JPH11176701A - Developing solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing solution without liquid leaking out, which does not make a material forming an electrochemical element deteriorated and which can make the electrochemical element thin and laminated. SOLUTION: In a developing solution, a salt in which polyvinyl imidazolimium compound is set to be a positive ion component is set to be electrolyte. Polyvinyl imidazolimium compound is set to be that expressed by a formula. In the formula, (n) represents an integer not less than 2, and R1 and R2 each represent alkyl groups the carbons number of which is 1-4, and R3 represents an alkyl group hydrogen or carbon number of which is 1-4. In the developing solution, more than one type of acid constituting salt in which the polyvinyl imidazolimium compound is set as a positive ion component is selected from a group constituted of carbon acid and inorganic acid or developing solution which is an aggregate which polyvinyl imidazolium compound cross-linkage is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic solution used for an electrolytic capacitor, an electric double layer capacitor, a secondary battery, an electrochromic display device and the like.

[0002]

2. Description of the Related Art Conventionally, as an electrolytic solution, particularly an electrolytic solution such as an electrolytic capacitor, Japanese Patent Application Laid-Open No. Sho 62-145715 discloses a method in which a quaternary ammonium salt of an aromatic carboxylic acid is used as an electrolyte. JP-A-145714 discloses an electrolyte using a quaternary ammonium salt of an aliphatic monocarboxylic acid, and JP-A-62-248217 discloses an electrolyte using a quaternary ammonium salt of an aliphatic monocarboxylic acid. Have been. Electrolyte solutions using these quaternary ammonium salts as electrolytes have the problem of deteriorating or corroding materials, such as resins, rubbers and metals, that form electrochemical elements due to the electrochemical alteration of quaternary ammonium. there were.

To solve these problems, Japanese Patent Application Laid-Open No. Hei 8-32440 discloses a method using a low-molecular-weight imidazoline compound as an electrolyte. However, with a method using a low-molecular-weight imidazoline compound as an electrolyte, liquid leakage cannot be completely suppressed. Further, since there is a possibility of liquid leakage, it has been difficult to reduce the thickness and stack the electrochemical devices.

[0004]

As described above, the electrolyte solutions proposed hitherto degrade the material forming the electrochemical element and cannot completely suppress the leakage. Therefore, there has been a demand for the development of an electrolyte solution that can reduce the thickness and stack the electrochemical elements and has no liquid leakage.

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrolyte solution which does not deteriorate the material forming the electrochemical element and which can be thinned and laminated without causing any leakage.

[0006]

Means for Solving the Problems As a result of intensive studies on the electrolyte, the present inventors have found that the use of a salt containing a polyvinyl imidazolinium compound as a cation component as an electrolyte allows the electrolyte without leakage to be obtained. The present inventors have found a novel fact that it can be obtained, and have completed the present invention.

That is, the present invention is an electrolytic solution using a salt containing a polyvinyl imidazolinium compound as a cation component as an electrolyte.

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

The polyvinyl imidazolinium compound used in the electrolytic solution of the present invention is a compound represented by the following chemical formula 2.

[0010]

Embedded image

(N is an integer of 2 or more; R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms; R ₃ is hydrogen or 1 to 4 carbon atoms;
Represents an alkyl group).

Examples of the alkyl group include a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl and tertiary butyl group.

The polyvinyl imidazolinium compound may or may not be cross-linked, but is preferably cross-linked because of its higher retention of the electrolyte.

Examples of the counter ion of polyvinyl imidazolinium used in the electrolyte of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid,
Tetrahydrophthalic acid, hexahydrophthalic acid, cytocholanic acid, dimethylmaleic acid, nitrophthalic acid, thiopropionic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, Carboxylates such as lauric acid, myristic acid, stearyl acid, behenic acid, acrylic acid, methacrylic acid, oleic acid, benzoic acid, nitrobenzoic acid, cinnamic acid, naphthoic acid, salicylic acid, mandelic acid, resorcylic acid, and phosphoric acid , Boric acid, chloride, fluoride, bromide, iodide, borofluoric acid, perchloric acid, and fluorophosphate ions. Preferred among these are
Maleic acid, phthalic acid, adipic acid, and benzoic acid, which are thermally stable and have high electric conductivity, are more preferable, and maleic acid and phthalic acid are more preferable.

Solvents used in the electrolyte of the present invention include butyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol,
Alcohols such as dipropylene glycol and glycerin, ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether and ethylene glycol dimethyl ether, N, N-dimethylformamide, N, N-diethylformamide, N, N
Amides such as -dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone,
3-Methyloxazolidine-2-one, dimethylsulfoxide, γ-butyrolactone, dimethyl carbonate and the like. Among them, particularly preferred are ethylene glycol, 1,3-dimethyl-2-imidazolidinone, 3-methyloxazolidin-2-one, and butyrolactone, which have high conductivity and are thermally stable. These may be used alone or as a mixture of two or more.

[0016]

EXAMPLES Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example 1 Polyacrylonitrile (average molecular weight: 86,000) 240
g, ethylenediamine 1200g, acetic acid 144g 2L
After the flask was purged with nitrogen, the temperature was raised.
After heating at 90 ° C. for 12 hours, the mixture was cooled, a viscous red solution was taken out, and poured into acetone to give a pale yellow solid. When this was dried, 575 g of a partially yellowed polyvinyl imidazoline powder partially crosslinked was obtained. This was reacted with dimethyl carbonate to obtain polyvinyl dimethyl imidazolinium carbonate. This was further reacted with maleic acid to obtain polyvinyldimethylimidazolinium maleate.

When a mixed solution of 0.6 times by weight of ethylene glycol and 2.4 times of γ-butyrolactone is added to this polyvinyl dimethyl imidazolinium maleate, the polyvinyl dimethyl imidazolinium maleate becomes The whole amount was absorbed to form a gel.

The conductivity of the gel electrolyte at 30 ° C. was 10.1 ms / cm.

COMPARATIVE EXAMPLE 1 A mixture of 1,2,3-trimethylimidazolinium maleate, 0.6 times by weight of ethylene glycol and 2.4 times of γ-butyrolactone was added to maleic acid. , 2,3-Trimethylimidazolinium did not gel and remained liquid.

Example 2 The polyvinyl dimethyl imidazolinium carbonate obtained in Example 1 was reacted with phthalic acid to obtain polyvinyl dimethyl imidazolinium phthalate. When a mixed solution of 0.6 times by weight of ethylene glycol and 2.4 times of γ-butyrolactone is added to the polyvinyl dimethyl imidazolinium phthalate, the polyvinyl dimethyl imidazolinium phthalate absorbs the entire amount of the mixed solution. It liquified and became a gel.

The conductivity of the gel electrolyte at 30 ° C. was 11.2 ms / cm.

[0023]

The electrolyte of the present invention does not leak, has high conductivity, and does not deteriorate the material forming the electrochemical element.
It can be used as an electrolyte without a liquid leak that can make the electrochemical element thinner and laminated.

Claims (4)

[Claims] 1. An electrolytic solution comprising a salt containing a polyvinyl imidazolinium compound as a cation component as an electrolyte. 2. The electrolytic solution according to claim 1, wherein the polyvinyl imidazolinium compound is a compound represented by the following formula 1. Embedded image (N is an integer of 2 or more, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, and R ₃ is hydrogen or an alkyl group having 1 to 4 carbon atoms) 3. The electrolytic solution according to claim 1, wherein the acid constituting the salt having a polyvinyl imidazolinium compound as a cation component is at least one selected from the group consisting of carboxylic acids and inorganic acids. . 4. The electrolytic solution according to claim 1, wherein the electrolyte is a crosslinked polymer of a polyvinyl imidazolinium compound.