JP2001043896A - Manufacture of polymeric solid electrolyte, polymeric solid electrolyte, and electrochemical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a polymeric solid electrolyte excellent in ionic conductivity, mechanical strength, and flexibility, a polymeric solid electrolyte excellent in ionic conductivity, mechanical strength, and flexibility, and an electrochemical device excellent in cycle life. SOLUTION: According to this manufacturing method of a polymeric solid electrolyte, an alkaline metallic salt is dissolved in a polyamide resin. The polyamide resin is obtained by reacting (A) a polyamide resin intermediate obtained by reacting (a) diisocyanate or diamine with (b) dicarboxylic acid, tricarboxylic acid, or tricarboxylic acid unhydride, (B) an epoxy resin, and (C) polyoxyalkylene monoamine, and has a residue of the (C) constituent as a side chain. A polymeric solid electrolyte is manufactured by this manufacturing method, and the polymeric solid electrolyte is used for an electrochemical device.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solid polymer electrolyte, a method for producing the solid polymer electrolyte, and an electrochemical device.

[0002]

2. Description of the Related Art With the advance of electronic technology, the performance of electronic equipment has been improved, miniaturization and portability have been advanced, and batteries with high energy density as power sources have been desired. Conventional secondary batteries include lead batteries and nickel-cadmium batteries, but they are still insufficient in obtaining energy density. Therefore, as an alternative to these batteries, lithium secondary batteries with high energy density have been developed and are rapidly spreading.

[0003] Lithium secondary batteries are generally applicable to various applications because they can obtain a high voltage of 3 V or more, and are lightweight and have high capacity. Such a lithium secondary battery is
Many used lithium cobalt oxide for the positive electrode and a carbon material for the negative electrode as an active material. Recently, active materials have been actively researched and developed to increase the capacity. Also, the development of electrolytes has been actively developed, and attempts have been made to improve ionic conductivity and withstand voltage. Organic electrolytes are used as electrolytes in most lithium secondary batteries, including lithium ion secondary batteries. In an actual battery, this is impregnated in a separator such as a microporous polypropylene membrane to secure an ion conduction path between the positive electrode and the negative electrode.

However, a problem often encountered in lithium secondary batteries is an internal short-circuit due to dendritic deposition of lithium growing from the negative electrode to the positive electrode. In an organic electrolyte system, it is particularly necessary to control short-circuit accidents due to the dendrite deposition. Have difficulty. The organic electrolyte itself is a fluid, and it is essentially difficult to suppress the growth of dendrite. When a separator is used, the current flowing between the positive electrode and the negative electrode is concentrated in the pores of the separator, which is a limited ion conduction path. As a result, the growth of lithium dendrite is concentrated in the pores of the separator. Promoted.

In order to overcome such a situation, a battery system using a polymer electrolyte has been devised and is currently under development. This polymer electrolyte is an ionic conductor in which an alkali metal salt is uniformly dissolved in a polymer. It is said that this functions as a separator-free solid electrolyte and that current flows uniformly over the entire surface of the electrolyte, thereby suppressing the generation and growth of lithium dendrite.

[0006] In recent years, a solid polymer electrolyte having a polyethylene oxide component has been actively studied. For example, a method of crosslinking both ends of a copolymer of ethylene oxide and propylene oxide as described in Japanese Patent No. 1898067, and a method having a polyethylene glycol component as described in JP-A-2-7935. By polymerizing the monomer and the monomer having a urethane group to increase the molecular weight or three-dimensionally crosslink, the mechanical strength is improved, and on the other hand, the decrease in ionic conductivity due to crystallization is also prevented, and it is practical. You are trying to get a polymer.

However, polymers containing a large amount of polyethylene oxide component have inherently high water absorption, making it extremely difficult to obtain a non-aqueous water content required for a lithium battery. The film strength must be low as long as it is non-crystalline. Also, its ionic conductivity is 10 ^-5 S / at room temperature.
cm, which is two orders of magnitude lower than that of the organic electrolyte. In addition, a polymer electrolyte containing no polyethylene oxide chain has been studied. For example, by swelling polyvinylidene fluoride with a non-aqueous electrolyte,
It is a gel polymer electrolyte with improved ionic conductivity.
However, polyvinylidene fluoride has a low swelling property with a non-aqueous electrolyte and cannot be said to have high ionic conductivity.

[0008] When such a polymer electrolyte having a low ionic conductivity is applied to a secondary battery, the internal resistance of the battery increases, causing problems such as heat generation during charging and discharging and a reduction in efficiency during discharging at a high discharge rate. .

[0009]

The object of the present invention is to provide a method for producing a solid polymer electrolyte having excellent ionic conductivity, mechanical strength and flexibility. The invention described in claim 2 provides the method of producing a solid polymer electrolyte having the effects of the invention described in claim 1 and further having excellent ion conductivity. The third aspect of the present invention provides a method for producing a polymer solid electrolyte having the effects of the first or second aspect of the present invention and further having excellent mechanical strength.

The fourth aspect of the present invention provides a solid polymer electrolyte having excellent ionic conductivity, mechanical strength and flexibility. The invention of claim 5 provides an electrochemical device having excellent cycle life.

[0011]

The present invention provides (A) and (a)
Diisocyanate or diamine and (b) dicarboxylic acid,
(C) component residue in the side chain obtained by reacting a polyamide resin intermediate obtained by reacting with tricarboxylic acid or tricarboxylic anhydride, (B) an epoxy resin and (C) a polyoxyalkylene monoamine The present invention relates to a method for producing a solid polymer electrolyte, characterized by dissolving an alkali metal salt in a polyamide resin having the following.

Further, the present invention provides a polyamide resin, wherein the compounding ratio of (C) polyoxyalkylene monoamine is as follows:
The present invention relates to a method for producing the polymer solid electrolyte, which is 1 to 20 mol% based on the total amount of the polyamide-based resin. In the present invention, the alkali metal salt may be LiClO ₄ , LiBF ₄ , LiP
The present invention relates to a method for producing the polymer solid electrolyte, which is at least one selected from the group consisting of F ₆ and LiN (CF ₃ SO ₂ ) ₂ .

[0013] The present invention also relates to a solid polymer electrolyte produced by the above method for producing a solid polymer electrolyte. Further, the present invention relates to an electrochemical device using the solid polymer electrolyte.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The method for producing a polymer solid electrolyte of the present invention comprises: (A) a polyamide resin intermediate obtained by reacting (a) a diisocyanate or a diamine with (b) a dicarboxylic acid, a tricarboxylic acid, or a tricarboxylic anhydride; ) It is necessary to dissolve an alkali metal salt in a polyamide resin having a (C) component residue in a side chain obtained by reacting an epoxy resin and (C) a polyoxyalkylene monoamine.

The above (A) polyamide resin intermediate must be obtained by reacting (a) diisocyanate or diamine with (b) dicarboxylic acid, tricarboxylic acid or tricarboxylic anhydride. .

The diisocyanate includes, for example,
4,4'-diphenylmethane diisocyanate, 2,6
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,
5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, 4,4'-
Aromatic diisocyanates such as diphenyl ether diisocyanate, m-xylylene diisocyanate, and m-tetramethyl xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene Aliphatic diisocyanates such as diisocyanate and lysine diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and 3,9- Heterocyclic diisocyanates such as bis (3-isocyanatopropyl) -2,4,8,10-tetraspiro [5,5] undecane; Aromatic diisocyanates are preferred from the standpoint of heat improved. These are used alone or in combination of two or more.

Examples of the diamine include aliphatic diamines such as alkylenediamine, diaminopolydimethylsiloxane and polyoxyalkylenediamine, alicyclic diamines such as isophoronediamine, 4,4'-dicyclohexylmethanediamine, and 3,9-diamine. Heterocyclic diamines such as bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine Amines, 4,4'-diaminodiphenylmethane 3,4'-diaminodiphenylmethane,
3,3'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether,
4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,4'-diaminodiphenylsulfone, 2,2'-diaminodiphenylsulfone, 4,4 '
-Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, 4,
Examples thereof include aromatic diamines such as 4'-benzophenonediamine, 3,3'-benzophenonediamine, 2,2-bis [4 (4-aminophenoxy) phenyl] propane, and 4,4'-diaminobenzanilide. These are used alone or in combination of two or more.

Either diisocyanate or diamine (a) may be used, but diisocyanate is preferred from the viewpoint of easy production of component (A) and improvement in yield.

The dicarboxylic acid, tricarboxylic acid or tricarboxylic anhydride (b) includes, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecane diacid, eicosane diacid, alkylene ether Bond-containing dicarboxylic acids, alkylene carbonate bond-containing dicarboxylic acids, butadiene bond-containing dicarboxylic acids, hydrogenated butadiene bond-containing dicarboxylic acids, dimethylsiloxane bond-containing dicarboxylic acids, and other aliphatic dicarboxylic acids, dimer acids, 1,4-cyclohexanedicarboxylic acids, and the like. Alicyclic dicarboxylic acid, heterocyclic dicarboxylic acid such as pyridine dicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 4,
4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, bis (4-carboxymethoxyphenyl) dimethylmethane, trimellitic anhydride / diamine = 2 mol / 1 mol Examples of the reaction product include an aromatic dicarboxylic acid such as an imide bond-containing dicarboxylic acid and an aromatic tricarboxylic acid such as trimellitic anhydride which are reaction products. These are used alone or in combination of two or more.

The (A) polyamide-based intermediate may be prepared, for example, by mixing (a) a diisocyanate or a diamine and (b) a dicarboxylic acid, a tricarboxylic acid or a tricarboxylic anhydride with a carboxyl group / isocyanate group or an amino group of 1 equivalent / 1 equivalent. It can be obtained by reacting at a compounding ratio such that it becomes less than. The mixing ratio is preferably less than 1 equivalent / 1 equivalent, preferably 1 equivalent / 0.5 equivalent to 1 equivalent / 0.1 equivalent.
More preferably 97 equivalents, 1 equivalent / 0.67
It is particularly preferable to set the equivalent to 1 equivalent / 0.95 equivalent, and it is extremely preferable to set the equivalent to 1 equivalent / 0.75 equivalent to 1 equivalent / 0.91 equivalent. When the mixing ratio is 1 equivalent / 1 equivalent or more, the component (a) tends to remain as an unreacted product, and the terminal of the reaction product is unlikely to become a carboxylic acid, and the yield of the component (A) is reduced. Tend. These components (A) are used alone or in combination of two or more.

The reaction between the component (a) and the component (b) is as follows:
For example, it can be performed in an organic solvent. Examples of the organic solvent include N-methyl-2-pyrrolidone, N,
Amide solvents such as N-dimethylacetamide, N, N-dimethylformamide, urea solvents such as N, N-dimethylethyleneurea, N, N-dimethylpropyleneurea, tetramethylurea, γ-butyrolactone, γ-caprolactone, etc. Lactone solvents, carbonate solvents such as propylene carbonate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate Ester solvents such as diglyme, triglyme, and tetraglyme; hydrocarbon solvents such as toluene, xylene and cyclohexane; and sulfone solvents such as sulfolane. Among them, amide-based solvents or urea-based solvents are preferred from the viewpoint of high solubility, high reaction promoting properties, etc. Among these, active hydrogen which easily inhibits the reaction between the component (a) and the component (b) is preferable. N- from the point of view
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylethyleneurea, N, N-dimethylpropyleneurea or tetramethylurea are more preferred, and among these, N-methyl-2-pyrrolidone is particularly preferred. preferable. These are used alone or in combination of two or more.

The amount of the organic solvent used is 30 to 200 parts by weight based on 100 parts by weight of the total of the components (a) and (b).
It is preferably 0 parts by weight, more preferably 50 to 1000 parts by weight, and particularly preferably 70 to 400 parts by weight. If the amount is less than 30 parts by weight, the solubility is poor, and the reaction system tends to be non-uniform or highly viscous. If the amount exceeds 2,000 parts by weight, the reaction does not easily proceed and the reaction tends to be difficult to complete. .

The temperature of the reaction between the components (a) and (b) is preferably 40 to 300 ° C., and 100 to 2 ° C.
The temperature is more preferably set to 50 ° C, particularly preferably 120 to 220 ° C. If the reaction temperature is lower than 40 ° C., the reaction does not easily proceed, and the reaction tends to be difficult to complete,
If the reaction temperature exceeds 300 ° C., gelation or the like due to a side reaction is likely to occur, and the reaction tends to be difficult to control. The reaction time between the component (a) and the component (b) is preferably about 10 minutes to 50 hours, more preferably about 20 minutes to 40 hours, and about 30 minutes to 30 hours. Particularly preferred.

Examples of the epoxy resin (B) in the present invention include bisphenol A epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, naphthalene epoxy resin, and biphenyl epoxy resin. , Bifunctional aromatic glycidyl ethers such as tetramethylbiphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin,
Dicyclopentadiene-phenol type epoxy resin, polyfunctional aromatic glycidyl ether such as tetraphenylolethane type epoxy resin, polyethylene glycol type epoxy resin, polypropylene glycol type epoxy resin,
Bifunctional aliphatic glycidyl ethers such as neopentyl glycol type epoxy resin, dibromoneopentyl glycol type epoxy resin, hexanediol type epoxy resin,
Bifunctional alicyclic glycidyl ethers such as hydrogenated bisphenol A type epoxy resin, trimethylol propane type epoxy resin, sorbitol type epoxy resin, polyfunctional aliphatic glycidyl ether such as glycerin type epoxy resin, diglycidyl phthalate, etc. Bifunctional alicyclic glycidyl esters such as bifunctional aromatic glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, N, N-diglycidylaniline, N, N-
Bifunctional aromatic glycidylamine such as diglycidyltrifluoromethylaniline, N, N, N ', N'-tetraglycidyl-4,4-diaminodiphenylmethane, 1,3
Polyfunctional aromatic glycidylamine such as -bis (N, N-glycidylaminomethyl) cyclohexane, N, N, O-triglycidyl-p-aminophenol, alicyclic diepoxy acetal, alicyclic diepoxy adipate, ali Bifunctional alicyclic epoxy resins such as cyclic diepoxycarboxylate and vinylcyclohexene dioxide; bifunctional heterocyclic epoxy resins such as diglycidylhydantoin; polyfunctional heterocyclic epoxy resins such as triglycidyl isocyanurate; organopoly Examples include a bifunctional or polyfunctional silicon-containing epoxy resin such as a siloxane-type epoxy resin, and among them, a bifunctional epoxy resin is preferable from the viewpoint of easy control of the reaction, and among the bifunctional epoxy resins, Bifunctional from the viewpoint of improving heat resistance More preferably aromatic glycidyl ether, among them, bisphenol A type epoxy resin from the viewpoint of inexpensive are particularly preferred. These are used alone or in combination of two or more.

The polyoxyalkylene monoamine (C) in the present invention includes, for example, a compound represented by the following general formula (I):

Embedded image (Wherein, R independently represents a hydrogen atom or a methyl group,
and n is a positive integer). Among the polyoxyalkylene monoamines represented by the general formula (I), the molecular weight of the polyoxyalkylene monoamine is from 600 to 200 from the viewpoint of obtaining a resin having a lower elastic modulus and excellent flexibility.
0 is preferred.

Examples of the polyoxyalkylene monoamine represented by the general formula (I) include, for example, Jeffamine M-600, M, manufactured by Huntsman Corporation.
-1000, M-2005, M-2070 and the like. These are used alone or in combination of two or more.

The components (A), (B) and (C) are (epoxy group in the component (B)) / (active hydrogen derived from the carboxyl group in the component (A) and active hydrogen in the component (C). (Equivalent amount of active hydrogen derived from amino groups) is preferably less than 1 equivalent / 1 equivalent, preferably 1 equivalent / 0.25 equivalent to 1 equivalent.
Equivalent / 0.90 equivalent is more preferable, and 1 equivalent / 0.33 equivalent to 1 equivalent / 0.83 equivalent is particularly preferable, 1 equivalent / 0.45 equivalent to 1 equivalent. It is extremely preferable to make the equivalent weight / 0.67 equivalent. If the mixing ratio is 1 equivalent / 1 equivalent or more, the thermosetting property tends to be impaired, and the chemical resistance tends to decrease.

The compounding ratio of the component (C) in the polyamide resin in the present invention is preferably from 1 to 20 mol%, more preferably from 2 to 15 mol%, based on the total amount of the polyamide resin. When the compounding ratio is less than 1 mol%, the ion conductivity tends to decrease, and when it exceeds 20 mol%, the mechanical strength of the gel composition tends to decrease.

In the reaction of the components (A), (B) and (C), it is preferred that the components (A) and (C) are not directly reacted. Specifically, after reacting the component (B) and the component (C), it is more preferable to react the component (A) with the reaction product, and to react the component (A) with the component (B). After the reaction, it is particularly preferable to react the component (C) with the reaction product. When the component (A) and the component (C) are directly reacted, a resin having a component (C) residue at a terminal is easily produced as a by-product, and the thermosetting resin of the present invention having a component (C) residue in a side chain. The yield of the polyamide resin tends to decrease.

The reaction of the components (A), (B) and (C) is carried out in an organic solvent. As the organic solvent, for example, the organic solvent that can be used when producing the above-mentioned component (A) can be used as it is. Among these, amide solvents, nitrogen-containing polar solvents such as urea solvents are preferable from the viewpoint of high solubility, high reaction promotion, and the like,
Among them, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like from the viewpoint that they do not have active hydrogen that easily inhibits the reaction of the components (A), (B) and (C). N, N-dimethylethylene urea, N, N-
Dimethylpropylene urea or tetramethyl urea is more preferred, of which N-methyl-2-pyrrolidone is particularly preferred. These are used alone or in combination of two or more.

The amount of the organic solvent used is as follows: component (A), component (B)
With respect to 100 parts by weight of the total amount of the component and the component (C), 30
2,000 parts by weight, preferably 50-100 parts by weight.
It is more preferably 0 parts by weight, particularly preferably 70 to 400 parts by weight. If the amount is less than 30 parts by weight, the solubility is poor, and the reaction system tends to be non-uniform or highly viscous. If the amount exceeds 2,000 parts by weight, the reaction does not easily proceed and the reaction tends to be difficult to complete. .

The reaction temperature of the components (A), (B) and (C) is preferably 40 to 300 ° C., more preferably 100 to 250 ° C., and 12
It is particularly preferable that the temperature be 0 to 220 ° C. If the reaction temperature is lower than 40 ° C., the reaction does not easily proceed and the reaction tends to be difficult to complete. If the reaction temperature exceeds 300 ° C., gelation or the like due to side reactions tends to occur, and the reaction tends to be difficult to control. The reaction time of the components (A), (B) and (C) is preferably about 10 minutes to 50 hours, more preferably about 20 minutes to 40 hours,
It is particularly preferable that the heating time is about 30 minutes to 30 hours.

In the reaction of the present invention, a catalyst or the like can be used as necessary. Examples of the catalyst include triethylamine, triethylenediamine, N,
N-dimethylaniline, N, N-diethylaniline,
N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, pyridine, picoline, 1,8-diazabicyclo [5,4,0] undecene-7 and the like Secondary amine, 2-
Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4- Imidazole compounds such as methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-azine-2-methylimidazole, dibutyltin dilaurate, 1,3-diacetoxytetrabutyldistannoxane, etc. Organic tin compounds, tetraethylammonium bromide,
Tetrabutylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, cetyltrimethylammonium bromide, tetrabutylammonium iodide, dodecyltrimethylammonium iodide, benzyldimethyltetradecylammonium acetate, tetraphenylphosphonium chloride, triphenyl chloride Quaternary onium salts such as methylphosphonium and tetramethylphosphonium bromide; organic phosphorus compounds such as 3-methyl-1-phenyl-2-phospholene-1-oxide; alkali metal salts of organic acids such as sodium benzoate and potassium benzoate Inorganic salts such as zinc chloride, iron chloride, lithium chloride and lithium bromide; and metal carbonyl compounds such as octacarbonyldicobalt (cobaltcarbonyl). These are used alone or in combination of two or more.

The polyamide resin obtained by the production method described above has a high polarity and a strong hydrogen bond between the nitrogen atom and the carbon atom of the amide bond, and has a large binding energy. Excellent heat resistance, adhesiveness and electrolyte resistance. Further, flexibility is excellent due to the polyoxyalkylene monoamine component residue of the side chain (C).

The weight average molecular weight of the polyamide resin in the present invention is preferably from 10,000 to 500,000, more preferably from 30,000 to 300,000, and more preferably from 50,000 to 300,000. 000
Is particularly preferred. This weight average molecular weight is 1
If it is less than 000, the flexibility and mechanical strength tend to decrease. If it exceeds 500,000, the solubility in an organic solvent decreases, the viscosity of the resin solution increases and the resin precipitates, and the handleability decreases. Tend to. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

As the alkali metal salt in the present invention,
For example, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiA
sF ₆ , LiCF ₃ SO ₃ , LiC ₂ F ₉ SO ₃ , LiN (C
Preferred examples thereof include lithium compounds such as F ₃ SO ₂ ) ₂ , and LiClO ₄ , LiBF ₄ , LiPF ₆ and LiN (C
F ₃ SO ₂ ) ₂ is more preferred. These are used alone or in combination of two or more.

The amount of the alkali metal salt used in the present invention is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, based on the total amount of the polyamide resin, the alkali metal salt and the non-aqueous electrolyte. More preferably, 5-2
It is particularly preferred that the content be 0% by weight. If the amount is less than 1% by weight, the ionic conductivity tends to decrease.
If the content is more than 10% by weight, the ionic conductivity tends to decrease.

The non-aqueous electrolytic solution in the present invention is preferably a non-aqueous system which can dissolve an alkali metal salt, is chemically stable, and is, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl. Carbonate compounds such as carbonate, tetrahydrofuran, dioxane, dimethoxyethane, ether compounds such as polyethylene oxide,
Lactone compounds such as γ-butyrolactone and propylpyrolactone. These are used alone or in combination of two or more.

The amount of the non-aqueous electrolyte in the present invention is preferably 10 to 95% by weight based on the total amount of the polyamide resin, the alkali metal salt and the non-aqueous electrolyte.
The content is more preferably 0 to 90% by weight, and 30 to 85% by weight.
It is particularly preferable to set the weight%. If the amount is less than 10% by weight, the ionic conductivity tends to decrease.
If the content exceeds% by weight, the mechanical strength tends to decrease.

The solid polymer electrolyte of the present invention is prepared, for example, by dissolving an alkali metal salt in a polyamide resin prepared from the above components (A), (B) and (C) to obtain a substrate having excellent mold releasability. After coating in a desired shape, a polymer film can be obtained by thermal crosslinking.

The solid polymer electrolyte of the present invention can be used for an electrochemical device. The electrochemical device, for example, is not particularly limited as long as it accumulates energy by electrochemical change, increases / decreases, releases, etc.
Batteries such as lithium batteries, nickel-metal hydride batteries, and fuel cells;
Examples include an electrochemical device such as an electrochemical sensor. Further, the polymer solid electrolyte of the present invention exhibits a change in color tone due to a potential difference. Therefore, a light control material such as a light control glass for room temperature control, a photoelectrochemical device such as a recording material, and a device using the same are used. It can also be applied to The battery can be used as a main power supply or a backup power supply for small electronic devices such as a mobile phone, a PHS, a notebook computer, and a portable terminal.In addition, a stationary load leveling power supply, a backup power supply during a power failure, It can be widely used for batteries for electric vehicles and the like.

The battery using the solid polymer electrolyte of the present invention may be, for example, a positive electrode using the solid polymer electrolyte of the present invention in the form of a film swollen with a non-aqueous electrolyte in a usual electrolyte type lithium ion secondary battery. The positive electrode sheet, the polymer solid electrolyte of the present invention, and the negative electrode are sandwiched between a positive electrode sheet obtained by casting a positive electrode material on a current collector sheet and a negative electrode sheet obtained by casting a negative electrode material on a negative electrode current collector sheet, and heated or pressed. The sheet is brought into close contact to form a portion that causes a battery reaction of the battery, and then, in order to isolate the obtained portion that causes the battery reaction from atmospheric moisture, oxygen, nitrogen, etc., for example, an insulated aluminum material is used. The container is sealed with a container or the like. At this time, the electrode portion is made of aluminum so that charging and discharging can be performed through the electrodes formed on the positive electrode sheet and the negative electrode sheet. Can be prepared by leaving exposed to the outside edge has been container. The battery using the polymer solid electrolyte of the present invention thus obtained is charged and charged.
The secondary battery can be discharged alternately.

The positive electrode current collector includes, for example, aluminum foil, nickel foil, gold foil, silver foil, titanium foil and the like, and is preferably aluminum foil from the viewpoint of high potential stability.

As the positive electrode material, for example, Li _1-x
CoO ₂ , Li _1-x NiO ₂ , Li _1-x Mn ₂ O ₄ , Li _1-x
MO ₂ (0 <x <1, M is a complex of Co, Ni, Mn, Fe, etc.), Li _2-y Mn ₂ O ₄ (0 <y <2), Li _1-x
V ₂ O ₅ (0 <x <1), Li _{2- y} V ₂ O ₅ (0 <y <
2), oxides such as Li _{1-x ′} Nb ₂ O ₅ (0 <x ′ <1.2), Li _1-x TiS ₂ , Li _1-x MoS ₂ , and Li _1-z NbS
Examples thereof include metal chalcogenides such as e ₃ (0 <z <3) and organic compounds such as dithiol derivatives and disulfide derivatives. These are used alone or in combination of two or more.

As the negative electrode current collector, for example, copper foil,
Nickel foil, gold foil, silver foil and the like can be mentioned, and copper foil is preferable from the viewpoint of good electron conductivity and low cost.

As the negative electrode material, for example, metallic lithium, aluminum / lithium alloy, magnesium / aluminum /
Lithium metal such as lithium alloy, AlSb, Mg ₂ G
e, an intermetallic compound such as NiSi ₂ , graphite, coke, a carbon-based material such as a low-temperature fired polymer, a SnM′-based oxide (M ′ indicates Si, Ge, Pb, etc.), Si _1-y M ″ _y
O _z (M "is W, Sn, Pb, shows etc. B) composite oxides of such as titanium oxide, lithium metal oxides such as iron oxide solid _{solution, Li 7 MnN 4, Li 3} FeN 4, Li 3 _-x Co _x
N, Li _3-x NiN, Li _3-x Co _x N, Li _3-x Cu
Ceramics such as nitrides such as _xN , Li ₃ BN ₂ , Li ₃ AlN ₂ , and Li ₃ SiN ₃ are exemplified. These are used alone or in combination of two or more.

[0047]

The present invention will be more specifically described below with reference to examples of the present invention and comparative examples.

The method for evaluating the solid polymer electrolyte obtained in this example is described below. <Ion conductivity> The ion conductivity is measured by an AC impedance method in which an electrochemical cell is constructed by sandwiching a solid polymer electrolyte between stainless steel electrodes at 25 ° C, and an alternating current is applied between the electrodes to measure the resistance component. And calculated from the real impedance intercept of the Cole-Cole plot.

<Compression modulus> 2 cm × 2 cm, thickness 500 μm
m of the solid polymer electrolyte was measured with a probe of 0.25 cm ² at a compression deformation rate of 1 mm / sec, and the mechanical strength was evaluated by measuring the compression modulus.

<Flexibility> The state of a polymer solid electrolyte having a size of 2 cm × 2 cm and a thickness of 100 μm when bent was evaluated as follows. ：: No crack occurs even when bent 180 degrees, and has elasticity to return to its original shape. C: No cracking occurs when bent at 90 degrees, but cracks when bent further. ×: No cracking occurs when bent at 45 degrees, but cracks when bent further.

<Charge / Discharge Characteristics> Lithium cobaltate, graphite, and polyvinylidene fluoride were used in an amount of 80: 10: 10% by volume.
And mixed with N-methyl-2-pyrrolidone to prepare a slurry-like solution. This solution was applied to an aluminum foil having a thickness of 20 μm and dried. The mixture application amount was 289 g / m ² . The mixture has a bulk density of 3.6 g / cm
³ and cut into 1 cm × 1 cm to form a positive electrode. Using lithium metal as the negative electrode, a solid polymer electrolyte was sandwiched between the positive electrode and the negative electrode, and a simple battery with a closed structure in which air did not enter was produced. At 20 ° C., constant current charging was performed up to 4.2 V with a charging current of 0.5 mA, and the voltage was changed to 4.
After reaching 2V, the discharge current is 0.5mA and the discharge end voltage is 3.
Constant current discharge was performed up to 5V. The charge / discharge under these conditions was defined as one cycle, and the charge / discharge was repeated until the initial discharge capacity reached 70% or less.

Example 1 In a 1-liter separable flask equipped with a stirrer, thermometer, cooling condenser and nitrogen gas inlet tube, under nitrogen atmosphere, (a) 75.07 g of 4,4'-diphenylmethane diisocyanate (a) as a diisocyanate 0.3
0 mol), (b) adipic acid as dicarboxylic acid 1
5.78 g (0.10 mol), 29.12 g sebacic acid
(0.14 mol) and 24.87 g of dodecanedioic acid
(0.10 mol) and N-methyl-2 as an organic solvent
-177.68 g of pyrrolidone was charged and heated to 130 ° C. On the way, the reaction system became a homogeneous solution at about 100 ° C., and carbon dioxide gas began to be generated due to the amidation reaction. When the reaction was allowed to proceed at 130 ° C. for 2 hours and then at 170 ° C. for 2 hours, the generation of carbon dioxide gas disappeared, and a solution of (A) a polyamide resin intermediate was obtained.

Subsequently, the solution of the (A) polyamide-based resin intermediate was kept at 170 ° C.
N-methyl-2-pyrrolidone 20 as an epoxy resin
138.00 g (0.3) of bisphenol A type epoxy resin (epoxy equivalent: 187 g / eq) dissolved in 7.00 g
69 mol) was added dropwise over 5 minutes. 1 at the same temperature
When the time reaction was advanced, (C) Jeffamine M-1000 (trade name, manufactured by Huntsman Corporation) (trade name of the above-described general formula (I)) dissolved in 216.90 g of N-methyl-2-pyrrolidone as a polyoxyalkylene monoamine was used. n: 22, R: hydrogen atom / methyl group = 19 /
3. A solution of 144.60 g (0.12 mol) of a primary amino group-equivalent molecular weight: 1,205 (the above catalog value) was added dropwise over 5 minutes. After further proceeding the reaction at the same temperature for 1 hour, the reaction was terminated, and 69 g of LiPF ₆ was added to obtain a polyamide resin solution.

This solution was applied on a substrate made of polyethylene terephthalate using an applicator, and then heated at 90 ° C. for 10 minutes.
Preliminary drying for 1 minute, followed by drying at 150 ° C. for 1 hour and thermal crosslinking to prepare a polymer film having a thickness of 100 μm, and measured for ionic conductivity, compression modulus and flexibility. Further, a simple battery was prepared by using the solution as a binder and an electrolyte by the method described above, and the initial charge / discharge characteristics were evaluated. Table 1 shows the results of the ionic conductivity, compression modulus, flexibility, and initial charge / discharge characteristics of the polymer solid electrolyte prepared in Example 1.

Example 2 62.56 g of 4,4'-diphenylmethane diisocyanate (a) as a diisocyanate was placed in a 1-liter separable flask equipped with a stirrer, a thermometer, a cooling condenser and a nitrogen gas inlet tube under a nitrogen atmosphere. 0.2
5 mol), (b) polyethylene glycol biscarboxymethyl ether 75.00 as a dicarboxylic acid
g (number average molecular weight: 250, 0.3 mol) and 173.34 g of N-methyl-2-pyrrolidone as an organic solvent were charged and the temperature was raised to 130 ° C. On the way, the reaction system became a homogeneous solution at about 100 ° C., and carbon dioxide gas began to be generated due to the amidation reaction. 2 hours at 130 ° C, then 1
When the reaction was allowed to proceed at 70 ° C. for 2 hours, generation of carbon dioxide was stopped, and a solution of (A) a polyamide resin intermediate was obtained.

Subsequently, the solution of the (A) polyamide resin intermediate was kept at 170 ° C.
N-methyl-2-pyrrolidone 17 as an epoxy resin
Bisphenol A type epoxy resin dissolved in 2.50 g (epoxy equivalent: 187 g / eq) 115.00 g (0.3
0 mol) was added dropwise over 5 minutes. When the reaction was allowed to proceed for 1 hour at the same temperature, the product was dissolved in 180.75 g of (C) N-methyl-2-pyrrolidone as a polyoxyalkylene monoamine. In (I), n: 22, R: hydrogen atom / methyl group = 19 /
3. Molecular weight in terms of primary amino group: 1205 (catalog value) 120.50 g (0.10 mol) of the solution was added dropwise over 5 minutes. After further proceeding the reaction at the same temperature for 1 hour, the reaction was terminated, and 69 g of LiPF ₆ was added to obtain a solution of a polyamide resin.

This solution was applied on a substrate made of polyethylene terephthalate using an applicator, and then heated at 90 ° C. for 10 minutes.
Preliminary drying for 1 minute, followed by drying at 150 ° C. for 1 hour and thermal crosslinking to prepare a polymer film having a thickness of 100 μm, and measured for ionic conductivity, compression modulus and flexibility. Further, a simple battery was prepared by using the solution as a binder and an electrolyte by the method described above, and the initial charge / discharge characteristics were evaluated.
Table 1 shows the results of the ionic conductivity, compression modulus, flexibility, and initial charge / discharge characteristics of the polymer solid electrolyte prepared in Example 2.

Example 3 50.05 g of 4,4'-diphenylmethane diisocyanate (a) as a diisocyanate was placed in a 1-liter separable flask equipped with a stirrer, a thermometer, a cooling condenser and a nitrogen gas introduction tube under a nitrogen atmosphere. 0.2
0 mol), and (b) polyethylene glycol biscarboxymethyl ether 144.0 as the dicarboxylic acid.
0 g (number average molecular weight 600, 0.24 mol) and N-methyl-2-pyrrolidone 264.67 g as an organic solvent
And heated to 130 ° C. On the way, the reaction system became a homogeneous solution at about 100 ° C., and carbon dioxide gas began to be generated due to the amidation reaction. When the reaction was allowed to proceed at 130 ° C. for 2 hours and then at 170 ° C. for 2 hours, the generation of carbon dioxide gas disappeared, and a solution of (A) a polyamide resin intermediate was obtained.

Subsequently, the solution of the polyamide-based resin intermediate (A) was kept at 170 ° C.
N-methyl-2-pyrrolidone 13 as an epoxy resin
92.00 g (0.24 g) of bisphenol A type epoxy resin (epoxy equivalent: 187 g / eq) dissolved in 8.00 g
Mol) was added dropwise over 5 minutes. When the reaction was allowed to proceed for 1 hour at the same temperature, (C) N-methyl-2-pyrrolidone was used as the polyoxyalkylene monoamine.
Jeffamine M-1000 (trade name, manufactured by Huntsman Corporation) dissolved in 144.60 g (n: 22, R: hydrogen atom / methyl group = 19 / in the general formula (1))
3. A solution of 96.40 g (0.08 mol) of a primary amino group-equivalent molecular weight: 1,205 (the above catalog value) was added dropwise over 5 minutes. After proceeding the reaction at the same temperature for another hour,
The reaction was terminated, and 69 g of LiPF ₆ was added to obtain a polyamide resin solution.

This solution was applied on a substrate made of polyethylene terephthalate using an applicator, and then heated at 90 ° C. for 10 minutes.
Preliminary drying for 1 minute, followed by drying at 150 ° C. for 1 hour and thermal crosslinking to prepare a polymer film having a thickness of 100 μm, and measured for ionic conductivity, compression modulus and flexibility. Further, a simple battery was prepared by using the solution as a binder and an electrolyte by the method described above, and the initial charge / discharge characteristics were evaluated.
Table 1 shows the results of the ionic conductivity, compression modulus, flexibility, and initial charge / discharge characteristics of the polymer solid electrolyte prepared in Example 3.

Example 4 The procedure of Example 3 was repeated, except that 42 g of LiBF ₄ was added instead of 69 g of LiPF ₆ . The ionic conductivity, compression modulus, flexibility, and initial charge / discharge characteristics of the polymer solid electrolyte prepared in Example 4 were evaluated. Table 1 shows the results.

[0062] LiN replacing Example _{5 LiPF 6 69g (CF 3 SO} 2) 2 1
Same as Example 3 except that 30 g was added. The ionic conductivity, compression modulus, flexibility, and initial charge / discharge characteristics of the polymer solid electrolyte prepared in Example 5 were evaluated. Table 1 shows the results.

Example 6 The procedure of Example 3 was repeated, except that 48 g of LiClO ₄ was added instead of 69 g of LiPF ₆ . The ionic conductivity, compression modulus, and the like of the polymer solid electrolyte prepared according to Example 6
Flexibility and initial charge / discharge characteristics were evaluated. Table 1 shows the results.
Shown in

Comparative Example 1 Polyethylene oxide having a number average molecular weight of 600,000
1 g of LiPF _{6 and} 0.23 g of acetonitrile
The solution was dissolved in 6.4 g, and uniformly stirred with a magnetic stirrer. This solution is applied on a glass substrate with a specific applicator, left in an argon atmosphere at normal pressure for 2 hours, and then heat-treated at 100 ° C. for 12 hours under vacuum to remove acetonitrile, and form a sheet-like polymer solid having a thickness of 100 μm. An electrolyte was obtained. The ionic conductivity, compression modulus and flexibility of the obtained solid polymer electrolyte according to Comparative Example 1 were measured. Next, this solution was used as a binder and an electrolyte to prepare a simple battery by the method described above, and the results of initial charge / discharge characteristics evaluation are shown in Table 1.

[0065]

[Table 1]

As shown in Table 1, the solid polymer electrolytes of Examples 1 to 6 had higher ionic conductivity than Comparative Example 1,
It can be seen that the compression modulus and flexibility are also excellent. Also, it can be seen that the batteries using the solid polymer electrolytes of Examples 1 to 6 also have better initial charge / discharge capacities than those using the solid polymer electrolyte of Comparative Example 1.

[0067]

The method for producing a solid polymer electrolyte according to the first aspect is excellent in ionic conductivity, mechanical strength and flexibility. The method for producing a solid polymer electrolyte according to the second aspect has the effects of the invention according to the first aspect, and further has excellent ion conductivity.
The method for producing a solid polymer electrolyte according to claim 3 is the method according to claim 1.
Or the effect of the invention described in 2 is achieved, and the mechanical strength is further excellent.

The solid polymer electrolyte according to the fourth aspect is excellent in ionic conductivity, mechanical strength and flexibility. The electrochemical device of claim 5 has an excellent cycle life.

Continued on the front page (72) Inventor Hiroyuki Sonobe 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. Chemical Industry Co., Ltd. Research Laboratory F-term (reference) 4J002 CD01X CD02X CD04X CD05X CD06X CD11X CD12X CD13X CH02Y CH05Y CL03W DE186 FD116 GQ02 4J036 AA01 AD08 FB12 FB13 5G301 DA22 DA28 DD10 5H029 AJ11 AM05 AL03 AM05 AL02 AM16 CJ11 EJ11 EJ12 HJ01

Claims (5)

[Claims] 1. A (A) polyamide-based resin intermediate obtained by reacting (a) a diisocyanate or a diamine with (b) a dicarboxylic acid, a tricarboxylic acid or a tricarboxylic anhydride, (B) an epoxy resin, and (C) A method for producing a solid polymer electrolyte, comprising dissolving an alkali metal salt in a polyamide resin having a component (C) residue in a side chain obtained by reacting with a polyoxyalkylene monoamine. 2. The method for producing a solid polymer electrolyte according to claim 1, wherein the blending ratio of the polyoxyalkylene monoamine (C) in the polyamide resin is 1 to 20 mol% based on the total amount of the polyamide resin. 3. The method according to claim 1, wherein the alkali metal salt is LiClO ₄ , LiB.
The method for producing a polymer solid electrolyte according to claim 1, wherein the method is at least one selected from the group consisting of F ₄ , LiPF ₆ and LiN (CF ₃ SO ₂ ) ₂ . 4. A polymer solid electrolyte produced by the method for producing a polymer solid electrolyte according to claim 1, 2 or 3. 5. An electrochemical device using the polymer solid electrolyte according to claim 4.