JP2017004603A - Non-aqueous electrolyte and non-aqueous secondary battery - Google Patents

Non-aqueous electrolyte and non-aqueous secondary battery Download PDF

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JP2017004603A
JP2017004603A JP2015113943A JP2015113943A JP2017004603A JP 2017004603 A JP2017004603 A JP 2017004603A JP 2015113943 A JP2015113943 A JP 2015113943A JP 2015113943 A JP2015113943 A JP 2015113943A JP 2017004603 A JP2017004603 A JP 2017004603A
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bis
trifluoroethyl
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JP6549420B2 (en
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青木　雅裕
Masahiro Aoki
雅裕 青木
大輔 平山
Daisuke Hirayama
大輔 平山
英之 三村
Hideyuki Mimura
英之 三村
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Tosoh F Tech Inc
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Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous electrolyte which achieves both safety and high ion conductivity and, furthermore, to provide a non-aqueous secondary battery superior in safety and output characteristics.SOLUTION: As a non-aqueous solvent, a non-aqueous electrolyte contains fluorine-containing phosphate ester having a 1-6C linear or branched alkyl group, a 6-10C aryl group or 1-6 linear, or a branched fluorine-containing alkyl group. Also, as electrolyte salt, the non-aqueous electrolyte contains fluorosulfonyl imide lithium salt having a fluorine atom or 1-4C linear, a branched alkyl group or 1-4C linear, or a branched fluorine-containing alkyl group.SELECTED DRAWING: None

Description

本発明は非水系二次電池に用いられる安全性とイオン伝導性に優れた非水電解液に関する。より詳細には、非水電解液の溶媒中に含フッ素リン酸エステルを含有させ、電解質塩としてフルオロスルホニルイミドリチウム塩を用いることによる、安全性と良好なイオン伝導性を有する非水電解液、および安全性と出力特性に優れる非水系二次電池に関する。   The present invention relates to a non-aqueous electrolyte excellent in safety and ion conductivity used for a non-aqueous secondary battery. More specifically, a nonaqueous electrolytic solution having safety and good ionic conductivity by containing a fluorine-containing phosphate ester in a solvent of the nonaqueous electrolytic solution and using a fluorosulfonylimide lithium salt as an electrolyte salt, The present invention also relates to a non-aqueous secondary battery having excellent safety and output characteristics.

リチウムイオン二次電池に代表される非水系二次電池は、高出力密度、高エネルギー密度を有し、携帯電話、ノートパソコン、タブレット型コンピューター等の電源として汎用されている。また、近年は二酸化炭素排出量の少ないクリーンなエネルギーとして、電力貯蔵や電気自動車用の大容量電源として、実用化がすすめられている。この様な大型の蓄電池、特に電気自動車やハイブリッド自動車では、瞬間的に大きな電流値を取り出す性能、即ち優れた出力性能を有する必要がある。この様な要求に対して、非水電解液には高いイオン伝導性が求められている（非特許文献１）。   Non-aqueous secondary batteries represented by lithium ion secondary batteries have high output density and high energy density, and are widely used as power sources for mobile phones, notebook computers, tablet computers, and the like. In recent years, it has been put into practical use as clean energy with low carbon dioxide emissions and as a large capacity power source for electric power storage and electric vehicles. Such a large storage battery, particularly an electric vehicle or a hybrid vehicle, needs to have a performance for taking out a large current value instantaneously, that is, an excellent output performance. In response to such demands, high ion conductivity is required for non-aqueous electrolytes (Non-Patent Document 1).

一方、このリチウムイオン二次電池に使われている非水電解液にはエチレンカーボネートやジメチルカーボネート等の可燃性溶媒に電解質として六フッ化リン酸リチウム（ＬｉＰＦ６）を溶解した可燃性の電解液が用いられており、電池の大型化に伴いこれら可燃性非水電解液の安全性の向上が求められている（非特許文献２）。 On the other hand, the non-aqueous electrolyte used in this lithium ion secondary battery is a flammable electrolyte obtained by dissolving lithium hexafluorophosphate (LiPF 6 ) as an electrolyte in a flammable solvent such as ethylene carbonate or dimethyl carbonate. Therefore, improvement of the safety of these combustible non-aqueous electrolytes is required with the increase in size of batteries (Non-Patent Document 2).

こうした非水電解液の安全性の向上に対しては、非水電解液溶媒として含フッ素リン酸エステル（特許文献１〜４）や含フッ素エーテル（特許文献５、６）、含フッ素エステル（特許文献７、８）、含フッ素カーボネート（特許文献９、１０）等の含フッ素溶媒を用いることが提案されている。中でも含フッ素リン酸エステルを含む非水電解液は、特に難燃性に優れており、引火点を有さない高度な安全性を有する電解液を構築できることが知られている（特許文献４）。   For improving the safety of such non-aqueous electrolytes, fluorine-containing phosphate esters (Patent Documents 1 to 4), fluorine-containing ethers (Patent Documents 5 and 6), and fluorine-containing esters (patents) Documents 7 and 8) and fluorine-containing solvents such as fluorine-containing carbonates (Patent Documents 9 and 10) have been proposed. Among these, non-aqueous electrolytes containing fluorine-containing phosphates are particularly excellent in flame retardancy, and it is known that an electrolyte with high safety that does not have a flash point can be constructed (Patent Document 4). .

この含フッ素リン酸エステルは、高エネルギー密度化を目的としたリチウムに対して４．５Ｖ以上の電位で動作する正極活物質を含むリチウムイオン二次電池に対しても、電解液の分解に由来するガス発生が少なく優れたサイクル特性に寄与する非水電解液溶媒として提案されている（特許文献１１）。また、こうした高電位で動作するリチウムイオン二次電池用の非水電解液の分解を更に抑制するための被膜形成剤として、非水電解液中にフルオロスルホニルアニオンを添加することについても提案されている（特許文献１２）。   This fluorine-containing phosphate ester is derived from the decomposition of the electrolytic solution even for a lithium ion secondary battery including a positive electrode active material that operates at a potential of 4.5 V or more with respect to lithium for the purpose of increasing energy density. It has been proposed as a non-aqueous electrolyte solvent that contributes to excellent cycle characteristics with less gas generation (Patent Document 11). In addition, as a film forming agent for further suppressing the decomposition of the non-aqueous electrolyte for a lithium ion secondary battery operating at such a high potential, the addition of a fluorosulfonyl anion to the non-aqueous electrolyte has also been proposed. (Patent Document 12).

特開平８−８８０２３号公報JP-A-8-88023 特開２００７−１４１７６０号公報JP 2007-141760 A 特開２００７−２５８０６７号公報JP 2007-258067 A 特開２０１３−２０７１３号公報JP 2013-20713 A 特開平９−０９７６２７号公報Japanese Patent Laid-Open No. 9-097627 特開平１１−２６０１５号公報JP-A-11-26015 特開平６−２０７１９号公報JP-A-6-20719 特開平１０−１１６６２７号公報JP-A-10-116627 特開平７−６７８６号公報Japanese Patent Laid-Open No. 7-6786 特開２００７−３０５３５２号公報JP 2007-305352 A 国際公開２０１２／０７７７１２号International Publication 2012/0777712 国際公開２０１４／０８０８７０号International Publication No. 2014/080870

「自動車用リチウムイオン電池」金村聖志編著、日刊工業新聞社、２０１０年１２月２０日発行"Automotive Lithium Ion Battery" edited by Seiji Kanamura, published by Nikkan Kogyo Shimbun, December 20, 2010 「リチウムイオン電池の高安全技術と材料」、株式会社シーエムシ―出版、佐藤登、吉野彰監修、２００９年２月１３日発行"High-safety technology and materials for lithium-ion batteries", CMC Publishing Co., Ltd., supervised by Noboru Sato and Akira Yoshino, published February 13, 2009

この様に含フッ素リン酸エステルは、非水系二次電池、特にリチウム二次電池の電解液として有用である事が知られているが、例えば、特許文献３に記載されている様に、多量にリン酸エステル類を添加することにより非水電解液の粘度の上昇及びイオン解離度の低下が引き起こされ、その結果イオン伝導度が低下し非水系二次電池の出力特性が低下することが知られていた。   Thus, the fluorine-containing phosphate ester is known to be useful as an electrolyte solution for non-aqueous secondary batteries, particularly lithium secondary batteries. For example, as described in Patent Document 3, It is known that the addition of phosphoric acid esters causes an increase in the viscosity of the nonaqueous electrolyte and a decrease in the degree of ionic dissociation, resulting in a decrease in ionic conductivity and a decrease in the output characteristics of the nonaqueous secondary battery. It was done.

本発明はこれらの課題に鑑みてなされたものである。即ち本発明は、非水電解液溶媒として含フッ素リン酸エステルを含む安全性の高い非水電解液において、従来困難であったイオン伝導性に優れた非水電解液を提供すること、さらには、この非水電解液を用いることによる出力特性に優れた非水系二次電池を提供することにある。   The present invention has been made in view of these problems. That is, the present invention provides a highly safe non-aqueous electrolyte containing a fluorinated phosphate ester as a non-aqueous electrolyte solvent, and provides a non-aqueous electrolyte having excellent ion conductivity, which has been difficult in the past. An object of the present invention is to provide a non-aqueous secondary battery having excellent output characteristics by using this non-aqueous electrolyte.

本発明者らは、先の課題を解決すべく鋭意検討を重ねた結果、非水電解液の溶媒に含フッ素リン酸エステルを含み、電解質塩として特定のイミドリチウム塩を用いることにより、安全性に優れ且つ優れたイオン伝導性を有する非水電解液が得られることを見出した。さらに本発明の非水電解液は、従来のＬｉＰＦ６を電解質塩として用いた場合に比べて、凝固点が低く、より低温での使用が可能になるという予期しなかった効果を有することも見出し、本発明を完成させるに至った。   As a result of intensive studies to solve the above-mentioned problems, the present inventors have included a fluorine-containing phosphate ester in the solvent of the non-aqueous electrolyte solution, and by using a specific imidolithium salt as an electrolyte salt, safety can be achieved. It was found that a non-aqueous electrolyte having excellent ion conductivity and excellent ion conductivity can be obtained. Furthermore, the nonaqueous electrolytic solution of the present invention has also been found to have an unexpected effect that the freezing point is low and can be used at a lower temperature than when conventional LiPF6 is used as an electrolyte salt. The invention has been completed.

即ち、本発明は下記の要旨に係わるものである。   That is, the present invention relates to the following gist.

（１） 非水溶媒として、下記一般式（１） (1) As a nonaqueous solvent, the following general formula (1)

（式中、Ｒｆ１、Ｒｆ２及びＲｆ３は、それぞれ独立して、炭素数１〜６の直鎖もしくは分岐のアルキル基もしくは炭素数６〜１０のアリール基または炭素数１〜６の直鎖もしくは分岐の含フッ素アルキル基を表し、且つＲｆ１〜Ｒｆ３の少なくとも１つは含フッ素アルキル基である）で表される含フッ素リン酸エステルを含み、電解質塩として下記一般式（２） (In the formula, Rf 1 , Rf 2 and Rf 3 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a linear chain having 1 to 6 carbon atoms. Or a branched fluorine-containing alkyl group, and at least one of Rf 1 to Rf 3 is a fluorine-containing alkyl group), and an electrolyte salt represented by the following general formula (2)

（式中Ｒｆ４はフッ素原子または炭素数１〜４の直鎖もしくは分岐のアルキル基または炭素数１〜４の直鎖もしくは分岐の含フッ素アルキル基を表す）で表されるフルオロスルホニルイミドリチウム塩を含む非水電解液。 (In the formula, Rf 4 represents a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 4 carbon atoms). Non-aqueous electrolyte containing.

（２） 非水溶媒として、更に環状カーボネート、鎖状カーボネート、環状エステル及びリン酸エステルから成る群から選ばれる少なくとも１種を存在させる（１）項に記載の非水電解液。 (2) The nonaqueous electrolytic solution according to (1), wherein at least one selected from the group consisting of a cyclic carbonate, a chain carbonate, a cyclic ester, and a phosphate ester is present as a nonaqueous solvent.

（３） 上記一般式（１）で表される含フッ素リン酸エステルが、リン酸トリス（２，２−ジフルオロエチル）、リン酸トリス（２，２，２−トリフルオロエチル）、リン酸トリス（２，２，３，３−テトラフルオロプロピル）、リン酸ビス（２，２，２−トリフルオロエチル）メチル、リン酸ビス（２，２，２−トリフルオロエチル）エチル、リン酸ビス（２，２，２−トリフルオロエチル）フェニル、リン酸ビス（２，２，２−トリフルオロエチル）２，２−ジフルオロエチル、リン酸ビス（２，２，２−トリフルオロエチル）２，２，３，３−テトラフルオロプロピル、リン酸ビス（２，２−ジフルオロエチル）２，２，２−トリフルオロエチル、リン酸ビス（２，２，３，３−テトラフルオロプロピル）２，２，２−トリフルオロエチル及びリン酸（２，２，２−トリフルオロエチル）（２，２，３，３−テトラフルオロプロピル）メチルからなる群から選ばれる少なくとも１種である（１）項または（２）項に記載の非水電解液。 (3) The fluorine-containing phosphate represented by the general formula (1) is tris (2,2-difluoroethyl) phosphate, tris (2,2,2-trifluoroethyl) phosphate, trisphosphate. (2,2,3,3-tetrafluoropropyl), bis (2,2,2-trifluoroethyl) methyl phosphate, bis (2,2,2-trifluoroethyl) ethyl phosphate, bis ( 2,2,2-trifluoroethyl) phenyl, bis (2,2,2-trifluoroethyl) phosphate 2,2-difluoroethyl, bis (2,2,2-trifluoroethyl) phosphate 2,2 , 3,3-tetrafluoropropyl, bis (2,2-difluoroethyl) phosphate 2,2,2-trifluoroethyl, bis (2,2,3,3-tetrafluoropropyl) 2,2, 2-Trifluoroe Or (2), which is at least one selected from the group consisting of (2,2,2-trifluoroethyl) (2,2,3,3-tetrafluoropropyl) methyl phosphate and phosphoric acid The non-aqueous electrolyte described.

（４） 電解質塩がジフルオロスルホニルイミドリチウムである（１）項から（３）項のいずれか１項に記載の非水電解液。 (4) The nonaqueous electrolytic solution according to any one of (1) to (3), wherein the electrolyte salt is difluorosulfonylimide lithium.

（５） 電解質塩として更にＬｉＰＦ６またはＬｉＢＦ４を含み、フルオロスルホニルイミドリチウム塩に対するＬｉＰＦ６またはＬｉＢＦ４の使用量がモル比で０．０１〜２である（１）項〜（４）項のいずれか１項に記載の非水電解液。 (5) further comprises LiPF 6 or LiBF 4 as an electrolyte salt, the amount of LiPF 6 or LiBF 4 relative fluorosulfonyl imide lithium salt is 0.01 to 2 molar ratio (1) to (4) of section The nonaqueous electrolytic solution according to any one of the above.

（６） 更に存在させる非水溶媒がエチレンカーボネート、プロピレンカーボネート、ビニレンカーボネート、ビニルエチレンカーボネート、フルオロエチレンカーボネート及びジフルオロエチレンカーボネートからなる群から選ばれる少なくとも１種の環状カーボネートである（２）項に記載の非水電解液。 (6) The nonaqueous solvent to be further present is at least one cyclic carbonate selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate and difluoroethylene carbonate. Non-aqueous electrolyte.

（７） 更に存在させる非水溶媒がジメチルカーボネート、ジエチルカーボネート及びエチルメチルカーボネートからなる群から選ばれる少なくとも１種の鎖状カーボネートである（２）項に記載の非水電解液。 (7) The nonaqueous electrolytic solution according to (2), wherein the nonaqueous solvent to be further present is at least one chain carbonate selected from the group consisting of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

（８） 更に存在させる非水溶媒がγ − ブチロラクトン、γ − バレロラクトン、δ−バレロラクトン、ε−カプロラクトン及びγ−ヘキサノラクトンからなる群から選ばれる少なくとも１種の環状エステルである（２）項に記載の非水電解液。 (8) The nonaqueous solvent to be further present is at least one cyclic ester selected from the group consisting of γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone and γ-hexanolactone (2) The nonaqueous electrolytic solution according to Item.

（９） 更に存在させる非水溶媒がリン酸トリメチル、リン酸トリエチル、リン酸トリ−ｎ−プロピル、リン酸トリイソプロピル、リン酸トリ−ｎ−ブチル、リン酸トリイソブチル及びリン酸トリフェニルからなる群から選ばれる少なくとも１種のリン酸エステルである（２）項に記載の非水電解液。 (9) Further, the non-aqueous solvent to be present comprises trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, and triphenyl phosphate. The nonaqueous electrolytic solution according to item (2), which is at least one phosphate ester selected from the group.

（１０）（１）項から（９）項のいずれか１項に記載の非水電解液を含む非水系二次電池。 (10) A nonaqueous secondary battery comprising the nonaqueous electrolyte solution according to any one of items (1) to (9).

本発明によれば、非水溶媒中に含フッ素リン酸エステルを含む電解液において、特定のフルオロスルホニルイミドリチウム塩を電解質塩として用いることにより、従来の電解液では困難であった安全性と高イオン伝導性を両立した非水電解液を提供できる。さらには、本発明の非水電解液を用いることにより、安全性と出力特性に優れた非水系二次電池を提供することができる。   According to the present invention, in an electrolytic solution containing a fluorine-containing phosphate ester in a non-aqueous solvent, by using a specific fluorosulfonylimide lithium salt as an electrolyte salt, safety and high performance that have been difficult with conventional electrolytic solutions are improved. A nonaqueous electrolytic solution having both ionic conductivity can be provided. Furthermore, by using the nonaqueous electrolytic solution of the present invention, a nonaqueous secondary battery excellent in safety and output characteristics can be provided.

測定例１［イオン伝導度］の測定で使用した白金電極を向い合せに組み合わせたガラス製電気化学セルを示す説明図である。It is explanatory drawing which shows the electrochemical cell made from glass which combined the platinum electrode used by the measurement of the measurement example 1 [ion conductivity] facing each other. 実施例６−１、比較例６−１で使用したコインセル型の非水系二次電池の構造を示す模式断面図である。It is a schematic cross section which shows the structure of the coin cell type non-aqueous secondary battery used in Example 6-1 and Comparative Example 6-1.

本発明の非水電解液は、第１の成分として前記一般式（１）で表される含フッ素リン酸エステルを含有する。一般式（１）において、Ｒｆ１、Ｒｆ２及びＲｆ３は、それぞれ独立して、炭素数１〜６の直鎖もしくは分岐のアルキル基もしくは炭素数６〜１０のアリール基または炭素数１〜６の直鎖もしくは分岐の含フッ素アルキル基を表し、且つＲｆ１〜Ｒｆ３の少なくとも１つは含フッ素アルキル基である。 The nonaqueous electrolytic solution of the present invention contains a fluorine-containing phosphate represented by the general formula (1) as a first component. In the general formula (1), Rf 1 , Rf 2 and Rf 3 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 1 to 6 carbon atoms. A linear or branched fluorine-containing alkyl group, and at least one of Rf 1 to Rf 3 is a fluorine-containing alkyl group.

炭素数１〜６の直鎖もしくは分岐のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ペンチル基、およびｎ−ヘキシル基等が挙げられ、炭素数１〜６の直鎖もしくは分岐の含フッ素アルキル基としては、トリフルオロメチル基、２，２−ジフルオロエチル基、２，２，２−トリフルオロエチル基、２，２，３，３−テトラフルオロプロピル基、２，２，３，３，３−ペンタフルオロプロピル基、ヘキサフルオロイソプロピル基、２，２，３，３，４，４，５，５−オクタフルオロペンチル基、２，２，３，３，４，４，５，５，５−ノナフルオロペンチル基及び３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル基等を挙げることができる。このような含フッ素リン酸エステルとして、例えば、リン酸トリス（トリフルオロメチル）、リン酸トリス（２，２−ジフルオロエチル）、リン酸トリス（２，２，２−トリフルオロエチル）、リン酸トリス（２，２，３，３−テトラフルオロプロピル）、リン酸トリス（２，２，３，３，３−ペンタフルオロプロピル）、リン酸トリス（ヘキサフルオロイソプロピル）、リン酸トリス（２，２，３，３，４，４，５，５−オクタフルオロペンチル）、リン酸トリス（２，２，３，３，４，４，５，５，５−ノナフルオロペンチル）、リン酸トリス（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）、リン酸ビス（２，２，２−トリフルオロエチル）メチル、リン酸ビス（２，２，２−トリフルオロエチル）エチル、リン酸ビス（２，２，２−トリフルオロエチル）２，２−ジフルオロエチル、リン酸ビス（２，２，２−トリフルオロエチル）２，２，３，３−テトラフルオロプロピル、リン酸ビス（２，２，３，３−テトラフルオロプロピル）２，２，２−トリフルオロエチル及びリン酸ビス（２，２，２−トリフルオロエチル）（２，２，３，３−テトラフルオロプロピル）メチル等を挙げることができる。   Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, and n -Hexyl group and the like, and examples of the linear or branched fluorine-containing alkyl group having 1 to 6 carbon atoms include trifluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, hexafluoroisopropyl group, 2,2,3,3,4,4,5,5-octa Fluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, etc. Can be mentioned. Examples of such a fluorine-containing phosphate ester include tris phosphate (trifluoromethyl), tris phosphate (2,2-difluoroethyl), tris phosphate (2,2,2-trifluoroethyl), and phosphoric acid. Tris (2,2,3,3-tetrafluoropropyl), Tris phosphate (2,2,3,3,3-pentafluoropropyl), Tris phosphate (hexafluoroisopropyl), Tris phosphate (2,2 , 3,3,4,4,5,5-octafluoropentyl), tris phosphate (2,2,3,3,4,4,5,5,5-nonafluoropentyl), tris phosphate (3 , 3,4,4,5,5,6,6,6-nonafluorohexyl), bis (2,2,2-trifluoroethyl) methyl phosphate, bis (2,2,2-trifluorophosphate) Ethyl) ethyl, biphosphate (2,2,2-trifluoroethyl) 2,2-difluoroethyl, bis (2,2,2-trifluoroethyl) phosphate 2,2,3,3-tetrafluoropropyl, bis (2, 2,3,3-tetrafluoropropyl) 2,2,2-trifluoroethyl and bis (2,2,2-trifluoroethyl) phosphate (2,2,3,3-tetrafluoropropyl) methyl, etc. Can be mentioned.

これら含フッ素リン酸エステルのうち、特に、構造中に含フッ素アルキル基を２つ以上有するリン酸トリス（２，２−ジフルオロエチル）、リン酸トリス（２，２，２−トリフルオロエチル）、リン酸トリス（２，２，３，３−テトラフルオロプロピル）、リン酸ビス（２，２，２−トリフルオロエチル）メチル、リン酸ビス（２，２，２−トリフルオロエチル）エチル、リン酸ビス（２，２，２−トリフルオロエチル）フェニル、リン酸ビス（２，２，２−トリフルオロエチル）２，２−ジフルオロエチル、リン酸ビス（２，２，２−トリフルオロエチル）２，２，３，３−テトラフルオロプロピル、リン酸ビス（２，２，３，３−テトラフルオロプロピル）２，２，２−トリフルオロエチル、リン酸ビス（２，２，２−トリフルオロエチル）（２，２，３，３−テトラフルオロプロピル）メチル等は、それ自体が不燃性を示すことからより好ましい。   Among these fluorine-containing phosphate esters, in particular, tris phosphate (2,2-difluoroethyl) having two or more fluorine-containing alkyl groups in the structure, tris phosphate (2,2,2-trifluoroethyl), Tris (2,2,3,3-tetrafluoropropyl) phosphate, bis (2,2,2-trifluoroethyl) methyl phosphate, bis (2,2,2-trifluoroethyl) ethyl phosphate, phosphorus Bis (2,2,2-trifluoroethyl) phenyl phosphate, bis (2,2,2-trifluoroethyl) phosphate, 2,2-difluoroethyl phosphate, bis (2,2,2-trifluoroethyl phosphate) 2,2,3,3-tetrafluoropropyl, bis (2,2,3,3-tetrafluoropropyl) 2,2,2-trifluoroethyl phosphate, bis (2,2,2-trifluorophosphate) Echi ) (2,2,3,3-tetrafluoro propyl) methyl and the like are themselves more preferable because it exhibits a non-flammable.

これら含フッ素リン酸エステルは、含フッ素エーテルや含フッ素カーボネートに比べて、電解質塩の溶解性に優れるため、含フッ素リン酸エステルを単独で電解液溶媒として使用することができるが、イオン伝導性をより向上させるためには、他の非水溶媒を共存させることが好ましい。非水溶媒としては、エチレンカーボネート、プロピレンカーボネート、ビニレンカーボネート、ビニルエチレンカーボネート、フルオロエチレンカーボネート及びジフルオロエチレンカーボネート等の環状カーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート等の鎖状カーボネート、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、ε−カプロラクトン、γ−ヘキサノラクトン等の環状エステル、リン酸トリメチル、リン酸トリエチル、リン酸トリ−ｎ−プロピル、リン酸トリイソプロピル、リン酸トリ−ｎ−ブチル、リン酸トリイソブチル、リン酸トリフェニル等のリン酸エステル、酢酸メチル、酢酸エチル、酪酸メチル等の鎖状エステル、テトラヒドロフラン、１，３−ジオキサン、ジメトキシエタン、ジエトキシエタン、メトキシエトキシエタン、トリグライム、テトラグライム等のエーテル類、アセトニトリル、ベンゾニトリル、アジポニトリル、グルタロニトリル等のニトリル類、ジオキソラン又はその誘導体、ジメチルスルホン、ジエチルスルホン等の鎖状スルホン類、スルホラン等の環状スルホン類、プロパンスルトン、ブタンスルトンの環状スルホン酸エステル等を例示することができる。これらの非水溶媒の中で、環状カーボネート、環状エステル、鎖状カーボネート、リン酸エステルからなる群から選ばれる少なくとも１種類または２種以上の混合物である事がイオン導電性の点から好ましい。   These fluorine-containing phosphate esters are superior in solubility to electrolyte salts compared to fluorine-containing ethers and fluorine-containing carbonates. Therefore, fluorine-containing phosphate esters can be used alone as an electrolyte solvent. In order to improve further, it is preferable to coexist other non-aqueous solvent. Nonaqueous solvents include ethylene carbonate, propylene carbonate, vinylene carbonate, vinyl ethylene carbonate, cyclic carbonates such as fluoroethylene carbonate and difluoroethylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate, γ-butyrolactone, Cyclic esters such as γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-hexanolactone, trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n phosphate -Phosphate esters such as butyl, triisobutyl phosphate, triphenyl phosphate, chain esters such as methyl acetate, ethyl acetate, methyl butyrate, tetrahydrofuran, 1,3-dioxane, di- Ethers such as methoxyethane, diethoxyethane, methoxyethoxyethane, triglyme and tetraglyme, nitriles such as acetonitrile, benzonitrile, adiponitrile and glutaronitrile, dioxolane or derivatives thereof, and chain sulfones such as dimethylsulfone and diethylsulfone And cyclic sulfones such as sulfolane, propane sultone, butane sultone cyclic sulfonate, and the like. Among these non-aqueous solvents, at least one kind or a mixture of two or more kinds selected from the group consisting of cyclic carbonate, cyclic ester, chain carbonate, and phosphate ester is preferable from the viewpoint of ion conductivity.

本発明の非水電解液は第２の必須成分として、電解質塩として前記一般式（２）で表されるフルオロスルホニルイミドリチウム塩を用いる。代表的なフルオロスルホニルイミドリチウム塩としては、ビス（フルオロスルホニル）イミドリチウム、フルオロスルホニル（トリフルオロメチルスルホニル）イミドリチウム、フルオロスルホニル（ペンタフルオロエチルスルホニル）イミドリチウムを例示することができ、その中でも特にビス（フルオロスルホニル）イミドリチウムがイオン伝導性をより向上できる点で好ましい。   The nonaqueous electrolytic solution of the present invention uses, as a second essential component, a fluorosulfonylimide lithium salt represented by the general formula (2) as an electrolyte salt. Examples of typical fluorosulfonylimide lithium salts include bis (fluorosulfonyl) imide lithium, fluorosulfonyl (trifluoromethylsulfonyl) imide lithium, and fluorosulfonyl (pentafluoroethylsulfonyl) imide lithium. Bis (fluorosulfonyl) imidolithium is preferred because it can further improve ionic conductivity.

また、本発明の非水電解液では、電解質塩として、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２等の他のリチウム塩を併用して用いてもよい。特にＬｉＰＦ６またはＬｉＢＦ４を併用した場合に、高いイオン伝導性を維持しながら非水系二次電池の寿命が改善される等の効果が得られる場合がある。この際、フルオロスルホニルイミドリチウム塩に対する他のリチウム塩との使用量は、モル比で０．０１〜２倍、好ましくは０．１〜１倍である。使用量が０．０１倍未満の場合、併用の効果が得られず、２倍を超える場合はイオン伝導性が十分でない。また、非水電解液における電解質塩の濃度の合計は０．２〜３．０ｍｏｌ／Ｌの範囲とすることが望ましく、特に１．０〜３．０ｍｏｌ／Ｌの高濃度で溶解させた場合にイオン伝導性が高く、長寿命の非水系二次電池が得られ易いため好ましい。０．２ｍｏｌ／Ｌ未満の場合、イオン伝導性が十分でなく、３．０ｍｏｌ／Ｌを超える場合は電解質塩が析出し易い等の問題がある。 In the non-aqueous electrolyte of the present invention, other lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 are used as the electrolyte salt. You may use together. In particular, when LiPF 6 or LiBF 4 is used in combination, effects such as improvement of the lifetime of the non-aqueous secondary battery may be obtained while maintaining high ionic conductivity. Under the present circumstances, the usage-amount with the other lithium salt with respect to the fluoro sulfonyl imide lithium salt is 0.01 to 2 times by mole ratio, Preferably it is 0.1 to 1 time. When the amount used is less than 0.01 times, the combined effect cannot be obtained, and when it exceeds 2 times, the ion conductivity is not sufficient. Further, the total concentration of the electrolyte salt in the non-aqueous electrolyte is preferably in the range of 0.2 to 3.0 mol / L, particularly when dissolved at a high concentration of 1.0 to 3.0 mol / L. It is preferable because a non-aqueous secondary battery having high ion conductivity and a long life can be easily obtained. When the concentration is less than 0.2 mol / L, the ion conductivity is not sufficient, and when it exceeds 3.0 mol / L, there is a problem that the electrolyte salt is likely to precipitate.

本発明の非水電解液を用いた非水系二次電池は、少なくとも正極、負極およびセパレータから成る。負極材料としては、金属リチウム、リチウム合金あるいはリチウムイオンをドープ・脱ドープ可能な炭素材料やケイ素材料、スズやチタンとリチウムの複合酸化物等を用いることができる。正極材料としては、例えば、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２、ＬｉＮｉ１／４Ｍｎ３／４Ｏ４、ＬｉＦｅＯ２、ＬｉＦｅＰＯ４等のリチウムと遷移金属の複合酸化物が用いられる。セパレータとしては、イオン透過性で電気絶縁性を有するものであれば使用できるが、敢えて例示すると、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂あるいはポリフッ化ビニリデン等のフッ素系樹脂の微多孔膜、セルロースや不織布等の線維状物質等を用いることができる。非水系二次電池の形状、形態としては、特に限定するものではないが、例えば、円筒型、角型、コイン型、カード型等が適宜選択される。 The non-aqueous secondary battery using the non-aqueous electrolyte of the present invention comprises at least a positive electrode, a negative electrode, and a separator. As the negative electrode material, metallic lithium, a lithium alloy, a carbon material that can be doped / undoped with lithium ions, a silicon material, a composite oxide of tin, titanium, and lithium, or the like can be used. Examples of the positive electrode material include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 1/4 Mn 3/4 O 4 , LiFeO 2 , LiFePO 4, and the like. A composite oxide of lithium and transition metal is used. The separator can be used as long as it is ion-permeable and electrically insulating. For example, a polyolefin resin such as polyethylene or polypropylene, or a microporous film of a fluorine resin such as polyvinylidene fluoride, cellulose or nonwoven fabric. Fibrous substances such as can be used. The shape and form of the nonaqueous secondary battery are not particularly limited, and for example, a cylindrical shape, a square shape, a coin shape, a card shape, and the like are appropriately selected.

以下に実施例を用いて本発明を詳細に説明するが、本発明はこの実施例によって限定されるものではない。   Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the examples.

測定例１
［イオン伝導度］
非水電解液のイオン伝導度（単位：ｍＳ／ｃｍ）の測定は、「電気化学測定マニュアル、基礎編、２００２、４５、電気化学会編、丸善株式会社」に記載の方法を用いて行った。すなわち、図１に記載のように白金電極２を向い合せに組み合わせたガラス製電気化学セル１に、あらかじめ電気伝導度既知の標準液でセル定数を算出した。調製した電解液をこの電気化学セルに注入し密封した。得られた電気化学セルを、２０℃恒温槽中に１時間静置した後、ポテンショスタット／ガルバノスタット（東陽テクニカ社製、ＶｅｒｓａＳＴＡＴ４−４００）を用い、複素インピーダンス法により溶液抵抗を測定した。得られた溶液抵抗値より、各非水電解液のイオン伝導度を算出した。 Measurement example 1
[Ionic conductivity]
The ion conductivity (unit: mS / cm) of the non-aqueous electrolyte was measured using the method described in “Electrochemical Measurement Manual, Fundamentals, 2002, 45, Electrochemical Society, Maruzen Co., Ltd.”. . That is, as shown in FIG. 1, cell constants were calculated in advance using a standard solution having a known electrical conductivity in a glass electrochemical cell 1 in which platinum electrodes 2 were combined facing each other. The prepared electrolyte was poured into this electrochemical cell and sealed. The obtained electrochemical cell was allowed to stand in a constant temperature bath at 20 ° C. for 1 hour, and then the solution resistance was measured by a complex impedance method using a potentiostat / galvanostat (manufactured by Toyo Technica, VersaSTAT4-400). The ionic conductivity of each non-aqueous electrolyte was calculated from the obtained solution resistance value.

算出式：イオン伝導度（ｍＳ／ｃｍ）＝溶液抵抗値（Ω）／セル定数   Calculation formula: ion conductivity (mS / cm) = solution resistance value (Ω) / cell constant

測定例２
［粘度］
非水電解液の粘度（単位：ｍＰａ・ｓｅｃ）の測定は、コーンプレート型回転粘度計（ＢｒｏｏｋＦｉｅｌｄ社製、ＤＶ−Ｉ ＰＲＩＭＥ）を用いて行った。すなわち、流動式恒温装置を接続した回転粘度計のカップに、調製した電解液を導入し、温度が２０℃で一定となるまで流通させて測定した。 Measurement example 2
[viscosity]
The viscosity (unit: mPa · sec) of the non-aqueous electrolyte was measured using a cone plate type rotational viscometer (manufactured by BrookField, DV-I PRIME). That is, the prepared electrolytic solution was introduced into a cup of a rotational viscometer connected with a fluid thermostat, and measured until the temperature became constant at 20 ° C.

測定例３
［凝固点］
非水電解液の凝固点（単位：℃）の測定は、ＪＩＳ Ｋ００６５「化学製品の凝固点測定方法」に準じて行った。すなわち、ガラス製二重管容器に、調製した電解液を導入し、氷浴（もしくは寒剤）によって間接的に冷却する。上下に振とうするガラス製のかき混ぜ棒により一定の速度で撹拌し、徐々に電解液を冷却する。凝固点の測定は、過冷却がない場合は静止した温度を読み取り、過冷却によって一度凝固点以下に温度が下がった後、再び一定の凝固点を示す場合は、温度上昇の最高温度を読み取ることで測定した。 Measurement example 3
[Freezing point]
Measurement of the freezing point (unit: ° C.) of the non-aqueous electrolyte was performed according to JIS K0065 “Method for measuring freezing point of chemical products”. That is, the prepared electrolyte solution is introduced into a glass double tube container and indirectly cooled by an ice bath (or cryogen). Stir at a constant speed with a glass stirring rod that shakes up and down, and gradually cool the electrolyte. The freezing point was measured by reading the static temperature when there was no supercooling, and by reading the maximum temperature of the temperature rise when it showed a certain freezing point again after the temperature once decreased below the freezing point due to supercooling. .

実施例１−１
リン酸トリス（２，２，２−トリフルオロエチル）（以下ＴＦＥＰと略す）に、電解質としてリチウムビス（フルオロスルホニル）イミド（以下、ＬｉＦＳＩと略す）を１．０ｍｏｌ／Ｌの濃度となるように加え、２０℃にて充分に撹拌して完全に溶解し、電解液を作成した（ＬｉＦＳＩ濃度＝１１．５質量％）。この電解液を用いて、測定例１の方法でイオン伝導度を測定した。また、同様の電解液を用いて、測定例２の方法で粘度を測定した。結果を表１に記す。 Example 1-1
Lithium bis (fluorosulfonyl) imide (hereinafter abbreviated as LiFSI) as an electrolyte is adjusted to a concentration of 1.0 mol / L in tris (2,2,2-trifluoroethyl) phosphate (hereinafter abbreviated as TFEP). In addition, the mixture was sufficiently stirred at 20 ° C. and completely dissolved to prepare an electrolyte solution (LiFSI concentration = 11.5% by mass). Using this electrolytic solution, the ionic conductivity was measured by the method of Measurement Example 1. Moreover, the viscosity was measured by the method of Measurement Example 2 using the same electrolytic solution. The results are shown in Table 1.

比較例１−１
ＴＦＥＰに、電解質として六フッ化リン酸リチウム（以下、ＬｉＰＦ６と略す）を０．５ｍｏｌ／Ｌの濃度となるように加え、２０℃にて充分に撹拌して完全に溶解し、電解液を作成した（ＬｉＰＦ６濃度＝４．５質量％）。この電解液を用いて、測定例１の方法でイオン伝導度を測定した。また、同様の電解液を用いて、測定例２の方法で粘度を測定した。結果を表１に記す。 Comparative Example 1-1
To TFEP, lithium hexafluorophosphate (hereinafter abbreviated as LiPF 6 ) was added as an electrolyte so as to have a concentration of 0.5 mol / L, and the mixture was thoroughly stirred at 20 ° C. to completely dissolve the electrolyte. It was prepared (LiPF 6 concentration = 4.5% by mass). Using this electrolytic solution, the ionic conductivity was measured by the method of Measurement Example 1. Moreover, the viscosity was measured by the method of Measurement Example 2 using the same electrolytic solution. The results are shown in Table 1.

比較例１−２
電解質としてリチウムビス（トリフルオロメチルスルホニル）イミド（以下、ＬｉＴＦＳＩと略す）を用いた以外は実施例１−１と同様の方法で電解液を調製し、イオン伝導度、粘度を測定した（ＬｉＴＦＳＩ濃度＝１７．２質量％）。結果を表１に記す。 Comparative Example 1-2
An electrolyte solution was prepared in the same manner as in Example 1-1 except that lithium bis (trifluoromethylsulfonyl) imide (hereinafter abbreviated as LiTFSI) was used as the electrolyte, and the ionic conductivity and viscosity were measured (LiTFSI concentration). = 17.2 mass%). The results are shown in Table 1.

実施例１−２
リン酸ビス（２，２，２−トリフルオロエチル）メチル（以下ＢＴＦＥＭＰと略す）に、電解質としてＬｉＦＳＩを１．０ｍｏｌ／Ｌの濃度となるように加えた以外は実施例１−１と同様の方法で電解液を調製し、イオン伝導度、粘度を測定した（ＬｉＦＳＩ濃度＝１２．０質量％）。結果を表１に記す。 Example 1-2
The same as Example 1-1 except that LiFSI was added to bis (2,2,2-trifluoroethyl) methyl phosphate (hereinafter abbreviated as BTFEMP) as an electrolyte so as to have a concentration of 1.0 mol / L. An electrolytic solution was prepared by the method, and ionic conductivity and viscosity were measured (LiFSI concentration = 12.0% by mass). The results are shown in Table 1.

比較例１−３
電解質としてＬｉＰＦ６を用いた以外は実施例１−２と同様の方法で１．０ｍｏｌ／Ｌの電解液を調製し、イオン伝導度、粘度を測定した（ＬｉＰＦ６濃度＝９．７質量％）。結果を表１に記す。 Comparative Example 1-3
A 1.0 mol / L electrolytic solution was prepared in the same manner as in Example 1-2 except that LiPF 6 was used as the electrolyte, and the ionic conductivity and viscosity were measured (LiPF 6 concentration = 9.7% by mass). . The results are shown in Table 1.

比較例１−４
電解質としてＬｉＴＦＳＩを用いた以外は実施例１−２と同様の方法で１．０ｍｏｌ／Ｌの電解液を調製し、イオン伝導度、粘度を測定した（ＬｉＴＦＳＩ濃度＝１８．１質量％）。結果を表１に記す。 Comparative Example 1-4
A 1.0 mol / L electrolytic solution was prepared in the same manner as in Example 1-2 except that LiTFSI was used as the electrolyte, and the ionic conductivity and viscosity were measured (LiTFSI concentration = 18.1% by mass). The results are shown in Table 1.

実施例１−３
リン酸ビス（２，２，２−トリフルオロエチル）エチル（以下ＢＴＦＥＥＰと略す）に、電解質としてＬｉＦＳＩを１．０ｍｏｌ／Ｌの濃度となるように加えた以外は実施例１−１と同様の方法で電解液を調製し、イオン伝導度、粘度を測定した（ＬｉＦＳＩ濃度＝１２．４質量％）。結果を表１に記す。 Example 1-3
The same as Example 1-1 except that LiFSI was added to bis (2,2,2-trifluoroethyl) ethyl phosphate (hereinafter abbreviated as BTFEEP) as an electrolyte so as to have a concentration of 1.0 mol / L. An electrolytic solution was prepared by the method, and ionic conductivity and viscosity were measured (LiFSI concentration = 12.4% by mass). The results are shown in Table 1.

比較例１−５
電解質としてＬｉＰＦ６を用いた以外は実施例１−３と同様の方法で１．０ｍｏｌ／Ｌの電解液を調製し、イオン伝導度、粘度を測定した（ＬｉＰＦ６濃度＝１０．２質量％）。結果を表１に記す。 Comparative Example 1-5
A 1.0 mol / L electrolytic solution was prepared in the same manner as in Example 1-3 except that LiPF 6 was used as the electrolyte, and the ionic conductivity and viscosity were measured (LiPF 6 concentration = 10.2% by mass). . The results are shown in Table 1.

比較例１−６
電解質としてＬｉＴＦＳＩを用いた以外は実施例１−３と同様の方法で１．０ｍｏｌ／Ｌの電解液を調製し、イオン伝導度、粘度を測定した（ＬｉＴＦＳＩ濃度＝１９．１質量％）。結果を表１に記す。 Comparative Example 1-6
A 1.0 mol / L electrolytic solution was prepared in the same manner as in Example 1-3 except that LiTFSI was used as the electrolyte, and the ionic conductivity and viscosity were measured (LiTFSI concentration = 19.1% by mass). The results are shown in Table 1.

ＬｉＦＳＩ：リチウムビス（フルオロスルホニル）イミド
ＬｉＰＦ６：六フッ化リン酸リチウム
ＬｉＴＦＳＩ：リチウムビス（トリフルオロメチルスルホニル）イミド
ＴＦＥＰ：リン酸トリス（２，２，２−トリフルオロエチル）
ＢＴＦＥＭＰ：リン酸ビス（２，２，２−トリフルオロエチル）メチル
ＢＴＦＥＥＰ：リン酸ビス（２，２，２−トリフルオロエチル）エチル LiFSI: Lithium bis (fluorosulfonyl) imide LiPF 6 : Lithium hexafluorophosphate LiTFSI: Lithium bis (trifluoromethylsulfonyl) imide TFEP: Tris (2,2,2-trifluoroethyl phosphate)
BTFEMP: bis (2,2,2-trifluoroethyl) methyl phosphate BTFEEP: bis (2,2,2-trifluoroethyl) ethyl phosphate

表１に示した実施例、比較例の結果から、フッ素系リン酸エステル単独の溶媒系において、ＬｉＦＳＩを電解質として用いた場合は、ＬｉＰＦ６やＬｉＴＦＳＩと比較してイオン伝導度が大きく向上していることが判る。このようにイオン伝導度が向上した理由は明らかではないが、ＬｉＦＳＩと含フッ素リン酸エステルとの相互作用によるＬｉＦＳＩの解離状態及びＬｉカチオンへの含フッ素リン酸エステルの配位状態が関係していると考えられる。 From the results of Examples and Comparative Examples shown in Table 1, when LiFSI is used as an electrolyte in a solvent system of a fluorine-based phosphate ester alone, the ionic conductivity is greatly improved compared to LiPF 6 and LiTFSI. I know that. The reason why the ionic conductivity is improved in this way is not clear, but is related to the dissociation state of LiFSI due to the interaction between LiFSI and the fluorine-containing phosphate ester and the coordination state of the fluorine-containing phosphate ester to the Li cation. It is thought that there is.

実施例１−４
ＴＦＥＰに対するＬｉＦＳＩの飽和溶解度を測定した。すなわち、ＴＦＥＰに過剰量のＬｉＦＳＩを混合し、撹拌条件下、２０℃の恒温条件で溶解した。１０時間以上撹拌し、十分溶解したことを確認してから、２時間静置し、上澄み中のＬｉＦＳＩ濃度を１９Ｆ-ＮＭＲ（ＢＲＵＫＥＲ製 ＡＶＡＮＣＥ ＩＩ ４００）により定量することで、ＴＦＥＰ中のＬｉＦＳＩ濃度を算出した。その結果、２０℃におけるＴＦＥＰ中のＬｉＦＳＩ飽和溶解度は２２．９質量％（１．２７ｍｏｌ／Ｌ）であった。 Example 1-4
The saturation solubility of LiFSI in TFEP was measured. That is, an excess amount of LiFSI was mixed with TFEP and dissolved under constant temperature conditions of 20 ° C. under stirring conditions. After stirring for 10 hours or more and confirming that it was sufficiently dissolved, the mixture was allowed to stand for 2 hours, and the LiFSI concentration in the supernatant was determined by 19 F-NMR (AVANCE II 400 manufactured by BRUKER) to determine the LiFSI concentration in TFEP. Was calculated. As a result, the LiFSI saturated solubility in TFEP at 20 ° C. was 22.9% by mass (1.27 mol / L).

比較例１−７
電解質をＬｉＰＦ６に代えた以外は、実施例１−４と同様の操作で飽和溶解度を測定した。その結果、２０℃におけるＴＦＥＰ中のＬｉＰＦ６飽和溶解度は５．６質量％（０．５８ｍｏｌ／Ｌ）であった。 Comparative Example 1-7
Saturation solubility was measured in the same manner as in Example 1-4, except that the electrolyte was changed to LiPF 6 . As a result, the LiPF 6 saturated solubility in TFEP at 20 ° C. was 5.6% by mass (0.58 mol / L).

実施例２−１
エチレンカーボネート（以下、ＥＣと略す）とジメチルカーボネート（以下、ＤＭＣと略す）とＴＦＥＰを体積比、３５／３５／３０の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１２．５質量％）。この電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表２に記す。 Example 2-1
Ethylene carbonate (hereinafter abbreviated as EC), dimethyl carbonate (hereinafter abbreviated as DMC) and TFEP were mixed at a volume ratio of 35/35/30, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L ( LiFSI concentration = 12.5% by mass). The electrolyte solution was measured for ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 2.

比較例２−１
電解質にＬｉＰＦ６を用いた以外は、実施例２−１と同様の方法でイオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１０．１質量％）。結果を表２に記す。 Comparative Example 2-1
Ion conductivity and viscosity were measured in the same manner as in Example 2-1, except that LiPF 6 was used as the electrolyte (LiPF 6 concentration = 10.1% by mass). The results are shown in Table 2.

ＥＣ：エチレンカーボネート、ＤＭＣ：ジメチルカーボネート EC: ethylene carbonate, DMC: dimethyl carbonate

実施例２−１、比較例２−１は、フッ素系リン酸エステルに環状カーボネートと鎖状カーボネートを混合した場合のイオン伝導度、粘度の測定例である。この結果からも明らかな様に、本発明のＬｉＦＳＩとの組み合せた場合にイオン伝導度の向上が認められる。   Example 2-1 and Comparative Example 2-1 are measurement examples of ion conductivity and viscosity when a cyclic carbonate and a chain carbonate are mixed with a fluorine-based phosphate ester. As is apparent from this result, an improvement in ionic conductivity is observed when combined with the LiFSI of the present invention.

実施例２−２
ＥＣとＴＦＥＰを体積比、７／３の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１２．７質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表３に記す。 Example 2-2
EC and TFEP were mixed at a volume ratio of 7/3, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 12.7% by mass). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 3.

実施例２−３
ＥＣ／ＴＦＥＰの混合比を体積比で５／５で混合した以外は、実施例２−２と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１２．３質量％）。結果を表３に記す。 Example 2-3
An electrolytic solution was prepared in the same manner as in Example 2-2 except that the EC / TFEP mixing ratio was 5/5 by volume, and the ionic conductivity and viscosity were measured (LiFSI concentration = 12). .3% by mass). The results are shown in Table 3.

さらにこの電解液を使用して、測定例３の方法で凝固点を測定した結果、凝固点は−５．１℃であった。比較例２−３の結果と比較するとＬｉＦＳＩを電解質として用いた場合、ＬｉＰＦ６に比べて凝固点が低下するという驚くべき効果を有することが判った。 Furthermore, as a result of measuring the freezing point by the method of Measurement Example 3 using this electrolytic solution, the freezing point was -5.1 ° C. If the LiFSI when compared with the results of Comparative Example 2-3 was used as the electrolyte, the freezing point as compared with LiPF 6 was found to have a surprising effect decreases.

実施例２−４
ＥＣ／ＴＦＥＰの混合比を体積比で３／７で混合した以外は、実施例２−２と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１２．０質量％）。結果を表３に記す。 Example 2-4
An electrolytic solution was prepared in the same manner as in Example 2-2 except that the EC / TFEP mixing ratio was 3/7 by volume, and the ionic conductivity and viscosity were measured (LiFSI concentration = 12). 0.0 mass%). The results are shown in Table 3.

比較例２−２
電解質にＬｉＰＦ６を使用した以外は、実施例２−２と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１０．１質量％）。結果を表３に記す。 Comparative Example 2-2
Except using LiPF6 as the electrolyte, an electrolyte solution was prepared in the same manner as in Example 2-2, the ion conductivity, the measurement of the viscosity was performed (LiPF 6 concentration = 10.1 mass%). The results are shown in Table 3.

比較例２−３
電解質にＬｉＰＦ６を使用した以外は、実施例２−３と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝９．９質量％）。結果を表３に記す。 Comparative Example 2-3
An electrolyte solution was prepared in the same manner as in Example 2-3, except that LiPF 6 was used as the electrolyte, and ion conductivity and viscosity were measured (LiPF 6 concentration = 9.9% by mass). The results are shown in Table 3.

さらにこの電解液を使用して、測定例３の方法で凝固点を測定した結果、凝固点は４．１℃であった。   Furthermore, as a result of measuring the freezing point by the method of Measurement Example 3 using this electrolytic solution, the freezing point was 4.1 ° C.

比較例２−４
電解質にＬｉＰＦ６を使用した以外は、実施例２−４と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝９．８質量％）。結果を表３に記す。 Comparative Example 2-4
An electrolyte solution was prepared in the same manner as in Example 2-4 except that LiPF 6 was used as the electrolyte, and the ionic conductivity and viscosity were measured (LiPF 6 concentration = 9.8% by mass). The results are shown in Table 3.

実施例２−２〜２−４、比較例２−２〜２−４は、フッ素系リン酸エステルと非水溶媒の比率を変えて検討した例である。全ての比率において、ＬｉＦＳＩを混合した方が、ＬｉＰＦ６を混合した場合を上回るイオン伝導度を示す。 Examples 2-2 to 2-4 and Comparative Examples 2-2 to 2-4 are examples examined by changing the ratio of the fluorine-based phosphate ester and the nonaqueous solvent. In all proportions, who were mixed LiFSI indicates ionic conductivity of greater than when mixed with LiPF 6.

実施例２−５
プロピレンカーボネート（以下ＰＣと略す）とＴＦＥＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１２．８質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表４に記す。 Example 2-5
Propylene carbonate (hereinafter abbreviated as PC) and TFEP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 12.8 mass%). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 4.

実施例２−６
フルオロエチレンカーボネート（以下ＦＥＣと略す）とＴＦＥＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１１．８質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表４に記す。 Example 2-6
Fluoroethylene carbonate (hereinafter abbreviated as FEC) and TFEP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 11.8% by mass). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 4.

実施例２−７
γ−ブチロラクトン（以下ＧＢＬと略す）とＴＦＥＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１３．４質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表４に記す。 Example 2-7
γ-Butyrolactone (hereinafter abbreviated as GBL) and TFEP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 13.4% by mass). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 4.

実施例２−８
ＰＣとＢＴＦＥＭＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１３．３質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表４に記す。 Example 2-8
PC and BTFEMP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 13.3 mass%). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 4.

実施例２−９
ＧＢＬとＢＴＦＥＭＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１３．３質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表４に記す。 Example 2-9
GBL and BTFEMP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 13.3 mass%). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 4.

比較例２−５
電解質にＬｉＰＦ６を使用した以外は、実施例２−５と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１０．３質量％）。結果を表４に記す。 Comparative Example 2-5
An electrolyte solution was prepared in the same manner as in Example 2-5, except that LiPF 6 was used as the electrolyte, and ionic conductivity and viscosity were measured (LiPF 6 concentration = 10.3 mass%). The results are shown in Table 4.

比較例２−６
電解質にＬｉＰＦ６を使用した以外は、実施例２−６と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝９．５質量％）。結果を表４に記す。 Comparative Example 2-6
An electrolyte solution was prepared in the same manner as in Example 2-6, except that LiPF 6 was used as the electrolyte, and ionic conductivity and viscosity were measured (LiPF 6 concentration = 9.5 mass%). The results are shown in Table 4.

比較例２−７
電解質にＬｉＰＦ６を使用した以外は、実施例２−７と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１０．７質量％）。結果を表４に記す。 Comparative Example 2-7
An electrolyte solution was prepared in the same manner as in Example 2-7, except that LiPF 6 was used as the electrolyte, and ionic conductivity and viscosity were measured (LiPF 6 concentration = 10.7% by mass). The results are shown in Table 4.

比較例２−８
電解質にＬｉＰＦ６を使用した以外は、実施例２−８と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１０．７質量％）。結果を表４に記す。 Comparative Example 2-8
Except for using LiPF 6 as the electrolyte, an electrolytic solution was prepared in the same manner as in Example 2-8, and the ionic conductivity and viscosity were measured (LiPF 6 concentration = 10.7% by mass). The results are shown in Table 4.

比較例２−９
電解質にＬｉＰＦ６を使用した以外は、実施例２−９と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１１．０質量％）。結果を表４に記す。 Comparative Example 2-9
Except for using LiPF 6 as the electrolyte, an electrolytic solution was prepared in the same manner as in Example 2-9, and the ionic conductivity and viscosity were measured (LiPF 6 concentration = 11.0% by mass). The results are shown in Table 4.

ＰＣ：プロピレンカーボネート ＦＥＣ：フルオロエチレンカーボネート
ＧＢＬ：γ-ブチロラクトン
実施例２−５〜２−９、比較例２−５〜２−９は、ＥＣ以外の環状カーボネートや環状エステルを用いた例を示す。この様に、ＥＣに限らず、様々な溶媒との組合せでイオン伝導度が向上することが判る。 PC: Propylene carbonate FEC: Fluoroethylene carbonate GBL: γ-butyrolactone Examples 2-5 to 2-9 and Comparative examples 2-5 to 2-9 show examples using cyclic carbonates and cyclic esters other than EC. Thus, it turns out that ion conductivity improves not only by EC but in combination with various solvents.

実施例３−１
リン酸トリエチル（以下、ＴＥＰと略す）とＴＦＥＰを体積比、７／３の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１４．５質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表５に記す。 Example 3-1
Triethyl phosphate (hereinafter abbreviated as TEP) and TFEP were mixed at a volume ratio of 7/3, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 14.5% by mass). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 5.

実施例３−２
ＴＥＰ／ＴＦＥＰの混合比を体積比で５／５で混合した以外は、実施例３−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１４．０質量％）。結果を表５に記す。 Example 3-2
An electrolyte solution was prepared in the same manner as in Example 3-1, except that the mixing ratio of TEP / TFEP was 5/5 by volume ratio, and ionic conductivity and viscosity were measured (LiFSI concentration = 14). 0.0 mass%). The results are shown in Table 5.

実施例３−３
ＴＥＰ／ＴＦＥＰの混合比を体積比で３／７で混合した以外は、実施例３−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１３．１質量％）。結果を表５に記す。 Example 3-3
An electrolyte solution was prepared in the same manner as in Example 3-1, except that the TEP / TFEP mixing ratio was 3/7 by volume, and the ionic conductivity and viscosity were measured (LiFSI concentration = 13). .1% by mass). The results are shown in Table 5.

実施例３−４
リン酸トリメチル（以下、ＴＭＰと略す）とＴＦＥＰを体積比、７／３の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１３．５質量％）。結果を表５に記す。 Example 3-4
Trimethyl phosphate (hereinafter abbreviated as TMP) and TFEP were mixed at a volume ratio of 7/3, and LiFSI as an electrolyte was dissolved at 1 mol / L. The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2 (LiFSI concentration = 13.5% by mass). The results are shown in Table 5.

実施例３−５
ＴＭＰ／ＴＦＥＰの混合比を体積比で５／５で混合した以外は、実施例３−４と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１３．２質量％）。結果を表５に記す。 Example 3-5
An electrolyte solution was prepared in the same manner as in Example 3-4, except that the mixing ratio of TMP / TFEP was 5/5 by volume ratio, and ionic conductivity and viscosity were measured (LiFSI concentration = 13). .2% by mass). The results are shown in Table 5.

実施例３−６
ＴＭＰ／ＴＦＥＰの混合比を体積比で３／７で混合した以外は、実施例３−４と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１２．２質量％）。結果を表５に記す。 Example 3-6
An electrolyte solution was prepared in the same manner as in Example 3-4, except that the TMP / TFEP mixing ratio was 3/7 by volume, and the ionic conductivity and viscosity were measured (LiFSI concentration = 12). .2% by mass). The results are shown in Table 5.

比較例３−１
電解質にリチウムビス（トリフルオロメチルスルホニル）イミド（以下、ＬｉＴＦＳＩと略す）を使用した以外は、実施例３−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＴＦＳＩ濃度＝２２．３質量％）。結果を表５に記す。 Comparative Example 3-1
An electrolyte solution was prepared in the same manner as in Example 3-1, except that lithium bis (trifluoromethylsulfonyl) imide (hereinafter abbreviated as LiTFSI) was used as the electrolyte, and ionic conductivity and viscosity were measured. (LiTFSI concentration = 22.3 mass%). The results are shown in Table 5.

比較例３−２
電解質にＬｉＴＦＳＩを使用した以外は、実施例３−２と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＴＦＳＩ濃度＝２１．２質量％）。結果を表５に記す。 Comparative Example 3-2
Except that LiTFSI was used as the electrolyte, an electrolytic solution was prepared in the same manner as in Example 3-2, and ionic conductivity and viscosity were measured (LiTFSI concentration = 21.2 mass%). The results are shown in Table 5.

さらにこの電解液を使用して、測定例３の方法で凝固点を測定した結果、凝固点は４．１℃であった。   Furthermore, as a result of measuring the freezing point by the method of Measurement Example 3 using this electrolytic solution, the freezing point was 4.1 ° C.

比較例３−３
電解質にＬｉＴＦＳＩを使用した以外は、実施例３−３と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＴＦＳＩ濃度＝１９．５質量％）。結果を表５に記す。 Comparative Example 3-3
An electrolyte solution was prepared in the same manner as in Example 3-3 except that LiTFSI was used as the electrolyte, and ionic conductivity and viscosity were measured (LiTFSI concentration = 19.5 mass%). The results are shown in Table 5.

比較例３−４
電解質にＬｉＴＦＳＩを使用した以外は、実施例３−４と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＴＦＳＩ濃度＝２０．９質量％）。結果を表５に記す。 Comparative Example 3-4
An electrolyte solution was prepared in the same manner as in Example 3-4 except that LiTFSI was used as the electrolyte, and ionic conductivity and viscosity were measured (LiTFSI concentration = 20.9 mass%). The results are shown in Table 5.

比較例３−５
電解質にＬｉＴＦＳＩを使用した以外は、実施例３−５と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＴＦＳＩ濃度＝２０．０質量％）。結果を表５に記す。 Comparative Example 3-5
Except having used LiTFSI for the electrolyte, an electrolytic solution was prepared in the same manner as in Example 3-5, and ionic conductivity and viscosity were measured (LiTFSI concentration = 20.0 mass%). The results are shown in Table 5.

比較例３−６
電解質にＬｉＴＦＳＩを使用した以外は、実施例３−５と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＴＦＳＩ濃度＝１９．０質量％）。結果を表５に記す。 Comparative Example 3-6
Except having used LiTFSI for the electrolyte, an electrolytic solution was prepared in the same manner as in Example 3-5, and ionic conductivity and viscosity were measured (LiTFSI concentration = 19.0 mass%). The results are shown in Table 5.

ＴＥＰ：リン酸トリエチル ＴＭＰ：リン酸トリメチル
ＬｉＴＦＳＩ：リチウムビス（トリフルオロメチルスルホニル）イミド TEP: Triethyl phosphate TMP: Trimethyl phosphate LiTFSI: Lithium bis (trifluoromethylsulfonyl) imide

実施例３−１〜３−６、比較例３−１〜３−６は、フッ素系リン酸エステルに非フッ素のリン酸エステルを混合し、比較電解質としてＬｉＴＦＳＩを用いた例を示す。この結果から明らかな様に、非フッ素のリン酸エステルと組合わせた場合でも、ＬｉＦＳＩ電解質を用いた方が、イオン伝導度が向上することが判る。   Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-6 show examples in which a non-fluorine phosphate ester is mixed with a fluorine phosphate ester and LiTFSI is used as a comparative electrolyte. As is clear from this result, even when combined with a non-fluorine phosphate ester, it is understood that the ionic conductivity is improved by using the LiFSI electrolyte.

実施例４−１
ＥＣとＢＴＦＥＭＰを体積比、７／３の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１２．８質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表６に記す。 Example 4-1
EC and BTFEMP were mixed at a volume ratio of 7/3, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L (LiFSI concentration = 12.8% by mass). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 6.

実施例４−２
ＥＣ／ＢＴＦＥＭＰの混合比を体積比で５／５で混合した以外は、実施例４−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１２．５質量％）。結果を表６に記す。 Example 4-2
An electrolytic solution was prepared in the same manner as in Example 4-1, except that the EC / BTFEMP mixing ratio was 5/5 by volume ratio, and the ionic conductivity and viscosity were measured (LiFSI concentration = 12). .5% by mass). The results are shown in Table 6.

実施例４−３
ＥＣ／ＢＴＦＥＭＰの混合比を体積比で３／７で混合した以外は、実施例４−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝１２．４質量％）。結果を表６に記す。 Example 4-3
An electrolyte solution was prepared in the same manner as in Example 4-1, except that the EC / BTFEMP mixing ratio was 3/7 by volume, and the ionic conductivity and viscosity were measured (LiFSI concentration = 12). .4 mass%). The results are shown in Table 6.

比較例４−１
電解質にＬｉＰＦ６を使用した以外は、実施例４−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１０．４質量％）。結果を表６に記す。 Comparative Example 4-1
Except using LiPF6 as the electrolyte, an electrolyte solution was prepared in the same manner as in Example 4-1, the ion conductivity, the measurement of the viscosity was performed (LiPF 6 concentration = 10.4 mass%). The results are shown in Table 6.

比較例４−２
電解質にＬｉＰＦ６を使用した以外は、実施例４−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝１０．２質量％）。結果を表６に記す。 Comparative Example 4-2
Except using LiPF6 as the electrolyte, an electrolyte solution was prepared in the same manner as in Example 4-1, the ion conductivity, the measurement of the viscosity was performed (LiPF 6 concentration = 10.2 mass%). The results are shown in Table 6.

比較例４−３
電解質にＬｉＰＦ６を使用した以外は、実施例４−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝９．９質量％）。結果を表６に記す。 Comparative Example 4-3
Except using LiPF6 as the electrolyte, an electrolyte solution was prepared in the same manner as in Example 4-1, the ion conductivity, the measurement of the viscosity was performed (LiPF 6 concentration = 9.9 wt%). The results are shown in Table 6.

実施例５−１
ＥＣとＴＦＥＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを０．５ｍｏｌ／Ｌ、ＬｉＰＦ６を０．５ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝６．１質量％、ＬｉＰＦ６濃度＝５．０質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表７に記す。 Example 5-1
EC and TFEP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved at 0.5 mol / L and LiPF6 was dissolved at 0.5 mol / L (LiFSI concentration = 6.1 mass%, LiPF 6 concentration = 5.0 mass%). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 7.

比較例５−１
電解質にＬｉＰＦ６を１ｍｏｌ／Ｌ溶解し、この電解液に１ｗｔ％のＬｉＦＳＩを加えた以外は、実施例５−１と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝９．９質量％）。結果を表７に記す。 Comparative Example 5-1
An electrolyte solution was prepared in the same manner as in Example 5-1, except that 1 mol / L of LiPF6 was dissolved in the electrolyte, and 1 wt% LiFSI was added to the electrolyte solution, and ionic conductivity and viscosity were measured. (LiPF 6 concentration = 9.9% by mass). The results are shown in Table 7.

実施例５−２
ＥＣとＴＦＥＰ、１，３-プロパンスルトンを体積比、４７．５／４７．５／５の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝１２．３質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表８に記す。 Example 5-2
EC, TFEP, and 1,3-propane sultone were mixed at a volume ratio of 47.5 / 47.5 / 5, and LiFSI as an electrolyte was dissolved at 1 mol / L (LiFSI concentration = 12.3 mass). %). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 8.

比較例５−２
電解質にＬｉＰＦ６を１ｍｏｌ／Ｌ溶解した以外は、実施例５−２と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝９．９質量％）。結果を表８に記す。 Comparative Example 5-2
Except that LiPF6 in the electrolyte was dissolved 1 mol / L, the electrolytic solution was prepared in the same manner as in Example 5-2, the ion conductivity, the measurement of the viscosity was performed (LiPF 6 concentration = 9.9 wt%). The results are shown in Table 8.

実施例５−３
ＥＣとＴＦＥＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを０．５ｍｏｌ／Ｌとなるように溶解した（ＬｉＦＳＩ濃度＝６．２質量％）。このように調製した電解液を測定例１、測定例２の方法によりイオン伝導度、粘度の測定を行った。結果を表９に記す。 Example 5-3
EC and TFEP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved so as to be 0.5 mol / L (LiFSI concentration = 6.2% by mass). The electrolyte solution thus prepared was subjected to measurement of ion conductivity and viscosity by the methods of Measurement Example 1 and Measurement Example 2. The results are shown in Table 9.

実施例５−４
ＬｉＦＳＩの濃度を２ｍｏｌ／Ｌになるように調製した以外は、実施例５−３と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝２３．７質量％）。結果を表９に記す。 Example 5-4
Except that the LiFSI concentration was adjusted to 2 mol / L, an electrolyte solution was prepared in the same manner as in Example 5-3, and ionic conductivity and viscosity were measured (LiFSI concentration = 23.7 mass). %). The results are shown in Table 9.

実施例５−５
ＬｉＦＳＩの濃度を３ｍｏｌ／Ｌになるように調製した以外は、実施例５−３と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＦＳＩ濃度＝３４．３質量％）。結果を表９に記す。 Example 5-5
Except that the LiFSI concentration was adjusted to 3 mol / L, an electrolyte solution was prepared in the same manner as in Example 5-3, and ion conductivity and viscosity were measured (LiFSI concentration = 34.3 mass). %). The results are shown in Table 9.

比較例５−３
電解質にＬｉＰＦ６を０．５ｍｏｌ／Ｌの濃度で溶解した以外は、実施例５−３と同様の方法で電解液を調製し、イオン伝導度、粘度の測定を行った（ＬｉＰＦ６濃度＝５．１質量％）。結果を表９に記す。 Comparative Example 5-3
Except that LiPF6 in the electrolyte was dissolved at a concentration of 0.5 mol / L, the electrolytic solution was prepared in the same manner as in Example 5-3, the ion conductivity was measured for viscosity (LiPF 6 concentration = 5. 1% by mass). The results are shown in Table 9.

比較例５−４
電解質にＬｉＰＦ６を２ｍｏｌ／Ｌの濃度で溶解した以外は、実施例５−４と同様の方法で電解液の調製を試みた。しかし、電解質は完全に溶解せず、電解液そのものが固結し、電解液の調製はできなかった。 Comparative Example 5-4
An electrolytic solution was prepared in the same manner as in Example 5-4 except that LiPF6 was dissolved in the electrolyte at a concentration of 2 mol / L. However, the electrolyte was not completely dissolved, and the electrolytic solution itself solidified, and the electrolytic solution could not be prepared.

比較例５−５
電解質にＬｉＰＦ６を３ｍｏｌ／Ｌの濃度で溶解した以外は、実施例５−５と同様の方法で電解液の調製を試みた。しかし、電解質は完全に溶解せず、電解液そのものが固結し、電解液の調製はできなかった。 Comparative Example 5-5
An electrolytic solution was prepared in the same manner as in Example 5-5 except that LiPF6 was dissolved in the electrolyte at a concentration of 3 mol / L. However, the electrolyte was not completely dissolved, and the electrolytic solution itself solidified, and the electrolytic solution could not be prepared.

参考として、実施例２−３、比較例２−３の結果を併記する。   For reference, the results of Example 2-3 and Comparative Example 2-3 are also shown.

実施例５−４、５−５と比較例５−４、５−５の様に、溶解性に差が表れた理由は明らかではないが、含フッ素リン酸エステルとＬｉＦＳＩもしくはＬｉＰＦ６の相互作用の違いにより、この様な溶解性の差を示したのではないかと考えられる。   The reason for the difference in solubility as in Examples 5-4 and 5-5 and Comparative Examples 5-4 and 5-5 is not clear, but the interaction between the fluorine-containing phosphate ester and LiFSI or LiPF6 is not clear. It is thought that such a difference in solubility was shown due to the difference.

作成例１
［コインセル型リチウムイオン二次電池の作成］
実施例６−１、比較例６−１では、非水電解液二次電池として、以下の方法でコインセル型リチウムイオン二次電池を作成し、充放電サイクル試験を行った。 Creation example 1
[Creation of coin cell type lithium ion secondary battery]
In Example 6-1 and Comparative Example 6-1, a coin cell type lithium ion secondary battery was prepared as a nonaqueous electrolyte secondary battery by the following method, and a charge / discharge cycle test was performed.

即ち、正極活物質としてＬｉＣｏＯ２を用い、これに導電助剤としてカーボンブラック、バインダーとしてポリフッ化ビニリデン（ＰＶＤＦ）を重量比で、ＬｉＣｏＯ２：カーボンブラック：ＰＶＤＦ＝９０：５：５となるように配合し、１−メチル−２−ピロリドンを用いてスラリー化したものをアルミ製集電体上に一定の膜厚で塗布し、乾燥させて正極を得た。 That is, LiCoO 2 is used as the positive electrode active material, carbon black is used as the conductive auxiliary agent, and polyvinylidene fluoride (PVDF) is used as the binder, so that LiCoO 2 : carbon black: PVDF = 90: 5: 5. What was blended and slurried using 1-methyl-2-pyrrolidone was applied on an aluminum current collector with a constant film thickness and dried to obtain a positive electrode.

負極活物質としては天然球状グラファイトを用い、バインダーとしてＰＶＤＦを重量比で、グラファイト：ＰＶＤＦ＝９：１となるように配合し、１−メチル−２−ピロリドンを用いてスラリー化したものを銅製集電体上に一定の膜厚で塗布し、乾燥させて負極を得た。   Natural spherical graphite is used as the negative electrode active material, PVDF is blended as a binder in a weight ratio of graphite: PVDF = 9: 1, and a slurry obtained using 1-methyl-2-pyrrolidone is made of copper. The negative electrode was obtained by applying a constant film thickness on the electric conductor and drying it.

セパレータは無機フィラー含有ポリオレフィン多孔質膜を用いた。   As the separator, an inorganic filler-containing polyolefin porous membrane was used.

以上の構成要素に本発明の非水電解液を加えて、図２に示した構造のコイン型セルを用いたリチウム二次電池を作成した。リチウム二次電池はセパレータ１０を挟んで正極３、負極７を対向配置し、これら正極３、セパレータ１０および負極７からなる積層体をガスケット１１に嵌め込んだ。このガスケット１１には正極ステンレスキャップ５と負極ステンレスキャップ６を取り付け、負極ステンレスキャップ６の内側に設けたステンレスバネ９によって前記積層体を構成する正極３を正極ステンレスキャップ５の内側に押し付け、コインセル型リチウムイオン二次電池を作成した。   The non-aqueous electrolyte of the present invention was added to the above components to produce a lithium secondary battery using a coin-type cell having the structure shown in FIG. In the lithium secondary battery, the positive electrode 3 and the negative electrode 7 were disposed opposite to each other with the separator 10 interposed therebetween, and a laminate including the positive electrode 3, the separator 10, and the negative electrode 7 was fitted into the gasket 11. A positive electrode stainless steel cap 5 and a negative electrode stainless steel cap 6 are attached to the gasket 11, and the positive electrode 3 constituting the laminate is pressed against the inside of the positive electrode stainless steel cap 5 by a stainless spring 9 provided inside the negative electrode stainless steel cap 6. A lithium ion secondary battery was prepared.

実施例６−１
ＥＣとＴＦＥＰを体積比、５／５の比率で混合し、電解質としてＬｉＦＳＩを１ｍｏｌ／Ｌとなるように溶解した。この電解液を用いて、作成例４の方法でコインセル型リチウム二次電池を作成した。２５℃の恒温条件下、０．１Ｃの充電電流で上限電圧を４．２Ｖとして充電し、続いて０．１Ｃの放電電流で３．０Ｖとなるまで放電した。この電池を２５℃の恒温条件下、１Ｃの充電電流で４．２Ｖの定電流-定電圧充電を行い、１Ｃの放電電流で終止電圧３．０Ｖまで定電流放電を行った。結果を表１０に記す。 Example 6-1
EC and TFEP were mixed at a volume ratio of 5/5, and LiFSI as an electrolyte was dissolved so as to be 1 mol / L. Using this electrolytic solution, a coin cell type lithium secondary battery was prepared by the method of Preparation Example 4. Under a constant temperature condition of 25 ° C., the battery was charged with an upper limit voltage of 4.2 V with a charging current of 0.1 C, and subsequently discharged to 3.0 V with a discharging current of 0.1 C. This battery was subjected to constant current-constant voltage charging at a constant current of 25 ° C. with a charging current of 1 C and a constant current discharging to a final voltage of 3.0 V with a discharging current of 1 C. The results are shown in Table 10.

比較例６−１
電解質にＬｉＰＦ６を用いた以外は、実施例６−１と同様の方法で電解液を調製し、コインセル型リチウム二次電池を作成した。２５℃の恒温条件下、０．１Ｃの充電電流で上限電圧を４．２Ｖとして充電し、続いて０．１Ｃの放電電流で３．０Ｖとなるまで放電した。この電池を２５℃の恒温条件下、１Ｃの充電電流で４．２Ｖの定電流-定電圧充電を行い、１Ｃの放電電流で終止電圧３．０Ｖまで定電流放電を行った。結果を表１０に記す。 Comparative Example 6-1
An electrolytic solution was prepared in the same manner as in Example 6-1 except that LiPF6 was used as the electrolyte, and a coin cell type lithium secondary battery was prepared. Under a constant temperature condition of 25 ° C., the battery was charged with an upper limit voltage of 4.2 V with a charging current of 0.1 C, and subsequently discharged to 3.0 V with a discharging current of 0.1 C. This battery was subjected to constant current-constant voltage charging at a constant current of 25 ° C. with a charging current of 1 C and a constant current discharging to a final voltage of 3.0 V with a discharging current of 1 C. The results are shown in Table 10.

実施例６−１、比較例６−１では電池の充放電性能について比較を行った。その結果、本発明の組成で、電池の充放電が可能になる事、また特に高レートでの試験でその差が顕著になることが明らかになった。この理由の詳細は明らかではないが、含フッ素リン酸エステルとＬｉＦＳＩの相互作用により非水電解液のイオン伝導度が増加し、その結果、特に高レートでの電池容量が向上したと考えられる。   In Example 6-1 and Comparative Example 6-1, the charge / discharge performance of the batteries was compared. As a result, it has been clarified that the composition of the present invention makes it possible to charge and discharge the battery, and that the difference becomes remarkable particularly in a test at a high rate. Although the details of this reason are not clear, it is considered that the ionic conductivity of the nonaqueous electrolytic solution is increased by the interaction between the fluorine-containing phosphate ester and LiFSI, and as a result, the battery capacity at a particularly high rate is improved.

本発明は、従来の電解液では困難であった安全性と高イオン伝導性を両立した非水電解液、さらには、安全性と出力特性に優れた非水系二次電池として有用である。   INDUSTRIAL APPLICABILITY The present invention is useful as a non-aqueous electrolyte that achieves both safety and high ionic conductivity, which was difficult with conventional electrolytes, and a non-aqueous secondary battery excellent in safety and output characteristics.

１ ガラス製電気化学セル
２ 白金製電極
３ 正極活物質
４ 正極集電体
５ 正極ステンレス製キャップ
６ 負極ステンレス製キャップ
７ 負極物質
８ 負極集電体
９ ステンレス製板バネ
１０ 無機フィラー含有ポリオレフィン多孔質セパレータ
１１ ガスケット DESCRIPTION OF SYMBOLS 1 Electrochemical cell made of glass 2 Electrode made of platinum 3 Positive electrode active material 4 Positive electrode current collector 5 Positive electrode stainless steel cap 6 Negative electrode stainless steel cap 7 Negative electrode material 8 Negative electrode current collector 9 Stainless steel leaf spring 10 Inorganic filler-containing polyolefin porous separator 11 Gasket

Claims (10)

非水溶媒として下記一般式（１）
（式中、Ｒｆ１、Ｒｆ２及びＲｆ３は、それぞれ独立して、炭素数１〜６の直鎖もしくは分岐のアルキル基もしくは炭素数６〜１０のアリール基または炭素数１〜６の直鎖もしくは分岐の含フッ素アルキル基を表し、且つＲｆ１〜Ｒｆ３の少なくとも１つは含フッ素アルキル基である）で表される含フッ素リン酸エステルを含み、電解質塩として下記一般式（２）
（式中Ｒｆ４はフッ素原子または炭素数１〜４の直鎖もしくは分岐のアルキル基または炭素数１〜４の直鎖もしくは分岐の含フッ素アルキル基を表す）で表されるフルオロスルホニルイミドリチウム塩を含む非水電解液。 The following general formula (1) as a non-aqueous solvent
(In the formula, Rf 1 , Rf 2 and Rf 3 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a linear chain having 1 to 6 carbon atoms. Or a branched fluorine-containing alkyl group, and at least one of Rf 1 to Rf 3 is a fluorine-containing alkyl group), and an electrolyte salt represented by the following general formula (2)
(In the formula, Rf 4 represents a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 4 carbon atoms). Non-aqueous electrolyte containing. 非水溶媒として、更に環状カーボネート、鎖状カーボネート、環状エステル及びリン酸エステルから成る群から選ばれる少なくとも１種を存在させる請求項１に記載の非水電解液。   The nonaqueous electrolytic solution according to claim 1, wherein at least one selected from the group consisting of a cyclic carbonate, a chain carbonate, a cyclic ester, and a phosphate ester is further present as the nonaqueous solvent. 一般式（１）で表される含フッ素リン酸エステルが、リン酸トリス（２，２−ジフルオロエチル）、リン酸トリス（２，２，２−トリフルオロエチル）、リン酸トリス（２，２，３，３−テトラフルオロプロピル）、リン酸ビス（２，２，２−トリフルオロエチル）メチル、リン酸ビス（２，２，２−トリフルオロエチル）エチル、リン酸ビス（２，２，２−トリフルオロエチル）フェニル、リン酸ビス（２，２，２−トリフルオロエチル）２，２−ジフルオロエチル、リン酸ビス（２，２，２−トリフルオロエチル）２，２，３，３−テトラフルオロプロピル、リン酸ビス（２，２−ジフルオロエチル）２，２，２−トリフルオロエチル、リン酸ビス（２，２，３，３−テトラフルオロプロピル）２，２，２−トリフルオロエチル及びリン酸（２，２，２−トリフルオロエチル）（２，２，３，３−テトラフルオロプロピル）メチルからなる群から選ばれる少なくとも１種である請求項１または請求項２に記載の非水電解液。   The fluorine-containing phosphoric acid ester represented by the general formula (1) is tris (2,2-difluoroethyl) phosphate, tris (2,2,2-trifluoroethyl) phosphate, tris (2,2). , 3,3-tetrafluoropropyl), bis (2,2,2-trifluoroethyl) methyl phosphate, bis (2,2,2-trifluoroethyl) ethyl phosphate, bis (2,2,2) phosphate 2-trifluoroethyl) phenyl, bis (2,2,2-trifluoroethyl) phosphate 2,2-difluoroethyl, bis (2,2,2-trifluoroethyl) phosphate 2,2,3,3 -Tetrafluoropropyl, bis (2,2-difluoroethyl) phosphate 2,2,2-trifluoroethyl, bis (2,2,3,3-tetrafluoropropyl) phosphate 2,2,2-trifluoro Ethyl and phosphorus The nonaqueous electrolytic solution according to claim 1 or 2, which is at least one selected from the group consisting of (2,2,2-trifluoroethyl) (2,2,3,3-tetrafluoropropyl) methyl. . フルオロスルホニルイミドリチウム塩がビス（フルオロスルホニル）イミドリチウムである請求項１乃至請求項３のいずれか１項に記載の非水電解液。   The nonaqueous electrolytic solution according to any one of claims 1 to 3, wherein the fluorosulfonylimide lithium salt is bis (fluorosulfonyl) imide lithium. 電解質塩として更にＬｉＰＦ６またはＬｉＢＦ４を含み、フルオロスルホニルイミドリチウム塩に対するＬｉＰＦ６またはＬｉＢＦ４の使用量がモル比で０．０１〜２である請求項１乃至請求項４のいずれか１項に記載の非水電解液。 Further comprising a LiPF 6 or LiBF 4 as an electrolyte salt, any one of claims 1 to 4 usage LiPF 6 or LiBF 4 relative fluorosulfonyl imide lithium salt is 0.01 to 2 molar ratio The non-aqueous electrolyte described. 更に存在させる非水溶媒がエチレンカーボネート、プロピレンカーボネート、ビニレンカーボネート、ビニルエチレンカーボネート、フルオロエチレンカーボネート及びジフルオロエチレンカーボネートからなる群から選ばれる少なくとも１種の環状カーボネートである請求項２に記載の非水電解液。   The nonaqueous electrolysis according to claim 2, wherein the nonaqueous solvent to be further present is at least one cyclic carbonate selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate and difluoroethylene carbonate. liquid. 更に存在させる非水溶媒がジメチルカーボネート、ジエチルカーボネート及びエチルメチルカーボネートからなる群から選ばれる少なくとも１種の鎖状カーボネートである請求項２に記載の非水電解液。   The nonaqueous electrolytic solution according to claim 2, wherein the nonaqueous solvent to be further present is at least one chain carbonate selected from the group consisting of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate. 更に存在させる非水溶媒がγ − ブチロラクトン、γ − バレロラクトン、δ−バレロラクトン、ε−カプロラクタム及びγ−ヘキサノラクトンからなる群から選ばれる少なくとも１種の環状エステルである請求項２に記載の非水電解液。   The nonaqueous solvent to be further present is at least one cyclic ester selected from the group consisting of γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactam and γ-hexanolactone. Non-aqueous electrolyte. 更に存在させる非水溶媒がリン酸トリメチル、リン酸トリエチル、リン酸トリ−ｎ−プロピル、リン酸トリイソプロピル、リン酸トリ−ｎ−ブチル、リン酸トリイソブチル及びリン酸トリフェニルからなる群から選ばれる少なくとも１種のリン酸エステルである請求項２に記載の非水電解液。   Further, the non-aqueous solvent to be present is selected from the group consisting of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate and triphenyl phosphate. The nonaqueous electrolytic solution according to claim 2, which is at least one phosphate ester. 請求項１乃至請求項９のいずれか１項に記載の非水電解液を含む非水系二次電池。   A nonaqueous secondary battery comprising the nonaqueous electrolyte solution according to any one of claims 1 to 9.
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