JPH06140014A - Separator for wound type battery - Google Patents

Separator for wound type battery

Info

Publication number
JPH06140014A
JPH06140014A JP4315886A JP31588692A JPH06140014A JP H06140014 A JPH06140014 A JP H06140014A JP 4315886 A JP4315886 A JP 4315886A JP 31588692 A JP31588692 A JP 31588692A JP H06140014 A JPH06140014 A JP H06140014A
Authority
JP
Japan
Prior art keywords
separator
fiber
battery
sheet
electrode
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
Application number
JP4315886A
Other languages
Japanese (ja)
Inventor
Osamu Ishida
修 石田
Tomohito Yamamoto
智史 山本
Yozo Nagai
陽三 長井
Hiroyuki Iida
博之 飯田
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.)
Maxell Holdings Ltd
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Hitachi Maxell 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 Nitto Denko Corp, Hitachi Maxell Ltd filed Critical Nitto Denko Corp
Priority to JP4315886A priority Critical patent/JPH06140014A/en
Publication of JPH06140014A publication Critical patent/JPH06140014A/en
Pending 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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

Abstract

PURPOSE:To obtain a separator which is not broken at the time of blacing it on a sheet-shaped electrode and winding them together in spiral manner even in the case that the separator is made thinner so as to be suitable for reducing the size and increasing capacity of a battery. CONSTITUTION:The present invention is related to a sheet-shaped wound type battery separator suitably used for a nickel-hydrogen battery and an alkali second battery using a spiral electrode piece made of such nickel-cadmium. The separator 3 consists of non-woven cloth including fiber A having graft efficiency of more than 20% and fiber B having graft efficiency of less than 20% and having unit weight of less than 70g/m<2>. The fiber A includes at least polyethylene on it surface part, the fiber B includes polypropylene as its main component and a ratio of usage for both fibers is suitably in a range from of 1/9 to 9/1 in weigh ratio.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、特にニッケル−水素電
池やニッケル−カドミウム電池などのようにシート状電
極とセパレータとを重ね合わせて渦巻状に巻回して作製
した渦巻状電極体を用いるアルカリ二次電池に好適に使
用される巻回型の電池用セパレータに関する。BACKGROUND OF THE INVENTION The present invention relates to an alkali using a spirally wound electrode body produced by stacking a sheet-shaped electrode and a separator and spirally winding them, such as a nickel-hydrogen battery or a nickel-cadmium battery. The present invention relates to a wound-type battery separator that is preferably used in secondary batteries.

【０００２】[0002]

【従来の技術】ニッケル−水素電池やニッケル−カドミ
ウム電池などのアルカリ二次電池のセパレータとして
は、ポリアミド繊維やポリオレフィン繊維などの合成繊
維の不織布が用いられている〔たとえば、吉沢四郎監修
「電池ハンドブック」、（株）電気書院、ｐ．３〜１５
（昭５０）〕。2. Description of the Related Art Nonwoven fabrics of synthetic fibers such as polyamide fibers and polyolefin fibers are used as separators for alkaline secondary batteries such as nickel-hydrogen batteries and nickel-cadmium batteries [see, for example, "Battery Handbook" edited by Shiro Yoshizawa. , "Denki Shoin Co., Ltd., p. 3 to 15
(Sho 50)].

【０００３】しかし、ポリアミド繊維は、親水性が優れ
ているものの、アルカリ電解液中での酸化雰囲気（過充
電時にこの雰囲気になる）での分解が大きく、その分解
生成物が自己放電を大きくさせるという問題があった
〔たとえば、Ｈ．Ｓ．Ｌｉｍ等：“Ｐｒｏｃｅｅｄｉｎ
ｇｓ ｏｆ ｔｈｅ ２７ｔｈ Ｐｏｗｅｒ Ｓｏｕｒ
ｃｅｓ Ｃｏｎｆｅｒｅｎｃｅ”，ｐ．８３〜８５（’
７６）〕。However, although polyamide fibers are excellent in hydrophilicity, they are largely decomposed in an oxidizing atmosphere in an alkaline electrolyte (which becomes this atmosphere when overcharged), and the decomposition products increase self-discharge. There was a problem [for example, H. S. Lim et al .: “Proceedin
gs of the 27th Power Source
ces Conference ", p.83-85 ('
76)].

【０００４】また、ポリオレフィン繊維はアルカリ電解
液中での酸化雰囲気に対しても優れた耐久性を有するも
のの、親水性が乏しく、電解液保持能力が小さい。その
ため、セパレータとして用いるポリオレフィン不織布
は、電解液に対する濡れ性を付与するために、あらかじ
め界面活性剤で表面処理することが行われている。Further, although polyolefin fibers have excellent durability even in an oxidizing atmosphere in an alkaline electrolyte, they have poor hydrophilicity and have a small electrolyte retaining ability. Therefore, the polyolefin nonwoven fabric used as the separator has been subjected to surface treatment with a surfactant in advance in order to impart wettability to the electrolytic solution.

【０００５】しかし、表面処理されたポリオレフィン不
織布は、初期の親水性は良好であるが、一旦電解液に接
触すると、界面活性剤が電解液に溶解し、それが自己放
電を大きくさせるという問題があった〔たとえば、特開
昭６４−５７５６８号公報〕。また、電解液保持能力の
低下により、電池の内部抵抗が増加し、放電電圧の低下
や活物質の利用率の低下を招くという問題もあった。However, although the surface-treated polyolefin nonwoven fabric has a good initial hydrophilicity, once it comes into contact with the electrolytic solution, the surfactant is dissolved in the electrolytic solution, which causes a problem of self-discharge. (For example, Japanese Patent Laid-Open No. 64-57568). In addition, there is a problem that the internal resistance of the battery increases due to the decrease in the electrolyte holding capacity, which causes a decrease in the discharge voltage and a decrease in the utilization rate of the active material.

【０００６】そのため、アルカリ電解液中での酸化雰囲
気に対しても優れた耐久性を有するポリプロピレンとポ
リエチレンからなる複合成分型繊維の不織布に、親水性
を有するアクリル酸、メタクリル酸などをグラフト共重
合させることによって、界面活性剤処理による場合のよ
うな電解液に溶解するおそれのない、親水性付与方法が
提案されている〔たとえば、特公平１−３６２３１号公
報〕。Therefore, a non-woven fabric of a composite component type fiber made of polypropylene and polyethylene which has excellent durability even in an oxidizing atmosphere in an alkaline electrolyte is graft-copolymerized with hydrophilic acrylic acid, methacrylic acid or the like. By doing so, there has been proposed a hydrophilicity-imparting method that is unlikely to be dissolved in an electrolytic solution as in the case of treating with a surfactant [eg, Japanese Patent Publication No. 1-36231].

【０００７】この場合における複合成分型繊維は、通
常、芯部と表面部からなる二層構造をしていて、芯部５
０％が高融点のポリプロピレンで構成され、表面部５０
％が不織布作製時に熱融着が容易なように低融点のポリ
エチレンで構成されている。In this case, the composite component type fiber usually has a two-layer structure composed of a core portion and a surface portion.
0% is composed of high melting point polypropylene, and the surface part 50
% Is made of polyethylene having a low melting point so that it can be easily heat-sealed when a nonwoven fabric is manufactured.

【０００８】このような複合成分型繊維にアクリル酸や
メタクリル酸などをグラフト共重合させた場合、グラフ
ト共重合は芯部のポリプロピレンに対してはほとんど行
われないが、グラフト共重合が容易な表面部のポリエチ
レンに対しては全体にわたってグラフト共重合が行われ
る。When acrylic acid, methacrylic acid or the like is graft-copolymerized on such a composite component type fiber, the graft-copolymerization is hardly performed on the polypropylene of the core part, but the surface on which the graft-copolymerization is easy is carried out. Graft copolymerization is carried out on all parts of polyethylene.

【０００９】また、電池を組み立てた際に、セパレータ
に電池反応に充分な量の電解液を保持させるためには、
アクリル酸やメタクリル酸などによるグラフト化率を大
きくする必要がある〔たとえば、丹宗他２名：ＹＵＡＳ
Ａ−ＪＩＨＯ，Ｎｏ．５９，ｐ．３５〜４４（’８
５）〕。When the battery is assembled, in order for the separator to retain a sufficient amount of electrolytic solution for the battery reaction,
It is necessary to increase the grafting ratio with acrylic acid, methacrylic acid, etc. [For example, Tanmune et al. 2 people: YUAS
A-JIHO, No. 59, p. 35-44 ('8
5)].

【００１０】しかし、グラフト化率を大きくすると繊維
自体が脆くなってしまう〔森他２名：高分子論文集，Ｖ
ｏｌ．４８，Ｎｏ．１，ｐ．１〜９〕。一般に、脆い材
料は応力集中が大きく〔前沢成一郎訳：“改訂材料力学
要論”，ｐ．５１（昭４７）〕、一旦亀裂が生じると、
それが容易に伝播し、切断してしまう。この現象の強弱
はエレメンドルフ引裂強度〔ＪＩＳ Ｐ ８１１６〕を
測定することによって知ることができる。However, if the grafting ratio is increased, the fiber itself becomes brittle [Mori et al. 2: Polymer Papers, V
ol. 48, No. 1, p. 1-9]. Generally, brittle materials have large stress concentration [Translated by Seiichiro Maezawa: "Revised Material Mechanics", p. 51 (Sho 47)], once a crack occurs,
It easily propagates and breaks. The strength and weakness of this phenomenon can be known by measuring the Elmendorf tear strength [JIS P 8116].

【００１１】ところで、どの電池でも同様であるが、小
形高容量化に対する要求に応えるために、アルカリ二次
電池でも高容量化を図る必要があり、そのため、電極の
活物質充填量を増加させることが行われている。一定体
積のなかで、活物質充填量を増加させようとすると、セ
パレータに割り当てる体積を減少させるのが最も簡単な
解決法である。By the way, as with any battery, in order to meet the demand for small size and high capacity, it is necessary to increase the capacity of the alkaline secondary battery as well. Therefore, the filling amount of the active material of the electrode should be increased. Is being done. The simplest solution is to reduce the volume allocated to the separator when trying to increase the active material filling amount within a fixed volume.

【００１２】そのため、薄いセパレータを使用すること
が必要になるが、薄いセパレータを使用すると必然的に
強度が低下し、特に単位重量が７０ｇ／ｍ2 以下になる
と、セパレータをシート状電極と重ね合わせて渦巻状に
巻回する際にセパレータが電極の角部に押圧されて破断
し、短絡が発生するようになる。Therefore, it is necessary to use a thin separator, but the use of a thin separator inevitably lowers the strength. Especially when the unit weight is 70 g / m 2 or less, the separator is superposed on the sheet electrode. When it is spirally wound, the separator is pressed against the corner portion of the electrode and is broken, so that a short circuit occurs.

【００１３】[0013]

【発明が解決しようとする課題】本発明は、グラフト化
により親水性を付与し、高容量化に対応できるように単
位重量を７０ｇ／ｍ2 以下にした薄いセパレータがシー
ト状電極と重ね合わせて渦巻状に巻回する際に破断する
という問題点を解決し、しなやかさを持たせてシート状
電極と重ね合わせて渦巻状に巻回する時に破断を防止し
得る巻回型の電池用セパレータを提供することを目的と
する。DISCLOSURE OF THE INVENTION According to the present invention, a thin separator having a unit weight of 70 g / m 2 or less is superposed on a sheet-like electrode so as to impart hydrophilicity by grafting and to cope with high capacity. A wound type battery separator that solves the problem of breakage when wound in a spiral shape and that has flexibility and can prevent breakage when wound in a spiral shape by overlapping with a sheet electrode. The purpose is to provide.

【００１４】[0014]

【課題を解決するための手段】本発明は、グラフト化率
２０％を超える繊維Ａと、グラフト化率２０％以下の繊
維Ｂとを含む単位重量７０ｇ／ｍ2 以下の不織布で電池
用セパレータを構成することによって、上記目的を達成
したものである。The present invention provides a battery separator made of a non-woven fabric containing a fiber A having a grafting rate of 20% or more and a fiber B having a grafting rate of 20% or less and having a unit weight of 70 g / m 2 or less. The above object is achieved by the configuration.

【００１５】すなわち、グラフト化によって繊維に親水
性を付与し、そのグラフト化率２０％を超える繊維Ａで
電解液の保持能力を確保し、グラフト化率２０％以下の
繊維Ｂで繊維本来のしなやかさを確保して、単位重量が
７０ｇ／ｍ2 という薄いセパレータでも、シート状電極
と重ね合わせて渦巻状に巻回する際の破断が生じないよ
うにしたものである。That is, by imparting hydrophilicity to the fiber by grafting, the fiber A having a grafting rate of more than 20% secures an electrolyte retaining ability, and the fiber B having a grafting rate of 20% or less makes the fiber inherently flexible. The thickness is ensured so that even a thin separator having a unit weight of 70 g / m 2 is prevented from being broken when the sheet-shaped electrode is superposed and spirally wound.

【００１６】上記グラフト化率２０％を超える繊維Ａ
は、少なくとも表面部にグラフト化が容易なポリエチレ
ンを含んでいることが必要であり、全体をポリエチレン
で構成するか、または表面部をポリエチレンで構成し、
芯部をポリプロピレンで構成したものが適している。Fiber A having a grafting ratio of more than 20%
It is necessary that at least the surface portion contains polyethylene that can be easily grafted, and the entire surface is made of polyethylene, or the surface portion is made of polyethylene,
A core made of polypropylene is suitable.

【００１７】グラフト化は、基材となる繊維に、酸また
は塩基と反応して直接あるいは間接に塩を形成し得るモ
ノマー、たとえばアクリル酸やメタクリル酸などをグラ
フト共重合させることによって行われる。Grafting is carried out by graft-copolymerizing a fiber as a base material with a monomer capable of directly or indirectly reacting with an acid or a base to form a salt, such as acrylic acid or methacrylic acid.

【００１８】グラフト化率は、下記の式 The grafting rate is calculated by the following formula

【００１９】により算出されるものであって、モノマー
が重合して長鎖状でグラフト化することが起こり得るの
で、グラフト化率が１００％を超えることもあり得る。The grafting ratio may exceed 100% because the monomer may be polymerized and grafted in a long chain form.

【００２０】この繊維Ａに関してグラフト化率が２０％
を超えることを必要としているのは、電池反応に必要な
電解液保持能力を確保するためである。グラフト化率が
大きくなると、それに伴って電解液保持力は大きくなっ
ていくが、その反面、脆くなるので、繊維Ｂと併用する
とはいえ、グラフト化率が大きくなりすぎるとシート状
電極と重ね合わせて渦巻状に巻回する時に破断が生じや
すくなるので、この繊維Ａに関してはグラフト化率が２
０％を超えて１００％以下のもの、特にグラフト化率２
０〜７０％のものが好ましい。The graft ratio of this fiber A is 20%.
The reason why it is necessary to exceed is to ensure the electrolytic solution holding capacity necessary for the battery reaction. When the grafting ratio increases, the electrolytic solution holding power increases accordingly, but on the other hand, it becomes brittle. Therefore, although it is used in combination with the fiber B, if the grafting ratio is too large, it will overlap with the sheet electrode. As the fiber A has a grafting ratio of 2 because it is likely to break when wound in a spiral shape.
More than 0% and 100% or less, especially grafting rate 2
It is preferably 0 to 70%.

【００２１】一方、グラフト化率２０％以下の繊維Ｂ
は、繊維本来のしなやかさを保ち、セパレータをシート
状電極と重ね合わせて渦巻状に巻回する時に破断を生じ
ないようにするためのものであり、この繊維Ｂはグラフ
ト化が進みすぎないポリプロピレンやポリフッ化ビニリ
デンのような含フッ素系ポリオレフィンを主成分として
構成することが好ましい。そして、この主成分とするも
のは、それらのみでもよいし、それらの特性を損なわな
い範囲で他のものが混入していてもよいという意味であ
る。On the other hand, a fiber B having a grafting ratio of 20% or less
Is to keep the original flexibility of the fiber and to prevent breakage when the separator is superposed on the sheet-like electrode and wound in a spiral shape. The fiber B is a polypropylene that does not undergo excessive grafting. It is preferable that the main component is a fluorinated polyolefin such as or polyvinylidene fluoride. This means that the main components may be only these, or other components may be mixed in as far as the characteristics thereof are not impaired.

【００２２】グラフト化率が小さいほど繊維としてのし
なやかさは高くなるが、グラフト化率が０％、つまり、
アクリル酸、メタクリル酸などをまったくグラフト共重
合させていない場合は親水性がなくなるので、この繊維
Ｂに関してはグラフト化率３〜２０％、特に５〜１５％
のものが好ましい。The smaller the grafting ratio, the higher the flexibility of the fiber, but the grafting ratio is 0%, that is,
The hydrophilicity is lost when acrylic acid, methacrylic acid, etc. are not graft-copolymerized at all, and therefore the graft ratio of this fiber B is 3 to 20%, particularly 5 to 15%.
Are preferred.

【００２３】上記繊維Ａと繊維Ｂを含む不織布中におい
て、繊維Ａと繊維Ｂの割合は重量比で１／９〜９／１の
範囲が好ましい。In the non-woven fabric containing the fibers A and B, the weight ratio of the fibers A to the fibers B is preferably in the range of 1/9 to 9/1.

【００２４】すなわち、繊維Ａの割合が上記範囲より多
くなると脆くなり、引裂強度で表現すると、エレメンド
ルフ引裂強度が２００ｇｆより小さくなって、セパレー
タとしてシート状電極に重ね合わせて渦巻状に巻回する
時にセパレータが電極の角部に押圧されて破断するよう
になる。That is, when the ratio of the fiber A is more than the above range, the fiber A becomes brittle, and in terms of tear strength, the Elemendorff tear strength becomes less than 200 gf, and it is spirally wound on the sheet electrode as a separator. Sometimes the separator will be pressed against the corners of the electrode and break.

【００２５】また、繊維Ａの割合が上記範囲より少なく
なると親水性が低下して電解液の保持能力が低下し、電
池の内部抵抗が増加するなど、電池の電気的特性が低下
する。When the proportion of the fiber A is less than the above range, the hydrophilicity is lowered, the electrolyte holding ability is lowered, the internal resistance of the battery is increased, and the electrical characteristics of the battery are deteriorated.

【００２６】本発明においては、高容量化に対応できる
ように、セパレータの単位重量を７０ｇ／ｍ2 以下にす
るが、薄くなりすぎると正極と負極を隔離する能力が低
下するので３５ｇ／ｍ2 程度までのものを使用するのが
好ましい。In the present invention, the unit weight of the separator is set to 70 g / m 2 or less so that the capacity can be increased. However, if the separator is too thin, the ability to separate the positive electrode from the negative electrode is lowered, so that the capacity is 35 g / m 2. It is preferred to use up to a degree.

【００２７】[0027]

【実施例】つぎに、実施例をあげて本発明をより具体的
に説明する。ただし、本発明はそれらの実施例のみに限
定されるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to only those examples.

【００２８】実施例１ 繊度１．５デニール、平均繊維長５ｍｍの複合成分型繊
維（芯部がポリプロピレンで、表面部がポリエチレンの
複合成分型繊維であり、その成分比は重量比で１：１で
ある）およびこれと同量の繊度１．５デニール、平均繊
維長５ｍｍのポリプロピレン単一成分型繊維を水に分散
させ、抄紙して繊維堆積シートを得た。Example 1 Composite component fiber having a fineness of 1.5 denier and an average fiber length of 5 mm (composite component fiber having a polypropylene core in the core and polyethylene in the surface, and the component ratio by weight is 1: 1). And a polypropylene monocomponent fiber having the same amount of fineness of 1.5 denier and an average fiber length of 5 mm was dispersed in water and paper-made to obtain a fiber deposited sheet.

【００２９】このシートを熱ロールでプレスして、繊維
を相互に接着するとともに厚さを調整して不織布を得
た。得られた不織布は単位重量が５０ｇ／ｍ2 で、厚さ
が１８０μｍであった。This sheet was pressed with a hot roll to bond the fibers to each other and adjust the thickness to obtain a nonwoven fabric. The obtained non-woven fabric had a unit weight of 50 g / m 2 and a thickness of 180 μm.

【００３０】この不織布に電子線を３Ｍｒａｄ照射し、
ラジカルを生成させた。このラジカル生成不織布を、ア
クリル酸１００重量部、水１００重量部およびモール塩
〔硫酸鉄（ＩＩ）アンモニウム六水塩〕１重量部からな
る溶液中に浸漬し、５０℃で１０分間加熱した。つぎ
に、７０℃の温水中に１時間浸漬して、未反応のアクリ
ル酸を洗浄して除去し、ついで、５０℃に加熱した２０
％水酸化カリウム水溶液中に１０分間浸漬してアクリル
酸を中和した後、水洗、乾燥してセパレータとした。This non-woven fabric was irradiated with an electron beam of 3 Mrad,
Generated radicals. This radical-generating nonwoven fabric was immersed in a solution consisting of 100 parts by weight of acrylic acid, 100 parts by weight of water, and 1 part by weight of Mohr's salt [iron (II) ammonium hexahydrate hexahydrate], and heated at 50 ° C. for 10 minutes. Next, it was immersed in warm water of 70 ° C. for 1 hour to wash and remove unreacted acrylic acid, and then heated to 50 ° C. 20
% Aqueous solution of potassium hydroxide for 10 minutes to neutralize acrylic acid, followed by washing with water and drying to obtain a separator.

【００３１】このセパレータのエレメンドルフ法によっ
て測定した引裂強度は４６０ｇｆであった。また、この
セパレータを構成する繊維のグラフト化率を赤外線分光
光度法により測定したところ、ポリエチレン−ポリプロ
ピレン複合成分型繊維のグラフト化率は２５％で、ポリ
プロピレン単一成分型繊維のグラフト化率は５％であっ
た。The tear strength of this separator measured by the Elmendorf method was 460 gf. The grafting ratio of the fibers constituting the separator was measured by infrared spectrophotometry. The grafting ratio of the polyethylene-polypropylene composite component type fiber was 25%, and the grafting ratio of the polypropylene single component type fiber was 5%. %Met.

【００３２】このセパレータを用い、シート状電極、つ
まりシート状の正極およびシート状の負極と重ね合わ
せ、渦巻状に巻回して渦巻状電極体にし、その渦巻状電
極体を用いて、図１に示す構造の単３形アルカリ二次電
池を作製した。Using this separator, a sheet-like electrode, that is, a sheet-like positive electrode and a sheet-like negative electrode, is superposed and spirally wound into a spirally wound electrode body, and the spirally wound electrode body is used as shown in FIG. An AA alkaline secondary battery having the structure shown was produced.

【００３３】上記電池の作製にあたって、正極には焼結
式ニッケル電極を用い、負極には焼結式水素吸蔵合金電
極を用い、電解液には濃度３０重量％の水酸化カリウム
水溶液を用いた。In the production of the above battery, a sintered nickel electrode was used for the positive electrode, a sintered hydrogen storage alloy electrode was used for the negative electrode, and an aqueous potassium hydroxide solution having a concentration of 30% by weight was used as the electrolytic solution.

【００３４】ここで、図１に示す電池について説明する
と、１は正極、２は負極、３はセパレータ、４は渦巻状
電極体、５は電池ケース、６は環状ガスケット、７は封
口蓋、８は端子板、９は封口板、１０は金属バネ、１１
は弁体、１２は正極リード体、１３は絶縁体、１４は絶
縁体である。The battery shown in FIG. 1 will now be described. 1 is a positive electrode, 2 is a negative electrode, 3 is a separator, 4 is a spiral electrode body, 5 is a battery case, 6 is an annular gasket, 7 is a sealing lid, 8 Is a terminal plate, 9 is a sealing plate, 10 is a metal spring, 11
Is a valve body, 12 is a positive electrode lead body, 13 is an insulator, and 14 is an insulator.

【００３５】正極１は活物質として水酸化ニッケルを含
むシート状の焼結式ニッケル電極であり、その寸法は３
９ｍｍ×８２ｍｍ×０．６６ｍｍで、理論電気容量は１
１６０ｍＡｈである。負極２は活物質となる水素吸蔵合
金そのものを焼結したシート状の水素吸蔵合金電極であ
り、その寸法は４１ｍｍ×１１１ｍｍ×０．３０ｍｍ
で、理論電気容量は１８００ｍＡｈである。The positive electrode 1 is a sheet-like sintered nickel electrode containing nickel hydroxide as an active material, and its size is 3
9mm x 82mm x 0.66mm, theoretical capacity is 1
It is 160 mAh. The negative electrode 2 is a sheet-shaped hydrogen storage alloy electrode obtained by sintering a hydrogen storage alloy itself as an active material, and its dimensions are 41 mm × 111 mm × 0.30 mm.
Therefore, the theoretical electric capacity is 1800 mAh.

【００３６】セパレータ３は上記のようにポリエチレン
−ポリプロピレン複合成分型繊維とポリプロピレン単一
成分型繊維との混合繊維の不織布にアクリル酸をグラフ
ト共重合させたものであり、その単位重量は５０ｇ／ｍ
2 で、複合成分型繊維のグラフト化率は２５％で、単一
成分型繊維のグラフト化率は５％である。そして、上記
正極１と負極２はこのセパレータ３を介して重ね合わせ
られ、渦巻状に巻回して渦巻状電極体４として電池ケー
ス５内に挿入され、その上部には絶縁体１４が配置され
ている。The separator 3 is obtained by graft-copolymerizing acrylic acid on a non-woven fabric of mixed fibers of polyethylene-polypropylene composite component type fibers and polypropylene single component type fibers as described above, and the unit weight thereof is 50 g / m.
At 2 , the composite component fiber has a grafting rate of 25% and the single component fiber has a grafting ratio of 5%. The positive electrode 1 and the negative electrode 2 are superposed on each other with the separator 3 interposed therebetween, spirally wound and inserted into the battery case 5 as the spirally wound electrode body 4, and the insulator 14 is arranged on the upper portion thereof. There is.

【００３７】また、上記渦巻状電極体４の電池ケース５
内への挿入に先立って、電池ケース５の底部に絶縁体１
３が配置され、電池ケース５と正極１との接触を防止し
ている。The battery case 5 of the spiral electrode body 4 is also provided.
Prior to insertion into the inside, the insulator 1 is attached to the bottom of the battery case 5.
3 is arranged to prevent contact between the battery case 5 and the positive electrode 1.

【００３８】環状ガスケット６はナイロン６６で作製さ
れ、封口蓋７は端子板８と封口板９とで構成され、電池
ケース５の開口部はこの封口蓋７と上記環状ガスケット
６とで封口されている。The annular gasket 6 is made of nylon 66, the sealing lid 7 is composed of the terminal plate 8 and the sealing plate 9, and the opening of the battery case 5 is sealed by the sealing lid 7 and the annular gasket 6. There is.

【００３９】つまり、電池ケース５内に渦巻状電極体４
や絶縁体１４などを挿入した後、電池ケース５の開口端
近傍部分に底部が内周側に突出した環状の溝５ａを形成
し、その溝５ａの内周側突出部で環状ガスケット６の下
部を支えさせて環状ガスケット６と封口蓋７とを電池ケ
ース５の開口部に配置し、電池ケース５の溝５ａから先
の部分を内方に締め付けて電池ケース５の開口部を封口
蓋７と環状ガスケット６とで封口している。That is, the spiral electrode body 4 is provided in the battery case 5.
After inserting the insulator 14 and the like, an annular groove 5a having a bottom protruding toward the inner peripheral side is formed in the vicinity of the open end of the battery case 5, and the inner peripheral protruding portion of the groove 5a forms a lower portion of the annular gasket 6. The annular gasket 6 and the sealing lid 7 are placed in the opening of the battery case 5 by supporting the above, and the portion of the battery case 5 beyond the groove 5a is tightened inward so that the opening of the battery case 5 becomes the sealing lid 7. It is sealed with the annular gasket 6.

【００４０】上記端子板８にはガス排出口８ａが設けら
れ、封口板９にはガス検知孔９ａが設けられ、端子板８
と封口板９との間には金属バネ１０と弁体１１とが配置
されている。そして、封口板９の外周部を折り曲げて端
子板８の外周部を挟み込んで端子板８と封口板９とを固
定している。The terminal plate 8 is provided with a gas discharge port 8a, the sealing plate 9 is provided with a gas detection hole 9a, and the terminal plate 8 is provided.
The metal spring 10 and the valve body 11 are arranged between the sealing plate 9 and the sealing plate 9. Then, the outer peripheral portion of the sealing plate 9 is bent to sandwich the outer peripheral portion of the terminal plate 8 to fix the terminal plate 8 and the sealing plate 9.

【００４１】この電池は、通常の状況下では金属バネ１
０の押圧力により弁体１１がガス検知孔９ａを閉鎖して
いるので、電池内部は密閉状態に保たれているが、電池
内部でガスが発生して電池内圧が異常に上昇した場合に
は、金属バネ１０が収縮して弁体１１とガス検知孔９ａ
との間に隙間が生じ、電池内部のガスはガス検知孔９ａ
およびガス排出孔８ａを通過して電池外部に放出され、
電池破裂が防止できるように構成されている。This battery has a metal spring 1 under normal circumstances.
Since the valve body 11 closes the gas detection hole 9a by the pressing force of 0, the inside of the battery is kept in a sealed state, but when gas is generated inside the battery and the internal pressure of the battery rises abnormally, , The metal spring 10 contracts and the valve body 11 and the gas detection hole 9a
A gap is created between the gas inside the battery and the gas inside the battery and the gas detection hole 9a
And is discharged to the outside of the battery through the gas discharge hole 8a,
It is configured to prevent the battery from bursting.

【００４２】上記電池を１００個作製し、作製直後に短
絡の有無を調べたところ、１００個とも短絡がなく、そ
の歩留りは１００％であった。つまり、この実施例１の
セパレータを用いた場合には、シート状電極と重ね合わ
せて渦巻状に巻回する時にセパレータの破断がまったく
なかった。When 100 batteries were produced and examined for short circuit immediately after the production, there was no short circuit and the yield was 100%. That is, when the separator of Example 1 was used, there was no breakage of the separator when the sheet-shaped electrode was superposed and spirally wound.

【００４３】また、上記１００個の電池を１００ｍＡで
１５時間充電し、２００ｍＡで０．９Ｖまで放電する充
放電サイクルを１０回繰り返し、１０回目の放電容量を
測定し、その平均値を算出したところ、平均放電容量は
１１００ｍＡｈであった。The 100 batteries were charged at 100 mA for 15 hours and discharged at 200 mA to 0.9 V for 10 charge / discharge cycles. The discharge capacity at the 10th time was measured and the average value was calculated. The average discharge capacity was 1100 mAh.

【００４４】実施例２ 繊度１．５デニール、平均繊維長５ｍｍのポリエチレン
単一成分型繊維およびこれと同量の繊度１．５デニー
ル、平均繊維長５ｍｍのポリプロピレン単一成分型繊維
を水に分散させ、抄紙して繊維堆積シートを得た。この
シートを熱ロールでプレスして、繊維を相互に接着させ
るとともに厚さを調整して不織布を得た。得られた不織
布は単位重量が５０ｇ／ｍ2 で、厚さが１８０μｍであ
った。Example 2 A polyethylene single component fiber having a fineness of 1.5 denier and an average fiber length of 5 mm and a polypropylene single component fiber having a fineness of 1.5 denier and an average fiber length of 5 mm of the same amount were dispersed in water. Then, papermaking was performed to obtain a fiber deposited sheet. This sheet was pressed with a hot roll to bond the fibers to each other and adjust the thickness to obtain a nonwoven fabric. The obtained non-woven fabric had a unit weight of 50 g / m 2 and a thickness of 180 μm.

【００４５】この不織布に電子線を３Ｍｒａｄ照射し、
ラジカルを生成させた。このラジカル生成不織布を、ア
クリル酸１００重量部、水１００重量部およびモール塩
１重量部からなる溶液中に浸漬し、５０℃で１０分間加
熱した。つぎに、７０℃の温水中に１時間浸漬して、未
反応のアクリル酸を洗浄して除去し、ついで、５０℃に
加熱した２０％水酸化カリウム水溶液中に１０分間浸漬
してアクリル酸を中和した後、水洗、乾燥してセパレー
タとした。This non-woven fabric was irradiated with an electron beam of 3 Mrad,
Generated radicals. This radical-generated nonwoven fabric was immersed in a solution of 100 parts by weight of acrylic acid, 100 parts by weight of water and 1 part by weight of Mohr's salt, and heated at 50 ° C. for 10 minutes. Next, it is immersed in warm water of 70 ° C. for 1 hour to wash and remove unreacted acrylic acid, and then immersed in a 20% aqueous potassium hydroxide solution heated to 50 ° C. for 10 minutes to remove acrylic acid. After neutralization, it was washed with water and dried to obtain a separator.

【００４６】このセパレータのエレメンドルフ引裂強度
は３５０ｇｆであった。また、このセパレータを構成す
る繊維のグラフト化率を赤外線分光光度法により測定し
たところ、ポリエチレン単一成分型繊維のグラフト化率
は３０％で、ポリプロピレン単一成分型繊維のグラフト
化率は５％であった。The Elemendorf tear strength of this separator was 350 gf. When the grafting ratio of the fibers constituting the separator was measured by infrared spectrophotometry, the grafting ratio of the polyethylene single-component fiber was 30% and the grafting ratio of the polypropylene single-component fiber was 5%. Met.

【００４７】このセパレータを用い、それ以外は実施例
１と同様にして、単３形アルカリ二次電池を１００個作
製し、作製直後に短絡発生の有無を調べたところ、短絡
の発生したものはまったくなく、歩留りは１００％であ
った。100 AA alkaline secondary batteries were manufactured in the same manner as in Example 1 except that this separator was used and the presence or absence of a short circuit was examined immediately after the production. There was nothing, and the yield was 100%.

【００４８】つまり、この実施例２のセパレータを用い
た場合には、シート状電極と重ね合わせて渦巻状に巻回
する時にセパレータの破断がまったくなかった。That is, when the separator of Example 2 was used, there was no breakage of the separator when the sheet-shaped electrode was superposed and spirally wound.

【００４９】また、これら１００個の電池について、実
施例１と同様に１０回目の放電容量を測定し、その平均
値を算出したところ、平均放電容量は１１００ｍＡｈで
あった。The discharge capacity of the 100th battery was measured in the same manner as in Example 1, and the average value was calculated. The average discharge capacity was 1100 mAh.

【００５０】比較例１ 繊度１．５デニール、平均繊維長５ｍｍの複合成分型繊
維（芯部がポリプロピレンで、表面部がポリエチレンの
複合成分型繊維であり、その成分比は重量比１：１であ
る）を単独で水に分散し、抄紙して繊維堆積シートを得
た。このシートを熱ロールでプレスして、繊維を相互に
接着させるとともに厚さを調整して不織布を得た。得ら
れた不織布は単位重量が５０ｇ／ｍ2 で、厚さが１８０
μｍであった。Comparative Example 1 A composite component fiber having a fineness of 1.5 denier and an average fiber length of 5 mm (a composite component fiber having a core of polypropylene and a surface of polyethylene, and the component ratio is 1: 1 by weight). A) was singly dispersed in water and paper-made to obtain a fiber-laid sheet. This sheet was pressed with a hot roll to bond the fibers to each other and adjust the thickness to obtain a nonwoven fabric. The obtained non-woven fabric has a unit weight of 50 g / m 2 and a thickness of 180.
was μm.

【００５１】この不織布に電子線を３Ｍｒａｄ照射し、
ラジカルを生成させた。このラジカル生成不織布を、ア
クリル酸１００重量部、水１００重量部およびモール塩
１重量部からなる溶液中に浸漬し、５０℃で１０分間加
熱した。つぎに、７０℃の温水中に１時間浸漬して、未
反応のアクリル酸を洗浄して除去し、ついで、５０℃に
加熱した２０％水酸化カリウム水溶液中に１０分間浸漬
してアクリル酸を中和した後、水洗、乾燥してセパレー
タとした。This non-woven fabric was irradiated with 3 Mrad of electron beam,
Generated radicals. This radical-generated nonwoven fabric was immersed in a solution of 100 parts by weight of acrylic acid, 100 parts by weight of water and 1 part by weight of Mohr's salt, and heated at 50 ° C. for 10 minutes. Next, it is immersed in warm water of 70 ° C. for 1 hour to wash and remove unreacted acrylic acid, and then immersed in a 20% aqueous potassium hydroxide solution heated to 50 ° C. for 10 minutes to remove acrylic acid. After neutralization, it was washed with water and dried to obtain a separator.

【００５２】このセパレータのエレメンドルフ引裂強度
は１６０ｇｆであった。また、このセパレータの構成繊
維のグラフト化率は４０％であった。The Elmendorf tear strength of this separator was 160 gf. The grafting rate of the constituent fibers of this separator was 40%.

【００５３】このセパレータを用い、それ以外は実施例
１と同様にして、単３形アルカリ二次電池を１００個作
製し、作製直後に短絡発生の有無を調べたところ、１０
０個の電池中４３個の電池が短絡しており、歩留りは５
７％であった。Using this separator, 100 AA-size alkaline secondary batteries were prepared in the same manner as in Example 1 and the presence or absence of short circuit was examined immediately after the production.
43 out of 0 batteries are short-circuited and the yield is 5
It was 7%.

【００５４】短絡の発生しなかった５７個の電池につい
て、実施例１と同様に１０回目の放電容量を測定し、そ
の平均値を算出したところ、平均放電容量は１１００ｍ
Ａｈであった。With respect to 57 batteries in which no short circuit occurred, the discharge capacity at the 10th time was measured in the same manner as in Example 1 and the average value was calculated. The average discharge capacity was 1100 m.
It was Ah.

【００５５】比較例２ 繊度１．５デニール、平均繊維長５ｍｍの複合成分型繊
維（芯部がポリプロピレンで、表面部がポリエチレンの
複合成分型繊維であり、その成分比は重量比で１：１で
ある）を単独で水に分散し、抄紙して繊維堆積シートを
得た。このシートを熱ロールでプレスして、繊維を相互
に接着させるとともに厚さを調整して不織布を得た。得
られた不織布は単位重量が７５ｇ／ｍ2 で、厚さが２３
０μｍであった。Comparative Example 2 A composite component fiber having a fineness of 1.5 denier and an average fiber length of 5 mm (composite component fiber having a polypropylene core portion and a polyethylene surface portion, the component ratio of which is 1: 1 by weight). Was independently dispersed in water and papermaking was carried out to obtain a fiber deposited sheet. This sheet was pressed with a hot roll to bond the fibers to each other and adjust the thickness to obtain a nonwoven fabric. The obtained non-woven fabric has a unit weight of 75 g / m 2 and a thickness of 23
It was 0 μm.

【００５６】この不織布に電子線を３Ｍｒａｄ照射し、
ラジカルを生成させた。このラジカル生成不織布を、ア
クリル酸１００重量部、水１００重量部およびモール塩
１重量部からなる溶液中に浸漬し、５０℃で１０分間加
熱した。つぎに、７０℃の温水中に１時間浸漬して、未
反応のアクリル酸を洗浄して除去し、ついで、５０℃に
加熱した２０％水酸化カリウム水溶液中に１０分間浸漬
してアクリル酸を中和した後、水洗、乾燥してセパレー
タとした。This non-woven fabric is irradiated with an electron beam of 3 Mrad,
Generated radicals. This radical-generated nonwoven fabric was immersed in a solution of 100 parts by weight of acrylic acid, 100 parts by weight of water and 1 part by weight of Mohr's salt, and heated at 50 ° C. for 10 minutes. Next, it is immersed in warm water of 70 ° C. for 1 hour to wash and remove unreacted acrylic acid, and then immersed in a 20% aqueous potassium hydroxide solution heated to 50 ° C. for 10 minutes to remove acrylic acid. After neutralization, it was washed with water and dried to obtain a separator.

【００５７】このセパレータのエレメンドルフ引裂強度
は２１０ｇｆであった。また、このセパレータを構成す
る繊維のグラフト化率は３５％であった。The Elemendorf tear strength of this separator was 210 gf. In addition, the grafting rate of the fibers constituting this separator was 35%.

【００５８】このセパレータを用い、実施例１と同様に
して、単３形アルカリ二次電池を１００個作製した。た
だし、セパレータの厚さが増した分、電極占有体積が減
少したため、正極寸法は３９ｍｍ×７２ｍｍ×０．６６
ｍｍになり、その理論電気容量は１０１０ｍＡｈに低下
し、負極寸法は４１ｍｍ×１０１ｍｍ×０．３０ｍｍに
なり、その理論電気容量は１６４０ｍＡｈに低下した。Using this separator, 100 AA alkaline secondary batteries were produced in the same manner as in Example 1. However, the positive electrode dimensions are 39 mm x 72 mm x 0.66 because the electrode occupancy volume decreased as the separator thickness increased.
mm, the theoretical electric capacity decreased to 1010 mAh, the negative electrode dimension became 41 mm × 101 mm × 0.30 mm, and the theoretical electric capacity decreased to 1640 mAh.

【００５９】この電池を１００個作製し、作製直後に短
絡発生の有無を調べたところ、短絡の発生したものはま
ったくなく、歩留りは１００％であった。When 100 batteries were prepared and the presence or absence of a short circuit was examined immediately after the production, none of the short circuits occurred and the yield was 100%.

【００６０】また、これら１００個の電池について、実
施例１と同様に１０回目の放電容量を測定し、その平均
値を算出したところ、平均放電容量は９７０ｍＡｈであ
り、実施例１〜２の電池に比べて、放電容量が低下して
いた。Further, with respect to these 100 batteries, the discharge capacities at the 10th time were measured in the same manner as in Example 1, and the average value was calculated. The average discharge capacity was 970 mAh. The discharge capacity was lower than that of.

【００６１】以上の結果を表１に示す。なお、表１では
ポリプロピレンをＰＰ、ポリエチレンをＰＥと表示す
る。The above results are shown in Table 1. In Table 1, polypropylene is indicated as PP and polyethylene is indicated as PE.

【００６２】[0062]

【表１】 [Table 1]

【００６３】表１に示すように、本発明の実施例１〜２
は電池作製時の歩留りが１００％と高く、また平均放電
容量も１１００ｍＡｈと大きかった。これに対して、比
較例１は平均放電容量は１１００ｍＡｈと大きかった
が、電池作製時の歩留りが５７％と低く、また比較例２
は電池作製時の歩留りが高いものの、平均放電容量が９
７０ｍＡｈと実施例１〜２に比べて小さかった。As shown in Table 1, Examples 1-2 of the present invention
Had a high yield at the time of battery production of 100%, and had a large average discharge capacity of 1100 mAh. On the other hand, Comparative Example 1 had a large average discharge capacity of 1100 mAh, but had a low yield of 57% when the battery was manufactured, and Comparative Example 2
Has a high yield at the time of battery production, but has an average discharge capacity of 9
It was 70 mAh, which was smaller than those of Examples 1 and 2.

【００６４】[0064]

【発明の効果】以上説明したように、本発明では、グラ
フト化率２０％を超える繊維とグラフト化率２０％以下
の繊維とを併用した不織布をセパレータとして用いるこ
とによって、単位重量が７０ｇ／ｍ2 以下という薄い場
合でも、シート状電極と重ね合わせて渦巻状に巻回する
際に電極の角部による破断のないセパレータを提供する
ことができた。As described above, in the present invention, a unit weight of 70 g / m 2 is used by using a nonwoven fabric in which fibers having a grafting rate of 20% or more and fibers having a grafting rate of 20% or less are used in combination. Even when the thickness was as thin as 2 or less, it was possible to provide a separator that was not broken by the corners of the electrode when the sheet-shaped electrode was superposed and spirally wound.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明のセパレータを用いたアルカリ二次電池
の一例を拡大して示す縦断面図である。FIG. 1 is an enlarged vertical sectional view showing an example of an alkaline secondary battery using a separator of the present invention.

【符号の説明】[Explanation of symbols]

１ 正極 ２ 負極 ３ セパレータ 1 Positive electrode 2 Negative electrode 3 Separator

フロントページの続き (72)発明者 長井 陽三 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内 (72)発明者 飯田 博之 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内Front Page Continuation (72) Inventor Yozo Nagai 1-2-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (72) Inventor Hiroyuki Iida 1-2 1-2 Shimohozumi, Ibaraki City, Osaka Nitto Denko Shares In the company

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 シート状電極とともに巻回する巻回型の
電池用セパレータにおいて、グラフト化率２０％を超え
る繊維Ａと、グラフト化率２０％以下の繊維Ｂとを含む
単位重量７０ｇ／ｍ2 以下の不織布からなることを特徴
とする巻回型の電池用セパレータ。1. A wound-type battery separator wound with a sheet-like electrode, comprising a fiber A having a grafting rate of more than 20% and a fiber B having a grafting rate of 20% or less, and a unit weight of 70 g / m 2. A wound battery separator comprising the following non-woven fabric. 【請求項２】 繊維Ａの少なくとも表面部がポリエチレ
ンを含み、繊維Ｂがポリプロピレンを含む請求項１記載
の巻回型の電池用セパレータ。2. The wound-type battery separator according to claim 1, wherein at least the surface portion of the fiber A contains polyethylene and the fiber B contains polypropylene. 【請求項３】 繊維Ａと繊維Ｂとが重量比１／９〜９／
１の範囲で含まれている請求項１記載の巻回型の電池用
セパレータ。3. The weight ratio of the fiber A and the fiber B is 1/9 to 9 /
The wound-type battery separator according to claim 1, which is included in the range of 1.
JP4315886A 1992-10-29 1992-10-29 Separator for wound type battery Pending JPH06140014A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4315886A JPH06140014A (en) 1992-10-29 1992-10-29 Separator for wound type battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4315886A JPH06140014A (en) 1992-10-29 1992-10-29 Separator for wound type battery

Publications (1)

Publication Number Publication Date
JPH06140014A true JPH06140014A (en) 1994-05-20

Family

ID=18070791

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4315886A Pending JPH06140014A (en) 1992-10-29 1992-10-29 Separator for wound type battery

Country Status (1)

Country Link
JP (1) JPH06140014A (en)

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