JP2010050021A - Nonaqueous electrolyte for battery and nonaqueous electrolyte secondary battery having the same - Google Patents

Nonaqueous electrolyte for battery and nonaqueous electrolyte secondary battery having the same Download PDF

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JP2010050021A
JP2010050021A JP2008215171A JP2008215171A JP2010050021A JP 2010050021 A JP2010050021 A JP 2010050021A JP 2008215171 A JP2008215171 A JP 2008215171A JP 2008215171 A JP2008215171 A JP 2008215171A JP 2010050021 A JP2010050021 A JP 2010050021A
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battery
aqueous electrolyte
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Yasuo Horikawa
泰郎 堀川
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Bridgestone Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte for a battery which is excellent in initial capacity and cycle life characteristics and can give high safety to the battery. <P>SOLUTION: The nonaqueous electrolyte for a battery includes a ring phosphazen compound expressed by formula (I) of (NPR<SP>1</SP><SB>2</SB>)<SB>n</SB>, a nonaqueous solvent, a sulfone compound expressed by formula (II), and supporting salt. Here, R<SP>1</SP>each independently shows fluorine, alkoxy, or aryloxy; and n shows 3-4. R<SP>2</SP>and R<SP>3</SP>in formula (II) are 1-3C alkyl, alkenyl, or phenyl which are respectively independent each other. However, R<SP>2</SP>and R<SP>3</SP>may form a ring by combining each other. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、電池用非水電解液及びそれを備えた非水電解液二次電池に関し、特には、不燃性を有する電池用非水電解液、並びに優れた初期容量およびサイクル寿命特性と高い安全性を有する非水電解液二次電池に関するものである。   The present invention relates to a non-aqueous electrolyte for a battery and a non-aqueous electrolyte secondary battery including the same, and in particular, a non-aqueous electrolyte for a battery having nonflammability, and excellent initial capacity and cycle life characteristics and high safety. The present invention relates to a non-aqueous electrolyte secondary battery having a property.

非水電解液は、リチウム電池やリチウムイオン二次電池、電気二重層キャパシタ等の電解質として使用されており、これらデバイスは、高電圧、高エネルギー密度を有することから、パソコン及び携帯電話等の駆動電源として広く用いられている。そして、これら非水電解液としては、一般にエステル化合物及びエーテル化合物等の非プロトン性有機溶媒に、ＬｉＰＦ6等の支持塩を溶解させたものが用いられている。しかしながら、非プロトン性有機溶媒は、可燃性であるため、上記デバイスから漏液した際に引火・燃焼する可能性があり、安全面での問題を有している。 Non-aqueous electrolytes are used as electrolytes for lithium batteries, lithium-ion secondary batteries, electric double layer capacitors, etc., and these devices have high voltage and high energy density, so they drive personal computers and mobile phones. Widely used as a power source. As these nonaqueous electrolytic solutions, generally used are solutions in which a supporting salt such as LiPF 6 is dissolved in an aprotic organic solvent such as an ester compound and an ether compound. However, since the aprotic organic solvent is flammable, it may ignite and burn when it leaks from the device, and has a safety problem.

この問題に対して、非水電解液を難燃化する方法が検討されており、例えば、非水電解液にリン酸トリメチル等のリン酸エステル類を用いたり、非プロトン性有機溶媒にリン酸エステル類を添加したりする方法が提案されている（特許文献１〜３参照）。しかしながら、これらリン酸エステル類は、充放電を繰り返すことで、徐々に負極で還元分解され、充放電効率及びサイクル特性等の電池特性が大きく劣化するという問題がある。   To solve this problem, methods for making non-aqueous electrolytes flame-retardant have been studied. For example, phosphoric acid esters such as trimethyl phosphate are used for non-aqueous electrolytes, or phosphoric acid is used for aprotic organic solvents. Methods for adding esters have been proposed (see Patent Documents 1 to 3). However, these phosphate esters have a problem in that they are gradually reduced and decomposed at the negative electrode by repeating charge and discharge, and battery characteristics such as charge and discharge efficiency and cycle characteristics are greatly deteriorated.

また、特開平６−１３１０８号公報（特許文献４）には、非水電解液に難燃性を付与するために、非水電解液にホスファゼン化合物を添加する方法が開示されている。該ホスファゼン化合物は、高い難燃性を示すものの、その種類、構造、または用いる電池極材種や非水電解液種によっては、電池の初期容量が低下したり、充放電特性に支障をきたすことがある。   Japanese Patent Application Laid-Open No. 6-13108 (Patent Document 4) discloses a method of adding a phosphazene compound to a nonaqueous electrolytic solution in order to impart flame retardancy to the nonaqueous electrolytic solution. Although the phosphazene compound exhibits high flame retardancy, the initial capacity of the battery may be reduced or the charge / discharge characteristics may be hindered depending on the type, structure, or battery electrode material type or nonaqueous electrolyte type used. There is.

このように、これまでの従来技術では、電解液の安全性と電池性能の両立という点で必ずしも十分に満足できるレベルとはいえない。
特開平４−１８４８７０号公報 特開平８−２２８３９号公報 特開２０００−１８２６６９号公報 特開平６−１３１０８号公報 As described above, the conventional techniques up to now cannot be said to be sufficiently satisfactory in terms of both the safety of the electrolytic solution and the battery performance.
JP-A-4-184870 JP-A-8-22839 JP 2000-182669 A JP-A-6-13108

そこで、本発明の目的は、上記従来技術の問題を解決し、不燃性を有する電池用非水電解液と、該電池用非水電解液を備え、初期容量およびサイクル寿命特性に優れ、高い安全性を有する非水電解液二次電池を提供することにある。   Accordingly, an object of the present invention is to solve the above-described problems of the prior art, and to provide a non-flammable battery non-aqueous electrolyte and the battery non-aqueous electrolyte, which have excellent initial capacity and cycle life characteristics, and high safety. An object of the present invention is to provide a non-aqueous electrolyte secondary battery having a property.

本発明者は、上記目的を達成するために鋭意検討した結果、特定の環状ホスファゼン化合物と非水溶媒に、さらに特定のスルホン化合物を組み合わせて非水電解液を構成することにより、電解液に高い難燃性を付与することができ、また、該電解液を用いた非水電解液二次電池が優れた電池性能を維持できることを見出し、本発明を完成させるに至った。   As a result of intensive studies to achieve the above object, the present inventor has a high electrolyte solution by configuring a non-aqueous electrolyte by combining a specific cyclic phosphazene compound and a non-aqueous solvent with a specific sulfone compound. It has been found that flame retardancy can be imparted, and that a non-aqueous electrolyte secondary battery using the electrolyte can maintain excellent battery performance, and the present invention has been completed.

即ち、本発明の電池用非水電解液は、
・下記一般式(I)：
(ＮＰＲ1 2)n ・・・ (I)
［式中、Ｒ1は、それぞれ独立してフッ素、アルコキシ基又はアリールオキシ基を表し；ｎは３〜４を表す］で表される環状ホスファゼン化合物と、
・非水溶媒と、
・下記一般式(II)：

Figure 2010050021
［式中、Ｒ2及びＲ3は、それぞれ独立して炭素数１〜３のアルキル基、アルケニル基又はフェニル基であり、但し、Ｒ2及びＲ3は互いに結合して環を形成してもよい］で表されるスルホン化合物と、
・支持塩と
を含むことを特徴とする。なお、式(I)で表される環状ホスファゼン化合物、非水溶媒、式(II)で表されるスルホン化合物及び支持塩のみからなる電池用非水電解液は、本発明の電池用非水電解液の好適一態様である。 That is, the non-aqueous electrolyte for a battery of the present invention is
-The following general formula (I):
(NPR 1 2 ) n ... (I)
[Wherein R 1 independently represents a fluorine, an alkoxy group or an aryloxy group; n represents 3 to 4], and a cyclic phosphazene compound represented by:
A non-aqueous solvent,
-The following general formula (II):
Figure 2010050021
 [Wherein R 2 and R 3 are each independently an alkyl group, alkenyl group or phenyl group having 1 to 3 carbon atoms, provided that R 2 and R 3 may be bonded to each other to form a ring. A sulfone compound represented by
-It is characterized by including supporting salt. The battery non-aqueous electrolyte consisting only of the cyclic phosphazene compound represented by formula (I), the non-aqueous solvent, the sulfone compound represented by formula (II) and the supporting salt is the non-aqueous electrolysis for battery of the present invention. This is a preferred embodiment of the liquid.

本発明の電池用非水電解液において、前記環状ホスファゼン化合物としては、前記一般式(I)において、Ｒ1のうち少なくとも４つがフッ素である化合物が好ましい。 In the non-aqueous electrolyte for a battery of the present invention, the cyclic phosphazene compound is preferably a compound in which at least four of R 1 in the general formula (I) are fluorine.

本発明の電池用非水電解液の好適例においては、前記一般式(I)で表される環状ホスファゼン化合物の含有量が電池用非水電解液全体の10〜60体積％である。   In a preferred example of the battery non-aqueous electrolyte of the present invention, the content of the cyclic phosphazene compound represented by the general formula (I) is 10 to 60% by volume of the whole battery non-aqueous electrolyte.

本発明の電池用非水電解液の他の好適例においては、前記スルホン化合物の含有量が電池用非水電解液全体の0.5〜2質量％である。   In another preferred embodiment of the battery non-aqueous electrolyte of the present invention, the content of the sulfone compound is 0.5 to 2% by mass of the whole battery non-aqueous electrolyte.

本発明の電池用非水電解液の他の好適例においては、前記非水溶媒が、非プロトン性有機溶媒であり、該非プロトン性有機溶媒としてエチレンカーボネート（ＥＣ）を含むことが更に好ましい。   In another preferred embodiment of the battery non-aqueous electrolyte of the present invention, the non-aqueous solvent is an aprotic organic solvent, and it is more preferable that the aprotic organic solvent contains ethylene carbonate (EC).

また、本発明の非水電解液二次電池は、上記電池用非水電解液と、正極と、負極とを備えることを特徴とする。   Moreover, the non-aqueous electrolyte secondary battery of the present invention comprises the above-described non-aqueous electrolyte for a battery, a positive electrode, and a negative electrode.

本発明によれば、非水溶媒に特定の環状ホスファゼン化合物を加え、好ましくは10体積％以上加えることにより高い難燃性を有し、さらに特定のスルホン化合物を組み合わせて用いることにより、非水電解液二次電池に使用した際に初期容量が大きく、サイクル寿命特性を改善することが可能な非水電解液を提供することができる。また、該非水電解液を備えた、高い安全性と優れた電池特性を有する非水電解液二次電池を提供することができる。   According to the present invention, a specific cyclic phosphazene compound is added to a non-aqueous solvent, and preferably has a high flame retardancy by adding 10% by volume or more, and further by using a specific sulfone compound in combination, When used in a liquid secondary battery, it is possible to provide a nonaqueous electrolytic solution that has a large initial capacity and can improve cycle life characteristics. Moreover, the nonaqueous electrolyte secondary battery provided with this nonaqueous electrolyte and having high safety and excellent battery characteristics can be provided.

本発明の電池用非水電解液においては、環状ホスファゼン化合物の反応、熱分解により生じる高不燃性ガス成分が、高い難燃性を発現するものと考えられる。また、理由は必ずしも明らかではないが、上記環状ホスファゼン化合物とスルホン化合物との２つの化合物の相乗効果により生じる電極表面の皮膜が、電解液の分解を効果的に抑制するため、安定した充放電特性が実現できるものと考えられる。   In the non-aqueous electrolyte for batteries of the present invention, it is considered that a highly incombustible gas component produced by reaction and thermal decomposition of a cyclic phosphazene compound exhibits high flame retardancy. Moreover, although the reason is not necessarily clear, since the film on the electrode surface generated by the synergistic effect of the two compounds of the cyclic phosphazene compound and the sulfone compound effectively suppresses the decomposition of the electrolyte, stable charge / discharge characteristics Can be realized.

＜電池用非水電解液＞
以下に、本発明の電池用非水電解液を詳細に説明する。本発明に係る電池用非水電解液は、上記一般式(I)で表される環状ホスファゼン化合物と、非水溶媒と、上記一般式(II)で表されるスルホン化合物とを含むことを特徴とし、更に、非水溶媒として、非プロトン性有機溶媒を含有することが好ましい。 <Non-aqueous electrolyte for batteries>
Below, the non-aqueous electrolyte for batteries of the present invention will be described in detail. A nonaqueous electrolytic solution for a battery according to the present invention includes a cyclic phosphazene compound represented by the general formula (I), a nonaqueous solvent, and a sulfone compound represented by the general formula (II). Furthermore, it is preferable to contain an aprotic organic solvent as the non-aqueous solvent.

本発明の電池用非水電解液に含まれる環状ホスファゼン化合物は、上記一般式(I)で表される。式(I)中のＲ1は、それぞれ独立してフッ素、アルコキシ基又はアリールオキシ基を表し、ｎは３〜４を表す。 The cyclic phosphazene compound contained in the nonaqueous electrolytic solution for batteries of the present invention is represented by the above general formula (I). R 1 in formula (I) each independently represent fluorine, an alkoxy group or an aryloxy radical, n represents 3-4.

式(I)のＲ1におけるアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等や、二重結合を含むアリルオキシ基等、またはメトキシエトキシ基、メトキシエトキシエトキシ基等のアルコキシ置換アルコキシ基等が挙げられる。更に、Ｒ1におけるアリールオキシ基としては、フェノキシ基、メチルフェノキシ基、キシレノキシ基（即ち、キシリルオキシ基）、メトキシフェノキシ基等が挙げられる。上記アルコキシ基及びアリールオキシ基中の水素元素は、ハロゲン元素で置換されていてもよく、フッ素で置換されていることが好ましい。また、式(I)中のＲ1は他のＲ1と連結していてもよく、この場合、２つのＲ1は、互いに結合して、アルキレンジオキシ基、アリーレンジオキシ基又はオキシアルキレンアリーレンオキシ基を形成し、かかる二価の基としては、エチレンジオキシ基、プロピレンジオキシ基、フェニレンジオキシ基等が挙げられる。 Examples of the alkoxy group in R 1 of the formula (I) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an allyloxy group containing a double bond, or an alkoxy-substituted alkoxy such as a methoxyethoxy group and a methoxyethoxyethoxy group. Groups and the like. Furthermore, examples of the aryloxy group in R 1 include a phenoxy group, a methylphenoxy group, a xylenoxy group (that is, a xylyloxy group), a methoxyphenoxy group, and the like. The hydrogen element in the alkoxy group and aryloxy group may be substituted with a halogen element, and is preferably substituted with fluorine. R 1 in formula (I) may be linked to other R 1, and in this case, two R 1 are bonded to each other to form an alkylenedioxy group, an aryleneoxy group or an oxyalkylene arylene. Examples of the divalent group that forms an oxy group include an ethylenedioxy group, a propylenedioxy group, and a phenylenedioxy group.

上記一般式(I)中のＲ1は、同一でも異なってもよい。また、式(I)のＲ1は、不燃性及び低粘性の両立の点で、Ｒ1のうち４つ以上がフッ素であることが好ましい。 R 1 in the general formula (I) may be the same or different. Further, R 1 in the formula (I) is preferably 4 or more of R 1 in terms of both nonflammability and low viscosity.

また、式(I)のｎは、３〜４であり、上記環状ホスファゼン化合物は、１種単独で使用してもよいし、２種以上を混合して用いてもよい。   Moreover, n of Formula (I) is 3-4, The said cyclic phosphazene compound may be used individually by 1 type, and may mix and use 2 or more types.

本発明の電池用非水電解液において、上記環状ホスファゼン化合物の含有量は、電池用非水電解液全体の5〜70体積％であることが好ましく、安全性と電池特性のバランスの観点から、10〜60体積％の範囲が更に好ましい。環状ホスファゼン化合物の含有量が70体積％を超えると、電池の容量や負荷特性が低下してしまうため好ましくなく、一方、5体積％未満では、引火点の低い有機溶媒を電解液に使用した場合に、不燃性を発現できないことがある。   In the battery non-aqueous electrolyte of the present invention, the content of the cyclic phosphazene compound is preferably 5 to 70% by volume of the whole battery non-aqueous electrolyte, from the viewpoint of the balance between safety and battery characteristics, A range of 10 to 60% by volume is more preferable. When the content of the cyclic phosphazene compound exceeds 70% by volume, the battery capacity and load characteristics are deteriorated, which is not preferable. In addition, incombustibility may not be exhibited.

本発明の電池用非水電解液は、更に上記一般式(II)で表わされるスルホン化合物を含むことを特徴とする。式(II)において、Ｒ2及びＲ3は、それぞれ独立して炭素数１〜３のアルキル基、アルケニル基又はフェニル基であり、但し、Ｒ2及びＲ3は互いに結合して環を形成してもよい。ここで、アルキル基としては、メチル基、エチル基、プロピル基等が挙げられ、アルケニル基としては、ビニル基、アリル基、メタリル基等が挙げられる。また、Ｒ2及びＲ3は互いに結合していてもよく、この場合、Ｒ2及びＲ3が結合して形成する基としては、テトラメチレン基、メチルテトラメチレン基、ブテニレン基等の二価の基が挙げられる。 The non-aqueous electrolyte for a battery according to the present invention further includes a sulfone compound represented by the general formula (II). In the formula (II), R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms, an alkenyl group, or a phenyl group, provided that R 2 and R 3 are bonded to each other to form a ring. May be. Here, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group, and examples of the alkenyl group include a vinyl group, an allyl group, and a methallyl group. R 2 and R 3 may be bonded to each other. In this case, the group formed by combining R 2 and R 3 is a divalent group such as a tetramethylene group, a methyltetramethylene group, or a butenylene group. Groups.

式(II)のスルホン化合物の具体例としては、ジメチルスルホン、メチルエチルスルホン、ジエチルスルホン、エチルプロピルスルホン、ジプロピルスルホン、メチルビニルスルホン、エチルビニルスルホン、プロピルビニルスルホン、ジビニルスルホン、メチルアリルスルホン、エチルアリルスルホン、アリルビニルスルホン、ジアリルスルホン、フェニルエチルスルホン、フェニルメチルスルホン、フェニルビニルスルホン、アリルフェニルスルホン、ジフェニルスルホン、スルホラン、メチルスルホラン、３-スルホレン等が挙げられる。これらの中でも、エチルビニルスルホン、アリルフェニルスルホン、スルホラン、３-スルホレンが好ましい。これらスルホン化合物は、１種単独で使用してもよく、２種以上を混合して使用してもよい。   Specific examples of the sulfone compound of the formula (II) include dimethylsulfone, methylethylsulfone, diethylsulfone, ethylpropylsulfone, dipropylsulfone, methylvinylsulfone, ethylvinylsulfone, propylvinylsulfone, divinylsulfone, methylallylsulfone, Examples include ethyl allyl sulfone, allyl vinyl sulfone, diallyl sulfone, phenyl ethyl sulfone, phenyl methyl sulfone, phenyl vinyl sulfone, allyl phenyl sulfone, diphenyl sulfone, sulfolane, methyl sulfolane, and 3-sulfolene. Among these, ethyl vinyl sulfone, allyl phenyl sulfone, sulfolane, and 3-sulfolene are preferable. These sulfone compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

上記スルホン化合物の含有量は、電池用非水電解液全体の0.1〜3質量％の範囲が好ましく、電池性能のバランスの観点から、0.5〜2質量％の範囲が更に好ましい。   The content of the sulfone compound is preferably in the range of 0.1 to 3% by mass of the whole battery non-aqueous electrolyte, and more preferably in the range of 0.5 to 2% by mass from the viewpoint of balance of battery performance.

本発明の電池用非水電解液において、非水溶媒としては、本発明の目的を損なわない範囲で従来より二次電池用非水電解液に使用されている種々の非プロトン性有機溶媒を使用することができる。なお、非水溶媒の含有量は、電池用非水電解液全体の30〜95体積％であることが好ましく、安全性と電池特性のバランスの観点から、40〜90体積％の範囲が更に好ましい。   In the non-aqueous electrolyte for batteries of the present invention, various non-protonic organic solvents conventionally used in non-aqueous electrolytes for secondary batteries are used as the non-aqueous solvent as long as the object of the present invention is not impaired. can do. The content of the non-aqueous solvent is preferably 30 to 95% by volume of the entire non-aqueous electrolyte for batteries, and more preferably in the range of 40 to 90% by volume from the viewpoint of the balance between safety and battery characteristics. .

上記非プロトン性有機溶媒として具体的には、ジメチルカーボネート（ＤＭＣ）、ジエチルカーボネート（ＤＥＣ）、ジフェニルカーボネート、エチルメチルカーボネート（ＥＭＣ）、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ビニレンカーボネート（ＶＣ）等のカーボネート類、酢酸メチル、プロピオン酸メチル、酪酸メチル等のカルボン酸エステル類、１,２-ジメトキシエタン（ＤＭＥ）、テトラヒドロフラン（ＴＨＦ）、ジエチルエーテル（ＤＥＥ）等のエーテル類、γ-ブチロラクトン（ＧＢＬ）、γ-バレロラクトン等のラクトン類、アセトニトリル等のニトリル類、ジメチルホルムアミド等のアミド類、エチレンスルフィド等のスルフィド類等が挙げられる。これらの中でも、環状ホスファゼン化合物との相溶性、および電池性能のバランスの点で、カーボネート類を用いることが好ましく、中でもエチレンカーボネート（ＥＣ）を用いることが、電池初期容量が優れる点でより好ましい。これら非プロトン性有機溶媒は、１種単独で使用してもよく、２種以上を混合して用いてもよい。   Specific examples of the aprotic organic solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), diphenyl carbonate, ethyl methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), and vinylene carbonate (VC). ), Carbonates such as methyl acetate, methyl propionate and methyl butyrate, ethers such as 1,2-dimethoxyethane (DME), tetrahydrofuran (THF) and diethyl ether (DEE), and γ-butyrolactone (GBL), lactones such as γ-valerolactone, nitriles such as acetonitrile, amides such as dimethylformamide, sulfides such as ethylene sulfide, and the like. Among these, carbonates are preferably used from the viewpoint of compatibility with the cyclic phosphazene compound and battery performance, and ethylene carbonate (EC) is more preferably used from the viewpoint of excellent battery initial capacity. These aprotic organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

本発明の電池用非水電解液に用いる支持塩としては、リチウムイオンのイオン源となる支持塩が好ましい。該支持塩としては、特に制限はないが、例えば、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＢＣ4Ｏ8、ＬｉＰＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＡｓＦ6、ＬｉＣ4Ｆ9ＳＯ3、Ｌｉ(ＦＳＯ2)2Ｎ、Ｌｉ(ＣＦ3ＳＯ2)2Ｎ及びＬｉ(Ｃ2Ｆ5ＳＯ2)2Ｎ等のリチウム塩が好適に挙げられる。これらの中でも、不燃性および電池性能に優れる点で、ＬｉＰＦ6、Ｌｉ(ＦＳＯ2)2Ｎ、Ｌｉ(ＣＦ3ＳＯ2)2Ｎがより好ましい。これら支持塩は、１種単独で使用してもよく、２種以上を組み合わせて用いてもよい。 As the supporting salt used in the non-aqueous electrolyte for a battery of the present invention, a supporting salt serving as a lithium ion source is preferable. The supporting salt is not particularly limited. For example, LiClO 4 , LiBF 4 , LiBC 4 O 8 , LiPF 6 , LiCF 3 SO 3 , LiAsF 6 , LiC 4 F 9 SO 3 , Li (FSO 2 ) 2 N Suitable examples include lithium salts such as Li (CF 3 SO 2 ) 2 N and Li (C 2 F 5 SO 2 ) 2 N. Among these, LiPF 6 , Li (FSO 2 ) 2 N, and Li (CF 3 SO 2 ) 2 N are more preferable in terms of excellent nonflammability and battery performance. These supporting salts may be used alone or in combination of two or more.

上記非水電解液中の支持塩の総濃度としては、0.3〜2.5 mol/L（Ｍ）が好ましく、0.8〜2.0 mol/L（Ｍ）が更に好ましい。支持塩の総濃度が0.3 mol/L未満では、電解液の導電性を充分に確保することができず、電池の放電特性及び充電特性に支障をきたすことがあり、2.5 mol/Lを超えると、電解液の粘度が上昇し、リチウムイオンの移動度を充分に確保できないため、前述と同様に電解液の導電性を充分に確保できず、電池の放電特性及び充電特性に支障をきたすことがある。   The total concentration of the supporting salt in the non-aqueous electrolyte is preferably 0.3 to 2.5 mol / L (M), more preferably 0.8 to 2.0 mol / L (M). If the total concentration of the supporting salt is less than 0.3 mol / L, the conductivity of the electrolyte cannot be sufficiently secured, which may hinder battery discharge characteristics and charge characteristics. As the viscosity of the electrolyte increases and the mobility of lithium ions cannot be sufficiently secured, the conductivity of the electrolyte cannot be sufficiently secured in the same manner as described above, which may hinder battery discharge characteristics and charge characteristics. is there.

また、非水電解液二次電池の形成に際して、本発明の電池用非水電解液は、そのまま用いることも可能であるが、例えば、適当なポリマーや多孔性支持体、或いはゲル状物質に含浸させる等して保持させる方法等で用いることもできる。   Further, when forming a non-aqueous electrolyte secondary battery, the non-aqueous electrolyte for a battery of the present invention can be used as it is. For example, an appropriate polymer, a porous support, or a gel material is impregnated. It can also be used by a method of holding it.

＜非水電解液二次電池＞
次に、本発明の非水電解液二次電池を詳細に説明する。本発明の非水電解液二次電池は、上述の電池用非水電解液と、正極と、負極とを備え、必要に応じて、セパレーター等の非水電解液二次電池の技術分野で通常使用されている他の部材を備える。なお、本発明の非水電解液二次電池には、非水電解液二次電池の他に、正極に分極性炭素電極、負極に予めリチウムイオンを吸蔵し、リチウムイオンを可逆的に吸蔵・脱離し得る非分極性炭素電極を用いた電気二重層キャパシタ（リチウムイオンキャパシタ又はハイブリッドキャパシタ）も含まれる。 <Nonaqueous electrolyte secondary battery>
Next, the nonaqueous electrolyte secondary battery of the present invention will be described in detail. The non-aqueous electrolyte secondary battery of the present invention includes the above-described non-aqueous electrolyte for a battery, a positive electrode, and a negative electrode, and is usually used in the technical field of a non-aqueous electrolyte secondary battery such as a separator as necessary. It includes other members that are used. In addition to the non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery of the present invention includes a polarizable carbon electrode in the positive electrode and lithium ions in the negative electrode in advance and reversibly occludes lithium ions. An electric double layer capacitor (lithium ion capacitor or hybrid capacitor) using a nonpolarizable carbon electrode that can be detached is also included.

本発明の非水電解液二次電池の正極活物質としては、Ｖ2Ｏ5、Ｖ6Ｏ13、ＭｎＯ2、ＭｎＯ3等の金属酸化物、ＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4、ＬｉＦｅＯ2及びＬｉＦｅＰＯ4等のリチウム含有複合酸化物、ＴｉＳ2、ＭｏＳ2等の金属硫化物、ポリアニリン等の導電性ポリマー、活性炭等の炭素材料等が好適に挙げられる。上記リチウム含有複合酸化物は、Ｆｅ、Ｍｎ、Ｃｏ、Ａｌ及びＮｉからなる群から選択される２種又は３種の遷移金属を含む複合酸化物であってもよく、この場合、該複合酸化物は、ＬｉＭｎxＣｏyＮｉ(1-x-y)Ｏ2［式中、０≦ｘ＜１、０≦ｙ＜１、０＜ｘ＋ｙ≦１］、ＬｉＭｎxＮｉ(1-x)Ｏ2［式中、０≦ｘ＜１］、ＬｉＭｎxＣｏ(1-x)Ｏ2［式中、０≦ｘ＜１］、ＬｉＣｏxＮｉ(1-x)Ｏ2［式中、０≦ｘ＜１］、ＬｉＣｏxＮｉyＡｌ(1-x-y)Ｏ2［式中、０≦ｘ＜１、０≦ｙ＜１、０＜ｘ＋ｙ≦１］、ＬｉＦｅxＣｏyＮｉ(1-x-y)Ｏ2［式中、０≦ｘ＜１、０≦ｙ＜１、０＜ｘ＋ｙ≦１］、或いはＬｉＭｎxＦｅyＯ2-x-y等で表される。これら正極活物質は、１種単独で使用してもよく、２種以上を併用してもよい。 As the positive electrode active material of the non-aqueous electrolyte secondary battery of the present invention, metal oxides such as V 2 O 5 , V 6 O 13 , MnO 2 , MnO 3 , LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiFeO Preferred examples include lithium-containing composite oxides such as 2 and LiFePO 4 , metal sulfides such as TiS 2 and MoS 2 , conductive polymers such as polyaniline, and carbon materials such as activated carbon. The lithium-containing composite oxide may be a composite oxide containing two or three transition metals selected from the group consisting of Fe, Mn, Co, Al, and Ni. In this case, the composite oxide LiMn x Co y Ni (1-xy) O 2 [where 0 ≦ x <1, 0 ≦ y <1, 0 <x + y ≦ 1], LiMn x Ni (1-x) O 2 [wherein , 0 ≦ x <1], LiMn x Co (1-x) O 2 [where 0 ≦ x <1], LiCo x Ni (1-x) O 2 [where 0 ≦ x <1], LiCo x Ni y Al [wherein, 0 ≦ x <1,0 ≦ y <1,0 <x + y ≦ 1] (1-xy) O 2, LiFe x Co y Ni (1-xy) O 2 [ wherein , 0 ≦ x <1, 0 ≦ y <1, 0 <x + y ≦ 1], or LiMn x Fe y O 2 -xy . These positive electrode active materials may be used individually by 1 type, and may use 2 or more types together.

本発明の非水電解液二次電池の負極活物質としては、リチウム金属自体、リチウムとＡｌ、Ｉｎ、Ｓｎ、Ｓｉ、Ｐｂ又はＺｎ等との合金、リチウムイオンをドープしたＴｉＯ2等の金属酸化物、ＴｉＯ2−Ｐ2Ｏ4等の金属酸化物複合材料、黒鉛等の炭素材料等が好適に挙げられる。これら負極活物質は、１種単独で使用してもよく、２種以上を併用してもよい。 As the negative electrode active material of the non-aqueous electrolyte secondary battery of the present invention, lithium metal itself, an alloy of lithium and Al, In, Sn, Si, Pb, Zn or the like, metal oxide such as TiO 2 doped with lithium ions And metal oxide composite materials such as TiO 2 —P 2 O 4 , carbon materials such as graphite, and the like. These negative electrode active materials may be used individually by 1 type, and may use 2 or more types together.

上記正極及び負極には、必要に応じて導電剤、結着剤を混合することができ、導電剤としてはアセチレンブラック等が挙げられ、結着剤としてはポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレン・ブタジエンゴム（ＳＢＲ）、カルボキシメチルセルロース（ＣＭＣ）等が挙げられる。これらの添加剤は、従来と同様の配合割合で用いることができる。   The positive electrode and the negative electrode can be mixed with a conductive agent and a binder as necessary. Examples of the conductive agent include acetylene black, and the binder includes polyvinylidene fluoride (PVDF) and polytetrafluoro. Examples include ethylene (PTFE), styrene / butadiene rubber (SBR), carboxymethyl cellulose (CMC), and the like. These additives can be used at a blending ratio similar to the conventional one.

本発明の非水電解液二次電池に使用できる他の部材としては、非水電解液二次電池において、正負極間に、両極の接触による電流の短絡を防止する役割で介在させるセパレーターが挙げられる。セパレーターの材質としては、両極の接触を確実に防止し得、且つ電解液を通したり含んだりできる材料、例えば、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、セルロース系、ポリブチレンテレフタレート、ポリエチレンテレフタレート等の合成樹脂製の不織布、薄層フィルム等が好適に挙げられる。これらは、単体でも、混合物でも、共重合体でもよい。これらの中でも、厚さ20〜50μm程度のポリプロピ
レン又はポリエチレン製の微孔性フィルム、セルロース系、ポリブチレンテレフタレート、ポリエチレンテレフタレート等のフィルムが特に好適である。本発明では、上述のセパレーターの他にも、通常二次電池に使用されている公知の各部材が好適に使用できる。 Other members that can be used in the non-aqueous electrolyte secondary battery of the present invention include a separator interposed in the non-aqueous electrolyte secondary battery between positive and negative electrodes to prevent current short-circuit due to contact between both electrodes. It is done. As the material of the separator, it is possible to reliably prevent contact between the two electrodes and to allow the electrolyte to pass through or to contain, for example, synthesis of polytetrafluoroethylene, polypropylene, polyethylene, cellulose, polybutylene terephthalate, polyethylene terephthalate, etc. Preferred examples include resin nonwoven fabrics and thin layer films. These may be a single substance, a mixture, or a copolymer. Of these, polypropylene or polyethylene microporous films having a thickness of about 20 to 50 μm, cellulose-based films, polybutylene terephthalate, polyethylene terephthalate, and the like are particularly suitable. In the present invention, in addition to the separators described above, known members that are normally used in secondary batteries can be suitably used.

以上に説明した本発明の非水電解液二次電池の形態としては、特に制限はなく、コインタイプ、ボタンタイプ、ペーパータイプ、角型又はスパイラル構造の円筒型電池等、種々の公知の形態が好適に挙げられる。ボタンタイプの場合は、シート状の正極及び負極を作製し、該正極及び負極でセパレーターを挟む等して、非水電解液二次電池を作製することができる。また、スパイラル構造の場合は、例えば、シート状の正極を作製して集電体を挟み、これにシート状の負極を重ね合わせて巻き上げる等して、非水電解液二次電池を作製することができる。   The form of the non-aqueous electrolyte secondary battery of the present invention described above is not particularly limited, and various known forms such as a coin type, a button type, a paper type, a square type or a spiral type cylindrical battery are available. Preferably mentioned. In the case of the button type, a non-aqueous electrolyte secondary battery can be manufactured by preparing a sheet-like positive electrode and negative electrode and sandwiching a separator between the positive electrode and the negative electrode. In the case of a spiral structure, for example, a non-aqueous electrolyte secondary battery is manufactured by, for example, preparing a sheet-like positive electrode, sandwiching a current collector, and superimposing and winding up the sheet-like negative electrode on the current collector. Can do.

以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

（実施例１）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがフェノキシ基で、５つがフッ素である環状ホスファゼン化合物 10体積％と、エチレンカーボネート 13体積％と、ジメチルカーボネート 37体積％と、プロピオン酸メチル 40体積％とからなる混合溶媒に、ＬｉＰＦ6を1.2 mol/Lになるように溶解させて、これにエチルビニルスルホン 0.5質量％を添加して非水電解液を調製した。次に、得られた非水電解液の難燃性を下記の方法で評価し、表１に示す結果を得た。 Example 1
10% by volume of cyclic phosphazene compound in which n is 3 in the above general formula (I), one of all R 1 is phenoxy group and 5 is fluorine, 13% by volume of ethylene carbonate, 37% by volume of dimethyl carbonate LiPF 6 was dissolved in a mixed solvent consisting of 40% by volume of methyl propionate so as to be 1.2 mol / L, and 0.5% by mass of ethyl vinyl sulfone was added thereto to prepare a non-aqueous electrolyte. Next, the flame retardancy of the obtained non-aqueous electrolyte was evaluated by the following method, and the results shown in Table 1 were obtained.

（１）難燃性の評価
ＵＬ（アンダーライティングラボラトリー）規格のＵＬ９４ＨＢ法をアレンジした方法で、大気環境下において着火した炎の燃焼長及び燃焼時間を測定・評価した。具体的には、ＵＬ試験基準に基づき、127 mm×12.7 mmのＳｉＯ2シートに上記電解液1.0 mLを染み込ませて試験片を作製して評価を行った。以下に不燃性・難燃性・自己消火性・燃焼性の評価基準を示す。
＜不燃性の評価＞試験炎を点火しても全く着火しなかった場合（燃焼長：0 mm）を不燃性ありと評価した。
＜難燃性の評価＞着火した炎が、装置の25 mmラインまで到達せず且つ網からの落下物にも着火が認められなかった場合を難燃性ありと評価した。
＜自己消火性の評価＞着火した炎が25〜100 mmラインで消火し且つ網からの落下物にも着火が認められなかった場合を自己消火性ありと評価した。
＜燃焼性の評価＞着火した炎が、100 mmラインを超えた場合を燃焼性と評価した。 (1) Flame Retardancy Evaluation The combustion length and combustion time of a flame ignited in an atmospheric environment were measured and evaluated by a method in which the UL94HB method of UL (Underwriting Laboratory) standard was arranged. Specifically, based on the UL test standard, a 127 mm × 12.7 mm SiO 2 sheet was impregnated with 1.0 mL of the electrolytic solution, and a test piece was prepared and evaluated. The evaluation criteria for nonflammability, flame retardancy, self-extinguishing properties, and flammability are shown below.
<Evaluation of nonflammability> When the test flame was ignited, it was not ignited at all (burning length: 0 mm).
<Evaluation of Flame Retardancy> The case where the ignited flame did not reach the 25 mm line of the apparatus and the fallen object from the net was not ignited was evaluated as flame retardant.
<Evaluation of self-extinguishing property> When the ignited flame was extinguished on the 25 to 100 mm line and no ignition was observed on the falling object from the net, it was evaluated as having self-extinguishing property.
<Evaluation of flammability> The case where the ignited flame exceeded the 100 mm line was evaluated as flammability.

（２）電池の作製
正極活物質としてＬｉＣｏ0.15Ｎｉ0.8Ａｌ0.05Ｏ2を用い、該酸化物と、導電剤であるアセチレンブラックと、結着剤であるポリフッ化ビニリデンとを、質量比94：3：3で混合し、これをＮ-メチルピロリドンに分散させてスラリーとしたものを、正極集電体としてのアルミニウム箔に塗布した後、乾燥・プレスを施すことで、厚さ70μmの正極シートを得た。これを矩形（4 cm×50 cm）に切り取り、アルミニウム箔の集電タブを溶接して正極を作製した。また、負極活物質として人造グラファイトを用い、該人造グラファイトと、結着剤であるポリフッ化ビニリデンとを質量比90：10で混合し、これを有機溶媒（酢酸エチルとエタノールとの50／50質量％混合溶媒）に分散させてスラリーとしたものを、負極集電体としての銅箔に塗布した後、乾燥・プレスを施すことで、厚さ50μmの負極シートを得た。これを矩形（4 cm×50 cm）に切り取り、ニッケル箔の集電タブを溶接して負極を作製した。次いで、セパレーター（微孔性フィルム：ポリエチレン製）を矩形（4 cm×50 cm）に切り取り、これを正極と負極とを介して挟み込み、4 cm×3 cmのスペーサーをベースに平巻きにした後、熱融着アルミラミネートフィルム（ポリエチレンテレフタレート／アルミニウム／ポリプロピレン）からなる外装材の中に挿入し、電解液を注入後、真空にしてすばやくヒートシールすることにより平板状ラミネート電池（非水電解液二次電池）を作製した。 (2) Production of Battery Using LiCo 0.15 Ni 0.8 Al 0.05 O 2 as a positive electrode active material, the oxide, acetylene black as a conductive agent, and polyvinylidene fluoride as a binder are in a mass ratio of 94: 3 : After mixing the mixture in 3 and dispersing it in N-methylpyrrolidone to apply to the aluminum foil as the positive electrode current collector, drying and pressing, a positive electrode sheet with a thickness of 70 μm was obtained. Obtained. This was cut into a rectangle (4 cm × 50 cm), and an aluminum foil current collecting tab was welded to produce a positive electrode. Further, artificial graphite is used as the negative electrode active material, and the artificial graphite and polyvinylidene fluoride as a binder are mixed at a mass ratio of 90:10, and this is mixed with an organic solvent (50/50 mass of ethyl acetate and ethanol). % Mixed solvent) was applied to a copper foil as a negative electrode current collector, followed by drying and pressing to obtain a negative electrode sheet having a thickness of 50 μm. This was cut into a rectangle (4 cm × 50 cm), and a nickel foil current collecting tab was welded to produce a negative electrode. Next, the separator (microporous film: made of polyethylene) is cut into a rectangle (4 cm x 50 cm), sandwiched between the positive electrode and the negative electrode, and flattened using a 4 cm x 3 cm spacer as a base Inserted into a heat-sealed aluminum laminate film (polyethylene terephthalate / aluminum / polypropylene) exterior material, injected the electrolyte, vacuumed and quickly heat-sealed to obtain a flat laminate battery (non-aqueous electrolyte 2 Secondary battery).

（３）サイクル寿命特性評価
上記のようにして作製したラミネート電池を用い、20℃の環境下で、上限電圧4.2Ｖ、下限電圧3.0Ｖ、0.25 mA/cm2の電流密度による充放電サイクルを２回繰り返し、この時の放電容量を既知の正極重量より除することにより初期放電容量（mAh/g）を求めた。さらに同様の充放電条件で100サイクルまで充放電を繰り返し、100サイクル後の放電容量を求め、下記の式：
容量残存率＝100サイクル後の放電容量／初期放電容量×１００（％）
に従って容量残存率を算出し、電池のサイクル寿命特性の指標とした。結果を表１に示す。 (3) Evaluation of cycle life characteristics Using the laminate battery produced as described above, 2 charging / discharging cycles with an upper limit voltage of 4.2 V, a lower limit voltage of 3.0 V, and a current density of 0.25 mA / cm 2 under an environment of 20 ° C. The initial discharge capacity (mAh / g) was determined by repeating this operation and dividing the discharge capacity at this time from the known positive electrode weight. Furthermore, charging / discharging is repeated up to 100 cycles under the same charging / discharging conditions, and the discharge capacity after 100 cycles is obtained by the following formula:
Capacity remaining rate = discharge capacity after 100 cycles / initial discharge capacity × 100 (%)
The capacity remaining rate was calculated according to the above and used as an index of the cycle life characteristics of the battery. The results are shown in Table 1.

（４）過充電安全性試験
上記と同じラミネート電池を作製し、過充電条件による電池安全性試験を行った。過充電試験の方法は、20℃の環境下で、4.2〜3.0Ｖの電圧範囲で、0.25 mA/cm2の電流密度による充放電サイクルを2回繰り返し、さらに4.2Ｖまで充電を行った後、該電池を温度調節機能つき電池ホルダー（ステンレス製）上に置き、20℃の電池温度条件で5.0 mA/cm2の電流密度により12.0Ｖまで充電を行い、同電圧でさらに0.25 mA/cm2の電流密度になるまで充電を継続し、破裂、発火の有無を調べた。結果を表１に示す。 (4) Overcharge safety test The same laminated battery as the above was produced, and the battery safety test by overcharge conditions was conducted. In the overcharge test method, a charge / discharge cycle with a current density of 0.25 mA / cm 2 was repeated twice in a voltage range of 4.2 to 3.0 V in an environment of 20 ° C., and further charged to 4.2 V. Place the cell on temperature control with battery holders (stainless steel), 20 by the current density of the battery temperature 5.0 mA / cm 2 of ℃ was charged to 12.0 V, yet 0.25 mA / cm 2 at the same voltage Charging was continued until the current density reached, and the presence or absence of rupture or ignition was examined. The results are shown in Table 1.

（実施例２）
上記一般式(I)においてｎが３であって、全Ｒ1のうち２つがエチレンジオキシ基で連結され、４つがフッ素である環状ホスファゼン化合物 5体積％と、上記一般式(I)においてｎが４であって、全Ｒ1のうち１つがメトキシ基で、７つがフッ素である環状ホスファゼン化合物 25体積％と、エチレンカーボネート 14体積％と、エチルメチルカーボネート 56体積％とからなる混合溶媒に、ＬｉＴＦＳＩ［Ｌｉ(ＣＦ3ＳＯ2)2Ｎ］を1.0 mol/Lになるように溶解させて、これにアリルフェニルスルホン 1質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 (Example 2)
In the above general formula (I), n is 3, 2 out of all R 1 are linked by an ethylenedioxy group and 4 are fluorine, 5% by volume of a cyclic phosphazene compound, and in the above general formula (I), n Is a mixed solvent composed of 25% by volume of a cyclic phosphazene compound in which one of all R 1 is a methoxy group and 7 is fluorine, 14% by volume of ethylene carbonate, and 56% by volume of ethyl methyl carbonate, LiTFSI [Li (CF 3 SO 2 ) 2 N] was dissolved at 1.0 mol / L, and 1% by mass of allyl phenyl sulfone was added thereto to prepare a non-aqueous electrolyte solution. The flame retardancy of the electrolyte was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（実施例３）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがトリフルオロエトキシ基で、５つがフッ素である環状ホスファゼン化合物 40体積％と、エチレンカーボネート 5体積％と、エチルメチルカーボネート 55体積％とからなる混合溶媒に、ＬｉＰＦ6を1.2 mol/Lになるように溶解させて、これにスルホラン 2質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 (Example 3)
In the above general formula (I), n is 3, cyclic phosphazene compound 40% by volume, ethylene carbonate 5% by volume, ethyl methyl carbonate, wherein one of all R 1 is trifluoroethoxy group and 5 is fluorine In a mixed solvent consisting of 55% by volume, LiPF 6 was dissolved to 1.2 mol / L, and 2% by mass of sulfolane was added thereto to prepare a non-aqueous electrolyte, and the obtained non-aqueous electrolyte The flame retardancy of was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（実施例４）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがエトキシ基で、５つがフッ素である環状ホスファゼン化合物 60体積％と、エチレンカーボネート 5体積％と、プロピオン酸メチル 35体積％とからなる混合溶媒に、ＬｉＰＦ6を1.0 mol/L及びＬｉＴＦＳＩ［Ｌｉ(ＣＦ3ＳＯ2)2Ｎ］を1.0 mol/Lになるように溶解させて、これに３-スルホレン 2質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 Example 4
In the above general formula (I), n is 3, and one of all R 1 is ethoxy group and 5 is fluorine. 60% by volume of cyclic phosphazene compound, 5% by volume of ethylene carbonate, 35% of methyl propionate In a mixed solvent consisting of 2% by weight, LiPF 6 is dissolved at 1.0 mol / L and LiTFSI [Li (CF 3 SO 2 ) 2 N] is dissolved at 1.0 mol / L. The nonaqueous electrolytic solution was prepared by adding, and the flame retardancy of the obtained nonaqueous electrolytic solution was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（比較例１）
エチレンカーボネート 20体積％と、ジメチルカーボネート 40体積％と、プロピオン酸メチル 40体積％とからなる混合溶媒に、ＬｉＰＦ6を1.2 mol/Lになるように溶解させて、これにエチルビニルスルホン 0.5質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 (Comparative Example 1)
LiPF 6 was dissolved in a mixed solvent consisting of 20% by volume of ethylene carbonate, 40% by volume of dimethyl carbonate and 40% by volume of methyl propionate so as to be 1.2 mol / L, and 0.5% by mass of ethyl vinyl sulfone was added thereto. Was added to prepare a nonaqueous electrolytic solution, and the flame retardancy of the obtained nonaqueous electrolytic solution was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（比較例２）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがエトキシ基で、５つがフッ素である環状ホスファゼン化合物 60体積％と、エチレンカーボネート 5体積％と、ジエチルカーボネート 35体積％とからなる混合溶媒に、ＬｉＰＦ6を1.0 mol/L及びＬｉＴＦＳＩ［Ｌｉ(ＣＦ3ＳＯ2)2Ｎ］を1.0 mol/Lになるように溶解させて非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 (Comparative Example 2)
In the above general formula (I), n is 3, and one of the total R 1 is ethoxy group and 5 is fluorine. 60% by volume of cyclic phosphazene compound, 5% by volume of ethylene carbonate, 35% by volume of diethyl carbonate A non-aqueous electrolyte was prepared by dissolving LiPF 6 at 1.0 mol / L and LiTFSI [Li (CF 3 SO 2 ) 2 N] at 1.0 mol / L in a mixed solvent consisting of The flame retardancy of the non-aqueous electrolyte was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（実施例５）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがフェノキシ基で、５つがフッ素である環状ホスファゼン化合物 3体積％と、エチレンカーボネート 14体積％と、ジメチルカーボネート 43体積％と、プロピオン酸メチル 40体積％とからなる混合溶媒に、ＬｉＰＦ6を1.2 mol/Lになるように溶解させて、これにエチルビニルスルホン 0.5質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 (Example 5)
In the above general formula (I), n is 3 and one of all R 1 is phenoxy group and 5 is fluorine. 3% by volume of cyclic phosphazene compound, 14% by volume of ethylene carbonate, 43% by volume of dimethyl carbonate Then, LiPF 6 was dissolved in a mixed solvent consisting of 40% by volume of methyl propionate so as to be 1.2 mol / L, and 0.5% by mass of ethyl vinyl sulfone was added thereto to prepare a non-aqueous electrolyte. The flame retardancy of the obtained non-aqueous electrolyte was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（実施例６）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがトリフルオロエトキシ基で、５つがフッ素である環状ホスファゼン化合物 72体積％と、エチレンカーボネート 3体積％と、エチルメチルカーボネート 30体積％とからなる混合溶媒に、ＬｉＰＦ6を0.8 mol/Lになるように溶解させて、これにスルホラン 2質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 (Example 6)
72% by volume of cyclic phosphazene compound in which n is 3 in the above general formula (I), one of R 1 is trifluoroethoxy group and 5 is fluorine, 3% by volume of ethylene carbonate, ethyl methyl carbonate LiPF 6 was dissolved in a mixed solvent of 30% by volume to 0.8 mol / L, and 2% by mass of sulfolane was added thereto to prepare a non-aqueous electrolyte, and the obtained non-aqueous electrolyte was obtained. The flame retardancy of was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（実施例７）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがエトキシ基で、５つがフッ素である環状ホスファゼン化合物 60体積％と、エチレンカーボネート 5体積％と、プロピオン酸メチル 35体積％とからなる混合溶媒に、ＬｉＰＦ6を1.0 mol/L及びＬｉＴＦＳＩ［Ｌｉ(ＣＦ3ＳＯ2)2Ｎ］を1.0 mol/Lになるように溶解させて、これに３-スルホレン 0.05質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。 (Example 7)
In the above general formula (I), n is 3, and one of all R 1 is ethoxy group and 5 is fluorine. 60% by volume of cyclic phosphazene compound, 5% by volume of ethylene carbonate, 35% of methyl propionate In a mixed solvent consisting of 1 wt.%, LiPF 6 is dissolved at 1.0 mol / L and LiTFSI [Li (CF 3 SO 2 ) 2 N] is dissolved at 1.0 mol / L, and 0.05% by mass of 3-sulfolene is added thereto. The nonaqueous electrolytic solution was prepared by adding, and the flame retardancy of the obtained nonaqueous electrolytic solution was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

（実施例８）
上記一般式(I)においてｎが３であって、全Ｒ1のうち１つがエトキシ基で、５つがフッ素である環状ホスファゼン化合物 60体積％と、エチレンカーボネート 5体積％と、プロピオン酸メチル 35体積％とからなる混合溶媒に、ＬｉＰＦ6を1.0 mol/L及びＬｉＴＦＳＩ［Ｌｉ(ＣＦ3ＳＯ2)2Ｎ］を1.0 mol/Lになるように溶解させて、これに３-スルホレン 4質量％を添加して非水電解液を調製し、得られた非水電解液の難燃性を評価した。また、実施例１と同様にして非水電解液二次電池を作製し、サイクル寿命特性評価および過充電安全性試験をそれぞれ実施した。結果を表１に示す。

(Example 8)
In the above general formula (I), n is 3, and one of all R 1 is ethoxy group and 5 is fluorine. 60% by volume of cyclic phosphazene compound, 5% by volume of ethylene carbonate, 35% of methyl propionate In a mixed solvent consisting of 1 wt.%, LiPF 6 is dissolved at 1.0 mol / L and LiTFSI [Li (CF 3 SO 2 ) 2 N] is dissolved at 1.0 mol / L, and 4-sulfolene 4% by mass is dissolved therein. The nonaqueous electrolytic solution was prepared by adding, and the flame retardancy of the obtained nonaqueous electrolytic solution was evaluated. In addition, a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, and cycle life characteristic evaluation and overcharge safety test were performed, respectively. The results are shown in Table 1.

Figure 2010050021
Figure 2010050021

表１の実施例１〜４に示すように、式(I)の化合物と式(II)で表されるスルホン化合物を含む非水電解液が不燃性を示すと共に、該非水電解液を用いた電池が高い初期容量と優れたサイクル寿命特性を有していることが分かる。このように、本発明の非水電解液により、不燃性を発現しつつ、サイクル寿命特性及び安全性に優れた非水電解液二次電池が得られることが確認された。   As shown in Examples 1 to 4 in Table 1, the non-aqueous electrolyte containing the compound of formula (I) and the sulfone compound represented by formula (II) showed nonflammability, and the non-aqueous electrolyte was used. It can be seen that the battery has a high initial capacity and excellent cycle life characteristics. Thus, it was confirmed that the nonaqueous electrolyte solution of the present invention provides a nonaqueous electrolyte secondary battery that exhibits nonflammability and is excellent in cycle life characteristics and safety.

なお、比較例２に示すように、式(II)で表されるスルホン化合物を添加しない場合においては、実施例４と比較して、サイクル寿命特性が劣っていることが分かる。   As shown in Comparative Example 2, it can be seen that the cycle life characteristics are inferior to Example 4 when the sulfone compound represented by Formula (II) is not added.

更に、実施例５に示すように、式(I)で表される化合物の含有量が5体積％未満では、不燃性が発現されず、過充電安全性試験においても破裂を抑制できなかった。   Furthermore, as shown in Example 5, when the content of the compound represented by the formula (I) was less than 5% by volume, nonflammability was not exhibited, and rupture could not be suppressed even in the overcharge safety test.

一方、実施例６に示すように、式(I)で表される化合物の含有量が70体積％を超える場合には、不燃性や電池安全性に問題はないものの、初期容量が小さくなる傾向が認められた。従って、式(I)の環状ホスファゼン化合物の含有量は、10〜60体積％程度が好ましいことが分かる。   On the other hand, as shown in Example 6, when the content of the compound represented by the formula (I) exceeds 70% by volume, there is no problem in nonflammability and battery safety, but the initial capacity tends to be small. Was recognized. Therefore, it can be seen that the content of the cyclic phosphazene compound of the formula (I) is preferably about 10 to 60% by volume.

また、実施例７に示すように、式(II)で表されるスルホン化合物の添加量が0.1質量％未満の場合には、サイクル寿命特性における改善効果がほとんどなく、実施例８に示すように、3質量％を超える場合には、初期容量が低下する傾向が認められた。従って、式(II)で表されるスルホン化合物の添加量は、0.5〜2質量％程度が好ましいことが分かる。   Further, as shown in Example 7, when the addition amount of the sulfone compound represented by the formula (II) is less than 0.1% by mass, there is almost no improvement effect in cycle life characteristics, and as shown in Example 8. When the content exceeds 3% by mass, the initial capacity tends to decrease. Therefore, it is understood that the addition amount of the sulfone compound represented by the formula (II) is preferably about 0.5 to 2% by mass.

以上の結果から、式(I)で表される環状ホスファゼン化合物と式(II)で表されるスルホン化合物を含有することを特徴とする非水電解液を用いることにより、高い安全性と優れた電池性能を両立させた非水電解液二次電池を提供できることが分かる。   From the above results, by using a non-aqueous electrolyte characterized by containing a cyclic phosphazene compound represented by formula (I) and a sulfone compound represented by formula (II), high safety and excellent It can be seen that a non-aqueous electrolyte secondary battery having both battery performances can be provided.

Claims (7)

下記一般式(I)：
(ＮＰＲ1 2)n ・・・ (I)
［式中、Ｒ1は、それぞれ独立してフッ素、アルコキシ基又はアリールオキシ基を表し；ｎは３〜４を表す］で表される環状ホスファゼン化合物と、非水溶媒と、下記一般式(II)：
Figure 2010050021
 ［式中、Ｒ2及びＲ3は、それぞれ独立して炭素数１〜３のアルキル基、アルケニル基又はフェニル基であり、但し、Ｒ2及びＲ3は互いに結合して環を形成してもよい］で表されるスルホン化合物と、支持塩とを含むことを特徴とする電池用非水電解液。 The following general formula (I):
(NPR 1 2 ) n ... (I)
[Wherein R 1 independently represents fluorine, an alkoxy group or an aryloxy group; n represents 3 to 4], a non-aqueous solvent, the following general formula (II ):
Figure 2010050021
 [Wherein R 2 and R 3 are each independently an alkyl group, alkenyl group or phenyl group having 1 to 3 carbon atoms, provided that R 2 and R 3 may be bonded to each other to form a ring. A non-aqueous electrolyte for a battery comprising a sulfone compound represented by the formula: 前記一般式(I)において、Ｒ1のうち少なくとも４つがフッ素であることを特徴とする請求項１に記載の電池用非水電解液。 2. The battery non-aqueous electrolyte according to claim 1, wherein in the general formula (I), at least four of R 1 are fluorine. 前記一般式(I)で表される環状ホスファゼン化合物の含有量が前記電池用非水電解液全体の10〜60体積％であることを特徴とする請求項１に記載の電池用非水電解液。   2. The nonaqueous electrolytic solution for a battery according to claim 1, wherein the content of the cyclic phosphazene compound represented by the general formula (I) is 10 to 60% by volume of the entire nonaqueous electrolytic solution for the battery. . 前記一般式(II)で表されるスルホン化合物の含有量が前記電池用非水電解液全体の0.5〜2質量％であることを特徴とする請求項１に記載の電池用非水電解液。   2. The battery non-aqueous electrolyte according to claim 1, wherein the content of the sulfone compound represented by the general formula (II) is 0.5 to 2 mass% of the whole battery non-aqueous electrolyte. 前記非水溶媒が非プロトン性有機溶媒であることを特徴とする請求項１に記載の電池用非水電解液。   The battery nonaqueous electrolyte solution according to claim 1, wherein the nonaqueous solvent is an aprotic organic solvent. 前記非プロトン性有機溶媒が、エチレンカーボネート（ＥＣ）を含むことを特徴とする請求項５に記載の電池用非水電解液。   The non-aqueous electrolyte for battery according to claim 5, wherein the aprotic organic solvent contains ethylene carbonate (EC). 請求項１〜６のいずれかに記載の電池用非水電解液と、正極と、負極とを備えた非水電解液二次電池。   A nonaqueous electrolyte secondary battery comprising the battery nonaqueous electrolyte solution according to claim 1, a positive electrode, and a negative electrode.
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