JP3031156B2 - Alkaline storage battery - Google Patents
Alkaline storage batteryInfo
- Publication number
- JP3031156B2 JP3031156B2 JP6043758A JP4375894A JP3031156B2 JP 3031156 B2 JP3031156 B2 JP 3031156B2 JP 6043758 A JP6043758 A JP 6043758A JP 4375894 A JP4375894 A JP 4375894A JP 3031156 B2 JP3031156 B2 JP 3031156B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- battery
- storage battery
- alkaline storage
- polyolefin
- 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 - Lifetime
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
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ニッケル・カドミウム
蓄電池やニッケル金属水素化物電池等に用いられるアル
カリ蓄電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline storage battery used for a nickel-cadmium storage battery or a nickel metal hydride battery.
【０００２】[0002]
【従来の技術】従来からアルカリ蓄電池用セパレータと
して、ナイロン繊維等のポリアミド系不織布がその優れ
た親水性および保液性から用いられて来た。しかしなが
ら、ポリアミド系セパレータは高温時の耐酸化性に問題
があり、これらセパレータを用いた電池を高温雰囲気下
で長期に渡り充放電を行った場合に、ポリアミド繊維が
容易に酸化分解を受けて、電池の内部短絡や早期の容量
低下等の不具合を生じるという欠点がある。これを解決
するために、耐酸化性に富むポリオレフィン系不織布が
開発されつつあるが、ポリオレフィン系繊維は本質的に
疎水性であるため、親水性を持たすための種々の工夫が
なされている。例えば、界面活性剤処理やスルホン化処
理、フッ素化処理、プラズマ処理等により繊維に極性基
を付与する方法がある。2. Description of the Related Art Conventionally, polyamide-based non-woven fabrics such as nylon fibers have been used as separators for alkaline storage batteries because of their excellent hydrophilicity and liquid retention. However, polyamide separators have a problem in oxidation resistance at high temperatures, and when batteries using these separators are charged and discharged for a long time under a high-temperature atmosphere, polyamide fibers are easily subjected to oxidative decomposition, There is a drawback that problems such as an internal short circuit of the battery and an early decrease in capacity are caused. In order to solve this, polyolefin-based nonwoven fabrics having high oxidation resistance are being developed. However, since polyolefin-based fibers are inherently hydrophobic, various devices have been devised for imparting hydrophilicity. For example, there is a method of imparting a polar group to the fiber by a surfactant treatment, a sulfonation treatment, a fluorination treatment, a plasma treatment or the like.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記セ
パレータにおいては、界面活性剤が遊離して親水性が持
続しないとか、製造工程が繁雑であり且つ高価となる等
の問題があり、ポリアミド系に替わる優れたポリオレフ
ィン系セパレータの開発が大きな課題となっている。ま
た、近年の電池の高容量化に対して、従来に増してより
薄いより緻密なセパレータの開発が強く望まれている
が、従来の２デニール程度の太い繊維を用いたのでは、
目付量の不均一や保液性の低下を生じて、電池の内部短
絡の防止や電解液の保持に優れた不織布の作製は困難で
ある。本発明は上記課題に鑑みてなされたものであり、
保液性や親水性に優れ、且つ高温時の耐酸化性に優れた
ポリオレフィン系セパレータを用いたアルカリ蓄電池を
提供するものである。However, in the above separator, there are problems that the surfactant is released and the hydrophilicity is not maintained and that the production process is complicated and expensive, and the separator is replaced with a polyamide type. Development of an excellent polyolefin-based separator is a major issue. In addition, in order to increase the capacity of batteries in recent years, the development of thinner and more dense separators has been strongly demanded, but if conventional thick fibers of about 2 denier were used,
It is difficult to produce a nonwoven fabric which is excellent in prevention of internal short circuit of the battery and holding of the electrolytic solution due to non-uniform basis weight and decrease in liquid retention. The present invention has been made in view of the above problems,
An object of the present invention is to provide an alkaline storage battery using a polyolefin-based separator having excellent liquid retention properties and hydrophilic properties and having excellent oxidation resistance at high temperatures.
【０００４】[0004]
【課題を解決するための手段】本発明のアルカリ蓄電池
は、セパレータがエチレンビニルアルコール共重合体と
ポリオレフィン重合体から構成された分割型複合繊維と
ポリオレフィン系繊維からなり、且つ該分割型複合繊維
が８０〜１００％分割されて０．５デニール以下に微繊
維化された不織布であることを特徴とするものである。In the alkaline storage battery of the present invention, the separator is composed of a splittable conjugate fiber composed of an ethylene vinyl alcohol copolymer and a polyolefin polymer and a polyolefin-based fiber, and the splittable conjugate fiber is It is a nonwoven fabric divided into 80 to 100% and finely divided into 0.5 denier or less.
【０００５】[0005]
【作用】セパレータの構成繊維のうち、ポリオレフィン
系繊維は高温時の耐酸化性を、エチレンビニルアルコー
ル共重合繊維は電解液への親和性を向上させる働きがあ
り、且つ分割型複合繊維を分割して微細繊維化すること
によって緻密で均一なものとすることが出来る結果、保
液性・親水性・耐酸化性の優れたセパレータが可能とな
る。該セパレータをアルカリ蓄電池に適用することによ
って、高温時の使用においても長寿命な電池が実現さ
れ、また、緻密且つ薄型化が可能なために高エネルギー
密度な電池の設計が可能となる。[Function] Of the constituent fibers of the separator, polyolefin fibers have a function of improving oxidation resistance at high temperatures, and ethylene vinyl alcohol copolymer fibers have a function of improving the affinity for an electrolytic solution. As a result, a separator having excellent liquid retention, hydrophilicity, and oxidation resistance can be obtained. By applying the separator to an alkaline storage battery, a long-life battery can be realized even when used at a high temperature, and a high-energy density battery can be designed because it is dense and thin.
【０００６】[0006]
【実施例】本発明の実施例として、ニッケル金属水素化
物電池について以下に説明する。正極は、亜鉛およびコ
バルトを固溶体添加した水酸化ニッケル粉末に一酸化コ
バルト粉末を１０重量％混合し、カルボキシメチルセル
ロースの増粘液にてペースト状とした後に、約９５％の
多孔度のニッケル繊維多孔体基板に所定量充填して、乾
燥、加圧を行い作製しニッケル電極とした。DESCRIPTION OF THE PREFERRED EMBODIMENTS As an embodiment of the present invention, a nickel metal hydride battery will be described below. The positive electrode was prepared by mixing 10% by weight of cobalt monoxide powder with nickel hydroxide powder to which a solid solution of zinc and cobalt was added, and forming a paste with a thickening solution of carboxymethylcellulose. The substrate was filled in a predetermined amount, dried and pressed to produce a nickel electrode.
【０００７】負極は、ＭｍＮｉＡｌＣｏ系（ＡＢ5 系）
水素吸蔵合金粉末をポリテトラフルオロエチレンを結着
剤としてペースト状とした後に、穿孔鋼板に所定量を塗
着し、乾燥・加圧を行い作製し水素吸蔵合金電極とし
た。The negative electrode is a MmNiAlCo-based (AB 5 -based)
After the hydrogen storage alloy powder was made into a paste using polytetrafluoroethylene as a binder, a predetermined amount was applied to a perforated steel sheet, and dried and pressed to produce a hydrogen storage alloy electrode.
【０００８】セパレータは、ポリプロピレン繊維とポリ
プロピレン／エチレンビニルアルコール共重合体分割型
複合繊維を湿式抄紙法により目付５０〜６０ｇ／ｍ2 の
不織布とし、高圧水流法で分割処理した後に熱カレンダ
ーロールで圧着・調厚して０．１２〜０．１８ｍｍとし
作製した。繊維の分割度は８０〜１００％とした。The separator is made of a nonwoven fabric having a basis weight of 50 to 60 g / m 2 by a wet papermaking method using a polypropylene fiber and a polypropylene / ethylene vinyl alcohol copolymer splittable conjugate fiber. -It was prepared by adjusting the thickness to 0.12 to 0.18 mm. The degree of fiber division was 80 to 100%.
【０００９】このようにして作製したニッケル電極と水
素吸蔵合金電極をセパレータを介して巻き込み、電解液
を注液して、１１００ｍＡｈのＡＡサイズ円筒型ニッケ
ル水素電池とした。比較例として、従来のナイロン不織
布をセパレータとして用いた電池を上記と同様にして作
製した。これらセパレータの特性値を表１に示す。The nickel electrode and the hydrogen-absorbing alloy electrode thus produced were wound around a separator, and an electrolytic solution was injected to obtain a 1100 mAh AA-size cylindrical nickel-metal hydride battery. As a comparative example, a battery using a conventional nylon nonwoven fabric as a separator was produced in the same manner as described above. Table 1 shows the characteristic values of these separators.
【００１０】[0010]
【表１】 [Table 1]
【００１１】本実施例の分割型複合繊維セパレータは、
従来ナイロン・セパレータに比較して約２倍の保液率を
持ち、アルカリ浸漬処理（比重１．３のＫＯＨ水溶液中
に８０℃にて７日間浸漬）した後に於ても、従来の界面
活性剤処理したポリオレフィン・セパレータのようなヌ
レ性の低下（保液率や電気抵抗の低下）がなく、優れた
親水性を保持するのがわかる。また、ヌレ性は、分割型
複合繊維の分割度を大きくして、微細繊維化（０．５デ
ニール以下）することによって向上するのが認められ
る。微細繊維化は、同時にセパレータの目付を均一化
し、親水性に優れた緻密な薄型セパレータを可能とす
る。The splittable conjugate fiber separator of this embodiment is
It has approximately twice the liquid retention rate as conventional nylon separators, and even after being immersed in an alkaline immersion treatment (immersed in an aqueous KOH solution with a specific gravity of 1.3 at 80 ° C for 7 days), It can be seen that there is no decrease in the wetting property (reduction in liquid retention rate or electric resistance) unlike the treated polyolefin separator, and excellent hydrophilicity is maintained. In addition, it is recognized that the wetting property is improved by increasing the degree of division of the splittable conjugate fiber and making it finer (0.5 denier or less). Fine fiberization makes the basis weight of the separator uniform at the same time, and enables a dense thin separator excellent in hydrophilicity.
【００１２】次に、電池に組み込まれた状態でのセパレ
ータの高温時の耐酸化・耐熱性を評価するために、これ
ら電池を６０℃雰囲気下で０．１ＣｍＡの電流で連続充
電して、セパレータの劣化程度を調べた。連続充電期間
（１ケ月、３ケ月、６ケ月）とセパレータの各種物性値
（保液率、電気抵抗値、引張強度）の変化を図１、２、
３に示した。ナイロン・セパレータを用いた電池におい
ては、３ケ月程度の連続充電にてナイロン・セパレータ
が著しく酸化分解されて劣化する結果、電池内部抵抗値
の顕著な増大や短絡を生じるに至る。これに対して、本
実施例の分割型複合繊維セパレータを用いた電池におい
ては、６ケ月後でもセパレータの劣化はほとんどなく、
かかる使用条件下でもすぐれた親水性、耐酸化性および
耐熱性を保持しており、短絡等の電池の不具合を来すこ
とのないことがわかる。Next, in order to evaluate the oxidation resistance and heat resistance of the separator at a high temperature in a state of being incorporated in the battery, these batteries were continuously charged at a current of 0.1 CmA in an atmosphere of 60 ° C. The degree of deterioration was examined. The changes in the continuous charging period (1 month, 3 months, 6 months) and various physical properties of the separator (liquid retention, electrical resistance, tensile strength) are shown in FIGS.
3 is shown. In a battery using a nylon separator, continuous charging for about three months causes the nylon separator to be significantly oxidized and degraded, resulting in a remarkable increase in the battery internal resistance value and a short circuit. On the other hand, in the battery using the splittable composite fiber separator of the present example, the separator hardly deteriorated even after 6 months,
It can be seen that the battery retains excellent hydrophilicity, oxidation resistance and heat resistance even under such use conditions, and does not cause a battery failure such as a short circuit.
【００１３】[0013]
【発明の効果】上述のように、本発明によれば、エチレ
ンビニルアルコール共重合体とポリオレフィン重合体か
ら構成された分割型複合繊維からなり、且つ８０〜１０
０％分割して微細繊維化された不織布をセパレータとし
て、ニッケル金属水素化物電池やニッケルカドミウム電
池に適用することによって、高温時の使用においても長
寿命な電池が実現され、また親水性や保液性に優れた緻
密な薄型セパレータが可能となるため更に高エネルギー
密度な電池を提供できるので、その工業的価値は極めて
大である。As described above, according to the present invention, a splittable conjugate fiber composed of an ethylene-vinyl alcohol copolymer and a polyolefin polymer is used.
By applying the nonwoven fabric divided into fine fibers by 0% as a separator to a nickel metal hydride battery or a nickel cadmium battery, a long-life battery can be realized even when used at high temperatures, and hydrophilicity and liquid retention can be achieved. Since a dense and thin separator having excellent properties can be provided, a battery having a higher energy density can be provided, and therefore, its industrial value is extremely large.
【図１】本発明と比較例の電池における連続充電期間と
電池内部抵抗の変化を示す図である。FIG. 1 is a diagram showing a continuous charging period and a change in battery internal resistance in batteries of the present invention and a comparative example.
【図２】本発明と比較例の電池における連続充電期間と
電池解体後のセパレータの引張強度の変化を示す図であ
る。FIG. 2 is a diagram showing a continuous charging period and a change in tensile strength of a separator after disassembly of a battery of the present invention and a battery of a comparative example.
【図３】本発明と比較例の電池における連続充電期間と
電池解体後のセパレータの保液率の変化を示す図であ
る。FIG. 3 is a diagram showing a change in the liquid retention of a separator after a continuous charge period and after disassembly of the batteries of the present invention and a comparative example.
フロントページの続き (56)参考文献 特開 平７−29561（ＪＰ，Ａ) 特開 平５−109397（ＪＰ，Ａ) 特開 平３−257755（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 2/16 H01M 2/18 Continuation of front page (56) References JP-A-7-29561 (JP, A) JP-A-5-109397 (JP, A) JP-A-3-257755 (JP, A) (58) Fields investigated (Int) .Cl. 7 , DB name) H01M 2/16 H01M 2/18
Claims (1)
れるアルカリ蓄電池において、該セパレータがエチレン
ビニルアルコール共重合体とポリオレフィン重合体から
構成された分割型複合繊維とポリオレフィン系繊維から
なり、且つ該分割型複合繊維が８０〜１００％分割され
て０．５デニール以下に微繊維化された不織布であるこ
とを特徴とするアルカリ蓄電池。1. An alkaline storage battery in which a positive electrode and a negative electrode are provided with a separator interposed therebetween, wherein the separator is composed of a splittable conjugate fiber composed of an ethylene vinyl alcohol copolymer and a polyolefin polymer, and a polyolefin-based fiber. An alkaline storage battery, wherein the splittable conjugate fiber is a nonwoven fabric in which 80 to 100% is split and finely divided to 0.5 denier or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6043758A JP3031156B2 (en) | 1994-03-15 | 1994-03-15 | Alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6043758A JP3031156B2 (en) | 1994-03-15 | 1994-03-15 | Alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07254399A JPH07254399A (en) | 1995-10-03 |
| JP3031156B2 true JP3031156B2 (en) | 2000-04-10 |
Family
ID=12672671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6043758A Expired - Lifetime JP3031156B2 (en) | 1994-03-15 | 1994-03-15 | Alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3031156B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291105B1 (en) | 1997-08-19 | 2001-09-18 | Daiwabo Co., Ltd. | Battery separator and method for manufacturing the same and battery |
| EP1598893A1 (en) * | 2003-01-31 | 2005-11-23 | Yuasa Corporation | Sealed alkaline storage battery, electrode structure thereof, charging method and charger for sealed alkaline storage battery |
-
1994
- 1994-03-15 JP JP6043758A patent/JP3031156B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07254399A (en) | 1995-10-03 |
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