JP3463926B2 - Electrolyte for electrochemical devices - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolyte having improved safety used in an electrochemical device such as a lithium cell, a lithium ion cell, and an electric double layer capacitor, etc. SOLUTION: The electrolyte for an electrochemical device uses an organic solvent including fluorine and also consists of at least one of combinations being a chemical structural formula indicated in a general formula 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic solution having improved safety which is used for electrochemical devices such as lithium batteries, lithium ion batteries and electric double layer capacitors.

[0002]

2. Description of the Related Art With the development of portable devices in recent years, the development of electrochemical devices utilizing electrochemical phenomena such as batteries and capacitors as the power source has been actively pursued. Became. Further, examples of the electrochemical device other than the power source include an electrochromic display (ECD) in which a color change is caused by an electrochemical reaction.

These electrochemical devices are generally composed of a pair of electrodes and an electrolytic solution filling the space between them. This electrolyte contains a solvent and a cation (A ⁺ ) called an electrolyte.
A solution in which a salt (AB) composed of an anion (B ⁻ ) and is dissolved is used. As this solvent, organic solvents such as propylene carbonate, dimethyl carbonate, and dimethoxyethane are often used, but these have a low flash point and may cause ignition, so recently, due to safety problems against fire, etc. However, the use of such a flammable electrolyte has become unfavorable.

On the other hand, a fluorine-containing organic solvent having a fluorine atom in its molecule, such as CFC, is nonflammable or flame retardant, so that it is an excellent solvent in terms of safety, but generally has a low dielectric constant. Therefore, salts used as electrolytes (for example, LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN
Since it has no ability to dissolve (CF ₃ SO ₂ ) ₂ , LiSbF _6, LiClO _4, etc.), it has been difficult to use as an electrolytic solution.

[0005]

[Means for Solving the Problems] The present inventors
As a result of intensive studies in view of the problems of the prior art, a flame-retardant electrolytic solution having excellent device performance was found by combining an electrolyte having a novel chemical structural characteristic and a fluorine-containing organic solvent, and arrived at the present invention. It was done.

That is, according to the present invention, in an electrochemical device using an organic electrolytic solution, a fluorine-containing organic solvent is used as a main solvent of the organic electrolytic solution, and at least one ligand of the anion portion of the electrolyte is C—F. An electrolyte for an electrochemical device consisting of an art complex having a bond,
The ate complex comprises at least one compound having a chemical structural formula represented by the general formula (1),

[0007]

[Chemical 2]

In this formula, A ^{q +} is a metal ion or an onium ion, M is a transition metal, III or IV of the periodic table.
Group or V group element, a is 0 to 3, c is 0 to 3 (a
Or at least one of c is not 0, a + b = 3,
c + d = 3), p is r / q, q is 1 to 3, r is 1
To 3, m is, 1 to 8, n is, 0 to 8, X ¹ is, O, S,
NR ⁵ , or NR ⁵ R ⁶ , R ¹ and R ² are each independently H, halogen, C _{1 to} C ₁₀ alkyl, or C ₁ to
C ₁₀ alkyl halide, R ³ is C _{1 to} C ₁₀ alkyl, C _{1 to} C ₁₀ alkyl halide, C _{4 to} C ₂₀ aryl, or C _{4 to} C ₂₀ aryl halide, R ⁴ Is
Halogen, C _{1 to} C ₁₀ alkyl, C _{1 to} C ₁₀ alkyl halide, C _{4 to} C ₂₀ aryl, C _{4 to} C ₂₀ aryl halide, or X ² R ⁷ , X ² is O, S, NR ⁵ ,
Or NR ⁵ R ⁶ , R ⁵ , and R ⁶ are H or C ₁ -C ₁₀ alkyl, R ⁷ is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkyl halide, C ₄ -C ₂₀ aryls, or C ₄
To C ₂₀ aryl halides, and further, among the carbonates, esters, ethers, lactones, nitriles, amides, or sulfones whose main solvent is a fluorine-containing organic solvent containing fluorine. And an organic compound containing a hetero element having a dielectric constant of 1 or more as an electrolyte dissociation promoter, and an electrolytic solution for an electrochemical device.

The alkyl, alkyl halide, aryl and aryl halide of the electrolyte used in the present invention include those having other functional groups such as branching, hydroxyl group and ether bond.

The present invention will be described in more detail below. The present invention comprises a combination of an electrolyte having a novel chemical structural characteristic and a fluorine-containing organic solvent, and the ate complex used as the electrolyte here means that a compound having Lewis acidity is a carbanion or an alkoxy compound. It is a general term for anionic complexes formed by complexing with anionic species having Lewis basicity such as anions. At least one of the ligands of the ate complex used in the present invention is C
By having the —F bond, the solubility in the fluorine-containing organic solvent is increased. Next, specific examples of the compound represented by the general formula (1) used as the electrolyte are shown below.

[0011]

[Chemical 3]

Although lithium ions are mentioned as A ^{q +} here, as cations other than lithium ions, for example, sodium ions, potassium ions, magnesium ions, calcium ions, barium ions, cesium ions, silver ions, zinc ions, copper. Ion, cobalt ion, iron ion, nickel ion, manganese ion, titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion, yttrium ion, lanthanoid ion, actinide ion, tetrabutylammonium ion, tetraethylammonium ion, tetramethylammonium ion Ion, triethylmethylammonium ion, triethylammonium ion, pyridinium ion, imidazolium ion, proton, tetraethylphosphoni Ion, tetramethyl phosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion, etc. is also used.

Considering applications such as electrochemical devices, lithium ions, tetraalkylammonium ions and protons are preferred. Valence number of cation of A ^{q +} q
Is preferably 1 to 3. When it is larger than 3, the crystal lattice energy becomes large, and there arises a problem that it becomes difficult to dissolve in a solvent. Therefore, 1 is more preferable when solubility is required. Similarly, the valence r of the anion
Similarly, 1 to 3 is preferable, and 1 is particularly preferable.
The constant p representing the ratio of the cation and the anion is inevitably determined by the ratio r / q of the valences of the two.

The electrolyte used in the present invention has an ionic metal complex structure, and the center M thereof is selected from a transition metal, a group III, IV or V element of the periodic table. Preferably, Al, B, V, Ti, Si, Zr, G
e, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi,
Either P, As, Sc, Hf, or Sb,
More preferably, it is Al, B, or P. It is possible to use various elements as the central M, but A
l, B, V, Ti, Si, Zr, Ge, Sn, Cu,
Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc,
In the case of Hf or Sb, the synthesis is relatively easy, and in the case of Al, B, or P, in addition to the ease of synthesis,
It has low toxicity, stability, cost, and excellent properties.

Next, the ligand portion which is a feature of the electrolyte (ionic metal complex) used in the present invention will be described. Hereafter, the organic or inorganic part bonded to M is referred to as a ligand. X ¹ in the general formula (1) is O,
S, NR ^5, or a NR ⁵ R ^6, bonded to M via these heteroatoms. Here, it is not impossible to bond with a compound other than O, S, and N, but it becomes very complicated in terms of synthesis.

The constant a in this ligand is 0 to 3, and c is
0 to 3 (at least one of a and c is not 0, and a
+ B = 3, c + d = 3), and R ¹ and R ² are each independently H, halogen, C ₁ -C ₁₀ alkyl, or C ₁ -C ₁₀ halogenated alkyl, R ³ is C ₁ To C ₁₀ alkyl, C _{1 to} C ₁₀ alkyl halide, C _{4 to} C ₂₀
Or an aryl halide of C _{4 to} C ₂₀ ,
R ⁴ is halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkyl halide, C ₄ -C ₂₀ aryl, C ₄ -C ₂₀
Aryl halide of, or X ² R ⁷ , X ² is O,
S, NR ⁵ , or NR ⁵ R ⁶ , R ⁵ , R ⁶ is H or C ₁ -C ₁₀ alkyl, R ⁷ is C ₁ -C ₁₀ alkyl,
C ₁ -C ₁₀ alkyl halide, C ₄ -C ₂₀ aryl, or C ₄ -C ₂₀ aryl halide are respectively represented, and preferably at least one of R ¹ and R ² is a fluorinated alkyl or fluorine. Yes, and more preferably R
^{Both 1} and R ² are fluorine. R ¹ , R ² , R ³ and R ⁴
The presence of electron-withdrawing fluorine or fluorinated alkyl disperses the negative charge of M at the center and increases the electrical stability of the anion, which greatly facilitates ion dissociation.
Solubility in solvents, ionic conductivity, catalytic activity, etc. increase. Further, other heat resistance, chemical stability and hydrolysis resistance are also improved. Further, since the structure is similar to that of the fluorine-containing organic solvent described later, the effect further increases the solubility. Further, the constants m and n related to the number of ligands described so far are determined by the type of central M, but m is preferably 0 to 8 and n is preferably 0 to 8. . The electrolyte as described above has a very high solubility in the fluorine-containing organic solvent in which the conventional electrolyte was hardly dissolved due to the characteristics of the structure. By utilizing this fact, it becomes possible to form a flame-retardant electrolytic solution, which has been impossible in the past.

Next, the fluorine-containing organic solvent used in the present invention may be one having a flash point of 100 ° C. or higher, and preferably fluorine-containing carbonates, esters, ethers, lactones and nitriles. , Amides,
Alternatively, sulfones may be mentioned, and those having a fluorine content of 50% or more are more preferable, and those having a common moiety with the ligand of the electrolyte used are more preferable. To safely use the electrochemical device which is the object of the present invention, the flash point of the fluorine-containing organic solvent is 100 ° C.
Or more, and carbonates,
Those containing a hetero element such as esters, ethers, lactones, nitriles, amides, or sulfones have higher solubility, and those having a common moiety with the ligand of the electrolyte are It is preferable because it has a higher dissolving power.

Specifically, CH ₃ OCOOCH ₂ CF ₃ ,
_{CH 3 OCOOCH 2 CF 2 CF 3} , CH 3 OCOOCH
(CF ₃ ) ₂ , C ₂ H ₅ OCOOCH ₂ CF ₃ , C ₂ H ₅ OCO
OCH ₂ CF ₂ CF ₃ , C ₂ H ₅ OCOOCH (CF ₃ ) ₂ ,
_{(CF 3) 2 CHOCOOCH (CF} 3) 2, CF 3 CH 2 O
Chain fluorine-containing carbonate such as COOCH ₂ CF ₃ ;

[0019]

[Chemical 4]

Cyclic fluorinated carbonates such as (CF
₃)₂CHOCH₃, C_FourF₉OCH₃, CF₃CFHCF₂O
CH₃, CF₃CF ₂CH₂OCF₂CF₂H, HCF₂CF₂
OCH₃, HCF₂CF₂OC₂H_Five, CF₃CH₂OCH₂C
F₃, C₃F₇OCHFCF₃ , (CF₃)₂CHOCH
₂F, CF₃CH₂OC₂H_FourOCH₂CF₃Chain-like inclusions such as
Fluorine ether,

[0021]

[Chemical 5]

Cyclic fluorine-containing ether such as CF ₃ CO
Fluorine-containing esters such as OC ₂ H ₅ , C ₄ F ₉ COOCH ₃ and C ₃ F ₇ COOCH ₃ ,

[0023]

[Chemical 6]

Fluorine-containing lactones such as CF ₃ CONHC
Fluorine-containing amides such as H ₂ CH ₂ CF ₃ , C ₃ F ₇ CON (CH ₃ ) ₂ and the like, CH ₂ FCN, CF ₃ CHFCN, (CF ₂ ) ₄
Fluorine-containing nitriles such as (CN) ₂ can be used.

Although the electrolyte used in the present invention has a very high solubility in these fluorine-containing organic solvents,
Since a fluorine-containing organic solvent having a high fluorine content generally has a low dielectric constant and a donor property, there is a problem that the ion conductivity required for an electrochemical device is lowered by inhibiting ion dissociation. Therefore, if a method of adding an organic compound containing a hetero element having a dielectric constant of 1 or more to the electrolytic solution of the present invention as an electrolyte dissociation promoter, the conductivity can be improved. The dissociation promoter is preferably an aprotic organic compound, for example, carbonates, esters, ethers, lactones,
Nitriles, amides, sulfones and the like can be used. Further, not only a single compound but also a mixture of two or more kinds may be used. Specific examples include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane, acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, nitromethane, N, N-dimethylformamide, dimethyl sulfoxide. , Sulfolane, γ-butyrolactone, polymers having polyethylene oxide in the main chain or side chain, methacrylic acid ester polymers, polyacrylonitrile and the like. However, since these dissociation promoters are flammable substances, the addition amount thereof is preferably 50 vol% or less in the electrolytic solution. Addition of these dissociation accelerators having a high dielectric constant makes LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ and LiN commonly used.
Electrolytes such as (CF ₃ SO ₂ ) ₂ , LiSbF ₆ or LiClO ₄ also seem to dissolve in the fluorine-containing organic solvent, but even if they can be mixed in the absence of these electrolytes, by adding these electrolytes However, since the fluorine-containing organic solvent and the dissociation promoter are phase-separated, they cannot be used as an electrolytic solution.

The concentration of the electrolyte in the electrolytic solution is 0.1 mol.
/ Dm ³ or more and a saturation concentration or less are preferable, and more preferably 0.5 to 1.5 mol / dm ³ . 0.1mo
If the concentration is lower than 1 / dm ³ , the ionic conductivity is low, which is not preferable.

When an electrochemical device is formed by using the electrolytic solution of the present invention, its basic constituent elements are an electrolytic solution, a negative electrode, a positive electrode, a current collector, a separator and a container.

The negative electrode material is not particularly limited,
In the case of a lithium battery, lithium metal or an alloy of lithium and another metal is used. Further, in the case of a lithium ion battery, a material utilizing a phenomenon called intercalation such as carbon, natural graphite, metal oxide, etc. obtained by firing a polymer, an organic material, pitch, etc. is used. In the case of the electric double layer capacitor, activated carbon, porous metal oxide, porous metal, conductive polymer or the like is used.

The positive electrode material is not particularly limited,
In the case of a lithium battery and a lithium ion battery, for example,
LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O
Lithium-containing oxides such as ₄ , TiO ₂ , V ₂ O ₅ , MoO ₃
And oxides such as TiS ₂ and FeS, and conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole. In the case of electric double layer capacitors, activated carbon, porous metal oxide,
Porous metals, conductive polymers, etc. are used.

[0030]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples.

Example 1 Lithium tetrakis (hexafluoroisopropoxy)
Aluminate

[0032]

[Chemical 7]

Di (hexafluoroisopropyl) carbonate

[0034]

[Chemical 8]

An electrolyte solution having a concentration of 1 mol / dm ³ was prepared by dissolving in, and the ionic conductivity was measured by an AC bipolar cell. As a result, the ionic conductivity at 25 ° C was 0.01
It was mS / cm. Further, a filter was impregnated with the electrolytic solution and a flame was applied to conduct a combustion test, but no combustion occurred.

Example 2 A 1: 1 (volume) mixture of propylene carbonate (PC) and dimethyl carbonate (DMC) was added to the electrolytic solution of Example 1 in an amount of 20% with respect to the electrolytic solution. Conductivity was measured with an AC bipolar cell. As a result, the ionic conductivity at 25 ° C. was 2.10 mS / cm. Further, a filter was impregnated with the electrolytic solution and a flame was applied to conduct a combustion test, but no combustion occurred.

Next, using this electrolyte, a half cell was prepared using LiCoO ₂ as a positive electrode material, and a battery charge / discharge test was actually carried out. The test cell was prepared as follows. In a weight ratio, to the LiCoO ₂ powder 90, polyvinylidene fluoride (PVDF) as a binder was mixed at a ratio of 5 and acetylene black as a conductive material was mixed at a ratio of 5, and N, N-dimethylformamide was further added to form a paste. I made it. This paste was applied onto an aluminum foil and dried to obtain a test positive electrode body. Lithium metal was used for the negative electrode. Then, using the glass fiber filter as a separator, the electrolytic solution was impregnated into this separator to assemble a cell.

The constant current charge / discharge test was carried out under the following conditions. Current density 0.35 mA / c for both charging and discharging
It performed in m ^2, charging, 4.2V, discharge, 3.0V (v
s. Li / Li ⁺ ). As a result, the initial discharge capacity was 125 mAh / g (positive electrode capacity). The charge and discharge was repeated 20 times, but the capacity of the 20th time was 88% of the initial capacity.

Further, using this electrolyte, a half cell was prepared using natural graphite as a negative electrode material, and a charge / discharge test of the battery was actually carried out. The test cell was prepared as follows.
Polyvinylidene fluoride (PVDF) as a binder was mixed at a weight ratio of 1 with natural graphite powder 9, and N, N-dimethylformamide was further added to form a slurry. By coating this slurry on a nickel mesh and drying at 150 ° C. for 12 hours,
It was used as a negative electrode for testing. Lithium metal was used for the counter electrode. Then, using the glass fiber filter as a separator, the electrolytic solution was impregnated into this separator to assemble a half cell. A constant current charge / discharge test was carried out under the following conditions. Current density of 0.3 mA / c for both charging and discharging
performed in m ^2, the charge is 0.0V, discharge is 1.5V (vs.
Li / Li ⁺ ). As a result, the initial discharge capacity was 320 mAh / g. Further, the charging and discharging was repeated 20 times, but the 20th capacity was 95% of the initial capacity.

Example 3 Lithium tetrakis (hexafluorocumylalkoxy) aluminate

[0041]

[Chemical 9]

Was dissolved in hexafluorobenzene to prepare an electrolytic solution having a concentration of 0.2 mol / dm ³ , and the ionic conductivity was measured by an AC bipolar cell. As a result, the ionic conductivity was 5 μS / cm.

When 10% of ethylene carbonate was added to this electrolytic solution, its ionic conductivity was 0.4.
It was mS / cm. Further, a filter was impregnated with the electrolytic solution and a flame was applied to conduct a combustion test, but no combustion occurred.

Example 4 Lithium tetrakis (hexafluoroisopropoxy)
Borate

[0045]

[Chemical 10]

Was dissolved in di (hexafluoroisopropyl) carbonate to prepare an electrolytic solution having a concentration of 1 mol / dm ³ , and the ionic conductivity was measured by an AC bipolar cell. As a result, the ionic conductivity at 25 ° C was 0.01 m.
It was S / cm.

When 10% of ethylene carbonate was added to this electrolytic solution, its ionic conductivity was 1.6.
It was mS / cm. Further, a filter was impregnated with the electrolytic solution and a flame was applied to conduct a combustion test, but no combustion occurred.

Example 5 Lithium tetrakis (hexafluoroisopropoxy)
Aluminate is 2,2-bis (trifluoromethyl)-
1,3-dioxolane

[0049]

[Chemical 11]

An electrolytic solution having a concentration of 0.5 mol / dm ³ was prepared by dissolving in, and the ionic conductivity was measured by an AC bipolar cell. As a result, the ionic conductivity at 25 ° C. was 0.
It was 02 mS / cm.

When 10% of 1,2-dimethoxyethane was added to this electrolytic solution, its ionic conductivity was 5.4 mS / cm. Further, a filter was impregnated with the electrolytic solution and a flame was applied to conduct a combustion test, but no combustion occurred.

Example 6 Lithium tetrakis (hexafluoroisopropoxy)
Aluminate is converted to methyl nonafluorobutyl ether (C
₄ F ₉ OCH ₃ ) to prepare an electrolytic solution having a concentration of 0.2 mol / dm ³ , and the ionic conductivity was measured by an AC bipolar cell. As a result, the ionic conductivity at 25 ° C. was 0.
It was 01 mS / cm.

When 5% of 1,2-dimethoxyethane was added to this electrolytic solution, its ionic conductivity was 2.
It was 5 mS / cm. Further, a filter was impregnated with the electrolytic solution and a flame was applied to conduct a combustion test, but no combustion occurred.

Comparative Example 1 LiPF ₆ was added to dissolve in di (hexafluoroisopropyl) carbonate, but it did not dissolve at all.

Next, when LiPF ₆ was added to di (hexafluoroisopropyl) carbonate containing 20% propylene carbonate to a concentration of 0.2 mol / dm ³ , LiPF ₆ was dissolved but the solution was 2%.
The phases were separated. Analysis of each phase revealed that one was di (hexafluoroisopropyl) carbonate and the other was LiPF ₆ / propylene carbonate solution.

Comparative Example 2 LiPF ₆ , LiN (CF ₃ SO ₂ ) ₂ , LiBF ₄ , Li
CF ₃ SO ₃ , LiSbF ₆ and LiClO ₄ were each subjected to a dissolution test in 2,2-bis (trifluoromethyl) -1,3-dioxolane. As a result, none of the electrolytes dissolved.

[0057]

EFFECTS OF THE INVENTION Since the electrolyte solution of the present invention can use a flame-retardant solvent, compared with the conventional electrolyte solutions used for electrochemical devices such as lithium batteries, lithium ion batteries and electric double layer capacitors, Very good in terms of safety.

─────────────────────────────────────────────────── ─── Continued Front Page (56) References JP 2001-85058 (JP, A) JP 11-111332 (JP, A) JP 8-301879 (JP, A) JP 6-215775 (JP, A) JP 8-287950 (JP, A) JP 11-195429 (JP, A) JP 8-138737 (JP, A) JP 2001-106694 (JP, A) JP 2001-6734 (JP, A) JP 10-12272 (JP, A) JP 9-251861 (JP, A) JP 11-86901 (JP, A) JP 2000-516930 (JP, A) ) (58) Fields surveyed (Int.Cl. ⁷ , DB name) H01M 10/40 H01G 9/038 H01M 6/16

Claims (5)

(57) [Claims] 1. An electrochemical device using an organic electrolytic solution, wherein a fluorine-containing organic solvent is used as a main solvent of the organic electrolytic solution, and the electrolyte has a C—F bond in at least one of its anion ligands. An electrolytic solution for an electrochemical device, comprising an art complex, wherein the art complex comprises at least one compound having a chemical structural formula represented by the general formula (1). [Chemical 1] A ^{q +} is a metal ion or an onium ion, M is a transition metal, Group III, IV, or V group element of the periodic table, a is 0 to 3, c is 0 to 3 (at least a or c) One is not 0, a + b = 3, c + d = 3), p is r / q, q is 1 to 3, r is 1 to 3, m is 1 to 8, and n is 0 to 8. X ¹ is O, S, NR ⁵ , or NR ⁵ R ⁶ , R ¹ and R ² are each independently H, halogen, C ₁ -C
₁₀ alkyl, or C ₁ -C ₁₀ halogenated alkyl, R ³ is C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₄ -C ₂₀ aryl, or C ₄ -C ₂₀ aryl halides, R ⁴ is halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkyl halide, C ₄ -C ₂₀ aryl, C ₄ -C ₂₀
Or a halogenated aryl of X ² R ⁷ , X ² is O, S, NR ⁵ , or NR ⁵ R ⁶ , R ⁵ , R ⁶ is H, or C ₁ -C ₁₀ alkyl, R ⁷ is It represents alkyl of C ₁ -C _10, alkyl halide C ₁ -C _10, of C ₄ -C ₂₀ aryl, or C ₄ -C ₂₀ in the aryl halide, respectively. 2. M is Al, B, V, Ti, Si, Z
r, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta,
The electrolytic solution for an electrochemical device according to claim 1, wherein the electrolytic solution is Bi, P, As, Sc, Hf, or Sb. 3. The electrolytic solution for an electrochemical device according to claim 1, wherein A ^{q +} is either a Li ion or a quaternary ammonium ion. 4. The fluorine-containing organic solvent comprises at least one of fluorine-containing carbonates, esters, ethers, lactones, nitriles, amides, and sulfones. The electrolytic solution for an electrochemical device according to any one of claims 1 to 3. 5. The electricity according to claim 1, wherein the organic electrolytic solution contains an organic compound containing a hetero element having a dielectric constant of 1 or more as an electrolyte dissociation promoter. Electrolyte for chemical devices.