JP4017091B2 - Polymerizable compound, polymer solid electrolyte using the same, and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having high ion conductivity at a room temperature or low temperature, and superior in the processability, the heavy-current characteristic, and the chemical.electrochemical stability by including a specific carbonate group, a polymer of at least one kind of polymerizable compound having a specific polymerizable functional group, and at least one kind of electrolytic salt. SOLUTION: An electrolyte includes a polymer of at least one kind of polymerizable compounds having a carbonate group represented by a formula I (in the formula, R1 is 1-10C divalent group optionally including a chained, branched or cyclic hetero atom, m is integer of 1-10, and n is integer of 1-1000. When a plurality of R1 exist, they are optionally same or different with each another), and a polymerizable functional group represented by a formula II (in the formula, R2 is a hydrogen atom or a 1-6C alkyl group, and R3 is a divalent group composed of 1-10C chained, branched or cyclic hydrocarbon), and at least one kind of electrolytic salt.

Description

【００１７】
［式中、Ｒ¹は炭素数が１〜１０の鎖状、分岐状または環状の、ヘテロ原子を含 んでいてもよい２価の基を表わし、ｍは１〜１０の整数であり、ｎは１〜1000の整数である。但し、複数存在するＲ¹は、それぞれ同一でもよいし異なってもよ い。］
で示されるカーボネート基と、下記一般式（２）
【化１７】

【００１８】
［式中、Ｒ²は水素原子または炭素数１〜６のアルキル基を表わし、Ｒ³は炭素数１から１０の鎖状、分岐状または環状の炭化水素からなる２価の基を表わす。］で示される重合性官能基とを有する少なくとも一種の重合性化合物の重合体及び少なくとも一種の電解質塩を含む高分子固体電解質。
［２］少なくとも一種の有機溶媒を含む前記［１］に記載の高分子固体電解質。
［３］少なくとも一種の無機酸化物を含む前記［１］または［２］に記載の高分子固体電解質。
［４］電解質塩が、アルカリ金属塩、４級アンモニウム塩及び４級ホスホニウム塩の少なくとも一種から選ばれる前記［１］に記載の高分子固体電解質。
［５］有機溶媒がカーボネート系化合物である前記［２］に記載の高分子固体電解質。
【００１９】
［６］前記［１］乃至［５］のいずれかに記載の高分子固体電解質を用いることを特徴とする電池。
［７］電池の負極として、リチウム、リチウム合金、リチウムイオンを吸蔵放出できる炭素材料、リチウムイオンを吸蔵放出できる無機酸化物、リチウムイオンを吸蔵放出できる無機カルコゲナイド及びリチウムイオンを吸蔵放出できる電導性高分子化合物から選ばれる少なくとも一つの材料を用いることを特徴とする前記［６］に記載のリチウム電池。
［８］イオン伝導性物質を介して分極性電極を配置した電気二重層コンデンサにおいて、イオン伝導性物質が、前記［１］乃至［５］のいずれかに記載の高分子固体電解質であることを特徴とする電気二重層コンデンサ。
【００２０】
［９］一般式（１）
【化１８】

【００２１】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示されるカーボネート基と、下記一般式（２）
【化１９】

【００２２】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示される重合性官能基とを有する少なくとも一種の重合性化合物（Ａ）及び少なくとも一種の電解質塩（Ｂ）を必須成分とし、さらに少なくとも一種の有機溶媒（Ｃ）及び／または少なくとも一種の無機酸化物（Ｄ）を含有していてもよい重合性組成物を支持体上に配置した後、重合性組成物を重合することを特徴とする高分子固体電解質の製造方法。
【００２３】
［１０］一般式（１）
【化２０】

【００２４】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示されるカーボネート基と、下記一般式（２）
【化２１】

【００２５】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示される重合性官能基とを有する少なくとも一種の重合性化合物（Ａ）、及び少なくとも一種の有機溶媒（Ｃ）を必須成分とし、さらに少なくとも一種の無機酸化物（Ｄ）を含有していてもよい重合性組成物を支持体上に配置した後、重合性組成物を重合し、得られた重合物を電解液と接触させることにより電解質塩（Ｂ）を含浸させることを特徴とする高分子固体電解質の製造方法。
【００２６】
［１１］一般式（１）
【化２２】

【００２７】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示されるカーボネート基と、下記一般式（２）
【化２３】

【００２８】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示される重合性官能基とを有する少なくとも一種の重合性化合物、及び少なくとも一種の電解質塩を必須成分とし、さらに少なくとも一種の有機溶媒及び／または少なくとも一種の無機酸化物を含有していてもよい重合性組成物を電池構成用構造体内に入れ、または支持体上に配置した後、重合性組成物を重合することを特徴とする電池の製造方法。
【００２９】
［１２］一般式（１）
【化２４】

【００３０】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示されるカーボネート基と、下記一般式（２）
【化２５】

【００３１】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示される重合性官能基とを有する少なくとも一種の重合性化合物、及び少なくとも一種の有機溶媒を必須成分とし、さらに少なくとも一種の無機酸化物を含有してもよい重合性組成物を電池構成用構造体内に入れ、または支持体上に配置した後、重合性組成物を重合し、得られた重合物を電解液と接触させることにより電解質塩を含浸させることを特徴とする電池の製造方法。
【００３２】
［１３］一般式（１）
【化２６】

【００３３】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示されるカーボネート基と、下記一般式（２）
【化２７】

【００３４】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示される重合性官能基とを有する少なくとも一種の重合性化合物、及び少なくとも一種の電解質塩を必須成分とし、さらに少なくとも一種の有機溶媒及び／または少なくとも一種の無機酸化物を含有してもよい重合性組成物を電気二重層コンデンサ構成用構造体内に入れ、または支持体上に配置した後、重合性組成物を重合することを特徴とする電気二重層コンデンサの製造方法。
【００３５】
［１４］一般式（１）
【化２８】

【００３６】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示されるカーボネート基と、下記一般式（２）
【化２９】

【００３７】
［式中の記号は前記［１］の記載と同じ意味を表わす。］
で示される重合性官能基とを有する少なくとも一種の重合性化合物、及び少なくとも一種の有機溶媒を必須成分とし、さらに少なくとも一種の無機酸化物を含有してもよい重合性組成物を電気二重層コンデンサ構成用構造体内に入れ、または支持体上に配置した後、重合性組成物を重合し、得られた重合物を電解液と接触させることにより電解質塩を含浸させることを特徴とする電気二重層コンデンサの製造方法。
【００３８】
［１５］一般式（３）
【化３０】

［式中、Ｒ¹は、炭素数が１〜１０の鎖状、分岐状または環状の、ヘテロ原子を 含んでいてもよい２価の基を表わし、Ｒ²は水素原子または炭素数１〜６のアル キル基を表わし、Ｒ³は炭素数１から１０の鎖状、分岐状または環状の炭化水素 からなる２価の基を表し、Ｒ⁴は鎖状、分岐状または環状の、ヘテロ原子を含ん でいてもよい有機基を表わし、ｍは１〜１０の整数であり、ｎは２〜1000の整数である。但し、複数存在するＲ¹は、それぞれ同一でもよいし異なってもよい。 ］で示される重合性化合物。
【００３９】
【発明の実施の態様】
以下、本発明を詳細に説明する。
［高分子固体電解質］
本発明の高分子固体電解質は、基本的には主要構成成分である(a)高分子化合 物、及び(b)電解質塩を含んでなる。さらに、(c)有機溶媒、(d)無機酸化物を含 んでもよい。以下、各成分について詳述する。
【００４０】
(a)高分子化合物
本発明の高分子固体電解質の主要構成成分である高分子化合物は非電子伝導性で、各種有機極性溶媒を吸液、保持できるものであり、下記一般式（１）で示されるカーボネート構造を有する架橋及び／または側鎖基が含まれる。
【化３１】

【００４１】
式中、Ｒ¹は炭素数が１〜１０の鎖状、分岐状または環状の、ヘテロ原子を含 んでいてもよい２価の基を表わし、ｍは１〜１０の整数であり、ｎは１〜1000の整数である。但し、複数存在するＲ¹は同一でも異なってもよい。
【００４２】
上記一般式（１）でｍが１０を超えると、高分子化合物中のカーボネート基が少なくなり、誘電率が低下し、電解質塩が解離しにくくなり好ましくない。好ましいｍは１〜５である。
【００４３】
上記一般式でのＲ¹の炭素数が１０を超えると、高分子化合物中のカーボネー ト基が少なくなり、誘電率が低下し、電解質塩が解離しにくくなり好ましくない。また、高分子化合物の疎水性が増加し、各種極性溶媒との相溶性が低下し、好ましくない。好ましいＲ¹の炭素数は１〜４である。
【００４４】
本発明の高分子固体電解質に用いられる高分子中の一般式（１）で示されるカーボネート基の繰り返し数ｎは１〜1000の範囲であり、３〜１００の範囲が好ましく、５〜５０が特に好ましい。
【００４５】
本発明の高分子固体電解質に用いられる高分子としては、一般式（１）で示されるカーボネート基を有し、さらに下記一般式（２）で示される重合性官能基
【化３２】

【００４６】
［式中、Ｒ²は水素原子または炭素数１〜６のアルキル基を表わし、Ｒ³は炭素数１〜１０の鎖状、分岐状または環状の、ヘテロ原子を含んでいてもよい２価の基を表わし、ｘは０または１〜１０の整数である。］を有する少なくとも一種の重合性化合物を重合することによって得られる。
【００４７】
本発明の高分子固体電解質に用いられる重合性分子中には、一般式（１）で示されるカーボネート基及び一般式（２）で示される重合性官能基が複数存在し得るが、この場合同一分子中に存在するＲ¹、Ｒ²、Ｒ³、Ｒ⁴、ｍ及びｎは同一でも異なっていてもよい。
【００４８】
具体的な重合性化合物としては、例えば以下の一般式（３）で示される化合物が挙げられる。
【化３３】

［式中、Ｒ⁴は炭素数１〜２０の鎖状、分岐状または環状の、ヘテロ原子を含ん でいてもよい基を表わし、その他の記号は前記と同じ意味を表わす。］
【００４９】
一般式（１）で示される基と一般式（２）で示される基とを有する重合性化合物を合成する方法に特に制限はないが、例えば、
【化３４】

で示されるビニル化合物のクロロホルメート（ＣＦ）体と末端にヒドロキシル基を有するカーボネートオールとを以下の様に反応させることにより容易に得ることができる。
【００５０】
【化３５】

［式中、Ｒ¹、Ｒ²、Ｒ³、ｍ及びｎは前記と同じ意味を表わす］。
【００５１】
ここで一般式（２）で示される官能基を１つしか有さない化合物を用いる場合には、重合して得られる高分子が架橋構造を有しておらず、膜強度不足のため、薄膜にすると短絡する危険が大きい。従って、その場合には、一般式（２）で示される官能基を２つ以上有する重合性化合物と共重合し、架橋させるか、一般式（２）で示される官能基を２つ以上有する重合性化合物から得られる高分子と併用することが好ましい。
【００５２】
本発明の高分子固体電解質の構成成分として好ましい高分子化合物は、前記重合性化合物の単独重合体であっても、同一カテゴリーに属する２種以上の共重合体であっても、あるいは前記重合性化合物の少なくとも一種と他の重合性化合物との共重合体であってもよい。
【００５３】
前記重合性化合物と共重合可能な他の重合性化合物は、特に制限はないが、例えば、メタクリル酸メチル、アクリル酸ｎ−ブチル等の（メタ）アクリル酸アルキルエステル、各種ウレタン（メタ）アクリレート、オキシアルキレン及び／またはオキシフルオロカーボン鎖を有する（メタ）アクリル酸エステル及び／またはウレタン（メタ）アクリレート、カーボネート鎖を有する（メタ）アクリル酸エステル及び／またはウレタン（メタ）アクリレート、（メタ）アクリル酸フッ素化アルキルエステル、アクリルアミド、メタクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミド、炭酸ビニレン、（メタ）アクリロイルカーボネート、Ｎ−ビニルピロリドン、アクリロイルモルホリン、メタクリロイルモルホリン、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド等の（メタ）アクリルアミド系化合物、スチレン、α−メチルスチレン等のスチレン系化合物、Ｎ−ビニルアセトアミド、Ｎ−ビニルホルムアミド等のＮ−ビニルアミド系化合物、エチルビニルエーテル等のアルキルビニルエーテルを挙げることができる。
【００５４】
これらの中で、好ましいのは（メタ）アクリル酸エステル、ウレタン（メタ）アクリレート、またはオキシアルキレン及び／またはオキシフルオロカーボン鎖を有する（メタ）アクリル酸エステル及び／またはウレタン（メタ）アクリレート、またはカーボネート鎖を有する（メタ）アクリル酸エステル及びウレタン（メタ）アクリレートが用いられる。これらの中で、ウレタン（メタ）アクリレートが重合性という観点で特に好ましい。
【００５５】
また、本発明の高分子固体電解質に用いる高分子化合物としては、前記重合性化合物の少なくとも一種から得られる重合体及び／または前記重合性化合物を共重合成分とする共重合体と、他の高分子化合物との混合物であってもよい。混合する他の高分子化合物としては、例えば、ポリエチレンオキサイド、ポリプロピレンキサイド、ポリアクリロニトリル、ポリカーボネート、ポリウレタン、ポリブタジエン、ポリメタクリル（またはアクリル）酸エステル類、ポリスチレン、ポリホスファゼン類、ポリシロキサンあるいはポリシラン、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等のポリマーが挙げられる。
【００５６】
前記一般式（１）で示されるカーボネート基を有する高分子由来の構造単位の量は、前記重合性化合物を単独重合するか、その他の共重合成分と共重合するか、さらに他の高分子化合物を混合するかにより、あるいはそれらの種類により異なるため、一概にはいえないが、高分子固体電解質に用いたときのイオン伝導度及び膜強度、耐熱性、電流特性を考慮すると、高分子成分全量に対し５０重量％以上含有することが好ましく、さらには７０重量％以上含有することが好ましい。
【００５７】
前記重合性化合物の重合は、官能基であるビニル基の重合性を利用した一般的な方法により行なうことができる。すなわち、前記重合性化合物単独、あるいは重合性化合物と他の前記共重合可能な重合性化合物の混合物に、アゾビスイソブチロニトリル、ベンゾイルパーオキサイド等のラジカル重合触媒、ＣＦ₃ＣＯＯ Ｈ等のプロトン酸、ＢＦ₃、ＡｌＣｌ₃等のルイス酸等のカチオン重合触媒、あるいはブチルリチウム、ナトリウムナフタレン、リチウムアルコキシド等のアニオン重合触媒を用いて、ラジカル重合、カチオン重合あるいはアニオン重合させることができる。また、重合性化合物または重合性混合物は膜状等の形に成形後、重合させることも可能である。
【００５８】
(b)電解質塩
本発明で用いる電解質塩の種類は特に限定されるものではなく、電荷でキャリアーとしたいイオンを含んだ電解質塩を用いればよいが、高分子固体電解質中での解離定数が大きいことが望ましく、ＬｉＣＦ₃ＳＯ₃、ＬｉＮ（ＣＦ₃ＳＯ₂₂、 ＬｉＮ（ＣＦ₃ＣＦ₂ＳＯ₂）₂、ＬｉＰＦ₆、ＬｉＣｌＯ₄、ＬｉＩ、ＬｉＢＦ₄、 ＬｉＳＣＮ、ＬｉＡｓＦ₆、ＮａＣＦ₃ＳＯ₃、ＮａＰＦ₆、ＮａＣｌＯ₄、ＮａＩ 、ＮａＢＦ₄、ＮａＡｓＦ₆、ＫＣＦ₃ＳＯ₃、ＫＰＦ₆、ＫＩ等のアルカリ金属塩 、（ＣＨ₃）₄ＢＦ₄等の４級アンモニウム塩、（ＣＨ₃）₄ＰＢＦ₄等の４級ホスホニウム塩、ＡｇＣｌＯ₄等の遷移金属塩、あるいは塩酸、過塩素酸、ホウフッ化 水素酸等のプロトン酸が好ましい。
【００５９】
本発明の高分子固体電解質中の電解質塩は複合して用いることができ、その複合比は、高分子の重量に対し、0.1〜５０重量％が好ましく、１〜３０重量％が 特に好ましい。複合に用いる電解質塩が５０重量％以上の比率で存在すると、イオンの移動が大きく阻害され、逆に0.1重量％以下の比率では、イオンの絶対量 が不足となってイオン伝導度が小さくなる。
【００６０】
(c)有機溶媒
本発明の高分子固体電解質中に有機溶媒を添加すると、高分子固体電解質のイオン伝導度がさらに向上するので好ましい。使用できる有機溶媒としては、本発明の高分子固体電解質に用いる一般式（１）で示される有機基を有する化合物との相溶性が良好で、誘電率が大きく、沸点が６０℃以上であり、電気化学的安定範囲が広い化合物が適している。
【００６１】
そのような溶媒としては、１，２−ジメトキシエタン、２−メチルテトラヒドロフラン、クラウンエーテル、トリエチレングリコールメチルエーテル、テトラエチレングリコールジメチルエーテル等のエーテル類、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート等のカーボネート類、ベンゾニトリル、トルニトリル等の芳香族ニトリル類、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン、Ｎ−ビニルピロリドン、スルホラン等の硫黄化合物、リン酸エステル類等が挙げられる。これらの中で、エーテル類及びカーボネート類が好ましく、カーボネート類が特に好ましい。
【００６２】
有機溶媒の添加量は、多いほど高分子固体電解質のイオン伝導度が向上する。このため、一般的にはその添加量を増やすことが望ましいが、反面、添加量が多過ぎると高分子固体電解質の機械的強度が低下する。好ましい添加量としては、本発明の高分子固体電解質に用いる高分子重量の２倍から１５倍量で、３倍から１０倍量以下が特に好ましい。
【００６３】
(d)無機酸化物
本発明の高分子固体電解質には各種無機酸化物を添加することが好ましい。無機酸化物の添加により、強度、膜厚均一性が改善するばかりでなく、無機酸化物と高分子間に微細な空孔が生じることになり、電解液中に浸漬した場合には空孔を通じて高分子固体電解質内にフリーの電解液が分散し、強度の改善効果を損ねることなく、イオン伝導度、イオン移動度を増加させることもできる。また、無機酸化物を添加することにより、重合性組成物の粘度が上昇し、高分子と溶媒の相溶性が不十分な場合にもその分離を抑える効果も現われる。
【００６４】
使用する無機酸化物としては非電子伝導性であり、かつ電気化学的に安定なものが選ばれる。また、イオン伝導性であればさらに好ましい。具体的にはα、β、γ−アルミナ、シリカ、チタニア、マグネシア、ハイドロタルサイト等のイオン伝導性または非電導性セラミックス微粒子が挙げられる。
高分子固体電解質中の電解液の保有量を多くし、イオン伝導性、移動度を増加させるという目的では、無機酸化物の比表面積はできるだけ大きいことが好ましく、ＢＥＴ法で１０ｍ²／ｇ以上、さらには５０ｍ²／ｇ以上が好ましい。
【００６５】
このような無機酸化物の結晶粒子径としては、重合性組成物と混合できれば特に限定はないが、平均粒径として0.001μｍ〜１０μｍが好ましく、0.01μｍ〜 １μｍが特に好ましい。
また、形状としては球形、卵形、立方体状、直方体状、円筒ないし棒状等の種々の形状のものを用いることができる。
無機酸化物の添加量は多すぎると高分子固体電解質の強度やイオン伝導性を低下させたり、成膜がしにくくなるという問題を生じる。好ましい添加量としては、高分子固体電解質に対して５０重量％以下であり、0.1から３０重量％の範囲 が特に好ましい。
【００６６】
［高分子固体電解質の製造方法］
本発明の高分子固体電解質は、前記重合性化合物の少なくとも一種から得られる重合体、あるいは前記重合性化合物を共重合成分とする共重合体を、例えばフィルム状に形成した後重合し、有機溶媒に溶解した電解質塩と接触させることにより製造するか、または前記重合性化合物とその他の成分とからなる重合性組成物を調製し、例えばフィルム状に形成した後、重合することにより製造することができる。
【００６７】
後者の方法を具体的に示せば、前記重合性化合物の少なくとも一種とアルカリ金属塩、４級アンモニウム塩、４級ホスホニウム塩または遷移金属塩のごとき少なくとも一種の電解質塩とを混合し、所望により、他の重合性化合物、可塑剤、有機溶媒及び／または無機酸化物を添加混合した重合性組成物を調製した後、フィルム状等に成形して、前記触媒の存在下あるいは非存在下に、加熱及び／または活性光線の照射により重合させ、本発明の高分子固体電解質を得る。この方法によれば、加工面での自由度が広がり、応用上の大きなメリットとなる。
【００６８】
重合時に溶媒を用いる場合の溶媒は、重合性化合物の種類や重合触媒の有無にもよるが、重合を阻害しなければいかなる溶媒でも良く、例えば、テトラヒドロフラン、アセトニトリル、トルエン等を用いることができる。
重合させる温度としては、前記重合性化合物の種類によるが、重合が起こる温度であれば良く、通常は、０℃から２００℃の範囲で行なえばよい。
活性光線照射により重合させる場合には、前記重合性化合物の種類によるが、例えば、ベンジルメチルケタール、ベンゾフェノン等の開始剤を使用して、数ｍＷ以上の紫外光またはγ線、電子線等を照射して重合させることができる。
【００６９】
また、本発明の高分子固体電解質を薄膜フィルムとして使用する場合、フィルム強度を向上させるために、他の多孔性フィルムとの複合フィルムとすることもできる。ただし、複合するフィルムの種類あるいは量によっては伝導度の低下や安定性の悪化を招くので、適したものを選ぶ必要がある。使用するフィルムとしては、ポリプロピレン製不織布やポリエチレン製ネットのような網状ポリオレフィンシート等の多孔性ポリオレフィンシート、セルガード（商品名）等のポリオレフィン製マイクロポーラスフィルム、ナイロン不織布等が挙げられ、中でも多孔性ポリオレフィンフィルムが好ましい。また、その空孔率としては、１０〜９５％程度あればよいが、強度の許す限りできるだけ空孔率の大きいものが良く、好ましい空孔率は４０〜９５％の範囲である。
【００７０】
複合方法には特に制限がないが、例えば、前記重合性化合物の少なくとも一種、またはこれに少なくとも一種の電解質塩、場合によっては、さらに他の成分を添加混合してなる重合性組成物を多孔性ポリマーフィルムに含浸後、（メタ）アクリロイル系化合物を重合することにより、均一に複合でき、膜厚の制御も簡便である。
【００７１】
［電池及びその製造方法］
本発明の電池として、薄膜固体二次電池の一例の概略断面図を図１に示す。図中、１は正極、２は高分子固体電解質、３は負極、４ａ、４ｂは集電体、５ａ、５ｂは絶縁性樹脂封止剤である。
本発明の電池の構成において、正極１に金属酸化物、金属硫化物、導電性高分子あるいは炭素材料のような高酸化還元電位の電極活物質（正極活物質）を用いることにより、高電圧、高容量の電池が得られるので好ましい。このような電極活物質の中では、充填密度が高く体積容量密度が高くなるという点で、酸化コバルト、酸化マンガン、酸化バナジウム、酸化ニッケル、酸化モリブデン等の金属酸化物、硫化モリブデン、硫化チタン、硫化バナジウム等の金属硫化物が好ましく、特に酸化マンガン、酸化ニッケル、酸化コバルト等が高容量、高電圧という点から好ましい。
【００７２】
この場合の金属酸化物や金属硫化物を製造する方法は特に限定されず、例えば、電気化学，第２２巻，５７４頁（1954年）に記載されているような、一般的な電解法や加熱法によって製造される。また、これらを電極活物質としてリチウム電池に使用する場合、電池の製造時に、例えば、Ｌｉ_xＣｏＯ₂やＬｉ_xＭｎＯ₂の形でリチウム元素を金属酸化物あるいは金属硫化物に挿入（複合）した状態で用いることが好ましい。リチウム元素を挿入する方法は特に限定されず、例えば、電気化学的にリチウムイオンを挿入する方法や、米国特許第4357215号に記載さ れているように、Ｌｉ₂ＣＯ₃の塩と金属酸化物を混合、加熱処理することによって実施できる。
【００７３】
また柔軟で、薄膜化しやすいという点では、導電性高分子が好ましい。導電性高分子の例としては、ポリアニリン、ポリアセチレン及びその誘導体、ポリパラフェニレン及びその誘導体、ポリピロール及びその誘導体、ポリチエニレン及びその誘導体、ポリピリジンジイル及びその誘導体、ポリイソチアナフテニレン及びその誘導体、ポリフリレン及びその誘導体、ポリセレノフェン及びその誘導体、ポリパラフェニレンビニレン、ポリチエニレンビニレン、ポリフリレンビニレン、ポリナフテニレンビニレン、ポリセレノフェンビニレン、ポリピリジンジイルビニレン等のポリアリーレンビニレン及びそれらの誘導体等が挙げられる。中でも有機溶媒に可溶性のアニリン誘導体の重合体が特に好ましい。これらの電池あるいは電極において電極活物質として用いられる導電性高分子は、後述のような化学的あるいは電気化学的方法、あるいはその他の公知の方法に従って製造される。
【００７４】
また、炭素材料としては、天然黒鉛、人造黒鉛、気相法黒鉛、石油コークス、石炭コークス、フッ化黒鉛、ピッチ系炭素、ポリアセン等が挙げられる。
本発明の電池の負極３に用いる負極活物質としては、アルカリ金属、アルカリ金属合金、炭素材料、金属酸化物や導電性高分子化合物のようなアルカリ金属イオンをキャリアーとする低酸化還元電位のものを用いることにより、高電圧、高容量の電池が得られるので好ましい。このような負極活物質の中では、リチウム金属あるいはリチウム／アルミニウム合金、リチウム／鉛合金、リチウム／アンチモン合金等のリチウム合金類が最も酸化還元電位が低く、かつ薄膜化が可能である点から特に好ましい。また炭素材料もリチウムイオンを吸蔵した場合、低酸化還元電位となり、しかも安定、安全であるという点で特に好ましい。リチウムイオンを吸蔵放出できる炭素材料としては、天然黒鉛、人造黒鉛、気相法黒鉛、石油コークス、石炭コークス、ピッチ系炭素、ポリアセン、Ｃ₆₀、Ｃ₇₀等のフラーレン類等が挙げられられる。
【００７５】
上記負極活物質を用い、アルカリ金属イオンをキャリアーとする電池に用いる場合、高分子固体電解質中の電解質塩としてはアルカリ金属塩を使用する。アルカリ金属塩としては例えば、ＬｉＣＦ₃ＳＯ₃、ＬｉＰＦ₆、ＬｉＣｌＯ₄、ＬｉＢＦ₄、ＬｉＳＣＮ、ＬｉＡｓＦ₆、ＬｉＮ（ＣＦ₃ＳＯ₂）₂、ＮａＣＦ₃ＳＯ₃、Ｌ ｉＮ（ＣＦ₃ＣＦ₂ＳＯ₂）₂、ＬｉＩ、ＮａＰＦ₆、ＮａＣｌＯ₄、ＮａＩ、ＮａＢＦ₄、ＮａＡｓＦ₆、ＫＣＦ₃ＳＯ₃、ＫＰＦ₆、ＫＩ等を挙げることができる。
【００７６】
本発明の電極及び電池の製造方法の一例について説明する。
正負極をお互いに接触しないように電池構成用構造体内に入れ、または支持体上に配置する。例えば、電極の端に適当な厚みのスペーサーまたは予め調製しておいた高分子固体電解質フィルムを介して正極と負極をはり合せて、前記構造体内に入れ、次に、正極と負極の間に、重合性化合物の少なくとも一種、またはこれに少なくとも一種の電解質塩、場合によっては、さらに他の重合性化合物及び／または可塑剤及び／または溶媒及び／または無機酸化物を添加混合した重合性組成物を注入した後、例えば、加熱及び／または活性光線照射により重合することにより、あるいは、さらに、重合後必要に応じてポリオレフィン樹脂、エポキシ樹脂等の絶縁性樹脂で封止することにより、電極と電解質が良好に接触した電池が得られる。
【００７７】
また、これ以外にも、重合性化合物の少なくとも一種及び溶媒、またはこれに他の重合性化合物及び／または可塑剤及び／または無機酸化物を添加混合した重合性組成物を重合して得られた重合物を介して正極と負極を貼り合わせて、予め電極に含浸させておいた電解液から電解質塩の一部を重合物に移行させることにより電池を製造することも可能である。
なお、前記電池構成用構造体あるいは前記支持体はＳＵＳ等の金属、ポリプロピレン、ポリイミド等の樹脂、あるいは導電性あるいは絶縁性ガラス等のセラミックス材料であればよいが、特にこれらの材料からなるものに限定されない。また、その形状は筒状、箱状、シート状その他いかなる形状でもよい。
【００７８】
捲回型電池を製造する場合は、予め調製しておいた高分子固体電解質フィルムを介して、上記正極及び負極をはりあわせ、捲回し、電池構成用構造体内に挿入後に更に前記重合性組成物を注入し、重合させるという方法も可能である。
【００７９】
［電気二重層コンデンサ及びその製造方法］
次に本発明の電気二重層コンデンサについて説明する。
本発明によれば、前記高分子固体電解質を用いることにより、出力電圧が高く、取り出し電流が大きく、また加工性、信頼性に優れた電気二重層コンデンサが提供される。
本発明の電気二重層コンデンサの一例の概略断面図を図２に示す。この例は、大きさ約１ｃｍ×１ｃｍ、厚み約0.5ｍｍの薄型セルで、７ａ、７ｂは集電体で あり、集電体の内側には一対の分極性電極６ａ、６ｂが配置されており、その間に高分子固体電解質膜８が配置されている。９は絶縁性樹脂封止剤、１０はリード線である。
【００８０】
集電体７ａ、７ｂは電子伝導性で電気化学的に耐食性があり、できるだけ比表面積の大きい材料を用いることが好ましい。例えば、各種金属及びその焼結体、電子伝導性高分子、カーボンシート等を挙げることができる。
分極性電極６ａ、６ｂは、通常電気二重層コンデンサに用いられる炭素材料等の分極性材料からなる電極であればよい。分極性材料としての炭素材料としては、比表面積が大きければ特に制限はないが、比表面積の大きいほど電気二重層の容量が大きくなり好ましい。例えば、ファーネスブラック、サーマルブラック（アセチレンブラックを含む）、チャンネルブラック等のカーボンブラック類や、椰子がら炭等の活性炭、天然黒鉛、人造黒鉛、気相法で製造したいわゆる熱分解黒鉛、ポリアセン及びＣ₆₀、Ｃ₇₀を挙げることができる。
【００８１】
本発明の電気二重層コンデンサの場合に複合に用いる電解質塩の種類は特に限定されるものではなく、電荷キャリアーとしたいイオンを含んだ化合物を用いればよいが、高分子固体電解質中での解離定数が大きく、分極性電極と電気二重層を形成しやすいイオンを含むことが望ましい。このような化合物としては、（ＣＨ₃）₄ＮＢＦ₄、（ＣＨ₃ＣＨ₂）₄ＮＣｌＯ₄等の４級アンモニウム塩、ピリジニ ウム塩、ＡｇＣｌＯ₄等の遷移金属塩、（ＣＨ₃）₄ＰＢＦ₄等の４級ホスホニウム塩、ＬｉＣＦ₃ＳＯ₃、ＬｉＰＦ₆、ＬｉＣｌＯ₄、ＬｉＩ、ＬｉＢＦ₄、ＬｉＳＣ Ｎ、ＬｉＡｓＦ₆、ＬｉＮ（ＣＦ₃ＳＯ₂）₂、ＬｉＮ（ＣＦ₃ＣＦ₂ＳＯ₂）₂、ＮａＣＦ₃ＳＯ₃、ＮａＰＦ₆、ＮａＣｌＯ₄、ＮａＩ、ＮａＢＦ₄、ＮａＡｓＦ₆、ＫＣＦ₃ＳＯ₃、ＫＰＦ₆、ＫＩ等のアルカリ金属塩、パラトルエンスルホン酸等の有 機酸及びその塩、塩酸、硫酸等の無機酸等が挙げられる。これらの中で、出力電圧が高く取れ、解離定数が大きいという点から、４級アンモニウム塩、ピリジニウム塩、４級ホスホニウム塩、アルカリ金属塩が好ましい。４級アンモニウム塩の中では、（ＣＨ₃ＣＨ₂）（ＣＨ₃ＣＨ₂ＣＨ₂ＣＨ₂）₃ＮＢＦ₄のような、アンモニウムイオンの窒素上の置換基が異なっているものが、高分子固体電解質への溶解性あるいは解離定数が大きいという点から好ましい。
【００８２】
次に本発明の電気二重層コンデンサの製造方法の一例について説明する。
分極性電極２枚をお互いに接触しないようにコンデンサ構成用構造体内に入れ、または支持体上に配置する。例えば、電極の端に適当な厚みのスペーサーまたは予め調製しておいた高分子固体電解質フィルムを介して分極性電極をはり合せて、前記構造体内に入れ、前記重合性化合物の少なくとも一種、またはこれに少なくとも一種の電解質塩、場合によっては、さらに他の重合性化合物及び／または可塑剤及び／または溶媒及び／または無機酸化物を添加混合した重合性組成物を注入した後、重合することにより、あるいは、さらに、重合後必要に応じてポリオレフィン樹脂、エポキシ樹脂等の絶縁性樹脂で封止することにより、電極と電解質が良好に接触した電気二重層コンデンサが得られる。本法により、特に薄型電気二重層コンデンサを製造することができる。
【００８３】
また、これ以外にも、重合性化合物の少なくとも一種及び溶媒、またはこれに他の重合性化合物及び／または可塑剤及び／または無機酸化物を添加混合した重合性組成物を重合して得られた重合物を介して２枚の分極性電極を貼り合わせて、予め分極性電極に含浸させておいた電解液から電解質塩の一部を重合物に移行させることにより電気二重層コンデンサを製造することも可能である。
【００８４】
なお、前記コンデンサ構成用構造体あるいは前記支持体は、ＳＵＳ等の金属、ポリプロピレン、ポリイミド等の樹脂、あるいは導電性あるいは絶縁性ガラス等のセラミックス材料であればよいが、特にこれらの材料からなるものに限定されるものではなく、また、その形状は、筒状、箱状、シート状その他いかなる形状でもよい。
【００８５】
電気二重層コンデンサの形状としては、図２のようなシート型のほかに、コイン型、あるいは分極性電極及び高分子固体電解質のシート状積層体を円筒状に捲回し、円筒管状のコンデンサ構成用構造体に入れ、封止して製造された円筒型等であっても良い。
捲回型コンデンサを製造する場合は、あらかじめ調製しておいた高分子固体電解質フィルムを介して、上記分極性電極をはりあわせ、捲回し、コンデンサ構成用構造体内に挿入後に更に前記重合性組成物を注入し、重合させるという方法も可能である。
【００８６】
【実施例】
以下に本発明について代表的な例を示しさらに具体的に説明する。なお、これらは説明のための単なる例示であって、本発明はこれらに何等制限されるものではない。
【００８７】
実施例１：化合物１、２及び３の合成
【化３６】

【００８８】
上記反応式（ａ）、（ｂ）及び（ｃ）に従い、常法で各種アルキレングリコールに窒素下、１０℃以下で過剰のホスゲンガスを吹き込み、約５時間反応させ、各種アルキレングリコールのビスクロロホルメート体である化合物１、化合物２、化合物３を合成した。これらの同定はＧＣ−ＭＳで行なった。
【００８９】
実施例２：化合物１、２、３のオリゴマー化（化合物４、５、６の合成）
【化３７】

【００９０】
上記反応式（ｄ）、（ｅ）及び（ｆ）に従い、常法で実施例１で合成した各種アルキレングリコールビスクロロホルメート体（化合物１、２、３）と各種アルキレングリコールとを、ピリジン存在下、２５℃以下、ジクロロメタン中で約６時間反応させた後、過剰の水を加え、残クロロホルメート末端を水酸基化し、両末端に水酸基を有するオリゴカーボネート（化合物４、化合物５、化合物６）を合成した。
【００９１】
ＧＰＣ分析により求めた、各オリゴカーボネートの重量平均分子量（Ｍｗ）、繰り返し数ｘ、ｙ、ｚの平均は以下の通りであった。
化合物４：Ｍｗ 〜約８００、ｘ：〜約８、
化合物５：Ｍｗ 〜約1500、 ｙ：〜約１０、
化合物６：Ｍｗ 〜約1200、 ｚ：〜約１０。
【００９２】
実施例３：化合物７の合成
【化３８】

【００９３】
常法により、上記反応式（ｇ）に従い実施例２で合成したカーボネートオリゴマー（化合物４）の無水ＴＨＦ溶液中に当モルのエチルクロロホルメートを、ピリジン存在下、２５℃以下、徐々に滴下後、約６時間反応させることにより、片末端を水酸基化したオリゴカーボネート（化合物７）を合成した。
【００９４】
実施例４：重合性化合物８の合成
【化３９】

【００９５】
化合物４（平均分子量８００）（40.0ｇ）及びＡＣＦ（アリルクロロホルメート）（13.7ｇ）を窒素雰囲気中でよく精製したジクロロメタン２００ｍｌに溶解した後、２５℃以下に冷却しながら、８ｇのピリジンを徐々に加えた。その後、２５℃で約３時間反応させ、常法により、ピリジン及びその塩酸塩を除去し、精製することにより、無色生成物を得た。その¹Ｈ−ＮＭＲ、ＩＲ及び元素分析の 結果から、化合物４とＡＣＦは１対２で反応し、化合物８が生成していることがわかった。
【００９６】
実施例５：重合性化合物９の合成
【化４０】

【００９７】
化合物５（平均分子量1500）（75.0ｇ）及びＡＣＦ（13.75ｇ）を窒素雰囲気 中でよく精製したジクロロメタン２００ｍｌに溶解した後、２５℃以下に冷却しながら、８ｇのピリジンを徐々に加えた。その後、２５℃で約３時間反応させ、常法により、ピリジン及びその塩酸塩を除去し、精製することにより、無色生成物を得た。その¹Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、化合物５とＡＣＦ は１対２で反応し、化合物９が生成していることがわかった。
【００９８】
実施例６：重合性化合物１０の合成
【化４１】

【００９９】
化合物６（平均分子量1200）（60.0ｇ）及びＡＣＦ（13.75ｇ）を窒素雰囲気 中でよく精製したジクロロメタン２００ｍｌに溶解した後、２５℃以下に冷却しながら、８ｇのピリジンを徐々に加えた。その後、２５℃で約３時間反応させ、常法により、ピリジン及びその塩酸塩を除去し、精製することにより、無色生成物を得た。その¹Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、化合物６とＡＣＦ は１対２で反応し、化合物１０が生成していることがわかった。
【０１００】
実施例７：重合性化合物１１の合成
【化４２】

【０１０１】
化合物７（平均分子量９００）（90.0ｇ）及びＡＣＦ（13.75ｇ）を窒素雰囲 気中でよく精製したジクロロメタン２００ｍｌに溶解した後、２５℃以下に冷却しながら、８ｇのピリジンを徐々に加えた。その後、２５℃で約３時間反応させ、常法により、ピリジン及びその塩酸塩を除去し、精製することにより、無色生成物を得た。その¹Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、化合物７とＡＣ Ｆは１対１で反応し、化合物１１が生成していることがわかった。
【０１０２】
実施例８：高分子固体電解質膜の製造（化合物８）
化合物８（2.0ｇ）、エチレンカーボネート（ＥＣ）（1.8ｇ）、ジエチルカーボネート（ＤＥＣ）（4.2ｇ）、ＬｉＰＦ₆（橋本化成製電池グレード）（0.60ｇ）、及び２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド（商品名，ルシリンＴＰＯ、ＢＡＳＦ社製）（0.050ｇ）をアルゴン雰囲気中でよ く混合し、光重合性組成物を得た。この組成物の含水量（カールフィッシャー）は３０ｐｐｍであった。この光重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ケミカル蛍光ランプ（三共電気社製，FL20S.BL）を１０分照射したところ、ＥＣ／ＤＥＣ系電解液を含浸した重合体（化合物８）フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、2.0×10^-3、0.5×10^-3Ｓ／ｃｍであった。
【０１０３】
実施例９：高分子固体電解質膜の製造（化合物９）
化合物８の代わりに、化合物９（2.0ｇ）を用いた以外は実施例８と同様にし て、ＥＣ／ＤＥＣ系電解液を含浸した重合体（化合物９）フィルムを約３０μｍの自立フィルムとして得た。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、1.8×10^-3、0.4×10^-3Ｓ／ｃｍであった。
【０１０４】
実施例１０：高分子固体電解質膜の製造（化合物１０）
化合物８の代わりに、化合物１０（2.0ｇ）を用いた以外は実施例８と同様に して、ＥＣ／ＤＥＣ系電解液を含浸した重合体（化合物１０）フィルムを約３０μｍの自立フィルムとして得た。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、2.2×10^-3、0.7×10^-3Ｓ／ｃｍであった。
【０１０５】
実施例１１：高分子固体電解質膜の製造（化合物９＋化合物１１）
化合物８の代わりに、化合物９（1.0ｇ）と化合物１１（1.0ｇ）との混合物を用いた以外は実施例８と同様にして、ＥＣ／ＤＥＣ系電解液を含浸した共重合体（化合物９＋化合物１１）フィルムを約３０μｍの自立フィルムとして得た。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、2.5×10^-3、0.8×10^-3Ｓ／ｃｍであった。
【０１０６】
実施例１２：高分子固体電解質複合膜の製造（化合物８＋化合物１０）
化合物８（0.5ｇ）、化合物１０（0.5ｇ）、1000℃熱処理したアルミニウムオキサイドＣ（日本アエロジル製，結晶粒子径0.013μｍ，平均二次粒子径約0.1μｍ（ＳＥＭ観察），ＢＥＴ比表面積１００ｍ²／ｇ）（0.33ｇ）、ＥＣ（1.8ｇ）、ＤＥＣ（4.2ｇ）、ＬｉＰＦ₆（橋本化成製電池グレード）（0.60ｇ）、及びルシリンＴＰＯ（ＢＡＳＦ社製）（0.050ｇ）をアルゴン雰囲気中でよく混合し、 光重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は３５ｐｐｍであった。
この光重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ケミカル蛍光ランプ（三共電気社製 FL20S.BL）を１０分照射したところ、ＥＣ／ＤＥ Ｃ電解液を含浸した共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、4.0×10^-3、1.0×10^-3Ｓ／ｃｍであった。
【０１０７】
実施例１３：高分子固体電解質膜の製造（化合物８＋化合物１０）
開始剤としてルシリンＴＰＯ（0.050ｇ）の代りに、パーヘキシルＰＶ（日本 油脂製）（0.040ｇ）を添加し、アルミニウムオキサイドＣを用いない以外は実 施例１２と同様にして、熱重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は３５ｐｐｍであった。
この熱重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ＰＰフィルムを被覆して、ホットプレート上で７０℃、３時間加熱したところ、ＥＣ／ＤＥＣ系電解液を含浸した共重合体（化合物８＋化合物１０）フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、3.6×10^-3、0.810^-3Ｓ／ｃｍであった。
【０１０８】
実施例１４：高分子固体電解質複合膜の製造（化合物９）
化合物８、１０の代わりに、化合物９（1.0ｇ）を用いた以外は実施例１２と 同様にして、ＥＣ／ＤＥＣ系電解液を含浸した重合体（化合物９）／アルミニウムオキサイドＣ複合フィルムを約３０μｍの自立フィルムとして得た。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、4.6×10^-3、1.2×10^-3Ｓ／ｃｍであった。
【０１０９】
実施例１５：高分子固体電解質複合膜の製造（化合物８＋化合物１０）
ＬｉＰＦ₆に代えて橋本化成製電池グレードＬｉＢＦ₄（0.50ｇ）を用いた以外は実施例１２と同様にして、光重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は５０ｐｐｍであった。
この光重合性組成物を実施例１２と同様にＰＥＴフィルム上に塗布及び光照射し、ＥＣ／ＤＥＣ電解液を含浸した共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルムを約３０μｍの自立フィルムとして得た。この固体電解質の２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、2.0×10^-3、0.6×10^-3Ｓ／ｃｍであった。
【０１１０】
実施例１６：高分子固体電解質複合膜の製造（化合物８＋化合物１０）
ＤＥＣ4.2ｇの代わりに、エチルメチルカーボネート（ＥＭＣ）4.2ｇを用いた以外は、実施例１２と同様にして光重合性組成物を得た。この組成物の含水量（カールフィッシャー）は３５ｐｐｍであった。
この光重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ケミカル蛍光ランプを１０分照射したところ、ＥＣ／ＥＭＣ系電解液を含浸した共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、4.3×10^-3、0.810^-3Ｓ／ｃｍであった。
【０１１１】
実施例１７：高分子固体電解質複合膜の製造（化合物８＋化合物１０）
アルミニウムオキサイドＣの代わりに、５００℃熱処理したハイドロタルサイト（ＫＷ2200，協和化学製，平均粒子径約0.1μｍ（ＳＥＭ観察），ＢＥＴ比表 面積１００ｍ²／ｇ）（0.33ｇ）を用いた以外は、実施例１２と同様にして光重 合性組成物を得た。この組成物の含水量（カールフィッシャー）は５０ｐｐｍであった。
この光重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ケミカル蛍光ランプを１０分照射したところ、ＥＣ／ＤＥＣ系電解液を含浸した共重合体（化合物８＋化合物１０）／ＫＷ2200複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、3.6×10^-3、0.7×10^-3Ｓ／ｃｍであった。
【０１１２】
実施例１８：高分子固体電解質複合膜の製造（化合物８＋化合物１０）
ＬｉＰＦ₆に代えて橋本化成製高純度テトラエチルアンモニウムテトラフルオ ロボレート（ＴＥＡＢ）（1.00ｇ）、溶媒としてＥＣ／ＤＥＣに代えてプロピレンカーボネート（6.0ｇ）を用いた以外は実施例１２と同様にして、光重合性組 成物を得た。この組成物の含水量（カールフィッシャー法）は１００ｐｐｍであった。
この光重合性組成物を実施例１２と同様に塗布及び光照射し、ＰＣ系電解液を含浸した共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルムを約３０μｍの自立フィルムとして得た。この固体電解質の２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、9.0×10^-3、1.5×10^-3Ｓ／ｃｍであった。
【０１１３】
実施例１９：高分子固体電解質膜の製造（化合物８＋化合物１０）
開始剤としてルシリンＴＰＯ（0.050g）の代りに、パーヘキシルＰＶ（日本油脂製）（0.040ｇ）を添加し、アルミニウムオキサイドＣを用いない以外は実施 例１８と同様にして、熱重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は１２０ｐｐｍであった。
この熱重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ＰＰフィルムを被覆して、ホットプレート上で８０℃、１時間加熱したところ、ＰＣ系電解液を含浸した共重合体（化合物８＋化合物１０）フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、8.5×10^-3、1.4×10^-3Ｓ／ｃｍであった。
【０１１４】
実施例２０：高分子固体電解質複合膜の製造（化合物８＋化合物１０）
ＬｉＰＦ₆を使用しない以外は実施例１２と同様にして、塩未添加光重合性組 成物を得た。この組成物の含水量（カールフィッシャー法）は１０ｐｐｍであった。
この光重合性組成物を実施例１２と同様に塗布及び光照射し、ＥＣ＋ＤＥＣ系溶媒を含浸した塩未添加の共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルムを約３０μｍの自立フィルムとして得た。このフィルムを1.2Ｍ ＬｉＰＦ₆／ＥＣ＋ＤＥＣ（重量比３：７）電解液中に約１時間浸漬することにより、フィルム中にＬｉＰＦ₆塩を後添加した。この塩後添加高分子固 体電解質フィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、4.3×10^-3、1.2×10^-3Ｓ／ｃｍであった。
【０１１５】
実施例２１：コバルト酸リチウム正極の製造
１１ｇのＬｉ₂ＣＯ₃と２４ｇのＣｏ₃Ｏ₄を良く混合し、酸素雰囲気下、８００℃で２４時間加熱後、粉砕することによりＬｉＣｏＯ₂粉末を得た。このＬｉＣ ｏＯ₂粉末とアセチレンブラック、ポリフッ化ビニリデンを重量比８：１：１で 混合し、さらに過剰のＮ−メチルピロリドン溶液を加え、ゲル状組成物を得た。この組成物を約２５μｍのアルミ箔上に１０ｍｍ×１０ｍｍ、約１８０μｍの厚さに塗布成型した。さらに、約１００℃で２４時間加熱真空乾燥することにより、コバルト酸リチウム正極（７５ｍｇ）を得た。
【０１１６】
実施例２２：黒鉛負極の製造
ＭＣＭＢ黒鉛（大阪ガス製）、気相法黒鉛繊維（昭和電工（株）製：平均繊維径、0.3μｍ、平均繊維長、2.0μｍ、2700℃熱処理品）、ポリフッ化ビニリデンの重量比8.6：0.4：1.0の混合物に過剰のＮ−メチルピロリドン溶液を加え、ゲ ル状組成物を得た。この組成物を約１５μｍの銅箔上に１０ｍｍ×１０ｍｍ、約２５０μｍの厚さに塗布成型した。さらに、約１００℃で２４時間加熱真空乾燥することにより、黒鉛負極（３５ｍｇ）を得た。
【０１１７】
実施例２３：Ｌｉイオン二次電池の製造
アルゴン雰囲気グローブボックス内で、実施例２２で製造した黒鉛負極（１０ｍｍ×１０ｍｍ）に電解液（1.2Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させたものに、実施例２０で調製した塩未添加共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルム（１２ｍｍ×１２ｍｍ）を貼り合わせ、さらに実施例２１で製造したコバルト酸リチウム正極（１）（１０ｍｍ×１０ｍｍ）に電解液（1.2Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させたものを貼り合わせ、さらに集電体（ＳＵＳ３０４プレート，１４ｍｍ×１４ｍｍ，厚み約１００μｍ）を貼り合わせ、電池端部をエポキシ樹脂で封印し、図１に示される構造の黒鉛／酸化コバルト系Ｌｉイオン二次電池を得た。
この電池を、６０℃、２５℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行なったところ、最大放電容量は各々7.2ｍＡｈ、7.2ｍＡｈであった。
また、２５℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を 繰返したところ、最大放電容量は7.0ｍＡｈで、容量が５０％に減少するまでの サイクル寿命は４８０回であった。
【０１１８】
実施例２４：Ｌｉイオン二次電池の製造
塩未添加共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルムの代りに、実施例１７で製造した高分子固体電解質（化合物８＋化合物１０）／ＫＷ2200複合フィルムを用いた以外は実施例２３と同様にして、図１に示される構造のＬｉイオン二次電池を製造した。
この電池を、６０℃、２５℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行なったところ、最大放電容量は各々7.2ｍＡｈ、7.2ｍＡｈであった。
また、２５℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を 繰返したところ、最大放電容量は6.6ｍＡｈで、容量が５０％に減少するまでの サイクル寿命は５１０回であった。
【０１１９】
実施例２５：Ｌｉイオン二次電池の製造
アルゴン雰囲気グローブボックス内で、実施例２２で製造した黒鉛負極（１０ｍｍ×１０ｍｍ）に電解液（１Ｍ ＬｉＰＦ₆／ＥＣ＋ＤＥＣ（３：７））を含 浸させた上に、実施例１２で調製した［化合物８＋化合物１０］／アルミニウムオキサイドＣ系光重合性組成物を厚み３０μｍとなるように塗布し、アルゴン雰囲気下、ケミカル蛍光ランプを１０分照射したところ、電解液を含浸した高分子固体電解質（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルムを黒鉛負極上に直接形成した。さらに実施例２１で製造したコバルト酸リチウム正極（１０ｍｍ×１０ｍｍ）に電解液（１Ｍ ＬｉＰＦ₆／ＥＣ＋ＤＥＣ（３： ７））を含浸させたものを貼り合わせ、さらに集電体（ＳＵＳ３０４プレート，１４ｍｍ×１４ｍｍ，厚み約１００μｍ）を貼り合わせ、電池端部をエポキシ樹脂で封印し、図１に示される構造の黒鉛／酸化コバルト系Ｌｉイオン二次電池を得た。
この電池を、６０℃、２５℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行なったところ、最大放電容量は各々7.2ｍＡｈ、7.0ｍＡｈであった。
また、２５℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を 繰返したところ、最大放電容量は6.6ｍＡｈで、容量が５０％に減少するまでの サイクル寿命は５３０回であった。
【０１２０】
実施例２６：Ｌｉイオン二次電池の製造
アルゴン雰囲気グローブボックス内で、実施例２２で製造した黒鉛負極（１０ｍｍ×１０ｍｍ）に実施例１３で調製した熱重合性組成物を含浸させたものに、実施例１７で調製した高分子固体電解質（化合物８＋化合物１０）／ＫＷ２２００複合フィルム（１２ｍｍ×１２ｍｍ）を黒鉛負極上に貼り合わせ、さらに実施例２１で製造したコバルト酸リチウム正極（１０ｍｍ×１０ｍｍ）に実施例１３で調製した熱重合性組成物を含浸させたものを貼り合わせ、さらに集電体（ＳＵＳ３０４プレート，１４ｍｍ×１４ｍｍ，厚み約１００μｍ）を貼り合わせ、電池端部をエポキシ樹脂で封印した。これを６０℃で３時間加熱し、熱重合性組成物を硬化させ、図１に示される構造の黒鉛／酸化コバルト系Ｌｉイオン二次電池を得た。。
この電池を、６０℃、２５℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行なったところ、最大放電容量は各々7.2ｍＡｈ、6.6ｍＡｈであった。
また、２５℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を 繰返したところ、最大放電容量は4.8ｍＡｈで、容量が５０％に減少するまでの サイクル寿命は３２０回であった。
【０１２１】
実施例２７：活性炭電極の製造
椰子がら活性炭とポリフッ化ビニリデンの重量比9.0：1.0の混合物に過剰のＮ−メチルピロリドン溶液を加え、ゲル状組成物を得た。この組成物をステンレス箔上に１０ｍｍ×１０ｍｍの大きさで約１５０μｍの厚さに塗布した。約１００℃で１０時間真空乾燥し、活性炭電極（14.0ｍｇ）を得た。
【０１２２】
実施例２８：電気二重層コンデンサの製造
アルゴン雰囲気グローブボックス内で、実施例２７で製造した活性炭電極（14ｍｇ）１０ｍｍ×１０ｍｍに、電解液（１Ｍ ＴＥＡＢ／ＰＣ＋ＥＣ（３：１））を含浸させた電極を二個用意した。次に、実施例１８で製造した共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルム（１２ｍｍ×１２ｍｍ）を一方の電極に貼り合わせ、さらにもう一枚の電極を貼り合わせ、さらに集電体（ＳＵＳ３０４プレート，１４ｍｍ×１４ｍｍ，厚み約１００μｍ）を貼り合わせ、図２に示される構造の電気二重層コンデンサを製造した。
このコンデンサを、６０℃、２５℃で作動電圧０〜2.5Ｖ、電流0.3ｍＡで充放電を行なったところ、最大容量は４７０ｍＦ、４７０ｍＦであった。また、２５℃、2.5ｍＡでの最大容量は４００ｍＦで、充放電を５０回繰り返してもほとん ど容量に変化はなかった。
【０１２３】
実施例２９：電気二重層コンデンサの製造
アルゴン雰囲気グローブボックス内で、実施例２７で製造した活性炭電極（14ｍｇ）１０ｍｍ×１０ｍｍに、実施例１９で調製した熱重合性組成物を含浸させた電極を二個用意した。次に、実施例１８で製造した共重合体（化合物８＋化合物１０）／アルミニウムオキサイドＣ複合フィルム（１２ｍｍ×１２ｍｍ）を一方の電極に貼り合わせ、さらにもう一枚の電極をはり合わせ、さらにリード線を接合したＳＵＳ３０４プレート製集電体（厚み約１００μｍ、１４ｍｍ×１４ｍｍ）を貼り合わせ、端部および周囲をエポキシ樹脂で封止後、熱重合性組成物を８０℃で３時間加熱重合させることにより、図２に示される構造の電気二重層コンデンサを製造した。
このコンデンサを、６０℃、２５℃で作動電圧０〜2.5Ｖ、電流0.3ｍＡで充放電を行なったところ、最大容量は４３０ｍＦ、４００ｍＦであった。また、２５℃、2.5ｍＡでの最大容量は２００ｍＦで、充放電を５０回繰り返してもほとん ど容量に変化はなかった。
【０１２４】
【発明の効果】
本発明のカーボネート基を主成分とする架橋及び／または側鎖基を有する高分子と電解質塩とを含む高イオン伝導性の高分子固体電解質は、膜強度が良好で、イオン伝導度が高く、加工性に優れ、さらに従来のオリゴオキシアルキレン系架橋及び／または側鎖基を有する高分子固体電解質に比較して大電流特性、高温耐久性に優れている。
本発明の高分子固体電解質を用いた電池及び電気二重層コンデンサはイオン伝導性物質が固体であるため液漏れの危険はなく長期間安定して使用できるものであり、また、この固体電解質を用いることにより薄型の電池やコンデンサを製造することができる。
【０１２５】
また、本発明の高分子固体電解質を使用することにより、薄膜化が容易であり、高容量で作動でき、長寿命で、大電流特性、高温耐久性、信頼性、安定性、加工性に優れた二次電池が得られる。この二次電池は、全固体型としては高容量、高電流で作動でき、あるいはサイクル性が良好で、安全性、信頼性に優れた電池であり、ポータブル機器用主電源、バックアップ電源をはじめとする電気製品用電源、電気自動車用、ロードレベリング用大型電源として使用可能である。薄膜化が容易に行なえるため、身分証明書用カード等のペーパー電池としても使用できる。
【０１２６】
さらに、本発明の高分子固体電解質を用いることによって、出力電圧が高く、取り出し電流が大きく、長寿命で、高温耐久性、加工性、信頼性、安定性に優れた電気二重層コンデンサが得られる。本発明の電気二重層コンデンサは、従来のコンデンサに比較して、高電圧、高容量、高電流で作動でき、あるいはサイクル性が良好で、安全性、信頼性に優れており、このためバックアップ電源だけでなく、小型電池との併用で、各種電気製品用電源として使用可能である。また、薄膜化等の加工性に優れているため、従来の電気二重層コンデンサの用途以外の用途にも期待できる。
【図面の簡単な説明】
【図１】 本発明による電池の一例である薄型電池の実施例の概略断面図。
【図２】 本発明による電気二重層コンデンサの実施例の概略断面図。
【符号の説明】
１ 正極
２ 高分子固体電解質
３ 負極
４ａ、４ｂ 集電体
５ａ、５ｂ 絶縁性樹脂封止剤
６ａ、６ｂ 分極性電極
７ａ、７ｂ 集電体
８ 高分子固体電解質
９ 絶縁性樹脂封止剤
１０ リード線[0001]
BACKGROUND OF THE INVENTION
The present invention is useful for various electrochemical devices, a high ion conductive polymer solid electrolyte containing a polymer compound mainly composed of a carbonate group and an electrolyte salt, a method for producing the same, and a battery using the polymer solid electrolyte And an electric double layer capacitor using the polymer solid electrolyte and a method for manufacturing the same.
[0002]
[Prior art]
In the flow of downsizing and solidification in the field of ionics, as a new ionic conductor that replaces the conventional electrolyte solution, electricity such as all-solid primary battery, secondary battery and electric double layer capacitor using solid electrolyte Application to chemical elements has been actively attempted.
In other words, the conventional electrochemical element using the electrolyte solution has a problem in long-term reliability because liquid leakage to the outside of the part or elution of the electrode active material is likely to occur, whereas a solid electrolyte is used. The product does not have such a problem and can be easily reduced in thickness. Furthermore, the solid electrolyte is excellent in heat resistance and is advantageous in the manufacturing process of products such as batteries.
[0003]
In particular, those using a polymer solid electrolyte mainly composed of a polymer compound have the advantage that the flexibility of the battery is increased and it can be processed into various shapes as compared with inorganic materials. However, what has been studied so far has left the problem that the extraction current is small because the ionic conductivity of the polymer solid electrolyte is low.
[0004]
The ionic conductivity of a polymer solid electrolyte that is generally studied is 10 at room temperature. ^-Four -10 ^-Five Although it has been improved to about S / cm, it is still at a level two orders of magnitude lower than that of the liquid ion conductive material. Moreover, when it becomes low temperature of 0 degrees C or less, generally ionic conductivity will fall extremely. Furthermore, when these solid electrolytes are combined with electrodes of elements such as batteries and electric double layer capacitors, or when these solid electrolytes are incorporated into elements such as batteries and electric double layer capacitors as thin films, Processing techniques such as compositing and ensuring contact are difficult, and there are problems in the manufacturing process.
[0005]
US Pat. No. 4,479,504 proposes that the ionic conductivity can be improved by using a cross-linked polymer solid electrolyte in which a continuous solution of polyethylene oxide is impregnated with an electrolyte composed of a metal salt and an aprotic solvent. Has been. However, the ionic conductivity is 10 ^-Four Since S / cm was still insufficient and a solvent was added, there was a problem that the film strength was lowered.
[0006]
Japanese Patent Publication No. 3-73081 and U.S. Pat. No. 4,908,283 describe that a composition comprising acryloyl-modified polyalkylene oxide such as polyethylene glycol diacrylate / electrolyte salt / organic solvent is irradiated with actinic rays such as ultraviolet rays to shorten the polymerization time. A method for forming a molecular solid electrolyte is disclosed.
Also, US Pat. No. 4,830,939 and Japanese Patent Laid-Open No. 5-109310 disclose that a composition comprising a crosslinkable polyethylenically unsaturated compound / electrolyte salt / active light inert solvent is irradiated with radiation such as ultraviolet rays and electron beams, thereby A similar method for forming a solid polymer electrolyte containing a liquid is disclosed. In these systems, since the amount of the electrolyte in the polymer solid electrolyte is increased, the ionic conductivity is improved, but it is still insufficient and the membrane strength tends to deteriorate.
[0007]
US Pat. No. 5,609,974 discloses a solid polymer electrolyte using a crosslinked polymer compound into which a monocarbonate side chain is introduced for the purpose of enhancing the dissociation ability of the electrolyte salt. Sufficient performance such as conductivity and current characteristics cannot be obtained.
Japanese Patent Laid-Open No. 1-311573 exemplifies methacrylate end-capped poly (ethylene ether carbonate) as one of polymers having a side chain not having an active hydrogen atom in a polymer solid electrolyte used in an electrochemical device. However, these have problems of insufficient ionic conductivity and insufficient chemical stability of methacrylate.
[0008]
In Japanese Patent Application Laid-Open No. 9-147912, a copolymer of methacrylate end-capped poly (alkylene (ether) carbonate) and methacrylate end-capped polyether is used as a polymer solid electrolyte, thereby providing both flexibility and rigidity. , Improved adhesion to alkali metal electrodes and interface resistance. However, as described above, the chemical stability of the methacrylate is insufficient and there is a problem in durability, the ion conductivity is not sufficient, and the durability of the polyether itself is also problematic.
[0009]
In JP-A-9-291123, a polymer solid electrolyte having high mechanical strength, high ionic conductivity, excellent chemical and electrochemical stability is obtained by using a polymer of allyl carbonate end-cap polyether. Yes. However, the ionic conductivity is still insufficient, and there is a problem with the durability of the polyether itself.
[0010]
Solid State Ionics, 1982, No. 7, p. 75 includes LiClO, a polymer solid electrolyte. _Four / It has been reported that by further combining alumina particles with a polyethylene oxide composite, the strength of the polymer solid electrolyte can be improved without lowering the ionic conductivity. JP-A-6-140052 proposes a solid electrolyte obtained by impregnating a polyalkylene oxide / isocyanate crosslinked / inorganic oxide composite with a nonaqueous electrolytic solution. Improvements are being made. However, these composite polymer solid electrolytes have insufficient properties of the polymer compound itself, and problems still remain in practical use in terms of ionic conductivity, processability, and stability.
[0011]
Japanese Patent Laid-Open No. 62-272161 discloses an electric double layer capacitor in which a polymer solid electrolyte using a polymer compound such as cyanoethylated cellulose is combined with an activated carbon electrode. However, the ionic conductivity of the polymer solid electrolyte used is insufficient, and it is difficult to combine with the activated carbon electrode, so that an electric double layer capacitor having satisfactory performance has not been obtained.
[0012]
[Problems to be solved by the invention]
The present invention has good strength even when a thin film of about several tens of μm, high ionic conductivity at room temperature and low temperature, excellent workability, large current characteristics, chemical and electrochemical stability, It aims at providing the polymeric compound useful from the polymeric compound useful for various electrochemical elements, the polymer solid electrolyte obtained from the polymeric compound, and its manufacturing method.
[0013]
Another object of the present invention is to provide a primary battery and a secondary battery that can be easily thinned, can be operated with a high capacity and a large current, and are excellent in workability and reliability, and a method for manufacturing the same.
Furthermore, an object of the present invention is to provide an electric double layer capacitor having a high output voltage, a large extraction current, excellent workability and reliability, and a method for manufacturing the same.
[0014]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have found that a polymer solid electrolyte containing a polymer compound having a carbonate group and a specific allyl carbonate group and an electrolyte salt has a good membrane strength, an ion It has been found that the polymer solid electrolyte has high conductivity, excellent workability, and excellent high current characteristics and high temperature characteristics as compared with conventional oligooxyalkylene systems.
Further, it has been found that by using the above-described polymer solid electrolyte, it is possible to obtain a primary battery and a secondary battery that can be easily formed into a thin film, can be operated with a high capacity and a large current, and have excellent reliability and stability. It was.
[0015]
Furthermore, it has been found that by using the above polymer solid electrolyte, an electric double layer capacitor having a high output voltage, a large extraction current, and excellent workability, reliability, and stability can be obtained.
Based on the above knowledge, the present inventors have the following (1) polymer solid electrolyte and production method thereof, (2) battery, electric double layer capacitor using the polymer solid electrolyte, and production method thereof. And (3) a polymerizable compound useful as a raw material for the polymer compound for the polymer solid electrolyte.
[0016]
That is, the present invention
[1] General formula (1)
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[0017]
[Wherein R ¹ Represents a linear, branched or cyclic divalent group having 1 to 10 carbon atoms which may contain a hetero atom, m is an integer of 1 to 10, and n is an integer of 1 to 1000. is there. However, there are multiple Rs ¹ May be the same or different. ]
And a carbonate group represented by the following general formula (2)
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[0018]
[Wherein R ² Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^Three Represents a divalent group composed of a linear, branched or cyclic hydrocarbon having 1 to 10 carbon atoms. A polymer solid electrolyte comprising a polymer of at least one polymerizable compound having a polymerizable functional group represented by formula (I) and at least one electrolyte salt.
[2] The polymer solid electrolyte according to [1], including at least one organic solvent.
[3] The polymer solid electrolyte according to [1] or [2], which contains at least one inorganic oxide.
[4] The polymer solid electrolyte according to [1], wherein the electrolyte salt is selected from at least one of an alkali metal salt, a quaternary ammonium salt, and a quaternary phosphonium salt.
[5] The polymer solid electrolyte according to [2], wherein the organic solvent is a carbonate compound.
[0019]
[6] A battery comprising the solid polymer electrolyte according to any one of [1] to [5].
[7] Lithium, lithium alloy, carbon material capable of occluding and releasing lithium ions, inorganic oxide capable of occluding and releasing lithium ions, inorganic chalcogenide capable of occluding and releasing lithium ions, and highly conductive lithium ions as an anode of batteries The lithium battery according to [6], wherein at least one material selected from molecular compounds is used.
[8] In the electric double layer capacitor in which the polarizable electrode is disposed via the ion conductive material, the ion conductive material is the polymer solid electrolyte according to any one of [1] to [5]. Features an electric double layer capacitor.
[0020]
[9] General formula (1)
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[0021]
[The symbols in the formula have the same meaning as described in [1] above. ]
And a carbonate group represented by the following general formula (2)
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[0022]
[The symbols in the formula have the same meaning as described in [1] above. ]
And at least one polymerizable compound (A) having at least one polymerizable functional group and at least one electrolyte salt (B) as essential components, and at least one organic solvent (C) and / or at least one inorganic oxidation. A method for producing a solid polymer electrolyte, comprising: polymerizing a polymerizable composition after disposing a polymerizable composition which may contain the product (D) on a support.
[0023]
[10] General formula (1)
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[0024]
[The symbols in the formula have the same meaning as described in [1] above. ]
And a carbonate group represented by the following general formula (2)
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[0025]
[The symbols in the formula have the same meaning as described in [1] above. ]
Even if it contains at least one kind of an inorganic oxide (D) as an essential component, at least one kind of polymerizable compound (A) having a polymerizable functional group represented by the formula (A), and at least one kind of organic solvent (C). A polymer characterized by placing a good polymerizable composition on a support, polymerizing the polymerizable composition, and impregnating the electrolyte salt (B) by bringing the resulting polymer into contact with an electrolytic solution A method for producing a solid electrolyte.
[0026]
[11] General formula (1)
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[0027]
[The symbols in the formula have the same meaning as described in [1] above. ]
And a carbonate group represented by the following general formula (2)
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[0028]
[The symbols in the formula have the same meaning as described in [1] above. ]
At least one polymerizable compound having a polymerizable functional group represented by the formula (1) and at least one electrolyte salt as essential components, and may further contain at least one organic solvent and / or at least one inorganic oxide. A method for producing a battery, comprising: polymerizing a polymerizable composition after the polymerizable composition is placed in a battery structure or disposed on a support.
[0029]
[12] General formula (1)
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[0030]
[The symbols in the formula have the same meaning as described in [1] above. ]
And a carbonate group represented by the following general formula (2)
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[0031]
[The symbols in the formula have the same meaning as described in [1] above. ]
A battery composition comprising a polymerizable composition having at least one polymerizable compound having a polymerizable functional group represented by the formula (1) and at least one organic solvent as essential components, and further containing at least one inorganic oxide. A method for producing a battery comprising impregnating an electrolyte salt by polymerizing a polymerizable composition after being placed in a body or placed on a support, and contacting the resulting polymer with an electrolytic solution.
[0032]
[13] General formula (1)
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[0033]
[The symbols in the formula have the same meaning as described in [1] above. ]
And a carbonate group represented by the following general formula (2)
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[0034]
[The symbols in the formula have the same meaning as described in [1] above. ]
Polymerization that contains at least one polymerizable compound having a polymerizable functional group represented by formula (1) and at least one electrolyte salt as essential components, and may further contain at least one organic solvent and / or at least one inorganic oxide. A method for producing an electric double layer capacitor, wherein the polymerizable composition is polymerized after the conductive composition is placed in a structure for constituting an electric double layer capacitor or disposed on a support.
[0035]
[14] General formula (1)
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[0036]
[The symbols in the formula have the same meaning as described in [1] above. ]
And a carbonate group represented by the following general formula (2)
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[0037]
[The symbols in the formula have the same meaning as described in [1] above. ]
An electric double layer capacitor comprising a polymerizable composition having at least one polymerizable compound having a polymerizable functional group represented by formula (1) and at least one organic solvent as essential components and further containing at least one inorganic oxide. An electric double layer characterized by being impregnated with an electrolyte salt by placing it in a structural structure or placing it on a support, then polymerizing the polymerizable composition, and bringing the resulting polymer into contact with an electrolytic solution Capacitor manufacturing method.
[0038]
[15] General formula (3)
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[Wherein R ¹ Represents a divalent group having 1 to 10 carbon atoms, which may contain a chain, branched or cyclic hetero atom, and R ² Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^Three Represents a divalent group consisting of a linear, branched or cyclic hydrocarbon having 1 to 10 carbon atoms, R ^Four Represents a chain, branched or cyclic organic group which may contain a hetero atom, m is an integer of 1 to 10, and n is an integer of 2 to 1000. However, there are multiple Rs ¹ May be the same or different. ] The polymerizable compound shown by this.
[0039]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[Polymer solid electrolyte]
The solid polymer electrolyte of the present invention basically comprises (a) a polymer compound and (b) an electrolyte salt, which are main constituent components. Further, it may contain (c) an organic solvent and (d) an inorganic oxide. Hereinafter, each component will be described in detail.
[0040]
(a) Polymer compound
The polymer compound which is the main constituent of the polymer solid electrolyte of the present invention is non-electron conductive, can absorb and hold various organic polar solvents, and has a carbonate structure represented by the following general formula (1). Cross-linked and / or side chain groups are included.
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[0041]
Where R ¹ Represents a linear, branched or cyclic divalent group having 1 to 10 carbon atoms which may contain a hetero atom, m is an integer of 1 to 10, and n is an integer of 1 to 1000. is there. However, there are multiple Rs ¹ May be the same or different.
[0042]
When m exceeds 10 in the above general formula (1), the number of carbonate groups in the polymer compound decreases, the dielectric constant decreases, and the electrolyte salt becomes difficult to dissociate, which is not preferable. Preferred m is 1-5.
[0043]
R in the above general formula ¹ If the number of carbon atoms exceeds 10, the number of carbonate groups in the polymer compound decreases, the dielectric constant decreases, and the electrolyte salt becomes difficult to dissociate. Further, the hydrophobicity of the polymer compound increases, and the compatibility with various polar solvents decreases, which is not preferable. Preferred R ¹ Has 1 to 4 carbon atoms.
[0044]
The repeating number n of the carbonate group represented by the general formula (1) in the polymer used in the polymer solid electrolyte of the present invention is in the range of 1 to 1000, preferably in the range of 3 to 100, particularly 5 to 50. preferable.
[0045]
The polymer used in the polymer solid electrolyte of the present invention has a carbonate group represented by the general formula (1) and further has a polymerizable functional group represented by the following general formula (2).
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[0046]
[Wherein R ² Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^Three Represents a chain, branched or cyclic divalent group which may contain a hetero atom, and x is 0 or an integer of 1 to 10. It is obtained by polymerizing at least one polymerizable compound having
[0047]
In the polymerizable molecule used in the polymer solid electrolyte of the present invention, a plurality of carbonate groups represented by the general formula (1) and a plurality of polymerizable functional groups represented by the general formula (2) may be present. R present in the molecule ¹ , R ² , R ^Three , R ^Four , M and n may be the same or different.
[0048]
Specific examples of the polymerizable compound include compounds represented by the following general formula (3).
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[Wherein R ^Four Represents a linear, branched or cyclic group having 1 to 20 carbon atoms which may contain a hetero atom, and other symbols have the same meanings as described above. ]
[0049]
There is no particular limitation on the method for synthesizing the polymerizable compound having the group represented by the general formula (1) and the group represented by the general formula (2).
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It can be easily obtained by reacting the chloroformate (CF) form of the vinyl compound represented by the following formula with carbonate all having a hydroxyl group at the end.
[0050]
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[Wherein R ¹ , R ² , R ^Three , M and n have the same meaning as described above].
[0051]
Here, when a compound having only one functional group represented by the general formula (2) is used, the polymer obtained by polymerization does not have a crosslinked structure, and the film strength is insufficient. If it is, there is a great risk of short circuit. Therefore, in that case, it is copolymerized with a polymerizable compound having two or more functional groups represented by the general formula (2) and crosslinked, or polymerization having two or more functional groups represented by the general formula (2). It is preferable to use in combination with a polymer obtained from a functional compound.
[0052]
The polymer compound preferable as a constituent of the solid polymer electrolyte of the present invention may be a homopolymer of the polymerizable compound, two or more kinds of copolymers belonging to the same category, or the polymerizability. It may be a copolymer of at least one compound and other polymerizable compounds.
[0053]
The other polymerizable compound copolymerizable with the polymerizable compound is not particularly limited, and examples thereof include (meth) acrylic acid alkyl esters such as methyl methacrylate and n-butyl acrylate, various urethane (meth) acrylates, (Meth) acrylic acid ester and / or urethane (meth) acrylate having oxyalkylene and / or oxyfluorocarbon chain, (meth) acrylic acid ester and / or urethane (meth) acrylate having carbonate chain, (meth) acrylic acid fluorine Alkyl ester, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, vinylene carbonate, (meth) acryloyl carbonate, N-vinylpyrrolidone, acryloylmorpholine, methacryloylmorpho (Meth) acrylamide compounds such as N, N-dimethylaminopropyl (meth) acrylamide, styrene compounds such as styrene and α-methylstyrene, N-vinylamide compounds such as N-vinylacetamide and N-vinylformamide And alkyl vinyl ethers such as ethyl vinyl ether.
[0054]
Among these, preferred are (meth) acrylic acid ester, urethane (meth) acrylate, or (meth) acrylic acid ester and / or urethane (meth) acrylate having an oxyalkylene and / or oxyfluorocarbon chain, or carbonate chain. (Meth) acrylic acid ester and urethane (meth) acrylate having Among these, urethane (meth) acrylate is particularly preferable from the viewpoint of polymerizability.
[0055]
The polymer compound used in the polymer solid electrolyte of the present invention includes a polymer obtained from at least one of the polymerizable compounds and / or a copolymer containing the polymerizable compound as a copolymer component, and other polymers. It may be a mixture with a molecular compound. Other polymer compounds to be mixed include, for example, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polycarbonate, polyurethane, polybutadiene, polymethacrylic (or acrylic) esters, polystyrene, polyphosphazenes, polysiloxane or polysilane, polyfluoride, and the like. And polymers such as vinylidene chloride and polytetrafluoroethylene.
[0056]
The amount of the structural unit derived from the polymer having a carbonate group represented by the general formula (1) may be obtained by homopolymerizing the polymerizable compound, copolymerizing with other copolymerization components, or other polymer compounds. The total amount of the polymer component is not considered in general because it differs depending on whether it is mixed or depending on the type, but considering the ionic conductivity, membrane strength, heat resistance, and current characteristics when used in a polymer solid electrolyte The content is preferably 50% by weight or more, more preferably 70% by weight or more.
[0057]
Polymerization of the polymerizable compound can be performed by a general method utilizing the polymerizability of a vinyl group that is a functional group. That is, a radical polymerization catalyst such as azobisisobutyronitrile and benzoyl peroxide is added to the polymerizable compound alone or a mixture of a polymerizable compound and another copolymerizable polymerizable compound, CF _Three Protic acids such as COOH, BF _Three AlCl _Three It is possible to carry out radical polymerization, cationic polymerization or anionic polymerization using a cationic polymerization catalyst such as Lewis acid or the like, or an anionic polymerization catalyst such as butyl lithium, sodium naphthalene or lithium alkoxide. Further, the polymerizable compound or polymerizable mixture can be polymerized after being formed into a film-like shape.
[0058]
(b) Electrolyte salt
The type of the electrolyte salt used in the present invention is not particularly limited, and an electrolyte salt containing an ion desired to be a carrier by charge may be used, but it is desirable that the dissociation constant in the polymer solid electrolyte is large, and LiCF _Three SO _Three , LiN (CF _Three SO _{twenty two} , LiN (CF _Three CF ₂ SO ₂ ) ₂ , LiPF ₆ LiClO _Four , LiI, LiBF _Four , LiSCN, LiAsF ₆ , NaCF _Three SO _Three , NaPF ₆ , NaClO _Four , NaI, NaBF _Four , NaAsF ₆ , KCF _Three SO _Three , KPF ₆ , Alkali metal salts such as KI, (CH _Three ) _Four BF _Four Quaternary ammonium salts such as (CH _Three ) _Four PBF _Four Quaternary phosphonium salts such as AgClO _Four Transition metal salts such as hydrochloric acid, or protonic acids such as hydrochloric acid, perchloric acid, or borohydrofluoric acid are preferred.
[0059]
The electrolyte salt in the polymer solid electrolyte of the present invention can be used in combination, and the composite ratio is preferably from 0.1 to 50% by weight, particularly preferably from 1 to 30% by weight, based on the weight of the polymer. If the electrolyte salt used in the composite is present at a ratio of 50% by weight or more, ion migration is greatly inhibited. Conversely, if the ratio is 0.1% by weight or less, the absolute amount of ions is insufficient and the ionic conductivity is decreased.
[0060]
(c) Organic solvent
It is preferable to add an organic solvent to the solid polymer electrolyte of the present invention because the ionic conductivity of the solid polymer electrolyte is further improved. As the organic solvent that can be used, the compatibility with the compound having an organic group represented by the general formula (1) used in the polymer solid electrolyte of the present invention is good, the dielectric constant is large, and the boiling point is 60 ° C. or higher. Compounds with a wide electrochemical stability range are suitable.
[0061]
Examples of such solvents include ethers such as 1,2-dimethoxyethane, 2-methyltetrahydrofuran, crown ether, triethylene glycol methyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl Examples thereof include carbonates such as methyl carbonate, aromatic nitriles such as benzonitrile and tolunitrile, sulfur compounds such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane, and phosphate esters. Among these, ethers and carbonates are preferable, and carbonates are particularly preferable.
[0062]
The greater the amount of organic solvent added, the better the ionic conductivity of the polymer solid electrolyte. For this reason, it is generally desirable to increase the amount of addition, but on the other hand, if the amount is too large, the mechanical strength of the polymer solid electrolyte is lowered. The preferred addition amount is 2 to 15 times the weight of the polymer used in the solid polymer electrolyte of the present invention, and particularly preferably 3 to 10 times the amount.
[0063]
(d) Inorganic oxide
It is preferable to add various inorganic oxides to the polymer solid electrolyte of the present invention. The addition of inorganic oxide not only improves the strength and film thickness uniformity, but also creates fine pores between the inorganic oxide and the polymer. Free electrolyte solution is dispersed in the polymer solid electrolyte, and the ion conductivity and ion mobility can be increased without impairing the strength improvement effect. Further, by adding an inorganic oxide, the viscosity of the polymerizable composition is increased, and the effect of suppressing the separation also appears when the compatibility between the polymer and the solvent is insufficient.
[0064]
As the inorganic oxide to be used, a non-electron conductive and electrochemically stable one is selected. Moreover, if it is ion conductivity, it is still more preferable. Specifically, ion conductive or nonconductive ceramic fine particles such as α, β, γ-alumina, silica, titania, magnesia, hydrotalcite and the like can be mentioned.
For the purpose of increasing the amount of electrolyte in the polymer solid electrolyte and increasing the ionic conductivity and mobility, the specific surface area of the inorganic oxide is preferably as large as possible. ² / G or more, 50m ² / G or more is preferable.
[0065]
The crystal particle diameter of such an inorganic oxide is not particularly limited as long as it can be mixed with the polymerizable composition, but the average particle diameter is preferably 0.001 μm to 10 μm, particularly preferably 0.01 μm to 1 μm.
In addition, various shapes such as a spherical shape, an oval shape, a cubic shape, a rectangular parallelepiped shape, a cylindrical shape or a rod shape can be used.
When the amount of the inorganic oxide added is too large, there arises a problem that the strength and ionic conductivity of the polymer solid electrolyte are lowered or film formation is difficult. A preferred addition amount is 50% by weight or less with respect to the solid polymer electrolyte, and a range of 0.1 to 30% by weight is particularly preferred.
[0066]
[Production method of solid polymer electrolyte]
The polymer solid electrolyte of the present invention is a polymer obtained from at least one of the polymerizable compounds, or a copolymer containing the polymerizable compound as a copolymerization component, for example, formed into a film and then polymerized to form an organic solvent. It can be produced by bringing it into contact with an electrolyte salt dissolved in it, or by preparing a polymerizable composition comprising the polymerizable compound and other components, for example, forming it into a film and then polymerizing it. it can.
[0067]
If the latter method is specifically shown, at least one of the polymerizable compounds is mixed with at least one electrolyte salt such as an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt, and if desired, After preparing a polymerizable composition in which other polymerizable compound, plasticizer, organic solvent and / or inorganic oxide are added and mixed, it is formed into a film and heated in the presence or absence of the catalyst. And / or polymerization by irradiation with actinic rays to obtain the solid polymer electrolyte of the present invention. According to this method, the degree of freedom in processing is widened, which is a great merit in application.
[0068]
The solvent in the case of using a solvent at the time of polymerization depends on the kind of the polymerizable compound and the presence or absence of the polymerization catalyst, but any solvent may be used as long as the polymerization is not inhibited, and for example, tetrahydrofuran, acetonitrile, toluene and the like can be used.
The polymerization temperature depends on the type of the polymerizable compound, but may be any temperature at which polymerization occurs, and is usually performed in the range of 0 ° C to 200 ° C.
When polymerizing by irradiation with actinic rays, depending on the type of the polymerizable compound, for example, using an initiator such as benzyl methyl ketal and benzophenone, irradiation with ultraviolet light of several mW or more, γ rays, electron beams, etc. And can be polymerized.
[0069]
Moreover, when using the polymer solid electrolyte of this invention as a thin film, in order to improve film strength, it can also be set as a composite film with another porous film. However, depending on the type or amount of the film to be combined, the conductivity may be lowered and the stability may be deteriorated, so it is necessary to select a suitable one. Examples of the film used include porous polyolefin sheets such as polypropylene nonwoven fabrics and reticulated polyolefin sheets such as polyethylene nets, polyolefin microporous films such as Celgard (trade name), nylon nonwoven fabrics, etc. A film is preferred. The porosity should be about 10 to 95%, but it should be as large as possible as long as the strength permits, and the preferable porosity is in the range of 40 to 95%.
[0070]
There is no particular limitation on the composite method, but for example, at least one of the polymerizable compounds, or at least one electrolyte salt, and in some cases, a polymerizable composition obtained by adding and mixing other components may be porous. By polymerizing a (meth) acryloyl compound after impregnation into the polymer film, it can be uniformly combined and the film thickness can be easily controlled.
[0071]
[Battery and manufacturing method thereof]
FIG. 1 shows a schematic cross-sectional view of an example of a thin film solid secondary battery as a battery of the present invention. In the figure, 1 is a positive electrode, 2 is a solid polymer electrolyte, 3 is a negative electrode, 4a and 4b are current collectors, and 5a and 5b are insulating resin sealants.
In the configuration of the battery of the present invention, by using an electrode active material (positive electrode active material) having a high oxidation-reduction potential such as a metal oxide, metal sulfide, conductive polymer, or carbon material for the positive electrode 1, a high voltage, A high capacity battery is obtained, which is preferable. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, molybdenum oxide, molybdenum sulfide, titanium sulfide, Metal sulfides such as vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide, and the like are particularly preferable in terms of high capacity and high voltage.
[0072]
The method for producing the metal oxide or metal sulfide in this case is not particularly limited. For example, a general electrolysis method or heating as described in Electrochemistry, Vol. 22, page 574 (1954). Manufactured by law. In addition, when these are used as an electrode active material in a lithium battery, for example, Li _x CoO ₂ Or Li _x MnO ₂ The lithium element is preferably used in the state of being inserted (composited) into a metal oxide or metal sulfide. The method for inserting the lithium element is not particularly limited. For example, a method for electrochemically inserting lithium ions or a method described in US Pat. No. 4,357,215 may be used. ₂ CO _Three This can be carried out by mixing and heat-treating a salt of the above and a metal oxide.
[0073]
Moreover, a conductive polymer is preferable in that it is flexible and easily thinned. Examples of the conductive polymer include polyaniline, polyacetylene and derivatives thereof, polyparaphenylene and derivatives thereof, polypyrrole and derivatives thereof, polythienylene and derivatives thereof, polypyridinediyl and derivatives thereof, polyisothianaphthenylene and derivatives thereof, polyfurylene. And its derivatives, polyselenophene and its derivatives, polyparaphenylene vinylene, polythienylene vinylene, polyfurylene vinylene, polynaphthenylene vinylene, polyselenophene vinylene, polypyridinediyl vinylene, and their derivatives, etc. Is mentioned. Among them, a polymer of an aniline derivative that is soluble in an organic solvent is particularly preferable. The conductive polymer used as an electrode active material in these batteries or electrodes is produced according to a chemical or electrochemical method as described later, or other known methods.
[0074]
Further, examples of the carbon material include natural graphite, artificial graphite, gas phase method graphite, petroleum coke, coal coke, fluorinated graphite, pitch-based carbon, and polyacene.
The negative electrode active material used for the negative electrode 3 of the battery of the present invention has a low redox potential with an alkali metal ion as a carrier, such as an alkali metal, an alkali metal alloy, a carbon material, a metal oxide or a conductive polymer compound. Is preferable because a battery having a high voltage and a high capacity can be obtained. Among such negative electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, and lithium / antimony alloy have the lowest redox potential and can be made thin. preferable. Carbon materials are also particularly preferred in that they have a low redox potential when lithium ions are occluded, and are stable and safe. Carbon materials that can occlude and release lithium ions include natural graphite, artificial graphite, gas-phase graphite, petroleum coke, coal coke, pitch-based carbon, polyacene, C ₆₀ , C ₇₀ And fullerenes.
[0075]
When the negative electrode active material is used for a battery using an alkali metal ion as a carrier, an alkali metal salt is used as an electrolyte salt in the polymer solid electrolyte. Examples of the alkali metal salt include LiCF _Three SO _Three , LiPF ₆ LiClO _Four , LiBF _Four , LiSCN, LiAsF ₆ , LiN (CF _Three SO ₂ ) ₂ , NaCF _Three SO _Three , L iN (CF _Three CF ₂ SO ₂ ) ₂ , LiI, NaPF ₆ , NaClO _Four , NaI, NaBF _Four , NaAsF ₆ , KCF _Three SO _Three , KPF ₆ , KI and the like.
[0076]
An example of the manufacturing method of the electrode and battery of this invention is demonstrated.
The positive and negative electrodes are placed in the battery structure so as not to contact each other, or placed on a support. For example, the positive electrode and the negative electrode are bonded to each other through a spacer having an appropriate thickness at the end of the electrode or a polymer solid electrolyte film prepared in advance, and then placed in the structure, and then between the positive electrode and the negative electrode, A polymerizable composition in which at least one polymerizable compound, or at least one electrolyte salt, and in some cases, another polymerizable compound and / or a plasticizer and / or a solvent and / or an inorganic oxide are added and mixed. After the injection, for example, by polymerization by heating and / or actinic ray irradiation, or further by sealing with an insulating resin such as polyolefin resin or epoxy resin as necessary after polymerization, the electrode and the electrolyte are A battery in good contact is obtained.
[0077]
In addition to this, it was obtained by polymerizing a polymerizable composition obtained by adding and mixing at least one polymerizable compound and a solvent, or another polymerizable compound and / or a plasticizer and / or an inorganic oxide. It is also possible to manufacture a battery by laminating a positive electrode and a negative electrode via a polymer, and transferring a part of the electrolyte salt from the electrolyte previously impregnated into the electrode to the polymer.
The battery structure or the support may be made of a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. It is not limited. Moreover, the shape may be any shape such as a cylinder, a box, a sheet or the like.
[0078]
When manufacturing a wound battery, the above-mentioned polymerizable composition is further bonded after the positive electrode and the negative electrode are bonded and wound through a polymer solid electrolyte film prepared in advance and inserted into the structure for battery construction. It is also possible to inject and polymerize.
[0079]
[Electric double layer capacitor and manufacturing method thereof]
Next, the electric double layer capacitor of the present invention will be described.
According to the present invention, the use of the polymer solid electrolyte provides an electric double layer capacitor having a high output voltage, a large extraction current, and excellent workability and reliability.
FIG. 2 shows a schematic cross-sectional view of an example of the electric double layer capacitor of the present invention. This example is a thin cell having a size of about 1 cm × 1 cm and a thickness of about 0.5 mm. 7a and 7b are current collectors, and a pair of polarizable electrodes 6a and 6b are arranged inside the current collectors. The polymer solid electrolyte membrane 8 is disposed between them. 9 is an insulating resin sealant, and 10 is a lead wire.
[0080]
The current collectors 7a and 7b are preferably made of a material having electronic conductivity and electrochemical corrosion resistance, and a specific surface area as large as possible. For example, various metals and their sintered bodies, electron conductive polymers, carbon sheets and the like can be mentioned.
The polarizable electrodes 6a and 6b may be electrodes made of a polarizable material such as a carbon material usually used for an electric double layer capacitor. The carbon material as the polarizable material is not particularly limited as long as the specific surface area is large, but the larger the specific surface area, the larger the capacity of the electric double layer is preferable. For example, carbon blacks such as furnace black, thermal black (including acetylene black), channel black, activated carbon such as coconut shell charcoal, natural graphite, artificial graphite, so-called pyrolytic graphite produced by gas phase method, polyacene and C ₆₀ , C ₇₀ Can be mentioned.
[0081]
The type of electrolyte salt used in the composite in the case of the electric double layer capacitor of the present invention is not particularly limited, and a compound containing an ion desired to be a charge carrier may be used, but the dissociation constant in the polymer solid electrolyte It is desirable to include ions that are large and easily form an electric double layer with a polarizable electrode. Such compounds include (CH _Three ) _Four NBF _Four , (CH _Three CH ₂ ) _Four NClO _Four Quaternary ammonium salts, pyridinium salts, AgClO _Four Transition metal salts such as (CH _Three ) _Four PBF _Four Quaternary phosphonium salts such as LiCF _Three SO _Three , LiPF ₆ LiClO _Four , LiI, LiBF _Four , LiSC N, LiAsF ₆ , LiN (CF _Three SO ₂ ) ₂ , LiN (CF _Three CF ₂ SO ₂ ) ₂ , NaCF _Three SO _Three , NaPF ₆ , NaClO _Four , NaI, NaBF _Four , NaAsF ₆ , KCF _Three SO _Three , KPF ₆ And alkali metal salts such as KI, organic acids such as p-toluenesulfonic acid and salts thereof, and inorganic acids such as hydrochloric acid and sulfuric acid. Of these, quaternary ammonium salts, pyridinium salts, quaternary phosphonium salts, and alkali metal salts are preferred from the viewpoints of high output voltage and a large dissociation constant. Among quaternary ammonium salts, (CH _Three CH ₂ ) (CH _Three CH ₂ CH ₂ CH ₂ ) _Three NBF _Four Those having different substituents on the nitrogen of the ammonium ion are preferable from the viewpoint of high solubility in the polymer solid electrolyte or high dissociation constant.
[0082]
Next, an example of the manufacturing method of the electric double layer capacitor of the present invention will be described.
The two polarizable electrodes are placed in the capacitor structure so as not to contact each other, or placed on the support. For example, a polarizable electrode is bonded to the end of the electrode via a spacer having an appropriate thickness or a polymer solid electrolyte film prepared in advance and placed in the structure, and at least one of the polymerizable compounds, or this By injecting a polymerizable composition in which at least one electrolyte salt, and in some cases, another polymerizable compound and / or a plasticizer and / or a solvent and / or an inorganic oxide are added and mixed, Alternatively, an electric double layer capacitor in which the electrode and the electrolyte are in good contact can be obtained by sealing with an insulating resin such as a polyolefin resin or an epoxy resin as necessary after polymerization. In particular, a thin electric double layer capacitor can be manufactured by this method.
[0083]
In addition to this, it was obtained by polymerizing a polymerizable composition obtained by adding and mixing at least one polymerizable compound and a solvent, or another polymerizable compound and / or a plasticizer and / or an inorganic oxide. Manufacturing an electric double layer capacitor by bonding two polarizable electrodes through a polymer and transferring a part of the electrolyte salt from the electrolyte previously impregnated into the polarizable electrode to the polymer Is also possible.
[0084]
The capacitor structure or the support may be a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. The shape is not limited to the above, and the shape may be any shape such as a cylinder, a box, a sheet or the like.
[0085]
As the shape of the electric double layer capacitor, in addition to the sheet type as shown in FIG. 2, a coin type, or a sheet-like laminate of a polarizable electrode and a polymer solid electrolyte is wound into a cylindrical shape to form a cylindrical tubular capacitor. It may be a cylindrical type manufactured by sealing in a structure.
When producing a wound type capacitor, the above polarizable electrode is bonded and wound through a polymer solid electrolyte film prepared in advance, and the polymerizable composition is further inserted after inserting into the capacitor structure. It is also possible to inject and polymerize.
[0086]
【Example】
The present invention will be described in more detail below with typical examples. Note that these are merely illustrative examples, and the present invention is not limited thereto.
[0087]
Example 1: Synthesis of compounds 1, 2 and 3
Embedded image

[0088]
In accordance with the above reaction formulas (a), (b) and (c), an excess of phosgene gas was blown into various alkylene glycols under nitrogen at 10 ° C. or lower in a conventional manner and reacted for about 5 hours. Compound 1, Compound 2, and Compound 3 were synthesized. These identifications were performed by GC-MS.
[0089]
Example 2: Oligomerization of compounds 1, 2, 3 (synthesis of compounds 4, 5, 6)
Embedded image

[0090]
According to the above reaction formulas (d), (e) and (f), various alkylene glycol bischloroformates synthesized in Example 1 (compounds 1, 2, 3) and various alkylene glycols in the presence of pyridine Then, after reacting in dichloromethane at 25 ° C. or lower for about 6 hours, excess water is added, the remaining chloroformate ends are hydroxylated, and oligocarbonates having hydroxyl groups at both ends (compound 4, compound 5, compound 6) Was synthesized.
[0091]
The average of the weight average molecular weight (Mw) and the number of repetitions x, y, and z of each oligocarbonate determined by GPC analysis was as follows.
Compound 4: Mw to about 800, x: to about 8,
Compound 5: Mw to about 1500, y: to about 10,
Compound 6: Mw to about 1200, z: to about 10.
[0092]
Example 3: Synthesis of compound 7
Embedded image

[0093]
In a conventional manner, an equimolar amount of ethyl chloroformate was added dropwise to an anhydrous THF solution of the carbonate oligomer (compound 4) synthesized in Example 2 according to the above reaction formula (g) in the presence of pyridine at 25 ° C. or less. By reacting for about 6 hours, an oligocarbonate (compound 7) having one end hydroxylated was synthesized.
[0094]
Example 4: Synthesis of polymerizable compound 8
Embedded image

[0095]
Compound 4 (average molecular weight 800) (40.0 g) and ACF (allyl chloroformate) (13.7 g) were dissolved in 200 ml of well-purified dichloromethane in a nitrogen atmosphere, and 8 g of pyridine was then cooled to 25 ° C. or lower. Gradually added. Then, it was made to react at 25 degreeC for about 3 hours, the pyridine and its hydrochloride were removed and refine | purified by the conventional method, and the colorless product was obtained. That ¹ From the results of 1 H-NMR, IR, and elemental analysis, it was found that Compound 4 and ACF reacted 1 to 2 to produce Compound 8.
[0096]
Example 5: Synthesis of polymerizable compound 9
Embedded image

[0097]
Compound 5 (average molecular weight 1500) (75.0 g) and ACF (13.75 g) were dissolved in 200 ml of well-purified dichloromethane in a nitrogen atmosphere, and 8 g of pyridine was gradually added while cooling to 25 ° C. or lower. Then, it was made to react at 25 degreeC for about 3 hours, the pyridine and its hydrochloride were removed and refine | purified by the conventional method, and the colorless product was obtained. That ¹ From the results of 1 H-NMR, IR, and elemental analysis, it was found that compound 5 reacted with ACF 1 to 2 to produce compound 9.
[0098]
Example 6: Synthesis of polymerizable compound 10
Embedded image

[0099]
Compound 6 (average molecular weight 1200) (60.0 g) and ACF (13.75 g) were dissolved in 200 ml of well-purified dichloromethane in a nitrogen atmosphere, and 8 g of pyridine was gradually added while cooling to 25 ° C. or lower. Then, it was made to react at 25 degreeC for about 3 hours, the pyridine and its hydrochloride were removed and refine | purified by the conventional method, and the colorless product was obtained. That ¹ From the results of 1 H-NMR, IR and elemental analysis, it was found that compound 6 and ACF reacted 1 to 2 to produce compound 10.
[0100]
Example 7: Synthesis of polymerizable compound 11
Embedded image

[0101]
Compound 7 (average molecular weight 900) (90.0 g) and ACF (13.75 g) were dissolved in 200 ml of well-purified dichloromethane in a nitrogen atmosphere, and then 8 g of pyridine was gradually added while cooling to 25 ° C. or lower. . Then, it was made to react at 25 degreeC for about 3 hours, the pyridine and its hydrochloride were removed and refine | purified by the conventional method, and the colorless product was obtained. That ¹ From the results of 1 H-NMR, IR, and elemental analysis, it was found that compound 7 and ACF reacted one-on-one to produce compound 11.
[0102]
Example 8: Production of solid polymer electrolyte membrane (Compound 8)
Compound 8 (2.0 g), ethylene carbonate (EC) (1.8 g), diethyl carbonate (DEC) (4.2 g), LiPF ₆ (Battery grade made by Hashimoto Kasei) (0.60 g) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name, Lucyrin TPO, manufactured by BASF) (0.050 g) were mixed well in an argon atmosphere, and light A polymerizable composition was obtained. The water content (Karl Fischer) of this composition was 30 ppm. This photopolymerizable composition was applied on a PET film in an argon atmosphere and then irradiated with a chemical fluorescent lamp (manufactured by Sankyo Electric Co., Ltd., FL20S.BL) for 10 minutes. As a result, a polymer impregnated with an EC / DEC electrolyte solution ( Compound 8) A film was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 2.0 × 10 respectively. ^-3 , 0.5 × 10 ^-3 S / cm.
[0103]
Example 9: Production of solid polymer electrolyte membrane (Compound 9)
A polymer (compound 9) film impregnated with an EC / DEC electrolyte was obtained as a free-standing film of about 30 μm in the same manner as in Example 8, except that compound 9 (2.0 g) was used instead of compound 8. . When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 1.8 × 10 6 respectively. ^-3 , 0.4 × 10 ^-3 S / cm.
[0104]
Example 10: Production of solid polymer electrolyte membrane (Compound 10)
A polymer (compound 10) film impregnated with an EC / DEC electrolyte was obtained as a free-standing film of about 30 μm in the same manner as in Example 8, except that compound 10 (2.0 g) was used instead of compound 8. It was. When the ionic conductivity at 25 ° C. and −20 ° C. of this film was measured by the impedance method, it was 2.2 × 10 4 respectively. ^-3 , 0.7 × 10 ^-3 S / cm.
[0105]
Example 11: Production of solid polymer electrolyte membrane (compound 9 + compound 11)
A copolymer (compound 9+) impregnated with an EC / DEC electrolyte solution was prepared in the same manner as in Example 8, except that a mixture of compound 9 (1.0 g) and compound 11 (1.0 g) was used instead of compound 8. Compound 11) A film was obtained as a free standing film of about 30 μm. When the ionic conductivity at 25 ° C. and −20 ° C. of this film was measured by the impedance method, it was 2.5 × 10 5 respectively. ^-3 , 0.8 × 10 ^-3 S / cm.
[0106]
Example 12: Production of polymer solid electrolyte composite membrane (compound 8 + compound 10)
Compound 8 (0.5 g), Compound 10 (0.5 g), aluminum oxide C heat-treated at 1000 ° C. (manufactured by Nippon Aerosil Co., Ltd., crystal particle size 0.013 μm, average secondary particle size about 0.1 μm (SEM observation), BET specific surface area 100 m ² / G) (0.33 g), EC (1.8 g), DEC (4.2 g), LiPF ₆ (Hashimoto Kasei Battery Grade) (0.60 g) and Lucillin TPO (BASF) (0.050 g) were mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content (Karl Fischer method) of this composition was 35 ppm.
This photopolymerizable composition was applied on a PET film in an argon atmosphere, and then irradiated with a chemical fluorescent lamp (FL20S.BL manufactured by Sankyo Electric Co., Ltd.) for 10 minutes. As a result, a copolymer impregnated with an EC / DEC electrolyte solution ( Compound 8 + Compound 10) / Aluminum oxide C composite film was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 4.0 × 10 4 respectively. ^-3 , 1.0 × 10 ^-3 S / cm.
[0107]
Example 13: Production of solid polymer electrolyte membrane (compound 8 + compound 10)
Thermally polymerizable composition in the same manner as in Example 12 except that perhexyl PV (manufactured by NOF Corporation) (0.040 g) is added instead of lucillin TPO (0.050 g) as an initiator and aluminum oxide C is not used. Got. The water content (Karl Fischer method) of this composition was 35 ppm.
After coating this thermopolymerizable composition on a PET film under an argon atmosphere, coating with a PP film and heating on a hot plate at 70 ° C. for 3 hours, a copolymer impregnated with an EC / DEC electrolyte solution A (compound 8 + compound 10) film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 3.6 × 10 6 respectively. ^-3 , 0.810 ^-3 S / cm.
[0108]
Example 14: Production of polymer solid electrolyte composite membrane (Compound 9)
A polymer (compound 9) / aluminum oxide C composite film impregnated with an EC / DEC electrolyte solution was treated in the same manner as in Example 12 except that compound 9 (1.0 g) was used instead of compounds 8 and 10. Obtained as a 30 μm free-standing film. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 4.6 × 10 4 respectively. ^-3 1.2 × 10 ^-3 S / cm.
[0109]
Example 15: Production of polymer solid electrolyte composite membrane (compound 8 + compound 10)
LiPF ₆ Instead of Hashimoto Kasei Battery Grade LiBF _Four A photopolymerizable composition was obtained in the same manner as in Example 12 except that (0.50 g) was used. The water content of this composition (Karl Fischer method) was 50 ppm.
The photopolymerizable composition was applied onto a PET film and irradiated with light in the same manner as in Example 12, and a copolymer (compound 8 + compound 10) / aluminum oxide C composite film impregnated with an EC / DEC electrolyte solution was about 30 μm. Obtained as a self-supporting film. When the ionic conductivity of this solid electrolyte at 25 ° C. and −20 ° C. was measured by the impedance method, it was 2.0 × 10 6. ^-3 , 0.6 × 10 ^-3 S / cm.
[0110]
Example 16: Production of polymer solid electrolyte composite membrane (compound 8 + compound 10)
A photopolymerizable composition was obtained in the same manner as in Example 12 except that 4.2 g of ethyl methyl carbonate (EMC) was used instead of 4.2 g of DEC. The water content (Karl Fischer) of this composition was 35 ppm.
When this photopolymerizable composition was applied on a PET film in an argon atmosphere and then irradiated with a chemical fluorescent lamp for 10 minutes, a copolymer (compound 8 + compound 10) / aluminum oxide C impregnated with an EC / EMC electrolyte was used. A composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 4.3 × 10 4 respectively. ^-3 , 0.810 ^-3 S / cm.
[0111]
Example 17: Production of polymer solid electrolyte composite membrane (compound 8 + compound 10)
Instead of aluminum oxide C, hydrotalcite heat treated at 500 ° C. (KW2200, manufactured by Kyowa Chemical, average particle size of about 0.1 μm (SEM observation), BET ratio table area 100 m ² / G) A photopolymerizable composition was obtained in the same manner as in Example 12 except that (0.33 g) was used. The water content (Karl Fischer) of this composition was 50 ppm.
After coating this photopolymerizable composition on a PET film in an argon atmosphere and irradiating it with a chemical fluorescent lamp for 10 minutes, a copolymer (compound 8 + compound 10) / KW2200 composite film impregnated with an EC / DEC electrolyte solution Was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 3.6 × 10 6 respectively. ^-3 , 0.7 × 10 ^-3 S / cm.
[0112]
Example 18: Production of polymer solid electrolyte composite membrane (compound 8 + compound 10)
LiPF ₆ Photopolymerization was carried out in the same manner as in Example 12, except that high-purity tetraethylammonium tetrafluoroborate (TEAB) (1.00 g) manufactured by Hashimoto Kasei was used instead of propylene carbonate (6.0 g) instead of EC / DEC as the solvent. A sexual composition was obtained. The water content (Karl Fischer method) of this composition was 100 ppm.
This photopolymerizable composition was applied and irradiated in the same manner as in Example 12 to obtain a copolymer (compound 8 + compound 10) / aluminum oxide C composite film impregnated with a PC electrolyte as a free-standing film of about 30 μm. . When the ionic conductivity of this solid electrolyte at 25 ° C. and −20 ° C. was measured by the impedance method, it was 9.0 × 10 ^-3 , 1.5 × 10 ^-3 S / cm.
[0113]
Example 19: Production of solid polymer electrolyte membrane (Compound 8 + Compound 10)
Instead of lucillin TPO (0.050 g) as an initiator, perhexyl PV (manufactured by NOF Corporation) (0.040 g) was added, and a thermopolymerizable composition was prepared in the same manner as in Example 18 except that aluminum oxide C was not used. Obtained. The water content of this composition (Karl Fischer method) was 120 ppm.
After coating this heat-polymerizable composition on a PET film in an argon atmosphere, coating the PP film, and heating on a hot plate at 80 ° C. for 1 hour, a copolymer impregnated with a PC electrolyte (compound) An 8+ compound 10) film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 8.5 × 10 5 respectively. ^-3 1.4 × 10 ^-3 S / cm.
[0114]
Example 20: Production of polymer solid electrolyte composite membrane (compound 8 + compound 10)
LiPF ₆ A salt-free photopolymerizable composition was obtained in the same manner as in Example 12 except that was not used. The water content (Karl Fischer method) of this composition was 10 ppm.
This photopolymerizable composition was coated and irradiated with light in the same manner as in Example 12, and a salt-free copolymer (compound 8 + compound 10) / aluminum oxide C composite film impregnated with EC + DEC solvent was about 30 μm. Got as. This film is 1.2M LiPF ₆ / EC + DEC (weight ratio 3: 7) LiPF in the film by immersing in electrolyte for about 1 hour ₆ Salt was added afterwards. When the ion conductivity at 25 ° C. and −20 ° C. of this post-salt-added polymer solid electrolyte film was measured by an impedance method, it was 4.3 × 10 6. ^-3 1.2 × 10 ^-3 S / cm.
[0115]
Example 21: Preparation of lithium cobaltate positive electrode
11g Li ₂ CO _Three And 24g Co _Three O _Four Were mixed well, heated at 800 ° C. for 24 hours in an oxygen atmosphere, and then pulverized to obtain LiCoO ₂ A powder was obtained. This LiC oO ₂ The powder, acetylene black, and polyvinylidene fluoride were mixed at a weight ratio of 8: 1: 1, and an excess N-methylpyrrolidone solution was added to obtain a gel composition. This composition was applied and molded on an aluminum foil of about 25 μm to a thickness of 10 mm × 10 mm and about 180 μm. Furthermore, by heating and vacuum drying at about 100 ° C. for 24 hours, a lithium cobaltate positive electrode (75 mg) was obtained.
[0116]
Example 22: Production of graphite negative electrode
MCMB graphite (manufactured by Osaka Gas), gas phase method graphite fiber (manufactured by Showa Denko KK: average fiber diameter, 0.3 μm, average fiber length, 2.0 μm, heat treated product at 2700 ° C.), weight ratio of polyvinylidene fluoride 8.6: 0.4 : An excess N-methylpyrrolidone solution was added to the 1.0 mixture to obtain a gel composition. This composition was applied and molded on a copper foil of about 15 μm to a thickness of 10 mm × 10 mm and about 250 μm. Furthermore, a graphite negative electrode (35 mg) was obtained by heating and vacuum drying at about 100 ° C. for 24 hours.
[0117]
Example 23: Production of Li-ion secondary battery
In an argon atmosphere glove box, the graphite negative electrode (10 mm × 10 mm) produced in Example 22 was applied to the electrolyte (1.2 M LiPF). ₆ / EC + EMC (3: 7)) and the salt-unadded copolymer (compound 8 + compound 10) / aluminum oxide C composite film (12 mm × 12 mm) prepared in Example 20 were bonded together and further carried out. The electrolyte (1.2M LiPF) was added to the lithium cobaltate positive electrode (1) (10 mm × 10 mm) produced in Example 21. ₆ / EC + EMC (3: 7)) and pasted together with a current collector (SUS304 plate, 14 mm × 14 mm, thickness of about 100 μm), and the end of the battery was sealed with epoxy resin. A graphite / cobalt oxide-based Li ion secondary battery having the structure shown was obtained.
When this battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C. and 25 ° C., the maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively.
Moreover, when charging / discharging was repeated at 25 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 7.0 mAh, and the cycle life until the capacity decreased to 50% was 480 times. there were.
[0118]
Example 24: Production of Li-ion secondary battery
Example 23 except that the solid polymer electrolyte (compound 8 + compound 10) / KW2200 composite film produced in Example 17 was used instead of the salt-free copolymer (compound 8 + compound 10) / aluminum oxide C composite film. In the same manner, a Li ion secondary battery having the structure shown in FIG. 1 was manufactured.
When this battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C. and 25 ° C., the maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively.
Moreover, when charging / discharging was repeated at 25 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 6.6 mAh, and the cycle life until the capacity decreased to 50% was 510 times. there were.
[0119]
Example 25: Production of Li-ion secondary battery
In the argon atmosphere glove box, an electrolytic solution (1M LiPF) was applied to the graphite negative electrode (10 mm × 10 mm) produced in Example 22. ₆ / EC + DEC (3: 7)), and the [compound 8 + compound 10] / aluminum oxide C-based photopolymerizable composition prepared in Example 12 was applied to a thickness of 30 μm and an argon atmosphere was applied. Under irradiation with a chemical fluorescent lamp for 10 minutes, a polymer solid electrolyte (compound 8 + compound 10) / aluminum oxide C composite film impregnated with an electrolytic solution was directly formed on the graphite negative electrode. Further, an electrolytic solution (1M LiPF) was added to the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 21. ₆ / EC + DEC (3: 7)), and a current collector (SUS304 plate, 14 mm × 14 mm, thickness of about 100 μm) are bonded together, and the end of the battery is sealed with epoxy resin. A graphite / cobalt oxide-based Li ion secondary battery having the structure shown was obtained.
When this battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C. and 25 ° C., the maximum discharge capacities were 7.2 mAh and 7.0 mAh, respectively.
Moreover, when charging / discharging was repeated at 25 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 6.6 mAh, and the cycle life until the capacity decreased to 50% was 530 times. there were.
[0120]
Example 26: Production of Li-ion secondary battery
A polymer solid electrolyte prepared in Example 17 was prepared by impregnating the graphite negative electrode (10 mm × 10 mm) produced in Example 22 with the thermopolymerizable composition prepared in Example 13 in an argon atmosphere glove box. Compound 8 + Compound 10) / KW2200 composite film (12 mm × 12 mm) was bonded onto the graphite negative electrode, and the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 21 was further prepared in Example 13. Then, a current collector (SUS304 plate, 14 mm × 14 mm, thickness of about 100 μm) was bonded, and the battery edge was sealed with an epoxy resin. This was heated at 60 ° C. for 3 hours to cure the thermopolymerizable composition, and a graphite / cobalt oxide Li ion secondary battery having the structure shown in FIG. 1 was obtained. .
When this battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C. and 25 ° C., the maximum discharge capacities were 7.2 mAh and 6.6 mAh, respectively.
Moreover, when charging / discharging was repeated at 25 ° C, operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 4.8 mAh, and the cycle life until the capacity decreased to 50% was 320 times. there were.
[0121]
Example 27: Production of activated carbon electrode
An excess N-methylpyrrolidone solution was added to a mixture of coconut shell activated carbon and polyvinylidene fluoride in a weight ratio of 9.0: 1.0 to obtain a gel composition. This composition was applied on a stainless steel foil in a size of 10 mm × 10 mm to a thickness of about 150 μm. It vacuum-dried at about 100 degreeC for 10 hours, and obtained the activated carbon electrode (14.0 mg).
[0122]
Example 28: Production of an electric double layer capacitor
In the argon atmosphere glove box, two electrodes were prepared by impregnating the activated carbon electrode (14 mg) 10 mm × 10 mm produced in Example 27 with the electrolyte (1M TEAB / PC + EC (3: 1)). Next, the copolymer (compound 8 + compound 10) / aluminum oxide C composite film (12 mm × 12 mm) produced in Example 18 was bonded to one electrode, and another electrode was bonded to the electrode. The body (SUS304 plate, 14 mm × 14 mm, thickness of about 100 μm) was bonded to manufacture an electric double layer capacitor having the structure shown in FIG.
When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.3 mA at 60 ° C. and 25 ° C., the maximum capacity was 470 mF and 470 mF. The maximum capacity at 25 ° C. and 2.5 mA was 400 mF, and there was almost no change in capacity even after repeated charging and discharging 50 times.
[0123]
Example 29: Production of an electric double layer capacitor
In an argon atmosphere glove box, two electrodes were prepared by impregnating the activated carbon electrode (14 mg) 10 mm × 10 mm produced in Example 27 with the thermopolymerizable composition prepared in Example 19. Next, the copolymer (compound 8 + compound 10) / aluminum oxide C composite film (12 mm × 12 mm) produced in Example 18 was bonded to one electrode, and another electrode was bonded, and further lead wire A SUS304 plate current collector (thickness: about 100 μm, 14 mm × 14 mm) was bonded to each other, the ends and the periphery were sealed with an epoxy resin, and then the thermopolymerizable composition was heated and polymerized at 80 ° C. for 3 hours. An electric double layer capacitor having the structure shown in FIG. 2 was produced.
When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.3 mA at 60 ° C. and 25 ° C., the maximum capacity was 430 mF and 400 mF. Further, the maximum capacity at 25 ° C. and 2.5 mA was 200 mF, and the capacity was hardly changed even after repeated charging and discharging 50 times.
[0124]
【The invention's effect】
The polymer solid electrolyte of high ionic conductivity containing a polymer having a crosslinking group and / or a side chain group mainly composed of a carbonate group of the present invention and an electrolyte salt has good membrane strength and high ionic conductivity. It is excellent in workability and further has excellent large current characteristics and high temperature durability as compared with conventional polymer solid electrolytes having oligooxyalkylene-based crosslinks and / or side chain groups.
The battery and the electric double layer capacitor using the polymer solid electrolyte of the present invention can be used stably for a long period of time without risk of liquid leakage because the ion conductive material is solid, and this solid electrolyte is used. Thus, a thin battery or capacitor can be manufactured.
[0125]
In addition, by using the solid polymer electrolyte of the present invention, thinning is easy, it can operate at high capacity, has a long life, high current characteristics, high temperature durability, reliability, stability, and excellent workability. A secondary battery is obtained. This secondary battery is a battery that can operate at high capacity and high current as an all-solid-state battery, has good cycleability, and is excellent in safety and reliability. It can be used as a power source for electric products, an electric vehicle, and a large power source for road leveling. Since it can be easily thinned, it can also be used as a paper battery such as an ID card.
[0126]
Furthermore, by using the solid polymer electrolyte of the present invention, an electric double layer capacitor having a high output voltage, a large take-out current, a long life, excellent high temperature durability, workability, reliability, and stability can be obtained. . The electric double layer capacitor of the present invention can operate at a high voltage, a high capacity, and a high current as compared with the conventional capacitor, or has good cycleability, and is excellent in safety and reliability. In addition, it can be used as a power source for various electrical products when used in combination with small batteries. Moreover, since it is excellent in workability, such as thin film formation, it can be expected for uses other than those of conventional electric double layer capacitors.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an embodiment of a thin battery which is an example of a battery according to the present invention.
FIG. 2 is a schematic cross-sectional view of an embodiment of an electric double layer capacitor according to the present invention.
[Explanation of symbols]
1 Positive electrode
2 Polymer solid electrolyte
3 Negative electrode
4a, 4b Current collector
5a, 5b Insulating resin sealant
6a, 6b Polarized electrode
7a, 7b Current collector
8 Polymer solid electrolyte
9 Insulating resin sealant
10 Lead wire

Claims (15)

General formula (1)

[In the formula, R ¹ represents a chain, branched or cyclic divalent group which may contain a heteroatom having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n is It is an integer of 3 to 1000. However, a plurality of R ¹ may be the same or different. ]
And a carbonate group represented by the following general formula (2)

[Wherein, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ represents a divalent group composed of a chain, branched or cyclic hydrocarbon having 1 to 10 carbon atoms. ]
A polymer solid electrolyte comprising a polymer of at least one polymerizable compound having a polymerizable functional group represented by formula (1) and at least one electrolyte salt.   The polymer solid electrolyte according to claim 1, comprising at least one organic solvent.   The polymer solid electrolyte according to claim 1, comprising at least one inorganic oxide.   The polymer solid electrolyte according to claim 1, wherein the electrolyte salt is selected from at least one of an alkali metal salt, a quaternary ammonium salt, and a quaternary phosphonium salt.   The polymer solid electrolyte according to claim 2, wherein the organic solvent is a carbonate compound. The polymerizable compound has the general formula (3)

[Wherein, R ⁴ represents a chain, branched or cyclic organic group which may contain a hetero atom, and other symbols have the same meaning as described in claim 1]. The polymer solid electrolyte according to claim 1, which is a polymerizable compound represented by the formula: Battery, which comprises using a polymer solid electrolyte according to any one of claims 1 to 6. As a negative electrode of a battery, lithium, lithium alloy, carbon material capable of occluding and releasing lithium ions, inorganic oxide capable of occluding and releasing lithium ions, inorganic chalcogenide capable of occluding and releasing lithium ions, and conductive polymer compounds capable of occluding and releasing lithium ions. The lithium battery according to claim 7 , wherein at least one selected material is used. An electric double layer capacitor in which a polarizable electrode is disposed via an ion conductive material, wherein the ion conductive material is a polymer solid electrolyte according to any one of claims 1 to 6. Capacitor. General formula (1)

[The symbols in the formula have the same meaning as in claim 1.] ]
And a carbonate group represented by the following general formula (2)

[The symbols in the formula have the same meaning as in claim 1.] ]
And at least one polymerizable compound (A) having at least one polymerizable functional group and at least one electrolyte salt (B) as essential components, and at least one organic solvent (C) and / or at least one inorganic oxidation. A method for producing a solid polymer electrolyte, comprising: polymerizing a polymerizable composition after disposing a polymerizable composition which may contain the product (D) on a support. General formula (1)

[The symbols in the formula have the same meaning as in claim 1.] ]
And a carbonate group represented by the following general formula (2)

[The symbols in the formula have the same meaning as in claim 1.] ]
Even if it contains at least one kind of an inorganic oxide (D) as an essential component, at least one kind of polymerizable compound (A) having a polymerizable functional group represented by the formula (A), and at least one kind of organic solvent (C). A polymer characterized by placing a good polymerizable composition on a support, polymerizing the polymerizable composition, and impregnating the electrolyte salt (B) by bringing the resulting polymer into contact with an electrolytic solution A method for producing a solid electrolyte. General formula (1)

[The symbols in the formula have the same meaning as in claim 1.] ]
And a carbonate group represented by the following general formula (2)

[The symbols in the formula have the same meaning as in claim 1.] ]
At least one polymerizable compound having a polymerizable functional group represented by the formula (1) and at least one electrolyte salt as essential components, and may further contain at least one organic solvent and / or at least one inorganic oxide. A method for producing a battery, comprising: polymerizing a polymerizable composition after the polymerizable composition is placed in a battery structure or disposed on a support. General formula (1)

[The symbols in the formula have the same meaning as in claim 1.] ]
And a carbonate group represented by the following general formula (2)

[The symbols in the formula have the same meaning as in claim 1.] ]
A battery composition comprising a polymerizable composition having at least one polymerizable compound having a polymerizable functional group represented by the formula (1) and at least one organic solvent as essential components, and further containing at least one inorganic oxide. A method for producing a battery comprising impregnating an electrolyte salt by polymerizing a polymerizable composition after being placed in a body or placed on a support, and contacting the resulting polymer with an electrolytic solution. General formula (1)

[The symbols in the formula have the same meaning as in claim 1.] ]
And a carbonate group represented by the following general formula (2)

[The symbols in the formula have the same meaning as in claim 1.] ]
Polymerization that contains at least one polymerizable compound having a polymerizable functional group represented by formula (1) and at least one electrolyte salt as essential components, and may further contain at least one organic solvent and / or at least one inorganic oxide. A method for producing an electric double layer capacitor, wherein the polymerizable composition is polymerized after the conductive composition is placed in a structure for constituting an electric double layer capacitor or disposed on a support. General formula (1)

[The symbols in the formula have the same meaning as in claim 1.] ]
And a carbonate group represented by the following general formula (2)

[The symbols in the formula have the same meaning as in claim 1.] ]
An electric double layer capacitor comprising a polymerizable composition having at least one polymerizable compound having a polymerizable functional group represented by formula (1) and at least one organic solvent as essential components and further containing at least one inorganic oxide. An electric double layer characterized by being impregnated with an electrolyte salt by placing it in a structural structure or placing it on a support, then polymerizing the polymerizable composition, and bringing the resulting polymer into contact with an electrolytic solution Capacitor manufacturing method.

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