JPH0582169A - Electrolyte composition and high-polymeric solid electrolyte - Google Patents

Abstract

PURPOSE:To provide a high-polymeric solid electrolyte having a high ion conductivity and a good shape holding property. CONSTITUTION:A high-polymeric solid electrolyte comprises a hardened matter or mixture of solvent, electrolytic salt, thermally metamorphic high polymer, and/or cellulose derivative, where the solvent includes polyatomic alcohol compound of a molecular weight of 200 or less, and the thermally methamorphic high polymer comprises egg albumen protein at least including ovalbumin, etc., and/or beta-1,3-glucan (except for the one for driving an electrolytic capacitor).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrolytic solution composition and a polymer solid electrolyte.

[0002]

2. Description of the Related Art Heretofore, as a solid polymer electrolyte, there has been known a semi-solid electrolyte obtained by adding alkyl polymethacrylate to an electrolytic solution. (JP-A-57-101352, etc.)

[0003]

However, this has a problem that the shape retention, particularly the shape retention at high temperature, is insufficient.

[0004]

Means for Solving the Problems The present inventor
The present invention has been achieved as a result of earnest studies to obtain a polymer solid electrolyte having excellent shape retention especially at high temperatures. That is, the present invention is an electrolytic solution composition comprising a solvent, an electrolyte salt, a heat-denaturing polymer and / or a cellulose derivative, wherein the solvent is a solvent containing a polyhydric alcohol compound having a molecular weight of 200 or less, and the heat-altering polymer is egg white. An electrolyte solution composition characterized by being a heat-denaturing polymer selected from proteins and / or β-1,3-glucan; and a polymer solid electrolyte comprising a cured product of this electrolyte solution composition (however, , Except for driving electrolytic capacitors).

In the present invention, as the polyhydric alcohol compound having a molecular weight of 200 or less, ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, glycerin, polyoxyalkylene polyol (polyethylene oxide having a molecular weight of 200 or less,
Polypropylene oxide, polyoxyethylene / oxypropylene glycol, and a combination of two or more of these) and the like. Among these, ethylene glycol,
Propylene glycol and diethylene glycol are preferred.

As the solvent, a polyhydric alcohol having a molecular weight of 200 or less may be used in combination with another solvent which is generally used for an electrolytic solution of an electrochemical device, if necessary. Other solvents include water, amide solvents (N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidinone, etc.), alcohol solvents (methanol, ethanol, etc.), ether solvents (methylal). , 1,2-dimethoxyethane, 1-ethoxy-2-methoxyethane, 1,2-diethoxyethane, etc.), nitrile solvents (acetonitrile, 3-methoxypropionitrile, etc.), furan solvents (2,5-dimethoxytetrahydrofuran) Etc.), carbonate solvents (propylene carbonate, ethylene carbonate, styrene carbonate, etc.), lactone solvents (γ-butyrolactone, γ-
Valerolactone, δ-valerolactone, 3-methyl-
1,3-oxazolidin-2-one, 3-ethyl-1,
3-oxazolidin-2-one etc.), imidazolidinone solvent (1,3-dimethyl-2-imidazolidinone etc.),
Examples include pyrrolidone solvent and the like, and combinations of two or more of these. If other solvents are used in combination, water,
Alcohol solvents, carbonate solvents, ether solvents, nitrile solvents and furan solvents are preferred.

In the present invention, examples of the electrolyte salt include metal salts and ammonium salts. Examples of the metal salt include salts of group I or group II metals, and among these, salts of Li, Na and K having a small cation radius are preferable. Examples of anions constituting these metal salts include halogen ions (F, Cl, Br, I, etc.), thiocyanate ion, perchlorate ion, trifluoromethanesulfonate ion, fluoroborate ion and the like. Among the anions constituting the metal salt, preferred are thiocyanate ion, perchlorate ion, trifluoromethanesulfonate ion and fluoroborate ion. Examples of the ammonium salt include ammonium salts of acids such as carboxylic acid (adipic acid, phthalic acid, azelaic acid, etc.), phosphoric acid, boric acid, sulfonic acid (aryl sulfonic acid, etc.), and hydrofluoroboric acid. You may mix and use these. Among these ammonium salts, ammonium carboxylate, ammonium phosphate and ammonium borate are preferred. A preferable one may be selected from the above metal salts and ammonium salts depending on the use of the solid polymer electrolyte.

In the present invention, examples of egg white protein include ovotransferrin, ovalbumin, and those containing at least 50% by weight of at least one of them.

In the present invention, the heat-denaturing polymer is the egg white protein and / or β-1,3 exemplified above.
-Selected from glucans.

Examples of the cellulose derivative in the present invention include alkyl cellulose (methyl cellulose, ethyl cellulose and the like), hydroxyalkyl cellulose (hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose and the like) and the like. Of these, hydroxyalkyl cellulose is preferable, and hydroxyethyl cellulose is particularly preferable.

The composition ratio (weight basis) of the electrolytic solution composition in the present invention will be described. The electrolyte salt is the solvent 10
It is usually 0.1 part to 50 parts, preferably 1.0 part to 40 parts per 0 part. Outside this range, the ionic conductivity is low.
The amount of the heat-modified polymer and / or cellulose derivative is usually 1.0 part to 100 parts, preferably 5 parts to 50 parts, relative to 100 parts of the solvent. If it is less than 1.0 part, the shape-retaining property is lowered, and if it exceeds 100 parts, the ionic conductivity is lowered. There is no particular limitation on the mixing ratio when the heat-denaturing polymer and the cellulose derivative are used in combination, and any mixing ratio may be used.

The electrolytic solution composition of the present invention may contain a resin. As the resin, those described in “Chemical products of 10889” (published by Kagaku Kogyo Nippo Co., Ltd.), pages 703 to 782 can be used. When this resin is contained, polyvinyl alcohol, polyethylene oxide and polyvinyl pyrrolidone are preferable among them.

The electrolytic solution composition of the present invention may be a composition of two or more liquids in which the respective components are mixed in an arbitrary combination, or all the components may be mixed into one liquid. As an example of the method for producing the polymer solid electrolyte of the present invention, in the case of using a heat-alterable polymer or a heat-alterable polymer and a cellulose derivative, the electrolytic solution composition (all-component mixture) of the present invention is heated at 50 ° C to 100 ° C. It can be produced by heating to ℃. This heating may use microwaves. When a cellulose derivative is used without using a heat-denaturing polymer, it is sufficient to mix the electrolytic solution composition of the present invention (mixture of all components) and leave it at room temperature for about 30 minutes, and heating is essential. Not a condition.

The polymer solid electrolyte of the present invention can be combined with an auxiliary material. In the case of forming a composite, an auxiliary material may be impregnated with the electrolytic solution composition of the present invention and then cured. Examples of auxiliary materials include films, papers, cloths, non-woven fabrics and the like.

[0015]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Hereinafter, parts are parts by weight.

Example 1 100 parts of ethylene glycol, 10 parts of diammonium adipic acid, 5 parts of water and 10 parts of ovalbumin were mixed to obtain an electrolytic solution composition of the present invention. This was heated to 70 ° C. to prepare the polymer solid electrolyte of the present invention. It exhibits shape retention at room temperature and 100 ° C, and has an ionic conductivity of 1.2 × 10 ^-3 S / c at 25 ° C according to the AC impedance method.
It was m.

Example 2 A polymer solid electrolyte of the present invention was prepared in the same manner as in Example 1 except that ovotransferrin was used instead of ovalbumin. This product exhibited shape retention properties at room temperature and 100 ° C., and had an ionic conductivity of 2.5 × 10 ⁻³ S / cm at 25 ° C. according to the AC impedance method.

Example 3 A solid polymer electrolyte of the present invention was prepared in the same manner as in Example 1 except that β-1,3-glucan was used instead of ovalbumin. This product exhibited shape retention at room temperature and 100 ° C., and had an ionic conductivity of 1.8 × 10 ⁻³ S / cm at 25 ° C. according to the AC impedance method.

Example 4 A solid polymer electrolyte of the present invention was prepared in the same manner as in Example 1 except that 8 parts of hydroxyethyl cellulose was used instead of 10 parts of ovalbumin, and the mixture was left at room temperature for 30 minutes instead of being heated. did. This one is at room temperature and 100
Shape retention at ℃, by AC impedance method 2
The ionic conductivity at 5 ° C. was 1 × 10 ⁻³ S / cm.

[0020]

【The invention's effect】

(1) The polymer solid electrolyte of the present invention can be easily obtained only by using the electrolytic solution composition of the present invention in a predetermined shape by casting or impregnating an auxiliary material and curing. (2) The polymer solid electrolyte of the present invention is superior to the conventional one in that it has no liquid leakage and has good shape retention particularly at high temperature. Furthermore, the ionic conductivity is also high. Therefore, the polymer solid electrolyte of the present invention is particularly useful as a polymer solid electrolyte used in a device such as a battery, an electrocardiographic electrode, an electrochromic device, a conductive roller, and a conductive mat, which is used even at a high temperature.

Claims (2)

[Claims] 1. An electrolytic solution composition comprising a solvent, an electrolyte salt, a heat-denaturing polymer and / or a cellulose derivative, wherein the solvent is a solvent containing a polyhydric alcohol compound having a molecular weight of 200 or less, and the heat-altering polymer is An electrolytic solution composition, which is a thermo-denaturing polymer selected from egg white protein and / or β-1,3-glucan. 2. A solid polymer electrolyte comprising a cured product of the electrolytic solution composition according to claim 1, except for driving an electrolytic capacitor.