JP2000299098A - Manufacture of separator for battery - Google Patents
Manufacture of separator for batteryInfo
- Publication number
- JP2000299098A JP2000299098A JP11107557A JP10755799A JP2000299098A JP 2000299098 A JP2000299098 A JP 2000299098A JP 11107557 A JP11107557 A JP 11107557A JP 10755799 A JP10755799 A JP 10755799A JP 2000299098 A JP2000299098 A JP 2000299098A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- nonwoven fabric
- battery
- battery separator
- separator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電池用セパレータの
製造方法に関し、特にアルカリ二次電池用セパレータの
製造方法に関する。The present invention relates to a method for manufacturing a separator for a battery, and more particularly to a method for manufacturing a separator for an alkaline secondary battery.
【０００２】[0002]
【従来の技術】ニッケル−カドミウム電池、ニッケル−
水素電池、ニッケル−亜鉛電池等のアルカリ二次電池
は、高出力、高エネルギー密度、高容量といった特性を
有していて、小型民生機器や大型機器の駆動電源として
広く使われている。このアルカリ二次電池に用いられて
いる電池用セパレータには、高い電解液（アルカリ性
水溶液）への親和性、耐アルカリ性、耐酸化性、
低い内部抵抗、高い通気性、薄膜かつ欠陥がないこ
と、高い機械的強度などの性質が求められている。2. Description of the Related Art Nickel-cadmium batteries, nickel-cadmium batteries
BACKGROUND ART Alkaline secondary batteries such as hydrogen batteries and nickel-zinc batteries have characteristics such as high output, high energy density and high capacity, and are widely used as drive power sources for small consumer appliances and large appliances. The battery separator used in the alkaline secondary battery has a high affinity for an electrolytic solution (alkaline aqueous solution), alkali resistance, oxidation resistance,
Properties such as low internal resistance, high air permeability, a thin film and no defects, and high mechanical strength are required.
【０００３】これらの性質を満たす電池用セパレータと
して、一般に不織布が用いられる。ニッケル−カドミウ
ム電池では、不織布を構成する繊維として、電解液への
親和性が優れているポリアミド系繊維を使用することが
多かった。しかし、ニッケル−水素電池では、ポリアミ
ド系繊維の加水分解によって発生する分解生成物が自己
放電現象を促進してしまうという問題が生じた。そこ
で、耐アルカリ性および耐酸化性に優れたポリオレフィ
ン系繊維が主に用いられてきた。[0003] As a battery separator satisfying these properties, a nonwoven fabric is generally used. In nickel-cadmium batteries, polyamide fibers having an excellent affinity for an electrolytic solution are often used as the fibers constituting the nonwoven fabric. However, the nickel-hydrogen battery has a problem that a decomposition product generated by hydrolysis of the polyamide fiber promotes a self-discharge phenomenon. Therefore, polyolefin fibers having excellent alkali resistance and oxidation resistance have been mainly used.
【０００４】ポリオレフィン系繊維で構成される不織布
は親水性が低いために、スルホン化処理、親水性単量体
のグラフト処理、コロナ放電処理、界面活性剤含浸処
理、親水性重合体塗布処理などを施して電池用セパレー
タとするのが一般的である。Since nonwoven fabrics composed of polyolefin fibers have low hydrophilicity, sulfonation treatment, graft treatment of hydrophilic monomers, corona discharge treatment, surfactant impregnation treatment, hydrophilic polymer coating treatment, etc. In general, it is applied to a battery separator.
【０００５】これらの親水化処理の中には、例えば不織
布を構成する繊維が１種類であるにもかかわらず、不織
布の厚み方向に対して親水性が均一にならないという問
題が生じる場合がある。例えば、親水性単量体のグラフ
ト処理においては、基材を劣化させないように紫外線を
用いるのが一般的であるが、不織布の内部には紫外線が
当たりにくいのでグラフト反応が起こりにくい。また、
コロナ放電処理による親水化処理も不織布の表面部分の
方が内部よりも進みやすく、内部まで親水化しようとし
て放電電圧を上げると、不織布が破壊される場合があっ
た。[0005] In these hydrophilic treatments, for example, there is a case where the problem that the hydrophilicity is not uniform in the thickness direction of the nonwoven fabric occurs even though only one kind of fiber is used for the nonwoven fabric. For example, in the grafting treatment of a hydrophilic monomer, it is common to use ultraviolet rays so as not to deteriorate the base material, but the ultraviolet rays hardly hit the inside of the nonwoven fabric, so that the graft reaction hardly occurs. Also,
In the surface treatment of the nonwoven fabric, the hydrophilization treatment by corona discharge treatment is more likely to proceed than the inside, and if the discharge voltage is increased to make the interior hydrophilic, the nonwoven fabric may be broken.
【０００６】また、親水性重合体塗布処理では、一般に
親水性重合体を溶解もしくは分散した液に不織布を浸漬
した後、乾燥させて電池用セパレータを得るが、乾燥方
法によっては親水性重合体が不織布の厚み方向で不均一
に分布し、親水性に差異が生じることがあった。In the hydrophilic polymer coating treatment, the nonwoven fabric is generally immersed in a solution in which the hydrophilic polymer is dissolved or dispersed, and then dried to obtain a battery separator. In some cases, the non-woven fabric was unevenly distributed in the thickness direction, resulting in a difference in hydrophilicity.
【０００７】一般に、アルカリ二次電池では、過充電状
態において負極で発生した酸素が正極に移行し、そこで
水になるという反応が起こることで、電池が加圧状態に
なることを防いでいる。この場合、酸素が正極に移行し
やすいように、電池用セパレータの正極に接する側の疎
水性を負極側よりも高めておくといった方法がとられる
場合がある。しかし、上記のように、不織布の親水性が
不均一で、特にその内部の親水性が低い不織布を電池用
セパレータとした場合、酸素が正極に速やかに移行しな
くなってしまうので、過充電状態における電池の内圧が
高くなり、危険であるという問題があった。In general, in an alkaline secondary battery, oxygen generated at the negative electrode in an overcharged state is transferred to the positive electrode, where it reacts with water, thereby preventing the battery from being pressurized. In this case, a method may be adopted in which the hydrophobicity of the battery separator side in contact with the positive electrode is made higher than that of the negative electrode side so that oxygen is easily transferred to the positive electrode. However, as described above, the hydrophilicity of the non-woven fabric is non-uniform, and particularly when the non-woven fabric having a low hydrophilicity inside the non-woven fabric is used as the battery separator, oxygen does not immediately transfer to the positive electrode. There is a problem that the internal pressure of the battery is increased, which is dangerous.
【０００８】[0008]
【発明が解決しようとする課題】本発明は不織布に親水
化処理を施す電池用セパレータの製造方法に関し、厚み
方向におけるセパレータの物性を均一にすることができ
る電池用セパレータの製造方法を提供することである。SUMMARY OF THE INVENTION The present invention relates to a method for producing a battery separator for subjecting a nonwoven fabric to a hydrophilic treatment, and to a method for producing a battery separator capable of making the physical properties of the separator uniform in the thickness direction. It is.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、次の発明を見出す
に至った。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found the following invention.
【００１０】（１）不織布に親水化処理を施す電池用セ
パレータの製造方法において、親水化処理を行った後に
水流交絡処理を施すことを特徴とする電池用セパレータ
の製造方法。(1) A method for producing a battery separator in which a nonwoven fabric is subjected to a hydrophilizing treatment, wherein a hydroentanglement treatment is performed after the hydrophilizing treatment.
【００１１】（２）純水を用いて水流交絡処理を施すこ
とを特徴とする上記（１）記載の電池用セパレータの製
造方法。(2) The method for producing a battery separator according to the above (1), wherein the hydroentanglement treatment is performed using pure water.
【００１２】本発明の電池用セパレータの製造方法によ
れば、親水化処理によって不織布の厚み方向で親水性の
差が生じてしまった場合、続いて行う水流交絡処理によ
って内部と表面の繊維が絡み合うので、不織布の親水性
が均一な状態に近くなる。親水化処理を施された不織布
は、イオン吸着能や粘着性が発現する場合がある。そこ
で、水流交絡処理に水道水や工業用水を使用すると、セ
パレータに金属イオンや有機物が付着してしまう。この
ような事態を避けるために、本発明の電池用セパレータ
の製造方法（２）のように、水流交絡処理に純水を用い
ることが望ましい。本発明の電池用セパレータの製造方
法で得られた電池用セパレータを用いてなる電池では、
通気性が阻害されないので、過充電状態でも電池の内圧
が上がることなく、安定した性能を得ることができる。According to the method for producing a battery separator of the present invention, when a difference in hydrophilicity occurs in the thickness direction of the nonwoven fabric due to the hydrophilic treatment, the fibers of the inside and the surface are entangled by the subsequent hydroentanglement treatment. Therefore, the hydrophilicity of the nonwoven fabric approaches a uniform state. The nonwoven fabric subjected to the hydrophilization treatment may exhibit ion adsorption ability and adhesiveness. Therefore, when tap water or industrial water is used for the hydroentanglement treatment, metal ions and organic substances adhere to the separator. In order to avoid such a situation, it is desirable to use pure water for the hydroentanglement treatment as in the method (2) for producing a battery separator of the present invention. In a battery using the battery separator obtained by the method for producing a battery separator of the present invention,
Since the air permeability is not hindered, stable performance can be obtained without increasing the internal pressure of the battery even in an overcharged state.
【００１３】[0013]
【発明の実施の形態】以下、本発明を詳説する。本発明
の電池用セパレータの製造方法に係わる不織布として
は、カード法、エアレイ法、スパンボンド法、メルトブ
ロー法等の乾式法や湿式法によって製造した不織布を使
用することができる。不織布は積層して用いても良い。
また、不織布を構成する繊維としては、ポリエステル
系、ポリオレフィン系、ポリ塩化ビニル系、ポリアクリ
ロニトリル系、ポリビニルアルコール系、ポリアミド系
のほか、再生繊維、半合成繊維、天然繊維等が挙げられ
る。また、これらの繊維を２種以上混合して使用しても
良い。繊維の断面形状は特に制限が無く、円形、楕円
形、三角形、星形、Ｔ型、Ｙ型、Ｕ型、葉状等の異型断
面形状でも良い。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As the nonwoven fabric according to the method for producing the battery separator of the present invention, a nonwoven fabric produced by a dry method such as a card method, an air lay method, a spun bond method, a melt blow method or a wet method can be used. Nonwoven fabrics may be used by laminating.
Examples of the fibers constituting the nonwoven fabric include polyester, polyolefin, polyvinyl chloride, polyacrylonitrile, polyvinyl alcohol, and polyamide fibers, as well as regenerated fibers, semi-synthetic fibers, and natural fibers. Further, two or more of these fibers may be used in combination. The cross-sectional shape of the fiber is not particularly limited, and may be an irregular cross-sectional shape such as a circle, an ellipse, a triangle, a star, a T shape, a Y shape, a U shape, and a leaf shape.
【００１４】本発明の電池用セパレータの製造方法に係
わる不織布を構成する繊維は、繊維径が１〜３０μｍ、
繊維長は１〜５０ｍｍが望ましい。繊維径が１μｍより
小さいと、不織布が密になりすぎて、通気性が悪くな
る。逆に繊維径が３０μｍを超えると、比表面積が低下
し、保液性が不足する。また、繊維長が１ｍｍより短い
と不織布の強度が低下し、繊維長が５０ｍｍを超えると
不織布の均一性が失われる。The fibers constituting the nonwoven fabric according to the battery separator manufacturing method of the present invention have a fiber diameter of 1 to 30 μm,
The fiber length is desirably 1 to 50 mm. When the fiber diameter is smaller than 1 μm, the nonwoven fabric becomes too dense, and the air permeability deteriorates. On the other hand, when the fiber diameter exceeds 30 μm, the specific surface area decreases, and the liquid retaining property becomes insufficient. On the other hand, if the fiber length is shorter than 1 mm, the strength of the nonwoven fabric decreases, and if the fiber length exceeds 50 mm, the uniformity of the nonwoven fabric is lost.
【００１５】本発明の電池用セパレータの製造方法に係
わる親水化処理としては、スルホン化処理、親水性単量
体のグラフト処理、コロナ放電処理、界面活性剤含浸処
理、親水性重合体塗布処理、プラズマ処理、フッ素ガス
処理等が挙げられる。これらのうち複数の処理を併用し
ても良い。The hydrophilic treatment according to the method for producing a battery separator of the present invention includes a sulfonation treatment, a graft treatment of a hydrophilic monomer, a corona discharge treatment, a surfactant impregnation treatment, a hydrophilic polymer coating treatment, and the like. Plasma treatment, fluorine gas treatment and the like can be mentioned. A plurality of these processes may be used in combination.
【００１６】本発明の電池用セパレータの製造方法に係
わる水流交絡処理は、不織布を支持体に載せて、上方か
ら水流を噴射して、不織布を構成する繊維を３次元交絡
させる。水流交絡処理は、片面からのみ施しても、両面
から施してもどちらでも良い。In the hydroentanglement process according to the method for producing a battery separator of the present invention, a nonwoven fabric is placed on a support, and a water flow is jetted from above to three-dimensionally entangle the fibers constituting the nonwoven fabric. The hydroentanglement treatment may be performed from only one side or from both sides.
【００１７】水流を噴射するためのノズル径は、１０〜
５００μｍの範囲が好ましい。ノズルの間隔は０．０１
０〜１５ｍｍが好ましい。これらのノズルは、不織布の
坪量、繊維の種類、加工速度、水圧を考慮して、適度な
交絡処理がなされるように、ノズルヘッドの数を変更す
ることができる。また、交絡回数も任意に選択すること
ができる。The diameter of the nozzle for injecting the water flow is 10 to
A range of 500 μm is preferred. Nozzle spacing is 0.01
0-15 mm is preferred. In these nozzles, the number of nozzle heads can be changed in consideration of the basis weight of the nonwoven fabric, the type of fiber, the processing speed, and the water pressure so that an appropriate entanglement process is performed. Also, the number of confounds can be arbitrarily selected.
【００１８】水流交絡処理の水圧は、１０〜２５０ｋｇ
ｆ／ｃｍ2の範囲が好ましい。１０ｋｇｆ／ｃｍ2未満で
は十分に繊維が交絡せず、厚み方向の親水性の差を無く
す効果が出ない。逆に２５０ｋｇｆ／ｃｍ2を超える
と、不織布が破壊されたり、ピンホールが開いたりする
ことがある。The water pressure of the hydroentanglement treatment is 10 to 250 kg.
The range of f / cm 2 is preferred. If it is less than 10 kgf / cm 2 , the fibers are not sufficiently entangled, and the effect of eliminating the difference in hydrophilicity in the thickness direction cannot be obtained. Conversely, if it exceeds 250 kgf / cm 2 , the nonwoven fabric may be broken or a pinhole may be opened.
【００１９】水流交絡処理の搬送速度は、５〜２００ｍ
／分の範囲から選ぶことができる。搬送速度が遅いと、
生産効率が低くなるので好ましくない。搬送速度が速す
ぎると、水圧を大きくした場合でも、繊維を交絡するの
に必要なエネルギーを与えることが不可能となる。The transport speed of the hydroentanglement process is 5 to 200 m
/ Min range. If the transport speed is slow,
It is not preferable because the production efficiency is lowered. If the transport speed is too high, it becomes impossible to provide the energy necessary for entanglement of the fibers even when the water pressure is increased.
【００２０】本発明の電池用セパレータの製造方法に係
わる純水としては、イオン交換水や蒸留水を使用するこ
とができる。As the pure water used in the method for producing a battery separator of the present invention, ion-exchanged water or distilled water can be used.
【００２１】[0021]
【実施例】以下、本発明を実施例で説明する。 実施例１ 芯成分であるポリプロピレンと鞘成分である高密度ポリ
エチレン（融点１２８℃）とからなる繊度０．７８ｄｔ
ｅｘ、平均繊維径１０μｍ、平均繊維長１０ｍｍである
繊維９５重量部とミクロフィブリル化セルロース（ダイ
セル製：セリッシュＫＹ−１００Ｇ）５重量部（乾燥重
量）とをノニオン性界面活性剤１重量％水溶液に含浸さ
せたものを高速ミキサーで１０分間撹拌して繊維を離解
させた。次いで、往復回転式撹拌機を装着したチェスト
内で緩やかに撹拌した。続いて、速やかにポリアクリル
アミド０．１重量％水溶液を適宜添加し、引き続き緩や
かに撹拌して均一なスラリーを得た。The present invention will be described below with reference to examples. Example 1 Fineness of 0.78 dt consisting of polypropylene as a core component and high-density polyethylene as a sheath component (melting point 128 ° C.)
ex, 95 parts by weight of a fiber having an average fiber diameter of 10 μm and an average fiber length of 10 mm, and 5 parts by weight (dry weight) of microfibrillated cellulose (manufactured by Daicel: Selish KY-100G) in a 1% by weight aqueous solution of a nonionic surfactant. The impregnated material was stirred with a high-speed mixer for 10 minutes to disintegrate the fibers. Next, the mixture was gently stirred in a chest equipped with a reciprocating rotary stirrer. Subsequently, a 0.1% by weight aqueous solution of polyacrylamide was promptly added as appropriate, followed by gentle stirring to obtain a uniform slurry.
【００２２】この均一なスラリーを用いて丸網抄紙機で
抄造し、次いで１４０℃のヤンキードライヤーで乾燥
と、鞘成分である高密度ポリエチレンの熱融着処理を行
って、坪量５０ｇ／ｍ2の湿式抄造不織布Ｉを得た。Using the uniform slurry, a round mesh paper machine is used to form a paper, followed by drying with a Yankee dryer at 140 ° C. and heat-sealing of high density polyethylene as a sheath component to obtain a basis weight of 50 g / m 2. Was obtained.
【００２３】不織布Ｉを、ポリオキシエチレンアルキル
プロペニルフェニルエーテル（旭電化製：ＮＥ−１０）
１重量部、アクリル酸５０重量部、ベンゾフェノン０．
５重量部、イオン交換水４９重量部からなる処理液に浸
漬した後、脱酸素下で低圧水銀灯を用いて低波長紫外線
を両面から１分間照射し、次いでイオン交換水を用いて
洗浄処理を行って、グラフト処理による親水化処理が施
された不織布IIを得た。The nonwoven fabric I is made of polyoxyethylene alkylpropenyl phenyl ether (NE-10, manufactured by Asahi Denka).
1 part by weight, acrylic acid 50 parts by weight, benzophenone 0.
After being immersed in a treatment solution consisting of 5 parts by weight and 49 parts by weight of ion-exchanged water, low-pressure ultraviolet rays are irradiated from both sides for 1 minute using a low-pressure mercury lamp under deoxygenation, and then a cleaning treatment is performed using ion-exchanged water. Thus, a nonwoven fabric II subjected to a hydrophilic treatment by a graft treatment was obtained.
【００２４】不織布IIを１００メッシュのステンレスワ
イヤーである多孔質支持体上に搬送して、表１の条件を
有する５つのノズルヘッドを用いて柱状水流により、両
面に交絡処理をした。交絡処理の速度は２０ｍ／分で、
交絡後サクションドラムドライヤーで１１０℃で乾燥さ
れ、不織布IIIを得た。水流交絡処理には、イオン交換
水（０．２μＳ／ｃｍ、温度 ４０℃）を使用した。こ
の不織布IIIを電池用セパレータＡとした。The non-woven fabric II was conveyed onto a porous support made of a 100-mesh stainless steel wire, and was entangled on both sides by a columnar water stream using five nozzle heads having the conditions shown in Table 1. The speed of the confounding process is 20 m / min,
After the confounding, it was dried at 110 ° C. with a suction drum dryer to obtain a nonwoven fabric III. For the hydroentanglement treatment, ion-exchanged water (0.2 μS / cm, temperature 40 ° C.) was used. This nonwoven fabric III was used as a battery separator A.
【００２５】[0025]
【表１】 [Table 1]
【００２６】比較例１ 上記不織布IIを比較例の電池用セパレータＹとした。Comparative Example 1 The nonwoven fabric II was used as a battery separator Y of a comparative example.
【００２７】実施例２ 不織布Ｉをイソプレン−スチレン共重合体のスルホン化
物（スルホン酸基含有量 １．０ｍｍｏｌ／ｇ、分子量
４０万）１重量部、１−ブタノール５重量部、イオン交
換水９４重量部からなる処理液に浸漬し、次いで１２０
℃のヤンキードライヤーで乾燥して、親水性重合体塗布
処理による親水化処理を施された不織布IVを得た。Example 2 Non-woven fabric I was prepared by mixing 1 part by weight of a sulfonated isoprene-styrene copolymer (sulfonic acid group content: 1.0 mmol / g, molecular weight: 400,000), 5 parts by weight of 1-butanol, and 94 parts by weight of ion-exchanged water Immersed in a processing solution consisting of
Drying was performed with a Yankee dryer at ℃ to obtain a nonwoven fabric IV which had been subjected to a hydrophilic treatment by a hydrophilic polymer coating treatment.
【００２８】不織布IIを１００メッシュのステンレスワ
イヤーである多孔質支持体上に搬送して、表１の条件を
有する５つのノズルヘッドを用いて柱状水流により、両
面に交絡処理をした。交絡処理の速度は２０ｍ／分で、
交絡後サクションドラムドライヤーで１１０℃で乾燥さ
れ、不織布Ｖを得た。水流交絡処理には、イオン交換水
（０．２μＳ／ｃｍ、温度 ４０℃）を使用した。この
不織布Ｖを電池用セパレータＢとした。The nonwoven fabric II was conveyed on a porous support made of a 100-mesh stainless steel wire, and subjected to entanglement treatment on both sides by a columnar water flow using five nozzle heads having the conditions shown in Table 1. The speed of the confounding process is 20 m / min,
After the confounding, the fabric was dried at 110 ° C. with a suction drum dryer to obtain a nonwoven fabric V. For the hydroentanglement treatment, ion-exchanged water (0.2 μS / cm, temperature 40 ° C.) was used. This nonwoven fabric V was used as a battery separator B.
【００２９】比較例２ 上記不織布IVを比較例の電池用セパレータＺとした。Comparative Example 2 The nonwoven fabric IV was used as a battery separator Z of a comparative example.
【００３０】電池用セパレータの評価 電池用セパレータＡ、Ｂ、Ｙ、Ｚに対して次の評価を行
った。 Evaluation of Battery Separator The following evaluation was performed on battery separators A, B, Y, and Z.
【００３１】（ｉ）ＥＤＳ測定：ＥＤＳ（ＪＥＯＬ製：
ＪＥＤ−２１１０）を用いて、各電池用セパレータに含
まれる元素量［重量％］を断面から測定した。測定値
は、各電池用セパレータの断面を図１のように分割し、
場所イ〜ハについて各１０か所測定し、平均値を算出し
た。(I) EDS measurement: EDS (manufactured by JEOL:
Using JED-2110), the amount of elements [% by weight] contained in each battery separator was measured from the cross section. The measured values were obtained by dividing the cross section of each battery separator as shown in FIG.
Measurements were made at 10 locations for each of locations A to C, and the average value was calculated.
【００３２】（ii）電池充放電試験：正極として発泡式
ニッケル極を、負極として水素吸蔵合金を、電解液とし
て比重１．３の水酸化カリウム水溶液を、セパレータと
して各電池用セパレータを用いて、ニッケル−水素電池
を作製した。これらの電池を１Ｃで１２０％定電流充電
した後、電池電圧が１．０Ｖになるまで１Ｃで定電流放
電する充放電サイクルを繰り返し、電池が安定に作動す
るサイクル数［回］を測定した。(Ii) Battery charge / discharge test: A foamed nickel electrode was used as a positive electrode, a hydrogen storage alloy was used as a negative electrode, a potassium hydroxide aqueous solution having a specific gravity of 1.3 was used as an electrolyte, and each battery separator was used as a separator. A nickel-hydrogen battery was manufactured. After these batteries were charged at a constant current of 120% at 1 C, a charge / discharge cycle of discharging at a constant current of 1 C was repeated until the battery voltage reached 1.0 V, and the number of cycles [times] at which the batteries operated stably was measured.
【００３３】[0033]
【表２】 [Table 2]
【００３４】電池用セパレータＹでは、アクリル酸がグ
ラフトされたことに由来する酸素Ｏの場所ロにおける含
有量が、場所イおよびハと比較して少なかった。これに
水流交絡処理を施した電池用セパレータＡでは、酸素Ｏ
の分布が厚さ方向で均一になっていることが確認され
た。したがって、電池用セパレータＡを用いてなる電池
では、１０００回以上充放電を繰り返しても、電池が安
定に作動していたが、電池用セパレータＹでは、２８０
回で電池セルが破壊された。In the battery separator Y, the content of oxygen O due to the grafting of acrylic acid at the location B was lower than at the locations A and C. In the battery separator A subjected to the hydroentanglement treatment, the oxygen O
Was confirmed to be uniform in the thickness direction. Therefore, in the battery using the battery separator A, the battery operated stably even after repeated charging and discharging 1000 times or more.
The battery cell was destroyed at times.
【００３５】また、電池用セパレータＺでは、親水性重
合体に含まれるスルホン酸基に由来する酸素Ｏと硫黄Ｓ
の場所ロにおける含有量が、場所イおよびハと比較して
少なかった。これに水流交絡処理を施した電池用セパレ
ータＢでは、酸素Ｏと硫黄Ｓの分布が厚さ方向で均一に
なっていることが確認された。したがって、電池用セパ
レータＢを用いてなる電池では、１０００回以上充放電
を繰り返しても、電池が安定に作動していたが、電池用
セパレータＺでは、２８０回で電池セルが破壊された。In the battery separator Z, oxygen O and sulfur S derived from sulfonic acid groups contained in the hydrophilic polymer are used.
The content in place b was lower than in places a and c. It was confirmed that the distribution of oxygen O and sulfur S in the battery separator B subjected to the hydroentanglement treatment was uniform in the thickness direction. Therefore, in the battery using the battery separator B, the battery operated stably even after repeated charging and discharging 1000 times or more. However, in the battery separator Z, the battery cell was destroyed 280 times.
【００３６】[0036]
【発明の効果】以上説明したごとく、本発明の電池用セ
パレータの製造方法では、親水化処理によって不織布の
厚み方向に生じた親水性の差を、続いて水流交絡処理を
施すことによって、均一な状態に近づけることが可能で
ある。このようにして得られた電池用セパレータを用い
てなる電池は、長期間安定に作動するという秀逸な効果
をもたらす。As described above, in the method for manufacturing a battery separator according to the present invention, the difference in hydrophilicity generated in the thickness direction of the nonwoven fabric due to the hydrophilization treatment is made uniform by the subsequent hydroentanglement treatment. It is possible to approach the state. A battery using the battery separator thus obtained has an excellent effect of operating stably for a long period of time.
【図１】電池用セパレータの断面図。FIG. 1 is a cross-sectional view of a battery separator.
フロントページの続き Ｆターム(参考） 4L033 AB07 AC07 BA04 BA14 BA19 BA28 BA98 CA03 CA12 CA13 CA19 CA48 CA55 CA69 4L047 AA14 AB08 AB09 BA04 BA21 CB07 CB10 CC12 5H021 BB07 BB09 CC02 EE34 Continued on front page F-term (reference) 4L033 AB07 AC07 BA04 BA14 BA19 BA28 BA98 CA03 CA12 CA13 CA19 CA48 CA55 CA69 4L047 AA14 AB08 AB09 BA04 BA21 CB07 CB10 CC12 5H021 BB07 BB09 CC02 EE34
Claims (2)
ータの製造方法において、親水化処理を行った後に水流
交絡処理を施すことを特徴とする電池用セパレータの製
造方法。1. A method for producing a battery separator, wherein the nonwoven fabric is subjected to a hydrophilization treatment, wherein a hydroentanglement treatment is performed after the hydrophilization treatment.
特徴とする請求項１記載の電池用セパレータの製造方
法。2. The method for producing a battery separator according to claim 1, wherein a hydroentanglement treatment is performed using pure water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11107557A JP2000299098A (en) | 1999-04-15 | 1999-04-15 | Manufacture of separator for battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11107557A JP2000299098A (en) | 1999-04-15 | 1999-04-15 | Manufacture of separator for battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000299098A true JP2000299098A (en) | 2000-10-24 |
Family
ID=14462211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11107557A Pending JP2000299098A (en) | 1999-04-15 | 1999-04-15 | Manufacture of separator for battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000299098A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001093350A1 (en) * | 2000-05-29 | 2001-12-06 | Mitsubishi Paper Mills Limited | Separator for electrochemical device and method for producing the same, and electrochemical device |
-
1999
- 1999-04-15 JP JP11107557A patent/JP2000299098A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001093350A1 (en) * | 2000-05-29 | 2001-12-06 | Mitsubishi Paper Mills Limited | Separator for electrochemical device and method for producing the same, and electrochemical device |
| US6905798B2 (en) | 2000-05-29 | 2005-06-14 | Mitsubishi Paper Mills Limited | Separator for electrochemical device and method for producing the same |
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