JP3355776B2 - Electrolyte for driving electrochemical element and electrochemical element using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic solution for driving an electrochemical device used for driving an electrochemical device such as an aluminum electrolytic capacitor, an electric double layer capacitor, a battery, an EL device, and an electrochemical device using the same. It relates to an element.

[0002]

2. Description of the Related Art A conventional electrolyte for driving an electrochemical device uses one of γ-butyrolactone, ethylene glycol, N, N-dimethylformamide, propylene carbonate, and ethylene carbonate as a main solvent.
To this, an inorganic acid salt or an organic acid salt was added as a supporting electrolyte, and in some cases, a phosphoric acid compound, an aromatic nitro compound, a saccharide, or the like was added as an additive in most cases. In particular, γ-butyrolactone as a main solvent has low toxicity and has better temperature characteristics than other glycol-based or carbonate-based solvents, so it is used for driving electrochemical elements such as aluminum electrolytic capacitors, electric double layer capacitors, and batteries. It is widely used as a solvent for electrolytes.

[0003]

However, in an electrolytic solution for driving an electrochemical device using γ-butyrolactone as a main solvent, the —COO— portion of the lactone ring undergoes hydrolysis even when only a trace amount of water is present. This causes problems in that the characteristics of the driving electrolyte are deteriorated and the decomposition potential of the driving electrolyte on the oxidation side is lowered.

[0004] The present invention solves the above-mentioned conventional problems, and can suppress the hydrolysis reaction of the -COO- moiety of the lactone ring to prevent the deterioration of the characteristics of the driving electrolyte from being promoted. At the same time, the decomposition potential of the driving electrolyte on the oxidation side can be increased, and in the products using this driving electrolyte, the electrochemical device driving electrolyte which can achieve a high withstand voltage and a long life can be obtained. It is an object to provide an electrochemical device used.

[0005]

Means for Solving the Problems To achieve the above object, an electrolytic solution for driving an electrochemical element of the present invention has a solvent and a solute, and at least one of R1 to R4 in the chemical formula ( 2 ) is used as the solvent. One or more unsaturated hydrocarbons with two or more carbon atoms
A compound containing at least a compound having a group is used.

[0006]

Embedded image

[0007]

According to the electrolytic solution for driving an electrochemical device having the above structure, at least one of R1 to R4 in the chemical formula ( 2 ) contains at least a compound having an unsaturated hydrocarbon group having two or more carbon atoms. In this case, the hydrolysis reaction of the —COO— portion of the lactone ring can be suppressed to prevent the characteristic deterioration of the driving electrolyte solution from being promoted, and the oxidation of the driving electrolyte solution can be prevented. The side decomposition potential can also be increased, and in the electrochemical element using the driving electrolyte, a high withstand voltage and a long life can be achieved.

[0008]

Embodiments of the present invention will be described below.

The electrolyte for driving an electrochemical device of the present invention basically has a solvent and a solute, and at least one of R1 to R4 in the chemical formula ( 2 ) has two or more carbon atoms.
And at least a compound having an unsaturated hydrocarbon group .

The compounds to be used in the present invention include, but are not limited to, the following.

[0011] beta - vinyl -γ- butyrolactone, .gamma. vinyl -γ- butyrolactone, beta - allyl -γ- butyrolactone, .gamma. allyl -γ- butyrolactone, beta - phenyl -γ- butyrolactone, .gamma.-phenyl -γ - Buchirora <br/> transfected emissions, beta - methoxy -γ- butyrolactone, .gamma.-methoxy -γ- butyrolactone, beta - ethoxy -γ- butyrolactone, .gamma. ethoxy -γ- butyrolactone, beta-propoxy -γ- butyrolactone, γ-propoxy-γ-
Butyrolactone, β - pentyloxy -γ- butyrolactone, γ- pentyloxy -γ- butyrolactone, β - isopentyloxy -γ- butyrolactone, γ- isopentyloxy -γ- butyrolactone, β - hexyloxy -γ- butyrolactone, γ -Hexyloxy-γ-butyrolact
Down, β - benzyloxy -γ- butyrolactone, γ- benzyloxy -γ- butyrolactone, β - phenoxy -γ-
Butyrolactone, γ-phenoxy-γ-butyrolact
Down, β - propionyl -γ- butyrolactone, γ- propionyl -γ- butyrolactone, β - butyryl -γ- butyrolactone, γ- butyryl -γ- butyrolactone, β
- isobutyryl -γ- butyrolactone, .gamma. isobutyryl -γ- butyrolactone, beta - valeryl -γ- butyrolactone, .gamma. valeryl -γ- butyrolactone, beta - chloro -γ- butyrolactone, .gamma.-chloro -γ- butyrolactone <br /> t, β - iodide -γ--butyrolactone, γ- iodide -
γ- butyrolactone, β - fluoride -γ--butyrolactone, γ- fluoride -γ- butyrolactone, β - bromide -γ-
Butyrolactone, γ- bromide -γ- butyrolactone, β -
Cyano -γ- butyrolactone, .gamma.-cyano -γ- Buchiro <br/> Lactobacillus emissions, beta - nitro -γ- butyrolactone, .gamma.-nitro -γ- butyrolactone, beta - amino -γ- butyrolactone, .gamma.-amino -γ - butyrolactone, beta - methylamino -γ- butyrolactone, .gamma.-methylamino -γ- Bed <br/> Chirorakuto emissions, beta - anilino -γ- butyrolactone, gamma
- anilino -γ- butyrolactone, beta - diphenylamino -γ- butyrolactone, .gamma. diphenylamino -γ-
Butyrolactone, beta - dimethylamino -γ- butyrolactone, .gamma.-dimethylamino -γ- butyrolactone, beta -
Diethylamino -γ- butyrolactone, .gamma.-diethylamino -γ- butyrolactone, beta - dipropylamino -γ
- butyrolactone, .gamma.-dipropylamino -γ- Buchiro <br/> Lactobacillus emissions, beta - ethylmethylamino -γ- butyrolactone, .gamma. ethylmethylamino -γ- butyrolactone, beta
- methylpropylamino -γ- butyrolactone, .gamma. methylpropylamino -γ- butyrolactone, beta - ethylpropylamino -γ- butyrolactone, there is .gamma. ethylpropylamino -γ- butyrolactone.

The solute of the electrolytic solution for driving an electrochemical device of the present invention includes ammonium salts, amine salts, phosphonium salts, and alkali metal salts. Specifically, ethylamine salt, triethylamine salt, ethanolamine salt,
Diethylamine salt, dipropylamine salt, tributylamine salt, 1,2-naphthylenediamine salt, benzylamine salt, triphenylamine salt, tetramethylammonium salt, tetraethylammonium salt, methyltriethylammonium salt, hydrazine, tetramethylphosphonium salt , Tetraethylphosphonium salts, methyltriethylphosphonium salts, lithium salts, potassium salts, sodium salts and the like. The acid groups constituting the solute of the driving electrolyte are organic monocarboxylic acid, dicarboxylic acid, boric acid, nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, tetrafluoroboric acid, fluoromethanesulfonic acid, and phosphotungstic acid And as the carboxylic acid, specifically, benzoic acid, maleic acid, phthalic acid, adipic acid, succinic acid,
Malonic acid, oxalic acid, glutaric acid, pimelic acid, suberic acid, formic acid, picric acid, γ-resorcylic acid, azelaic acid, salicylic acid, sebacic acid, citric acid, acrylic acid, propionic acid, lactic acid, butyric acid, valeric acid, D -Gluconic acid, octanoic acid, palmitic acid, oleic acid, stearic acid, P-nitrobenzoic acid, anthranilic acid, N-methylanthranilic acid, gallic acid, diphenylacetic acid, tartronic acid, citraconic acid, L-malic acid, L- Tartaric acid, nitrophthalic acid, tricarballylic acid, and the like, as well as partially alkyl-substituted and nitro-substituted compounds of the above compounds. Preferred solutes include lithium perchlorate, sodium perchlorate, tetraethylammonium phthalate, tetraethylammonium maleate, tetraethylammonium tetraethylfluoroborate, tetramethylammonium phthalate, tetramethylammonium maleate, tetramethylammonium tetrafluoroborate Ammonium, methyltriethylammonium phthalate,
Examples include methyltriethylammonium maleate and methyltriethylammonium tetrafluoroborate. The concentration of the solute constituting the driving electrolyte solution of the present invention is desirably 50 wt% or less in order to prevent a decrease in the conductivity of the solute due to a decrease in the mobility of the solute due to an increase in the concentration of the solute.

[0013] Solvents and additives mixed in the driving electrolyte of the present invention include propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, diacetone alcohol, benzyl alcohol, 2-diethylaminoethanol, Triethylene glycol, phenyl glycol, diethyl ether, diethylene glycol dimethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, acetone, N-methylformamide, N, N-dimethylacetamide, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether,
Diethylene glycol, glycerin, γ-butyrolactone, N, N-dimethylformamide, N-methylacetamide, formamide, water, heavy water, ammonia, sulfuric acid,
Carbon disulfide, carbon tetrachloride, pentane, hexane, cyclohexane, isooctane, octane, benzene, toluene, chloroform, 1,2-dichloroethane, 1,2-
Dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, 0-dichlorobenzene, methanol, ethanol, 2,2,2-trifluoroethanol, isopentyl alcohol, cyclohexanol, 2-ethoxyethanol, phenol, 1,4-dioxane , Anisole, 1,2-dimethoxyethane, methyl carbitol, ethyl carbitol, furfural, ethyl methyl ketone, cyclohexanone, formic acid, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, ethyl acetate, butyl acetate, ethylene carbonate, propylene Carbonate, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrove Zen, ethylenediamine, pyridine, morpholine, dimethylsulfoxide, sulfolane, monobutyl ester, p- nitrobenzoic acid,
p-nitrophenol, polyoxyethylene octyl phenyl ether phosphate, 0-cresol, orthophosphoric acid, tributyl phosphate, phosphorus pentoxide, pyrophosphoric acid, butyl polyphosphate, phosphorous acid, D-sorbit, mannitol , Polyvinyl alcohol, glycerin, polyethylene glycol and the like. The solvent and additives to be mixed are 80 watts in the driving electrolyte of the present invention.
It is desirable that t% or less be dissolved.

The amount of water contained in the electrolytic solution for driving an electrochemical device of the present invention is 5 wt% in order to prevent the characteristic deterioration of the driving electrolytic solution due to the ring opening reaction of the -COO- portion of the lactone ring.
The following is desirable.

Hereinafter, specific examples of the electrolytic solution for driving an electrochemical device of the present invention and the electrochemical device using the same will be described, but the present invention is not limited thereto. The present invention suppresses the hydrolysis reaction of the -COO- moiety of the lactone ring by introducing an unsaturated hydrocarbon group having two or more carbon atoms into γ-butyrolactone, which is a solvent of the conventional driving electrolyte. It is possible to prevent the property deterioration of the driving electrolyte from being promoted, and it is also possible to increase the oxidative decomposition potential of the driving electrolyte, and to increase the withstand voltage in products using this electrolyte. It is also possible to provide an electrolytic solution for driving an electrochemical device which can achieve a longer life and an electrochemical device using the same.

Table 1 shows an aluminum electrolyte having a rated voltage of 25 V and a rated capacity of 1000 μF using the driving electrolyte of Conventional Example 1 and the driving electrolytes of Examples 1, 2, 3, 4, and 5 of the present invention. It shows the rate of change of capacitance of each of the capacitors after a rated voltage load of 105 ° C. was applied for 2000 hours. As a solute of these driving electrolytes, 20 wt% of tetramethyl ammonium maleate or 20 wt% of tetramethyl ammonium phthalate was used.

[0017]

[Table 1]

As is clear from Table 1, the aluminum electrolytic capacitors using the driving electrolyte of Examples 1, 2, 3, 4, and 5 of the present invention use the driving electrolyte of Conventional Example 1. Since the rate of change in capacitance can be reduced as compared with the aluminum electrolytic capacitor described above, the life of the aluminum electrolytic capacitor can be extended.

Table 2 shows conventional examples 1 and 2 using propylene carbonate or γ-butyrolactone as a solvent.
2, the decomposition potential of the driving electrolyte of Example 1 of the present invention using β-vinyl-γ-butyrolactone as a solvent, and the decomposition of the driving electrolyte of Conventional Examples 1 and 2 and that of the present invention. 3 shows the withstand voltage of an electric double layer capacitor having a rated capacity of 0.33 F using the driving electrolyte of Example 1.

As the decomposition potential, the potential on the working electrode side was swept at 2 mV / s by a function generator, and the potential at which a current of 1 μA flowed to the reference electrode of the counter electrode was defined as the decomposition potential.
The withstand voltage of the electric double layer capacitor is 200
The current value flowing through the electric double layer capacitor after the time application was measured, and the potential at which a current of 1 μA flowed was taken as the withstand voltage of the electric double layer capacitor. And 0.6 M-tetraethylammonium tetrafluoroborate was used as a solute of these driving electrolytes.

[0021]

[Table 2]

As is clear from Table 2, the electric double layer capacitor using the driving electrolyte of the first embodiment of the present invention is an electric double layer capacitor using the driving electrolyte of the first and second conventional examples. This makes it possible to greatly improve the withstand voltage as compared with.

[0023]

As described above, according to the electrolytic solution for driving an electrochemical device of the present invention, R1 in the chemical formula (1) is used as a solvent.
At least one of R4 is unsaturated having two or more carbon atoms
Since a compound having at least a compound having a hydrocarbon group is used, it is possible to suppress the hydrolysis reaction of the -COO- portion of the lactone ring and to prevent the property deterioration of the driving electrolyte from being promoted. In addition to this, the decomposition potential on the oxidation side of the driving electrolyte can be increased, and in the electrochemical element using the driving electrolyte, a high withstand voltage and a long life can be achieved.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-84703 (JP, A) JP-A-62-216171 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01G 9/02

Claims (11)

(57) [Claims] 1. A solvent and a solute, wherein at least one of R1 to R4 in the chemical formula (1) is a charcoal.
An electrolyte for driving an electrochemical device, comprising an electrolyte containing at least a compound having an unsaturated hydrocarbon group having two or more prime numbers . Embedded image 2. The unsaturated hydrocarbon group having 2 or more carbon atoms is
The electrolyte for driving an electrochemical device according to claim 1, wherein the electrolyte is any one of a phenyl group, a vinyl group, and an allyl group . 3. The electrolyte for driving an electrochemical device according to claim 1, wherein R2, R3 and R4 are hydrogen and R1 is a vinyl group. Wherein the solute include ammonium salts, phosphonium salts, electrochemical device driving electrolyte according to claim 1, wherein comprising at least one or more alkali metal salts. 5. The electrolyte for driving an electrochemical element according to claim 4 , wherein the acid groups constituting the solute are carboxylic acid, nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, tetrafluoroboric acid, and fluoromethanesulfonic acid. 6. The electrolytic solution for driving an electrochemical element according to claim 5 , wherein the carboxylic acid in the acid group constituting the solute is benzoic acid, maleic acid, phthalic acid or adipic acid. Ammonium salt of 7. Among the bases constituting the solute, tetra ammonium salts, tetraethylammonium salts, according to claim 4 which is methyl triethyl ammonium salt
An electrolytic solution for driving an electrochemical element according to the above. 8. The electrolyte for driving an electrochemical device according to claim 4 , wherein the concentration of the solute is 50 wt% or less. 9. The water content is an electrochemical device driving electrolyte according to claim 1, wherein at most ,, 5 wt% in the electrolyte. As claimed in claim 10 additives, phosphorus compounds, electrochemical device driving electrolyte according to claim 1, wherein the addition of the aromatic nitro compound. 11. The electrochemical device using the electrochemical device driving electrolyte according to any one of claims 1-10.