JP4076738B2 - Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery - Google Patents
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Abstract
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に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、リチウム電池またはリチウムイオン電池に関する。
【０００２】
【従来の技術】
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】
【発明が解決しようとする課題】
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。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】
【課題を解決するための手段】
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を数種類組み合わせた系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、化学式が下記式（１ａ）、式（１ｂ）、式（１ｃ）、式（１ｄ）、または式（１ｅ）で示されるいずれかの化合物と、
【化７】
【化８】
【化９】
【化１０】
【化１１】
一般式（２）、一般式（３）、または一般式（４）で示される化学構造式よりなる化合物のうち少なくとも一つよりなる、アルミニウム集電体を備えるリチウム電池及びリチウムイオン電池用電解質で、
【０００７】
【化１２】
Ａ ａ＋ は、リチウムイオン、ａは、１、Ｙ １ 、Ｙ２、Ｙ３は、それぞれ独立で、ＳＯ２基を、Ｒ５、Ｒ６、Ｒ７は、それぞれ独立で、一般式（２）の場合、Ｒ ５ は、ＣＦ ３ ＣＨ ２ または（ＣＦ ３ ） ２ ＣＨ、一般式（３）の場合、Ｒ ５ とＲ ６ は、それぞれＣＦ ３ ＣＨ ２ または（ＣＦ ３ ） ２ ＣＨ、あるいはＲ ５ とＲ ６ が共に（ＣＦ ３ ） ３ Ｃ、一般式（４）の場合、Ｒ ５ 、Ｒ ６ 、Ｒ ７ は、（ＣＦ ３ ） ２ ＣＨをそれぞれ表す、アルミニウム集電体を備えるリチウム電池及びリチウムイオン電池用電解質であり、該電解質を非水溶媒に溶解したものよりなる、アルミニウム集電体を備えるリチウム電池及びリチウムイオン電池用電解液または該電解質をポリマーに溶解したものよりなる、アルミニウム集電体を備えるリチウム電池及びリチウムイオン電池用固体電解質、及び少なくとも正極、負極、電解液または固体電解質からなり、該電解液または固体電解質に該電解質を含む、アルミニウム集電体を備えるリチウム電池またはリチウムイオン電池を提供するものである。
【００１０】
以下に、本発明をより詳細に説明する。
【００１８】
ここではＡａ＋としてリチウムイオンが挙げられる。
【００２０】
本発明の構成の一部である化学式が式（１ａ）、式（１ｂ）、式（１ｃ）、式（１ｄ）、または式（１ｅ）で示される電解質は、イオン性金属錯体構造を採っており、その中心となる金属は、Ｂ、またはＰである。さらに、Ｂ、またはＰの場合、合成の容易性のほか、低毒性、安定性、コストとあらゆる面で優れた特性を有する。
【００２７】
次に、一般式（２）、一般式（３）、一般式（４）で示される化合物の具体例としては、ＣＦ３ＣＨ２ＯＳＯ３Ｌｉ、（ＣＦ３）２ＣＨＯＳＯ３Ｌｉ、（ＣＦ３ＣＨ２ＯＳＯ２）２ＮＬｉ、（（ＣＦ３）２ＣＨＯＳＯ２）２ＮＬｉ、（ＣＦ３ＣＨ２ＯＳＯ２）（（ＣＦ３）２ＣＨＯＳＯ２）ＮＬｉ、（（ＣＦ３）３ＣＯＳＯ２）２ＮＬｉ、および（（ＣＦ３）２ＣＨＯＳＯ２）３ＣＬｉ、等が挙げられる。これらの電解質は単独で使用すると、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、充放電サイクルを繰り返すと容量が低下するという問題点を有する。本発明ではこれらのスルホニル基を有する電解質と、化学式が式（１ａ）、式（１ｂ）、式（１ｃ）、式（１ｄ）、または式（１ｅ）で示される電解質を混合して使用することで、このアルミニウムの集電体の腐食を防止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、化学式が式（１ａ）、式（１ｂ）、式（１ｃ）、式（１ｄ）、または式（１ｅ）で示される電解質が電極表面でわずかに分解してアルミニウム表面にその配位子からなる皮膜が形成され、その腐食を防止するものと推測される。
【００２８】
これらの電解質の使用割合は、アルミニウム集電体を備えるリチウム電池及びリチウムイオン電池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。化学式が式（１ａ）、式（１ｂ）、式（１ｃ）、式（１ｄ）、または式（１ｅ）で示される電解質と、一般式（２）、一般式（３）、一般式（４）の電解質のモル比は、１：９９〜９９：１、好ましくは２０：８０〜８０：２０である。化学式が式（１ａ）、式（１ｂ）、式（１ｃ）、式（１ｄ）、または式（１ｅ）で示される電解質が１より少ない場合は、アルミニウムの腐食防止の効果が小さいため、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、一般式（２）、一般式（３）、一般式（４）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。
【００２９】
本発明の電解質を用いてアルミニウム集電体を備えるリチウム電池またはリチウムイオン電池を構成する場合、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。
【００３０】
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。
【００３１】
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。
【００３２】
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。
【００３３】
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。
【００３４】
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および金属間化合物が使用される。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。
【００３５】
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 、Ｖ2 Ｏ5、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。
【００３６】
【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。
【００３７】
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、
【００３８】
【化９】
の構造を有するホウ酸リチウム誘導体を０．０１ｍｏｌ／ｌと（（ＣＦ3）2ＣＨＯＳＯ2）2ＮＬｉを０．９９ｍｏｌ／ｌとを溶解した電解液を調製し、この電解液を用いてアルミニウム集電体の腐食試験を実施した。試験用セルは作用極としてアルミニウム、対極及び参照極としてリチウム金属を有するビーカー型のものを用いた。作用極を５Ｖ（Ｌｉ／Ｌｉ+）に保持したところ、全く電流は流れなかった。試験後に作用極表面をＳＥＭで観察したが試験前と比べて変化は認められなかった。
【００４０】
さらに、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。
【００４１】
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。
【００４２】
次に、以下のような条件で定電流充放電試験を実施した。環境温度２５℃で充電、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８７％という結果が得られた。
【００４３】
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、実施例１と同様の構造を有するホウ酸リチウム誘導体を０．９０ｍｏｌ／ｌと（ＣＦ3ＣＨ2ＯＳＯ2）2ＮＬｉを０．１０ｍｏｌ／ｌとを溶解した電解液を調製し、実施例１と同様に、この電解液を用いてアルミニウム集電体の腐食試験を実施した。作用極を５Ｖ（Ｌｉ／Ｌｉ+）に保持したところ、全く電流は流れなかった。試験後に作用極表面をＳＥＭで観察したが試験前と比べて変化は認められなかった。
【００４４】
さらに、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。環境温度６０℃で充電、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。
【００４５】
実施例３
エチレンカーボネート５０ｖｏｌ％とエチルメチルカーボネート５０ｖｏｌ％の混合溶媒中に、
【００４６】
【化１０】
の構造を有するホウ酸リチウム誘導体を０．７０ｍｏｌ／ｌと（（ＣＦ3）2ＣＨＯＳＯ2）2ＮＬｉを０．３０ｍｏｌ／ｌとを溶解した電解液を調製し、実施例１と同様に、この電解液を用いてアルミニウム集電体の腐食試験を実施した。作用極を５Ｖ（Ｌｉ／Ｌｉ+）に保持したところ、全く電流は流れなかった。試験後に作用極表面をＳＥＭで観察したが試験前と比べて変化は認められなかった。
【００４８】
さらに、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。環境温度６０℃で充電、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８９％という結果が得られた。
【００４９】
実施例４
平均分子量１００００のポリエチレンオキシド７０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ホウ酸リチウム誘導体を５重量部、（（ＣＦ3）2ＣＨＯＳＯ2）2ＮＬｉを２５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。
【００５０】
次に、この高分子固体電解質膜を用いてアルミニウム集電体の腐食試験を実施した。この膜を作用極のアルミニウム電極とリチウム電極で挟み、圧着し測定を行った。作用極を５Ｖ（Ｌｉ／Ｌｉ+）に保持したところ、全く電流は流れなかった。試験後に作用極表面をＳＥＭで観察したが試験前と比べて変化は認められなかった。
【００５１】
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ＬｉＣｏＯ2を正極材料、リチウム金属箔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、１００回充放電を繰り返したが１００回目の容量は初回の９２％という結果が得られた。
【００５２】
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、（（ＣＦ3）2ＣＨＯＳＯ2）2ＮＬｉを１．０ｍｏｌ／ｌを溶解した電解液を調製し、実施例１と同様に、この電解液を用いてアルミニウム集電体の腐食試験を実施した。作用極を５Ｖ（Ｌｉ／Ｌｉ+）に保持したところ、腐食電流が観察された。また、試験後に作用極表面をＳＥＭで観察したところ、その表面に腐食によるものと思われるピットが多数観察された。
【００５３】
次に、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。環境温度２５℃で充電、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６２％という結果が得られた。
【００５４】
比較例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、（ＣＦ3ＣＨ2ＯＳＯ2）2ＮＬｉを１．０ｍｏｌ／ｌを溶解した電解液を調製し、実施例１と同様に、この電解液を用いてアルミニウム集電体の腐食試験を実施した。作用極を５Ｖ（Ｌｉ／Ｌｉ+）に保持したところ、腐食電流が観察された。また、試験後に作用極表面をＳＥＭで観察したところ、その表面に腐食によるものと思われるピットが多数観察された。
【００５５】
次に、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。環境温度６０℃で充電、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５８％という結果が得られた。
【００５６】
比較例３
エチレンカーボネート５０ｖｏｌ％とエチル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ホウ酸リチウム誘導体を１．０ｍｏｌ／ｌを溶解した電解液を調製し、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。環境温度６０℃で充電、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６５％という結果が得られた。
【００５７】
【発明の効果】
本発明は、リチウム電池、リチウムイオン電池に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、アルミニウム集電体を備えるリチウム電池またはリチウムイオン電池を可能としたものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lithium battery, an electrolyte exhibiting excellent cycle characteristics used for a lithium ion battery , an electrolytic solution or a solid electrolyte, and a lithium battery or a lithium ion 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]
[Problems to be solved by the invention]
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. 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 have high stability and ionic conductivity. It is a very excellent electrolyte because it is high, 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]
[Means for Solving the Problems]
As a result of intensive studies in view of the problems of the prior art, the present inventors have found a system in which several kinds of electrolytes having novel chemical structural characteristics are combined and have reached the present invention.
[0006]
That is, the present invention relates to any compound represented by the following formula (1a), formula (1b), formula (1c), formula (1d), or formula (1e) :
[Chemical 7]
[Chemical 8]
[Chemical 9]
[Chemical Formula 10]
Embedded image
A lithium battery including an aluminum current collector and an electrolyte for a lithium ion battery, comprising at least one of compounds represented by the chemical structural formula represented by the general formula (2), the general formula (3), or the general formula (4). ,
[0007]
Embedded image
A a + is a lithium ion, a is 1 , Y 1 , Y 2 , Y 3 are each independent, and SO 2 groups are independent of each other, R 5 , R 6 , R 7 are each independent, and the general formula (2) In this case, R 5 is CF 3 CH 2 or (CF 3 ) 2 CH, and in the case of general formula (3), R 5 and R 6 are CF 3 CH 2 or (CF 3 ) 2 CH, or R 5, respectively. And R 6 are both (CF 3 ) 3 C and general formula (4), R 5 , R 6 , R 7 each represent (CF 3 ) 2 CH , a lithium battery with an aluminum current collector and lithium an electrolyte for ion battery, consisting obtained by dissolving a electrolyte in a nonaqueous solvent composed of those dissolved in the polymer electrolyte solution or electrolyte for a lithium battery and a lithium-ion battery comprising an aluminum current collector, an aluminum current collector Li with a body Um batteries and lithium ion batteries for a solid electrolyte, and at least becomes a positive electrode, a negative electrode, from the electrolyte or solid electrolyte comprises electrolyte in the electrolyte solution or a solid electrolyte, a lithium battery or a lithium ion battery comprising an aluminum current collector To do.
[0010]
Hereinafter, the present invention will be described in more detail.
[0018]
Here, lithium ions are exemplified as A a + .
[0020]
The electrolyte represented by the formula (1a), formula (1b), formula (1c), formula (1d), or formula (1e) , which is a part of the structure of the present invention, has an ionic metal complex structure. cage, metal serving as the center is a B or P,. Furthermore, in the case of B or P, in addition to the ease of synthesis, it has excellent properties in all aspects such as low toxicity, stability and cost.
[0027]
Next, specific examples of the compounds represented by the general formula (2), the general formula (3), and the general formula (4) include CF 3 CH 2 OSO 3 Li, (CF 3 ) 2 CHOSO 3 Li, and (CF 3 CH 2 OSO 2 ) 2 NLi, ((CF 3 ) 2 CHOSO 2 ) 2 NLi, (CF 3 CH 2 OSO 2 ) ((CF 3 ) 2 CHOSO 2 ) NLi, ((CF 3 ) 3 COSO 2 ) 2 NLi , And ((CF 3 ) 2 CHOSO 2 ) 3 CLi, and the like . When these electrolytes are used alone, the aluminum current collector in the battery is corroded in a state where an electric potential is applied, so that there is a problem that the capacity decreases when the charge / discharge cycle is repeated. In the present invention, an electrolyte having these sulfonyl groups and an electrolyte having a chemical formula of formula (1a), formula (1b), formula (1c), formula (1d), or formula (1e) are mixed and used. Thus, corrosion of the aluminum current collector can be prevented. Although the details of the principle are not clear, the electrolyte represented by the formula (1a), (1b), (1c), (1d), or (1e) is slightly decomposed on the electrode surface. It is presumed that a film composed of the ligand is formed on the aluminum surface and prevents the corrosion.
[0028]
The usage ratio of these electrolytes is preferably in the range shown below in consideration of the cycle characteristics and the effect of improving storage stability of a lithium battery and a lithium ion battery including an aluminum current collector . An electrolyte having a chemical formula of formula (1a), formula (1b), formula (1c), formula (1d), or formula (1e), and general formula (2), general formula (3), or general formula (4) The molar ratio of the electrolyte is 1:99 to 99: 1, preferably 20:80 to 80:20. When the chemical formula is less than 1 in the formula (1a), the formula (1b), the formula (1c), the formula (1d), or the formula (1e), the effect of preventing the corrosion of aluminum is small. The storage stability is deteriorated, and when it is greater than 99, the high ion conductivity and electrochemical stability of the general formula (2), the general formula (3), and the general formula (4) are sufficient. I can't show it.
[0029]
When a lithium battery or a lithium ion battery including an aluminum current collector is configured using the electrolyte of the present invention, the basic components include an ion conductor, a negative electrode, a positive electrode, a current collector, a separator, a container, and the like.
[0030]
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.
[0031]
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.
[0032]
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.
[0033]
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.
[0034]
Although it does not specifically limit as a negative electrode material, In the case of a lithium battery, the alloy and intermetallic compound of lithium metal, lithium, and another metal are 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 .
[0035]
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 .
[0036]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by this Example.
[0037]
Example 1
In a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of dimethyl carbonate,
[0038]
[Chemical 9]
An electrolytic solution in which 0.01 mol / l of a lithium borate derivative having a structure of (mol) and (0.99 CF / l) of ((CF 3 ) 2 CHOSO 2 ) 2 NLi is dissolved is prepared. An electrical corrosion test was conducted. The test cell was a beaker type having aluminum as a working electrode, a counter electrode and lithium metal as a reference electrode. When the working electrode was held at 5 V (Li / Li + ), no current flowed. After the test, the surface of the working electrode was observed with SEM, but no change was observed compared to before the test.
[0040]
Furthermore, using this electrolytic solution, a cell was fabricated using LiCoO 2 as a positive electrode material and natural graphite as a negative electrode material, and a battery charge / discharge test was actually performed. The test cell was produced as follows.
[0041]
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.
[0042]
Next, a constant current charge / discharge test was performed under the following conditions. Charging and discharging were performed at an environmental temperature of 25 ° C. at a current density of 0.35 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, charging / discharging was repeated 500 times, but the 500th capacity was 87% of the first time.
[0043]
Example 2
In a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate, 0.90 mol / l of a lithium borate derivative having the same structure as in Example 1 and 0.10 mol / l of (CF 3 CH 2 OSO 2 ) 2 NLi An electrolytic solution in which 1 was dissolved was prepared, and a corrosion test of an aluminum current collector was performed using this electrolytic solution in the same manner as in Example 1. When the working electrode was held at 5 V (Li / Li + ), no current flowed. After the test, the surface of the working electrode was observed with SEM, but no change was observed compared to before the test.
[0044]
Further, 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. Charging and discharging were performed at an environmental temperature of 60 ° C. at a current density of 0.35 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, charging / discharging was repeated 500 times, but the 500th capacity was 84% of the initial capacity.
[0045]
Example 3
In a mixed solvent of ethylene carbonate 50 vol% and ethyl methyl carbonate 50 vol%,
[0046]
[Chemical Formula 10]
An electrolyte solution prepared by dissolving 0.70 mol / l of a lithium borate derivative having the structure of (0.3) mol / l of ((CF 3 ) 2 CHOSO 2 ) 2 NLi was prepared. A corrosion test was conducted on the aluminum current collector using the electrolytic solution. When the working electrode was held at 5 V (Li / Li + ), no current flowed. After the test, the surface of the working electrode was observed with SEM, but no change was observed compared to before the test.
[0048]
Further, 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. Charging and discharging were performed at an environmental temperature of 60 ° C. at a current density of 0.35 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, charging / discharging was repeated 500 times, but the 500th capacity was 89% of the first time.
[0049]
Example 4
Acetonitrile was added to 70 parts by weight of polyethylene oxide having an average molecular weight of 10000 to prepare a solution, and 5 parts by weight of a lithium borate derivative having the same structure as in Example 1 was added to this solution ((CF 3 ) 2 CHOSO 2 ). A polymer solid electrolyte membrane was prepared by adding 25 parts by weight of 2NLi, casting it on glass, and drying to remove acetonitrile as a solvent.
[0050]
Next, a corrosion test of the aluminum current collector was performed using this polymer solid electrolyte membrane. This film was sandwiched between an aluminum electrode and a lithium electrode as working electrodes, and measured by pressure bonding. When the working electrode was held at 5 V (Li / Li + ), no current flowed. After the test, the surface of the working electrode was observed with SEM, but no change was observed compared to before the test.
[0051]
Next, a cell using LiCoO 2 as a positive electrode material and lithium metal foil as a negative electrode material was prepared using this polymer solid electrolyte membrane as an electrolyte and a separator, and charged at a constant current at 70 ° C. under the following conditions. A discharge test was performed. 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 100 times, the capacity | capacitance of the 100th time obtained the result of 92% of the first time.
[0052]
Comparative Example 1
An electrolytic solution was prepared by dissolving 1.0 mol / l of ((CF 3 ) 2 CHOSO 2 ) 2 NLi in a mixed solvent of 50 vol% ethylene carbonate and 50 vol% dimethyl carbonate. The corrosion test of the aluminum electrical power collector was implemented using the liquid. When the working electrode was held at 5 V (Li / Li + ), a corrosion current was observed. Further, when the surface of the working electrode was observed with an SEM after the test, many pits that were thought to be due to corrosion were observed on the surface.
[0053]
Next, 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. Charging and discharging were performed at an environmental temperature of 25 ° C. at a current density of 0.35 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, charging / discharging was repeated 500 times, but the capacity at the 500th time was 62% of the first time.
[0054]
Comparative Example 2
An electrolytic solution in which 1.0 mol / l of (CF 3 CH 2 OSO 2 ) 2 NLi was dissolved in a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate was prepared. Was used to conduct corrosion tests on aluminum current collectors. When the working electrode was held at 5 V (Li / Li + ), a corrosion current was observed. Further, when the surface of the working electrode was observed with an SEM after the test, many pits that were thought to be due to corrosion were observed on the surface.
[0055]
Next, 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. Charging and discharging were performed at an environmental temperature of 60 ° C. at a current density of 0.35 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, charging / discharging was repeated 500 times, but the capacity at the 500th time was 58% of the first time.
[0056]
Comparative Example 3
An electrolyte solution was prepared by dissolving 1.0 mol / l of a lithium borate derivative having the same structure as in Example 1 in a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of ethyl methyl carbonate. A cell using LiCoO 2 as a positive electrode material and natural graphite as a negative electrode material was prepared, and a constant current charge / discharge test was performed under the following conditions. Charging and discharging were performed at an environmental temperature of 60 ° C. at a current density of 0.35 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, charging / discharging was repeated 500 times, but the capacity at the 500th time was 65% of the first time.
[0057]
【The invention's effect】
The present invention as compared to conventional electrolytes utilized lithium battery, lithium ion battery, excellent cycle characteristics, a electrolyte with storage characteristics, the electrolyte solution or a solid electrolyte and using them, the aluminum current collector A lithium battery or a lithium ion battery can be provided .
Claims (5)
一般式（２）、一般式（３）、または一般式（４）で示される化学構造式よりなる化合物のうち少なくとも一つよりなる、アルミニウム集電体を備えるリチウム電池及びリチウムイオン電池用電解質。
ａは、１をそれぞれ表し、
Ｙ１、Ｙ２、Ｙ３は、ＳＯ２基、
Ｒ５、Ｒ６、Ｒ７は、それぞれ独立で、一般式（２）の場合、Ｒ ５ は、ＣＦ ３ ＣＨ ２ または（ＣＦ ３ ） ２ ＣＨ、一般式（３）の場合、Ｒ ５ とＲ ６ は、それぞれＣＦ ３ ＣＨ ２ または（ＣＦ ３ ） ２ ＣＨ、あるいはＲ ５ とＲ ６ が共に（ＣＦ ３ ） ３ Ｃ、一般式（４）の場合、Ｒ ５ 、Ｒ ６ 、Ｒ ７ は、（ＣＦ ３ ） ２ ＣＨをそれぞれ表す。 Any compound represented by the following formula (1a), formula (1b), formula (1c), formula (1d), or formula (1e) ;
An electrolyte for a lithium battery and an lithium ion battery, comprising an aluminum current collector , comprising at least one of compounds represented by the chemical structural formula represented by the general formula (2), the general formula (3), or the general formula (4).
a represents 1 and
Y 1 , Y 2 and Y 3 are SO 2 groups,
R 5 , R 6 and R 7 are independent of each other. In the case of the general formula (2), R 5 is CF 3 CH 2 or (CF 3 ) 2 CH, and in the case of the general formula (3), R 5 and R 6 is CF 3 CH 2 or (CF 3 ) 2 CH, or when both R 5 and R 6 are (CF 3 ) 3 C, and in general formula (4), R 5 , R 6 , R 7 are ( Each represents CF 3 ) 2 CH .
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001177867A JP4076738B2 (en) | 2001-06-13 | 2001-06-13 | Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery |
| DE60143070T DE60143070D1 (en) | 2000-10-03 | 2001-10-01 | Electrolyte for electrochemical device |
| EP01123577A EP1195834B1 (en) | 2000-10-03 | 2001-10-01 | Electrolyte for electrochemical device |
| US09/969,127 US6783896B2 (en) | 2000-10-03 | 2001-10-03 | Electrolyte for electrochemical device |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2001177867A JP4076738B2 (en) | 2001-06-13 | 2001-06-13 | Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery |
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| Publication Number | Publication Date |
|---|---|
| JP2002373703A JP2002373703A (en) | 2002-12-26 |
| JP4076738B2 true JP4076738B2 (en) | 2008-04-16 |
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| JP2001177867A Expired - Fee Related JP4076738B2 (en) | 2000-10-03 | 2001-06-13 | Lithium battery and electrolyte for lithium ion battery, electrolyte solution or solid electrolyte thereof, and lithium battery or lithium ion battery |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4186115B2 (en) | 2003-06-11 | 2008-11-26 | ソニー株式会社 | Lithium ion secondary battery |
| JP4941423B2 (en) * | 2003-06-11 | 2012-05-30 | ソニー株式会社 | Lithium ion secondary battery |
| JP4795654B2 (en) * | 2003-06-16 | 2011-10-19 | 株式会社豊田中央研究所 | Lithium ion secondary battery |
| JP2005243504A (en) * | 2004-02-27 | 2005-09-08 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JP5796417B2 (en) | 2011-08-31 | 2015-10-21 | セントラル硝子株式会社 | Non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery |
| JP6440331B2 (en) | 2014-05-08 | 2018-12-19 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Organic electrolyte and lithium battery employing this electrolyte |
| JP6098684B2 (en) | 2015-08-12 | 2017-03-22 | セントラル硝子株式会社 | Non-aqueous electrolyte secondary battery electrolyte and non-aqueous electrolyte secondary battery using the same |
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| JP2002373703A (en) | 2002-12-26 |
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