JP2002100403A - Nonaqueous electrolyte and nonaqueous electrochemical device containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new nonaqueous electrolyte, having thermal stability of the same level as that of boric acid lithium tetrafluoride, high electro- negativity of an anion part, and containing a solute susceptible to ionic dissociation. SOLUTION: The feature is that this nonaqueous electrolyte comprises a nonaqueous solvent and a solute expressed by a general formula MBR1R2R3 R4 (M is an alkali metal or an ammonium group, R1-R4 is an electron attractive group, and R1-R4 will not simultaneously be fluorine atoms).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous electrolyte comprising a non-aqueous solvent and a specific borate as a solute, and a non-aqueous electrochemical device containing the same.

[0002]

2. Description of the Related Art A non-aqueous electrochemical device containing a non-aqueous electrolyte is
It is used in a wide range of electrical and electronic devices. Non-aqueous electrochemical devices include, for example, non-aqueous electrolyte batteries such as lithium ion batteries, and non-aqueous electrolyte electrolytic capacitors such as electric double layer capacitors. The non-aqueous electrochemical device includes a non-aqueous electrolyte, and the non-aqueous electrolyte is composed of a non-aqueous solvent and a solute dissolved therein. The concentration of the solute in the non-aqueous electrolyte is about 1 mol / liter.

It is desirable that the non-aqueous electrolyte used in the non-aqueous electrochemical device has high ionic conductivity. To obtain such a non-aqueous electrolyte, a non-aqueous solvent having a high relative dielectric constant and a low viscosity is required. However, a non-aqueous solvent having a high relative dielectric constant has a strong polarity, and thus has a high viscosity. Therefore, in the current practical battery, ethylene carbonate (relative dielectric constant: 9)
Non-aqueous solvent having a high dielectric constant represented by 0) and a low dielectric constant represented by dimethyl carbonate (relative dielectric constant: 3.1), ethylmethyl carbonate (relative dielectric constant: 2.9), etc. A non-aqueous electrolytic solution in combination with a non-aqueous solvent is used.

As a solute, lithium perchlorate (LiC
lO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium trifluoromethanesulfonate (LiSO ₃ CF ₃ ), lithium bistrifluoromethanesulfonimide ((CF ₃ S
O ₂ ) ₂ NLi) and the like are used. Among these, lithium hexafluorophosphate (LiPF) exhibits high ionic conductivity in a nonaqueous solvent and has a wide potential window.
₆ ) is often used.

[0005]

The non-aqueous electrolyte containing lithium hexafluorophosphate has a high ionic conductivity of about 8.5 mS / cm at room temperature, but has poor thermal stability. Further, lithium hexafluorophosphate has a problem that it reacts with moisture very sharply and decomposes.

The use of lithium trifluoromethanesulfonate (LiSO ₃ CF ₃ ), lithium bistrifluoromethanesulfonimide ((CF ₃ SO ₂ ) ₂ NLi) and the like has been studied. Many of them corrode the aluminum current collector used for the positive electrode of the nonaqueous electrolyte battery, and thus have not been put into practical use.

On the other hand, lithium tetrafluoroborate (LiBF ₄ ) generally used in lithium primary batteries has higher thermal stability than lithium hexafluorophosphate (LiPF ₆ ), and It has a potential window comparable to lithium. However, even if lithium tetrafluoroborate is dissolved in a non-aqueous solvent, only a non-aqueous electrolyte having a low ionic conductivity of about 2.9 mS / cm at room temperature can be obtained. Not been.

[0008] The ionic conductivity of lithium tetrafluoroborate is lower than that of lithium hexafluorophosphate because six fluorines having an electron withdrawing property are bonded to phosphorus,
This is because only four atoms are bonded to boron. Since the electronegativity of the BF ₄ anion moiety is smaller than that of the PF ₆ anion moiety corresponding to the number of bonded fluorines,
It is considered that lithium tetrafluoroborate is difficult to dissociate ions. In addition, since the BF ₄ anion has a small anion diameter, it is considered that the BF ₄ anion easily associates to lower the ionic conductivity of the electrolytic solution.

In the non-aqueous electrolytic solution of the electrolytic capacitor,
Solutes that generate BF ₄ anions by ion dissociation are often used. In an electrolytic capacitor, a nonaqueous electrolyte is interposed between a dielectric layer formed on an anode foil and made of an oxide such as aluminum or tantalum and a cathode foil. Therefore, the ionic conductivity of the non-aqueous electrolyte has a large effect on the dielectric loss of the electrolytic capacitor. When the dielectric loss increases,
The frequency characteristics of the electrolytic capacitor decrease, and the charge / discharge characteristics also decrease.

[0010]

The present invention relates to a non-aqueous solvent and a general formula: MBR ₁ R ₂ R ₃ R ₄ (M is an alkali metal or ammonium group, R _{1 to} R ₄ are electron withdrawing groups, ₁ to
R ₄ is not a fluorine atom at the same time). The solute is usually composed of an anion and a cation, and an ionic bond is formed between the two, so that the general formula: MBR ₁ R ₂
R ₃ R ₄ can also be represented, for example, by the general formula: M ⁺ · (BR ₁ R ₂ R ₃ R ₄ ) ^- .

At least one of the electron-withdrawing groups has a general formula: C _n F _{2n + 1} (n is an integer of 1 to 4) or C _m F _{2m + 1} S
Preferably, it is represented by O ₂ (m is an integer of 1 to 4).
Further, the remaining groups are preferably fluorine atoms.
In addition, as the ammonium group, a compound represented by the general formula: NR ₅ R ₆
Preferably, R ₇ R ₈ (R _{5 to} R ₈ are each independently a hydrogen atom, an alkyl group, an alkenyl group or an aryl group). The present invention also relates to a non-aqueous electrochemical device containing the non-aqueous electrolyte.

Non-aqueous electrolysis contained in, for example, non-aqueous electrolyte batteries
When a liquid is obtained, the solute is LiB (CF_Three)_Four, LiB
F (CF_Three)_Three, LiBF_Two(CF_Three)_Two, LiBF_Three(CF
_Three), LiB (C_TwoF_Five)_Four, LiBF (C_TwoF_Five)_Three, Li
BF_Two(C_TwoF_Five)_Two, LiBF _Three(C_TwoF_Five), LiB (C
F_ThreeSO_Two)_Four, LiBF (CF_ThreeSO_Two)_Three, LiBF
_Two(CF_ThreeSO_Two)_Two, LiBF_Three(CF_ThreeSO_Two), LiB
(C_TwoF_FiveSO_Two)_Four, LiBF (C_TwoF_FiveSO_Two)_Three, LiB
F_Two(C_TwoF_FiveSO_Two)_TwoAnd LiBF_Three(C_TwoF_FiveSO_Two)
At least one selected from the group consisting of
preferable. The present invention also provides a positive electrode, a negative electrode,
Between the separator and the non-aqueous electrolyte
And a non-aqueous electrolyte battery.

For example, non-aqueous electrolysis contained in an electrolytic capacitor
When a liquid is obtained, the solute is (CH _Three)_FourNB (C
F_Three)_Four, (CH_Three)_FourNBF (CF_Three)_Three, (CH_Three)_FourNB
F_Two(CF_Three)_Two, (CH_Three)_FourNBF_Three(CF_Three), (C
H_Three)_FourNB (C_TwoF_Five)_Four, (CH_Three)_FourNBF (C
_TwoF_Five)_Three, (CH_Three)_FourNBF_Two(C_TwoF_Five)_Two, (CH_Three)_Four
NBF_Three(C_TwoF_Five), (C_TwoH_Five)_FourNB (CF_Three)_Four, (C
_TwoH_Five)_FourNBF (CF_Three)_Three, (C_TwoH_Five)_FourNBF_Two(C
F_Three)_Two, (C_TwoH_Five)_FourNBF_Three(CF_Three), (C_TwoH_Five)_FourN
B (C_TwoF_Five)_Four, (C_TwoH_Five)_FourNBF (C_TwoF_Five)_Three, (C_Two
H_Five)_FourNBF_Two(C_TwoF_Five)_Two, (C_TwoH_Five)_FourNBF_Three(C_Two
F_Five), ((CH_Three)_ThreeC)_FourNB (CF_Three)_Four, ((C
H_Three)_ThreeC)_FourNBF (CF_Three)_Three, ((CH_Three)_ThreeC)_FourNB
F_Two(CF_Three)_Two, ((CH_Three)_ThreeC)_FourNBF_Three(CF_Three),
((CH_Three)_ThreeC)_FourNB (C_TwoF_Five)_Four, ((CH_Three)_ThreeC)
_FourNBF (C_TwoF_Five)_Three, ((CH_Three)_ThreeC)_FourNBF_Two(C_Two
F_Five)_Two, ((CH_Three)_ThreeC) _FourNBF_Three(C_TwoF_Five), (CH
_Three)_FourNB (CF_ThreeSO_Two)_Four, (CH_Three)_FourNBF (CF_ThreeS
O_Two)_Three, (CH_Three)_FourNBF_Two(CF_ThreeSO_Two)_Two, (C
H_Three)_FourNBF_Three(CF_ThreeSO_Two), (CH_Three)_FourNB (C_TwoF
_FiveSO_Two)_Four, (CH_Three)_FourNBF (C_TwoF_FiveSO_Two) _Three, (C
H_Three)_FourNBF_Two(C_TwoF_FiveSO_Two)_Two, (CH_Three)_FourNBF
_Three(C_TwoF_FiveSO_Two), (C_TwoH_Five)_FourNB (CF_ThreeSO_Two)_Four,
(C_TwoH_Five)_FourNBF (CF_ThreeSO_Two)_Three, (C_TwoH_Five)_FourNB
F_Two(CF_ThreeSO_Two)_Two, (C_TwoH_Five)_FourNBF_Three(CF_ThreeS
O_Two), (C_TwoH_Five)_FourNB (C_TwoF_FiveSO_Two)_Four, (C_TwoH_Five)
_FourNBF (C_TwoF_FiveSO_Two)_Three, (C_TwoH_Five)_FourNBF_Two(C_TwoF
_FiveSO_Two)_Two, (C_TwoH_Five)_FourNBF_Three(C_TwoF_FiveSO_Two),
((CH_Three)_ThreeC)_FourNB (CF_ThreeSO_Two)_Four, ((CH_Three)_Three
C)_FourNBF (CF_ThreeSO_Two)_Three, ((CH_Three)_ThreeC)_FourNB
F_Two(CF_ThreeSO_Two)_Two, ((CH_Three)_ThreeC)_FourNBF_Three(CF
_ThreeSO_Two), ((CH_Three)_ThreeC)_FourNB (C_TwoF_FiveSO_Two)_Four,
((CH_Three)_ThreeC)_FourNBF (C_TwoF_FiveSO_Two)_Three, ((C
H_Three)_ThreeC)_FourNBF_Two(C_TwoF_FiveSO_Two)_TwoAnd ((C
H_Three)_ThreeC)_FourNBF_Three(C_TwoF_FiveSO_Two)
It is preferable that it is made of at least one kind of metal. The present invention
Is an anode foil having a dielectric layer, a cathode foil,
Separator interposed between the foil and the cathode foil and the non-water
The present invention relates to a non-aqueous electrolyte electrolytic capacitor comprising an electrolytic solution.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a borate having the same thermal stability as lithium tetrafluoroborate, a high electronegativity of the anion portion, and easily ion dissociating in a non-aqueous solvent is used. Used. In the borate, for example, part or all of the fluorine bonded to boron of the tetrafluoroborate is converted to a perfluoroalkyl group (C _n F _{2n + 1} ) or a perfluoroalkyl sulfonic acid group (C _m F _{2m + 1} SO ₂ ).
Since perfluoroalkyl groups or perfluoroalkylsulfonic acid groups have strong electron-withdrawing properties, borates having these groups are easily ion dissociated in a non-aqueous solvent. Therefore, by using the borate, it is possible to obtain a non-aqueous electrolyte having high thermal stability and a high ionic conductivity as compared with lithium hexafluorophosphate, and to perform high-rate charging and discharging satisfactorily. It is possible to provide a non-aqueous electrochemical device.

The electronegativity of the anion portion of the solute increases as the number of electron-withdrawing groups bonded to boron increases, and the solute is easily ion-dissociated. In addition, it is considered that the larger the number of electron-withdrawing groups bonded to boron, the larger the anion diameter becomes, so that the association of anions is less likely to occur.

Embodiment 1 In this embodiment, a non-aqueous electrolyte suitable for batteries such as a lithium primary battery, a lithium secondary battery, a lithium ion battery, and a polymer battery will be described. The non-aqueous electrolyte of the present embodiment can be obtained by dissolving the following solutes in the following non-aqueous solvent.

(I) Solute The non-aqueous electrolyte of the present embodiment has a general formula: M'BR ₁ R ₂ R
₃ R ₄ (M 'is Li, Na, alkali metals K, etc., R ₁ ~
R ₄ is an electron-withdrawing group, and R _{1 to} R ₄ are not simultaneously a fluorine atom). As the electron withdrawing group, a general formula: C _n F _{2n + 1} (n is 1 to 4)
Or an integer of C _m F _{2m + 1} SO ₂ (m is an integer of 1 to 4). The anion having a group represented by the general formula: C _n F _{2n + 1} is represented by the general formula: C _m F _{2m + 1} SO ₂
Is smaller than the anion having a group represented by the formula, the ionic conductivity of the non-aqueous electrolyte containing the former is higher. Accordingly, the general _{formula: C n F 2n + 1 (} n is an integer from 1 to 4) and more preferably is more of the groups represented by.

The number of electron withdrawing groups other than fluorine may be one or more, but is preferably two or three in view of easy synthesis. For example, the general formula: M′B (C _n F _{2n + 1} ) ₂ F
_The solute represented by ₂ and the solute represented by the general formula: M′B (C _n F _{2n + 1} ) ₃ F are preferred. n and m may be integers of 1 to 4. However, if n and m are too small, the electron-withdrawing effect of the electron-withdrawing group becomes small, and if n and m are too large, the anion diameter becomes large. Preferably, there is.

As a specific example of the solute, LiB (CF
_Three)_Four, LiBF (CF_Three)_Three, LiBF_Two(CF_Three)_Two, L
iBF_Three(CF_Three), LiB (C_TwoF_Five)_Four, LiBF (C_Two
F_Five) _Three, LiBF_Two(C_TwoF_Five)_Two, LiBF_Three(C
_TwoF_Five), LiB (CF_ThreeSO_Two)_Four, LiBF (CF_ThreeSO
_Two)_Three, LiBF_Two(CF_ThreeSO_Two)_Two, LiBF_Three(CF_ThreeS
O_Two), LiB (C_TwoF_FiveSO_Two)_Four, LiBF (C_TwoF_FiveS
O_Two)_Three, LiBF_Two(C_TwoF_FiveSO_Two)_Two, LiBF_Three(C_Two
F_FiveSO_Two). These can be used alone
Also, two or more kinds may be used in combination.

The non-aqueous electrolyte further contains LiClO ₄ , Li
BF ₄ , LiPF ₆ , LiAlCl ₄ , LiSbF ₆ , Li
SCN, LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , Li (CF ₃
SO ₂ ) ₂ , LiAsF ₆ , LiB ₁₀ Cl ₁₀ , lithium lower aliphatic carboxylate, LiCl, LiBr, LiI, lithium chloroborane, bis (1,2-benzenediolate (2-)-O, O ′) borane Lithium oxide, bis (2,3-
Lithium naphthalene dioleate (2-)-O, O ') borate, bis (2,2'-biphenyldiolate (2-)
-O, O ') lithium borate, bis (5-fluoro-2)
- oleate-1-benzenesulfonic acid -O, O ') borate lithium borate, bis tetrafluoromethane imide lithium _{((CF 3 SO 2) 2} NLi),
Lithium tetrafluoromethanesulfonate nonafluorobutanesulfonimide (LiN (CF ₃ SO ₂ ) (C ₄
F ₉ SO ₂ )) or imide salts such as lithium bispentafluoroethanesulfonimide ((C ₂ F ₅ SO ₂ ) ₂ NLi).

(Ii) Nonaqueous Solvents Nonaqueous solvents include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate, and derivatives thereof, and chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. Derivatives, γ-butyrolactone, cyclic carboxylic esters such as γ-valerolactone and derivatives thereof, methyl formate, methyl acetate, methyl propionate, aliphatic carboxylic esters such as ethyl propionate and derivatives thereof, dimethoxymethane, diethyl ether, Chain ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, 1,3-dimethoxypropane and derivatives thereof, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3
-Cyclic ethers such as dioxolane and derivatives thereof, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative , Sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, ethyl ether, 1,3-propanesultone, anisole, dimethylsulfoxide, N-methylpyrrolidone and the like. Can be. These may be used alone or in combination of two or more.

The concentration of the solute in the non-aqueous electrolyte is not particularly limited, but is preferably from 0.2 to 2 mol / l, particularly preferably from 0.5 to 1.5 mol / l.

Embodiment 2 In this embodiment, a non-aqueous electrolyte battery including the non-aqueous electrolyte of Embodiment 1 will be described. The non-aqueous electrolyte battery includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.

(I) Negative electrode The negative electrode contains, for example, a negative electrode active material, a conductive agent, a binder and the like.
It is produced by applying an electrode mixture to the surface of the current collector. Negative electrode active material
As for the quality, it absorbs and releases metallic lithium and lithium ions.
Use a material that can be delivered. lithium ion
Pyrolytic coal is a material that can store and release
Raw coke (pitch coke, needle coke, stone
Oil coke, etc.), graphite, glassy carbon, organic high
Fired molecular compound (such as phenolic resin or furan resin)
Carbonized by firing at appropriate temperature), carbon fiber, activated carbon
Carbon materials such as carbon, polyacetylene, polypyrrole, poly
Polymers such as acene, Li_4/3Ti_5/3O_Four, TiS _TwoEtc.
Lithium-containing transition metal oxide or transition metal sulfide,
Al, Pb, Sn, Bi, S alloyed with alkali metal
Since metals such as i and alkali metals are inserted between lattices,
Cubic intermetallic compounds (AlSb, Mg_TwoSi,
NiSi_Two) And lithium nitrogen compounds (Li_3-xM_xN (M:
Transition metal)). These can be used alone
Also, two or more kinds may be used in combination. these
At home, carbon that can store and release alkali metal ions
Materials are mainstream.

The conductive agent for the negative electrode may be any material as long as it is an electron conductive material. For example, conductive fibers such as graphite such as natural graphite (flaky graphite) and artificial graphite, carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black, carbon fiber, and metal fiber. And metal powders such as carbon fluoride, copper and nickel, and organic conductive materials such as polyphenylene derivatives. These may be used alone or in combination of two or more. Among them, artificial graphite, acetylene black and carbon fiber are particularly preferred. The amount of the conductive agent is not particularly limited, but is 1 to 100 parts by weight of the negative electrode active material.
It is preferably 50 parts by weight, particularly preferably 1 to 30 parts by weight. In addition, since the negative electrode active material has electronic conductivity, a conductive agent need not be used.

The binder for the negative electrode may be either a thermoplastic resin or a thermosetting resin. Preferred binders include, for example, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-
Perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer,
Ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexa Fluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethylvinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer And ethylene-methyl methacrylate copolymer. These can be used alone or 2
It can be used as a mixture of more than one species. Of these, styrene-butadiene rubber, polyvinylidene fluoride, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, and ethylene-methyl methacrylate copolymer are particularly preferred.

As the current collector for the negative electrode, any electronic conductor which does not cause a chemical change inside the battery may be used. For example, stainless steel, nickel,
Copper, titanium, carbon, conductive resin, copper or stainless steel having carbon, nickel, titanium, or the like attached or coated thereon, or the like is used. Among these, copper or an alloy containing copper is particularly preferable. Further, the surfaces of these materials can be oxidized and used. In addition, it is desirable to form irregularities on the current collector surface. Examples of the shape of the current collector include a foil, a film, a sheet, a net, a punched material, a lath body, a porous body, a foamed body, and a molded body of a fiber group. The thickness of the current collector is not particularly limited, but is generally 1 to 500 μm.

(Ii) Positive electrode The positive electrode is produced by applying a positive electrode mixture containing, for example, a positive electrode active material, a conductive agent, a binder and the like to the surface of the current collector. As the positive electrode active material, for example, Li _x CoO ₂ , Li _x NiO ₂ , Li _x
MnO ₂ , Li _x Co _y Ni _1-y O ₂ , Li _x Co _y M _1-y O _z ,
_{Li x Ni 1-y M y} O z, Li x Mn 2 O 4, Li x Mn 2-y M y O
₄ (where M = Na, Mg, Sc, Y, Mn, Fe, Co,
At least one selected from the group consisting of Ni, Cu, Zn, Al, Cr, Pb, Sb and B, 0 ≦ x ≦ 1.2, 0 ≦
y ≦ 0.9, 2.0 ≦ z ≦ 2.3). The x value increases or decreases due to charging and discharging of the battery. It is also possible to use a positive electrode active material such as a transition metal chalcogenide, a vanadium oxide or a niobium oxide which may contain lithium, an organic conductive material made of a conjugated polymer, and a Chevrel phase compound. It is also possible to use a mixture of a plurality of different positive electrode active materials. The average particle size of the positive electrode active material particles is not particularly limited, but is preferably 1 to 30 μm.

The conductive agent for the positive electrode may be any electronic conductive material which does not cause a chemical change at the charge / discharge potential of the positive electrode active material used. For example, conductive materials such as graphite such as natural graphite (flaky graphite), artificial graphite and the like, carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black, carbon fiber and metal fiber. Conductive fibers, metal powders such as carbon fluoride, copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and organic conductive materials such as polyphenylene derivatives. Is mentioned. These may be used alone or in combination of two or more. Among these, artificial graphite, acetylene black and nickel powder are particularly preferred. The amount of the conductive agent is not particularly limited, but is preferably 1 to 50 parts by weight, and particularly preferably 1 to 30 parts by weight, per 100 parts by weight of the positive electrode active material. However, in the case of carbon black or graphite, the amount is particularly preferably 2 to 15 parts by weight based on 100 parts by weight of the positive electrode active material.

The binder for the positive electrode may be either a thermoplastic resin or a thermosetting resin. Preferred binders in the present invention are, for example, polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene- Perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, vinylidene fluoride- Pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene Tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene- Methyl methacrylate copolymer can be mentioned. Among these, polyvinylidene fluoride and polytetrafluoroethylene are particularly preferred.

As the current collector for the positive electrode, any electronic conductor which does not cause a chemical change in the charge / discharge potential of the positive electrode active material to be used may be used. For example, as a material, stainless steel, aluminum, titanium, carbon, conductive resin, or a material obtained by attaching or coating carbon, titanium, or the like to the surface of aluminum or stainless steel is used. In particular, aluminum or an alloy containing aluminum is preferable. The surface of these materials can be oxidized and used. In addition, it is desirable to form irregularities on the current collector surface. The shape of the current collector is
A foil, a film, a sheet, a net, a punched material, a lath body, a porous body, a foamed body, a fiber group, a molded article of a nonwoven fabric, and the like are used. The thickness of the current collector is not particularly limited, but is generally 1 to 500 μm.

The positive electrode mixture or the negative electrode mixture may contain various additives in addition to the conductive agent and the binder.

As the separator, an insulating microporous thin film having a high ion permeability and a predetermined mechanical strength is used. Further, it is preferable to have a function of closing a hole at a certain temperature or higher to increase resistance. From the viewpoints of organic solvent resistance and hydrophobicity, a sheet, nonwoven fabric or woven fabric made of an olefin polymer such as polypropylene or polyethylene or glass fiber is used. The pore diameter of the pores of the separator is desirably in a range in which the positive electrode active material, the negative electrode active material, the binder, and the conductive agent detached from the electrode do not pass, for example, 0.01 to 1 μm. The thickness of the separator is generally from 10 to 300 μm. The porosity is generally desirably 30 to 80%.

A gel holding a non-aqueous electrolyte is included in a positive electrode mixture or a negative electrode mixture, or a porous separator made of a polymer material holding a non-aqueous electrolyte is integrated with a positive electrode or a negative electrode. Alternatively, a battery can be formed. The polymer material is not particularly limited as long as it can hold a non-aqueous electrolyte, and a copolymer of vinylidene fluoride and hexafluoropropylene is particularly preferable.

The shape of the non-aqueous battery includes a coin shape, a button shape, a sheet shape, a stacked shape, a cylindrical shape, a flat shape, a square shape, and a large size used for electric vehicles and the like. The non-aqueous electrolyte battery of the present invention can be used for personal digital assistants, portable electronic devices, small household power storage devices, motorcycles, electric vehicles, hybrid electric vehicles, and the like, but is not particularly limited thereto. Absent.

Embodiment 3 In this embodiment, a non-aqueous electrolyte suitable for an electrolytic capacitor will be described. The non-aqueous electrolyte of the present embodiment can be obtained by dissolving the following solutes in the following non-aqueous solvent.

(I) Solute The non-aqueous electrolyte of the present embodiment has a general formula: M ″ BR ₁ R ₂ R
₃ R ₄ (M ″ is an ammonium group, R _{1 to} R ₄ are electron withdrawing groups, and R _{1 to} R ₄ are not simultaneously a fluorine atom)
Contains the solute represented by

The electron-withdrawing group is represented by the general formula: C _n F
_{2n +} 1 (n is an integer of 1 to 4) (is an integer of 1 to 4 m) is a group represented by the preferred or _{C m F 2m + 1 SO 2} . In addition, since the anion having a group represented by the general formula: C _n F _{2n + 1} is smaller than the anion having a group represented by the general formula: C _m F _{2m + 1} SO ₂ , The ionic conductivity of the electrolyte is higher. Therefore, the general formula: C _n F _{2n + 1} (n is 1 to
(An integer of 4) is more preferred. The number of electron withdrawing groups other than fluorine may be one or more, but is preferably two or three in view of easy synthesis. For example,
General _{formula: M "B (C n F} 2n + 1) 2 solute and represented by the general formula _{F 2: M" B (C} n F 2n + 1) solute is preferably represented by the ₃ F. n and m may be integers of 1 to 4, but if n and m are too small, the electron-withdrawing effect of the electron-withdrawing group decreases,
If it is too large, the anion diameter becomes large, so that it is particularly preferably 2.

The ammonium group is represented by the general formula: NR ₅ R ₆ R ₇
Those represented by R ₈ (R _{5 to} R ₈ are each independently a hydrogen atom, an alkyl group, an alkenyl group or an aryl group) are preferred. Among them, all of R _{5 to} R ₈ are preferably an alkyl group, and particularly preferably an alkyl group having 1 to 4 carbon atoms. For example, the general formula: N (C _k H
An ammonium group represented by _{2k + 1} ) ₄ (k is an integer of 1 to 4) is preferable.

As a specific example of the solute, (CH_Three)_FourN
B (CF_Three)_Four, (CH_Three)_FourNBF (CF_Three)_Three, (C
H_Three)_FourNBF_Two(CF_Three)_Two, (CH_Three)_FourNBF_Three(C
F_Three), (CH_Three)_FourNB (C_TwoF_Five)_Four, (CH_Three)_FourNBF
(C_TwoF_Five)_Three, (CH_Three)_FourNBF_Two(C_TwoF_Five)_Two, (C
H_Three)_FourNBF_Three(C_TwoF_Five), (C_TwoH_Five)_FourNB (C
F_Three)_Four, (C_TwoH_Five)_FourNBF (CF_Three)_Three, (C_TwoH_Five)_FourN
BF_Two(CF_Three)_Two, (C_TwoH_Five)_FourNBF_Three(CF_Three), (C
_TwoH_Five)_FourNB (C_TwoF_Five)_Four, (C_TwoH_Five)_FourNBF (C
_TwoF_Five)_Three, (C_TwoH_Five)_FourNBF_Two(C_TwoF_Five)_Two, (C_TwoH_Five)
_FourNBF_Three(C_TwoF_Five), ((CH_Three)_ThreeC)_FourNB (CF_Three)
_Four, ((CH_Three)_ThreeC)_FourNBF (CF_Three)_Three, ((CH_Three)_Three
C) _FourNBF_Two(CF_Three)_Two, ((CH_Three)_ThreeC)_FourNBF
_Three(CF_Three), ((CH_Three)_ThreeC)_FourNB (C_TwoF_Five)_Four,
((CH_Three)_ThreeC)_FourNBF (C_TwoF_Five)_Three((CH_Three)_ThreeC)
_FourNBF_Two(C_TwoF_Five)_Two, ((CH_Three)_ThreeC)_FourNBF_Three(C_Two
F_Five), (CH_Three)_FourNB (CF _ThreeSO_Two)_Four, (CH_Three)_FourN
BF (CF_ThreeSO_Two)_Three, (CH_Three)_FourNBF_Two(CF_ThreeS
O _Two)_Two, (CH_Three)_FourNBF_Three(CF_ThreeSO_Two), (CH_Three)
_FourNB (C_TwoF_FiveSO_Two)_Four, (CH_Three)_FourNBF (C_TwoF_FiveS
O_Two)_Three, (CH_Three)_FourNBF_Two(C_TwoF_FiveSO_Two)_Two, (C
H_Three)_FourNBF_Three(C_TwoF_FiveSO_Two), (C_TwoH_Five)_FourNB (C
F_ThreeSO_Two)_Four, (C_TwoH_Five)_FourNBF (CF_ThreeSO_Two)_Three,
(C_TwoH_Five)_FourNBF_Two(CF_ThreeSO_Two)_Two, (C_TwoH_Five)_FourNB
F_Three(CF_ThreeSO_Two), (C_TwoH_Five)_FourNB (C_TwoF_FiveS
O_Two)_Four, (C_TwoH_Five)_FourNBF (C_TwoF_FiveSO_Two)_Three, (C_TwoH
_Five)_FourNBF_Two(C_TwoF_FiveSO_Two)_Two, (C_TwoH_Five)_FourNBF
_Three(C_TwoF_FiveSO_Two), ((CH_Three)_ThreeC)_FourNB (CF_ThreeSO
_Two)_Four, ((CH_Three)_ThreeC)_FourNBF (CF_ThreeSO_Two)_Three,
((CH_Three)_ThreeC)_FourNBF_Two(CF_ThreeSO_Two)_Two, ((C
H_Three)_ThreeC)_FourNBF_Three(CF_ThreeSO_Two), ((CH_Three)_ThreeC)
_FourNB (C_TwoF_FiveSO_Two) _Four, ((CH_Three)_ThreeC)_FourNBF (C
_TwoF_FiveSO_Two)_Three, ((CH_Three)_ThreeC)_FourNBF_Two(C _TwoF_FiveSO
_Two)_Two, ((CH_Three)_ThreeC)_FourNBF_Three(C_TwoF_FiveSO_Two)
can give. These may be used alone or in combination of two or more.
They may be used in combination. Use of such a solute
And can be used over a wide temperature range and has low dielectric loss
To obtain a non-aqueous electrolyte electrolytic capacitor with excellent charge / discharge characteristics
Can be

The non-aqueous electrolyte further contains MCIO ₄ , MBF
₄ , MPF ₆ , MAlCl ₄ , MSbF ₆ , MSCN, MCF
₃ SO ₃ , MCF ₃ CO ₂ , M (CF ₃ SO ₂ ) ₂ , MAsF
₆ , MB ₁₀ Cl ₁₀ , quaternary ammonium salt of lower aliphatic carboxylic acid, MCl, MBr, MI, quaternary ammonium salt of chloroborane, lithium bistetrafluoromethanesulfonimide ((CF ₃ SO ₂ ) ₂ NLi), Lithium tetrafluoromethanesulfonic acid nonafluorobutanesulfonic acid imide (LiN (CF ₃ SO ₂ ) (C ₄ F ₉ S)
O ₂ )) and imide salts such as lithium bispentafluoroethanesulfonimide ((C ₂ F ₅ SO ₂ ) ₂ NLi).

(Ii) Nonaqueous Solvents Nonaqueous solvents include protic organic polar solvents such as ethanol, propanol, butanol, pentanol, and the like.
Monohydric alcohols such as hexanol, cyclobutanol, cyclopentanol, and benzyl alcohol; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, methyl cellosolve, ethyl cellosolve, methoxypropylene glycol, and dimethoxypropanol; and oxyalcohol compounds. . Examples of aprotic organic polar solvents include amide compounds such as N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, and γ-butyrolactone and γ-valerolactone. Cyclic carboxylate, ethylene carbonate, propylene carbonate, butylene carbonate, cyclic carbonate such as vinylene carbonate, dimethyl sulfoxide, 1,3-dioxolan, formamide, acetamide, dimethylformamide, dioxolan, acetonitrile, propyl nitrile, nitromethane, ethyl monoglyme, Triester phosphate, trimethoxymethane, dioxolane derivative, sulfolane, methylsulfolane, 1,3-dimethyl-2-
Examples thereof include imidazolidinone, 3-methyl-2-oxazolidinone, ethyl ether, 1,3-propanesultone, anisole, dimethylsulfoxide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.

The amount of the solute with respect to the non-aqueous solvent is not particularly limited.
Parts by weight are preferred.

Examples of the non-aqueous electrolyte include boric acid, complex compounds of boric acid and polysaccharides (such as mannitol and sorbitol), and boric acid and polyhydric alcohols (such as ethylene glycol and glycerin).
With the addition of a complex compound, a surfactant, colloidal silica, and the like, the withstand voltage can be improved.
Furthermore, for the purpose of reducing leakage current and absorbing hydrogen gas, aromatic nitro compounds such as p-nitrobenzoic acid and p-nitrophenol, and phosphorous such as phosphoric acid, phosphorous acid, polyphosphoric acid, and acid phosphate ester compounds. A contained compound, an oxycarboxylic acid compound, or the like may be added to the electrolytic solution.

Embodiment 4 In this embodiment, a non-aqueous electrolyte electrolytic capacitor including the non-aqueous electrolyte of Embodiment 3 will be described. Non-aqueous electrolyte electrolytic capacitor is an anode foil having a dielectric layer, a cathode foil,
It comprises a separator and a non-aqueous electrolyte interposed between the anode foil and the cathode foil. A capacitor element is formed by winding the laminated anode foil and cathode foil with a separator interposed therebetween, impregnating the capacitor element with a non-aqueous electrolyte, and storing the capacitor element containing the non-aqueous electrolyte in an outer case, When the case is sealed with a sealing body, an electrolytic capacitor is obtained.

As the anode foil, for example, an aluminum foil is used. In order to form a dielectric layer on the anode foil, for example, a voltage of 300 to 600 V may be applied in boric acid after performing an etching treatment for increasing the surface area of the anode foil. Through such steps, an oxide film serving as a dielectric is formed on the anode foil. As the cathode foil, for example, an aluminum foil or the like is used. As the separator, for example, a nonwoven fabric or a woven fabric made of kraft pulp fiber is used.

[0047]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. However, the present invention is not limited to the following examples.

Example 1 Electrolyte solutions AR were prepared by dissolving the solutes shown in Table 1 at a concentration of 1.0 mol / liter in a mixed solvent of ethylene carbonate and ethyl methyl carbonate (volume ratio 1: 3). did. Table 1 shows the results of the ionic conductivity of each electrolytic solution measured at 20 ° C. using a bridge-type conductivity meter. In addition,
For comparison, the same concentration of electrolyte solution using LiBF ₄ and LiPF ₆ was also measured.

[0049]

[Table 1]

The results of this example show that the use of a borate in which at least one of the fluorine atoms of the BF ₄ anion moiety is substituted with a perfluoroalkyl group or a perfluoroalkyl sulfonic acid group is more effective than the case where LiBF ₄ is used. It was found that the ionic conductivity of the non-aqueous electrolyte increased.

Example 2 Electrolyte A prepared in Example 1
-R potential windows were measured. L for reference and counter electrodes
A platinum plate (1 cm ^{2 in} surface area) was used for the i foil and the sample electrode.
Potential scanning was performed at a rate of 10 mV / sec from the natural potential toward the anode, and the potential at which a current of 100 μA / cm ² flowed was defined as the oxidative decomposition potential. On the other hand, in the same cell, potential scanning was performed from the natural potential in the reduction direction at a speed of 10 mV / sec, and 100
The potential at which a current of μA / cm ² passed was defined as the reductive decomposition potential. Table 2 shows the results.

[0052]

[Table 2]

According to the results of this example, the potential window of a borate in which at least one of the fluorine atoms of the BF ₄ anion was substituted by a perfluoroalkyl group or a perfluoroalkyl sulfonic acid group was equal to or higher than that of LiBF _4. From the above, it can be seen that these borates are suitable for non-aqueous electrolyte batteries such as lithium ion batteries.

Example 3 Electrolyte A prepared in Example 1
To R, cylindrical lithium ion batteries A to R were manufactured, respectively. FIG. 1 shows a longitudinal sectional view of the manufactured battery.
The positive electrode plate 1 is prepared by mixing 85 parts by weight of lithium cobalt oxide powder, 10 parts by weight of carbon powder as a conductive agent, and 5 parts by weight of polyvinylidene fluoride as a binder, and dispersing the mixture in dehydrated N-methylpyrrolidinone to prepare a slurry. Then, it was applied on a positive electrode current collector of aluminum foil, dried, and then rolled.

The negative electrode plate 2 was prepared by mixing 75 parts by weight of artificial graphite powder, 20 parts by weight of carbon powder as a conductive agent and 5 parts by weight of polyvinylidene fluoride as a binder, and dispersing the mixture in dehydrated N-methylpyrrolidinone. Was prepared, applied on a copper foil negative electrode current collector, dried, and then rolled.

A laminate of the positive electrode plate 1, the negative electrode plate 2, and the polyethylene separator 3 interposed therebetween is spirally wound a plurality of times to obtain an electrode plate group, which is placed in a battery case 8 made of stainless steel. Stowed. Then, a positive electrode lead 4 made of aluminum was pulled out from the positive electrode plate 1 and connected to the sealing plate 9. A negative electrode lead 5 made of nickel was pulled out from the negative electrode plate 2 and connected to the bottom of the battery case 8. 6
And 7 are insulating rings provided on the upper and lower portions of the electrode plate group, respectively. After the electrolytes A to R were injected into the battery case, finally, the battery case 8 was sealed with the sealing plate 9 to obtain a battery.

The obtained battery had a diameter of 18 mm and a height of 65 m.
m, the nominal capacity is 1800 mAh. This battery was 4.2
Batteries charged at a constant voltage of 360 mA and 3600
Table 3 shows the discharge capacities obtained by discharging the batteries at a discharge current of mA. After the discharge at 360 mA, 4.
Table 3 also shows the discharge capacity when the battery stored at 60 ° C. for one month after charging at a constant voltage of 2 V was discharged at 3600 mA.

[0058]

[Table 3]

As shown in Table 3, according to the present invention, a highly reliable lithium ion battery having excellent high-rate discharge characteristics and excellent high-temperature storage characteristics can be obtained.

Example 4 A non-aqueous electrolyte solution 1 was prepared by dissolving the solutes shown in Table 4 at a concentration of 1.0 mol / liter in a mixed solvent of ethylene carbonate and ethyl methyl carbonate (volume ratio 1: 3).
27 was prepared. 20 ° C using a bridge type conductivity meter
Table 4 shows the results of the ionic conductivity of each electrolytic solution measured in the above. For comparison, (CH ₃ ) ₄ NBF ₄ , (C
₂ H ₅₎ were also subjected to measurement for ₄ NBF ₄ and ((CH _{3) 3} C) the concentration of the electrolyte solution with ₄ NBF _4.

[0061]

[Table 4]

From the results of this example, it was found that when a borate in which at least one of the fluorine atoms of the BF ₄ anion moiety was substituted with a perfluoroalkyl group was used, a borate salt in which fluorine was not substituted with a perfluoroalkyl group was used. It can be seen that the ionic conductivity of the non-aqueous electrolyte is higher than that in the case where the electrolyte is used.

EXAMPLE 5 The potential windows of the non-aqueous electrolyte solutions 1 to 27 prepared in Example 4 were measured in the same manner as in Example 2.
Table 5 shows the results.

[0064]

[Table 5]

According to the results of this example, the potential window of the borate in which at least one of the fluorines of the BF ₄ anion was substituted with a perfluoroalkyl group was the same as that in which the fluorine was not substituted with the perfluoroalkyl group. Because they are equal or better, these borates are suitable for electrolytic capacitors.

Example 6 Electrolyte solution 1 prepared in Example 4
To 27 were respectively prepared as driving electrolytes in the following manner. First, an aluminum foil having a thickness of 100 μm was prepared, and the surface thereof was subjected to electrolytic etching. Then, immerse the aluminum foil in boric acid,
A voltage of 500 V was applied and left for 15 minutes. As a result, a film of aluminum oxide serving as a dielectric layer was formed on the surface of the aluminum foil. Next, a capacitor element was formed by winding an anode foil having a dielectric layer laminated with a separator made of kraft pulp fiber and an aluminum foil cathode foil. This capacitor element was impregnated with a non-aqueous electrolyte, the capacitor element containing the non-aqueous electrolyte was housed in an aluminum outer case, and the case was sealed with a sealing body to obtain an electrolytic capacitor.

The frequency characteristics of the obtained electrolytic capacitor were evaluated. First, based on a circuit as shown in FIG. 2, a DC power supply 11, an electrolytic capacitor (C) 12, a resistor (R) 1
3. A charging / discharging device including the relay switch 14 and the voltmeter 15 was assembled. The negative electrode of the DC power supply, the cathode foil side of the electrolytic capacitor, and the resistor were grounded. Then, a pulse voltage was applied to the electrolytic capacitor by switching the relay switch at a duty ratio of 0.5 (50%) at 60 Hz (cycles / second). However, the upper limit of the applied voltage was set to 3.0V. FIG. 3 shows a change in the difference between the potential of the cathode foil and the potential of the anode foil in the electrolytic capacitor. Here, in each charging section, the voltage value of the electrolytic capacitor at 1/240 second after the start of charging was recorded. The measurement was performed for 10 seconds, and the average value of the voltage values recorded during the measurement is shown in Table 6. It can be said that the faster the potential of the anode foil increases due to charging, the better the charge / discharge characteristics.

[0068]

[Table 6]

From the results of this example, it can be seen that a capacitor using a borate in which at least one of the fluorine atoms of the BF ₄ anion moiety is substituted with a perfluoroalkyl group has a high frequency characteristic due to an increase in the ionic conductivity of the non-aqueous electrolyte. It can be seen that is improved.

When the same measurement was carried out while increasing the charging voltage, the electrolytic capacitor using a borate in which at least one of the fluorine atoms of the BF ₄ anion was substituted with a perfluoroalkyl group was found to have a good charge / discharge characteristic. Almost no deterioration occurred. It is considered that the deterioration of the charge / discharge characteristics is caused by decomposition of anions having low oxidation resistance. From these results, it was found that by using a borate in which at least one of the fluorine atoms of the BF ₄ anion was substituted with a perfluoroalkyl group, the withstand voltage of the electrolytic capacitor could be improved.

[0071]

According to the present invention, since a solute which has the same thermal stability as lithium tetrafluoroborate, a high electronegativity of the anion part and is easily ion-dissociated is used, A new non-aqueous electrochemical device with improved ionic conductivity of the electrolyte and excellent high-rate charge / discharge characteristics can be obtained.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of an example of a cylindrical nonaqueous electrolyte battery of the present invention.

FIG. 2 is a diagram showing a circuit of a charging / discharging device used for examining frequency characteristics of an electrolytic capacitor.

FIG. 3 is a diagram showing a change in a potential difference between both sides of an electrolytic capacitor to which a pulse voltage is applied.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode plate 2 Negative electrode plate 3 Separator 4 Positive electrode lead 5 Negative electrode lead 6, 7 Insulation ring 8 Battery case 9 Sealing plate 11 DC power supply 12 Electrolytic capacitor 13 Resistor 14 Relay switch 15 Voltmeter

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuya Iwamoto 1006 Kazuma Kadoma, Kazuma City, Osaka Prefecture F-term within Matsushita Electric Industrial Co., Ltd. AL04 AL06 AL07 AL08 AL11 AL12 AL16 AL18 AM02 AM03 AM04 AM05 AM07 HJ02

Claims (8)

[Claims] 1. A non-aqueous solvent and a general formula: MBR ₁ R ₂ R ₃
R ₄ (M is an alkali metal or ammonium group, R _{1 to} R
₄ is an electron-withdrawing group, and R _{1 to} R ₄ are not simultaneously a fluorine atom). 2. The method according to claim 1, wherein at least one of the electron-withdrawing groups has a general formula: C _n F _{2n + 1} (n is an integer of 1 to 4) or C _m F _{2m + 1.}
Nonaqueous electrolytic solution according to claim 1, wherein represented by SO ₂ (m is an integer from 1 to 4). 3. The method according to claim 1, wherein the solute is LiB (CF ₃ ) ₄ , LiB
F (CF ₃ ) ₃ , LiBF ₂ (CF ₃ ) ₂ , LiBF ₃ (CF
₃ ), LiB (C ₂ F ₅ ) ₄ , LiBF (C ₂ F ₅ ) ₃ , Li
BF ₂ (C ₂ F ₅ ) ₂ , LiBF ₃ (C ₂ F ₅ ), LiB (C
F ₃ SO ₂ ) ₄ , LiBF (CF ₃ SO ₂ ) ₃ , LiBF
₂ (CF ₃ SO ₂ ) ₂ , LiBF ₃ (CF ₃ SO ₂ ), LiB
(C ₂ F ₅ SO ₂ ) ₄ , LiBF (C ₂ F ₅ SO ₂ ) ₃ , LiB
F ₂ (C ₂ F ₅ SO ₂ ) ₂ and LiBF ₃ (C ₂ F ₅ SO ₂ )
2. The non-aqueous electrolyte according to claim 1, comprising at least one member selected from the group consisting of: 4. The method according to claim 1, wherein the ammonium group has the general formula: NR ₅
(In each of R ₅ to R ₈ independently represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group) R ₆ R ₇ R ₈ nonaqueous electrolytic solution according to claim 1, wherein represented by. 5. The method according to claim 1, wherein the solute is (CH)_Three)_FourNB (C
F_Three)_Four, (CH_Three)_FourNBF (CF_Three)_Three, (CH_Three)_FourNB
F_Two(CF_Three)_Two, (CH_Three)_FourNBF_Three(CF_Three), (C
H_Three)_FourNB (C_TwoF_Five)_Four, (CH_Three)_FourNBF (C
_TwoF_Five)_Three, (CH_Three)_FourNBF_Two(C_TwoF_Five)_Two, (CH_Three)_Four
NBF_Three(C_TwoF_Five), (C_TwoH_Five)_FourNB (CF_Three)_Four, (C
_TwoH_Five)_FourNBF (CF_Three)_Three, (C_TwoH_Five)_FourNBF_Two(C
F_Three)_Two, (C_TwoH_Five)_FourNBF_Three(CF_Three), (C_TwoH_Five)_FourN
B (C_TwoF_Five)_Four, (C_TwoH_Five)_FourNBF (C_TwoF_Five)_Three, (C_Two
H_Five)_FourNBF_Two(C_TwoF_Five)_Two, (C_TwoH_Five)_FourNBF_Three(C_Two
F_Five), ((CH_Three) _ThreeC)_FourNB (CF_Three)_Four, ((C
H_Three)_ThreeC)_FourNBF (CF_Three)_Three, ((CH_Three)_ThreeC)_FourNB
F_Two(CF_Three)_Two, ((CH_Three)_ThreeC)_FourNBF_Three(CF_Three),
((CH_Three)_ThreeC)_FourNB (C_TwoF_Five)_Four, ((CH_Three)_ThreeC)
_FourNBF (C_TwoF_Five)_Three, ((CH_Three)_ThreeC) _FourNBF_Two(C_Two
F_Five)_Two, ((CH_Three)_ThreeC)_FourNBF_Three(C_TwoF_Five), (CH
_Three)_FourNB (CF_ThreeSO_Two)_Four, (CH_Three)_FourNBF (CF_ThreeS
O_Two)_Three, (CH_Three)_FourNBF_Two(CF_ThreeSO_Two)_Two, (C
H_Three)_FourNBF_Three(CF_ThreeSO_Two), (CH_Three)_FourNB (C_TwoF
_FiveSO _Two)_Four, (CH_Three)_FourNBF (C_TwoF_FiveSO_Two)_Three, (C
H_Three)_FourNBF_Two(C_TwoF_FiveSO_Two) _Two, (CH_Three)_FourNBF
_Three(C_TwoF_FiveSO_Two), (C_TwoH_Five)_FourNB (CF_ThreeSO_Two)_Four,
(C_TwoH_Five)_FourNBF (CF_ThreeSO_Two)_Three, (C_TwoH_Five)_FourNB
F_Two(CF_ThreeSO_Two)_Two, (C_TwoH_Five)_FourNBF_Three(CF_ThreeS
O_Two), (C_TwoH_Five)_FourNB (C_TwoF_FiveSO_Two)_Four, (C_TwoH_Five)
_FourNBF (C_TwoF_FiveSO_Two)_Three, (C_TwoH_Five)_FourNBF_Two(C_TwoF
_FiveSO_Two)_Two, (C_TwoH_Five)_FourNBF_Three(C_TwoF_FiveSO_Two),
((CH_Three)_ThreeC)_FourNB (CF_ThreeSO_Two)_Four, ((CH_Three)_Three
C)_FourNBF (CF_ThreeSO_Two)_Three, ((CH_Three)_ThreeC)_FourNB
F_Two(CF_ThreeSO_Two)_Two, ((CH_Three)_ThreeC)_FourNBF_Three(CF
_ThreeSO_Two), ((CH_Three)_ThreeC)_FourNB (C_TwoF_FiveSO_Two)_Four,
((CH_Three)_ThreeC)_FourNBF (C_TwoF_FiveSO_Two)_Three, ((C
H_Three)_ThreeC)_FourNBF _Two(C_TwoF_FiveSO_Two)_TwoAnd ((C
H_Three)_ThreeC)_FourNBF_Three(C_TwoF_FiveSO_Two)
2. The non-aqueous electrolysis according to claim 1, comprising at least one of the following:
liquid. 6. A non-aqueous electrochemical device comprising the non-aqueous electrolyte according to claim 1. 7. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and the non-aqueous electrolyte according to claim 3. 8. A non-aqueous electrolyte electrolytic capacitor comprising an anode foil having a dielectric layer, a cathode foil, a separator interposed between the anode foil and the cathode foil, and a non-aqueous electrolyte according to claim 5.