JPH07153489A - Manufacture of secondary battery with gel electrolyte - Google Patents
Manufacture of secondary battery with gel electrolyteInfo
- Publication number
- JPH07153489A JPH07153489A JP5321438A JP32143893A JPH07153489A JP H07153489 A JPH07153489 A JP H07153489A JP 5321438 A JP5321438 A JP 5321438A JP 32143893 A JP32143893 A JP 32143893A JP H07153489 A JPH07153489 A JP H07153489A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- gel
- electrolyte
- gel electrolyte
- solution
- 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.)
- Pending
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ゲルを電解質とし、そ
の界面層もしくは内部で導電性高分子を重合し、電極活
物質とする２次電池の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a secondary battery in which a gel is used as an electrolyte and a conductive polymer is polymerized in an interface layer or inside thereof to make an electrode active material.
【０００２】[0002]
【従来の技術】従来の２次電池では、例えばシート状の
正負極間に、（Ａ）セパレターと電解質溶液を介在させ
たもの、（Ｂ）ポリエチレンオキシドとナトリウム塩と
の複合体を介在させたものなどが知られている。2. Description of the Related Art In a conventional secondary battery, for example, (A) a separator and an electrolyte solution are interposed and (B) a complex of polyethylene oxide and a sodium salt is interposed between a positive electrode and a negative electrode. Things are known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
２次電池、特に、上記（Ａ）の構成では、薄型かつ大面
積（例えば、単位セル厚が１ｍｍ程度、面積が３０ｃｍ
×３０ｃｍ以上）の積層型電池を作成する際、電解質溶
液の注入プロセスが困難となる。また、活物質の脱落や
デントライトの析出により、サイクル寿命が短くなって
しまうという問題点があった。However, in the conventional secondary battery, in particular, in the configuration of (A) above, it is thin and has a large area (for example, the unit cell thickness is about 1 mm and the area is 30 cm).
When making a laminated battery (× 30 cm or more), the process of injecting the electrolyte solution becomes difficult. Further, there is a problem that the cycle life is shortened due to the fall of the active material and the deposition of dentrite.
【０００４】また、上記（Ｂ）の構成では、固体電解質
の導電率が１０-4Ｓ・ｃｍ-1以下と小さいうえに、電極
と固体電界質との密着性を保つことが困難なため、界面
インピーダンスが大きくなって、分極の増大を招くとい
う問題点があった。Further, in the above configuration (B), the conductivity of the solid electrolyte is as small as 10 -4 S · cm −1 or less, and it is difficult to maintain the adhesion between the electrode and the solid electrolyte. There has been a problem that the interface impedance becomes large and polarization is increased.
【０００５】また、上記構成の２次電池の製造方法は、
電極活物質を成形したのち、容器に組付けて、その中に
電解液を注入するものである。このとき、電極活物質が
空気中にさらされ、劣化するという問題点があった。The method of manufacturing the secondary battery having the above structure is
After molding the electrode active material, it is assembled in a container and the electrolytic solution is injected therein. At this time, there is a problem that the electrode active material is exposed to the air and deteriorates.
【０００６】本発明の目的は、（Ｃ）薄型かつ大面積の
２次電池の作成を容易にすること、（Ｄ）活物質の脱落
やデントライトの析出を防止してサイクル寿命を向上さ
せること、（Ｅ）電極と電解質の密着性を良好にし、電
解質溶液なみの界面インピーダンスを得ること、（Ｆ）
導電性高分子の単量体（モノマー）と電解液を混合した
溶液を含有するゲル状電解質を作成し、これを密封した
のちに電極活物質とするため、電極活物質の劣化の原因
となる空気との接触を経ない２次電池の製造方法を提供
するものである。An object of the present invention is to (C) facilitate the production of a thin and large-area secondary battery, and (D) prevent the active material from falling off and depositing dendrite to improve the cycle life. , (E) To improve the adhesion between the electrode and the electrolyte, and obtain an interface impedance similar to that of the electrolyte solution, (F)
A gel electrolyte containing a solution of a conductive polymer monomer (monomer) and an electrolytic solution is created, and this is used as an electrode active material after sealing it, which causes deterioration of the electrode active material. It is intended to provide a method for manufacturing a secondary battery that does not come into contact with air.
【０００７】[0007]
【課題を解決するための手段】本発明に係わるゲル電解
質を用いた２次電池の製造方法は、シートもしくはフイ
ルム状の高分子架橋体を電解液と導電性高分子の単量体
（モノマー）を混合した溶液に浸せきして、ゲル状電解
質を作成する第１工程と、このゲル状電解質を２枚の電
極に挟んで通電する第２工程とを備えたものである。A method for manufacturing a secondary battery using a gel electrolyte according to the present invention is a sheet or film-shaped crosslinked polymer, which is composed of an electrolyte solution and a monomer of a conductive polymer. It is provided with a first step of making a gel electrolyte by immersing the gel electrolyte in a mixed solution and a second step of energizing the gel electrolyte by sandwiching it between two electrodes.
【０００８】これらの工程により、正極電極とゲル界面
層、もしくはゲル内部に導電性高分子を電界重合し、同
時に、負極電極とゲル界面層に電解液中のカチオンを負
極活物質として析出するものである。By these steps, a conductive polymer is electro-polymerized inside the positive electrode and the gel interface layer or inside the gel, and at the same time, the cation in the electrolytic solution is deposited as the negative electrode active material on the negative electrode and the gel interface layer. Is.
【０００９】[0009]
【作用】本発明は、薄型かつ大面積の２次電池の製造を
容易にし、しかも、作成時の電極活物質の劣化が生じる
ことがないものである。The present invention facilitates the production of a thin and large-area secondary battery, and does not cause deterioration of the electrode active material during production.
【００１０】[0010]
【実施例】図１は、本発明に係わるゲル電解質を用いた
２次電池の製造方法の一実施例を示すブロック図であ
る。図において、１は例えばアクリルゴムなどの高分子
架橋体をシート状もしくはフイルム状に作成する第１工
程、２は、例えば、過塩素酸リチウムの炭酸プロピレン
溶液２．０ｍｏｌ／ｌとピロール単量体を混合して電解
液・単量体混合液を作成する第２工程である。EXAMPLE FIG. 1 is a block diagram showing an example of a method of manufacturing a secondary battery using a gel electrolyte according to the present invention. In the figure, 1 is a first step of forming a cross-linked polymer such as acrylic rubber into a sheet or film, and 2 is, for example, 2.0 mol / l of a propylene carbonate solution of lithium perchlorate and a pyrrole monomer. Is a second step of preparing an electrolytic solution / monomer mixed solution.
【００１１】３は上記第１工程で作成した高分子架橋体
を、上記第２工程２で作成した電解液・単量体混合液に
浸せきし、膨潤過程を経てゲル状電解質を作成する第３
工程である。The third step is to immerse the polymer cross-linked product prepared in the first step in the electrolytic solution / monomer mixed solution prepared in the second step 2 and prepare a gel electrolyte through a swelling process.
It is a process.
【００１２】４はこの第３工程３で得られたゲル状電解
質を２枚の白金電極（図示せず）に挟み込み、その外周
を熱可塑樹脂フイルムで密閉するように組付ける第４工
程である。The fourth step is a fourth step in which the gel electrolyte obtained in the third step 3 is sandwiched between two platinum electrodes (not shown) and the outer periphery thereof is sealed with a thermoplastic resin film. .
【００１３】５は定電圧電源（図示せず）により、上記
白金電極（図示せず）に、所定の電圧、例えば、４．０
Ｖを印加し、通電しながら正極側ゲル界面層もしくはゲ
ル内部に導電性高分子（ポリピロール）を電界重合し、
同時に負極側ゲル界面に負極活物質（金属リチウム）を
析出する第５工程である。Numeral 5 is a constant voltage power source (not shown) applied to the platinum electrode (not shown) at a predetermined voltage, for example 4.0.
By applying V and energizing, a conductive polymer (polypyrrole) is electropolymerized in the gel interface layer on the positive electrode side or inside the gel,
At the same time, it is the fifth step of depositing the negative electrode active material (metal lithium) on the negative electrode side gel interface.
【００１４】次に、上記構成によるゲル電解質を用いた
２次電池の製造方法について、図２および図３を参照し
て説明する。例えば、アクリルゴムなどの高分子架橋体
をシート状もしくはフイルム状に作成する（第１工
程）。一方、例えば過塩素酸リチウムの炭酸プロピレン
溶液２．０ｍｏｌ／ｌとピロール単量体を混合して電解
液・単量体混合液を作成する（第２工程）。Next, a method of manufacturing a secondary battery using the gel electrolyte having the above structure will be described with reference to FIGS. 2 and 3. For example, a cross-linked polymer such as acrylic rubber is formed in a sheet shape or a film shape (first step). On the other hand, for example, 2.0 mol / l of a propylene carbonate solution of lithium perchlorate and a pyrrole monomer are mixed to prepare an electrolytic solution / monomer mixed solution (second step).
【００１５】そして、上記第１工程１で作成した高分子
架橋体を、上記第２工程２で作成した電解液・単量体混
合液に浸せきし、膨潤過程を経て、ゲル状電解質６を作
成する。そして、図２に示すように、得られたゲル状電
解質６を２枚の白金電極７ａおよび７ｂで挟み込み、外
周を熱可塑性樹脂フイルム８で密閉する。Then, the cross-linked polymer prepared in the first step 1 is dipped in the electrolytic solution / monomer mixed solution prepared in the second step 2 and subjected to a swelling process to prepare a gel electrolyte 6. To do. Then, as shown in FIG. 2, the obtained gel electrolyte 6 is sandwiched between two platinum electrodes 7a and 7b, and the outer periphery is sealed with a thermoplastic resin film 8.
【００１６】そして、この白金電極７ａおよび７ｂに、
定電圧電源（図示せず）によって所定の電圧、例えば、
４．０Ｖを印加し、通電すると、図３に示すように正極
側ゲル界面もしくはゲル内部に導電性高分子（ポリピロ
ール）９を電界重合し、同時に負極側ゲル界面に負極活
物質（金属リチウム）１０を析出することができ、２次
電池として機能させることができる。Then, on the platinum electrodes 7a and 7b,
A predetermined voltage, for example, by a constant voltage power supply (not shown),
When 4.0 V is applied and energized, as shown in FIG. 3, the conductive polymer (polypyrrole) 9 is electropolymerized on the gel interface on the positive electrode side or inside the gel, and at the same time, the negative electrode active material (metal lithium) is formed on the gel interface on the negative electrode side. 10 can be deposited and can function as a secondary battery.
【００１７】なお、以上の説明では、高分子架橋体とし
て、アクリルゴムを用いたが、これに限定せず、ウレタ
ン、アクリロニトリルブタジエンゴム、ヒドリンゴム、
フッ素ゴム、ポリエーテル、ポリエステル、ポリイミ
ン、ポリビニルアルコール、ポリアクリル酸などの高極
性有機化合物およびその誘導体の架橋物を用いてもよい
ことは、もちろんである。In the above description, acrylic rubber was used as the crosslinked polymer, but it is not limited to this, and urethane, acrylonitrile butadiene rubber, hydrin rubber,
Of course, crosslinked products of highly polar organic compounds such as fluororubber, polyether, polyester, polyimine, polyvinyl alcohol and polyacrylic acid and their derivatives may be used.
【００１８】[0018]
【発明の効果】以上、詳細に説明したように、本発明に
係わるゲル電解質を用いた２次電池の製造方法によれ
ば、（イ）薄型かつ大面積の２次電池の作成が容易であ
ること、（ロ）活物質の脱落やデントライトの析出を防
止できること、（ハ）作成時の電極活物質の劣化が生じ
ないため、充放電のサイクル特性と電気容量の安定性が
良好であること、（ホ）電解質溶液と同等な界面インピ
ーダンスが得られること、などの効果がある。As described above in detail, according to the method of manufacturing a secondary battery using the gel electrolyte according to the present invention, (a) it is easy to make a thin secondary battery having a large area. (B) It is possible to prevent the active material from falling off and the deposition of dentrite, and (c) the electrode active material does not deteriorate during preparation, so the charge / discharge cycle characteristics and the stability of the electric capacity are good. (E) The same interface impedance as that of the electrolyte solution can be obtained.
【図１】本発明に係わるゲル電解質を用いた２次電池の
製造方法の一実施例を示すブロック図である。FIG. 1 is a block diagram showing an example of a method of manufacturing a secondary battery using a gel electrolyte according to the present invention.
【図２】図１の製造方法を説明するための図である。FIG. 2 is a diagram for explaining the manufacturing method of FIG.
【図３】図１に示す製造方法により、２次電池として機
能する図である。FIG. 3 is a diagram that functions as a secondary battery by the manufacturing method shown in FIG.
１ 第１工程 ２ 第２工程 ３ 第３工程 ４ 第４工程 ５ 第５工程 ６ ゲル状電解質 ７ａ，７ｂ 白金電極 ８ 熱可塑性樹脂フイルム ９ 導電性高分子 １０ 負極活物質 1 1st process 2 2nd process 3 3rd process 4 4th process 5 5th process 6 Gel electrolyte 7a, 7b Platinum electrode 8 Thermoplastic resin film 9 Conductive polymer 10 Negative electrode active material
Claims (2)
体を電解液と導電性高分子の単量体（モノマー）を混合
した溶液に浸せきして、ゲル状電解質を作成する第１工
程と、このゲル状電解質を２枚の電極に挟んで通電する
第２工程とを備え、正極電極とゲル界面層、もしくはゲ
ル内部に導電性高分子を電界重合し、同時に、負極電極
とゲルとの界面層に電解液中のカチオンを負極活物質と
して析出することを特徴とするゲル電解質を用いた２次
電池の製造方法。1. A first step for preparing a gel electrolyte by immersing a sheet or film cross-linked polymer in a solution in which an electrolyte solution and a monomer of a conductive polymer are mixed, A second step in which a gel electrolyte is sandwiched between two electrodes and energized, and a positive electrode and a gel interface layer, or a conductive polymer is electropolymerized inside the gel, and at the same time, an interface layer between the negative electrode and the gel A method for producing a secondary battery using a gel electrolyte, characterized in that cations in an electrolytic solution are deposited as a negative electrode active material.
は、パラフェニレン、ピロール、チオフェン、アニリン
などの共役結合を有する有機化合物及びその誘導体であ
って、電解液中で電界重合が可能であり、電界重合と同
時に電解液中のアニオンによりドーピングが進行する性
質を有する物質群の中から選ばれる１つ、もしくは２つ
以上の組合せからなることを特徴とする請求項１記載の
ゲル電解質を用いた２次電池の製造方法。2. A monomer of the conductive polymer.
Is an organic compound having a conjugated bond such as paraphenylene, pyrrole, thiophene, or aniline and its derivative, which can be electropolymerized in an electrolytic solution, and the doping proceeds by the anion in the electrolytic solution simultaneously with the electrolytic polymerization. The method for producing a secondary battery using a gel electrolyte according to claim 1, comprising one or a combination of two or more selected from a substance group having properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5321438A JPH07153489A (en) | 1993-11-26 | 1993-11-26 | Manufacture of secondary battery with gel electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5321438A JPH07153489A (en) | 1993-11-26 | 1993-11-26 | Manufacture of secondary battery with gel electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07153489A true JPH07153489A (en) | 1995-06-16 |
Family
ID=18132562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5321438A Pending JPH07153489A (en) | 1993-11-26 | 1993-11-26 | Manufacture of secondary battery with gel electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07153489A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000051198A2 (en) * | 1999-02-26 | 2000-08-31 | Reveo, Inc. | Solid gel membrane |
| US6605391B2 (en) | 1999-02-26 | 2003-08-12 | Reveo, Inc. | Solid gel membrane |
| US6849702B2 (en) | 1999-02-26 | 2005-02-01 | Robert W. Callahan | Polymer matrix material |
-
1993
- 1993-11-26 JP JP5321438A patent/JPH07153489A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000051198A2 (en) * | 1999-02-26 | 2000-08-31 | Reveo, Inc. | Solid gel membrane |
| WO2000051198A3 (en) * | 1999-02-26 | 2001-01-11 | Reveo Inc | Solid gel membrane |
| US6358651B1 (en) | 1999-02-26 | 2002-03-19 | Reveo, Inc. | Solid gel membrane separator in rechargeable electrochemical cells |
| US6605391B2 (en) | 1999-02-26 | 2003-08-12 | Reveo, Inc. | Solid gel membrane |
| US6849702B2 (en) | 1999-02-26 | 2005-02-01 | Robert W. Callahan | Polymer matrix material |
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