JPH06140051A - Solid electrolyte - Google Patents
Solid electrolyteInfo
- Publication number
- JPH06140051A JPH06140051A JP30660192A JP30660192A JPH06140051A JP H06140051 A JPH06140051 A JP H06140051A JP 30660192 A JP30660192 A JP 30660192A JP 30660192 A JP30660192 A JP 30660192A JP H06140051 A JPH06140051 A JP H06140051A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- organic solvent
- ion
- polymer
- polyvinyl alcohol
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、イオン伝導度と機械的
強度に優れて薄型電池等の形成に好適な固体電解質に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolyte having excellent ionic conductivity and mechanical strength, which is suitable for forming thin batteries and the like.
【０００２】[0002]
【従来の技術】従来、ポリエチレンオキシドやエチレン
オキシドオリゴマーを側鎖に有するポリマーに金属塩と
有機溶媒を含有させてなる固体電解質が知られていた。
有機溶媒の添加は、イオン伝導度の向上を目的とするも
のでその添加により１／１０7〜１／１０5Ｓ／cmと室温
におけるイオン伝導度に劣って電池としての実用性に乏
しいものを、１／１０4〜１／１０3Ｓ／cm程度にイオン
伝導度を向上させることができる。しかしながら、有機
溶媒の添加で前記の如くイオン伝導度は向上するもの
の、固体電解質の機械的強度が著しく低下し、実用が困
難な問題点があった。2. Description of the Related Art Heretofore, a solid electrolyte has been known in which a polymer having polyethylene oxide or an ethylene oxide oligomer in a side chain contains a metal salt and an organic solvent.
The addition of the organic solvent is intended to improve the ionic conductivity. The addition of the organic solvent is 1/10 7 to 1/10 5 S / cm, which is inferior in the ionic conductivity at room temperature and has poor practicability as a battery. The ionic conductivity can be improved to about 1/10 4 to 1/10 3 S / cm. However, although the ionic conductivity is improved by the addition of the organic solvent as described above, the mechanical strength of the solid electrolyte is remarkably lowered, and there is a problem that it is difficult to put into practical use.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、有機溶媒を
添加してイオン伝導度の向上をはかることができると共
に、有機溶媒を含有しても機械的強度に優れて実用性に
優れる固体電解質の開発を課題とする。DISCLOSURE OF THE INVENTION The present invention provides a solid electrolyte which can be added with an organic solvent to improve the ionic conductivity and has excellent mechanical strength and practicality even if it contains an organic solvent. Is the development of.
【０００４】[0004]
【課題を解決するための手段】本発明は、エチレンオキ
シド又は／及びプロピレンオキシドを成分とするポリマ
ーとポリビニルアルコールとの混合ポリマーに、金属塩
と有機溶媒を含有させてなることを特徴とする固体電解
質を提供するものである。DISCLOSURE OF THE INVENTION The present invention provides a solid electrolyte comprising a mixed polymer of a polymer containing ethylene oxide and / or propylene oxide as a component and polyvinyl alcohol containing a metal salt and an organic solvent. Is provided.
【０００５】[0005]
【作用】上記の如くポリビニルアルコールを併用するこ
とにより、有機溶媒の添加でイオン伝導度を向上させる
ことができると共に、機械的強度に優れる固体電解質と
することができる。有機溶媒を添加しても実用上充分な
機械的強度を示す点は、有機溶媒の含有でポリビニルア
ルコールがゴム状の弾性を具備するに至り、その機械的
強度の向上がエチレンオキシド等を成分とするポリマー
の強度低下分を陵駕することによるものと考えられる。
またイオン伝導度の向上は、ポリビニルアルコールのブ
レンドと有機溶媒の含有でエチレンオキシド等を成分と
するポリマーの結晶度が低下することによるものと考え
られる。By using polyvinyl alcohol in combination as described above, it is possible to improve the ionic conductivity by adding an organic solvent and to obtain a solid electrolyte having excellent mechanical strength. The fact that even if an organic solvent is added, it shows practically sufficient mechanical strength, the polyvinyl alcohol has rubber-like elasticity due to the inclusion of the organic solvent, and its mechanical strength is improved by using ethylene oxide as a component. It is considered that this is due to the decrease in the strength of the polymer.
Further, it is considered that the improvement of the ionic conductivity is due to the decrease in the crystallinity of the polymer containing ethylene oxide or the like as a result of the inclusion of the blend of polyvinyl alcohol and the organic solvent.
【０００６】[0006]
【実施例】本発明の固体電解質は、エチレンオキシド又
は／及びプロピレンオキシドを成分とするポリマーとポ
リビニルアルコールとの混合ポリマーに、金属塩と有機
溶媒を含有させたものである。EXAMPLES The solid electrolyte of the present invention is a mixed polymer of a polymer containing ethylene oxide and / or propylene oxide as components and polyvinyl alcohol, which contains a metal salt and an organic solvent.
【０００７】エチレンオキシド又は／及びプロピレンオ
キシドを成分とするポリマーとしては、例えばポリエチ
レンオキシド、ポリプロピレンオキシド、エチレンオキ
シド・プロピレンオキシド共重合体などを主鎖又は側鎖
に有するものなどがあげられる。エチレンオキシド・プ
ロピレンオキシド共重合体の形態は任意で、ランダム共
重合体であってもよいし、ブロック共重合体であっても
よい。前記のポリエチレンオキシド等を側鎖に有するポ
リマーの場合、その側鎖はオリゴマー程度の重合度であ
ってもよく、主鎖は例えばポリシロキサンなどの任意な
ポリマーであってよい。Examples of the polymer containing ethylene oxide and / or propylene oxide include those having polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide copolymer, etc. in the main chain or side chain. The form of the ethylene oxide / propylene oxide copolymer is arbitrary, and may be a random copolymer or a block copolymer. In the case of the above-mentioned polymer having polyethylene oxide or the like in the side chain, the side chain may have a polymerization degree of an oligomer and the main chain may be any polymer such as polysiloxane.
【０００８】混合ポリマーは、エチレンオキシド又は／
及びプロピレンオキシドを成分とするポリマーとポリビ
ニルアルコールを、例えば溶媒による溶液としたものの
混合方式や溶融混合方式などの適宜な方式で混合するこ
とにより得ることができる。混合割合は、目的とするイ
オン伝導度や機械的強度などに応じて適宜に決定するこ
とができ、一般にはエチレンオキシド又は／及びプロピ
レンオキシドを成分とするポリマー１００重量部に対
し、３０〜３００重量部のポリビニルアルコールが用い
られる。The mixed polymer is ethylene oxide or /
It can be obtained by mixing the polymer containing propylene oxide as a component and polyvinyl alcohol by an appropriate method such as a mixing method of a solution in a solvent or a melt mixing method. The mixing ratio can be appropriately determined according to the desired ionic conductivity and mechanical strength, and is generally 30 to 300 parts by weight with respect to 100 parts by weight of a polymer containing ethylene oxide and / or propylene oxide as a component. Polyvinyl alcohol is used.
【０００９】混合ポリマーは、任意な成形形態で固体電
解質の形成に供することができ、一般にはフィルムや繊
維、ないし不織布などの形態とされる。ちなみにフィル
ム状の形態とされる場合その厚さは、適宜に決定するこ
とができるが通例、５００μm以下、就中１０〜２００
μmとされる。The mixed polymer can be used for forming the solid electrolyte in any molding form, and is generally in the form of a film, a fiber, or a non-woven fabric. By the way, in the case of a film-like form, the thickness thereof can be appropriately determined, but is generally 500 μm or less, preferably 10 to 200.
It is assumed to be μm.
【００１０】混合ポリマーに含有させる金属塩について
は特に限定はなく、一般には例えばＬiイオン、Ｎaイオ
ン、Ｋイオン等の陽イオンと、Ｉイオン、ＣＦ3ＳＯ3イ
オン、ＢＦ4イオン、ＣlＯ4イオン、ＡlＣl4イオン、Ｐ
Ｆ6イオン、ＡsＦ6イオン等の陰イオンとの組合せから
なるアルカリ金属塩などが用いられる。The metal salt contained in the mixed polymer is not particularly limited, and generally, for example, cations such as Li ion, Na ion and K ion, and I ion, CF 3 SO 3 ion, BF 4 ion, ClO 4 ion. , AlCl 4 ion, P
An alkali metal salt or the like formed by combining with an anion such as F 6 ion or AsF 6 ion is used.
【００１１】混合ポリマーに含有させる有機溶媒につい
ては適宜に決定することができ、機械的強度の点よりは
ジメチルスルホキシドの如くポリビニルアルコールをゴ
ム状の弾性体に変性させうるものが好ましく用いられ
る。有機溶媒は、必要に応じて２種以上を用いることが
できる。The organic solvent contained in the mixed polymer can be appropriately determined, and from the viewpoint of mechanical strength, those capable of modifying polyvinyl alcohol into a rubber-like elastic body such as dimethyl sulfoxide are preferably used. Two or more kinds of organic solvents can be used as necessary.
【００１２】固体電解質の形成は、適宜な方法で行うこ
とができる。その例としては、混合ポリマーの有機溶媒
溶液と金属塩溶液との混合溶液をキャストする方法、混
合ポリマーからなるフィルム等をそれが不溶な溶剤を用
いた金属塩溶液中に浸漬して金属塩を含浸させる方法、
混合ポリマーからなるフィルム等に添加用の有機溶媒を
用いた金属塩溶液を含浸させる方法などがあげられる。
添加用の有機溶媒は、予め形成した金属塩含有の混合ポ
リマーフィルム等に液体や蒸気の状態で含浸させること
もできる。なお金属塩溶液を形成するための溶剤として
は、例えばプロピレンカーボネートやアセトニトリルの
如き適宜な溶剤を用いうる。The solid electrolyte can be formed by an appropriate method. As an example, a method of casting a mixed solution of an organic solvent solution of a mixed polymer and a metal salt solution, a film made of the mixed polymer, etc. is immersed in a metal salt solution using an insoluble solvent to form a metal salt. Impregnation method,
Examples include a method of impregnating a film made of a mixed polymer with a metal salt solution using an organic solvent for addition.
The organic solvent for addition may be impregnated in a liquid or vapor state in a preformed metal salt-containing mixed polymer film or the like. As the solvent for forming the metal salt solution, an appropriate solvent such as propylene carbonate or acetonitrile can be used.
【００１３】本発明の固体電解質においては、電池とし
た場合の電流の安定性や高さ等の点より金属塩の陰イオ
ンの含有量を可及的に抑制することが好ましい。かかる
陰イオンの含有量を抑制した、従って金属塩の金属イオ
ンをリッチに含有する固体電解質の形成は例えば、金属
塩溶液を含浸させた不織布やガラスフィルター等に混合
ポリマーからなるフィルムを密着させてその両側に電極
を設け、その混合ポリマーフィルム側の電極が負極とな
るように電圧を印加する方法により行うことができる。In the solid electrolyte of the present invention, it is preferable to suppress the content of the anion of the metal salt as much as possible in view of the stability of the current and the height of the battery. The formation of a solid electrolyte that suppresses the content of such anions, and thus contains the metal ions of the metal salt in a rich manner, for example, involves adhering a film made of a mixed polymer to a non-woven fabric or a glass filter impregnated with a metal salt solution. Electrodes may be provided on both sides of the mixed polymer film, and a voltage may be applied so that the electrode on the mixed polymer film side becomes a negative electrode.
【００１４】従って本発明の固体電解質は、混合ポリマ
ーの任意形態の成形体からなり、金属塩と有機溶媒を含
有するものを適宜な方法で形成することにより得ること
ができる。得られた固体電解質は、電池などの種々の製
品の形成に好ましく用いることができる。Therefore, the solid electrolyte of the present invention comprises a molded product of a mixed polymer having an arbitrary form, and can be obtained by forming a compound containing a metal salt and an organic solvent by an appropriate method. The obtained solid electrolyte can be preferably used for forming various products such as batteries.
【００１５】実施例１ 平均分子量５０万のポリエチレンオキシド１００重量部
と平均分子量２．２万のポリビニルアルコール１００重
量部との混合物をプレス加工して厚さ１００μmのフィ
ルムを形成しそのフィルムを、ＬiＣlＯ4の１モル／リ
ットル濃度のプロピレンカーボネート溶液中に５０℃で
２４時間浸漬してＬiＣlＯ4を含浸させた後、それをジ
メチルスルホキシドとアセトニトリルの蒸気中に２分間
ずつさらして５０℃のオーブン中に６時間放置する操作
を５回繰り返して目的とする固体電解質を得た。Example 1 A mixture of 100 parts by weight of polyethylene oxide having an average molecular weight of 500,000 and 100 parts by weight of polyvinyl alcohol having an average molecular weight of 22,000 was pressed to form a film having a thickness of 100 μm. After dipping in 1 mol / l propylene carbonate solution of 4 at 50 ° C. for 24 hours to impregnate LiClO 4 , it was exposed to vapors of dimethyl sulfoxide and acetonitrile for 2 minutes each and placed in an oven at 50 ° C. The operation of leaving for 6 hours was repeated 5 times to obtain the desired solid electrolyte.
【００１６】前記で得た固体電解質は、ゴム弾性を有し
てピンセットで持ち上げても破断することなくその取扱
性に優れていた。また交流インピーダンスアナライザー
により室温におけるイオン伝導度を測定したところ、
２．５／１０3Ｓ／cmの値を示し、電池として実用しう
るイオン伝導度を示した。The solid electrolyte obtained above had rubber elasticity and did not break even when lifted by tweezers and was excellent in handleability. When the ionic conductivity at room temperature was measured with an AC impedance analyzer,
A value of 2.5 / 10 3 S / cm was shown, indicating an ionic conductivity that can be practically used as a battery.
【００１７】比較例１ 平均分子量５０万のポリエチレンオキシドをプレス加工
して厚さ１００μmのフィルムを形成しそのフィルム
を、ＬiＣlＯ4の１モル／リットル濃度のプロピレンカ
ーボネート溶液中に５０℃で２４時間浸漬してＬiＣlＯ
4を含浸させた後、それをアセトニトリルの蒸気中に２
分間さらして５０℃のオーブン中に６時間放置する操作
を５回繰り返して固体電解質を得た。この固体電解質
は、ピンセットで持ち上げると自重で破断し、取扱いで
きない程度に機械的強度が乏しいものであった。Comparative Example 1 Polyethylene oxide having an average molecular weight of 500,000 was pressed to form a film having a thickness of 100 μm, and the film was immersed in a 1 mol / liter propylene carbonate solution of LiClO 4 at 50 ° C. for 24 hours. Then LiClO
After impregnation with 4 , it was placed in 2
The operation of exposing for 5 minutes and leaving it in an oven at 50 ° C. for 6 hours was repeated 5 times to obtain a solid electrolyte. This solid electrolyte was broken by its own weight when lifted with tweezers, and had poor mechanical strength to the extent that it could not be handled.
【００１８】比較例２ 平均分子量２．２万のポリビニルアルコールをプレス加
工して厚さ１００μmのフィルムを形成しそのフィルム
を、ＬiＣlＯ4の１モル／リットル濃度のプロピレンカ
ーボネート溶液中に５０℃で２４時間浸漬してＬiＣlＯ
4を含浸させた後、それをジメチルスルホキシドの蒸気
中に２分間さらして５０℃のオーブン中に６時間放置す
る操作を５回繰り返して固体電解質を得た。この固体電
解質は、ゴム弾性を示したものの室温におけるイオン伝
導度が７／１０4Ｓ／cmと劣るものであった。Comparative Example 2 Polyvinyl alcohol having an average molecular weight of 22,000 was pressed to form a film having a thickness of 100 μm, and the film was immersed in a 1 mol / liter propylene carbonate solution of LiClO 4 at 50 ° C. for 24 hours. Soak for a while
After impregnation with 4 , the operation of exposing it to the vapor of dimethyl sulfoxide for 2 minutes and leaving it in an oven at 50 ° C. for 6 hours was repeated 5 times to obtain a solid electrolyte. Although this solid electrolyte showed rubber elasticity, it had an inferior ionic conductivity of 7/10 4 S / cm at room temperature.
【００１９】[0019]
【発明の効果】本発明の固体電解質は、ポリビニアルコ
ールの併用により、機械的強度に優れて取扱性に優れる
と共に、イオン伝導度に優れている。INDUSTRIAL APPLICABILITY The solid electrolyte of the present invention is excellent in mechanical strength and handling, and is also excellent in ionic conductivity when used in combination with polyvinyl alcohol.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 71/02 ＬＱＤ 9167−4Ｊ ＬＱＥ 9167−4Ｊ Ｈ０１Ｂ 1/06 Ａ 7244−5Ｇ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08L 71/02 LQD 9167-4J LQE 9167-4J H01B 1/06 A 7244-5G
Claims (1)
オキシドを成分とするポリマーとポリビニルアルコール
との混合ポリマーに、金属塩と有機溶媒を含有させてな
ることを特徴とする固体電解質。1. A solid electrolyte comprising a mixed polymer of a polymer containing ethylene oxide and / or propylene oxide as a component and polyvinyl alcohol, which contains a metal salt and an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30660192A JP3283926B2 (en) | 1992-10-20 | 1992-10-20 | Solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30660192A JP3283926B2 (en) | 1992-10-20 | 1992-10-20 | Solid electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06140051A true JPH06140051A (en) | 1994-05-20 |
| JP3283926B2 JP3283926B2 (en) | 2002-05-20 |
Family
ID=17959040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30660192A Expired - Fee Related JP3283926B2 (en) | 1992-10-20 | 1992-10-20 | Solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3283926B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000056815A1 (en) * | 1999-03-23 | 2000-09-28 | Nisshinbo Industries, Inc. | Composition for ionically conductive solid polymer, ionically conductive solid polyelectrolyte, binder resin, and secondary battery |
| US6159638A (en) * | 1997-07-24 | 2000-12-12 | Sharp Kabushiki Kaisha | Solid polymer electrolyte and preparation method therefor |
| CN100424129C (en) * | 2003-03-26 | 2008-10-08 | 日本高度纸工业株式会社 | Solid electrolyte and electrochemical system using said solid electrolyte |
-
1992
- 1992-10-20 JP JP30660192A patent/JP3283926B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6159638A (en) * | 1997-07-24 | 2000-12-12 | Sharp Kabushiki Kaisha | Solid polymer electrolyte and preparation method therefor |
| WO2000056815A1 (en) * | 1999-03-23 | 2000-09-28 | Nisshinbo Industries, Inc. | Composition for ionically conductive solid polymer, ionically conductive solid polyelectrolyte, binder resin, and secondary battery |
| US6537468B1 (en) | 1999-03-23 | 2003-03-25 | Nisshinbo Industries, Inc. | Composition for ionically conductive solid polymer, ionically conductive solid polyelectrolyte, binder resin, and secondary battery |
| CN100424129C (en) * | 2003-03-26 | 2008-10-08 | 日本高度纸工业株式会社 | Solid electrolyte and electrochemical system using said solid electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3283926B2 (en) | 2002-05-20 |
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