JP3814074B2 - Non-aqueous electrochemical element - Google Patents

Description

【００１７】
２．図２は請求項２の構成要件を満足する部材の実施態様（実施態様２）を示す図である。
（ａ）および（ｃ）は側面図であり、また（ｂ）および（ｄ）は平面図である。図２中、１６はポリ４フッ化エチレンからなる角型ブロックであり、（ａ）および（ｂ）の１９は角型ブロック１６に設けた貫通孔であり、（ｃ）および（ｄ）の２０は角型ブロック１６に設けた切欠である（他は、従来例または実施態様１と同じ）。前記貫通孔１９により、気体成分の除去による減圧、真空引き、そして電解液の注液の流路として働き、より短時間でかつより確実に行うことができるようになった。貫通孔の下部の孔は、下部のラミネートフィルムに接触しているため、実施態様１の上部の場合の隙間と同様ではあるが、実用上十分な結果であった。また、電極内部の残存気体が減少しているためか、サイクル劣化が減少し、信頼性が向上していることも確認できた。
下表２に、切欠部を設けた場合の本実施態様の実験結果を示す。
【００１８】
３．図３は請求項３の構成要件を満足する部材の実施態様（実施態様３）を示す図である。
（ａ）は側面図、（ｂ）は平面図、（ｃ）は左側面図である。２１は角型ブロック１６に設けた貫通孔であり、これは方向を横方向に変化させてある（他は、従来例または実施態様１と同じ）。この貫通孔２１により、気体成分の除去による減圧、真空引き、そして電解液の注液の流路として働き、より短時間でかつより確実に行うことができるようになった。貫通孔の一方を横にすることにより、実施態様２では下部のラミネートフィルムに接触していて隙間から行っていた真空引きと注液が、確実な流路を確保することができたため、とくに真空引きに要する時間が良好な結果であった。
前記図３に示す横に孔を変化させた場合の他に、切欠部の形状を変化させることも同様に効果があることも確認されている。
下表２に、横に孔を変化させたた場合の本実施態様の実験結果を示す。
【００１９】
４．図４は請求項４の構成要件を満足する部材の実施態様（実施態様４）を示す図である。
（ａ）は平面図、（ｂ）は側面図、また（ｃ）は下部から見た底面図である。
２２ａおよび２２ｂは部材（角型ブロック）１６に設けた貫通孔であり、孔の直径を若干大きくすることにより断面積を大きくしている（他は、従来例または実施態様１と同じ）。この貫通孔２２ａおよび２２ｂにより、気体成分の除去による減圧、真空引き、そして電解液の注液の流路として働き、より短時間でかつより確実に行うことができるようになった。ただし、実施態様の貫通孔と同様にこれは下部のラミネートフィルムに接触しているため、隙間として気体および液体の流路を確保しているので、ブロックの低面積が小さくなったことが作用する影響もあると考えられる。しかし、同様の断面積を大きくすることより注液に効果的なことは、実施態様３の横方向に孔の方向が変化している場合にも確認できた。
下表２に、図４の場合の実施態様の実験結果を示す。
【００２０】
５．図５は請求項５の構成要件を満足する部材の実施態様（実施態様５）を示す図である。
（ａ）は平面図、（ｂ）は側面図、また（ｃ）は側面図である。
２３ａ、２３ｂ、２３ｃは角型ブロック１６に設けた貫通孔であり、これは方向を横方向に変化させ、かつ横方向の断面積が同じになるように半円形をしてある（他は、従来例または実施態様１と同じ）。
貫通孔の一方を横にかつ２分割することにより、流路を２方向に確保できるので、より流路の抵抗の少ない状態を実現しやすくなった。これは、横方向には、端子方向、電極方向、封止部分方向、そしてそれ以外の方向と４つの異なる方向があり、ラミネート封止をした場合に、ラミネートフィルム自体が柔らかいため一様な形になりにくく、流路として２方向を確保しておくことは、片方の流路の口が小さく塞がれ気味でも、もう一方の流路を確保することができるので、効果的である。また、２つの方向が機能した場合にはさらに、流れの方向が異なることがより真空引き、注液をしやすくさせていると考えられる。この分割は、２分割以上、多くても構わない。
下表２に、図５の場合の実験結果を示す。注液以外に、真空引きのタクトを改良することができた。
【００２１】
６．図６は、請求項６の構成要件を満足する部材の実施態様（実施態様６）を示す図であり、側面からみた図である。２４は多孔質ガラスのバイコールガラスと類似したブロックからなっている。形状は、１６のポリ４フッ化エチレンの角型ブロックと同様であるが、材質自体に微少な孔があいており、気体、液体を容易に流すことができる。また、マクロの孔があいていないために、強度が強く、塞いだ外装部材の破損する可能性が小さくなる。
下表２に、図６の場合の実験結果を示す。大きな孔を設けていないにも関わらず、２分割した孔をもつブロックと同様の効果が確認された。
また、このような多孔質体を、ポリ４フッ化エチレンブロックの孔に埋め込むことにより複合させることも同様である。
【００２２】
【表２】

【００２３】
７．図７は、請求項７の構成要件を満足する実施態様（実施態様７）を示す図である。
孔部を有する上部の外装部材５の裏面下部に貫通孔を有する部材１６をあらかじめ接着しておき、これと下部外装部材４との間に、正極、負極、セパレータ、端子から主としてなる電池要素２５を挟みながら位置決め、積層を行った後に、４辺を封止する。これは、上部外装部材と部材１６との位置決めはいらなくなり、２つの孔のずれがなくなるので効果的である。ただし、電池要素に一部が重なると、その段差により１６が傾くため、電池要素との位置決めをきちんと行うことが必要である。下表３に、実施態様１と実施態様７の位置決めとそれにつづく積層の工程タクトを４段階で表示する。あわせて、容器の厚さが厚くなる場合を×、変わらない場合を○として併記する。
【００２４】
８．図８は、本発明の構成要件、孔部または切欠部を有する外装部材と部材の少なくとも一部分とが固定されていることを満足する実施態様（実施態様８）を示す図である。
前記電池要素２５に部材１６をあらかじめ接着しておき、これを上下の外装部材との間に挟みながら位置決め、積層を行った後に、４辺を封止する。これは、電池要素と部材１６との位置決めはいらなくなるため、２つの孔のズレがないようにだけ注意して位置決めするだけであり、片方の孔、とくに外装部材の方の孔を大きくすることにより、簡単に位置決めすることができるようになる。ただし、図示するように電池要素の活物質層のある部分の集電体の使用しない裏面に１６を設けると、電池の厚さがこの部材１６の分だけ増加するため、体積エネルギー密度的には若干落ちる。しかし、簡単に、接着、位置決め、積層ができるようになる。
下表３に、実施態様１と本実施態様８の位置決めとそれにつづく積層の工程タクトを４段階で表示する。あわせて、容器の厚さが厚くなる場合を×、変わらない場合を○として併記する。
【００２５】
９．図９は、本発明の構成要件を満足する実施態様（実施態様９）を示す図である。
（ａ）は平面図、（ｂ）は側面断面図である。前記電池要素２５の集電体１と端子６との接続部分に細長の部材２６をあらかじめ接着しておき、これを上下の外装部材との間に挟みながら位置決め、積層を行った後に、４辺を封止する。これは、電池要素と部材２６との位置決めはいらなくなるため、２つの孔のズレがないようにだけ注意して位置決めするだけであり、片方の孔、とくに外装部材の方の孔を大きくすることにより、簡単に位置決めすることができるようになる。また、図示するように電池要素の活物質層の存在しない部分に２６を設けているので、全体の厚さを増加させない。ただ、部材２６の構造が端子の厚さを避ける形状になるため複雑になり、部品コストはわずかながら上昇する。
下表３に、実施態様１と本実施態様９の位置決めとそれにつづく積層の工程タクトを４段階で表示する。あわせて、容器の厚さが厚くなる場合を×、変わらない場合を○として併記する。
【００２６】
【表３】

【００２７】
１０．図１０は、本発明の構成要件を満足する実施態様（実施態様１０）を示す概要図であり、（ａ）は外装部材の孔２８が上面にある場合であり、（ｂ）は外装部材の孔２８が側面または複数の外装部材より形成される場合であり、２７は細長の部材であり、この２７には、正極および負極の外部端子２９、３０があらかじめ埋め込まれており、外容器の内部で内部端子と接続しており、３１は２７に設けた孔であり、３２はその孔３１を塞ぐ外装部材であり、３３は熱融着部である。
図１０の（ａ）は、注液用の部材を兼用することにより、コンパクトで信頼性に優れた強い端子を簡単に実現すると同時に、外装部材の孔の数は同じであるため、水分増加等の封止不良が生じにくい。また、図１０の（ｂ）はさらに、端子を偏平な方向に設けられていることから、外部との接続状態においても、偏平な薄さを維持でき、薄型機器に効果的である。
【００２８】
１１．図１１は、本発明の構成要件を満足する実施態様（実施態様１１）を示す図である。
（ａ）はラミネート外装の電池がパッケージまたは機器に固定されて使用される状態であり、（ｂ）はラミネート外装の電池がパッケージまたは機器に固定されかつ薄板状端子から電気的出力を取り出す状態であり、３７は電池、３４はパッケージ、３５は固定用ばね部材、３６は固定用突き当て部材であり、３８ａ、３８ｂは固定兼集電用ばね部材であり、３９は使用機器である。
ラミネート外装は、本来フィルム状の外装であるため強度が小さく、機器内で固定して使用する方法が、他の缶型電池と異なる。つまり、ラミネート部分を挟んで固定するとラミネート部分を破損しやすくなり、薄板の端子部分を挟んで固定すると、端子が破損しやすくなる。しかし、本実施態様では、ラミネート外装の内部に、部材を設けたため、ラミネートを、そのまま、または端子ごと挟んで固定しても、内部の部材によってラミネートフィルムや端子が変形して破損することを防止する効果がある。
従来は、ラミネート外装の外部に封止能力の向上を主な目的として強度の大きい樹脂で被覆した例はあるが、これは厚さも大きくなり、重くなる。実際に電池の脱着を部材がある場合とない場合とで、前記（ａ）および（ｂ）の構造で確認したところ、外装部材や端子の厚さにもよるが、破損不良平均寿命を約２倍以上は大きくでき、信頼性を高めることができることが解った。前記破損不良平均寿命とは、機器への脱着の回数試験において、ラミネートフィルムの破損（目視による変形または容量劣化が急に生じたもの）および端子の破損（目視による変形）を簡易的に調べた結果を指すものである。
【００２９】
１２．図１２は、本発明の構成要件を満足する実施態様（実施態様１２）を示す図である。
側面から見た図であり、外装部材の孔を塞ぐもう一つの外装部材１７の熱融着剤にアイオノマー樹脂層４０を用いることにより、電解液で孔付近が濡れた場合においても、非常に密着力と密閉力の高い封止が行えることが解った。一般的なポリエチレンの場合に比較して、数分の１の水分増加と、５割増しの引き剥がし接着力が得られた。
【００３０】
１３．図１３は、本発明の構成要件を満足する実施態様（実施態様１３）を示す図であり、側面から見た図であり、外装部材の孔を塞ぐもう一つの外装部材自体に、エポキシ接着剤層４１を用いることにより、簡単に外装部材の孔を塞ぐことができた。孔の形状にも自由に対応でき、生産性が増加し、コストは低下した。また、外装部材に融着剤、接着剤、ピッチまたはグリースの少なくとも一つを用いても同様であり、少なくとも最初に粘性をもつものを使用することにより、簡単に孔を塞ぐことが可能となった。もちろん、これらの電解液に対する耐薬品性は、十分に留意する必要がある。
【００３１】
１４．図１４は、本発明の構成要件を満足する実施態様（実施態様１４）を示す図である。
（ａ）の１６は部材であり、横方向に孔を曲げて設けてあり、熱融着層４２に印加する圧力および温度を他の部分よりどちらも若干小さくすることにより、他の部分より内部圧力に対する封止部の破損強度が小さくしたものであり、これは内圧が上昇することにより（ｂ）に示すように開口４３して安全弁としても機能することができ、（ｃ）に示すものはポリプロピレン部材４４に小さな切れ込みを中央部に設けたものであり、これは周辺４５の部分で熱融着をしており、これもまた内庄が増加した場合には、他の外装部材のラミネート部分よりも小さな圧力で破損する強度にしており、中央部から破損して開いて、安全弁として機能することができる。このように、部材と重なる位置に設けた外装部材の孔を塞ぐ外装部材の強度、接着力を小さく設定して設けることにより、部品点数を増加させることなく簡単に安全弁を設けることができる。
【００３２】
以下、詳細に作製方法を説明する．
正極１１はＬｉＣｏＯ₂とグラファイトとＰＶＤＦ（ポリフツ化ビニリデン）を９０：７：３の重量比てＮＭＰ（Ｎ−メチル−２−ピロリドン）溶液に分散させて、これを２０μｍのＡｌ基板に塗布し、１２０度で乾燥して約１００μｍの活物質層をもつ正極電極を作製した。負極はグラファイトとＰＶＤＦを９０：１０の重量比でＮＭＰ溶液に分散させて、これを１０μｍのＣｕ基板に塗布し、１２０度で乾燥して約７０μｍの活物質層をもつ負極電極を作製した。正極電極、負極電極ともロールプレスをしてから用いた。電解液は、ＥＣ（エチレンカーボネート）とＤＭＣ（ジメチルカーボネート）の混合溶媒の１Ｍ−ＬｉＰＦ₆溶液を用いた。セパレータには、空孔部率４０％以上で厚さ２５μｍのものを用いた。
【００３３】
上記正極活物質には、ＬｉＣｏＯ₂以外にＶ₂０₅、ＬｉＮｉＯ₂、ＬｉＭｎ₂Ｏ₄等のリチウムのインターカレーションを伴う酸化物やポリアニリン、ポリピロール等の高分子材料等の非水系２次電池正極材料、従来の乾電池、アルカリ電池、ニッケル水素電池等の水系の１次、２次電池材料などを用いても同様である。また、正極活物質に混合するグラファイトは、天然グラファイトでも人工グラファイトでもよく、非結晶カーボンでもよい。また、結着剤には、ＰＶＤＦ以外に、フツ素含有のＮＭＰ可溶のポリマーや、ＰＶＰ（ポリビニルピロリドン）等でもよい。
【００３４】
電解液には、アクリレート系モノマーと熱重合開始剤を含む非水系電解液を用いた。具体的には、エチレンカーボネートとジメチルカーボネートの等量混合溶媒に１．５ＭのＬｉＰＦ₆を溶解した電解液に、約１３ｗｔ％の単官能モノマーと０．２ｗｔ％の３官能モノマーと熱重合開始剤を加えたものを用いた。実際には、真空引きの場合と同様ポリ４フッ化エチレンからなる部材１６とラミネートフィルム５との間に微小な隙間部分から電解液がラミネート外装容器中へゆっくりではあるが注液される。注液が終了した後、この孔１３の上部に別のラミネートフィルムからなる外装部材１７を配置し、この部分の上下を挟んで圧力と上部にのみ温度１３０度を短時間だけ印加することにより、熱融着をおこない孔１３を塞ぐ。その後、外装容器全体を６０度に１時間放置することにより、モノマーの重合を行い、電解液をゲル化して固体電解質にしてポリマー電池を作製する。
【００３５】
上記アクリル系モノマーを含み、熱重合によるゲル化可能な固体電解質を構成する注液するもとの電解液には、炭酸系エステルである環状カーボネートや鎖状カーボネート、またカルボン酸系エステル、アセトニトリル、ジメチルホルムアミド、ジメチルスルホキシド等の非水系電解液でもよく、さらに非水系２次電池でない場合は水でもよい。また、支持塩には、ＬｉＢＦ₄、ＬｉＣｌＯ₄、ＬｉＡｓＦ₆、ＬｉＳＯ₃ＣＦ₃、ＬｉＣ（ＳＯ₂ＣＦ₃）₃、ＬｉＮ（ＳＯ₂ＣＦ₃）₂等でもよい。また、上記の電解質を含むアクリル系モノマー以外にも、ポリアクリロニトリル、ポリエチレンオキサイド、ポリビニル共重合体等のポリマー粒子を分散していてもよい。また、ＰＶＤＦ−ＨＦＰ系ポリマーでもよい。
また、セパレータは、ポリマーを用いた場合には使用しなくてもよい。
【００３６】
熱重合開始剤としては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、ラウロイルパーオキサイド、エチルメチルケトンペルオキシド、ビス−（４−ｔ−ブチルシクロへキシル）パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート等のパーオキシジカーボネート等を挙げることができる。
アクリレート系モノマーとしては、（メタ）アクリレート、詳しくはアクリレートまたはメタアクリレートがあり、単官能アクリレートとしては、アルキル（メタ）アクリレート｛メチル（メタ）アクリレート、ブチル（メタ）アクリレート、トリフルオロエチル（メタ）アクリレート等｝、脂環式（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート（ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート等）、ヒドロキシポリオキシアルキレン（オキシアルキレン基の炭素数は好ましくは１〜４）（メタ）アクリレート｛ヒドロキシポリオキシエチレン（メタ）アクリレート、ヒドロキシポリオキシプロピレン（メタ）アクリレート等｝およびアルコキシアルキル（アルコキシ基の炭素数は好ましくは１〜４）（メタ）アクリレート｛メトキシエチルアクリレート、エトキシエチルアクリレート、フェノキシエチルアクリレート等｝が挙げられる。三官能以上の多官能（メタ）アクリレートの例としては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールへキサ（メタ）アクリレート等が好ましい。
その他の（メタ）アクリレートの具体例としては、たとえばメチルエチレングリコール（メタ）アクリレート、エチルエチレングリコール（メタ）アクリレート、プロピルエチレングリコール（メタ）アクリレート、フェニルエチレングリコール、エトキシジエチレングリコールアクリレート、メトキシエチルアクリレート、メトキシジエチレングリコールメタクリレート、メトキシトリエチレングリコールアクリレート、メトキシトリエチレングリコールメタクリレート、メトキシテトラエチレングリコールメタクリレート等のアルキルエチレングリコール（メタ）アクリレート、エチルプロピレングリコールアクリレート、ブチルプロピレングリコールアクリレート、メトキシプロピレングリコールアクリレート等のアルキルプロピレングリコール（メタ）アクリレート等が挙げられる。
これらのアクリレート系モノマーと熱重合開始剤を最適な処方で用いることにより、６０度、１時間でも、熱重合を行いゲル化させポリマー電解質を得ることが可能である。
【００３７】
上記ラミネートフィルムは、２５μｍ厚のアルミニウムに電極側に融着材料であるポリエチレンを被覆してあり、外側に同様にポリエステル等のポリマーを被覆してある融着材料であってもよい。内側の熱融着剤としては、ポリエチレン以外に、ポリプロピレン等のポリオレフィン、カルボキシル基を含む変性ポリオレフィン、イオノマーでもよく、また接着剤層としてホットメルト樹脂を用ちいてもよく、またエポキシ樹脂の接着剤層を封止部だけにもうけてもよい。
外側の被覆には、ポリイミド、ポリアミド、ポリフェニレンオキシド等でもよく、また内側と同じポリオレフィン系の融着材料でもよい。ただし、別の外装部材１７との密着力に優れることが必要である。また、ラミネートフィルムでなくとも、少なくとも一方がハードケースであり、ケースの封止を融着材または接着剤等により行うものであってもよい。また封止部のフィルム構造は、外装部材の電極がある厚さと比較して十分に薄くて融着または接着を用いていれば、見かけ上フィルム的でなくてもかまわない。
【００３８】
【効果】
（１）信頼性の高い真空注液を短時間に行えることができる
（２）請求項７及び８記載の発明により、電池製作時の位置決め、積層の工程を短時間で行うことができる。
（３）請求項９記載の発明により、コンパクトで信頼性に優れた強い端子を簡単に実現できる。
（４）部材と重なる外装部材の外側の一部に、破損しにくい高い信頼性の電池を提供できる。
（５）請求項１０記載の発明により、簡単に安全弁として兼用することができる。
【図面の簡単な説明】
【図１】 本発明の構成要件を満足する１実施態様を説明する図である。（ａ）は側面図、（ｂ）は平面図である。
【図２】 本発明の構成要件を満足する部材の１実施態様を説明する図である。
（ａ）および（ｃ）は側面図であり、また（ｂ）および（ｄ）は平面図である。
【図３】 本発明の構成要件を満足する部材の１実施態様を説明する図である。
（ａ）は側面図、（ｂ）は平面図、（ｃ）は左側面図である。
【図４】 本発明の構成要件を満足する部材の１実施態を説明する図である。
（ａ）は平面図、（ｂ）は側面図、また（ｃ）は下部から見た底面図である。
【図５】 本発明の構成要件を満足する部材の１実施態様を説明する図である。
（ａ）は平面図、（ｂ）は側面図、また（ｃ）は左側面図である。
【図６】 本発明の構成要件を満足する部材の１実施態様を説明する図であり、側面からみた図である。
【図７】 本発明の構成要件を満足する１実施態様を説明する図である。
【図８】 本発明の構成要件を満足する１実施態様を説明する図である。
【図９】 本発明の構成要件を満足する１実施態様を説明する図である。
（ａ）は平面図、（ｂ）は側面図である。
【図１０】 本発明の構成要件を満足する１実施態様を示す概要図である。（ａ）は外装部材の孔２８が上面にある場合であり、（ｂ）は外装部材の孔２８が側面にあり、この部材が１つまたは複数の外装部材に接している場合である。
【図１１】 本発明の構成要件を満足する１実施態様を説明する図である。（ａ）はラミネート外装の電池がパッケージまたは機器に固定されて使用される状態であり、（ｂ）はラミネート外装の電池がパッケージまたは機器に固定されかつ薄板状端子から電気的出力を取り出す状態を示す。
【図１２】 本発明の構成要件を満足する１実施態様を説明する図である。
【図１３】 本発明の構成要件を満足する１実施態様を説明する図である。
【図１４】 本発明の構成要件を満足する１実施態様を説明する図である。（ａ）は、熱融着層４２に印加する圧力および温度を他の部分より小さくして熱融着した状態を示す図、（ｂ）は、内圧により孔部が開口した状態を示す図および（ｃ）は、小さな切れ込みを設けたポリプロピレン部材を孔部に熱融着して塞いだ状態を示す図である。
【図１５】 従来例の偏平型電池を説明する図である。
（ａ）は断面図であり、（ｂ）は平面図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrochemical element having a novel exterior structure using a film-like exterior member at least in part, particularly a flat type comprising a non-aqueous electrolyte. Non-aqueous It is applied to a capacitor or battery which is an electrochemical element, and further to a Li secondary battery, particularly a LiI ion battery and a polymer type Li ion battery.
[0002]
[Prior art]
1. JP 60-117542 A
This is a manufacturing method in which a solid electrolyte battery terminal covered with a laminate film has a hollow structure and can be evacuated therefrom. However, it is difficult to easily seal a terminal having a hollow structure made of a conductive metal or the like, and since it tends to be thick, moisture or the like tends to enter from the outside.
2. JP-A-2-139873
This is a manufacturing method in which two outlets are provided on the outer packaging material of a thin secondary battery to inject liquid. However, when the vacuum injection is performed, the mouth tends to collapse when the pressure is reduced to a certain level or more, and it takes time to obtain a sufficient vacuum, or a jig such as a thin injection nozzle is required.
3. JP 60-49568 A
This is a solid electrolyte battery in which the sealing performance is improved by coating the outside of the solid electrolyte battery covered with a laminate film with a thermosetting resin. At the same time, the strength can be increased, but the flexibility of the laminate film is impaired, and at the same time, a mold is required and the mass productivity is lacking.
[0003]
A lightweight thin secondary battery for portable devices or a lightweight large secondary battery for automobiles is desired. As an exterior container for this purpose, it is inexpensive, lightweight, small and highly reliable as well as a simple manufacturing process. is necessary.
As a non-aqueous flat battery outer container using a conventional laminated film-like heat-sealing resin or the like as a main outer member, its sealed and sealed structure, terminal extraction structure, and manufacturing process enabling it, etc. Various improvements have been made. In general, after a battery element including an electrochemical reaction element is included in a laminate film, at least a part of the periphery of the laminate film is thermally fused to perform sealing. In addition, since the outer packaging material itself is flat and the sealing portion is flat, the terminal portion is not a terminal like a single type dry battery, but the electrode current collector is directly placed in the plane direction of the flat outer packaging material. A structure is used in which the terminal is exposed (Japanese Patent Laid-Open No. 57-174860) or the terminal of the sealing portion of the exterior material is sealed together and the terminal is taken out in the sealing direction (Japanese Patent Laid-Open No. 62-61268). It is done.
[0004]
Furthermore, these battery elements need to be impregnated with an electrolyte during the manufacturing process. In the case where the battery element is integrated with the battery element using a solid electrolyte that has been solidified or gelled in advance, the battery element impregnation step of this electrolytic solution can be omitted, but a battery having a liquid electrolyte that is not a solid electrolyte, or a solid electrolyte When a battery element electrolytic impregnation step is required as a solidification or gelation step or a pre-step, it is necessary to lower the water concentration of the electrolyte and lower the dissolved gas concentration. Desirably, it is more preferable if it can be performed without being exposed to the atmosphere.
[0005]
Even in the case of a polymer battery, an electrolytic solution or a container containing an electrolytic solution may be injected. As a specific example, an electrolytic solution in which a PAN-based, acrylate-based, or PVDF-based polymer is dispersed is injected after the battery element is sealed. When it is heated and gelled, or when a battery element containing a PVDF-HFP polymer part is sealed and then injected and gelled, or after the battery element is sealed, an acrylate system In some cases, an electrolytic solution that dissolves the monomer and the thermal polymerization initiator is injected and then heated to gel. However, an exterior member using a laminate film, which is a film-like exterior member, differs from a strong can-type exterior member made of iron, stainless steel, or aluminum used in a normal battery, and has a large degree of freedom in shape and sealing. In spite of the characteristics of being light and thin, it is difficult to perform the liquid injection step after sealing because of its low strength.
[0006]
For this reason, as shown in, for example, Japanese Patent Laid-Open No. 2-139873, two outlets are provided, and the electrolyte solution is simply impregnated into the battery element by flowing the electrolyte solution as a post-process after laminating and sealing using this. be able to. However, even in this method, it is difficult to completely impregnate the electrolyte component in a short time to the minute part of the electrode of the battery element, and a minute gas component remains, which inhibits the electrochemical reaction of the active material of the electrode. In addition to degrading the capacity, the Li / Ion battery's local capacity ratio between the positive electrode and the negative electrode deviates from the design value, thereby increasing the cycle deterioration or, in some cases, depositing Li on the negative electrode to significantly reduce the safety. There is a case.
[0007]
In addition, a method of removing gas components in the battery element in advance from one port by vacuum or pressure reduction and injecting it into the battery is generally performed for can-type batteries. However, if it is carried out from one port, the strength of the laminate exterior is small, so the suction port itself tends to be crushed by the internal reduced pressure, and gas components often remain in the fine parts of the electrode of the battery element. In addition, when injecting, the part that is originally sealed and inflated is inflated, and the electrolyte is injected from there, so the shape of the laminate exterior is easier to swell than originally, and a little more electrolyte is injected. It is easy to control the amount of electrolyte. Furthermore, since the inner surface of the liquid injection port is easily wetted with the electrolyte, the reliability of sealing at that portion is slightly reduced.
[0008]
Moreover, when the electrolyte solution is injected from a liquid injection port provided in advance by evacuating the entire laminate-sealed product inside and outside and then submerging it in the electrolyte solution, The electrolyte solution can be impregnated to the fine part of the electrode. This is a method that is also used for medium-sized capacitors and the like. However, the larger the battery, the longer it takes, the greater the waste of electrolyte and deterioration due to the atmosphere, and the higher the cost. Moreover, since not only the liquid injection port but all the outside of the exterior member gets wet with the electrolyte, it is necessary to clean it.
[0009]
Further, as disclosed in, for example, Japanese Patent Application Laid-Open No. 60-117542, there is a manufacturing method in which a terminal of a solid electrolyte battery covered with a laminate film has a hollow structure and can be evacuated therefrom. This can also be poured using this hollow structure. However, it is difficult to easily seal a terminal having a hollow structure made of a conductive metal or the like, and since it tends to be thick, moisture or the like tends to enter from the outside. Further, when the inner diameter is reduced, the liquid injection speed is reduced. In addition, since the strength of this laminate exterior is weaker than that of a can type, when other parts are provided on the laminate exterior member, it is easily deformed due to insufficient strength of the part, and other parts are It was necessary to reduce the force for contact.
[0010]
Further, in the case of a terminal as shown in Japanese Patent Application Laid-Open No. 57-174860, if the thickness of the terminal is increased, the sealing performance is reduced, and therefore it is mainly 200 microns or less, and therefore the strength of the terminal is weak. It was easy to break, and it was necessary to reduce the force required for other parts to come into contact as in the case of the outer container. This is not preferable from normal usage such as storing the battery in a pack or equipment, taking out the electrical output from the terminal, adding an electric circuit, or replacing the battery, and at the same time lowering the reliability. However, the design freedom as a power source including peripheral parts was lowered, and it was difficult to replace or became larger, and the use conditions were deteriorated.
Further, since the strength of this laminate exterior is weaker than that of the can type, the structure and material of the safety valve are greatly different from the can type, and it is difficult to cut the can itself like the can type.
[0011]
Hereinafter, a conventional flat battery will be described in detail.
(A) of FIG. 15 is sectional drawing, (b) is a top view.
1 is a positive electrode current collector, 11 is a positive electrode active material layer, 2 is a negative electrode current collector, 12 is a negative electrode active material layer, 3 is a separator layer, and 4 is a positive electrode side laminate film. Yes, 14 is a positive-side heat-sealed layer coated on the positive-side laminate film 4, 5 is a negative-side laminated film, and 15 is a negative-side heat-fused layer coated on the negative-side laminated film 5. , 6 is a positive electrode terminal, 7 is a negative electrode terminal, and these 6 and 7 are welded to the current collectors 1 and 2 respectively, and although not shown, the active material layers 11 and 12 and the separator layer 3 Is impregnated with an electrolyte solution, and the heat-seal layer 14 on the positive electrode side and the heat-seal layer 15 on the negative electrode side are heat-sealed at both ends of the figure with the positive electrode terminal 6 and the negative electrode terminal 7 sandwiched therebetween. 8 and 9 are the positive terminal side and the negative terminal side, respectively. A void thickness of the active material layer of a certain electrode causes mainly, 10C is heat-sealed portion from 10A, 10D is Minetsu fused portion.
[0012]
In FIG. 15, the battery elements 1, 1, 1, 2, 12, 6, and 7 are sandwiched between the positive electrode and the negative electrode side exterior materials 4 and 5, and portions 10 </ b> A, B, and C are heat-sealed. Then, this is put in a container in which an electrolytic solution is previously installed, and is sucked to reduce the pressure and vacuum, and thereafter, the unheated fused portion 10D is used as a liquid inlet to impregnate or electrolyze the electrolytic solution downward. By filling the inside of the container with the liquid and then bringing the inside of the container to normal pressure, it becomes possible to impregnate the battery element in the laminate exterior with the electrolytic solution. However, as described above, this is unsuitable for mass production, and the exterior of the laminate needs to be washed because it is wetted with the electrolyte, and the inner surface of the unheat-bonded portion 10D is wetted with the electrolyte so that it is sealed. Reliability decreases.
In addition, since the battery element is thick, void portions 8 and 9 are formed, and it is difficult to control the volume, the amount of electrolyte, and the shape of these portions, and the strength is weak, so that it is easily damaged by external pressure. .
[0013]
[Problems to be solved by the invention]
Therefore, in the present invention, in order to solve the above-mentioned problems seen in the structure of an outer container using a conventional film-like laminate exterior, a member is provided inside the exterior member, and a part of the exterior member and the member are further provided. By providing a hole or notch, it is easy to manufacture, has high reliability, high sealing performance, high mechanical strength of the exterior member, and high energy density. Non-aqueous An object is to provide an electrochemical element.
[0014]
[Means for Solving the Problems]
Hereinafter, the present invention Non-aqueous The electrochemical device will be specifically described with reference to the drawings. However, the present invention Non-aqueous The electrochemical device is not limited to that shown in the following drawings.
1. FIG. 1 is a diagram showing an embodiment (embodiment 1) that satisfies the constituent requirements of claim 1.
13 is a circular hole provided in the negative electrode side exterior member 5, 16 is a member (a square block made of polytetrafluoroethylene), and 17 is different from 5 made of aluminum having a heat fusion layer 18. The outer member 17 is heat-sealed to 5 to close the hole 13 (others are the same as the conventional example). The positive and negative electrode exterior members 4 and 5 are laminate films formed by coating a 50-micron polyethylene layer on the inner surface of a 25-micron aluminum film.
Further, the member 16 may be a flat shape, a cylindrical shape, or a polygonal column shape instead of the illustrated shape. The material is not limited to polytetrafluoroethylene, but may be any material as long as it is resistant to an electrolytic solution such as polyacetal, polypropylene, polyimide, ceramic, glass, rubber, and various metals. Moreover, the surface may be roughened and processed. However, in the case of metal, it is necessary to consider the shape and arrangement so as not to cause an internal short circuit.
In addition, this embodiment is a laminated paper battery using one positive electrode and one negative electrode for explanation, but may be a laminated multi-layer battery provided with several positive electrodes and negative electrodes. In this case, a terminal, a positive electrode, and a negative electrode are used by connecting them in advance by ultrasonic waves, spot welding or the like.
[0015]
Table 1 shows a comparison between the first embodiment and the conventional example. The results of the experiment are shown in four stages: ◎, ○, Δ, ×. The process tact is very process tactile because the conventional example requires another container for evacuating the entire outer container. In this embodiment, since vacuuming and liquid injection are performed from the gap between the film and the block, the tact can be reliably shortened, although it is not a great improvement. In addition, since the main portion of Embodiment 1 can be sealed without getting wet with the electrolytic solution, the sealing can be easily performed in a short time. Furthermore, when cycle deterioration was evaluated as reliability, there was a large difference between the conventional example and this embodiment. This is considered that the residual gas in the electrode active material due to an increase in moisture due to poor sealing or poor liquid injection is involved.
Also, in this experiment, the time for vacuuming to reach a predetermined pressure, the time for injecting until the change in the amount of injection disappears, the sealing is the actual time of actual work, and the cycle deterioration is 1/3 C, 30 cycles It was measured and evaluated by subsequent capacity deterioration.
[0016]
[Table 1]

[0017]
2. FIG. 2 is a view showing an embodiment (embodiment 2) of a member that satisfies the structural requirements of claim 2.
(A) and (c) are side views, and (b) and (d) are plan views. In FIG. 2, 16 is a square block made of polytetrafluoroethylene, 19 in (a) and (b) is a through hole provided in the square block 16, and 20 in (c) and (d). Is a notch provided in the square block 16 (others are the same as in the conventional example or embodiment 1). The through hole 19 serves as a flow path for depressurization, evacuation, and electrolyte injection by removing a gas component, and can be performed in a shorter time and more reliably. Since the lower hole of the through hole is in contact with the lower laminate film, the result is practically sufficient although it is the same as the gap in the upper part of Embodiment 1. It was also confirmed that the cycle deterioration was reduced and the reliability was improved because the residual gas inside the electrode was reduced.
Table 2 below shows the experimental results of this embodiment when notches are provided.
[0018]
3. FIG. 3 is a view showing an embodiment (embodiment 3) of a member that satisfies the structural requirements of claim 3.
(A) is a side view, (b) is a plan view, and (c) is a left side view. Reference numeral 21 denotes a through hole provided in the square block 16, and the direction is changed in the horizontal direction (others are the same as those of the conventional example or embodiment 1). This through hole 21 serves as a flow path for decompression, evacuation, and electrolyte injection by removing gas components, and can be performed in a shorter time and more reliably. By placing one of the through holes on the side, in the second embodiment, the vacuuming and the liquid injection performed from the gap in contact with the lower laminate film could secure a reliable flow path. The time required for pulling was a good result.
In addition to the case where the hole is changed to the side shown in FIG. 3, it has been confirmed that changing the shape of the notch is also effective.
Table 2 below shows the experimental results of this embodiment when the holes are changed laterally.
[0019]
4). FIG. 4 is a view showing an embodiment (embodiment 4) of a member that satisfies the constituent requirements of claim 4. In FIG.
(A) is a plan view, (b) is a side view, and (c) is a bottom view as seen from below.
22a and 22b are through-holes provided in the member (square block) 16, and the cross-sectional area is increased by slightly increasing the diameter of the holes (others are the same as in the conventional example or embodiment 1). These through holes 22a and 22b function as a flow path for depressurization, evacuation, and electrolyte injection by removing gas components, and can be performed in a shorter time and more reliably. However, like the through-hole of the embodiment, since it is in contact with the lower laminate film, gas and liquid flow paths are secured as gaps, so that the low area of the block is reduced. There is also an impact. However, the fact that the same cross-sectional area was increased was more effective for liquid injection, even when the direction of the hole was changed in the lateral direction of the third embodiment.
Table 2 below shows the experimental results of the embodiment in the case of FIG.
[0020]
5). FIG. 5 is a diagram showing an embodiment (embodiment 5) of a member that satisfies the structural requirements of claim 5.
(A) is a plan view, (b) is a side view, and (c) is a side view.
23a, 23b, and 23c are through-holes provided in the square block 16, which are semicircular so that the direction is changed in the horizontal direction and the cross-sectional area in the horizontal direction is the same (otherwise, Same as conventional example or embodiment 1).
By dividing one of the through holes sideways and into two, the flow path can be secured in two directions, so that it is easier to realize a state in which the flow path has less resistance. There are four different directions in the lateral direction: the terminal direction, the electrode direction, the sealing portion direction, and the other directions. When laminated, the laminate film itself is soft and has a uniform shape. It is effective to secure two directions as the flow path because the other flow path can be secured even if the mouth of one flow path is small and closed. Further, when the two directions function, it is considered that the difference in the flow direction further facilitates vacuum drawing and liquid injection. This division may be more than two divisions.
Table 2 below shows the experimental results in the case of FIG. In addition to liquid injection, the vacuum pulling tact could be improved.
[0021]
6). FIG. 6 is a view showing an embodiment (embodiment 6) of a member that satisfies the structural requirements of claim 6 and is a view from the side. Reference numeral 24 denotes a block similar to the porous glass Vycor glass. The shape is the same as that of the 16 polytetrafluoroethylene square block, but the material itself has minute holes, allowing gas and liquid to flow easily. In addition, since there are no macro holes, the strength is high and the possibility of breakage of the sealed exterior member is reduced.
Table 2 below shows the experimental results in the case of FIG. Although the large hole was not provided, the same effect as the block having the hole divided into two was confirmed.
It is also the same that such a porous body is combined by being embedded in the pores of the polytetrafluoroethylene block.
[0022]
[Table 2]

[0023]
7). FIG. 7 is a diagram showing an embodiment (embodiment 7) that satisfies the structural requirements of claim 7.
A member 16 having a through hole is bonded in advance to the lower part of the back surface of the upper exterior member 5 having a hole, and a battery element 25 mainly composed of a positive electrode, a negative electrode, a separator, and a terminal is provided between the member 16 and the lower exterior member 4. After positioning and laminating while sandwiching, four sides are sealed. This is effective because the positioning of the upper exterior member and the member 16 is not required and the two holes are not displaced. However, if a part of the battery element overlaps, 16 is inclined due to the step, and therefore it is necessary to position the battery element properly. In Table 3 below, the positioning tact of the first embodiment and the seventh embodiment and the process tact of the subsequent lamination are displayed in four stages. In addition, the case where the thickness of the container becomes thick is indicated as x, and the case where it does not change is indicated as ○.
[0024]
8). FIG. The present invention It is a figure which shows the aspect (embodiment 8) which satisfies that the exterior member which has a structural requirement, a hole part or a notch, and at least one part of a member are being fixed.
The member 16 is bonded in advance to the battery element 25, and after positioning and stacking while sandwiching it between the upper and lower exterior members, the four sides are sealed. This is because positioning of the battery element and the member 16 is not necessary, and the positioning is made only with care so that there is no misalignment between the two holes. By enlarging one of the holes, particularly the hole of the exterior member, To be able to position easily. However, if 16 is provided on the back side of the battery element active material layer where the current collector is not used as shown in the figure, the thickness of the battery increases by the amount of the member 16, so that the volume energy density is Slightly falls. However, bonding, positioning, and lamination can be easily performed.
Table 3 below shows the positioning tact and the stacking process tact of the first embodiment and the eighth embodiment in four stages. In addition, the case where the thickness of the container becomes thick is indicated as x, and the case where it does not change is indicated as ○.
[0025]
9. FIG. The present invention It is a figure which shows the embodiment (embodiment 9) which satisfies the component requirements.
(A) is a top view, (b) is side sectional drawing. An elongated member 26 is bonded in advance to the connection portion between the current collector 1 and the terminal 6 of the battery element 25, and after positioning and stacking while sandwiching it between the upper and lower exterior members, four sides Is sealed. This eliminates the need for positioning between the battery element and the member 26, so that the positioning is made only with care so that there is no misalignment between the two holes. By enlarging one of the holes, particularly the hole on the exterior member, To be able to position easily. Further, as shown in the figure, since 26 is provided in the portion where the active material layer of the battery element does not exist, the overall thickness is not increased. However, since the structure of the member 26 has a shape that avoids the thickness of the terminal, the structure becomes complicated, and the component cost slightly increases.
Table 3 below shows the positioning tact of the embodiment 1 and the embodiment 9 and the subsequent process tact in four stages. In addition, the case where the thickness of the container becomes thick is indicated as x, and the case where it does not change is indicated as ○.
[0026]
[Table 3]

[0027]
10. FIG. Of the present invention It is a schematic diagram showing an embodiment (Embodiment 10) that satisfies the structural requirements, (a) is a case where the hole 28 of the exterior member is on the upper surface, (b) is a side surface or a plurality of holes 28 of the exterior member This is a case formed by an exterior member, and 27 is an elongated member. In this 27, positive and negative external terminals 29 and 30 are embedded in advance and connected to the internal terminal inside the outer container. , 31 is a hole provided in 27, 32 is an exterior member that closes the hole 31, and 33 is a heat fusion part.
(A) in FIG. 10 can easily achieve a compact and reliable strong terminal by using the liquid injection member at the same time, and at the same time the number of holes in the exterior member is the same. Insufficient sealing is unlikely to occur. Further, in FIG. 10B, since the terminals are provided in a flat direction, the flat thickness can be maintained even in a connection state with the outside, which is effective for a thin device.
[0028]
11. FIG. Of the present invention It is a figure which shows the embodiment (embodiment 11) which satisfies a structural requirement.
(A) is a state in which a laminate-sheathed battery is fixed to a package or a device, and (b) is a state in which a laminate-sheathed battery is fixed to a package or a device and an electrical output is taken out from a thin plate terminal. , 37 is a battery, 34 is a package, 35 is a fixing spring member, 36 is a fixing abutting member, 38a and 38b are fixing and collecting spring members, and 39 is a device used.
Since the laminate exterior is originally a film-like exterior, its strength is small, and the method of fixing and using it in the device is different from other can batteries. That is, if the laminate portion is fixed while being sandwiched, the laminate portion is easily damaged, and if the thin plate terminal portion is fixed, the terminal is easily damaged. However, in this embodiment, since the member is provided inside the laminate exterior, even if the laminate is fixed as it is or sandwiched together with the terminals, the laminated film and terminals are prevented from being deformed and damaged by the internal members. There is an effect to.
Conventionally, there is an example in which the exterior of the laminate is coated with a resin having a high strength mainly for the purpose of improving the sealing ability, but this increases the thickness and becomes heavy. When the battery is actually attached or detached with or without a member, the structure of (a) and (b) was confirmed. The average life of failure was about 2 although it depends on the thickness of the exterior member and terminal. It was found that more than double can be increased, and reliability can be improved. The average failure life is a simple examination of laminate film breakage (visual deformation or sudden deterioration in capacity) and terminal breakage (visual deformation) in the test for the number of times of attachment to and removal from the equipment. It indicates the result.
[0029]
12 FIG. Of the present invention It is a figure which shows the embodiment (embodiment 12) which satisfies a structural requirement.
It is the figure seen from the side, and even when the vicinity of a hole gets wet with an electrolyte solution by using an ionomer resin layer 40 as a heat sealing agent of another exterior member 17 that closes the hole of the exterior member It was found that sealing with high strength and sealing force can be performed. Compared to the case of general polyethylene, the water content was reduced by a fraction and the peeling adhesive strength was increased by 50%.
[0030]
13. FIG. Of the present invention It is a figure which shows the embodiment (embodiment 13) which satisfies a constituent requirement, and is a figure seen from the side, and by using the epoxy adhesive layer 41 for another exterior member itself which plugs up the hole of an exterior member, The hole of the exterior member could be easily blocked. The shape of the hole can be accommodated freely, increasing productivity and reducing costs. The same applies to the case where at least one of a fusing agent, an adhesive, pitch, or grease is used for the exterior member, and it is possible to easily close the hole by using at least the first viscous material. It was. Of course, it is necessary to pay careful attention to the chemical resistance to these electrolytes.
[0031]
14 FIG. Of the present invention It is a figure which shows the embodiment (embodiment 14) which satisfies a structural requirement.
(A) 16 is a member, which is formed by bending a hole in the lateral direction, and by making the pressure and temperature applied to the heat-fusible layer 42 slightly smaller than the other part, it is more internal than the other part. The damage strength of the sealing part with respect to pressure is reduced, and this can also function as a safety valve by opening 43 as shown in (b) by increasing the internal pressure. The polypropylene member 44 is provided with a small notch in the central portion, which is heat-sealed at the peripheral 45 portion, and when this increases also, the laminated portion of other exterior members It has a strength that can be broken with a smaller pressure, and can break and open from the center to function as a safety valve. Thus, by setting the strength and adhesive strength of the exterior member that closes the hole of the exterior member provided at a position overlapping with the member to be small, it is possible to easily provide the safety valve without increasing the number of parts.
[0032]
The production method is described in detail below.
The positive electrode 11 is LiCoO ₂ And graphite and PVDF (polyvinylidene fluoride) in a weight ratio of 90: 7: 3 are dispersed in an NMP (N-methyl-2-pyrrolidone) solution, which is applied to a 20 μm Al substrate and dried at 120 degrees. A positive electrode having an active material layer of about 100 μm was prepared. As the negative electrode, graphite and PVDF were dispersed in an NMP solution at a weight ratio of 90:10, applied to a 10 μm Cu substrate, and dried at 120 ° C. to prepare a negative electrode having an active material layer of about 70 μm. Both the positive electrode and the negative electrode were used after roll pressing. The electrolyte is 1M-LiPF, a mixed solvent of EC (ethylene carbonate) and DMC (dimethyl carbonate). ₆ The solution was used. A separator having a porosity of 40% or more and a thickness of 25 μm was used.
[0033]
The positive electrode active material includes LiCoO. ₂ Besides V ₂ 0 _Five , LiNiO ₂ , LiMn ₂ O _Four Non-aqueous secondary battery positive electrode materials such as oxides such as lithium intercalation, polymer materials such as polyaniline and polypyrrole, conventional primary batteries and secondary batteries such as conventional dry batteries, alkaline batteries and nickel metal hydride batteries The same applies to the use of materials. The graphite mixed with the positive electrode active material may be natural graphite, artificial graphite, or amorphous carbon. In addition to PVDF, the binder may be fluorine-containing NMP soluble polymer, PVP (polyvinylpyrrolidone), or the like.
[0034]
As the electrolytic solution, a non-aqueous electrolytic solution containing an acrylate monomer and a thermal polymerization initiator was used. Specifically, 1.5M LiPF in an equivalent mixed solvent of ethylene carbonate and dimethyl carbonate ₆ A solution obtained by adding about 13 wt% of a monofunctional monomer, 0.2 wt% of a trifunctional monomer, and a thermal polymerization initiator to the electrolytic solution in which was dissolved. Actually, the electrolytic solution is slowly poured into the laminate outer container from the minute gap between the member 16 made of polytetrafluoroethylene and the laminate film 5 as in the case of evacuation. After the liquid injection is finished, an exterior member 17 made of another laminate film is disposed above the hole 13, and a pressure of 130 degrees is applied only to the pressure and the upper part across the upper and lower portions of this part, Heat sealing is performed to close the hole 13. Thereafter, the entire outer container is left at 60 ° C. for 1 hour to polymerize the monomer, and the electrolytic solution is gelled to form a solid electrolyte, thereby producing a polymer battery.
[0035]
The electrolyte to be injected that contains the acrylic monomer and constitutes a gelable solid electrolyte by thermal polymerization includes cyclic carbonates and chain carbonates that are carbonate esters, carboxylic acid esters, acetonitrile, Non-aqueous electrolytes such as dimethylformamide and dimethyl sulfoxide may be used, and water may be used when the battery is not a non-aqueous secondary battery. The supporting salt includes LiBF _Four LiClO _Four , LiAsF ₆ , LiSO _Three CF _Three , LiC (SO ₂ CF _Three ) _Three , LiN (SO ₂ CF _Three ) ₂ Etc. In addition to the acrylic monomer containing the electrolyte, polymer particles such as polyacrylonitrile, polyethylene oxide, and polyvinyl copolymer may be dispersed. Further, PVDF-HFP-based polymer may be used.
The separator may not be used when a polymer is used.
[0036]
Examples of thermal polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, and diisopropylperoxydicarbonate. Examples thereof include oxydicarbonate.
As acrylate monomers, there are (meth) acrylates, specifically acrylates or methacrylates, and monofunctional acrylates include alkyl (meth) acrylate {methyl (meth) acrylate, butyl (meth) acrylate, trifluoroethyl (meth) Acrylate etc.}, alicyclic (meth) acrylate, hydroxyalkyl (meth) acrylate (hydroxyethyl acrylate, hydroxypropyl acrylate, etc.), hydroxypolyoxyalkylene (oxyalkylene group preferably has 1 to 4 carbon atoms) (meth) Acrylate {Hydroxypolyoxyethylene (meth) acrylate, hydroxypolyoxypropylene (meth) acrylate, etc.} and alkoxyalkyl (the alkoxy group preferably has 1 to 4 carbon atoms) Meth) acrylate {methoxyethyl acrylate, ethoxyethyl acrylate, phenoxyethyl acrylate, and the like} and the like. As an example of the trifunctional or higher polyfunctional (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.
Specific examples of other (meth) acrylates include, for example, methylethylene glycol (meth) acrylate, ethylethylene glycol (meth) acrylate, propylethylene glycol (meth) acrylate, phenylethylene glycol, ethoxydiethylene glycol acrylate, methoxyethyl acrylate, methoxy Alkylpropylene such as diethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, and other alkylethylene glycol (meth) acrylates, ethylpropylene glycol acrylate, butylpropylene glycol acrylate, methoxypropylene glycol acrylate, etc. Recall (meth) acrylate.
By using these acrylate monomers and thermal polymerization initiators in an optimum formulation, it is possible to obtain a polymer electrolyte by performing thermal polymerization and gelation even at 60 ° C. for 1 hour.
[0037]
The laminate film may be a fusion material in which 25 μm thick aluminum is coated with polyethylene, which is a fusion material, on the electrode side, and a polymer such as polyester is similarly coated on the outside. In addition to polyethylene, the inner heat fusion agent may be a polyolefin such as polypropylene, a modified polyolefin containing a carboxyl group, an ionomer, a hot melt resin may be used as an adhesive layer, and an epoxy resin adhesive The layer may be provided only on the sealing portion.
The outer coating may be polyimide, polyamide, polyphenylene oxide, or the like, and may be the same polyolefin-based fusion material as the inner coating. However, it is necessary to have excellent adhesion with another exterior member 17. Moreover, even if it is not a laminate film, at least one may be a hard case, and a case may be sealed with a fusing material or an adhesive. Further, the film structure of the sealing portion may not be apparently film-like as long as the electrode of the exterior member is sufficiently thin as compared with a certain thickness and uses fusion or adhesion.
[0038]
【effect】
(1) Highly reliable vacuum injection can be performed in a short time.
(2) According to the inventions of claims 7 and 8, Positioning and stacking processes during battery production can be performed in a short time.
(3) According to the invention of claim 9, A compact, reliable and strong terminal can be easily realized.
(4) A highly reliable battery that is not easily damaged can be provided on a part of the outer side of the exterior member that overlaps the member.
(5) According to the invention of claim 10, It can easily be used as a safety valve.
[Brief description of the drawings]
[Figure 1] Of the present invention It is a figure explaining one embodiment which satisfies composition requirements. (A) is a side view, (b) is a plan view.
[Figure 2] Of the present invention It is a figure explaining one embodiment of the member which satisfies a constituent requirement.
(A) and (c) are side views, and (b) and (d) are plan views.
[Fig. 3] Of the present invention It is a figure explaining one embodiment of the member which satisfies a constituent requirement.
(A) is a side view, (b) is a plan view, and (c) is a left side view.
[Fig. 4] Of the present invention It is a figure explaining 1 embodiment of the member which satisfies a constituent requirement.
(A) is a plan view, (b) is a side view, and (c) is a bottom view as seen from below.
[Figure 5] Of the present invention It is a figure explaining one embodiment of the member which satisfies a constituent requirement.
(A) is a plan view, (b) is a side view, and (c) is a left side view.
[Fig. 6] Of the present invention It is a figure explaining one embodiment of the member which satisfies composition requirements, and is a figure seen from the side.
[Fig. 7] Of the present invention It is a figure explaining one embodiment which satisfies composition requirements.
[Fig. 8] Of the present invention It is a figure explaining one embodiment which satisfies composition requirements.
FIG. 9 Of the present invention It is a figure explaining one embodiment which satisfies composition requirements.
(A) is a top view, (b) is a side view.
FIG. 10 Of the present invention It is an outline figure showing one embodiment which satisfies composition requirements. (A) is the case where the hole 28 of the exterior member is on the top surface, and (b) is the case where the hole 28 of the exterior member is on the side surface and this member is in contact with one or more exterior members.
FIG. 11 Of the present invention It is a figure explaining one embodiment which satisfies composition requirements. (A) is a state in which a laminate-sheathed battery is fixed to a package or device, and (b) is a state in which the laminate-sheathed battery is fixed to the package or device and an electrical output is taken out from a thin plate terminal. Show.
FIG. Of the present invention It is a figure explaining one embodiment which satisfies composition requirements.
FIG. 13 Of the present invention It is a figure explaining one embodiment which satisfies composition requirements.
FIG. 14 Of the present invention It is a figure explaining one embodiment which satisfies composition requirements. (A) is the figure which shows the state which made the pressure and temperature applied to the heat sealing | fusion layer 42 smaller than another part, and was thermally fused, (b) is the figure which shows the state which the hole opened by internal pressure, and (C) is a figure which shows the state which heat-sealed and sealed the polypropylene member which provided the small notch in the hole.
FIG. 15 is a diagram illustrating a conventional flat battery.
(A) is sectional drawing, (b) is a top view.

Claims (10)

(A) an electrochemical element, (b) a film-shaped exterior member composed of at least two or more opposing sealing parts, and at least one sealing part being a film, An exterior member for storing an electrochemical element provided with a hole for evacuating and injecting liquid in the film-shaped exterior member in a manufacturing process ; (c) a current generated from the electrochemical element to the outside of the exterior member or A terminal for outputting a voltage; (d) a member different from an electrochemical element or terminal provided in the exterior member in the vicinity of the hole of the film-shaped exterior member (hereinafter also simply referred to as a member); and (e) the hole. A non-aqueous electrochemical element having an exterior member that closes the hole, which is different from the exterior member provided with the above. The non-aqueous electrochemical element according to claim 1, wherein a hole or a notch is provided in at least a part of the member at a position where the hole of the member and the exterior member overlap. A hole or notch (A) in which the hole or notch of the member penetrates to the position where the hole of the member and the exterior member overlaps, and a hole of a different direction or shape from the hole or notch (A) Or it has a notch part (B) and the said both hole part or notch part is connected in the said member, The non-aqueous electrochemical element in any one of Claims 1-2. A hole or notch (B) having a cross-sectional area of a hole or notch (A) penetrating to the position where the hole of the member and the exterior member overlaps is different from the hole or notch (A). The non-aqueous electrochemical device according to claim 3, wherein the non-aqueous electrochemical device is the same as or smaller than the cross-sectional area. A hole or notch (B) having a different direction or shape from the hole or notch (A) in the number of holes or notches (A) penetrating to the position where the hole of the member and the exterior member overlap. The non-aqueous electrochemical element according to claim 3, wherein the number is the same as or less than the number of the non-aqueous electrochemical elements. The non-aqueous electrochemical element according to claim 1, wherein at least a part of the hole or notch of the member is formed of a porous body having minute holes . The non-aqueous electrochemical element according to claim 1, wherein the exterior member and at least a part of the member are fixed. The member is fixedly disposed so as to overlap with a connection portion between the electrochemical element and the terminal or a current collector exposed portion of the electrochemical element. Non-aqueous electrochemical element. The non-aqueous electrochemical element according to claim 1, wherein the member has a part of a terminal. 2. The internal pressure damage strength of a portion overlapping with an exterior member different from the exterior member having the hole portion covering the hole portion of the member and the exterior member has the smallest value among the exterior members. The non-aqueous electrochemical element in any one of -9.

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