JPH1180296A - Gel form polymer electrolyte - Google Patents
Gel form polymer electrolyteInfo
- Publication number
- JPH1180296A JPH1180296A JP9246369A JP24636997A JPH1180296A JP H1180296 A JPH1180296 A JP H1180296A JP 9246369 A JP9246369 A JP 9246369A JP 24636997 A JP24636997 A JP 24636997A JP H1180296 A JPH1180296 A JP H1180296A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- polymer electrolyte
- electrolyte
- sheet
- gel
- 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
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム一次電
池、リチウム二次電池、電気二重層キャパシタ、エレク
トロクロミックディスプレイ等の電気化学素子に応用す
ることができるゲル状ボリマー電解質に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gel-like polymer electrolyte which can be applied to electrochemical devices such as lithium primary batteries, lithium secondary batteries, electric double layer capacitors, and electrochromic displays.
【０００２】[0002]
【従来の技術】LiBF4、LiPF6等の塩を溶解した非プロト
ン性有機溶媒からなる有機電解液を、有機高分子化合物
でゲル化あるいは保持して流動性を無くしたゲル状ポリ
マー電解質、いわゆる、ポリマーゲル電解質を用いる
と、見かけは固体状の電池を構成することができる。2. Description of the Related Art A gel polymer electrolyte in which an aprotic organic solvent in which salts such as LiBF4 and LiPF6 are dissolved is gelled or held with an organic polymer compound to lose fluidity, that is, a so-called polymer When a gel electrolyte is used, an apparently solid battery can be formed.
【０００３】このようなポリマーゲル電解質としては例
えば、有機電解液をフッ化ビニリデンと３フッ化エチレ
ンの共重合体で保持したポリマーゲル電解質が特開昭５
８−７５７７９で提案されている。また、有機電解液を
フッ化ビニリデンと６フッ化プロピレンの共重合体で保
持したポリマーゲル電解質が米国特許第５２９６３１８
号に提案されている。また、有機電解液をポリアクリロ
ニトリルでゲル化したポリマーゲル電解質が、特開昭５
８−７５７７９で提案されている。さらに、アクリロニ
トリル共重合体でゲル化したポリマーゲル電解質が特開
平７−５７７１３号に提案されている。As such a polymer gel electrolyte, for example, a polymer gel electrolyte in which an organic electrolytic solution is held by a copolymer of vinylidene fluoride and ethylene trifluoride is disclosed in
8-75779. Further, a polymer gel electrolyte in which an organic electrolytic solution is held by a copolymer of vinylidene fluoride and propylene hexafluoride is disclosed in US Pat. No. 5,296,318.
No. has been proposed. Further, a polymer gel electrolyte obtained by gelling an organic electrolyte with polyacrylonitrile is disclosed in
8-75779. Further, a polymer gel electrolyte gelled with an acrylonitrile copolymer is proposed in Japanese Patent Application Laid-Open No. 7-57713.
【０００４】[0004]
【発明が解決しようとする課題】ポリマーゲル電解質に
求められる特性としては、高いイオン伝導性を有し、多
量の有機電解液を保持でき、熱的、化学的に安定で、電
池の動作電圧無いで酸化還元により分解しない電気化学
的な安定性があり、薄いシート状に加工しても十分な機
械強度を有していること、電極に混合して用いられる際
は、電極材料粉末粒子を結着保持する十分な接着性と粘
弾性が必要である。The characteristics required for the polymer gel electrolyte include high ionic conductivity, a large amount of organic electrolyte can be held, thermal and chemical stability, and no operating voltage of the battery. It has electrochemical stability that does not decompose due to oxidation and reduction, has sufficient mechanical strength even when processed into a thin sheet, and binds the electrode material powder particles when used in an electrode. Sufficient adhesiveness and viscoelasticity for holding and holding are required.
【０００５】従来より提案されているポリマーゲル電解
質は、イオン伝導性が低い、薄膜状にした際の機械強度
が不十分、有機電解液を十分保持できない、還元性の金
属リチウムと反応して高抵抗の不働態膜を形成する等の
課題がある。さらに、二次電池の活物質であるLiCoO2や
LiMn2O4等の金属酸化物よりなる電極材料と混合した際
酸化分解する、電極材料粉末を結着保持するための接着
性と粘弾性とが不十分である等の課題も有しており、上
記の特性を全て満たすものがないのが現状である。The conventionally proposed polymer gel electrolytes have low ionic conductivity, insufficient mechanical strength when formed into a thin film, cannot hold an organic electrolytic solution sufficiently, and react with reducing metallic lithium to give high performance. There are problems such as formation of a passive film of resistance. Furthermore, LiCoO 2 which is the active material of the secondary battery,
It also has problems such as decomposition by oxidation when mixed with an electrode material composed of a metal oxide such as LiMn 2 O 4 and insufficient adhesiveness and viscoelasticity for binding and holding the electrode material powder. At present, none of the above characteristics are satisfied.
【０００６】本発明が解決しようとする課題は、室温動
作のリチウム一次電池、リチウム二次電池、電気二重層
キャパシタ、エレクトロクロミックディスプレイ等の電
気化学素子に用い実用上十分な特性を発揮することを目
的とし、室温で１ｍS/cm 以上の高いリチウムイオン伝
導度を有し、熱的化学的に安定で、金属リチウムと接触
しても高抵抗の不働態膜を形成し難い電気化学的な安定
性を有し、厚み１００μの薄膜状に加工が可能で、電極
材料粉末を十分に結着保持する接着性と粘弾性とを有す
るゲル状のポリマー電解質を提供することである。The problem to be solved by the present invention is to exhibit practically sufficient characteristics when used in electrochemical devices such as lithium primary batteries, lithium secondary batteries, electric double layer capacitors, and electrochromic displays which operate at room temperature. The purpose is to have high lithium ion conductivity of 1mS / cm or more at room temperature, thermochemically stable, and electrochemical stability that makes it difficult to form a high-resistance passive film even when in contact with metallic lithium. The present invention is to provide a gel-like polymer electrolyte which can be processed into a thin film having a thickness of 100 μm and has sufficient adhesiveness and viscoelasticity to sufficiently bind and hold the electrode material powder.
【０００７】[0007]
【課題を解決するための手段】本発明は、特定の熱可塑
性エラストマーを用いることで上記課題を解決したゲル
状ポリマー電解質を提供する。すなわち、リチウム塩を
溶解した非プロトン性有機溶媒（Ｂ）を、フッ化ビニリ
デンポリマーセグメントとアクリロニトリルポリマーセ
グメントのブロックまたはグラフト共重合体を骨格とす
る熱可塑性エラストマー（Ａ）でゲル化して得られるゲ
ル状ポリマー電解質により、上述の課題を解決すること
が出来る。SUMMARY OF THE INVENTION The present invention provides a gel polymer electrolyte which solves the above-mentioned problems by using a specific thermoplastic elastomer. That is, a gel obtained by gelling an aprotic organic solvent (B) in which a lithium salt is dissolved with a thermoplastic elastomer (A) having a block or graft copolymer of a vinylidene fluoride polymer segment and an acrylonitrile polymer segment as a skeleton. The above-mentioned problems can be solved by the polymer electrolyte.
【０００８】さらに、リチウム塩を溶解した非プロトン
性有機溶媒（Ｂ）を、フッ化ビニリデンポリマーセグメ
ントとアクリロニトリルポリマーセグメントのブロック
またはグラフト共重合体を骨格とする熱可塑性エラスト
マー（Ａ）でゲル化し、これに電気絶縁性無機粉末
（Ｃ）を添加したゲル状ポリマー電解質により、上述の
課題を解決することが出来る。Further, the aprotic organic solvent (B) in which a lithium salt is dissolved is gelled with a thermoplastic elastomer (A) having a block or graft copolymer of a vinylidene fluoride polymer segment and an acrylonitrile polymer segment as a skeleton, The above-mentioned problem can be solved by the gel polymer electrolyte to which the electrically insulating inorganic powder (C) is added.
【０００９】[0009]
【発明の実施の形態】本発明の熱可塑性エラストマー
（Ａ）は通常のブロック共重合またはグラフト共重合に
より得ることができる。BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic elastomer (A) of the present invention can be obtained by ordinary block copolymerization or graft copolymerization.
【００１０】その作製方法は、まずメタクリロイル基や
スチリル基等の重合性官能基を片末端あるいは両末端に
有するアクリロニトリル（重合度が２００〜６００）の
マクロホモモノマー（あるいはマクロコモノマー）を、
通常の官能性連鎖移動剤を用いたラジカル重合反応によ
り合成する。他方、フッ化ビニリデンまたはフッ化ビニ
リデンと共重合可能な６フッ化プロピレン（または４フ
ッ化エチレン）などのモノマーを溶解した溶媒を作製
し、これにアゾイソブチロニトリルなどの重合開始剤を
添加する。最後に上述のマクロホモモノマー（あるいは
コモノマー）をこれに加え、ラジカル重合を行うことで
熱可塑性エラストマー（Ａ）を作製することが出来る。[0010] The production method is as follows: first, a macro homo monomer (or macro comonomer) of acrylonitrile (polymerization degree: 200 to 600) having a polymerizable functional group such as a methacryloyl group or a styryl group at one end or both ends is prepared.
It is synthesized by a radical polymerization reaction using an ordinary functional chain transfer agent. On the other hand, a solvent is prepared by dissolving a monomer such as vinylidene fluoride or propylene hexafluoride (or ethylene tetrafluoride) copolymerizable with vinylidene fluoride, and a polymerization initiator such as azoisobutyronitrile is added thereto. I do. Finally, the above-mentioned macro homo monomer (or comonomer) is added thereto, and radical polymerization is performed to produce the thermoplastic elastomer (A).
【００１１】また、上述の熱可塑性エラストマー（Ａ）
の合成は、フッ化ビニリデンの片末端あるいは両末端に
メタクリロイル基等の重合性官能基を付加したマクロホ
モモノマーあるいはマクロコモノマー（重合度が２００
〜６００）を、通常の官能性連鎖移動剤を用いたラジカ
ル重合反応により合成したのち、これをアクリロニトリ
ルまたは、アクリロニトリルと共重合可能なアクリル酸
メチル、酢酸ブチル、塩化ビニルなどのビニルモノマー
を溶解した溶媒に添加し、アゾイソブチロニトリルなど
の重合開始剤を添加した後、ラジカル重合反応を行うこ
とで得ることも可能である。Further, the above-mentioned thermoplastic elastomer (A)
Is synthesized by adding a macro homo monomer or macro comonomer having a polymerizable functional group such as a methacryloyl group to one end or both ends of vinylidene fluoride (having a polymerization degree of 200).
~ 600) was synthesized by a radical polymerization reaction using a normal functional chain transfer agent, and then this was dissolved in acrylonitrile or a vinyl monomer such as methyl acrylate, butyl acetate and vinyl chloride copolymerizable with acrylonitrile. It can also be obtained by adding a polymerization initiator such as azoisobutyronitrile to a solvent and then performing a radical polymerization reaction.
【００１２】フッ化ビニリデンと、フッ化ビニリデンと
共重合可能なモノマーの合計量は全モノマー量に対し１
から９９モル％であり、またアクリロニトリルと、アク
リロニトリルと共重合可能なモノマーの合計量は全モノ
マー量に対し９９〜１モル％であるのが好ましい。The total amount of vinylidene fluoride and the monomer copolymerizable with vinylidene fluoride is 1 to the total monomer amount.
To 99 mol%, and the total amount of acrylonitrile and monomers copolymerizable with acrylonitrile is preferably 99 to 1 mol% based on the total amount of monomers.
【００１３】熱可塑性エラストマー（Ａ）の分子量は、
１０万から１００万のものが使用可能である。分子量
は、ブロックあるいは共重合の際のモノマー濃度、開始
剤濃度、連鎖移動剤濃度、温度により制御することが可
能である。組成は、仕込みモノマー組成により制御可能
である。The molecular weight of the thermoplastic elastomer (A) is:
One hundred thousand to one million can be used. The molecular weight can be controlled by the monomer concentration, initiator concentration, chain transfer agent concentration, and temperature at the time of block or copolymerization. The composition can be controlled by the charged monomer composition.
【００１４】本発明で用いるリチウム塩を溶解した非プ
ロトン性有機溶媒（Ｂ）は、非プロトン性有機溶媒にリ
チウム塩を０．５〜２モル／リットル溶解したものであ
る。溶解するリチウム塩としては、ＬｉＣｌＯ4、Ｌｉ
ＢＦ4、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＯＳＯ2ＣＦ3、
ＬｉＮ（ＳＯ2ＣＦ3）2、Ｌｉ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ
4Ｆ9）、ＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ2Ｆ5）などが
用いられる。非プロトン性有機溶媒としては、プロピレ
ンカーボネート（ＰＣ）、エチレンカーボネート（Ｅ
Ｃ）、ジメチルカーボネート（ＤＭＣ）、ジエチルカー
ボネート（ＤＥＣ）、エチルメチルカーボネート（ＥＭ
Ｃ）、ジメトキシエタン（ＤＭＥ）、スルホラン（Ｓ
Ｆ）、テトラハイドロフラン（ＴＨＦ）などが単独であ
るいは混合して用いられる。The aprotic organic solvent (B) in which a lithium salt is dissolved used in the present invention is a solution in which a lithium salt is dissolved in an aprotic organic solvent in an amount of 0.5 to 2 mol / l. LiClO 4 , Li
BF 4 , LiPF 6 , LiAsF 6 , LiOSO 2 CF 3 ,
LiN (SO 2 CF 3 ) 2 , Li (SO 2 CF 3 ) (SO 2 C
4 F 9), LiN (SO 2 CF 3) (SO 2 C 2 F 5) or the like is used. As aprotic organic solvents, propylene carbonate (PC), ethylene carbonate (E
C), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EM
C), dimethoxyethane (DME), sulfolane (S
F), tetrahydrofuran (THF) or the like is used alone or as a mixture.
【００１５】本発明で用いる電気絶縁性無機粉末（Ｃ）
としては、アルミナ粉末、シリカ粉末、シリカアルミナ
粉末、チタニア粉末、多孔質ガラス粉末、珪酸アルミニ
ウム、ジルコニア粉末、ゼオライト粉末等、大きさが
０．１μｍから数１０μｍの粉末が用いられる。これら
の粉末は、球状、繊維状、板状、中空体、多孔体のいず
れであってもよい。表面をビニルモノマーの重合体で改
質したものは、特に、高い機械強度を有するゲル状ポリ
マー電解質となる。The electrically insulating inorganic powder (C) used in the present invention
As the powder, powder having a size of 0.1 μm to several tens μm, such as alumina powder, silica powder, silica alumina powder, titania powder, porous glass powder, aluminum silicate, zirconia powder, and zeolite powder, is used. These powders may be spherical, fibrous, plate-like, hollow, or porous. The one whose surface is modified with a polymer of a vinyl monomer is particularly a gel polymer electrolyte having high mechanical strength.
【００１６】熱可塑性エラストマー（Ａ）は、リチウム
塩を溶解した非プロトン性有機溶媒（Ｂ）１００重量部
に対し、０．５〜２０重量部が使用可能であり、そのう
ち特に２重量部から１０重量部の範囲で用いると、フレ
キシブルで有機溶媒の浸みだしのないマイナス１０℃か
ら８０℃まで、形状の安定した優れた信頼性を有するゲ
ル状ポリマー電解質を得ることができる。The thermoplastic elastomer (A) can be used in an amount of 0.5 to 20 parts by weight, based on 100 parts by weight of the aprotic organic solvent (B) in which the lithium salt is dissolved, and especially 2 to 10 parts by weight. When used in the range of parts by weight, it is possible to obtain a gel polymer electrolyte having a stable shape and excellent reliability from −10 ° C. to 80 ° C. that is flexible and does not exude the organic solvent.
【００１７】電気絶縁性無機物質粉末（Ｃ）は、熱可塑
性エラストマー（Ａ）とリチウム塩を溶解した非プロト
ン性有機溶媒（Ｂ）の合計の重量に対し０．０５％から
１０％の範囲で使用可能である。この範囲であると、イ
オン伝導度を大きく低下することなく、特に高い機械強
度を有するゲル状ポリマー電解質を得ることができる。The electrically insulating inorganic substance powder (C) is contained in an amount of 0.05% to 10% with respect to the total weight of the thermoplastic elastomer (A) and the aprotic organic solvent (B) in which a lithium salt is dissolved. Can be used. Within this range, a gel polymer electrolyte having particularly high mechanical strength can be obtained without significantly lowering the ionic conductivity.
【００１８】熱可塑性エラストマー（Ａ）の粉末をリチ
ウム塩を溶解した非プロトン性有機溶媒（Ｂ）に分散し
た液を、密閉容器で加熱したのち、室温あるいはマイナ
ス２０℃の冷凍庫で冷却することでゲル状ポリマー電解
質が得られる。得られたゲル状電解質を熱ローラで圧延
することで好みの厚さ、大きさのシートを得ることがで
きる。また、ゲル状ポリマー電解質と電極活物質とを複
合し、電池の正極あるいは負極を作製には、粉末状の電
極活物質と熱可塑性エラストマー（Ａ）の粉末と必要に
応じて導電剤粉末とを均一に混合し、次に、リチウム塩
を溶解した非プロトン性有機溶媒（Ｂ）を添加して混練
する。混練物を加圧下で加熱成形することで複合物の塊
を得る。この塊を、熱プレスローラ等で圧延することで
シート状の電極を得ることができる。あるいは、混合機
を備えた押し出し成形機で均一混合、混練、押し出し成
形することでシート状の電極を得ることもできる。A liquid obtained by dispersing a powder of the thermoplastic elastomer (A) in an aprotic organic solvent (B) in which a lithium salt is dissolved is heated in a closed container, and then cooled in a freezer at room temperature or minus 20 ° C. A gel polymer electrolyte is obtained. By rolling the obtained gel electrolyte with a hot roller, a sheet having a desired thickness and size can be obtained. Further, in order to form a positive electrode or a negative electrode of a battery by combining a gel polymer electrolyte and an electrode active material, a powdery electrode active material, a thermoplastic elastomer (A) powder, and a conductive agent powder as necessary are used. The mixture is uniformly mixed, and then an aprotic organic solvent (B) in which a lithium salt is dissolved is added and kneaded. A mass of a composite is obtained by subjecting the kneaded material to heat molding under pressure. This lump is rolled with a hot press roller or the like to obtain a sheet-like electrode. Alternatively, a sheet-like electrode can be obtained by uniformly mixing, kneading, and extruding with an extruder equipped with a mixer.
【００１９】（実施の形態１）アクリロニトリルモノマ
ー（ＡＮ）と酢酸ビニルモノマー（ＶＡｃ）とメタアク
リル酸モノマーを用いラジカル重合にて平均重合度が４
５０、ＡＮ／ＶＡｃモル比が９５／５、メタアクリロイ
ル末端基を有すマクロコモノマーを得た。このマクロコ
モノマーとフッ化ビニリデンモノマー（ＶｄＦ）をラジ
カル重合することで、フッ化ビニリデン鎖のモノマーユ
ニットの平均繰り返し数が３５０〜５００、フッ化ビニ
リデンの含有量が２０モル％、スチレン換算数平均分子
量４１０，０００のブロック共重合体粉末（AN-VAc-VdF
-1）を得た。(Embodiment 1) An acrylonitrile monomer (AN), a vinyl acetate monomer (VAc) and a methacrylic acid monomer are used to obtain an average degree of polymerization of 4 by radical polymerization.
A macrocomonomer having a methacryloyl end group of 50 and an AN / VAc molar ratio of 95/5 was obtained. By subjecting this macrocomonomer and vinylidene fluoride monomer (VdF) to radical polymerization, the average number of repeating vinylidene fluoride monomer units is 350 to 500, the content of vinylidene fluoride is 20 mol%, and the number average molecular weight in terms of styrene. 410,000 block copolymer powder (AN-VAc-VdF
-1) was obtained.
【００２０】次に、ＥＣとＥＭＣを１：３（モル比）に
混合した有機溶媒にＬｉＰＦ6を１．５モル／リットル
溶解しEC-EMC-LiPF6電解液を得た。Next, 1.5 mol / l of LiPF 6 was dissolved in an organic solvent in which EC and EMC were mixed at a ratio of 1: 3 (molar ratio) to obtain an EC-EMC-LiPF 6 electrolyte.
【００２１】AN-VAc-VdF-1粉末２．５ｇを、EC-EMC-LiP
F6電解液２３ｇに分散した液をテフロン製の１００ｍｌ
の密閉容器中で１４０℃に加熱することで透明な粘性体
を得た後、これを、マイナス２０℃に冷却しゲル状ポリ
マー電解質の塊を得た。この塊を、８０℃に加熱した熱
プレスローラで圧延し、厚さ８０μｍのゲル状ポリマー
電解質シート（ＳＰＥ−Ａ）を得た。得られたシートは
強靱で、柔軟性があり、引っ張り強度０．８ｋｇ／５ｃ
ｍを有していた。室温で３０日保存後、電解液の浸みだ
しはなかった。このシートを２ｘ２ｃｍに切断し、厚さ
２００μｍの金属リチウムで挟んで組み立てたセルにつ
いて周波数１０ＫＨｚ、振幅１０ｍＶの交流信号を印加
して測定した伝導度を表１にまとめて示す。伝導度値
は、セルの組立直後、セルを２０℃で３ヶ月保存した後
も全く変化なく、金属リチウムとの接触界面は安定して
いる。2.5 g of AN-VAc-VdF-1 powder was added to EC-EMC-LiP
A solution dispersed in 23 g of F 6 electrolytic solution was made of Teflon 100 ml.
A transparent viscous body was obtained by heating to 140 ° C. in an airtight container, and then cooled to −20 ° C. to obtain a mass of a gel polymer electrolyte. This lump was rolled with a hot press roller heated to 80 ° C. to obtain a gel polymer electrolyte sheet (SPE-A) having a thickness of 80 μm. The resulting sheet is tough, flexible and has a tensile strength of 0.8 kg / 5 c
m. After storage at room temperature for 30 days, there was no seepage of the electrolyte. Table 1 summarizes the conductivity measured by applying an AC signal having a frequency of 10 KHz and an amplitude of 10 mV to a cell assembled by cutting this sheet into 2 × 2 cm and sandwiching it with lithium metal having a thickness of 200 μm. The conductivity value does not change at all immediately after the cell is assembled and after the cell is stored at 20 ° C. for 3 months, and the contact interface with metallic lithium is stable.
【００２２】ＬｉＣｏＯ2粉末２．５ｇ、アセチレンブ
ラック０．２０ｇ、AN-VAc-VdF-1粉末０．１５ｇを均一
に混合した粉体に、EC-EMC-LiPF6電解液を１．５ｇ添加
し、混練してフレーク状の正極組成物を得た。 この正
極組成物を電解液がしみ出さない圧力で加圧成形し直径
１ｃｍのペレットとした。ペレットを内径が１．１ｃｍ
のテフロン製のシリンダー内に空間がほとんど残らない
ように密閉し、１４０℃で１時間加熱した。このペレッ
トを、８０℃に加熱した熱プレスローラで圧延し、厚さ
１０５μｍの正極組成物シートを得た。得られたシート
を厚さ２０μｍのアルミ箔に熱プレスローラで熱圧着し
てアルミ箔をあわせた厚みが１２０μｍの正極−Ａを得
た。To a powder obtained by uniformly mixing 2.5 g of LiCoO 2 powder, 0.20 g of acetylene black, and 0.15 g of AN-VAc-VdF-1 powder, 1.5 g of EC-EMC-LiPF6 electrolyte was added. The mixture was kneaded to obtain a flake-shaped positive electrode composition. This positive electrode composition was molded under pressure at a pressure at which the electrolyte did not exude, to give a pellet having a diameter of 1 cm. Pellets with an inner diameter of 1.1 cm
And heated at 140 ° C. for 1 hour. The pellet was rolled with a hot press roller heated to 80 ° C. to obtain a positive electrode composition sheet having a thickness of 105 μm. The obtained sheet was thermocompression-bonded to a 20-μm-thick aluminum foil with a hot press roller to obtain a 120-μm-thick positive electrode-A including the aluminum foil.
【００２３】２５００℃で黒鉛化したメソフェーズマイ
クロビーズカーボン粉末２．５ｇ、アセチレンブラック
０．２５ｇ、AN-VAc-VdF-1粉末０．２０ｇを均一に混合
した粉末に、EC-EMC-LiPF6電解液を２．０ｇ添加し、混
練してフレーク状の負極組成物を得た。この負極組成物
を電解液がしみ出さない圧力で加圧成形し直径１ｃｍの
ペレットとした。ペレットを内径が１．１cｍのテフロ
ン製のシリンダー内に空間がほとんど残らないように密
閉し、１４０℃で１時間加熱した。このペレットを、８
０℃に加熱した熱プレスローラで圧延し、厚さ１０５μ
ｍの負極組成物シートを得た。得られたシートを厚さ２
０μｍのアルミ箔に熱プレスローラで熱圧着してアルミ
箔をあわせた厚みが１２０μｍの負極−Ａを得た。An EC-EMC-LiPF 6 electrolytic solution was added to a powder obtained by uniformly mixing 2.5 g of mesophase microbead carbon powder graphitized at 2500 ° C., 0.25 g of acetylene black, and 0.20 g of AN-VAc-VdF-1 powder. 2.0 g of the liquid was added and kneaded to obtain a flake-shaped negative electrode composition. The negative electrode composition was molded under pressure at a pressure at which the electrolyte did not exude, to form a pellet having a diameter of 1 cm. The pellet was sealed in a Teflon cylinder having an inner diameter of 1.1 cm so that almost no space was left, and heated at 140 ° C. for 1 hour. This pellet is
Rolled by hot press roller heated to 0 ° C, thickness 105μ
m of the negative electrode composition sheet was obtained. The thickness of the obtained sheet is 2
A negative electrode A having a thickness of 120 μm was obtained by thermocompression bonding to a 0 μm aluminum foil with a hot press roller.
【００２４】ＳＰＥ−Ａを正極−Ａと負極−Ａの間に挟
んで、熱プレスローラで加熱圧着したのち、３層となっ
たシートを２ｘ２ｃｍの大きさに裁断して得られたセル
を、チタン箔電極リードを備え、ポリエチレン／アルミ
箔／ポリエチレンの３層よるなるアルミラミネートシー
トよりなる電池パッケージ内に真空封入して試験電池−
Ａを得た。 試験電池−Ａを、２０℃で、１ｍＡの一定
電流値で、充電終了電圧４．２０、放電終了電圧３．０
Ｖで、繰り返し充放電を行った。１０サイクル後、５．
２ｍＡｈの放電容量（Ｑｄｉｓ）が得られ、１００サイ
クル後、Ｑｄｉｓ＝４．９ｍＡｈ、３００サイクル後、
Ｑｄｉｓ＝４．５ｍＡｈの安定した充放電サイクル特性
が得られた。A cell obtained by sandwiching the SPE-A between the positive electrode-A and the negative electrode-A, applying heat and pressure with a hot press roller, and cutting the three-layered sheet into a size of 2 × 2 cm, Test battery with titanium foil electrode leads, vacuum sealed in a battery package consisting of an aluminum laminated sheet consisting of three layers of polyethylene / aluminum foil / polyethylene
A was obtained. The test battery-A was charged at a constant current value of 1 mA at 20 ° C. with a charge end voltage of 4.20 and a discharge end voltage of 3.0.
At V, charging and discharging were repeatedly performed. After 10 cycles, 5.
A discharge capacity (Qdis) of 2 mAh was obtained, and after 100 cycles, Qdis = 4.9 mAh, after 300 cycles,
A stable charge / discharge cycle characteristic of Qdis = 4.5 mAh was obtained.
【００２５】（実施の形態２）フッ化ビニリデンモノマ
ー（ＶｄＦ）と６フッ化プロピレンモノマー（ＨＦＰ）
とスチレンモノマーを用いラジカル重合にて平均重合度
が４５０、ＶｄＦ／ＨＦＰモル比が８５／１５、スチリ
ル末端基を有すマクロコモノマーを得た。このマクロコ
モノマーとアクリロニトリルモノマー（ＡＮ）と酢酸ビ
ニルモノマー（ＶＡｃ）を、ＡＮ／ＶＡｃ＝９３／７の
モル比でラジカル重合することで、アクリロニトリルモ
ノマーユニットの平均繰り返し数が約４５０、アクリロ
ニトリルの含有量が１５モル％、スチレン換算数平均分
子量３８０，０００のブロック共重合体粉末（AN-VAc-V
dF-HFP-2）を得た。(Embodiment 2) Vinylidene fluoride monomer (VdF) and propylene hexafluoride monomer (HFP)
And a styrene monomer to obtain a macrocomonomer having an average degree of polymerization of 450, a VdF / HFP molar ratio of 85/15, and a styryl end group. By subjecting this macro comonomer, acrylonitrile monomer (AN) and vinyl acetate monomer (VAc) to radical polymerization at a molar ratio of AN / VAc = 93/7, the average number of acrylonitrile monomer units is about 450 and the content of acrylonitrile Is a block copolymer powder having a number average molecular weight of 380,000 in terms of styrene (AN-VAc-V
dF-HFP-2) was obtained.
【００２６】次に、ＥＣとＰＣを２：１（モル比）に混
合した有機溶媒にＬｉＢＦ4を１．５モル／リットル溶
解しEC-PC-LiBF4電解液を得た。Next, 1.5 mol / l of LiBF 4 was dissolved in an organic solvent in which EC and PC were mixed at a molar ratio of 2: 1 to obtain an EC-PC-LiBF 4 electrolytic solution.
【００２７】AN-VAc-VdF-HFP-2粉末２．５ｇを、EC-PC-
LiBF4電解液２３ｇに分散した液をテフロン製の１００
ｍｌの密閉容器中で１４０℃に加熱することで透明な粘
性体を得た後、これを、マイナス２０℃に冷却しゲル状
ポリマー電解質の塊を得た。この塊を、８０℃に加熱し
た熱プレスローラで圧延し、厚さ８０μｍのゲル状ポリ
マー電解質シート（ＳＰＥ−B）を得た。得られたシー
トは強靱で、柔軟性があり、引っ張り強度１．２ｋｇ／
５ｃｍを有していた。室温で３０日保存後、電解液の浸
みだしはなかった。このシートを２ｘ２ｃｍに切断し、
厚さ２００μｍの金属リチウムで挟んで組み立てたセル
について周波数１０ＫＨｚ、振幅１０ｍＶの交流信号を
印加して測定した伝導度を表１にまとめて示す。伝導度
値は、セルの組立直後、セルを２０℃で３ヶ月保存した
後も全く変化なく、金属リチウムとの接触界面は安定し
ている。2.5 g of AN-VAc-VdF-HFP-2 powder was added to EC-PC-
A solution dispersed in 23 g of LiBF 4 electrolyte was treated with Teflon 100
After heating to 140 ° C. in a closed container of ml to obtain a transparent viscous body, it was cooled to −20 ° C. to obtain a mass of a gel polymer electrolyte. This lump was rolled with a hot press roller heated to 80 ° C. to obtain a gel polymer electrolyte sheet (SPE-B) having a thickness of 80 μm. The resulting sheet is tough, flexible and has a tensile strength of 1.2 kg /
Had 5 cm. After storage at room temperature for 30 days, there was no seepage of the electrolyte. Cut this sheet into 2x2cm,
Table 1 summarizes the conductivity measured by applying an AC signal having a frequency of 10 KHz and an amplitude of 10 mV to a cell assembled with metal lithium having a thickness of 200 μm. The conductivity value does not change at all immediately after the cell is assembled and after the cell is stored at 20 ° C. for 3 months, and the contact interface with metallic lithium is stable.
【００２８】ＬｉＣｏＯ2粉末２．５ｇ、アセチレンブ
ラック０．２０ｇ、AN-VAc-VdF-HFP-1粉末０．１５ｇを
均一に混合した粉体に、EC-PC-LiBF4電解液を１．５ｇ
添加し、混練してフレーク状の正極組成物を得た。 こ
の正極組成物を電解液がしみ出さない圧力で加圧成形し
直径１ｃｍのペレットとした。ペレットを内径が１．１
ｃｍのテフロン製のシリンダー内に空間がほとんど残ら
ないように密閉し、１４０℃で１時間加熱した。このペ
レットを、８０℃に加熱した熱プレスローラで圧延し、
厚さ１１５μｍの正極組成物シートを得た。得られたシ
ートを厚さ２０μｍのアルミ箔に熱プレスローラで熱圧
着してアルミ箔をあわせた厚みが１３０μｍの正極−B
を得た。1.5 g of EC-PC-LiBF 4 electrolyte was added to a uniformly mixed powder of 2.5 g of LiCoO 2 powder, 0.20 g of acetylene black and 0.15 g of AN-VAc-VdF-HFP-1 powder.
It was added and kneaded to obtain a flake-shaped positive electrode composition. This positive electrode composition was molded under pressure at a pressure at which the electrolyte did not exude, to give a pellet having a diameter of 1 cm. Pellets with an inner diameter of 1.1
The tube was sealed so that almost no space was left in a Teflon cylinder of 1 cm and heated at 140 ° C. for 1 hour. This pellet is rolled by a hot press roller heated to 80 ° C.
A positive electrode composition sheet having a thickness of 115 μm was obtained. The obtained sheet was thermocompression-bonded to a 20-μm-thick aluminum foil with a hot press roller to combine the aluminum foil with a 130 μm-thick positive electrode-B.
I got
【００２９】フェーノール樹脂を９００℃で炭化してい
たソフトカーボン粉末２．５ｇ、アセチレンブラック
０．２５ｇ、AN-VAc-VdF-HFP-2粉末０．２０ｇを均一に
混合した粉末に、EC-PC-LiBF4電解液を２．０ｇ添加
し、混練してフレーク状の負極組成物を得た。この負極
組成物を電解液がしみ出さない圧力で加圧成形し直径１
ｃｍのペレットとした。ペレットを内径が１．１ｃｍの
テフロン製のシリンダー内に空間がほとんど残らないよ
うに密閉し、１４０℃で１時間加熱した。このペレット
を、８０℃に加熱した熱プレスローラで圧延し、厚さ９
５μｍの負極組成物シートを得た。得られたシートを厚
さ２０μｍのアルミ箔に熱プレスローラで熱圧着してア
ルミ箔をあわせた厚みが１１０μｍの負極−Ｂを得た。EC-PC was added to a powder obtained by uniformly mixing 2.5 g of soft carbon powder, 0.25 g of acetylene black, and 0.20 g of AN-VAc-VdF-HFP-2 powder, which was obtained by carbonizing a phenol resin at 900 ° C. -LiBF 4 electrolyte solution (2.0 g) was added and kneaded to obtain a flake-shaped negative electrode composition. The negative electrode composition was molded under pressure at a pressure at which the electrolyte did not exude, and the diameter of the negative electrode composition was reduced to 1 mm.
cm pellets. The pellet was sealed in a Teflon cylinder having an inner diameter of 1.1 cm so that almost no space was left, and heated at 140 ° C. for 1 hour. This pellet was rolled with a hot press roller heated to 80 ° C.
A 5 μm negative electrode composition sheet was obtained. The obtained sheet was thermocompression-bonded to an aluminum foil having a thickness of 20 μm with a hot press roller to obtain a negative electrode-B having a thickness of 110 μm including the aluminum foil.
【００３０】ＳＰＥ−Ｂを正極−Ｂと負極−Ｂの間に挟
んで、熱プレスローラで加熱圧着したのち、３層となっ
たシートを２ｘ２ｃｍの大きさに裁断して得られたセル
を、チタン箔電極リードを備え、ポリエチレン／アルミ
箔／ポリエチレンの３層よるなるアルミラミネートシー
トよりなる電池パッケージ内に真空封入して試験電池−
Ａを得た。 試験電池−Ａを、２０℃で、１ｍＡの一定
電流値で、充電終了電圧４．２０、放電終了電圧２．５
Ｖで、繰り返し充放電を行った。１０サイクル後、５．
８ｍＡｈの放電容量（Ｑｄｉｓ）が得られ、１００サイ
クル後、Ｑｄｉｓ＝５．２ｍＡｈ、３００サイクル後、
Ｑｄｉｓ＝４．９ｍＡｈの安定した充放電サイクル特性
が得られた。A cell obtained by sandwiching SPE-B between the positive electrode-B and the negative electrode-B, applying heat and pressure with a hot press roller, and cutting the three-layered sheet into a size of 2 × 2 cm, Test battery with titanium foil electrode leads, vacuum sealed in a battery package consisting of an aluminum laminated sheet consisting of three layers of polyethylene / aluminum foil / polyethylene
A was obtained. The test battery-A was charged at 20 ° C. at a constant current value of 1 mA at a charge end voltage of 4.20 and a discharge end voltage of 2.5.
At V, charging and discharging were repeatedly performed. After 10 cycles, 5.
A discharge capacity (Qdis) of 8 mAh was obtained, and after 100 cycles, Qdis = 5.2 mAh, after 300 cycles,
A stable charge / discharge cycle characteristic of Qdis = 4.9 mAh was obtained.
【００３１】（実施の形態３）アクリロニトリルモノマ
ー（ＡＮ）とメタアクリル酸モノマー（ＭＡ）を用いラ
ジカル重合にて平均重合度が３００〜４５０、ＡＮ／Ｍ
Ａモル比が９７／３、メタアクリロイル末端基を有すマ
クロコモノマーを得た。このマクロコモノマーとフッ化
ビニリデンモノマー（ＶｄＦ）をラジカル重合すること
で、フッ化ビニリデン鎖のモノマーユニットの平均繰り
返し数が３５０〜５００、フッ化ビニリデンの含有量が
４５モル％、スチレン換算数平均分子量３６０，０００
のブロック共重合体粉末（AN-MA-VdF-3）を得た。(Embodiment 3) An acrylonitrile monomer (AN) and a methacrylic acid monomer (MA) are used in radical polymerization to obtain an average degree of polymerization of 300 to 450, AN / M
A macromonomer having an A molar ratio of 97/3 and having methacryloyl end groups was obtained. By subjecting this macro comonomer and vinylidene fluoride monomer (VdF) to radical polymerization, the average number of repeating monomer units of the vinylidene fluoride chain is 350 to 500, the content of vinylidene fluoride is 45 mol%, and the number average molecular weight in terms of styrene. 360,000
Was obtained as a block copolymer powder (AN-MA-VdF-3).
【００３２】次に、ＥＣとＰＣとＤＭＥ（ジメトキシエ
タン）１：１：０．２（モル比）に混合した有機溶媒に
ＬｉＰＦ6を０．５モル／リットル、ＬｉＢＦ4を１．０
モル／リットル溶解しEC-PC-DME-LiPF6-LiBF4電解液を
得た。[0032] Next, EC, PC and DME (dimethoxyethane) 1: 1: 0.2 mixed organic solvent in the LiPF6 in (molar ratio) 0.5 mol / liter, LiBF 4 1.0
The resulting mixture was dissolved in mol / liter to obtain an EC-PC-DME-LiPF6-LiBF 4 electrolyte.
【００３３】AN-MA-VdF-2粉末２．５ｇを、EC-PC-DME-L
iPF6-LiBF4電解液２３ｇに分散した液をテフロン製の１
００ｍｌの密閉容器中で１４０℃に加熱することで透明
な粘性体を得た後、これを、マイナス２０℃に冷却しゲ
ル状ポリマー電解質の塊を得た。この塊を、８０℃に加
熱した熱プレスローラで圧延し、厚さ８０μｍのゲル状
ポリマー電解質シート（ＳＰＥ−Ｃ）を得た。得られた
シートは強靱で、柔軟性があり、引っ張り強度１．６ｋ
ｇ／５ｃｍを有していた。室温で３０日保存後、電解液
の浸みだしはなかった。 このシートを２ｘ２ｃｍに切
断し、厚さ２００μｍの金属リチウムで挟んで組み立て
たセルについて周波数１０ＫＨｚ、振幅１０ｍＶの交流
信号を印加して測定した伝導度を表１にまとめて示す。
伝導度値は、セルの組立直後、セルを２０℃で３ヶ月保
存した後も全く変化なく、金属リチウムとの接触界面は
安定している。2.5 g of AN-MA-VdF-2 powder was added to EC-PC-DME-L
The solution dispersed in 23 g of the iPF 6 -LiBF 4 electrolytic solution is made of Teflon 1
After heating to 140 ° C. in a 00 ml closed container to obtain a transparent viscous body, it was cooled to −20 ° C. to obtain a mass of a gel polymer electrolyte. This lump was rolled by a hot press roller heated to 80 ° C. to obtain a gel polymer electrolyte sheet (SPE-C) having a thickness of 80 μm. The sheet obtained is tough, flexible and has a tensile strength of 1.6k.
g / 5 cm. After storage at room temperature for 30 days, there was no seepage of the electrolyte. Table 1 summarizes the conductivity measured by applying an AC signal having a frequency of 10 KHz and an amplitude of 10 mV to a cell assembled by cutting this sheet into 2 × 2 cm and sandwiching it with lithium metal having a thickness of 200 μm.
The conductivity value does not change at all immediately after the cell is assembled and after the cell is stored at 20 ° C. for 3 months, and the contact interface with metallic lithium is stable.
【００３４】ＬｉＭｎ2Ｏ4粉末２．５ｇ、アセチレンブ
ラック０．２０ｇ、AN-VAc-VdF-1粉末０．１５ｇを均一
に混合した粉体に、EC-PC-DME-LiPF6-LiBF4電解液を
１．５ｇ添加し、混練してフレーク状の正極組成物を得
た。 この正極組成物を電解液がしみ出さない圧力で加
圧成形し直径１ｃｍのペレットとした。ペレットを内径
が１．１ｃｍのテフロン製のシリンダー内に空間がほと
んど残らないように密閉し、１４０℃で１時間加熱し
た。このペレットを、８０℃に加熱した熱プレスローラ
で圧延し、厚さ１０５μｍの正極組成物シートを得た。
得られたシートを厚さ２０μｍのアルミ箔に熱プレスロ
ーラで熱圧着してアルミ箔をあわせた厚みが１２０μｍ
の正極−Ｃを得た。EC-PC-DME-LiPF 6 -LiBF 4 was mixed with a powder obtained by uniformly mixing 2.5 g of LiMn 2 O 4 powder, 0.20 g of acetylene black and 0.15 g of AN-VAc-VdF-1 powder. 1.5 g of the liquid was added and kneaded to obtain a flake-shaped positive electrode composition. This positive electrode composition was molded under pressure at a pressure at which the electrolyte did not exude, to give a pellet having a diameter of 1 cm. The pellet was sealed in a Teflon cylinder having an inner diameter of 1.1 cm so that almost no space was left, and heated at 140 ° C. for 1 hour. The pellet was rolled with a hot press roller heated to 80 ° C. to obtain a positive electrode composition sheet having a thickness of 105 μm.
The obtained sheet is thermocompressed with a hot press roller to an aluminum foil having a thickness of 20 μm, and the thickness of the combined aluminum foil is 120 μm.
Of positive electrode-C was obtained.
【００３５】Ｌｉ4/3Ｔｉ5/3Ｏ4粉末２．５ｇ、アセチ
レンブラック０．２５ｇ、AN-MA-VdF-3粉末０．２０ｇ
を均一に混合した粉末に、EC-PC-DME-LiPF6-LiBF4電解
液を２．０ｇ添加し、混練してフレーク状の負極組成物
を得た。この負極組成物を電解液がしみ出さない圧力で
加圧成形し直径１ｃｍのペレットとした。ペレットを内
径が１．１cｍのテフロン製のシリンダー内に空間がほ
とんど残らないように密閉し、１４０℃で１時間加熱し
た。このペレットを、８０℃に加熱した熱プレスローラ
で圧延し、厚さ１０５μｍの負極組成物シートを得た。
得られたシートを厚さ２０μｍのアルミ箔に熱プレスロ
ーラで熱圧着してアルミ箔をあわせた厚みが１２０μｍ
の負極−Cを得た。2.5 g Li 4/3 Ti 5/3 O 4 powder, 0.25 g acetylene black, 0.20 g AN-MA-VdF-3 powder
Was uniformly mixed, and 2.0 g of an EC-PC-DME-LiPF 6 -LiBF 4 electrolyte was added and kneaded to obtain a flake-shaped negative electrode composition. The negative electrode composition was molded under pressure at a pressure at which the electrolyte did not exude, to form a pellet having a diameter of 1 cm. The pellet was sealed in a Teflon cylinder having an inner diameter of 1.1 cm so that almost no space was left, and heated at 140 ° C. for 1 hour. The pellet was rolled with a hot press roller heated to 80 ° C. to obtain a negative electrode composition sheet having a thickness of 105 μm.
The obtained sheet is thermocompressed with a hot press roller to an aluminum foil having a thickness of 20 μm, and the thickness of the combined aluminum foil is 120 μm.
Of negative electrode-C was obtained.
【００３６】ＳＰＥ−Cを正極−Cと負極−Cの間に挟ん
で、熱プレスローラで加熱圧着したのち、３層となった
シートを２ｘ２ｃｍの大きさに裁断して得られたセル
を、チタン箔電極リードを備え、ポリエチレン／アルミ
箔／ポリエチレンの３層よるなるアルミラミネートシー
トよりなる電池パッケージ内に真空封入して試験電池−
Ａを得た。 試験電池−Cを、２０℃で、０．２ｍＡの
一定電流値で、充電終了電圧２．５０Ｖ、放電終了電圧
０．５Ｖで、繰り返し充放電を行った。１０サイクル
後、３．８ｍＡｈの放電容量（Ｑｄｉｓ）が得られ、１
００サイクル後、Ｑｄｉｓ＝３．６ｍＡｈ、３００サイ
クル後、Ｑｄｉｓ＝３．５ｍＡｈの安定した充放電サイ
クル特性が得られた。A cell obtained by sandwiching the SPE-C between the positive electrode-C and the negative electrode-C, applying heat and pressure with a hot press roller, and cutting the three-layered sheet into a size of 2 × 2 cm, Test battery with titanium foil electrode leads, vacuum sealed in a battery package consisting of an aluminum laminated sheet consisting of three layers of polyethylene / aluminum foil / polyethylene
A was obtained. The test battery-C was repeatedly charged and discharged at 20 ° C. at a constant current value of 0.2 mA, at a charge end voltage of 2.50 V and a discharge end voltage of 0.5 V. After 10 cycles, a discharge capacity (Qdis) of 3.8 mAh was obtained and 1
After 00 cycles, stable charge-discharge cycle characteristics of Qdis = 3.6 mAh and after 300 cycles, Qdis = 3.5 mAh were obtained.
【００３７】（実施の形態４）アクリロニトリルモノマ
ー（ＡＮ）とメタアクリル酸モノマー（ＭＡ）を用いラ
ジカル重合にて平均重合度が３００〜４５０、ＡＮ／Ｍ
Ａモル比が９７／３、メタアクリロイル末端基を有すマ
クロコモノマーを得た。フッ化ビニリデンモノマー（Ｖ
ｄＦ）と６フッ化プロピレンモノマー（ＨＦＰ）とスチ
レンモノマーを用いラジカル重合にて平均重合度が４５
０、ＶｄＦ／ＨＦＰモル比が８５／１５、スチリル末端
基を有すマクロコモノマーを得た。これらのマクロコモ
ノマーをラジカル重合することで、フッ化ビニリデン鎖
のモノマーユニットの平均繰り返し数が３５０〜５０
０、フッ化ビニリデンの含有量が５５モル％、スチレン
換算数平均分子量５２０，０００のブロック共重合体粉
末（AN-MA-VdF-HFP-4）を得た。 次に、ＥＣとＤＥＣ
を１：１（モル比）に混合した有機溶媒にＬｉＯＳＯ 2
ＣＦ3を１．５モル／リットル溶解しEC-DEC-LiOSO2CF3
電解液を得た。(Embodiment 4) Acrylonitrile monomer
-(AN) and methacrylic acid monomer (MA)
The average degree of polymerization is 300 to 450 by dical polymerization, AN / M
A having a molar ratio of 97/3 and a methacryloyl end group
Crocomonomer was obtained. Vinylidene fluoride monomer (V
dF), propylene hexafluoride monomer (HFP) and polystyrene
The average degree of polymerization is 45 by radical polymerization using
0, VdF / HFP molar ratio is 85/15, styryl terminal
A macrocomonomer having a group was obtained. These Macro Como
Radical polymerization of nomers produces vinylidene fluoride chains.
The average number of repeating monomer units is from 350 to 50
0, the content of vinylidene fluoride is 55 mol%, styrene
Block copolymer powder with reduced number average molecular weight of 520,000
Powder (AN-MA-VdF-HFP-4). Next, EC and DEC
In a 1: 1 (molar ratio) mixed organic solvent with LiOSO Two
CFThreeEC-DEC-LiOSOTwoCFThree
An electrolyte was obtained.
【００３８】多孔性のシルカゲル粉末（平均粒径２．４
μｍ、比表面積２２０ｍ２／ｇ）を２００℃で１７時間
真空乾燥して、シリカゲル粉末を得た。Porous silica gel powder (average particle size 2.4)
(μm, specific surface area: 220 m 2 / g) was vacuum dried at 200 ° C. for 17 hours to obtain a silica gel powder.
【００３９】AN-MA-VdF-HFP-4粉末２．５ｇ、シリカゲ
ル粉末０．２ｇをEC-DEC-LiOSO2CF3電解液２３ｇに分散
した液をテフロン製の１００ｍｌの密閉容器中で１４０
℃に加熱することで透明な粘性体を得た後、これを、マ
イナス２０℃に冷却しゲル状ポリマー電解質の塊を得
た。この塊を、８０℃に加熱した熱プレスローラで圧延
し、厚さ８０μｍのゲル状ポリマー電解質シート（ＳＰ
Ｅ−D）を得た。得られたシートは強靱で、柔軟性があ
り、引っ張り強度２．２ｋｇ／５ｃｍを有していた。室
温で３０日保存後、電解液の浸みだしはなかった。この
シートを２ｘ２ｃｍに切断し、厚さ２００μｍの金属リ
チウムで挟んで組み立てたセルについて周波数１０ＫＨ
ｚ、振幅１０ｍＶの交流信号を印加して測定した伝導度
を表１にまとめて示す。伝導度値は、セルの組立直後、
セルを２０℃で３ヶ月保存した後も全く変化なく、金属
リチウムとの接触界面は安定していた。A solution obtained by dispersing 2.5 g of the AN-MA-VdF-HFP-4 powder and 0.2 g of the silica gel powder in 23 g of the EC-DEC-LiOSO 2 CF 3 electrolyte solution was placed in a 100 ml Teflon-made closed container.
After obtaining a transparent viscous body by heating to ℃, it was cooled to minus 20 ℃ to obtain a mass of gel polymer electrolyte. This lump is rolled with a hot press roller heated to 80 ° C., and a gel polymer electrolyte sheet (SP
ED) was obtained. The resulting sheet was tough, flexible, and had a tensile strength of 2.2 kg / 5 cm. After storage at room temperature for 30 days, there was no seepage of the electrolyte. This sheet was cut into 2 × 2 cm, and the cell assembled with lithium metal having a thickness of 200 μm was assembled at a frequency of 10 KH.
Table 1 summarizes the conductivity measured by applying an AC signal of z and an amplitude of 10 mV. Conductivity values are measured immediately after cell assembly,
Even after the cell was stored at 20 ° C. for 3 months, there was no change, and the contact interface with metallic lithium was stable.
【００４０】（実施の形態５）実施例１のAN-VAc-VdF-1
粉末２．５ｇ、２００℃で１７時間真空乾燥した平均粒
径３．８μｍのアルミナ粉末０．１５ｇを、実施例１の
EC-EMC-LiPF6電解液２３ｇに分散した液をテフロン製の
１００ｍｌの密閉容器中で１４０℃に加熱することで透
明な粘性体を得た後、これを、マイナス２０℃に冷却し
ゲル状ポリマー電解質の塊を得た。この塊を、８０℃に
加熱した熱プレスローラで圧延し、厚さ８０μｍのゲル
状ポリマー電解質シート（ＳＰＥ−E）を得た。得られ
たシートは強靱で、柔軟性があり、引っ張り強度１．４
ｋｇ／５ｃｍを有していた。室温で３０日保存後、電解
液の浸みだしはなかった。このシートを２ｘ２ｃｍに切
断し、厚さ２００μｍの金属リチウムで挟んで組み立て
たセルについて周波数１０ＫＨｚ、振幅１０ｍＶの交流
信号を印加して測定した伝導度を表１にまとめて示す。
伝導度値は、セルの組立直後、セルを２０℃で３ヶ月保
存した後も全く変化なく、金属リチウムとの接触界面は
安定していた。(Embodiment 5) AN-VAc-VdF-1 of Embodiment 1
2.5 g of powder and 0.15 g of alumina powder having an average particle size of 3.8 μm dried in vacuum at 200 ° C. for 17 hours
A transparent viscous substance was obtained by heating the liquid dispersed in 23 g of the EC-EMC-LiPF 6 electrolyte solution to 140 ° C. in a Teflon-made 100 ml closed container, and then cooled to −20 ° C. to form a gel. A mass of polymer electrolyte was obtained. This lump was rolled with a hot press roller heated to 80 ° C. to obtain a gel polymer electrolyte sheet (SPE-E) having a thickness of 80 μm. The resulting sheet is tough, flexible and has a tensile strength of 1.4.
kg / 5 cm. After storage at room temperature for 30 days, there was no seepage of the electrolyte. Table 1 summarizes the conductivity measured by applying an AC signal having a frequency of 10 KHz and an amplitude of 10 mV to a cell assembled by cutting this sheet into 2 × 2 cm and sandwiching it with lithium metal having a thickness of 200 μm.
The conductivity value did not change at all after the cell was stored at 20 ° C. for 3 months immediately after the cell was assembled, and the contact interface with lithium metal was stable.
【００４１】（実施の形態６）多孔性のシリカゲル粉末
（平均粒径２．８μｍ、比表面積３５０ｍ2／ｇを、蒸
留水５０ｍｌに分散したのち、セチルトリエチルアンモ
ニウムブロマイドを０．７ｍｍｏｌ、過硫酸カリウムを
０．２ｍｌ加え、さらにアクリル酸メチルを３．５ｍｍ
ｏｌ加えた後、６０℃で１７時間重合を行う。沈殿物を
メタノールで洗浄したのち、９０℃で７２時間真空乾燥
して、表面を改質したシリカゲル粉末を得た。(Embodiment 6) A porous silica gel powder (average particle size: 2.8 μm, specific surface area: 350 m 2 / g) was dispersed in 50 ml of distilled water, then 0.7 mmol of cetyltriethylammonium bromide, potassium persulfate Was added, and methyl acrylate was further added to 3.5 mm.
After the addition, polymerization is carried out at 60 ° C. for 17 hours. After the precipitate was washed with methanol, it was vacuum-dried at 90 ° C. for 72 hours to obtain a silica gel powder having a modified surface.
【００４２】実施例２のAN-VAc-VdF-HFP-2粉末２．５
ｇ、表面を改質したシリカゲル粉末０．２ｇを、実施例
２のEC-PC-LiBF4電解液２３ｇに分散した液をテフロン
製の１００ｍｌの密閉容器中で１４０℃に加熱すること
で透明な粘性体を得た後、これを、マイナス２０℃に冷
却しゲル状ポリマー電解質の塊を得た。この塊を、８０
℃に加熱した熱プレスローラで圧延し、厚さ８０μｍの
ゲル状ポリマー電解質シート（ＳＰＥ−Ｆ）を得た。得
られたシートは強靱で、柔軟性があり、引っ張り強度
１．８ｋｇ／ｃｍを有していた。室温で３０日保存後、
電解液の浸みだしはなかった。このシートを２ｘ２ｃｍ
に切断し、厚さ２００μｍの金属リチウムで挟んで組み
立てたセルについて周波数１０ＫＨｚ、振幅１０ｍＶの
交流信号を印加して測定した伝導度を表１にまとめて示
す。伝導度値は、セルの組立直後、セルを２０℃で３ヶ
月保存した後も全く変化なく、金属リチウムとの接触界
面は安定していた。AN-VAc-VdF-HFP-2 powder of Example 2 2.5
g, a surface-modified silica gel powder of 0.2 g was dispersed in 23 g of the EC-PC-LiBF 4 electrolytic solution of Example 2 and heated to 140 ° C. in a Teflon-made 100 ml closed container to obtain a transparent liquid. After obtaining the viscous body, it was cooled to minus 20 ° C. to obtain a mass of a gel polymer electrolyte. This lump is 80
Rolling was performed with a hot press roller heated to ℃ to obtain a gel polymer electrolyte sheet (SPE-F) having a thickness of 80 μm. The resulting sheet was tough, flexible, and had a tensile strength of 1.8 kg / cm. After storage at room temperature for 30 days,
There was no seepage of the electrolyte. This sheet is 2x2cm
Table 1 summarizes the conductivity measured by applying an AC signal having a frequency of 10 KHz and an amplitude of 10 mV to a cell assembled by cutting into 200 μm-thick metallic lithium. The conductivity value did not change at all after the cell was stored at 20 ° C. for 3 months immediately after the cell was assembled, and the contact interface with lithium metal was stable.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【発明の効果】以上のように、本発明に従うゲル状ポリ
マー電解質は、１００μｍ以下の薄膜状にしても自己形
状保持性に富み、高い引っ張り強度を与え、可撓性に優
れ、しかも高い伝導度を与える。さらに、本発明のゲル
状ポリマー電解質は、電極材料と均一に混合することが
でき、可撓性のある薄膜状の、安定した充放電サイクル
特性を与える電極シートを与える。電池、電気二重層キ
ャパシタ、エレクトロクロミック表示素子等の薄形の折
り曲げ可能な電気化学素子に有効に用いることができ
る。As described above, the gel polymer electrolyte according to the present invention is rich in self-shape retention, gives high tensile strength, is excellent in flexibility, and has high conductivity even in the form of a thin film of 100 μm or less. give. Furthermore, the gelled polymer electrolyte of the present invention can be uniformly mixed with the electrode material to provide a flexible thin film electrode sheet that provides stable charge / discharge cycle characteristics. It can be effectively used for a thin, foldable electrochemical device such as a battery, an electric double layer capacitor, and an electrochromic display device.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 53/00 Ｃ０８Ｌ 53/00 Ｈ０１Ｍ 6/18 Ｈ０１Ｍ 6/18 Ｅ 6/22 6/22 Ｃ 10/40 10/40 Ｂ Continued on the front page (51) Int.Cl. 6 Identification code FI C08L 53/00 C08L 53/00 H01M 6/18 H01M 6/18 E 6/22 6/22 C 10/40 10/40 B
Claims (2)
トとアクリロニトリルポリマーセグメントのブロックま
たはグラフト共重合体を主骨格とする熱可塑性エラスト
マーと、（Ｂ）リチウム塩を溶解した非プロトン性有機
溶媒を含有するゲル状ポリマー電解質。1. A thermoplastic elastomer having (A) a vinylidene fluoride polymer segment and an acrylonitrile polymer segment block or graft copolymer as a main skeleton, and (B) an aprotic organic solvent in which a lithium salt is dissolved. Gel-like polymer electrolyte.
トとアクリロニトリルポリマーセグメントのブロックま
たはグラフト共重合体を主骨格とする熱可塑性エラスト
マーと、（Ｂ）リチウム塩を溶解した非プロトン性有機
溶媒と、（Ｃ）電気絶縁性無機物質粉末を含有するゲル
状ポリマー電解質。(2) a thermoplastic elastomer having a main skeleton of a block or graft copolymer of a vinylidene fluoride polymer segment and an acrylonitrile polymer segment, (B) an aprotic organic solvent in which a lithium salt is dissolved, C) A gel polymer electrolyte containing an electrically insulating inorganic substance powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9246369A JPH1180296A (en) | 1997-09-11 | 1997-09-11 | Gel form polymer electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9246369A JPH1180296A (en) | 1997-09-11 | 1997-09-11 | Gel form polymer electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1180296A true JPH1180296A (en) | 1999-03-26 |
Family
ID=17147529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9246369A Pending JPH1180296A (en) | 1997-09-11 | 1997-09-11 | Gel form polymer electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1180296A (en) |
Cited By (10)
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|---|---|---|---|---|
| JP2000090728A (en) * | 1998-09-10 | 2000-03-31 | Korea Advanced Inst Of Sci Technol | Homogenous solid polymer-alloy electrolyte and manufacture thereof, composite electrode using electrolyte, lithium high polymer battery and lithium ion high polymer battery, and manufacture thereof |
| WO2006080259A1 (en) * | 2005-01-27 | 2006-08-03 | Kureha Corporation | Vinylidene fluoride based core-shell type polymer and use thereof in nonaqueous electrochemical device |
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1997
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000090728A (en) * | 1998-09-10 | 2000-03-31 | Korea Advanced Inst Of Sci Technol | Homogenous solid polymer-alloy electrolyte and manufacture thereof, composite electrode using electrolyte, lithium high polymer battery and lithium ion high polymer battery, and manufacture thereof |
| WO2006080259A1 (en) * | 2005-01-27 | 2006-08-03 | Kureha Corporation | Vinylidene fluoride based core-shell type polymer and use thereof in nonaqueous electrochemical device |
| US7851084B2 (en) * | 2005-01-27 | 2010-12-14 | Kureha Corporation | Vinylidene fluoride based core-shell type polymer and use thereof in nonaqueous electrochemical device |
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| JP7133749B1 (en) * | 2021-03-31 | 2022-09-08 | リンテック株式会社 | solid electrolytes and batteries |
| WO2022210774A1 (en) * | 2021-03-31 | 2022-10-06 | リンテック株式会社 | Solid electrolyte and battery |
| CN114597501A (en) * | 2022-03-02 | 2022-06-07 | 中国科学院金属研究所 | Polymer electrolyte, preparation method thereof and application thereof in solid-state lithium battery with wide temperature range and high rate |
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