JP2923542B2 - Ion conductive polymer electrolyte - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an ion conductive polymer electrolyte.

[Conventional technology]

Conventionally, ion conductive polymer electrolytes include, for example, an organic polymer electrolyte of polyethylene oxide and an organic polymer electrolyte in which a polyethylene oxide portion and a propylene oxide portion of a polyfunctional polyether molecular structure are randomly copolymerized (Japanese Patent Publication No. 62-249361). ), A solid polymer electrolyte comprising an ethylene oxide copolymer containing a ionic compound in a dissolved state (Japanese Patent Application Laid-Open No. 61-83249), and a polymer solid substance having plasticity further comprising a thermoplastic polymer having no cross-linking. An ion-conducting polymer electrolyte substantially composed of a molecular chain of a united or copolymer (JP-A-55-98480) is known.

However, such a conventional ion conductive polymer electrolyte has, for example, the following problems.

First, the organic polymer electrolyte of polyethylene oxide shows relatively good lithium ion conductivity in the temperature range of 40 ° C or higher, but its characteristics are sharply degraded in the room temperature range of about 25 ° C. It is very difficult to apply to

The organic polymer electrolyte described in JP-B-62-249361 is 25%.
Although there is no sharp decrease in lithium ion conductivity in a room temperature range of about ° C, below 0 ° C, which is considered as a practical temperature range, the decrease proceeds and practical ion conductivity cannot be obtained.

The organic polymer electrolyte described in JP-A-61-83249 is an organic polymer obtained by random copolymerization of ethylene oxide and other monomers, by random copolymerization,
As a result, the structure of the organic polymer is made amorphous. However, in this case, due to the difference in reactivity between various monomers, the amorphousness is insufficient and the quality tends to be unstable.

Further, since the organic polymer electrolyte described in Japanese Patent Application Laid-Open No. 55-98480 is thermoplastic, only a simple film can be prepared, and the film has poor adhesion.

[Problems to be solved by the invention]

An object of the present invention is to solve all these problems and to provide an easy-to-handle ion-conductive polymer electrolyte exhibiting excellent ionic conductivity.

[Means for solving the problem]

The gist of the present invention is an ion-conductive polymer electrolyte comprising an organic polymer compound obtained by subjecting an organic compound represented by the following general formula to a cross-linking reaction, a soluble electrolyte salt compound, and an organic solvent.

Z-[-EY] _k ... That is, the ion-conductive polymer electrolyte of the present invention is characterized by comprising an organic polymer compound obtained by cross-linking an organic compound as described above, a soluble electrolyte salt compound, and an organic solvent.

The organic compound of the general formula used as a raw material of the organic polymer compound is a polyether obtained by copolymerizing an active hydrogen-containing compound with a glycidyl ether and an alkylene oxide having 3 or more carbon atoms in a block type and / or a random type. Further, a compound having a polymerization-reactive functional group-containing compound reacted with the obtained polyether, and a compound having a polymerization-reactive functional group introduced into a main chain terminal active hydrogen group of the polyether,
The average molecular weight is preferably 20,000 or less.

Examples of the aforementioned active hydrogen-containing compounds include, for example, polyhydric alcohols such as methanol, ethanol, ethylene glycol, propylene glycol, 1.4-butanediol, glycerin, trimethylolpropane, sorbitol, sucrose, and polyglycerin, butylamine, 2-ethylhexylamine Amine compounds such as ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aniline, benzylamine and phenylenediamine, phenolic active hydrogen compounds such as bisphenol-A, hydroquinone and novolak, 1 such as monoethanolamine and diethanolamine
Examples of the compound include a compound having a different type of active hydrogen-containing group in the molecule, and among them, a polyhydric alcohol is preferable.

Next, as the glycidyl ethers to be reacted with the active hydrogen-containing compound, alkyl or alkenyl or aryl or alkylaryl polyethylene glycol glycidyl ales represented by the following formula: (Where n is an integer of 0 to 25 and R ¹ represents an alkyl group, alkenyl group, aryl group or alkylaryl group having 1 to 20 carbon atoms). Typically, R is, for example, methyl, ethyl, propyl,
Linear alkyl group such as butyl group, isopropyl group, sec-
Butyl group, tert-butyl group, etc., branched alkyl group, vinyl group, allyl group, 1-propenyl group, alkenyl group such as 1.3-butadienyl group, phenyl group, naphthyl group, nonylphenyl group, tolyl group, benzyl And an aryl or alkylaryl group such as a group.
15, the number of carbon atoms in R ¹ is more preferably 1-12.

Further, alkylene oxides having 3 or more carbon atoms used in combination with glycidyl ethers include, for example, 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2 An α-olefin oxide having 4 to 9 carbon atoms, such as epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane,
Examples thereof include α-olefin oxides having 10 or more and styrene oxides, and among them, the use of α-olefin oxides having 4 to 20 carbon atoms is preferable.

The number of these added moles is 1 to 230 moles per active hydrogen in the case of glycidyl ethers and 1 to 360 moles in the case of alkylene oxides having 3 or more carbon atoms. It is preferable to select appropriately from the range of the number of added moles so as to satisfy the above.

Examples of the catalyst used for these reactions include basic catalysts such as sodium methylate, sodium hydroxide, sodium hydroxide, lithium carbonate, acidic catalysts such as boron trifluoride, amine catalysts such as trimethylamine and triethylamine, and the like. The amount used is arbitrary.

In the case of copolymerizing glycidyl ethers and alkylene oxides having 3 or more carbon atoms, the copolymerization form is not particularly limited such as random type and / or block type, and there is no particular restriction on the arrangement order and mixing ratio. Absent.

As a method of performing a cross-linking reaction on the organic compound thus obtained, when the main chain terminal group Y is an active hydrogen group, cross-linking is performed using a cross-linking agent.

Examples of the crosslinking agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, triphenylmethane diisocyanate, and tris (isocyanatephenyl) thiophosphate. , Lysine ester triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, burette bond
HMDI, isocyanurate-bound HMDI, trimethylolpropane TDI 3 mol adduct, or a mixture thereof, and the like.

The quantitative ratio of the crosslinking agent is such that the number of isocyanate groups becomes 1 to 1.5 times the number of active hydrogen groups at the main chain terminal of the organic compound.

At this time, as a catalyst to complete the crosslinking reaction early, for example, dibutyltin dilaurate, dibutyltin diacetate, phenylmercury propionate, organometallic catalysts such as lead octenoate, triethylenediamine, N,
An amine catalyst such as N'-dimethylpiperazine, N-methylmorpholine, tetramethylguanidine, triethylamine and the like may be used.

Further, when the main chain terminal group Y is a polymerization reactive functional group, a polymerization reactive functional group is introduced into the main chain terminal of the obtained polyether. Examples of the polymerization reactive functional group include an alkenyl group such as a vinyl group, a group having an unsaturated bond such as an acryloyl group and a methacryloyl group, and a group having a linear or cyclic portion containing Si. However, these groups are introduced into the molecule by reacting the polyether with a compound having a polymerization reactive functional group as described above.

Examples of the compound having a polymerization reactive functional group include compounds such as acrylic acid, methacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid and p-vinylbenzoic acid.
A compound having a carboxyl group and an unsaturated bond in the molecule,
Acid anhydrides of the compounds, or acid chlorides of the compounds, allyl glycidyl ether, glycidyls such as glycidyl methacrylate, isocyanates such as methacryloyl isocyanate, or dichlorosilane, compounds containing Si such as dimethylvinylchlorosilane and the like. Can be

When a crosslinking reaction by polymerization is carried out, the reaction is carried out by light, heat, ionizing radiation or the like using a polymerization initiator or a sensitizer as necessary.

Next, as a soluble electrolyte salt compound to be doped, for example, LiI, LiCl, LiClO ₄ , LiSCN, LiBF ₄ , LiAs
F ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiHgI ₃ , NaI, NaSCN, NaBr,
At least L such as KI, CsSCN, AgNO ₃ , CuC ₁₂ Mg (ClO ₄ )
i, Na, K, Cs, Ag, Cu or Mg, an inorganic ionic salt containing one kind, (CH ₃ ) ₄ NBF ₄ , (CH ₃ ) ₄ NBr, (C ₂ H ₅ ) ₄ NClO ₄ , (C ₂ H ₅ ) N
I, (C ₃ H ₇ ) ₄ NBr, (nC ₄ H ₉ ) ClO ₄ , (nC ₄ H ₉ ) ₄ NI, (nC ₅ H ₄ )
₄ Organic ions such as quaternary ammonium salts such as NI, lithium stearyl sulfonate, sodium octyl sulfonate, lithium dodecyl benzene sulfonate, sodium naphthalene sulfonate, lithium dibutyl naphthalene sulfonate, potassium octyl naphthalene sulfonate, potassium dodecyl sulfonate Salts. Further, two or more of these soluble electrolyte salt compounds may be used in combination.

The compounding ratio of the soluble electrolyte salt compound is 0.0001 to 5.0 mol, preferably 0.005 to 2.
It is preferably 0 mol. If the amount of the soluble electrolyte salt compound used is too large, an excessive amount of the soluble electrolyte salt compound, for example, an inorganic ionic salt is not dissociated, but merely mixed, resulting in a decrease in ionic conductivity.

The doping method and timing of the soluble electrolyte salt compound are not particularly limited. For example, after dissolving in an organic solvent such as methyl ethyl ketone (MEK) or tetrahydrofuran (THF) and uniformly mixing with the organic compound, A method of removing the organic solvent by vacuum decompression and the like can be given.

Next, the organic solvent present together with the soluble electrolyte salt compound in the organic polymer compound may be any solvent that can dissolve the soluble electrolyte salt compound as a solute, and may be tetrahydrofuran, 2-methyltetrahydro Furan, 1,3-dioxolane, 4,4-dimethyl-1,3-dioxolane, γ-butyllactone, ethylene carbonate, propylene carbonate, butylene carbonate,
Sulfolane, 3-methyl sulfone, tert-butyl ether, iso-butyl ether, 1,2-dimethoxyethane, 1,
Examples include, but are not limited to, 2-ethoxymethoxyethane, ethylene glycol diethyl ether, or a mixture of two or more thereof. These organic solvents can significantly improve the conductivity without changing the basic skeleton of the organic polymer compound.

The blending ratio of the organic solvent, the method and the timing are not particularly limited, for example, when a crosslinking reaction of an organic compound, a soluble electrolyte salt compound and an arbitrary amount of an organic solvent are added together under a nitrogen atmosphere, and the crosslinking reaction is performed. A method for obtaining an ion-conductive polymer electrolyte, a method for obtaining an ion-conductive polymer electrolyte by impregnating an organic polymer compound with the organic solvent as desired, and before or after a crosslinking reaction, using any method Is also good.

[Action]

In the present invention, since the organic polymer compound uses a monomer having a specific structure, the organic compound structure becomes amorphous and has a side chain similar to the main chain, so that the crystallization temperature of the organic polymer compound is lowered, When an ionic compound such as a lithium salt is included, the movement of lithium ions is facilitated, so that the lithium ion conductivity is improved in a temperature range of room temperature or lower, the quality is stabilized, and the thermosetting property is various. It is intended to provide a practically excellent ion-conductive polymer electrolyte having a good shape, capable of producing a film having excellent adhesion to the electrode surface, and having improved low-temperature characteristics.

〔Example〕

Example 1. Starting from 15 g of glycerin, 1.3 g of caustic potassium was used as a catalyst.
Is reacted with 370 g of 1,2-epoxybutane, and thereafter, methyltriethylene glycol glycidyl ether represented by the following formula: 285 g were reacted and purified by desalting to obtain 509 g of a polyether having a molecular weight of 3740 (calculated from the hydroxyl value).

This polyether and 1.1 equivalents of acrylic acid based on the number of hydroxyl groups of the polyether are put in benzene equivalent to the acrylic acid, and sulfuric acid 0.01 mol% is used at 80 to 90 ° C.
And reacted while blowing air. The completion of the reaction was confirmed by measuring the amount of effluent and the acid value. After completion of the reaction, the mixture was neutralized with an aqueous solution of sodium hydroxide, washed with a saturated aqueous solution of sodium sulfate, washed with water, and the pressure was reduced to remove benzene. 480 g corresponding to the general formula).

The terminal acrylate polyether thus obtained 3.
To 6 g, LiClO ₄ 0.12 g of a 1% (0.018 mole / ether-bonded oxygen) and a polymerization initiator were dissolved in methyl ethyl ketone 3 ml, after 1 hour standing at 80 ° C. in a normal pressure nitrogen flow, the degree of vacuum 1 × 10 ^-3 the To
After heat treatment at the same temperature for 8 hours to remove methyl ethyl ketone, 1.8 g of propylene carbonate was impregnated in a nitrogen atmosphere to obtain a 42-μm-thick ion-conductive polymer electrolyte.

Example 2. Starting from 23 g of sorbitol, 3 g of potassium hydroxide was used as a catalyst.
Using methyl hexaethylene glycol glycidyl ether represented by the following formula And a mixture of α-olefin oxides having 12 carbon atoms (molar ratio
1: 1) 1477 g was reacted, desalted and purified, and the molecular weight was 11,4.
1021 g of a polyether having an 80 (calculated from the hydroxyl value) was obtained.

This polyether and 1.1 equivalents of methacrylic acid with respect to the number of hydroxyl groups of the polyether are put in benzene equivalent to the methacrylic acid, and sulfuric acid is used in an amount of 80 to 100% by weight.
The reaction was carried out at 90 ° C. while blowing air. Reaction completion
It was confirmed by measuring the amount of effluent and the acid value. After completion of the reaction, neutralize with an aqueous sodium hydroxide solution, wash with a saturated aqueous sodium sulfate solution, remove benzene under reduced pressure, and obtain 801 g of a terminal methacrylate polyether having a molecular weight of 11890 according to the following bromine value and saponification value. Generation was confirmed.

Terminal methacrylate polyether thus obtained
To 3.6 g, LiClO ₄ 0.28 g (0.044 mol / ether-bonded oxygen)
And 1% of a polymerization initiator are dissolved in 3 ml of methyl ethyl ketone,
After standing at 80 ° C for 1 hour in a nitrogen stream under normal pressure, the degree of vacuum is 1 × 10 ^-3
After heat treatment at Torr or lower at the same temperature for 8 hours to remove methyl ethyl ketone, the resultant was impregnated with 1.8 g of propylene carbonate under a nitrogen atmosphere to obtain an ion-conductive polymer electrolyte having a thickness of 42 µm.

Example 3. Starting from 30 g of glycerin, 5.3 g of potassium hydroxide was used as a catalyst.
Using, methyl diethylene glycol glycidyl ether represented by the following formula After 2300 g were reacted, 330 g of 1,2-epoxyhexane was reacted and desalted and purified to obtain 2261 g of polyether having a molecular weight of 7290 (calculated from the hydroxyl value).

This polyether and 1.1 equivalents of acrylic acid based on the number of hydroxyl groups of the polyether are put in benzene equivalent to the acrylic acid, and sulfuric acid 0.01 mol% is used at 80 to 90 ° C.
And reacted while blowing air. The completion of the reaction was confirmed by measuring the amount of effluent and the acid value. After the completion of the reaction, the mixture was neutralized with an aqueous solution of sodium hydroxide, washed with a saturated aqueous solution of sodium sulfate, washed with water, and benzene was removed under reduced pressure. Generation was confirmed.

The terminal acrylate polyether thus obtained 3.
6 g, 0.15 g of LiClO ₄ (0.019 mol / ether-bonded oxygen) and 1% of a sensitizer were dissolved in 3 ml of methyl ethyl ketone, and the solution was discharged on a petri dish, and dried under reduced pressure to remove methyl ethyl ketone. After irradiation for 2 minutes at 6 mW / cm ² using an ultra-high pressure mercury lamp of 250 W, impregnation with 2.0 g of γ-butyl lactone was carried out to obtain a 42 μm thick ion-conductive polymer electrolyte.

Example 4. Starting from 30 g of glycerin, 5.3 g of potassium hydroxide was used as a catalyst.
Using, methyl diethylene glycol glycidyl ether represented by the following formula 2300 g was reacted, then 330 g of 1,2-epoxyhexane
Was subjected to desalting and purification to confirm the formation of 2261 g of polyether having the following molecular weight of 7290 (calculated from the hydroxyl value).

To 3.6 g of this polyether, 0.15 g of LiClO ₄ (0.019 mol /
Ether-linked oxygen), tolylene diisocyanate (1.5 equivalents of polyether) and dibutyltin dilaurate
0.01 g was dissolved in 3 ml of methyl ethyl ketone, poured out into a petri dish, left at 60 ° C. for 30 minutes in a nitrogen atmosphere under normal pressure, and then heat-treated at a vacuum of 1 × 10 ⁻³ Torr or less at the same temperature for 8 hours to remove methyl ethyl ketone. After the removal, 2.0 g of γ-butyl lactone was impregnated in an N ₂ atmosphere to obtain an ion-conductive polymer electrolyte having a thickness of 42 μm.

Example 5. n-butyl triethylene glycol glycidyl ether represented by the following formula using 31 g of ethylene glycol as a starting material and potassium hydroxide as a catalyst The mixture was reacted with 2590 g of a mixture of 1,2-epoxybutane (molar ratio 3: 7), and subjected to desalting and purification to confirm the production of 2270 g of a polyether having the following molecular weight of 5110 (calculated from the hydroxyl value).

3.6 g of this polyether, 0.06 g of NaSCN (0.020 mol / ether-bonded oxygen), HMDI buret-bonded (1.5 equivalents of polyether) and 0.01 g of dibutyltin dilaurate are dissolved in 3 ml of methyl ethyl ketone.
At 30 ° C for 30 minutes, and at a vacuum of 1 × 10 ⁻³ Torr or less and 8 at the same temperature.
After heat treatment for a period of time to remove methyl ethyl ketone, impregnated with 1.8 g of propylene carbonate under a nitrogen atmosphere,
An ion conductive polymer electrolyte having a thickness of 42 μm was obtained.

Example 6. Phenylhexaethylene glycol glycidyl ether represented by the following formula using 30 g of ethylenediamine as a starting material and caustic potash as a catalyst 3990 g of a mixture of 1,2-epoxybutane and 1,2-epoxybutane (molar ratio: 2: 1) was reacted and purified by desalting to obtain 3610 g of a polyether having a molecular weight of 7,940 (calculated from a hydroxyl value).

This polyether and 1.1 equivalents of acrylic acid based on the number of hydroxyl groups of the polyether are put in benzene equivalent to the acrylic acid, and sulfuric acid 0.01 mol% is used at 80 to 90 ° C.
And reacted while blowing air. The completion of the reaction was confirmed by measuring the amount of effluent and the acid value. After the completion of the reaction, the mixture was neutralized with an aqueous solution of sodium hydroxide, washed with a saturated aqueous solution of sodium sulfate, washed with water, and then the benzene was removed under reduced pressure. Generation was confirmed.

The terminal acrylate polyether thus obtained 3.
In 6 g, 0.11 g (0.030 mol / ether-bonded oxygen) of LiClO ₄ and 1% of a polymerization initiator are dissolved in 3 ml of methyl ethyl ketone, and left standing at 80 ° C. in a nitrogen stream at normal pressure for 10 hours, and the degree of vacuum is 1 × 10 ⁻³ To
rr or less, and heat-treated at the same temperature for 8 hours to remove methyl ethyl ketone.
2.0 g was impregnated to obtain an ion conductive polymer electrolyte having a thickness of 42 μm.

Example 7. Using 46.4 g of pentaethylenehexamine as a starting material,
Using caustic potash as a catalyst, ethyl tetraethylene glycol glycidyl ether represented by the following formula And a mixture of α-olefin oxides having 12 carbon atoms (molar ratio
4: 1) 1974 g was reacted, desalted and purified, and the molecular weight was 9970
1651 g of polyether (calculated from the hydroxyl value) were obtained.

This polyether and 1.1 equivalents of methacrylic acid with respect to the number of hydroxyl groups of the polyether are put in benzene equivalent to the methacrylic acid, and sulfuric acid is used in an amount of 80 to 100% by weight.
The reaction was carried out at 90 ° C. while blowing air. Reaction completion
It was confirmed by measuring the amount of effluent and the acid value. After completion of the reaction, neutralize with an aqueous sodium hydroxide solution, wash with a saturated aqueous sodium sulfate solution, remove benzene under reduced pressure, and obtain a bromine number and a saponification value of 1610 g of a terminal methacrylate polyether having a molecular weight of 10514 shown below. Generation was confirmed.

Terminal methacrylate polyether thus obtained
To 3.6 g, 0.16 g of NaClO ₄ (0.020 mol / ether-bonded oxygen)
And 1% of a polymerization initiator are dissolved in 3 ml of methyl ethyl ketone,
After standing at 80 ° C for 1 hour in a nitrogen stream under normal pressure, the degree of vacuum is 1 × 10 ^-3
After heat-treating at Torr or lower at the same temperature for 8 hours to remove methyl ethyl ketone, the sample was impregnated with 2.0 g of γ-butyl lactone under a nitrogen atmosphere to obtain an ion-conductive polymer electrolyte having a thickness of 42 μm.

Example 8. Phenyl diethylene glycol glycidyl ether represented by the following formula, using bisphenol-A57g as a starting material, and using caustic potassium as a catalyst, And a mixture of α-olefin oxides having 6 carbon atoms (molar ratio)
3: 2) 1958 g was reacted and subjected to desalination purification to confirm the production of 1745 g of polyether having the following molecular weight of 7815 (calculated from the hydroxyl value).

To 3.6 g of the polyether thus obtained, LiClO ₄ 0.18
g (0.030 mol / ether bond oxygen), burette bond
HMDI (1.5 equivalents of polyether) and 0.01 g of dibutyltin dilaurate are dissolved in 3 ml of methyl ethyl ketone, and left standing at 60 ° C. for 30 minutes in a nitrogen stream at normal pressure, and then the degree of vacuum is 1 × 10 ⁻³ Torr.
Thereafter, a heat treatment was carried out at the same temperature for 8 hours to remove methyl ethyl ketone, and then impregnated with 1.8 g of propylene carbonate under a nitrogen atmosphere to obtain an ion-conductive polymer electrolyte having a thickness of 42 μm.

Example 9. Methyldodecaethylene glycol glycidyl ether represented by the following formula, using caustic potash as a catalyst, using 20 g of ethanolamine as a starting material 4990 g of a mixture of 1,2-epoxybutane and 1,2-epoxybutane (molar ratio: 1: 1) was reacted and purified by desalting to obtain 4378 g of a polyether having a molecular weight of 14090 (calculated from a hydroxyl value).

This polyether and 1.1 equivalents of P-vinylbenzoic acid with respect to the number of hydroxyl groups of the polyether are placed in an equivalent amount of benzene to the P-vinylbenzoic acid, and sulfuric acid is used in an amount of 80 to 100%. The reaction was carried out at 90 ° C. while blowing air.
The completion of the reaction was confirmed by measuring the amount of effluent and the acid value. After completion of the reaction, neutralize with an aqueous sodium hydroxide solution, wash with a saturated aqueous sodium sulfate solution, remove benzene under reduced pressure, and esterify with terminal P-vinylbenzoic acid having a molecular weight of 14478 according to bromine value and saponification value. The production of 4061 g of the following polyether was confirmed.

The terminal acrylate polyether thus obtained 3.
To 6 g, LiClO ₄ 0.17 g of a 1% (0.020 mole / ether-bonded oxygen) and a polymerization initiator were dissolved in methyl ethyl ketone 3 ml, after 1 hour standing at 80 ° C. in a normal pressure nitrogen flow, the degree of vacuum 1 × 10 ^-3 the To
After heat treatment at the same temperature for 8 hours to remove methyl ethyl ketone, 1.8 g of propylene carbonate was impregnated in a nitrogen atmosphere to obtain a 42 μm-thick ion-conductive polymer electrolyte.

Example 10. Using 20 g of ethylene glycol as a starting material and 3 g of caustic potassium as a catalyst, methyl glycidyl ether represented by the following formula: And a mixture of α-olefin oxides having 4 carbon atoms (molar ratio
9: 1) 6440 g was reacted, desalted and purified, and the molecular weight was 1925.
5810 g of polyether of 0 (calculated from hydroxyl value) was obtained.

This polyether and 1.1 equivalents of methacrylic acid with respect to the number of hydroxyl groups of the polyether are put in benzene equivalent to the methacrylic acid, and sulfuric acid is used in an amount of 80 to 100% by weight.
The reaction was carried out at 90 ° C. while blowing air. Reaction completion
It was confirmed by measuring the amount of effluent and the acid value. After completion of the reaction, neutralize with an aqueous sodium hydroxide solution, wash with a saturated aqueous sodium sulfate solution, remove benzene under reduced pressure, and obtain 5470 g of a terminal methacrylate polyether having a molecular weight of 19381 according to the following bromine value and saponification value. Generation was confirmed.

The terminal acrylate polyether thus obtained 3.
In 6 g, 0.08 g (0.020 mol / ether-bonded oxygen) of LiClO ₄ and 1% of a polymerization initiator are dissolved in 3 ml of methyl ethyl ketone, and left at 80 ° C. for 1 hour in a nitrogen stream at normal pressure, and then the degree of vacuum is 1 × 10 ^-3 To
rr or less at the same temperature for 8 hours to remove methyl ethyl ketone, and then propylene carbonate in a nitrogen atmosphere.
1.8 g was impregnated to obtain an ion conductive polymer electrolyte having a thickness of 42 μm.

Comparative example. Instead of the organic polymer used in Example 1, ethylene oxide / propylene oxide = 8/2, average molecular weight 300
Using a random ether of 0, 3.6 g of an organic polymer acrylated in the same manner as in Example 1 and 0.20 g of 0.12 g of LiClO ₄
An ion-conductive polymer electrolyte was obtained in the same manner as in Example 1 except that the electrolyte was used.

[Lithium ion conductivity test]

The ion-conductive polymer electrolytes obtained in Examples 1 to 10 and Comparative Example were sandwiched between platinum plates, the AC impedance between the electrodes was measured, and complex impedance analysis was performed. The results are shown in the following table.

[Effect of the Invention] The ion-conductive polymer electrolyte of the present invention has an organic compound structure that is amorphous.
Low Tg, no crystallization in the low temperature range, and no sharp drop in conductivity. Further, by using glycidyl ethers, the amount of the soluble electrolyte salt compound used can be reduced, and by using an organic solvent in combination, the characteristics of the organic compound become more remarkable and the conductivity can be further increased.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 71/00-71/03 H01M 10/40 H01M 6/18 H01B 1/06

Claims (5)

(57) [Claims] 1. An ion-conductive polymer electrolyte comprising an organic polymer compound obtained by crosslinking an organic compound represented by the following general formula, a soluble electrolyte salt compound, and an organic solvent. Z-[-EY] _k ... 2. The ion conductive polymer electrolyte according to claim 1, wherein said organic compound has an average molecular weight of 20,000 or less. 3. The ion conductive polymer electrolyte according to claim 1, wherein said organic solvent is a compound containing at least one oxygen atom and / or nitrogen atom in its structure. 4. The method according to claim 1, wherein when the main chain terminal group Y of the organic compound is an active hydrogen group, the organic polymer compound is cross-linked using a cross-linking agent. Ion conductive polymer electrolyte. 5. When the main chain terminal group Y of the organic compound is a polymerization-reactive functional group, the organic polymer compound may be prepared by using an organic compound, if necessary, with a sensitizer and / or a polymerization initiator. 3. The ion-conductive polymer electrolyte according to claim 1, wherein the polymer is cross-linked by polymerization using heat, light, or ionizing radiation.