JP5004066B2 - Multilayer structure and lithium battery using the same - Google Patents
Multilayer structure and lithium battery using the same Download PDFInfo
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- JP5004066B2 JP5004066B2 JP2001206457A JP2001206457A JP5004066B2 JP 5004066 B2 JP5004066 B2 JP 5004066B2 JP 2001206457 A JP2001206457 A JP 2001206457A JP 2001206457 A JP2001206457 A JP 2001206457A JP 5004066 B2 JP5004066 B2 JP 5004066B2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910052744 lithium Inorganic materials 0.000 title abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 69
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 66
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005839 GeS 2 Inorganic materials 0.000 description 1
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- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910007860 Li3.25Ge0.25P0.75S4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 229910017053 inorganic salt Inorganic materials 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Secondary Cells (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、可動イオン種がリチウムイオンであるリチウムイオン伝導性固体電解質成型体とそれを用いたリチウム電池に関する。
【０００２】
【従来の技術】
近年、パーソナルコンピュータ・携帯電話等のポータブル機器の開発に伴い、その電源として電池の需要は非常に大きなものとなっている。特に、リチウム電池は、リチウムの原子量が小さく、かつイオン化エネルギーが大きな物質であることから、高エネルギー密度を得ることができる電池として盛んに研究が行われ、現在ではポータブル機器の電源として広範囲に用いられている。
【０００３】
その一方、リチウム電池の汎用化につれて、含有活物質量の増加による内部エネルギーの増加と、更に電解質に用いられている可燃性物質である有機溶媒の含有量の増加により、電池の発火などの危険性に対する関心が近年クローズアップされてきた。
【０００４】
リチウム電池の安全性を確保するための方法としては、有機溶媒電解質に代えて不燃性の物質である固体電解質を用いることが極めて有効であり、種々の無機リチウムイオン伝導性固体電解質粉末を適用することで高い安全性を備えた全固体リチウム電池の開発が進んでいる。
【０００５】
リチウムイオン伝導性無機固体電解質の開発においては、前記無機固体電解質中のリチウムイオン伝導性を高めることを主眼として行われてきたが、電池等のデバイスへ応用する際には、高いリチウムイオン伝導性と共に優れた加工性をもつことが重要である。固体電解質層を薄型化することにより、内部インピーダンスを低減し出力特性を向上させることができるのみならず、電池内に占める固体電解質層の体積割合が低くなり電池のエネルギー密度も向上するからである。
【０００６】
そこで、加工性を付与させるべく高濃度のリチウムイオン伝導性を有する無機塩とゴム状の高分子よりなる” ポリマー イン ソルト（ｐｏｌｙｍｅｒ ｉｎ ｓａｌｔ）”型と名付けられた新規な固体電解質の提案が近年なされている〔Ｃ．Ａ．エンジェル、Ｃ．リュー、及びＥ．サンチェ、「ネーチャー」（Ｃ．Ａ． Ａｎｇｅｌｌ， Ｃ． Ｌｉｕ， ａｎｄ Ｅ． Ｓａｎｃｈｅｚ， Ｎａｔｕｒｅ，）第６３２巻（１９９３）第１３７頁〕が、その伝導度は十分とはいえない。
【０００７】
そこで、最近、ゴム状でない高分子を混合してなる複合リチウムイオン伝導性固体電解質が提案されている（稲田太郎、高田和典、梶山亮尚、高口 勝、近藤繁雄、渡辺 遵、第２６回固体イオニクス討論会要旨集、ｐ１１４）。この方法では、主として溶媒を用いない乾式混合により複合化したリチウムイオン伝導性固体電解質が良好な伝導度を示している。
【０００８】
しかし、全固体リチウム電池への応用等を念頭に量産性を考慮した場合、簡便に薄膜・大面積の電解質層を連続的に作製することのできるドクターブレード法などに代表される湿式法を採用することが望ましいが、前記の方法による場合には、高分子が無機リチウムイオン伝導性固体電解質の粒子表面をフィルム状に覆うため、複合体中のイオン拡散が阻害され、イオン伝導性が低下する問題がある。
【０００９】
【発明が解決しようとする課題】
本発明は、以上の課題を解決し、特定の高分子を用いることにより無機リチウムイオン伝導性固体電解質の粒子表面が被覆されてリチウムイオン伝導性固体電解質成型体のイオン伝導性が低下する現象を回避し、その結果、実用的な特性を有するリチウム電池を提供することを目的としている。
【００１０】
【課題を解決するための手段】
すなわち、本発明は、層状のリチウムイオン伝導性固体電解質成型体の両主面に電極体を設けてなる多層構造体であって、前記リチウムイオン伝導性固体電解質成型体が無機リチウムイオン伝導性固体電解質粒子とシリコーンゴム未架橋体よりなる架橋体とからなり、前記無機リチウムイオン伝導性固体電解質粒子は前記シリコーンゴム未架橋体よりなる架橋体中に分散し、且つ、前記無機リチウムイオン伝導性固体電解質粒子同士が接触していることを特徴とする多層構造体であり、好ましくは、前記シリコーンゴム未架橋体よりなる架橋体が、ＪＩＳ Ｋ‐７１１１に規定されるシャルピー衝撃試験で破壊しないことを特徴とする前記の多層構造体である。そして、本発明は、前記の多層構造体を用いてなることを特徴とする電池である。
【００１１】
また、本発明は、無機リチウムイオン伝導性固体電解質粒子とシリコーンゴム未架橋体（以下、化学架橋性の液状高分子ともいう）とを混合し、成型して層状となし、前記層の両主面に電極体を加圧接合して前記無機リチウムイオン伝導性固体電解質粒子同士を接触せしめ、さらに前記シリコーンゴム未架橋体を架橋体に変換せしめることを特徴とする多層構造体の製造方法である。
【００１２】
本発明の多層構造体は、層状のリチウムイオン伝導性固体電解質成型体の両主面に電極体を設けてなる多層構造体であって、前記リチウムイオン伝導性固体電解質成型体が無機リチウムイオン伝導性固体電解質と化学架橋性の液状高分子よりなる架橋体とからなり、イオン伝導性に優れ全固体リチウム電池を容易に得ることができる特徴を有する。
【００１３】
本発明者らは、リチウムイオン伝導性固体電解質と高分子とを混合しリチウムイオン伝導性固体電解質複合体を得るに際し、組成、粒子状態等の色々な条件について実験的に検討した結果、高分子として化学架橋性の液状高分子を用いるときに、得られるリチウムイオン伝導性固体電解質複合体のイオン伝導性が良好であるばかりでなく、加工性、特に薄膜への加工性が優れること、そして、前記リチウムイオン伝導性固体電解質複合体を成型して得られるリチウムイオン伝導性固体電解質成型体が薄型の全固体リチウムイオン電池に好適であるという知見を得て、本発明に至ったものである。
【００１４】
前記の理由については、明らかでないが、リチウムイオン伝導性固体電解質複合体内における前記高分子の分布が仮にリチウムイオン伝導性無機固体電解質の粒子表面を覆うような状態であったとしても、これを一軸プレスやローラー等により加圧処理することにより、前記高分子の分布状態はリチウムイオン伝導性無機固体電解質の粒子同士の接触を妨げない程度まで変化し、その結果得られたリチウムイオン伝導性固体電解質成型体内においては、固体電解質粒子同士の接触が良好なものとなるためと推察される。
【００１５】
上記推察に基づけば、リチウムイオン伝導性無機固体電解質に未架橋構造の高分子（以下、未架橋体という）を配合した後に架橋反応を生じさせたときに、リチウムイオン伝導性無機固体電解質の粒子表面の存在状況が変化するもののうち、本発明の目的・効果を達成できるものが、本発明の化学架橋性の液状高分子と同等物であることが容易に類推できる。
【００１６】
【発明の実施の形態】
以下、本発明を具体的に説明する。
架橋構造を有する高分子（以下、架橋体という）には、大別してスチレンブタジエンブロック共重合体のようにハードセグメントとソフトセグメントが絡み合った高次構造によってゴム弾性が発現する物理架橋体と、加硫ゴムのように架橋反応で生じる化学結合によってゴム弾性が発現する化学架橋体がある。本発明においては、得られるリチウムイオン伝導性固体電解質複合体の加工性を確保するために、液状の未架橋体を架橋することにより得られる高分子架橋体が、従って、後者の化学架橋体が選択される。なお、高分子が化学架橋体であるか否かについては、溶解度パラメータが同等である溶媒への浸漬で膨潤するかどうかにより評価することが可能である。
【００１７】
化学架橋性のゴム状高分子としては、シリコーンゴム以外に、例えば炭化水素系では天然ゴム、イソプレンやブタジエンなどの合成ゴムが知られている。これらの未架橋体は室温で様々な粘度のものが知られており、中には固体状に見える場合もあるが、その場合でも長時間の放置でコールドフローと呼ばれる流動性を示すが、実際は液状の物質である。これらのうち、高流動性液体の未架橋体が無機リチウムイオン伝導性固体電解質粒子への高分子の被覆を低減するためには好ましい。この点については、後述する実施例で示すとおりに、例えば０．８〜１．０Ｐａ・ｓ程度の低粘度シリコーンゴム未架橋体が特に好適な高分子の一つといえる。またシリコーンゴムの未架橋体は電気化学的安定性及び電子絶縁性に優れているので、得られる架橋体の特性の上からも本発明に適当である。
【００１８】
また、本発明において、前記化学架橋性の液状高分子よりなる架橋体が、ＪＩＳ Ｋ‐７１１１に規定されるシャルピー衝撃試験で破壊しないことが望ましい。しかるに、化学架橋性の液状高分子よりなる架橋体の存在が、リチウムイオン伝導性固体電解質複合体の機械的特性を改善して、実使用における応力の付加等に対して耐性を改善し得るからで、前記要件を満足するとき、リチウムイオン伝導性固体電解質複合体、惹いてはリチウム電池の機械的、従って電気的信頼性を高めることができる。
【００１９】
本発明に用いる無機リチウムイオン伝導性固体電解質としては、種々の種類が知られているが、例えば、０．０１Ｌｉ3ＰＯ4・０．６３Ｌｉ2Ｓ・０．３６ＳｉＳ2のような組成を有する硫化物ガラス〔Ｎ．アオタニ、Ｋ．イワモト、Ｋ．タカダ、及びＳ．コンドウ、「ソリッド ステート アイオニクス」（N. Aotani, K. Iwamoto, K. Takada, and S. Kondo, Solid State Ionics,）第６８巻（１９９４）第３５頁〕や、Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4のような組成を有するリチウムゲルマニウムチオ−ホスフェート（以下、チオ−リシコンと記載する）（村山昌宏，菅野了次，河本洋二，神山 崇、電気化学会第６８回大会講演要旨集、ｐ１８３）が伝導度が高く、適当である。
【００２０】
本発明において、無機リチウムイオン伝導性固体電解質に対する化学架橋性の液状高分子よりなる架橋体の割合については、両者の全体のうちで化学架橋性の液状高分子よりなる架橋体の体積百分率が２〜１０％であることが好ましい。化学架橋性の液状高分子よりなる架橋体が２体積％未満では、加工性や柔軟性に富む成型体が得難くなることがあるし、１０体積％を超えると成型、硬化の仕方により時として充分なリチウムイオン伝導性のある成型体を得ることができないことがある。前記範囲内の添加であれば、３×１０-4Ｓ・ｃｍ-1以上の高いイオン伝導度を有するリチウムイオン伝導性固体電解質成型体が得られる。
【００２１】
本発明の多層構造体は、前述の特定のリチウムイオン伝導性固体電解質成型体からなる層状成型体の両主面に電極体を設けた構造を有している。前記層状成型体の厚さについては、全固体リチウム電池に対しては２０〜１００μｍ程度の厚さであれば良い。更に、成型体の機械的特性を向上させるために、電気絶縁性構造体を利用することもでき、例えばポリエステルメッシュを前記リチウムイオン伝導性固体電解質成型体に内在あるいは接触配置することができる。
【００２２】
本発明における電極体とは、正極体と負極体とを含んでいる。
正極体としては、例えば、正極活物質、無機リチウムイオン伝導性固体電解質、導電助剤を含んでなる混合物に、本発明のリチウムイオン伝導性固体電解質成型体部分に用いたのと同じ化学架橋性の液状高分子を添加してなるものが、リチウムイオン伝導性固体電解質複合体との密着性で優れるので、好ましいが、本発明はこれに限定されない。
【００２３】
前記正極活物質としては、例えばコバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウムのような酸化物又はその遷移金属を一部他の金属に置換したものが挙げられる。また、導電助剤としては例えばアセチレンブラックのような炭素粉末、ニッケルや鉄のような金属粉末などが挙げられる。
【００２４】
前記正極体は例えば、これをスラリー化したものを集電体の上に塗布することにより、集電性や機械強度が向上する。正極の集電体としては、アルミニウム箔、ニッケルからなる箔、若しくは、アルミニウム、ニッケル、又はステンレスからなるメッシュが利用可能である。シートの良好な加工性を得るためにはアルミニウム箔が最も取扱が容易である。アルミニウム箔に上記正極スラリーを塗付する際には、その接着性を向上させるため、予めアルミニウム箔を粗面化し、及び／又はカーボンと樹脂を含有してなる複合導電性スラリーを塗布しプライマー層を形成しておくことも有効である。この複合導電性スラリーとしてはカーボンドータイトなどの市販品のほか、低融点テルペン系樹脂とカーボンを溶媒中混合して自作することも可能である。
【００２５】
カーボンドータイトの場合、溶媒がトルエン系であることから、正極スラリーの溶媒はトルエンを少量含む飽和炭化水素系溶媒が望ましい。少量のトルエンでプライマーの表面が溶けて、良好な接着性が発現する。低融点のテルペン系樹脂を用いる場合、例えばフェノール系テルペン樹脂を選べば飽和炭化水素系の溶媒には不溶である。そのためこのような樹脂を用いる際には、正極スラリーを飽和炭化水素系の溶媒で作製塗付後、１００℃以上に加熱しテルペン樹脂融解を利用して接着させる。この加熱処理はシリコーンの架橋反応と兼ねてもよい。その場合１５０℃程度の加熱温度が望ましい。
【００２６】
負極体としては、例えば、負極活物質、無機リチウムイオン伝導性固体電解質、導電助剤を含んでなる混合物に、本発明のリチウムイオン伝導性固体電解質成型体部分に用いたのと同じ化学架橋性の液状高分子を添加してなるものが、リチウムイオン伝導性固体電解質複合体との密着性で優れるので、好ましいが、本発明はこれに限定されない。本発明の負極体に用いられる活物質としては、例えばインジウム箔、リチウム箔又はそれらの合金箔、あるいは負極集電体上に作製したグラファイト膜が挙げられる。また、負極体に対しても正極の場合と同様に集電体の上にスラリー化したものを塗布することが、例えば、負極活物質、無機リチウムイオン伝導性固体電解質、導電助剤を含んでなる混合物からなる負極体を用いた時に有効である。負極の集電体としては銅箔やステンレスメッシュなどが挙げられる。
【００２７】
本発明の多層構造体は、例えば、無機リチウムイオン伝導性固体電解質（以下、単に電解質という）と化学架橋性の液状高分子とを混合し、成型して層状となし、前記層の両主面に電極体を接合し、更に前記液状高分子を架橋体に変換せしめることで得ることができる。この際に、上述したとおりに、正極、負極のいずれにも無機リチウムイオン伝導性固体電解質と化学架橋性の液状高分子とを混合しておけば、リチウムイオン伝導性固体電解質成型体を得るために架橋化する時に、正極と負極と中に存在する化学架橋性の液状高分子も併せて架橋化でき、しかも電極体とリチウムイオン伝導性固体電解質成型体との密着が極めて良くなるので、好ましい。接合の方法は、例えば正極集電体上に、正極体、電解質の層（以下、単に電解質層という）、負極体、負極集電体の順に重ねても良いし、又は正極集電体上に正極体を重ねた正極部品と、負極集電体上に負極体を重ねた負極部品を別々に作製し、どちらか一方の部品に電解質層を塗布してから両部品を接合しても良い。負極については活物質として合金の箔を用いた場合には、負極集電体の接合は、別途ケースに封じ入れる直前でもよい。接合の際には各部品を重ねた後で、一軸プレス又はローラーにより加圧してから加熱処理するか、あるいは加圧しつつ加熱処理することにより、架橋反応を起こさせる。
【００２８】
また、本発明は、前記の多層構造体を用いてなる電池であり、有機溶媒からなる電解液を含まないことから、耐引火性など高い安全性能を有する。また、電解液の分解のような副反応も起こらないことから、保存特性も優れており、長期保存において自己放電が起こらない。本発明の電池は、前述した、本発明の多層構造体を用い、これに集電体やリード部を設け、更に、ケースに封じることで得ることができる。
【００２９】
【実施例】
以下、本発明を実施例により更に具体的に説明する。
無機リチウムイオン伝導性固体電解質はチオ−リシコンＬｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4であり、Ｌｉ2Ｓ、ＧｅＳ2、Ｐ2Ｓ5を真空下７００℃で加熱することにより合成した。前記リチウムイオン伝導性固体電解質の粉砕、シリコーンゴム等の混合、薄型化、イオン伝導度測定用の試料調整、及びイオン伝導度測定はすべて乾燥アルゴン雰囲気下で行った。また、前記粉砕操作については、走査型電子顕微鏡による観察により粒子径が１〜５μｍとなるまで行った。
【００３０】
実施例１〜３
表１に示す重量の、付加反応により硬化する二液タイプのシリコーン（粘度０．８Ｐａ・ｓ）を、乾燥ヘプタンに、室温下で加えた。次いで得られた溶液に、粉砕したチオ−リシコンを１．４７ｇ添加し、スラリーとした。負極となるインジウムシート（厚み０．１ｍｍ）上に、前記スラリーをキャストし、ヘプタンを留去して電解質／負極複合シートを得た。
【００３１】
一方、コバルト酸リチウム２．４ｇ、チオ−リシコン１．４ｇ、アセチレンブラック４０ｍｇを乾式混合して混合粉末を得た。次いで２重量％トルエンを含有するヘプタン溶液に、電解質スラリーに用いたものと同じシリコーン未架橋体を１０．３ｍｇ溶かし、そこに前記混合粉末を１．４７ｇ添加して、正極スラリーを得た。カーボンドータイトを塗付して乾燥したアルミ箔上に、前記正極スラリーを塗布して正極体シートを得た。
【００３２】
得られた正極体シートと前記電解質／負極複合シートを合せ、０．１ＧＰａで加圧しながら接合し、そのままの状態で１５０℃で３０分加熱し、未架橋のシリコーンを架橋させた。
【００３３】
上記操作で得られた多層構造体について、イオン伝導性を評価したところ表１に示す通りに、良好であった。更に実施例１の多層構造体を用いて全固体リチウム電池を作製したところ、何らの異常もなく２次電池動作特性を示した。また、ブンゼンバーナーの火炎中に１０分間放置したが、引火することはなかった。更に、６０℃で３０日放置したが、自己放電が起こらなかった。
【００３４】
【表１】
【発明の効果】
本発明の多層構造体はリチウムイオン伝導性に優れる特徴があり、これを用いて薄型の全固体リチウム電池を安定して容易に得ることができるので、産業上非常に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lithium ion conductive solid electrolyte molded body in which movable ion species are lithium ions, and a lithium battery using the same.
[0002]
[Prior art]
In recent years, with the development of portable devices such as personal computers and mobile phones, the demand for batteries as the power source has become very large. In particular, lithium batteries are materials that have a low atomic weight of lithium and a large ionization energy. Therefore, lithium batteries have been actively researched as batteries that can achieve high energy density, and are now widely used as power sources for portable devices. It has been.
[0003]
On the other hand, as lithium batteries become more and more versatile, dangers such as battery ignition due to an increase in internal energy due to an increase in the amount of active material and an increase in the content of flammable organic solvents used in electrolytes. Sexual interest has been highlighted in recent years.
[0004]
As a method for ensuring the safety of a lithium battery, it is extremely effective to use a solid electrolyte that is a nonflammable substance instead of an organic solvent electrolyte, and various inorganic lithium ion conductive solid electrolyte powders are applied. Therefore, the development of all-solid-state lithium batteries with high safety is progressing.
[0005]
In the development of lithium ion conductive inorganic solid electrolytes, the main focus has been to increase lithium ion conductivity in the inorganic solid electrolytes. However, when applied to devices such as batteries, high lithium ion conductivity It is important to have excellent processability. This is because by reducing the thickness of the solid electrolyte layer, not only can the internal impedance be reduced and the output characteristics can be improved, but also the volume ratio of the solid electrolyte layer in the battery is reduced and the energy density of the battery is also improved. .
[0006]
Therefore, in recent years, a proposal of a new solid electrolyte named “polymer in salt” type, which is composed of an inorganic salt having a high concentration of lithium ion conductivity and rubber-like polymer to impart workability, has been proposed. [C. A. Angel, C.I. Liu and E. Sanche, “Nature” (CA Angell, C. Liu, and E. Sanchez, Nature, Vol. 632 (1993), p. 137), the conductivity is not sufficient.
[0007]
Therefore, a composite lithium ion conductive solid electrolyte made by mixing non-rubber polymers has recently been proposed (Taro Inada, Kazunori Takada, Ryohisa Hiyama, Masaru Takaguchi, Shigeo Kondo, Osamu Watanabe, 26th Abstracts of Solid State Ionics Discussion Meeting, p114). In this method, a lithium ion conductive solid electrolyte compounded mainly by dry mixing without using a solvent exhibits good conductivity.
[0008]
However, when mass productivity is considered in consideration of application to all-solid-state lithium batteries, etc., we adopt a wet method typified by the doctor blade method that can easily produce a thin film and large-area electrolyte layer continuously. However, in the case of the above-described method, since the polymer covers the surface of the particles of the inorganic lithium ion conductive solid electrolyte in a film form, ion diffusion in the composite is inhibited and the ion conductivity is lowered. There's a problem.
[0009]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems and reduces the ion conductivity of the lithium ion conductive solid electrolyte molded body by coating the particle surface of the inorganic lithium ion conductive solid electrolyte by using a specific polymer. The object is to provide a lithium battery that avoids and as a result has practical properties.
[0010]
[Means for Solving the Problems]
That is, the present invention is a multilayer structure in which electrode bodies are provided on both main surfaces of a layered lithium ion conductive solid electrolyte molded body, and the lithium ion conductive solid electrolyte molded body is an inorganic lithium ion conductive solid. Ri Do and a crosslinked product made of the electrolyte particles and the silicone rubber uncrosslinked form, the inorganic lithium ion conductive solid electrolyte particles dispersed crosslinked material during consisting the silicone rubber uncrosslinked form, and, wherein the inorganic lithium ion conducting a multilayer structure, characterized that you have to contact the solid electrolyte particles to each other, it preferably, the crosslinked product made of the silicone rubber uncrosslinked form is not destroyed by the Charpy impact test specified in JIS K-7111 The multilayer structure described above. And this invention is a battery characterized by using the said multilayer structure.
[0011]
In addition, the present invention mixes inorganic lithium ion conductive solid electrolyte particles and an uncrosslinked silicone rubber (hereinafter also referred to as a chemically crosslinkable liquid polymer) and molds them to form a layer. An electrode body is pressure-bonded to the surface to bring the inorganic lithium ion conductive solid electrolyte particles into contact with each other, and the silicone rubber uncrosslinked body is converted into a crosslinked body. .
[0012]
The multilayer structure of the present invention is a multilayer structure in which electrode bodies are provided on both main surfaces of a layered lithium ion conductive solid electrolyte molded body, and the lithium ion conductive solid electrolyte molded body is inorganic lithium ion conductive. It has a characteristic that it is excellent in ion conductivity and can easily obtain an all-solid-state lithium battery.
[0013]
The present inventors experimentally studied various conditions such as composition and particle state when mixing a lithium ion conductive solid electrolyte and a polymer to obtain a lithium ion conductive solid electrolyte composite. When using a chemically crosslinkable liquid polymer as the lithium ion conductive solid electrolyte composite obtained, not only has good ion conductivity, but also excellent workability, particularly thin film workability, and The present inventors have obtained the knowledge that a lithium ion conductive solid electrolyte molded body obtained by molding the lithium ion conductive solid electrolyte composite is suitable for a thin all solid lithium ion battery, and have reached the present invention.
[0014]
Although the reason for this is not clear, even if the distribution of the polymer in the lithium ion conductive solid electrolyte complex is in a state covering the particle surface of the lithium ion conductive inorganic solid electrolyte, this is uniaxial. By applying pressure treatment with a press or a roller, the distribution state of the polymer changes to such an extent that it does not interfere with the contact between the particles of the lithium ion conductive inorganic solid electrolyte, and the resulting lithium ion conductive solid electrolyte is obtained. It is inferred that the contact between the solid electrolyte particles becomes good in the molded body.
[0015]
Based on the above inference, lithium ion conductive inorganic solid electrolyte particles when a cross-linking reaction is caused after blending an uncrosslinked polymer (hereinafter referred to as uncrosslinked body) with lithium ion conductive inorganic solid electrolyte. It can be easily inferred that among those whose surface conditions change, those which can achieve the object and effect of the present invention are equivalent to the chemically crosslinkable liquid polymer of the present invention.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
Polymers having a cross-linked structure (hereinafter referred to as cross-linked products) are roughly divided into physical cross-linked products that exhibit rubber elasticity due to higher-order structures in which hard segments and soft segments are entangled, such as styrene-butadiene block copolymers. There is a chemically crosslinked body such as rubber rubber that exhibits rubber elasticity by a chemical bond generated by a crosslinking reaction. In the present invention, in order to ensure the workability of the resulting lithium ion conductive solid electrolyte composite, a polymer crosslinked product obtained by crosslinking a liquid uncrosslinked product is obtained, and therefore the latter chemical crosslinked product is obtained. Selected. Whether or not the polymer is a chemically crosslinked product can be evaluated by whether or not the polymer swells when immersed in a solvent having the same solubility parameter.
[0017]
As the chemically crosslinkable rubbery polymer, in addition to silicone rubber, for example, in the case of hydrocarbon, natural rubber, synthetic rubber such as isoprene and butadiene are known. These uncrosslinked products are known to have various viscosities at room temperature, and some of them may appear solid, but even in that case, they exhibit fluidity called cold flow when left for a long time. It is a liquid substance. Of these, an uncrosslinked product of a high fluidity liquid is preferable in order to reduce the coating of the polymer on the inorganic lithium ion conductive solid electrolyte particles. In this regard, as shown in Examples described later, an uncrosslinked low-viscosity silicone rubber having a viscosity of, for example, about 0.8 to 1.0 Pa · s is one of particularly suitable polymers. In addition, since the uncrosslinked product of silicone rubber is excellent in electrochemical stability and electronic insulation, it is also suitable for the present invention in view of the properties of the obtained crosslinked product.
[0018]
Further, in the present invention, it is desirable that the cross-linked body made of the chemically cross-linkable liquid polymer does not break in the Charpy impact test specified in JIS K-7111. However, the presence of a cross-linked product made of a chemically cross-linkable liquid polymer improves the mechanical properties of the lithium ion conductive solid electrolyte composite and can improve the resistance against the application of stress in actual use. Therefore, when the above requirements are satisfied, the mechanical and thus electrical reliability of the lithium ion conductive solid electrolyte composite, and thus the lithium battery, can be improved.
[0019]
As the inorganic lithium ion conductive solid electrolyte used in the present invention, various kinds are known, e.g., sulfide having a composition as 0.01Li 3 PO 4 · 0.63Li 2 S · 0.36SiS 2 Glass [N. Aotani, K.A. Iwamoto, K. Takada and S.H. Kondo, “Solid State Ionics” (N. Aotani, K. Iwamoto, K. Takada, and S. Kondo, Solid State Ionics, Vol. 68 (1994), p. 35) and Li 3.25 Ge 0.25 P 0.75 S lithium germanium thio having the composition as 4 - phosphate (hereinafter, thio - to as Rishikon) (Masahiro Murayama, Kanno Ryotsugi, Yoji Kawamoto, Takashi Kamiyama, electrochemical Society 68th Conference Abstracts, P183) is High conductivity is suitable.
[0020]
In the present invention, the ratio of the cross-linked product made of the chemically crosslinkable liquid polymer to the inorganic lithium ion conductive solid electrolyte is 2% by volume of the cross-linked product made of the chemically crosslinkable liquid polymer. It is preferably 10% to 10%. If the cross-linked product composed of a chemically crosslinkable liquid polymer is less than 2% by volume, it may be difficult to obtain a molded product having high workability and flexibility. A molded body having sufficient lithium ion conductivity may not be obtained. If it is addition within the said range, the lithium ion conductive solid electrolyte molded object which has a high ion conductivity of 3x10 < -4 > S * cm < -1 > or more will be obtained.
[0021]
The multilayer structure of the present invention has a structure in which electrode bodies are provided on both main surfaces of a layered molded body made of the above-described specific lithium ion conductive solid electrolyte molded body. About the thickness of the said layered molded object, what is necessary is just about 20-100 micrometers in thickness with respect to an all-solid-state lithium battery. Furthermore, in order to improve the mechanical properties of the molded body, an electrically insulating structure can be used. For example, a polyester mesh can be disposed in or in contact with the lithium ion conductive solid electrolyte molded body.
[0022]
The electrode body in the present invention includes a positive electrode body and a negative electrode body.
As the positive electrode body, for example, the same chemical crosslinkability as that used for the lithium ion conductive solid electrolyte molded body part of the present invention in a mixture comprising a positive electrode active material, an inorganic lithium ion conductive solid electrolyte, and a conductive additive. However, the present invention is not limited to this because it is preferable to add the above liquid polymer because it has excellent adhesion to the lithium ion conductive solid electrolyte composite.
[0023]
Examples of the positive electrode active material include oxides such as lithium cobaltate, lithium nickelate, and lithium manganate or transition metals partially substituted with other metals. Examples of the conductive assistant include carbon powder such as acetylene black and metal powder such as nickel and iron.
[0024]
For example, by applying a slurry of the positive electrode body onto a current collector, the current collecting property and mechanical strength are improved. As the positive electrode current collector, an aluminum foil, a foil made of nickel, or a mesh made of aluminum, nickel, or stainless steel can be used. Aluminum foil is the easiest to handle in order to obtain good processability of the sheet. When applying the positive electrode slurry to the aluminum foil, in order to improve its adhesion, the aluminum foil is roughened in advance and / or a composite conductive slurry containing carbon and a resin is applied to the primer layer. It is also effective to form As this composite conductive slurry, in addition to commercially available products such as carbon dotite, a low melting point terpene resin and carbon can be mixed in a solvent and made by themselves.
[0025]
In the case of carbon dotite, since the solvent is toluene-based, the solvent of the positive electrode slurry is preferably a saturated hydrocarbon solvent containing a small amount of toluene. The primer surface melts with a small amount of toluene, and good adhesion is developed. When a terpene resin having a low melting point is used, for example, if a phenol terpene resin is selected, it is insoluble in a saturated hydrocarbon solvent. Therefore, when using such a resin, the positive electrode slurry is prepared and coated with a saturated hydrocarbon solvent, and then heated to 100 ° C. or higher and bonded using terpene resin melting. This heat treatment may also serve as a silicone crosslinking reaction. In that case, a heating temperature of about 150 ° C. is desirable.
[0026]
As the negative electrode body, for example, the same chemical crosslinkability as that used for the lithium ion conductive solid electrolyte molded body part of the present invention in a mixture comprising a negative electrode active material, an inorganic lithium ion conductive solid electrolyte, and a conductive auxiliary agent However, the present invention is not limited to this because it is preferable to add the above liquid polymer because it has excellent adhesion to the lithium ion conductive solid electrolyte composite. Examples of the active material used in the negative electrode body of the present invention include an indium foil, a lithium foil, or an alloy foil thereof, or a graphite film produced on the negative electrode current collector. In addition, as in the case of the positive electrode, it is also possible to apply a slurry on the current collector, including, for example, a negative electrode active material, an inorganic lithium ion conductive solid electrolyte, and a conductive auxiliary agent. This is effective when a negative electrode body made of a mixture is used. Examples of the current collector for the negative electrode include copper foil and stainless steel mesh.
[0027]
The multilayer structure of the present invention includes, for example, an inorganic lithium ion conductive solid electrolyte (hereinafter simply referred to as an electrolyte) and a chemically crosslinkable liquid polymer, which are molded into a layer shape. It can be obtained by bonding an electrode body to the substrate and further converting the liquid polymer into a crosslinked body. At this time, as described above, if an inorganic lithium ion conductive solid electrolyte and a chemically crosslinkable liquid polymer are mixed in both the positive electrode and the negative electrode, a lithium ion conductive solid electrolyte molded body can be obtained. When cross-linking, the chemically cross-linkable liquid polymer present in the positive electrode and the negative electrode can be cross-linked together, and the adhesion between the electrode body and the lithium ion conductive solid electrolyte molded body is extremely good, which is preferable. . The bonding method may be, for example, stacking a positive electrode body, an electrolyte layer (hereinafter simply referred to as an electrolyte layer), a negative electrode body, and a negative electrode current collector on the positive electrode current collector, or on the positive electrode current collector. Alternatively, a positive electrode component in which the positive electrode body is overlaid and a negative electrode component in which the negative electrode body is overlaid on the negative electrode current collector are separately produced, and an electrolyte layer is applied to one of the components, and then both the components are joined. For the negative electrode, when an alloy foil is used as the active material, the negative electrode current collector may be joined immediately before being sealed in a case. At the time of joining, each component is stacked, and then subjected to a heat treatment after being pressed with a uniaxial press or a roller, or a heat treatment is performed while applying a pressure, thereby causing a crosslinking reaction.
[0028]
Further, the present invention is a battery using the multilayer structure described above, and does not include an electrolytic solution made of an organic solvent, and thus has high safety performance such as fire resistance. In addition, since side reactions such as decomposition of the electrolytic solution do not occur, the storage characteristics are excellent, and self-discharge does not occur during long-term storage. The battery of the present invention can be obtained by using the multilayer structure of the present invention described above, providing a current collector or a lead portion on the multilayer structure, and further sealing the case.
[0029]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
The inorganic lithium ion conductive solid electrolyte was thio-ricicone Li 3.25 Ge 0.25 P 0.75 S 4 , which was synthesized by heating Li 2 S, GeS 2 , P 2 S 5 at 700 ° C. under vacuum. The pulverization of the lithium ion conductive solid electrolyte, mixing of silicone rubber, etc., thinning, sample preparation for ionic conductivity measurement, and ionic conductivity measurement were all performed in a dry argon atmosphere. Moreover, about the said grinding | pulverization operation, it was performed until the particle diameter became 1-5 micrometers by observation with a scanning electron microscope.
[0030]
Examples 1-3
Two-part silicone (viscosity 0.8 Pa · s) of the weight shown in Table 1 that cures by addition reaction was added to dry heptane at room temperature. Next, 1.47 g of pulverized thio-lysicon was added to the resulting solution to form a slurry. The slurry was cast on an indium sheet (thickness 0.1 mm) to be a negative electrode, and heptane was distilled off to obtain an electrolyte / negative electrode composite sheet.
[0031]
On the other hand, 2.4 g of lithium cobaltate, 1.4 g of thio-ricicone, and 40 mg of acetylene black were dry mixed to obtain a mixed powder. Next, 10.3 mg of the same uncrosslinked silicone as used in the electrolyte slurry was dissolved in a heptane solution containing 2 wt% toluene, and 1.47 g of the mixed powder was added thereto to obtain a positive electrode slurry. The positive electrode slurry was applied onto an aluminum foil that had been coated with carbon dotite and dried to obtain a positive electrode sheet.
[0032]
The obtained positive electrode sheet and the electrolyte / negative electrode composite sheet were combined, joined while being pressurized at 0.1 GPa, and heated as it was at 150 ° C. for 30 minutes to crosslink uncrosslinked silicone.
[0033]
The multilayer structure obtained by the above operation was evaluated for ionic conductivity, as shown in Table 1, and was good. Furthermore, when the all-solid-state lithium battery was produced using the multilayer structure of Example 1, the operating characteristics of the secondary battery were shown without any abnormality. Moreover, it was left in the flame of the Bunsen burner for 10 minutes, but it did not ignite. Furthermore, although it was left to stand at 60 ° C. for 30 days, no self-discharge occurred.
[0034]
[Table 1]
【Effect of the invention】
The multilayer structure of the present invention is characterized by excellent lithium ion conductivity, and a thin all-solid lithium battery can be stably and easily obtained by using this, so that it is very useful industrially.
Claims (4)
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| JP5286516B2 (en) * | 2006-06-05 | 2013-09-11 | 国立大学法人三重大学 | Positive electrode material for all-solid-state lithium batteries |
| JP2014116164A (en) * | 2012-12-07 | 2014-06-26 | Samsung R&D Institute Japan Co Ltd | Solid-state battery |
| JP6429412B2 (en) * | 2015-02-04 | 2018-11-28 | 富士フイルム株式会社 | All-solid secondary battery, solid electrolyte composition and battery electrode sheet used therefor, battery electrode sheet and method for producing all-solid secondary battery |
| CN107112587B (en) * | 2015-02-12 | 2019-03-19 | 富士胶片株式会社 | All-solid-state secondary battery, solid electrolyte composition, battery electrode sheet |
| PL3570358T3 (en) * | 2017-03-16 | 2025-03-17 | Lg Energy Solution, Ltd. | Electrode assembly for solid state battery and method for manufacturing the same |
| JP6793813B2 (en) * | 2017-03-22 | 2020-12-02 | エルジー・ケム・リミテッド | Electrodes for all-solid-state batteries and their manufacturing methods |
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| JPS63239775A (en) * | 1987-03-27 | 1988-10-05 | Japan Synthetic Rubber Co Ltd | solid electrolyte battery |
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