JPS5836824B2 - Separator for alkaline batteries - Google Patents
Separator for alkaline batteriesInfo
- Publication number
- JPS5836824B2 JPS5836824B2 JP52065582A JP6558277A JPS5836824B2 JP S5836824 B2 JPS5836824 B2 JP S5836824B2 JP 52065582 A JP52065582 A JP 52065582A JP 6558277 A JP6558277 A JP 6558277A JP S5836824 B2 JPS5836824 B2 JP S5836824B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- crystallinity
- polyvinyl alcohol
- battery
- alkaline batteries
- 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
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)
Description
【発明の詳細な説明】
本発明はアルカリ電池用ポリビニルアルコール系セパレ
ーターの改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in polyvinyl alcohol separators for alkaline batteries.
従来アルカリ電池用セパレーターとしてはセルローズ系
セパレーター、ポリビニルアルコール系セパレーター、
多孔質ポリオレフイン系セハレーターなどが提案されて
いるが、高温のアルカリ溶液に耐え、しかも電気抵抗の
小さなセパレーターは得られていない。Conventional separators for alkaline batteries include cellulose separators, polyvinyl alcohol separators,
Porous polyolefin-based sehalators have been proposed, but a separator that can withstand high-temperature alkaline solutions and has low electrical resistance has not been obtained.
即ち、セルローズ系セパレーターは熱アルカリ中、特に
その酸化性環境では醇解してしまう。That is, the cellulose separator dissolves in a hot alkali, especially in an oxidizing environment.
また多孔質ポリオレフィン系セパレーターは熱に弱く、
電気抵抗の経時的な増加が見られる。In addition, porous polyolefin separators are sensitive to heat.
An increase in electrical resistance over time is observed.
ポリビニルアルコール系セパレーターは電気抵抗も小さ
く、有望なセパレーター材料テあるが、従来検討されて
きたポリビニルアルコールは、結晶化度が０．３〜０．
３５程度のものであり、このものは耐アルカリ性、耐酸
化性に乏しく実用上問題があった。Polyvinyl alcohol separators have low electrical resistance and are a promising separator material, but the polyvinyl alcohol that has been studied so far has a crystallinity of 0.3 to 0.
35, which had a practical problem due to poor alkali resistance and oxidation resistance.
このため表面をアセタール化したり、ホー酸により架橋
するなどの処理が試みられたが、親水性が低下し、電池
の内部抵抗を著しく高める結果となり、電池電圧を低下
させていた。For this reason, treatments such as acetalizing the surface or crosslinking with formic acid have been attempted, but these have resulted in a decrease in hydrophilicity, significantly increasing the internal resistance of the battery, and lowering the battery voltage.
本発明はこれに鑑み、電気抵抗の小さく親水性が犬であ
り、しかも耐熱、耐アルカリ、耐酸化性の優れたアルカ
リ電池用セパレーターを提供することを目的とするもの
である。In view of this, it is an object of the present invention to provide a separator for alkaline batteries that has low electrical resistance, is highly hydrophilic, and has excellent heat resistance, alkali resistance, and oxidation resistance.
即ち本発明は結晶化度０．４以上のポリビニルアルコー
ルかラ成ルアルカリ電池用セパレーターである。That is, the present invention is a separator for polyvinyl alcohol or aluminum alkaline batteries having a crystallinity of 0.4 or more.
アルカリ電池用セパレーターとして使用する場合のポリ
ビニルアルコールの耐アルカリ性及び耐酸化性は、ポリ
ビニルアルコールの結晶化度と関係あることが分った。It has been found that the alkali resistance and oxidation resistance of polyvinyl alcohol when used as a separator for alkaline batteries are related to the degree of crystallinity of the polyvinyl alcohol.
第１表は、種々の結晶化度のポリビニルアルコールの耐
アルカリ試験及び耐酸化試験の結果を示すものである。Table 1 shows the results of alkali resistance tests and oxidation resistance tests of polyvinyl alcohols with various degrees of crystallinity.
なおここで耐アルカリ試験結果は、５０μ厚さのポリビ
ニルアルコール試験片を、水酸化カリウム（４７５ｇ／
ｌ）と水酸化リチウム（１．１＃）との混合物（液温１
００℃）中に１時間浸漬し、そのときの減量を重量％で
示したものである。Note that the alkali resistance test results here are based on potassium hydroxide (475g/
l) and lithium hydroxide (1.1#) (liquid temperature 1
00°C) for 1 hour, and the weight loss at that time is shown in weight %.
耐酸化試験の結果は、水酸化カリウ／
ム（４７５ｇ／ｌ）、水酸化リチウム（ １３ｇ／１０
、及び過硫酸カリウム（５Ｏｇ，＃）の混合溶液（液温
８０℃）中に２時間浸漬した場合の状態又は減量率を示
したものである。The results of the oxidation resistance test were potassium hydroxide (475g/l), lithium hydroxide (13g/10
, and potassium persulfate (5Og, #) (liquid temperature: 80°C) for 2 hours.
この結果から明らかなように本発明のセパレーターは化
学的に安定であり優れた性能を有する。As is clear from these results, the separator of the present invention is chemically stable and has excellent performance.
結晶化度の異るポリビニルアルコールは、加熱又は延伸
、加圧などの方法により得ることができる。Polyvinyl alcohols having different degrees of crystallinity can be obtained by methods such as heating, stretching, and pressing.
例えば、２００℃で１０分間加熱を行ったポリビニルア
ルコールの結晶化度は０．５２でアリ、１４０℃で６０
分間加熱したポリビニルアルコールの結晶化度は０．４
３であった。For example, the crystallinity of polyvinyl alcohol heated at 200°C for 10 minutes is 0.52, and at 140°C it is 60°.
The crystallinity of polyvinyl alcohol heated for 0.4 minutes
It was 3.
結晶化度の高いポリビニルアルコールは柔軟性がやや乏
しいので、軟化処理を行って使用することが望ましい。Since polyvinyl alcohol with a high degree of crystallinity has somewhat poor flexibility, it is desirable to perform a softening treatment before use.
軟化処理は、吸湿性溶液、例えばグリセリン、エチレン
グリコールなどの水溶液に浸漬することにより可能であ
る。The softening treatment is possible by immersion in a hygroscopic solution, for example an aqueous solution such as glycerin or ethylene glycol.
本発明のセパレーターは正極、負極、又はその他の補助
電極を隔離するような形状で実施される。The separator of the present invention is implemented in a shape that isolates a positive electrode, negative electrode, or other auxiliary electrode.
例えば、フイルム状、シート状などが望ましい形状であ
る。For example, desirable shapes include a film shape and a sheet shape.
次に本発明の実施例について述べる。Next, examples of the present invention will be described.
害施例
結晶化度０．５５を有する５０ミクロン厚のポリビニル
アルコールフィルムを２０重量％のクリセリン溶液に浸
漬して軟化した後乾燥して本発明のセパレーターを調製
した。EXAMPLE A separator of the present invention was prepared by immersing a 50 micron thick polyvinyl alcohol film having a crystallinity of 0.55 in a 20% by weight chrycerin solution, softening it, and then drying it.
このセパレーターヲ用い、正極には酸化ニッケル電極、
負極には亜鉛極を使用してニッケル亜鉛電池を組立てた
。Using this separator, a nickel oxide electrode was used as the positive electrode.
A nickel-zinc battery was assembled using a zinc electrode as the negative electrode.
なお比較のために結晶化度０．３３のポリビニルアルコ
ールフイルム（５０ミクロン厚）、及びこのフイルムを
アセタール化したものの２種類の公知のセパレーターを
用いて同様にニッケル亜鉛電池を組立てた。For comparison, nickel-zinc batteries were similarly assembled using two types of known separators: a polyvinyl alcohol film (50 microns thick) with a crystallinity of 0.33 and an acetalized version of this film.
これらの電池に４７５ｇ／１３の水酸化カリウム、１
３ ９／ｌの水酸化リチウム、４０ｆｌ／１３の酸化亜
鉛を含む水醇液を電解液として注入して、充放電試験を
行った。475g/13 potassium hydroxide, 1
A charge/discharge test was conducted by injecting an aqueous solution containing 39/l of lithium hydroxide and 40 fl/13 of zinc oxide as an electrolyte.
この結果を第２表に示す。実施例２、比較例
結晶化度がそれぞれ、０．３３（比較例）、０．３９（
比較例）、０．４３（実施例）及び０．５２（実施例）
で厚さはいずれも５０ミクロンのポリビニルアルコール
フイルムを４種類用意し、各フイルムを１５重量％のポ
リエチレングリコール（重合度２００）溶液に２０分間
浸漬し軟化処理を行った後乾燥してセパレーターを調製
した。The results are shown in Table 2. Example 2 and Comparative Example Crystallinity was 0.33 (Comparative Example) and 0.39 (
Comparative example), 0.43 (Example) and 0.52 (Example)
Four types of polyvinyl alcohol films, each with a thickness of 50 microns, were prepared, and each film was immersed in a 15% by weight polyethylene glycol (degree of polymerization 200) solution for 20 minutes, softened, and then dried to prepare a separator. did.
これらの各セパレーターを使用して、正極に酸化ニッケ
ル電極８枚、負極に亜鉛極７枚を使用して公称容量１０
Ａｈ（アンペアアワー）のニッケルー亜鉛電池をそれぞ
れ組立てた。Using each of these separators, a nominal capacity of 10
Each Ah (ampere hour) nickel-zinc battery was assembled.
次にかくして得た４種類の各電池について、充電２ Ａ
Ｘ ６ ｈ ｒ 、放電１０Ａ、放電終止電圧１．２
■の条件で、サイクル寿命試験を行い、セパレーターの
結晶化度と電池のサイクル寿命との関係を求めた。Next, charge 2 A for each of the four types of batteries thus obtained.
X 6 hr, discharge 10A, discharge end voltage 1.2
A cycle life test was conducted under the conditions (2) to determine the relationship between the crystallinity of the separator and the cycle life of the battery.
なお寿命終了は、放電により電圧が１．２■にまで降下
するに要する放電時間が３０分以下となった時点とした
。The end of life was defined as the point in time when the discharge time required for the voltage to drop to 1.2 square meters due to discharge became 30 minutes or less.
また、上記各電池の放電時の平均電圧は、いずれも１５
２Ｖであり、各電池間ではその差はほとんどなかった。In addition, the average voltage during discharge of each of the above batteries is 15
2V, and there was almost no difference between the batteries.
上記試験結果得られた、セパレーターの結晶化度と電池
のサイクル寿命との関係を図面にグラフで示した。The relationship between the crystallinity of the separator and the cycle life of the battery, obtained from the above test results, is shown graphically in the drawing.
この図より明らかな如く、セパレーターの結晶化度が０
．４を越えると急速に電池のサイクル寿命が改善されて
おり、したがって結晶化度０．４以上のポリビニルアル
コールからなるアルカリ電池用セパレーターが著しく優
れた電池寿命特性を有することが判る。As is clear from this figure, the crystallinity of the separator is 0.
．． When the value exceeds 4, the cycle life of the battery is rapidly improved, and it is therefore clear that an alkaline battery separator made of polyvinyl alcohol with a crystallinity of 0.4 or more has extremely excellent battery life characteristics.
この結果からも明らかなように、本発明のセパレーター
を使用したアルカリ電池は、平均電圧が高くサイクル寿
命が長く、本発明のセパレーターが有用であることが分
る。As is clear from this result, the alkaline battery using the separator of the present invention has a high average voltage and a long cycle life, indicating that the separator of the present invention is useful.
図は本発明実施例２及び比較例によるセパレーターの結
晶化度と電池のサイクル寿命との関係を示すグラフであ
る。The figure is a graph showing the relationship between the crystallinity of the separator and the cycle life of the battery according to Example 2 of the present invention and Comparative Example.
Claims (1)
るアルカリ電池用セパレーター。 ２ 吸湿性溶液に浸漬して軟化処理を施した特許請求の
範囲第１項に記載するアルカリ電池用セパレーター。[Claims] 1. A separator for alkaline batteries made of polyvinyl alcohol having a crystallinity of 0.4 or more. 2. The alkaline battery separator according to claim 1, which is subjected to a softening treatment by immersing it in a hygroscopic solution.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52065582A JPS5836824B2 (en) | 1977-06-03 | 1977-06-03 | Separator for alkaline batteries |
| GB24529/78A GB1602678A (en) | 1977-06-03 | 1978-05-30 | Galvanic cell containing polyvinyl alcohol separator |
| DE2824312A DE2824312C3 (en) | 1977-06-03 | 1978-06-02 | Separator for a galvanic element |
| US06/066,062 US4277572A (en) | 1977-06-03 | 1979-08-13 | Galvanic cell separator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52065582A JPS5836824B2 (en) | 1977-06-03 | 1977-06-03 | Separator for alkaline batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54742A JPS54742A (en) | 1979-01-06 |
| JPS5836824B2 true JPS5836824B2 (en) | 1983-08-11 |
Family
ID=13291134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52065582A Expired JPS5836824B2 (en) | 1977-06-03 | 1977-06-03 | Separator for alkaline batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5836824B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6748422B2 (en) * | 2015-12-10 | 2020-09-02 | 日本バイリーン株式会社 | Alkaline battery separator and method of manufacturing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4978140A (en) * | 1972-12-01 | 1974-07-27 | ||
| JPS49105934A (en) * | 1973-02-16 | 1974-10-07 |
-
1977
- 1977-06-03 JP JP52065582A patent/JPS5836824B2/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4978140A (en) * | 1972-12-01 | 1974-07-27 | ||
| JPS49105934A (en) * | 1973-02-16 | 1974-10-07 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54742A (en) | 1979-01-06 |
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