JPS6130380B2 - - Google Patents
Info
- Publication number
- JPS6130380B2 JPS6130380B2 JP52064425A JP6442577A JPS6130380B2 JP S6130380 B2 JPS6130380 B2 JP S6130380B2 JP 52064425 A JP52064425 A JP 52064425A JP 6442577 A JP6442577 A JP 6442577A JP S6130380 B2 JPS6130380 B2 JP S6130380B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- thin film
- cellophane
- ion
- synthetic resin
- 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
- -1 polypropylene Polymers 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims 1
- 239000010409 thin film Substances 0.000 description 19
- 229920000298 Cellophane Polymers 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 229920003002 synthetic resin Polymers 0.000 description 10
- 239000000057 synthetic resin Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 229940081735 acetylcellulose Drugs 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229920003174 cellulose-based polymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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】
本発明は銀電池用セパレーターの改良に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in separators for silver batteries.
周知のごとく酸化銀電池においては従来からセ
ロハン薄膜がセパレーターとして使用されてい
る。このセロハン薄膜は銀イオンの移行を阻止
し、電池の内部放電を防ぐ目的には有効であるが
陽極である酸化銀電極の強い酸化力によつて劣化
されると同様に、陽極自身もこの酸化反応によつ
て部分的に消費される。 As is well known, cellophane thin films have been used as separators in silver oxide batteries. This cellophane thin film is effective in blocking the migration of silver ions and preventing internal discharge of the battery, but it is degraded by the strong oxidizing power of the silver oxide electrode, which is the anode, and the anode itself is also affected by this oxidation. Partially consumed by reaction.
この欠点を改善するために、イオン透過性合成
樹脂薄膜をセロハン薄膜に重ね合せたもの、或は
イオン透過性合成樹脂薄膜を、カルボキシメチル
セルロースあるいはポリビニルアルコールなどの
水溶液を接着剤としてセロハン薄膜に積層した複
合セパレーターが提案されている。このような複
合セパレーターにおいては、銀イオンの透過はセ
ロハン薄膜にて阻止され、またセロハン薄膜自体
の陽極による劣化は、イオン透過性合成樹脂薄膜
をセロハン薄膜と陽極の間に位置する様に複合セ
パレーターを装填することによつて防止されるの
で、効果的に機能が発揮される。 In order to improve this drawback, an ion-permeable synthetic resin thin film was laminated on a cellophane thin film, or an ion-permeable synthetic resin thin film was laminated on a cellophane thin film using an aqueous solution of carboxymethyl cellulose or polyvinyl alcohol as an adhesive. Composite separators have been proposed. In such a composite separator, the permeation of silver ions is blocked by the cellophane thin film, and deterioration of the cellophane thin film itself due to the anode can be avoided by placing the ion-permeable synthetic resin thin film between the cellophane thin film and the anode. This can be prevented by loading, so the function can be effectively demonstrated.
しかしながら、この様にセロハン薄膜とイオン
透過性合成樹脂薄膜をカルボキシメチルセルロー
スあるいはポリビニルアルコールなどの水溶液を
接着剤として積層する場合には次のような重大な
欠点を生じる。すなわちカルボキシメチルセルロ
ースあるいはポリビニルアルコールの水溶液がセ
ロハン薄膜上にコーテイングされた場合、セロハ
ン膜は水分を吸収して膨潤するが、乾燥状態のセ
ロハン薄膜がひとたび水分を吸収して柔かい膨潤
状態になると、積層機のロール上を通過している
間に、折れ皺が非常に発生し易くなる。この様に
折れ皺を生じたまゝの状態でイオン透過性合成樹
脂薄膜と積層された複合セパレーターは、外観上
の問題を生ずるのみならず、その折れ皺の部分の
電気抵抗値が高くなるため電池としての性能を低
下させると共に、とくに銀電池の場合のようにセ
パレーターが小さい面積で使用される時には、電
気抵抗値のバラツキを生じる原因にもなる。 However, when a thin cellophane film and a thin ion-permeable synthetic resin film are laminated together using an aqueous solution of carboxymethyl cellulose or polyvinyl alcohol as an adhesive, the following serious drawbacks occur. In other words, when an aqueous solution of carboxymethyl cellulose or polyvinyl alcohol is coated on a thin cellophane film, the cellophane film absorbs water and swells. While passing over the rolls, creases are very likely to occur. A composite separator laminated with an ion-permeable synthetic resin thin film with folds in this way not only causes problems in appearance, but also has high electrical resistance at the folds, which can cause problems in batteries. In addition to deteriorating the performance of the separator, it also causes variations in electrical resistance, especially when the separator is used in a small area as in the case of silver batteries.
また、このように接着剤で薄膜を貼合せるのは
加工上の歩留りが悪いし、また、ボタン型銀電池
ケースをかしめる際に二層がづれるというような
欠点を生じる場合もある。 Furthermore, bonding thin films with adhesive in this manner has a poor processing yield, and may also cause problems such as the two layers shifting when caulking the button-shaped silver battery case.
本発明はかかる欠点を解消し、加工性を向上せ
しめる銀電池用に適したセパレーターを提供する
ものである。本発明においては従来のようにセロ
ハン薄膜とイオン透過性合成樹脂薄膜とを積層す
るのではなく、イオン透過性合成樹脂薄膜の片面
又は両面に有機溶剤可溶性にしてアルカリ水溶液
不溶性の皮膜形成材料と界面活性剤との配合物の
有機溶剤溶液を塗布、乾燥して皮膜を形成せしめ
る事によつて前記した加工性の向上のみならず、
セパレーターとしての性能改善をもはかるもので
ある。本発明では界面活性剤を皮膜形成材料と一
緒に配合することにより、セロハン薄膜とイオン
透過性合成樹脂薄膜とを接着積層せしめたものと
同等の電気抵抗が得られ、しかも上記のごとき従
来の積層接着品の欠点を除くことが出来る。 The present invention eliminates these drawbacks and provides a separator suitable for silver batteries that improves processability. In the present invention, instead of laminating a cellophane thin film and an ion-permeable synthetic resin thin film as in the past, the ion-permeable synthetic resin thin film is coated with an organic solvent-soluble film-forming material and an alkali aqueous solution-insoluble film-forming material on one or both sides of the ion-permeable synthetic resin thin film. By applying an organic solvent solution of the mixture with the activator and drying it to form a film, it is possible to not only improve the processability described above, but also to
It also aims to improve its performance as a separator. In the present invention, by blending a surfactant with a film-forming material, it is possible to obtain an electrical resistance equivalent to that obtained by adhesively laminating a cellophane thin film and an ion-permeable synthetic resin thin film. Defects of adhesive products can be removed.
本発明に使用されるイオン透過性合成樹脂薄膜
の材質としては、ポリプロピレン、ポリエチレン
などのポリオレフインが用いられ、例えばポリプ
ラスチツクス(株)から「ジユラガード」の商品名で
市販されているマイクロポーラスポリプロピレン
フイルムが適当である。また本発明で使用される
有機溶剤に可溶性にしてかつアルカリ水溶液に不
溶性の皮膜形成材料としては、セルロースアセテ
ートなどのセルロースエステル類、メチルセルロ
ース、エチルセルロース、ハイドロオキシエチル
セルロース、ハイドロオキシプロピルセルロース
などのセルロースエーテル類などのセルロース系
ポリマーが適当である。 The material of the ion-permeable synthetic resin thin film used in the present invention is polyolefin such as polypropylene or polyethylene, such as microporous polypropylene film commercially available from Polyplastics Co., Ltd. under the trade name "Jyuraguard". is appropriate. Film-forming materials that are soluble in organic solvents and insoluble in alkaline aqueous solutions used in the present invention include cellulose esters such as cellulose acetate, cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose. Cellulose-based polymers such as, for example, are suitable.
界面活性剤としてはポリオキシエチレンアルキ
ルエーテルの如きノニオン界面活性剤が使用され
る。有機溶剤としては単独或は混合溶剤の何れで
もよい。又、溶液中に皮膜形成材料を溶解させな
い程度の水の存在は差支えない。 As the surfactant, a nonionic surfactant such as polyoxyethylene alkyl ether is used. The organic solvent may be used alone or in combination. Further, the presence of water in the solution to an extent that does not dissolve the film-forming material may be sufficient.
即ち本発明によればジユラガードの如きマイク
ロポーラスポリプロピレンフイルムの片面又は両
面にセルロースアセテートの如きセルロース系ポ
リマーをノニオン界面活性剤と共に有機溶剤に溶
解してなる溶液を塗布して、セルロース系ポリマ
ーの皮膜を形成せしめてなる銀電池用セパレータ
ーが提供される。この際塗布前に皮膜の密着性を
向上せしめるため、ジユラガード表面に適宜前処
理を行なうことが好ましい。 That is, according to the present invention, a solution of a cellulose polymer such as cellulose acetate dissolved in an organic solvent together with a nonionic surfactant is coated on one or both sides of a microporous polypropylene film such as Jyuraguard to form a film of the cellulose polymer. A separator for a silver battery is provided. At this time, in order to improve the adhesion of the film before application, it is preferable to pre-treat the surface of Jyuragard as appropriate.
本発明のセパレーターは製造が簡単容易であ
り、しかもボタン型銀電池をつくる際のかしめに
よつてもずれる様なことがなく、しかも界面活性
剤が配合されない場合には非常に電気抵抗が増大
するのに対し、界面活性剤の配合によつて電気抵
抗値は従来の接着積層品と同じ程度の値が得ら
れ、セパレーターとして使用するのに何等差支え
ない。 The separator of the present invention is simple and easy to manufacture, does not shift even when caulked during the production of button-type silver batteries, and has a significantly increased electrical resistance when no surfactant is added. On the other hand, by incorporating a surfactant, an electrical resistance value comparable to that of conventional adhesive laminates can be obtained, and there is no problem in using it as a separator.
尚本発明に於て皮膜の厚さは１ミクロン〜40ミ
クロン程度が適当であり、又、界面活性剤の配合
量は５〜100％程度が適当である。 In the present invention, the thickness of the film is suitably about 1 micron to 40 microns, and the amount of surfactant added is suitably about 5 to 100%.
以下本発明の実施例を示す。 Examples of the present invention will be shown below.
実施例
メチレンクロライド220ｇ、エタノール22ｇの
混合溶剤にアセチルセルロース（酢化度55％）12
ｇ、ノニオン界面活性剤（ポリオキシエチレンア
ルキルエーテル）４ｇを溶解したドープを常法に
よつて親水性ジユラガードの片面に塗布した。こ
の製品の40％KOH水溶液中における電気抵抗値
は40ｍΩ―in2で、親水性ジユラガードの片面に
セルロースアセテートのみを塗布した製品の110
×103ｍΩ―in2に比して非常に小さく、又CMC水
溶液を接着剤として親水性ジユラガードに450番
手普通セロハンを積層した製品の38ｍΩ―in2と
同程度の値を示し、銀電池用セパレーターとして
使用し得ることが確認された。Example: Acetyl cellulose (acetylation degree 55%) 12 in a mixed solvent of 220 g of methylene chloride and 22 g of ethanol
g. A dope in which 4 g of a nonionic surfactant (polyoxyethylene alkyl ether) was dissolved was applied to one side of the hydrophilic Diyuraguard by a conventional method. The electrical resistance value of this product in a 40% KOH aqueous solution is 40 mΩ-in 2 , which is 110 mΩ-in 2 compared to a product with only cellulose acetate coated on one side of hydrophilic Jyura Guard.
×10 3 mΩ-in 2 , which is very small compared to 38 mΩ-in 2, and the same value as 38 mΩ-in 2 of a product made by laminating 450-size ordinary cellophane on hydrophilic Jyuragard using CMC aqueous solution as an adhesive. It was confirmed that it can be used as a separator.
Claims (1)
片面あるいは両面に、セルロース系ポリマーとノ
ニオン界面活性剤との配合物の有機溶剤溶液を塗
布乾燥してセルロース系ポリマーの皮膜を形成せ
しめてなる銀電池用セパレーター。1. A silver battery separator made by applying an organic solvent solution of a combination of a cellulose polymer and a nonionic surfactant to one or both sides of a microporous polypropylene film and drying it to form a cellulose polymer film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6442577A JPS53149632A (en) | 1977-06-01 | 1977-06-01 | Improvement of separator for alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6442577A JPS53149632A (en) | 1977-06-01 | 1977-06-01 | Improvement of separator for alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS53149632A JPS53149632A (en) | 1978-12-27 |
| JPS6130380B2 true JPS6130380B2 (en) | 1986-07-12 |
Family
ID=13257904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6442577A Granted JPS53149632A (en) | 1977-06-01 | 1977-06-01 | Improvement of separator for alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS53149632A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0427343Y2 (en) * | 1988-02-03 | 1992-06-30 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51623A (en) * | 1974-06-21 | 1976-01-06 | Fuji Electrochemical Co Ltd | ARUKARIDENCHOSEPAREETANO SEIZOHOHO |
| JPS5117534A (en) * | 1974-08-02 | 1976-02-12 | Seiko Instr & Electronics | ARUKARI DENCHI |
-
1977
- 1977-06-01 JP JP6442577A patent/JPS53149632A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51623A (en) * | 1974-06-21 | 1976-01-06 | Fuji Electrochemical Co Ltd | ARUKARIDENCHOSEPAREETANO SEIZOHOHO |
| JPS5117534A (en) * | 1974-08-02 | 1976-02-12 | Seiko Instr & Electronics | ARUKARI DENCHI |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0427343Y2 (en) * | 1988-02-03 | 1992-06-30 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53149632A (en) | 1978-12-27 |
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