JP3152264B2 - Polymer solid electrolyte and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer solid electrolyte and a method for producing the same, and more particularly, to a polymer solid electrolyte having a sufficient ionic conductivity applicable to a high energy density battery such as a lithium battery, which is easy to manufacture and cost effective. The present invention relates to a polymer solid electrolyte which is inexpensive and has excellent mechanical strength and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, there has been an increasing need for a rechargeable battery having a high energy density as a power source for small, portable electronic devices. A typical example of a battery satisfying such needs is a lithium secondary battery. However, currently commercially available lithium secondary batteries have an organic electrolyte as an electrolyte therein, and therefore have problems such as liquid leakage and dendrite short-circuit. Therefore, solidification of the electrolyte, that is, realization of an all-solid-state battery using the solid electrolyte is strongly desired. As solid electrolytes, those made of inorganic materials and those made of polymer materials are known, but polymer solid electrolytes are manufactured by a vacuum process such as sputtering because they can be easily processed in a large area. The capacity can be increased as compared with the inorganic solid electrolyte, and a reduction in manufacturing cost can be expected. Also, the solid polymer electrolyte is
Since it can be processed into various shapes such as a flexible sheet shape, a battery of an arbitrary shape can be manufactured, which can contribute to customization of electronic devices.

As for polymer solid electrolytes, polyethers such as polyethylene oxide have been actively studied (R. Spinder and DFShriver, J. Amer. Chem.
Soc., 21,648 (1988)). These are solid electrolytes of a type (polyether type) in which ions included in the polymer chain move with the thermal motion (segment motion) of the polymer chain. Recently, a polar polymer (polyacrylonitrile) impregnated with a metal salt electrolyte (M.Wa
tanabe et al., J. Polym.Sci.Polym.Phis., 21, 939 (198
3)) or a liquid mixture consisting of a polar polymer, an electrolyte, and a photosensitive cross-linking agent cured by ultraviolet irradiation (KM
Abraham and M. Alamgir, J. Electrochem. Soc., 137, 165
7 (1990)), and some solid electrolytes of this type have achieved ionic conductivity of 10 @ -3 S / cm.

[0004]

However, in the above-mentioned polyether-type solid electrolyte, since the segmental motion of the polymer chain near room temperature is limited, high ionic conductivity exceeding 10 ^-4 S / cm is exhibited. Was difficult. Furthermore, in order to improve the ionic conductivity by increasing the motion of the polymer chain, it is necessary to lower the molecular weight or soften the polymer, which greatly reduces the mechanical strength of the polymer solid electrolyte. The result was inviting. In the case of a polar polymer type solid electrolyte, impregnating the polar polymer with a metal salt electrolyte plasticizes the polar polymer itself, so that the mechanical strength is significantly reduced. Also,
The production method still has problems, such as a dangerous and expensive process of ultraviolet irradiation. Accordingly, the present invention provides a solid polymer electrolyte having sufficient ionic conductivity, and easy to manufacture and low in cost, and excellent in mechanical strength,
It is intended to provide a manufacturing method thereof.

[0005]

The object of the present invention is to provide a high-polarity high
Consists of a molecular phase and a low-polarity polymer phase that retains the particle shape
The high polarity of the polymer matrix having a phase separation structure
The polymer phase is impregnated with an electrolyte solution in the polymer phase.
Can be solved. Also, such a solid polymer electrolyte,
After preparing a polymer matrix having a phase separation structure, a method of impregnating the polymer matrix with an electrolyte solution, or having a phase separation structure and preparing a polymer matrix containing an electrolyte, It is made by a method of impregnating a liquid that dissolves the contained electrolyte.

Hereinafter, the polymer solid electrolyte of the present invention will be described in detail. The polymer solid electrolyte of the present invention is characterized in that an electrolyte solution is contained in a polymer matrix having a phase-separated structure, and the polymer solid electrolyte has a morphological difference caused by a difference in a manufacturing method described later. Can be classified into two types . That is, a low-polarity polymer phase (support phase) formed by aggregating low-polarity polymer particles.
And an amorphous ion conduction path in which an electrolyte solution is impregnated into a high-polar polymer phase formed by aggregating the high-polar polymer particles, and the support phase retains the particle shape,
A support phase retains the particle shape in the same manner, the ion conduction path of the amorphous, which is two to further composed of a second ion conducting path formed in a mesh shape in the support phase. This will be described below with reference to the drawings.

FIG. 1 is a diagram showing the structure of an example of a solid polymer electrolyte which retains the shape of particles, and polystyrene / polybutadiene latex (SB) is used as low-polar polymer particles.
(R) A diagram schematically showing a result of observing a cross section of an ultra-thin section of a polymer solid electrolyte prepared using polyacrylonitrile / polybutadiene latex (NBR) particles as particles and high-polar polymer particles with a transmission electron microscope. It is. In the figure, reference numeral 1 denotes an ion conduction path, which is NB
The R particle aggregate is impregnated with an electrolyte solution to form an amorphous form. Further, the ion conduction path 1 is surrounded by a support phase 2 composed of an SBR aggregate maintaining the particle shape. Here, latex particles mean polymer particles obtained by removing a dispersion medium from a polymer particle dispersion (latex) in which the polymer particles are dispersed in a dispersion medium in the presence of a stabilizer. It is defined that the stabilizer remains on the particle surface.

FIG. 2 is a view showing another embodiment of the solid polymer electrolyte retaining the particle shape. As shown in FIG. 1, the solid polymer electrolyte has an ion conduction path 1 and a support phase 2. A second ion conduction path 3 made of an electrolyte solution is formed in a mesh.

As shown here, in the solid polymer electrolyte of the present invention, the mechanical strength is maintained by the support phase 2 made of the low-polarity polymer phase, and the high-polarity polymer phase forming the ionic conduction path 1 is formed. The ion conductivity in the impregnated electrolyte solution and / or the electrolyte solution existing in the second ion conduction path 3 formed in a network in the support phase 2 is exhibited by the ion transfer, so that the conventional high ion conductivity is exhibited. Significant improvement in ionic conductivity is achieved as compared to molecular solid electrolytes.

The high-polarity polymer component used in the high-polarity polymer phase forming the ionic conduction path 1 of the solid polymer electrolyte of the present invention is not particularly limited as long as it is a high-polarity polymer capable of impregnating the electrolyte solution. For example, the following polymers may be used alone or as a mixture: polyacrylonitrile, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, polymethacrylic acid (and metal). Salts), polyacrylic acid (and metal salts), polyvinyl alcohol, polyvinylidene chloride, polyethyleneimine, polymethacrylonitrile, polyvinyl acetate, polyvinylpyrrolidone, and derivatives thereof. Further, copolymers containing these highly polar polymer components, for example, polyacrylonitrile / polybutadiene copolymer, polyacrylonitrile / polystyrene copolymer,
Polyacrylonitrile / polybutadiene / polystyrene copolymers, polyacrylonitrile / polyisoprene copolymers and the like can be impregnated with a large amount of any kind of electrolyte solution, and thus can be suitably used as the high polar polymer component. . Among them, polyacrylonitrile / polybutadiene copolymer and polyacrylonitrile / polyisoprene copolymer are flexible and have rubber elasticity.
It is particularly preferable because it shows good adhesion to the electrode. The content of the highly polar polymer component in these copolymers, in the above example, the polyacrylonitrile component is preferably 10% by weight or more.

On the other hand, the low-polarity polymer component used in the low-polarity polymer phase forming the support phase 2 of the polymer solid electrolyte of the present invention is such that the impregnation with the electrolyte solution which is a highly polar liquid is negligible. The material is not particularly limited as long as the material is small, that is, a polymer having a low polarity. For example, a hydrocarbon polymer or a copolymer thereof is suitable. Specific examples include the following polymers: polystyrene, polypropylene, polyisobutene, polyethylene, polybutadiene, polyisoprene, polychloroprene, poly (α-methylstyrene), polybutyl methacrylate, polybutyl acrylate, poly (2 -Ethylhexyl acrylate), polydibutyl phthalate, polyvinyl butyl ether, polyvinyl butyral, polyvinyl formal, and derivatives thereof, and copolymers containing these components. Among these, a solid polymer electrolyte prepared from a polymer containing a conjugated diene bond, such as polybutadiene, polyisoprene, and polychloroprene, is particularly preferable because it has flexibility and rubber elasticity and exhibits good adhesion to electrodes.

The electrolyte which is a component of the electrolyte solution forming the ion conduction path 1 of the solid polymer electrolyte of the present invention differs depending on the use of the solid polymer electrolyte to be produced and is not particularly limited. For example, considering the application to lithium batteries, LiClO4, LiAlCl4, LiBF4, LiPF6, LiNbF6, LiSCN, LiCl, L
Lithium salts such as i (CF3SO3) and Li (C6H5SO3) are used alone or in combination. Also, the solvent of this electrolyte solution is
There is no particular limitation as long as it dissolves the electrolyte to be used.Similarly, considering application to a lithium battery, a solvent dissolving the above lithium salt, for example, propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl carbonate, dimethyl Aprotic polar solvents such as sulfoxide, acetonitrile, sulfolane, dimethylformamide, dimethylacetamide, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, methyl acetate, and mixtures thereof; It is preferably used. The concentration of the electrolyte solution is preferably 0.01 to 5 mol / kg in terms of molarity.

Further, the high-polarity or low-polarity polymer component constituting the solid polymer electrolyte of the present invention may contain a polar organic component. This polar organic component exerts a surfactant activity when polymer particles are dispersed in a dispersion medium and serves to assist the dispersion of the polymer particles. Most commonly known. The polar organic component is directly incorporated into a polymer chain or a polymer molecule chain constituting a polymer particle by a covalent bond. For example, the following compounds are used alone or as a mixture: acrylic acid and the like. Metal salt, methacrylic acid and its metal salt, ethacrylic acid and its metal salt, itaconic acid and its metal salt, styrene sulfonic acid and its metal salt, ethylene sulfonic acid and its metal salt, unsaturated fatty acid and its metal salt, vinyl acetate , Acrylonitrile and the like. These polar organic components are incorporated into the polymer particles by covalent bonds in the form of copolymerization, graft polymerization, or by directly reacting with the functional group of the main component of the polymer particles. Further, the main component of the polymer particles may be treated with sulfuric acid or the like to introduce a polar organic component.

Further, the high-polarity or low-polarity polymer component constituting the polymer solid electrolyte of the present invention may contain a crosslinking component. The cross-linking component forms a cross-linked structure between polymer particles, within polymer particles, between polymer chains, or within polymer chains, and functions to improve the mechanical strength of the polymer matrix. The cross-linking component is introduced by covalently bonding two or more types of polar organic components to a molecular chain constituting a polymer component or a polymer particle. That is, a polymer component having two or more polar organic components and polymer particles are heated to cause a cross-linking reaction within the polymer particles and between the polymer particles to form a cross-linked component.
Examples of such a crosslinking reaction include an esterification reaction, an amidation reaction, and an epoxy group ring-opening reaction. In order to carry out this cross-linking between molecules or within a molecule, two or more kinds of amide groups, hydroxyl groups, carboxyl groups and epoxy groups may be provided in the polymer chain. Such a polymer is called a self-crosslinkable polymer. For example, a self-crosslinkable polymer can be obtained by copolymerizing the above-mentioned monomer as the main component of the polymer particles and two or more kinds of crosslinkable monomers. The crosslinking monomer is not particularly limited, but includes acrylamide, diacetone acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylic acid, methacrylic acid,
Itaconic acid, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and the like are preferably used.

Further, the high-polarity or low-polarity polymer phase constituting the solid polymer electrolyte of the present invention may contain a stabilizer. The stabilizer is not particularly limited as long as it has a function of stabilizing the polymer particle dispersion, and a surfactant is suitable, and examples thereof include the following: fatty acid metal salt, alkylbenzene sulfonic acid Metal salts, metal alkyl sulfates, metal dioctyl sulfosuccinates, polyoxyethylene nonyl phenyl ether, polyoxyethylene stearic acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, poly Ether-modified silicone oils and mixtures thereof. Further, as a stabilizer, a dispersing medium-soluble polymer or the like may be used alone or in combination with the above surfactant. The dispersing medium-soluble polymer varies depending on the dispersing medium. For example, when water is used as the dispersing medium, hydroxyethyl cellulose, polyvinyl alcohol, a metal salt of polyacrylic acid, methyl cellulose, polyoxyethylene, polyvinyl pyrrolidone, etc. are used alone. Alternatively, they are suitably used by mixing.

Next, a method for producing the solid polymer electrolyte of the present invention will be described. The method for producing a solid polymer electrolyte of the present invention comprises a step of preparing a polymer matrix composed of a high-polar polymer component and a low-polar polymer component, and a step of impregnating the polymer matrix with an electrolyte solution. . In the step of producing the polymer matrix,
The following method is adopted. Method A: A method of preparing a polymer matrix by removing the dispersion medium from a polymer particle dispersion in which high polarity polymer particles and low polarity polymer particles are dispersed in a dispersion medium.

In the step of impregnating the polymer matrix with an electrolyte solution, the following two methods are employed. Method a: a method of impregnating an electrolyte solution after preparing a polymer matrix. The method b: in the step of preparing a polymer matrix in advance by dissolving an electrolyte in a polymer particle dispersion, to produce a polymer matrix containing the electrolyte and removing the dispersion medium or a solvent, then dissolving an electrolyte A method of impregnating a liquid.

In the step of preparing the polymer matrix, the above-mentioned method A is adopted, and the two steps of impregnating the electrolyte solution of the method a or b can be combined. Can take two methods combining them. The respective manufacturing methods will be described in detail below.

[Production Method 1 (Combination of Method A and Method a)] In this method, a dispersion medium is removed from a polymer particle dispersion in which high-polar polymer particles and low-polar polymer particles are dispersed in a dispersion medium. After preparing a polymer matrix, the polymer solution is impregnated with an electrolyte solution. The method for preparing the polymer particle dispersion liquid as the raw material is not different between the high-polarity polymer and the low-polarity polymer, and specifically, it is preferable to prepare the emulsion by polymerizing the monomer in an aqueous dispersion medium. . A method for producing a polymer dispersion by this emulsion polymerization method is generally known, and is a method as outlined below. When a surfactant is added to water at a concentration higher than the critical micelle concentration and the main component monomer is introduced,
Part of the main component monomer is taken into the surfactant micelle. When a water-soluble polymerization initiator (for example, metal persulfate) is added and heated, a polymerization initiator radical is generated,
When this enters the micelle filled with the monomer, the main component monomer is polymerized to synthesize polymer particles. While the polymer particles are growing by the polymerization reaction, the main component monomer is supplied from the emulsified monomer droplets to the micelles, which are reaction sites, through dissolution in water. After a suitable time has elapsed, the polymerization reaction is terminated by cooling to obtain a polymer particle dispersion.

The diameter of the polymer particles can be controlled by adjusting the polymerization time, and those having the particle diameter adjusted to 0.01 to 500 μm are preferably used. Further, the reaction mixture may contain a polar organic component monomer and a crosslinking component monomer. In this case, the polar organic component monomer and the crosslinking component monomer also cause a polymerization reaction in the micelle that is a reaction field, and Is obtained. Since the polar organic component has low compatibility with the main component, it is distributed more near the outer surface of the polymer particle. Although the composition ratio of the main component and the polar organic component is not particularly limited, it is preferable that the main component polymer contains 20% or more. To the prepared polymer particle dispersion, a stabilizer such as a surfactant and a polymer soluble in a dispersion medium may be further added. The polymer dispersion may be produced by dispersion polymerization in a polar solvent such as alcohol (Y. Almog, et al., British Polymer Journal, 14, 13).
1 (1982)) Further, the polymer dispersion may be prepared by developing and dispersing the polymer solution in a dispersion medium to form particles, and then stabilizing with a stabilizer.

The low-polarity polymer dispersion and the high-polarity polymer dispersion prepared as described above are mixed at a desired ratio and mechanically stirred. Next, the mixed dispersion is cast on a substrate, and the dispersion medium is removed by heating and drying to obtain a film-shaped polymer matrix composed of aggregates of polymer particles. The heating method may be an ordinary method, and may be performed under reduced pressure. However, in order to produce a uniform polymer matrix, it is preferable to heat the polymer particles to a temperature higher than the glass transition temperature of the components of the used polymer particles.

The mixing ratio of the high-polarity polymer particles and the low-polarity polymer particles is not particularly limited, but in order to exhibit both high ionic conductivity and mechanical strength, both are 10% by weight.
It is preferable to mix the above. When the self-crosslinking polymer particles having a crosslinking component are used as the polymer particles, when removing the dispersion medium as described above, the crosslinking reaction within the polymer particles or between the polymer particles is performed by heating. Will wake up. The introduction of this crosslinked structure improves the mechanical strength of the resulting solid polymer electrolyte. In order to cause this crosslinking reaction, it is preferable to heat to 100 ° C. or higher. If necessary, the polymer matrix may be formed into an arbitrary shape by pressing under pressure. On the other hand, when the used dispersion medium has an adverse effect on the environment in which the solid electrolyte is used, for example, a battery or the like, the dispersion medium is heated to a temperature higher than the boiling point of the dispersion medium or a combination of heating and reduced pressure treatment to completely disperse the dispersion medium. It is preferable to remove it. The polymer matrix thus prepared is immersed in an electrolyte solution, and the electrolyte solution is impregnated in the polymer matrix. The amount of the electrolyte solution to be impregnated can be controlled by the time of immersing the polymer matrix in the electrolyte solution, but it is preferable to impregnate the obtained polymer solid electrolyte by 10% by weight or more.

[Production Method 2 (Combination of Method A and Method b)] This method comprises dispersing a high-polarity polymer particle and a low-polarity polymer particle in a dispersion medium and dispersing them in a polymer particle dispersion in which an electrolyte is dissolved. After removing the medium and preparing a polymer matrix containing an electrolyte, the polymer matrix is impregnated with a solvent that dissolves the electrolyte. The method for preparing a polymer particle dispersion in which an electrolyte serving as a raw material is dissolved is to previously dissolve the electrolyte in one or both of a high-polarity polymer dispersion and a low-polarity polymer dispersion,
These dispersions may be mixed, or a high-polarity polymer dispersion and a low-polarity polymer dispersion may first be mixed, and the electrolyte may be dissolved in the mixed dispersion. The method for producing these polymer dispersions is the same as that in Production method 1.

The dispersion medium is removed from the polymer dispersion in which the electrolyte thus prepared is dissolved to prepare a polymer matrix containing the electrolyte. The method is manufacturing method 1
Is the same as Next, the polymer matrix containing the electrolyte is immersed in a liquid that dissolves the contained electrolyte, and the liquid solvent is impregnated, and the contained electrolyte is dissolved, and the polymer solid electrolyte is dissolved. And The amount of liquid solvent to be impregnated is controlled by the immersion time,
The content is preferably at least 10% by weight of the obtained solid polymer electrolyte. Here, the liquid to be impregnated may be a solvent alone or an electrolyte solution containing the same or different electrolyte as the electrolyte contained in the polymer matrix.

According to such a manufacturing method, the dispersion of polymeric particles, solvent removal, and to produce a polymer solid electrolyte having excellent properties described above by less costly operations in simple impregnation or the like of the liquid Will be possible.

[0026] Incidentally, a solid polymer electrolyte of the present invention, depending on whether to adopt any of the above manufacturing method, the microstructure of the resulting polymer solid electrolyte is known to be different. The solid polymer electrolyte manufactured by the manufacturing method 1 is composed of an amorphous high-polar polymer phase (ion conduction path 1) impregnated with an electrolyte solution and a low-polar polymer having a particle shape as shown in FIG. It has a phase separation structure consisting of a phase (support phase 2). The solid polymer electrolyte manufactured by the manufacturing method 2 is composed of an amorphous high-polar polymer phase (ion conduction path 1) impregnated with an electrolyte solution and a low-polar polymer having a particle shape as shown in FIG. It has a phase separation structure composed of a phase (support phase 2), and further has a second ion conduction path 3 composed of an electrolyte solution formed in a mesh in the support phase 2.

[0027] This is because you are in the production method 1 and 2, a polymer matrix comprising a polymer particle agglomerates produced by removing the dispersion medium from the polymer particle dispersion material,
It is considered that the shape of the base polymer particles remains. In the case of the production method 2, when the electrolyte dissolved in the polymer particle dispersion liquid removes the dispersion medium, not only the high polarity polymer phase but also the low polarity polymer particles (for example, SB)
It is considered that the electrolyte remaining between the particles dissolves to form a second ion conduction path made of an electrolyte solution when the solvent is next impregnated. The existence of the second ion conduction path has been confirmed from the results of a transmission electron microscope.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Among the materials used in each of the examples, low-polar polymer, low-polar polymer particles, high-polar polymer, butadiene content in high-polar polymer particles, low-polar polymer particles and high-polar polymer For the mixing ratio of the particles, the mixing ratio of the low-polarity polymer component and the high-polarity polymer component, the type of the electrolyte and the solvent of the electrolyte solution and the impregnation rate thereof, and the ionic conductivity of the obtained polymer solid electrolyte, see Table. Are shown together. In the table, HPP means a high polarity polymer, and LPP means a low polarity polymer. The item of modification indicates the presence or absence of a polar organic component and a cross-linking component, and A indicates that the polar organic component contains a carboxyl-modified component, and B indicates
Represents that a crosslinking component is contained. Also,
In the term of the solvent of the electrolyte solution, γ-BL is γ-butyrolactone, EC is ethylene carbonate, PC is propylene carbonate, DME is 1,2-dimethoxyethane,
MeTHF shall represent 2-methyltetrahydrofuran. The average particle diameter is a value determined by dynamic light scattering measurement.

[ Examples by Production Method 1] (Examples 1 to 17) Carboxyl-modified polystyrene / butadiene copolymer-based latex (Nipol LX42 manufactured by Zeon Corporation)
4) and carboxyl-modified polyacrylonitrile /
Butadiene copolymer latex (Nihon Zeon Ni
pol1571) was mixed so that the solid content weight ratio was as shown in Table 1. Next, the mixed latex was spread on a glass Petri dish, dried at normal temperature and normal pressure for 3 hours, and then dried for 24 hours.
Further drying was performed at 105 ° C. under vacuum (0.01 Torr or less) to obtain a rubbery polymer matrix film.
Next, this film was mixed with 1 mol / mol of the composition shown in Table 2.
1 of the electrolyte solution to obtain a solid polymer electrolyte of the present invention. This polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength. The electrolyte concentrations in the electrolyte solutions in the following examples are all the same as in this example, and are 1 mol / l.

[0030] (Examples 18 to 20) a carboxyl-modified polystyrene / butadiene copolymer latex (manufactured by Zeon Corporation NipolLX42
4) and polyacrylonitrile / butadiene copolymer latex (Nipol1551 manufactured by Zeon Corporation) were mixed such that the weight ratio of solids was as shown in Table 1. Subsequent steps are the same as in Examples 1 to 17. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength. (Examples 21 to 23) A polystyrene / butadiene copolymer latex (Nipol LX110 manufactured by Zeon Corporation) and a carboxyl-modified polyacrylonitrile / butadiene copolymer latex (Nipol1571 manufactured by Zeon Corporation) having a solid content weight ratio of Table 1 And mixed so that Subsequent steps are the same as in Examples 1 to 17. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

[0031] (Example 24-26) polystyrene / butadiene copolymer latex (manufactured by Nippon Zeon Co., Ltd. NipolLX110), polyacrylonitrile / butadiene copolymer latex (manufactured by Nippon Zeon Co., Ltd. Nipol1551) the solid weight ratio of Table 1 And mixed so that The subsequent steps are described in Examples 1-1.
Same as 7. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

Examples 27 to 29 Polystyrene / butadiene copolymer latex having a self-crosslinking component (Nipol 2750X manufactured by Zeon Corporation)
5) and carboxyl-modified polyacrylonitrile /
Butadiene copolymer latex (Nihon Zeon Ni
pol1571) was mixed so that the solid content weight ratio was as shown in Table 1. Subsequent steps are the same as in Examples 1 to 17. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

[0033]

[Table 1]

[0034]

[Table 2]

[ Examples by Production Method 2] (Examples 30 to 45) Carboxyl-modified polystyrene / butadiene copolymer-based latex (Nipol LX42 manufactured by Zeon Corporation)
4) and carboxyl-modified polyacrylonitrile /
Butadiene copolymer latex (Nihon Zeon Ni
pol1571) was mixed so that the solid content weight ratio was as shown in Table 3, and the mixed latex was added to Table 4
Was dissolved in an amount of 0.5 mol per unit solid component weight of the mixed latex. Next, the mixed latex was spread on a glass Petri dish, and kept at room temperature for 3 hours.
After drying at normal pressure, vacuum (0.01 To
(rr or less) to obtain a rubber-like polymer matrix film. Next, this film was immersed in a solvent shown in Table 4 to obtain a solid polymer electrolyte of the present invention.
This polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

[0036] (Example 46-48) carboxyl-modified polystyrene / butadiene copolymer latex (manufactured by Zeon Corporation NipolLX42
4) and a polyacrylonitrile / butadiene copolymer-based latex (Nipol1551 manufactured by Zeon Corporation) were mixed so that the solid content weight ratio was as shown in Table 3, and the mixed latex was further mixed with the electrolyte shown in Table 4. Is 0.5 mol per unit solid component weight of the mixed latex
Dissolved. The subsequent steps are the same as in Examples 30 to 45. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

(Examples 49 to 51) A polystyrene / butadiene copolymer latex (Nipol LX110 manufactured by Nippon Zeon) and a carboxyl-modified polyacrylonitrile / butadiene copolymer latex (Nipol 1571 manufactured by Nippon Zeon) were used at a solid content weight ratio. The mixture was mixed as shown in Table 3, and the electrolyte shown in Table 4 was dissolved in the mixed latex in an amount of 0.5 mol per unit solid component weight of the mixed latex. The subsequent steps are the same as in Examples 30 to 45. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

(Examples 52 to 54) A polystyrene / butadiene copolymer latex (Nipol LX110 manufactured by Zeon Corporation) and a polyacrylonitrile / butadiene copolymer latex (Nipol1551 manufactured by Zeon Corporation) having a solid content weight ratio of Table 3 were used. Then, the electrolyte shown in Table 4 was dissolved in the mixed latex in an amount of 0.5 mol per unit solid component weight of the mixed latex. The subsequent steps are the same as in Examples 30 to 45. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

[0039] (Example 55-57) Self-crosslinking component containing polystyrene / butadiene copolymer latex (manufactured by Zeon Corporation Nipol2570
X5) and a carboxyl-modified polyacrylonitrile / butadiene copolymer latex (Nippon Zeon Co., Ltd.)
ipol1571) was mixed so that the solid content weight ratio was as shown in Table 3, and 0.5 mol of the electrolyte shown in Table 4 was dissolved in the mixed latex with respect to the unit solid component weight of the mixed latex. Was. After that,
This is the same as Examples 30 to 45. The obtained polymer solid electrolyte film maintained a rubber state and exhibited sufficient mechanical strength.

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

As described in detail above, according to the solid polymer electrolyte of the present invention, a support made of an electrolyte solution impregnated in a high-polar polymer phase forming an ion conduction path and / or a low-polar polymer is used. Since the ionic conductivity is exhibited by the electrolyte solution of the second ionic conduction path formed in a network in the phase, the ionic conductivity is significantly improved as compared with the conventional solid polymer electrolyte. The support phase is in particle form
, The polymer is not plasticized by impregnation with the electrolyte solution, and sufficient mechanical strength is maintained. Further, according to the method for producing a polymer solid electrolyte of the present invention, a polymer solid electrolyte having the above-mentioned excellent properties can be obtained by a simple and low-cost operation such as dispersion of polymer particles , solvent removal, and liquid impregnation. It becomes possible to manufacture. Therefore, according to the present invention, a solid polymer electrolyte having excellent mechanical strength and high ionic conductivity can be obtained at low cost and in a simple process.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing the structure of an example of a solid polymer electrolyte produced by Production Method 1 of the present invention.

FIG. 2 is a schematic cross-sectional view showing a structure of an example of a solid polymer electrolyte produced by a production method 2 of the present invention.

FIG. 3 is a photograph showing a particle structure of a polymer solid electrolyte produced by Production Method 1 of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Ion conduction path, 2 ... Support phase, 3 ... Second ion conduction path

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-95802 (JP, A) JP-A-5-290616 (JP, A) JP-A-1-294768 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) H01M 6/18 H01M 10/40 H01B 1/06 C08K 3/00 C08L 101/00

Claims (6)

(57) [Claims] Claims: 1. A highly polar polymer phase and retains its particle shape.
Polymer mat with phase separation structure composed of low polar polymer phase
Rix's highly polar polymer phase was impregnated with an electrolyte solution
A solid polymer electrolyte characterized by the above-mentioned. 2. The solid polymer electrolyte according to claim 1,
The electrolyte solution is also present in a part of the low-polarity polymer phase.
A solid polymer electrolyte characterized by being present. 3. The method according to claim 1, wherein the highly polar polymer phase is polyacrylonitrile.
Tolyl / polybutadiene copolymer, polyacrylonitrile
/ Polystyrene copolymer, polyacrylonitrile / Po
Libutadiene / polystyrene copolymer, polyacrylonitrile
One or more selected from tolyl / polyisoprene copolymer
The height according to claim 1 or 2, wherein
Molecular solid electrolyte. 4. The method according to claim 1, wherein the low-polar polymer phase is a conjugated diene bond.
Characterized by being made from a polymer containing
The solid polymer electrolyte according to any one of claims 1 to 3.
quality. 5. The method of claim 1, wherein the high-polarity polymer particles and the low-polarity polymer particles are
From the polymer particle dispersion liquid dispersed in the dispersion medium, the dispersion
Remove the medium to obtain a polymer matrix with a phase-separated structure
After fabrication, impregnate the polymer matrix with an electrolyte solution
A method for producing a solid polymer electrolyte. 6. The method according to claim 6, wherein the high-polarity polymer particles and the low-polarity polymer particles are
Polymer particles dispersed in a dispersion medium and dissolved in an electrolyte
Removing the dispersion medium from the dispersion, having a phase separation structure,
After preparing a polymer matrix containing an electrolyte,
Impregnating a liquid that dissolves the electrolyte into a molecular matrix
A method for producing a solid polymer electrolyte.