JPH07254399A - Alkaline storage battery - Google Patents
Alkaline storage batteryInfo
- Publication number
- JPH07254399A JPH07254399A JP6043758A JP4375894A JPH07254399A JP H07254399 A JPH07254399 A JP H07254399A JP 6043758 A JP6043758 A JP 6043758A JP 4375894 A JP4375894 A JP 4375894A JP H07254399 A JPH07254399 A JP H07254399A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- storage battery
- alkaline storage
- polyolefin
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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]
【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 as a nickel-cadmium storage battery, a nickel metal hydride battery or the like.
【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 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, the polyamide-based separator has a problem in oxidation resistance at high temperatures, and when the battery using these separators is charged and discharged for a long period of time in a high-temperature atmosphere, the polyamide fiber easily undergoes oxidative decomposition, There is a drawback that problems such as internal short circuit of the battery and early capacity decrease occur. In order to solve this problem, a polyolefin-based nonwoven fabric having excellent oxidation resistance is being developed, but since polyolefin-based fibers are essentially hydrophobic, various measures have been taken to impart 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 liberated and the hydrophilicity does not last, and the manufacturing process is complicated and expensive, so that it is replaced with the polyamide type. The development of excellent polyolefin separators has become a major issue. In addition, in order to increase the capacity of batteries in recent years, there is a strong demand for the development of thinner and more dense separators than ever before. However, using conventional thick fibers of about 2 denier,
It is difficult to produce a non-woven fabric excellent in prevention of internal short circuit of the battery and retention of the electrolytic solution due to non-uniform basis weight and deterioration of liquid retention. The present invention has been made in view of the above problems,
It is intended to provide an alkaline storage battery using a polyolefin-based separator having excellent liquid retention and hydrophilicity and 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, a separator is composed of a splittable conjugate fiber composed of an ethylene vinyl alcohol copolymer and a polyolefin polymer and a polyolefin fiber, and the splittable conjugate fiber is The nonwoven fabric is divided into 80 to 100% and finely fibrillated to 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] Among the constituent fibers of the separator, the polyolefin fiber has the function of improving the oxidation resistance at high temperature, and the ethylene vinyl alcohol copolymer fiber has the function of improving the affinity for the electrolytic solution. As a result of making fine fibers into a fine and uniform one, it becomes possible to obtain a separator excellent in liquid retention, hydrophilicity and oxidation resistance. By applying the separator to an alkaline storage battery, a battery having a long service life can be realized even when used at high temperatures, and a battery having a high energy density can be designed because it can be made 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。EXAMPLE A nickel metal hydride battery will be described below as an example of the present invention. The positive electrode was prepared by mixing 10% by weight of cobalt monoxide powder with nickel hydroxide powder to which zinc and cobalt were added as a solid solution and making a paste with a thickening solution of carboxymethyl cellulose. A substrate was filled with a predetermined amount, dried and pressed to prepare 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 an MmNiAlCo type (AB 5 type)
A hydrogen storage alloy electrode was prepared by forming a hydrogen storage alloy powder into a paste using polytetrafluoroethylene as a binder, coating a predetermined amount on a perforated steel sheet, and drying and pressing 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。As the separator, a polypropylene fiber and a polypropylene / ethylene vinyl alcohol copolymer division type composite fiber are made into a non-woven fabric having a basis weight of 50 to 60 g / m 2 by a wet papermaking method, subjected to a division treatment by a high pressure water flow method, and then pressure-bonded by a heat calender roll. -The thickness was adjusted to 0.12 to 0.18 mm to manufacture. 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 storage alloy electrode produced in this manner were rolled up via a separator, and an electrolytic solution was injected to obtain a 1100 mAh AA size cylindrical nickel hydrogen battery. As a comparative example, a battery using a conventional nylon nonwoven fabric as a separator was prepared in the same manner as above. The characteristic values of these separators are shown in Table 1.
【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 composite fiber separator of this embodiment is
It has a liquid retention rate that is about twice that of conventional nylon separators, and even after being immersed in an alkali (soaked in a KOH aqueous solution with a specific gravity of 1.3 at 80 ° C for 7 days), the conventional surfactant It can be seen that it retains excellent hydrophilicity without the deterioration of wetting property (reduction of liquid retention rate and electric resistance) unlike the treated polyolefin separator. Further, it is recognized that the wettability is improved by increasing the degree of splitting of the splittable conjugate fiber to make it finer (0.5 denier or less). At the same time, the fine fiberization makes the basis weight of the separator uniform and enables a dense and 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 at high temperature of the separator assembled in the battery, these batteries were continuously charged at a current of 0.1 CmA in an atmosphere at 60 ° C. The deterioration degree of was investigated. Figures 1 and 2 show changes in continuous charging period (1 month, 3 months, 6 months) and various physical properties of the separator (retention rate, electric resistance, tensile strength).
Shown in 3. In a battery using a nylon separator, the nylon separator is significantly oxidized and decomposed and deteriorated after continuous charging for about three months, resulting in a significant increase in the internal resistance value of the battery and a short circuit. On the other hand, in the battery using the splittable composite fiber separator of this example, the separator hardly deteriorated even after 6 months,
It can be seen that the excellent hydrophilicity, oxidation resistance, and heat resistance are maintained even under such use conditions, and battery defects such as short circuits do not occur.
【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, the split type conjugate fiber composed of the ethylene vinyl alcohol copolymer and the polyolefin polymer is used, and 80 to 10
By applying 0% divided finely woven non-woven fabric as a separator to nickel metal hydride batteries and nickel cadmium batteries, long-life batteries can be realized even when used at high temperatures, and hydrophilicity and liquid retention Since a dense thin separator having excellent properties can be provided, a battery with 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 changes in continuous charging period and 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 charge period and changes in tensile strength of a separator after battery disassembly in batteries of the present invention and 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 continuous charge period and changes in the liquid retention rate of the separator after the battery is disassembled in the batteries of the present invention and the comparative example.
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 comprising a positive electrode and a negative electrode with a separator interposed therebetween, wherein the separator comprises a splittable conjugate fiber composed of an ethylene vinyl alcohol copolymer and a polyolefin polymer, and a polyolefin fiber, and An alkaline storage battery, characterized in that the splittable conjugate fiber is a non-woven fabric divided into 80 to 100% and finely fibrillated 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 true JPH07254399A (en) | 1995-10-03 |
| JP3031156B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0903794A1 (en) * | 1997-08-19 | 1999-03-24 | Daiwabo Co. Ltd. | Battery separator and method for manufacturing the same, and battery |
| WO2004068625A1 (en) * | 2003-01-31 | 2004-08-12 | 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
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0903794A1 (en) * | 1997-08-19 | 1999-03-24 | Daiwabo Co. Ltd. | Battery separator and method for manufacturing the same, and battery |
| US6291105B1 (en) | 1997-08-19 | 2001-09-18 | Daiwabo Co., Ltd. | Battery separator and method for manufacturing the same and battery |
| WO2004068625A1 (en) * | 2003-01-31 | 2004-08-12 | Yuasa Corporation | Sealed alkaline storage battery, electrode structure thereof, charging method and charger for sealed alkaline storage battery |
| US7527890B2 (en) | 2003-01-31 | 2009-05-05 | Yuasa Corporation | Sealed alkaline storage battery, electrode structure and charging method for the same, and charger for sealed alkaline storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3031156B2 (en) | 2000-04-10 |
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