JPH0518221B2 - - Google Patents

Info

Publication number
JPH0518221B2
JPH0518221B2 JP60096786A JP9678685A JPH0518221B2 JP H0518221 B2 JPH0518221 B2 JP H0518221B2 JP 60096786 A JP60096786 A JP 60096786A JP 9678685 A JP9678685 A JP 9678685A JP H0518221 B2 JPH0518221 B2 JP H0518221B2
Authority
JP
Japan
Prior art keywords
frame
electrode
separator
framed
weight
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.)
Expired - Fee Related
Application number
JP60096786A
Other languages
Japanese (ja)
Other versions
JPS61256560A (en
Inventor
Yasuo Ando
Yoshinori Kishimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Meidensha Electric Manufacturing Co Ltd
Original Assignee
Meidensha Electric Manufacturing Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Meidensha Electric Manufacturing Co Ltd filed Critical Meidensha Electric Manufacturing Co Ltd
Priority to JP60096786A priority Critical patent/JPS61256560A/en
Publication of JPS61256560A publication Critical patent/JPS61256560A/en
Publication of JPH0518221B2 publication Critical patent/JPH0518221B2/ja
Granted legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H01M12/085—Zinc-halogen cells or batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Cell Separators (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

Ａ 産業上の利用分野 本発明は、金属ハロゲン（例Zn−Br2）電解液
循環型積層二次電池における電池構成部材の寸法
精度の改善に関するものである。 Ｂ 発明の概要 本発明においては、金属ハロゲン電解液循環型
積層二次電池の電池構成部材のうち、少くともを
枠付電極、枠付セパレータの枠体材料としてポリ
オレフイン系樹脂に、無機フイラーとしてガラス
フアイバーを適量混合、混練したものを用いるも
のであり、、また上記組成に、更にエチレン−プ
ロピレンゴムを適量混合、混練したものを用いた
り、マトリツクスのMI値を適度とすることによ
り、枠体の成型時に発生する材料収縮率を大巾に
改善するものである。 Ｃ 従来の技術 一般に、金属ハロゲン電解液循環型積層二次電
池においては、従来より電極として活物質のハロ
ゲンに耐性を有するポリエチレン、ポリプロピレ
ン等のポリオレフイン系樹脂をマトリツクスと
し、これに導電性物質例えばカーボン等を混合、
混練したいわゆるカーボンプラスチツク電極
（CP電極）が用いられている。又、セパレータ
（隔膜）の材料には同様活物質のハロゲンに耐性
を有するポリエチレン等のポリオレフイン系樹脂
を用い、これに臭素等のハロゲン透過性を良好な
らしめるため、多孔質とした隔膜素材が用いられ
ている。 また一方、これらの電極、セパレータ等を積層
電池へ組込む場合は、通常、それぞれの周縁部に
インジエクシヨンモールド法等によつて枠体が一
体成型され、これら枠付電極、枠付セパレータを
積層し、枠部に設けたボルト通孔にボルトを挿入
し、これを締付けることによつて電池本体が一体
に形成される。この枠体材料としては上述の電極
及びセボレータの材料とされているポリオレフイ
ン系樹脂と、ほぼ同一のポリオレフイン系樹脂に
無機フイラーを混ぜないものか、混ぜても僅かの
量しか混ぜないものが用いられていた。 Ｄ 発明が解決しようとする問題点 ところが、従来インズエクシヨンモールド法で
枠付成型を行つた後の成型収縮率は、1.5〜3.0％
と大きいため、その枠体の中央位置にインサート
されるCP電極およびセパレータは、枠体の収縮
のため大きな擦みを生じ、特にCP電極の場合は、
剛性の高いことに起因するクラツクの発生が避け
られなかつた。 本発明では、上記の問題を解決するための枠体
材料を開発することを目的としている。 Ｅ 問題点を解決するための手段 即ち、本発明においては、積層二次電池の構成
部材のうち、少くとも枠付電極、枠付セパレータ
の枠体を形成する材料としてポリオレフイン系樹
脂に、無機フイラーのガラスフアイバーを適量
（好ましくは20〜50重量％）混合、混練したもの
を用いるものであり、また上記組成に、更にエチ
レン−プロピレンゴムを適量（好ましくは５〜20
重量％）混合、混練したものを用いるものであ
る。 なお、マトリツクスとして用いるポリオレフイ
ン系樹脂には、従来のCP電極等に用いられてい
たもの（好ましくはポリエチレン密度0.94ｇ／cm2
以上、ポリプロピレン密度0.90ｇ／cm2以上、MI
値８ｇ／10min以上）を利用することができる
し、またエチレン−プロピレンゴムとしては、分
子内に二重結合を持たないものを用いることが、
耐臭素性上好ましい。 Ｆ 作用 以上の如くしたことにより、本発明において
は、枠付電極、枠付セパレータの枠体の成型時の
材料収縮率が大巾に改善される。 Ｇ 発明の実施例 次に、本発明の実施例を挙げる。 (i) 枠材マトリツクス：ポリエチレン密度0.94ｇ／cm2
以上 ポリプロピレン密度0.90ｇ／cm2以上 MI値８ｇ／10min以上 (ii) フイラーのガラス フアイバー：直径３〜50μｍ、長さ３〜５mmのガラ スフアイバーを予め上記マトリツクスに 混合、混練した後５mm程度のペレツトと した後インジエクシヨン成形する。 (iii) 使用可能なCP電極マトリツクスの組成は上記枠
材のものと 同一、これにカーボンブラツク及びグラ フアイト10〜60（重量）％と、金属 酸化物（TiO2，Al2O3，SiO2等）を 少量混合、混練したものを成形する。 (iv) 使用可能セパレータ：ポリオレフイン系微細多孔
質膜、スチレ ン−ジビニルベンゼン系イオン交換膜そ の他ミクロフイルター等の多孔膜。 (v) エチレン−プロピレン ゴム：分子内に二重結合を特に持たないものが 耐臭素性を有する。よう素価０、配合比 率が20重量％を超えると機械的強度が 小さくなる。 上記(i)の枠材マトリツクスに(ii)のガラス単繊維
（φ13mm×長さ３mm）を20〜50（重量）％混合、混
練してペレツトとしたものを素材とし、一部に
EPラバー（エチレン−プロピレンコポリマーか
らなるよう素価０、分子内二重結合を持たないも
の）を添加して枠材に弾性を付与したものも実施
例に加えた。これらの各組成からなるペレツトを
枠体形成用素材とし、インサートとして上記(iii)の
CP電極、(iv)のセパレータを装着した周囲に金型
温度70℃、射出樹脂温度270℃、金型加圧350〜
600ton／cm2、射出圧力960Kgｆ／cm2、保持圧640Kg
ｆ／cm2という条件でインジエクシヨンモールデイ
グにより枠付加工を行つた。その各収縮率を以下
の式によつて求め、次表に示す。 金型寸法（設計寸法）−成形品寸法／金型寸法（設計
寸法）×100＝収縮率（％）。 但しEPラバーは日本合成ゴム、EP02Pであつ
た。 A. Field of Industrial Application The present invention relates to improving the dimensional accuracy of battery components in a metal halogen (eg Zn-Br 2 ) electrolyte circulating type stacked secondary battery. B. Summary of the Invention In the present invention, at least among the battery components of a metal halogen electrolyte circulation type stacked secondary battery, polyolefin resin is used as the frame material of the framed electrode and framed separator, and glass is used as the inorganic filler. The frame is made by mixing and kneading an appropriate amount of fibers, and by using an appropriate amount of ethylene-propylene rubber mixed and kneaded in addition to the above composition, or by adjusting the MI value of the matrix. This greatly improves the material shrinkage rate that occurs during molding. C. PRIOR TECHNOLOGY In general, in a metal halogen electrolyte circulation type stacked secondary battery, a polyolefin resin such as polyethylene or polypropylene, which is resistant to halogen as an active material, is used as an electrode as a matrix, and a conductive material such as carbon is added to the matrix. Mix etc.
A kneaded carbon plastic electrode (CP electrode) is used. In addition, as the material for the separator (diaphragm), a polyolefin resin such as polyethylene, which is resistant to the halogen of the active material, is used, and in order to improve the permeability of halogens such as bromine, a porous diaphragm material is used. It is being On the other hand, when incorporating these electrodes, separators, etc. into a laminated battery, a frame is usually integrally molded on the peripheral edge of each by injection molding, etc., and these framed electrodes and framed separators are laminated. Then, the battery body is integrally formed by inserting a bolt into a bolt hole provided in the frame and tightening the bolt. The frame material used is a polyolefin resin that is almost the same as the polyolefin resin used as the material for the electrodes and sevolators mentioned above, but does not contain an inorganic filler, or even if it is mixed, it mixes only a small amount. was. D Problems to be Solved by the Invention However, the molding shrinkage rate after frame molding using the conventional insexion molding method is 1.5 to 3.0%.
Because of its large size, the CP electrode and separator inserted in the center of the frame will cause a lot of abrasion due to the shrinkage of the frame, especially in the case of the CP electrode.
Occurrence of cracks due to high rigidity was unavoidable. The present invention aims to develop a frame material for solving the above problems. E Means for Solving the Problems That is, in the present invention, among the constituent members of the laminated secondary battery, an inorganic filler is added to the polyolefin resin as a material for forming at least the frame of the framed electrode and the framed separator. A suitable amount (preferably 20 to 50% by weight) of glass fibers is mixed and kneaded, and an appropriate amount (preferably 5 to 20% by weight) of ethylene-propylene rubber is further added to the above composition.
weight%) mixed and kneaded. The polyolefin resin used as the matrix is one that has been used in conventional CP electrodes (preferably polyethylene with a density of 0.94 g/cm 2
or more, polypropylene density 0.90g/ cm2 or more, MI
value of 8g/10min or more), and as ethylene-propylene rubber, it is best to use one that does not have double bonds in the molecule.
Preferable in terms of bromine resistance. F Effect As described above, in the present invention, the material shrinkage rate during molding of the frame of the framed electrode and framed separator is greatly improved. G. Examples of the invention Next, examples of the invention will be described. (i) Frame material matrix: Polyethylene density 0.94g/cm 2
 Polypropylene density: 0.90 g/cm 2 or more MI value: 8 g/10 min or more (ii) Glass fiber for filler: Glass fibers with a diameter of 3 to 50 μm and a length of 3 to 5 mm are mixed and kneaded in the above matrix in advance, and then pellets of about 5 mm are formed. After that, in-die extension molding is performed. (iii) The composition of the usable CP electrode matrix is the same as that of the above-mentioned frame material, plus 10-60% (by weight) of carbon black and graphite, and metal oxides (TiO 2 , Al 2 O 3 , SiO 2 etc.) are mixed and kneaded and then molded. (iv) Usable separators: Porous membranes such as polyolefin microporous membranes, styrene-divinylbenzene ion exchange membranes, and other microfilters. (v) Ethylene-propylene rubber: Rubber that does not have double bonds in its molecules has bromine resistance. If the iodine value is 0 and the blending ratio exceeds 20% by weight, the mechanical strength will decrease. The material is made by mixing 20 to 50% (by weight) of the glass single fibers (φ13 mm x length 3 mm) of (ii) in the frame material matrix of (i) above and kneading them into pellets.
A frame material in which elasticity was imparted to the frame material by adding EP rubber (composed of an ethylene-propylene copolymer with an iodine value of 0 and no double bond in the molecule) was also added to the examples. Pellets made of each of these compositions are used as a material for forming the frame, and the above (iii) is used as an insert.
The mold temperature is 70℃, the injection resin temperature is 270℃, and the mold pressure is 350~ around the CP electrode and (iv) separator attached.
600ton/cm 2 , injection pressure 960Kgf/cm 2 , holding pressure 640Kg
Frame processing was carried out using in-die extension molding under the conditions of f/cm 2 . The respective shrinkage rates were determined using the following formulas and are shown in the following table. Mold dimensions (design dimensions) - molded product dimensions/mold dimensions (design dimensions) x 100 = shrinkage rate (%). However, the EP rubber was Japanese synthetic rubber, EP02P.

【表】 Ｈ 発明の効果 以上の説明で理解されるように、ポリオレフイ
ン系樹脂の種類によらずガラスフアイバーの添加
量によつて収縮率が変動する。また、配合率40
（重量）％で収縮率が一定となり、50（重量）％で
もその値は変らない。 このことから、枠体として用いるマトリツクス
のポリオレフイン系樹脂に、ガラスフアイバーを
20〜50（重量）％、望ましくは30〜50（重量）％添
加することが本発明の目的上好ましく、これによ
り平らな反りのない枠付電極、枠付セパレータを
得ることが可能となり、次の効果を奏することが
できた。 (イ) 枠体の収縮が小さく、電極、セパレータ等の
成形品の寸法安定性が向上した。 (ロ) 平坦な電極膜が得られたことにより、積層電
池の積層部の寸法も安定した。 (ハ) 積層電池からの液洩れが防止された。 (ニ) 積層電池を組立てる際のボルト締めにより電
極、セパレータの枠部の割れ事故が防止され
た。[Table] H Effects of the Invention As understood from the above explanation, the shrinkage rate varies depending on the amount of glass fiber added, regardless of the type of polyolefin resin. Also, the blending rate is 40
The shrinkage rate is constant at (weight)%, and the value does not change even at 50 (weight)%. For this reason, glass fibers were added to the polyolefin resin of the matrix used as the frame.
It is preferable for the purpose of the present invention to add 20 to 50% (by weight), preferably 30 to 50% (by weight), and this makes it possible to obtain flat, unwarped framed electrodes and framed separators. was able to achieve this effect. (a) The shrinkage of the frame is small, and the dimensional stability of molded products such as electrodes and separators is improved. (b) Since a flat electrode film was obtained, the dimensions of the stacked portion of the stacked battery were also stabilized. (c) Liquid leakage from the laminated battery was prevented. (d) Accidental cracking of the electrode and separator frames was prevented by tightening the bolts when assembling the stacked battery.

Claims (1)

【特許請求の範囲】 １ 電極周縁部に枠体を一体成型してなる枠付電
極と、セパレータ周縁部に枠体を一体成型してな
る枠付セパレータとを積層し、積層された枠体部
を締付けることによつて一体に形成される枠付電
極およびセパレータを有する積層電池において、 前記枠体は、ポリオレフイン系樹脂に、ガラス
フアイバーを20〜50（重量）％混合した材料から
なることを特徴とする枠付電極およびセパレータ
を有する積層電池。 ２ 前記枠体は、ポリオレフイン系樹脂に、エチ
レン−プロピレンゴムを５〜20（重量）％とガラ
スフアイバーを20〜50（重量）％とを混合した材
料からなることを特徴とする特許請求の範囲第１
項記載の枠付電極およびセパレータを有する積層
電池。 ３ 前記ポリオレフイン系樹脂のメルトインデツ
クス（MI値）を８以上としたことを特徴とする
特許請求の範囲第１項又は第２項記載の枠付電極
およびセパレータを有する積層電池。[Scope of Claims] 1. A frame body formed by laminating an electrode with a frame formed by integrally molding a frame on the peripheral edge of the electrode and a separator with frame formed by integrally molding the frame on the peripheral edge of the separator. A laminated battery having a framed electrode and a separator integrally formed by tightening, the frame being made of a material consisting of a polyolefin resin mixed with 20 to 50% (by weight) of glass fiber. A laminated battery having a framed electrode and a separator. 2. The frame body is made of a material obtained by mixing polyolefin resin with 5 to 20% (by weight) of ethylene-propylene rubber and 20 to 50% (by weight) of glass fiber. 1st
A laminated battery having a framed electrode and a separator as described in 2. 3. A laminated battery having a framed electrode and a separator according to claim 1 or 2, wherein the polyolefin resin has a melt index (MI value) of 8 or more.
JP60096786A 1985-05-09 1985-05-09 Laminated cell having framed electrode and separator Granted JPS61256560A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60096786A JPS61256560A (en) 1985-05-09 1985-05-09 Laminated cell having framed electrode and separator

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60096786A JPS61256560A (en) 1985-05-09 1985-05-09 Laminated cell having framed electrode and separator

Publications (2)

Publication Number Publication Date
JPS61256560A JPS61256560A (en) 1986-11-14
JPH0518221B2 true JPH0518221B2 (en) 1993-03-11

Family

ID=14174319

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60096786A Granted JPS61256560A (en) 1985-05-09 1985-05-09 Laminated cell having framed electrode and separator

Country Status (1)

Country Link
JP (1) JPS61256560A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016076047A1 (en) * 2014-11-13 2016-05-19 日本碍子株式会社 Separator structure body for use in zinc secondary battery
CN113258210B (en) * 2021-04-26 2023-05-26 东华理工大学 Lithium ion battery etching diaphragm material and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5145191Y2 (en) * 1974-08-03 1976-11-01
JPS5244410A (en) * 1975-10-03 1977-04-07 Sekisui Koji Kk Tank bottom plates

Also Published As

Publication number Publication date
JPS61256560A (en) 1986-11-14

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