JP2014013719A - Electrolytic solution for nonaqueous secondary battery, and secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an electrolytic solution for a nonaqueous secondary battery, exhibiting good performance in high-temperature cycle characteristics and rate characteristics, in an electrolytic solution to which a polymerizable compound is added; and a nonaqueous secondary battery.SOLUTION: An electrolytic solution for a nonaqueous secondary battery contains an enamine compound represented by the following formula (1), a polymerizable compound and an electrolyte, in an organic solvent. The electrolytic solution for a nonaqueous secondary battery contains 1-100 (in molar ratio base) of the enamine compound per 100 of the polymerizable compound.(In the formula, R, Rand Reach independently represent a hydrogen atom or an organic group, Rand Rmay bond with each other to form a ring, Rand Rrepresent an organic group nonconjugated with N, and Rand Rmay bond with each other to form a ring.)

Description

  The present invention relates to an electrolyte solution for a non-aqueous secondary battery containing an organic solvent, and a secondary battery using the same.

  Recently, secondary batteries called lithium ion batteries, which are attracting attention, use secondary batteries (so-called lithium ion secondary batteries) that use insertion and extraction of lithium in charge and discharge reactions, and precipitation and dissolution of lithium. They are roughly classified into secondary batteries (so-called lithium metal secondary batteries). These can obtain a large energy density as compared with lead batteries and nickel cadmium batteries. Utilizing this characteristic, in recent years, it has become widespread as a power source for portable electronic devices such as a camera-integrated VTR (video tape recorder), a mobile phone, or a notebook personal computer. With the further expansion of applications, lithium ion secondary batteries that are lightweight and can obtain high energy density are being developed as power sources for portable electronic devices. Furthermore, in recent years, miniaturization, long life, and high safety have been strongly demanded.

  As an electrolytic solution of a lithium ion secondary battery or a lithium metal secondary battery (hereinafter, these may be simply referred to as a lithium secondary battery), the conductivity is high and the potential is stable. A combination of a carbonate ester solvent such as propylene or diethyl carbonate and an electrolyte salt such as lithium hexafluorophosphate is widely used.

  On the other hand, with regard to the additive component of the electrolytic solution, a technique for incorporating various additives into the electrolytic solution has been proposed for the purpose of improving cycle characteristics and the like. For example, Patent Documents 1 to 3 disclose techniques for adding a polymerizable compound to a non-aqueous solvent.

JP 2009-99448 A Japanese Patent No. 4,050,251 Japanese Patent Laid-Open No. 11-97059

  The application range of the lithium secondary battery is widespread not only for portable devices but also for automobiles. Accordingly, compatibility with various usage environments such as high temperature conditions and high-speed charging / discharging has been demanded. In order to cope with such diversified usage environments, the above-described conventional technology is still not sufficient. Accordingly, an object of the present invention is to provide a nonaqueous secondary battery electrolyte solution and a nonaqueous secondary battery that exhibit good performance in high temperature cycle characteristics and rate characteristics in an electrolyte solution to which a polymerizable compound is added. To do.

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３は、各々独立に水素原子又は有機基を示す。Ｒ^１２、Ｒ^１３は互いに結合し、環を形成していてもよい。Ｒ^１４、Ｒ^１５は、Ｎと共役しない有機基を示す。Ｒ^１４、Ｒ^１５は互いに結合し、環を形成していてもよい。）
〔２〕式（１）が、下式（２）で表される〔１〕に記載の非水二次電池用電解液。

（式中、Ｒ^１6、Ｒ^１7、Ｒ^１8、Ｒ^１9は、各々独立に水素原子、アルキル基、アルコキシ基、又はアミノ基を示す。Ａは、水素原子、有機基を示し、同一でも異なっていてもよい。Ａは互いに結合し、環を形成していてもよい。Ｒ^１１〜Ｒ^１３は式（１）と同義である。）
〔３〕式（２）が、下式（３−ａ）または（３−ｂ）で表される〔１〕または〔２〕に記載の非水二次電池用電解液。

（式中、Ｒ²⁰、Ｒ²¹は、各々独立に水素原子又はアルキル基を示す。Ｄ、Ｇは、それぞれ、水素原子、アルキル基、アルコキシ基、又はアミノ基を示し、同一でも異なっていてもよい。Ｒ²²、Ｒ²³は、各々独立に水素原子又はアルキル基を示す。Ｅは連結基を示し、アルキレン連結、エーテル連結、アミノ連結、又はこれらを組み合わせた基を示す。Ｒ^１１〜Ｒ^１３は式（１）と同義である。）
〔４〕式（３−ｂ）においてＲ^１２とＲ^１３が環を形成する〔３〕に記載の非水二次電池用電解液。
〔５〕式（３−ｂ）においてＲ^１２とＲ^１３で形成した環または連結基Ｅを伴う環が５員環あるいは６員環である〔３〕または〔４〕に記載の非水二次電池用電解液。
〔６〕重合性化合物が、式（ｉ）〜（ｉｖ）のいずれかで表される〔１〕〜〔５〕のいずれか１項に記載の非水二次電池用電解液。

（式中、Ｒ^３は水素原子またはアルキル基を表す。Ｒ^４は芳香族基、複素環基、ニトリル基、アルコキシ基、またはアシルオキシ基を表す。Ｒ^５は水素、アルキル基、またはシアノ基を表す。Ｒ^６はアルキル基またはアルコキシ基、アミノ基を表す。Ｒ^７及びＲ^８は水素、アルキル基または芳香族基を表す。Ｘ、Ｙ、Ｚは、５または６員環を形成することができる−Ｏ−、−Ｓ−、−（Ｃ＝Ｏ）−、−Ｃ（＝Ｓ）−、−ＮＲ−、−ＳＯ−、−ＳＯ_２−から選択される２価連結基を表す。Ｒはアルキル基または芳香族基を表す。Ｒ^９は水素原子又はアルキル基を表す。）
〔７〕式（１）で表される化合物を０．０００１〜０．１ｍｏｌ／Ｌで含有させる〔１〕〜〔６〕のいずれか１項に記載の非水二次電池用電解液。
〔８〕重合性化合物を０．００１〜０．５ｍｏｌ／Ｌで含有させる〔１〕〜〔７〕のいずれか１項に記載の非水二次電池用電解液。
〔９〕含まれる各有機成分の平均分子量が１０００以下である〔１〕〜〔８〕のいずれか１項に記載の非水二次電池用電解液。
〔１０〕〔１〕〜〔９〕のいずれか１項に記載の非水二次電池用電解液を用いた非水二次電池。
〔１１〕二次電池が正極を構成する材料として、ニッケル原子及び／又はマンガン原子を含有するリチウム金属複合酸化物を含有する〔１０〕に記載の非水二次電池。
本明細書において、隣接する置換基は特に断らなくても互いに結合ないし縮合して環を形成していてもよい。 The above problem has been solved by the following means.
[1] An electrolyte solution for a non-aqueous secondary battery containing an enamine compound represented by the following formula (1), a polymerizable compound, and an electrolyte in an organic solvent, the polymerizable compound 100 (based on a molar ratio) ) An electrolyte solution for a non-aqueous secondary battery containing 1 to 100 enamine compounds.

^{(Wherein, R 11, R 12, R} 13 are each independently represent a hydrogen atom or an organic group ^{.R 12, R 13} are bonded to each other, may also form a ring ^{.R 14, R 15} is And represents an organic group that is not conjugated with N. R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring.)
[2] The electrolyte solution for a non-aqueous secondary battery according to [1], wherein the formula (1) is represented by the following formula (2).

(Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an amino group. A represents a hydrogen atom or an organic group, which may be the same or different. A may be bonded to each other to form a ring, and R ^{11 to} R ¹³ have the same meanings as those in formula (1).
[3] The electrolyte solution for a non-aqueous secondary battery according to [1] or [2], wherein the formula (2) is represented by the following formula (3-a) or (3-b).

(In the formula, R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group. D and G each represent a hydrogen atom, an alkyl group, an alkoxy group, or an amino group, and may be the same or different. R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group, E represents a linking group, and represents an alkylene linkage, an ether linkage, an amino linkage, or a combination thereof, R ^{11 to} R ^13. Is synonymous with formula (1).)
[4] The electrolyte solution for a nonaqueous secondary battery according to [3], wherein R ¹² and R ¹³ form a ring in the formula (3-b).
[5] The non-aqueous secondary according to [3] or [4], wherein the ring formed by R ¹² and R ¹³ in formula (3-b) or the ring with the linking group E is a 5-membered ring or a 6-membered ring Battery electrolyte.
[6] The electrolyte solution for a nonaqueous secondary battery according to any one of [1] to [5], wherein the polymerizable compound is represented by any one of formulas (i) to (iv).

(In the formula, R ³ represents a hydrogen atom or an alkyl group. R ⁴ represents an aromatic group, a heterocyclic group, a nitrile group, an alkoxy group, or an acyloxy group. R ⁵ represents a hydrogen, an alkyl group, or a cyano group. R ⁶ represents an alkyl group, an alkoxy group, or an amino group, R ⁷ and R ⁸ represent hydrogen, an alkyl group, or an aromatic group, and X, Y, and Z may form a 5- or 6-membered ring. can -O -, - S -, - (C = O) -, - C (= S) -, - NR -, - SO -, - SO 2 - .R that represents a divalent linking group selected from Represents an alkyl group or an aromatic group, and R ⁹ represents a hydrogen atom or an alkyl group.)
[7] The electrolyte solution for a non-aqueous secondary battery according to any one of [1] to [6], wherein the compound represented by the formula (1) is contained at 0.0001 to 0.1 mol / L.
[8] The electrolyte solution for a non-aqueous secondary battery according to any one of [1] to [7], wherein the polymerizable compound is contained at 0.001 to 0.5 mol / L.
[9] The electrolyte solution for a non-aqueous secondary battery according to any one of [1] to [8], wherein an average molecular weight of each organic component contained is 1000 or less.
[10] A non-aqueous secondary battery using the electrolyte for a non-aqueous secondary battery according to any one of [1] to [9].
[11] The nonaqueous secondary battery according to [10], wherein the secondary battery contains a lithium metal composite oxide containing nickel atoms and / or manganese atoms as a material constituting the positive electrode.
In the present specification, adjacent substituents may be bonded to or condensed with each other to form a ring, unless otherwise specified.

  The non-aqueous secondary battery electrolyte and non-aqueous secondary battery according to the present invention improve the performance of the non-aqueous electrolyte containing a polymerizable compound, and are particularly excellent in cycle characteristics at high temperatures and rate characteristics (high-speed discharge properties). ) Exhibit good performance.

It is sectional drawing which shows typically the mechanism of the lithium secondary battery which concerns on preferable embodiment of this invention. It is sectional drawing which shows the specific structure of the lithium secondary battery which concerns on preferable embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. However, the configuration of the present invention is not construed as being limited by the contents.

[Electrolyte for non-aqueous secondary battery]
The electrolyte solution for nonaqueous secondary batteries of the present invention contains an enamine compound and a polymerizable compound represented by the following formula (1). By using these two kinds of additive components in combination, the cycle characteristics and the rate characteristics are compatible at a high level. Although this reason includes an unknown point, it is considered as follows. That is, the enamine compound represented by the following formula (1) undergoes one-electron oxidation on the surface of the positive electrode to generate a cation radical of the enamine compound, and an addition reaction between the active radical and the polymerizable compound results in a polymer film of the polymerizable compound. Is estimated to be formed. Hereinafter, the present invention will be described in detail focusing on preferred embodiments thereof.

(Compound represented by Formula (1))
In the present invention, an enamine compound represented by the following formula (1) is used.

· ^R 11 ~R ¹³
In formula, R < ¹¹ > -R < ¹³ > shows a hydrogen atom or an organic group each independently. Although it does not specifically limit as an organic group, The example of the postscript substituent T is mentioned. Among these, as R ¹¹ , a hydrogen atom, an alkyl group (preferably a methyl group, an ethyl group, an isopropyl group), an aryl group (preferably a phenyl group), an alkoxycarbonyl group, or a cyano group is preferable, and a hydrogen atom, An alkyl group (preferably a methyl group or an ethyl group) or an aryl group (preferably a phenyl group) is more preferable, and a hydrogen atom or a methyl group is particularly preferable. R ¹² is preferably a hydrogen atom, an alkyl group (preferably a methyl group, an ethyl group, an isopropyl group), an aryl group (preferably a phenyl group), an alkoxycarbonyl group, or a cyano group, and preferably a hydrogen atom, an alkyl group ( Preferably, a methyl group, an ethyl group), an alkoxycarbonyl group, or a cyano group is more preferable, and a hydrogen atom, a methyl group, or an ethyl group is particularly preferable. R ¹³ is preferably a hydrogen atom, an alkyl group (preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group) or an aryl group (preferably a phenyl group), a hydrogen atom, an alkyl group (Preferably, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an isobutyl group) is more preferable. The substituents listed above as R ^{11 to} R ¹³ may further have a substituent, preferably an alkoxy group, an amino group, or an alkylthio group, and more preferably an alkoxy group or an amino group.
R ¹² and R ¹³ may be bonded to each other to form a ring. Although the ring formed here is not specifically limited, It is preferable that it is a non-aromatic ring especially and it is preferable that it is a 3-8 membered non-aromatic ring. The non-aromatic ring may contain a hetero atom (for example, N, S, O). This ring may have a substituent, and this substituent is preferably a substituent T described later. The substituent may be bonded or condensed to form a ring.

The ring formed by R ¹² and R ¹³ preferably has the following structure.

In formula, * represents the site | part couple | bonded with the nitrogen atom of an enamine skeleton.
^RM is an alkyl group (preferably 1 to 6 carbon atoms), an alkoxy group (preferably 1 to 6 carbon atoms), an amino group (preferably 0 to 6 carbon atoms), an acyl group (preferably 1 to 6 carbon atoms). , An alkoxycarbonyl group (preferably having 1 to 6 carbon atoms) and an aryl group (preferably having 6 to 24 carbon atoms).
^RN is a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), an acyl group (preferably having 1 to 6 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 6 carbon atoms), an aryl group (preferably having a carbon number). 6-24).
n is an integer whose upper limit is the number that can be substituted, and is preferably an integer of 0 to 4, more preferably an integer of 0 to 2. D may be linked or condensed to form a ring.

・ R ¹⁴ , R ¹⁵
R ¹⁴ and R ¹⁵ represent an organic group that is not conjugated with N, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Although it does not specifically limit as an organic group, The example of the postscript substituent T is mentioned. Among these, as R ¹⁴ , an alkyl group is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an isobutyl group are more preferable. R ¹⁵ is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an isobutyl group. The substituents listed above as R ¹⁴ and R ¹⁵ may further have a substituent, preferably an alkoxy group, an amino group, or an alkylthio group, and more preferably an alkoxy group or an amino group. The ring that may be formed is not particularly limited, but is preferably a nitrogen-containing saturated hydrocarbon ring containing nitrogen in the formula, and more preferably a 3- to 8-membered nitrogen-containing saturated hydrocarbon ring.
Here, in terms of the relationship with the action of the present compound in the electrolytic solution, it is preferable that the atom (group) adjacent to N (the atom (group) at the α-position) in the above formula is not electron withdrawing. When the atom (group) adjacent to N (α-position atom (group)) is electron withdrawing, the one-electron oxidation potential of the enamine compound is increased. For example, a carbonyl group is an electron-withdrawing linking group. When such a linking group is adjacent to N of the enamine, it is hardly oxidized at the positive electrode potential driven as a battery, and the film formation of the present invention is not caused. Since it does not proceed, it is preferable that the electron withdrawing group is not adjacent to N in order to bring out the desired effect of the present invention.

The compound represented by the formula (1) is preferably an enamine compound represented by the following formula (2).

· ^{R 16} ~R ¹⁹
In the formula, R ^{16 to} R ¹⁹ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 5 carbon atoms), an alkoxy group (preferably having 1 to 5 carbon atoms), or an amino group (preferably having 2 to 2 carbon atoms). 7). R ^{16 to} R ¹⁹ may further have a substituent T.

・ A
A represents a hydrogen atom or an organic group, and may be the same or different. Although it does not specifically limit as an organic group, The example of the postscript substituent T is mentioned. Among them, as A, a hydrogen atom, an alkyl group (preferably having 1 to 5 carbon atoms), an alkoxy group (preferably having 1 to 5 carbon atoms), or an amino group (preferably having 2 to 7 carbon atoms) is preferable. An atom and an alkyl group (preferably having 1 to 5 carbon atoms) are more preferred. A may be bonded to each other to form a ring. A preferred ring has the same meaning as in formula (1).

The compound represented by the formula (2) is more preferably an enamine compound represented by the following formula (3-a) or (3-b).

· R ^20, R ²¹
In the formula, R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 3 carbon atoms).

・ D, G
D and G each represent a hydrogen atom, an alkyl group (preferably having 1 to 3 carbon atoms), an alkoxy group (preferably having 1 to 3 carbon atoms), or an amino group (preferably having 2 to 7 carbon atoms). It may be.

· R ^22, R ²³
R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group.

・ E
E represents a linking group, and represents an alkylene linking group (preferably having 2 to 5 carbon atoms), an ether linking group (preferably having 1 to 5 carbon atoms), or an amino linking group (preferably having 2 to 10 carbon atoms).

  The nitrogen-containing ring formed together with the linking group E preferably has the following structure.

In formula, * represents the site | part couple | bonded with the vinyl group of an enamine skeleton.
^RM is a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), an alkoxy group (preferably having 1 to 6 carbon atoms), an amino group (preferably having 0 to 6 carbon atoms), an acyl group (preferably having 1 carbon atom). -6), an alkoxycarbonyl group (preferably having 1 to 6 carbon atoms), and an aryl group (preferably having 6 to 24 carbon atoms).
^RN is a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms), an acyl group (preferably having 1 to 6 carbon atoms), an alkoxycarbonyl group (preferably having 1 to 6 carbon atoms), an aryl group (preferably having a carbon number). 6-24).
n is an integer whose upper limit is the number that can be substituted, and is preferably an integer of 0 to 4, more preferably an integer of 0 to 2. D may be linked or condensed to form a ring.

Specific examples of the compound represented by the formula (1) are shown below, but the present invention is not construed as being limited thereto.

  The content of the compound represented by the formula (1) in the electrolytic solution is preferably 0.0001 mol / L or more and 0.0005 mol / L or more as a lower limit value from the viewpoint of improving cycleability. It is more preferable. Although there is no upper limit in particular, it is preferably 0.1 mol / L or less, and more preferably 0.05 mol / L or less.

  If it says in relation with a postscript polymerizable compound, the compound represented by the said Formula (1) will be added 1 or more with respect to the polymeric compound 100 (molar ratio reference | standard). It is more preferable to add this at 5 or more. Although there is no upper limit in particular, it adds at 100 or less, It is more preferable to add at 70 or less, It is still more preferable to add at 50 or less.

(Organic solvent)
Examples of the organic solvent used in the present invention include cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methylpropyl carbonate, γ-butyrolactone, cyclic esters such as γ-valerolactone, chain ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, Chain ethers such as 1,3-dioxane, 1,4-dioxane and other cyclic ethers, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylacetate and ethyl trimethylacetate Nitrile compounds such as steal, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N′-dimethylimidazolidinone Nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide or dimethyl sulfoxide phosphoric acid. These may be used alone or in combination of two or more. Among them, at least one selected from the group consisting of cyclic carbonates (preferably ethylene carbonate, propylene carbonate), chain carbonates (preferably dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate), cyclic esters (preferably γ-butyrolactone). It is preferable to contain a seed, more preferably a solvent containing a cyclic carbonate and a chain carbonate, or a solvent containing a cyclic carbonate and a cyclic ester, particularly preferably a high solvent such as ethylene carbonate or propylene carbonate. A combination of a viscosity (high dielectric constant) solvent (for example, dielectric constant ε ≧ 30) and a low viscosity solvent (for example, viscosity ≦ 1 mPa · s) such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, or γ-butyrolactone. . This is because the dissociation property of the electrolyte salt and the ion mobility are improved.
However, the organic solvent (nonaqueous solvent) used in the present invention is not limited to the above examples.

(Electrolytes)
Examples of the electrolyte that can be used in the electrolytic solution of the present invention include metal ions or salts thereof, and metal ions or salts thereof belonging to Group 1 or Group 2 of the periodic table are preferred. It is appropriately selected depending on the purpose of use of the electrolytic solution, for example, lithium salt, potassium salt, sodium salt, calcium salt, magnesium salt and the like. When used in a secondary battery, the lithium salt is used from the viewpoint of output. Is preferred. When the electrolytic solution of the present invention is used as an electrolyte of a non-aqueous electrolytic solution for a lithium secondary battery, a lithium salt may be selected as a metal ion salt. The lithium salt is not particularly limited as long as it is a lithium salt usually used for an electrolyte of a non-aqueous electrolyte solution for a lithium secondary battery. For example, those described below are preferable.

(L-1) Inorganic lithium salts: inorganic fluoride salts such as LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ ; perhalogenates such as LiClO ₄ , LiBrO ₄ , LiIO ₄ ; inorganic chloride salts such as LiAlCl ₄ etc.

(L-2) Fluorine-containing organic lithium salt: Perfluoroalkane sulfonate such as LiCF ₃ SO ₃ ; LiN (CF ₃ SO ₂ ) ₂ , LiN (CF ₃ CF ₂ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , Perfluoroalkanesulfonylimide salts such as LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ); perfluoroalkanesulfonylmethide salts such as LiC (CF ₃ SO ₂ ) ₃ ; Li [PF ₅ (CF ₂ CF ₂ CF ₃ )], Li [PF ₄ (CF ₂ CF ₂ CF ₃ ) ₂ ], Li [PF ₃ (CF ₂ CF ₂ CF ₃ ) ₃ ], Li [PF ₅ (CF ₂ CF ₂ CF ₂ CF _{3 )], Li [PF 4 (} CF 2 CF 2 CF 2 CF 3) 2], Li [PF 3 (CF 2 CF 2 CF 2 CF 3) 3] fluoroalkyl fluoride such as potash Acid salts, and the like.

(L-3) Oxalatoborate salt: lithium bis (oxalato) borate, lithium difluorooxalatoborate and the like.
Among these, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiSbF ₆ , LiClO ₄ , Li (Rf ¹ SO ₃ ), LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ) ₂ is preferred, such as LiPF ₆ , LiBF ₄ , LiN (Rf ¹ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , and LiN (Rf ¹ SO ₂ ) (Rf ² SO ₂ ) ₂ The lithium imide salt is more preferable. Here, Rf ¹ and Rf ² each represent a perfluoroalkyl group.
In addition, the lithium salt used for electrolyte solution may be used individually by 1 type, or may combine 2 or more types arbitrarily.
The content of the metal ions belonging to Group 1 or Group 2 of the periodic table or the metal salt thereof in the electrolytic solution is added in an amount so as to obtain a preferable salt concentration described below in the method for preparing the electrolytic solution. The salt concentration is appropriately selected depending on the purpose of use of the electrolytic solution, but is generally 10% by mass to 50% by mass, more preferably 15% by mass to 30% by mass, based on the total mass of the electrolytic solution. In addition, when evaluating as an ion density | concentration, what is necessary is just to calculate by salt conversion with the metal applied suitably.

(Polymerizable compound)
In the electrolytic solution of the present invention, when a polymerizable compound is used in addition to the compound of the formula (1), the effect is further remarkable. The type of the polymerizable compound that can be used in the present invention is not particularly defined as long as it does not depart from the gist of the present invention. Examples thereof include radical polymerizable compounds, anionic polymerizable compounds, and cationic polymerizable compounds. And / or anionic polymerizable compounds are preferred.
The radical polymerizable compound and the anion polymerizable compound are preferably compounds having a carbon-carbon multiple bond. Examples of the compound having a carbon-carbon multiple bond include vinyl compounds, styrene derivatives, (meth) acrylate derivatives, cyclic olefins (which may contain heteroatoms in the ring), and the like. More preferably, it is a compound having a carbon-carbon multiple bond and a polar functional group, and examples of the polar functional group include ester group, carbonate group, nitrile group, amide group, urea group, sulfolane group, sulfoxide group, sulfone group, and sulfonic acid. Examples include esters, cyclic ether groups, polyalkylene oxide groups, and the like. These polar groups may form a chain structure or a cyclic structure.
Examples of the cationic polymerizable compound include an epoxy compound, an oxetane compound, and a vinyl ether compound.
Among them, it is particularly preferable to use a compound having a structure represented by the following formulas (i) to (iv).

・ R ³
R ³ represents a hydrogen atom or an alkyl group. A preferable alkyl group as R ³ is an alkyl group having 1 to 10 carbon atoms (methyl, ethyl, hexyl, cyclohexyl, etc.), and R ³ is more preferably a hydrogen atom.

・ R ⁴
R ⁴ represents an aromatic group, a heterocyclic group, a nitrile group, an alkoxy group, or an acyloxy group. The aromatic group of R ⁴ is preferably a 2π-aromatic group having 6 to 10 carbon atoms (phenyl, naphthyl, etc.), and the heterocyclic group is a heteroaromatic group having 4 to 9 carbon atoms (furyl, pyridyl, pyrazyl, Pyrimidyl, quinolyl, etc.) are preferred, the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms (methoxy, ethoxy, butoxy, etc.), and the acyloxy group is an acyloxy group having 1 to 10 carbon atoms (acetyl group, hexanoyloxy). Group) and the like, and R ⁴ is more preferably a phenyl group.

・ R ⁵
R ⁵ represents hydrogen, an alkyl group or a cyano group, and a preferable alkyl group is an alkyl group having 1 to 10 carbon atoms (methyl, ethyl, hexyl, cyclohexyl, etc.), more preferably hydrogen or a methyl group.

・ R ⁶
R ⁶ represents an alkyl group, an alkoxy group or an amino group, and the alkoxy group, that is, the formula (3-b) is more preferably an acrylic ester or a methacrylic ester. In this case, the alkoxy group corresponding to the alcohol portion of the ester is preferably an alkoxy group having 1 to 10 carbon atoms (methoxy, ethoxy, butoxy, etc.), more preferably a methoxy group or an ethoxy group.

・ R ⁷ , R ⁸
R ⁷ and R ⁸ represent hydrogen, an alkyl group or an aromatic group. It is preferred that R ⁷ and R ⁸ are hydrogen, or R ⁷ is hydrogen and R ⁸ is an aromatic group. A preferable aromatic group in this case is an aromatic group having 6 to 10 carbon atoms (phenyl, naphthyl, etc.).

・ X, Y, Z
X, Y and Z can form a 5- or 6-membered ring -O-, -S-,-(C = O)-, -C (= S)-, -NR-, -SO-, A divalent linking group selected from —SO ₂ — is represented, and X and Y are preferably —O—, and Z is preferably — (C═O) —. R represents an alkyl group or an aromatic group. The preferred alkyl group has the same meaning as R ^3, and the preferred aromatic group has the same meaning as R ⁴ .

・ R ⁹
R ⁹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl, ethyl, hexyl, cyclohexyl, etc.), more preferably hydrogen or a methyl group.

The substituents of R ^{3 to} R ⁹ described above may further contain another substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocycle having at least one oxygen atom, sulfur atom, nitrogen atom) A cyclic group is preferable, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc., an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, for example, Methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryloxy groups (preferably aryloxy groups having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), An alkoxycarbonyl group (preferably an alkoxycarbonyl having 2 to 20 carbon atoms) Nyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc., amino groups (preferably including amino groups having 0 to 20 carbon atoms, alkylamino groups, arylamino groups, such as amino, N, N-dimethyl Amino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl groups (preferably sulfonamido groups having 0 to 20 carbon atoms, such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl) Etc.), an acyl group (preferably an acyl group having 1 to 20 carbon atoms, such as acetyl, propionyl, butyryl, benzoyl, etc.), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, Benzoyloxy, etc.), carbamoyl groups (preferably C 1-20 carbon atoms) Rubamoyl groups such as N, N-dimethylcarbamoyl and N-phenylcarbamoyl), acylamino groups (preferably having 1 to 20 carbon atoms, such as acetylamino and benzoylamino), sulfonamido groups (preferably Is a sulfamoyl group having 0 to 20 carbon atoms, such as methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-ethylbenzenesulfonamide, etc., an alkylthio group (preferably an alkylthio having 1 to 20 carbon atoms). Groups such as methylthio, ethylthio, isopropylthio, benzylthio, etc., arylthio groups (preferably arylthio groups having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio ), An alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, benzenesulfonyl, etc.), a hydroxyl group, a cyano group, more preferably an alkyl group, Alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, hydroxyl group or halogen atom, particularly preferably alkyl group, alkenyl group, heterocyclic group, alkoxy group An alkoxycarbonyl group, an amino group, an acylamino group or a hydroxyl group.
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.

  When the compound or substituent / linking group contains an alkyl group / alkylene group, alkenyl group / alkenylene group, etc., these may be cyclic or chain-like, and may be linear or branched, and substituted as described above. It may be substituted or unsubstituted. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.

  In addition, what was shown as a compound in this specification is used in the meaning containing the salt, complex, and its ion other than the said compound itself. Moreover, it is the meaning including the derivative | guide_body which changed the predetermined part in the range with the desired effect. In addition, in the present specification, a substituent or a linking group for which substitution / non-substitution is not specified clearly means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

  The following can be illustrated as a polymeric compound. However, the present invention is not construed as being limited by these examples.

Ｒ_１は水素原子、アルキル基、ハロゲン原子、シアノ基を表す。
ｎは１〜２０を表す。
Ｍｅはメチル基を表す。

R ₁ represents a hydrogen atom, an alkyl group, a halogen atom, or a cyano group.
n represents 1-20.
Me represents a methyl group.

  When the amount of the polymerizable compound added is small, the effect of improving the cycle characteristics and rate characteristics is small, and when it is too large, the internal resistance of the battery is increased and the initial characteristics of the battery are impaired. The concentration range of the polymerizable compound is preferably in the range of 0.001M to 0.5M, more preferably in the range of 0.002M to 0.1M, and still more preferably in the range of 0.003 to 0.05M.

(Other ingredients)
In the electrolytic solution according to the present invention, various additives can be used depending on the purpose as long as the effects of the present invention are not impaired in order to improve battery performance. As such an additive, such a functional additive such as an overcharge inhibitor, a negative electrode film forming agent, a positive electrode protective agent, a flame retardant, and the like may be used.

  Moreover, the combined use of a negative electrode film forming agent and a positive electrode protective agent, or the combined use of an overcharge inhibitor, a negative electrode film forming agent, and a positive electrode protective agent is particularly preferable.

  The content ratio of these other additives in the non-aqueous electrolyte solution is not particularly limited, but is preferably 0.01% by mass or more, particularly preferably 0.1% by mass with respect to the total organic components of the non-aqueous electrolyte solution. % Or more, more preferably 0.2% by mass or more, and the upper limit is preferably 5% by mass or less, particularly preferably 3% by mass or less, and further preferably 2% by mass or less. By adding these compounds, it is possible to suppress rupture / ignition of the battery at the time of abnormality due to overcharge, and to improve the capacity maintenance characteristic and cycle characteristic after high-temperature storage.

In the electrolytic solution for a non-aqueous secondary battery of the present invention, each organic component in the electrolytic solution is preferably composed of one having a molecular weight of 1000 or less, more preferably 500 or less. This is a premise in the embodiment of the present invention, and that the non-aqueous secondary battery or the electrolytic solution of the present invention is not related to a solid electrolyte type secondary battery or a polymer electrolyte type secondary battery. means. Note that the electrolyte for a non-aqueous secondary battery is not a material used for a solid electrolyte type secondary battery or a polymer electrolyte type secondary battery, that is, a secondary battery using a liquid electrolyte (referred to as “liquid electrolysis”). It may be referred to as a “liquid type secondary battery”).
Unless otherwise specified, the molecular weight is a value measured using a GPC (gel filtration chromatography) method, and the molecular weight is a weight average molecular weight in terms of polystyrene. The gel packed in the column used in the GPC method is preferably a gel having an aromatic compound as a repeating unit, and examples thereof include a gel made of a styrene-divinylbenzene copolymer. It is preferable to use 2 to 6 columns connected together. Examples of the solvent used include ether solvents such as tetrahydrofuran, amide solvents of N-methylpyrrolidone, halogen solvents such as chloroform, and aromatic solvents such as 1,2-dichlorobenzene. The measurement is preferably performed at a solvent flow rate in the range of 0.1 to 2 mL / min, and most preferably in the range of 0.5 to 1.5 mL / min. By performing the measurement within this range, the apparatus is not loaded and the measurement can be performed more efficiently. The measurement temperature is preferably 10 to 50 ° C, most preferably 20 to 40 ° C. Measurement can also be performed at 50 ° C. to 200 ° C. using a column having a high usable temperature. The column and carrier to be used can be appropriately selected according to the physical properties of the compound to be measured.

  The electrolyte solution for a non-aqueous secondary battery of the present invention has a viscosity (25 ° C.) of preferably 20 mPa · s or less, more preferably 10 mPa · s or less, and preferably 5 mPa · s or less. Further preferred. Although there is no lower limit in particular, it is practical that it is 0.5 mPa · s or more. Such a viscosity range is set for distinction from the solid electrolyte. If the viscosity is defined in the solid electrolyte, it becomes ∞. In the present specification, the value of viscosity means a value measured by the method described in Examples below unless otherwise specified. The polymer raw material solution constituting the solid electrolyte may be in the viscosity range defined above, but this is a raw material solution (precursor) of the electrolytic solution, not the electrolytic solution.

[Method for preparing electrolytic solution]
The electrolyte solution for a non-aqueous secondary battery of the present invention is prepared by a conventional method by dissolving each of the above components in the non-aqueous electrolyte solvent, including an example in which a lithium salt is used as a metal ion salt.

  In the present invention, “non-water” means that water is not substantially contained, and a trace amount of water may be contained as long as the effects of the invention are not hindered. In view of obtaining good characteristics, the water content is preferably 200 ppm or less, and more preferably 100 ppm or less. Although there is no particular lower limit, it is practical that it is 10 ppm or more considering inevitable mixing.

[Secondary battery]
In this invention, it is preferable to set it as the non-aqueous secondary battery containing the said non-aqueous electrolyte. As a preferred embodiment, a lithium ion secondary battery will be described with reference to FIG. 1 schematically showing the mechanism. The lithium ion secondary battery 10 of this embodiment includes the electrolyte solution 5 for a non-aqueous secondary battery of the present invention and a positive electrode C capable of inserting and releasing lithium ions (a positive electrode current collector 1 and a positive electrode active material layer 2). And a negative electrode A (negative electrode current collector 3, negative electrode active material layer 4) capable of inserting and releasing lithium ions or dissolving and depositing lithium ions. In addition to these essential members, considering the purpose of use of the battery, the shape of the potential, etc., a separator 9 disposed between the positive electrode and the negative electrode, a current collecting terminal (not shown), an outer case, etc. (Not shown). If necessary, a protective element may be attached to at least one of the inside of the battery and the outside of the battery. By adopting such a structure, lithium ion transfer a and b occurs in the electrolyte 5, charging α and discharging β can be performed, and operation or storage is performed via the circuit wiring 7 and the operation mechanism 6. be able to. Hereinafter, the configuration of the lithium secondary battery which is a preferred embodiment of the present invention will be described in more detail.

(Battery shape)
The battery shape to which the lithium secondary battery of the present embodiment is applied is not particularly limited, and examples thereof include a bottomed cylindrical shape, a bottomed square shape, a thin shape, a sheet shape, and a paper shape. Any of these may be used. Further, it may be of a different shape such as a horseshoe shape or a comb shape considering the shape of the system or device to be incorporated. Among them, from the viewpoint of efficiently releasing the heat inside the battery to the outside, a square shape such as a bottomed square shape or a thin shape having at least one surface that is relatively flat and has a large area is preferable.

  In a battery having a bottomed cylindrical shape, since the outer surface area with respect to the power generating element to be filled becomes small, it is preferable to design so that Joule heat generated by the internal resistance at the time of charging and discharging efficiently escapes to the outside. Moreover, it is preferable to design so that the filling ratio of the substance having high thermal conductivity is increased and the temperature distribution inside is reduced. FIG. 2 is an example of a bottomed cylindrical lithium secondary battery 100. This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18.

In the bottomed square shape, the ratio of the area S of the largest surface (the product of the width and height of the outer dimensions excluding the terminal portion, unit cm ² ) to the thickness T (unit cm) of the battery outer shape The 2S / T value is preferably 100 or more, and more preferably 200 or more. By increasing the maximum surface, it is possible to improve characteristics such as cycle performance and high-temperature storage even for high-power and large-capacity batteries, and increase the heat dissipation efficiency during abnormal heat generation. It is possible to suppress a dangerous state of “rupture”.

(Members constituting the battery)
The lithium secondary battery according to the present embodiment is configured to include the electrolytic solution 5, the positive electrode and negative electrode electrode mixtures C and A, and the separator basic member 9, based on FIG. 1. Hereinafter, each of these members will be described. The nonaqueous secondary battery of the present invention includes at least the electrolyte solution for a nonaqueous battery of the present invention as an electrolytic solution.
(Electrode mixture)
The electrode mixture is obtained by applying a dispersion of an active material and a conductive agent, a binder, a filler, etc. on a current collector (electrode substrate). In a lithium battery, the active material is a positive electrode active material. It is preferable to use a negative electrode mixture in which the positive electrode mixture and the active material are a negative electrode active material. Next, each component in the dispersion (electrode composition, electrode mixture) constituting the electrode mixture will be described.

-Positive electrode active material You may use a particulate positive electrode active material for a positive electrode active material. Specifically, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used, but a lithium-containing transition metal oxide is preferably used. Preferred examples of the lithium-containing transition metal oxide preferably used as the positive electrode active material include oxides containing lithium-containing Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, and W. Alkali metals other than lithium (elements of Group 1 (Ia) and Group 2 (IIa) of the periodic table) and / or Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P , B, etc. may be mixed. The mixing amount is preferably 0 to 30 mol% with respect to the transition metal.

  Among the lithium-containing transition metal oxides preferably used as the positive electrode active material, a lithium compound / transition metal compound (wherein the transition metal is selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mo, W) It is more preferable that the mixture is synthesized so that the total molar ratio of the compound is 0.3 to 2.2.

Further, among the lithium compounds / transition metal compounds, Li _g M3O ₂ (M3 represents one or more elements selected from Co, Ni, Fe, and Mn. G represents 0 to 1.2. ) Or a material having a spinel structure represented by Li _h M4 ₂ O (M4 represents Mn. H represents 0 to 2). As M3 and M4, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, and B may be mixed in addition to the transition metal. The mixing amount is preferably 0 to 30 mol% with respect to the transition metal.

The _Li g M3O material containing _2, among the materials having the spinel structure represented by _{Li h M4 2 O, Li g} CoO 2, Li g NiO 2, Li g MnO 2, Li g Co j Ni 1-j O _{2, Li h Mn 2 O 4} , LiNi j Mn 1-j O 2, LiCo j Ni h Al 1-j-h O 2, LiCo j Ni h Mn 1-j-h O 2, LiMn h Al 2-h O ₄ , LiMn _h Ni _{2 -h} O ₄ (where g represents 0.02 to 1.2, j represents 0.1 to 0.9, and h represents 0 to 2) is particularly preferable. , most preferably _{Li g CoO 2, LiMn 2 O} 4, LiNi 0.85 Co 0.01 Al 0.05 O 2, and is _{LiNi 0.33 Co 0.33 Mn 0.33 O 2} . Of these, an electrode containing Ni is more preferable from the viewpoint of high capacity and high output. Here, the g value and the h value are values before the start of charge / discharge, and are values that increase / decrease due to charge / discharge. In particular,
LiCoO ₂ , LiNi _0.5 Mn _0.5 O ₂ , LiNi _0.85 Co _0.01 Al _0.05 O ₂ ,
LiNi _0.33 Co _0.33 Mn _0.33 O ₂ , LiMn _1.8 Al _0.2 O ₄ ,
LiMn _1.5 Ni _0.5 O ₄ and the like.

As the transition metal of the lithium-containing transition metal phosphate compound, V, Ti, Cr, Mn, Fe, Co, Ni, Cu and the like are preferable, and specific examples include, for example, LiFePO ₄ , Li ₃ Fe ₂ (PO ₄ ). ₃ , iron phosphates such as LiFeP ₂ O ₇ , cobalt phosphates such as LiCoPO ₄ , and some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are Al, Ti, V, Cr, Mn , Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Si and the like substituted with other metals.

In the present invention, it is preferable to use a material having a charge region of 4.25 V or more for the positive electrode active material. Although there is no particular upper limit, it is practical that it is 5 V or less.
The following are mentioned as a positive electrode active material which has the said specific charge area | region.
(I) LiNi _x Mn _y Co _z O ₂ (x> 0.2, y> 0.2, z ≧ 0, x + y + z = 1),
Representative:
LiNi _1/3 Mn _1/3 Co _1/3 O ₂ (also described as LiNi _0.33 Mn _0.33 Co _0.33 O ₂ )
LiNi _1/2 Mn _1/2 O ₂ (also described as LiNi _0.5 Mn _0.5 O ₂ )
(Ii) LiNi _x Co _y Al _z O ₂ (x> 0.7, y> 0.1, 0.1>z> 0.05, x + y + z = 1)
Representative:
LiNi _0.8 Co _0.15 Al _0.05 O ₂
The following can be used as the positive electrode active material having the specific charging region.
(A) LiCoMnO ₄
(B) Li ₂ FeMn ₃ O ₈
(C) Li ₂ CuMn ₃ O ₈
(D) Li ₂ CrMn ₃ O ₈
(E) Li ₂ NiMn ₃ O ₈

In the non-aqueous secondary battery, the average particle size of the positive electrode active material used is not particularly limited, but is preferably 0.1 μm to 50 μm. No particular limitation is imposed on the specific surface area, preferably from 0.01m ² / g~50m ² / g by the BET method. Further, the pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.

  In order to make the positive electrode active substance have a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a vibration ball mill, a vibration mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill, a sieve, or the like is used. The positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

・ Negative electrode active material The negative electrode active material is not particularly limited as long as it can reversibly insert and release lithium ions. Carbonaceous materials, metal oxides such as tin oxide and silicon oxide, metal composite oxides, Examples thereof include lithium alloys such as lithium alone and lithium aluminum alloys, and metals capable of forming an alloy with lithium such as Sn and Si.
These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and a ratio. Of these, carbonaceous materials or lithium composite oxides are preferably used from the viewpoint of safety.
Further, the metal composite oxide is not particularly limited as long as it can occlude and release lithium, but it preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics. .

  The carbonaceous material used as the negative electrode active material is a material substantially made of carbon. Examples thereof include carbonaceous materials obtained by baking various synthetic resins such as artificial pitches such as petroleum pitch, natural graphite, and vapor-grown graphite, and PAN-based resins and furfuryl alcohol resins. Furthermore, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, mesophase micro Examples thereof include spheres, graphite whiskers, and flat graphite.

  These carbonaceous materials can be divided into non-graphitizable carbon materials and graphite-based carbon materials depending on the degree of graphitization. Further, the carbonaceous material preferably has the surface spacing, density, and crystallite size described in JP-A-62-222066, JP-A-2-6856, and 3-45473. The carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. You can also.

  The metal oxide and metal composite oxide, which are negative electrode active materials used in the nonaqueous secondary battery, need only contain at least one of them. As the metal oxide and metal complex oxide, amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. The term “amorphous” as used herein means an X-ray diffraction method using CuKα rays, which has a broad scattering band having an apex in the region of 20 ° to 40 ° in terms of 2θ values, and is a crystalline diffraction line. You may have. The strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.

Among the compound group consisting of the amorphous oxide and the chalcogenide, an amorphous oxide of a metalloid element and a chalcogenide are more preferable, and elements of Groups 13 (IIIB) to 15 (VB) of the periodic table, Particularly preferred are oxides and chalcogenides composed of one kind of Al, Ga, Si, Sn, Ge, Pb, Sb, Bi or a combination of two or more kinds thereof. Specific examples of preferable amorphous oxides and chalcogenides include, for example, Ga ₂ O ₃ , SiO, GeO, SnO, SnO ₂ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₂ O ₄ , Pb ₃ O ₄ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , Bi ₂ O ₃ , Bi ₂ O ₄ , SnSiO ₃ , GeS, SnS, SnS ₂ , PbS, PbS ₂ , Sb ₂ S ₃ , Sb ₂ S ₅ , such as SnSiS ₃ may preferably be mentioned. Moreover, these may be a complex oxide with lithium oxide, for example, Li ₂ SnO ₂ .

  In the nonaqueous secondary battery of the present invention, the average particle size of the negative electrode active material used is preferably 0.1 μm to 60 μm. To obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill or a sieve is preferably used. When pulverizing, wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary. In order to obtain a desired particle size, classification is preferably performed. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.

  The chemical formula of the compound obtained by the firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method and a mass difference between powders before and after firing as a simple method.

  In the present invention, as the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centering on Sn, Si, Ge, a carbon material capable of inserting and extracting lithium ions or lithium metal, lithium, Preferred examples include lithium alloys and metals that can be alloyed with lithium.

In the present invention, it is also preferable to use lithium titanate, more specifically, lithium-titanium oxide (Li [Li _1/3 Ti _5/3 ] O ₄ ) as the negative electrode active material. By using this as the negative electrode active material, the effect of the compound represented by the formula (1) or the combination of this and the polymerizable compound is further enhanced, and more excellent battery performance can be exhibited.

-Conductive material As the conductive material, any electronic conductive material that does not cause a chemical change in the configured secondary battery may be used, and any known conductive material may be used. Usually, natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber and metal powder (copper, nickel, aluminum, silver (Japanese Patent Laid-Open No. Sho 63- 10148,554)), metal fibers or polyphenylene derivatives (described in JP-A-59-20971) can be contained as a single type or a mixture thereof. Among these, the combined use of graphite and acetylene black is particularly preferable. As addition amount of the said electrically conductive agent, 1-50 mass% is preferable and 2-30 mass% is more preferable. In the case of carbon or graphite, 2 to 15% by mass is particularly preferable.

-Binder In this invention, it is preferable to use the binder for hold | maintaining the said electrode compound material.
Examples of the binder include polysaccharides, thermoplastic resins, and polymers having rubber elasticity. Among them, for example, starch, carboxymethylcellulose, cellulose, diacetylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium alginate, Polyacrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, water-soluble polymers such as styrene-maleic acid copolymer, polyvinyl chloride , Polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene Ride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate and other (meth) acrylic (Meth) acrylic acid ester copolymer containing acid ester, (meth) acrylic acid ester-acrylonitrile copolymer, polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene-butadiene copolymer, acrylonitrile -Butadiene copolymer, polybutadiene, neoprene rubber, fluororubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane Tan resins, polyester resins, phenolic resins, emulsion (latex) or a suspension such as an epoxy resin is preferable, a latex of polyacrylate, carboxymethyl cellulose, polytetrafluoroethylene, polyvinylidene fluoride is more preferable.

  A binder can be used individually by 1 type or in mixture of 2 or more types. When the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the capacity per electrode unit volume or unit mass decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.

-Filler The electrode compound material may contain the filler. As the material for forming the filler, any fibrous material that does not cause a chemical change in the secondary battery of the present invention can be used. Usually, fibrous fillers made of materials such as olefin polymers such as polypropylene and polyethylene, glass, and carbon are used. Although the addition amount of a filler is not specifically limited, 0-30 mass% is preferable in a dispersion.

-Current collector As the positive / negative electrode current collector, an electron conductor that does not cause a chemical change in a non-aqueous electrolyte secondary battery is used. As the current collector of the positive electrode, in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.

  As the negative electrode current collector, aluminum, copper, stainless steel, nickel, and titanium are preferable, and aluminum, copper, and a copper alloy are more preferable.

As the shape of the current collector, a film sheet shape is usually used, but a net, a punched material, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like can also be used. The thickness of the current collector is not particularly limited, but is preferably 1 μm to 500 μm. Moreover, it is also preferable that the current collector surface is roughened by surface treatment.
An electrode mixture of the lithium secondary battery is formed by a member appropriately selected from these materials.

(Separator)
The separator used in the non-aqueous secondary battery is particularly limited as long as it is a material that mechanically insulates the positive electrode and the negative electrode, has ion permeability, and has oxidation / reduction resistance at the contact surface between the positive electrode and the negative electrode. There is nothing. As such a material, a porous polymer material, an inorganic material, an organic-inorganic hybrid material, glass fiber, or the like is used. These separators preferably have a shutdown function for ensuring safety, that is, a function of closing the gap at 80 ° C. or higher to increase resistance and interrupting current, and the closing temperature is 90 ° C. or higher and 180 ° C. or lower. Preferably there is.

  The shape of the hole of the separator is usually circular or elliptical, and the size is 0.05 μm to 30 μm, preferably 0.1 μm to 20 μm. Furthermore, it may be a rod-like or irregular-shaped hole as in the case of making by a stretching method or a phase separation method. The ratio of these gaps, that is, the porosity, is 20% to 90%, preferably 35% to 80%.

  The polymer material may be a single material such as cellulose nonwoven fabric, polyethylene, or polypropylene, or may be a composite material of two or more types. What laminated | stacked the 2 or more types of microporous film which changed the hole diameter, the porosity, the obstruction | occlusion temperature of a hole, etc. is preferable.

  As the inorganic substance, oxides such as alumina and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate are used, and those having a particle shape or fiber shape are used. As the form, a thin film shape such as a non-woven fabric, a woven fabric, or a microporous film is used. In the thin film shape, those having a pore diameter of 0.01 μm to 1 μm and a thickness of 5 μm to 50 μm are preferably used. In addition to the independent thin film shape, a separator formed by forming a composite porous layer containing the inorganic particles on the surface layer of the positive electrode and / or the negative electrode using a resin binder can be used. For example, alumina particles having a 90% particle diameter of less than 1 μm are formed on both surfaces of the positive electrode as a porous layer using a fluororesin binder.

(Production of non-aqueous secondary battery)
As described above, the shape of the nonaqueous secondary battery of the present invention can be applied to any shape such as a sheet shape, a square shape, and a cylinder shape. A positive electrode active material or a mixture of negative electrode active materials is mainly used after being applied (coated), dried and compressed on a current collector.

  Hereinafter, with reference to FIG. 2, a configuration and a manufacturing method thereof will be described using the bottomed cylindrical lithium secondary battery 100 as an example. In a battery having a bottomed cylindrical shape, since the outer surface area with respect to the power generating element to be filled becomes small, it is preferable to design so that Joule heat generated by the internal resistance at the time of charging and discharging efficiently escapes to the outside. Moreover, it is preferable to design so that the filling ratio of the substance having high thermal conductivity is increased and the temperature distribution inside is reduced. FIG. 2 shows an example of a bottomed cylindrical lithium secondary battery 100. This battery is a bottomed cylindrical lithium secondary battery 100 in which a positive electrode sheet 14 and a negative electrode sheet 16 overlapped with a separator 12 are wound and accommodated in an outer can 18. In addition, in the figure, 20 is an insulating plate, 22 is a sealing plate, 24 is a positive current collector, 26 is a gasket, 28 is a pressure-sensitive valve element, and 30 is a current interruption element. In addition, although the illustration in the enlarged circle has changed hatching in consideration of visibility, each member corresponds to the whole drawing by reference numerals.

  First, a negative electrode active material is mixed with a binder or filler used as desired in an organic solvent to prepare a slurry-like or paste-like negative electrode mixture. The obtained negative electrode mixture is uniformly applied over the entire surface of both surfaces of the metal core as a current collector, and then the organic solvent is removed to form a negative electrode mixture layer. Further, the laminate of the current collector and the negative electrode composite material layer is rolled with a roll press or the like to prepare a predetermined thickness to obtain a negative electrode sheet (electrode sheet). At this time, the coating method of each agent, the drying of the coated material, and the method of forming the positive and negative electrodes may be in accordance with conventional methods.

  In the present embodiment, a cylindrical battery is taken as an example, but the present invention is not limited to this, for example, after the positive and negative electrode sheets produced by the above method are overlapped via a separator, After processing into a sheet battery as it is, or inserting it into a rectangular can after being folded and electrically connecting the can and the sheet, injecting an electrolyte and sealing the opening using a sealing plate A square battery may be formed.

  In any embodiment, the safety valve can be used as a sealing plate for sealing the opening. In addition to the safety valve, the sealing member may be provided with various conventionally known safety elements. For example, a fuse, bimetal, PTC element, or the like is preferably used as the overcurrent prevention element.

  In addition to the safety valve, as a countermeasure against the increase in the internal pressure of the battery can, a method of cutting the battery can, a method of cracking the gasket, a method of cracking the sealing plate, or a method of cutting the lead plate can be used. Further, the charger may be provided with a protection circuit incorporating measures against overcharge and overdischarge, or may be connected independently.

  For the can and lead plate, a metal or alloy having electrical conductivity can be used. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum, or alloys thereof are preferably used.

  As a method for welding the cap, the can, the sheet, and the lead plate, a known method (eg, direct current or alternating current electric welding, laser welding, ultrasonic welding) can be used. As the sealing agent for sealing, a conventionally known compound or mixture such as asphalt can be used.

[Applications of non-aqueous secondary batteries]
According to the present invention, since a secondary battery with good cycleability can be manufactured, it is applied to various uses. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. It is done. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Example 1 and Comparative Example 1>
Preparation of Electrolyte 1M LiBF ₄ ethylene carbonate / γ-butyrolactone volume ratio 3 to 7 The electrolyte was added to the electrolyte in the amounts shown in Table 1 in the amounts shown in the table, and the electrolyte for examples and comparative examples An electrolyte solution was prepared. All the prepared electrolyte solutions had a viscosity at 25 ° C. of 5 mPa · s or less.
<Production of battery (1)>
The positive electrode is made of active material: nickel manganese lithium cobaltate (LiNi _1/3 Mn _1/3 Co _1/3 O ₂ ) 85% by mass, conductive auxiliary agent: carbon black 7% by mass, binder: PVDF 8% by mass, The negative electrode was prepared with 94% by mass of active material: lithium titanate (Li ₄ Ti ₅ O ₁₂ ), conductive auxiliary agent: 3% by mass of carbon black, and binder: 3% by mass of PVDF. The separator is made of cellulose and has a thickness of 40 μm. Using the above positive and negative electrodes and separator, a 2032 type coin battery was prepared for each test electrolyte, and the following items were evaluated. The results are shown in Table 1.

<High temperature cycle test>
After charging the 2032 type coin battery in a constant temperature bath at 45 ° C. until the battery voltage reaches 2.75 V, the current value becomes 0.12 mA at 2.75 V constant voltage, or charge for 2 hours. Then, 1C constant current discharge was performed until the battery voltage became 1.2 V, and the discharge amount in the first cycle was measured as one cycle. This was repeated until 500 cycles were reached, and the discharge capacity at the 500th cycle was measured.

(High temperature capacity retention rate HTratio (%)) =
{(Discharge capacity at 500th cycle / Discharge capacity at 1st cycle)} × 100

<High rate discharge capacity maintenance rate>
In a constant temperature bath at 30 ° C., after charging with a constant current of 0.1 C until the battery voltage becomes 2.75 V, the current value becomes 0.06 mA at a constant voltage of 2.75 V, or charging is performed for 2 hours, and then the battery A 0.2 C constant current discharge was performed until the voltage reached 1.2 V, and the battery capacity was measured. Again, after charging with a constant current of 0.1 C until the battery voltage reaches 2.75 V, the current value becomes 0.06 mA at a constant voltage of 2.75 V, or after 2 hours of charging, the battery voltage becomes 1.2 V. 5C constant current discharge was performed until the high rate discharge capacity was measured. The high rate discharge capacity retention rate was calculated by the following formula. The larger the value, the better the discharge capacity deterioration at a high rate, even when charging and discharging are repeated.

(High rate discharge capacity maintenance rate HRratio (%)) =
{(5C discharge capacity) / (initial 0.2C discharge capacity)} × 100

<Notes on the table>
* Those beginning with c are comparative examples. Otherwise, examples of the present invention (electrolyte or secondary battery sample number).
Comp. : Compound Conc. : Concentration (M)
NMP: N-methyl-2-pyrrolidone NVP: N-vinyl-2-pyrrolidone

  As described above, according to the nonaqueous electrolytic solution of the present invention and the secondary battery using the same, it is possible to achieve improvement in capacity maintenance when repeatedly charged and discharged at high temperature and capacity maintenance during high rate discharge. it can.

<Example 2>
-Preparation of electrolyte solution The components shown in Table 2 were added to 1M LiPF ₆ ethylene carbonate / diethyl carbonate volume ratio 1 to 2 electrolyte solution in the amounts shown in the table, and each test No. 1 was prepared. An electrolyte solution corresponding to was prepared. All the prepared electrolyte solutions had a viscosity at 25 ° C. of 5 mPa · s or less.

· Preparation positive electrode of the battery (2) is an active material and lithium cobaltate (LiCoO _2), the negative electrode except that the active material and graphite, to produce a 2032 form coin cell in the same manner as in Example (2), the following items Was evaluated. The results are shown in Table 2.

<High temperature cycle test>
The evaluation was performed under the same conditions as the evaluation performed for the battery 1 except that the upper limit voltage during charging was 4.3 V and the lower limit voltage during discharge was 2.75 V.

<High rate discharge capacity maintenance rate>
The evaluation was performed under the same conditions as those of the battery 1 except that the upper limit voltage during charging was 4.3 V, the lower limit voltage during discharge was 2.75 V, and the high rate discharge was 4 C.

・表中の注記は表１と同様

・ Notes in the table are the same as in Table 1

  As described above, it can be seen that when an electrolytic solution containing a specific enamine compound and a polymerizable compound of the present invention is used, good performance can be obtained even in a system using a Co-based active material having a relatively low potential. However, it can be seen that a particularly excellent effect is obtained in a system to which a high potential Mn-based active material is applied.

DESCRIPTION OF SYMBOLS 1 Positive electrode conductive material 2 Positive electrode active material 3 Negative electrode conductive material 4 Negative electrode active material 5 Electrolyte 6 Operation means 7 Wiring 9 Separator 10 Lithium ion secondary battery 12 Separator 14 Positive electrode sheet 16 Negative electrode sheet 18 The outer can 20 which also serves as a negative electrode Insulating plate 22 Sealing plate 24 Positive electrode current collector 26 Gasket 28 Pressure sensitive valve element 30 Current interrupting element 100 Bottomed cylindrical lithium secondary battery

Claims (11)

An electrolyte solution for a non-aqueous secondary battery containing an enamine compound represented by the following formula (1), a polymerizable compound, and an electrolyte in an organic solvent, wherein the polymerizable compound 100 (based on a molar ratio) On the other hand, the electrolyte solution for non-aqueous secondary batteries containing 1-100 said enamine compounds.

^{(Wherein, R 11, R 12, R} 13 are each independently represent a hydrogen atom or an organic group ^{.R 12, R 13} are bonded to each other, may also form a ring ^{.R 14, R 15} is And represents an organic group that is not conjugated with N. R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring.) The electrolyte solution for nonaqueous secondary batteries according to claim 1, wherein the formula (1) is represented by the following formula (2).

(Wherein R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an amino group. A represents a hydrogen atom or an organic group, which may be the same or different. A may be bonded to each other to form a ring, and R ^{11 to} R ¹³ have the same meanings as those in formula (1). The electrolyte solution for nonaqueous secondary batteries according to claim 1 or 2, wherein the formula (2) is represented by the following formula (3-a) or (3-b).

(In the formula, R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group. D and G each represent a hydrogen atom, an alkyl group, an alkoxy group, or an amino group, and may be the same or different. R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group, E represents a linking group, and represents an alkylene linkage, an ether linkage, an amino linkage, or a combination thereof, R ^{11 to} R ^13. Is synonymous with formula (1).) The electrolyte solution for nonaqueous secondary batteries according to claim 3, wherein in the formula (3-b), R ¹² and R ¹³ form a ring. The electrolyte for a non-aqueous secondary battery according to claim 3 or 4, wherein the ring formed by R ¹² and R ¹³ in the formula (3-b) or the ring with the linking group E is a 5-membered ring or a 6-membered ring. . The electrolyte solution for nonaqueous secondary batteries according to any one of claims 1 to 5, wherein the polymerizable compound is represented by any one of formulas (i) to (iv).

(In the formula, R ³ represents a hydrogen atom or an alkyl group. R ⁴ represents an aromatic group, a heterocyclic group, a nitrile group, an alkoxy group, or an acyloxy group. R ⁵ represents a hydrogen, an alkyl group, or a cyano group. R ⁶ represents an alkyl group, an alkoxy group, or an amino group, R ⁷ and R ⁸ represent hydrogen, an alkyl group, or an aromatic group, and X, Y, and Z may form a 5- or 6-membered ring. can -O -, - S -, - (C = O) -, - C (= S) -, - NR -, - SO -, - SO 2 - .R that represents a divalent linking group selected from Represents an alkyl group or an aromatic group, and R ⁹ represents a hydrogen atom or an alkyl group.)   The electrolyte solution for nonaqueous secondary batteries according to any one of claims 1 to 6, wherein the compound represented by the formula (1) is contained at 0.0001 to 0.1 mol / L.   The electrolyte solution for nonaqueous secondary batteries according to any one of claims 1 to 7, wherein the polymerizable compound is contained at 0.001 to 0.5 mol / L.   The average molecular weight of each organic component contained is 1000 or less, The electrolyte solution for nonaqueous secondary batteries of any one of Claims 1-8.   The non-aqueous secondary battery using the electrolyte solution for non-aqueous secondary batteries of any one of Claims 1-9.   The non-aqueous secondary battery according to claim 10, wherein the secondary battery contains a lithium metal composite oxide containing nickel atoms and / or manganese atoms as a material constituting the positive electrode.

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