JP3557477B2 - Polymer solid electrolyte, battery and solid electric double layer capacitor using the same, method for producing them, and polymer solid electrolyte material - Google Patents

Abstract

PURPOSE: To obtain a solid polymer electrolyte which can give a membrane having good strengths, improved room-temperature and low-temperature inoic conductivity and processability by composing it of at least a polymer of a specified compound and/or a copolymer containing the compound and at least one electrolyte. CONSTITUTION: A solid polymer electrolyte comprising a complex containing at least one polymer of a compound containing units of the formula [wherein R<1> is H or methyl; R<2> is a linear, branched or cyclic group and may contain at least one element other than C, H and O; (x) and (y) are each an integer of 0-5; (z) is an integer of 0-10; provided that z=0 when (x) and (y) are 0; and (CH2 ) groups and (CH(CH3 )) groups may be bonded to each other at random, provided that R<1> , R<2> , (x), (y) and (z) in a plurality of units of the formula are independent of each other in the same molecule] and/or a copolymer containing the above compound as a comonomer and at least one molecule, per 1-100 carbonate groups in the side chains or in the bridging chains of the polymer, of at least one electrolyte.

Description

［式中、Ｒ^１ は水素またはメチル基を表し、Ｒ^２ は有機基を表す。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の数値を表す。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（Ｉ）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。］
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、並びに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。
【００２０】
２） 一般式（ＩＩ）
【化１６】

［式中、Ｒ^１ は水素またはメチル基を表し、Ｒ^２ 、Ｒ^３ は有機基を表す。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の数値を表す。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。］
で表される構造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、並びに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。
【００２１】
３） 電解質の少なくとも一種が、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、または遷移金属塩である前記１）または２）記載の高分子固体電解質。
４） 可塑剤が添加されていることを特徴とする前記１）ないし３）記載の高分子固体電解質。
５） 前記１）ないし４）記載の高分子固体電解質を含有することを特徴とする電池。
６） リチウム、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を含む負極を有する前記５）記載の電池。
７） 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を含む正極を有する前記５）記載の電池。
【００２２】
８） 一般式（Ｉ）
【化１７】

［式中の記号は前記１）と同じ。］
で表されるユニットを有する化合物の少なくとも一種及び少なくとも一種の電解質を含有する重合性モノマー混合物、またはこれに可塑剤が添加された重合性モノマー混合物を、電池構成用構造体内に入れ、または支持体上に配置し、かかる重合性モノマー混合物を重合する工程を有することを特徴とする電池の製造方法。
９） 一般式（ＩＩ）
【化１８】

［式中の記号は前記２）と同じ。］
で表される構造を有する化合物の少なくとも一種及び少なくとも一種の電解質を含有する重合性モノマー混合物、またはこれに可塑剤が添加された重合性モノマー混合物を、電池構成用構造体内に入れ、または支持体上に配置し、かかる重合性モノマー混合物を重合する工程を有することを特徴とする電池の製造方法。
【００２３】
１０） 一般式（Ｉ）
【化１９】

［式中の記号は前記１）と同じ。］
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、並びに電極活物質または分極性材料を含むことを特徴とする電極。
１１） 一般式（ＩＩ）
【化２０】

［式中の記号は前記２）と同じ。］
で表される構造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、並びに電極活物質または分極性材料を含むことを特徴とする電極。
【００２４】
１２） 電極活物質または分極性材料が、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である前記１０）もしくは１１）記載の電極。
１３） イオン伝導性物質を介して分極性電極を配置した電気二重層コンデンサであって、イオン伝導性物質が前記１）ないし４）記載の高分子固体電解質であることを特徴とする電気二重層コンデンサ。
【００２５】
１４） 一般式（Ｉ）
【化２１】

［式中の記号は前記１）と同じ。］
で表されるユニットを有する化合物の少なくとも一種及び少なくとも一種の電解質を含有する重合性モノマー混合物、またはこれに可塑剤が添加された重合性モノマー混合物を、電気二重層コンデンサ構成用構造体内に入れ、または支持体上に配置し、かかる重合性モノマー混合物を重合する工程を有することを特徴とする電気二重層コンデンサの製造方法。
１５） 一般式（ＩＩ）
【化２２】

［式中の記号は前記２）と同じ。］
で表される構造を有する化合物の少なくとも一種及び少なくとも一種の電解質を含有する重合性モノマー混合物、またはこれに可塑剤が添加された重合性モノマー混合物を、電気二重層コンデンサ構成用構造体内に入れ、または支持体上に配置し、かかる重合性モノマー混合物を重合する工程を有することを特徴とする電気二重層コンデンサの製造方法。
【００２６】
１６） イオン伝導性物質を介して分極性電極を配置した電気二重層コンデンサであって、分極性電極が一般式（Ｉ）
【化２３】

［式中の記号は前記１）と同じ。］
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炭素材料を含む複合物からなることを特徴とする電気二重層コンデンサ。
１７） イオン伝導性物質を介して分極性電極を配置した電気二重層コンデンサであって、分極性電極が一般式（ＩＩ）
【化２４】

［式中の記号は前記２）と同じ。］
で表される構造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炭素材料を含む複合物からなることを特徴とする電気二重層コンデンサ。
【００３１】
以下に本発明を詳細に説明する。
本発明においてカーボネート基とは、化学式−ＯＣＯＯ−で表される原子団を示し、カーボネート（側）鎖とは化学式−ＯＣＯＯ−で表される原子団を有する（側）鎖を示す。
本発明の高分子固体電解質を製造するためのモノマーである前記一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物は、次式の反応で得ることができる。
ＣＨ_２ ＝Ｃ（Ｒ^１ ）ＣＯ（Ｏ（ＣＨ_２ ）_ｘ （ＣＨ（ＣＨ_３ ））_ｙ ）_ｚ ＮＣＯ＋
【化２９】

→
【化３０】

【００３２】
一例として次式の反応のように２−メタクリロイルオキシエチルイソシアナート（以下、ＭＯＩと略記する。）とヒドロキシ炭酸プロピレンとを１：１のモル比でスズ系触媒下、加熱反応させることにより２−メタクリロイルオキシエチルカルバミド酸炭酸プロピレンエステルが得られる。
ＣＨ_２ ＝Ｃ（ＣＨ_３ ）ＣＯＯ（ＣＨ_２ ）_２ ＮＣＯ＋
【化３１】

→
【化３２】

【００３３】
本発明の高分子固体電解質に含まれる重合体は、前記一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物を重合し、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。
重合は、これらモノマー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出来る。すなわち、これらモノマーを、あるいはこれらモノマーと他の重合性化合物との混合物を、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、カチオンあるいはアニオン重合させることができる。
【００３４】
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。本発明のように高分子固体電解質を電池や電気二重層コンデンサに用いる場合には、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。
【００３５】
すなわち、前記一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物とアルカリ金属塩、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、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。
【００３６】
本発明の高分子固体電解質を製造するためのモノマーである前記一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物と混合する重合性化合物に特に限定はなく、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物と共重合可能なものであればよい。例えば、以下の一般式（ＩＩＩ）
（ＣＨ_２ ＝Ｃ（Ｒ^１ ）ＣＯ（Ｏ（ＣＨ_２ ）_ｘ （ＣＨ（ＣＨ_３ ））_ｙ ）_ｚ ＮＨＣＯＯＲ^２ −） （ＩＩＩ）
（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価の有機鎖を表す。該有機鎖は直鎖状、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の整数を表す。但し、ｘ＝０及びｙ＝０の時は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（ＩＩＩ）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。）で表されるユニットを一つ以上有する（メタ）アクリロイルカルバミド酸エステル等の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、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）アクリル酸エステル、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、メタクリルアミド、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、炭酸ビニレン、ビニルピロリドン、マレイミド等の環状ビニル化合物等を挙げることができる。
【００３７】
この中で高誘電率で重合物の低ガラス転移点と言う点を考慮して、オキシアルキレン鎖を有するウレタン（メタ）アクリレートや（メタ）アクリル酸エステルが好ましく、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。
【００３８】
溶媒を用いる場合には、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物の種類や重合触媒の有無にもよるが、重合を阻害しな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。
【００３９】
重合させる温度としては、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造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、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造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。
【００４０】
本発明の高分子固体電解質に用いる重合体は、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物の単独重合体であっても、２種以上の一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物の共重合体であっても、あるいは少なくとも一種の一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物と他の重合性化合物との共重合体であってもよく、それらの混合物であってもよい。
【００４１】
また、本発明の高分子固体電解質に用いる重合体は、かかる一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物の単独重合体であっても、２種以上の一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物の共重合体であっても、あるいは少なくとも一種の一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物と他の重合性化合物との共重合体のうちの少なくとも１種と他の重合体との混合物であってもよい。他の重合体とは例えば、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中から選ばれる１種以上の重合体が挙げられる。
【００４２】
上記の共重合体あるいは重合体混合物の中に含まれる一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物由来の構造単位の量としては、かかる共重合体あるいは重合体混合物の２０重量％以上であれば、そのウレタン結合を有するカーボネート鎖の特性を十分に発揮できるので好ましい。
本発明の高分子固体電解質に用いる重合体の分子量は１０００以上１００万以下が好ましく、５０００以上５万以下が特に好ましい。重合体の分子量が高くなると加工後の膜強度等の膜特性が良好となる反面、キャリアーイオン移動に重要な熱運動に制約を生じ、イオン伝導性を低下させたり、溶剤にも溶けにくくなり、加工面で不利になる。逆に、分子量が低すぎると、成膜性、膜強度等が悪化し、基本的な物理特性が劣ることになる。
【００４３】
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１００℃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、ジエチルカーボネート、炭酸ビニレン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。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、（Ｍ）ＡＣＥ重合体重量の５倍量以下である。
【００４４】
本発明の高分子固体電解質中重合体と複合に用いる電解質の複合比は、側鎖もしくは架橋鎖のカーボネート基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カーボネート基の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ため、好ましくない。
【００４５】
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良いが、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。
【００４６】
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。
このアルカリ金属塩の種類としては、例えば、ＬｉＮ（ＣＦ_３ ＳＯ_２ ）_２ 、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。
【００４７】
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。
【００４８】
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、気相法黒鉛、石油コークス、石炭コークス、ピッチ系炭素、ポリアセン、Ｃ_６０、Ｃ_７０等のフラーレン類等が挙げられる。
【００４９】
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。また、柔軟で薄膜にし易いという点では、特にポリアニリン等の導電性高分子が好ましい。
【００５０】
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。
【００５１】
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。
【００５２】
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。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特に有利である。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。
【００５３】
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。
【００５４】
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。
【００５５】
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。
【００５６】
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（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する少なくとも一種の化合物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。
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。
【００５７】
本発明によれば、上記のように、有機溶媒可溶性のアニリン系重合体のごとき可溶性の導電性高分子であっても、本発明の高分子固体電解質に用いる重合体を用いることにより、柔軟で薄膜の電極を製造することができるので、本発明の電極あるいは電池において用いることのできる前記導電性高分子は有機溶媒可溶性であっても、不溶性であっても良い。
【００５８】
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（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物を、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（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物から得られる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。
【００５９】
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（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物と、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（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物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。かかる前述の重合性モノマー混合物を重合して得た電極を用いた場合には、電極と電解質が特に良好に接触した電池が得られる。なお、かかる重合性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電池により適切なものとする。なお、前記電池構成用構造体あるいは前記支持体はＳＵＳ等の金属、ポリプロピレン、ポリイミド等の樹脂、または導電性もしくは絶縁性ガラス等のセラミックス材料が好ましいが、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。
【００６０】
前述したように、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物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、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物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。
【００６１】
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は集電体であるステンレス箔、５はスペーサーである絶縁性ポリイミドフィルムであり、６は絶縁性樹脂封止剤である。
【００６２】
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。
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。
【００６３】
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。
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黒鉛、ポリアセン及びＣ_６０、Ｃ_７０を挙げることができる。
【００６４】
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、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物を少なくとも一種の電解質と混合して、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、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物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。
【００６５】
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（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物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、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物を、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、前述の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。
【００６６】
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、一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物と、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、または導電性もしく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。
【００６７】
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。
【００６８】
【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、複合できるウレタン結合を有するカーボネート基を側鎖に導入した高誘電率の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。
【００６９】
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。
【００７０】
また、本発明の正極が、前記一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物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。
さらにまた、本発明の、前記一般式（Ｉ）で表されるユニットを有する化合物及び／または（ＩＩ）で表される構造を有する化合物から選ばれる少なくとも一種の化合物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。
【００７１】
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。
【００７２】
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、複合できるウレタン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。
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、特に全個体型電気二重層コンデサが提供される。
【００７３】
【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。
実施例１＜メタクリロイルオキシエチルカルバミド酸炭酸プロピレンエステル（ＭＯＥＣＰ）の合成＞
アリルグリシジルエーテル３４．２ｇにトリフェニルリンを触媒として炭酸ガスを１０〜１５ｋｇ／ｃｍ^２ の高圧下、１００℃で１４時間付加させることにより、アリロキシ炭酸プロピレンを４２．３ｇ得た。次いで、白金触媒を加え、４０℃で５時間反応させることにより、脱アリル化し、ヒドロキシ炭酸プロピレン２５ｇを得た。
【００７４】
このヒドロキシ炭酸プロピレン０．１ｍｏｌ（＝１１．８ｇ）と２−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）を窒素雰囲気中でよく精製したＴＨＦ１００ｍｌに溶解した後、０．３３ｇ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、無色の液体としてＭＯＥＣＰを２７ｇ得た。
生成物がＭＯＥＣＰであることは以下の分析により確認した。

以上の結果から、ＭＯＩとヒドロキシ炭酸プロピレンは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。
【００７５】
実施例２＜ＭＯＥＣＰ系高分子固体電解質の作製と評価＞
実施例１で合成したＭＯＥＣＰ１．５ｇをＴＨＦ１０ｃｃに溶解させ、ＬｉＣＦ_３ ＳＯ_３ ０．１５ｇを加えてよく混合した。次いでＴＨＦを室温減圧下で除去し、ＭＯＥＣＰ／ＬｉＣＦ_３ ＳＯ_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、８０℃で１時間加熱したところ、ＭＯＥＣＰ／ＬｉＣＦ_３ ＳＯ_３ 複合体が約５０μｍの透明な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。
【００７６】
実施例３
実施例２で用いたＬｉＣＦ_３ ＳＯ_３ に代えて、ＬｉＢＦ_４ ０．２０ｇ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、４×１０^−５Ｓ／ｃｍであった。
この固体電解質フィルムのイオン伝導度の温度変化をインピーダンス法にて測定したところ、図３のようになった。図３の縦軸はイオン伝導度を対数で示し、横軸は温度を１０００／絶対温度で示したアレニウスプロットで、その傾きはＭＯＥＣＰ重合体／ＬｉＢＦ_４ 系固体電解質中のイオン移動の活性化エネルギーを表している。
【００７７】
実施例４＜２−メタクリロイルオキシエチルカルバミド酸２−メタクリロイルオキシエチルカルバモイルオリゴオキシエチル／オキシプロピルエステル（ＭＣＭＣ（８００））の合成＞
ＭＯＩ０．２ｍｏｌ（＝３１．０ｇ）、平均分子量８００のオリゴエチレングリコール／プロピレングリコール共重合体０．１ｍｏｌ（＝８０ｇ）を窒素雰囲気中でよく精製したＴＨＦ１００ｍｌ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、無色のゲル状固体としてＭＣＭＣ（８００）を得た。そのＨ１−ＮＭＲ、ＩＲ及び元素分析の結果から、ＭＯＩとオリゴエチレングリコール／プロピレングリコール共重合体は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。
【００７８】
実施例５＜ＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体高分子固体電解質の作製と評価＞
実施例１で合成したＭＯＥＣＰ１．５０ｇと実施例４で合成したＭＣＭＣ（８００）１．５０ｇをＴＨＦ２０ｃｃに溶解させ、ＬｉＣＦ_３ ＳＯ_３ ０．３０ｇを加えてよく混合した。次いで、ＴＨＦを室温減圧下で除去し、ＭＯＥＣＰ／ＭＣＭＣ（８００）／ＬｉＣＦ_３ ＳＯ_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、８０℃で１時間加熱したところ、ＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体／ＬｉＣＦ_３ ＳＯ_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^−４Ｓ／ｃｍであった。
この固体電解質フィルムのイオン伝導度の温度変化をインピーダンス法にて測定したところ、図３のようになった。図３の縦軸はイオン伝導度を対数で示し、横軸は温度を１０００／絶対温度で示したアレニウスプロットで、その傾きはＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体／ＬｉＣＦ_３ ＳＯ_３ 系固体電解質中のイオン移動の活性化エネルギーを表している。
【００７９】
実施例６
実施例５で用いたＬｉＣＦ_３ ＳＯ_３ に代えて、ＬｉＰＦ_６ を０．３０ｇ用いた以外は実施例５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、３×１０^−４Ｓ／ｃｍであった。
【００８０】
実施例７
実施例５で用いたＬｉＣＦ_３ ＳＯ_３ に代えて、ＮａＣＦ_３ ＳＯ_３ を０．２６ｇ用いた以外は実施例５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、８×１０^−５Ｓ／ｃｍであった。
【００８１】
実施例８
実施例５で用いたＬｉＣＦ_３ ＳＯ_３ に代えて、ＡｇＩを０．６０ｇ用いた以外は実施例５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。
【００８２】
実施例９
実施例５で用いたＬｉＣＦ_３ ＳＯ_３ に代えて、テトラエチルアンモニウムテトラフルオロボレート（ＴＥＡＢ）を０．４３ｇ用いた以外は実施例５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、２×１０^−４Ｓ／ｃｍであった。
【００８３】
実施例１０＜２−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（ＭＥＣＭＥ（５５０））の合成＞
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ＴＨＦ１００ｍｌに溶解した後、０．６６ｇのジブチルチンジラウレートを添加する。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ＭＥＣＭＥ（５５０）を得た。そのＨ１−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。
【００８４】
実施例１１＜ＭＯＥＣＰ／ＭＥＣＭＣ（５５０）共重合体高分子固体電解質の作製と評価＞
実施例１で合成したＭＯＥＣＰ１．５０ｇと実施例１０で合成したＭＥＣＭＣ（５５０）１．５０ｇをＴＨＦ２０ｃｃに溶解させ、ＬｉＢＦ_４ を０．２０ｇ加えてよく混合した。次いで、ＴＨＦを室温減圧下で除去し、ＭＯＥＣＰ／ＭＥＣＭＣ（５５０）／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、８０℃で１時間加熱したところ、ＭＯＥＣＰ／ＭＥＣＭＣ（５５０）共重合体／ＬｉＢＣＦ_４ 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^−４Ｓ／ｃｍであった。
【００８５】
比較例１＜ＭＣＭＣ（８００）系高分子固体電解質の作製と評価＞
実施例４で合成したＭＣＭＣ（８００）１．５ｇをＴＨＦ１０ｃｃに溶解させ、ＬｉＣＦ_３ ＳＯ_３ ０．１５ｇを加えてよく混合した。次いでＴＨＦを室温減圧下で除去し、ＭＣＭＣ（８００）／ＬｉＣＦ_３ ＳＯ_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、８０℃で１時間加熱したところ、ＭＣＭＣ（８００）／ＬｉＣＦ_３ ＳＯ_３ 複合体が約５０μｍの透明な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、８×１０^−６Ｓ／ｃｍであった。
【００８６】
実施例１２＜Ｎ−メタクリロイルカルバミド酸炭酸プロピレンエステル（ＮＭＣＰ）の合成＞
実施例１で合成したヒドロキシ炭酸プロピレン０．１ｍｏｌ（＝１１．８ｇ）とＮ−メタクリロイルイソシアナート（ＭＡＩ）０．１ｍｏｌ（＝１１．１ｇ）を、窒素雰囲気中でよく精製したＴＨＦ１００ｍｌに溶解した後、０．３３ｇ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、無色の液体としてＮＭＣＰを２２ｇ得た。
生成物がＮＭＣＰであることは以下の分析により確認した。

以上の結果から、ＭＡＩとヒドロキシ炭酸プロピレンは１対１で反応し、さらにＭＡＩ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。
【００８７】
実施例１３＜ＮＭＣＰ系高分子固体電解質の作製と評価＞
実施例１２で合成したＮＭＣＰ１．５ｇをＴＨＦ１０ｃｃに溶解させ、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、８０℃で１時間加熱したところ、ＮＭＣＰ／ＬｉＢＦ_４ 複合体が約５０μｍの透明な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、１×１０^−５Ｓ／ｃｍであった。
【００８８】
実施例１４＜ＮＭＣＰ／ＭＣＭＣ（８００）共重合体高分子固体電解質の作製と評価＞
実施例１２で合成したＮＭＣＰ１．５０ｇと実施例４で合成したＭＣＭＣ（８００）１．５０ｇをＴＨＦ２０ｃｃに溶解させ、ＬｉＢＦ_４ ０．２０ｇを加えてよく混合した。次いで、ＴＨＦを室温減圧下で除去し、ＮＭＣＰ／ＭＣＭＣ（８００）／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、８０℃で１時間加熱したところ、ＮＭＣＰ／ＭＣＭＣ（８００）共重合体／ＬｉＢＦ_４ 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、１×１０^−４Ｓ／ｃｍであった。
【００８９】
実施例１５＜可塑剤添加ＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体高分子固体電解質の作製と評価＞
実施例１で合成したＭＯＥＣＰ１．８０ｇと実施例４で合成したＭＣＭＣ（８００）１．８０ｇ、ＬｉＢＦ_４ ０．６３ｇ、プロピレンカーボネート（ＰＣ）３．６ｇをアルゴン雰囲気中でよく混合し、ＭＯＥＣＰ／ＭＣＭＣ（８００）／ＰＣ／ＬｉＢＦ_４ 混合物である重合性モノマー溶液を粘稠液体として得た。
この重合性モノマー溶液をアルゴン雰囲気下、ガラス板状に塗布後、１００℃で１時間加熱したところ、ＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体／ＰＣ／ＬｉＢＦ_４ 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、それぞれ３．５×１０^−３、１．５×１０^−３Ｓ／ｃｍであった。
【００９０】
実施例１６
実施例１５で用いたプロピレンカーボネートの代りに、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、ＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体／ＴＧ／ＬｉＢＦ_４ 複合体を約５０μｍ の透明な自立フィルムとして得た。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、９×１０^−４Ｓ／ｃｍであった。
【００９１】
実施例１７
実施例１５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１５と全く同様の方法で、ＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体／ＤＥＣ／ＬｉＢＦ_４ 複合体を約５０μｍ の透明な自立フィルムとして得た。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、１．５×１０^−３Ｓ／ｃｍであった。
【００９２】
実施例１８
実施例１５で用いたＬｉＢＦ_４ ０．６３ｇの代わりにＬｉＰＦ_６ ０．９５ｇを用いた以外は、実施例１５と全く同様の方法で、ＭＯＥＣＰ／ＭＣＭＣ（８００）共重合体／ＰＣ／ＬｉＰＦ_６ 複合体を約５０μｍ の透明な自立フィルムとして得た。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^−３Ｓ／ｃｍであった。
【００９３】
比較例２＜可塑剤添加ＭＣＭＣ（８００）系重合体高分子固体電解質の作製と評価＞
実施例４で合成したＭＣＭＣ（８００）３．６０ｇ、ＬｉＢＦ_４ ０．６３ｇ、プロピレンカーボネート（ＰＣ）３．６ｇをアルゴン雰囲気中でよく混合し、ＭＣＭＣ（８００）／ＰＣ／ＬｉＢＦ_４ 混合物である重合性モノマー溶液を粘稠液体として得た。
この重合性モノマー溶液をアルゴン雰囲気下、ガラス板状に塗布後、１００℃で１時間加熱したところ、ＭＣＭＣ（８００）重合体／ＰＣ／ＬｉＢＦ_４ 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、それぞれ８．０×１０^−４、３．２×１０^−４Ｓ／ｃｍであった。
【００９４】
実施例１９＜重合性モノマー溶液の調製＞
実施例１で合成したＭＯＥＣＰ１．８０ｇと実施例４で合成したＭＣＭＣ（８００）１．８０ｇ、ＬｉＢＦ_４ ０．６３ｇ、プロピレンカーボネート（ＰＣ）１．８ｇ、エチレンカーボネート（ＥＣ）１．８ｇをアルゴン雰囲気中でよく混合し、ＭＯＥＣＰ／ＭＣＭＣ（８００）／ＰＣ／ＥＣ／ＬｉＢＦ_４ 混合物である重合性モノマー溶液を粘稠液体として得た。
この重合性モノマー溶液をアルゴン雰囲気下、ガラス板状に塗布後、１００℃で１時間加熱したところ、ＭＯＥＣＰ（５５０）／ＭＣＭＣ（８００）共重合体／ＰＣ／ＥＣ／ＬｉＢＦ_４ 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、それぞれ４．０×１０^−３、１．５×１０^−３Ｓ／ｃｍであった。
【００９５】
実施例２０＜酸化コバルト正極の製造＞
Ｌｉ_２ ＣＯ_３ １１ｇとＣｏ_３ Ｏ_４ ２４ｇ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１９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（７０ｍｇ）を得た。
【００９６】
実施例２１＜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１９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２０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０．３ｍＡで充放電を繰返したところ、最大放電容量は４．０ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は２００回であった。
同様の方法で製造した電池を、作動電圧２．０〜４．３Ｖ、電流０．３ｍＡ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２５１回であった。
【００９７】
実施例２２＜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、０．３μｍ、平均繊維長、２．０μｍ、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１９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（２５ｍｇ）を得た。
【００９８】
実施例２３＜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２２で製造した気相法黒鉛負極を用いた以外は実施例２１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０．３ｍＡで充放電を繰返したところ、最大放電容量は４．０ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は３２３回であった。
【００９９】
実施例２４＜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−プ状態のポリアニリン粉末約１６ｇを得た。
【０１００】
次に、３００ｍｌの３つ口フラスコにヒドラジン１水和物、１５０ｍｌを加え、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。
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。
【０１０１】
実施例２５＜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１９で製造した重合性モノマー溶液を実施例２４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１０×１０ｍｍ、厚さ２００μｍになるようにステンレス箔上に塗布した。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、重合を行ない、ポリアニリン／高分子固体電解質複合正極（２０ｍｇ）を得た。
【０１０２】
実施例２６＜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、スペーサーとして厚さ１０μｍのポリイミドフィルムで被覆した。次に、実施例１９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２５で製造したポリアニリン／高分子固体電解質複合正極を張り合わせ、１００℃、１時間加熱後、電池端部をエポキシ樹脂で封印し、図１と同様の構成を有するリチウム／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０．３ｍＡ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３８０回であった。
【０１０３】
実施例２７＜重合性モノマー溶液の調製＞
実施例１で合成したＭＯＥＣＰ１．８０ｇと実施例４で合成したＭＣＭＣ（８００）１．８０ｇ、テトラエチルアンモニウムテトラフルオロボレート（ＴＥＡＢ）１．３５ｇ、プロピレンカーボネート（ＰＣ）３．６ｇをアルゴン雰囲気中でよく混合し、ＭＯＥＣＰ／ＭＣＭＣ（８００）／ＰＣ／ＴＥＡＢ混合物である重合性モノマー溶液を粘稠液体として得た。
この重合性モノマー溶液をアルゴン雰囲気下、ガラス板状に塗布後、１００℃で１時間加熱したところ、ＭＯＥＣＰ（５５０）／ＭＣＭＣ（８００）共重合体／ＰＣ／ＴＥＡＢ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、それぞれ３．８×１０^−３、１．２×１０^−３Ｓ／ｃｍであった。
【０１０４】
実施例２８＜活性炭電極の製造＞
椰子がら活性炭と実施例２７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（１５ｍｇ）を得た。
【０１０５】
実施例２９＜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２８で製造した活性炭電極（１５ｍｇ）１ｃｍ×１ｃｍの端部約１ｍｍ四方を、スペーサーとして厚さ１０μｍのポリイミドフィルムで被覆した。次に、実施例２７で調製した重合性モノマー溶液を電極上に塗布し、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０．３ｍＡで充放電を行なったところ、最大容量は２３０ｍＦ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。
【０１０６】
実施例３０＜固体電気二重層コンデンサの製造＞
実施例２７で製造した重合性モノマー溶液に用いた塩ＴＥＡＢの代わりに、ＬｉＢＦ_４ ０．６３ｇを用いて、重合性モノマー溶液を調製した。この重合性モノマー溶液を用いた以外は実施例２９と同様の方法で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０．３ｍＡで充放電を行なったところ、最大容量は１７３ｍＦ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。
【０１０７】
実施例３１＜アセチレンブラック電極の製造＞
アセチレンブラックと実施例２７で製造した重合性モノマー溶液を、アルゴン雰囲気下、重量比６：４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時間加熱重合することにより、アセチレンブラック／高分子固体電解質複合電極（１５ｍｇ）を得た。
【０１０８】
実施例３２＜固体電気二重層コンデンサの製造＞
実施例３１で製造したアセチレンブラック電極（１５ｍｇ）を用いた以外は、実施例２９と同様の方法で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０．３ｍＡで充放電を行なったところ、最大容量は５５ｍＦ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。
【０１０９】
【発明の効果】
本発明の高分子固体電解質は、ウレタン結合により結合したカーボネート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。
【０１１０】
本発明の、ウレタン結合により結合したカーボネート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。
【０１１１】
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。
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。
【図３】ＭＯＥＣＰ系及びＭＯＥＣＰ／ＭＣＭＣ（８００）共重合系高分子固体電解質フィルムのイオン伝導度の温度変化。
【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 relates to a solid polymer electrolyte having high ionic conductivity using a polymer into which a carbonate side chain and / or a crosslinked chain having a urethane bond are introduced, an electrode using the polymer, a method for producing the same, and the polymer. The present invention relates to a battery using the solid electrolyte or the electrode and a method for producing the same, an electric double layer capacitor using the polymer solid electrolyte and a method for producing the same, the polymer, and a monomer of the polymer.
[0002]
[Prior art]
In the field of downsizing and all-solidification in the field of ionics, solid electrolytes are being applied to all-solid-state primary batteries, secondary batteries, and electric double-layer capacitors as new ion conductors that replace conventional electrolyte solutions. Has been 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.
The present inventors have found that a polymer solid electrolyte having good membrane strength and high ionic conductivity can be obtained by introducing a urethane bond into a side chain and / or a cross-linked chain in a polymer ( JP-A-6-187822).
However, the dielectric constant of the polymer is still insufficient, and the ionic conductivity is insufficient for practical use in batteries and the like, and it is necessary to add a low molecular compound having a high dielectric constant.
[0013]
[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 membrane, has high ionic conductivity at room temperature and low temperature, and has excellent workability. In addition, the present invention provides a primary battery and a secondary battery which can be easily formed into a thin film, can be operated at a high capacity and a high current, have good cyclability, and have excellent reliability by using the polymer solid electrolyte. The purpose is to develop batteries. Another object of the present invention is to provide an electrode having high electrochemical activity and flexibility and a secondary battery using the same.
[0014]
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.
[0015]
[Means for Solving the Problems]
The present inventors promote the ionic dissociation of the electrolyte salt by using a material in which a carbonate having a high dielectric constant is further introduced into the side chain and / or the crosslinked chain, and use other high dielectric constants for promoting the ionic dissociation. It has been found that it is possible to eliminate or reduce the addition of a high-performance compound, and to obtain a polymer solid electrolyte having more excellent ionic conductivity, thermal stability or membrane strength.
[0016]
Furthermore, they have found that by using this polymer solid electrolyte, a battery having a high output voltage, a large take-out current, a long cycle life, and excellent workability and reliability can be obtained.
Further, the present inventors, for example, when using this polymer solid electrolyte to make a thin solid-state battery, 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 a carbonate side chain and / or a cross-linked chain having a urethane bond are introduced, the electrochemical activity of the electrode active material can be improved. An electrode having high electrochemical activity and flexibility can be obtained without impairing the activity. Further, for example, the electrode can be thinned by a solvent casting method or other methods. It was found that the deposition is possible.
[0017]
Further, the present inventors have proposed a polarizable material used as a polarizable electrode of an electric double layer capacitor, a carbon material as described below, and a polymer having a carbonate side chain and / or a cross-linked chain having a urethane bond introduced therein. By using, a polarizable electrode suitable for the capacitor can be obtained without impairing the polarization characteristics of such a polarizable material. Further, for example, a thin film of an electrode can be formed by a solvent casting method or another method. Was found.
[0018]
Furthermore, the present inventors have obtained that by using the above-mentioned polymer solid electrolyte, an electric double layer capacitor having a high output voltage, a large take-out current, excellent workability, and excellent reliability can be obtained. Type electric double layer capacitor.
[0019]
That is, the present invention provides the following.
1) General formula (I)
Embedded image

[Wherein, R ¹ Represents hydrogen or a methyl group; ² Represents an organic 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 (I) in the same molecule ¹ , R ² 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 a composite containing at least one electrolyte.
[0020]
2) General formula (II)
Embedded image

[Wherein, R ¹ Represents hydrogen or a methyl group; ² , R ³ Represents an organic 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. ]
A polymer solid electrolyte comprising a polymer obtained from at least one compound having a structure represented by the formula and / or a copolymer containing the compound as a copolymer component, and a composite containing at least one electrolyte.
[0021]
3) The polymer solid electrolyte according to the above 1) or 2), wherein at least one of the electrolytes is an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt.
4) The polymer solid electrolyte as described in 1) to 3) above, wherein a plasticizer is added.
5) A battery comprising the polymer solid electrolyte described in 1) to 4) above.
6) The battery according to 5), further including a negative electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions.
7) The battery according to 5), further including a positive electrode containing an organic solvent-soluble aniline-based polymer or another conductive polymer, a metal oxide, a metal sulfide, or a carbon material.
[0022]
8) General formula (I)
Embedded image

[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: a step of polymerizing the polymerizable monomer mixture disposed on the battery.
9) General formula (II)
Embedded image

[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 structure represented by and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture, is placed in a battery structure, or a support. A method for producing a battery, comprising: a step of polymerizing the polymerizable monomer mixture disposed on the battery.
[0023]
10) General formula (I)
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[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.
11) General formula (II)
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[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 structure represented by the formula and / or a copolymer containing the compound as a copolymer component, and an electrode active material or a polarizable material.
[0024]
12) The electrode according to 10) or 11) above, wherein the electrode active material or the polarizable material is an organic solvent-soluble aniline 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 material, wherein the ion conductive material is the solid polymer electrolyte described in 1) to 4) above. Capacitors.
[0025]
14) General formula (I)
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[The symbols in the formula are the same as in the above 1). ]
A polymerizable monomer mixture containing at least one electrolyte and at least one electrolyte having a unit represented by a unit, or a polymerizable monomer mixture to which a plasticizer is added, is placed in the structure for forming an electric double layer capacitor, Alternatively, a method for producing an electric double layer capacitor, comprising a step of disposing the polymerizable monomer mixture on a support and polymerizing the polymerizable monomer mixture.
15) General formula (II)
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[The symbols in the formula are the same as in the above 2). ]
A polymerizable monomer mixture containing at least one electrolyte and at least one electrolyte having a structure represented by, or a polymerizable monomer mixture to which a plasticizer is added, placed in the structure for forming an electric double layer capacitor, Alternatively, a method for producing an electric double layer capacitor, comprising a step of disposing the polymerizable monomer mixture on a support and polymerizing the polymerizable monomer mixture.
[0026]
16) An electric double-layer capacitor in which a polarizable electrode is arranged via an ion-conductive substance, wherein the polarizable electrode has a general formula (I)
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[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 and a carbon material.
17) An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, wherein the polarizable electrode is represented by the general formula (II)
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[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 structure represented by the formula and / or a composite containing a copolymer containing the compound as a copolymer component and a carbon material.
[0031]
Hereinafter, the present invention will be described in detail.
In the present invention, a carbonate group refers to an atomic group represented by a chemical formula -OCOO-, and a carbonate (side) chain refers to a (side) chain having an atomic group represented by a chemical formula -OCOO-.
A compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II), which is a monomer for producing the polymer solid electrolyte of the present invention, is obtained by a reaction represented by the following formula. Obtainable.
CH ₂ = C (R ¹ ) CO (O (CH ₂ ) _x (CH (CH ₃ )) _y ) _z NCO +
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→
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[0032]
As an example, 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as MOI) and propylene hydroxycarbonate are heated and reacted at a molar ratio of 1: 1 under a tin-based catalyst as in the reaction of the following formula. Methacryloyloxyethylcarbamic acid propylene carbonate is obtained.
CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ NCO +
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→
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[0033]
The polymer contained in the solid polymer electrolyte of the present invention comprises at least one compound selected from a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II). It is obtained by polymerization or by polymerizing the compound as a copolymerization component.
For the polymerization, a general method utilizing the polymerizability of an acryloyl group or a methacryloyl group of these monomers can be employed. That is, these monomers, or a mixture of these monomers and other polymerizable compounds, is reacted with a radical polymerization catalyst such as azobisisobutyronitrile and benzoyl peroxide, CF ₃ Protonic acid such as COOH, BF ₃ , AlCl ₃ Radical, cationic or anionic polymerization can be carried out using a cationic polymerization catalyst such as a Lewis acid or the like, or an anionic polymerization catalyst such as butyllithium, sodium naphthalene or lithium alkoxide.
[0034]
It is also possible to polymerize such a polymerizable monomer mixture after forming it into a film or the like. When the polymer solid electrolyte is used for a battery or an electric double layer capacitor as in the present invention, it is particularly advantageous to polymerize the polymerizable monomer mixture after film formation.
[0035]
That is, at least one compound selected from a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II) and an alkali metal salt, a quaternary ammonium salt, and a quaternary phosphonium At least one electrolyte such as a salt or a transition metal salt is mixed, and the polymerizable monomer mixture is polymerized in the presence or absence of the catalyst by heating and / or irradiating electromagnetic waves such as light in some cases. . 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.
[0036]
The polymerizable compound mixed with the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by the formula (II), which is a monomer for producing the polymer solid electrolyte of the present invention, There is no particular limitation, as long as it can be copolymerized with a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II). For example, the following general formula (III)
(CH ₂ = C (R ¹ ) CO (O (CH ₂ ) _x (CH (CH ₃ )) _y ) _z NHCOOR ² −) (III)
(Where R ¹ Represents hydrogen or a methyl group; ² Represents a divalent organic chain containing an oxyalkylene group. The organic chain may have any of a linear, branched and 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 0 or an integer of 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 (III) in the same molecule ¹ , R ² And the values of x, y, z are independent of each other and need not be the same. (Meth) having an oxyalkylene chain such as a urethane (meth) acrylate having an oxyalkylene chain such as a (meth) acryloylcarbamic acid ester having at least one unit represented by formula (1) or ω-methyl oligooxyethyl ethyl methacrylate; (Meth) acrylic acid alkyl esters such as acrylates, methyl methacrylate, n-butyl acrylate, methacrylamide, acrylamide, N, N-dimethylmethacrylamide, acryloylmorpholine, methacryloylmorpholine, N, N-dimethylaminopropyl ( (Meth) acrylamide compounds such as (meth) acrylamide; styrene compounds such as styrene and α-methylstyrene; N-vinylamide compounds such as N-vinylacetamide and N-vinylformamide; Cyclic vinyl compounds such as alkyl vinyl ethers such as vinyl ether, vinylene carbonate, vinyl pyrrolidone, and maleimide.
[0037]
Of these, urethane (meth) acrylates and (meth) acrylates having an oxyalkylene chain are preferable in view of the fact that the polymer has a high dielectric constant and a low glass transition point of the polymer, and urethane (meta) having an oxyalkylene chain is preferred. ) Acrylates are particularly preferred.
[0038]
When a solvent is used, the polymerization is not inhibited, depending on the type of the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by the formula (II) and the presence or absence of a polymerization catalyst. Any solvent may be used as long as it is a solvent, for example, tetrahydrofuran, acetonitrile, toluene and the like can be used.
[0039]
The polymerization temperature depends on the type of the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by the formula (II), but may be any temperature at which polymerization occurs. The heat treatment may be performed in the range of 0 ° C. to 200 ° C. When polymerizing by electromagnetic wave irradiation, depending on the type of the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by the formula (II), for example, benzyl methyl ketal, benzophenone, etc. Using an initiator, polymerization can be carried out by irradiating ultraviolet light or γ-ray of several mW or more.
[0040]
The polymer used for the polymer solid electrolyte of the present invention may be a homopolymer of a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II). A copolymer of at least one compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II), or at least one compound represented by the general formula (I) It may be a copolymer of a compound having a unit represented by formula (1) and / or a compound having a structure represented by formula (II) and another polymerizable compound, or a mixture thereof.
[0041]
The polymer used for the solid polymer electrolyte of the present invention is a homopolymer of the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by the formula (II). Or a copolymer of a compound having two or more units represented by the general formula (I) and / or a compound having a structure represented by the formula (II), or at least one compound of the general formula (I A mixture of at least one of a compound having a unit represented by formula (1) and / or a copolymer of a compound having a structure represented by formula (II) with another polymerizable compound and another polymer. You may. Examples of the other polymer include one or more polymers selected from polyethylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic (or acrylic) esters, polyphosphazenes, polysiloxane, and polysilane.
[0042]
The amount of the structural unit derived from the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by the formula (II) contained in the copolymer or the polymer mixture is as follows: The content of 20% by weight or more of the copolymer or the polymer mixture is preferable because the properties of the carbonate chain having a urethane bond can be sufficiently exhibited.
The molecular weight of the polymer used for the solid polymer electrolyte of the present invention is preferably from 1,000 to 1,000,000, and particularly preferably from 5,000 to 50,000. When the molecular weight of the polymer increases, the film properties such as film strength after processing become good, but on the other hand, the thermal motion important for carrier ion transfer is restricted, the ionic conductivity is reduced, and it becomes difficult to dissolve in the solvent, It is disadvantageous in processing. Conversely, if the molecular weight is too low, film formability, film strength, and the like will deteriorate, and basic physical properties will be inferior.
[0043]
It is preferable to add an organic compound usually used as a so-called plasticizer (referred to 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 a plasticizer that can be used, a compound that has good compatibility with the monomer used for the polymer solid electrolyte of the present invention, a large dielectric constant, a boiling point of 100 ° 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, diethyl carbonate and vinylene carbonate, aromatic nitriles such as benzonitrile and tolunitrile. Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, sulfur compounds such as sulfolane, and phosphoric esters. Of these, oligoethers and carbonates are preferred, and carbonates are particularly preferred. 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. A preferable addition amount is not more than 5 times the weight of the (M) ACE polymer.
[0044]
The composite ratio of the polymer in the solid polymer electrolyte of the present invention and the electrolyte used for the composite is preferably a ratio of one electrolyte molecule to one to 100 carbonate groups of side chains or cross-linked chains. If the electrolyte used in the composite is present at a ratio of one or more of the carbonate groups, the movement of ions is greatly inhibited. On the other hand, at a ratio of 1/100 or less, the absolute amount of ions becomes insufficient and the ion conductivity becomes small. Is not preferred.
[0045]
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.However, it is preferable that the dissociation constant in the polymer solid electrolyte is 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.
[0046]
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.
As the kind of the alkali metal salt, for example, LiN (CF ₃ SO ₂ ) ₂ , 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.
[0047]
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.
[0048]
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, vapor-grown graphite, petroleum coke, coal coke, pitch-based carbon, polyacene, C ₆₀ , C ₇₀ And other fullerenes.
[0049]
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. In addition, a conductive polymer such as polyaniline is particularly preferable in that it is flexible and easily formed into a thin film.
[0050]
The method for producing a metal oxide or metal sulfide is not particularly limited, and may be, for example, a general electrolytic method or a heating method as described in “Electrochemistry, Vol. 22, pp. 574, 1954”. Manufactured. 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.
[0051]
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.
[0052]
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. 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 particularly advantageous when a thin film battery is manufactured. . 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.
[0053]
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.
[0054]
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.
[0055]
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.
[0056]
The undoped or reduced aniline-based polymer thus obtained is soluble in various organic solvents, and in a solution state, has a compound having a unit represented by the general formula (I) and / or ( It can be mixed with a polymerizable monomer solution containing at least one compound having the structure represented by II), and using the mixture thus prepared, for example, by a coating method or the like, onto various supports such as electrodes. An electrode can be manufactured by forming a thin film or forming it into another shape.
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.
[0057]
According to the present invention, as described above, even a soluble conductive polymer such as an organic solvent-soluble aniline-based polymer can be made flexible by using the polymer used for the polymer solid electrolyte of the present invention. Since a thin-film electrode can be manufactured, the conductive polymer that can be used in the electrode or the battery of the present invention may be soluble or insoluble in an organic solvent.
[0058]
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 comprises, for example, at least one compound selected from a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II), and optionally another compound. A polymerizable compound and / or a plasticizer are added and 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 is carried out in the case of obtaining a polymer obtained from at least one compound selected from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by the formula (II). The polymerization can be performed by the same polymerization method as described above. For example, polymerization can be performed by heating and / or irradiation with 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.
[0059]
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 are put into the structure. Then, a unit represented by the general formula (I) is provided between the positive electrode and the negative electrode. At least one compound selected from compounds and / or compounds having a structure represented by (II) is mixed with at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts. After injecting a polymerizable monomer mixture prepared by adding and mixing a hydrophilic compound and / or a plasticizer, for example, polymerizing by heating and / or irradiation with electromagnetic waves, the polymer has a unit represented by the above general formula (I). A polymer obtained from at least one compound selected from a compound and / or a compound having a structure represented by (II) and / or a copolymerization component comprising the compound By polymerizing in the same manner as the polymerization method in the case of obtaining a copolymer to be obtained, or by further sealing with an insulating resin such as a polyolefin resin or an epoxy resin as needed after the polymerization, the electrode and the electrolyte are A battery with good contact is obtained. When an electrode obtained by polymerizing the above-mentioned polymerizable monomer mixture is used, a battery in which the electrode and the electrolyte are in particularly good contact is obtained. When preparing such a polymerizable monomer mixture, the ratio of each component to be mixed is determined to be more appropriate for the intended battery. The battery structure or the support is preferably a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass, but is particularly limited to those made of these materials. However, the shape may be cylindrical, box, sheet, or any other shape.
[0060]
As described above, a monomer mixture containing at least one compound selected from a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II) is mixed with at least one electrolyte. Polymerizing the mixed solution obtained in the step (b) to obtain a polymer obtained from at least one compound selected from a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II). A method for producing a solid polymer electrolyte comprising a composite containing a copolymer and / or a copolymer containing the compound as a copolymer component and at least one electrolyte is particularly useful when producing a thin film battery.
[0061]
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 polymer solid electrolyte, 3 is a negative electrode, 4 is a stainless steel foil as a current collector, 5 is an insulating polyimide film as a spacer, and 6 is an insulating resin sealant. .
[0062]
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.
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.
[0063]
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.
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 graphite produced by a gas phase method; ₆₀ , C ₇₀ Can be mentioned.
[0064]
Next, an example of a method for manufacturing a solid electric double layer capacitor of the present invention will be described.
As described above, when at least one compound selected from a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II) is mixed with at least one electrolyte, In some cases, a polymerizable monomer mixture obtained by adding and mixing another polymerizable compound and / or a plasticizer is further polymerized to form a compound having a unit represented by the general formula (I) and / or (II). A polymer obtained from at least one compound selected from the compounds having the structures represented and / or a copolymer containing the compound as a copolymer component and at least one electrolyte can be obtained. It is particularly useful when manufacturing the solid electric double layer capacitor of the present invention.
[0065]
A polarizable material such as a carbon material and a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by the formula (II) preferably used in the solid electric double layer capacitor of the present invention. When producing a polarizable electrode containing a polymer obtained from at least one selected compound and / or a copolymer containing the compound as a copolymer component, first, for example, a unit represented by the general formula (I) is used. At least one compound selected from compounds having a structure represented by formula (II) and / or a compound having a structure represented by formula (II), if necessary, further mixed with a polymerizable compound and / or a plasticizer, and mixed with a polarizable material. . In that case, the ratio of each component to be mixed is determined to be more appropriate for the intended capacitor. After the polymerizable monomer / polarizable material mixture thus obtained is formed into a film on a support, for example, a current collector, the polymer is subjected to polymerization by, for example, heating and / or irradiation with electromagnetic waves. A polarizable electrode is produced by polymerizing in the same manner as in the case of obtaining. According to this method, a composite thin-film electrode that is in good contact with the current collector can be manufactured.
[0066]
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, both electrodes are attached to the end of the electrode via a spacer having an appropriate thickness, and the two electrodes are put into the above-mentioned structure. Next, between the two polarizable electrodes, the general formula (I) is used. At least one compound selected from a compound having a unit and / or a compound having a structure represented by (II) is mixed with at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts. After injecting a polymerizable monomer mixture prepared by adding and mixing other polymerizable compounds and / or plasticizers, and then polymerizing by the same method as described above, or further, after polymerization, if necessary, a polyolefin resin, By sealing with an insulating resin such as an 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.
[0067]
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.
[0068]
[Action]
As described above, the polymer solid electrolyte of the present invention is formed of a polymer having a high dielectric constant in which a carbonate group having a urethane bond that can be easily formed into a film from a polymerizable monomer mixture as a raw material thereof is compounded. It is an ion-conductive solid electrolyte, has good film strength, and is excellent in thin film workability.
[0069]
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.
[0070]
Further, the positive electrode of the present invention may be a polymer obtained from at least one compound selected from a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by (II), and / or Or an electrode containing an active material such as a copolymer containing the compound as a copolymer component and an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide or a carbon material; A battery characterized by using the polymer solid electrolyte as described above is easy to process such as thinning, there is no possibility of short circuit even in a thin film, a large take-out current, a high capacity, a highly reliable battery, Particularly, an all-solid-state battery can be used.
Furthermore, a polymer obtained from at least one compound selected from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by (II) of the present invention, and / or An electrode containing an electrode active material such as a copolymer having the compound as a copolymer component and an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide or a carbon material; The manufacturing method is to provide an electrode having flexibility as required without impairing the electrochemical activity of the electrode active material having excellent activity as an electrode, for example, a thin film electrode Can be provided, and the electrodes are useful as electrodes for various batteries.
[0071]
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.
[0072]
The electric double-layer capacitor of the present invention can be easily formed into a polymerizable monomer mixture, and can be formed into a comb-type polymer or a network-like polymer in which an oxyalkyl group having a urethane 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.
In particular, according to the electric double layer capacitor and the method of manufacturing the same of the present invention, good contact between the polarizable electrode and the solid polymer electrolyte, which is an ion-conductive substance, is not short-circuited 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.
[0073]
【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.
Example 1 <Synthesis of methacryloyloxyethylcarbamic acid propylene carbonate (MOECP)>
Carbon dioxide gas is added to 34.2 g of allyl glycidyl ether and triphenyl phosphorus as a catalyst at 10 to 15 kg / cm. ² Under high pressure at 100 ° C. for 14 hours, 42.3 g of allyloxypropylene carbonate was obtained. Subsequently, a platinum catalyst was added thereto, and the reaction was carried out at 40 ° C. for 5 hours to deallylate, thereby obtaining 25 g of propylene hydroxycarbonate.
[0074]
After dissolving 0.1 mol (= 11.8 g) of this propylene hydroxycarbonate and 0.1 mol (= 15.5 g) of 2-methacryloyloxyethyl isocyanate (MOI) in 100 ml of well-purified THF in a nitrogen atmosphere, 0.33 g Of dibutyltin dilaurate was added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain 27 g of MOECP as a colorless liquid.
The following analysis confirmed that the product was MOECP.

From the above results, it was found that the MOI and the propylene hydroxycarbonate reacted one-to-one, the isocyanate group of the MOI disappeared, and a urethane bond was formed.
[0075]
Example 2 <Preparation and evaluation of MOECP-based polymer solid electrolyte>
1.5 g of MOECP synthesized in Example 1 was dissolved in 10 cc of THF, and ₃ SO ₃ 0.15 g was added and mixed well. The THF was then removed under reduced pressure at room temperature and MOECP / 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 80 ° C. for 1 hour. ₃ SO ₃ The composite was obtained as a clear 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.
[0076]
Example 3
LiCF used in Example 2 ₃ SO ₃ Instead of LiBF ₄ A solid electrolyte was prepared in the same manner as in Example 2 except that 0.20 g was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 4 × 10 ^-5 S / cm.
The temperature change of the ionic conductivity of this solid electrolyte film was measured by the impedance method, and the result was as shown in FIG. The ordinate of FIG. 3 shows the ionic conductivity in logarithm, and the abscissa shows the Arrhenius plot showing the temperature in 1000 / absolute temperature. The slope is MOECP polymer / LiBF. ₄ It shows the activation energy of ion transfer in a solid electrolyte.
[0077]
Example 4 <Synthesis of 2-methacryloyloxyethylcarbamic acid 2-methacryloyloxyethylcarbamoyl oligooxyethyl / oxypropyl ester (MCMC (800))>
After dissolving 0.2 mol (= 31.0 g) of MOI and 0.1 mol (= 80 g) of an oligoethylene glycol / propylene glycol copolymer having an average molecular weight of 800 in 100 ml of well-purified THF in a nitrogen atmosphere, 0.66 g of dibutyltin was dissolved. Dilaurate was added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain MCMC (800) as a colorless gel-like solid. From the results of the H1-NMR, IR, and elemental analysis, it was found that the MOI and the oligoethylene glycol / propylene glycol copolymer reacted two-to-one, the isocyanate group of the MOI disappeared, and a urethane bond was formed. I understood.
[0078]
Example 5 <Preparation and evaluation of MOECP / MCMC (800) copolymer solid polymer electrolyte>
1.50 g of MOECP synthesized in Example 1 and 1.50 g of MCMC (800) synthesized in Example 4 were dissolved in 20 cc of THF, and LiCF was dissolved. ₃ SO ₃ 0.30 g was added and mixed well. Then, THF was removed under reduced pressure at room temperature, and MOECP / MCMC (800) / 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 80 ° C. for 1 hour to obtain MOECP / MCMC (800) copolymer / LiCF 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, 2 × 10 ^-4 S / cm.
The temperature change of the ionic conductivity of this solid electrolyte film was measured by the impedance method, and the result was as shown in FIG. The ordinate of FIG. 3 shows the ionic conductivity in logarithm, and the abscissa shows the Arrhenius plot showing the temperature in 1000 / absolute temperature, the slope of which is MOECP / MCMC (800) copolymer / LiCF. ₃ SO ₃ It shows the activation energy of ion transfer in a solid electrolyte.
[0079]
Example 6
LiCF used in Example 5 ₃ SO ₃ Instead of LiPF ₆ Was used in the same manner as in Example 5 except that 0.30 g of was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 3 × 10 ^-4 S / cm.
[0080]
Example 7
LiCF used in Example 5 ₃ SO ₃ Instead of NaCF ₃ SO ₃ Was prepared in the same manner as in Example 5 except that 0.26 g of was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 8 × 10 ^-5 S / cm.
[0081]
Example 8
LiCF used in Example 5 ₃ SO ₃ In place of the above, a solid electrolyte was produced in the same manner as in Example 5, except that 0.60 g of AgI was used. When the ionic conductivity of the solid electrolyte at 25 ° C. was measured by an impedance method, it was 5 × 10 ^-4 S / cm.
[0082]
Example 9
LiCF used in Example 5 ₃ SO ₃ Instead of using 0.43 g of tetraethylammonium tetrafluoroborate (TEAB), a solid electrolyte was produced in the same manner as in Example 5. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, 2 × 10 ^-4 S / cm.
[0083]
Example 10 <Synthesis of 2-methacryloyloxyethylcarbamic acid ω-methyl oligooxyethyl ester (MECME (550))>
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 well-purified THF in a nitrogen atmosphere. 66 g of dibutyltin dilaurate are added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain MECME (550) as a colorless viscous liquid. From the results of the H1-NMR, IR, and elemental analysis, it was found that the MOI and monomethyl oligoethylene glycol reacted one to one, the isocyanate group of the MOI disappeared, and a urethane bond was generated.
[0084]
Example 11 <Preparation and evaluation of MOECP / MECMC (550) copolymer solid polymer electrolyte>
1.50 g of MOECP synthesized in Example 1 and 1.50 g of MECMC (550) synthesized in Example 10 were dissolved in 20 cc of THF, and LiBF was dissolved. ₄ Was added and mixed well. The THF was then removed under reduced pressure at room temperature, and MOECP / MECMC (550) / 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 80 ° C. for 1 hour to obtain MOECP / MECMC (550) copolymer / LiBCF ₄ 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 ^-4 S / cm.
[0085]
Comparative Example 1 <Preparation and evaluation of MCMC (800) -based polymer solid electrolyte>
1.5 g of MCMC (800) synthesized in Example 4 was dissolved in 10 cc of THF, and LiCF was dissolved. ₃ SO ₃ 0.15 g was added and mixed well. The THF was then removed under reduced pressure at room temperature and MCMC (800) / LiCF ₃ SO ₃ The mixture was obtained as a viscous liquid. This mixture was applied to a glass plate under an argon atmosphere and heated at 80 ° C. for 1 hour to obtain MCMC (800) / LiCF ₃ SO ₃ The composite was obtained as a clear film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, it was 8 × 10 ^-6 S / cm.
[0086]
Example 12 <Synthesis of N-methacryloylcarbamic acid propylene carbonate (NMCP)>
After dissolving 0.1 mol (= 11.8 g) of propylene hydroxycarbonate and 0.1 mol (= 11.1 g) of N-methacryloyl isocyanate (MAI) synthesized in Example 1 in 100 ml of well-purified THF in a nitrogen atmosphere. , 0.33 g of dibutyltin dilaurate were added. Thereafter, the mixture was reacted at 50 ° C. for about 3 hours to obtain 22 g of NMCP as a colorless liquid.
The following analysis confirmed that the product was NMCP.

From the above results, it was found that MAI and propylene hydroxycarbonate reacted one-to-one, the isocyanate group of MAI disappeared, and a urethane bond was formed.
[0087]
Example 13 <Preparation and evaluation of NMCP-based polymer solid electrolyte>
1.5 g of NMCP synthesized in Example 12 was dissolved in 10 cc of THF, and LiBF was dissolved. ₄ The mixture was obtained as a viscous liquid. This mixture was coated on a glass plate under an argon atmosphere, and heated at 80 ° C. for 1 hour to obtain NMCP / LiBF ₄ The composite was obtained as a clear film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by an impedance method, 1 × 10 ^-5 S / cm.
[0088]
Example 14 <Preparation and evaluation of NMCP / MCMC (800) copolymer solid polymer electrolyte>
1.50 g of NMCP synthesized in Example 12 and 1.50 g of MCMC (800) synthesized in Example 4 were dissolved in 20 cc of THF, and LiBF was dissolved. ₄ 0.20 g was added and mixed well. The THF was then removed under reduced pressure at room temperature and NMCP / MCMC (800) / 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 80 ° C. for 1 hour to obtain NMCP / MCMC (800) copolymer / LiBF ₄ 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, 1 × 10 ^-4 S / cm.
[0089]
Example 15 <Preparation and evaluation of MOECP / MCMC (800) copolymer solid electrolyte with added plasticizer>
1.80 g of MOECP synthesized in Example 1, 1.80 g of MCMC (800) synthesized in Example 4, LiBF ₄ 0.63 g and propylene carbonate (PC) 3.6 g were mixed well in an argon atmosphere, and MOECP / MCMC (800) / PC / LiBF ₄ A polymerizable monomer solution as a mixture was obtained as a viscous liquid.
This polymerizable monomer solution was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour to obtain a MOECP / MCMC (800) copolymer / PC / LiBF ₄ 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, each was 3.5 × 10 5 ^-3 , 1.5 × 10 ^-3 S / cm.
[0090]
Example 16
MOECP / MCMC (800) copolymer / TG / LiBF was obtained in the same manner as in Example 15 except that tetraglyme (TG) was used instead of propylene carbonate used in Example 15. ₄ 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, 9 × 10 ^-4 S / cm.
[0091]
Example 17
MOECP / MCMC (800) copolymer / DEC / LiBF was obtained in the same manner as in Example 15 except that diethyl carbonate (DEC) was used instead of propylene carbonate used in Example 15. ₄ 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 1.5 × 10 ^-3 S / cm.
[0092]
Example 18
LiBF used in Example 15 ₄ LiPF instead of 0.63g ₆ MOECP / MCMC (800) copolymer / PC / LiPF was obtained in the same manner as in Example 15 except that 0.95 g was used. 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. was measured by an impedance method, it was 4 × 10 ^-3 S / cm.
[0093]
Comparative Example 2 <Preparation and evaluation of MCMC (800) -based polymer solid electrolyte with added plasticizer>
3.60 g of MCMC (800) synthesized in Example 4, LiBF ₄ 0.63 g and 3.6 g of propylene carbonate (PC) are mixed well in an argon atmosphere, and MCMC (800) / PC / LiBF is mixed. ₄ A polymerizable monomer solution as a mixture was obtained as a viscous liquid.
This polymerizable monomer solution was coated on a glass plate under an argon atmosphere and then heated at 100 ° C. for 1 hour to obtain MCMC (800) polymer / PC / LiBF ₄ 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 8.0 × 10 4 ^-4 , 3.2 × 10 ^-4 S / cm.
[0094]
Example 19 <Preparation of polymerizable monomer solution>
1.80 g of MOECP synthesized in Example 1, 1.80 g of MCMC (800) synthesized in Example 4, LiBF ₄ 0.63 g, 1.8 g of propylene carbonate (PC) and 1.8 g of ethylene carbonate (EC) are mixed well in an argon atmosphere, and MOECP / MCMC (800) / PC / EC / LiBF ₄ A polymerizable monomer solution as a mixture was obtained as a viscous liquid.
This polymerizable monomer solution was coated on a glass plate under an argon atmosphere, and heated at 100 ° C. for 1 hour to obtain a MOECP (550) / MCMC (800) copolymer / PC / EC / LiBF ₄ 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 4.0 × 10 4 each. ^-3 , 1.5 × 10 ^-3 S / cm.
[0095]
Example 20 <Production of cobalt oxide positive electrode>
Li ₂ CO ₃ 11g and Co ₃ O ₄ 24 g, mixed in an oxygen atmosphere, heated at 800 ° C. for 24 hours, 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 19 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 (70 mg) was obtained.
[0096]
Example 21 <Production of polymer solid electrolyte secondary battery>
In an argon atmosphere glove box, a 75 μm-thick lithium foil was cut into 1 × 1 cm (5.3 mg), and about 1 mm on each end thereof was covered with a 5 μm polyimide film as a spacer. Next, the polymerizable monomer solution prepared in Example 19 was applied on a lithium foil, and the cobalt oxide positive electrode produced in Example 20 was adhered thereto. After heating at 100 ° C. for 1 hour, the battery end 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 the battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.3 V and a current of 0.3 mA, the maximum discharge capacity was 4.0 mAh, and the cycle life until the capacity was reduced to 50% was 200 times. there were.
When the battery manufactured in the same manner was repeatedly charged and discharged at an operating voltage of 2.0 to 4.3 V and a current of 0.3 mA, the maximum discharge capacity was 3.8 mAh, and the cycle until the capacity was reduced to 50% was obtained. The life was 251 times.
[0097]
Example 22 <Production of vapor phase graphite negative electrode>
A mixture of 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.) and 2.5 ml of a hexane solution containing 2.5 M butyllithium was mixed for 8 hours at room temperature. Stirred. 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 19 were mixed in an argon atmosphere, and a portion 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 (25 mg).
[0098]
Example 23 <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 21 except that the vapor phase graphite negative electrode produced in Example 22 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 0.3 mA, the maximum discharge capacity was 4.0 mAh, and the cycle life until the capacity was reduced to 50% was 323 times. there were.
[0099]
Example 24 <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, this 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 a polyaniline powder in a undoped state.
[0100]
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.
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.
[0101]
Example 25 <Production of polyaniline positive electrode>
The polymerizable monomer solution prepared in Example 19 was mixed with the 5 wt% polyaniline / NMP solution prepared in Example 24 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 on a stainless steel foil so as to have a size of 10 × 10 mm and a thickness of 200 μm. Next, by heating at 60 ° C., 80 ° C., and 100 ° C. for 1 hour each, drying and polymerization were performed to obtain a polyaniline / polymer solid electrolyte composite positive electrode (20 mg).
[0102]
Example 26 <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 its ends were covered by a 10-μm-thick polyimide film as spacers on about 2 mm squares. Next, the polymerizable monomer solution prepared in Example 19 was applied on a lithium foil, and the polyaniline / polymer solid electrolyte composite positive electrode produced in Example 25 was laminated and heated at 100 ° C. for 1 hour. Was sealed with an epoxy resin to obtain a lithium / polyaniline solid secondary battery having the same configuration as that of FIG.
When the battery was repeatedly charged and discharged at an operating voltage of 2 to 4 V and a current of 0.3 mA, the maximum discharge capacity was 1.2 mAh, and the cycle life until the capacity was reduced to 50% was 380 times.
[0103]
Example 27 <Preparation of polymerizable monomer solution>
1.80 g of MOECP synthesized in Example 1, 1.80 g of MCMC (800) synthesized in Example 4, 1.35 g of tetraethylammonium tetrafluoroborate (TEAB), and 3.6 g of propylene carbonate (PC) were sufficiently placed in an argon atmosphere. After mixing, a polymerizable monomer solution as a MOECP / MCMC (800) / PC / TEAB mixture was obtained as a viscous liquid.
This polymerizable monomer solution was coated on a glass plate under an argon atmosphere and then heated at 100 ° C. for 1 hour. The MOECP (550) / MCMC (800) copolymer / PC / TEAB composite was about 50 μm transparent. Obtained as a free standing film. When the ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method, it was 3.8 × 10 ^-3 , 1.2 × 10 ^-3 S / cm.
[0104]
Example 28 <Production of activated carbon electrode>
The coconut palm activated carbon and the polymerizable monomer solution prepared in Example 27 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, by heating at about 100 ° C. for 1 hour to carry out polymerization, an activated carbon / polymer solid electrolyte composite electrode (15 mg) was obtained.
[0105]
Example 29 <Production of solid electric double layer capacitor>
In an argon atmosphere glove box, the activated carbon electrode (15 mg) manufactured in Example 28, about 1 mm × 1 cm and about 1 mm square was coated with a 10 μm-thick polyimide film as a spacer. Next, the polymerizable monomer solution prepared in Example 27 was applied on the electrodes, and another electrode was bonded thereto, heated at 100 ° C. for 1 hour, and sealed at the capacitor end with epoxy resin. A solid electric double layer capacitor as shown in FIG.
When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.3 mA, the maximum capacity was 230 mF. Also, even if charging and discharging were repeated 50 times under these conditions, there was almost no change in the capacity.
[0106]
Example 30 <Production of solid electric double layer capacitor>
Instead of the salt TEAB used for the polymerizable monomer solution prepared in Example 27, LiBF ₄ A polymerizable monomer solution was prepared using 0.63 g. A solid electric double layer capacitor was manufactured in the same manner as in Example 29 except that this polymerizable monomer solution was used.
When this capacitor was charged and discharged at an operating voltage of 0 to 2.0 V and a current of 0.3 mA, the maximum capacity was 173 mF. Also, even if charging and discharging were repeated 50 times under these conditions, there was almost no change in the capacity.
[0107]
Example 31 <Production of acetylene black electrode>
Acetylene black and the polymerizable monomer solution prepared in Example 27 were mixed in an argon atmosphere at a weight ratio of 6: 4, 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 and polymerized at about 100 ° C. for 1 hour to obtain an acetylene black / polymer solid electrolyte composite electrode (15 mg).
[0108]
Example 32 <Production of solid electric double layer capacitor>
A solid electric double layer capacitor was manufactured in the same manner as in Example 29 except that the acetylene black electrode (15 mg) manufactured in Example 31 was used.
When the capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.3 mA, the maximum capacity was 55 mF. Also, even if charging and discharging were repeated 50 times under these conditions, there was almost no change in the capacity.
[0109]
【The invention's effect】
The solid polymer electrolyte of the present invention is composed of a complex of a polymer having a carbonate group in a side chain bonded by a urethane bond and at least one electrolyte, and is easily obtained as a thin film having good film strength, And 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.
[0110]
The electrode active material of the present invention, such as a polymer having a carbonate group bonded to the side chain by a urethane bond and an organic solvent-soluble polyaniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. Or an electrode containing a polarizable material and its manufacturing method can provide an electrode having high electrochemical activity and flexibility, particularly can provide a thin electrode, electrodes used in various batteries or electric double layer capacitors and the like and Useful as a manufacturing method.
[0111]
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.
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.
FIG. 3 is a graph showing the change in ionic conductivity of a MOECP-based and MOECP / MCMC (800) copolymer-based solid polymer electrolyte film with temperature.
[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 (I)

[Wherein, R ¹ represents hydrogen or a methyl group, and R ² represents an organic 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 and x, y, z in a plurality of units represented by the above general formula (I) in the same molecule are independent of each other 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 (1) and / or a copolymer containing the compound as a copolymer component, and a composite containing at least one electrolyte. General formula (II)

[In the formula, R ¹ represents hydrogen or a methyl group, and R ² and R ³ represent an organic 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. ] A polymer solid electrolyte comprising a polymer obtained from at least one of the compounds having the structure represented by formula (I) and / or a copolymer containing the compound as a copolymer component, and a composite containing at least one electrolyte. 3. The polymer solid electrolyte according to claim 1, wherein at least one of the electrolytes is an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt. 4. The polymer solid electrolyte according to claim 1, wherein a plasticizer is added. A battery comprising the polymer solid electrolyte according to claim 1. The battery according to claim 5, further comprising a negative electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions. The battery according to claim 5, further comprising a positive electrode containing an aniline-based polymer or another conductive polymer soluble in an organic solvent, a metal oxide, a metal sulfide, or a carbon material. General formula (I)

[Wherein, R ¹ represents hydrogen or a methyl group, and R ² represents an organic 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 and x, y, z in a plurality of units represented by the above general formula (I) in the same molecule are independent of each other and need not be the same. 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 a step of disposing the polymerizable monomer mixture on a body and polymerizing the polymerizable monomer mixture. General formula (II)

[In the formula, R ¹ represents hydrogen or a methyl group, and R ² and R ³ represent an organic 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. A polymerizable monomer mixture containing at least one compound having a structure represented by the formula 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 a step of disposing the polymerizable monomer mixture on a body and polymerizing the polymerizable monomer mixture. General formula (I)

[Wherein, R ¹ represents hydrogen or a methyl group, and R ² represents an organic 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 and x, y, z in a plurality of units represented by the above general formula (I) in the same molecule are independent of each other and need not be the same. 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. General formula (II)

[In the formula, R ¹ represents hydrogen or a methyl group, and R ² and R ³ represent an organic 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. An electrode comprising: a polymer obtained from at least one compound having a structure represented by the formula: and / or a copolymer containing the compound as a copolymer component; and an electrode active material or a polarizable material. 12. The electrode according to claim 10, wherein the electrode active material or the polarizable material is an organic solvent-soluble aniline-based polymer or another conductive polymer, a metal oxide, a metal sulfide, or a carbon material. An electric double layer capacitor having a polarizable electrode 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. General formula (I)

[Wherein, R ¹ represents hydrogen or a methyl group, and R ² represents an organic 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 and x, y, z in a plurality of units represented by the above general formula (I) in the same molecule are independent of each other and need not be the same. 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 to which a plasticizer is added, is placed in the structure for forming an electric double layer capacitor. Or a method for producing an electric double layer capacitor, comprising a step of disposing the polymerizable monomer mixture on a support. General formula (II)

[In the formula, R ¹ represents hydrogen or a methyl group, and R ² and R ³ represent an organic 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. A polymerizable monomer mixture containing at least one compound having a structure represented by the formula and at least one electrolyte, or a polymerizable monomer mixture obtained by adding a plasticizer to the mixture, is placed in the structure for forming an electric double layer capacitor. Or a method of disposing the polymerizable monomer mixture on a support and polymerizing the polymerizable monomer mixture. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, wherein the polarizable electrode has a general formula (I)

[Wherein, R ¹ represents hydrogen or a methyl group, and R ² represents an organic 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 and x, y, z in a plurality of units represented by the above general formula (I) in the same molecule are independent of each other and need not be the same. ] An electric double-layer capacitor comprising a polymer obtained from at least one compound having a unit represented by formula (1) and / or a composite containing a copolymer containing the compound as a copolymer component and a carbon material. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, wherein the polarizable electrode has a general formula (II)

[In the formula, R ¹ represents hydrogen or a methyl group, and R ² and R ³ represent an organic 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. ] An electric double-layer capacitor comprising a polymer obtained from at least one compound having a structure represented by the formula:

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