JP2006294334A - Nonaqueous electrolyte solution, nonaqueous electrolyte solution battery, nonaqueous electrolyte solution electric double-layer capacitor, and safety evaluation method of nonaqueous electrolyte solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide nonaqueous electrolyte solution of high safety and a new evaluation method of safety of nonaqueous electrolyte solution. <P>SOLUTION: The nonaqueous electrolyte solution has (A) a maximum heat generation rate of 550 kW/m<SP>2</SP>or less as measured by a cone calorimeter and/or (B) a gross calorific value of 10 MJ/m<SP>2</SP>or less as measured by cone calorimeter, and the safety evaluation method of the nonaqueous electrolyte solution measures a maximum heat generation rate and/or a gross calorific value of the nonaqueous electrolyte solution with the use of the cone calorimeter. The nonaqueous electrolyte solution is applied for a nonaqueous electrolyte solution battery and a nonaqueous electrolyte solution electric double-layer capacitor. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a non-aqueous electrolyte, a non-aqueous electrolyte battery including the non-aqueous electrolyte, a non-aqueous electrolyte electric double layer capacitor, and a method for evaluating the safety of the non-aqueous electrolyte, and in particular, a maximum heat generation rate during combustion. Alternatively, the present invention relates to a non-aqueous electrolyte solution having a low total calorific value and high safety.

  In recent years, a light-weight, long-life, high-energy-density battery has been demanded as a power source for small electronic devices or a main power source or auxiliary power source for electric vehicles and fuel cell vehicles. In contrast, a non-aqueous electrolyte battery using lithium as a negative electrode active material is known as one of batteries having a high energy density because the electrode potential of lithium is the lowest among metals and the electric capacity per unit volume is large. Many types of batteries, whether primary batteries or secondary batteries, are actively researched and put into practical use and supplied to the market.

  In addition, the electric double layer capacitor is excellent in instantaneous charge / discharge characteristics, and even after repeated charge / discharge, the instantaneous charge / discharge characteristics are hardly deteriorated, and there is no charge / discharge overvoltage at the time of charge / discharge. In addition, the remaining capacity is easy to understand, has a durable temperature characteristic over a wide temperature range of -30 to 90 ° C, and has various excellent points such as non-polluting. Therefore, in recent years, as a new energy storage product that is friendly to the global environment, it has come into the limelight as a power source for energy regeneration and engine start of electric vehicles, fuel cell vehicles and hybrid electric vehicles. Conventionally known aqueous electrolytes, non-aqueous electrolytes, solid electrolytes, etc. as the electrolyte of the electric double layer capacitor can be set at a high operating voltage in order to improve the energy density of the electric double layer capacitor. Non-aqueous electrolytes are particularly in the spotlight and are being put to practical use.

  The nonaqueous electrolytic solution used for the battery and the electric double layer capacitor is generally obtained by dissolving a supporting salt in an aprotic organic solvent such as an ester compound or an ether compound. The aprotic organic solvent is, for example, a battery. When the capacitor or the capacitor heats up abnormally, there is a risk that it will vaporize and decompose to generate gas, or the generated gas and heat may cause the battery and capacitor to burst or ignite.

  Accordingly, an object of the present invention is to solve the above-described problems of the prior art and provide a highly safe non-aqueous electrolyte. Another object of the present invention is to provide a non-aqueous electrolyte battery and a non-aqueous electrolyte electric double layer capacitor provided with such a non-aqueous electrolyte. Furthermore, another object of the present invention is to provide a novel method for evaluating the safety of a non-aqueous electrolyte.

  As a result of intensive studies to achieve the above object, the present inventors have found that a non-aqueous electrolyte having a maximum heat generation rate or total heat generation during combustion of a certain value or less has excellent safety, and batteries and capacitors Even if abnormal heat is generated, the risk of rupture and ignition can be greatly suppressed.In addition, the maximum heat generation rate or total heat generation of the non-aqueous electrolyte can be measured to improve the safety of the non-aqueous electrolyte. The inventors have found that it can be evaluated and have completed the present invention.

That is, the non-aqueous electrolyte of the present invention has (A) a maximum heat generation rate measured with a corn calorimeter of 550 kW / m ² or less and / or (B) a total calorific value measured with a corn calorimeter of 10 MJ / m 2. ² or less.

  Moreover, the safety evaluation method for a non-aqueous electrolyte of the present invention is characterized by measuring the maximum heat generation rate and / or the total heat generation amount of the non-aqueous electrolyte using a corn calorimeter.

［式中、Ｒ²は、それぞれ独立してハロゲン元素、アルコキシ基及びアリールオキシ基のいずれかであり、２つのＲ²のうち少なくとも１つは、アルコキシ基又はアリールオキシ基である］で表されるフルオロリン酸エステル化合物を含む非水溶媒と、支持塩とからなることが好ましい。ここで、前記式(II)において、２つのＲ²のうち１つがフッ素であり、他の１つがアルコキシ基又はアリールオキシ基であることが更に好ましい。また、前記式(I)において、Ｒ¹が、それぞれ独立してフッ素、アルコキシ基及びアリールオキシ基のいずれかであることも更に好ましい。更に、前記式(I)において、Ｒ¹のうち少なくとも３つがフッ素であることも更に好ましい。なお、前記式(I)で表される環状ホスファゼン化合物と前記式(II)で表されるフルオロリン酸エステル化合物との体積比は、30／70〜70／30の範囲であることが好ましい。また、前記非水溶媒は、更に非プロトン性有機溶媒を含むことができる。更に、前記非水溶媒における、前記式(I)で表される環状ホスファゼン化合物と前記式(II)で表されるフルオロリン酸エステル化合物との総含有量は、15体積％以上であることが好ましく、70体積％以上であることが更に好ましい。 The non-aqueous electrolyte of the present invention has the following formula (I):
(NPR ¹ ₂ ) _n ... (I)
[Wherein R ¹ independently represents a halogen element or a monovalent substituent; n represents 3 to 4] and a cyclic phosphazene compound represented by the following formula (II):

[Wherein, R ² is independently a halogen element, an alkoxy group or an aryloxy group, and at least one of the two R ² is an alkoxy group or an aryloxy group] The non-aqueous solvent containing a fluorophosphate ester compound and a supporting salt are preferable. Here, in the formula (II), it is more preferable that one of the two R ² is fluorine and the other is an alkoxy group or an aryloxy group. In the formula (I), it is further preferable that R ¹ is independently any one of fluorine, an alkoxy group and an aryloxy group. Furthermore, in the formula (I), it is further preferable that at least three of R ¹ are fluorine. The volume ratio between the cyclic phosphazene compound represented by the formula (I) and the fluorophosphate compound represented by the formula (II) is preferably in the range of 30/70 to 70/30. The non-aqueous solvent may further contain an aprotic organic solvent. Furthermore, the total content of the cyclic phosphazene compound represented by the formula (I) and the fluorophosphate compound represented by the formula (II) in the non-aqueous solvent is 15% by volume or more. Preferably, it is 70% by volume or more.

The nonaqueous electrolytic solution of the present invention preferably contains a phosphine oxide compound having a PF bond and / or a P—NH ₂ bond in the molecule and a supporting salt. Here, the content of the phosphine oxide compound in the non-aqueous electrolyte is preferably 3% by volume or more, and more preferably 5% by volume or more. The phosphine oxide compound has the following formula (III):
O = PR ³ ₃ ... (III)
[Wherein, R ³ is each independently a monovalent substituent or a halogen element, and at least one R ³ is fluorine or an amino group]. More preferably, R ³ in the formula (III) is independently selected from the group consisting of fluorine, amino group, alkyl group and alkoxy group, and at least one R ³ is fluorine or amino group. More preferably, at least one R ³ in the formula (III) is fluorine and at least one R ^{3 in} the formula (III) is an amino group. It is further preferred that R ³ in the formula (III) is independently a fluorine or an amino group. Note that the non-aqueous electrolyte may further contain an aprotic organic solvent.

［式中、Ｒ⁴は、それぞれ独立して炭素数１〜４の脂肪族炭化水素基又は芳香族炭化水素基又は炭素−炭素二重結合を有する炭素数２〜６の炭化水素基を示し；Ａ⁴は、アミノ基又はハロゲン元素を示す］で表されることが好ましく、前記ホスフィネートは、下記式(V)：

［式中、Ｒ⁵は、炭素数１〜４の脂肪族炭化水素基又は芳香族炭化水素基又は炭素−炭素二重結合を有する炭素数２〜６の炭化水素基を示し；Ａ⁵は、それぞれ独立してアミノ基又はハロゲン元素を示す］で表されることが好ましい。 The nonaqueous electrolytic solution of the present invention is also preferably obtained by dissolving a supporting salt in a solvent composed only of a phosphate ester derivative. Here, the phosphate ester derivative is preferably at least one selected from the group consisting of phosphonates and phosphinates. The phosphonate has the following formula (IV):

[Wherein, R ⁴ independently represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an aromatic hydrocarbon group or a hydrocarbon group having 2 to 6 carbon atoms having a carbon-carbon double bond; A ⁴ preferably represents an amino group or a halogen element], and the phosphinate is represented by the following formula (V):

Wherein, R ⁵ is an aliphatic having from 1 to 4 carbon atoms hydrocarbon group or an aromatic hydrocarbon group or C - represents a hydrocarbon group having 2 to 6 carbon atoms and having a carbon double bond; in A ^5, Each independently represents an amino group or a halogen element].

［式中、Ｒ⁶は、それぞれ独立して一価の置換基又はハロゲン元素を表し；Ｙ⁶は、それぞれ独立して２価の連結基、２価の元素又は単結合を表し；Ｘは、炭素、ケイ素、ゲルマニウム、スズ、窒素、リン、ヒ素、アンチモン、ビスマス、酸素、硫黄、セレン、テルル及びポロニウムからなる群から選ばれる元素の少なくとも１種を含む置換基を表す］で表される鎖状ホスファゼン化合物又は下記式(VII)：
(ＮＰＲ⁷ ₂)_m ・・・ (VII)
［式中、Ｒ⁷はそれぞれ独立して一価の置換基又はハロゲン元素を表し；ｍは３〜１５を表す］で表される環状ホスファゼン化合物であることが好ましい。 The nonaqueous electrolytic solution of the present invention is preferably obtained by dissolving a supporting salt in a solvent composed of only 40 to 100% by volume of a phosphate ester derivative and 60 to 0% by volume of a phosphazene compound. Here, it is more preferable that the solvent of the non-aqueous electrolyte is composed only of a phosphate ester derivative. The phosphate ester derivative is preferably at least one selected from the group consisting of phosphonates and phosphinates. Further, the phosphonate is preferably represented by the formula (IV), and the phosphinate is preferably represented by the formula (V). Furthermore, the phosphazene compound has the following formula (VI):

[Wherein, R ⁶ each independently represents a monovalent substituent or a halogen element; Y ⁶ each independently represents a divalent linking group, a divalent element or a single bond; Chain representing a substituent containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium and polonium] Phosphazene compound or the following formula (VII):
(NPR ⁷ ₂ ) _m ... (VII)
[Wherein, R ⁷ independently represents a monovalent substituent or a halogen element; m represents 3 to 15], and is preferably a cyclic phosphazene compound represented by:

  Furthermore, the non-aqueous electrolyte battery of the present invention is characterized by comprising the above-described non-aqueous electrolyte, a positive electrode, and a negative electrode, and the non-aqueous electrolyte electric double layer capacitor of the present invention includes the above-mentioned non-aqueous electrolysis A liquid, a positive electrode, and a negative electrode are provided.

  ADVANTAGE OF THE INVENTION According to this invention, the non-aqueous electrolyte which has the safety | security which was excellent in the maximum heat release rate or total calorific value at the time of combustion below a fixed value can be provided. Moreover, a highly safe nonaqueous electrolyte battery and a nonaqueous electrolyte electric double layer capacitor provided with such a nonaqueous electrolyte can be provided. Furthermore, the novel evaluation method of the safety | security of a non-aqueous electrolyte can be provided.

<Nonaqueous electrolyte and its safety evaluation method>
Hereinafter, the nonaqueous electrolytic solution of the present invention will be described in detail. The non-aqueous electrolyte of the present invention has (A) a maximum heat generation rate measured with a corn calorimeter of 550 kW / m ² or less and / or (B) a total calorific value measured with a corn calorimeter of 10 MJ / m ² or less. It is necessary to be. Moreover, the safety evaluation method for a non-aqueous electrolyte of the present invention is characterized by measuring the maximum heat generation rate and / or the total heat generation amount of the non-aqueous electrolyte using a corn calorimeter. As a result of studies by the present inventors, the maximum heat generation rate and the total heat generation amount of the non-aqueous electrolyte are related to the safety of the non-aqueous electrolyte, that is, the non-aqueous electrolyte has a low maximum heat generation rate and / or a total heat generation amount. It has been found that the electrolyte is difficult to ignite and ignite, while the non-aqueous electrolyte having a high maximum heat generation rate and / or high total calorific value tends to ignite and ignite easily. The non-aqueous electrolyte with a maximum heat generation rate of 550 kW / m ² or less and the non-aqueous electrolyte with a total calorific value of 10 MJ / m ² or less are self-extinguishing and have a critical oxygen index of about 21% by volume or more. And found that the safety is high. Therefore, the safety of the non-aqueous electrolyte can be evaluated by measuring the maximum heat generation rate and / or the total calorific value of the non-aqueous electrolyte using a corn calorimeter.

Nonaqueous electrolytes with a maximum heat generation rate of 470 kW / m ² or less and nonaqueous electrolytes with a total calorific value of 8.8 MJ / m ² or less have flame retardancy and a critical oxygen index of about 23% by volume or more. Therefore, safety is higher. Furthermore, non-aqueous electrolytes with a maximum heat generation rate of 395 kW / m ² or less and non-aqueous electrolytes with a total calorific value of 7.4 MJ / m ² or less are non-flammable and have a critical oxygen index of about 25% by volume or more. Therefore, safety is much higher. Self-extinguishing / flame retardant / non-flammability is defined by a method that complies with UL94HB method. Soak a non-flammable quartz fiber with 1.0 mL of electrolyte and add a 127 mm x 12.7 mm test piece. When the specimen is ignited in an atmospheric environment, the fire is extinguished between 25 and 100 mm line, and when the fallen object from the net is not ignited, self-extinguishing is considered. If the ignited flame does not reach the 25mm line of the device, and the object falling from the net is not ignited, it is considered to be flame retardant, and the case where no ignition is observed (combustion length 0mm) is nonflammable. It has a nature.

Here, in the present invention, the maximum heat generation rate and the total heat generation amount of the non-aqueous electrolyte are calculated from the heat generation behavior of a flame ignited in an atmospheric environment by a method in which the ISO 5660 standard cone calorimeter (cone calorimeter) method is arranged. Specifically, based on the ISO standard, a non-aqueous electrolyte 7.0 mL was impregnated on a nonflammable quartz fiber to produce a 100 mm × 100 mm test piece, and a cone calorimeter with a set heat flux of 50 kW / m ² ( It is measured by subjecting the test piece to a cone calorimeter).

The maximum heat generation rate (maximum HRR) is the maximum value of the heat generation rate (HRR) from the start to the end of the test, and the heat generation rate (HRR) can be obtained from the following equation.
HRR = q (t) / A _S
q (t) = CV × 1.1048 C × (ΔP / T) ^1/2 × (X ₀ −X ₀₂ ) / (1 + 0.5X ₀ −1.5X ₀₂ )
[Where CV = conversion factor ≒ 13.1 x 10 ³ (kJ / kg)
C = Calibration factor T = Differential pressure temperature (K): Exhaust duct temperature ΔP = Differential pressure (Pa): Pressure difference on exhaust duct flow measurement device X ₀ = O ₂ baseline X ₀₂ = O ₂ Reading A _S = sample area (m ² )]

The total calorific value (THR) is the total calorific value from the time when HRR> 0 until the end, and can be obtained from the following equation.
THR = HRR (kW / m ² ) × 0.001 (MW / kW) × Δt
[Where Δt = sampling time (s)]

  The nonaqueous electrolytic solution of the present invention includes a nonaqueous solvent comprising a cyclic phosphazene compound represented by the above formula (I) and a fluorophosphate ester compound represented by the above formula (II), and a supporting salt. A water electrolyte is preferable, and the non-aqueous electrolyte may further contain an aprotic organic solvent as a non-aqueous solvent. By using the cyclic phosphazene compound of the formula (I) and the fluorophosphate ester compound of the formula (II) in combination, the maximum heat generation rate and the total heat generation amount of the non-aqueous electrolyte can be reduced. Although the reason is not necessarily clear, for example, when the non-aqueous electrolyte is used in a battery, due to the synergistic effect of the phosphazene compound of the formula (I) and the fluorophosphate ester compound of the formula (II), A stable film is formed, and as a result, the charge / discharge characteristics of the battery are also stabilized.

R ^{1 in the} above formula (I) is not particularly limited as long as it is a halogen element or a monovalent substituent, and each R ¹ may be the same or different. Here, as the halogen element in R ¹ , fluorine, chlorine, bromine and the like are preferable, and among these, fluorine is most preferable in terms of low viscosity, and then chlorine is preferable. Examples of the monovalent substituent in R ¹ include an alkoxy group, an aryloxy group, an alkyl group, an aryl group, an acyl group, a substituted or unsubstituted amino group, an alkylthio group, and an arylthio group. Among these, An alkoxy group and an aryloxy group are preferable in terms of excellent nonflammability. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an allyloxy group containing a double bond, an alkoxy-substituted alkoxy group such as a methoxyethoxy group, a methoxyethoxyethoxy group, and the like. Examples of the aryloxy group include a phenoxy group, a methylphenoxy group, and a methoxyphenoxy group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Includes a phenyl group, a tolyl group, a naphthyl group, etc. The substituted or unsubstituted amino group includes an amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an aziridyl group, a pyrrolidyl group, and the like. Examples of the alkylthio group include methylthio group, ethylthio group Include groups such as the above-described arylthio group, a phenylthio group, and the like. The hydrogen element in these monovalent substituents may be substituted with a halogen element, and is preferably substituted with fluorine. R ¹ in formula (I) is preferably a halogen element from the viewpoint of improving safety, and more preferably fluorine from the viewpoint of low viscosity. Moreover, it is preferable that 3 or more of R < ¹ > is fluorine from the point of coexistence of safety | security and low viscosity. Further, n in the formula (I) is 3 to 4, but n is preferably 3 in terms of cost and easy preparation. In addition, the cyclic phosphazene compound of the formula (I) may be used singly or in combination of two or more.

R ² in the above formula (II) is any one of a halogen element, an alkoxy group, and an aryloxy group, and at least one of the two R ² is an alkoxy group or an aryloxy group. Here, as the halogen element in R ² , fluorine, chlorine, bromine and the like are preferable, and among these, fluorine is most preferable in terms of low viscosity. Examples of the alkoxy group in R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, an allyloxy group containing a double bond, an alkoxy-substituted alkoxy group such as a methoxyethoxy group and a methoxyethoxyethoxy group, and the like. . The hydrogen element in these alkoxy groups may be substituted with a halogen element, and is preferably substituted with fluorine. Among these, a methoxy group, an ethoxy group, a trifluoroethoxy group, and a propoxy group are more preferable in terms of excellent safety and low viscosity. Examples of the aryloxy group for R ² include a phenoxy group, a methylphenoxy group, and a methoxyphenoxy group. The hydrogen element in these aryloxy groups may be substituted with a halogen element, and is preferably substituted with fluorine. Among these, a phenoxy group and a fluorophenoxy group are more preferable in terms of excellent safety and low viscosity. Two R ^{2 s in} the above formula (II) may be the same or different and may be bonded to each other to form a ring. Further, in terms of both safety and low viscosity, a difluorophosphate ester in which one of the two R ² is fluorine and the other is an alkoxy group or an aryloxy group is most preferable. In addition, the fluorophosphate ester of the formula (II) may be used alone or in combination of two or more.

  Specific examples of the fluorophosphate ester of the above formula (II) include dimethyl fluorophosphate, diethyl fluorophosphate, bistrifluoroethyl fluorophosphate, ethylene fluorophosphate, dipropyl fluorophosphate, diallyl fluorophosphate, fluorophosphate Dibutyl acid, diphenyl fluorophosphate, difluorophenyl fluorophosphate, methyl chlorofluorophosphate, ethyl chlorofluorophosphate, trifluoroethyl chlorofluorophosphate, propyl chlorofluorophosphate, allyl chlorofluorophosphate, chlorofluorophosphoric acid Butyl, cyclohexyl chlorofluorophosphate, methoxyethyl chlorofluorophosphate, methoxyethoxyethyl chlorofluorophosphate, phenyl chlorofluorophosphate, fluorophenyl chlorofluorophosphate, difluro Methyl orophosphate, ethyl difluorophosphate, trifluoroethyl difluorophosphate, propyl difluorophosphate, allyl difluorophosphate, butyl difluorophosphate, cyclohexyl difluorophosphate, methoxyethyl difluorophosphate, methoxyethoxyethyl difluorophosphate, difluoro Examples thereof include phenyl phosphate and fluorophenyl difluorophosphate. Among these, methyl difluorophosphate, ethyl difluorophosphate, trifluoroethyl difluorophosphate, propyl difluorophosphate, and phenyl difluorophosphate are preferable.

  The volume ratio of the cyclic phosphazene compound of the above formula (I) and the fluorophosphate ester compound of the formula (II) is preferably in the range of 5/95 to 95/5, and the battery when a non-aqueous electrolyte is used for the battery From the viewpoint of balance between performance and safety, the range of 30/70 to 70/30 is more preferable.

  In addition, an aprotic organic solvent is added to the nonaqueous electrolytic solution containing the cyclic phosphazene compound of the above formula (I) and the fluorophosphate ester compound of the formula (II) as long as the object of the present invention is not impaired. Can do. The amount of the aprotic organic solvent added is 85% by volume or less in the non-aqueous electrolyte, so that the non-aqueous electrolyte can be made non-flammable, but higher non-flammability is imparted to the non-aqueous electrolyte. In order to achieve this, it is preferable to make it 30% by volume or less. Here, when the non-aqueous electrolyte is used in a non-aqueous electrolyte battery, the aprotic organic solvent added to the non-aqueous electrolyte includes dimethyl carbonate (DMC), diethyl carbonate (DEC), diphenyl carbonate, ethyl Carbonates such as methyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), diethyl ether (DEE), Ethers such as phenyl methyl ether, carboxylic acid esters such as γ-butyrolactone (GBL), γ-valerolactone, methyl formate (MF), nitriles such as acetonitrile, amides such as dimethylformamide, dimethyl sulfoxide, etc. Sulfones It is below. When the non-aqueous electrolyte is used in a non-aqueous electrolyte electric double layer capacitor, the aprotic organic solvent added to the non-aqueous electrolyte includes acetonitrile (AN), propiononitrile, butyronitrile, isobutyro Nitrile compounds such as nitrile and benzonitrile; ether compounds such as 1,2-dimethoxyethane (DME) and tetrahydrofuran (THF); dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene carbonate ( Preferred examples include ester compounds such as EC), propylene carbonate (PC), diphenyl carbonate, γ-butyrolactone (GBL), and γ-valerolactone. Among these, propylene carbonate, γ-butyrolactone and acetonitrile are preferable.

As the non-aqueous electrolyte of the present invention, a non-aqueous electrolyte containing a phosphine oxide compound having a PF bond and / or a P-NH ₂ bond in the molecule and a supporting salt is also preferable. If necessary, the aprotic organic solvent described above may be included. By adding the phosphine oxide compound to the nonaqueous electrolytic solution, the maximum heat generation rate and the total calorific value of the nonaqueous electrolytic solution can be reduced.

The phosphine oxide compound is not particularly limited as long as it has a PF bond and / or a P-NH ₂ bond in the molecule. Among such phosphine oxide compounds, the phosphine oxide compound represented by the above formula (III) is preferable. In the formula (III), each R ³ is independently a monovalent substituent or a halogen element, and at least one R ³ is fluorine or an amino group. Here, preferred examples of the halogen element in R ³ include fluorine, chlorine, bromine and the like, and among these, fluorine is particularly preferred. On the other hand, examples of the monovalent substituent in R ³ include an amino group, an alkoxy group, an aryloxy group, an alkyl group, a carboxyl group, an acyl group, and an aryl group. Among these, the ignition and ignition of the electrolyte solution An amino group and an alkoxy group are preferable because they are excellent in the effect of reducing the risk. Examples of the alkoxy group include a methoxy group, an ethoxy group, a methoxyethoxy group, and a propoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the alkyl group include a methyl group and an ethyl group. , A propyl group, a butyl group, a pentyl group, etc., and the acyl group includes a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and the like, and the aryl group includes a phenyl group , Tolyl group, naphthyl group and the like. The hydrogen element in these monovalent substituents is preferably substituted with a halogen element, and preferred examples of the halogen element include fluorine, chlorine, bromine, etc., with fluorine being most preferred, and then chlorine being preferred. .

  In the phosphine oxide compound, 10% by mass or more in the molecule is preferably a halogen element, and more preferably 15% by mass or more in the molecule is a halogen element. Further, in the phosphine oxide compound, 7% by mass or more in the molecule is preferably fluorine, and more preferably 10% by mass or more in the molecule is fluorine. A phosphine oxide compound in which 10% by mass or more in the molecule is a halogen element is excellent in reducing the maximum heat generation rate and total calorific value of the non-aqueous electrolyte, and a phosphine oxide compound in which 7% by mass or more in the molecule is fluorine. Is particularly excellent in the effect of reducing the maximum heat generation rate and the total heat generation amount of the non-aqueous electrolyte.

Examples of the phosphine oxide compound, at least one fluorine in R ³ in formula (III), and at least one is an amino group phosphine oxide compound of R ³ in formula (III), and, in formula (III) A phosphine oxide compound in which two or more of R ³ are fluorine or an amino group is particularly preferable. These phosphine oxide compounds have a high proportion of fluorine and amino groups in the molecule that contributes to the reduction in the maximum heat generation rate and total heat generation of the electrolyte, and thus greatly reduce the maximum heat generation rate and total heat generation of the electrolyte. be able to.

Specific examples of the phosphine oxide compound of the above formula (III) include trifluorophosphine oxide [O = PF ₃ ], triaminophosphine oxide [O═P (NH ₂ ) ₃ ], aminodifluorophosphine oxide [O═PF. ₂ NH ₂ ], diaminofluorophosphine oxide [O═PF (NH ₂ ) ₂ ], methyldiaminophosphine oxide [O═P (NH ₂ ) ₂ CH ₃ ], methylaminofluorophosphine oxide [O═PF (NH ₂ ) CH ₃ ], dimethoxyfluorophosphine oxide [O═PF (OCH ₃ ) ₂ ], ethoxydifluorophosphine oxide [O═PF ₂ (OC ₂ H ₅ )], methoxydifluorophosphine oxide [O═PF ₂ (OCH ₃ )] , dimethylfluorosilyl phosphine oxide _{[O = PF (CH 3)} 2], Jietokishifu Oro phosphine oxide _{[O = PF (OC 2 H} 5) 2], methyl difluoro phosphine oxide _{[O = PF 2 (CH 3} )] , and the like.

  The content of the phosphine oxide compound in the nonaqueous electrolytic solution is preferably 3% by volume or more, and more preferably 5% by volume or more. If the content of the phosphine oxide compound in the non-aqueous electrolyte is 3% by volume or more, the maximum heat generation rate and total heat generation of the non-aqueous electrolyte will be sufficiently reduced, and the risk of ignition and ignition of the non-aqueous electrolyte Sex can be sufficiently suppressed. In addition, the said phosphine oxide compound may be used individually by 1 type, and may mix and use 2 or more types.

  As the nonaqueous electrolytic solution of the present invention, a nonaqueous electrolytic solution obtained by dissolving a supporting salt in a solvent composed only of a phosphate ester derivative is also preferable. The non-aqueous electrolyte is composed only of a phosphate ester derivative and does not contain an aprotic organic solvent such as an ester compound or an ether compound used in conventional non-aqueous electrolytes. The amount is low enough. In addition, even if a large current suddenly flows when a battery or capacitor is short-circuited, abnormal heat is not generated, and no combustible gas derived from an aprotic organic solvent is generated from the exhaust pressure valve. There is no danger of ignition. In addition, the chain ester decomposition of the polymer material used in the battery or capacitor is suppressed by the action of the phosphoric acid ester derivative constituting the non-aqueous electrolyte, so that the risk of ignition and ignition is low. Furthermore, since the non-aqueous electrolyte contains a phosphate ester derivative and the conductivity of the phosphate ester derivative is very high, the internal resistance of the battery or capacitor can be reduced.

  The phosphate ester derivative is a compound derived from a phosphate ester and does not include the phosphate ester itself. Here, in the non-aqueous electrolyte, among the phosphoric acid ester derivatives, phosphonates and phosphinates are preferable, and phosphonates represented by the above formula (IV) and phosphinates represented by the above formula (V) are more preferable. The solvent of the non-aqueous electrolyte solution consists only of a phosphate ester derivative, but when the phosphate ester derivative is a phosphonate, the reduction resistance on the negative electrode is poor, or the charge / discharge gradually increases as the number of charge / discharge cycles increases. Capacity decreases. Therefore, when the non-aqueous electrolyte is used for a battery, phosphinate is preferable as the chemical structure of the phosphate ester derivative from the viewpoint of electrochemical stability and long life for repeated charge and discharge of the battery.

In the above formula (IV), R ⁴ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an aromatic hydrocarbon group or a hydrocarbon group having 2 to 6 carbon atoms having a carbon-carbon double bond, R ⁴ may be the same or different, while A ⁴ is an amino group or a halogen element. In the formula (V), R ⁵ is an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an aromatic hydrocarbon group or a hydrocarbon group having 2 to 6 carbon atoms having a carbon-carbon double bond, On the other hand, A ⁵ is an amino group or a halogen element, and each A ⁵ may be the same or different. These phosphonates and phosphinates may be used alone or in combination of two or more.

In R ⁴ and R ⁵ of formula (V) of the formula (IV), the aliphatic hydrocarbon group having 1 to 4 carbon atoms, alkyl such as methyl group, ethyl group, n- propyl, and i- propyl Examples of aromatic hydrocarbon groups include aryl groups such as phenyl and tolyl groups, and aralkyl groups such as benzyl and phenethyl groups (arylalkyl groups), and carbons having a carbon-carbon double bond. Examples of the hydrocarbon group having 2 to 6 include alkenyl groups such as allyl groups and vinyl groups. Among these, R ^{4 in the} above formula (IV) and R ^{5 in the} formula (V) are preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms and a phenyl group. Further, in A ⁴ and A ⁵ of the formula (V) of the formula (IV), as the halogen element, fluorine, chlorine, bromine and the like. Here, as A ⁴ in the above formula (IV) and A ^{5 in the} formula (V), an amino group and fluorine are preferable.

  Specifically, the phosphonate of formula (IV) includes dimethyl fluorophosphate, diethyl fluorophosphate, bistrifluoroethyl fluorophosphate, dipropyl fluorophosphate, dibutyl fluorophosphate, diphenyl fluorophosphate, difluoro fluorophosphate. On the other hand, the phosphinates of the above formula (V) include methyl chlorofluorophosphate, ethyl chlorofluorophosphate, trifluoroethyl chlorofluorophosphate, propyl chlorofluorophosphate, butyl chlorofluorophosphate, Methoxyethyl chlorofluorophosphate, methoxyethoxyethyl chlorofluorophosphate, phenyl chlorofluorophosphate, fluorophenyl chlorofluorophosphate, methyl difluorophosphate, ethyl difluorophosphate, trifluoride difluorophosphate Roethyl, propyl difluorophosphate, butyl difluorophosphate, methoxyethyl difluorophosphate, methoxyethoxyethyl difluorophosphate, phenyl difluorophosphate, fluorophenyl difluorophosphate, and the like.

  As the nonaqueous electrolytic solution of the present invention, a nonaqueous electrolytic solution obtained by dissolving a supporting salt in a solvent composed only of 40 to 100% by volume of a phosphoric ester derivative and 60 to 0% by volume of a phosphazene compound is also preferable. The non-aqueous electrolyte is a phosphate ester derivative alone or a mixed solvent of a phosphate ester derivative and a phosphazene compound, and an aprotic organic solvent such as an ester compound or an ether compound used in a conventional non-aqueous electrolyte. The maximum heat generation rate and the total heat generation amount are sufficiently low. In addition, even if a large current suddenly flows when a battery or capacitor is short-circuited and abnormally generates heat, flammable gas derived from an aprotic organic solvent is not generated, and there is a risk of sparks generated when a short-circuit occurs. There is no sex. Further, the chain ester decomposition of the polymer material used in the battery or the capacitor is suppressed by the action of the phosphoric acid ester derivative constituting the nonaqueous electrolytic solution, so that the risk of ignition and ignition is low. Furthermore, when the non-aqueous electrolyte contains a phosphazene compound, the phosphazene compound decomposes when the battery or capacitor abnormally generates heat to generate nitrogen gas, phosphate ester, etc. Can suppress the combustion of the polymer material constituting the battery or capacitor, and the generated phosphate ester acts in the same manner as the above-mentioned phosphate ester derivative to suppress the chain decomposition of the polymer material constituting the battery or capacitor. Therefore, the risk of ignition and ignition can be further effectively reduced. Furthermore, the non-aqueous electrolyte contains a phosphate ester derivative, and the conductivity of the phosphate ester derivative is higher than the conductivity of the phosphazene compound. Therefore, the non-aqueous electrolyte is more conductive than the electrolyte using a phosphazene compound alone. Is expensive. Therefore, the non-aqueous electrolyte has a large discharge capacity. In addition, the effect of reducing the maximum heat generation rate and total calorific value of the non-aqueous electrolyte and reducing the risk of ignition and ignition is generally higher for phosphazene compounds than phosphate ester derivatives, while the conductivity is In general, phosphate ester derivatives are higher than phosphazene compounds, so using a mixed solvent of phosphate ester derivatives and phosphazene compounds brings out the advantages of both and highly balances the conductivity and safety of the electrolyte. I believe you can.

  The solvent of the non-aqueous electrolyte solution is composed of only 40 to 100% by volume of the phosphoric acid ester derivative and 60 to 0% by volume of the phosphazene compound. Here, when the content of the phosphate ester derivative is less than 40% by volume, the effect of improving the conductivity of the non-aqueous electrolyte is small. Further, from the viewpoint of the conductivity of the non-aqueous electrolyte, the solvent of the non-aqueous electrolyte is preferably as the phosphate ester derivative content is high, and is particularly preferably composed of only the phosphate ester derivative.

  The phosphoric acid ester derivative used for the non-aqueous electrolyte is as described above. On the other hand, preferred examples of the phosphazene compound that can be used in the non-aqueous electrolyte include a chain phosphazene compound represented by the above formula (VI) and a cyclic phosphazene compound represented by the above formula (VII). Among the phosphazene compounds represented by the above formula (VI) or formula (VII), those which are liquid at 25 ° C. (room temperature) are preferable. The viscosity at 25 ° C. of the liquid phosphazene compound is preferably 300 mPa · s (300 cP) or less, more preferably 20 mPa · s (20 cP) or less, and particularly preferably 5 mPa · s (5 cP) or less. When the viscosity of the phosphazene compound at 25 ° C exceeds 300 mPa · s, the supporting salt becomes difficult to dissolve, the wettability to the positive electrode material, negative electrode material, separator, etc. decreases, and the ionic conductivity increases due to the increase in the viscous resistance of the electrolyte. In particular, the performance becomes insufficient when used under low temperature conditions such as below the freezing point. These phosphazene compounds may be used alone or in combination of two or more.

R ^{6 in the} above formula (VI) is not particularly limited as long as it is a monovalent substituent or a halogen element, and each R ⁶ may be the same or different. Here, examples of the monovalent substituent in R ⁶ include an alkoxy group, an alkyl group, a carboxyl group, an acyl group, an aryl group, etc. Among these, an alkoxy group is preferable in that the phosphazene compound has low viscosity. preferable. On the other hand, preferred examples of the halogen element for R ⁶ include fluorine, chlorine, bromine and the like. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and alkoxy-substituted alkoxy groups such as methoxyethoxy group and methoxyethoxyethoxy group. Among these, methoxy group, ethoxy group, methoxy group, etc. An ethoxy group and a methoxyethoxyethoxy group are preferable, and a methoxy group and an ethoxy group are more preferable from the viewpoint of low viscosity and high dielectric constant. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a valeryl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. The hydrogen element in these monovalent substituents is preferably substituted with a halogen element. As the halogen element, fluorine, chlorine and bromine are preferred, fluorine is most preferred, and chlorine is then preferred.

Y ^{6 in the} formula (VI) is not particularly limited as long as it is a divalent linking group, a divalent element, or a single bond, and each Y ⁶ may be the same or different. Here, as the divalent linking group in Y ^6, in addition to CH ₂ group, oxygen, sulfur, selenium, nitrogen, boron, aluminum, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, Contains at least one element selected from the group consisting of tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt, nickel A divalent linking group is exemplified, and a divalent linking group containing an element of sulfur and / or selenium is preferable from the viewpoint of effectively reducing the risk of ignition and ignition of the electrolyte. The divalent element in Y ^6, oxygen, sulfur, selenium and the like. Among these, Y ^{6 in} the formula (VI) is preferably a single bond.

［式(VIII)、式(IX)及び式(X)中、Ｒ⁸、Ｒ⁹及びＲ¹⁰は、それぞれ独立に一価の置換基又はハロゲン元素を表し；Ｙ⁸、Ｙ⁹及びＹ¹⁰は、それぞれ独立に２価の連結基、２価の元素又は単結合を表し；Ｚは２価の基又は２価の元素を表す］で表される置換基が更に好ましい。また、これら置換基の中でも、特に効果的に発火・引火の危険性を低減し得る点で、式(VIII)で表されるようなリンを含む置換基が特に好ましく、また、電解液の小界面抵抗化の点で、式(IX)で表されるような硫黄を含む置換基が特に好ましい。 X in the formula (VI) is a substitution containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium and polonium. There is no particular limitation as long as it is a group. From the viewpoint of consideration for toxicity, environment, etc., X in formula (VI) is preferably a substituent containing at least one element selected from the group consisting of carbon, silicon, nitrogen, phosphorus, oxygen and sulfur. The following formula (VIII), formula (IX) or formula (X):

[In formula (VIII), formula (IX) and formula (X), R ⁸ , R ⁹ and R ¹⁰ each independently represents a monovalent substituent or a halogen element; Y ⁸ , Y ⁹ and Y ¹⁰ are And each independently represents a divalent linking group, a divalent element or a single bond; and Z represents a divalent group or a divalent element]. Further, among these substituents, a substituent containing phosphorus as represented by the formula (VIII) is particularly preferable in that the risk of ignition / flammability can be particularly effectively reduced. In terms of interfacial resistance, a substituent containing sulfur as represented by the formula (IX) is particularly preferable.

R ⁸ in formula (VIII), R ⁹ in formula (IX), and R ^{10 in} formula (X) may be any of the same monovalent substituents or halogen elements as described for R ⁶ in formula (VI). Are also preferred. Note that two R ^{8 s} in the formula (VIII) and two R ^{10 s in} the formula (X) may be the same or different, and may be bonded to each other to form a ring. Y ⁸ in formula (VIII), Y ⁹ in formula (IX) and Y ^{10 in} formula (X) are the same divalent linking groups or divalent groups as those described for Y ⁶ in formula (VI). Any of these elements is preferably mentioned. Similarly, a divalent linking group containing sulfur and / or selenium is particularly preferable because the risk of ignition and ignition of the electrolyte can be greatly reduced. Y ⁸ , Y ⁹ and Y ¹⁰ are also preferably single bonds. Two Y ⁸ in the formula (VIII) and two Y ^{10 in} the formula (X) may be the same or different.

Z in the formula (VIII) is not particularly limited as long as it is a divalent group or a divalent element. Here, as the divalent group, CH ₂ group, CHR group (where R represents an alkyl group, alkoxy group, phenyl group, etc.), NR group, oxygen, sulfur, selenium, boron, aluminum , Scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten , A divalent group containing at least one element selected from the group consisting of iron, cobalt, and nickel; and examples of the divalent element include oxygen, sulfur, and selenium. Among these, Z in the formula (VIII) is preferably a divalent group containing at least one element selected from the group consisting of oxygen, sulfur and selenium in addition to a CH ₂ group, a CHR group and an NR group. In particular, a divalent group containing an element of sulfur and / or selenium is preferable because the risk of ignition and ignition of the electrolyte can be greatly reduced.

R ^{7 in the} above formula (VII) is not particularly limited as long as it is a monovalent substituent or a halogen element. Here, examples of the monovalent substituent in R ⁷ include an alkoxy group, an aryloxy group, an alkyl group, a carboxyl group, an acyl group, and an aryl group. Among these, a phosphazene compound has a low viscosity. An alkoxy group is preferred. On the other hand, preferred examples of the halogen element for R ⁷ include fluorine, chlorine, bromine, etc. Among these, fluorine is particularly preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a methoxyethoxy group, and a propoxy group. Examples of the aryloxy group include a phenoxy group. Among these, a methoxy group, an ethoxy group, and a methoxyethoxy group. A phenoxy group is particularly preferred. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group; examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, and a valeryl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. R ⁷ may be a substituent such as an allyloxy group having a carbon-carbon double bond in the substituent. The hydrogen element in these monovalent substituents is preferably substituted with a halogen element. Preferred examples of the halogen element include fluorine, chlorine, bromine and the like. Examples of the substituent substituted with a fluorine atom include And a trifluoroethoxy group. Moreover, m of Formula (VII) is 3-15, and the range of 3-4 is preferable.

When the non-aqueous electrolyte of the present invention is used in a non-aqueous electrolyte battery, the support salt used for the non-aqueous electrolyte is preferably a support salt that serves as a lithium ion source. The supporting salt is not particularly limited, and for example, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiAsF ₆ , LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N and Li ( Preferable examples include lithium salts such as C ₂ F ₅ SO ₂ ) ₂ N. Among these, LiPF ₆ is more preferable in terms of excellent nonflammability. These supporting salts may be used alone or in combination of two or more. Moreover, as a density | concentration of the support salt in the non-aqueous electrolyte for batteries, 0.2-1.5 mol / L (M) is preferable and 0.5-1 mol / L (M) is still more preferable. If the concentration of the supporting salt is less than 0.2 mol / L, the conductivity of the electrolyte cannot be sufficiently ensured, and the discharge characteristics and charging characteristics of the battery may be hindered. Since the viscosity of the electrolytic solution increases and the mobility of lithium ions cannot be ensured sufficiently, the conductivity of the electrolytic solution cannot be sufficiently ensured in the same manner as described above, which may hinder battery discharge characteristics and charge characteristics. .

On the other hand, when the non-aqueous electrolyte of the present invention is used in a non-aqueous electrolyte electric double layer capacitor, the supporting salt used in the non-aqueous electrolyte is preferably a quaternary ammonium salt. The quaternary ammonium salt is a solute that plays a role as an ion source for forming an electric double layer in a nonaqueous electrolytic solution, and can effectively improve electrical characteristics such as electrical conductivity of the electrolytic solution. In view of the possibility, a quaternary ammonium salt capable of forming a multivalent ion is preferable. Examples of the quaternary ammonium salt include (CH ₃ ) ₄ N · BF ₄ , (CH ₃ ) ₃ C ₂ H ₅ N · BF ₄ , (CH ₃ ) ₂ (C ₂ H ₅ ) ₂ N · BF _4. CH ₃ (C ₂ H ₅ ) ₃ N · BF ₄ , (C ₂ H ₅ ) ₄ N · BF ₄ , (C ₃ H ₇ ) ₄ N · BF ₄ , CH ₃ (C ₄ H ₉ ) ₃ N · BF ₄ , (C ₄ H ₉ ) ₄ N · BF ₄ , (C ₆ H ₁₃ ) ₄ N · BF ₄ , (C ₂ H ₅ ) ₄ N · ClO ₄ , (C ₂ H ₅ ) ₄ N · AsF ₆ , (C ₂ H ₅ ) ₄ N · SbF ₆ , (C ₂ H ₅ ) ₄ N · CF ₃ SO ₃ , (C ₂ H ₅ ) ₄ N · C ₄ F ₉ SO ₃ , (C ₂ H ₅ ) ₄ N · (CF ₃ SO ₂ ) ₂ N, (C ₂ H ₅ ) ₄ N · BCH ₃ (C ₂ H ₅ ) ₃ , (C ₂ H ₅ ) ₄ N · B (C ₂ H ₅ ) ₄ , (C ₂ H ₅ ) ₄ N · B (C ₄ H ₉ ) ₄ , (C ₂ H ₅ ) ₄ N · B (C ₆ H ₅ ) _{4 and the} like are preferable. Also preferred are hexafluorophosphates in which the anion portion (for example, • BF ₄ , • ClO ₄ , • AsF _6, etc.) of these quaternary ammonium salts is replaced with • PF ₆ . Among these, quaternary ammonium salts in which different alkyl groups are bonded to N atoms are preferable in that the solubility can be improved by increasing the polarizability. Furthermore, as the quaternary ammonium salt, for example, compounds represented by the following formulas (a) to (j) are also preferable. Here, in the formulas (a) to (j), Me represents a methyl group, and Et represents an ethyl group.

Among these quaternary ammonium salts, salts that can generate (CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ^+, etc. as cations, in particular, from the viewpoint of ensuring high electrical conductivity. preferable. Further, a salt capable of generating an anion having a small formula weight is preferable. These quaternary ammonium salts may be used individually by 1 type, and may use 2 or more types together. Moreover, as a density | concentration of the support salt in the non-aqueous electrolyte for electric double layer capacitors, 0.2-2.5 mol / L (M) is preferable and 0.8-1.5 mol / L (M) is still more preferable. If the concentration of the supporting salt is less than 0.2 mol / L, sufficient electrical properties such as the electrical conductivity of the electrolyte may not be ensured. If the concentration exceeds 2.5 mol / L, the viscosity of the electrolyte will increase, resulting in electrical conductivity. The electrical characteristics such as the above may deteriorate.

<Nonaqueous electrolyte battery>
Next, the nonaqueous electrolyte battery of the present invention will be described in detail. The non-aqueous electrolyte battery of the present invention includes the above-described non-aqueous electrolyte, a positive electrode, and a negative electrode, and, if necessary, other non-aqueous electrolyte batteries that are usually used in the technical field of non-aqueous electrolyte batteries such as separators. A member is provided.

The positive electrode active material of the non-aqueous electrolyte battery of the present invention is partially different between the primary battery and the secondary battery. For example, as the positive electrode active material of the non-aqueous electrolyte primary battery, fluorinated graphite [(CF _x ) _n ], MnO ₂ (which may be electrochemical synthesis or chemical synthesis), V ₂ O ₅ , MoO ₃ , Ag ₂ CrO ₄ , CuO, CuS, FeS ₂ , SO ₂ , SOCl ₂ , TiS _2, etc. Among these, MnO ₂ and fluorinated graphite are preferable from the viewpoints of high capacity and high safety, and high discharge potential and excellent wettability of the electrolytic solution. On the other hand, as the positive electrode active material of the non-aqueous electrolyte secondary battery, 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 _{2 are used.} Preferable examples include lithium-containing composite oxides such as LiFePO ₄ , metal sulfides such as TiS ₂ and MoS ₂ , and conductive polymers such as polyaniline. 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, and Ni. In this case, the composite oxide includes: LiFe _x Co _y Ni (wherein, 0 ≦ x <1,0 ≦ y <1,0 <x + y ≦ 1) (1-xy) O 2, LiMn x Fe y O 2-xy or LiNi _x Co _y Mn, It is represented by _1-xy O ₂ or the like. Among these, LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ are high in capacity, high in safety, and excellent in wettability of the electrolyte. Particularly preferred. These positive electrode active materials may be used individually by 1 type, and may use 2 or more types together.

  Further, the negative electrode active material of the nonaqueous electrolyte battery of the present invention is partially different between the primary battery and the secondary battery. For example, as the negative electrode active material of the nonaqueous electrolyte primary battery, lithium metal itself, lithium An alloy etc. are mentioned. Examples of the metal that forms an alloy with lithium include Sn, Si, Pb, Al, Au, Pt, In, Zn, Cd, Ag, and Mg. Among these, Al, Zn, and Mg are preferable from the viewpoints of rich reserves and toxicity. On the other hand, as the negative electrode active material of the non-aqueous electrolyte secondary battery, lithium metal itself, an alloy of lithium and Al, In, Sn, Si, Pb, Zn, or the like, or a carbon material such as graphite doped with lithium is preferable. Among these, carbon materials such as graphite are preferable, and graphite is particularly preferable in that it is higher in safety and excellent in wettability of the electrolytic solution. Here, examples of graphite include natural graphite, artificial graphite, mesophase carbon microbeads (MCMB), and the like, and widely include graphitizable carbon and non-graphitizable carbon. These negative electrode active materials may be used individually by 1 type, and may use 2 or more types together.

  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. Moreover, there is no restriction | limiting in particular as a shape of the said positive electrode and a negative electrode, It can select suitably from well-known shapes as an electrode. For example, a sheet shape, a columnar shape, a plate shape, a spiral shape, and the like can be given.

  Other members that can be used in the non-aqueous electrolyte battery of the present invention include a separator that is interposed between positive and negative electrodes in a role of preventing current short-circuiting due to contact between both electrodes in the non-aqueous electrolyte battery. 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 non-woven fabrics and thin layer films. 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 batteries can be suitably used.

  The form of the non-aqueous electrolyte battery of the present invention described above is not particularly limited, and various known forms such as a coin-type, button-type, paper-type, square-type or spiral-type cylindrical battery are suitable. Can be mentioned. In the case of the button type, a non-aqueous electrolyte battery can be produced 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 battery can be manufactured by preparing a sheet-like positive electrode, sandwiching a current collector, and stacking and winding up a sheet-like negative electrode on the current collector. it can.

<Non-aqueous electrolyte electric double layer capacitor>
Next, the non-aqueous electrolyte electric double layer capacitor of the present invention will be described in detail. The non-aqueous electrolyte electric double layer capacitor of the present invention includes the above-described non-aqueous electrolyte, a positive electrode, and a negative electrode, and is usually used in the technical field of electric double layer capacitors such as a separator as necessary. Other members are provided.

  Although there is no restriction | limiting in particular as a positive electrode and a negative electrode of the nonaqueous electrolyte electric double layer capacitor of this invention, Usually, a porous carbon type polarizable electrode is preferable. The electrode is preferably one having characteristics such as a large specific surface area and bulk specific gravity, electrochemical inactivity, and low resistance. Here, activated carbon etc. are mentioned as said porous carbon.

  The electrode generally contains porous carbon such as activated carbon, and contains other components such as a conductive agent and a binder as necessary. There is no restriction | limiting in particular as a raw material of the activated carbon which can be used suitably for the said electrode, For example, various heat resistant resins, pitch, etc. other than a phenol resin are mentioned suitably. Preferable examples of the heat resistant resin include polyimide, polyamide, polyamideimide, polyetherimide, polyethersulfone, polyetherketone, bismaleimide triazine, aramid, fluororesin, polyphenylene, polyphenylene sulfide and the like. These may be used alone or in combination of two or more. The activated carbon is preferably in the form of powder, fiber cloth or the like from the viewpoint of increasing the specific surface area and increasing the charge capacity of the non-aqueous electrolyte electric double layer capacitor. Further, these activated carbons may be subjected to treatment such as heat treatment, stretch molding, vacuum high temperature treatment, and rolling for the purpose of increasing the charge capacity of the electric double layer capacitor.

  The conductive agent used for the electrode is not particularly limited, and examples thereof include graphite and acetylene black. The binder used for the electrode is not particularly limited, and examples thereof include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (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.

  The non-aqueous electrolyte electric double layer capacitor of the present invention preferably includes a separator, a current collector, a container and the like in addition to the above-described electrodes (positive electrode and negative electrode) and non-aqueous electrolyte, and moreover, a normal electric double layer capacitor. Each known member used can be provided. Here, the separator is interposed between the positive and negative electrodes for the purpose of preventing a short circuit of the non-aqueous electrolyte electric double layer capacitor. There is no restriction | limiting in particular as this separator, Usually, the well-known separator used as a separator of a nonaqueous electrolyte electric double layer capacitor is used suitably. As a material for the separator, for example, a microporous film, a nonwoven fabric, paper, and the like are preferably exemplified. Specifically, a nonwoven fabric made of a synthetic resin such as polytetrafluoroethylene, polypropylene, and polyethylene, a thin layer film, and the like are preferable. Among these, a microporous film made of polypropylene or polyethylene having a thickness of about 20 to 50 μm is particularly suitable. There is no restriction | limiting in particular as said collector, The well-known thing normally used as a collector of a nonaqueous electrolyte electric double layer capacitor is used suitably. The current collector is preferably one having excellent electrochemical corrosion resistance, chemical corrosion resistance, workability, mechanical strength, and low cost, such as a current collector layer of aluminum, stainless steel, conductive resin, etc. Is preferred. Moreover, there is no restriction | limiting in particular as said container, The well-known thing normally used as a container of a nonaqueous electrolyte electric double layer capacitor is mentioned suitably. As the material of the container, for example, aluminum, stainless steel, conductive resin and the like are suitable.

  There is no restriction | limiting in particular as a form of the non-aqueous-electrolyte electric double layer capacitor of this invention, Well-known forms, such as a cylinder type (cylindrical type and a square type), a flat type (coin type), are mentioned suitably. These non-aqueous electrolyte electric double layer capacitors are, for example, main power supplies or auxiliary power supplies for electric vehicles and fuel cell vehicles, memory backup devices for various electronic devices, industrial devices, aircraft devices, toys, cordless devices, etc. It is suitably used as a power source for electromagnetic holding such as industrial equipment, gas equipment and instantaneous water heater equipment, and for watches such as watches, wall clocks, solar watches, AGS watches and the like.

  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.

Example 1
In the above formula (I), 70% by volume of a cyclic phosphazene compound in which n is 3, 2 of all R ¹ are methoxy groups (MeO) and 4 are fluorine (F), and 30 volumes of ethyl difluorophosphate A nonaqueous electrolyte was prepared by dissolving LiPF ₆ at 1 mol / L in a mixed solvent of 2%. The maximum exothermic rate, total calorific value, and critical oxygen index of the obtained nonaqueous electrolytic solution were evaluated and measured by the following methods, and the results shown in Table 1 were obtained.

(1) Measurement of maximum heat generation rate and total calorific value of electrolyte The maximum calorific value of non-aqueous electrolyte from the exothermic behavior of flames ignited in an atmospheric environment using the ISO 5660 standard cone calorimeter (cone calorimeter) method. The speed and total calorific value were determined. Specifically, based on the ISO standard, a non-aqueous electrolyte solution 7.0 mL was impregnated on a nonflammable quartz fiber to prepare a 100 mm × 100 mm test piece, and a cone calorimeter (manufactured by FTT) with a set heat flux of 50 kW / m ² The test piece was applied to a corn calorimeter.

(2) Limiting oxygen index of electrolyte The limiting oxygen index of the electrolyte was measured according to JIS K7201. The larger the limiting oxygen index, the more difficult the electrolyte is to burn. Specifically, a SiO ₂ sheet (quartz filter paper, non-combustible) 127 mm × 12.7 mm can be reinforced with a U-shaped aluminum foil so that it can be self-supporting, and the SiO ₂ sheet is impregnated with 1.0 mL of the electrolyte solution, and a test piece Was made. The test piece was perpendicular to the test piece support, and a combustion cylinder (with an inner diameter of 75 mm, a height of 450 mm, and a diameter of 4 mm was uniformly filled with a thickness of 100 ± 5 mm from the bottom, and a metal net was placed thereon. It is attached so that it is located at a distance of 100 mm or more from the upper end of the object), and then oxygen (JIS K 1101 or equivalent) or nitrogen (JIS K 1107 grade 2 or equivalent or more) is attached to the combustion cylinder. The test piece was ignited under a predetermined oxygen concentration (the heat source was JIS K 2240 Type 1 No. 1), and the combustion state was examined. However, the total flow rate in the combustion cylinder is 11.4 L / min. This test was performed three times, and the average value is shown in Table 1. The oxygen index refers to the value of the minimum oxygen concentration expressed by the volume percent necessary for the material to continue burning. In this application, the test piece burns continuously for 3 minutes or longer, From the minimum oxygen flow rate required for burning 50 mm or more and the nitrogen flow rate at that time, the following formula:
Critical oxygen index = (oxygen flow rate) / [(oxygen flow rate) + (nitrogen flow rate)] × 100
The limiting oxygen index was calculated according to

Next, 3 parts by mass of acetylene black (conductive agent) and 3 parts by mass of polyvinylidene fluoride (binder) are added to 94 parts by mass of LiCoO ₂ (positive electrode active material), and an organic solvent (ethyl acetate and (50/50 mass% mixed solvent with ethanol), and the kneaded product is applied to a 25 μm thick aluminum foil (current collector) with a doctor blade and further dried with hot air (100 to 120 ° C.). A positive electrode sheet having a thickness of 80 μm was prepared. Also, 10 parts by weight of polyvinylidene fluoride (binder) was added to 90 parts by weight of artificial graphite (negative electrode active material), and kneaded with an organic solvent (50/50% by weight mixed solvent of ethyl acetate and ethanol). Thereafter, the kneaded product was applied to a copper foil (current collector) having a thickness of 25 μm with a doctor blade, and further dried with hot air (100 to 120 ° C.) to prepare a negative electrode sheet having a thickness of 80 μm. On the obtained positive electrode sheet, a negative electrode sheet was overlapped and wound up via a separator (microporous film: made of polypropylene) having a thickness of 25 μm to produce a cylindrical electrode. The positive electrode length of the cylindrical electrode was about 260 mm. The above electrolyte was injected into the cylindrical electrode and sealed to prepare an AA lithium battery (non-aqueous electrolyte secondary battery). The initial discharge capacity and cycle characteristics of the obtained battery were measured by the following methods, and the results shown in Table 1 were obtained.

(3) Evaluation of initial discharge capacity and cycle characteristics of battery
Under an environment of 20 ° C, charge and discharge are performed under the conditions of an upper limit voltage of 4.3 V, a lower limit voltage of 3.0 V, a discharge current of 50 mA, and a charge current of 50 mA, and the initial discharge capacity is obtained by dividing the discharge capacity at this time by the known electrode weight. (MAh / g) was determined. Furthermore, charge / discharge was repeated up to 50 cycles under the same charge / discharge conditions, and the discharge capacity after 50 cycles was determined.
Capacity remaining rate S = discharge capacity after 50 cycles / initial discharge capacity × 100 (%)
The capacity remaining rate S was calculated according to the above and used as an index of the cycle characteristics of the battery.

(Example 2)
In place of the mixed solvent used in “Preparation of Nonaqueous Electrolyte” in Example 1, in the above formula (I), n is 3, 2 out of all R ¹ are chlorine (Cl), and 4 are A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that a mixed solvent of 50% by volume of a cyclic phosphazene compound as fluorine (F) and 50% by volume of methyl difluorophosphate was used. Evaluate and measure the maximum heat generation rate and total calorific value of the water electrolyte, and the critical oxygen index, and make a non-aqueous electrolyte secondary battery in the same manner as in Example 1 and measure the initial discharge capacity and cycle characteristics. ·evaluated. The results are shown in Table 1.

(Example 3)
In place of the mixed solvent used in “Preparation of Nonaqueous Electrolyte” in Example 1, in the above formula (I), n is 3, ^one of all R ¹ is an ethoxy group (EtO), 5 A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that a mixed solvent of 30% by volume of a cyclic phosphazene compound of which fluorine (F) is one and 70% by volume of propyl difluorophosphate was used. Evaluate and measure the maximum heat generation rate and total calorific value of the non-aqueous electrolyte, and the critical oxygen index, and make a non-aqueous electrolyte secondary battery in the same manner as in Example 1 to determine the initial discharge capacity and cycle characteristics. Measured and evaluated. The results are shown in Table 1.

Example 4
In place of the mixed solvent used in “Preparation of Nonaqueous Electrolytic Solution” in Example 1, in the above formula (I), n is 3, and ^one of all R ¹ is a trifluoroethoxy group (TFEO). Other than using a mixed solvent of 40% by volume of cyclic phosphazene compound, 5 of which is fluorine (F), 30% by volume of methyl difluorophosphate, 10% by volume of ethylene carbonate, and 20% by volume of ethyl methyl carbonate. A nonaqueous electrolytic solution was prepared in the same manner as in Example 1, and the maximum exothermic rate and total calorific value and critical oxygen index of the obtained nonaqueous electrolytic solution were evaluated and measured. A water electrolyte secondary battery was prepared, and the initial discharge capacity and cycle characteristics were measured and evaluated. The results are shown in Table 1.

(Example 5)
Instead of the mixed solvent used in “Preparation of Nonaqueous Electrolyte” in Example 1, a cyclic phosphazene compound having a volume of 40 in the above formula (I), wherein n is 4 and all R ¹ are fluorine (F) %, 30% by volume of dimethyl fluorophosphate, 10% by volume of ethylene carbonate, 5% by volume of vinylene carbonate, and 15% by volume of diethyl carbonate. Prepare the electrolyte, evaluate and measure the maximum heat generation rate and total calorific value, and the critical oxygen index of the obtained non-aqueous electrolyte, and produce a non-aqueous electrolyte secondary battery in the same manner as in Example 1. The initial discharge capacity and cycle characteristics were measured and evaluated. The results are shown in Table 1.

(Example 6)
In place of the mixed solvent used in “Preparation of Nonaqueous Electrolyte” in Example 1, in the above formula (I), n is 4, ^one of all R ¹ is a methoxy group (MeO), 7 Example 1 except that a mixed solvent of 10% by volume of a cyclic phosphazene compound, one of which is fluorine (F), 5% by volume of phenyl difluorophosphate, 28% by volume of ethylene carbonate, and 57% by volume of dimethyl carbonate was used. Similarly, a nonaqueous electrolytic solution was prepared, and the maximum exothermic rate and total calorific value and critical oxygen index of the obtained nonaqueous electrolytic solution were evaluated and measured. In the same manner as in Example 1, the nonaqueous electrolytic solution was measured. A secondary battery was prepared, and the initial discharge capacity and cycle characteristics were measured and evaluated. The results are shown in Table 1.

(Comparative Example 1)
Instead of the mixed solvent used in “Preparation of Nonaqueous Electrolyte” in Example 1, a mixed solvent of 33% by volume of ethylene carbonate and 67% by volume of ethyl methyl carbonate was used in the same manner as in Example 1. The non-aqueous electrolyte was prepared, and the maximum exothermic rate and total calorific value of the obtained non-aqueous electrolyte and the critical oxygen index were evaluated and measured. A battery was prepared, and the initial discharge capacity and cycle characteristics were measured and evaluated. The results are shown in Table 1.

(Example 7)
Instead of the mixed solvent used in “Preparation of non-aqueous electrolyte solution” in Example 1, a mixed solvent of 30% by volume of trimethyl phosphate, 23% by volume of ethylene carbonate, and 47% by volume of ethyl methyl carbonate was used. Prepared a non-aqueous electrolyte in the same manner as in Example 1, and evaluated and measured the maximum heat generation rate and total calorific value, and the limiting oxygen index of the obtained non-aqueous electrolyte. A non-aqueous electrolyte secondary battery was prepared, and the initial discharge capacity and cycle characteristics were measured and evaluated. The results are shown in Table 1.

(Example 8)
Instead of the mixed solvent used in “Preparation of non-aqueous electrolyte solution” in Example 1, a mixed solvent of 30% by volume of phenyl difluorophosphate, 23% by volume of ethylene carbonate, and 47% by volume of ethyl methyl carbonate was used. Others were prepared in the same manner as in Example 1, and the maximum exothermic rate and total calorific value and critical oxygen index of the obtained nonaqueous electrolytic solution were evaluated and measured. Similarly, a non-aqueous electrolyte secondary battery was produced, and the initial discharge capacity and cycle characteristics were measured and evaluated. The results are shown in Table 1.

Example 9
In place of the mixed solvent used in “Preparation of Nonaqueous Electrolyte” in Example 1, in the above formula (I), n is 3, ^one of all R ¹ is phenoxy group (PhO), 5 A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that a mixed solvent of 18% by volume of a cyclic phosphazene compound, one of which is fluorine (F), 27% by volume of ethylene carbonate, and 55% by volume of diethyl carbonate was used. Then, the maximum heat generation rate, the total heat generation amount, and the critical oxygen index of the obtained nonaqueous electrolyte solution were evaluated and measured, and a nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1 for initial discharge. Capacity and cycle characteristics were measured and evaluated. The results are shown in Table 1.

(Example 10)
In place of the mixed solvent used in “Preparation of Nonaqueous Electrolyte” in Example 1, in the above formula (I), n is 3, ^one of all R ¹ is phenoxy group (PhO), 5 A nonaqueous electrolytic solution was prepared in the same manner as in Example 1 except that a mixed solvent of 50% by volume of a cyclic phosphazene compound, one of which is fluorine (F), and 50% by volume of triethyl phosphate was used. Evaluate and measure the maximum heat generation rate and total calorific value of the water electrolyte, and the critical oxygen index, and make a non-aqueous electrolyte secondary battery in the same manner as in Example 1 and measure the initial discharge capacity and cycle characteristics. ·evaluated. The results are shown in Table 1.

  From the examples in Table 1, it can be seen that the non-aqueous electrolyte having the maximum heat generation rate and the total heat generation within the ranges defined in the present invention has a high critical oxygen index and high safety. From the results of Examples 1 to 6, the non-aqueous electrolyte containing the cyclic phosphazene compound of the above formula (I) and the fluorophosphate ester of the above formula (II) has a very low maximum heat generation rate and total heat generation amount. It can be seen that the discharge capacity and the cycle characteristics are very excellent. In addition, since the non-aqueous electrolytes of Examples 7 to 10 had lower battery characteristics than the non-aqueous electrolytes of Examples 1 to 6, when considering the battery characteristics in addition to safety, the above formula (I) It can be seen that it is preferable to add the cyclic phosphazene compound of formula (II) and the fluorophosphate ester of the above formula (II) to the non-aqueous electrolyte.

(Examples 11-14)
Methoxydifluorophosphine oxide [O═PF ₂ (OCH ₃ )], dimethoxyfluorophosphine oxide [O═PF (OCH ₃ ) ₂ ], aminodifluorophosphine oxide [O═PF ₂ NH ₂ ] or cyclic phosphazene compound A [the above formula A cyclic phosphazene compound represented by (I), where n is 3, ^{1 of} 6 R ¹ , 1 is an ethoxy group and 5 is fluorine, viscosity at 25 ° C .: 1.2 mPa · s] 10% by volume, propylene Carbonate (PC) 90% by volume was mixed, and tetraethylammonium tetrafluoroborate [Et ₄ N · BF ₄ ] (supporting salt) was dissolved to 1 mol / L to prepare a nonaqueous electrolytic solution. The maximum exothermic rate and total calorific value, and critical oxygen index of the obtained nonaqueous electrolytic solution were measured by the above methods, and the results shown in Table 2 were obtained.

Next, the activated carbon [AC, trade name: Kuractive-1500, manufactured by Kuraray Chemical Co., Ltd.], acetylene black (conductive agent), and polyvinylidene fluoride (PVDF) (binder) are each in a mass ratio (activated carbon: acetylene black: PVDF) was mixed to 8: 1: 1 to obtain a mixture. 100 mg of the obtained mixture was sampled, put into a 20 mmφ pressure-resistant carbon container, and compacted under conditions of a pressure of 150 kgf / cm ² and a normal temperature to prepare a positive electrode and a negative electrode (electrode). A cell was assembled using the obtained electrodes (positive electrode and negative electrode), an aluminum metal plate (current collector) (thickness: 0.5 mm), and a polypropylene / polyethylene plate (separator) (thickness: 25 μm), and vacuum dried. Dry thoroughly. The cell was impregnated with the above non-aqueous electrolyte to produce a non-aqueous electrolyte electric double layer capacitor. The cycle characteristics and low temperature characteristics of the obtained electric double layer capacitor were tested by the following methods. The results are shown in Table 2.

(4) Cycle characteristics of the electric double layer capacitor For the obtained non-aqueous electrolyte electric double layer capacitor, the initial discharge capacity and the discharge capacity after 1000 cycles were measured at 20 ° C. From the discharge capacity of the following formula:
Capacity retention ratio S = discharge capacity after 1000 cycles / initial discharge capacity × 100 (%)
The capacity retention rate S was calculated according to the above and used as an index of the cycle characteristics of the capacitor.

(5) Low-temperature characteristics of electric double layer capacitor The obtained non-aqueous electrolyte electric double layer capacitor was measured for discharge capacity after 1000 cycles of charge and discharge in each environment of 20 ° C and -20 ° C. From the discharge capacity after 1000 cycles at 20 ° C and the discharge capacity after 1000 cycles at -20 ° C, the following formula:
Capacity maintenance ratio L = discharge capacity (-20 ° C.) / Discharge capacity (20 ° C.) × 100 (%)
The capacity retention ratio L was calculated according to the above and used as an index of the low temperature characteristics of the capacitor.

As shown in Table 2, it can be seen that the non-aqueous electrolyte in which the maximum heat generation rate and the total heat generation amount are within the ranges defined in the present invention has a high critical oxygen index and high safety. In addition, by adding a phosphine oxide compound having a PF bond and / or a P—NH ₂ bond in the molecule to the electrolytic solution, the maximum heat generation rate and the total heat generation amount of the nonaqueous electrolytic solution are further reduced. It was confirmed that the safety of the electrolyte can be further improved.

LiPF ₆ (supporting salt) was dissolved at a concentration of 1 M (mol / L) in a solvent having the composition shown in Table 3 to prepare a nonaqueous electrolytic solution. The maximum exothermic rate and total calorific value of the obtained nonaqueous electrolytic solution and the critical oxygen index were measured and evaluated by the above methods. The results are shown in Table 3.

Next, 3 parts by mass of acetylene black (conductive agent) and 3 parts by mass of polyvinylidene fluoride (binder) are added to 94 parts by mass of LiCoO ₂ (positive electrode active material), and an organic solvent (ethyl acetate and (50/50 mass% mixed solvent with ethanol), and the kneaded product was coated on a 25 μm thick aluminum foil (current collector) with a doctor blade and then dried with hot air (100 to 120 ° C.). A positive electrode sheet having a thickness of 80 μm was prepared. Next, the positive electrode sheet and the lithium metal sheet were overlapped and rolled up through a separator having a thickness of 25 μm (microporous film: made of polypropylene) to produce a cylindrical electrode. The positive electrode length of the cylindrical electrode was about 260 mm. The above electrolyte was injected into the cylindrical electrode and sealed to prepare an AA lithium battery (non-aqueous electrolyte secondary battery). The obtained battery was repeatedly charged and discharged up to 50 cycles under the conditions of an upper limit voltage of 4.2 V, a lower limit voltage of 3.0 V, and a discharge current of 0.2 C in a 20 ° C. environment. The discharge capacity of was measured. Also, the following formula:
Discharge capacity retention rate = discharge capacity after 50 cycles / initial discharge capacity × 100 (%)
From this, the discharge capacity retention rate was calculated. The results are shown in Table 3.

In Table 3, phosphate ester derivative A is ethyl difluorophosphate [F ₂ P (O) OEt]; phosphate ester derivative B is methyl difluorophosphate [F ₂ P (O) OMe]; Phosphate ester derivative C is phenyl difluorophosphate [F ₂ P (O) OPh]; Phosphate ester derivative D is diethyl fluorophosphate [FP (O) (OEt) ₂ ]; Phosphate ester Derivative E is dimethyl fluorophosphate [FP (O) (OMe) ₂ ]; phosphate ester X is triethyl phosphate [P (O) (OEt) ₃ ]; phosphate ester Y is phosphorus Acid trimethyl [P (O) (OMe) ₃ ]; EC is ethylene carbonate; DEC is diethyl carbonate; EMC is ethyl methyl carbonate; DMC is dimethyl carbonate .

  From the examples in Table 3, it can be seen that the non-aqueous electrolyte having the maximum heat generation rate and the total heat generation within the ranges defined in the present invention has a high critical oxygen index and high safety. In addition, from the results of Examples 15 to 19, the non-aqueous electrolyte obtained by dissolving the supporting salt in the solvent composed only of the phosphate ester derivative has a very low maximum heat generation rate and total heat generation, and has a discharge capacity retention rate. Is very expensive. In addition, since the non-aqueous electrolyte of Examples 20 and 21 had a lower discharge capacity retention rate than the non-aqueous electrolytes of Examples 15 to 19, when considering battery characteristics in addition to safety, phosphate ester It can be seen that a nonaqueous electrolytic solution obtained by dissolving a supporting salt in a solvent composed only of a derivative is preferable.

LiBF ₄ (supporting salt) was dissolved in a solvent having the composition shown in Table 4 at a concentration of 0.75 mol / L to prepare a nonaqueous electrolytic solution. The maximum exothermic rate and total calorific value of the obtained nonaqueous electrolytic solution and the critical oxygen index were measured and evaluated by the above methods. The results are shown in Table 4.

Next, after mixing and kneading MnO ₂ (positive electrode active material), acetylene black (conductive agent) and polyvinylidene fluoride (binder) in a ratio (mass ratio) of 8: 1: 0.6, The kneaded product was pressure-bonded and pelletized on a nickel foil (current collector) having a thickness of 25 μm, and further heated and dried (100 to 120 ° C.) to produce a positive electrode pellet having a thickness of 500 μm. The obtained positive electrode pellet punched out to φ16 mm was used as the positive electrode, the lithium foil (thickness 0.5 mm) punched out to φ16 mm was used as the negative electrode, and the positive and negative electrodes were connected via a cellulose separator [TF4030 manufactured by Nippon Kogyo Paper Industries Co. It was made to face, the said electrolyte solution was inject | poured and sealed, and the CR2016 type nonaqueous electrolyte primary battery (lithium primary battery) was produced. The obtained battery was discharged at 0.2 C at a lower limit voltage of 1.5 V in an environment of 25 ° C., and the discharge capacity was measured. The results are shown in Table 4.

In Table 4, the phosphoric acid ester derivatives A to D are the same as the phosphoric acid ester derivatives A to D in Table 3. Phosphazene X is represented by formula (VI) in which all Y ⁶ R ⁶ are ethoxy groups, X Is a chain phosphazene compound in which Z in formula (VIII) is oxygen and all Y ⁸ R ⁸ are fluorine; phosphazene Y is a substituent represented by formula (VIII); a cyclic phosphazene compound (viscosity at 25 ° C .: 1.7 mPa · s, boiling point 195 ° C.) in which m is 3, and one of six R ⁷ is phenoxy group (PhO—) and five is fluorine; , Propylene carbonate.

  From the examples in Table 4, it can be seen that the non-aqueous electrolyte having the maximum heat generation rate and the total heat generation within the ranges defined in the present invention has a high critical oxygen index and high safety. In addition, from the results of Examples 22 to 41, the non-aqueous electrolyte obtained by dissolving the supporting salt in a solvent consisting only of 40 to 100% by volume of the phosphate ester derivative and 60 to 0% by volume of the phosphazene compound has a maximum exotherm. It can be seen that the speed and total heat generation are very low and the discharge capacity is very high. The non-aqueous electrolytes of Examples 42 to 44 have a smaller discharge capacity than the non-aqueous electrolytes of Examples 22 to 41, and the non-aqueous electrolytes of Examples 45 to 47 are those of Examples 22 to 41. When considering both safety and battery characteristics, 40 to 100% by volume of a phosphoric acid ester derivative and 60 to 0% by volume of a phosphazene compound have higher maximum heat generation rate and higher total heat generation than non-aqueous electrolytes. It can be seen that a non-aqueous electrolyte solution in which a supporting salt is dissolved in a solvent consisting solely of is preferable.

Claims (32)

A non-aqueous electrolyte characterized in that the maximum heat generation rate measured with a corn calorimeter is 550 kW / m ² or less. A non-aqueous electrolyte characterized in that the total calorific value measured with a corn calorimeter is 10 MJ / m ² or less. Formula (I) below:
(NPR ¹ ₂ ) _n ... (I)
[Wherein R ¹ independently represents a halogen element or a monovalent substituent; n represents 3 to 4] and a cyclic phosphazene compound represented by the following formula (II):

[Wherein, R ² is independently a halogen element, an alkoxy group or an aryloxy group, and at least one of the two R ² is an alkoxy group or an aryloxy group] The nonaqueous electrolytic solution according to claim 1, comprising a nonaqueous solvent containing a fluorophosphate ester compound and a supporting salt. 4. The nonaqueous electrolytic solution according to claim 3, wherein in the formula (II), one of two R ² is fluorine, and the other is an alkoxy group or an aryloxy group. 4. The nonaqueous electrolytic solution according to claim 3, wherein, in the formula (I), R ¹ is each independently any one of fluorine, an alkoxy group, and an aryloxy group. In the formula (I), non-aqueous electrolyte according to claim 3 or 5 wherein at least three of R ^1, wherein the fluorine.   The volume ratio of the cyclic phosphazene compound represented by the formula (I) and the fluorophosphate compound represented by the formula (II) is in the range of 30/70 to 70/30. 3. A non-aqueous electrolyte solution according to 3.   The nonaqueous electrolytic solution according to claim 3, wherein the nonaqueous solvent further contains an aprotic organic solvent.   The total content of the cyclic phosphazene compound represented by the formula (I) and the fluorophosphate compound represented by the formula (II) in the non-aqueous solvent is 15% by volume or more. The nonaqueous electrolytic solution according to any one of claims 3 to 8.   The total content of the cyclic phosphazene compound represented by the formula (I) and the fluorophosphate compound represented by the formula (II) in the non-aqueous solvent is 70% by volume or more. The nonaqueous electrolytic solution according to claim 9. The nonaqueous electrolytic solution according to claim 1, comprising a phosphine oxide compound having a P—F bond and / or a P—NH ₂ bond in a molecule, and a supporting salt.   The content rate of the said phosphine oxide compound is 3 volume% or more, The nonaqueous electrolyte solution of Claim 11 characterized by the above-mentioned.   The non-aqueous electrolyte according to claim 12, wherein the content of the phosphine oxide compound is 5% by volume or more. The phosphine oxide compound is represented by the following formula (III):
O = PR ³ ₃ ... (III)
12. wherein R ³ is each independently a monovalent substituent or a halogen element, and at least one R ³ is fluorine or an amino group. Non-aqueous electrolyte. R ³ in the formula (III) is independently selected from the group consisting of fluorine, amino group, alkyl group and alkoxy group, and at least one R ³ is fluorine or amino group. The nonaqueous electrolytic solution according to claim 14. The nonaqueous electrolytic solution according to claim 15, wherein at least one of R ³ in the formula (III) is fluorine, and at least one of R ^{3 in} the formula (III) is an amino group. The nonaqueous electrolytic solution according to claim 15, wherein R ³ in the formula (III) is independently a fluorine or an amino group.   The nonaqueous electrolytic solution according to claim 11, further comprising an aprotic organic solvent.   The nonaqueous electrolytic solution according to claim 1 or 2, wherein a supporting salt is dissolved in a solvent composed only of a phosphate ester derivative.   The nonaqueous electrolytic solution according to claim 19, wherein the phosphate ester derivative is at least one selected from the group consisting of phosphonates and phosphinates. The phosphonate is represented by the following formula (IV):

[Wherein, R ⁴ independently represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an aromatic hydrocarbon group or a hydrocarbon group having 2 to 6 carbon atoms having a carbon-carbon double bond; The nonaqueous electrolytic solution according to claim 20, wherein A ⁴ represents an amino group or a halogen element. The phosphinate is represented by the following formula (V):

Wherein, R ⁵ is an aliphatic having from 1 to 4 carbon atoms hydrocarbon group or an aromatic hydrocarbon group or C - represents a hydrocarbon group having 2 to 6 carbon atoms and having a carbon double bond; in A ^5, The nonaqueous electrolytic solution according to claim 20, wherein each independently represents an amino group or a halogen element.   The nonaqueous electrolytic solution according to claim 1 or 2, wherein the supporting salt is dissolved in a solvent composed of only 40 to 100% by volume of a phosphoric ester derivative and 60 to 0% by volume of a phosphazene compound.   The nonaqueous electrolytic solution according to claim 23, wherein a solvent of the nonaqueous electrolytic solution is composed of only a phosphate ester derivative.   The nonaqueous electrolytic solution according to claim 23 or 24, wherein the phosphate ester derivative is at least one selected from the group consisting of phosphonates and phosphinates.   The non-aqueous electrolyte according to claim 25, wherein the phosphonate is represented by the formula (IV).   The non-aqueous electrolyte according to claim 25, wherein the phosphinate is represented by the formula (V). The phosphazene compound has the following formula (VI):

[Wherein, R ⁶ each independently represents a monovalent substituent or a halogen element; Y ⁶ each independently represents a divalent linking group, a divalent element or a single bond; Chain representing a substituent containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium and polonium] Phosphazene compound or the following formula (VII):
(NPR ⁷ ₂ ) _m ... (VII)
24. The cyclic phosphazene compound represented by the formula: wherein R ⁷ each independently represents a monovalent substituent or a halogen element; m represents 3 to 15. Non-aqueous electrolyte.   A nonaqueous electrolyte battery comprising the nonaqueous electrolyte solution according to any one of claims 1 to 28, a positive electrode, and a negative electrode.   A non-aqueous electrolyte electric double layer capacitor comprising the non-aqueous electrolyte according to claim 1, a positive electrode, and a negative electrode.   A method for evaluating the safety of a non-aqueous electrolyte, comprising measuring the maximum heat generation rate of the non-aqueous electrolyte using a corn calorimeter.   A method for evaluating the safety of a non-aqueous electrolyte, comprising measuring a total calorific value of the non-aqueous electrolyte using a corn calorimeter.