JP3748995B2 - Polymer solid electrolyte and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer solid electrolyte which is satisfactory in strength, even when it is formed into a thin film, high in ion conductivity at room temperature and at low temperatures, and superior in workability, heat resistance, and large-current characteristics, and a battery, an electric double- layer capacitor, using the same, and their manufacturing methods. SOLUTION: In this electrolyte, at least one kind of magnesium-containing oxide fine particles with a BET specific surface area 30 m<2> /g or more, the largest grain size <=10 &mu;m, the water content <=3000 ppm is added in the range of 0.5 wt.% to 50 wt.% to a polymer solid electrolyte, including at least one kind of polymer compound and at least one kind of electrolytic salt, or to a high polymer solid electrolyte further including at least one kind of organic solvent.

Description

（式中、Ｒ¹及びＲ²は水素原子またはアルキル基を表わし、Ｒ³は炭素数１〜１０の直鎖状、分岐状、環状構造のヘテロ原子を含んでいてもよい２価の基を表わし、ｘは０または１〜１０の整数である。但し、同一分子に複数存在するＲ¹、Ｒ²、Ｒ³及びｘは、それぞれ同一でもよいし、異なってもよい。）で示される重合性官能基を有する少なくとも一種の熱及び／または活性光線重合性化合物の重合体である前記１に記載の高分子固体電解質。
３）電解質塩が、アルカリ金属塩、４級アンモニウム塩、４級ピリジニウム塩、４級ホスホニウム塩から選ばれる前記１または２に記載の高分子固体電解質。
４）有機溶媒がカーボネート系化合物である前記１〜３のいずれかに記載の高分子固体電解質。
５）電解質塩が、ＬｉＰＦ₆及び／またはＬｉＢＦ₄及び／またはＬｉＮ（ＣＦ₃ＳＯ₃）₂である前記３に記載の高分子固体電解質。
６）前記１〜５のいずれかに記載の高分子固体電解質を用いることを特徴とする電池。
７）電池の負極として、リチウム、リチウム合金またはリチウムイオンを吸蔵放出できる炭素材料、リチウムイオンを吸蔵放出できる無機酸化物、リチウムイオンを吸蔵放出できる無機カルコゲナイド、リチウムイオンを吸蔵放出できる電導性高分子化合物から選ばれる少なくとも一つの材料を用いることを特徴とする前記６に記載のリチウム電池。
８）イオン伝導性物質を介して分極性電極を配置した電気二重層コンデンサにおいて、イオン伝導性物質が、前記１〜５のいずれかに記載の高分子固体電解質であることを特徴とする電気二重層コンデンサ。
９）一般式（１）及び／または一般式（２）で示される重合性官能基を有する少なくとも一種の熱及び／または活性光線重合性化合物と、ＢＥＴ比表面積が３０ｍ²／ｇ以上で、最大粒径が１０μｍ以下、含水量が3000ｐｐｍ以下であるマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子と、少なくとも一種の電解質塩とを含む重合性混合物、またはこれに少なくとも一種の有機溶媒が添加された重合性混合物を基材上に配置後、前記重合性混合物を加熱及び／または活性光線照射により硬化させることを特徴とする高分子固体電解質の製造方法。
１０）一般式（１）及び／または一般式（２）で示される重合性官能基を有する少なくとも一種の熱及び／または活性光線重合性化合物と、ＢＥＴ比表面積が３０ｍ²／ｇ以上で、最大粒径が１０μｍ以下、含水量が3000ｐｐｍ以下であるマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子と、少なくとも一種の有機溶媒とを含む重合性混合物を基材上に配置後、前記重合性混合物を加熱及び／または活性光線照射により硬化させ、得られた硬化物を電解液と接触させることにより電解質塩を含浸させることを特徴とする高分子固体電解質の製造方法。
１１）一般式（１）及び／または一般式（２）で示される重合性官能基を有する少なくとも一種の熱及び／または活性光線重合性化合物と、ＢＥＴ比表面積が３０ｍ²／ｇ以上で、最大粒径が１０μｍ以下、含水量が3000ｐｐｍ以下であるマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子と、少なくとも一種の電解質塩とを含む重合性混合物、またはこれに少なくとも一種の有機溶媒が添加された重合性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た後、前記重合性混合物を硬化することを特徴とする電池の製造方法。
１２）一般式（１）及び／または一般式（２）で示される重合性官能基を有する少なくとも一種の熱及び／または活性光線重合性化合物と、ＢＥＴ比表面積が３０ｍ²／ｇ以上で、最大粒径が１０μｍ以下、含水量が3000ｐｐｍ以下であるマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子と、少なくとも一種の有機溶媒とを含む重合性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た後、前記重合性混合物を硬化させ、得られた硬化物を電解液と接触させることにより電解質塩を含浸させることを特徴とする電池の製造方法。
１３）一般式（１）及び／または一般式（２）で示される重合性官能基を有する少なくとも一種の熱及び／または活性光線重合性化合物と、ＢＥＴ比表面積が３０ｍ²／ｇ以上で、最大粒径が１０μｍ以下、含水量が3000ｐｐｍ以下であるマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子と、少なくとも一種の電解質塩とを含む重合性混合物、またはこれに少なくとも一種の有機溶媒が添加された重合性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た後、前記重合性混合物を硬化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。
１４）一般式（１）及び／または一般式（２）で示される重合性官能基を有する少なくとも一種の熱及び／または活性光線重合性化合物と、ＢＥＴ比表面積が３０ｍ²／ｇ以上で、最大粒径が１０μｍ以下、含水量が3000ｐｐｍ以下であるマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子と、少なくとも一種の有機溶媒とを含む重合性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た後、前記重合性混合物を硬化させ、得られた硬化物を電解液と接触させることにより電解質塩を含浸させることを特徴とする電気二重層コンデンサの製造方法。
【００１９】
【発明の実施の態様】
以下に本発明を詳細に説明する。
［高分子固体電解質］本発明の高分子固体電解質は、基本的には主要構成成分である(a)高分子化合物、(b)電解質塩、及び(c)マグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子を含んでなり、さらに(d)有機溶媒を含んでもよい。以下、各成分について詳述する。
【００２０】
(a)高分子化合物
本発明の高分子固体電解質の主要構成成分である高分子化合物は非電子伝導性で各種有機極性溶媒を吸液、保持できるものでなければならない。
そのような高分子化合物としては、ポリアルキレンオキシド、ポリアルキルイミン、ポリアクリロニトリル、ポリカーボネート、ポリ（メタ）アクリル酸エステル、ポリフォスファゼン、ポリフッ化ビニリデン、ポリウレタン、ポリアミド、ポリエステル、ポリシロキサン等のヘテロ原子を有する極性の熱可塑性高分子化合物や架橋高分子化合物が挙げられる。特に架橋高分子化合物が、溶媒吸液後の強度が高く、溶媒保持力も高く、さらに粘弾性体であることから、本発明の高分子固体電解質には適している。ここでいう架橋とは、架橋鎖が共有結合で形成されているもの以外に、側鎖がイオン結合や水素結合等で架橋されているもの、各種添加物を介して物理架橋されたものをも含む。
【００２１】
上記高分子化合物の中ではポリアルキレンオキシド、ポリウレタン、ポリカーボネート等のオキシアルキレン、ウレタン、カーボネート構造を分子構造内に含むものが、各種極性溶媒との相溶性が良好で、しかも電気化学的安定性も良好であるので好ましい。安定性の面からポリフッ化ビニリデン等のフルオロカーボン基を分子構造内に有するものも好ましい。また、オキシアルキレン、ウレタン、カーボネート、フルオロカーボン基が同一高分子化合物中に含まれていても良い。これらの基の繰り返し数は各々１〜1000の範囲であればよく、５〜１００の範囲が好ましい。
【００２２】
本発明の高分子固体電解質に用いられる高分子化合物としては、上記高分子化合物の中で一般式（１）及び／または（２）で示される重合性官能基
【００２３】
【化９】

（式中、Ｒ¹及びＲ²は水素原子またはアルキル基を表わし、Ｒ³は炭素数１〜１ ０の直鎖状、分岐状、環状構造のヘテロ原子を含んでいてもよい２価の基を表わし、ｘは０または１〜１０の整数である。但し、同一分子に複数存在するＲ¹、 Ｒ²、Ｒ³及びｘは、それぞれ同一でもよいし、異なってもよい。）
を有する少なくとも一種の熱及び／または活性光線重合性化合物を加熱及び／または活性光線照射により硬化させて得られる高分子化合物が、溶媒や無機酸化物微粒子を含んだ状態で高分子固体電解質を成膜しやすく、膜強度が良好であり、また、各種電気化学素子に用いられる電極との複合が容易で有り好ましい。
【００２４】
一般式（１）で示される基を有する重合性化合物を合成する方法に特に限定はないが、例えば、酸クロライドと末端にヒドロキシル基を有するオリゴオキシアルキレンオールとを以下の工程で反応させることにより容易に得られる。
【化１０】

式中、Ｒ⁴は水素原子または炭素数１０以下のアルキル基を表わし、Ｒ⁵は炭素数１０以下のアルキル基を表わし、ｍは１〜1000、好ましくは１〜５０の範囲の整数である。その他の記号は前記と同じ意味を表わす。
【００２５】
一般式（２）で示される基を有する重合性化合物を合成する方法に特に限定はないが、例えば、
【化１１】

（式中の記号は前記と同じ意味を表わす。）
で表わされるイソシアネート化合物と末端にヒドロキシル基を有するオリゴオキシアルキレンオールとを反応させることにより容易に得ることができる。
【００２６】
具体的方法として、一般式（２）で示される官能基を一つ有する化合物は、例えば、メタクリロイルイソシアナート系化合物（以下、ＭＩ類と略記する。）あるいはアクリロイルイソシアナート系化合物（以下、ＡＩ類と略記する。）とモノアルキルアルキレングリコールとを、以下の反応式により１：１のモル比で反応させることにより、容易に得られる。
【化１２】

（式中の記号は前記と同じ意味を表わす。）
【００２７】
また、一般式（２）で示される官能基を二つ有する化合物は、例えば、ＭＩ類あるいはＡＩ類とオリゴアルキレングリコールとを、２：１のモル比で反応させることにより、容易に得られる。
また、一般式（２）で示される官能基を三つ有する化合物は、例えばＭＩ類及び／またはＡＩ類と、グリセリン等の３価アルコールにオリゴアルキレングリコールを付加重合させたトリオールとを、３：１のモル比で反応させることにより、容易に得られる。
【００２８】
また、一般式（２）で示される官能基を四つ有する化合物は、例えばＭＩ類及び／またはＡＩ類と、ペンタエリスリトール等の４価アルコールにオリゴアルキレングリコールを付加重合させたテトラオールとを４：１のモル比で反応させることにより、容易に得られる。
また、一般式（２）で示される官能基を五つ有する化合物は、例えばＭＩ類及び／またはＡＩ類と、α−Ｄ−グルコピラノースにオリゴアルキレングリコールを付加重合させたペンタオールとを、５：１のモル比で反応させることにより、容易に得られる。
また、一般式（２）で示される官能基を六つ有する化合物は、例えばＭＩ類及び／またはＡＩ類と、マンニットにオリゴアルキレングリコールを付加重合させたヘキサオールとを６：１のモル比で反応させることにより、容易に得られる。
【００２９】
ここで一般式（１）あるいは（２）で示される官能基を１つしか有さない化合物を重合して得られる高分子化合物は、架橋構造を有しておらず、膜強度不足のため、薄膜にすると短絡する危険が大きい。従って、一般式（１）あるいは（２）で示される官能基を２つ以上有する重合性化合物と共重合し、架橋させるか、一般式（１）あるいは（２）で示される官能基を２つ以上有する重合性化合物から得られる高分子化合物と併用する方が好ましい。
これら高分子化合物を薄膜として使用する場合、その強度から考慮して、１分子中に含まれる一般式（１）あるいは（２）で示される官能基の数は、３つ以上がより好ましい。
【００３０】
また前記一般式（２）で示される重合性官能基を有する化合物を重合して得られる高分子化合物は、ウレタン基を含んでおり、誘電率が高くなり、高分子固体電解質とした場合のイオン伝導度が高くなるため好ましい。さらに一般式（２）で示される重合性官能基を有する化合物は重合性が良好で、薄膜にしたときの膜強度も大きく電解液の包含量が多くなり好ましい。
【００３１】
本発明の高分子固体電解質の構成成分として好ましい高分子化合物は、一般式（１）及び／または一般式（２）で示される官能基を有する化合物の単独重合体であっても、該カテゴリーに属する２種以上の共重合体であっても、あるいは該化合物の少なくとも一種と他の重合性化合物との共重合体であってもよい。
【００３２】
前記一般式（１）及び／または一般式（２）で示される官能基を有する化合物と共重合可能な他の重合性化合物としては、特に制限はないが、例えば、アクリルアミド、メタクリルアミド、Ｎ，Ｎ−ジメチルメタクリルアミド、炭酸ビニレン、Ｎ−ビニルピロリドン、アクリロイルモルホリン、メタクリロイルモルホリン、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド等の（メタ）アクリルアミド系化合物、スチレン、α−メチルスチレン等のスチレン系化合物、Ｎ−ビニルアセトアミド、Ｎ−ビニルホルムアミド等のＮ−ビニルアミド系化合物、エチルビニルエーテル等のアルキルビニルエーテルを挙げることができる。
【００３３】
本発明の高分子固体電解質に用いる好ましい高分子化合物は、前記一般式（１）及び／または一般式（２）で示される官能基を有する化合物の少なくとも一種から得られる重合体及び／または該化合物を共重合成分とする共重合体と、他の高分子化合物との混合物であってもよい。混合する他の高分子化合物としては、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリアクリロニトリル、ポリブタジエン、ポリメタクリル（またはアクリル）酸エステル類、ポリスチレン、ポリホスファゼン類、ポリシロキサンあるいはポリシラン、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等のポリマーが挙げられる。
【００３４】
共重合体または混合物としたとき前記一般式（１）及び／または一般式（２）で示される官能基を有する化合物由来の構造単位の量は、その他の共重合成分あるいは重合体混合物成分の種類によって異なるが、高分子固体電解質に用いたときのイオン伝導度および膜強度、耐熱性、電流特性を考慮すると、この共重合体または重合体混合物全量に対し４０重量％以上含有することが好ましく、さらには６０重量％以上含有することが好ましい。
【００３５】
一般式（１）及び／または一般式（２）で示される官能基を有する化合物の重合は、官能基である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により行なうことができる。すなわち、これら化合物単独、あるいはこれら化合物と他の前記共重合可能な重合性化合物の混合物に、アゾビスイソブチロニトリル、ベンゾイルパーオキサイド等のラジカル重合触媒、ＣＦ₃Ｃ ＯＯＨ等のプロトン酸、ＢＦ₃、ＡｌＣｌ₃等のルイス酸等のカチオン重合触媒、あるいはブチルリチウム、ナトリウムナフタレン、リチウムアルコキシド等のアニオン重合触媒を用いて、ラジカル重合、カチオン重合あるいはアニオン重合させることができる。また、重合性化合物によっては無酸素状態で加熱のみでラジカル重合することも可能である。また、重合性化合物あるいは重合性混合物は膜状等の形に成形後、重合させることも可能である。
【００３６】
(b)電解質塩
本発明で用いる電解質塩の種類は特に限定されるものではなく、電荷でキャリアーとしたいイオンを含んだ電解質塩を用いればよいが、高分子固体電解質中での解離定数が大きいことが望ましく、ＬｉＣＦ₃ＳＯ₃、ＬｉＮ(ＣＦ₃ＳＯ₂)₂、 ＬｉＰＦ₆、ＬｉＣｌＯ₄、ＬｉＩ、ＬｉＢＦ₄、ＬｉＳＣＮ、ＬｉＡｓＦ₆、ＮａＣＦ₃ＳＯ₃、ＮａＰＦ₆、ＮａＣｌＯ₄、ＮａＩ、ＮａＢＦ₄、ＮａＡｓＦ₆、ＫＣＦ₃ＳＯ₃、ＫＰＦ₆、ＫＩ等のアルカリ金属塩、(ＣＨ₃)₄ＮＢＦ₄等の４級アンモニウム塩、(ＣＨ₃)₄ＰＢＦ₄等の４級ホスホニウム塩、ＡｇＣｌＯ₄等の遷移金属塩あるいは塩酸、過塩素酸、ホウフッ化水素酸等のプロトン酸が好ましい。
本発明の高分子固体電解質中の電解質塩は複合して用いることができ、その複合比は、高分子化合物の重量に対し、0.1〜５０重量％が好ましく、１〜３０重 量％が特に好ましい。複合に用いる電解質塩が５０重量％以上の比率で存在すると、イオンの移動が大きく阻害され、逆に0.1重量％以下の比率では、イオンの 絶対量が不足となってイオン伝導度が小さくなる。
【００３７】
(c)マグネシウムと他の金属との複合酸化物（ハイドロタルサイト）
本発明の高分子固体電解質はマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子が添加されることに特徴がある。この添加により、高分子固体電解質フィルムの強度、膜厚均一性が改善されるばかりでなく、酸化物微粒子と高分子間に微細な空孔が生じることになり、電解液中に浸漬した場合には空孔を通じて高分子固体電解質内にフリーの電解液が分散し、強度の改善効果を損ねることなく、逆にイオン伝導度、移動度を増加させることもできる。また、マグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子を添加することにより、重合性組成物の粘度が上昇し、高分子化合物と溶媒の相溶性が不十分な場合にもその分離を抑える効果も現われる。
【００３８】
また添加するマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子としては、高比表面積で吸着水が低減された表面活性の高いものを使用するので、非水系の電池やコンデンサ系内の不純物（水分、遊離酸、遊離塩基等）を非常によく吸着することができ、封止材料や他の電池材料の劣化を低減することに大きな効果を発揮でき、結果として素子の寿命を改善できる。
【００３９】
高分子固体電解質中の電解液の保有量を多くし、イオン伝導性、移動度を増加させるという目的では、無機酸化物の比表面積はできるだけ大きいことが好ましく、ＢＥＴ法で１０ｍ²／ｇ以上、さらには３０ｍ²／ｇ以上が好ましい。
このような無機酸化物の結晶粒子径としては、重合性組成物と混合できれば特に限定はないが、大きさとしては0.001μｍ〜１０μｍが好ましく、0.005μｍ〜５μｍが特に好ましい。
また、形状としては球形、卵形、立方体状、直方体状、円筒ないし棒状等の種々の形状のものを用いることができる。
【００４０】
本発明で使用するマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）の具体例としては、キョーワード（協和化学製）等が挙げられる。これらの中でも、マグネシウムとアルミニウムの複合酸化物であるハイドロタルサイト（キョーワード（ＫＷ）2000、2200等）が安定性、不純物吸着能の点で優れており、好ましい。無機酸化物の添加量は多すぎると高分子固体電解質の強度やイオン伝導性を低下させたり、成膜がしにくくなるという問題を生じる。従って好ましい添加量は、高分子固体電解質に対して５０重量％以下であり、0.1から３０重量％の範囲が特に好ましい。
【００４１】
本発明のマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子は高分子固体電解質に添加する前に熱処理することが好ましい。熱処理により、酸化物微粒子の表面吸着水を低減し、他材料に拡散する遊離水分を抑えるばかりでなく、逆に他材料の不純物を吸着することができ、素子内の安定性が向上する。熱処理の温度、時間は用いるマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子の形状や種類によって異なるが、１００〜1200℃の範囲で２時間〜３００時間行なえば良く、２００〜８００℃の範囲が特に好ましい。
【００４２】
熱処理温度はできるだけ高い方が好ましいが、1200℃を越えるとマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子の焼結が進み、また表面の活性も低下するので好ましくない。熱処理時の雰囲気は減圧、空気中、不活性雰囲気中と特に限定されないが、熱処理後は水分等の再吸着を防止するため、露点−３０℃以下の雰囲気で取り扱うことが必要で、露点−５０℃以下が特に好ましい。このようにして熱処理したマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子の含水量はカールフィッシャー法で定量した場合、3000ｐｐｍ以下の値になることが必要である。
【００４３】
(d)有機溶媒
本発明の高分子固体電解質中に有機溶媒を添加すると、高分子固体電解質のイオン伝導度がさらに向上するので好ましい。使用できる溶媒としては、本発明の高分子固体電解質に用いる高分子化合物との相溶性が良好で、誘電率が大きく、沸点が６０℃以上であり、電気化学的安定範囲が広い化合物が適している。
そのような溶媒としては、１，２−ジメトキシエタン、２−メチルテトラヒドロフラン、クラウンエーテル、トリエチレングリコールメチルエーテル、テトラエチレングリコールジメチルエーテル等のエーテル類、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート等のカーボネート類、ベンゾニトリル、トルニトリル等の芳香族ニトリル類、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン、Ｎ−ビニルピロリドン、スルホラン等の硫黄化合物、リン酸エステル類等が挙げられる。これらの中で、エーテル類及びカーボネート類が好ましく、特にカーボネート類が好ましい。
有機溶媒の添加量は、多いほど高分子固体電解質のイオン伝導度が向上する。このため、一般的にはその添加量を増やすことが望ましいが、反面、添加量が多過ぎると高分子固体電解質の機械的強度が低下する。好ましい添加量としては、本発明の高分子固体電解質に用いる高分子重量の２倍から１５倍量で、３倍から１０倍量以下が特に好ましい。
【００４４】
［高分子固体電解質の製造方法］
本発明の高分子固体電解質は、一般式（１）及び／または一般式（２）で示される官能基を有する化合物とその他の成分とからなる重合性混合物を調製し、例えばフィルム状に形成した後、重合することにより製造することができる。具体的には、前記一般式（１）及び／または一般式（２）で示される官能基を有する化合物の少なくとも一種と、マグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子と、アルカリ金属塩、４級アンモニウム塩、４級ホスホニウム塩または遷移金属塩のごとき少なくとも一種の電解質塩とを混合し、所望により他の重合性化合物、可塑剤及び／または有機溶媒を添加混合し重合性組成物を調製した後、フィルム状等に成形して、前記触媒の存在下あるいは非存在下に、加熱及び／または活性光線の照射により重合させ、本発明の高分子固体電解質を得る。この方法によれば、加工面での自由度が広がり、応用上の大きなメリットとなる。また、電解質塩は重合性混合物を重合させた後に移行させることも可能である。すなわち、電解質塩を除いた上記重合性組成物を調製して重合させた後、得られた重合物（硬化物）を電解液と接触させることにより電解質塩を含浸させる方法によっても製造可能である。なお、電解液と接触させる方法としては、直接電解液に浸漬する以外にも、電解液を含浸させた電極などと接触させる方法をとることもできる。
【００４５】
重合時に溶媒を用いる場合には、重合性化合物の種類や重合触媒の有無にもよるが、重合を阻害しな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（ＴＨＦ）、アセトニトリル、トルエン等を用いることができる。
重合させる温度としては、前記一般式（１）及び／または一般式（２）で示される官能基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℃の範囲で行なえばよい。
活性光線照射により重合させる場合には、前記一般式（１）及び／または一般式（２）で示される官能基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、電子線等を照射して重合させることができる。
【００４６】
また、本発明の高分子固体電解質を薄膜フィルムとして使用する場合、フィルム強度を向上させるために、他の多孔性フィルムとの複合フィルムとすることもできる。ただし、複合するフィルムの種類あるいは量によっては伝導度の低下や安定性の悪化を招くので、適したものを選ぶ必要がある。使用するフィルムとしては、ポリプロピレン製不織布やポリエチレン製ネットのような網状ポリオレフィンシート等の多孔性ポリオレフィンシート、セルガード（商品名）等のポリオレフィン製マイクロポーラスフィルム、ナイロン不織布等が挙げられ、中でも多孔性ポリオレフィンフィルムが好ましい。また、その空孔率としては、１０〜９５％程度あればよいが、強度の許す限りできるだけ空孔率の大きいものが良く、好ましい空孔率は４０〜９５％の範囲である。
複合方法には特に制限はないが、例えば、一般式（１）及び／または一般式（２）で表わされる官能基を有する化合物の少なくとも一種と高比表面積で低含水量の特定のマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子の混合物に少なくとも一種の電解質塩、場合によっては、さらに他の重合性化合物及び／または可塑剤及び／または溶媒を添加混合した重合性組成物を多孔性ポリマーフィルムに含浸後、（メタ）アクリロイル系化合物を重合する方法に付すことにより、均一に複合でき、膜厚の制御も簡便である。
【００４７】
［電池及びその製造方法］
本発明の電池として、薄膜二次電池の一例の概略断面図を図１に示す。図中、１は正極、２は高分子固体電解質、３は負極、４は集電体、５は絶縁性樹脂封止剤である。
本発明の非水電池の構成において、正極１に金属酸化物、金属硫化物、導電性高分子あるいは炭素材料のような高酸化還元電位の電極活物質（正極活物質）を用いることにより、高電圧、高容量の電池が得られるので好ましい。このような電極活物質の中では、充填密度が高く体積容量密度が高くなるという点で、酸化コバルト、酸化マンガン、酸化バナジウム、酸化ニッケル、酸化モリブデン等の金属酸化物、硫化モリブデン、硫化チタン、硫化バナジウム等の金属硫化物が好ましく、特に酸化マンガン、酸化ニッケル、酸化コバルト等が高容量、高電圧という点から好ましい。
【００４８】
この場合の金属酸化物や金属硫化物を製造する方法は特に限定されず、例えば、電気化学，第２２巻，５７４頁（1954年）に記載されているような、一般的な電解法や加熱法によって製造される。また、これらを電極活物質としてリチウム電池に使用する場合、電池の製造時に、例えば、Ｌｉ_xＣｏＯ₂やＬｉ_xＭｎＯ₂等の形でリチウム元素を金属酸化物あるいは金属硫化物に挿入（複合）した状態で用いることが好ましい。リチウム元素を挿入する方法は特に限定されず、例えば、電気化学的にリチウムイオンを挿入する方法や、米国特許第4357215号に記載 されているように、Ｌｉ₂ＣＯ₃の塩と金属酸化物を混合、加熱処理することによって実施できる。
【００４９】
また柔軟で、薄膜化しやすいという点では、導電性高分子が好ましい。導電性高分子の例としては、ポリアニリン、ポリアセチレン及びその誘導体、ポリパラフェニレン及びその誘導体、ポリピロール及びその誘導体、ポリチエニレン及びその誘導体、ポリピリジンジイル及びその誘導体、ポリイソチアナフテニレン及びその誘導体、ポリフリレン及びその誘導体、ポリセレノフェン及びその誘導体、ポリパラフェニレンビニレン、ポリチエニレンビニレン、ポリフリレンビニレン、ポリナフテニレンビニレン、ポリセレノフェンビニレン、ポリピリジンジイルビニレン等のポリアリーレンビニレン及びそれらの誘導体等が挙げられる。中でも有機溶媒に可溶性のアニリン誘導体の重合体が特に好ましい。これらの電池あるいは電極において電極活物質として用いられる導電性高分子は、後述のような化学的あるいは電気化学的方法、あるいはその他の公知の方法に従って製造される。
【００５０】
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。
【００５１】
本発明の非水電池の負極３に用いる負極活物質としては、アルカリ金属、アルカリ金属合金、炭素材料、金属酸化物や導電性高分子化合物のようなアルカリ金属イオンをキャリアーとする低酸化還元電位のものを用いることにより、高電圧、高容量の電池が得られるので好ましい。このような負極活物質の中では、リチウム金属あるいはリチウム／アルミニウム合金、リチウム／鉛合金、リチウム／アンチモン合金等のリチウム合金類が最も酸化還元電位が低く、かつ薄膜化が可能である点から特に好ましい。また炭素材料もリチウムイオンを吸蔵した場合、低酸化還元電位となり、しかも安定、安全であるという点で特に好ましい。リチウムイオンを吸蔵放出できる材料としては、天然黒鉛、人造黒鉛、気相法黒鉛、石油コークス、石炭コークス、ピッチ系炭素、ポリアセン、Ｃ₆₀、Ｃ₇₀等のフラーレン類等が挙げられられる。
【００５２】
上記負極活物質を用い、アルカリ金属イオンをキャリアーとする電池に用いる場合、高分子固体電解質中の電解質塩としてはアルカリ金属塩を使用する。アルカリ金属塩としては例えば、ＬｉＣＦ₃ＳＯ₃、ＬｉＰＦ₆、ＬｉＣｌＯ₄、ＬｉＢＦ₄、ＬｉＳＣＮ、ＬｉＡｓＦ₆、ＬｉＮ（ＣＦ₃ＳＯ₂）₂、ＮａＣＦ₃ＳＯ₃、Ｌ ｉＩ、ＮａＰＦ₆、ＮａＣｌＯ₄、ＮａＩ、ＮａＢＦ₄、ＮａＡｓＦ₆、ＫＣＦ₃Ｓ Ｏ₃、ＫＰＦ₆、ＫＩ等を挙げることができる。
【００５３】
本発明の電極及び電池の製造方法の一例について説明する。正負極をお互いに接触しないように電池構成用構造体内に入れ、または支持体上に配置する。例えば、電極の端に適当な厚みのスペーサーまたは予め調製しておいた高分子固体電解質フィルムを介して正極と負極をはり合せて、前記構造体内に入れ、次に、正極と負極の間に、一般式（１）及び／または一般式（２）で表わされる官能基を有する化合物の少なくとも一種と、高比表面積で低含水量の特定のマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子の混合物に少なくとも一種の電解質塩、場合によっては、さらに他の重合性化合物及び／または可塑剤及び／または溶媒を添加混合した重合性組成物を注入した後、例えば、加熱及び／または活性光線照射により重合することにより、あるいは、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。
【００５４】
また、これ以外にも、重合性化合物の少なくとも一種、溶媒及び高比表面積で低含水量の特定のマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子、あるいはこれに他の重合性化合物及び／または可塑剤を添加混合した重合性組成物を重合して得られた重合物を介して正極と負極を貼り合わせて、予め電極に含浸させておいた電解液から電解質塩の一部を重合物に移行させることにより、電池を製造することも可能である。
【００５５】
なお、前記電池構成用構造体あるいは前記支持体はＳＵＳ等の金属、ポリプロピレン、ポリイミド等の樹脂、あるいは導電性あるいは絶縁性ガラス等のセラミックス材料であればよいが、特にこれらの材料からなるものに限定されない。また、その形状は、筒状、箱状、シート状その他いかなる形状でもよい。
捲回型電池を製造する場合は、予め調製しておいた高分子固体電解質フィルムを介して、上記正極及び負極をはりあわせ、捲回し、電池構成用構造体内に挿入後に更に前記重合性組成物を注入し、重合させるという方法も可能である。
【００５６】
［電気二重層コンデンサ及びその製造方法］
次に本発明の電気二重層コンデンサについて説明する。
本発明によれば、前記高分子固体電解質を用いることにより、出力電圧が高く、取り出し電流が大きく、あるいは加工性、信頼性に優れた電気二重層コンデンサが提供される。
本発明の電気二重層コンデンサの一例の概略断面図を図２に示す。この例は、大きさ１ｃｍ×１ｃｍ、厚み約0.5ｍｍの薄型セルであり、集電体７の内側には 一対の分極性電極６が配置されており、その間に高分子固体電解質膜８が配置されている。９は絶縁性樹脂封止剤、１０はリード線である。
【００５７】
分極性電極６は、通常電気二重層コンデンサに用いられる炭素材料等の分極性材料からなる電極であればよい。分極性材料としての炭素材料は、比表面積が大きければ特に制限はないが、比表面積の大きいほど電気二重層の容量が大きくなり好ましい。例えば、ファーネスブラック、サーマルブラック（アセチレンブラックを含む）、チャンネルブラック等のカーボンブラック類や、椰子がら炭等の活性炭、天然黒鉛、人造黒鉛、気相法で製造したいわゆる熱分解黒鉛、ポリアセン及びＣ₆₀、Ｃ₇₀を挙げることができる。
集電体７は電子伝導性で電気化学的に耐食性があり、できるだけ比表面積の大きい材料を用いることが好ましい。例えば、各種金属及びその焼結体、電子伝導性高分子、カーボンシート等を挙げることができる。
【００５８】
本発明の電気二重層コンデンサの場合に複合に用いる電解質塩の種類は、特に限定されるものではなく、電荷キャリアーとしたいイオンを含んだ化合物を用いればよいが、高分子固体電解質中での解離定数が大きく、分極性電極と電気二重層を形成しやすいイオンを含むことが望ましい。
このような化合物としては、（ＣＨ₃）₄ＮＢＦ₄、(ＣＨ₃ＣＨ₂）₄ＮＣｌＯ₄等の４級アンモニウム塩、アルキルピリジニウムテトラフルオロボレート等のピリジニウム塩、ＡｇＣｌＯ₄等の遷移金属塩、（ＣＨ₃）₄ＰＢＦ₄等の４級ホスホニウム塩、ＬｉＣＦ₃ＳＯ₃、ＬｉＰＦ₆、ＬｉＣｌＯ₄、ＬｉＩ、ＬｉＢＦ₄、Ｌｉ ＳＣＮ、ＬｉＡｓＦ₆、ＬｉＮ(ＣＦ₃ＳＯ₂）₂、ＮａＣＦ₃ＳＯ₃、ＮａＰＦ₆、ＮａＣｌＯ₄、ＮａＩ、ＮａＢＦ₄、ＮａＡｓＦ₆、ＫＣＦ₃ＳＯ₃、ＫＰＦ₆、ＫＩ等のアルカリ金属塩、パラトルエンスルホン酸等の有機酸及びその塩、塩酸、硫酸等の無機酸等が挙げられる。これらの中で、出力電圧が高く取れ、解離定数が大きいという点から、４級アンモニウム塩、ピリジニウム塩、４級ホスホニウム塩、アルカリ金属塩が好ましい。４級アンモニウム塩の中では、（ＣＨ₃ＣＨ₂）（ＣＨ₃ＣＨ₂ＣＨ₂ＣＨ₂）₃ＮＢＦ₄のような、アンモニウムイオンの窒素上の置換基が異なっているものが、高分子固体電解質への溶解性あるいは解離定数が大きいという点から好ましい。
【００５９】
次に本発明の電気二重層コンデンサの製造方法の一例について説明する。分極性電極２枚をお互いに接触しないようにコンデンサ構成用構造体内に入れ、または支持体上に配置する。例えば、電極の端に適当な厚みのスペーサーまたは予め調製しておいた高分子固体電解質フィルムを介して分極性電極をはり合せて、前記構造体内に入れ、一般式（１）及び／または一般式（２）で表わされる官能基を有する化合物の少なくとも一種と高比表面積で低含水量の特定のマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子の混合物に少なくとも一種の電解質塩、場合によっては、さらに他の重合性化合物及び／または可塑剤及び／または溶媒を添加混合した重合性組成物を注入した後、重合することにより、あるいは、さらに、重合後必要に応じてポリオレフィン樹脂、エポキシ樹脂等の絶縁性樹脂で封止することにより、電極と電解質が良好に接触した電気二重層コンデンサが得られる。本法により、特に薄型電気二重層コンデンサを製造することができる。
【００６０】
また、これ以外にも、重合性化合物の少なくとも一種、溶媒及び高比表面積で低含水量の特定のマグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子、あるいはこれに他の重合性化合物及び／または可塑剤を添加混合した重合性組成物を重合して得られた重合物を介して２枚の分極性電極を貼り合わせて、予め分極性電極に含浸させておいた電解液から電解質塩の一部を重合物に移行させることにより、電気二重層コンデンサを製造することも可能である。
【００６１】
なお、前記コンデンサ構成用構造体あるいは前記支持体は、ＳＵＳ等の金属、ポリプロピレン、ポリイミド等の樹脂、あるいは導電性あるいは絶縁性ガラス等のセラミックス材料であればよいが、特にこれらの材料からなるものに限定されるものではなく、また、その形状は、筒状、箱状、シート状その他いかなる形状でもよい。
【００６２】
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よい。
捲回型コンデンサを製造する場合は、予め調製しておいた高分子固体電解質フィルムを介して、上記分極性電極をはりあわせ、捲回し、コンデンサ構成用構造体内に挿入後に更に前記重合性組成物を注入し、重合させるという方法も可能である。
【００６３】
【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。
【００６４】
実施例１：化合物３の合成
【化１３】

化合物１（ＫＯＨ価34.0ｍｇ／ｇ、ｓ／ｔ＝７／３）（50.0ｇ）及び化合物２（4.6ｇ）を窒素雰囲気中でよく精製したテトラヒドロフラン（ＴＨＦ）（１０ ０ｍｌ）に溶解した後、ジブチルチンジラウレート（0.44ｇ）を添加した。その後、２５℃で約１５時間反応させることにより、無色生成物を得た。その¹Ｈ− ＮＭＲ、ＩＲ及び元素分析の結果から、化合物１と化合物２は１対３で反応し、さらに、化合物２のイソシアナート基が消失し、ウレタン結合が生成しており、化合物３が生成していることがわかった。
【００６５】
実施例２：高分子固体電解質複合膜の製造
化合物３（1.0ｇ）、５００℃熱処理したハイドロタルサイト粒子（協和化学 製、ＫＷ２２００、平均粒子径約1.0μｍ、ＢＥＴ比表面積１３５ｍ²／ｇ、含水量1000ｐｐｍ）（0.33ｇ）、エチレンカーボネート（ＥＣ）（1.8ｇ）、エチル メチルカーボネート（ＥＭＣ）（4.2ｇ）、ＬｉＰＦ₆（橋本化成製電池グレード）（0.60ｇ）、及びルシリンＴＰＯ（ＢＡＳＦ社製）（0.005ｇ）をアルゴン雰 囲気中でよく混合し、光重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は３５ｐｐｍであった。
この光重合性組成物をアルゴン雰囲気下、ポリエチレンテレフタレート（ＰＥＴ）フィルム上に塗布後、ケミカル蛍光ランプ（三共電気社製FL20S.BL）を１０分照射したところ、ＥＣ／ＥＭＣ電解液を含浸した化合物３の重合体／ＫＷ２２００複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、5.5×10^-3、1.4×10^-3Ｓ／ｃｍであった。
【００６６】
実施例３：高分子固体電解質複合膜の製造
開始剤としてルシリンＴＰＯ（0.005ｇ）の代りに、パーロイルＴＣＰ（日本 油脂社製)(0.01ｇ）を添加した以外は実施例２と同様にして、熱重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は３５ｐｐｍであった。
この熱重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ポリプロピレン（ＰＰ）フィルムを被覆して、ホットプレート上で６０℃、３０分加熱したところ、ＥＣ／ＥＭＣ電解液を含浸した化合物３の重合体／ＫＷ２２００複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、5.3×10^-3、1.0×10^-3Ｓ／ｃｍであった。
【００６７】
実施例４：高分子固体電解質複合膜の製造
ＬｉＰＦ₆に代えて橋本化成製電池グレードＬｉＢＦ₄（0.50ｇ）を用いた以外は実施例２と同様にして、光重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は４５ｐｐｍであった。
この光重合性組成物を実施例２と同様に塗布、光照射することにより、電解液を含浸した化合物３の重合体／ＫＷ２２００複合フィルムを約３０μｍの自立フィルムとして得た。この固体電解質の２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、4.3×10^-3、0.8×10^-3Ｓ／ｃｍであった。
【００６８】
実施例５：高分子固体電解質複合膜の製造
ＬｉＰＦ₆に代えて橋本化成製高純度テトラエチルアンモニウムテトラフルオ ロボレート（ＴＥＡＢ）（1.00ｇ）、溶媒をＥＣ、ＥＭＣに代えてプロピレンカーボネート（ＰＣ）（6.0ｇ）を用いた以外は実施例２と同様にして、光重合性 組成物を得た。この組成物の含水量（カールフィッシャー法）は１１０ｐｐｍであった。この光重合性組成物を実施例２と同様に塗布、光照射することにより、ＰＣ系電解液を含浸した化合物３の重合体／ＫＷ２２００複合フィルムを約３０μｍの自立フィルムとして得た。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、9.0×10^-3、1.5×10^-3Ｓ／ｃｍであった。
【００６９】
実施例６：化合物５の合成
【化１４】

【００７０】
化合物４（平均分子量５５０）（５５ｇ）、化合物２（15.5ｇ）を窒素雰囲気中でよく精製したＴＨＦ（１００ｍｌ）に溶解した後、ジブチルチンジラウレート（0.66ｇ）を添加した。その後、２５℃で約１５時間反応させることにより、無色粘ちょう液体を得た。その¹Ｈ−ＮＭＲ、ＩＲ及び元素分析の結果から、化 合物４と化合物２は１対１で反応し、さらに、化合物３のイソシアナート基が消失し、ウレタン結合が生成しており、化合物５が生成していることがわかった。
【００７１】
比較例１：高分子固体電解質複合膜の製造
化合物３（0.5ｇ）、化合物５（0.5ｇ）、５００℃熱処理酸化マグネシウム粒子（協和化学製、ミクロマグ３−３０、平均粒子径3.1μｍ、ＢＥＴ比表面積１０５ｍ²／ｇ、含水量1200ｐｐｍ）（0.66ｇ）、ＥＣ（1.8ｇ）、ＥＭＣ（4.2ｇ）、ＬｉＰＦ₆（橋本化成製電池グレード）（0.60ｇ）及びルシリンＴＰＯ（0.005ｇ）をアルゴン雰囲気中でよく混合し、光重合性組成物を得た。この組成物の含水量（カールフィッシャー）は３０ｐｐｍであった。この光重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ケミカル蛍光ランプを１０分照射したところ、ＥＣ／ＥＭＣ系電解液を含浸した共重合体(化合物３＋化合物５)／ミクロマグ３−３０複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、4.8×１０^-3、1.2×１０^-3Ｓ／ｃｍであった。
【００７２】
比較例２：高分子固体電解質複合膜の製造
化合物３（0.5ｇ）、化合物５（0.5ｇ）、１００℃熱処理酸化マグネシウム粒子（協和化学製、ミクロマグ３−３０、平均粒子径3.1μｍ、ＢＥＴ比表面積１０５ｍ²／ｇ、含水量8000ｐｐｍ）（0.66ｇ）、ＥＣ（1.8ｇ）、ＥＭＣ（4.2ｇ）、ＬｉＰＦ₆（橋本化成製電池グレード）（0.60ｇ）及びルシリンＴＰＯ（0.005ｇ）をアルゴン雰囲気中でよく混合し、光重合性組成物を得た。この組成物の含水量（カールフィッシャー）は４００ｐｐｍであった。この光重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ケミカル蛍光ランプを１０分照射したところ、ＥＣ／ＥＭＣ系電解液を含浸した共重合体(化合物３＋化合物５)／ミクロマグ３−３０複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、4.3×１０^-3、0.8×１０^-3Ｓ／ｃｍであった。
【００７３】
比較例３：高分子固体電解質複合膜の製造
化合物６；
【化１５】

【００７４】
（日本油脂、ブレンマーＡＥ−４００，Ｍｗ４００）（0.3ｇ）、化合物３（0.7ｇ）、５００℃熱処理ミクロマグ３−３０（0.66ｇ）、ＥＣ（1.8ｇ）、ジエチ ルカーボネート（ＤＥＣ）（4.2ｇ）、ＬｉＢＦ₄（橋本化成製電池グレード）（0.40ｇ）及びルシリンＴＰＯ（0.005ｇ）をアルゴン雰囲気中でよく混合し、光 重合性組成物を得た。この組成物の含水量（カールフィッシャー）は８０ｐｐｍであった。
この光重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ケミカル蛍光ランプを１０分照射したところ、ＥＣ／ＤＥＣ系電解液を含浸した共重合体(化合物３＋化合物６)／ミクロマグ３−３０複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、3.8×10^-3、0.6×10^-3Ｓ／ｃｍであった。
【００７５】
実施例７：高分子固体電解質複合膜の製造
開始剤としてルシリンＴＰＯ（0.005ｇ）の代りに、パーロイルＴＣＰ（日本油脂製）（0.04ｇ）を添加した以外は実施例５と同様にして、熱重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は１２０ｐｐｍであった。この熱重合性組成物をアルゴン雰囲気下、ＰＥＴフィルム上に塗布後、ＰＰフィルムを被覆して、ホットプレート上で８０℃、１時間加熱したところ、ＰＣ系電解液を含浸した化合物３の重合体／ＫＷ２２００複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、8.8×１０^-3、1.6×１０^-3Ｓ／ｃｍであった。
【００７６】
実施例８：コバルト酸リチウム正極の製造
Ｌｉ₂ＣＯ₃（１１ｇ）とＣｏ₃Ｏ₄（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ＬｉＣｏＯ₂粉末を得た。このＬｉＣｏＯ₂粉末とアセチレンブラック、ポリフッ化ビニリデンを重量比８：１：１で混合し、さらに過剰のＮ−メチルピロリドン溶液を加え、ゲル状組成物を得た。この組成物を約２５μｍのアルミ箔上に１０ｍｍ×１０ｍｍ、約１８０μｍの厚さに塗布成形した。さらに、約１００℃で２４時間加熱真空乾燥することにより、コバルト酸リチウム正極（７５ｍｇ）を得た。
【００７７】
実施例９：黒鉛負極の製造
ＭＣＭＢ黒鉛（大阪ガス製）、気相法黒鉛繊維（昭和電工（株）製：平均繊維径、0.3μｍ、平均繊維長、2.0μｍ、2700℃熱処理品）、ポリフッ化ビニリデンの重量比8.6：0.4：1.0の混合物に過剰のＮ−メチルピロリドン溶液を加え、ゲル状組成物を得た。この組成物を約１５μｍの銅箔上に１０ｍｍ×１０ｍｍ、約２５０μｍの厚さに塗布成形した。さらに、約１００℃で２４時間加熱真空乾燥することにより、黒鉛負極（３５ｍｇ）を得た。
【００７８】
実施例１０：Ｌｉイオン二次電池の製造
アルゴン雰囲気グローブボックス内で、実施例９で製造した黒鉛負極（１０ｍｍ×１０ｍｍ）に電解液（１Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させたものに、実施例２で調製した高分子固体電解質(化合物３)／ＫＷ２２００複合フィルム（１２ｍｍ×１２ｍｍ）を貼り合わせ、さらに実施例８で製造したコバルト酸リチウム正極（１０ｍｍ×１０ｍｍ）に電解液（１Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させたものを貼り合わせ、電池端部をエポキシ樹脂で封印し、図１に示される構造の黒鉛／酸化コバルト系Ｌｉイオン二次電池を得た。この電池を、６０℃、２５℃、−１０℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行ったところ、最大放電容量は各々7.2ｍＡｈ、7.2ｍＡｈ、5.6ｍＡｈであった。また、６０℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を繰返したところ、最大放電容量は7.0ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は３５０回であった。
【００７９】
比較例４：Ｌｉイオン二次電池の製造
高分子固体電解質(化合物３)／ＫＷ２２００複合フィルムの代りに、比較例１で製造した高分子固体電解質(化合物３＋化合物５)／ミクロマグ３−３０フィルムを用いた以外は実施例１０と同様にして図１に示される構造のＬｉイオン二次電池を製造した。この電池を、６０℃、２５℃、−１０℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行ったところ、最大放電容量は各々7.2ｍＡｈ、7.2ｍＡｈ、4.8ｍＡｈであった。また、６０℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を繰返したところ、最大放電容量は7.2ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は２８０回であった。
【００８０】
比較例５：Ｌｉイオン二次電池の製造
高分子固体電解質(化合物３)／ＫＷ２２００複合フィルムの代りに、比較例２で製造した高分子固体電解質(化合物３＋化合物５)／ミクロマグ３−３０フィルムを用いた以外は実施例１０と同様にして図１に示される構造のＬｉイオン二次電池を製造した。この電池を、６０℃、２５℃、−１０℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行ったところ、最大放電容量は各々7.0ｍＡｈ、6.8ｍＡｈ、4.0ｍＡｈであった。また、６０℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を繰り返したところ、最大放電容量は6.6ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は１２５回であった。
【００８１】
実施例１１：Ｌｉイオン二次電池の製造
アルゴン雰囲気グローブボックス内で、実施例９で製造した黒鉛負極（１０ｍｍ×１０ｍｍ）に電解液（１Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させた上に、実施例２で調製した化合物３／ＫＷ２２００系光重合性組成物を厚み３０μｍとなるように塗布し、アルゴン雰囲気下、ケミカル蛍光ランプを１０分照射したところ、電解液を含浸した高分子固体電解質（化合物３）／ＫＷ２２００複合フィルムを黒鉛負極上に直接形成した。さらに実施例８で製造したコバルト酸リチウム正極（１０ｍｍ×１０ｍｍ）に電解液（１Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させたものを貼り合わせ、電池端部をエポキシ樹脂で封印し、図１に示される構造の黒鉛／酸化コバルト系Ｌｉイオン二次電池を得た。この電池を、６０℃、２５℃、−１０℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行ったところ、最大放電容量は各々7.2ｍＡｈ、7.2ｍＡｈ、6.0ｍＡｈであった。また、６０℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を繰返したところ、最大放電容量は7.2ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は３３０回であった。
【００８２】
実施例１２：全固体Ｌｉイオン二次電池の製造
アルゴン雰囲気グローブボックス内で、実施例９で製造した黒鉛負極（１０ｍｍ×１０ｍｍ）に実施例３で調製した熱重合性組成物を含浸させたものに、実施例２で調製した高分子固体電解質(化合物３)／ＫＷ２２００複合フィルム（１２ｍｍ×１２ｍｍ）を貼り合わせ、さらに実施例８で製造したコバルト酸リチウム正極（１０ｍｍ×１０ｍｍ）に実施例３で調製した熱重合性組成物を含浸させたものを貼り合わせ、電池端部をエポキシ樹脂で封印し、さらに、７０℃で１時間熱重合性組成物を硬化させ、図１に示される構造の黒鉛／酸化コバルト系全固体Ｌｉイオン二次電池を得た。この電池を、６０℃、２５℃、−１０℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行ったところ、最大放電容量は各々7.2ｍＡｈ、6.8ｍＡｈ、2.5ｍＡｈであった。また、６０℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を繰返したところ、最大放電容量は6.8ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は４１０回であった。
【００８３】
実施例１３：活性炭電極の製造
椰子がら活性炭とポリフッ化ビニリデンの重量比9.0：1.0の混合物に過剰のＮ−メチルピロリドン溶液を加え、ゲル状組成物を得た。この組成物をステンレス箔上に１０ｍｍ×１０ｍｍの大きさで約１５０μｍの厚さに塗布した。約１００℃で１０時間真空乾燥し、活性炭電極（14.0ｍｇ）を得た。
【００８４】
実施例１４：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１３で製造した活性炭電極（１４ｍｇ）１０ｍｍ×１０ｍｍに、電解液（１Ｍ ＴＥＡＢ／ＰＣ）を含浸させた電極を２個用意した。次に、実施例５で製造した高分子固体電解質(化合物３)／ＫＷ２２００複合フィルム（１２ｍｍ×１２ｍｍ）を一方の電極に貼り合わせ、さらにもう一枚の電極をはり合わせ、コンデンサ端部をエポキシ樹脂で封止することにより、図２に示される構造の電気二重層コンデンサを製造した。このコンデンサを、６０℃、２５℃で作動電圧０〜2.5Ｖ、電流0.2ｍＡで充放電を行なったところ、最大容量は４７０ｍＦ、４７０ｍＦであった。また、６０℃、2.5ｍＡでの最大容量は４３０ｍＦで、充放電を５０回繰り返しても殆ど容量に変化はなかった。
【００８５】
実施例１５：全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１３で製造した活性炭電極（１４ｍｇ）１０ｍｍ×１０ｍｍに、実施例７で調製した熱重合性組成物を含浸させた電極を２個用意した。次に、実施例５で製造した高分子固体電解質(化合物３)／ＫＷ２２００複合フィルム（１２ｍｍ×１２ｍｍ）を一方の電極に貼り合わせ、さらにもう一枚の電極をはり合わせ、コンデンサ端部をエポキシ樹脂で封止し、熱重合性組成物を７０℃で１時間加熱重合させることにより、図２に示すような全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、６０℃、２５℃で作動電圧０〜2.5Ｖ、電流0.2ｍＡで充放電を行なったところ、最大容量は４６０ｍＦ、４１０ｍＦであった。また、６０℃、2.5ｍＡでの最大容量は４１０ｍＦで、充放電を５０回繰り返しても殆ど容量に変化はなかった。
【００８６】
実施例１６：高分子固体電解質複合膜の製造
化合物３（1.0ｇ）、５００℃熱処理したハイドロタルサイト粒子（協和化学製、ＫＷ２２００、平均粒子径約1.0μｍ、ＢＥＴ比表面積１３５ｍ²／ｇ、含水量1000ｐｐｍ）（0.33ｇ）、エチレンカーボネート（ＥＣ）（1.8ｇ）、エチルメチルカーボネート（ＥＭＣ）（4.2ｇ）、及びルシリンＴＰＯ（ＢＡＳＦ社製）（0.005ｇ）をアルゴン雰囲気中でよく混合し、光重合性組成物を得た。この組成物の含水量（カールフィッシャー法）は３０ｐｐｍであった。この光重合性組成物をアルゴン雰囲気下、ポリエチレンテレフタレート（ＰＥＴ）フィルム上に塗布後、ケミカル蛍光ランプ（三共電気社製FL20S.BL）を１０分照射したところ、ＥＣ／ＥＭＣ溶媒を含浸した化合物３の重合体／ＫＷ２２００複合フィルムが約３０μｍの自立フィルムとして得られた。このフィルムを電解液（1.2Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（重量比３：７））中に約１時間浸漬することにより、フィルム中にＬｉＰＦ₆塩を後添加した。このフィルムの２５℃、−２０℃でのイオン伝導度をインピーダンス法にて測定したところ、それぞれ、6.1×１０^-3、1.6×１０^-3Ｓ／ｃｍであった。
【００８７】
実施例１７：Ｌｉイオン二次電池の製造
アルゴン雰囲気グローブボックス内で、実施例９で製造した黒鉛負極（１０ｍｍ×１０ｍｍ）に電解液（1.2Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させたものに、実施例１６で調製したＥＣ／ＥＭＣ溶媒を含浸した化合物３の重合体／ＫＷ２２００複合フィルム（１２ｍｍ×１２ｍｍ）を貼り合わせ、さらに実施例８で製造したコバルト酸リチウム正極（１０ｍｍ×１０ｍｍ）に電解液（1.2Ｍ ＬｉＰＦ₆／ＥＣ＋ＥＭＣ（３：７））を含浸させたものを貼り合わせ、電池端部をエポキシ樹脂で封印し、図１に示される構造の黒鉛／酸化コバルト系Ｌｉイオン二次電池を得た。
この電池を、６０℃、２５℃、−１０℃で作動電圧2.75〜4.1Ｖ、電流0.5ｍＡで充放電を行ったところ、最大放電容量は各々7.2ｍＡｈ、7.2ｍＡｈ、6.0ｍＡｈであった。また、６０℃、作動電圧2.75〜4.1Ｖ、充電0.5ｍＡ、放電3.0ｍＡで充放電を繰返したところ、最大放電容量は7.1ｍＡｈで、容量が５０％に減少するまでのサイクル寿命は３２０回であった。
【００８８】
実施例１８：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１３で製造した活性炭電極（１４ｍｇ）１０ｍｍ×１０ｍｍに、電解液（1.2Ｍ ＴＥＡＢ／ＰＣ）を含浸させた電極を２個用意した。次に、実施例１６で製造したＥＣ／ＥＭＣ溶媒を含浸した化合物３の重合体／ＫＷ２２００複合フィルム（１２ｍｍ×１２ｍｍ）を一方の電極に貼り合わせ、さらにもう一枚の電極をはり合わせ、コンデンサ端部をエポキシ樹脂で封止することにより、図２に示される構造の電気二重層コンデンサを製造した。このコンデンサを、６０℃、２５℃で作動電圧０〜2.5Ｖ、電流0.2ｍＡで充放電を行なったところ、最大容量は４７０ｍＦ、４７０ｍＦであった。また、６０℃、2.5ｍＡでの最大容量は４５０ｍＦで、充放電を５０回繰り返しても殆ど容量に変化はなかった。
【００８９】
【発明の効果】
本発明の高分子化合物、マグネシウムと他の金属との複合酸化物（ハイドロタルサイト）微粒子及び電解質塩を含む高イオン伝導性の高分子固体電解質は、膜強度が良好で、イオン伝導度が高く、加工性に優れ、さらに従来の高分子固体電解質に比較して大電流特性、高温耐久性に優れている。本発明の高分子固体電解質を用いた電池及び電気二重層コンデンサはイオン伝導性物質が固体であるため液漏れの危険はなく長期間安定して使用できるものであり、また、この固体電解質を用いることにより薄型の電池やコンデンサを製造することができる。
【００９０】
また、本発明の高分子固体電解質を使用することにより、薄膜化が容易であり、高容量で作動でき、長寿命で、大電流特性、高温耐久性、信頼性、安定性、加工性に優れた二次電池が得られる。この二次電池は、全固体型としては高容量、高電流で作動でき、あるいはサイクル性が良好で、安全性、信頼性に優れた電池であり、ポータブル機器用主電源、バックアップ電源をはじめとする電気製品用電源、電気自動車用、ロードレベリング用大型電源として使用可能である。薄膜化が容易に行なえるため、身分証明書用カード等のペーパー電池としても使用できる。
【００９１】
さらに、本発明の高分子固体電解質を用いることによって、出力電圧が高く、取り出し電流が大きく、長寿命で、高温耐久性、加工性、信頼性、安定性に優れた電気二重層コンデンサが得られる。本発明の電気二重層コンデンサは、従来のコンデンサと比較しても、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、信頼性に優れており、このためバックアップ電源だけでなく、小型電池との併用で、各種電気製品用電源として使用可能である。また、薄膜化等の加工性に優れているため、従来の電気二重層コンデンサの用途以外の用途にも期待できる。
【図面の簡単な説明】
【図１】 本発明による電池の一例である薄型電池の実施例の概略断面図。
【図２】 本発明による電気二重層コンデンサの実施例の概略断面図。
【符号の説明】
１ 正極
２ 高分子固体電解質
３ 負極
４ 集電体
５ 絶縁性樹脂封止剤
６ 分極性電極
７ 集電体
８ 高分子固体電解質膜
９ 絶縁性樹脂封止剤
１０ リード線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polymer solid electrolyte containing composite oxide (hydrotalcite) fine particles of magnesium and other metals, a method for producing the same, a nonaqueous battery using the polymer solid electrolyte, a method for producing the same, and the high The present invention relates to a non-aqueous electric double layer capacitor using a molecular solid electrolyte and a method for producing the same.
[0002]
[Prior art]
In the flow of downsizing and total solidification in the field of ionics, as a new ion conductor that replaces the conventional electrolyte solution, all-solid primary batteries, secondary batteries and electric double layer capacitors using solid electrolytes are used. Application to chemical elements has been actively attempted.
In other words, electrochemical elements using an electrolyte solution have problems with long-term reliability because liquid leakage to the outside of the part or elution of the electrode active material is likely to occur, whereas products using solid electrolytes There is no such problem, and it is easy to reduce the thickness. Furthermore, the solid electrolyte is excellent in heat resistance and is advantageous in the manufacturing process of products such as batteries.
In particular, those using a polymer solid electrolyte mainly composed of a polymer compound have the advantage that the flexibility of the battery is increased and it can be processed into various shapes as compared with inorganic materials. However, what has been studied so far has left the problem that the extraction current is small because the ionic conductivity of the polymer solid electrolyte is low.
[0003]
Recently, LiCoO ₂ , LiNiO ₂ LiMnO ₂ , MoS ₂ Many researches have been made on lithium secondary batteries using metal oxides and metal sulfides such as lithium ions, lithium alloys, carbon materials capable of occluding and releasing lithium ions, inorganic compounds, and polymer compounds as negative electrodes. For example, J. Electrochem. Soc., Volume 138 (No. 3), page 665 (1991) contains MnO ₂ Or NiO ₂ Has been reported. These are attracting attention because of their high capacity per weight or volume.
Furthermore, in recent years, an electric double layer capacitor in which an ion conductive solution is placed between a carbon material having a large specific surface area such as activated carbon or carbon black as a polarizable electrode has been widely used for a memory backup power source or the like. For example, in Functional Materials, February 1989, page 33, a capacitor using a carbon-based polarizable electrode and an organic electrolyte is described. 173th Electrochemical Society Meeting Atlanta Georgia, May 1988 (No. 18) describes an electric double layer capacitor using a sulfuric acid aqueous solution.
JP-A 63-244570 discloses Rb having high electrical conductivity. ₂ Cu _Three I _Three Cl ₇ Capacitors using as an inorganic solid electrolyte are disclosed.
[0004]
However, current batteries and electric double-layer capacitors that use electrolyte solutions are prone to liquid leakage to the outside of the battery or capacitor during abnormal conditions such as long-term use or when a high voltage is applied. There are problems with long-term use and reliability. On the other hand, conventional batteries and electric double layer capacitors using inorganic ion conductive materials have problems that the decomposition voltage of the ion conductive material is low and the output voltage is low, and it is difficult to form the interface between the electrolyte and the electrode. There was a problem such as processing.
[0005]
Furthermore, Japanese Patent Application Laid-Open No. H4-253771 proposes that a polyphosphazene polymer compound is used as an ion conductive material for a battery or an electric double layer capacitor, and a solid containing such a polymer compound as a main component. A material using an ion conductive material has an advantage that the output voltage is higher than that of an inorganic ion conductive material, it can be processed into various shapes, and sealing is easy. However, in this case, the ionic conductivity of the polymer solid electrolyte is 10 ^-Four -10 ^-6 There was a drawback that the extraction current was small because the S / cm level was not sufficient. Further, 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 with a carbon material having a large specific surface area because it is a mixture of solids.
[0006]
The ionic conductivity of a polymer solid electrolyte that is generally studied is 10 at room temperature. ^-Four -10 ^-Five Although improved to about S / cm, the level is still at least two orders of magnitude lower than that of liquid ion conductive materials. Moreover, when it becomes low temperature of 0 degrees C or less, generally ionic conductivity will fall extremely. Furthermore, when these solid electrolytes are combined with electrodes of elements such as electric double layer capacitors, or when these solid electrolytes are incorporated into batteries as thin films, processing technologies such as compounding with electrodes and ensuring contact However, there were problems with the manufacturing method.
As an example of these polymer solid electrolytes, the British Polymer Journal (Br. Polym. J.), 319, 137 (1975) describes a composite of polyethylene oxide and an inorganic alkali metal salt as an ion conducting material. The ionic conductivity at room temperature is 10 ^-7 S / cm is low.
[0007]
Recently, many reports have shown that comb polymer compounds having oligooxyethylene introduced in the side chain enhance the thermal mobility of the oxyethylene chain responsible for ionic conductivity and improve the ionic conductivity. For example, in Journal of Physical Chemistry (J. Phys. Chem.), 89, 987 (1984), an alkali metal salt is added to the side chain of polymethacrylic acid to which oligooxyethylene is added. A composite example is described.
Furthermore, Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 106, p. 6854 (1984), compounded polyphosphazenes with oligooxyethylene side chains with alkali metal salts. The ionic conductivity is 10 ^-Five It was still insufficient with about S / cm.
[0008]
US Pat. No. 4,435,401 reports that a solid polymer electrolyte consisting of a cross-linked polymer containing a heteroatom and an ionizable salt has improved crystallinity, low glass transition point, and improved ionic conductivity. 10 ^-Five It was still insufficient with about S / cm.
Cross-linked polymers such as polyacrylonitrile and polyvinylidene fluoride gel as described in Journal of Applied Electrochem. Vol. 5, pp. 63-69 (1975) It has been reported that a so-called polymer gel electrolyte obtained by adding a solvent and an electrolyte to a compound has high ionic conductivity. JP-B-58-36828 reports that a similar polymer gel electrolyte obtained by adding a solvent and an electrolyte to polymethacrylic acid alkyl ester has high ionic conductivity.
[0009]
However, these polymer gel electrolytes have high ionic conductivity, but because they impart fluidity, they cannot be handled as complete solids, have poor film strength and film formability, and are applied to electric double layer capacitors and batteries. Then, a short circuit is likely to occur, and a sealing problem occurs like the liquid ion conductive material.
[0010]
On the other hand, US Pat. No. 4,792,504 improves ionic conductivity by using a cross-linked solid polymer electrolyte in which a continuous network of poly (ethylene oxide) is impregnated with an electrolyte composed of a metal salt and an aprotic solvent. Has been proposed. However, the ionic conductivity is 10 ^-Four Since S / cm was still insufficient and the solvent was added, there was a problem that the film strength was lowered.
Japanese Patent Publication No. 3-73081 and U.S. Pat. No. 4908283 disclose a polymer solid by irradiating a composition comprising acryloyl-modified polyalkylene oxide / electrolyte salt / organic solvent such as polyethylene glycol diacrylate with ultraviolet rays or the like. Methods for forming the electrolyte have been disclosed and attempts have been made to shorten the polymerization time.
[0011]
Also, US Pat. No. 4,830,939 and Japanese Patent Laid-Open No. 5-109310 disclose that a composition comprising a crosslinkable polyethylenically unsaturated compound / electrolyte salt / active light inert solvent is irradiated with radiation such as ultraviolet rays and electron beams to perform electrolysis. A similar method for forming a solid polymer electrolyte containing a liquid is disclosed. In these systems, since the amount of the electrolyte in the polymer solid electrolyte was increased, the ionic conductivity was improved, but it was still insufficient, and the membrane strength tends to deteriorate.
[0012]
Solid State Ionics, 1982, No. 7, p. 75, LiClO, a polymer solid electrolyte _Four / It has been reported that by further combining alumina particles with a polyethylene oxide composite, the strength of the polymer solid electrolyte can be improved without lowering the ionic conductivity.
Japanese Patent Laid-Open No. 4-245170 discloses that a solid polymer electrolyte thin film containing an inorganic compound whose surface has been hydrophobized has improved strength and does not cause a short-circuit due to an increase in area. The lithium-based polymer solid electrolyte containing insulating inorganic powder at a volume fraction of 5 to 60% is excellent in ionic conductivity and cation transport number, and easy to process, thin and increase in area. Is described.
Furthermore, Japanese Patent Application Laid-Open No. 6-140052 has proposed a solid electrolyte obtained by impregnating a polyalkylene oxide / isocyanate crosslinked / inorganic oxide composite with a nonaqueous electrolytic solution. Up is planned.
However, in these composite polymer solid electrolytes, the optimization of inorganic compounds and the characteristics of the polymer itself are insufficient, and there are still problems in practical use in terms of ionic conductivity, processability, and stability. .
[0013]
The inventors of the present invention have already proposed an ion conductive polymer solid electrolyte using a composite comprising a polymer and an electrolyte obtained from a (meth) acrylate prepolymer containing an oxyalkylene group having a urethane bond. 6-187822). The ionic conductivity of this polymer solid electrolyte is 10 when no solvent is added. ^-Four S / cm (room temperature) is a high level, and when a solvent is further added, it is 10 at room temperature or lower. ^-3 S / cm or more, the film quality was good, and the film was improved to the extent that it could be obtained as a free-standing film. In addition, this prepolymer has a good polymerizability, and when applied to a battery, it has a processing advantage that it can be polymerized and solidified after being incorporated in the battery in a prepolymer state.
[0014]
However, these systems also have a problem that the film strength is insufficient for use as a separator for batteries and the like, and it is difficult to handle industrially. In addition, there is a problem in that the polymer compound, particularly the oxyalkylene moiety is easily deteriorated at a high temperature due to a small amount of impurities in the battery system such as moisture, electrolyte salt decomposition products, electrode material impurities, etc., which affects the battery life.
In addition, when applied to a battery or an electric double layer capacitor, there is a problem that the capacity drop during high current discharge is large.
[0015]
[Problems to be solved by the invention]
The present invention is a polymer solid having good strength, high ionic conductivity at room temperature and low temperature, excellent workability, heat resistance, and large current characteristics even when a solvent addition system is used to form a thin film of about several tens of μm. An object of the present invention is to provide an electrolyte and a method for manufacturing the electrolyte.
In addition, the present invention provides a primary battery and a secondary battery that can be easily formed into a thin film by using the solid polymer electrolyte, can be operated with a high capacity and a high current, and have excellent reliability, and a method for manufacturing the same. The purpose is to do.
Furthermore, an object of the present invention is to provide an electric double layer capacitor having a high output voltage, a large extraction current, excellent workability and reliability, and a method for producing the same, by using the polymer solid electrolyte. To do.
[0016]
[Means for Solving the Problems]
As a result of intensive studies in view of the above-mentioned problems, the present inventors have added a composite oxide (hydrotalcite) fine particle of magnesium and another metal having a high specific surface area and a low water content. It has been found that strength and stability, particularly high temperature stability and current characteristics are improved. In addition, by using the above polymer solid electrolyte, it is easy to make a thin film, can be operated with a high capacity and a high current, and can be a non-aqueous primary battery and a secondary battery excellent in reliability and stability. I found. Furthermore, it has been found that by using the polymer solid electrolyte, an electric double layer capacitor having a high output voltage, a large extraction current, and excellent workability, reliability, and stability can be obtained.
[0017]
Based on the above knowledge, the present inventors have the following (1) polymer solid electrolyte and method for producing the same, and (2) battery, electric double layer capacitor using the polymer solid electrolyte, and production thereof. Provide a method.
[0018]
1) A polymer solid electrolyte containing at least one polymer compound and at least one electrolyte salt, or a polymer solid electrolyte further containing at least one organic solvent has a BET specific surface area of 30 m. ² / G or more, a composite oxide (hydrotalcite) fine particle of magnesium and another metal having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less is added in a range of 0.5 wt% to 50 wt%. A solid polymer electrolyte characterized by the above.
2) The polymer compound is represented by the general formula (1) and / or the general formula (2)
[Chemical 8]

(Wherein R ¹ And R ² Represents a hydrogen atom or an alkyl group, R ^Three Represents a divalent group which may contain a straight, branched or cyclic hetero atom having 1 to 10 carbon atoms, and x is 0 or an integer of 1 to 10. However, multiple Rs exist in the same molecule. ¹ , R ² , R ^Three And x may be the same or different. 2. The polymer solid electrolyte according to 1 above, which is a polymer of at least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by
3) The polymer solid electrolyte according to 1 or 2, wherein the electrolyte salt is selected from an alkali metal salt, a quaternary ammonium salt, a quaternary pyridinium salt, and a quaternary phosphonium salt.
4) The polymer solid electrolyte according to any one of 1 to 3, wherein the organic solvent is a carbonate compound.
5) The electrolyte salt is LiPF ₆ And / or LiBF _Four And / or LiN (CF _Three SO _Three ) ₂ 4. The solid polymer electrolyte as described in 3 above.
6) A battery using the solid polymer electrolyte according to any one of 1 to 5 above.
7) Lithium, lithium alloy or carbon material capable of occluding and releasing lithium ions, inorganic oxide capable of occluding and releasing lithium ions, inorganic chalcogenide capable of occluding and releasing lithium ions, conductive polymer capable of occluding and releasing lithium ions as the negative electrode of the battery 7. The lithium battery as described in 6 above, wherein at least one material selected from compounds is used.
8) An electric double layer capacitor in which a polarizable electrode is disposed via an ion conductive material, wherein the ion conductive material is the polymer solid electrolyte according to any one of 1 to 5 above. Multilayer capacitor.
9) At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by formula (1) and / or formula (2), and a BET specific surface area of 30 m ² / G or more, a polymerizable mixture containing composite oxide (hydrotalcite) fine particles of magnesium and other metals having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one electrolyte salt, or A method for producing a solid polymer electrolyte, comprising: placing a polymerizable mixture to which at least one organic solvent is added on a substrate; and curing the polymerizable mixture by heating and / or actinic ray irradiation.
10) At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and / or the general formula (2), and a BET specific surface area of 30 m ² / G or more, based on a polymerizable mixture containing composite oxide (hydrotalcite) fine particles of magnesium and other metals having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one organic solvent. A polymer solid electrolyte characterized in that after being placed on a material, the polymerizable mixture is cured by heating and / or actinic ray irradiation, and the resulting cured product is impregnated with an electrolyte salt by contacting with the electrolytic solution. Production method.
11) At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and / or the general formula (2), and a BET specific surface area of 30 m ² / G or more, a polymerizable mixture containing composite oxide (hydrotalcite) fine particles of magnesium and other metals having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one electrolyte salt, or A method for producing a battery, wherein a polymerizable mixture to which at least one organic solvent is added is placed in a structure for battery construction or placed on a support, and then the polymerizable mixture is cured.
12) At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and / or the general formula (2), and a BET specific surface area of 30 m ² A polymerizable mixture containing magnesium / other metal complex oxide (hydrotalcite) particles having a maximum particle size of 10 μm or less, a water content of 3000 ppm or less, and at least one organic solvent. After being placed in a structural structure or placed on a support, the polymerizable mixture is cured, and the resulting cured product is impregnated with an electrolyte salt by contacting with the electrolytic solution. Method.
13) At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by the general formula (1) and / or the general formula (2), and a BET specific surface area of 30 m ² / G or more, a polymerizable mixture containing magnesium and other metal composite oxide (hydrotalcite) particles having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one electrolyte salt, or An electric double layer characterized in that a polymerizable mixture to which at least one organic solvent is added is placed in a structure for constituting an electric double layer capacitor or disposed on a support, and then the polymerizable mixture is cured. Capacitor manufacturing method.
14) At least one heat and / or actinic ray polymerizable compound having a polymerizable functional group represented by formula (1) and / or formula (2), and a BET specific surface area of 30 m ² / G or more, a polymerizable mixture containing magnesium and other metal composite oxide (hydrotalcite) particles having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one organic solvent. After being placed in a structure for constituting a double-layer capacitor or disposed on a support, the polymerizable mixture is cured, and the resulting cured product is impregnated with an electrolyte solution to be impregnated with an electrolyte salt. Manufacturing method of electric double layer capacitor.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is described in detail below.
[Polymer Solid Electrolyte] The polymer solid electrolyte of the present invention basically comprises (a) a polymer compound, (b) an electrolyte salt, and (c) composite oxidation of magnesium and another metal, which are main constituent components. The product (hydrotalcite) fine particles may be included, and (d) an organic solvent may be further included. Hereinafter, each component will be described in detail.
[0020]
(a) polymer compound
The polymer compound that is the main constituent of the polymer solid electrolyte of the present invention must be non-electron-conducting and capable of absorbing and holding various organic polar solvents.
Such high molecular compounds include heteroatoms such as polyalkylene oxide, polyalkylimine, polyacrylonitrile, polycarbonate, poly (meth) acrylate, polyphosphazene, polyvinylidene fluoride, polyurethane, polyamide, polyester, polysiloxane, etc. And a polar thermoplastic polymer compound and a crosslinked polymer compound. In particular, the crosslinked polymer compound is suitable for the polymer solid electrolyte of the present invention because it has high strength after solvent absorption, high solvent retention, and is a viscoelastic body. The term “crosslinking” as used herein includes, in addition to those in which the crosslinking chain is formed by a covalent bond, those in which the side chain is crosslinked by an ionic bond, a hydrogen bond, or the like, Including.
[0021]
Among the above polymer compounds, those containing oxyalkylene, urethane, carbonate structures such as polyalkylene oxide, polyurethane, and polycarbonate in the molecular structure have good compatibility with various polar solvents, and also have electrochemical stability. It is preferable because it is good. From the viewpoint of stability, those having a fluorocarbon group such as polyvinylidene fluoride in the molecular structure are also preferred. Moreover, the oxyalkylene, urethane, carbonate, and fluorocarbon group may be contained in the same polymer compound. The repeating number of these groups should just be the range of 1-1000, respectively, and the range of 5-100 is preferable.
[0022]
Examples of the polymer compound used in the polymer solid electrolyte of the present invention include a polymerizable functional group represented by the general formula (1) and / or (2) among the polymer compounds.
[0023]
[Chemical 9]

(Wherein R ¹ And R ² Represents a hydrogen atom or an alkyl group, R ^Three Represents a divalent group which may contain a straight, branched or cyclic hetero atom having 1 to 10 carbon atoms, and x is 0 or an integer of 1 to 10. However, multiple Rs exist in the same molecule. ¹ , R ² , R ^Three And x may be the same or different. )
A polymer compound obtained by curing at least one kind of heat and / or actinic ray polymerizable compound having a heat and / or actinic ray irradiation forms a polymer solid electrolyte in a state containing a solvent and inorganic oxide fine particles. The film is easy to form, has good film strength, and can be easily combined with electrodes used in various electrochemical devices, which is preferable.
[0024]
The method for synthesizing the polymerizable compound having the group represented by the general formula (1) is not particularly limited. For example, by reacting an acid chloride with an oligooxyalkylene ol having a hydroxyl group at the terminal in the following steps. Easy to get.
[Chemical Formula 10]

Where R ^Four Represents a hydrogen atom or an alkyl group having 10 or less carbon atoms, and R ^Five Represents an alkyl group having 10 or less carbon atoms, and m is an integer in the range of 1 to 1000, preferably 1 to 50. Other symbols have the same meaning as described above.
[0025]
The method for synthesizing the polymerizable compound having the group represented by the general formula (2) is not particularly limited.
Embedded image

(The symbols in the formula have the same meaning as described above.)
It can be easily obtained by reacting an isocyanate compound represented by the following with an oligooxyalkylene ol having a hydroxyl group at the terminal.
[0026]
As a specific method, the compound having one functional group represented by the general formula (2) is, for example, a methacryloyl isocyanate compound (hereinafter abbreviated as MI) or an acryloyl isocyanate compound (hereinafter referred to as AI). And a monoalkylalkylene glycol can be easily obtained by reacting at a molar ratio of 1: 1 according to the following reaction formula.
Embedded image

(The symbols in the formula have the same meaning as described above.)
[0027]
In addition, the compound having two functional groups represented by the general formula (2) can be easily obtained by reacting MI or AI with oligoalkylene glycol at a molar ratio of 2: 1, for example.
In addition, the compound having three functional groups represented by the general formula (2) includes, for example, MIs and / or AIs and a triol obtained by addition-polymerizing an oligoalkylene glycol with a trihydric alcohol such as glycerin: It can be easily obtained by reacting at a molar ratio of 1.
[0028]
The compound having four functional groups represented by the general formula (2) is, for example, a mixture of MIs and / or AIs and tetraol obtained by addition polymerization of oligoalkylene glycol with a tetrahydric alcohol such as pentaerythritol. It can be easily obtained by reacting at a molar ratio of 1: 1.
In addition, the compound having five functional groups represented by the general formula (2) includes, for example, MI and / or AI and pentaol obtained by addition polymerization of α-D-glucopyranose with oligoalkylene glycol. It can be easily obtained by reacting at a molar ratio of 1: 1.
The compound having six functional groups represented by the general formula (2) is, for example, a 6: 1 molar ratio of MIs and / or AIs and hexaol obtained by addition-polymerization of oligoalkylene glycol to mannitol. It can be easily obtained by reacting with
[0029]
Here, the polymer compound obtained by polymerizing the compound having only one functional group represented by the general formula (1) or (2) does not have a cross-linked structure, and the film strength is insufficient. There is a greater risk of short-circuiting if a thin film is used. Therefore, it is copolymerized with a polymerizable compound having two or more functional groups represented by the general formula (1) or (2) and crosslinked, or two functional groups represented by the general formula (1) or (2). It is preferable to use in combination with a polymer compound obtained from the polymerizable compound.
When these polymer compounds are used as thin films, the number of functional groups represented by the general formula (1) or (2) contained in one molecule is more preferably 3 or more in consideration of the strength.
[0030]
In addition, the polymer compound obtained by polymerizing the compound having a polymerizable functional group represented by the general formula (2) contains a urethane group, has a high dielectric constant, and is an ion in the case of a polymer solid electrolyte. This is preferable because of high conductivity. Furthermore, the compound having a polymerizable functional group represented by the general formula (2) is preferable because it has good polymerizability, has high film strength when formed into a thin film, and increases the amount of electrolyte contained.
[0031]
A polymer compound preferable as a constituent of the solid polymer electrolyte of the present invention is a homopolymer of a compound having a functional group represented by the general formula (1) and / or the general formula (2), and falls into this category. It may be a copolymer of two or more types to which it belongs, or a copolymer of at least one of the compounds and another polymerizable compound.
[0032]
The other polymerizable compound copolymerizable with the compound having the functional group represented by the general formula (1) and / or the general formula (2) is not particularly limited, and examples thereof include acrylamide, methacrylamide, N, N-dimethylmethacrylamide, vinylene carbonate, N-vinylpyrrolidone, acryloylmorpholine, methacryloylmorpholine, (meth) acrylamide compounds such as N, N-dimethylaminopropyl (meth) acrylamide, styrenes such as styrene and α-methylstyrene Examples thereof include N-vinylamide compounds such as compounds, N-vinylacetamide and N-vinylformamide, and alkyl vinyl ethers such as ethyl vinyl ether.
[0033]
A preferred polymer compound used for the polymer solid electrolyte of the present invention is a polymer obtained from at least one of the compounds having a functional group represented by the general formula (1) and / or the general formula (2) and / or the compound. It may be a mixture of a copolymer having a copolymer component with other polymer compound. Other polymer compounds to be mixed include, for example, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic (or acrylic) esters, polystyrene, polyphosphazenes, polysiloxane or polysilane, polyvinylidene fluoride, polytetra Examples thereof include polymers such as fluoroethylene.
[0034]
When the copolymer or mixture is used, the amount of the structural unit derived from the compound having the functional group represented by the general formula (1) and / or the general formula (2) is the type of other copolymer component or polymer mixture component. Depending on the ionic conductivity and membrane strength, heat resistance, and current characteristics when used in the polymer solid electrolyte, it is preferable to contain 40% by weight or more based on the total amount of the copolymer or polymer mixture, Furthermore, it is preferable to contain 60 weight% or more.
[0035]
The polymerization of the compound having a functional group represented by the general formula (1) and / or the general formula (2) can be performed by a general method utilizing the polymerizability of the acryloyl group or methacryloyl group which is a functional group. That is, a radical polymerization catalyst such as azobisisobutyronitrile, benzoyl peroxide, CF, etc., alone or in a mixture of these compounds and other copolymerizable polymerizable compounds. _Three Protic acids such as COOH, BF _Three AlCl _Three It is possible to carry out radical polymerization, cationic polymerization or anionic polymerization using a cationic polymerization catalyst such as Lewis acid or the like, or an anionic polymerization catalyst such as butyl lithium, sodium naphthalene or lithium alkoxide. Further, depending on the polymerizable compound, radical polymerization can be performed only by heating in an oxygen-free state. In addition, the polymerizable compound or polymerizable mixture can be polymerized after being formed into a film-like shape.
[0036]
(b) Electrolyte salt
The type of the electrolyte salt used in the present invention is not particularly limited, and an electrolyte salt containing an ion desired to be a carrier by charge may be used, but it is desirable that the dissociation constant in the polymer solid electrolyte is large, and LiCF _Three SO _Three , LiN (CF _Three SO ₂ ) ₂ , LiPF ₆ LiClO _Four , LiI, LiBF _Four , LiSCN, LiAsF ₆ , NaCF _Three SO _Three , NaPF ₆ , NaClO _Four , NaI, NaBF _Four , NaAsF ₆ , KCF _Three SO _Three , KPF ₆ , Alkali metal salts such as KI, (CH _Three ) _Four NBF _Four Quaternary ammonium salts such as (CH _Three ) _Four PBF _Four Quaternary phosphonium salts such as AgClO _Four Transition metal salts such as, or protonic acids such as hydrochloric acid, perchloric acid, and borohydrofluoric acid are preferred.
The electrolyte salt in the polymer solid electrolyte of the present invention can be used in combination, and the composite ratio is preferably from 0.1 to 50% by weight, particularly preferably from 1 to 30% by weight, based on the weight of the polymer compound. . If the electrolyte salt used in the composite is present in a ratio of 50% by weight or more, the ion migration is greatly inhibited. Conversely, if the ratio is 0.1% by weight or less, the absolute amount of ions is insufficient and the ionic conductivity is decreased.
[0037]
(c) Magnesium and other metal complex oxides (hydrotalcite)
The polymer solid electrolyte of the present invention is characterized by the addition of composite oxide (hydrotalcite) fine particles of magnesium and other metals. This addition not only improves the strength and film thickness uniformity of the polymer solid electrolyte film, but also creates fine pores between the oxide microparticles and the polymer. On the other hand, free electrolyte is dispersed in the polymer solid electrolyte through the pores, and the ion conductivity and mobility can be increased without impairing the strength improvement effect. Further, by adding fine particles of composite oxide (hydrotalcite) of magnesium and other metals, the viscosity of the polymerizable composition increases, and the compatibility between the polymer compound and the solvent is insufficient. The effect of suppressing separation also appears.
[0038]
Also, as the composite oxide (hydrotalcite) fine particles of magnesium and other metals to be added, those with high specific surface area and high surface activity with reduced adsorbed water are used. It can adsorb impurities (water, free acid, free base, etc.) very well, and can be very effective in reducing the deterioration of sealing materials and other battery materials, resulting in improved device life. it can.
[0039]
For the purpose of increasing the amount of electrolyte in the polymer solid electrolyte and increasing the ionic conductivity and mobility, the specific surface area of the inorganic oxide is preferably as large as possible. ² / G or more, or 30m ² / G or more is preferable.
The crystal particle diameter of such an inorganic oxide is not particularly limited as long as it can be mixed with the polymerizable composition, but the size is preferably 0.001 μm to 10 μm, particularly preferably 0.005 μm to 5 μm.
In addition, various shapes such as a spherical shape, an oval shape, a cubic shape, a rectangular parallelepiped shape, a cylindrical shape or a rod shape can be used.
[0040]
Specific examples of the composite oxide (hydrotalcite) of magnesium and other metals used in the present invention include Kyoward (manufactured by Kyowa Chemical). Among these, hydrotalcite (Kyoward (KW) 2000, 2200, etc.), which is a composite oxide of magnesium and aluminum, is preferable because of its excellent stability and impurity adsorption ability. When the amount of the inorganic oxide added is too large, there arises a problem that the strength and ionic conductivity of the polymer solid electrolyte are lowered or film formation is difficult. Therefore, the preferable addition amount is 50% by weight or less with respect to the solid polymer electrolyte, and the range of 0.1 to 30% by weight is particularly preferable.
[0041]
The composite oxide (hydrotalcite) fine particles of magnesium and other metals of the present invention are preferably heat-treated before being added to the polymer solid electrolyte. The heat treatment not only reduces the surface adsorbed water of the oxide fine particles and suppresses free moisture that diffuses to other materials, but also can adsorb impurities of other materials, and improves the stability in the device. The temperature and time of the heat treatment vary depending on the shape and type of the composite oxide (hydrotalcite) fine particles of magnesium and other metals to be used, but it may be 2 to 300 hours in the range of 100 to 1200 ° C., 200 to 800 A range of ° C is particularly preferred.
[0042]
The heat treatment temperature is preferably as high as possible. However, if the temperature exceeds 1200 ° C., sintering of composite oxide (hydrotalcite) particles of magnesium and other metals proceeds and the surface activity also decreases, which is not preferable. The atmosphere during the heat treatment is not particularly limited to reduced pressure, air, or inert atmosphere. However, after the heat treatment, it is necessary to handle in an atmosphere having a dew point of −30 ° C. or less in order to prevent resorption of moisture, etc. A temperature of not higher than ° C is particularly preferred. The water content of the composite oxide (hydrotalcite) fine particles of magnesium and other metals thus heat-treated needs to be a value of 3000 ppm or less when determined by the Karl Fischer method.
[0043]
(d) Organic solvent
It is preferable to add an organic solvent to the polymer solid electrolyte of the present invention because the ionic conductivity of the polymer solid electrolyte is further improved. As a solvent that can be used, a compound having good compatibility with the polymer compound used in the polymer solid electrolyte of the present invention, a large dielectric constant, a boiling point of 60 ° C. or more, and a wide electrochemical stability range is suitable. Yes.
Examples of such solvents include ethers such as 1,2-dimethoxyethane, 2-methyltetrahydrofuran, crown ether, triethylene glycol methyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl Examples thereof include carbonates such as methyl carbonate, aromatic nitriles such as benzonitrile and tolunitrile, sulfur compounds such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane, and phosphate esters. Among these, ethers and carbonates are preferable, and carbonates are particularly preferable.
The greater the amount of organic solvent added, the better the ionic conductivity of the polymer solid electrolyte. For this reason, it is generally desirable to increase the amount of addition, but on the other hand, if the amount is too large, the mechanical strength of the polymer solid electrolyte is lowered. The preferred addition amount is 2 to 15 times the weight of the polymer used in the solid polymer electrolyte of the present invention, and particularly preferably 3 to 10 times the amount.
[0044]
[Production method of solid polymer electrolyte]
The polymer solid electrolyte of the present invention was prepared by preparing a polymerizable mixture comprising a compound having a functional group represented by the general formula (1) and / or the general formula (2) and other components, for example, in the form of a film. Thereafter, it can be produced by polymerization. Specifically, at least one compound having a functional group represented by the general formula (1) and / or the general formula (2), composite oxide (hydrotalcite) fine particles of magnesium and another metal, At least one electrolyte salt such as an alkali metal salt, quaternary ammonium salt, quaternary phosphonium salt or transition metal salt is mixed, and if desired, other polymerizable compounds, plasticizers and / or organic solvents are added and mixed to be polymerizable. After preparing the composition, it is formed into a film or the like and polymerized by heating and / or irradiation with actinic rays in the presence or absence of the catalyst to obtain the polymer solid electrolyte of the present invention. According to this method, the degree of freedom in processing is widened, which is a great merit in application. In addition, the electrolyte salt can be transferred after the polymerizable mixture is polymerized. That is, it can also be produced by a method in which the polymerizable composition excluding the electrolyte salt is prepared and polymerized, and then the obtained polymer (cured product) is brought into contact with the electrolytic solution to impregnate the electrolyte salt. . In addition, as a method of contacting with the electrolytic solution, a method of contacting with an electrode or the like impregnated with the electrolytic solution can be used besides direct immersion in the electrolytic solution.
[0045]
When a solvent is used at the time of polymerization, depending on the type of polymerizable compound and the presence or absence of a polymerization catalyst, any solvent that does not inhibit the polymerization may be used. For example, tetrahydrofuran (THF), acetonitrile, toluene, etc. are used. be able to.
The polymerization temperature depends on the type of the compound having the functional group represented by the general formula (1) and / or the general formula (2), but may be any temperature at which the polymerization occurs, and is usually 0 ° C to 200 ° C. It may be performed in the range of.
When polymerizing by actinic ray irradiation, depending on the type of the compound having the functional group represented by the general formula (1) and / or the general formula (2), for example, an initiator such as benzylmethyl ketal or benzophenone is used. Then, it can be polymerized by irradiation with ultraviolet light of several mW or more, γ ray, electron beam or the like.
[0046]
Moreover, when using the polymer solid electrolyte of this invention as a thin film, in order to improve film strength, it can also be set as a composite film with another porous film. However, depending on the type or amount of the film to be combined, the conductivity may be lowered and the stability may be deteriorated, so it is necessary to select a suitable one. Examples of the film to be used include porous polyolefin sheets such as reticulated polyolefin sheets such as polypropylene nonwoven fabric and polyethylene net, polyolefin microporous films such as Celgard (trade name), nylon nonwoven fabrics, etc. A film is preferred. The porosity should be about 10 to 95%, but it should be as large as possible as long as the strength permits, and the preferable porosity is in the range of 40 to 95%.
The compounding method is not particularly limited, but for example, at least one compound having a functional group represented by the general formula (1) and / or the general formula (2), a specific magnesium having a high specific surface area and a low water content, and the like. A polymerizable composition obtained by adding and mixing at least one electrolyte salt, and in some cases, another polymerizable compound and / or a plasticizer and / or a solvent, to a mixture of fine metal oxide (hydrotalcite) particles. By impregnating the porous polymer film and then subjecting it to a method of polymerizing the (meth) acryloyl-based compound, it can be uniformly combined and the film thickness can be easily controlled.
[0047]
[Battery and manufacturing method thereof]
As a battery of the present invention, a schematic cross-sectional view of an example of a thin film secondary battery is shown in FIG. In the figure, 1 is a positive electrode, 2 is a polymer solid electrolyte, 3 is a negative electrode, 4 is a current collector, and 5 is an insulating resin sealant.
In the configuration of the non-aqueous battery of the present invention, a high oxidation-reduction potential electrode active material (positive electrode active material) such as a metal oxide, metal sulfide, conductive polymer, or carbon material is used for the positive electrode 1. Since a battery having a high voltage and voltage is obtained, it is preferable. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, molybdenum oxide, molybdenum sulfide, titanium sulfide, Metal sulfides such as vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide, and the like are particularly preferable in terms of high capacity and high voltage.
[0048]
The method for producing the metal oxide or metal sulfide in this case is not particularly limited. For example, a general electrolysis method or heating as described in Electrochemistry, Vol. 22, page 574 (1954). Manufactured by law. In addition, when these are used as an electrode active material in a lithium battery, for example, Li _x CoO ₂ Or Li _x MnO ₂ The lithium element is preferably used in a state of being inserted (composited) into a metal oxide or metal sulfide. The method for inserting the lithium element is not particularly limited. For example, a method for electrochemically inserting lithium ions or a method described in US Pat. No. 4,357,215 may be used. ₂ CO _Three This can be carried out by mixing and heat-treating a salt of the above and a metal oxide.
[0049]
Moreover, a conductive polymer is preferable in that it is flexible and easily thinned. Examples of the conductive polymer include polyaniline, polyacetylene and derivatives thereof, polyparaphenylene and derivatives thereof, polypyrrole and derivatives thereof, polythienylene and derivatives thereof, polypyridinediyl and derivatives thereof, polyisothianaphthenylene and derivatives thereof, polyfurylene. And its derivatives, polyselenophene and its derivatives, polyparaphenylene vinylene, polythienylene vinylene, polyfurylene vinylene, polynaphthenylene vinylene, polyselenophene vinylene, polypyridinediyl vinylene, and their derivatives, etc. Is mentioned. Among them, a polymer of an aniline derivative that is soluble in an organic solvent is particularly preferable. The conductive polymer used as an electrode active material in these batteries or electrodes is produced according to a chemical or electrochemical method as described later, or other known methods.
[0050]
Further, examples of the carbon material include natural graphite, artificial graphite, gas phase method graphite, petroleum coke, coal coke, fluorinated graphite, pitch-based carbon, and polyacene.
[0051]
As a negative electrode active material used for the negative electrode 3 of the nonaqueous battery of the present invention, a low redox potential using an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material, a metal oxide or a conductive polymer compound as a carrier. Is preferable because a battery having a high voltage and a high capacity can be obtained. Among such negative electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, and lithium / antimony alloy have the lowest redox potential and can be made thin. preferable. In addition, the carbon material is particularly preferable because it has a low redox potential when lithium ions are occluded, and is stable and safe. Materials that can occlude and release lithium ions include natural graphite, artificial graphite, gas phase method graphite, petroleum coke, coal coke, pitch-based carbon, polyacene, C ₆₀ , C ₇₀ And fullerenes.
[0052]
When the negative electrode active material is used for a battery using an alkali metal ion as a carrier, an alkali metal salt is used as an electrolyte salt in the polymer solid electrolyte. Examples of the alkali metal salt include LiCF _Three SO _Three , LiPF ₆ LiClO _Four , LiBF _Four , LiSCN, LiAsF ₆ , LiN (CF _Three SO ₂ ) ₂ , NaCF _Three SO _Three , LiI, NaPF ₆ , NaClO _Four , NaI, NaBF _Four , NaAsF ₆ , KCF _Three S O _Three , KPF ₆ , KI and the like.
[0053]
An example of the manufacturing method of the electrode and battery of this invention is demonstrated. The positive and negative electrodes are placed in the battery structure so as not to contact each other, or are arranged on a support. For example, the positive electrode and the negative electrode are bonded to each other through a spacer having an appropriate thickness at the end of the electrode or a polymer solid electrolyte film prepared in advance, and then placed in the structure, and then between the positive electrode and the negative electrode, A complex oxide (hydrotalcite) of at least one compound having a functional group represented by the general formula (1) and / or the general formula (2) with a specific magnesium having a high specific surface area and a low water content and another metal ) After injecting a polymerizable composition in which at least one electrolyte salt, and in some cases, other polymerizable compounds and / or plasticizers and / or solvents are added and mixed into the mixture of fine particles, for example, heating and / or activity Electrode can be electrolyzed by polymerization by irradiation with light or by sealing with an insulating resin such as polyolefin resin or epoxy resin as necessary after polymerization. Battery is good contact is obtained.
[0054]
In addition to this, at least one kind of polymerizable compound, solvent and high specific surface area and low water content of specific magnesium and other metal complex oxide (hydrotalcite) fine particles, or other polymerizable compounds Part of the electrolyte salt from the electrolytic solution in which the positive electrode and the negative electrode are bonded together via a polymer obtained by polymerizing a polymerizable composition in which a compound and / or a plasticizer is added and mixed, and the electrode is impregnated in advance. It is also possible to produce a battery by transferring the polymer to a polymer.
[0055]
The battery structure or the support may be made of a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. It is not limited. Moreover, the shape may be any shape such as a cylinder, a box, a sheet or the like.
When manufacturing a wound battery, the above-mentioned polymerizable composition is further bonded after the positive electrode and the negative electrode are bonded and wound through a polymer solid electrolyte film prepared in advance and inserted into the structure for battery construction. It is also possible to inject and polymerize.
[0056]
[Electric double layer capacitor and manufacturing method thereof]
Next, the electric double layer capacitor of the present invention will be described.
According to the present invention, by using the polymer solid electrolyte, an electric double layer capacitor having a high output voltage, a large extraction current, or excellent workability and reliability is provided.
FIG. 2 shows a schematic cross-sectional view of an example of the electric double layer capacitor of the present invention. This example is a thin cell having a size of 1 cm × 1 cm and a thickness of about 0.5 mm, and a pair of polarizable electrodes 6 are arranged inside the current collector 7, and a polymer solid electrolyte membrane 8 is arranged between them. Has been. 9 is an insulating resin sealant, and 10 is a lead wire.
[0057]
The polarizable electrode 6 may be an electrode made of a polarizable material such as a carbon material usually used for an electric double layer capacitor. The carbon material as the polarizable material is not particularly limited as long as the specific surface area is large, but the larger specific surface area is preferable because the capacity of the electric double layer is increased. For example, carbon blacks such as furnace black, thermal black (including acetylene black), channel black, activated carbon such as coconut shell charcoal, natural graphite, artificial graphite, so-called pyrolytic graphite produced by gas phase method, polyacene and C ₆₀ , C ₇₀ Can be mentioned.
The current collector 7 is preferably made of a material having an electron conductivity, electrochemical corrosion resistance, and a specific surface area as large as possible. For example, various metals and their sintered bodies, electron conductive polymers, carbon sheets and the like can be mentioned.
[0058]
The type of electrolyte salt used for the composite in the case of the electric double layer capacitor of the present invention is not particularly limited, and a compound containing an ion desired to be a charge carrier may be used, but dissociation in a polymer solid electrolyte It is desirable to include ions that have a large constant and easily form a polarizable electrode and an electric double layer.
Such compounds include (CH _Three ) _Four NBF _Four , (CH _Three CH ₂ ) _Four NClO _Four Quaternary ammonium salts such as alkyl pyridinium tetrafluoroborate, AgClO _Four Transition metal salts such as (CH _Three ) _Four PBF _Four Quaternary phosphonium salts such as LiCF _Three SO _Three , LiPF ₆ LiClO _Four , LiI, LiBF _Four , Li SCN, LiAsF ₆ , LiN (CF _Three SO ₂ ) ₂ , NaCF _Three SO _Three , NaPF ₆ , NaClO _Four , NaI, NaBF _Four , NaAsF ₆ , KCF _Three SO _Three , KPF ₆ And alkali metal salts such as KI, organic acids such as p-toluenesulfonic acid and salts thereof, and inorganic acids such as hydrochloric acid and sulfuric acid. Of these, quaternary ammonium salts, pyridinium salts, quaternary phosphonium salts, and alkali metal salts are preferred from the viewpoints of high output voltage and a large dissociation constant. Among quaternary ammonium salts, (CH _Three CH ₂ ) (CH _Three CH ₂ CH ₂ CH ₂ ) _Three NBF _Four Those having different substituents on the nitrogen of the ammonium ion are preferable from the viewpoint of high solubility in the polymer solid electrolyte or high dissociation constant.
[0059]
Next, an example of the manufacturing method of the electric double layer capacitor of the present invention will be described. The two polarizable electrodes are placed in the capacitor structure so as not to contact each other, or placed on the support. For example, a polarizable electrode is bonded to the end of the electrode via a spacer having an appropriate thickness or a polymer solid electrolyte film prepared in advance, and placed in the structure, and the general formula (1) and / or the general formula At least one electrolyte salt in a mixture of at least one compound having a functional group represented by (2) and a composite oxide (hydrotalcite) fine particle of a specific magnesium and other metal having a high specific surface area and a low water content; In some cases, after injecting a polymerizable composition in which another polymerizable compound and / or a plasticizer and / or a solvent are added and mixed, and then polymerizing, or further after polymerization, a polyolefin resin, if necessary. By sealing with an insulating resin such as an epoxy resin, an electric double layer capacitor in which the electrode and the electrolyte are in good contact can be obtained. In particular, a thin electric double layer capacitor can be manufactured by this method.
[0060]
In addition to this, at least one kind of polymerizable compound, solvent and high specific surface area and low water content of specific magnesium and other metal complex oxide (hydrotalcite) fine particles, or other polymerizable compounds From an electrolyte solution in which two polarizable electrodes are bonded together through a polymer obtained by polymerizing a polymerizable composition to which a compound and / or a plasticizer is added and mixed, and the polarizable electrode is impregnated in advance. It is also possible to manufacture an electric double layer capacitor by transferring a part of the electrolyte salt to a polymer.
[0061]
The capacitor structure or the support may be a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. The shape is not limited to the above, and the shape may be any shape such as a cylinder, a box, a sheet or the like.
[0062]
As the shape of the electric double layer capacitor, in addition to the sheet type as shown in FIG. 2, a coin type, or a sheet-like laminate of a polarizable electrode and a polymer solid electrolyte is wound into a cylindrical shape to form a cylindrical tubular capacitor. It may be a cylindrical type manufactured by sealing in a structure.
When manufacturing a wound type capacitor, the above-mentioned polymerizable composition is further bonded after the polarizable electrodes are bonded and wound through a polymer solid electrolyte film prepared in advance and inserted into the capacitor structure. It is also possible to inject and polymerize.
[0063]
【Example】
The present invention will be described in more detail below with typical examples. Note that these are merely illustrative examples, and the present invention is not limited thereto.
[0064]
Example 1 Synthesis of Compound 3
Embedded image

Compound 1 (KOH value 34.0 mg / g, s / t = 7/3) (50.0 g) and Compound 2 (4.6 g) were dissolved in well-purified tetrahydrofuran (THF) (100 ml) in a nitrogen atmosphere. Dibutyltin dilaurate (0.44 g) was added. Then, the colorless product was obtained by making it react at 25 degreeC for about 15 hours. That ¹ From the results of 1 H-NMR, IR, and elemental analysis, compound 1 and compound 2 reacted 1 to 3, and the isocyanate group of compound 2 disappeared, a urethane bond was formed, and compound 3 was formed. I found out.
[0065]
Example 2: Production of polymer solid electrolyte composite membrane
Compound 3 (1.0 g), hydrotalcite particles heat treated at 500 ° C. (Kyowa Chemical Co., Ltd., KW2200, average particle size of about 1.0 μm, BET specific surface area of 135 m) ² / G, water content 1000 ppm) (0.33 g), ethylene carbonate (EC) (1.8 g), ethyl methyl carbonate (EMC) (4.2 g), LiPF ₆ (Hashimoto Kasei Battery Grade) (0.60 g) and Lucillin TPO (BASF) (0.005 g) were mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content (Karl Fischer method) of this composition was 35 ppm.
This photopolymerizable composition was coated on a polyethylene terephthalate (PET) film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp (FL20S.BL, manufactured by Sankyo Electric Co., Ltd.) for 10 minutes. A compound impregnated with an EC / EMC electrolyte solution 3 polymer / KW2200 composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 5.5 × 10 5 respectively. ^-3 1.4 × 10 ^-3 S / cm.
[0066]
Example 3: Production of polymer solid electrolyte composite membrane
A thermopolymerizable composition was obtained in the same manner as in Example 2 except that peroyl TCP (manufactured by NOF Corporation) (0.01 g) was added instead of lucillin TPO (0.005 g) as an initiator. The water content (Karl Fischer method) of this composition was 35 ppm.
A compound impregnated with an EC / EMC electrolyte solution after coating the thermopolymerizable composition on a PET film under an argon atmosphere, coating a polypropylene (PP) film, and heating on a hot plate at 60 ° C. for 30 minutes. 3 polymer / KW2200 composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 5.3 × 10 5 respectively. ^-3 , 1.0 × 10 ^-3 S / cm.
[0067]
Example 4: Production of solid polymer electrolyte composite membrane
LiPF ₆ Instead of Hashimoto Kasei Battery Grade LiBF _Four A photopolymerizable composition was obtained in the same manner as in Example 2 except that (0.50 g) was used. The water content of this composition (Karl Fischer method) was 45 ppm.
This photopolymerizable composition was applied and irradiated with light in the same manner as in Example 2 to obtain a polymer / KW2200 composite film of Compound 3 impregnated with an electrolytic solution as a free-standing film of about 30 μm. When the ionic conductivity of this solid electrolyte at 25 ° C. and −20 ° C. was measured by the impedance method, it was 4.3 × 10 4. ^-3 , 0.8 × 10 ^-3 S / cm.
[0068]
Example 5: Production of polymer solid electrolyte composite membrane
LiPF ₆ Instead of Hashimoto Kasei high-purity tetraethylammonium tetrafluoroborate (TEAB) (1.00 g), the solvent was EC, and propylene carbonate (PC) (6.0 g) was used instead of EMC. A photopolymerizable composition was obtained. The water content of this composition (Karl Fischer method) was 110 ppm. The photopolymerizable composition was applied and irradiated with light in the same manner as in Example 2 to obtain a polymer / KW2200 composite film of Compound 3 impregnated with a PC electrolyte as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 9.0 × 10 ^-3 , 1.5 × 10 ^-3 S / cm.
[0069]
Example 6: Synthesis of compound 5
Embedded image

[0070]
Compound 4 (average molecular weight 550) (55 g) and compound 2 (15.5 g) were dissolved in well-purified THF (100 ml) in a nitrogen atmosphere, and then dibutyltin dilaurate (0.66 g) was added. Then, the colorless viscous liquid was obtained by making it react at 25 degreeC for about 15 hours. That ¹ From the results of 1 H-NMR, IR, and elemental analysis, Compound 4 and Compound 2 reacted one-to-one, and further, the isocyanate group of Compound 3 disappeared, and a urethane bond was formed. It was found that it was generated.
[0071]
Comparative Example 1: Production of polymer solid electrolyte composite membrane
Compound 3 (0.5 g), Compound 5 (0.5 g), heat-treated magnesium oxide particles at 500 ° C. (manufactured by Kyowa Chemical, Micromag 3-30, average particle size 3.1 μm, BET specific surface area 105 m ² / G, water content 1200ppm) (0.66g), EC (1.8g), EMC (4.2g), LiPF ₆ (Hashimoto Kasei Battery Grade) (0.60 g) and Lucillin TPO (0.005 g) were mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content (Karl Fischer) of this composition was 30 ppm. When this photopolymerizable composition was applied on a PET film in an argon atmosphere and then irradiated with a chemical fluorescent lamp for 10 minutes, a copolymer impregnated with an EC / EMC electrolyte (compound 3 + compound 5) / micromag 3- A 30 composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 4.8 × 10 4 respectively. ^-3 1.2 × 10 ^-3 S / cm.
[0072]
Comparative Example 2: Production of polymer solid electrolyte composite membrane
Compound 3 (0.5 g), Compound 5 (0.5 g), 100 ° C. heat-treated magnesium oxide particles (manufactured by Kyowa Chemical, Micromag 3-30, average particle size 3.1 μm, BET specific surface area 105 m ² / G, water content 8000 ppm) (0.66 g), EC (1.8 g), EMC (4.2 g), LiPF ₆ (Hashimoto Kasei Battery Grade) (0.60 g) and Lucillin TPO (0.005 g) were mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content (Karl Fischer) of this composition was 400 ppm. When this photopolymerizable composition was applied on a PET film in an argon atmosphere and then irradiated with a chemical fluorescent lamp for 10 minutes, a copolymer impregnated with an EC / EMC electrolyte (compound 3 + compound 5) / micromag 3- A 30 composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 4.3 × 10 4 respectively. ^-3 0.8 × 10 ^-3 S / cm.
[0073]
Comparative Example 3: Production of polymer solid electrolyte composite membrane
Compound 6;
Embedded image

[0074]
(Japanese fats and oils, Bremer AE-400, Mw400) (0.3 g), compound 3 (0.7 g), 500 ° C. heat treated micromag 3-30 (0.66 g), EC (1.8 g), diethyl carbonate (DEC) (4.2 g ), LiBF _Four (Hashimoto Kasei Battery Grade) (0.40 g) and Lucillin TPO (0.005 g) were mixed well in an argon atmosphere to obtain a photopolymerizable composition. The water content (Karl Fischer) of this composition was 80 ppm.
When this photopolymerizable composition was applied on a PET film in an argon atmosphere and then irradiated with a chemical fluorescent lamp for 10 minutes, a copolymer (compound 3 + compound 6) / micromag 3-impregnated with an EC / DEC electrolyte was used. A 30 composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 3.8 × 10 6 respectively. ^-3 , 0.6 × 10 ^-3 S / cm.
[0075]
Example 7: Production of polymer solid electrolyte composite membrane
A thermopolymerizable composition was obtained in the same manner as in Example 5 except that peroyl TCP (manufactured by NOF Corporation) (0.04 g) was added as an initiator instead of lucillin TPO (0.005 g). The water content of this composition (Karl Fischer method) was 120 ppm. After applying this heat-polymerizable composition onto a PET film in an argon atmosphere, coating the PP film, and heating on a hot plate at 80 ° C. for 1 hour, a polymer of Compound 3 impregnated with a PC electrolyte solution / KW2200 composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by the impedance method, it was 8.8 × 10 4 respectively. ^-3 1.6 × 10 ^-3 S / cm.
[0076]
Example 8: Production of lithium cobaltate positive electrode
Li ₂ CO _Three (11g) and Co _Three O _Four (24 g) was mixed well, heated at 800 ° C. for 24 hours in an oxygen atmosphere, and then pulverized to thereby produce LiCoO. ₂ A powder was obtained. This LiCoO ₂ The powder, acetylene black, and polyvinylidene fluoride were mixed at a weight ratio of 8: 1: 1, and an excess N-methylpyrrolidone solution was added to obtain a gel composition. This composition was applied and molded on an aluminum foil of about 25 μm to a thickness of 10 mm × 10 mm and about 180 μm. Furthermore, by heating and vacuum drying at about 100 ° C. for 24 hours, a lithium cobaltate positive electrode (75 mg) was obtained.
[0077]
Example 9: Production of graphite negative electrode
MCMB graphite (manufactured by Osaka Gas), gas phase method graphite fiber (manufactured by Showa Denko KK: average fiber diameter, 0.3 μm, average fiber length, 2.0 μm, heat treated product at 2700 ° C.), weight ratio of polyvinylidene fluoride 8.6: 0.4 : An excess N-methylpyrrolidone solution was added to the 1.0 mixture to obtain a gel composition. This composition was applied and molded on a copper foil of about 15 μm to a thickness of 10 mm × 10 mm and about 250 μm. Furthermore, a graphite negative electrode (35 mg) was obtained by heating and vacuum drying at about 100 ° C. for 24 hours.
[0078]
Example 10: Production of Li-ion secondary battery
In the argon atmosphere glove box, the graphite negative electrode (10 mm × 10 mm) produced in Example 9 was applied to the electrolyte (1M LiPF). ₆ / EC + EMC (3: 7)) impregnated with the polymer solid electrolyte (compound 3) / KW2200 composite film (12 mm × 12 mm) prepared in Example 2, and cobalt produced in Example 8 Lithium acid positive electrode (10mm x 10mm) and electrolyte (1M LiPF ₆ / EC + EMC (3: 7)) impregnated with each other and the ends of the battery were sealed with an epoxy resin to obtain a graphite / cobalt oxide Li ion secondary battery having the structure shown in FIG. When this battery was charged and discharged at 60 ° C., 25 ° C., and −10 ° C. with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 5.6 mAh, respectively. Moreover, when charging / discharging was repeated at 60 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 7.0 mAh, and the cycle life until the capacity decreased to 50% was 350 times. there were.
[0079]
Comparative Example 4: Production of Li-ion secondary battery
Instead of the polymer solid electrolyte (compound 3) / KW2200 composite film, the polymer solid electrolyte (compound 3 + compound 5) / micromag 3-30 film produced in Comparative Example 1 was used. A Li ion secondary battery having the structure shown in FIG. 1 was produced. When this battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C., 25 ° C. and −10 ° C., the maximum discharge capacities were 7.2 mAh, 7.2 mAh and 4.8 mAh, respectively. Moreover, when charging / discharging was repeated at 60 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 7.2 mAh, and the cycle life until the capacity decreased to 50% was 280 times. there were.
[0080]
Comparative Example 5: Production of Li-ion secondary battery
Instead of the polymer solid electrolyte (compound 3) / KW2200 composite film, the same procedure as in Example 10 was used, except that the polymer solid electrolyte (compound 3 + compound 5) / micromag 3-30 film produced in Comparative Example 2 was used. A Li ion secondary battery having the structure shown in FIG. 1 was produced. When this battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C., 25 ° C. and −10 ° C., the maximum discharge capacities were 7.0 mAh, 6.8 mAh and 4.0 mAh, respectively. Moreover, when charging / discharging was repeated at 60 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 6.6 mAh, and the cycle life until the capacity decreased to 50% was 125 times. there were.
[0081]
Example 11: Production of Li-ion secondary battery
In the argon atmosphere glove box, the graphite negative electrode (10 mm × 10 mm) produced in Example 9 was applied to the electrolyte (1M LiPF). ₆ / EC + EMC (3: 7)), the compound 3 / KW2200 photopolymerizable composition prepared in Example 2 was applied to a thickness of 30 μm, and a chemical fluorescent lamp was applied under an argon atmosphere to 10 Upon partial irradiation, a polymer solid electrolyte (compound 3) / KW2200 composite film impregnated with the electrolytic solution was directly formed on the graphite negative electrode. Furthermore, an electrolytic solution (1M LiPF) was added to the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 8. ₆ / EC + EMC (3: 7)) impregnated with each other and the ends of the battery were sealed with an epoxy resin to obtain a graphite / cobalt oxide Li ion secondary battery having the structure shown in FIG. When this battery was charged and discharged at 60 ° C., 25 ° C., and −10 ° C. with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 6.0 mAh, respectively. Moreover, when charging / discharging was repeated at 60 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 7.2 mAh, and the cycle life until the capacity decreased to 50% was 330 times. there were.
[0082]
Example 12: Production of an all-solid-state Li-ion secondary battery
In an argon atmosphere glove box, a graphite negative electrode (10 mm × 10 mm) produced in Example 9 was impregnated with the thermopolymerizable composition prepared in Example 3, and the polymer solid electrolyte prepared in Example 2 ( Compound 3) / KW2200 composite film (12 mm × 12 mm) was bonded, and the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 8 was impregnated with the thermopolymerizable composition prepared in Example 3. The battery ends are sealed with an epoxy resin, and the thermopolymerizable composition is cured at 70 ° C. for 1 hour to obtain a graphite / cobalt oxide-based all solid Li ion secondary battery having the structure shown in FIG. It was. When this battery was charged and discharged at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA at 60 ° C., 25 ° C. and −10 ° C., the maximum discharge capacities were 7.2 mAh, 6.8 mAh and 2.5 mAh, respectively. Moreover, when charging / discharging was repeated at 60 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 6.8 mAh, and the cycle life until the capacity decreased to 50% was 410 times. there were.
[0083]
Example 13: Production of activated carbon electrode
An excess N-methylpyrrolidone solution was added to a mixture of coconut shell activated carbon and polyvinylidene fluoride in a weight ratio of 9.0: 1.0 to obtain a gel composition. This composition was applied on a stainless steel foil in a size of 10 mm × 10 mm to a thickness of about 150 μm. It vacuum-dried at about 100 degreeC for 10 hours, and obtained the activated carbon electrode (14.0 mg).
[0084]
Example 14: Production of an electric double layer capacitor
In an argon atmosphere glove box, two electrodes were prepared by impregnating the activated carbon electrode (14 mg) 10 mm × 10 mm produced in Example 13 with an electrolyte (1M TEAB / PC). Next, the polymer solid electrolyte (compound 3) / KW2200 composite film (12 mm × 12 mm) produced in Example 5 was bonded to one electrode, and another electrode was bonded, and the capacitor end was bonded to an epoxy resin. The electric double layer capacitor having the structure shown in FIG. 2 was manufactured. When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.2 mA at 60 ° C. and 25 ° C., the maximum capacity was 470 mF and 470 mF. Further, the maximum capacity at 60 ° C. and 2.5 mA was 430 mF, and there was almost no change in capacity even when charging and discharging were repeated 50 times.
[0085]
Example 15: Production of an all-solid-state electric double layer capacitor
In an argon atmosphere glove box, two electrodes were prepared by impregnating the activated carbon electrode (14 mg) 10 mm × 10 mm produced in Example 13 with the thermopolymerizable composition prepared in Example 7. Next, the polymer solid electrolyte (compound 3) / KW2200 composite film (12 mm × 12 mm) produced in Example 5 was bonded to one electrode, and another electrode was bonded, and the capacitor end was bonded to an epoxy resin. Then, the thermopolymerizable composition was heated and polymerized at 70 ° C. for 1 hour to produce an all-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 0.2 mA at 60 ° C. and 25 ° C., the maximum capacity was 460 mF and 410 mF. Further, the maximum capacity at 60 ° C. and 2.5 mA was 410 mF, and the capacity was hardly changed even after repeated charging and discharging 50 times.
[0086]
Example 16: Production of polymer solid electrolyte composite membrane
Compound 3 (1.0 g), hydrotalcite particles heat-treated at 500 ° C. (Kyowa Chemical, KW2200, average particle size of about 1.0 μm, BET specific surface area of 135 m ² / G, water content 1000 ppm) (0.33 g), ethylene carbonate (EC) (1.8 g), ethyl methyl carbonate (EMC) (4.2 g), and Lucillin TPO (BASF) (0.005 g) in an argon atmosphere. Mix well to obtain a photopolymerizable composition. The water content of this composition (Karl Fischer method) was 30 ppm. This photopolymerizable composition was applied on a polyethylene terephthalate (PET) film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp (FL20S.BL manufactured by Sankyo Electric Co., Ltd.) for 10 minutes. As a result, Compound 3 impregnated with an EC / EMC solvent The polymer / KW2200 composite film was obtained as a free-standing film of about 30 μm. This film was added to the electrolyte (1.2M LiPF ₆ / EC + EMC (weight ratio 3: 7)) for about 1 hour, LiPF in the film ₆ Salt was added afterwards. When the ionic conductivity at 25 ° C. and −20 ° C. of this film was measured by the impedance method, it was 6.1 × 10 respectively. ^-3 1.6 × 10 ^-3 S / cm.
[0087]
Example 17: Production of Li-ion secondary battery
In an argon atmosphere glove box, the graphite negative electrode (10 mm × 10 mm) produced in Example 9 was applied to the electrolyte (1.2 M LiPF). ₆ / EC + EMC (3: 7)) and the polymer / KW2200 composite film (12 mm × 12 mm) of Compound 3 impregnated with the EC / EMC solvent prepared in Example 16 were bonded together. Electrolytic solution (1.2M LiPF) on lithium cobaltate positive electrode (10mm × 10mm) manufactured in ₆ / EC + EMC (3: 7)) impregnated with each other and the ends of the battery were sealed with an epoxy resin to obtain a graphite / cobalt oxide Li ion secondary battery having the structure shown in FIG.
When this battery was charged and discharged at 60 ° C., 25 ° C., and −10 ° C. with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh, 7.2 mAh, and 6.0 mAh, respectively. Moreover, when charging / discharging was repeated at 60 ° C., operating voltage 2.75 to 4.1 V, charging 0.5 mA, discharging 3.0 mA, the maximum discharge capacity was 7.1 mAh, and the cycle life until the capacity decreased to 50% was 320 times. there were.
[0088]
Example 18: Production of an electric double layer capacitor
In an argon atmosphere glove box, two electrodes were prepared by impregnating the activated carbon electrode (14 mg) 10 mm × 10 mm produced in Example 13 with an electrolytic solution (1.2 M TEAB / PC). Next, the polymer / KW2200 composite film (12 mm × 12 mm) of the compound 3 impregnated with the EC / EMC solvent produced in Example 16 was bonded to one electrode, and another electrode was bonded to the capacitor end. The electric double layer capacitor having the structure shown in FIG. 2 was manufactured by sealing the part with an epoxy resin. When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.2 mA at 60 ° C. and 25 ° C., the maximum capacity was 470 mF and 470 mF. The maximum capacity at 60 ° C. and 2.5 mA was 450 mF, and there was almost no change in capacity even when charging and discharging were repeated 50 times.
[0089]
【The invention's effect】
The polymer compound of the present invention, a high solid electrolyte polymer electrolyte including fine oxide (hydrotalcite) fine particles of magnesium and other metals and an electrolyte salt has good membrane strength and high ionic conductivity. It has excellent processability, and also has high current characteristics and high temperature durability compared to conventional solid polymer electrolytes. The battery and the electric double layer capacitor using the polymer solid electrolyte of the present invention can be used stably for a long period of time without risk of liquid leakage because the ion conductive material is solid, and this solid electrolyte is used. Thus, a thin battery or capacitor can be manufactured.
[0090]
In addition, by using the solid polymer electrolyte of the present invention, thinning is easy, it can operate at high capacity, has a long life, high current characteristics, high temperature durability, reliability, stability, and excellent workability. A secondary battery is obtained. This secondary battery is a battery that can operate at high capacity and high current as an all-solid-state battery, has good cycleability, and is excellent in safety and reliability. It can be used as a power source for electric products, an electric vehicle, and a large power source for road leveling. Since it can be easily thinned, it can also be used as a paper battery such as an ID card.
[0091]
Furthermore, by using the solid polymer electrolyte of the present invention, an electric double layer capacitor having a high output voltage, a large take-out current, a long life, excellent high temperature durability, workability, reliability, and stability can be obtained. . The electric double layer capacitor of the present invention can operate at a high voltage, a high capacity, and a high current, or has a good cycleability, safety and reliability compared to conventional capacitors. It can be used not only as a power source but also as a power source for various electric products when used in combination with a small battery. Moreover, since it is excellent in workability, such as thin film formation, it can be expected for uses other than those of conventional electric double layer capacitors.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an embodiment of a thin battery which is an example of a battery according to the present invention.
FIG. 2 is a schematic cross-sectional view of an embodiment of an electric double layer capacitor according to the present invention.
[Explanation of symbols]
1 Positive electrode
2 Polymer solid electrolyte
3 Negative electrode
4 Current collector
5 Insulating resin sealant
6-polar electrode
7 Current collector
8 Polymer solid electrolyte membrane
9 Insulating resin sealant
10 Lead wire

Claims (14)

A polymer solid electrolyte containing at least one polymer compound and at least one electrolyte salt, or a polymer solid electrolyte further containing at least one organic solvent has a BET specific surface area of 30 m ² / g or more and a maximum particle size. A solid polymer electrolyte characterized in that mixed oxide (hydrotalcite) fine particles of magnesium and other metals having a content of 10 μm or less and a water content of 3000 ppm or less are added in the range of 0.5 to 50% by weight. . The polymer compound is represented by the general formula (1) and / or the general formula (2).

(In the formula, R ¹ and R ² represent a hydrogen atom or an alkyl group, and R ³ represents a divalent group optionally containing a hetero atom having a linear, branched or cyclic structure having 1 to 10 carbon atoms. X is an integer of 0 or 1 to 10, provided that R ¹ , R ² , R ³ and x existing in the same molecule may be the same or different. The polymer solid electrolyte according to claim 1, which is a polymer of at least one heat and / or actinic ray polymerizable compound having a functional functional group.   The polymer solid electrolyte according to claim 1 or 2, wherein the electrolyte salt is selected from an alkali metal salt, a quaternary ammonium salt, a quaternary pyridinium salt, and a quaternary phosphonium salt.   The polymer solid electrolyte according to any one of claims 1 to 3, wherein the organic solvent is a carbonate compound. The polymer solid electrolyte according to claim 3, wherein the electrolyte salt is LiPF ₆ and / or LiBF ₄ and / or LiN (CF ₃ SO ₃ ) ₂ .   A battery comprising the solid polymer electrolyte according to any one of claims 1 to 5.   As a negative electrode of a battery, lithium, lithium alloy, or a carbon material capable of occluding and releasing lithium ions, an inorganic oxide capable of occluding and releasing lithium ions, an inorganic chalcogenide capable of occluding and releasing lithium ions, and a conductive polymer compound capable of occluding and releasing lithium ions. The lithium battery according to claim 6, wherein at least one selected material is used.   6. An electric double layer capacitor in which a polarizable electrode is disposed via an ion conductive material, wherein the ion conductive material is a solid polymer electrolyte according to claim 1. Capacitor. General formula (1) and / or general formula (2)

(The symbols in the formula represent the same meaning as described in claim 2 ) and at least one heat and / or actinic ray polymerizable compound having a polymerizable functional group, and a BET specific surface area of 30 m ² / g. Above, a polymerizable mixture containing composite oxide (hydrotalcite) fine particles of magnesium and other metals having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one electrolyte salt, or A method for producing a solid polymer electrolyte, comprising: placing a polymerizable mixture to which at least one organic solvent is added on a substrate; and curing the polymerizable mixture by heating and / or actinic ray irradiation. General formula (1) and / or general formula (2)

(The symbols in the formula represent the same meaning as described in claim 2 ) and at least one heat and / or actinic ray polymerizable compound having a polymerizable functional group, and a BET specific surface area of 30 m ² / g. A polymerizable mixture containing magnesium and other metal composite oxide (hydrotalcite) particles having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less and at least one organic solvent is formed on the substrate. The polymer solid mixture is cured by heating and / or actinic ray irradiation after being placed on the substrate, and impregnated with an electrolyte salt by bringing the resulting cured product into contact with an electrolytic solution. . General formula (1) and / or general formula (2)

(The symbols in the formula represent the same meaning as described in claim 2 ) and at least one heat and / or actinic ray polymerizable compound having a polymerizable functional group, and a BET specific surface area of 30 m ² / g. Above, a polymerizable mixture containing composite oxide (hydrotalcite) fine particles of magnesium and other metals having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one electrolyte salt, or A method for producing a battery, comprising: placing a polymerizable mixture to which at least one organic solvent has been added in a battery structure or placing the polymerizable mixture on a support; and then curing the polymerizable mixture. General formula (1) and / or general formula (2)

(The symbols in the formula represent the same meaning as described in claim 2 ) and at least one heat and / or actinic ray polymerizable compound having a polymerizable functional group, and a BET specific surface area of 30 m ² / g. Thus, a polymerizable mixture containing magnesium and other metal composite oxide (hydrotalcite) particles having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less and at least one organic solvent is used for battery construction. A method for producing a battery, wherein the polymerizable mixture is cured after being placed in a structure or disposed on a support, and the resulting cured product is impregnated with an electrolyte solution to be impregnated with the electrolyte salt. General formula (1) and / or general formula (2)

(The symbols in the formula represent the same meaning as described in claim 2 ) and at least one heat and / or actinic ray polymerizable compound having a polymerizable functional group, and a BET specific surface area of 30 m ² / g. Above, a polymerizable mixture containing composite oxide (hydrotalcite) fine particles of magnesium and other metals having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one electrolyte salt, or An electric double layer capacitor characterized in that a polymerizable mixture to which at least one organic solvent is added is placed in a structure for constituting an electric double layer capacitor or disposed on a support, and then the polymerizable mixture is cured. Production method. General formula (1) and / or general formula (2)

(The symbols in the formula represent the same meaning as described in claim 2 ) and at least one heat and / or actinic ray polymerizable compound having a polymerizable functional group, and a BET specific surface area of 30 m ² / g. An electric double layer comprising a polymerizable mixture containing magnesium and other metal composite oxide (hydrotalcite) particles having a maximum particle size of 10 μm or less and a water content of 3000 ppm or less, and at least one organic solvent. After being placed in a capacitor structure or disposed on a support, the polymerizable mixture is cured, and the resulting cured product is impregnated with an electrolyte solution by contacting with an electrolytic solution. Manufacturing method of multilayer capacitor.

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