JPH06275320A - Organic electrolyte and its manufacture - Google Patents

Abstract

PURPOSE:To provide an organic electrolyte of high ionic conductivity and excellent moldability both in the vicinity of room temperature by composing at least a series of phases in a macromolecular composition mainly of polar macromolecules. CONSTITUTION:Each ion conducting passage is necessary to achieve high ionic conductivity for an organic electrolyte, and each supporting phase is necessary to give moldability to the electrolyte. The ion conducting passage can be formed by impregnating each polar macromolecule with a metallic salt-containing electrolyte, while the supporting phase can be formed by forming each nonpolar macromolecular phase. In order to achieve the high ionic conductivity for the organic electrolyte, it is necessary for the ion conducting passages to be serially interconnected in the organic electrolyte, so that the structure of polar macromolecular phases serially interconnected is desirable. For example, consideration can be given by such sea island structure that each nonpolar macromolecular component may form an island while each polar macromolecular component may form a sea. In order to form such phase separation structure like this, such a grain that a core may have the nonpolar macromolecular component while a shell may have the polar macromolecular component is formed, and then these grains may be formed into a film. A material corresponding to the macromolecular component is a macromolecular blend, a block copolymer, a graft copolymer, or each of these two or three mixtures. The organic electrolyte can thus be obtained with high ionic conductivity and excellent moldability.

Description

Detailed Description of the Invention

[0001]

This invention relates to organic electrolytes and processes. More specifically, it relates to an organic electrolyte used for a secondary battery, an electrochromic device, a sensor, and the like, and a method for manufacturing the same.

[0002]

2. Description of the Related Art A liquid is often used as an electrolyte used in conventional lithium secondary batteries and the like.
There were many problems such as liquid leakage, liquid evaporation, and dendrite generation. In recent years, salts of polyoxyethylene (PEO) with metal ions such as LiCF ₃ SO ₃ and LiClO _{4 have been used.}
It has been found to function as a solid electrolyte by adding such as [P. Vashis (P. Vashis
ta) et al. First Fast Transport
Fast Ion Transport in Solid, 1st
31 (1979)] since then, an organic solid electrolyte using a PEO derivative (JP-A-60-14800).
No. 3, No. 60-217263, No. 63-135477.
No. 2, JP-A-2-60925, etc.), but only those having low ionic conductivity could be obtained. In addition to PEO, fluorine-containing polymers (JP-A-60-
31554), poly (iminoethylene) (JP-A-62-140306), polycation / polyanion complex (JP-A-60-23974), styrene-butadiene-styrene block copolymer (special Kaihei 2-87415, 2-148655, 2-1
(Japanese Patent No. 48656) and the like have been studied, but those having high ionic conductivity have not been obtained.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrolyte which exhibits high ionic conductivity even at around room temperature and is excellent in moldability.

[0004]

The present invention will be summarized as follows. The first invention of the present invention relates to an organic electrolyte,
An organic electrolyte comprising a polymer composition having a phase-separated structure and an electrolytic solution containing a metal salt is characterized in that at least one continuous phase of the polymer composition contains a polar polymer as a main component. A second invention of the present invention relates to a method for producing an organic electrolyte, which is characterized in that a polymer composition having a phase separation structure is impregnated with an electrolytic solution containing a metal salt.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an ionic conduction path is required to achieve high ionic conductivity, and a support phase is required to provide moldability. Found that is necessary. The ion conduction path can be formed by impregnating a polar polymer with an electrolytic solution containing a metal salt, and forming a non-polar polymer phase as a supporting phase. In order to achieve high ionic conductivity, it is essential that the ionic conduction path is continuous in the electrolyte. Therefore, a structure in which polar polymer phases are continuous is desirable, and for example, a sea-island structure in which a non-polar component is an island and a polar component is the sea is conceivable. As a method of producing such a phase-separated structure of the sea-island structure, we have developed a method in which particles having a non-polar polymer component in the core and a polar polymer component in the shell are prepared and formed into a film. FIG. 1 shows a conceptual diagram of the organic electrolyte according to the present invention.

As such a phase-separated structure having both phases, a polymer blend, a block copolymer or a graft copolymer, and a mixture thereof are considered. The inventors have found that high ionic conductivity can be achieved by impregnating a polymer composition having such a phase-separated structure with an electrolytic solution containing a metal salt, and completed the present invention.

In the present invention, the polymer composition may be any as long as it has a phase-separated structure, and examples thereof include polymer blends, block copolymers or graft copolymers, and mixtures thereof. Is a typical example. For example, in a system in which a polar polymer is blended with a non-polar polymer, it is preferable to use a block copolymer or a graft copolymer as an interface stabilizer in order to stabilize the phase separation structure.

Any block copolymer may be used as long as it shows a phase separation state, but it is desirable that at least one component is a polar polymer and the other at least one component is a nonpolar polymer. Further, in order to have excellent moldability, it is desirable that the glass transition temperature or melting point of at least one of the components be room temperature or higher, and the glass transition temperature or melting point of the other at least one component be room temperature or lower.

Examples of such block copolymers include poly (acetaldehyde) -b-poly (oxypropylene) and poly [5- (p-acrylamidophenyl).
-10,15,20-Triphenylporphine] -b-
Poly (styrene), poly (acrylonitrile) -b-poly (butadiene), poly (acrylonitrile) -b-poly (butadiene) -b-epoxy resin, poly (acrylonitrile) -b-poly (oxyethylene), poly (acrylonitrile) ) -B-Poly (oxymethylene), poly [2,2-bis (4-hydroxyphenyl) propane]
-B-epoxy resin, poly (butadiene) -b-poly (ε-caprolactam), poly (butadiene) -b-poly (oxymethylene), poly (butadiene) -b-poly (methyl-2-ethyl-2- Silazane), poly (butadiene) -b-poly (styrene), poly (butadiene)-
b-poly (oxy-1,4-phenylene-isopropylidene-1,4-phenylene), poly (butadiene-co)
-Styrene) -b-epoxy resin, poly (n-butylisocyanate) -b-poly (styrene), poly (tert-
Butyl methacrylate) -b-poly (oxyethylene), poly (β-butyrolactone) -b-poly (oxyethylene), poly (β-butyrolactone) -b-poly (oxypropylene), poly (β-butyrolactone)-
b-poly (propiolactone), poly (ε-caprolactam) -b-poly (isobutene) -b-poly (ε-caprolactam), poly (ε-caprolactam) -b-poly (styrene), poly (ε-) Caprolactam) -b-poly (1,4-butylene glycol-co-4,4-diphenylmethane diisocyanate), poly (ε-caprolactam) -b-poly (lactide), poly (ε-caprolactam) -b-poly (D , L-lactide) -b-poly (ε
-Caprolactam), poly (ε-caprolactam) -b
-Poly (oxyethylene), poly (ε-caprolactam) -b-poly (β-propiolactone), poly (dimethylsilylene) -b-poly (styrene), poly (dimethylsilylene) -b-poly (styrene) -B-poly (dimethylsilylene), poly (1,3-dioxalane) -b-
Poly (p-methoxystyrene), Poly (isoprene)-
b-poly (styrene), poly (isoprene) -b-poly (oxytetramethylene), poly (isoprene) -b-
Poly (2,4-toluene diisocyanate), poly [styrene-co-5,10,15,20-tetra (α,
α, α, α-o-methacrylamidophenyl) porphine], poly (styrene) -b- (1-methyl-2,4-
Diisocyanate cyclohexane), poly (2-methyl-ethyl-2-silazane) -b-poly (propylene sulfide), poly (methyl glycidyl ether) -b-poly (oxytetramethylene), poly (methyl methacrylate) -b-poly (2,4-toluene diisocyanate), poly (methyl methacrylate) -b-poly (oxytetramethylene) -b-poly (methyl methacrylate), poly (methyl methacrylate) -b-poly (oxyethylene) -b-poly ( Methylmethacrylate), poly (methylmethacrylate) -b-poly (styrene),
Poly (methyl methacrylate) -b-poly (styrene)
-B-poly (methyl methacrylate), poly (α-methylstyrene) -b-poly (propylene sulfide) -b
-Poly (α-methylstyrene), poly (α-methylstyrene) -b-poly (oxytetramethylene), poly (oxydimethylsilylene) -b-poly (oxymethylsilylene), poly (oxyethyleneoxyadipoyl) ) -B
-Poly (styrene) -b-poly (methylmethacrylate), poly (oxyethylene) -b-poly (ethylmethacrylate), poly (oxyethylene) -b-poly (isoprene) -b-poly (styrene) -b- Poly (isoprene) -b-poly (oxyethylene), poly (oxyethylene) -b-poly (methacrylonitrile), poly (oxyethylene) -b-poly (methylmethacrylate)-
b-poly (oxyethylene), poly (oxyethylene)
-B-poly (α-methylstyrene), poly (oxyethylene) -b-poly (oxyethyleneoxyadipoyl), poly (oxyethylene) -b-poly (oxyethylene) -co-bis (4-isocyanate) Natophenyl) methane-co-poly (oxyethylene adipoyl) -b-poly (oxyethylene), poly (oxyethylene) -b-
Poly (oxyethylene) -co-bis (4-isocyanatophenyl) methane-co-poly (oxyethyleneoxyadipoyl) -b-poly (oxyethylene), poly (oxyethylene) -b-poly (oxyethylene) Oxyadipoyl) -1-methyl-2,4-diisocyanatobenzene-poly (oxyethyleneoxyadipoyl) -b
-Poly (oxyethylene), Poly (oxyethylene)-
b-poly (oxypropylene), poly (oxyethylene) -b-poly (styrene), poly (oxyethylene)
-B-poly (styrene) -b-poly (isoprene) -b
-Poly (styrene) -b-poly (oxyethylene), poly (oxyethylene) -b-poly (2-vinylpyridine), poly (oxyethylene) -b-poly (4-vinylpyridine), poly (oxycarbonyl) Oxy-1,4-
Phenylene isopropylidene-1,4-phenylene)-
alt-poly (isobutene), poly (oxymethylene)
-B-poly (isoprene), poly (oxymethylene)-
b-poly (α-methylstyrene), poly (oxymethylene) -b-poly (2-methyl-5-vinylpyridine),
Poly (oxymethylene) -b-poly (styrene), poly (oxypropylene) -b-poly (styrene), poly (oxypropylene) -b-poly (oxytetramethylene), poly (styrene) -b-poly ( Butadiene) -b
-Poly (styrene), poly (styrene) -b-poly (butadiene) -b-poly (4-vinylpyridine), poly (styrene) -b-poly (butadiene) -b-poly (2
-Vinylpyridine), poly (butadiene) -b-poly (vinylpyrrolidone), poly (butadiene-co-styrene) -b-poly (vinylpyrrolidone), poly (acrylonitrile-co-butadiene-co-styrene) -b
-Poly (vinylpyrrolidone), Poly (styrene) -b-
Poly (isoprene) -b-poly (4-vinylpyridine), poly (styrene) -b-poly (isoprene) -b
-Poly (2-vinylpyridine), poly (styrene) -b
-Poly (isoprene) -b-Poly (ethylene sulfide), Poly (styrene) -b-Poly (isoprene) -b
-Poly (styrene), poly (styrene) -b-poly (oxytetramethylene), poly (styrene) -b-poly (oxyethylene), poly (styrene) -b-poly (oxyethylene) -b-poly ( Styrene), poly (styrene) -b-poly (2,3-dimethylbutadiene) -b-
Poly (styrene), poly (styrene) -b-poly (oxypropylene), poly (2,3-dimethylbutadiene)
Examples include -b-poly (styrene) and poly [2,2-bis (4-hydroxyphenyl) propane-co-bis (4-hydroxy-2,5-dichlorophenyl) methane-co-phosgene].

In the present invention, the graft copolymer may be any one having a phase-separated structure, but it is desirable that at least one component is a polar polymer and the other at least one component is a non-polar polymer. . Further, in order to have excellent moldability, it is desirable that the glass transition temperature or melting point of at least one of the components be room temperature or higher, and the glass transition temperature or melting point of the other at least one component be room temperature or lower.

Examples of such a graft copolymer include acrylonitrile-butadiene-styrene copolymer, poly (acrylic acid) -g-poly (β-alanine),
Poly (acrylonitrile) -g-poly (iminoadipoyliminohexamethylene), poly (acrylonitrile)
-G-poly (imino-1,3-phenyleneiminophthaloyl), poly (epoxide) -g-poly (organosiloxane), poly (α-hydroxyisobutyric acid anhydrosulfate) -g-poly (acrylonitrile), poly (Methyl methacrylate) -g-poly (imino-1-)
(Oxohexamethylene), poly (methylmethacrylate) -g-poly (iminoadipoyliminohexamethylene), poly (methylmethacrylate) -g-poly (oxy-1-oxohexamethylene), poly (2-methyl-)
2-oxazoline) -g-poly (vinyl chloride), poly (oxyethylene) -g-poly (n-butyl methacrylate), poly (oxyethylene) -g-poly (iminoadipoyliminohexamethylene), poly ( Oxyethylene) -g-poly (oxytetramethylene), poly (oxyethylene) -g-poly (n-propylmethacrylate), poly (butadiene) -g-poly (vinylpyrrolidone), poly (butadiene-co-styrene) -G-poly (vinylpyrrolidone), poly (acrylonitrile-co
-Butadiene-co-styrene) -g-poly (vinylpyrrolidone), poly (oxyethylene) -g-poly (methylmethacrylate), poly (oxyethyleneoxycarbonylimino-1,4-phenylenemethylene-1,4-
Phenyleneiminocarbonyl) -g-poly (acrylonitrile), poly (oxyethyleneoxyterephthaloyl) -g-poly (oxyethyleneoxysuccinoyl), poly (oxyethyleneoxyterephthaloyl)-
g-poly (styrene), poly (oxyethylene oxyterephthaloyl) -g-poly (vinyl acetate), poly (oxymethyleneoxyethylene) -g-poly (p-methoxystyrene), poly (2,3,4) , 5,6-Pentafluorostyrene) -g-poly (oxy-1-oxohexamethylene), poly (pivalolactone) -g-poly (ethylene-co-propylene-co-1,4-hexadiene), poly (propylene) ) -G-poly [2- (2-hydroxy-5-vinylphenyl) 2H-benzotriazole], poly (styrene) -g-poly (imino-1-oxohexamethylene), poly (styrene) -g-poly [oxy full Malo yl oxy (methylene) _n], poly (styrene)-g-poly (oxy-maleoyl oxyhexamethylene), poly (styrene -G-poly (siloxane), poly (vinylpyrrolidone) -g-poly (oxytetramethyleneoxycarbonylimino-1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl), poly (vinylpyrrolidone) -g-poly [Oxy (cis-butenylene) oxycarbonylimino-1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl],
Examples thereof include poly (vinylpyrrolidone) -g-poly (oxypropyleneoxycarbonylimino-1,4-phenylenemethylene-1,4-phenyleneiminocarbonyl).

Any polar polymer may be used as long as it dissolves or swells in a polar solvent. When a copolymer is used as a surfactant, the polar component used in the copolymer is used from the viewpoint of compatibility. The same thing as is desirable. Poly (vinylpyrrolidone) is suitable as a typical polar polymer,
Poly (acrylic acid), poly (methacrylic acid), poly (methyl acrylate), poly (methyl methacrylate), poly (ethyl acrylate), poly (ethyl methacrylate),
Poly (acrylamide), poly (N-isopropylacrylamide), poly (N, N-dimethylacrylamide), poly (ethyleneimine), poly (oxyethylene), poly (2-methoxyethoxyethylene), poly (vinyl alcohol), Poly (3-morphylinyl ethylene), poly (vinyl sulfonic acid), poly (2-vinyl pyridine), poly (4-vinyl pyridine), poly (hydroxyethyl acrylate), poly (styrene sulfonic acid), poly (amide) ), Poly (ester), poly (siloxane), poly (phosphate), poly (sulfide), poly (urea), poly (amino acid)
, Cellulose derivatives, amylose, amylopectin,
It is also possible to use polysaccharides such as starch alone or in combination.

Any non-polar polymer may be used, but when a copolymer is used as the surfactant, the same non-polar component as that used for the copolymer should be used from the viewpoint of compatibility. desirable. Examples of such non-polar polymers include poly (diene) s such as poly (butadiene) and poly (isoprene),
Typical examples are poly (alkene) s such as poly (ethylene) and poly (propylene), and styrene derivatives such as poly (styrene) and poly (α-methylstyrene). (Butadiene-
Co-styrene) and the like, and can be used as a mixture. Even when halogen such as fluorine or polar organic substance such as carboxyl group, amino group and sulfonic acid group is bonded to these non-polar polymers, the number is 2 or less per 10 monomer repeating units. If so, it can be used as a nonpolar polymer.

The metal salt used in the present invention may be any salt as long as it dissociates into ions. For example, lithium salts such as LiClO ₄ , LiAlCl ₄ , Li
_{BF 4, LiPF 6, LiAsF 6} , LiNbF 6, L
iSCN, LiCl, Li (CF ₃ SO ₃ ), Li (C
₆ H ₅ SO ₃ ), etc. and mixtures thereof.

Any polar solvent may be used,
Propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl carbonate, dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide, dimethylacetamide, 1,2-diethoxyethane, 1,2-ethoxymethoxyethane, which are well known as electrolytic solutions. 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, methyl acetate and the like are preferable. These substances can be used alone or as a mixture thereof or a mixture with an organic solvent other than these.

As a method for producing the polymer composition, there is a method in which a latex having a core-shell structure is synthesized and then formed into a film to produce the polymer composition. At this time, it is preferable to use a polar solvent such as water or alcohol as the dispersion medium because the nonpolar component becomes the core. Examples of such polymers include dienes such as butadiene and isoprene, monomers such as styrene derivatives, vinyl ether derivatives, and vinyl ester derivatives, alone or in combination, and polar polymers such as poly (vinylpyrrolidone) and poly (oxyethylene). The method of polymerizing in the presence of By removing the dispersion medium from the polymer latex thus obtained, a polymer composition exhibiting phase separation can be obtained.
As a method for removing the dispersion medium, a heating method or a depressurizing method may be used. Here, if the speed of removing the dispersion medium is too high, the film formation is carried out while the progress of phase separation is insufficient, so it is necessary to remove the solvent at an appropriate speed. The metal salt can be added in advance while the latex is dispersed.

Another method for producing a polymer composition is a method of forming micelles to obtain a film. The micelle can be formed by adding a block copolymer or a graft copolymer to an organic solvent and stirring vigorously. The metal salt can be dissolved in the organic solvent in advance, but it is also possible to add the metal salt after forming micelles. A factor to be considered when selecting a solvent is its ability to dissolve in a polymer component. It is necessary to dissolve at least one component of the block copolymer or graft copolymer composed of two or more components and not dissolve the remaining at least one component. For example, in the case of a block copolymer or a graft copolymer consisting of a polar component and a nonpolar component,
Micelles can be formed using either a polar solvent or a non-polar solvent. In such a case, when an electrolytic solution containing a metal salt is used as a solvent, it becomes a polar solvent, so that micelles are formed in which the nonpolar component serves as the nucleus and the polar component serves as the shell. However, in the case of a block copolymer or a graft copolymer composed of components having similar polarities, it is often difficult to form micelles with a single solvent, and for example, another organic solvent may be added to the electrolytic solution containing a metal salt. The micelles can be formed by gradually changing the solubility of the solution and adjusting the solubility to an appropriate level. By removing the solvent of the micelles thus obtained, a polymer composition film having a phase-separated structure can be obtained. The method for removing the solvent may be a method by heating,
You may use the method by pressure reduction. Here, if the rate of removing the solvent is too fast, a film is formed while the progress of phase separation remains insufficient, so it is necessary to remove the solvent at an appropriate rate.

The block copolymer or graft copolymer can be molded by adding a polar polymer to the film by melt molding such as hot pressing, roll, injection molding, extrusion molding, blow molding and the like. At this time, the molding temperature needs to be higher than the glass transition temperatures and melting points of all the polymer components. However, molding at an excessively high temperature is not desirable because it may decompose a part of the polymer component. To produce a polymer composition containing a metal salt in a film by impregnating a film of the polymer composition consisting of a block copolymer or a graft copolymer and a polar polymer with an electrolytic solution containing a metal salt. You can

An organic electrolyte can be obtained by impregnating the polymer composition thus obtained with an electrolytic solution. In addition, when the metal salt is added to the polymer composition in advance, the organic electrolyte can be obtained only by impregnating the electrolyte solvent.

[0020]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 The method for producing a polymer composition was as follows. 100 ml
0.62 g of poly (vinylpyrrolidone) (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 40,000) and 0.037 g of potassium persulfate were placed in the pressure-resistant glass tube of No. 1 and dissolved in 22.36 g of water. 1,3-Butadiene (Tokyo Chemical Industry Co., Ltd.) 12.4
After adding 2 g and sealing the glass tube, the glass tube was shaken at 70 ° C. for 15 hours to form latex and the aqueous solution became turbid. The emulsion was diluted and the particle size of the latex was examined with a dynamic light scattering analyzer (DLS-700, manufactured by Otsuka Electronics). As a result, the average particle size was 360 nm. The obtained latex was ¹³ C by an NMR apparatus (MSL-400 type manufactured by Bruker).
As a result of NMR analysis, double bond carbon (130 ppm) and single bond carbon (3
2ppm), double bond carbon (129ppm) due to 1,4-cis structure and single bond carbon (27ppm), double bond carbon due to 1,2-vinyl structure (142ppm, 114)
ppm) was observed, confirming the formation of poly (butadiene). Also, of course, signals due to poly (vinylpyrrolidone) were observed at 18, 31, 42, 177 ppm. The polybutadiene content in the polymer latex estimated from the NMR signal was 62%.

The produced latex liquid was transferred to a glass petri dish, allowed to stand at room temperature for 3 hours, and then heated at 105 ° C. for 24 hours to obtain a film. The film was flexible and tough. As a result of measuring the infrared absorption spectrum of the film, a large absorption peak at 1688 cm ^-1 due to the carbonyl absorption of polyvinylpyrrolidone was observed.
-H absorption at 2928 cm ^-1 , C-derived from 1,4-cis, 1,4-trans, 1,2-vinyl of polybutadiene
H absorption is 967cm ^-1, 733cm ^-1, appeared to 911cm ^-1. Scanning differential thermal analyzer (Perkin Elmer, DS
When the glass transition temperature of the film is measured with C-7),
There was a transition point at, and it was the same as that of polybutadiene. From this, it was revealed that polybutadiene and poly (vinylpyrrolidone) were phase-separated in the film. As a result of scanning electron microscope observation (S-800 manufactured by Hitachi, Ltd.), the polymer showed granularity in the film, and the X-ray with a UTW type detector was attached to the scanning transmission electron microscope (VG Microscope, HB501). Microscopic analysis (Quebex, super-80
When the nitrogen content of the inside and the outer peripheral portion of the particle was examined using 00), it was found that nitrogen did not exist inside the particle and 12% existed in the outer peripheral portion. From these, it was demonstrated that this polymer composition has a phase-separated structure in which poly (butadiene) is in the core and poly (vinylpyrrolidone) is in the shell.

This polymer composition film was impregnated with a 1 mol / liter γ-butyrolactone / dimethoxymethane (50 wt% / 50 wt%) mixed electrolyte solution of lithium perchlorate for 36 hours. The ionic conductivity was 1% with a weight increase of 26% after impregnation.
It reached 2 × 10 ⁻³ S / cm. The ionic conductivity was measured by an AC two-terminal method using an impedance meter (4284A PRECISION LCR METER manufactured by Hewlett-Packard Co.). The electrodes were made of stainless steel, the applied voltage was 100 mV, and the frequency was swept by computer control in the range of 20 Hz to 1 MHz. The ionic conductivity of the electrolyte was calculated from the resistance value obtained from the Cole-Cole plot of the complex impedance and the shape factor (film thickness of the electrolyte / electrode area). The measurement temperature was 25 ° C.

Example 2 A polymer composition film was prepared in the same manner as in Example 1. This polymer composition film was impregnated with a 1 mol / liter lithium perchlorate γ-butyrolactone electrolyte solution for 15 hours. The film, including the electrolyte, had a weight gain of 36%. The ionic conductivity of this film is 5.6 × 10 ^-4 S
It was / cm.

Example 3 In the method for preparing the polymer composition of Example 1, 2.23 g was used instead of 0.62 g of poly (vinylpyrrolidone).
6.21 g instead of 12.42 g of 1,3-butadiene,
Further, poly (butadiene-co) was prepared in the same manner as in Example 1 except that 2.03 g of styrene (manufactured by Wako Pure Chemical Industries, Ltd.) was added.
-Styrene) / poly (vinylpyrrolidone) polymer composition was obtained. This polymer composition has a lithium perchlorate concentration of 1
It was impregnated with a mol / l γ-butyrolactone / dimethoxyethane (50 wt% / 50 wt%) mixed electrolytic solution. The ionic conductivity is 2.5 x 10 when the weight increase after impregnation is 28%.
It was ^-3 S / cm.

Example 4 The same polymer composition as in Example 3 was used, and this was impregnated with a propylene carbonate / ethylene carbonate (50 wt% / 50 wt%) mixed electrolytic solution having a lithium perchlorate concentration of 1 mol / liter. Ionic conductivity increased by 4 after impregnation
The 7.6% content was 1.7 × 10 ⁻³ S / cm.

Example 5 The same polymer composition as in Example 3 was used, and this was impregnated with a γ-butyrolactone electrolyte solution having a lithium perchlorate concentration of 1 mol / liter. The ionic conductivity increased 39. after the impregnation.
The content of 4% was 7.3 × 10 ⁻⁴ S / cm.

Example 6 The same polymer composition as in Example 3 was used, and this was impregnated with a propylene carbonate / dimethoxyethane (50 wt% / 50 wt%) mixed electrolytic solution having a lithium perchlorate concentration of 1 mol / liter. The ionic conductivity was 3.9 × 10 ⁻⁴ S / cm when the weight increase after impregnation was 50%.

Example 7 The same polymer composition as in Example 3 was used, and this was impregnated with a propylene carbonate electrolytic solution having a lithium perchlorate concentration of 1 mol / liter. Ionic conductivity increased by 4 after impregnation
The content of 1.6% was 1.3 × 10 ⁻³ S / cm.

Comparative Example 1 A poly (butadiene) film was obtained in the same manner as in Example 1 except that poly (vinylpyrrolidone) was not added in the method for producing a polymer in Example 1. This poly (butadiene) film was impregnated with a mixed electrolyte of γ-butyrolactone / dimethoxyethane (50 wt% / 50 wt%) having a lithium perchlorate concentration of 1 mol / liter, but there was no weight change after a weight increase of 13%. . The ionic conductivity is 1.
It was 0 × 10 ⁻⁸ S / cm or less.

Comparative Example 2 A poly (butadiene) film was obtained in the same manner as in Example 1 except that poly (vinylpyrrolidone) was not added in the method for producing a polymer in Example 1. This poly (butadiene) film was impregnated with a 1 mol / l lithium perchlorate γ-butyrolactone electrolyte solution, but there was no weight change after a weight increase of 3%. The ionic conductivity is 1.
It was 0 × 10 ⁻⁹ S / cm or less.

Comparative Example 3 A poly (butadiene-co-styrene) film was obtained in the same manner as in Example 1 except that poly (vinylpyrrolidone) was not added in the method for producing a polymer in Example 3.
This poly (butadiene-co-styrene) film was impregnated with a mixed electrolyte of γ-butyrolactone / dimethoxyethane (50 wt% / 50 wt%) having a lithium perchlorate concentration of 1 mol / liter. There was no change. The ionic conductivity was 1.0 × 10 ⁻⁷ S / cm or less.

[0033]

According to the present invention, an electrolyte having a high ionic conductivity near room temperature can be obtained. Further, it is possible to obtain an electrolyte having a high ionic conductivity near room temperature and having excellent moldability as a film.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of an organic electrolyte according to the present invention.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Toshihiro Ichino 1-1-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corporation

Claims (3)

[Claims] 1. An organic electrolyte comprising a polymer composition having a phase-separated structure and an electrolyte solution containing a metal salt, wherein at least one continuous phase of the polymer composition contains a polar polymer as a main component. And an organic electrolyte. 2. An organic electrolyte comprising a polymer composition having a core-shell type phase-separated structure and an electrolytic solution containing a metal salt, wherein the core contains a non-polar polymer as a main component and the shell contains a polar polymer as a main component. An organic electrolyte characterized by: 3. A method for producing an organic electrolyte, which comprises impregnating a polymer composition having a phase-separated structure with an electrolytic solution containing a metal salt.