 1982-05-11 JP JP57077443A patent/JPS58197669A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62154585A (en) * | 1985-12-27 | 1987-07-09 | Tanaka Kikinzoku Kogyo Kk | Halogen battery |
| JPS62184775A (en) * | 1986-02-06 | 1987-08-13 | Tanaka Kikinzoku Kogyo Kk | Halogen battery |
| JPH01134879A (en) * | 1987-11-19 | 1989-05-26 | Meidensha Corp | Electrode for secondary battery |
| JPH02135672A (en) * | 1988-11-17 | 1990-05-24 | Meidensha Corp | End plate electrode of liquid circulation type stacked cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0139635B2 (en) | 1989-08-22 |
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