JP2001335707A - Polyelectrolyte gel composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ionically conductive polyelectrolyte gel composition useful as a material for electrochemical devices and to provide a method for producing the same. SOLUTION: Provided are a novel polyelectrolyte gel composition essentially consisting of a cationically crosslinked polymer into which a polymerizable amino-containing or quaternary-ammonium-salt-group-containing amine component compound is introduced, in which the residues of the amino component compound are in a free state in which they do not form a salt with an acid except a carboxylic acid, and which has a crosslinked structure, a nonaqueous solvent and a supporting electrolyte, and a method for producing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polymer electrolyte gel composition and a method for producing the same, and more particularly, to a polymer electrolyte gel composition having heat resistance of 80 ° C. or higher and high ionic conductivity, and The present invention relates to the manufacturing method.

[0002]

2. Description of the Related Art In lithium secondary ion batteries, capacitors, capacitors and the like using an electrolyte mainly composed of an organic solvent, the electrolyte is sealed in order to prevent a fire due to a liquid leakage or a short circuit accident, or an accident due to an impact is caused. In order to prevent this, a strong casing is required, and it has been difficult to reduce the weight.

In order to remedy this drawback, it has been desired to solidify the electrolyte. For this purpose, acrylonitrile-based (hereinafter PAN) applicable to electrochemical devices such as batteries, capacitors, capacitors and sensors
System), alkylene oxide system (hereinafter referred to as PEO system) and acrylate system (hereinafter referred to as PMMA system).
Focusing on the development of polymer electrolyte gels using polymers, for example, JP-A-4-306506 and JP-A-7-45271 for the PAN type, and JP-A-62-145271 for the PEO type.
-285954, JP-A-6-68906 and so on. However, none of these polymer electrolyte gels was satisfactory in terms of heat resistance and ion conductivity.

As a method of improving the heat resistance, PAN is used.
A method for regulating the molecular weight of the polymer and the content of acrylonitrile has also been proposed in Japanese Patent Application Laid-Open No. 10-144137. However, even in these methods, the ionic conductivity is not always stable, and a lithium secondary ion battery or electrolytic capacitor is not provided. However, the problem that not only conductivity is unstable immediately after production but also repeated charging / discharging causes an increase in resistance and a rapid decrease in ionic conductivity has not been sufficiently solved.

[0005] The present inventors have pursued this cause and have intensively studied measures for eliminating these disadvantages. The PAN-based polymers found in the reports so far are all simply diverted general-purpose polymers used for acrylic fibers and resins, and in order to impart high ion conductivity, I learned that there was little focus on solving the essential problem of what polymer structure should be.

[0006] PAN-based polymers used for fibers and resins are, in addition to acrylonitrile, in order to improve the dyeability of fibers and the processability of resins. In order to achieve the object described above, it is customary to copolymerize various monomers or to add a chemical substance that imparts plasticity.
For this reason, a polymer electrolyte gel in which such a polymer is diverted as it is contains many impurities that inhibit ion conductivity, which is the most important as an electrolyte gel.

For example, in the field of clothing which is most widely used, a homopolymer of acrylonitrile is not used, and in order to improve the dyeability of a cationic dye having high light fastness, sodium sulfonate is contained in the molecule. And an unsaturated monomer to which sodium carboxylate is bonded. In order to improve the processability and flexibility of the fiber, it is common to copolymerize vinyl acetate, acrylic acid, acrylic acid ester, acrylamide and other unsaturated monomers as monomers for imparting plasticity.

PAN containing many copolymer components as described above
The system copolymer has a low softening temperature, and the gel obtained therefrom naturally has low heat resistance. Furthermore,
When a monomer containing an anionic group or a cationic group is copolymerized in order to improve the dyeability, a large amount of an alkali or alkaline earth metal cation as a counter ion,
Alternatively, an anion of an acid such as sulfuric acid or nitric acid coexists.

As impurities of the PAN-based polymer, an alkali or alkaline earth metal ion other than lithium ion is used.
In the case of the electrolyte gel containing more than 0 ppm, not only the moving speed of lithium ions, that is, the ionic conductivity is low, but also the ionic conductivity is reduced more and more by repeating charge and discharge,
The service life of the secondary battery is shortened, and the battery cannot be put to practical use. This is because there are more ionic impurities with a larger ionic radius than lithium ions, which hinders the movement of lithium ions in the electrolyte gel due to charge and discharge,
Alternatively, it is considered that the adhesion to the surface of the electrode material lowers the function of the electrode material.

In the case of PEO-based polymers, there has been proposed a method of using a comb-shaped polymer in which many side chains are introduced using a special compound in order to improve ion conductivity.
(For example, Polymers for Advanced Tech. 4, 90. 1993,
Electrochimica Acta, 43, 1177. 1998). However, although the ionic conductivity is improved to some extent, the ionic conductivity at room temperature is 1 × 10 ⁻³ S /
cm or less, which is not sufficiently satisfactory.

Further, in the above-mentioned report examples which have been published so far, in each case, a gel of a polymer electrolyte is formed in advance, and then the gelled material is combined with a positive electrode material, a negative electrode material, or a separator. I make batteries, capacitors and capacitors. Because of this, the adhesiveness of the interface between the positive and negative electrode materials and the separator and the solidified polymer electrolyte gel caused by laminating the polymer electrolyte gel is not always good. In comparison with the above, the interface resistance was higher and the interface resistance fluctuated more.

[0012]

Any cationic or anionic impurities in the polymer used to form the electrolyte gel have an ionic radius larger than that of lithium ions, so that the impurities in the polymer electrolyte gel may be reduced. Not only does this cause a reduction in the movement speed of lithium ions, that is, the ionic conductivity, but also repeated charging and discharging causes deterioration of the electrode material and electrolyte, gradually lowering the conductivity, shortening the life of batteries and capacitors. It will be.

An object of the present invention is to provide a polymer electrolyte gel composition which is more excellent in ion conductivity and more durable than a conventionally known polymer electrolyte gel using a polymer and a method for producing the same. To provide. A further object of the present invention is to propose a new method for improving the adhesiveness of the interface where the electrode material such as the positive and negative electrode materials and the separator and the polymer electrolyte gel are in contact with each other, and lowering the interface resistance.

[0014]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Polymerizable primary amine compounds, secondary amine compounds, tertiary amine compounds, quaternary ammonium compounds and compounds having a plurality of amino groups belonging to the same or different classes in one molecule (hereinafter referred to as amine components) At least one amine component compound selected from the group consisting of a compound having a cross-linked structure, wherein the at least one amine component compound residue is in a free state in which it does not form a salt with an acid other than carboxylic acid, and further has a crosslinked structure. This is achieved by a polymer electrolyte gel composition comprising a crosslinked polymer, a non-aqueous solvent and a supporting electrolyte as essential components.

[0015] The present invention further provides a cationic crosslinked polymer,
An amine component compound is obtained by a crosslinking reaction between the introduced cationic polymer and the reactive compound, and the cationic polymer is a hydroxyl group in addition to an amino group,
A polymer having at least one functional group selected from a methylol group, a carboxylic acid group, and a glycidyl group; and the reactive compound is selected from a hydroxyl group, a methylol group, a carboxylic acid group, a glycidyl group, and an isocyanate group. This is highly achieved by a polymer electrolyte gel composition characterized by having one or more functional groups.

In addition to this, the total amount of alkali and alkaline earth metal ions other than lithium in the polymer electrolyte gel composition is 100 ppm or less, and the polymer electrolyte gel composition was heated to 80 ° C. In this case, the object is more highly achieved by the solidified gel composition not being redissolved or separated into a liquid phase and a solid phase.

The polymer electrolyte gel composition comprises a mixture prepared by dissolving a cationic polymer, a reactive compound and a supporting electrolyte as essential components in a non-aqueous solvent, and then reacting with the cationic polymer. The compound is obtained by a production method characterized by crosslinking a reactive compound and converting the mixture into a gel.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the amine component compound referred to in the present application will be described.
The compound must have polymerizability. That is, it must be a polymerizable monomer. The amine component compounds include primary to tertiary amine compounds and quaternary ammonium compounds, and compounds having a plurality of amino groups in one molecule. Is a generic term for compounds having a plurality of groups belonging to different classes or a plurality of groups belonging to the same class.

Incidentally, the number of amino groups contained in the amine component compound is not limited to one per molecule, and a plurality of amino groups may be contained. As described above, the group is not limited to one kind, and may be a mixture of first to fourth grades. Examples of such amine component compounds include allylamine, methallylamine, Nethylaminoacrylate, Npropylaminomethacrylate, Nmonoethylaminoethylmethacrylate, Ndimethylaminoethylacrylate, Ndiethylaminoethylacrylate, Ndiethylaminoethylmethacrylate, Ndimethylaminopropyl. Acrylamide, N-dimethylaminopropyl methacrylamide, N-diethylaminoethyl methacrylamide and the like can be mentioned.

Examples of a compound having a plurality of amino groups include a complex of primary and secondary amines such as N-aminoethyl methallylamine, N-dimethylaminopropyl allylamine, N-dimethylaminopropyl methallylamine, and (N-diethylamino). Examples of a complex of a secondary and tertiary amine such as ethyl) -N'ethylaminoethyl methacrylate are also preferably used. Examples of the quaternary ammonium compound include trimethylaminoethyl acrylate, trimethylaminoethyl methacrylate, trimethylaminoethyl methacrylate hydroxide, triethylaminoethyl acrylate, and triethylaminoethyl methacrylate, and these are also preferably used.

Next, the cationic crosslinked polymer of the present invention is:
It has a chemical structure in which one or more amine component compounds described above are introduced, and the amine component compound residue is in a free state in which it does not form a salt with an acid other than carboxylic acid, and further has a crosslinked structure. There is no particular limitation as long as it is present. As such a cationic crosslinked polymer, for example, a diamine which is a kind of an amine component compound of a reactive group-containing noncationic noncrosslinked polymer which does not have an amino group but has a reactive group (described later) There are cross-linked products by cross-linking agents represented by system compounds. Here, the reactive group is a group such as a glycidyl group capable of reacting with a diamine or the like, and may be present in the chain of the non-crosslinked polymer or as a side chain. However, from the viewpoint of easiness of production and quality, the cationic cross-linked polymer is preferably obtained by a cross-linking reaction between a reactive polymer and a cationic polymer into which an amine component compound has been introduced. It was done. Therefore,
Hereinafter, this case will be mainly described.

Here, the cationic polymer is not particularly limited as long as one or more amine component compounds are introduced therein and can form a crosslinked structure with a reactive compound described later. It may be a single polymer, a copolymer of another monomer copolymerizable with the compound, or a mixture of a homopolymer and a copolymer.

Accordingly, the cationic polymer referred to in the present application is 1) a case of a homopolymer of an amine component compound,
2) A case of a copolymer having an amine component compound as one copolymer component, and 3) A case of a polymer obtained by mixing the polymers of 1) and 2) is included. Further, the cationic polymer in cases 1) and 2) may be a polymer of a single amine component compound, a polymer of a plurality of amine component compounds, or a mixture of polymers from these amine component compounds. .

Other monomers copolymerized with the amine component compound include, for example, acrylonitrile, methacrylonitrile, vinyl compounds and acrylate compounds, and include a hydroxyl group and a methylol group which are functional groups capable of crosslinking with the reactive compound. , A carboxylic acid group, a monomer having at least one of a glycidyl group, for example, allyl alcohol, methallyl alcohol, N methylol acrylamide, N methylol methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy Propyl methacrylate, methylenebisacrylamide, methylenebismethacrylamide, glycerol monomethacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, glycidyl acrylate, glycidyl meth Reactive monomers such as acrylate and the like.

The reactive compound is not particularly limited as long as it reacts with the cationic polymer to form a cationic crosslinked polymer.
It may be a reactive low molecular weight compound) or a high molecular weight compound (hereinafter, referred to as a reactive high molecular weight compound), but a hydroxyl group, a methylol group, a carboxylic acid group, a glycidyl group And those having at least one reactive functional group selected from isocyanate groups can be suitably used. In addition, since it forms a crosslinked polymer, it is needless to say that it is necessary that the molecule contains two or more reactive functional groups described above.

Examples of the reactive low molecular weight compound having two reactive functional groups in one molecule which can be used in the present invention include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and 1,4-butylene glycol diglycidyl. Diglycidyl compounds such as ether, 1,6 hexanediol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; hexamethylene diisocyanate;
4, toluene diisocyanate, 2,6 toluene diisocyanate, 1,5 naphthalene diisocyanate, 4,
4 'diphenyl diisocyanate, 3,3' dimethoxy 4,4 'biphenylene diisocyanate and other diisocyanate compounds.

Examples of the reactive low-molecular compound having three or more functional groups bonded thereto include trimethylpropane triglycidyl ether, trimethylolmelamine, triphenylmethane triisocyanate, and other polyisocyanates.

The reactive polymer compound includes monomers such as acrylonitrile, methacrylonitrile, vinyl compound and acrylate compound, allyl alcohol, methallyl alcohol, N-methylol acrylamide, N-methylol methacrylamide, hydroxyethyl acrylate and hydroxyethyl. Obtained by copolymerizing one or more reactive monomers such as methacrylate, hydroxypropyl methacrylate, methylenebisacrylamide, methylenebismethacrylamide, glycerol monomethacrylate, acrylic acid, methacrylic acid, itaconic acid, glycidyl acrylate, and glycidyl methacrylate. Can be Furthermore, primary and secondary amine compounds can also be used as reactive monomers. In addition, it is also possible to add the above-mentioned reactive low-molecular compound to this reactive polymer compound to advance a crosslinking reaction with the cationic polymer.

The ratio of the amine component compound in the cationic crosslinked polymer is determined in consideration of the target level of ionic conductivity, the value of the polarization current to be obtained, or the hardness and heat resistance of the obtained gel composition. Usually, the molar ratio of the amine component compound / other polymerizable monomer is about 1/99 to 80/20. When the content of the amine component compound in the cationic crosslinked polymer is less than 1 mol%, the effect of increasing the transport number of lithium ions is scarcely exerted due to the small amount of amino groups, and high conductivity and high polarization current are obtained. The gel composition shown is not obtained. If the amount of the amine component compound exceeds 80 mol%, it is difficult to obtain a gel composition having appropriate hardness and heat resistance of 80 ° C. or higher.

As described above, the amino group of the residue of the amine component compound in the cationic crosslinked polymer must not form a salt with an acid other than a carboxylic acid. However, this means that, as a method for producing the gel composition of the present invention, only monomers having a free amino group which is not salt-formed with an acid other than carboxylic acid must be selected as the monomer of the amine component compound. It does not mean that there is a limitation.

That is, in preparing the polymer electrolyte gel composition of the present invention, it is sufficient that free amino groups are formed before the supporting electrolyte is added.
When the free amine component compound is unstable and a cationic polymer cannot be obtained as it is, after polymerization using a salt formed with an acid, the polymer is lithium hydroxide, Sodium, washing with a solution of potassium hydroxide, etc., to convert to a free cationic polymer that does not form a salt with acid, or at the stage of dissolving the cationic polymer in a non-aqueous solvent, the anion exchange resin By converting to a free cationic polymer that has not formed a salt with an acid by using the cationic polymer to form a cationic crosslinked polymer that is a component of the polymer electrolyte gel composition using the cationic polymer, The requirement that free amino groups be formed before the supporting electrolyte is added is achieved.

However, when the amino group in the cationic cross-linked polymer forms a salt with a carboxylic acid, a polymer having no amino group at all, although having slightly lower ionic conductivity than the free form, is used. It shows higher conductivity than the electrolyte gel used. This is because the supporting electrolyte dissolved in the non-aqueous solvent is a strong acid salt, and the carboxylic acid that has formed a salt with an amino group is unsalted by the anion of the supporting electrolyte. The amino group in the conductive polymer is almost the same as the one starting from the cationic polymer that has been released before coming into contact with the supporting electrolyte. It is presumed that it does not hinder sex.

Here, the weight mixing ratio of the reactive compound used to form the gel composition by reacting with the cationic polymer is in the range of about 0.1 to 2 parts by weight per 1 part by weight of the polymer. Is appropriate. When the weight mixing ratio of the reactive compound is less than 0.1 part by weight of the cationic polymer, it is difficult to sufficiently gel the solution of the cationic polymer, and when it is 2 parts by weight or more, Since a highly crosslinked structure is formed, the flexibility of the gelled product is poor, and it is difficult to obtain a practical gelled product.

Next, as a supporting electrolyte employed in the present invention, inorganic compounds such as LiClO ₄ , LiBF ₄ , LiPF ₆ and LiAsF ₆ , CF ₃ SO ₃ Li, LiC (SO ₂ CF ₃ )
Organic fluorine lithium salts such as ₃ , tetraethylammonium tetrafluoroborate, tetraethylammonium hexafluorophosphate, monomethyltriethylammonium tetrafluoroborate, monomethyltriethylammonium hexafluorophosphate, etc. are preferably used, but non-aqueous Any substance that dissolves in a solvent may be used, and the present invention is not limited thereto. Depending on the use, an ammonium salt of a dicarboxylic acid, a tetrafluoroborate or a carboxylate of a diamine may be used. The concentration of these supporting electrolytes in the gel composition is determined in consideration of the type of the supporting electrolyte and the target level of conductivity, but is preferably about 1 to 30% by weight, preferably about 1 to 30% by weight, based on the non-aqueous solvent. Is often used in the range of 5 to 25% by weight.

Here, the non-aqueous solvent used in the present invention is a non-aqueous solvent having a water content of 1% by weight or less, a cationic polymer,
It means a solvent that can dissolve the reactive compound and the supporting electrolyte. Examples of such a non-aqueous solvent include ethylene carbonate (abbreviated as EC) and propylene carbonate (abbreviated as P
C), butylene carbonate (abbreviated BC), diethyl carbonate (abbreviated DEC), dimethyl carbonate (abbreviated DMC), methyl ethyl carbonate (abbreviated MEC)
And ether compounds such as ethylene glycol, propylene glycol, methyl cellosolve and ethyl cellosolve, and gamma-butyrolactone (abbreviation γ-
BL), sulfolane, dimethylsulfoxide, adiponitrile, glutaronitrile, N-methylpyrrolidone, trimethyl phosphate, or a mixture of two or more solvents is recommended.

These non-aqueous solvents preferably have a high boiling point as long as the cationic polymer, the reactive compound and the supporting electrolyte are excellent in dissolving ability, and the solvent having a boiling point of 90 ° C. or less is easily evaporated. And the high vapor pressure tends to cause problems.

The mixing weight ratio of the cationic polymer and the non-aqueous solvent cannot be univocally determined depending on the molecular weight and composition of the polymer, but is generally in a proper range of 1/99 to 50/50. If the ratio of the polymer is less than 1 part by weight, it is difficult to obtain a gelled product, and if it exceeds 50 parts by weight,
The obtained gelled material is poor in flexibility and easily cracked in the gelled material, so that it is not practical.

According to the present invention, in order to solve the problem that the electrochemical characteristics of secondary ion batteries, capacitors, electrolytic capacitors and the like according to the prior art are unstable, the polymer which is an impurity in a cationic polymer is used. An alkali or alkaline earth metal ion other than lithium ion present as a counter ion of the anionic group of
It is desirable to reduce it to 00 ppm or less, preferably 50 ppm or less. In order to reduce ionic metal impurities, in addition to not copolymerizing monomers having ionic impurities, monomers used as raw materials for forming polymers are used to polymerize The choice of the polymerization catalyst is also very important.

That is, depending on the type of the polymerization catalyst, a part thereof is taken into the polymer as a polymer terminal group exhibiting ionicity. For example, in redox polymerization using sodium sulfite and sodium persulfate, the polymer is used. Sodium sulfonate derived from polymerization catalyst radicals is formed as a terminal group, resulting in a large amount of sodium ions in the polymer. To remove the alkali metal or alkaline earth metal incorporated in the polymer,
Although there is a method of washing with a strongly acidic aqueous solution, it is not an efficient method for industrial production. Therefore, in order to reduce ionic impurities, it is desirable to minimize the use of such a polymerization catalyst or to avoid its use.

From such a viewpoint, industrially,
It is recommended to carry out solution polymerization by means of a polymerization catalyst containing no alkali metal such as an organic peroxide or an azo type, or by means of electron beam irradiation, ultraviolet irradiation, or the like. The amount of polymerization catalyst used is
Since it depends on the type of the catalyst and the size of the target molecular weight, it cannot be limited unconditionally.
1 to 5 weight percent.

It is needless to say that the gel composition preferably has a stable form even at a high temperature. However, since the use temperature differs depending on the use and structure of the gel composition, it cannot be determined unconditionally.
Even after heating at 0 ° C. for 1 hour, the gel composition does not redissolve or separate into the liquid phase of the non-aqueous solvent and the solid phase of the gel solid,
Further, the gel composition is desirably thermally stable to the extent that the transparency of the gel composition is not reduced.

The structure of the polymer forming the polymer electrolyte gel composition according to the present invention is such that the cationic polymer itself forms a crosslinked body chemically bonded to a reactive compound. Therefore, it has excellent heat resistance and morphological stability.

Here, the gel composition of the present invention is a gelled product composed of a cationic crosslinked polymer into which an amine component compound has been introduced, a non-aqueous solvent, and a supporting electrolyte as essential components. It is also possible to incorporate a third polymer that does not form crosslinks, as long as the characteristics such as excellent conductivity, heat resistance, and morphological stability are not impaired.

For example, it is usually difficult to copolymerize an alkylene oxide with a vinyl monomer, and a copolymer cannot be obtained. However, a homopolymer such as polyethylene oxide, polypropylene oxide, polybutylene oxide, The polymer electrolyte gel composition of the present invention can be formed by preparing a copolymer of alkylene oxides and mixing this with a cationic crosslinked polymer. When the terminal group is an OH group, such a polyalkylene oxide is also used as a reactive compound.However, when the terminal group is substituted with an alkoxy group such as a methoxy group or an ethoxy group, the reactive compound is Not available. However, it is possible to use such a non-reactive polymer as the third polymer in combination with the cationic cross-linked polymer. For example, Example 14
As shown in, in a non-aqueous solvent containing a supporting electrolyte, dimethylaminoethyl acrylate was selected as an amine component compound, and a terpolymer of acrylonitrile and hydroxyethyl methacrylate was prepared. A gel composition prepared by mixing dimethoxypolyethylene glycol (molecular weight: about 1200), which is a molecule, and adding 2,4-toluene diisocyanate as a reactive compound thereto, has high ionic conductivity and excellent polarization. It has been found that a current can be obtained. As described above, a gel composition in which a cationic crosslinked polymer and a polymer having no crosslinked structure are mixed is also included in the scope of the present invention.

The polymer electrolyte gel composition of the present invention is prepared by mixing a cationic polymer, a reactive compound and a supporting electrolyte as essential components in a non-aqueous solvent, and then mixing the cationic polymer with the reactive compound. Can be suitably produced by a method in which the mixture is crosslinked and the mixture is gelled. As described above, the third polymer may be added when the mixture is prepared. Of course, as described above, when the cationic polymer has a salt-forming amino group, the polymer and a non-aqueous solvent are first mixed to form a polymer solution, and then subjected to a desalting treatment. An appropriate means such as adding a supporting electrolyte to be added and dissolving it is adopted. It should be noted that in these manufacturing steps, it is naturally important to carry out in a dry atmosphere having a dew point of −40 ° C. or less in a state where the outside air is blocked in order to prevent an increase in moisture due to moisture absorption.

The method for preparing such a mixture is not particularly limited. For example, a method in which a reactive compound is dissolved in a polymer solution in which a cationic polymer is dissolved in a non-aqueous solvent, and then a supporting electrolyte is dissolved. A method of adding a non-aqueous solution in which a supporting electrolyte and a reactive compound are dissolved to a polymer solution, and a polymer solution in which a cationic polymer is dissolved in a non-aqueous solvent in which a supporting electrolyte is previously dissolved; And a method of mixing a reactive compound solution obtained by dissolving a reactive compound in a nonaqueous solvent.

The polymer solution containing a cationic polymer dissolved in a non-aqueous solvent used herein may be a solution in which a cationic polymer obtained by polymerization is previously dissolved in a non-aqueous solvent, or It may be a solution prepared by a solution polymerization method in which a monomer is reacted in a non-aqueous solvent. Industrially, the latter is a particularly recommended method since the drying and dissolving steps can be omitted, so that the production efficiency is high and a homogeneous polymer solution is easily obtained.

The supporting electrolyte to be used may be added after preparing a polymer solution, or the polymer may be dissolved using a non-aqueous solvent in which the supporting electrolyte has been dissolved in advance. Further, a method of directly preparing a polymer solution by employing a solution polymerization method in a non-aqueous solvent containing a supporting electrolyte may be used.

The method for crosslinking the cationic polymer and the reactive compound is not particularly limited, either. For example, a method such as heating, ultraviolet irradiation, or electron beam irradiation can be used.

The excellent features of the present invention described in detail above are as follows.
A polymer solution in which a cationic polymer is dissolved in a non-aqueous solvent, and a solution of a reactive compound or a reactive polymer dissolved in a solution-type reactive compound or a non-aqueous solvent, a non-aqueous solvent containing a supporting electrolyte, or A solution in which these are mixed is injected in a solution state into an electrochemical device such as a battery, a capacitor or a capacitor, and after being sufficiently contacted with an electrode material or a separator, cross-linked by heating or electron beam irradiation. It is possible to convert to a gel composition. As described above, the device according to the present invention has improved wettability with the electrode material surface, improved adhesion at the contact interface between the two, and reduced electrical resistance at the adhesive interface of each material, as compared with the conventional product. It can be done.

When contacting the electrode material and the separator, the prepared solution is injected after reducing the pressure inside the device, so that the prepared solution sufficiently penetrates into the voids. The electric resistance is improved.
As a result, a low interface resistivity, a high ionic conductivity, and a high polarization current value are provided, and a high-performance device can be produced. On the other hand, in the method of assembling the device by gelling the polymer in advance and then bonding it to the electrode material or separator, it is difficult to sufficiently penetrate the gelled material into the fine voids, The interface resistance tends to be higher than that of the above-described method.

As a method for reducing such an interface resistance, there is a method in which a monomer and a non-aqueous solvent are directly injected into a device to simultaneously carry out polymerization and gelation in the device. It is difficult to remove unreacted monomers in the gel, and a gelled product with many impurities is formed. In particular, when an unreacted monomer having a low boiling point such as acrylonitrile remains, the unreacted monomer may generate bubbles in the gel by heating, and it is difficult to form a high-performance electrolyte gel. Further, if an unreacted monomer is to be removed under reduced pressure from the gelled polymer electrolyte, the unreacted monomer is gasified, bubbles in the gelled substance are increased, and a dense gelled substance cannot be obtained. .

On the other hand, in the present invention, a polymer purified in advance is dissolved in a non-aqueous solvent, or a polymer is synthesized in a non-aqueous solvent, and then an unreacted monomer having a low boiling point is reduced under reduced pressure. Since the removed polymer solution is used, it is an excellent production method with few impurities and no risk of generating bubbles in the gelled product.

[0054]

The polymer electrolyte gel composition using the cationic polymer containing the amine component compound of the present invention has a polarization measured by a cyclic voltammetry method, which is higher than that of a conventional polymer gel composed of acrylonitrile and vinyl acetate. When the preferred conditions are adopted, the effect of increasing the current by as much as five times is exhibited.

This is because, for example, in a lithium compound often used as an electrolyte, a lithium ion having a larger ionic radius than a lithium ion forming a pair with the lithium ion is used.
Anions such as F ₄ ⁻ , PF ₆ ⁻ , and AsF ₆ ⁻ are trapped by the amino group which is a cationic group in the cationic polymer electrolyte gel composition of the present invention, whereby the transfer rate of lithium ions, that is, It is thought that the lithium ion transport number may be improved.

Therefore, the amino group of the amine component compound is
If a compound that has already formed a salt with a strong acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and sulfonic acid is used, the function of improving the transport number of lithium ions is reduced. The effect of improving ionic conductivity is also diminished, but still compared to conventional gels that do not contain amino groups,
High ionic conductivity. Although the reason for this is not clear, a large bulky side chain is bonded to the salt-forming amino group-containing cationic polymer, so that a space where lithium ions can move relatively easily in the gel composition. It is presumed that it exists.

[0057]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to typical examples and comparative examples, but the present invention is not limited to these examples. The parts described in the following examples are parts by weight unless otherwise specified.
Percentages are weight percentages.

The evaluation methods used in the following Examples and Comparative Examples are shown. [Evaluation of Electrochemical Characteristics] The preparation method was as follows. A cell for evaluating electrochemical characteristics described below was connected to an AC impedance measuring device (1286 + 1250, manufactured by Solartone), and the temperature was measured at 25 ° C.
Then, the AC impedance from 100 kHz to 1 Hz was measured, and the impedance at the measurement frequencies of 100 kHz and 100 Hz was defined as the bulk resistance value and the interface resistance value, respectively. The ionic conductivity was calculated from the bulk resistance value and the thickness and area of the cell. After the AC impedance measurement was continued for 24 hours, the measurement cell was connected to an electrochemical measurement device (Sl-1280B manufactured by Solartone), and at 25 ° C., a reversal voltage of ± 0.5 V and a potential sweep speed of 10 m.
Polarization electrolysis was performed by cyclic voltammetry of V / s, and the polarization current value at +0.5 V in the third cycle was measured, and this was defined as the polarization current value for the lithium anode CV.
Hereinafter, the polarization current value of the lithium negative electrode CV is simply referred to as a polarization current. Further, after the measurement of the polarization current, the AC impedance was measured again to determine the interface resistance value 24 hours after the cell was formed. From these measurement results, the ratio between the interface resistance immediately after the start of the measurement and the interface resistance after 24 hours was determined.
The increase rate of the interface resistance was used.

[Evaluation of Heat Resistance] A gel film as a gel composition having a thickness of about 200 μm was cut into a size of 1 × 2 cm and placed in a sample bottle having an inner diameter of 24 mm and a height of 40 mm.
After covering with an aluminum foil cap and heating it for 1 hour in a hot air circulating thermostat at 80 ° C., take it out of the thermostat and immediately observe the state of the gel film to classify it into the following three ranks. A: No change in morphology of the gel film before and after heating. B: The gel film is partially dissolved or slightly phase-separated after heating. C: More than half of the gel film is dissolved or has much phase separation after heating.

[Evaluation of flexibility] The same thickness as the evaluation of heat resistance, about 2
When a 00 μm gel film is bent at an angle of 90 degrees at room temperature, it is observed whether or not a crack occurs at the bent portion, and the gel film is classified into the following ranks. A: good flexibility (no cracks, no folds left) B: flexible (no cracks, but folds left) C: poor flexibility (cracks)

[Measurement of Sodium Ion Concentration] The sodium ion concentration of the gel composition or the cationic polymer is measured by an atomic absorption method. The equipment is AA-6 manufactured by Shimadzu Corporation.
Although 500 was used, the detection sensitivity of metal ions was 10 pp.
m. In addition, although alkali metal ions other than sodium and alkaline earth metal ions were also measured by this apparatus, the detection limit was 10 ppm or less in all gel films throughout the Examples, Comparative Examples and Reference Examples.

Example 1, Comparative Example 1 93.75 g of LiBF ₄ as a supporting electrolyte was dissolved in 1 liter of a nonaqueous solvent in which ethylene carbonate (EC) and propylene carbonate (PC) were mixed at a volume ratio of 2/1. The supporting electrolyte-containing nonaqueous solvent thus prepared was prepared. To 80 g of the nonaqueous solvent containing the supporting electrolyte, 10 g of acrylonitrile (hereinafter abbreviated as AN), 5 g of dimethylaminoethyl acrylate (hereinafter abbreviated as DAA), 5 g of hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), and as a polymerization catalyst, Benzyl dimethyl ketal (hereinafter abbreviated as BDK)
0.6 g was added and dissolved. It has a peak wavelength at 360 nm, and the illuminance at this wavelength is 15 mW / cm ^2.
After irradiating with UV light for 10 minutes, polymerization was carried out at 50 ° C. in a vacuum vessel having a gauge pressure of −0.09 MPa, and unreacted AN was removed to prepare a polymer solution of a cationic polymer. Separately, the same nonaqueous solvent containing supporting electrolyte 60
g and 40 g of 2,4 toluene diisocyanate as a reactive compound are mixed to prepare a reactive compound solution. A lithium foil having a thickness of 0.2 mm is placed on the bottom of a stainless steel Petri dish, and a square spacer made of Teflon (registered trademark) having a thickness of 0.2 mm is set thereon. A suitable amount of a solution prepared by mixing 0.5 g of the reactive compound solution and 2.5 g of the reactive compound solution was placed thereon. A lithium foil having a thickness of 0.2 mm was placed thereon, and the dish was covered with a lid. By heating for a period of time to crosslink the cationic polymer and the reactive compound, a 200 μm-thick gel film of Example 1 which was the polymer electrolyte gel composition of the present invention was prepared.

The gel film sandwiched between the lithium foils was sandwiched between nickel plates having a lead wire and having a thickness of 0.3 mm, inserted between two glass plates, fixed with clips, and evaluated for electrochemical characteristics. A cell was prepared and attached to the apparatus, and the electrochemical characteristics were measured. The gel film of Example 1 for evaluation of heat resistance and flexibility was prepared in the same manner as the above gel film except that no lithium foil was used, and evaluated by the method described in the evaluation method. Table 1 shows the results. The preparation of the gel film, the assembly of the cell, and the measurement of the electrochemical characteristics were performed using a glove box in an argon gas atmosphere at a dew point of -50 ° C. On the other hand, as Comparative Example 1, only 15 g of the same polymer solution as in Example 1 was heat-treated in the same manner as in Example 1 to form a gel film without adding the reactive compound solution, but the solution did not gel. No gel film could be obtained. As shown in Table 1, the gel membrane of Example 1 was a polymer electrolyte gel composition having high ionic conductivity and excellent heat resistance and flexibility. In particular, since the methylol group introduced into the cationic polymer and the isocyanate group of the reactive compound react to form a crosslinked structure, the gel film does not change its shape even when heated to 150 ° C. , And had excellent thermal stability.

[0064]

[Table 1]

<Example 2, Comparative Example 2> A solution obtained by adding 12 g of AN and 3 g of methallylamine to 85 g of the same non-aqueous solvent containing a supporting electrolyte as in Example 1 was added, and 0.45 g of BDK was added. Was polymerized by irradiating ultraviolet rays, and the unreacted AN was similarly removed by a reduced pressure treatment to prepare a polymer solution of a cationic polymer. Separately, a reactive compound solution was prepared by dissolving 30 g of polyethylene glycol diglycidyl ether having a degree of polymerization of 9 as a reactive compound in 70 g of a nonaqueous solvent containing a supporting electrolyte as in Example 1. A prepared solution obtained by adding 5 g of the reactive compound solution to 10 g of the polymer solution was treated in the same manner as in Example 1 to prepare a 200 μm-thick gel film and cell which was the polymer electrolyte gel composition of the present invention. The electrochemical properties, heat resistance and flexibility were evaluated. The results are shown in Table 1. The gel film of Example 2 exhibited excellent electrochemical properties, high heat resistance, and excellent flexibility. On the other hand, as Comparative Example 2, only 15 g of the same polymer solution as in Example 2 was heat-treated in the same manner as in Example 1 to form a gel film without adding the reactive compound solution.
Since the solution did not gel, no gel film was obtained.

Example 3, Comparative Example 3 93.75 g of LiBF ₄ was dissolved as a supporting electrolyte in 1 liter of a non-aqueous solvent in which EC / γ-BL was mixed at a volume ratio of 1/3. 80 g of aqueous solvent, 12 g of AN, DAA
4 g and HEMA 4 g were added, and BD was added thereto as a polymerization catalyst.
0.6 g of K was added, and the same procedure as in Example 1 was performed to prepare a polymer solution of a cationic polymer. 5 g of the reactive compound solution of Example 1 was added to 10 g of the polymer solution, and a gel film and a cell were prepared in the same manner as in Example 1, and the characteristics were evaluated (Example 3). On the other hand, as Comparative Example 3, Example 3
80 g of the nonaqueous solvent containing the same supporting electrolyte as in
g, 5 g of vinyl acetate, and 0.6 g of BDK were added, and the same procedure as in Example 1 was performed to prepare a polymer solution. The same reactive compound solution 5 as in Example 1 was added to 10 g of this polymer solution.
g was added, and a gel film was prepared in the same manner as in Example 1, and the characteristics were evaluated. The evaluation results of Example 3 and Comparative Example 3 are also shown in Table 1. However, the film of Comparative Example 3 did not completely gel at room temperature, but was a mixture of a partially gelled solid and a solution,
A gel film capable of evaluating electrochemical properties was not obtained. This incomplete gel material gelled when cooled to 0 ° C., but was again separated into a solution and a solid when heated to 50 ° C., and had low heat resistance. On the other hand, the gel film of Example 3 which is a product of the present invention has a
Even when heated to ℃, the gel film did not change its shape, had heat resistance and flexibility, and had excellent electrochemical properties.

Example 4, Comparative Example 4 800 ml of pure water adjusted to pH 2.0 by adding nitric acid was placed in a 2 liter polymerization flask attached to a thermostat set at 65 ° C., and 106 g of AN was added thereto. 14.3 g DAA, 39 g HEMA
And, separately, 2,2 ′ as a polymerization catalyst
A solution in which 1.4 g of azobis (2-amidinopropane) dihydrochloride was dissolved in 120 ml of pure water was continuously supplied over 2 hours. After the completion of the supply, the polymerization was further continued at 65 ° C. for 2 hours. The pH in the flask at the end of the polymerization was 2.6. After the polymerization was completed, the flask was water-cooled to room temperature, and the content was dehydrated with a centrifugal dehydrator to obtain a cationic polymer. The obtained cationic polymer was washed three times with pure water to remove unreacted monomers and polymerization catalyst residues, and then an aqueous solution of lithium hydroxide of pH 10.5 heated to 50 ° C. was used. Then, the substrate was washed three times, and then again washed with pure water three times. The cationic polymer was dried in a vacuum dryer at 70 ° C. overnight to remove water. Measurement of the infrared absorption spectrum before the polymer is washed with an aqueous solution of lithium hydroxide, to 1385cm ^-1, NO ₃ ^- No peak is observed, those treated with an aqueous solution of lithium hydroxide, the peak full It was confirmed that the NO ₃ ⁻ that had formed a salt with DAA was completely removed. This cationic polymer has an AN / DAA / HEMA composition of 8
It was 6/4/10 mol and the weight average molecular weight was 120,000.

On the other hand, as Comparative Example 4, 800 ml of pure water adjusted to pH 2.5 by adding nitric acid to a 2 l polymerization flask was used.
And a mixed solution of 106 g of AN and 8.6 g of vinyl acetate, a solution of 0.5 g of sodium methallylsulfonate in 120 ml of pure water, and 0.6 g of sodium disulfite and 0.2 g of ammonium persulfate as polymerization catalysts, respectively. Each of the solutions dissolved in 120 ml of pure water was continuously supplied over 2 hours, and polymerization was carried out in the same manner as in Example 4 to produce a polymer. The obtained polymer was washed with water and dried in the same manner as in Example 4, except that the washing step with a lithium hydroxide aqueous solution was omitted. The molecular weight of this polymer is 8
10,000, the composition ratio of AN / vinyl acetate is 92/8 mol,
The sodium in this polymer was 1500 ppm.

15 g of each of the cationic polymer of Example 4 and the polymer of Comparative Example 4 were mixed well with 85 g of the same non-aqueous solvent containing a supporting electrolyte as in Example 1, and then 100 ° C.
And completely dissolved to prepare respective polymer solutions. 5 g of the same reactive compound solution as in Example 1 was mixed with 10 g of each of these polymer solutions, and a gel film and a cell were prepared in the same manner as in Example 1, and the characteristics were evaluated.
The evaluation results of Example 4 and Comparative Example 4 are shown in Table 1,
The gel film of Example 4 which is a product of the present invention is superior to the gel film of Comparative Example 4 in all points of heat resistance, flexibility and electrochemical properties, and is a high-performance polymer electrolyte gel composition. Proven. The gel film of Comparative Example 4 was gelled at room temperature, but was merely mixed with the polymer and the reactive compound.
Since it does not have a chemical bond, when heated to 60 ° C. or more, the gelled substance dissolves, the heat resistance is low, and the sodium ion in the gel also exceeds 100 ppm, and the increase in interface resistance is remarkable. there were. The polymerization catalyst of Comparative Example 4 is a general polymerization catalyst for producing a polymer for acrylic fiber, and the polymer of Comparative Example 4 has a chemical composition generally used for acrylic fiber. It is a copolymer.

<Example 5, Reference Example 1> The weight ratio of EC /
As a supporting electrolyte in 92 parts of a non-aqueous solvent mixed to γ-BL = 1/3, as a supporting electrolyte, 8.5 g of a supporting electrolyte-containing non-aqueous solvent in which 8 parts of LiBF ₄ was dissolved, 1.2 g of AN and 0.2 g of N-dimethylaminopropyl methacrylamide. 3 g, N-methylolacrylamide 0.2 g, BDK0.05 as polymerization catalyst
The solution to which g was added was prepared and polymerized by irradiation with ultraviolet rays in the same manner as in Example 1 to prepare a polymer solution of a cationic polymer. A mixed solution was prepared by adding 5 g of the same reactive compound solution as in Example 1 to this polymer solution. In preparing a gel film from this solution in the same manner as in Example 1, a film having a thickness of 2 mm was placed on a lithium foil placed on the bottom of a stainless steel petri dish.
5 μm polypropylene nonwoven fabric (7 g /
m ² ) was repeated, processing was performed in the same manner as in Example 1 except that the prepared solution was injected, a gel film and a cell were prepared, and the characteristics were evaluated. On the other hand, apart from this, as Reference Example 1, in the same manner as in Example 5 except that no lithium foil was used,
Only a gel film without lithium foil was prepared. The gel film prepared in advance in this manner is taken out of the petri dish, and the same lithium foil and nickel plate as in Example 1 are stuck on both sides thereof,
An evaluation cell was assembled and evaluated similarly. The results of Example 5 and Reference Example 1 are also shown in Table 1.

As is clear from the results, the gel composition of the present invention is constructed by a conventional method in which a gel film is prepared in advance as in Reference Example 1 and then an electrode material is attached. In this case, it has properties that can withstand practical use. However, as in Example 5, a solution comprising a non-crosslinked polymer and a reactive compound containing a non-aqueous solvent, a supporting electrolyte, and a cationic polymer as essential components. Was injected into a cell, i.e., an electrochemical device, and the solution was gelled therein, the ionic conductivity was lower, the interface resistance increased somewhat, and the electrochemical properties were generally lower. .

Examples 6 to 11 Examples of amino groups include primary amine, secondary amine, tertiary amine and quaternary ammonium base, and the following amine components containing these various amino groups 5 g of each compound, 92 g of AN, HEMA
Except for using 3 g, polymerization was carried out by the ultraviolet irradiation method in the same manner as in Example 1, and the same treatment was carried out to prepare a polymer solution of a cationic polymer. Example 6 Ethylamino methacrylate (primary amine) Example 7 N monoethylaminoethyl methacrylate (secondary amine) Example 8 N diethylaminoethyl methacrylate (tertiary amine) Example 9 N trimethylaminoethyl methacrylate hydroxide (Quaternary ammonium compound) Example 10 N-aminoethyl methallylamine (mixed type of primary and secondary amines) Example 11 N-dimethylaminopropyl methallylamine (mixed type of secondary and tertiary amines) To each of 10 g of the polymer solution of these cationic polymers, 5 g of the same reactive compound solution as in Example 1 was added at a time to prepare a preparation solution, and a gel film and a cell were prepared as in Example 1, The characteristics were similarly evaluated, and the results are shown in Table 2. Incidentally, the sodium ion concentration in each of these gel compositions was lower than the detection sensitivity (10 ppm).
Each of the gel membranes prepared from these cationic polymers has an ionic conductivity of 3 × 10 ⁻³ S at room temperature (25 ° C.).
/ Cm 2 or more, and the polarization current was 6 mA / cm ² or more, demonstrating that this is an excellent polymer electrolyte gel.

[0073]

[Table 2]

<Examples 12, 13 and Comparative Example 5> AN9g
And 0.4 g of an amino compound having the following amino group:
Polymerization was carried out by the same ultraviolet irradiation method as in Example 1 except that 0.6 g of methylol acrylamide was used to prepare a polymer solution of a cationic polymer. To each of these polymer solutions, prepared solutions were prepared by adding 5 g of the same reactive compound solution as in Example 1, and a gel film and a cell were prepared in the same manner as in Example 1, and the characteristics were evaluated. Here, the first embodiment
In Example 13, the amino group of the amine component compound used in Example 2 was not salt-formed with an acid, but in Example 13, the amino group was acetate, and in Comparative Example 5,
Used was a hydrochloride. Example 12 N-dimethylaminoethyl acrylate Example 13 N-dimethylaminoethyl acrylate acetate Comparative Example 5 N-dimethylaminoethyl acrylate hydrochloride The results are as shown in Table 2, and compared to Example 12, hydrochloric acid and salt formation. In Comparative Example 5, it is clear that the rate of increase in the interface resistance is high and the polarization current is low. In Example 13, although the amino group forms a salt with acetic acid, it shows characteristics superior to Comparative Example 5. The reason for this is that, as described in the text, acetic acid forming a salt with an amino group is a weak acid, so that CH ₃ COO ⁻ and B of the electrolyte LiBF ₄
This is presumably because F ₄ ^- was substituted and acetic acid, which had formed a salt with the amino group, was released, so that the transfer of Li ⁺ was not hindered much.

Example 14 10 g of a cationic polymer solution prepared in the same manner as in Example 1 and 2.5 g of a reactive compound solution were added to a third polymer of dimethoxy polyethylene having a molecular weight of about 1200. 2.5 glycol
A gel film and a cell were prepared in the same manner as in Example 1 except that g was added, and the characteristics were evaluated in the same manner as in Example 1.
The results are shown in Table 2, and all of them have excellent heat resistance, flexibility and electrochemical properties. Further, when the ionic conductivity of the gel film at -20 ° C. was measured, it showed a value of 1.0 × 10 ⁻³ S / cm, and it was confirmed that the gel film had excellent low-temperature characteristics as a battery.

[0076]

The polymer electrolyte gel composition of the present invention has an excellent ionic conductivity of 3 × 10 ⁻³ S / cm or more, an interface resistance increase rate of 2 times or less, and a polarization current of 6 mA / cm ² or more. Since it has electrochemical characteristics and is also excellent in heat resistance and flexibility, it can be applied to electrochemical devices such as batteries, capacitors, capacitors, and sensors. In addition, according to the method of the present invention, a gel composition can be formed in an electrochemical device. Therefore, excellent electrochemical properties are expected due to tighter integration with the electrode material as compared with the conventional method. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01G 9/038 H01M 10/40 B 9/035 H01G 9/00 301D 9/00 9/02 311 H01M 10 / 40 9/24 A F term (reference) 4F070 AA32 AA34 AA35 AA38 AA74 AA75 AC18 AC35 AC48 AE06 AE08 GA09 GB05 GB09 4J002 BE011 BG011 BG071 BG091 BG101 BG121 BH021 BJ001 CD191 DD036 DE196 DH006 DK00 EN136 AJ06 AM01 AM03 AM04 AM05 AM07 AM16 CJ08 CJ11 DJ09 HJ10 HJ14

Claims (7)

[Claims] 1. A polymerizable primary amine compound, secondary amine compound, tertiary amine compound, quaternary ammonium compound and one molecule having a plurality of amino groups belonging to the same or different classes. One or more amine component compounds selected from compounds (hereinafter referred to as amine component compounds) are introduced, and the amine component compound residues are in a free state in which they do not form a salt with an acid other than carboxylic acid; A polymer electrolyte gel composition comprising, as essential components, a cationic crosslinked polymer having a structure, a non-aqueous solvent, and a supporting electrolyte. 2. The cationic crosslinked polymer according to claim 1, wherein the cationic crosslinked polymer is obtained by a crosslinking reaction between a cationic polymer into which an amine component compound has been introduced and a reactive compound. Molecular electrolyte gel composition. 3. The cationic polymer according to claim 1, wherein the polymer has at least one functional group selected from a hydroxyl group, a methylol group, a carboxylic acid group, and a glycidyl group in addition to the amino group. 3. The polymer electrolyte gel composition according to 2. 4. The reactive compound according to claim 2, wherein the reactive compound has at least one functional group selected from a hydroxyl group, a methylol group, a carboxylic acid group, a glycidyl group, and an isocyanate group. 4. The polymer electrolyte gel composition according to item 1. 5. The polymer electrolyte gel composition according to claim 1, wherein the total amount of other alkali and alkaline earth metal ions excluding lithium is 100 ppm or less.
5. The polymer electrolyte gel composition according to any one of 4. 6. The solidified gel composition does not redissolve or phase separate into a liquid phase and a solid phase when heated to 80 ° C. A polymer electrolyte gel composition. 7. A mixture in which a cationic polymer, a reactive compound and a supporting electrolyte are dissolved as essential components in a non-aqueous solvent is prepared, and then the cationic polymer and the reactive compound are cross-linked to form a gel. The method for producing a polymer electrolyte gel composition according to any one of claims 1 to 6, wherein