JP2002252029A - Electrolyte for electrochemistry device, its electrolytic solution or solid electrolyte and battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolyte, an electrolytic solution or solid electrolyte, and a battery using them, which shows an outstanding cycle characteristic, used for electrochemistry devices, such as a lithium battery, a lithium ion battery, electric double layer capacitor or the like. SOLUTION: They are the electrolyte for electrochemistry devices, the electrolytic solution using this electrolyte or the solid electrolyte, and the battery, which contain a compound expressed by formula (1) and A<q+> (PF6 <-> )q , A<q+> (ClO4 <-> )q , A<q+> (BF4 <-> )q , A<q+> (AsF6 <-> )q , or A<q+> (SbF6 <-> )q .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyte, an electrolyte or a solid electrolyte exhibiting excellent cycle characteristics and used for electrochemical devices such as lithium batteries, lithium ion batteries, and electric double layer capacitors. Battery.

[0002]

2. Description of the Related Art With the development of portable equipment in recent years, electrochemical devices utilizing electrochemical phenomena such as batteries and capacitors as power sources have been actively developed. In addition, electrochemical devices other than power supplies include:
An electrochromic display (ECD) in which a color change is caused by an electrochemical reaction is given.

[0003] These electrochemical devices are generally composed of a pair of electrodes and an ionic conductor filling the space between the electrodes. The ion conductor, a solvent, and the cation (A ⁺⁾ called the electrolyte in the polymer, or a mixture thereof anions (B ^-) is obtained by dissolving a from consisting salts (AB) is used. When this electrolyte is dissolved, it dissociates into cations and anions and conducts ions. In order to obtain the ion conductivity required for the device, it is necessary that this electrolyte be dissolved in a sufficient amount in a solvent or a polymer. Actually, a substance other than water is often used as a solvent, and only a few types of electrolytes having sufficient solubility in such organic solvents and polymers are presently used. For example, as electrolytes for lithium batteries, LiClO ₄ , LiPF ₆ , LiBF ₄ , L
iAsF ₆ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C _{2
F 5) 2, LiN (SO} 2 CF 3) (SO 2 C 4 F 9) and LiCF ₃ SO ₃ only. The cation portion is often determined by the device, such as lithium ion of a lithium battery, but the anion portion can be used if it satisfies the condition of high solubility.

[0004] As the application range of devices has been diversified, the most suitable electrolyte for each application has been sought. However, at present, optimization has reached the limit due to the small number of anions. In addition, existing electrolytes have various problems, and an electrolyte having a novel anion moiety is demanded. Specifically, ClO ₄ ion is explosive, A
sF ₆ ions are toxic and cannot be used for safety reasons. The only commercially available LiPF ₆ also has problems such as heat resistance and hydrolysis resistance. In addition, LiN (CF ₃
SO ₂ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiN (SO ₂ C
F ₃ ) (SO ₂ C ₄ F ₉ ) and LiCF ₃ SO ₃ are very good electrolytes because of their high stability and high ionic conductivity, but the potential was applied to the aluminum current collector in the battery. It is difficult to use because it corrodes in a state.

[0005]

[Specific means for solving the problem]
As a result of intensive studies in view of the problems of the prior art, the present inventors have found that excellent characteristics can be obtained by a system in which an electrolyte having a novel chemical structural characteristic is combined with a conventional electrolyte, and have reached the present invention.

That is, the present invention provides a compound represented by the general formula (1)
A compound having the chemical structural formula ^{q +}(PF₆ ^-)_q, A
^{q +}(ClO_Four ^-)_q , A^{q +}(BF_Four ^-)_q , A^{q +}(As
F₆ ^-)_qOr A^{q +}(SbF₆ ^-)_qCompound represented by
An electrochemical device comprising at least one of the following:
In resolving,

[0007]

Embedded image

A^{q +}Is a metal ion, hydrogen ion, or
N is a transition metal, group III of the periodic table, IV
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 1-3, r is 1
-3, m represents 0-8, n represents 0-8, and X
¹Is O, S, NR^Five, Or NR^FiveR⁶, R¹And R^TwoIs
Each independently, H, halogen, C₁~ C_TenAn alkyl,
Or C₁~ C_TenAlkyl halides (these
The alkyl and alkyl halides have substituents,
May have terror atoms. ), R^ThreeIs H, halogen,
C₁~ C_TenAlkyl, C₁~ C_TenHalogenated Alky
Le, C_Four~ C₂₀Aryl, or C_Four~ C₂₀Halogen
Aryl halides (these alkyls, alkyl halides,
Aryl, aryl halide is a substituent in its structure,
It may have a hetero atom. ), R^FourIs halogen, C₁
~ C_TenAlkyl, C₁~ C_TenAn alkyl halide,
C_Four~ C₂₀Aryl, C_Four~ C₂₀Halogenated ally
Or X^TwoR⁷(These alkyl and halogenated al
Kills, aryls, and aryl halides are placed in the structure.
It may have a substituent or a hetero atom. ), X^TwoIs O,
S, NR^Five, Or NR^FiveR⁶, R^Five, R⁶Is H, or
C ₁~ C_TenAlkyl of R⁷Is C₁~ C_TenAn alkyl,
C₁~ C_TenAlkyl halide of C_Four~ C₂₀Ally
Or C_Four~ C₂₀Aryl halides (of these
Alkyl, alkyl halide, aryl, halogenated
Aryl has substituents and heteroatoms in its structure.
Good. ) Each represents an electrolyte for an electrochemical device
And an electric power comprising the electrolyte dissolved in a non-aqueous solvent.
Electrolyte for chemical devices or dissolving the electrolyte in polymer
A solid electrolyte for an electrochemical device comprising
And at least a positive electrode, negative electrode, electrolyte or solid electrolyte
The electrolyte or the solid electrolyte containing the electrolyte.
It provides a pond.

The alkyl, alkyl halide, aryl and aryl halide used in the present invention include those having another functional group such as a branch, a hydroxyl group and an ether bond.

Hereinafter, the present invention will be described in more detail.

First, specific examples of the compound represented by formula (1) used in the present invention are shown below.

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

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

In consideration of applications such as electrochemical devices, lithium ions, tetraalkylammonium ions, and hydrogen ions are preferable. The valence ^q of the cation of A ^{q +} is preferably from 1 to 3. If it is larger than 3, the crystal lattice energy becomes large, so that there is a problem that it becomes difficult to dissolve in a solvent. Therefore, when solubility is required, 1 is more preferable. Similarly, the valence r of the anion is preferably from 1 to 3, and particularly preferably 1. The constant p representing the ratio of cation to anion is the ratio r of the valences of both.
/ Q inevitably determines.

The electrolyte represented by the general formula (1), which is a part of the constitution of the present invention, has an ionic metal complex structure, and the center M is a transition metal, III of the periodic table.
Selected from Group IV, IV, or V elements. Preferably,
Al, B, V, Ti, Si, Zr, Ge, Sn, Cu,
Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc,
Hf or Sb, and more preferably Al, B or P. M centered on various elements
It is possible to use Al, B, V, T
i, Si, Zr, Ge, Sn, Cu, Y, Zn, Ga,
Nb, Ta, Bi, P, As, Sc, Hf, or Sb
Is relatively easy to synthesize, and in the case of Al, B or P, in addition to the ease of synthesis, low toxicity, stability,
It has excellent properties in terms of cost and all aspects.

Next, a description will be given of a ligand part which is a feature of the electrolyte (ionic metal complex) represented by the general formula (1). Hereinafter, the organic or inorganic portion bonded to M is referred to as a ligand.

X ¹ in the general formula (1) is O, S, NR ⁵ ,
Or NR ⁵ R ⁶ , and through these heteroatoms, M
To join. Here, bonding other than O, S, and N is not impossible but very complicated in synthesis.

The constant a in this ligand is 0 to 3, and c is
0-3 (at least one of a or c is not 0,
+ B = 3, c + d = 3), and R ¹ and R ² are each independently H, halogen, C _{1 to} C ₁₀ alkyl, or C _{1 to} C ₁₀ halogenated alkyl, and R ³ is C ₁ alkyl -C _10, alkyl halide _{C 1 ~C 10, C 4 ~C} 20
Aryl, or an aryl halide having ₄ to ₂₀ carbon atoms,
R ⁴ is halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ halogenated alkyl, C ₄ -C ₂₀ aryl, C ₄ -C ₂₀
Aryl halide, or X ² R ⁷ and X ² are O,
S, NR ⁵ , or NR ⁵ R ⁶ , R ⁵ , R ⁶ are H or C ₁ -C ₁₀ alkyl, R ⁷ is C ₁ -C ₁₀ alkyl,
Represents a C _{1 to} C ₁₀ halogenated alkyl, a C _{4 to} C ₂₀ aryl, or a C _{4 to} C ₂₀ halogenated aryl, and preferably at least one of R ¹ and R ² is a fluorinated alkyl and fluorine. 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, the central negative charge of M is dispersed, and the electrical stability of the anion increases, making it very easy for ions to dissociate,
The solubility in a solvent, ionic conductivity, catalytic activity, and the like are increased. Further, other heat resistance, chemical stability and hydrolysis resistance are also improved. Furthermore, the alkyl, alkyl halide, aryl and aryl halide in this compound may have a substituent and a hetero atom in the structure. Specifically, alkyl, halogenated alkyl, aryl, halogen instead of hydrogen on the aryl halide, a chain or cyclic alkyl group, aryl group, alkenyl group, alkoxy group, aryloxy group, sulfonyl group, amino group, Cyano group, carbonyl group, acyl group, amide group, hydroxyl group,
In addition, a structure in which nitrogen, sulfur, or oxygen is introduced instead of carbon on alkyl, alkyl halide, aryl, or aryl halide can be given. Also, the constants m and n related to the number of ligands described so far.
Is determined by the type of M at the center, but m is preferably from 0 to 8 and n is preferably from 0 to 8 (however,
m and n never become 0 at the same time. ).

Next, the compound represented by the general formula (1) is mixed with
A used together^{q +}(PF₆ ^-)_q, A^{q +}(ClO_Four ^-)_q
 , A^{q +}(BF_Four ^-)_q , A^{q +}(AsF₆ ^-)_q, A^{q +}(S
bF ₆ ^-)_qWill be described below. A^{q +}Is the general formula
Those common to the compound of (1) are preferred. These electrolysis
When used alone, at high temperatures above 60 ° C
Thermal decomposition occurs to generate a Lewis acid, which removes the solvent
When it decomposes and deteriorates the performance and life of the device
Problem may occur. In addition, the mixing of
The anion undergoes hydrolysis to form an acid,
Also degrade device performance and life. Departure
In Ming, these electrolytes are mixed with the electrolyte of the general formula (1).
To suppress this thermal decomposition and hydrolysis
It became possible. Details of its principle are not clear
Is due to some interaction with the electrolyte of the general formula (1)
It is presumed that the physical properties of the entire solution have changed.

The use ratio of these electrolytes is
Considering the effect of improving device cycle characteristics and storage stability
Then, the following ranges are preferable. Shown by general formula (1)
Electrolyte and A^{q +}(PF₆ ^-)_q, A^{q +}(ClO_Four ^-)
_q , A^{q +}(BF_Four ^-)_q , A^{q +}(AsF₆ ^-)_qOr A
^{q +}(SbF₆ ^-)_qThe molar ratio of the electrolyte selected from
Or 1:99 to 99: 1, more preferably 20: 8
0 to 80:20. The electrolyte of the general formula (1) is more than 1.
If the amount is small, the effect of suppressing decomposition is small.
Poor properties and storage stability, and greater than 99
In case A^{q +}(PF₆ ^-)_q, A^{q +}(ClO_Four ^-)_q , A^{q +}
(BF_Four ^-)_q , A^{q +}(AsF₆ ^-)_q, A ^{q +}(SbF₆ ^-)
_qHigh ionic conductivity and sufficient electrochemical stability
I can't do it.

When an electrochemical device is constructed using the electrolyte of the present invention, its basic constituent elements include an ion conductor, a negative electrode, a positive electrode, a current collector, a separator, a container, and the like.

As the ionic conductor, a mixture of an electrolyte and a non-aqueous solvent or polymer is used. If a non-aqueous solvent is used, the ionic conductor is generally called an electrolytic solution, and if a polymer is used, the ionic conductor is called a polymer solid electrolyte. Polymer solid electrolytes include those containing a non-aqueous solvent as a plasticizer.

The non-aqueous solvent is not particularly limited as long as it is an aprotic solvent capable of dissolving the electrolyte of the present invention. Examples thereof include carbonates, esters, ethers, lactones, nitriles, and amides. , Sulfones and the like can be used. Further, not only a single solvent but also a mixed solvent 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, dimethylsulfoxide. , Sulfolane,
And γ-butyrolactone.

However, when two or more kinds of mixed solvents are used, when the electrolyte in which A ^{q + in} the general formula (1) is Li ion, an aprotic solvent having a dielectric constant of 20 or more among these non-aqueous solvents is used. It is preferable to prepare an electrolytic solution by dissolving the same in a mixed solvent comprising an aprotic solvent having a dielectric constant of 10 or less. In particular, lithium salts have low solubility in aprotic solvents having a dielectric constant of 10 or less, such as diethyl ether and dimethyl carbonate, and do not provide sufficient ionic conductivity by themselves, and conversely, aprotic solvents having a dielectric constant of 20 or more. When used alone, the solubility is high but the viscosity is high, so that ions are difficult to move, and sufficient ion conductivity cannot be obtained. If these are mixed, appropriate solubility and mobility can be secured, and sufficient ionic conductivity can be obtained.

The polymer for dissolving the electrolyte is not particularly limited as long as it is an aprotic polymer. For example, a polymer having polyethylene oxide in a main chain or a side chain, a homopolymer or copolymer of polyvinylidene fluoride, a methacrylate polymer, a polyacrylonitrile, and the like can be given. When adding a plasticizer to these polymers, the above-mentioned aprotic non-aqueous solvents can be used. The mixed electrolyte concentration of the present invention in these ionic conductors is 0.1 mol /
dm ³ or more and saturated concentration or less, preferably 0.5 mol
/ Dm ³ or more and 1.5 mol / dm ³ or less. 0.1
If the concentration is lower than mol / dm ³ , the ion conductivity is low, which is not preferable.

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

The material of the positive electrode is not particularly limited.
For lithium batteries and lithium ion batteries, for example,
LiCoO_Two , LiNiO_Two , LiMnO_Two , LiMn
_Two O _Four Lithium-containing oxides such as TiO_Two , V_Two O_Five ,
MoO_Three Oxides such as TiS _Two , Sulfides such as FeS,
Or polyacetylene, polyparaphenylene, polyani
Conductive polymers such as phosphorus and polypyrrole are used
You. Activated carbon, porous metal for electric double layer capacitors
An oxide, a porous metal, a conductive polymer, or the like is used.

[0038]

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

Example 1 In a mixed solvent of 50 vol% of ethylene carbonate and 50 vol% of dimethyl carbonate,

[0040]

Embedded image

An electrolytic solution was prepared by dissolving 0.01 mol / l of a lithium aluminate derivative having the structure described above and 0.99 mol / l of LiPF ₆ , and LiC
A cell was produced using oO ₂ as a cathode material and natural graphite as an anode material, and a battery charge / discharge test was actually performed. The test cell was prepared as follows.

To 90 parts by weight of LiCoO ₂ powder, 5 parts by weight of polyvinylidene fluoride (PVD) were used as a binder.
F), 5 parts by weight of acetylene black was mixed as a conductive material, and N, N-dimethylformamide was further added to form a paste. This paste was applied on an aluminum foil and dried to obtain a positive electrode for testing.
Also, 90 parts by weight of natural graphite powder were added
0 parts by weight of polyvinylidene fluoride (PVDF) was mixed, and N, N-dimethylformamide was further added to form a slurry. This slurry is applied on a copper foil and
By drying at 50 ° C. for 12 hours, a test negative electrode body was obtained. Then, the cell was assembled by infiltrating the electrolytic solution into a polyethylene separator.

Next, a constant current charge / discharge test was performed under the following conditions. 0.35 mA current density for both charging and discharging
/ Cm ² , charging is 4.2V, discharging is 3.0V
Until the test temperature was 70 ° C. As a result, charge / discharge was repeated 500 times, but the capacity at the 500th time was 84% of the initial capacity.
The result was obtained.

Example 2 In a mixed solvent of 50 vol% of ethylene carbonate and 50 vol% of diethyl carbonate,

[0045]

Embedded image

Lithium borate derivative having the structure
An electrolyte was prepared by dissolving 20 mol / l and 0.80 mol / l of LiPF _6, and a cell was prepared using this electrolyte in the same manner as in Example 1 using LiCoO ₂ as a positive electrode material and natural graphite as a negative electrode material. A battery charge / discharge test was performed.

Next, a constant current charge / discharge test was performed under the following conditions. 0.35 mA current density for both charging and discharging
/ Cm ² , charging is 4.2V, discharging is 3.0V
(Vs. Li ^/ Li ⁺ ) at 70 ° C. As a result, the charge and discharge were repeated 500 times, but the capacity at the 500th time was 91% of the initial capacity.

Example 3 In a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of dimethyl carbonate, a lithium aluminate derivative having the same structure as in Example 1 was added in an amount of 0.05 mol /%.
of LiBF _{4 and} 0.95 mol / l of LiBF ₄ were prepared, and LiC was used in the same manner as in Example 1 using this electrolytic solution.
A cell using oO ₂ as a positive electrode material and natural graphite as a negative electrode material was produced, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm ^2. Charging was 4.2 V and discharging was 3.0 V (vs. L
Test temperature was 70 ° C. until i / Li ⁺ ). As a result, charge / discharge was repeated 500 times, and the capacity at the 500th time was 82% of the initial capacity.

Example 4 In a mixed solvent of 50 vol% of ethylene carbonate and 50 vol% of dimethyl carbonate,

[0050]

Embedded image

An electrolyte was prepared by dissolving 0.95 mol / l of a lithium aluminate derivative having the structure described above and 0.05 mol / l of LiBF _4, and LiCoO ₂ was used as a positive electrode in the same manner as in Example 1 using this electrolyte. A cell using a lithium metal material as a negative electrode material was prepared, and a constant current charge / discharge test was performed under the following conditions. The current density is 0 for both charging and discharging.
Performed at 35 mA / cm ² , charging was 4.2 V, discharging was
Test temperature up to 3.0 V (vs. Li ^/ Li ⁺ ) at 70 ° C.
I went in. As a result, charge and discharge were repeated 500 times, but 5
As a result, the capacity at the 00th time was 79% of that at the first time.

Example 5 Acetonitrile was added to 80 parts by weight of polyethylene oxide having an average molecular weight of 10,000 to prepare a solution. 10 parts by weight of a lithium aluminate derivative having the same structure as in Example 1 and LiPF ₆ were added to the solution. 10 parts by weight were added, and this was cast on glass and dried to remove acetonitrile as a solvent to prepare a solid polymer electrolyte membrane.

Next, this polymer solid electrolyte membrane was used in place of the electrolyte and the separator, and LiC
A cell using oO ₂ as a positive electrode material and natural graphite as a negative electrode material was prepared, and a constant current charge / discharge test was performed at 70 ° C. under the following conditions. Current density of 0.1 mA / cm for both charging and discharging
^The charge is performed at 4.2 V, and the discharge is performed at 3.0 V (v
s. Li / Li ⁺ ). As a result, the initial discharge capacity was 120 mAh / g (capacity of the positive electrode). The charge / discharge was repeated 500 times, and the capacity at the 500th time was 83% of the initial capacity.

Comparative Example 1 LiPF ₆ was added to a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of dimethyl carbonate.
A mol / l dissolved electrolyte solution was prepared.

Using this electrolytic solution, Li was used in the same manner as in Example 1.
A cell using CoO ₂ as a positive electrode material and natural graphite as a negative electrode material was manufactured, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm ^2. Charging was 4.2 V and discharging was 3.0 V (vs. L
Test temperature was 70 ° C. until i / Li ⁺ ). As a result, charge / discharge was repeated 500 times, and the capacity at the 500th time was 64% of the initial capacity.

Comparative Example 2 LiBF ₄ was added to a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of dimethyl carbonate in an amount of 1.0%.
A mol / l dissolved electrolyte solution was prepared.

Using this electrolytic solution, Li was used in the same manner as in Example 1.
A cell using CoO ₂ as a positive electrode material and natural graphite as a negative electrode material was manufactured, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at a current density of 0.35 mA / cm ^2. Charging was 4.2 V and discharging was 3.0 V (vs. L
Test temperature was 70 ° C. until i / Li ⁺ ). As a result, charge and discharge were repeated 500 times, but the capacity at the 500th time was 46% of the initial capacity.

[0058]

The present invention is an electrolyte having superior cycle characteristics and storage characteristics as compared with conventional electrolytes used for electrochemical devices such as lithium batteries, lithium ion batteries, and electric double layer capacitors. An electrolyte or a solid electrolyte and a battery using the same are made possible.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mikihiro Takahashi 2805, Imafukunakadai, Kawagoe-shi, Saitama Central Research Institute of Chemical Research Co., Ltd. (72) Inventor Hiromi Sugimoto 2805, Imafukunakadai, Kawagoe-shi, Saitama Central Glass Inside the Chemical Research Laboratories (72) Inventor Makoto Koide 2805 Imafukunakadai, Kawagoe-shi, Saitama Central Glass F-term in the Chemical Research Laboratories Co., Ltd. AM16 HJ02 HJ20

Claims (9)

[Claims] ^1. A compound having a chemical structural formula represented by the general formula (1), A ^{q +} (PF ₆ ⁻ ) _q , A ^{q +} (ClO ₄ ⁻ )
_q , A ^{q +} (BF ₄ ⁻ ) _q , A ^{q +} (AsF ₆ ⁻ ) _q , or A
^{q +} (SbF ₆ ⁻ ) An electrolyte for an electrochemical device, comprising at least one of the compounds represented by _q . Embedded image A ^{q +} is a metal ion, a hydrogen ion, or an onium ion, M is a transition metal, group III, group IV, or
Group V elements, a is 0 to 3, c is 0 to 3 (at least one of a and c is not 0, a + b = 3, c + d =
3), p is r / q, q is 1-3, r is 1-3, m
Represents 0 to 8, n represents 0 to 8, and X ¹ represents
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 (these alkyls). And the alkyl halide may have a substituent and a hetero atom in its structure.), R ³ is H, halogen, C _1-
Alkyl of C _10, alkyl halide C ₁ ~C _10, C ₄
Aryl -C ₂₀ or C ₄ -C ₂₀ halogenated aryl, (the alkyl, halogenated alkyl, aryl, halogenated aryl substituent in its structure, may have a hetero atom.), 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, or X ² R ⁷ (these alkyls, alkyl halides, aryls and aryl halides may have substituents and heteroatoms in the structure). , X ² are 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 halogenated alkyl, C ₄ -C 10 ₂₀ aryls, or C ₄
Aryl halide -C ₂₀ (these alkyl, halogenated alkyl, aryl, halogenated aryl substituent in its structure, may have a hetero atom.) Are expressed, respectively. 2. M is Al, B, V, Ti, Si, Z
r, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta,
2. The electrolyte for an electrochemical device according to claim 1, wherein the electrolyte is any of Bi, P, As, Sc, Hf, and Sb. 3. The electrolyte for an electrochemical device according to claim 1, wherein A ^{q +} is one of a Li ion and a quaternary ammonium ion. 4. An electrolytic solution for an electrochemical device, comprising an electrolyte according to claim 1 dissolved in a non-aqueous solvent. 5. The electrochemical device according to claim 4, wherein the non-aqueous solvent is a mixed solvent comprising an aprotic solvent having a dielectric constant of 20 or more and an aprotic solvent having a dielectric constant of 10 or less. Electrolyte. 6. The electrolytic solution for an electrochemical device according to claim 4, wherein A ^{q + of the} electrolyte is a Li ion. 7. A solid electrolyte for an electrochemical device, comprising the electrolyte according to claim 1 dissolved in a polymer. 8. The solid electrolyte for an electrochemical device according to claim 7, wherein A ^{q + of the} electrolyte is a Li ion. 9. A battery comprising at least a positive electrode, a negative electrode, an electrolytic solution or a solid electrolyte, wherein the electrolytic solution or the solid electrolyte contains the electrolyte according to claim 1.