JP2003151637A - Electrolyte for electrochemical device, electrolytic solution or solid electrolyte thereof, and battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide electrolyte having excellent cycle characteristics and used in an electrochemical device such as a lithium battery, a lithium-ion battery, and an electric double layer capacitor, to provide electrolytic solution or solid electrolyte, and to provide a battery using the same. SOLUTION: The electrolyte for an electrochemical device composed of a compound expressed by a formula (1) and compounds expressed by formulas (2), (3), (4) is provided. Further, the electrolytic solution or solid electrolyte, and the battery using the electrolyte are provided.

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 solution or a solid electrolyte having excellent cycle characteristics, which is used for an electrochemical device such as a lithium battery, a lithium ion battery and an electric double layer capacitor, and the use thereof. It was about the battery.

[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 their power sources has become active. Also, as an electrochemical device other than the power source,
An electrochromic display (ECD) in which a color change is caused by an electrochemical reaction is mentioned.

These electrochemical devices are generally composed of a pair of electrodes and an ionic conductor filling between them. As the ionic conductor, a solvent, a polymer, or a mixture thereof in which a salt (AB) composed of a cation (A ⁺ ) and an anion (B ⁻ ) called an electrolyte is dissolved is used. When this electrolyte dissolves, it dissociates into cations and anions, and conducts ions. In order to obtain the ionic conductivity required for the device, this electrolyte must be dissolved in a solvent or polymer in a sufficient amount. In fact, a substance other than water is often used as a solvent, and at present, there are only a few types of electrolytes having sufficient solubility in such organic solvents and polymers. For example, as an electrolyte for a lithium battery, 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, like the lithium ion of a lithium battery, but the anion portion can be used if it satisfies the condition of high solubility.

While the range of application of devices has been diversified, the optimum electrolyte for each use has been sought, but the optimization has reached the limit because the number of anions is small at present. In addition, existing electrolytes have various problems, and an electrolyte having a new anion portion is desired. Specifically, ClO ₄ ion is explosive, A
Since sF ₆ ion is toxic, it cannot be used for safety reasons. The only commercially available LiPF ₆ also has problems such as heat resistance and hydrolysis resistance. LiN (CF ₃ SO ₂ )
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 are excellent electrolytes because they have high stability and high ionic conductivity, but they corrode the aluminum current collector in the battery under the condition that a potential is applied. Therefore, it is difficult to use.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the problems of the prior art, the present inventors have found a system combining an electrolyte having a novel chemical structural characteristic and a conventional one, and The invention has been reached.

That is, the present invention comprises a compound having the chemical structural formula represented by the general formula (1) and a chemical structural formula represented by the general formula (2), the general formula (3) or the general formula (4). An electrolyte for an electrochemical device comprising at least one of compounds,

[0007]

[Chemical 2]

A^{q +}Is a metal ion, hydrogen ion, or
Nium ion, M is a transition metal, group III, 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
~ 3, m represents 0-8, n represents 0-8, respectively, X
¹Is O, S, NR^Five, Or NR^FiveR⁶, R¹And R²Is that
Independently H, halogen, C₁~ C_TenAn alkyl of
Or C₁~ C_TenAlkyl halides of these
Kill and alkyl halides have substituents,
May have terrorist atoms. ), R³Is H, halogen,
C₁~ C_TenAlkyl, C₁~ C_TenThe halogenated alky
Le, C_Four~ C₂₀Aryl or C_Four~ C₂₀The halogen
Aryl halides (these alkyls, halogenated alkyls,
Aryl and aryl halide are substituents in the structure,
It may have a hetero atom. ), R^FourIs halogen, C₁
~ C_TenAlkyl, C₁~ C_TenAn alkyl halide of
C_Four~ C₂₀Aryl, C_Four~ C₂₀The halogenated ally
Or X²R⁷(These alkyl and halogenated
Kill, aryl and aryl halides are placed in the structure.
It may have a substituent or a hetero atom. ), X²Is O,
S, NR^Five, Or NR^FiveR⁶, R^Five, R⁶Is H, or
C ₁~ C_TenAlkyl of R⁷Is C₁~ C_TenAn alkyl of
C₁~ C_TenAlkyl halide of C_Four~ C₂₀Ally
Or C_Four~ C₂₀Of aryl halides (of these
Alkyl, halogenated alkyl, aryl, halogenated
Aryl has substituents and heteroatoms in its structure
Good. ) Respectively, Y¹, Y², Y³Respectively
Independent, SO₂Group or CO group, R⁸, R⁹, R^TenIs that
Each is an independent, electron-withdrawing organic substituent (these structures
R may have a substituent or a hetero atom, and R⁸,
R⁹, R^TenMay combine with each other to form a ring
However, it may be combined with an adjacent molecule to form a polymer. )
And an electrolyte for an electrochemical device,
An electrochemical solution consisting of an electrolyte dissolved in a non-aqueous solvent.
Vice electrolyte solution or the electrolyte dissolved in a polymer
Solid electrolyte for electrochemical devices consisting of
At least a positive electrode, a negative electrode, an electrolytic solution or a solid electrolyte,
Provided is a battery containing the electrolyte in the electrolytic solution or solid electrolyte.
To do.

The alkyl, alkyl halide, aryl and aryl halide 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.

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

[0012]

[Chemical 3]

Lithium ions are mentioned here as A ^{q +} , but 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, triethylmethyl ammonium ion, triethyl ammonium ion, pyridinium ion, imidazolium ion, hydrogen ion, tetraethyl phospho Ion, tetramethyl phosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion, etc. is also used.

In consideration of applications such as electrochemical devices, lithium ion, tetraalkylammonium ion and hydrogen ion are preferable. The valence ^q of the cation of A ^{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 is also preferably 1 to 3, and particularly preferably 1. 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 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 thereof is a transition metal, III of the periodic table.
It is selected from Group III, IV or V elements. Preferably,
Al, B, V, Ti, Si, Zr, Ge, Sn, Cu,
Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc,
It is either Hf or Sb, and more preferably Al, B, or P. M centered on various elements
Can be used as 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 characteristics in cost and all aspects.

Next, the ligand portion which is a feature of the electrolyte (ionic metal complex) represented by the general formula (1) 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 NR ⁵ R ⁶ and M via these heteroatoms
Bind to. 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, the alkyl, alkyl halide, aryl and aryl halide in this compound may have a substituent or a hetero atom in the structure. Specifically, alkyl, alkyl halide, 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,
Further, a structure in which nitrogen, sulfur, or oxygen is introduced instead of carbon on the alkyl, alkyl halide, aryl, or aryl halide can be given. In addition, the constants m and n related to the number of ligands described so far are
Is determined depending on the type of M at the center, but m is preferably 0 to 8 and n is preferably 0 to 8.

Next, specific examples of the compounds represented by the general formula (2), the general formula (3) and the general formula (4) include CF ₃ C.
H ₂ OSO ₃ Li, (CF ₃ ) ₂ CHOSO ₃ Li, (CF ₃
CH ₂ OSO ₂ ) ₂ NLi, ((CF ₃ ) ₂ CHOSO ₂ ) ₂
NLi , (CF ₃ CH ₂ OSO ₂ ) ((CF ₃ ) ₂ CHOS
O ₂ ) NLi, ((CF ₃ ) ₃ COSO ₂ ) ₂ NLi , And ((CF ₃ ) ₂ CHOSO ₂ ) ₃ CLi, and the like. In addition, [N (Li) SO ₂ OCH ₂ (CF ₂ ) ₄ CH ₂
A polymer or oligomer such as OSO ₂ ] _n (n = _{2 to} 1000) may be used. If these electrolytes are used alone, they will corrode the aluminum current collector in the battery under the condition that an electric potential is applied, so that there is a problem that the capacity decreases when the charge / discharge cycle is repeated. In the present invention, it is possible to prevent corrosion of the aluminum current collector by mixing and using the electrolyte having the sulfonyl group and the electrolyte of the general formula (1).
Although the details of the principle are not clear, it is presumed that the electrolyte of the general formula (1) is slightly decomposed on the electrode surface to form a film made of the ligand on the aluminum surface and prevent the corrosion. .

The ratio of these electrolytes used is preferably in the following range in consideration of the effect of improving the cycle characteristics and storage stability of the electrochemical device. The molar ratio of the electrolyte of the general formula (1) to the electrolytes of the general formulas (2), (3) and (4) is 1:99 to 99: 1, preferably 2
It is 0:80 to 80:20. When the amount of the electrolyte of the general formula (1) is less than 1, the effect of preventing corrosion of aluminum is small, so the cycle characteristics and the storage stability are deteriorated.
On the other hand, when it is larger than 99, the high ion conductivity and electrochemical stability of the general formula (2), the general formula (3) and the general formula (4) cannot be sufficiently exhibited.

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

As the ionic conductor, a mixture of an electrolyte and a non-aqueous solvent or polymer is used. When a non-aqueous solvent is used, this ionic conductor is generally called an electrolytic solution, and when a polymer is used, it is called a polymer solid electrolyte. The polymer solid electrolyte also includes 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, and examples thereof include carbonates, esters, ethers, lactones, nitriles and amides. And sulfones 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, dimethyl sulfoxide. , Sulfolane,
And γ-butyrolactone and the like.

However, when two or more kinds of mixed solvents are used, and in the case of an electrolyte in which A ^{q +} of the general formula (1) is Li ion, an aprotic solvent having a dielectric constant of 20 or more among these non-aqueous solvents. It is preferable to prepare an electrolytic solution by dissolving it in a mixed solvent composed of 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 cannot obtain sufficient ionic conductivity alone, and conversely, aprotic solvents having a dielectric constant of 20 or more. Even if it has a high solubility by itself, its viscosity is also high, so that it becomes difficult for ions to move and sufficient ionic conductivity cannot be obtained. If these are mixed, appropriate solubility and mobility can be ensured and sufficient ionic conductivity can be obtained.

The polymer dissolved in the electrolyte is not particularly limited as long as it is an aprotic polymer. Examples thereof include polymers having polyethylene oxide in the main chain or side chains, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile and the like. When a plasticizer is added to these polymers, the above aprotic non-aqueous solvent can be used. The concentration of the mixed electrolyte of the present invention in these ionic conductors is 0.1 mol /
dm ³ or more and saturation concentration or less, preferably 0.5 mol
/ Dm ³ or more and 1.5 mol / dm ³ or less. 0.1
When the concentration is lower than mol / dm ³ , the ionic conductivity is low, which is not preferable.

The negative electrode material is not particularly limited,
In the case of lithium batteries, lithium metal, alloys of lithium with other metals and intermetallic compounds are 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,
LiCoO₂ , LiNiO₂ , LiMnO₂ , LiMn
₂ O _Four Lithium-containing oxides, such as TiO₂ , V₂ O_Five ,
MoO₃ Oxides such as TiS ₂ , Sulfides such as FeS,
Rui polyacetylene, polyparaphenylene, polyani
Conductive polymers such as phosphorus and polypyrrole are used.
It For electric double layer capacitors, activated carbon, porous metal
Oxides, porous metals, conductive polymers, etc. are used.

[0028]

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

[0030]

[Chemical 4]

The lithium aluminate derivative having the structure of 0.01 mol / l and ((CF ₃ ) ₂ CHOSO ₂ ) ₂ N
An electrolytic solution in which Li was dissolved in 0.99 mol / l was prepared, and a corrosion test of an aluminum current collector was carried out using this electrolytic solution. The test cell has aluminum as the working electrode,
A beaker type having lithium metal was used as the counter electrode and the reference electrode. When the working electrode was kept at 5 V (Li / Li ⁺ ), no current flowed. After the test, the surface of the working electrode was observed by SEM, but no change was observed as compared with that before the test.

Further, using this electrolyte, LiCoO ₂
To produce a cell using the positive electrode material and natural graphite as the negative electrode material,
A battery charge / discharge test was actually carried out. The test cell was prepared as follows.

90 parts by weight of LiCoO ₂ powder and 5 parts by weight of polyvinylidene fluoride (PVD) as a binder
F) and 5 parts by weight of acetylene black as a conductive material were mixed, and N, N-dimethylformamide was further added to form a paste. This paste was applied onto an aluminum foil and dried to obtain a test positive electrode body.
90 parts by weight of natural graphite powder and 1 as a binder
0 parts by weight of polyvinylidene fluoride (PVDF) was mixed, and N, N-dimethylformamide was further added to form a slurry. Apply this slurry on copper foil and
It was dried at 50 ° C. for 12 hours to obtain a test negative electrode body. Then, the electrolyte was impregnated into the polyethylene separator to assemble the cell.

Next, a constant current charge / discharge test was carried out under the following conditions. Both charging and discharging were performed at an environmental temperature of 25 ° C. with a current density of 0.35 mA / cm ² , and charging was 4.2 V,
The discharge was performed up to 3.0 V (vs. Li ^/ Li ⁺ ).
As a result, the charge and discharge was repeated 500 times, but the capacity at the 500th time was 85% of the initial capacity.

Example 2 0.90 mol of a lithium aluminate derivative having the same structure as in Example 1 was added to a mixed solvent of 50 vol% ethylene carbonate and 50 vol% diethyl carbonate.
/ L and 0.10 mol of (CF ₃ CH ₂ OSO ₂ ) ₂ NLi
/ L was dissolved to prepare an electrolytic solution, and as in Example 1,
A corrosion test of an aluminum current collector was carried out using this electrolytic solution. When the working electrode was kept at 5 V (Li / Li ⁺ ), no current flowed. After the test, S
Observed by EM, no change was observed compared to before the test.

Further, using this electrolyte, a cell using LiCoO ₂ as a positive electrode material and natural graphite as a negative electrode material was prepared in the same manner as in Example 1, and a constant current charge / discharge test was carried out under the following conditions. Both charging and discharging were performed at an environmental temperature of 60 ° C. with a current density of 0.35 mA / cm ² , charging was performed to 4.2 V, and discharging was performed to 3.0 V (vs. Li / Li ⁺ ). As a result, the charging and discharging was repeated 500 times, but the capacity at the 500th time was 87% of the initial capacity.

Example 3 In a mixed solvent of 50 vol% ethylene carbonate and 50 vol% ethyl methyl carbonate,

[0038]

[Chemical 5]

The lithium borate derivative having the structure of 0.70 mol / l and ((CF ₃ ) ₂ CHOSO ₂ ) ₂ NL
An electrolytic solution was prepared by dissolving i of 0.30 mol / l,
In the same manner as in Example 1, a corrosion test of an aluminum current collector was carried out using this electrolytic solution. 5V (Li / Li
⁺ ), No current flowed. After the test, the surface of the working electrode was observed by SEM, but no change was observed compared with before the test.

Further, using this electrolyte, a cell using LiCoO ₂ as a positive electrode material and natural graphite as a negative electrode material was prepared in the same manner as in Example 1, and a constant current charge / discharge test was carried out under the following conditions. Both charging and discharging were performed at an environmental temperature of 60 ° C. with a current density of 0.35 mA / cm ² , charging was performed to 4.2 V, and discharging was performed to 3.0 V (vs. Li / Li ⁺ ). As a result, the charging and discharging was repeated 500 times, but the capacity at the 500th time was 89% of the initial capacity.

Example 4 A solution was prepared by adding acetonitrile to 70 parts by weight of polyethylene oxide having an average molecular weight of 10,000, and 5 parts by weight of a lithium aluminate derivative having the same structure as in Example 1 ((CF ₃ ) ₂ CHOSO ₂ ) ₂ NLi (25 parts by weight) was added, and this was cast on glass and dried to remove the solvent acetonitrile, thereby preparing a polymer solid electrolyte membrane.

Next, a corrosion test of an aluminum current collector was carried out using this polymer solid electrolyte membrane. This film was sandwiched between an aluminum electrode and a lithium electrode of a working electrode and pressure-bonded for measurement. When the working electrode was kept at 5 V (Li / Li ⁺ ), no current flowed. After the test, the surface of the working electrode was observed by SEM, but no change was observed as compared with that before the test.

Next, a cell having LiCoO ₂ as a positive electrode material and a lithium metal foil as a negative electrode material was prepared by using this solid polymer electrolyte membrane as a substitute for an electrolytic solution and a separator.
A constant current charge / discharge test was carried out at 0 ° C. under the following conditions. Both charging and discharging were performed at a current density of 0.1 mA / cm ² , charging was 4.2 V and discharging was 3.0 V (vs. Li).
/ Li ⁺ ). As a result, the initial discharge capacity is
It was 120 mAh / g (capacity of positive electrode). Also, 10
The charge and discharge was repeated 0 times, but the capacity of the 100th time was 9
A result of 1% was obtained.

Comparative Example 1 ((CF ₃ ) ₂ CHO was added to a mixed solvent of 50 vol% ethylene carbonate and 50 vol% dimethyl carbonate.
An electrolytic solution in which 1.0 mol / l of SO ₂ ) ₂ NLi was dissolved was prepared, and a corrosion test of an aluminum current collector was carried out using this electrolytic solution in the same manner as in Example 1. Working electrode 5V (L
Corrosion current was observed when held at i / Li ⁺ ). Further, when the surface of the working electrode was observed by SEM after the test, many pits which were considered to be caused by corrosion were observed on the surface.

Next, using this electrolytic solution, a cell was prepared using LiCoO ₂ as a positive electrode material and natural graphite as a negative electrode material in the same manner as in Example 1, and a constant current charge / discharge test was carried out under the following conditions. . Both charging and discharging were performed at an environmental temperature of 25 ° C. with a current density of 0.35 mA / cm ² , charging was performed to 4.2 V, and discharging was performed to 3.0 V (vs. Li / Li ⁺ ). As a result, the charging and discharging was repeated 500 times, but the capacity at the 500th time was 62% of the initial capacity.

Comparative Example 2 (CF ₃ CH ₂ OSO) was added to a mixed solvent of 50 vol% ethylene carbonate and 50 vol% diethyl carbonate.
₂ ) An electrolytic solution in which 1.0 mol / l of ₂ NLi was dissolved was prepared, and a corrosion test of an aluminum current collector was carried out using this electrolytic solution in the same manner as in Example 1. Working electrode 5V (Li /
Corrosion current was observed when kept at Li ⁺ ). Further, when the surface of the working electrode was observed by SEM after the test, many pits which were considered to be caused by corrosion were observed on the surface.

Next, using this electrolytic solution, a cell was prepared using LiCoO ₂ as a positive electrode material and natural graphite as a negative electrode material in the same manner as in Example 1, and a constant current charge / discharge test was carried out under the following conditions. . Both charging and discharging were performed at an environmental temperature of 60 ° C. with a current density of 0.35 mA / cm ² , charging was performed to 4.2 V, and discharging was performed to 3.0 V (vs. Li / Li ⁺ ). As a result, the charging and discharging was repeated 500 times, but the capacity at the 500th time was 58% of the initial capacity.

Comparative Example 3 A lithium aluminate derivative having the same structure as in Example 1 was added in an amount of 1.0 mo in a mixed solvent of ethylene carbonate 50 vol% and ethyl methyl carbonate 50 vol%.
An electrolytic solution in which 1 / l was dissolved was prepared, and as in Example 1,
A cell was prepared using LiCoO ₂ as a positive electrode material and natural graphite as a negative electrode material, and a constant current charge / discharge test was performed under the following conditions. Both charging and discharging were performed at an environmental temperature of 60 ° C. with a current density of 0.35 mA / cm ² , charging was performed to 4.2 V, and discharging was performed to 3.0 V (vs. Li / Li ⁺ ). As a result, the charging and discharging was repeated 500 times, but the capacity at the 500th time was 62% of the initial capacity.

[0049]

INDUSTRIAL APPLICABILITY The present invention is an electrolyte having excellent 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. It enables an electrolytic solution or a solid electrolyte and a battery using these.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Mikihiro Takahashi             2805 Imafuku Nakadai Centra, Kawagoe City, Saitama Prefecture             Le Glass Co., Ltd. F-term (reference) 5G301 CA30 CD01                 5H029 AJ07 AJ12 AJ13 AK02 AK03                       AK05 AK16 AL02 AL07 AL12                       AM03 AM04 AM05 AM07 AM16                       HJ02 HJ20

Claims (9)

[Claims] 1. A compound having a chemical structural formula represented by general formula (1) and a compound having a chemical structural formula represented by general formula (2), general formula (3), or general formula (4): An electrolyte for an electrochemical device comprising at least one. [Chemical 1] A ^{q +} is a metal ion, hydrogen ion, or onium ion, M is a transition metal, Group III or IV of the periodic table, or
Group V element, 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 to 3, r is 1 to 3, m
Represents 0 to 8 and n represents 0 to 8, respectively, 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 to} C ₁₀ alkyl, or C _{1 to} C ₁₀ alkyl halide (these alkyls And alkyl halide may have a substituent or a hetero atom in its structure.), R ³ is H, halogen, C ₁ to
C ₁₀ alkyl, C ₁ -C ₁₀ alkyl halide, C ₄
To C ₂₀ aryl, or C _{4 to} C ₂₀ aryl halide (these alkyl, halogenated alkyl, aryl and aryl halide may have a substituent or a hetero atom in the structure), R ⁴ Is halogen, C _{1 to} C ₁₀
Alkyl, C ₁ -C ₁₀ alkyl halide, C ₄ -C
₂₀ aryls, C ₄ -C ₂₀ aryl halides, or X ² R ⁷ (these alkyls, halogenated alkyls, aryls, aryl halides may have a substituent or a hetero atom in the structure). , 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
Represents aryl halide -C ₂₀ (these alkyl, halogenated alkyl, aryl, halogenated aryl substituent in its structure, may have a hetero atom.), ^{Respectively, Y 1, Y 2, Y} 3 Are each independently, SO ₂ group or CO group, R ⁸ , R ⁹ , and R ¹⁰ are each independently, electron-withdrawing organic substituent (even if a substituent or a hetero atom is contained in these structures). R ⁸ , R ⁹ and R ¹⁰ may be bonded to each other to form a ring, or may be bonded to an adjacent molecule to form a polymer). 2. M is Al, B, V, Ti, Si, Z
r, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta,
The electrolyte for an electrochemical device according to claim 1, wherein the electrolyte is Bi, P, As, Sc, Hf, or Sb. 3. The electrolyte for an electrochemical device according to claim 1, wherein A ^{q +} is either a Li ion or a quaternary alkylammonium ion. 4. An electrolytic solution for an electrochemical device, comprising the 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 composed of 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 or 5, wherein A ^{q + of the} electrolyte is 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 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.