JP3575108B2 - Polymer solid electrolyte, its material and use - Google Patents

Abstract

PURPOSE: To obtain a macromolecular solid electrolyte useful in cells or batteries which is a composite comprising a novel polymer prepared from a specific monomer mixture and an electrolyte, maintains a sufficient strength, even when it is made into a thin film of some several tens &mu;m thickness, shows high ionic conductivity with high processability. CONSTITUTION: This electrolyte is a composite comprising (A) a polymer obtained from at least one compound having the unit of the formula (R<1> and R<2> are each H, an alkyl; R<3> is a divalent organic group containing oxyalkylene; x and y are each 0, 1-5; z is 0, 1-10 where z=0 in the case of x=0 and y=0) and/or (B) a copolymer containing component A and/or (C) at least one of electrolyte, preferably at least one selected from alkali metal salt, quaternary ammonium salt, quaternary phosphonium salt or transition metal, salt.

Description

［式中、Ｒ^１は水素またはアルキル基を表し、Ｒ^４はそれぞれに−（ＣＨ_２）_２−または−ＣＨ（ＣＨ_３）ＣＨ_２−を表し、ｎは１以上の整数を表す。ｘ及びｙはそれぞれ０または１〜５の整数を、ｚは０または１〜１０の数値を示す。但しｘ＝０及びｙ＝０のときはｚ＝０である。また（ＣＨ_２）と（ＣＨ（ＣＨ_３））は不規則に配列してもよい。但し、同一分子中の複数個の上記一般式（４）で表されるユニット中のＲ^１、Ｒ^４及びｘ、ｙ、ｚの値は、それぞれ独立であり、同じである必要はない。］で表される化合物。
【００３５】
２０）一般式（５）
【化３】

［式中、Ｒ^１は水素またはアルキル基を表し、Ｒ^４はそれぞれに−（ＣＨ_２）_２−または−ＣＨ（ＣＨ_３）ＣＨ_２−を表し、ｎは１以上の整数を表す。ｘ及びｙはそれぞれ０または１〜５の整数を、ｚは０または１〜１０の数値を示す。但しｘ＝０及びｙ＝０のときはｚ＝０である。また（ＣＨ_２）と（ＣＨ（ＣＨ_３））は不規則に配列してもよい。但し、同一分子中の複数個の上記一般式（５）で表されるユニット中のＲ^１、Ｒ^４及びｘ、ｙ、ｚの値は、それぞれ独立であり、同じである必要はない。］で表される化合物。
【００３６】
２１）一般式（６）
【化４】

［式中、Ｒ^１は水素またはアルキル基を表し、Ｒ^４はそれぞれに−（ＣＨ_２）_２−または−ＣＨ（ＣＨ_３）ＣＨ_２−を表し、ｎは１以上の整数を表す。ｘ及びｙはそれぞれ０または１〜５の整数を、ｚは０または１〜１０の数値を示す。但しｘ＝０及びｙ＝０のときはｚ＝０である。また（ＣＨ_２）と（ＣＨ（ＣＨ_３））は不規則に配列してもよい。但し、同一分子中の複数個の上記一般式（６）で表されるユニット中のＲ^１、Ｒ^４及びｘ、ｙ、ｚの値は、それぞれ独立であり、同じである必要はない。］で表される化合物。
【００３７】
以下に本発明を詳細に説明する。
本発明の高分子固体電解質用のモノマーである一般式（１）あるいは（２）で表されるユニットを有する化合物は、分子中に一つ以上のエチレン性不飽和基を有する。
一般式（１）あるいは（２）で表されるユニットを有する化合物は、ＣＨ_２＝Ｃ（Ｒ^１ ）ＣＯ［Ｏ（ＣＨ_２ ）_ｘ （ＣＨ（ＣＨ_３ ））_ｙ ］_ｚ ＮＣＯとオキシエチレン基を有する一級もしくは二級アミンの反応により得ることができる（ただし、式中Ｒ^１ 、ｘ、ｙ，ｚはそれぞれ一般式（１）と同じ。）。
【００３８】
具体的方法として一つのエチレン性不飽和基を有する化合物は、例えば、メタクリロイルイソシアナート系化合物（以下ＭＩ類と略記する。）あるいはアクリロイルイソシアナート系化合物（以下ＡＩ類と略記する。）とモノアミノモノアルコキシオリゴアルキレングリコールとを、１：１のモル比で反応させることにより、容易に得られる。
【００３９】
また二つのエチレン性不飽和基を有する化合物は、例えば、ＭＩ類あるいはＡＩ類とジアミノオリゴアルキレングリコールとを、２：１のモル比で反応させることにより、容易に得られる。
また、三つのエチレン性不飽和基を有する化合物は、例えばＭＩ類及び／またはＡＩ類と、グリセリン等の３価アルコールにアルキレンオキサイドを付加重合させ、その末端をアミンに置換したトリアミンとを、３：１のモル比で反応させることにより、容易に得られる。
【００４０】
また、四つのエチレン性不飽和基を有する化合物は、例えばＭＩ類及び／またはＡＩ類と、ペンタエリスリトール等の４価アルコールにアルキレンオキサイドを付加重合させ、その末端をアミンに置換したテトラミンとを４：１のモル比で反応させることにより、容易に得られる。
また、五つのエチレン性不飽和基を有する化合物は、例えばＭＩ類及び／またはＡＩ類と、α−Ｄ−グルコピラノースにアルキレンオキシドを付加重合させ、その末端をアミンに置換したペンタミンとを、５：１のモル比で反応させることにより、容易に得られる。
また、六つのエチレン性不飽和基を有する化合物は、例えばＭＩ類及び／またはＡＩ類と、マンニットにアルキレンオキシドを付加重合させ、その末端をアミンに置換したヘキサミンとを６：１のモル比で反応させることにより、容易に得られる。
【００４１】
本発明の高分子固体電解質の重合体に用いるモノマーは、前記一般式（１）あるいは（２）で表されるユニットを有する化合物を使用することが必要である。一般式（１）あるいは（２）で表されるユニットを１つしか有さない化合物を重合してできる重合体を、電解質と共に高分子固体電解質の重合体として用いた場合には、電極との接着性や複合効率にはすぐれているが膜強度不足のため、薄膜にすると短絡する恐れがある。このように、できた固体電解質の薄膜強度を考慮すると、１分子中に含まれる一般式（１）あるいは（２）で表されるユニットの数は、２つ以上がより好ましい。
【００４２】
また前記一般式（１）で表されるユニットを有する化合物の中で、一般式（２）で表されるユニットを有する化合物が、薄膜にしたときの膜強度が大きく、得られる重合体中にオキシアルキレン基をより多く導入できるので、室温、低温でのイオン伝導度が高くなることから好ましい。
【００４３】
本発明の高分子固体電解質に含まれる重合体は、一般式（１）及びまたは一般式（２）で表されるユニットを有する化合物の少なくとも一種を重合し、あるいは該化合物を共重合成分として重合することにより得られる。
【００４４】
前記一般式（１）及び／または一般式（２）で表されるユニットを有する化合物と共重合可能な他の重合性化合物としては、特に制限はない。例えば、Ｎ−メタクリロイルカルバミド酸ω−メチルオリゴオキシエチルエステル、メタクリロイルオキシエチルカルバミド酸ω−メチルオリゴオキシエチルエステル等の下記一般式（３）で表されるユニットを１分子中に少なくとも１つ有する化合物（以下、この化合物をオキシアルキレン鎖を有するウレタン（メタ）アクリレートという。）
ＣＨ_２＝Ｃ（Ｒ^１ ）ＣＯ［Ｏ（ＣＨ_２ ）_ｘ （ＣＨ（ＣＨ_３ ））_ｙ ］_ｚ ＮＨＣＯＯＲ^２ − （３）
［式中、Ｒ^１ は水素またはメチル基を表し、Ｒ^２ はオキシアルキレン基を含む２価の有機基を表す。該有機基は直鎖状、分岐状、環状構造のいずれからなるものでもよく、炭素、水素及び酸素以外の元素が１個以上含まれていてもよい。ｘ及びｙはそれぞれ０または１〜５の整数を、ｚは０または１〜１０の数値を示す。但しｘ＝０及びｙ＝０のときはｚ＝０である。また（ＣＨ_２ ）と（ＣＨ（ＣＨ_３ ））は不規則に配列してもよい。但し、同一分子中の複数個の上記一般式（３）で表されるユニット中のＲ^１ 、Ｒ^２ 及びｘ、ｙ、ｚの値は、それぞれ独立であり、同じである必要はない。］、
メタクリル酸ω−メチルオリゴオキシエチルエステル等のオキシアルキレン鎖を有する（メタ）アクリルエステル、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、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、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。これらの中で好ましいのは、オキシアルキレン鎖を有するウレタン（メタ）アクリレート、オキシアルキレン鎖を有する（メタ）アクリルエステル、（メタ）アクリルアミド系化合物が用いられる。これらの中で、重合体中にウレタン基やオキシアルキレン基をより多く導入できることを考慮すると、オキシアルキレン鎖を有するウレタン（メタ）アクリレートが、特に好ましい。
【００４５】
重合は、モノマー化合物中のアクリロイル基もしくはメタクリロイル基の重合性を利用した一般的な方法を採用することができる。即ち、これらモノマー単独、あるいはこれらモノマーと他の前記の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、ＣＦ_３ ＣＯＯＨ等のプロトン酸、ＢＦ_３ 、ＡｌＣｌ_３ 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。さらに、前記一般式（１）で表されるユニットを有する化合物とオキシアルキレン鎖を有するウレタン（メタ）アクリレートの合計の含有量が全モノマー重量に対して、２０重量％を越えるような場合は、無酸素条件下で、温度を７０℃以上に昇温するだけで重合を行うことができる。
【００４６】
また、かかる重合性モノマー混合物を膜状等の形に成形後重合させることも可能である。前記一般式（１）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体を、本発明のような高分子固体電解質の重合体に用いる場合には、特にこのように、重合性モノマー混合物を成膜後に重合することが有利である。
【００４７】
即ち、前記一般式（１）で表されるユニットを有する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とを混合し、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／または溶媒を添加混合し、これら重合性モノマー混合物を前記触媒の存在下あるいは非存在下に、場合によっては加熱及び／または光等の電磁波を照射して重合させる。特に、該重合性モノマー混合物を膜状等の形状に成形後に、例えば加熱及び／または光等の電磁波を照射して、重合させ、膜状重合物とすることにより、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。
【００４８】
溶媒を用いる場合には、モノマーの種類や重合触媒の有無にもよるが、重合を阻害しない溶媒であ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、前記一般式（１）で表されるユニットを有する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℃の範囲で行えばよい。電磁波照射により重合させる場合には、前記一般式（１）で表されるユニットを有する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線等を照射して重合させることができる。
【００４９】
本発明の高分子固体電解質に用いる重合体は、前記のように、前記一般式（１）で表されるユニットを有する化合物の単独重合体であっても、該カテゴリーに属する２種以上の共重合体であっても、あるいは該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。また、本発明の高分子固体電解質に用いる重合体は、前記一般式（１）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と他の重合体との混合物であってもよい。例えば、前記一般式（１）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と、ポリエチレンオキサイド、ポリアクリロニトリル、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等のポリマーとの混合物を本発明の高分子固体電解質に用いてもよい。
【００５０】
共重合体としたとき前記一般式（１）で表されるユニットを有する化合物由来の構造単位の量は、その他の共重合成分あるいは重合体混合物成分の種類によって異なるが、オキシアルキレン鎖を有するウレタン（メタ）アクリレートを共重合成分として含まない場合は、高分子固体電解質に用いたときのイオン伝導度および膜強度を考慮すると、この共重合体全量に対し２０重量％以上含有することが好ましく、さらに好ましくは５０重量％以上含有することである。
【００５１】
また、前記一般式（１）で表されるユニットを有する化合物を共重合成分とする共重合体の量が、高分子固体電解質に用いる重合体の総量に対して５０重量％以上になることが望ましい。前記一般式（１）で表されるユニットを有する化合物由来の構造単位が、上記指定量範囲である場合は、重合体の膜強度を十分に発現でき、また、高分子固体電解質としたときのイオン伝導度も大きい。
【００５２】
本発明の高分子固体電解質に用いる（共）重合体を得るために用いられる一般式（１）あるいは一般式（２）で表されるユニットを有する化合物で、エチレン性不飽和基を一つ有している化合物の重合により櫛形高分子が、２つ以上有している化合物の重合により網目状高分子が得られる。従って、一般式（１）あるいは一般式（２）で表されるユニットを１分子中に１つ有する化合物と二つ以上有する化合物とを混合し、重合することにより、熱運動性が大きく、膜強度が良好な重合体を得ることも可能である。重合体の側鎖となるオキシアルキル基中のオキシアルキレン鎖数（すなわち前記一般式（１）におけるＲ^２ 中に含まれるオキシアルキレン基の数、あるいは例えば、前記一般式（２）におけるｎ）は１〜１０００の範囲が好ましく、５〜５０の範囲が特に好ましい。
【００５３】
尚、本発明の高分子固体電解質に用いる（共）重合体中のモノマーは、モノマー中に存在する一般式（１）
ＣＨ_２＝Ｃ（Ｒ^１ ）ＣＯ［Ｏ（ＣＨ_２ ）_ｘ （ＣＨ（ＣＨ_３ ））_ｙ ］_ｚ ＮＨＣＯＮＲ^２ −Ｒ^３ − （１）
で表されるユニットにおいて、
（ａ）ｘが０〜２、ｙが０または１、ｚが０または１（但しｘ＝０、ｙ＝０のときはｚ＝０）の場合は、原料となる対応イソシアネート化合物
ＣＨ_２＝Ｃ（Ｒ^１ ）ＣＯ［Ｏ（ＣＨ_２ ）_ｘ （ＣＨ（ＣＨ_３ ））_ｙ ］_ｚ ＮＣＯ
の反応性が高く、種々のオキシアルキレン化合物との反応により容易に製造できる。またこれらの対応イソシアネート化合物は液体で粘性が低く、溶媒系での反応が容易という利点がある。
【００５４】
一方高分子固体電解質に用いる（共）重合体中の必須成分である上記モノマーにおいて、
（ｂ）ｘ＝３〜５、ｙ＝０、ｚ＝１〜１０、
（ｃ）ｘ＝１〜５、ｙ＝１〜５（ランダム配列）、ｚ＝１〜１０または
（ｄ）ｘ＝０、ｙ＝１〜５、ｚ＝１〜１０の化合物は、重合性は低くなるため、保存安定性が良好となり、重合性モノマーとしての取扱い性は良好である。
【００５５】
特に（ｃ）および（ｄ）の場合において、オキシプロピレン基を導入すると、オキシエチレン基を有しているモノマーより誘電率は低下するが、分子量が大きくなっても融点、粘性が高くならない特徴があり、用途によっては極めて有利な重合性モノマーである。従って、これら重合性モノマーの特性を利用し、適したこれら重合性モノマーを組合せることにより、あるいは他の重合性モノマー及び／またはポリマーと組合わせることにより用途に適した高分子固体電解質とすることができる。
【００５６】
また本発明の高分子固体電解質中に通常いわゆる可塑剤として用いられている有機化合物（本発明においては可塑剤と表現する）を添加すると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。使用できる可塑剤としては、本発明の高分子固体電解質に用いるモノマーとの相溶性が良好で、誘電率が大きく、沸点が７０℃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。そのような可塑剤としては、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オリゴエーテル類、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、炭酸ビニレン、（メタ）アクリロイ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。この中で、オリゴ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。
【００５７】
可塑剤の添加量が多いほど高分子固体電解質のイオン伝導度は高くなるが、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モノマー重量の５倍量以下である。また、可塑剤として炭酸ビニレン、（メタ）アクリロイルカーボネート、Ｎ−ビニルピロリドンのような重合性の化合物を、適度に非重合性可塑剤と併用して前記一般式（１）及び／または（２）で表されるユニットを有する化合物と共重合することにより、機械的強度を低下させずに、可塑剤の添加量を増加させ、イオン伝導度を改善することもできるので好ましい。
【００５８】
本発明の高分子固体電解質中の一般式（１）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と複合に用いる電解質の複合比は、側鎖のエーテル酸素原子１個〜１００個に対し、電解質分子１個の割合が好ましい。複合に用いる電解質がエーテル酸素原子の１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１／１００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。側鎖のエーテル酸素原子４個〜１００個に対し、電解質分子１個の割合がさらに好ましい。
【００５９】
複合に用いる電解質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、アルカリ金属塩、（ＣＨ_３ ）_４ ＮＢＦ_４ 等の４級アンモニウム塩、（ＣＨ_３ ）_４ ＰＢＦ_４ 等の４級ホスホニウム塩、ＡｇＣｌＯ_４ 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推奨される。
【００６０】
本発明の電池に用いる負極活物質としては，後述のように、アルカリ金属、アルカリ金属合金、炭素材料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。従って、かかる負極を用い、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の高分子固体電解質中の電解質としてはアルカリ金属塩が必要となる。
【００６１】
このアルカリ金属塩の種類としては、例えば、ＬｉＣＦ_３ ＳＯ_３ 、ＬｉＰＦ_６ 、ＬｉＣｌＯ_４ 、ＬｉＩ、ＬｉＢＦ_４ 、ＬｉＳＣＮ、ＬｉＡｓＦ_６ 、ＮａＣＦ_３ ＳＯ_３ 、ＮａＰＦ_６ 、ＮａＣｌＯ_４ 、ＮａＩ、ＮａＢＦ_４ 、ＮａＡｓＦ_６ 、ＫＣＦ_３ ＳＯ_３ 、ＫＰＦ_６ 、ＫＩ等を挙げることができる。この中で、アルカリ金属としては、リチウムまたはリチウム合金を用いた場合が、高電圧、高容量であり、かつ薄膜化が可能である点から最も好ましい。また、炭素材負極の場合には、アルカリ金属イオンだけでなく、４級アンモニウム塩、４級ホスホニウム塩、遷移金属塩、各種プロトン酸が使用できる。
【００６２】
固体電気二重層コンデンサの場合に複合に用いる電解質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、（ＣＨ_３ ）_４ ＮＢＦ_４ 、（ＣＨ_３ ＣＨ_２ ）_４ ＮＣｌＯ_４ 等の４級アンモニウム塩、ＡｇＣｌＯ_４ 等の遷移金属塩、（ＣＨ_３ ）_４ ＰＢＦ_４ 等の４級ホスホニウム塩、ＬｉＣＦ_３ ＳＯ_３ 、ＬｉＰＦ_６ 、ＬｉＣｌＯ_４ 、ＬｉＩ、ＬｉＢＦ_４ 、ＬｉＳＣＮ、ＬｉＡｓＦ_６ 、ＮａＣＦ_３ ＳＯ_３ 、ＮａＰＦ_６ 、ＮａＣｌＯ_４ 、ＮａＩ、ＮａＢＦ_４ 、ＮａＡｓＦ_６ 、ＫＣＦ_３ ＳＯ_３ 、ＫＰＦ_６ 、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、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、（ＣＨ_３ ＣＨ_２ ）（ＣＨ_３ ＣＨ_２ ＣＨ_２ ＣＨ_２ ）_３ ＮＢＦ_４ 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では好ましい。
【００６３】
本発明の電池の構成において、負極にアルカリ金属、アルカリ金属合金、炭素材料、導電性高分子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電極活物質（負極活物質）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、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低酸化還元電位であるため特に好ましい。また、炭素材料もＬｉ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。Ｌｉ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、気相法で合成した熱分解カーボン及びその黒鉛化物、石油コークス、石炭コークス、ピッチ系炭素、ポリアセン、Ｃ_６０、Ｃ_７０等のフラーレン類等が挙げられる。
【００６４】
本発明の電池の構成において、正極に金属酸化物、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、充填密度が高くなり、体積容量密度が高くなるという点では、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。
【００６５】
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_ｘ ＣｏＯ_２ やＬｉ_ｘ ＭｎＯ_２ 等の形でＬｉ元素を金属酸化物あるいは金属硫化物に挿入（複合）した状態で用いるのが好ましい。このようにＬｉ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Ｌｉ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、Ｌｉ_２ ＣＯ_３ 等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。
【００６６】
また柔軟で、薄膜にし易いという点では、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、ポリピロリレン及びその誘導体、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。
【００６７】
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。
また、本発明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炭素材料は、市販のものを用いることができ、あるいは公知の方法に従って製造される。
【００６８】
本発明の電極あるいは電池における正極活物質として、特に有機溶媒可溶性のアニリン系重合体を用いると、成形を溶液塗布で行なうことができるので有利であり、薄膜電池を作製する場合に極めて有利である。アニリン系重合体としては、ポリアニリン、ポリ−ｏ−トルイジン、ポリ−ｍ−トルイジン、ポリ−ｏ−アニシジン、ポリ−ｍ−アニシジン、ポリキシリジン類、ポリ−２，５−ジメトキシアニリン、ポリ−２，６−ジメトキシアニリン、ポリ−２，５−ジエトキシアニリン、ポリ−２，６−ジエトキシアニリン、ポリ−ｏ−エトキシアニリン、ポリ−ｍ−エトキシアニリン及びこれらの共重合体を挙げることができるが、特にこれらに限定されるものではなく、アニリン誘導体から導かれる繰返し単位を有する重合体であれば良い。また、有機溶媒可溶性のアニリン系重合体中の側鎖の導入量は、多いほど溶解性という点では都合が良いが、導入量が増加するほど、正極としての重量あたりの容量が低下するというマイナス面が表れる。従って、好ましいアニリン系重合体としては、例えば、ポリアニリン、ポリ−ｏ−トルイジン、ポリ−ｍ−トルイジン、ポリ−ｏ−アニシジン、ポリ−ｍ−アニシジン、ポリキシリジン類が挙げられる。
【００６９】
本発明において用いられるアニリン系重合体の重合方法は特に限定されるものではないが、一般には、例えば、「ジャーナル・オブ・ケミカル・ソサエティー、ケミカル・コミュニケーション、１７８４頁（１９８７）」等で報告されているように、アニリン、ｏ−アニシジン等のアニリン誘導体を電気化学的または化学的に酸化重合する方法が挙げられる。
【００７０】
電気化学的酸化重合は、陽極酸化によって行われ、電流密度約０．０１〜５０ｍＡ／ｃｍ^２ 、電解電圧０．１〜３０Ｖの範囲で、定電流法、定電圧法あるいはそれ以外の如何なる方法をも用いることができる。電解液のｐＨとしては特に制限はないが、好ましくはｐＨが３以下、特に好ましくは２以下である。ｐＨ調節に用いる酸の具体例としては、ＨＣｌ、ＨＢＦ_４ 、ＣＦ_３ ＣＯＯＨ、Ｈ_２ ＳＯ_４ 、ＨＮＯ_３ 、パラトルエンスルホン酸等の強酸を挙げることができるが、特にこれらに限定されるものではない。
化学的酸化重合の場合には、例えば、アニリン誘導体を酸性溶液中で過酸化物、過硫酸塩のような酸化剤で酸化重合させることができる。この場合に用いる酸としては、電気化学的酸化重合の場合に用いるものと同様のものを用いることが出来るが、これらに限定されるものではない。
【００７１】
このような方法で得られる、本発明で用いられるアニリン系重合体の分子量は特に限定されないが、通常２０００以上のものであれば好ましい。
このような方法によって得られるアニリン系重合体は、一般的に重合溶液中のアニオンをドーパントとして含んだ状態で得られる場合が多く、溶解性や重量当りの容量の面で不利となる。従って、例えば成膜成形法により、電極に成形する前に、これらアニオンを脱ドープし、さらに、還元型にすることが好ましい。脱ドープの方法としては特に制限はないが、一般的にはアンモニア水、水酸化ナトリウム等の塩基で処理する方法がとられる。また、還元方法についても特に制限はなく、一般的な化学的あるいは電気化学的還元を行なえばよい。例えば、化学的還元方法については、ヒドラジンやフェニルヒドラジン溶液中に塩基で処理したアニリン系重合体を室温下浸漬もしくは撹拌することで容易に還元できる。
【００７２】
このようにして得た脱ドープ型もしくは還元型アニリン系重合体は、種々の有機溶媒に可溶であり、溶液状態で、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種を含有する重合性モノマー溶液と混合でき、そのように調製した混合物を用いて、例えば塗布法等により、種々の支持体、例えば、電極上へ薄膜形成したり、あるいはその他の形状へ成形することにより、電極を製造することができる。
【００７３】
アニリン系重合体が溶解する溶媒としては、ベンゼン環上の置換基の種類によるので、特に限定されないが、Ｎ−メチルピロリドンのようなピロリドン類、ジメチルホルムアミドのようなアミド類、ｍ−クレゾール、ジメチルプロピレンウレア等の極性溶媒等が挙げられる。
【００７４】
次に、本発明の電極及び電池の製造方法の一例について詳しく説明する。
本発明の電極は、例えば、一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種を、場合によっては、更に他の重合性化合物及び／または可塑剤を添加して、前記の電極活物質（正極活物質または負極活物質）と混合する。その場合、混合する各成分の比率は、目的とする電池により適切なものとする。このようにして得た重合性モノマー／電極活物質混合物を膜状等の形状に成形後、重合を行うことにより電極を製造する。この方法において、重合は前述の一般式（１）及び／または（２）で表されるユニットを有する化合物（モノマー）から重合体を得る場合と同様の重合方法によることができ、例えば、加熱及び／または電磁波照射により重合を行なうことができる。電極活物質が、例えば有機溶媒可溶性のアニリン系重合体の場合のように、流動性の高い重合性モノマー／電極活物質混合物を与える場合には、該混合物を集電体あるいはその他ガラス等の支持体上に塗布して成膜する等の方法で成形後重合することにより電極を製造する。
【００７５】
このようにして製造した、前記の電極活物質を含む電極を少なくとも一方の電極とし、同様にして製造した他の電極活物質を含む電極あるいはその他通常用いられる電極をもう一方の電極とし、両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、一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種と、アルカリ金属塩のごとき前記の電解質から選ばれる少なくとも一種の電解質を混合し、場合によっては、更に他の重合性化合物及び／または可塑剤を添加混合して調製した重合性モノマー混合物を注入した後、例えば、加熱及び／または電磁波照射により重合する等、前述の一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体を得る場合の重合方法と同様の方法で重合することにより、あるいは、更に、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。
【００７６】
尚、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。
【００７７】
前述したように、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種を含むモノマー混合物と少なくとも一種の電解質を混合して得られる混合液を重合することにより、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と少なくとも一種の電解質を含む複合体からなる高分子固体電解質を製造する方法が、薄膜電池を製造する場合に特に有用である。
【００７８】
このようにして製造される本発明の電池の一例として、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、４は集電体、５はスペーサーである絶縁性樹脂フィルムであり、６は絶縁性樹脂封止剤である。
【００７９】
捲回型電池を製造する場合は、あらかじめ、調製しておいた高分子固体電解質シートを介して、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モノマー混合物を注入し、重合させるという方法も可能である。
【００８０】
次に本発明の固体電気二重層コンデンサについて説明する。
本発明の固体電気二重層コンデンサにおいて、本発明の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、あるいは加工性、信頼性に優れた全固体電気二重層コンデンサが提供される。
本発明の固体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１ｃｍ×１ｃｍ、厚み約０．５ｍｍの薄型セルで、８は集電体であり、集電体の内側には一対の分極性電極７が配置されており、その間に高分子固体電解質膜９が配置されている。１０はスペーサーであり、この例では絶縁性フィルムが用いられ、１１は絶縁性樹脂封止剤、１２はリード線である。
【００８１】
集電体８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、各種金属及びその燒結体、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７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が、かかる炭素材料に本発明の高分子固体電解質を複合させたものが好ましい。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カーボン及びその黒鉛化物、ポリアセン及びＣ_６０、Ｃ_７０を挙げることができる。
【００８２】
次に本発明の固体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。前述したように、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種と少なくとも一種の電解質を混合して、場合によっては更に他の重合性化合物及び／または可塑剤を添加混合して得られる重合性モノマー混合物を重合することにより、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と少なくとも一種の電解質を含む複合体が得られるが、この方法が本発明の固体電気二重層コンデンサを製造する場合に特に有用である。
【００８３】
本発明の固体電気二重層コンデンサにおいて好ましく用いられる、炭素材料のごとき分極性材料と前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体を含む分極性電極を製造する場合、まず、例えば、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種を、場合によっては、更に他の重合性化合物及び／または可塑剤を添加して、分極性材料と混合する。その場合、混合する各成分の比率は、目的とするコンデンサにより適切なものとする。このようにして得た重合性モノマー／分極性材料混合物を、支持体上、例えば集電体上に成膜した後、例えば、加熱及び／または電磁波照射により重合を行なう等、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体を得る場合の重合方法と同様の方法により重合することにより、分極性電極を製造する。本法によれば、集電体に良好に接触した複合薄膜電極を製造できる。
【００８４】
このようにして製造した分極性電極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を介して両電極をはり合せて、前記構造体内に入れ、次に、この２枚の分極性電極の間に、モノマーと電解質を混合し、場合によってはさらに他の重合性化合物及び／または可塑剤を添加混合して調製した重合性モノマー混合物を注入した後、上記と同様の方法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気二重層コンデンサが得られる。かかるモノマー混合物を調製する場合、混合する各成分の比率は、目的とするコンデンサにより適切なものとする。本法により、特に薄型全固体電気二重層コンデンサを製造することができる。尚、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シートを介して、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モノマー混合物を注入し、重合させるという方法も可能である。
【００８６】
【作用】
本発明の高分子固体電解質は、前述のとおり、その原料である重合性モノマー混合物から容易に成膜、複合できる尿素結合を有するオキシアルキル基を側鎖に導入した櫛型高分子または網目状高分子からなる高イオン伝導性の固体電解質であり、膜強度も良好であり、薄膜加工性にも優れている。
【００８７】
本発明の電池は、イオン伝導性物質として前記高分子固体電解質を用いることにより、薄膜化など加工も容易であり、薄膜でも短絡の恐れがなく、取り出し電流が大きく、信頼性の高い電池であり、特に全固体型電池とすることができる。また、本発明の、負極がリチウムまたはリチウム合金またはリチウムイオンを吸蔵放出できる炭素材料等の活物質を含む電極からなる電池は、イオン伝導性物質として前記高分子固体電解質を用いることにより、薄膜化など加工も容易であり、薄膜でも短絡の恐れがなく、取り出し電流が大きく、信頼性の高い電池であり、特に全固体型電池とすることができる。
【００８８】
また、本発明の正極が、前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と有機溶媒可溶性のアニリン系重合体もしくはその他の導電性高分子、金属酸化物、金属硫化物または炭素材料等の活物質を含む電極からなり、電解質として前記高分子固体電解質を用いることを特徴とする電池は、薄膜化など加工も容易であり、薄膜でも短絡の恐れがなく、取り出し電流が大きく、高容量で、信頼性の高い電池であり、特に全固体型電池とすることができる。
【００８９】
さらにまた、本発明の前記一般式（１）及び／または（２）で表されるユニットを有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と有機溶媒可溶性のアニリン系重合体もしくはその他の導電性高分子、金属酸化物、金属硫化物または炭素材料等の電極活物質を含む電極及び該電極の製造方法は、電極としての活性度に優れた該電極活物質の電気化学的活性度を損なうことなく、必要に応じた柔軟性を有する電極を提供するものであり、例えば、薄膜状の電極を提供することができ、該電極は種々の電池の電極として有用である。
【００９０】
また、本発明の電池の製造方法によれば、種々の形状の電池を製造することができ、特に電池の薄型化が容易であり、高容量、高電流で作動でき、あるいはサイクル性が良好な信頼性に優れた電池を製造することができ、特に全固体型電池を製造することができる。
【００９１】
本発明の電気二重層コンデンサは、重合性モノマー混合物から容易に成膜、複合できる尿素結合を有するオキシアルキル基を側鎖に導入した櫛型高分子または網目状高分子となる重合性モノマー混合物に電解質を溶解させたものを重合させて、高イオン伝導性で膜強度の良好な高分子固体電解質としたものをイオン伝導性物質として用いることによって製造される、薄膜でも短絡がなく、出力電圧及び取り出し電流が大きく、信頼性の高い電気二重層コンデンサであり、特に全固体型電気二重層コンデンサとすることができる。
【００９２】
特に、本発明の電気二重層コンデンサ及びその製造方法によれば、分極性電極とイオン伝導性物質である高分子固体電解質との接触が良好になされており、薄膜でも短絡がなく、出力電圧及び取り出し電流が大きく、信頼性の高い電気二重層コンデンサが提供され、特に全固体型電気二重層コンデンサが提供される。
【００９３】
【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。
【００９４】
［実施例１］＜モノマー１の合成＞
文献（ジャーナル オーガニック ケミストリー、１９９３年、５８巻、２６号、７５２４ページ）の方法に従い、下式に示す反応でモノメチルオリゴエチレングリコール（平均分子量５５０ アルドリッチ製）の末端水酸基をアミン化した原料１を得た。
【化１】

^１Ｈ−ＮＭＲ２．８ｐｐｍ付近に窒素／メチレン結合を、赤外吸収スペクトル３３００ｃｍ^−１付近にＮＨの伸縮振動を確認した。また水素、酸素、窒素の元素分析値は理論値と０．１％以内で合っていた。ＧＰＣで測定した平均分子量は５５０ であった。
【００９５】
次に下式に示す様な反応でモノマー１を合成した。

具体的には０．１ｍｏｌ（＝１５．５ｇ）のメタクリロイルオキシエチルイソシアナート（ＭＯＩ）、０．１ｍｏｌ（＝５５ｇ）の原料１を窒素雰囲気中でよく精製した１００ｍｌ のＴＨＦに溶解した後、０．６６ｇ のジブチルチンジラウレートを添加した。その後、５０℃で約３時間反応させることにより、無色の粘稠液体として６８ｇ のモノマー１を得た。
【００９６】
^１Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、ＭＯＩと原料１は１対１で反応し、さらに、ＭＯＩのイソシアナート基が消失し、尿素結合が生成していることがわかった。水素、酸素、窒素の元素分析値は理論値と０．１％以内で合っていた。ＧＰＣで測定した平均分子量は７００ であった。融点（ＤＳＣの吸熱ピーク）は約１０℃であった。^１Ｈ−ＮＭＲ：ＣＨ_２＝Ｃ−（５．６，６．１ｐｐｍ），−ＮＨＣＯ−（５．４ｐｐｍ），−ＣＨ_２０−（３．６ 〜３．７ｐｐｍ），−ＣＨ_２Ｎ−（３．５ｐｐｍ），−ＯＣＨ_３（３．３ｐｐｍ），＝Ｃ−ＣＨ_３（１．９ｐｐｍ）
【００９７】
［実施例２］＜モノマー１系高分子固体電解質の作製と評価＞
２．０９ｇ のモノマー１を１０ｃｃのＴＨＦに溶解し、０．１４ｇ のＬｉＣＦ_３ＳＯ_３を加えてよく混合した。次いで、ＴＨＦを室温、減圧下で除去し、モノマー１／ＬｉＣＦ_３ＳＯ_３混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１重合体／ＬｉＣＦ_３ＳＯ_３複合体が約１００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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 ×１０^−５Ｓ／ｃｍであった。
【００９８】
［実施例３］
実施例２で用いたＬｉＣＦ_３ＳＯ_３に代えて、ＮａＣＦ_３ＳＯ_３を０．１５ｇ 用いた以外は実施例２と同様にして、固体電解質を作製した。この固体電解質の２５℃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、６ ×１０^−５Ｓ／ｃｍであった。
【００９９】
［実施例４］
実施例２で用いたＬｉＣＦ_３ＳＯ_３に代えて、ＬｉＩ を０．１１ｇ 用いた以外は実施例２と同様にして、固体電解質を作製した。この固体電解質の２５℃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、１ ×１０^−４Ｓ／ｃｍであった。
【０１００】
［実施例５］＜モノマー２の合成＞
下式に示す様な反応でモノマー２を合成した。

具体的にはメタクリロイルオキシエチルイソシアナート（ＭＯＩ）０．２ｍｏｌ（＝３１ｇ）、ＪＥＦＦＡＭＩＮ ＥＤ９００（アルドリッチ製、平均分子量９００）０．１ｍｏｌ（＝９０ｇ）を窒素雰囲気中でよく精製した ２００ｍｌのＴＨＦに溶解した後、０．６６ｇ のジブチルチンジラウレートを添加した。その後、５０℃で約３時間反応させることにより、無色の粘稠液体としてモノマー２を１１５ｇ得た。
【０１０１】
^１Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、ＭＯＩとＪＥＦＦＡＭＩＮ ＥＤ９００は２ 対１で反応し、さらに、ＭＯＩのイソシアナート基が消失し、尿素結合が生成していることがわかった。水素、酸素、窒素の元素分析値は理論値と０．１％以内で合っていた。ＧＰＣで測定した平均分子量は７００ であった。融点らしきＤＳＣの吸熱ピークは−７０ ℃以上では観察できなかった。^１Ｈ−ＮＭＲ：ＣＨ_２＝Ｃ−（５．６，６．１ｐｐｍ），−ＮＨＣＯ−（５．２〜５．５ｐｐｍ），−ＣＨ_２０−（３．５〜３．８ｐｐｍ），−ＣＨ_２Ｎ−（３．３〜３．５ｐｐｍ），＝Ｃ−ＣＨ_３（２．０ｐｐｍ），−Ｃ−ＣＨ_３（１．２ｐｐｍ）
【０１０２】
［実施例６］＜モノマー１／モノマー２共重合系高分子固体電解質の作製と評価＞
２．１０ｇ のモノマー１と０．５１ｇ のモノマー２を２０ｃｃのＴＨＦに溶解し、０．１４ｇ のＬｉＣＦ_３ＳＯ_３を加えてよく混合した。次いで、ＴＨＦを室温、減圧下で除去し、モノマー１／モノマー２／ＬｉＣＦ_３ＳＯ_３混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１／モノマー２共重合体／ＬｉＣＦ_３ＳＯ_３複合体が約５０μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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 ×１０^−５Ｓ／ｃｍであった。
【０１０３】
［実施例７］＜モノマー３／モノマー２共重合系高分子固体電解質の作製と評価＞
まず、下式に示す反応でモノマー３を合成した。

具体的にはメタクリロイルオキシエチルイソシアナート（ＭＯＩ）０．１ｍｏｌ（＝１５．５ｇ）、平均分子量５５０のモノメチルオリゴエチレングリコール０．１ｍｏｌ（＝５５ｇ）を窒素雰囲気中でよく精製した １００ｍｌのＴＨＦに溶解した後、０．６６ｇ のジブチルチンジラウレートを添加した。その後、５０℃で約３時間反応させることにより、無色の粘稠液体としてモノマー３を得た。その^１Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、ＭＯＩとモノメチルオリゴエチレングリコールは１対１で反応し、さらに、ＭＯＩのイソシアナート基が消失し、ウレタン結合が生成していることがわかった。
【０１０４】
次に、２．１０ｇ のモノマー３と０．５１ｇ のモノマー２を２０ｃｃのＴＨＦに溶解し、０．１４ｇ のＬｉＣＦ_３ＳＯ_３を加えてよく混合した。次いで、ＴＨＦを室温、減圧下で除去し、モノマー３／モノマー２／ＬｉＣＦ_３ＳＯ_３混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー３／モノマー２共重合体／ＬｉＣＦ_３ＳＯ_３複合体が約２００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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 ×１０^−５Ｓ／ｃｍであった。
【０１０５】
［実施例８］＜モノマー１／モノマー４共重合系高分子固体電解質の作製と評価＞
まず、下式に示す反応でモノマー４を合成した。

具体的にはメタクリロイルオキシエチルイソシアナート（ＭＯＩ）０．２ｍｏｌ（＝３１ｇ）、アデカカーポールＰＨ８０（平均分子量８００）０．１ｍｏｌ（＝８０ｇ）を窒素雰囲気中でよく精製した １００ｍｌのＴＨＦに溶解した後、０．６６ｇ のジブチルチンジラウレートを添加した。その後、５０℃で約３時間反応させることにより、無色の粘稠液体としてモノマー４を得た。その^１Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、ＭＯＩとＰＨ８０は２ 対１で反応し、さらに、ＭＯＩのイソシアナート基が消失し、ウレタン結合が生成していることがわかった。
【０１０６】
次に２．１０ｇ のモノマー１と０．５１ｇ のモノマー４を２０ｃｃのＴＨＦに溶解し、０．１４ｇ のＬｉＣＦ_３ＳＯ_３を加えてよく混合した。次いで、ＴＨＦを室温、減圧下で除去し、モノマー１／モノマー４／ＬｉＣＦ_３ＳＯ_３混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１／モノマー４共重合体／ＬｉＣＦ_３ＳＯ_３複合体が約１００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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、３ ×１０^−５Ｓ／ｃｍであった。
【０１０７】
［実施例９］＜モノマー５の合成＞
まず、実施例１と同様の方法で、下式に示す反応でアデカカーポールＧＨ−５（平均分子量５０００、トリオール、ＫＯＨ価 ３４．０ｍｇ ／ｇ ）の末端水酸基をアミン化したモノマー５の原料２を合成した。
【化２】

^１Ｈ−ＮＭＲ２．８ｐｐｍ付近に窒素／メチレン結合を、赤外吸収スペクトル３３００ｃｍ^−１付近にＮＨの伸縮振動を確認した。また水素、酸素、窒素の元素分析値は理論値と０．１％以内で合っていた。ＧＰＣで測定した平均分子量は５０００であった。
【０１０８】
次に下式に示す様な反応でモノマー５を合成した。
【化３】

具体的にはメタクリロイルオキシエチルイソシアナート（ＭＯＩ）０．１ｍｏｌ（＝１５．５ｇ）、０．０３３ｍｏｌ（＝１６５ｇ） の原料２を窒素雰囲気中でよく精製した ３００ｍｌのＴＨＦに溶解した後、０．６６ｇ のジブチルチンジラウレートを添加した。その後、５０℃で約３時間反応させることにより、無色の粘稠液体としてモノマー５を１７５ｇ得た。
【０１０９】
^１Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、ＭＯＩと原料２は３対１で反応し、さらに、ＭＯＩのイソシアナート基が消失し、尿素結合が生成していることがわかった。水素、酸素、窒素の元素分析値は理論値と０．１％以内で合っていた。ＧＰＣで測定した平均分子量は６０００であった。融点らしきＤＳＣの吸熱ピークは−７０ ℃以上では観察できなかった。^１Ｈ−ＮＭＲ：ＣＨ_２＝Ｃ−（５．６，６．１ｐｐｍ），−ＮＨＣＯ−（５．２〜５．６ｐｐｍ），−ＣＨ_２０−（３．４〜３．８ｐｐｍ），−ＣＨ_２Ｎ−（３．３〜３．６ｐｐｍ），＝Ｃ−ＣＨ_３（１，９〜２．１ｐｐｍ），−Ｃ−ＣＨ_３（１．１〜１．２ｐｐｍ）
【０１１０】
［実施例１０］＜モノマー５系高分子固体電解質の作製と評価＞
２．０９ｇ のモノマー５を１０ｃｃのＴＨＦに溶解し、０．１４ｇ のＬｉＣＦ_３ＳＯ_３を加えてよく混合した。次いで、ＴＨＦを室温、減圧下で除去し、モノマー５／ＬｉＣＦ_３ＳＯ_３混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー５重合体／ＬｉＣＦ_３ＳＯ_３複合体が約５０μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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、３ ×１０^−５Ｓ／ｃｍであった。
【０１１１】
［実施例１１］
実施例１０で用いたＬｉＣＦ_３ＳＯ_３に代えて、ＬｉＢＦ_４ を０．１０ｇ 用いた以外は実施例１０と同様にして、固体電解質を作製した。この固体電解質の２５℃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 ×１０^−５Ｓ／ｃｍであった。
【０１１２】
［実施例１２］
実施例１０で用いたＬｉＣＦ_３ＳＯ_３に代えて、ＬｉＰＦ_６ を０．１５ｇ 用いた以外は実施例１０と同様にして、固体電解質を作製した。この固体電解質の２５℃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、５ ×１０^−４Ｓ／ｃｍであった。
【０１１３】
［実施例１３］＜モノマー１／モノマー５共重合系高分子固体電解質の作製と評価＞
１．００ｇ のモノマー１と１．６１ｇ のモノマー５を２０ｃｃのＴＨＦに溶解し、０．１０ｇ のＬｉＢＦ_４ を加えてよく混合した。次いで、ＴＨＦを室温、減圧下で除去し、モノマー１／モノマー５／ＬｉＢＦ_４ 混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１／モノマー５共重合体／ＬｉＢＦ_４ 複合体が約１００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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、５ ×１０^−５Ｓ／ｃｍであった。
【０１１４】
［実施例１４］＜モノマー３／モノマー５共重合系高分子固体電解質の作製と評価＞
１．００ｇ のモノマー３と１．６１ｇ のモノマー５を２０ｃｃのＴＨＦに溶解し、０．１０ｇ のＬｉＢＦ_４ を加えてよく混合した。次いで、ＴＨＦを室温、減圧下で除去し、モノマー３／モノマー５／ＬｉＢＦ_４ 混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー３／モノマー５共重合体／ＬｉＢＦ_４ 複合体が約１００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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、５ ×１０^−５Ｓ／ｃｍであった。
【０１１５】
［実施例１５］
１．００ｇ のモノマー１、０．５０ｇ のモノマー２、 １．３０ｇのプロピレンカーボネート（ＰＣ）、１．３０ｇ のエチレンカーボネート（ＥＣ）、及び０．５６ｇ のＬｉＢＦ_４ をアルゴン雰囲気中でよく混合し、モノマー１／モノマー２／ＰＣ／ＥＣ／ＬｉＢＦ_４ 混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１＋モノマー２共重合体／ＰＣ／ＥＣ／ＬｉＢＦ_４ 複合体が約２００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃、−１０℃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 ×１０^−３Ｓ／ｃｍ、６ ×１０^−４Ｓ／ｃｍであった。
【０１１６】
［実施例１６］
実施例１５で用いたＰＣ，ＥＣの代りに、テトラグライム（ＴＧ）を用いた以外は、実施例１５と全く同様の方法で、モノマー１＋モノマー２共重合体／ＴＧ／ＬｉＢＦ_４ 複合体を約２００μｍ の透明な自立フィルムとして得た。このフィルムの２５℃，−１０℃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、８ ×１０^−４，１ ×１０^−４Ｓ／ｃｍであった。
【０１１７】
［実施例１７］
０．５０ｇ のモノマー１、１．０ｇのモノマー５、 １．３０ｇのプロピレンカーボネート（ＰＣ）、１．３０ｇ のエチレンカーボネート（ＥＣ）、及び０．５６ｇ のＬｉＢＦ_４ をアルゴン雰囲気中でよく混合し、モノマー１／モノマー５／ＰＣ／ＥＣ／ＬｉＢＦ_４ 混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１＋モノマー５共重合体／ＰＣ／ＥＣ／ＬｉＢＦ_４ 複合体が約１００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃、−１０℃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、３ ×１０^−３Ｓ／ｃｍ、７ ×１０^−４Ｓ／ｃｍであった。
【０１１８】
［実施例１８］
実施例１７で用いたＬｉＢＦ_４ の代りに、ＬｉＰＦ_６ を０．８４ｇ 用いた以外は、実施例１７と全く同様の方法で、モノマー１＋モノマー５共重合体／ＰＣ／ＥＣ／ＬｉＰＦ_６ 複合体を約１００μｍ の透明な自立フィルムとして得た。このフィルムの２５℃，−１０℃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、３ ×１０^−３，１ ×１０^−３Ｓ／ｃｍであった。
【０１１９】
［実施例１９］
実施例１７で用いたプロピレンカーボネートの代りに、ジエチルカーボネート（ＤＥＣ）を用いた以外は、実施例１７と全く同様の方法で、モノマー１＋モノマー５共重合体／ＤＥＣ／ＥＣ／ＬｉＢＦ_４ 複合体を約１００μｍ の透明な自立フィルムとして得た。このフィルムの２５℃， −１０℃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、１ ×１０^−３、２ ×１０^−４Ｓ／ｃｍであった。
【０１２０】
［実施例２０］
１．５ｇのモノマー５、 １．３０ｇのプロピレンカーボネート（ＰＣ）、１．３０ｇ のエチレンカーボネート（ＥＣ）、及び０．８４ｇ のＬｉＰＦ_６ をアルゴン雰囲気中でよく混合し、モノマー５／ＰＣ／ＥＣ／ＬｉＰＦ_６ 混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー５重合体／ＰＣ／ＥＣ／ＬｉＰＦ_６ 複合体が約５０μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃、−１０℃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、２．５ ×１０^−３Ｓ／ｃｍ、８ ×１０^−４Ｓ／ｃｍであった。
【０１２１】
［実施例２１］
１．１ｇのモノマー１、０．２ｇのＮ，Ｎ−ジメチルアクリルアミドを１００ｃｃ のＴＨＦに溶解し、０．１０ｇ のＬｉＢＦ_４ を加えてよく混合した。次いで、ＴＨＦを室温減圧下で除去し、モノマー１／Ｎ，Ｎ−ジメチルアクリルアミド／ＬｉＢＦ_４ 混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１＋Ｎ，Ｎ−ジメチルアクリルアミド共重合体／ＬｉＢＦ_４ 複合体が約２０μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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、３ ×１０^−５Ｓ／ｃｍであった。
【０１２２】
［実施例２２］
１．１ｇのモノマー１、ポリエチレンオキサイドＰＥＯ−１（住友精化（株）製）０．２ｇを１００ｃｃ のＴＨＦに溶解し、０．１０ｇ のＬｉＢＦ_４ を加えてよく混合した。次いで、ＴＨＦを室温減圧下で除去し、モノマー１／ＰＥＯ−１／ＬｉＢＦ_４ 混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１／ＰＥＯ−１／ＬｉＢＦ_４ 複合体が約２０μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃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 ×１０^−５Ｓ／ｃｍであった。
【０１２３】
［実施例２３］＜酸化コバルト正極の製造＞
１１ｇ のＬｉ_２ ＣＯ_３ と２４ｇ のＣｏ_３ Ｏ_４ 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ＬｉＣｏＯ_２ 粉末を得た。このＬｉＣｏＯ_２ 粉末と実施例１８で調製した重合性モノマー溶液を、アルゴン雰囲気下、重量比７：３で混合し、ステンレス箔上に１×１ｃｍ、約２００μｍの厚さに塗布した。さらに、約１００℃で１時間加熱重合することにより、酸化コバルト／高分子固体電解質複合正極（６５ｍｇ）を得た。
【０１２４】
［実施例２４］＜高分子固体電解質二次電池の製造＞
アルゴン雰囲気グローブボックス内で、厚さ７５μｍ のリチウム箔を１×１ｃｍに切出し（５．３ｍｇ ）、その端部約１ｍｍ四方を５μｍ のポリイミドフィルムで、スペーサーとして被覆した。次に、実施例２０で調製した重合性モノマー溶液をリチウム箔上に塗布し、さらに実施例２３で製造した酸化コバルト正極を張り合わせ、１００℃、１時間加熱後、電池端部をエポキシ樹脂で封印し、リチウム／酸化コバルト固体二次電池を得た。
得られた電池の断面図を図１に示す。
この電池を、作動電圧２．０ 〜４．３Ｖ、電流０．１ｍＡ で充放電を繰返したところ、最大放電容量は３．８ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は２５５回であった。
【０１２５】
［実施例２５］＜ポリアニリン正極の製造＞
アニリン０．５Ｍ，ＨＢＦ_４１．５Ｍ 水溶液を重合溶液として、対極にグラファイトフォイルを用いて、１×１ｃｍステンレス箔上に、１ｍＡ の定電流法で約１００μｍ の厚さに電解酸化重合した。次いで、メタノールで洗浄後、８０℃で２４時間真空乾燥した。
次いでこの膜をアルゴン雰囲気のグローブボックス内に移し、実施例１８で調製した重合性モノマー溶液をしみ込ませ、１００℃、１時間で重合することにより、ポリアニリン／高分子固体電解質複合正極（４５ｍｇ）を得た。
【０１２６】
［実施例２６］＜高分子固体電解質二次電池の製造＞
酸化コバルト正極のかわりに実施例２５で製造したポリアニリン正極を用いた以外は実施例２４と同様にして、リチウム／ポリアニリン固体二次電池を得た。この電池を、作動電圧２．０ 〜４．０Ｖ、電流０．１ｍＡ で充放電を繰返したところ、最大放電容量は０．８ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は４１１回であった。
【０１２７】
［実施例２７］＜気相法黒鉛負極の製造＞
昭和電工製気相法黒鉛繊維（平均繊維径、０．３ μｍ 、平均繊維長、２．０ μｍ 、２７００℃熱処理品）１０ｇ と２．５Ｍブチルリチウム含有ヘキサン溶液２００ｍｌを混合し、室温で８時間攬拌した。次いでヘキサンで洗浄後乾燥して、リチウムイオンが予備挿入された黒鉛繊維を得た。Ｃ／Ｌｉ原子比を元素分析から求めたところ１２／１であった。このようにして得たリチウム含有黒鉛繊維６ｇと実施例１８で調製した重合性モノマー混合物４ｇを、アルゴン雰囲気下で混合し、その一部をとってステンレス箔上に１×１ｃｍ、約１５０μｍの厚さに塗布した。さらに、約１００℃ で１時間加熱重合することにより、気相法黒鉛／高分子固体電解質複合負極（２１ｍｇ）を得た。
【０１２８】
［実施例２８］＜高分子固体電解質二次電池の製造＞
リチウム箔のかわりに実施例２７で製造した気相法黒鉛負極を用いた以外は実施例２４と同様にして、気相法黒鉛／酸化コバルト固体二次電池を得た。
この電池を、作動電圧１．５ 〜４．３Ｖ、電流０．１ｍＡ で充放電を繰返したところ、最大放電容量は３．５ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は２０１回であった。
【０１２９】
［実施例２９］＜有機溶媒可溶性ポリアニリンの合成＞
１Ｌの４つ口フラスコに、温度計、撹拌機、コンデンサ−を取り付け、１規定のＨＣｌ水溶液を５００ｍｌ加え、窒素をバブルしながら２０．３ｇのアニリンを溶解した。次いで、撹拌下、窒素バブルしながら、１１．５ｇの過硫酸アンモニウムを固体のまま、約３０分かけて添加した。反応温度は約２２℃に保った。添加後、さらに２２時間反応させた後ろ過し、ろ残を５００ｍｌの蒸留水で洗浄した。次いで、この生成物をビーカーに移し、５００ｍｌの５％アンモニア水で約１時間撹拌後、ろ過、蒸留水洗浄、減圧乾燥することにより、脱ドープ状態のポリアニリン粉末約１６ｇを得た。
【０１３０】
次に、３００ｍｌの３つ口フラスコにヒドラジン１水和物を１５０ｍｌ加え、撹拌しながら窒素気流下で室温で上記脱ドープポリアニリン粉末を約１時間かけて添加した。さらに窒素気流下、約１０時間、室温で撹拌後、窒素雰囲気中でろ過し、減圧乾燥した。さらに窒素雰囲気下で精製ＴＨＦ、精製エーテルで洗浄、減圧乾燥することにより、還元状態のポリアニリン粉末約１４ｇを得た。
【０１３１】
この還元状態のポリアニリン粉末の元素分析値は炭素、水素、窒素の総和が９８％であり、炭素／水素／窒素の元素比は６．００／４．９５／１．０１と理論値とほぼ一致した。
この粉末はアルゴン雰囲気下で精製Ｎ−メチルピロリドン（ＮＭＰ）に約５ｗｔ％の濃度まで溶解した。この溶液のＧＰＣ測定から求めたポリアニリンの数平均分子量は、ポリスチレン換算で約２００００であった。
【０１３２】
［実施例３０］＜ポリアニリン正極の製造＞
アルゴン雰囲気のグローブボックス中で実施例１８で製造した重合性モノマー溶液を実施例２９で調製した５ｗｔ％ポリアニリン／ＮＭＰ溶液に、ポリアニリンと重合性モノマー溶液の重量比が１：１になるように混合した。この混合溶液を５０μｍのポリイミドフィルムを３ｍｍの幅で四方の端部に貼りつけた１５×１５ｍｍ、厚さ１００μｍのステンレス箔上のポリイミドフィルムに囲まれた部分に塗布した。
次いで６０℃、８０℃、１００℃で各々１時間づつ加熱することにより、乾燥、重合を行なった。
【０１３３】
［実施例３１］＜高分子固体電解質二次電池の製造＞
アルゴン雰囲気グローブボックス内で、厚さ２５μｍ のリチウム箔を１２×１２ｍｍ（２．６ｍｇ ）に切出し、その端部約２ｍｍ四方を５μｍのポリイミドフィルムで、スペーサーとして被覆した。次に、実施例２０で調製した重合性モノマー溶液をリチウム箔上に塗布し、さらに実施例２９で製造したポリアニリン正極を張り合わせ、１００℃、１時間加熱後、電池端部をエポキシ樹脂で封印し、図１に示すようなリチウム／ポリアニリン固体二次電池を得た。
この電池を、作動電圧２〜４Ｖ、電流０．１ｍＡで充放電を繰返したところ、最大放電容量は１．２ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は２５３回であった。
【０１３４】
［実施例３２］＜重合性モノマー溶液の調製＞
１．００ｇ のモノマー１、０．５０ｇ のモノマー２、２．６ｇのプロピレンカーボネート（ＰＣ）、及び１．１０ｇ のテトラエチルアンモニウムパークロレート（ＴＥＡＰ）をアルゴン雰囲気中でよく混合し、モノマー１／モノマー２／ＰＣ／ＴＥＡＰ混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー１＋モノマー２共重合体／ＰＣ／ＴＥＡＰ複合体が約２００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃、−１０℃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、２．５ ×１０^−３Ｓ／ｃｍ、８ ×１０^−４Ｓ／ｃｍであった。
【０１３５】
［実施例３３］＜重合性モノマー溶液の調製＞
１．５０ｇ のモノマー５、２．６ｇのプロピレンカーボネート（ＰＣ）、及び１．１０ｇ のテトラエチルアンモニウムパークロレート（ＴＥＡＰ）をアルゴン雰囲気中でよく混合し、モノマー５／ＰＣ／ＴＥＡＰ混合物を粘稠液体として得た。アルゴン雰囲気下、この混合物をガラス板状に塗布後、１００℃で１時間加熱したところ、モノマー５重合体／ＰＣ／ＴＥＡＰ複合体が約１００μｍ の透明な自立フィルムとして得られた。このフィルムの２５℃、−１０℃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、３．０ ×１０^−３Ｓ／ｃｍ、８ ×１０^−４Ｓ／ｃｍであった。
【０１３６】
［実施例３４］＜活性炭電極の製造＞
椰子がら活性炭と実施例３２で調製した重合性モノマー混合物を、アルゴン雰囲気下、重量比１：１で混合し、ステンレス箔上に１ｃｍ×１ｃｍの大きさで約１５０μｍの厚さに塗布した。さらに、約１００℃で１時間加熱して重合させることにより、活性炭／高分子固体電解質複合電極（１３ｍｇ）を得た。
【０１３７】
［実施例３５］＜固体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３４で製造した活性炭電極（１３ｍｇ）１ｃｍ×１ｃｍの端部約１ｍｍ四方を厚さ５μｍのポリイミドフィルムをスペーサーとして被覆した。次に、実施例３３で調製した重合性モノマー混合物を電極上に塗布し、さらにもう一枚の電極をはり合わせ、１００℃、１時間加熱後、コンデンサ端部をエポキシ樹脂で封止し、図２に示すような固体電気二重層コンデンサを製造した。
このコンデンサを、作動電圧０〜２．５Ｖ、電流０．１ｍＡで充放電を行なったところ、最大容量は１８０ｍＦであった。また、この条件で充放電を５０回繰り返してもほとんど容量に変化はなかった。
【０１３８】
［実施例３６］＜固体電気二重層コンデンサの製造＞
実施例１５で製造した重合性モノマー混合物を用いた以外は、実施例３４と同様の方法で活性炭電極（１３ｍｇ）を製造した。
この電極と実施例１７で製造した重合性モノマー溶液を用いた以外は実施例３５と同様にして固体電気二重層コンデンサを製造した。
このコンデンサを、作動電圧０〜２．０Ｖ、電流０．１ｍＡで充放電を行なったところ、最大容量は１５０ｍＦであった。また、この条件で充放電を５０回繰り返してもほとんど容量に変化はなかった。
【０１３９】
【発明の効果】
本発明の高分子固体電解質は、尿素結合により結合したオキシアルキル基を側鎖に有する高分子と少なくとも一種の電解質との複合体から構成されており、膜強度が良好な薄膜として得られ易く、また、高イオン伝導性という特徴を有している。
本発明の高分子固体電解質を用いた電池及び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。
【０１４０】
本発明の、尿素結合により結合したオキシアルキル基を側鎖に有する高分子及び有機溶媒可溶性のポリアニリン系重合体もしくはその他の導電性高分子、金属酸化物、金属硫化物または炭素材料等の電極活物質または分極性材料を含む電極及びその製造方法は、高い電気化学的活性と柔軟性を有する電極を提供でき、特に薄型電極を提供でき、種々の電池または電気二重層コンデンサ等に用いられる電極及びその製造方法として有用である。
【０１４１】
また、本発明の電池は、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。また、薄膜化が容易にできるので、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。
【０１４２】
更に、本発明の電気二重層コンデンサは、従来の全固体型コンデンサと比較しても、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、信頼性に優れた電気二重層コンデンサであり、かかる特徴を有する全固体電気二重層コンデンサとすることができる。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おり、従来の固体型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】本発明の電池の一例として示す、薄型の固体電池の実施例の概略断面図である。
【図２】本発明の固体電気二重層コンデンサの実施例の概略断面図である。
【符号の説明】
１ 正極
２ 高分子固体電解質
３ 負極
４ 集電体
５ スペーサー
６ 絶縁性樹脂封止剤
７ 分極性電極
８ 集電体
９ 高分子固体電解質膜
１０ スペーサー
１１ 絶縁性樹脂封止剤
１２ リード線[0001]
[Industrial applications]
The present invention provides a polymer solid electrolyte having high ionic conductivity using a composite comprising a novel polymer and an electrolyte containing a monomer mixture containing an oxyalkylene derivative having a urea bond, and an electrode using the polymer. Method for producing the same, battery using the polymer solid electrolyte or the electrode and method for producing the same, electric double layer capacitor using the polymer solid electrolyte or the electrode and the method for producing the same, polymer, and polymer For monomers.
[0002]
[Prior art]
In the trend of downsizing and all-solidification in the field of ionics, application to all solid-state primary batteries, secondary batteries and electric double-layer capacitors using solid electrolytes as a new ion conductor instead of conventional electrolyte solutions Have been actively tried. A battery using a current electrolyte solution has a problem in long-term reliability because liquid leakage to the outside of a component or elution of an electrode material easily occurs. On the other hand, a product using a solid electrolyte does not have such a problem, and it is easy to reduce the thickness. Further, the solid electrolyte is excellent in heat resistance, and is advantageous in a process of manufacturing a product such as a battery.
[0003]
In particular, those using a solid electrolyte containing a polymer as a main component have the advantages that the flexibility of the battery is increased and that the battery can be processed into various shapes as compared with inorganic substances. However, those studied so far have a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low.
[0004]
As an example of these polymer electrolytes, "British Polymer Journal (Br. Polym. J.), Vol. 319, p. 137, 1975" describes a composite of polyethylene oxide and an inorganic alkali metal salt as an ion conductive material. Although it is described that the ionic conductivity at room temperature, the ionic conductivity at room temperature is 10 ^-7 Low as S / cm.
[0005]
Recently, it has been reported that a comb polymer in which oligooxyethylene is introduced into a side chain enhances the thermal mobility of an oxyethylene chain that is responsible for ionic conductivity and improves ionic conductivity. For example, “Journal of Physical Chemistry (J. Phys. Chem.), Vol. 89, p. 987, 1984” describes that a polymethacrylic acid obtained by adding oligooxyethylene to a side chain thereof is an alkali metal salt. Are described. Further, "Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 106, p. 6854, 1984" discloses that an alkali metal salt is added to polyphosphazene having an oligooxyethylene side chain. A composite example is described.
[0006]
Recently, LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , MoS ₂ Many studies have been made on lithium secondary batteries using a metal oxide or metal sulfide such as the above for the positive electrode. For example, "Journal of Electrochemical Society (J. Electrochem. Soc.), Vol. 138 (No. 3), p. 665, 1991" discloses MnO. ₂ Or NiO ₂ A battery having a positive electrode has been reported. These have attracted attention because of their high capacity per weight or volume.
[0007]
Also, there are many reports on batteries using a conductive polymer as an electrode active material. For example, a lithium secondary battery using a polyaniline as a positive electrode is described in, for example, "27th Battery Symposium, 3A05L and 3A06L, 1986". Has been launched by Bridgestone and Seiko as coin-type batteries for backup power. In addition, polyaniline has attracted attention as a positive electrode active material having high capacity and excellent flexibility.
[0008]
Further, in recent years, an electric double layer capacitor in which a carbon material having a large specific surface area, such as activated carbon or carbon black, is used as a polarizable electrode and an ion conductive solution is arranged between the polarizable electrodes for use as a memory backup power supply or the like has been widely used. For example, in “Functional Materials, February 1989, p. 33”, a capacitor using a carbon-based polarizable electrode and an organic electrolyte is described in “173rd Electrochemical Society Meeting Atlanta Georgia, May, No. 18, 1988 "describes an electric double layer capacitor using a sulfuric acid aqueous solution. In Japanese Patent Application Laid-Open No. 63-244570, Rb having high electrical conductivity is disclosed. ₂ Cu ₃ I ₃ Cl ₇ Discloses a capacitor using as an inorganic solid electrolyte.
[0009]
However, with current electric double-layer capacitors using electrolyte solutions, long-term use or high-voltage imposed abnormalities tend to cause leakage of liquid to the outside of the capacitor. There is a problem with sex. On the other hand, a conventional electric double layer capacitor using an inorganic ion conductive material has a problem that the decomposition voltage of the ion conductive material is low and the output voltage is low.
[0010]
Japanese Patent Application Laid-Open No. Hei 4-253771 discloses that a polyphosphazene polymer is used as an ion conductive material for batteries and electric double layer capacitors. The used one has the advantages that the output voltage is higher than that of the inorganic ion conductive substance, that it can be processed into various shapes, and that the sealing is simple.
[0011]
However, in this case, the ionic conductivity of the solid polymer electrolyte is 10 ^-4 -10 ^-6 S / cm was not sufficient, and there was a drawback that the take-out current was small. It is also possible to increase the ionic conductivity by adding a plasticizer to the polymer solid electrolyte, but since it imparts fluidity, it cannot be treated as a complete solid and has poor film strength and film formability. When applied to an electric double layer capacitor or a battery, a short circuit is likely to occur, and a sealing problem occurs similarly to a liquid ion conductive material. On the other hand, when assembling a solid electrolyte together with a polarizable electrode into a capacitor, there is also a problem that it is difficult to uniformly combine the solid electrolyte with a carbon material having a large specific surface area since the solids are mixed.
[0012]
The ionic conductivity of a generally studied polymer solid electrolyte is 10 at room temperature. ^-4 -10 ^-5 Although improved to the order of S / cm, it is still at least two orders of magnitude lower than liquid ion conductive materials. Further, when the temperature is lowered to 0 ° C. or lower, the ionic conductivity is further reduced extremely. Furthermore, when these solid electrolytes are incorporated into an element such as an electric double layer capacitor, or when these solid electrolytes are incorporated into a battery as a thin film, processing techniques such as compounding with electrodes and securing contactability are difficult, and even in a manufacturing method. There was a problem.
[0013]
In order to solve these problems, the present inventors have developed a polymer using a (meth) acrylate monomer mixture containing an oxyalkylene group having a urethane bond and an ion-conductive polymer using a composite comprising an electrolyte. A solid electrolyte (JP-A-6-187822) has been proposed. The ionic conductivity of this solid polymer electrolyte was 10 when no plasticizer was added. ^-4 S / cm (room temperature), which is a high level, but when a plasticizer is further added, even at room temperature or lower, 10 ^-3 S / cm or more, and the film quality was improved to such an extent that a thick film could be obtained as a free-standing film. In addition, this monomer has good polymerizability, and has an advantage in processing when applied to batteries and electric double layer capacitors. However, in the case of a plasticizer-added system, when a thin film having a thickness of about several tens of μm is used, the film strength is inferior.
[0014]
The polymer solid electrolyte layer in the battery and the capacitor is responsible only for ion transfer. The thinner the layer, the smaller the volume of the entire battery and the capacitor, and the higher the energy density of the battery and the capacitor. Further, when the polymer solid electrolyte layer is thinned, the electric resistance of the battery and the capacitor can be reduced, the take-out current and the charging current can be increased, and the power density of the battery can be improved. Further, corrosion of ions, particularly alkali metal ions, hardly occurs, and the cycle life is improved. Accordingly, there has been a demand for a polymer solid electrolyte having high ionic conductivity, which has as good a film strength as possible and which can be formed into a thin film.
[0015]
[Problems to be solved by the invention]
An object of the present invention is to provide a polymer solid electrolyte which has good strength even when formed into a thin film of about several tens of μm, has high ionic conductivity at room temperature and low temperature, and has excellent workability. Another object of the present invention is to develop a primary battery and a secondary battery which can be easily formed into a thin film, can operate at a high capacity and a high current, and have excellent reliability by using the polymer solid electrolyte. And Another object of the present invention is to provide an electrode having high electrochemical activity and flexibility, and a secondary battery using the same and having good cyclability.
[0016]
Another object of the present invention is to provide an electrode used in an electric double layer capacitor, which has good polarizability, has good strength when formed into a film, and has good contact with a solid electrolyte.
Further, the present invention has a high output voltage and a large take-out current by utilizing a polymer solid electrolyte having high ionic conductivity even at room temperature or lower temperature, and having excellent membrane strength and processability. It is an object of the present invention to provide an electric double layer capacitor excellent in processability and reliability.
[0017]
[Means for Solving the Problems]
The present inventors have found that a composite comprising a polymer containing an oxyalkylene group having a strong urea bond and a hydrogen bond more strongly than a urethane bond and an electrolyte has good membrane strength, high ionic conductivity, and It has been found that the resulting polymer solid electrolyte has excellent properties. In the description of the present specification, the expression “oxyalkyl” includes oligooxyalkylene and polyoxyalkylene each containing at least one oxyalkylene group.
Furthermore, it has been found that by using this polymer solid electrolyte for a battery, the problems of ionic conductivity, membrane strength, workability and the like are improved.
[0018]
Further, the present inventors, for example, when making a thin solid-state battery using this polymer solid electrolyte, and made a study with the recognition that thinning of the electrode is important, the electrode active material Polyaniline and its derivatives, which are excellent as conductive polymers, that is, aniline-based polymers that are soluble in organic solvents, or other conductive polymers, metal oxides, metal sulfides or carbon By using a material or another electrode active material (a positive electrode active material or a negative electrode active material) and a polymer into which an oxyalkyl side chain having a urea bond is introduced, the electrochemical activity of such an electrode active material is impaired. Therefore, it is possible to form an electrode having high electrochemical activity and flexibility, and it is possible to form a thin film of the electrode by, for example, a solvent casting method or another method. It was found that.
[0019]
Furthermore, the present inventors use a polarizable material used as a polarizable electrode of an electric double layer capacitor, a carbon material as described below, and a polymer into which an oxyalkyl side chain having a urea bond is introduced. Accordingly, a polarizable electrode suitable for the capacitor can be obtained without impairing the polarization characteristics of the polarizable material, and further, for example, a thin film of the electrode can be formed by a solvent casting method or another method. Was found.
Furthermore, the present inventors have obtained that by using the above-mentioned polymer solid electrolyte, it is possible to obtain an electric double layer capacitor having a high output voltage, a large take-out current, and excellent workability and reliability. Type electric double layer capacitor.
[0020]
That is, the present invention provides the following.
1) General formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ³ -(1)
[Wherein, R ¹ , R ² Represents hydrogen or an alkyl group; ³ Represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. Also (CH ₂ ) And (CH (CH ₃ )) May be arranged irregularly. However, R in a plurality of units represented by the above general formula (1) in the same molecule ¹ , R ² , R ³ And the values of x, y, and z are independent and need not be the same. ]
A polymer solid electrolyte comprising a polymer obtained from at least one compound having a unit represented by the formula and / or a copolymer containing the compound as a copolymer component and at least one electrolyte.
[0021]
2) General formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n -(2)
[Wherein, R ¹ , R ² Represents hydrogen or an alkyl group; ⁴ Is-(CH ₂ ) ₂ -Or -CH (CH ₃ ) CH ₂ Represents-, and n represents an integer of 1 or more. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. Also (CH ₂ ) And (CH (CH ₃ )) May be arranged irregularly. However, R in a plurality of units represented by the above general formula (2) in the same molecule ¹ , R ² , R ⁴ And the values of x, y, and z are independent and need not be the same. ]
A polymer obtained from at least one compound having a unit represented by the formula and / or a copolymer containing the compound as a copolymer component, and a composite containing at least one electrolyte. Electrolytes.
[0022]
3) The polymer solid electrolyte according to 1) or 2) above, wherein the electrolyte is at least one selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts.
4) The polymer solid electrolyte according to 1) to 3) above, wherein a plasticizer is added to the polymer solid electrolyte containing the electrolyte.
[0023]
5) A battery using the polymer solid electrolyte described in 1) to 4) above.
6) The battery according to 5) above, wherein the negative electrode of the battery comprises an electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions.
7) The battery according to 5) or 6) above, wherein the positive electrode of the battery comprises an electrode containing an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material.
[0024]
8) As the polymer solid electrolyte, the general formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ³ -(1)
[The symbols in the formula are the same as in the above 1). ]
A polymerizable monomer mixture containing at least one type of compound having at least one unit represented by and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture, is placed in the battery structure, or a support. A method for producing a battery, comprising: disposing the polymerizable monomer mixture disposed on the polymerizable monomer mixture.
[0025]
9) As the polymer solid electrolyte, the general formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n -(2)
[The symbols in the formula are the same as in the above 2). ]
A polymerizable monomer mixture containing at least one type of compound having at least one unit represented by and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture, is placed in the battery structure, or a support. A method for producing a battery, comprising: disposing the polymerizable monomer mixture disposed on the polymerizable monomer mixture.
[0026]
10) As a material for forming an electrode, a general formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ³ -(1)
[The symbols in the formula are the same as in the above 1). ]
An electrode comprising: a polymer obtained from at least one compound having a unit represented by the formula: and / or a copolymer containing the compound as a copolymer component; and an electrode active material or a polarizable material.
[0027]
11) As a material for forming an electrode, a general formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n -(2)
[The symbols in the formula are the same as in the above 2). ]
An electrode comprising: a polymer obtained from at least one compound having a unit represented by the formula: and / or a copolymer containing the compound as a copolymer component; and an electrode active material or a polarizable material.
[0028]
12) The electrode as described in 10) or 11) above, wherein the electrode active material or the polarizable material is an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material.
13) An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is the solid polymer electrolyte described in 1) to 4) above. .
[0029]
14) In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, the polarizable electrode is made of a carbon material and a general formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ³ -(1)
[The symbols in the formula are the same as in the above 1). ]
An electric double layer capacitor comprising a polymer obtained from at least one compound having a unit represented by the formula and / or a composite containing a copolymer containing the compound as a copolymer component.
[0030]
15) In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, the polarizable electrode is made of a carbon material and a general formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n -(2)
[The symbols in the formula are the same as in the above 2). ]
An electric double layer capacitor comprising a polymer obtained from at least one compound having a unit represented by the formula and / or a composite containing a copolymer containing the compound as a copolymer component.
[0031]
16) The compound represented by the general formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ³ -(1)
[The symbols in the formula are the same as in the above 1). ]
A polymerizable monomer mixture containing at least one kind of compound having a unit represented by the formula and at least one electrolyte or a polymerizable monomer mixture to which a plasticizer is added is put in the structure for forming an electric double layer capacitor, or supported. A method for producing an electric double layer capacitor, comprising disposing the mixture on a body and polymerizing the polymerizable monomer mixture.
[0032]
17) The compound represented by the general formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n -(2)
[The symbols in the formula are the same as in the above 2). ]
A polymerizable monomer mixture containing at least one kind of compound having a unit represented by the formula and at least one electrolyte or a polymerizable monomer mixture to which a plasticizer is added is put in the structure for forming an electric double layer capacitor, or supported. A method for producing an electric double layer capacitor, comprising disposing the mixture on a body and polymerizing the polymerizable monomer mixture.
[0033]
18) General formula (3)
CH _Two = C (R ¹ ) CO [O (CH _Two ) _x (CH (CH _Three )) _y ] _z NHCONH- (R ^Four O) _n -R ^Five (3)
[Wherein, R ¹ Represents hydrogen or an alkyl group; ⁴ Is-(CH ₂ ) ₂ -Or -CH (CH ₃ ) CH ₂ Represents-, n represents an integer of 1 or more; ⁵ Represents an alkyl group having 1 to 4 carbon atoms which may have a branch. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. Also (CH ₂ ) And (CH (CH ₃ )) May be arranged irregularly. However, R in a plurality of units represented by the above general formula (3) in the same molecule ¹ , R ⁴ , R ⁵ And the values of x, y, and z are independent and need not be the same. ] The compound represented by these.
[0034]

[Wherein, R ¹ Represents hydrogen or an alkyl group; ⁴ Is-(CH ₂ ) ₂ -Or -CH (CH ₃ ) CH ₂ Represents-, and n represents an integer of 1 or more. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. Also (CH ₂ ) And (CH (CH ₃ )) May be arranged irregularly. However, R in a plurality of units represented by the above general formula (4) in the same molecule ¹ , R ⁴ And the values of x, y, and z are independent and need not be the same. ] The compound represented by these.
[0035]
20) General formula (5)
Embedded image

[Wherein, R ¹ Represents hydrogen or an alkyl group; ⁴ Is-(CH ₂ ) ₂ -Or -CH (CH ₃ ) CH ₂ Represents-, and n represents an integer of 1 or more. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. Also (CH ₂ ) And (CH (CH ₃ )) May be arranged irregularly. However, R in a plurality of units represented by the above general formula (5) in the same molecule ¹ , R ⁴ And the values of x, y, and z are independent and need not be the same. ] The compound represented by these.
[0036]
21) General formula (6)
Embedded image

[Wherein, R ¹ Represents hydrogen or an alkyl group; ⁴ Is-(CH ₂ ) ₂ -Or -CH (CH ₃ ) CH ₂ Represents-, and n represents an integer of 1 or more. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. Also (CH ₂ ) And (CH (CH ₃ )) May be arranged irregularly. However, R in a plurality of units represented by the above general formula (6) in the same molecule ¹ , R ⁴ And the values of x, y, and z are independent and need not be the same. ] The compound represented by these.
[0037]
Hereinafter, the present invention will be described in detail.
The compound having a unit represented by the general formula (1) or (2), which is a monomer for a polymer solid electrolyte of the present invention, has one or more ethylenically unsaturated groups in the molecule.
The compound having a unit represented by the general formula (1) or (2) is CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z It can be obtained by reacting NCO with a primary or secondary amine having an oxyethylene group (where R ¹ , X, y, z are the same as in the general formula (1). ).
[0038]
As a specific method, a compound having one ethylenically unsaturated group is, for example, a methacryloyl isocyanate-based compound (hereinafter abbreviated as MIs) or an acryloyl isocyanate-based compound (hereinafter abbreviated as AIs) and monoamino. It can be easily obtained by reacting with a monoalkoxy oligoalkylene glycol at a molar ratio of 1: 1.
[0039]
The compound having two ethylenically unsaturated groups can be easily obtained, for example, by reacting MIs or AIs with diaminooligoalkylene glycol at a molar ratio of 2: 1.
Further, the compound having three ethylenically unsaturated groups can be obtained, for example, by mixing MIs and / or AIs with a triamine obtained by addition-polymerizing an alkylene oxide to a trihydric alcohol such as glycerin and substituting the terminal with an amine. It is easily obtained by reacting at a molar ratio of 1: 1.
[0040]
Compounds having four ethylenically unsaturated groups include, for example, MIs and / or AIs and tetramines obtained by addition-polymerizing an alkylene oxide to a tetrahydric alcohol such as pentaerythritol and substituting the amine with an amine. It is easily obtained by reacting at a molar ratio of 1: 1.
Compounds having five ethylenically unsaturated groups include, for example, MIs and / or AIs and α-D-glucopyranose, which is obtained by addition polymerization of alkylene oxide with pentamine, the terminal of which is substituted with an amine. It is easily obtained by reacting at a molar ratio of 1: 1.
The compound having six ethylenically unsaturated groups can be prepared, for example, by mixing MIs and / or AIs with hexamine, which is obtained by addition-polymerizing an alkylene oxide to mannitol and substituting the terminal with an amine at a molar ratio of 6: 1. And can be easily obtained.
[0041]
As the monomer used for the polymer of the solid polymer electrolyte of the present invention, it is necessary to use a compound having a unit represented by the general formula (1) or (2). When a polymer obtained by polymerizing a compound having only one unit represented by the general formula (1) or (2) is used together with an electrolyte as a polymer of a solid polymer electrolyte, the polymer may be in contact with an electrode. Although excellent in adhesiveness and composite efficiency, there is a risk of short-circuiting when made into a thin film due to insufficient film strength. Considering the strength of the thin film of the solid electrolyte thus formed, the number of units represented by the general formula (1) or (2) contained in one molecule is more preferably two or more.
[0042]
Further, among the compounds having the unit represented by the general formula (1), the compound having the unit represented by the general formula (2) has a large film strength when formed into a thin film, and is contained in the obtained polymer. Since more oxyalkylene groups can be introduced, ionic conductivity at room temperature and low temperature is high, which is preferable.
[0043]
The polymer contained in the polymer solid electrolyte of the present invention is obtained by polymerizing at least one of the compounds having units represented by the general formula (1) and / or the general formula (2), or using the compound as a copolymerization component. It is obtained by doing.
[0044]
The other polymerizable compound copolymerizable with the compound having a unit represented by the general formula (1) and / or the general formula (2) is not particularly limited. For example, compounds having at least one unit represented by the following general formula (3) in one molecule, such as N-methacryloylcarbamic acid ω-methyl oligooxyethyl ester and methacryloyloxyethyl carbamic acid ω-methyl oligooxyethyl ester (Hereinafter, this compound is referred to as a urethane (meth) acrylate having an oxyalkylene chain.)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOOR ² -(3)
[Wherein, R ¹ Represents hydrogen or a methyl group; ² Represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. Also (CH ₂ ) And (CH (CH ₃ )) May be arranged irregularly. However, R in a plurality of units represented by the above general formula (3) in the same molecule ¹ , R ² And the values of x, y, and z are independent and need not be the same. ],
(Meth) acrylic esters having an oxyalkylene chain such as methacrylic acid ω-methyl oligooxyethyl ester, alkyl (meth) acrylates such as methyl methacrylate and n-butyl acrylate, acrylamide, methacrylamide, N, N- (Meth) acrylamide compounds such as dimethylacrylamide, N, N-dimethylmethacrylamide, acryloylmorpholine, methacryloylmorpholine, N, N-dimethylaminopropyl (meth) acrylamide, styrene compounds such as styrene and α-methylstyrene, N -Vinylacetamide, N-vinylformamide and other N-vinylamide compounds, and ethylvinylether and other alkylvinylethers. Among these, urethane (meth) acrylate having an oxyalkylene chain, (meth) acryl ester having an oxyalkylene chain, and (meth) acrylamide-based compound are preferably used. Among these, urethane (meth) acrylates having an oxyalkylene chain are particularly preferable, considering that more urethane groups and oxyalkylene groups can be introduced into the polymer.
[0045]
For the polymerization, a general method utilizing the polymerizability of an acryloyl group or a methacryloyl group in the monomer compound can be employed. That is, a radical polymerization catalyst such as azobisisobutyronitrile and benzoyl peroxide, CF is added to these monomers alone or a mixture of these monomers and the other copolymerizable polymerizable compound. ₃ Protonic acid such as COOH, BF ₃ , AlCl ₃ Radical polymerization, cationic polymerization or anionic polymerization can be carried out 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, when the total content of the compound having the unit represented by the general formula (1) and the urethane (meth) acrylate having an oxyalkylene chain exceeds 20% by weight based on the total monomer weight, Polymerization can be carried out under oxygen-free conditions only by raising the temperature to 70 ° C. or higher.
[0046]
It is also possible to polymerize such a polymerizable monomer mixture after forming it into a shape such as a film. A polymer obtained from at least one compound having a unit represented by the general formula (1) and / or a copolymer containing the compound as a copolymer component may be used as a polymer of a solid polymer electrolyte as in the present invention. In this case, it is particularly advantageous to polymerize the polymerizable monomer mixture after film formation.
[0047]
That is, at least one compound having a unit represented by the general formula (1) is mixed with at least one electrolyte such as an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt. May be further mixed by adding another polymerizable compound and / or a plasticizer and / or a solvent, and mixing the polymerizable monomer mixture in the presence or absence of the catalyst, if necessary, by heating and / or electromagnetic waves such as light. To polymerize. In particular, after the polymerizable monomer mixture is formed into a film-like shape or the like, for example, heating and / or irradiation with electromagnetic waves such as light is performed to polymerize the polymerizable monomer mixture into a film-like polymer. Spreading is a great merit in application.
[0048]
In the case of using a solvent, any solvent may be used as long as it does not inhibit the polymerization, for example, tetrahydrofuran, acetonitrile, toluene, etc., depending on the type of monomer and the presence or absence of a polymerization catalyst.
The temperature for the polymerization depends on the type of the compound having the unit represented by the general formula (1), but may be any temperature at which the polymerization occurs, and is usually in the range of 0 ° C. to 200 ° C. In the case of polymerizing by electromagnetic wave irradiation, depending on the type of the compound having the unit represented by the general formula (1), for example, using an initiator such as benzyl methyl ketal or benzophenone, ultraviolet light of several mW or more is used. Alternatively, polymerization can be performed by irradiating γ rays or the like.
[0049]
As described above, the polymer used in the polymer solid electrolyte of the present invention may be a homopolymer of the compound having the unit represented by the general formula (1), but may be a copolymer of two or more compounds belonging to the category. It may be a polymer or a copolymer of at least one of the compounds and another polymerizable compound. Further, the polymer used for the polymer solid electrolyte of the present invention is a polymer obtained from at least one compound having a unit represented by the general formula (1) and / or a copolymer containing the compound as a copolymer component. It may be a mixture of the union and another polymer. For example, a polymer obtained from at least one compound having a unit represented by the general formula (1) and / or a copolymer containing the compound as a copolymer component, polyethylene oxide, polyacrylonitrile, polybutadiene, and polymethacrylic Mixtures with (or acrylic) acid esters, polystyrene, polyphosphazenes, polymers such as polysiloxanes or polysilanes may be used for the solid polymer electrolyte of the present invention.
[0050]
When the copolymer is used, the amount of the structural unit derived from the compound having the unit represented by the general formula (1) varies depending on the type of the other copolymer component or polymer mixture component, but the urethane having an oxyalkylene chain is used. In the case where (meth) acrylate is not contained as a copolymer component, it is preferably contained in an amount of 20% by weight or more based on the total amount of the copolymer in consideration of ionic conductivity and membrane strength when used in a solid polymer electrolyte, More preferably, the content is 50% by weight or more.
[0051]
Further, the amount of the copolymer containing the compound having the unit represented by the general formula (1) as a copolymer component may be 50% by weight or more based on the total amount of the polymer used for the solid polymer electrolyte. desirable. When the structural unit derived from the compound having the unit represented by the general formula (1) is within the above-specified amount range, the film strength of the polymer can be sufficiently exhibited, and when the polymer solid electrolyte is used. Also has high ionic conductivity.
[0052]
A compound having a unit represented by the general formula (1) or (2) used for obtaining the (co) polymer used for the polymer solid electrolyte of the present invention, and having one ethylenically unsaturated group. The comb-like polymer is obtained by the polymerization of the compound, and the network polymer is obtained by the polymerization of the compound having two or more. Therefore, a compound having one unit represented by the general formula (1) or the general formula (2) in a molecule and a compound having two or more units are mixed and polymerized, so that the thermal motility is large and the film is formed. It is also possible to obtain a polymer having good strength. The number of oxyalkylene chains in the oxyalkyl group serving as a side chain of the polymer (that is, R in formula (1)) ² The number of oxyalkylene groups contained therein, or, for example, n) in the general formula (2) is preferably in the range of 1 to 1,000, particularly preferably in the range of 5 to 50.
[0053]
The monomer in the (co) polymer used for the solid polymer electrolyte of the present invention is represented by the general formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ³ -(1)
In the unit represented by
(A) In the case where x is 0 to 2, y is 0 or 1, and z is 0 or 1 (provided that x = 0 and y = 0, z = 0), the corresponding isocyanate compound as a raw material
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NCO
Is highly reactive and can be easily produced by reaction with various oxyalkylene compounds. In addition, these corresponding isocyanate compounds have the advantage that they are liquid and have low viscosity, and are easy to react in a solvent system.
[0054]
On the other hand, in the above-mentioned monomer which is an essential component in the (co) polymer used for the polymer solid electrolyte,
(B) x = 3 to 5, y = 0, z = 1 to 10,
(C) x = 1 to 5, y = 1 to 5 (random array), z = 1 to 10 or
(D) Compounds with x = 0, y = 1 to 5, and z = 1 to 10 have low polymerizability, so that storage stability is good and handleability as a polymerizable monomer is good.
[0055]
In particular, in the cases of (c) and (d), when an oxypropylene group is introduced, the dielectric constant is lower than that of a monomer having an oxyethylene group, but the melting point and viscosity do not increase even when the molecular weight increases. It is a very advantageous polymerizable monomer depending on the application. Therefore, by utilizing the properties of these polymerizable monomers, by combining these suitable polymerizable monomers, or by combining with other polymerizable monomers and / or polymers, a polymer solid electrolyte suitable for use can be obtained. Can be.
[0056]
Further, it is preferable to add an organic compound usually used as a so-called plasticizer (expressed as a plasticizer in the present invention) to the polymer solid electrolyte of the present invention because the ionic conductivity of the solid electrolyte is further improved. As the plasticizer that can be used, a compound that has good compatibility with the monomer used in the polymer solid electrolyte of the present invention, a large dielectric constant, a boiling point of 70 ° C. or higher, and a wide electrochemical stability range is suitable. . Examples of such a plasticizer include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate, (meth) acryloyl carbonate, and benzo. Aromatic nitriles such as nitrile and tolunitrile; sulfur compounds such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, and sulfolane; and phosphate esters. Of these, oligoethers and carbonates are preferred, and carbonates are particularly preferred.
[0057]
The ionic conductivity of the polymer solid electrolyte increases as the amount of the plasticizer added increases, but if the amount is too large, the mechanical strength of the polymer solid electrolyte decreases. The preferable addition amount is 5 times or less the weight of the monomer used for the solid polymer electrolyte of the present invention. Further, a polymerizable compound such as vinylene carbonate, (meth) acryloyl carbonate, or N-vinylpyrrolidone is appropriately used in combination with a non-polymerizable plasticizer as a plasticizer, and the compound represented by the general formula (1) and / or (2) is used. By copolymerizing with a compound having a unit represented by the following formula, the amount of the plasticizer added can be increased and the ionic conductivity can be improved without lowering the mechanical strength.
[0058]
In the solid polymer electrolyte of the present invention, a polymer obtained from at least one compound having a unit represented by the general formula (1) and / or a copolymer containing the compound as a copolymer component and an electrolyte used in a composite. The compounding ratio is preferably a ratio of one electrolyte molecule to one to 100 ether oxygen atoms in the side chain. If the electrolyte used in the composite is present at a ratio of 1 or more of ether oxygen atoms, the movement of ions is greatly inhibited, and at a ratio of 1/100 or less, the absolute amount of ions becomes insufficient and the ion conductivity decreases. . The ratio of one electrolyte molecule to 4 to 100 ether oxygen atoms in the side chain is more preferable.
[0059]
The type of electrolyte used for the composite is not particularly limited, and an electrolyte containing an ion to be used as a carrier with a charge may be used.It is desirable that the dissociation constant in the polymer solid electrolyte be large, and an alkali metal salt, (CH ₃ ) ₄ NBF ₄ Quaternary ammonium salts such as (CH ₃ ) ₄ PBF ₄ Quaternary phosphonium salts such as AgClO ₄ And the like, or a transition acid salt such as hydrochloric acid, or a protic acid such as hydrochloric acid, perchloric acid, or borofluoric acid.
[0060]
As the negative electrode active material used in the battery of the present invention, as described later, an alkali metal, an alkali metal alloy, or a material having a low oxidation-reduction potential using an alkali metal ion such as a carbon material as a carrier is used, so that a high voltage, This is preferable because a high-capacity battery can be obtained. Therefore, when such a negative electrode is used in a battery using an alkali metal ion as a carrier, an alkali metal salt is required as an electrolyte in the solid polymer electrolyte.
[0061]
As the kind of the alkali metal salt, for example, LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiSCN, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF ₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KPF ₆ , KI and the like. Among them, the case where lithium or a lithium alloy is used as the alkali metal is most preferable because it has a high voltage, a high capacity, and can be formed into a thin film. In the case of a carbon material negative electrode, not only alkali metal ions but also quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and various protonic acids can be used.
[0062]
The type of electrolyte used for the composite in the case of the solid-state electric double layer capacitor is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used, but the dissociation constant in the polymer solid electrolyte is large, It is desirable to include ions that easily form the polarizable electrode and the electric double layer. Such compounds include (CH ₃ ) ₄ NBF ₄ , (CH ₃ CH ₂ ) ₄ NCLO ₄ Quaternary ammonium salts such as AgClO ₄ Transition metal salts such as (CH ₃ ) ₄ PBF ₄ Quaternary phosphonium salts, such as LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiSCN, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF ₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KPF ₆ And organic acids such as paratoluenesulfonic acid and salts thereof, and inorganic acids such as hydrochloric acid and sulfuric acid. Among them, quaternary ammonium salts, quaternary phosphonium salts, and alkali metal salts are preferable in that the output voltage is high and the dissociation constant is large. Among the quaternary ammonium salts, (CH ₃ CH ₂ ) (CH ₃ CH ₂ CH ₂ CH ₂ ) ₃ NBF ₄ Are preferable in that the substituents on the nitrogen of the ammonium ion are different from each other in that the solubility in the polymer solid electrolyte or the dissociation constant is large.
[0063]
In the configuration of the battery of the present invention, a low oxidation-reduction potential electrode active material (negative electrode active material) using an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material, or a conductive polymer as a carrier is used for the negative electrode. Thus, a high-voltage, high-capacity battery can be obtained, which is preferable. Among such electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy and lithium / antimony alloy are particularly preferable because they have the lowest redox potential. In addition, the carbon material is particularly preferable in that it has a low oxidation-reduction potential when occluding Li ions, and is stable and safe. Examples of carbon materials capable of inserting and extracting Li ions include natural graphite, artificial graphite, pyrolytic carbon synthesized by a gas phase method and its graphitized products, petroleum coke, coal coke, pitch-based carbon, polyacene, C ₆₀ , C ₇₀ And other fullerenes.
[0064]
In the configuration of the battery of the present invention, by using an electrode active material having a high oxidation-reduction potential (a positive electrode active material) such as a metal oxide, a metal sulfide, a conductive polymer, or a carbon material for the positive electrode, a high voltage and a high voltage can be obtained. This is preferable because a battery having a capacity can be obtained. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, and molybdenum oxide; molybdenum sulfide; Metal sulfides such as titanium and 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.
[0065]
The method for producing the metal oxide or metal sulfide in this case is not particularly limited. For example, a general electrolytic method such as described in “Electrochemistry, Vol. 22, pp. 574, 1954” or the like. It is manufactured by a heating method. Further, when these are used in a lithium battery as an electrode active material, for example, Li _x CoO ₂ And Li _x MnO ₂ It is preferable to use the Li element in a state of being inserted (composite) into the metal oxide or metal sulfide in such a form. The method for inserting the Li element in this way is not particularly limited, and for example, a method for electrochemically inserting Li ions or a method for inserting Li ions as described in US Pat. No. 4,357,215. ₂ CO ₃ Can be carried out by mixing and heat-treating such a salt with a metal oxide.
[0066]
In addition, a conductive polymer is preferable because it is flexible and easily formed into a thin film. Examples of the conductive polymer include polyaniline, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polypyrrolylene and its derivatives, polythienylene and its derivatives, polypyridinediyl and its derivatives, polyisothianaphthenylene and its derivatives, and polyfurylene. And its derivatives, polyselenophene and its derivatives, polyparaphenylenevinylene, polythienylenevinylene, polyfurylenevinylene, polynaphthenylenevinylene, polyselenophenevinylene, polyarylenevinylene such as polypyridinediylvinylene and derivatives thereof, etc. Is mentioned. Among them, a polymer of an aniline derivative soluble in an organic solvent is particularly preferable. The conductive polymer used as an electrode active material in these batteries or electrodes is manufactured according to a chemical or electrochemical method described later or other known methods.
[0067]
Examples of the carbon material include natural graphite, artificial graphite, vapor-grown graphite, petroleum coke, coal coke, fluorinated graphite, pitch-based carbon, and polyacene.
Further, as the carbon material used as the electrode active material in the battery or the electrode of the present invention, a commercially available carbon material can be used, or it is manufactured according to a known method.
[0068]
The use of an organic solvent-soluble aniline-based polymer as the positive electrode active material in the electrode or battery of the present invention is particularly advantageous because molding can be performed by solution coating, and is extremely advantageous in the case of producing a thin film battery. . Examples of the aniline-based polymer include polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, polyxylidines, poly-2,5-dimethoxyaniline, and poly-2,6. -Dimethoxyaniline, poly-2,5-diethoxyaniline, poly-2,6-diethoxyaniline, poly-o-ethoxyaniline, poly-m-ethoxyaniline and copolymers thereof. The polymer is not particularly limited thereto, and may be any polymer having a repeating unit derived from an aniline derivative. In addition, the introduction amount of the side chain in the organic solvent-soluble aniline-based polymer is more convenient in terms of solubility as the amount is larger, but as the introduction amount increases, the capacity per weight as the positive electrode decreases. A surface appears. Therefore, preferred aniline-based polymers include, for example, polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, and polyxylidine.
[0069]
The polymerization method of the aniline polymer used in the present invention is not particularly limited, but is generally reported in, for example, "Journal of Chemical Society, Chemical Communication, p. 1784 (1987)". As described above, there is a method of electrochemically or chemically oxidatively polymerizing an aniline derivative such as aniline or o-anisidine.
[0070]
The electrochemical oxidative polymerization is performed by anodic oxidation and has a current density of about 0.01 to 50 mA / cm. ² As long as the electrolysis voltage is in the range of 0.1 to 30 V, a constant current method, a constant voltage method, or any other method can be used. The pH of the electrolytic solution is not particularly limited, but is preferably 3 or less, particularly preferably 2 or less. Specific examples of the acid used for pH adjustment include HCl, HBF ₄ , CF ₃ COOH, H ₂ SO ₄ , HNO ₃ And strong acids such as paratoluenesulfonic acid, but are not particularly limited thereto.
In the case of chemical oxidative polymerization, for example, the aniline derivative can be oxidatively polymerized with an oxidizing agent such as peroxide or persulfate in an acidic solution. As the acid used in this case, the same acid as that used in the case of electrochemical oxidation polymerization can be used, but it is not limited thereto.
[0071]
Although the molecular weight of the aniline-based polymer used in the present invention obtained by such a method is not particularly limited, it is usually preferable that the molecular weight be 2000 or more.
The aniline-based polymer obtained by such a method is generally obtained in many cases in which an anion in a polymerization solution is contained as a dopant, which is disadvantageous in terms of solubility and capacity per weight. Therefore, it is preferable that these anions are dedoped before being formed into an electrode by, for example, a film forming method, and further reduced. Although there is no particular limitation on the method of undoping, a method of treating with a base such as aqueous ammonia or sodium hydroxide is generally employed. Also, there is no particular limitation on the reduction method, and general chemical or electrochemical reduction may be performed. For example, as for the chemical reduction method, the aniline-based polymer treated with a base in a hydrazine or phenylhydrazine solution can be easily reduced by dipping or stirring at room temperature.
[0072]
The undoped or reduced aniline-based polymer thus obtained is soluble in various organic solvents, and in a solution state, a unit represented by the general formula (1) and / or (2) It can be mixed with a polymerizable monomer solution containing at least one of the compounds having, using the mixture thus prepared, for example, by a coating method or the like, to various supports, for example, to form a thin film on an electrode, or other An electrode can be manufactured by shaping it into a shape.
[0073]
The solvent in which the aniline-based polymer dissolves is not particularly limited because it depends on the type of the substituent on the benzene ring, but pyrrolidones such as N-methylpyrrolidone, amides such as dimethylformamide, m-cresol, dimethyl And polar solvents such as propylene urea.
[0074]
Next, an example of the method for manufacturing the electrode and the battery of the present invention will be described in detail.
The electrode of the present invention is obtained, for example, by adding at least one compound having a unit represented by the general formula (1) and / or (2), and optionally further adding another polymerizable compound and / or a plasticizer. Then, it is mixed with the above-mentioned electrode active material (a positive electrode active material or a negative electrode active material). In that case, the ratio of each component to be mixed is determined to be more appropriate for the intended battery. The polymerizable monomer / electrode active material mixture thus obtained is shaped into a film or the like and then polymerized to produce an electrode. In this method, the polymerization can be carried out by the same polymerization method as in the case of obtaining a polymer from the compound (monomer) having the unit represented by the above general formula (1) and / or (2). Polymerization can be performed by irradiation of electromagnetic waves. When the electrode active material gives a highly flowable polymerizable monomer / electrode active material mixture as in the case of an organic solvent-soluble aniline-based polymer, for example, the mixture is supported on a current collector or other glass or the like. An electrode is manufactured by polymerizing after molding by a method such as coating on a body and forming a film.
[0075]
The electrode containing the electrode active material manufactured in this manner is used as at least one electrode, an electrode containing another electrode active material manufactured in the same manner or another commonly used electrode is used as the other electrode, and both electrodes are used. It is put in the structure for battery construction so as not to contact with each other or placed on the support. For example, a positive electrode and a negative electrode are attached to the end of the electrode via a spacer having an appropriate thickness, and the positive electrode and the negative electrode are put into the structure. Next, between the positive electrode and the negative electrode, the general formula (1) and / or (2) At least one compound having a unit represented by the formula and at least one electrolyte selected from the above electrolytes such as alkali metal salts are mixed, and in some cases, another polymerizable compound and / or a plasticizer are added and mixed. After injecting the polymerizable monomer mixture prepared as described above, for example, by polymerizing by heating and / or irradiation with electromagnetic waves, at least one of the compounds having a unit represented by the aforementioned general formula (1) and / or (2) is used. Polymerization is carried out by the same method as the polymerization method for obtaining the obtained polymer and / or a copolymer containing the compound as a copolymer component, or further after polymerization. Correspondingly polyolefin resin, followed by sealing with an insulating resin such as epoxy resin, battery electrodes and electrolyte has good contact is obtained.
[0076]
Incidentally, the battery 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, and the shape may be cylindrical, box, sheet, or any other shape.
[0077]
As described above, by polymerizing a mixture obtained by mixing a monomer mixture containing at least one compound having a unit represented by the general formula (1) and / or (2) with at least one electrolyte. A polymer obtained from at least one compound having a unit represented by the general formula (1) and / or (2) and / or a copolymer containing the compound as a copolymer component and at least one electrolyte. The method for producing a solid polymer electrolyte comprising a composite is particularly useful for producing a thin film battery.
[0078]
FIG. 1 shows a schematic cross-sectional view of an example of a thin-film solid state secondary battery as an example of the battery of the present invention thus manufactured. In the figure, 1 is a positive electrode, 2 is a solid polymer electrolyte, 3 is a negative electrode, 4 is a current collector, 5 is an insulating resin film serving as a spacer, and 6 is an insulating resin sealant.
[0079]
When manufacturing a wound type battery, the positive electrode and the negative electrode are pasted together through a previously prepared polymer solid electrolyte sheet, wound, and inserted into the battery structure, and then the polymerizable monomer is further added. It is also possible to inject the mixture and polymerize it.
[0080]
Next, the solid electric double layer capacitor of the present invention will be described.
In the solid electric double layer capacitor of the present invention, the use of the polymer solid electrolyte of the present invention provides an all solid electric double layer capacitor having a high output voltage, a large take-out current, or excellent workability and reliability. Is done.
FIG. 2 shows a schematic sectional view of an example of the solid electric double layer capacitor of the present invention. This example is a thin cell having a size of 1 cm × 1 cm and a thickness of about 0.5 mm. Reference numeral 8 denotes a current collector, and a pair of polarizable electrodes 7 is arranged inside the current collector. A molecular solid electrolyte membrane 9 is provided. Reference numeral 10 denotes a spacer, an insulating film is used in this example, 11 is an insulating resin sealant, and 12 is a lead wire.
[0081]
The current collector 8 is preferably made of a material having electron conductivity and electrochemical corrosion resistance, and having 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 electrode 7 may be any electrode made of a polarizable material such as a carbon material usually used for an electric double layer capacitor, and it is preferable that the carbon material is combined with the polymer solid electrolyte of the present invention. The carbon material as the polarizable material is not particularly limited as long as the specific surface area is large. However, the larger the specific surface area, the larger the capacity of the electric double layer, which is preferable. For example, carbon blacks such as furnace black, thermal black (including acetylene black), and channel black; activated carbon such as coconut charcoal; natural graphite; artificial graphite; so-called pyrolytic carbon produced by a gas phase method; , Polyacene and C ₆₀ , C ₇₀ Can be mentioned.
[0082]
Next, an example of a method for manufacturing a solid electric double layer capacitor of the present invention will be described. As described above, at least one compound having a unit represented by the general formula (1) and / or (2) is mixed with at least one electrolyte, and in some cases, another polymerizable compound and / or By polymerizing a polymerizable monomer mixture obtained by adding and mixing a plasticizer, a polymer obtained from at least one compound having a unit represented by the general formula (1) and / or (2) and / or A composite containing the copolymer containing the compound as a copolymer component and at least one electrolyte can be obtained, and this method is particularly useful for producing the solid electric double layer capacitor of the present invention.
[0083]
A polymer obtained from a polarizable material such as a carbon material and at least one compound having a unit represented by the general formula (1) and / or (2), which is preferably used in the solid electric double layer capacitor of the present invention; In the case of producing a polarizable electrode containing a copolymer containing the compound as a copolymer component, at least one of compounds having a unit represented by the general formula (1) and / or (2) is used. Is mixed with the polarizable material, optionally with the addition of other polymerizable compounds and / or plasticizers. In that case, the ratio of each component to be mixed is determined to be more appropriate for the intended capacitor. The polymerizable monomer / polarizable material mixture thus obtained is formed into a film on a support, for example, a current collector, and then polymerized by heating and / or electromagnetic wave irradiation. ) And / or a polymer obtained from at least one compound having a unit represented by formula (2) and / or a polymer obtained by the same method as a polymerization method for obtaining a copolymer containing the compound as a copolymer component. Thus, a polarizable electrode is manufactured. According to this method, a composite thin-film electrode that is in good contact with the current collector can be manufactured.
[0084]
The two polarizable electrodes manufactured in this manner are placed in a structure for forming a capacitor so as not to come into contact with each other, or are arranged on a support. For example, the two electrodes are bonded to each other through a spacer having an appropriate thickness at the end of the electrode, and put into the structure. Next, a monomer and an electrolyte are mixed between the two polarizable electrodes, and in some cases, Is injected with a polymerizable monomer mixture prepared by adding and mixing another polymerizable compound and / or a plasticizer, and then polymerizing by the same method as described above. By sealing with an insulating resin such as resin or epoxy resin, an electric double layer capacitor in which the electrodes and the electrolyte are in good contact can be obtained. When preparing such a monomer mixture, the ratio of each component to be mixed is determined to be appropriate for the intended condenser. By this method, a particularly thin all-solid-state electric double layer capacitor can be manufactured. The structure for forming the capacitor 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. However, the shape is not limited to this, and the shape may be cylindrical, box, sheet, or any other shape.
[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 or the like manufactured by sealing in a structure.
When manufacturing a wound capacitor, the above-mentioned polarizable electrode is stuck through a polymer solid electrolyte sheet that has been prepared in advance, wound, and inserted into the structure for forming a capacitor, and then the polymerizable monomer mixture is further added. Can be injected and polymerized.
[0086]
[Action]
As described above, the polymer solid electrolyte of the present invention can be easily formed into a film from the polymerizable monomer mixture, which is a raw material thereof, and can be formed into a comb-shaped polymer having a urea bond-containing oxyalkyl group introduced into a side chain or a mesh-shaped polymer. It is a solid electrolyte with high ionic conductivity composed of molecules, with good film strength and excellent thin film workability.
[0087]
The battery of the present invention, by using the polymer solid electrolyte as the ion-conductive substance, is easy to process such as thinning, there is no risk of short-circuiting even in a thin film, a large take-out current, a highly reliable battery. In particular, an all-solid-state battery can be used. In addition, the battery of the present invention, in which the negative electrode comprises an electrode containing an active material such as lithium or a lithium alloy or a carbon material capable of inserting and extracting lithium ions, can be formed into a thin film by using the polymer solid electrolyte as an ion conductive material. Such a battery is easy to process, has no danger of short circuit even in a thin film, has a large take-out current, and has high reliability. In particular, it can be an all solid-state battery.
[0088]
Further, the positive electrode of the present invention is a polymer obtained from at least one compound having a unit represented by the general formula (1) and / or (2) and / or a copolymer containing the compound as a copolymer component. And an electrode containing an active material such as an aniline polymer or other conductive polymer soluble in an organic solvent, a metal oxide, a metal sulfide, or a carbon material, and using the polymer solid electrolyte as an electrolyte. Such a battery is easy to process such as thinning, has no risk of short-circuiting even in a thin film, has a large take-out current, is high in capacity, and has high reliability. In particular, it can be an all solid-state battery.
[0089]
Furthermore, a polymer obtained from at least one of the compounds having units represented by the general formulas (1) and / or (2) of the present invention and / or a copolymer containing the compound as a copolymer component and an organic compound An electrode containing an electrode active material such as a solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide or a carbon material, and a method for producing the electrode have excellent activity as an electrode. It is intended to provide an electrode having flexibility as required without impairing the electrochemical activity of the electrode active material.For example, a thin-film electrode can be provided. Useful as an electrode.
[0090]
Further, according to the battery manufacturing method of the present invention, batteries of various shapes can be manufactured, in particular, the battery can be easily made thin, and can operate at high capacity and high current, or has good cycleability. A battery having excellent reliability can be manufactured, and in particular, an all-solid-state battery can be manufactured.
[0091]
The electric double-layer capacitor of the present invention can be easily formed into a film from a polymerizable monomer mixture, and can be formed into a comb-like polymer or a network-like polymer in which an oxyalkyl group having a urea bond capable of being compounded is introduced into a side chain. It is manufactured by polymerizing a dissolved electrolyte and using a solid polymer electrolyte with high ionic conductivity and good film strength as an ion conductive material. It is a highly reliable electric double-layer capacitor with a large take-out current, and particularly an all-solid-state electric double-layer capacitor.
[0092]
In particular, according to the electric double layer capacitor and the method for manufacturing the same of the present invention, good contact is made between the polarizable electrode and the solid polymer electrolyte that is an ion conductive substance, there is no short circuit even in a thin film, and the output voltage and Provided is an electric double-layer capacitor having a large extraction current and high reliability, and particularly an all-solid-state electric double-layer capacitor.
[0093]
【Example】
Hereinafter, the present invention will be described more specifically by showing typical examples. These are merely examples for explanation, and the present invention is not limited to these.
[0094]
Example 1 <Synthesis of Monomer 1>
According to the method of a literature (Journal Organic Chemistry, 1993, vol. 58, No. 26, p. 7524), a raw material 1 in which the terminal hydroxyl group of monomethyl oligoethylene glycol (average molecular weight: 550, manufactured by Aldrich) was aminated by a reaction represented by the following formula was obtained. Was.
Embedded image

¹ A nitrogen / methylene bond was formed around 2.8 ppm of H-NMR, and an infrared absorption spectrum of 3300 cm ^-1 The stretching vibration of NH was confirmed in the vicinity. The elemental analysis values of hydrogen, oxygen, and nitrogen matched the theoretical values within 0.1%. The average molecular weight measured by GPC was 550.
[0095]
Next, Monomer 1 was synthesized by the reaction shown in the following formula.

Specifically, 0.1 mol (= 15.5 g) of methacryloyloxyethyl isocyanate (MOI) and 0.1 mol (= 55 g) of raw material 1 were dissolved in 100 ml of well-purified THF in a nitrogen atmosphere. .66 g of dibutyltin dilaurate were added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain 68 g of Monomer 1 as a colorless viscous liquid.
[0096]
¹ From the results of H-NMR, IR and elemental analysis, it was found that the MOI and the raw material 1 reacted one-to-one, the isocyanate group of the MOI disappeared, and a urea bond was formed. Elemental analysis values of hydrogen, oxygen, and nitrogen matched the theoretical values within 0.1%. The average molecular weight measured by GPC was 700. The melting point (endothermic peak of DSC) was about 10 ° C. ¹ H-NMR: CH ₂ = C- (5.6,6.1 ppm), -NHCO- (5.4 ppm), -CH ₂ 0- (3.6 to 3.7 ppm), -CH ₂ N- (3.5 ppm), -OCH ₃ (3.3 ppm), = C-CH ₃ (1.9 ppm)
[0097]
[Example 2] <Preparation and evaluation of monomer 1-based polymer solid electrolyte>
Dissolve 2.09 g of Monomer 1 in 10 cc of THF and add 0.14 g of LiCF ₃ SO ₃ Was added and mixed well. The THF was then removed at room temperature under reduced pressure and the monomer 1 / LiCF ₃ SO ₃ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate in an argon atmosphere and heated at 100 ° C. for 1 hour. ₃ SO ₃ The composite was obtained as a transparent freestanding film of about 100 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 4 × 10 ^-5 S / cm.
[0098]
[Example 3]
LiCF used in Example 2 ₃ SO ₃ Instead of NaCF ₃ SO ₃ Was used in the same manner as in Example 2 except that 0.15 g of the solid electrolyte was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 6 × 10 ^-5 S / cm.
[0099]
[Example 4]
LiCF used in Example 2 ₃ SO ₃ , And a solid electrolyte was produced in the same manner as in Example 2 except that 0.11 g of LiI was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 1 × 10 ^-4 S / cm.
[0100]
Example 5 <Synthesis of Monomer 2>
Monomer 2 was synthesized by the reaction shown in the following formula.

Specifically, 0.2 mol (= 31 g) of methacryloyloxyethyl isocyanate (MOI) and 0.1 mol (= 90 g) of JEFFAMIN ED900 (manufactured by Aldrich, average molecular weight 900) are dissolved in 200 ml of THF which is well purified in a nitrogen atmosphere. After that, 0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain 115 g of monomer 2 as a colorless viscous liquid.
[0101]
¹ From the results of 1 H-NMR, IR and elemental analysis, it was found that MOI and JEFFAMINE ED900 reacted at a ratio of 2: 1 and further, the isocyanate group of MOI disappeared and a urea bond was formed. Elemental analysis values of hydrogen, oxygen, and nitrogen matched the theoretical values within 0.1%. The average molecular weight measured by GPC was 700. An endothermic peak of DSC which seems to be a melting point could not be observed at -70 ° C or higher. ¹ H-NMR: CH ₂ = C- (5.6,6.1 ppm), -NHCO- (5.2-5.5 ppm), -CH ₂ 0- (3.5 to 3.8 ppm), -CH ₂ N- (3.3-3.5 ppm), = C-CH ₃ (2.0 ppm), -C-CH ₃ (1.2 ppm)
[0102]
[Example 6] <Preparation and evaluation of monomer / monomer 2 copolymer type polymer solid electrolyte>
2. Dissolve 10 g of monomer 1 and 0.51 g of monomer 2 in 20 cc of THF and add 0.14 g of LiCF ₃ SO ₃ Was added and mixed well. The THF was then removed at room temperature under reduced pressure, and monomer 1 / monomer 2 / LiCF ₃ SO ₃ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour. ₃ SO ₃ The composite was obtained as a transparent free standing film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 2 × 10 ^-5 S / cm.
[0103]
[Example 7] <Preparation and evaluation of monomer 3 / monomer 2 copolymer type polymer solid electrolyte>
First, monomer 3 was synthesized by the reaction shown in the following formula.

Specifically, 0.1 mol (= 15.5 g) of methacryloyloxyethyl isocyanate (MOI) and 0.1 mol (= 55 g) of monomethyl oligoethylene glycol having an average molecular weight of 550 are dissolved in 100 ml of THF which is well purified in a nitrogen atmosphere. After that, 0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain a monomer 3 as a colorless viscous liquid. That ¹ From the results of 1 H-NMR, IR and elemental analysis, it was found that the MOI and the monomethyl oligoethylene glycol reacted one to one, the isocyanate group of the MOI disappeared, and a urethane bond was formed.
[0104]
Next, 2.10 g of monomer 3 and 0.51 g of monomer 2 were dissolved in 20 cc of THF, and 0.14 g of LiCF was dissolved. ₃ SO ₃ Was added and mixed well. The THF was then removed at room temperature under reduced pressure and monomer 3 / monomer 2 / LiCF ₃ SO ₃ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour, and the monomer 3 / monomer 2 copolymer / LiCF ₃ SO ₃ The composite was obtained as a transparent free standing film of about 200 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 2 × 10 ^-5 S / cm.
[0105]
Example 8 <Preparation and Evaluation of Monomer 1 / Monomer 4 Copolymer Type Polymer Solid Electrolyte>
First, monomer 4 was synthesized by the reaction shown in the following formula.

Specifically, 0.2 mol (= 31 g) of methacryloyloxyethyl isocyanate (MOI) and 0.1 mol (= 80 g) of Adekacarpol PH80 (average molecular weight: 800) were dissolved in 100 ml of THF which was well purified in a nitrogen atmosphere. Thereafter, 0.66 g of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain a monomer 4 as a colorless viscous liquid. That ¹ From the results of H-NMR, IR and elemental analysis, it was found that the MOI and PH80 reacted at a ratio of 2: 1 and that the isocyanate group of the MOI disappeared and a urethane bond was formed.
[0106]
Next, 2.10 g of monomer 1 and 0.51 g of monomer 4 were dissolved in 20 cc of THF, and 0.14 g of LiCF was dissolved. ₃ SO ₃ Was added and mixed well. The THF was then removed at room temperature under reduced pressure, and monomer 1 / monomer 4 / LiCF ₃ SO ₃ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate in an argon atmosphere and heated at 100 ° C. for 1 hour. ₃ SO ₃ The composite was obtained as a transparent freestanding film of about 100 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 3 × 10 ^-5 S / cm.
[0107]
Example 9 <Synthesis of Monomer 5>
First, in the same manner as in Example 1, a raw material 2 of a monomer 5 obtained by aminating the terminal hydroxyl group of ADEKA CARPOL GH-5 (average molecular weight 5000, triol, KOH value 34.0 mg / g) by the reaction shown by the following formula: Was synthesized.
Embedded image

¹ A nitrogen / methylene bond was formed around 2.8 ppm of H-NMR, and an infrared absorption spectrum of 3300 cm ^-1 The stretching vibration of NH was confirmed in the vicinity. The elemental analysis values of hydrogen, oxygen, and nitrogen matched the theoretical values within 0.1%. The average molecular weight measured by GPC was 5,000.
[0108]
Next, monomer 5 was synthesized by the reaction shown in the following formula.
Embedded image

Specifically, 0.1 mol (= 15.5 g) of methacryloyloxyethyl isocyanate (MOI) and 0.033 mol (= 165 g) of the raw material 2 were dissolved in 300 ml of well-purified THF in a nitrogen atmosphere. 66 g of dibutyltin dilaurate were added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain 175 g of monomer 5 as a colorless viscous liquid.
[0109]
¹ From the results of H-NMR, IR and elemental analysis, it was found that the MOI and the raw material 2 reacted 3 to 1, and further, the isocyanate group of the MOI disappeared, and a urea bond was formed. Elemental analysis values of hydrogen, oxygen, and nitrogen matched the theoretical values within 0.1%. The average molecular weight measured by GPC was 6000. An endothermic peak of DSC which seems to be a melting point could not be observed at -70 ° C or higher. ¹ H-NMR: CH ₂ = C- (5.6,6.1 ppm), -NHCO- (5.2-5.6 ppm), -CH ₂ 0- (3.4 to 3.8 ppm), -CH ₂ N- (3.3-3.6 ppm), = C-CH ₃ (1,9-2.1 ppm), -C-CH ₃ (1.1-1.2 ppm)
[0110]
[Example 10] <Production and evaluation of monomer 5-based polymer solid electrolyte>
Dissolve 2.09 g of Monomer 5 in 10 cc of THF and add 0.14 g of LiCF ₃ SO ₃ Was added and mixed well. The THF was then removed at room temperature under reduced pressure and the monomer 5 / LiCF ₃ SO ₃ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate in an argon atmosphere and heated at 100 ° C. for 1 hour. ₃ SO ₃ The composite was obtained as a transparent free standing film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 3 × 10 ^-5 S / cm.
[0111]
[Example 11]
LiCF used in Example 10 ₃ SO ₃ Instead of LiBF ₄ Was used in the same manner as in Example 10 except that 0.10 g of was used to prepare a solid electrolyte. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 4 × 10 ^-5 S / cm.
[0112]
[Example 12]
LiCF used in Example 10 ₃ SO ₃ Instead of LiPF ₆ Was used in the same manner as in Example 10 except that 0.15 g of the solid electrolyte was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 5 × 10 ^-4 S / cm.
[0113]
[Example 13] <Preparation and evaluation of polymer 1 / monomer 5 copolymer solid electrolyte>
1.00 g of Monomer 1 and 1.61 g of Monomer 5 were dissolved in 20 cc of THF, and 0.10 g of LiBF was dissolved. ₄ Was added and mixed well. The THF was then removed at room temperature under reduced pressure, and monomer 1 / monomer 5 / LiBF ₄ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour to obtain a monomer / monomer 5 copolymer / LiBF ₄ The composite was obtained as a transparent freestanding film of about 100 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 5 × 10 ^-5 S / cm.
[0114]
[Example 14] <Preparation and evaluation of monomer 3 / monomer 5 copolymer based polymer solid electrolyte>
1.00 g of Monomer 3 and 1.61 g of Monomer 5 were dissolved in 20 cc of THF, and 0.10 g of LiBF was dissolved. ₄ Was added and mixed well. The THF was then removed at room temperature under reduced pressure and monomer 3 / monomer 5 / LiBF ₄ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate in an argon atmosphere, and heated at 100 ° C. for 1 hour. ₄ The composite was obtained as a transparent freestanding film of about 100 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 5 × 10 ^-5 S / cm.
[0115]
[Example 15]
1.00 g of monomer 1, 0.50 g of monomer 2, 1.30 g of propylene carbonate (PC), 1.30 g of ethylene carbonate (EC), and 0.56 g of LiBF ₄ Are mixed well in an argon atmosphere, and monomer 1 / monomer 2 / PC / EC / LiBF ₄ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour to obtain a monomer 1 + monomer 2 copolymer / PC / EC / LiBF ₄ The composite was obtained as a transparent free standing film of about 200 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, 2 × 10 ^-3 S / cm, 6 × 10 ^-4 S / cm.
[0116]
[Example 16]
A monomer 1 + monomer 2 copolymer / TG / LiBF was prepared in the same manner as in Example 15 except that tetraglyme (TG) was used instead of PC and EC used in Example 15. ₄ The composite was obtained as a transparent free-standing film of about 200 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 8 × 10 ^-4 , 1 x 10 ^-4 S / cm.
[0117]
[Example 17]
0.50 g monomer 1, 1.0 g monomer 5, 1.30 g propylene carbonate (PC), 1.30 g ethylene carbonate (EC), and 0.56 g LiBF ₄ Are mixed well in an argon atmosphere, and monomer 1 / monomer 5 / PC / EC / LiBF ₄ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour. ₄ The composite was obtained as a transparent freestanding film of about 100 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 3 × 10 ^-3 S / cm, 7 × 10 ^-4 S / cm.
[0118]
[Example 18]
LiBF used in Example 17 ₄ Instead of LiPF ₆ Of monomer 1 + monomer 5 / PC / EC / LiPF in the same manner as in Example 17 except that 0.84 g of ₆ The composite was obtained as a transparent free standing film of about 100 μm. The ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method. ^-3 , 1 x 10 ^-3 S / cm.
[0119]
[Example 19]
A monomer 1 + monomer 5 copolymer / DEC / EC / LiBF was obtained in the same manner as in Example 17 except that diethyl carbonate (DEC) was used instead of propylene carbonate used in Example 17. ₄ The composite was obtained as a transparent free standing film of about 100 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 1 × 10 ^-3 , 2 x 10 ^-4 S / cm.
[0120]
[Example 20]
1.5 g monomer 5, 1.30 g propylene carbonate (PC), 1.30 g ethylene carbonate (EC), and 0.84 g LiPF ₆ Are mixed well in an argon atmosphere, and monomer 5 / PC / EC / LiPF ₆ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour. The monomer 5 polymer / PC / EC / LiPF ₆ The composite was obtained as a transparent free standing film of about 50 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 2.5 × 10 ^-3 S / cm, 8 × 10 ^-4 S / cm.
[0121]
[Example 21]
1.1 g of monomer 1, 0.2 g of N, N-dimethylacrylamide were dissolved in 100 cc of THF, and 0.10 g of LiBF was dissolved. ₄ Was added and mixed well. Then, THF was removed under reduced pressure at room temperature, and monomer 1 / N, N-dimethylacrylamide / LiBF ₄ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour to obtain a monomer 1 + N, N-dimethylacrylamide copolymer / LiBF ₄ The composite was obtained as a transparent freestanding film of about 20 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 3 × 10 ^-5 S / cm.
[0122]
[Example 22]
1.1 g of Monomer 1 and 0.2 g of polyethylene oxide PEO-1 (manufactured by Sumitomo Seika Co., Ltd.) were dissolved in 100 cc of THF, and 0.10 g of LiBF was dissolved. ₄ Was added and mixed well. The THF was then removed under reduced pressure at room temperature, and the monomer 1 / PEO-1 / LiBF ₄ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour to obtain monomer 1 / PEO-1 / LiBF ₄ The composite was obtained as a transparent freestanding film of about 20 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 2 × 10 ^-5 S / cm.
[0123]
Example 23 <Production of Cobalt Oxide Positive Electrode>
11 g of Li ₂ CO ₃ And 24g of Co ₃ O ₄ Are mixed well, heated at 800 ° C. for 24 hours in an oxygen atmosphere, and then pulverized to obtain LiCoO 2. ₂ A powder was obtained. This LiCoO ₂ The powder and the polymerizable monomer solution prepared in Example 18 were mixed in an argon atmosphere at a weight ratio of 7: 3, and applied on a stainless steel foil to a thickness of 1 × 1 cm and a thickness of about 200 μm. Furthermore, by heating and polymerizing at about 100 ° C. for 1 hour, a cobalt oxide / polymer solid electrolyte composite positive electrode (65 mg) was obtained.
[0124]
[Example 24] <Manufacture of polymer solid electrolyte secondary battery>
A 75 μm-thick lithium foil was cut into 1 × 1 cm (5.3 mg) in an argon atmosphere glove box, and about 1 mm on each end thereof was covered with a polyimide film of 5 μm as a spacer. Next, the polymerizable monomer solution prepared in Example 20 was applied on a lithium foil, and the cobalt oxide positive electrode produced in Example 23 was adhered thereto. After heating at 100 ° C. for 1 hour, the end of the battery was sealed with an epoxy resin. Thus, a lithium / cobalt oxide solid secondary battery was obtained.
FIG. 1 shows a cross-sectional view of the obtained battery.
When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.3 V and a current of 0.1 mA, the maximum discharge capacity was 3.8 mAh, and the cycle life until the capacity was reduced to 50% was 255 times. there were.
[0125]
[Example 25] <Production of polyaniline positive electrode>
Aniline 0.5M, HBF ₄ Using a 1.5 M aqueous solution as a polymerization solution, electrolytic oxidation polymerization was carried out on a 1 × 1 cm stainless steel foil to a thickness of about 100 μm by a constant current method of 1 mA using graphite foil as a counter electrode. Next, after washing with methanol, it was vacuum dried at 80 ° C. for 24 hours.
Then, the film was transferred into a glove box under an argon atmosphere, and the polymerizable monomer solution prepared in Example 18 was impregnated with the film and polymerized at 100 ° C. for 1 hour to obtain a polyaniline / polymer solid electrolyte composite positive electrode (45 mg). Obtained.
[0126]
[Example 26] <Manufacture of polymer solid electrolyte secondary battery>
A lithium / polyaniline solid secondary battery was obtained in the same manner as in Example 24 except that the polyaniline positive electrode produced in Example 25 was used instead of the cobalt oxide positive electrode. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.0 V and a current of 0.1 mA, the maximum discharge capacity was 0.8 mAh, and the cycle life until the capacity was reduced to 50% was 411 times. there were.
[0127]
[Example 27] <Production of vapor phase graphite negative electrode>
10 g of Showa Denko vapor-grown graphite fiber (average fiber diameter, 0.3 μm, average fiber length, 2.0 μm, heat-treated at 2700 ° C.) was mixed with 200 ml of a 2.5 M butyllithium-containing hexane solution, and the mixture was stirred at room temperature for 8 hours. The mixture was stirred for an hour. Next, it was washed with hexane and dried to obtain a graphite fiber into which lithium ions had been preliminarily inserted. The C / Li atomic ratio was 12/1 as determined by elemental analysis. 6 g of the lithium-containing graphite fiber thus obtained and 4 g of the polymerizable monomer mixture prepared in Example 18 were mixed under an argon atmosphere, and a part thereof was taken on a stainless steel foil to a thickness of 1 × 1 cm and a thickness of about 150 μm. Was applied. Further, the mixture was heated and polymerized at about 100 ° C. for 1 hour to obtain a vapor phase graphite / polymer solid electrolyte composite negative electrode (21 mg).
[0128]
[Example 28] <Production of solid polymer electrolyte secondary battery>
A vapor phase graphite / cobalt oxide solid secondary battery was obtained in the same manner as in Example 24 except that the vapor phase graphite negative electrode produced in Example 27 was used instead of the lithium foil.
When this battery was repeatedly charged and discharged at an operating voltage of 1.5 to 4.3 V and a current of 0.1 mA, the maximum discharge capacity was 3.5 mAh, and the cycle life until the capacity was reduced to 50% was 201 times. there were.
[0129]
[Example 29] <Synthesis of organic solvent-soluble polyaniline>
A thermometer, a stirrer, and a condenser were attached to a 1 L four-necked flask, and 500 ml of a 1N HCl aqueous solution was added, and 20.3 g of aniline was dissolved while bubbling nitrogen. Then, 11.5 g of ammonium persulfate was added over about 30 minutes while stirring and while bubbling nitrogen, while remaining solid. The reaction temperature was kept at about 22 ° C. After the addition, the mixture was further reacted for 22 hours, followed by filtration, and the residue was washed with 500 ml of distilled water. Next, the product was transferred to a beaker, stirred with 500 ml of 5% aqueous ammonia for about 1 hour, filtered, washed with distilled water, and dried under reduced pressure to obtain about 16 g of undoped polyaniline powder.
[0130]
Next, 150 ml of hydrazine monohydrate was added to a 300 ml three-necked flask, and the above-mentioned undoped polyaniline powder was added at room temperature under a nitrogen stream with stirring over about 1 hour. After stirring at room temperature for about 10 hours under a nitrogen stream, the mixture was filtered in a nitrogen atmosphere and dried under reduced pressure. Further, by washing with purified THF and purified ether in a nitrogen atmosphere and drying under reduced pressure, about 14 g of reduced polyaniline powder was obtained.
[0131]
The elemental analysis value of this reduced polyaniline powder was 98% in total of carbon, hydrogen and nitrogen, and the elemental ratio of carbon / hydrogen / nitrogen was 6.00 / 4.95 / 1.01, which was almost in agreement with the theoretical value. did.
This powder was dissolved in purified N-methylpyrrolidone (NMP) under an argon atmosphere to a concentration of about 5 wt%. The number average molecular weight of polyaniline determined by GPC measurement of this solution was about 20,000 in terms of polystyrene.
[0132]
[Example 30] <Production of polyaniline positive electrode>
The polymerizable monomer solution prepared in Example 18 was mixed with the 5 wt% polyaniline / NMP solution prepared in Example 29 in a glove box under an argon atmosphere so that the weight ratio of polyaniline and the polymerizable monomer solution was 1: 1. did. This mixed solution was applied to a portion surrounded by a polyimide film on a 15 × 15 mm, 100 μm thick stainless steel foil in which a 50 μm polyimide film was attached to the four end portions with a width of 3 mm.
Then, drying and polymerization were performed by heating at 60 ° C., 80 ° C., and 100 ° C. for 1 hour each.
[0133]
[Example 31] <Production of polymer solid electrolyte secondary battery>
In an argon atmosphere glove box, a 25 μm-thick lithium foil was cut into 12 × 12 mm (2.6 mg), and about 2 mm on each end thereof was covered with a 5 μm polyimide film as a spacer. Next, the polymerizable monomer solution prepared in Example 20 was applied on a lithium foil, and the polyaniline positive electrode produced in Example 29 was adhered thereto. After heating at 100 ° C. for 1 hour, the battery end was sealed with an epoxy resin. Thus, a lithium / polyaniline solid secondary battery as shown in FIG. 1 was obtained.
When the battery was repeatedly charged and discharged at an operating voltage of 2 to 4 V and a current of 0.1 mA, the maximum discharge capacity was 1.2 mAh, and the cycle life until the capacity was reduced to 50% was 253 times.
[0134]
[Example 32] <Preparation of polymerizable monomer solution>
1.00 g of monomer 1, 0.50 g of monomer 2, 2.6 g of propylene carbonate (PC), and 1.10 g of tetraethylammonium perchlorate (TEAP) were mixed well in an argon atmosphere, and monomer 1 / monomer 2 A / PC / TEAP mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour to obtain a monomer 1 + monomer 2 copolymer / PC / TEAP composite as a transparent self-supporting film having a thickness of about 200 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 2.5 × 10 ^-3 S / cm, 8 × 10 ^-4 S / cm.
[0135]
[Example 33] <Preparation of polymerizable monomer solution>
1.50 g of monomer 5, 2.6 g of propylene carbonate (PC) and 1.10 g of tetraethylammonium perchlorate (TEAP) are mixed well in an argon atmosphere, and the monomer 5 / PC / TEAP mixture is converted into a viscous liquid. Obtained. This mixture was coated on a glass plate under an argon atmosphere and heated at 100 ° C. for 1 hour to obtain a monomer 5 polymer / PC / TEAP composite as a transparent self-supporting film having a thickness of about 100 μm. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 3.0 × 10 3 ^-3 S / cm, 8 × 10 ^-4 S / cm.
[0136]
[Example 34] <Production of activated carbon electrode>
Coconut palm activated carbon and the polymerizable monomer mixture prepared in Example 32 were mixed in an argon atmosphere at a weight ratio of 1: 1 and applied to a stainless foil at a size of 1 cm × 1 cm and a thickness of about 150 μm. Further, the mixture was heated at about 100 ° C. for 1 hour for polymerization to obtain an activated carbon / polymer solid electrolyte composite electrode (13 mg).
[0137]
[Example 35] <Production of solid electric double layer capacitor>
In an argon atmosphere glove box, the activated carbon electrode (13 mg) produced in Example 34, about 1 mm × 1 cm, about 1 mm square was coated with a 5 μm thick polyimide film as a spacer. Next, the polymerizable monomer mixture prepared in Example 33 was applied onto the electrodes, and another electrode was bonded thereto, heated at 100 ° C. for 1 hour, and then sealed at the capacitor end with epoxy resin. A solid electric double layer capacitor as shown in FIG.
When the capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.1 mA, the maximum capacity was 180 mF. Also, even if charging and discharging were repeated 50 times under these conditions, there was almost no change in the capacity.
[0138]
[Example 36] <Manufacture of solid electric double layer capacitor>
An activated carbon electrode (13 mg) was produced in the same manner as in Example 34, except that the polymerizable monomer mixture produced in Example 15 was used.
A solid electric double layer capacitor was produced in the same manner as in Example 35 except that this electrode and the polymerizable monomer solution produced in Example 17 were used.
When this capacitor was charged and discharged at an operating voltage of 0 to 2.0 V and a current of 0.1 mA, the maximum capacity was 150 mF. Also, even if charging and discharging were repeated 50 times under these conditions, there was almost no change in the capacity.
[0139]
【The invention's effect】
The solid polymer electrolyte of the present invention is composed of a complex of a polymer having an oxyalkyl group bonded by a urea bond in a side chain and at least one electrolyte, and is easily obtained as a thin film having good film strength, Further, it has a feature of high ionic conductivity.
Batteries and capacitors using the polymer solid electrolyte of the present invention can be used stably for a long time without danger of liquid leakage because the ion-conductive substance is a solid. Batteries and capacitors can be manufactured.
[0140]
The electrode activity of a polymer having an oxyalkyl group bonded by a urea bond in a side chain and an organic solvent-soluble polyaniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide or a carbon material of the present invention. An electrode containing a substance or a polarizable material and a method for producing the same can provide an electrode having high electrochemical activity and flexibility, can provide a particularly thin electrode, and can be used for various batteries or electric double layer capacitors and the like. It is useful as a manufacturing method.
[0141]
Further, the battery of the present invention is a battery that can operate at high capacity and high current as an all solid type, or has good cycleability, and is excellent in safety and reliability. It can be used as a power supply for electric products, electric vehicles, and large power supplies for road leveling. Further, since it can be easily thinned, it can be used as a paper battery for an identification card or the like.
[0142]
Furthermore, the electric double layer capacitor of the present invention can operate at a high voltage, a high capacity, and a high current, or has good cycleability, and is excellent in safety and reliability, as compared with conventional all-solid-state capacitors. It is an electric double layer capacitor, and can be an all solid electric double layer capacitor having such characteristics. For this reason, it can be used not only as a backup power supply but also as a power supply for various electric products in combination with a small battery. Moreover, it is excellent in workability such as thinning, and can be expected for uses other than the use of the conventional solid type electric double layer capacitor.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of a thin solid-state battery shown as an example of the battery of the present invention.
FIG. 2 is a schematic sectional view of an embodiment of the solid-state electric double layer capacitor of the present invention.
[Explanation of symbols]
1 positive electrode
2 Polymer solid electrolyte
3 Negative electrode
4 Current collector
5 Spacer
6 Insulating resin sealant
7-minute polar electrode
8 Current collector
9 Polymer solid electrolyte membrane
10 Spacer
11 Insulating resin sealant
12 Lead wire

Claims (17)

General formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ^3- (1)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, and R ³ represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ³ and x, y, z in a plurality of units represented by the above general formula (1) in the same molecule are independent of each other and need not be the same. Absent. ] A polymer solid electrolyte comprising a polymer obtained from at least one compound having a unit represented by the formula (1) and / or a composite containing the compound as a copolymer component and at least one electrolyte. General formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n- (2)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, R ⁴ represents — (CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents an integer of 1 or more. . x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ⁴ and x, y, z in a plurality of units represented by the above general formula (2) in the same molecule are independent of each other, and need not be the same. Absent. A polymer obtained from at least one compound having a unit represented by the formula: Solid electrolyte. 3. The polymer solid electrolyte according to claim 1, wherein the electrolyte is at least one selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. The polymer solid electrolyte according to claim 1, wherein a plasticizer is added to the polymer solid electrolyte containing the electrolyte. A battery comprising the polymer solid electrolyte according to claim 1. 6. The battery according to claim 5, wherein the negative electrode of the battery is an electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions. 7. The battery according to claim 5, wherein the positive electrode of the battery comprises an electrode containing an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. General formula (1) as a polymer solid electrolyte
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ^3- (1)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, and R ³ represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ³ and x, y, z in a plurality of units represented by the above general formula (1) in the same molecule are independent of each other and need not be the same. Absent. A polymerizable monomer mixture containing at least one compound having a unit represented by formula (1) and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the polymerizable monomer mixture, is placed in a battery structure, or is supported. A method for producing a battery, comprising disposing the polymerizable monomer mixture on a body and polymerizing the polymerizable monomer mixture. As a polymer solid electrolyte, general formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n- (2)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, R ⁴ represents — (CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents an integer of 1 or more. . x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ⁴ and x, y, z in a plurality of units represented by the above general formula (2) in the same molecule are independent of each other, and need not be the same. Absent. A polymerizable monomer mixture containing at least one compound having a unit represented by formula (1) and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the polymerizable monomer mixture, is placed in a battery structure, or is supported. A method for producing a battery, comprising disposing the polymerizable monomer mixture on a body and polymerizing the polymerizable monomer mixture. As a material for forming an electrode, a general formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ^3- (1)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, and R ³ represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ³ and x, y, z in a plurality of units represented by the above general formula (1) in the same molecule are independent of each other and need not be the same. Absent. An electrode comprising a polymer obtained from at least one compound having a unit represented by formula (1) and / or a copolymer containing the compound as a copolymer component, and an electrode active material or a polarizable material. As a material for forming an electrode, a general formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n- (2)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, R ⁴ represents — (CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents an integer of 1 or more. . x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ⁴ and x, y, z in a plurality of units represented by the above general formula (2) in the same molecule are independent of each other, and need not be the same. Absent. An electrode comprising a polymer obtained from at least one compound having a unit represented by formula (1) and / or a copolymer containing the compound as a copolymer component, and an electrode active material or a polarizable material. The electrode according to claim 10 or 11, wherein the electrode active material or the polarizable material is an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. An electric double layer capacitor in which a polarizable electrode is disposed via an ion conductive material, wherein the ion conductive material is the polymer solid electrolyte according to any one of claims 1 to 4. In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, the polarizable electrode is made of a carbon material and a general formula (1)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ^3- (1)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, and R ³ represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ³ and x, y, z in a plurality of units represented by the above general formula (1) in the same molecule are independent of each other and need not be the same. Absent. An electric double-layer capacitor comprising a polymer obtained from at least one compound having a unit represented by the formula: and / or a composite containing a copolymer containing the compound as a copolymer component. In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, the polarizable electrode is made of a carbon material and a general formula (2)
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n- (2)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, R ⁴ represents — (CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents an integer of 1 or more. . x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ⁴ and x, y, z in a plurality of units represented by the above general formula (2) in the same molecule are independent of each other, and need not be the same. Absent. An electric double-layer capacitor comprising a polymer obtained from at least one compound having a unit represented by the formula: and / or a composite containing a copolymer containing the compound as a copolymer component. Formula (1) as a composite
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² -R ^3- (1)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, and R ³ represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ³ and x, y, z in a plurality of units represented by the above general formula (1) in the same molecule are independent of each other and need not be the same. Absent. A polymerizable monomer mixture containing at least one kind of compound having a unit represented by formula (1) and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture, or A method for producing an electric double layer capacitor, comprising disposing the polymerizable monomer mixture on a support and polymerizing the polymerizable monomer mixture. Formula (2) as a composite
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCONR ² (R ⁴ O) _n- (2)
[Wherein, R ¹ and R ² represent hydrogen or an alkyl group, R ⁴ represents — (CH ₂ ) ₂ — or —CH (CH ₃ ) CH ₂ —, and n represents an integer of 1 or more. . x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, the values of R ¹ , R ² , R ⁴ and x, y, z in a plurality of units represented by the above general formula (2) in the same molecule are independent of each other, and need not be the same. Absent. A polymerizable monomer mixture containing at least one kind of compound having a unit represented by formula (1) and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture, or A method for producing an electric double layer capacitor, comprising disposing the polymerizable monomer mixture on a support and polymerizing the polymerizable monomer mixture.

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