JP4104289B2 - Electrolyte for electrochemical device, electrolyte or solid electrolyte thereof, and battery - Google Patents
Electrolyte for electrochemical device, electrolyte or solid electrolyte thereof, and battery Download PDFInfo
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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
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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
- Y02E60/13—Energy storage using capacitors
Description
【０００１】
【発明の属する技術分野】
本発明は、リチウム電池、リチウムイオン電池、電気二重層キャパシタ等の電気化学ディバイス用として利用される優れたサイクル特性を示す電解質、電解液または固体電解質、及びそれを用いた電池に関する。
【０００２】
【従来技術】
近年の携帯機器の発展に伴い、その電源として電池やキャパシタのような電気化学的現象を利用した電気化学ディバイスの開発が盛んに行われるようになった。また、電源以外の電気化学ディバイスとしては、電気化学反応により色の変化が起こるエレクトロクロミックディスプレイ（ＥＣＤ）が挙げられる。
【０００３】
これらの電気化学ディバイスは、一般に一対の電極とその間を満たすイオン伝導体から構成される。このイオン伝導体には、溶媒、高分子またはそれらの混合物中に電解質と呼ばれるカチオン（Ａ+）とアニオン（Ｂ-）からなる塩類（ＡＢ）を溶解したものが用いられる。この電解質は溶解することにより、カチオンとアニオンに解離して、イオン伝導する。ディバイスに必要なイオン伝導度を得るためには、この電解質が溶媒や高分子に十分な量溶解することが必要である。実際は水以外のものを溶媒として用いる場合が多く、このような有機溶媒や高分子に十分な溶解度を持つ電解質は現状では数種類に限定される。例えば、リチウム電池用電解質としては、ＬｉＣｌＯ4、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＡｓＦ6、ＬｉＮ（ＳＯ2ＣＦ3）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2 、ＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）およびＬｉＣＦ3ＳＯ3のみである。カチオンの部分はリチウム電池のリチウムイオンのように、ディバイスにより決まっているものが多いが、アニオンの部分は溶解性が高いという条件を満たせば使用可能である。
【０００４】
ディバイスの応用範囲が多種多様化している中で、それぞれの用途に対する最適な電解質が探索されているが、現状ではアニオンの種類が少ないため最適化も限界に達している。また、既存の電解質は種々の問題を持っており、新規のアニオン部を有する電解質が要望されている。具体的にはＣｌＯ4イオンは爆発性、ＡｓＦ6イオンは毒性を有するため安全上の理由で使用できない。唯一実用化されているＬｉＰＦ6も耐熱性、耐加水分解性などの問題を有する。また、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（ＳＯ2Ｃ2Ｆ5）2 、ＬｉＮ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）およびＬｉＣＦ3ＳＯ3は安定性が高く、イオン伝導度も高いため非常に優れた電解質であるが、電池内のアルミニウムの集電体を電位がかかった状態で腐食するため使用が困難である。
【０００５】
【問題点を解決するための具体的手段】
本発明者らは、かかる従来技術の問題点に鑑み鋭意検討の結果、新規の化学構造的な特徴を有する電解質と従来の電解質を組み合わせた系により優れた特性が得られることを見出し本発明に到達したものである。
【０００６】
すなわち本発明は、次の［発明１］〜［発明８］を含む。
［発明１］下記式（１ａ）
【化５】
ＬｉＰＦ 6 もしくはＬｉＢＦ ４ から選ばれる何れか１種の無機塩と、
を有する、電気化学ディバイス用電解質であって、
上記アルミン酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、
上記電気化学ディバイス用電解質。
【０００７】
［発明２］下記式（１ｂ）
【化６】
ＬｉＰＦ 6 の構造を有する無機塩と、
を有する、電気化学ディバイス用電解質であって、
上記ホウ酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、
上記電気化学ディバイス用電解質。
【０００８】
［発明３］ 下記式（１ｃ）
【化７】
ＬｉＢＦ ４ の構造を有する無機塩と、
を有する、電気化学ディバイス用電解質であって、
上記アルミン酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、
上記電気化学ディバイス用電解質。
【０００９】
［発明４］ 発明１乃至発明３の何れかに記載の電気化学ディバイス用電解質を、非水溶媒に溶解したものよりなることを特徴とする、電気化学ディバイス用電解液。
【００１０】
［発明５］ 非水溶媒がエチレンカーボネートを含む溶媒であることを特徴とする、発明４に記載の電気化学ディバイス用電解液。
【００１１】
［発明６］ 下記式（１ａ）
【化８】
ＬｉＰＦ 6 の構造を有する無機塩と、
を有する、電気化学ディバイス用電解質であって、
上記アルミン酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、
上記電気化学ディバイス用電解質を、ポリマーに溶解したものよりなることを特徴とする、電気化学ディバイス用固体電解質。
【００１２】
［発明７］ ポリマーがポリエチレンオキシドポリマーである、発明６に記載の、電気化学ディバイス用固体電解質。
【００１３】
［発明８］ 少なくとも正極、負極、電解液または固体電解質からなり、該電解液が発明４又は発明５に記載の電気化学ディバイス用電解液であり、該固体電解質が発明６又は発明７に記載の電気化学ディバイス用固体電解質であることを特徴とする電池。
【００１４】
以下に、本発明をより詳細に説明する。
【００１５】
まず、式（１ａ）の構造を有するアルミン酸リチウム誘導体と混合して使用される無機塩は、ＬｉＰＦ 6 もしくはＬｉＢＦ ４ から選ばれる何れか１種の無機塩である。
また、式（１ｂ）の構造を有するホウ酸リチウム誘導体と混合して使用される無機塩は 、ＬｉＰＦ 6 である。
また、式（１ｃ）の構造を有するアルミン酸リチウム誘導体と混合して使用される無機塩は、ＬｉＢＦ ４ である。
これらの電解質は単独で使用すると、６０℃以上の高温に於いてアニオンの熱分解が起こりルイス酸を発生してそれが溶媒を分解し、ディバイスの性能及び寿命を悪化させるという問題が起こる場合がある。また、極微量の水分の混入によりアニオンが加水分解を受けて酸を発生し、これも同様にディバイスの性能及び寿命を悪化させる。本発明ではこれらの電解質と式（１ａ）の構造を有するアルミン酸リチウム誘導体、式（１ｂ）の構造を有するホウ酸リチウム誘導体または式（１ｃ）の構造を有するアルミン酸リチウム誘導体の電解質を混合して使用することで、この熱分解及び加水分解を抑制することが可能となった。その原理の詳細は明らかではないが、一般式（１ａ）〜（１ｃ）の電解質との何らかの相互作用により溶液全体の物性が変化しているものと推測される。
【００１６】
これらの電解質の使用割合は、電気化学ディバイスのサイクル特性や保存安定性の向上効果を考慮すると、以下に示す範囲が好ましい。式（１ａ）の構造を有するアルミン酸リチウム誘導体、式（１ｂ）の構造を有するホウ酸リチウム誘導体または式（１ｃ）の構造を有するアルミン酸リチウム誘導体の電解質と、ＬｉＰＦ 6 もしくはＬｉＢＦ ４ から選ばれる無機塩又はＬｉＰＦ 6 の構造を有する無機塩の電解質のモル比は、１：９９〜９９：１であり、さらに好ましくは２０：８０〜８０：２０である。一般式（１ａ）〜（１ｃ）の電解質が１より少ない場合は、分解の抑制効果が小さいため、サイクル特性、保存安定性が悪くなるし、また、９９より大きい場合は、ＬｉＰＦ 6 もしくはＬｉＢＦ ４ から選ばれる無機塩又はＬｉＰＦ 6 の構造を有する無機塩の電解質のイオン伝導性の高さ、電気化学的安定性が充分に発揮できない。
【００１７】
本発明の電解質を用いて電気化学ディバイスを構成する場合、その基本構成要素としては、イオン伝導体、負極、正極、集電体、セパレーターおよび容器等から成る。
【００１８】
イオン伝導体としては、電解質と非水系溶媒又はポリマーの混合物が用いられる。非水系溶媒を用いれば、一般にこのイオン伝導体は電解液と呼ばれ、ポリマーを用いれば、ポリマー固体電解質と呼ばれるものになる。ポリマー固体電解質には可塑剤として非水系溶媒を含有するものも含まれる。
【００１９】
非水溶媒としては、本発明の電解質を溶解できる非プロトン性の溶媒であれば特に限定されるものではなく、例えば、カーボネート類、エステル類、エーテル類、ラクトン類、ニトリル類、アミド類、スルホン類等が使用できる。また、単一の溶媒だけでなく、二種類以上の混合溶媒でもよい。具体例としては、プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、メチルエチルカーボネート、ジメトキシエタン、アセトニトリル、プロピオニトリル、テトラヒドロフラン、２−メチルテトラヒドロフラン、ジオキサン、ニトロメタン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、スルホラン、およびγ−ブチロラクトン等を挙げることができる。
【００２０】
ただし、二種類以上の混合溶媒にする場合、これらの非水溶媒のうち誘電率が２０以上の非プロトン性溶媒と誘電率が１０以下の非プロトン性溶媒からなる混合溶媒に溶解することにより電解液を調製することが好ましい。特にリチウム塩ではジエチルエーテル、ジメチルカーボネート等の誘電率が１０以下の非プロトン性溶媒に対する溶解度が低く単独では十分なイオン伝導度が得られず、また、逆に誘電率２０以上の非プロトン性溶媒単独では溶解度は高いもののその粘度も高いため、イオンが移動しにくくなりやはり十分なイオン伝導度が得られない。これらを混合すれば、適当な溶解度と移動度を確保することができ十分なイオン伝導度を得ることができる。
【００２１】
また、電解質を溶解するポリマーとしては、非プロトン性のポリマーであれば特に限定されるものではない。例えば、ポリエチレンオキシドを主鎖または側鎖に持つポリマー、ポリビニリデンフロライドのホモポリマーまたはコポリマー、メタクリル酸エステルポリマー、ポリアクリロニトリルなどが挙げられる。これらのポリマーに可塑剤を加える場合は、上記の非プロトン性非水溶媒が使用可能である。これらのイオン伝導体中における本発明の混合電解質濃度は、０．１ｍｏｌ／ｄｍ3以上、飽和濃度以下、好ましくは、０．５ｍｏｌ／ｄｍ3以上、１．５ｍｏｌ／ｄｍ3以下である。０．１ｍｏｌ／ｄｍ3より濃度が低いとイオン伝導度が低いため好ましくない。
【００２２】
負極材料としては、特に限定されないが、リチウム電池の場合、リチウム金属やリチウムと他の金属との合金が使用される。また、リチウムイオン電池の場合、ポリマー、有機物、ピッチ等を焼成して得られたカーボンや天然黒鉛、金属酸化物等のインターカレーションと呼ばれる現象を利用した材料が使用される。電気二重層キャパシタの場合、活性炭、多孔質金属酸化物、多孔質金属、導電性ポリマー等が用いられる。
【００２３】
正極材料としては、特に限定されないが、リチウム電池及びリチウムイオン電池の場合、例えば、ＬｉＣｏＯ2 、ＬｉＮｉＯ2、ＬｉＭｎＯ2 、ＬｉＭｎ2 Ｏ4 等のリチウム含有酸化物、ＴｉＯ2 、Ｖ2Ｏ5 、ＭｏＯ3 等の酸化物、ＴｉＳ2 、ＦｅＳ等の硫化物、あるいはポリアセチレン、ポリパラフェニレン、ポリアニリン、およびポリピロール等の導電性高分子が使用される。電気二重層キャパシタの場合、活性炭、多孔質金属酸化物、多孔質金属、導電性ポリマー等が用いられる。
【００２４】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はかかる実施例により限定されるものではない。
【００２５】
実施例１
エチレンカーボネート５０ｖｏｌ％とジメチルカーボネート５０ｖｏｌ％の混合溶媒中に、
【００２６】
【化９】
の構造を有するアルミン酸リチウム誘導体０．０１ｍｏｌ／ｌとＬｉＰＦ6０．９９ｍｏｌ／ｌとを溶解した電解液を調製し、この電解液を用いてＬｉＣｏＯ2を正極材料、天然黒鉛を負極材料としてセルを作製し、実際に電池の充放電試験を実施した。試験用セルは以下のように作製した。
【００２８】
ＬｉＣｏＯ2粉末９０重量部に、バインダーとして５重量部のポリフッ化ビニリデン（ＰＶＤＦ）、導電材としてアセチレンブラックを５重量部混合し、さらにＮ，Ｎ−ジメチルホルムアミドを添加し、ペースト状にした。このペーストをアルミニウム箔上に塗布して、乾燥させることにより、試験用正極体とした。また、天然黒鉛粉末９０重量部に、バインダーとして１０重量部のポリフッ化ビニリデン（ＰＶＤＦ）を混合し、さらにＮ，Ｎ−ジメチルホルムアミドを添加し、スラリー状にした。このスラリーを銅箔上に塗布して、１５０℃で１２時間乾燥させることにより、試験用負極体とした。そして、ポリエチレン製セパレータに電解液を浸み込ませてセルを組み立てた。
【００２９】
次に、以下のような条件で定電流充放電試験を実施した。充電、放電ともに電流密度０．３５ｍＡ／ｃｍ2 で行い、充電は、４．２Ｖ、放電は、３．０Ｖまで、試験温度は７０℃で行った。その結果、５００回充放電を繰り返したが５００回目の容量は初回の８４％という結果が得られた。
【００３０】
実施例２
エチレンカーボネート５０ｖｏｌ％とジエチルカーボネート５０ｖｏｌ％の混合溶媒中に、
【００３１】
【化１０】
の構造を有するホウ酸リチウム誘導体０．２０ｍｏｌ／ｌとＬｉＰＦ6０．８０ｍｏｌ／ｌとを溶解した電解液を調製し、この電解液を用いて実施例１と同様にＬｉＣｏＯ2を正極材料、天然黒鉛を負極材料としたセルを作製し、電池の充放電試験を実施した。
【００３３】
次に、以下のような条件で定電流充放電試験を実施した。充電、放電ともに電流密度０．３５ｍＡ／ｃｍ2 で行い、充電は、４．２Ｖ、放電は、３．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ+）まで試験温度は７０℃で行った。その結果、５００回充放電を繰り返したが５００回目の容量は初回の９１％という結果が得られた。
【００３４】
実施例３
エチレンカーボネート５０ｖｏｌ％とジメチルカーボネート５０ｖｏｌ％の混合溶媒中に、実施例１と同様の構造を有するアルミン酸リチウム誘導体０．０５ｍｏｌ／ｌとＬｉＢＦ4０．９５ｍｏｌ／ｌとを溶解した電解液を調製し、この電解液を用いて実施例１と同様にＬｉＣｏＯ2を正極材料、天然黒鉛を負極材料としたセルを作製し、以下のような条件で定電流充放電試験を実施した。充電、放電ともに電流密度０．３５ｍＡ／ｃｍ2で行い、充電は、４．２Ｖ、放電は、３．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）まで試験温度は７０℃で行った。その結果、５００回充放電を繰り返したが５００回目の容量は初回の８２％という結果が得られた。
【００３５】
実施例４
エチレンカーボネート５０ｖｏｌ％とジメチルカーボネート５０ｖｏｌ％の混合溶媒中に、
【００３６】
【化１１】
の構造を有するアルミン酸リチウム誘導体０．９５ｍｏｌ／ｌとＬｉＢＦ4０．０５ｍｏｌ／ｌとを溶解した電解液を調製し、この電解液を用いて実施例１と同様にＬｉＣｏＯ2を正極材料、リチウム金属を負極材料としたセルを作製し、以下のような条件で定電流充放電試験を実施した。充電、放電ともに電流密度０．３５ｍＡ／ｃｍ2で行い、充電は、４．２Ｖ、放電は、３．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）まで試験温度は７０℃で行った。その結果、５００回充放電を繰り返したが５００回目の容量は初回の７９％という結果が得られた。
【００３８】
実施例５
平均分子量１００００のポリエチレンオキシド８０重量部にアセトニトリルを添加して溶液を調整し、この溶液に実施例１と同様の構造を有するアルミン酸リチウム誘導体を１０重量部、ＬｉＰＦ6を１０重量部加え、これをガラス上にキャストし、乾燥して溶媒のアセトニトリルを除去することにより高分子固体電解質膜を作製した。
【００３９】
次にこの高分子固体電解質膜を電解液とセパレータの代わりとして用いて実施例１と同様にＬｉＣｏＯ2を正極材料、天然黒鉛を負極材料としたセルを作製し、７０℃で以下のような条件で定電流充放電試験を実施した。充電、放電ともに電流密度０．１ｍＡ／ｃｍ2で行い、充電は、４．２Ｖ、放電は、３．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）まで行った。その結果、初回の放電容量は、１２０ｍＡｈ／ｇ（正極の容量）であった。また、５００回充放電を繰り返したが５００回目の容量は初回の８３％という結果が得られた。
【００４０】
比較例１
エチレンカーボネート５０ｖｏｌ％とジメチルカーボネート５０ｖｏｌ％の混合溶媒中に、ＬｉＰＦ6を１．０ｍｏｌ／ｌ溶解した電解液を調製した。
【００４１】
この電解液を用いて実施例１と同様にＬｉＣｏＯ2を正極材料、天然黒鉛を負極材料としたセルを作製し、以下のような条件で定電流充放電試験を実施した。充電、放電ともに電流密度０．３５ｍＡ／ｃｍ2で行い、充電は、４．２Ｖ、放電は、３．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）まで試験温度は７０℃で行った。その結果、５００回充放電を繰り返したが５００回目の容量は初回の６４％という結果が得られた。
【００４２】
比較例２
エチレンカーボネート５０ｖｏｌ％とジメチルカーボネート５０ｖｏｌ％の混合溶媒中に、ＬｉＢＦ4を１．０ｍｏｌ／ｌ溶解した電解液を調製した。
【００４３】
この電解液を用いて実施例１と同様にＬｉＣｏＯ2を正極材料、天然黒鉛を負極材料としたセルを作製し、以下のような条件で定電流充放電試験を実施した。充電、放電ともに電流密度０．３５ｍＡ／ｃｍ2で行い、充電は、４．２Ｖ、放電は、３．０Ｖ（ｖｓ．Ｌｉ／Ｌｉ+ ）まで試験温度は７０℃で行った。その結果、５００回充放電を繰り返したが５００回目の容量は初回の４６％という結果が得られた。
【００４４】
【発明の効果】
本発明は、リチウム電池、リチウムイオン電池、電気二重層キャパシタ等の電気化学ディバイス用として利用される従来の電解質に比べ、優れたサイクル特性、保存特性を有する電解質であり、その電解液または固体電解質並びにこれらを用いた電池を可能としたものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrolyte, an electrolytic solution, or a solid electrolyte that exhibits excellent cycle characteristics used for electrochemical devices such as lithium batteries, lithium ion batteries, and electric double layer capacitors, and a battery using the same.
[0002]
[Prior art]
With the development of portable devices in recent years, the development of electrochemical devices using electrochemical phenomena such as batteries and capacitors as a power source has become active. Further, as an electrochemical device other than the power source, an electrochromic display (ECD) in which a color change is caused by an electrochemical reaction can be given.
[0003]
These electrochemical devices are generally composed of a pair of electrodes and an ionic conductor filling them. As the ionic conductor, a solution in which a salt (AB) composed of a cation (A + ) and an anion (B − ) called an electrolyte is dissolved in a solvent, a polymer, or a mixture thereof is used. When this electrolyte is dissolved, it dissociates into a cation and an anion, and conducts ions. In order to obtain the ionic conductivity necessary for the device, it is necessary that this electrolyte is dissolved in a sufficient amount in a solvent or a polymer. Actually, a solvent other than water is often used as a solvent, and there are currently only a few types of electrolytes having sufficient solubility in such organic solvents and polymers. For example, as an electrolyte for a lithium battery, LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ) and LiCF 3 SO 3 only. The cation portion is often determined by the device, such as the lithium ion of a lithium battery, but the anion portion can be used if the condition that the solubility is high is satisfied.
[0004]
While the application range of devices is diversifying, the optimum electrolyte for each application is being searched for, but at present, optimization is reaching its limit because there are few types of anions. Moreover, the existing electrolyte has various problems, and an electrolyte having a novel anion portion is desired. Specifically, ClO 4 ions are explosive and AsF 6 ions are toxic and cannot be used for safety reasons. The only practically used LiPF 6 also has problems such as heat resistance and hydrolysis resistance. Also, LiN (CF 3 SO 2 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ) and LiCF 3 SO 3 are highly stable and have ionic conductivity. It is a very good electrolyte because it is high in degree, but it is difficult to use because the aluminum current collector in the battery is corroded in a state where a potential is applied.
[0005]
[Concrete means for solving the problem]
As a result of intensive studies in view of the problems of the prior art, the present inventors have found that an excellent characteristic can be obtained by a system in which an electrolyte having a novel chemical structural feature and a conventional electrolyte are combined. It has been reached.
[0006]
That is, the present invention includes the following [Invention 1] to [Invention 8] .
[Invention 1] The following formula (1a)
[Chemical formula 5]
Any one inorganic salt selected from LiPF 6 or LiBF 4 ;
An electrolyte for an electrochemical device, comprising:
The molar ratio of the lithium aluminate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
Electrolyte for the above electrochemical device .
[0007]
[Invention 2] The following formula (1b)
[Chemical 6]
An inorganic salt having the structure of LiPF 6 ;
An electrolyte for an electrochemical device, comprising:
The molar ratio of the lithium borate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
Electrolyte for the above electrochemical device .
[0008]
[Invention 3] The following formula (1c)
[Chemical 7]
An inorganic salt having the structure of LiBF 4 ;
An electrolyte for an electrochemical device, comprising:
The molar ratio of the lithium aluminate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
Electrolyte for the above electrochemical device.
[0009]
[Invention 4] invention 1 to an electrochemical devices for electrolyte according to any one of Inventions 3, characterized in that consists of those dissolved in a nonaqueous solvent, electrochemical devices for electrolyte.
[0010]
[Invention 5] The electrolytic solution for an electrochemical device according to Invention 4, wherein the non-aqueous solvent is a solvent containing ethylene carbonate.
[0011]
[Invention 6] The following formula (1a)
[Chemical 8]
An inorganic salt having the structure of LiPF 6 ;
An electrolyte for an electrochemical device, comprising:
The molar ratio of the lithium aluminate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
A solid electrolyte for an electrochemical device, wherein the electrolyte for an electrochemical device is dissolved in a polymer .
[0012]
[Invention 7] The solid electrolyte for an electrochemical device according to Invention 6, wherein the polymer is a polyethylene oxide polymer.
[0013]
[Invention 8] At least a positive electrode, a negative electrode, an electrolytic solution, or a solid electrolyte , and the electrolytic solution is an electrolytic solution for an electrochemical device according to Invention 4 or Invention 5, and the solid electrolyte is described in Invention 6 or Invention 7. A battery characterized by being a solid electrolyte for an electrochemical device .
[0014]
Hereinafter, the present invention will be described in more detail.
[0015]
First, the inorganic salt used by mixing with the lithium aluminate derivative having the structure of the formula (1a) is any one inorganic salt selected from LiPF 6 or LiBF 4 .
An inorganic salt used by mixing with a lithium borate derivative having the structure of the formula (1b) is LiPF 6 .
The inorganic salt used as a mixture with lithium aluminate derivatives having the structure of formula (1c) is LiBF 4.
When these electrolytes are used alone, it may generates a Lewis acid occurs thermal decomposition of the anion at the temperature higher than 60 ° C. It decomposes the solvent, a problem that causes deterioration of the devices of the performance and life occurs is there. In addition, when an extremely small amount of water is mixed, the anion is hydrolyzed to generate an acid, which similarly deteriorates the performance and life of the device. In the present invention, these electrolytes are mixed with lithium aluminate derivatives having the structure of the formula (1a), lithium borate derivatives having the structure of the formula (1b), or lithium aluminate derivatives having the structure of the formula (1c). It is possible to suppress this thermal decomposition and hydrolysis. Although the details of the principle are not clear, it is presumed that the physical properties of the whole solution are changed by some interaction with the electrolytes of the general formulas (1a) to (1c) .
[0016]
The usage ratio of these electrolytes is preferably in the following range in consideration of the cycle characteristics of the electrochemical device and the effect of improving storage stability. Lithium aluminate derivatives having the structure of formula (1a), is selected from the electrolyte of lithium aluminate derivatives having the structure of formula (1b) lithium borate derivative or formula having the structure of (1c), LiPF 6 or LiBF 4 The molar ratio of the electrolyte of the inorganic salt or the inorganic salt having the structure of LiPF 6 is 1:99 to 99: 1 , more preferably 20:80 to 80:20. When the electrolytes of the general formulas (1a) to (1c) are less than 1, the decomposition suppressing effect is small, so that the cycle characteristics and the storage stability are deteriorated. When the electrolyte is more than 99, LiPF 6 or LiBF 4 The high ion conductivity and electrochemical stability of the electrolyte of the inorganic salt selected from the above or the inorganic salt having the structure of LiPF 6 cannot be sufficiently exhibited.
[0017]
When an electrochemical device is constituted using the electrolyte of the present invention, its basic components are composed of an ion conductor, a negative electrode, a positive electrode, a current collector, a separator, a container, and the like.
[0018]
As the ionic conductor, a mixture of an electrolyte and a non-aqueous solvent or polymer is used. If a non-aqueous solvent is used, this ionic conductor is generally called an electrolytic solution, and if a polymer is used, it becomes a polymer solid electrolyte. The polymer solid electrolyte includes those containing a non-aqueous solvent as a plasticizer.
[0019]
The non-aqueous solvent is not particularly limited as long as it is an aprotic solvent capable of dissolving the electrolyte of the present invention, and examples thereof include carbonates, esters, ethers, lactones, nitriles, amides, sulfones. Can be used. Moreover, not only a single solvent but 2 or more types of mixed solvents may be sufficient. Specific examples include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, nitromethane, N, N-dimethylformamide, dimethyl sulfoxide. , Sulfolane, and γ-butyrolactone.
[0020]
However, when two or more kinds of mixed solvents are used, electrolysis is achieved by dissolving them in a mixed solvent composed of an aprotic solvent having a dielectric constant of 20 or more and an aprotic solvent having a dielectric constant of 10 or less. It is preferable to prepare a liquid. In particular, lithium salts have low solubility in an aprotic solvent having a dielectric constant of 10 or less, such as diethyl ether and dimethyl carbonate, so that sufficient ionic conductivity cannot be obtained by themselves, and conversely, an aprotic solvent having a dielectric constant of 20 or more. Independently, the solubility is high, but the viscosity is also high, so that ions are difficult to move and sufficient ionic conductivity cannot be obtained. If these are mixed, appropriate solubility and mobility can be ensured, and sufficient ionic conductivity can be obtained.
[0021]
The polymer that dissolves the electrolyte is not particularly limited as long as it is an aprotic polymer. Examples thereof include polymers having polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile and the like. When a plasticizer is added to these polymers, the above-mentioned aprotic non-aqueous solvent can be used. Mixing the electrolyte concentration of the present invention in these ion conductors in the, 0.1 mol / dm 3 or more, the saturation concentration or less, preferably, 0.5 mol / dm 3 or more and 1.5 mol / dm 3 or less. When the concentration is lower than 0.1 mol / dm 3 , the ionic conductivity is low, which is not preferable.
[0022]
Although it does not specifically limit as a negative electrode material, In the case of a lithium battery, the alloy of lithium metal and lithium and another metal is used. In the case of a lithium ion battery, a material that uses a phenomenon called intercalation such as carbon, natural graphite, or metal oxide obtained by firing a polymer, an organic material, pitch, or the like is used. In the case of an electric double layer capacitor, activated carbon, porous metal oxide, porous metal, conductive polymer, or the like is used.
[0023]
As the cathode material is not particularly limited, a lithium battery and a lithium ion battery, for example, LiCoO 2, LiNiO 2, LiMnO 2, lithium-containing oxides such as LiMn 2 O 4, TiO 2, V 2 O 5, MoO Oxides such as 3 , sulfides such as TiS 2 and FeS, or conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole are used. In the case of an electric double layer capacitor, activated carbon, porous metal oxide, porous metal, conductive polymer, or the like is used.
[0024]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this Example.
[0025]
Example 1
In a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of dimethyl carbonate,
[0026]
[Chemical 9]
An electrolytic solution in which 0.01 mol / l of a lithium aluminate derivative having a structure of 1 and LiPF 6 0.99 mol / l are dissolved is prepared, and the cell is prepared using LiCoO 2 as a positive electrode material and natural graphite as a negative electrode material. The battery was actually charged and discharged. The test cell was produced as follows.
[0028]
To 90 parts by weight of LiCoO 2 powder, 5 parts by weight of polyvinylidene fluoride (PVDF) as a binder and 5 parts by weight of acetylene black as a conductive material were mixed, and N, N-dimethylformamide was further added to form a paste. The paste was applied on an aluminum foil and dried to obtain a test positive electrode body. Further, 90 parts by weight of natural graphite powder was mixed with 10 parts by weight of polyvinylidene fluoride (PVDF) as a binder, and N, N-dimethylformamide was further added to form a slurry. This slurry was applied on a copper foil and dried at 150 ° C. for 12 hours to obtain a test negative electrode body. Then, the electrolyte was immersed in a polyethylene separator to assemble the cell.
[0029]
Next, a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm 2 , charging was performed at 4.2 V, discharging was performed at 3.0 V, and a test temperature was 70 ° C. As a result, charging / discharging was repeated 500 times, but the 500th capacity was 84% of the initial capacity.
[0030]
Example 2
In a mixed solvent of 50 vol% ethylene carbonate and 50 vol% diethyl carbonate,
[0031]
[Chemical Formula 10]
An electrolytic solution in which 0.20 mol / l of a lithium borate derivative having the structure of the above and 0.88 mol / l of LiPF 6 were dissolved was prepared, and LiCoO 2 was used as a positive electrode material in the same manner as in Example 1 using this electrolytic solution. A cell using graphite as a negative electrode material was prepared, and a battery charge / discharge test was performed.
[0033]
Next, a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm 2 , charging was performed at 4.2 V, and discharging was performed at a test temperature of 70 ° C. up to 3.0 V (vs. Li / Li + ). As a result, charging / discharging was repeated 500 times, but the 500th capacity was 91% of the initial capacity.
[0034]
Example 3
An electrolytic solution was prepared by dissolving 0.05 mol / l of a lithium aluminate derivative having the same structure as in Example 1 and 0.95 mol / l of LiBF 4 in a mixed solvent of 50 vol% of ethylene carbonate and 50 vol% of dimethyl carbonate. Using this electrolytic solution, a cell using LiCoO 2 as a positive electrode material and natural graphite as a negative electrode material was prepared in the same manner as in Example 1, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm 2 , charging was performed at 4.2 V, and discharging was performed at a test temperature of 70 ° C. up to 3.0 V (vs. Li / Li + ). As a result, charging / discharging was repeated 500 times, but the capacity at the 500th time was 82% of the first time.
[0035]
Example 4
In a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of dimethyl carbonate,
[0036]
Embedded image
An electrolytic solution in which 0.95 mol / l of a lithium aluminate derivative having the structure of the above and 0.05 mol / l of LiBF 4 were dissolved was prepared, and LiCoO 2 was used as a positive electrode material and lithium as in Example 1 using this electrolytic solution. A cell using metal as a negative electrode material was prepared, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm 2 , charging was performed at 4.2 V, and discharging was performed at a test temperature of 70 ° C. up to 3.0 V (vs. Li / Li + ). As a result, charging / discharging was repeated 500 times, but the capacity at the 500th time was 79% of the first time.
[0038]
Example 5
Acetonitrile was added to 80 parts by weight of polyethylene oxide having an average molecular weight of 10000 to prepare a solution. To this solution, 10 parts by weight of a lithium aluminate derivative having the same structure as in Example 1 and 10 parts by weight of LiPF 6 were added. Was cast on glass and dried to remove acetonitrile as a solvent, thereby preparing a polymer solid electrolyte membrane.
[0039]
Next, a cell using LiCoO 2 as a positive electrode material and natural graphite as a negative electrode material was prepared in the same manner as in Example 1 by using this polymer solid electrolyte membrane instead of an electrolyte and a separator. A constant current charge / discharge test was conducted. Both charging and discharging were performed at a current density of 0.1 mA / cm 2 , charging was performed at 4.2 V, and discharging was performed up to 3.0 V (vs. Li / Li + ). As a result, the initial discharge capacity was 120 mAh / g (capacity of the positive electrode). Moreover, although charging / discharging was repeated 500 times, the capacity of the 500th time was 83% of the first time.
[0040]
Comparative Example 1
An electrolyte solution was prepared by dissolving LiPF 6 in an amount of 1.0 mol / l in a mixed solvent of ethylene carbonate 50 vol% and dimethyl carbonate 50 vol%.
[0041]
Using this electrolytic solution, a cell using LiCoO 2 as a positive electrode material and natural graphite as a negative electrode material was produced in the same manner as in Example 1, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm 2 , charging was performed at 4.2 V, and discharging was performed at a test temperature of 70 ° C. up to 3.0 V (vs. Li / Li + ). As a result, charging / discharging was repeated 500 times, but the capacity at the 500th time was 64% of the first time.
[0042]
Comparative Example 2
An electrolyte solution was prepared by dissolving 1.0 mol / l of LiBF 4 in a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of dimethyl carbonate.
[0043]
Using this electrolytic solution, a cell using LiCoO 2 as a positive electrode material and natural graphite as a negative electrode material was produced in the same manner as in Example 1, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm 2 , charging was performed at 4.2 V, and discharging was performed at a test temperature of 70 ° C. up to 3.0 V (vs. Li / Li + ). As a result, charging / discharging was repeated 500 times, but the 500th capacity was 46% of the initial capacity.
[0044]
【The invention's effect】
The present invention is an electrolyte having excellent cycle characteristics and storage characteristics as compared with conventional electrolytes used for electrochemical devices such as lithium batteries, lithium ion batteries, and electric double layer capacitors. In addition, a battery using these is made possible.
Claims (8)
ＬｉＰＦLiPF 66 もしくはＬｉＢＦOr LiBF ４4 から選ばれる何れか１種の無機塩と、Any one inorganic salt selected from
を有する、電気化学ディバイス用電解質であって、An electrolyte for an electrochemical device, comprising:
上記アルミン酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、The molar ratio of the lithium aluminate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
上記電気化学ディバイス用電解質。Electrolyte for the above electrochemical device.
ＬｉＰＦLiPF 66 の構造を有する無機塩と、An inorganic salt having the structure:
を有する、電気化学ディバイス用電解質であって、An electrolyte for an electrochemical device, comprising:
上記ホウ酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、The molar ratio of the lithium borate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
上記電気化学ディバイス用電解質。Electrolyte for the above electrochemical device.
ＬｉＢＦLiBF ４4 の構造を有する無機塩と、An inorganic salt having the structure:
を有する、電気化学ディバイス用電解質であって、An electrolyte for an electrochemical device, comprising:
上記アルミン酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、The molar ratio of the lithium aluminate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
上記電気化学ディバイス用電解質。Electrolyte for the above electrochemical device.
ＬｉＰＦLiPF 66 の構造を有する無機塩と、An inorganic salt having the structure:
を有する、電気化学ディバイス用電解質であって、An electrolyte for an electrochemical device, comprising:
上記アルミン酸リチウム誘導体と上記無機塩のモル比が、１：９９〜９９：１の範囲である、The molar ratio of the lithium aluminate derivative to the inorganic salt is in the range of 1:99 to 99: 1.
上記電気化学ディバイス用電解質を、ポリマーに溶解したものよりなることを特徴とする、電気化学ディバイス用固体電解質。A solid electrolyte for an electrochemical device, wherein the electrolyte for an electrochemical device is dissolved in a polymer.
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|---|---|---|---|---|
| EP2827430A1 (en) * | 2013-07-19 | 2015-01-21 | Basf Se | Use of lithium alkoxyborates and lithium alkoxyaluminates as conducting salts in electrolytes of lithium ion batteries |
| DE102016200079A1 (en) * | 2016-01-07 | 2017-07-13 | Robert Bosch Gmbh | Electrolyte and battery cell containing this |
-
2001
- 2001-02-27 JP JP2001051414A patent/JP4104289B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002252029A (en) | 2002-09-06 |
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