JP3230610B2 - Polymer solid electrolyte and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is applicable to a high energy battery such as a lithium battery, and has a sufficient ion conductivity, a simple manufacturing method, low cost, and high strength and high reliability. It relates to a molecular solid electrolyte.

[0002]

2. Description of the Related Art In recent years, there has been an increasing need for batteries having a high energy density as power supplies for small and portable electronic devices. A representative example of a battery that satisfies such needs is a lithium battery using an alkali metal, particularly lithium as a negative electrode. However, since lithium batteries use an organic electrolyte solution in which a lithium salt is dissolved in the electrolyte, liquid leakage, dendrite short-circuit, etc. occur,
The reliability in terms of safety is not enough. Therefore, realization of an all-solid-state battery using a solid electrolyte made of an inorganic material or a polymer material has been expected. Among them, the inorganic solid electrolyte is generally produced by a process using a vacuum apparatus such as a sputtering method, so that the production cost is increased and its application is limited to high value-added products. On the other hand, polymer solid electrolytes have been extensively researched and developed because of their low production cost and excellent processability. Above all, studies on polyethers such as polyethylene oxide belonging to a molecular chain motion type in which ions included in the molecular chain move with the thermal motion of the polymer molecular chain have been actively conducted [Watanabe, Ogata; Metal Surface Technology, No. 37
Vol. 5, No. 5, pp. 214-221 (1986)]. Recently, attention has been focused on an electrolyte-impregnated polymer solid electrolyte in which a polar polymer is impregnated with a lithium salt electrolyte solution (eg, Koksbang).
Other; Journal of Power Sources
f Power Sources), Vol. 32, pp. 175-185 (1990)].

[0003]

However, in the case of a conventional polymer solid electrolyte of the molecular chain motion type, there is a limit to the molecular chain motion near room temperature, and in order to increase the molecular chain motion, Since it is necessary to lower the molecular weight and soften the polymer, the mechanical strength of the polymer solid electrolyte has been greatly reduced. In addition, in the case of the electrolyte-impregnated polymer solid electrolyte, since radiation is involved in the production, there is a disadvantage in that it is dangerous and costly. Furthermore, since the polymer matrix serving as a support has a high polarity, the affinity between the electrolyte and the polymer matrix is strong, and the electrolyte is diffused into the polymer matrix at a molecular level, and the interaction between the two causes an ionic problem. The movement destroys the fine structure of the polymer matrix and the ionic conduction path, and there is a problem that the mechanical strength and the ionic conductivity are reduced by long-term use. Therefore, it has been strongly desired to realize a solid polymer electrolyte having excellent ion conductivity, a simple manufacturing method, low cost, and high strength and reliability, and a method for manufacturing the same. The present invention has been made in view of such circumstances, and has a sufficient ion conductivity, can be applied to a high energy battery such as a lithium battery, has a simple manufacturing method, is inexpensive, and has high strength reliability. It is an object of the present invention to provide a polymer solid electrolyte having a property and a production method thereof.

[0004]

SUMMARY OF THE INVENTION To summarize the present invention, a first invention of the present invention relates to a solid polymer electrolyte, and comprises a fused body of polymer fine particles and a fused body of the polymer fine particles.
In the body, and fusion adherend and phase separation of the polymer particles, characterized by comprising the ion conducting path formed in a mesh shape continuously. In the following, in the present specification and the drawings,
The term "fused polymer particles" is referred to as "polymer matrix".
Abbreviation ".

The second invention of the present invention relates to a method for producing a solid polymer electrolyte, and a method in which a solution in which a low-polar polymer is dissolved in a low-polar solvent is converted into a polymer or a polymer soluble in a polar solvent. A step of producing a polymer fine particle dispersion by adding to a polar solvent in which a surfactant or a mixture of both is dissolved with stirring; and heating and evaporating the low-polarity solvent and the polar solvent from the polymer fine particle dispersion. By letting
The polymer particles are fused together to form a polymer matrix, and the polymer or surfactant soluble in the polar solvent, which is continuously distributed in a network in the polymer matrix, or a mixture of both. Forming a polar member comprising an aggregated portion of the above, and impregnating the polar member with a metal salt electrolyte comprising a metal salt and an electrolyte solvent to form an ion conduction path phase-separated from the polymer matrix. It is characterized by consisting of.

Further, a third invention of the present invention relates to another method for producing a solid polymer electrolyte, in which a solution prepared by dissolving a low-polarity polymer in a low-polarity solvent is converted into a high-soluble solution which is soluble in a polar solvent. Adding to a polar solvent in which a molecule or a surfactant, or a mixture of both are dissolved, with stirring to produce a first polymer fine particle dispersion, and adding a metal to the first polymer fine particle dispersion. Dissolving a salt to produce a second polymer fine particle dispersion, and heating and evaporating the low polarity solvent and the polar solvent from the second polymer fine particle dispersion, thereby melting the polymer fine particles with each other. To form a polymer matrix, and a polar member comprising a polymer or a surfactant soluble in the polar solvent continuously distributed in a network in the polymer matrix, or an aggregate of a mixture of both. And metal salt Forming a portion, and a step of impregnating the aggregating portion of the polar member and the metal salt with an electrolyte solvent dissolving the metal salt to form an ion conduction path phase-separated from the polymer matrix. It is characterized by.

Further, a fourth invention of the present invention relates to another method for producing a solid polymer electrolyte, wherein a solution obtained by dissolving a low-polar polymer in a low-polar solvent is dissolved in a polar solvent. Adding a polymer or surfactant, or a mixture of both, to a polar solvent in which the polymer is dissolved while stirring to produce a first polymer fine particle dispersion; Dissolving a metal salt, further mixing an electrolyte solvent having a boiling point higher than that of the polar solvent and dissolving the metal salt to produce a second polymer fine particle dispersion, and the second polymer By heating and evaporating the low-polar solvent and the polar solvent from the fine particle dispersion, the high-molecular fine particles are fused together to form a high-molecular matrix,
Further, in the polymer matrix, a polymer or a surfactant which is phase-separated from the polymer matrix and is soluble in the continuous network-like polar solvent containing the metal salt electrolyte solution comprising the metal salt and the electrolyte solution solvent Or a step of forming an ion conduction path made of a mixture of the two.

Further, a fifth invention of the present invention relates to another method for producing a solid polymer electrolyte, which comprises a polymer or a surfactant soluble in a polar solvent or a polar solvent containing a mixture of both. In addition, from a polymer fine particle dispersion in which low polarity polymer fine particles are uniformly dispersed, by heating and evaporating the polar solvent, the polymer fine particles are fused together to form a polymer matrix. In the polymer matrix, a polar member composed of agglomerates of the surfactant continuously distributed in a network is formed, and the polar member is impregnated with a metal salt electrolyte to separate the polymer matrix from the polymer matrix. It is characterized by forming an ion conduction path.

The sixth invention of the present invention relates to another method for producing a solid polymer electrolyte, which comprises dissolving a polymer or a surfactant soluble in a polar solvent, or a mixture of both, and a metal salt. From a polymer fine particle dispersion in which low polarity polymer fine particles are uniformly dispersed in a polar solvent, by heating and evaporating the polar solvent, the polymer fine particles are fused together to form a polymer matrix. Further, in the polymer matrix, a polar member comprising a polymer or a surfactant which is soluble in the polar solvent continuously distributed in a network, or a mixture of the both, and an aggregation portion of a metal salt are formed. In the agglomerated portion of the polar member and the metal salt,
The method is characterized in that an electrolyte solvent for dissolving the metal salt is impregnated to form an ion conduction path phase-separated from the polymer matrix.

A seventh invention of the present invention relates to another method for producing a solid polymer electrolyte, which comprises a polymer or a surfactant soluble in a polar solvent, or a mixture of both, and a metal salt. A polymer particle dispersion in which low-polarity polymer particles are uniformly dispersed in a dissolved polar solvent is mixed with an electrolyte solvent having a boiling point higher than that of the polar solvent and dissolving the metal salt. By heating and evaporating the polar solvent from the fine particle dispersion, the polymer fine particles are fused together to form a polymer matrix, and further, in the polymer matrix, phase-separated from the polymer matrix, A continuous network containing a metal salt electrolyte solution composed of a solvent and an electrolyte solvent is formed into a continuous mesh-like polymer soluble in the polar solvent or a surfactant, or an ion conduction path formed of a mixture of both. The features.

In order to achieve the above object, the present inventors have made intensive studies on various existing polymer solid electrolytes and their ionic conductivity. As a result, in order to obtain a stable and excellent ionic conductivity, It has been elucidated that the medium in which ions move, that is, the ion conduction path, must be the electrolyte itself. As a result, the following measures were taken to realize a solid polymer electrolyte having sufficient ion conductivity, a simple manufacturing method, low cost, and high strength and reliability.

In the present invention, attention is paid particularly to an electrolytic solution impregnated type polymer solid electrolyte, and a polymer matrix and a phase separated from the polymer matrix in the polymer matrix are formed in a continuous network. It is characterized by having an ion conduction path.

FIG. 1 is a schematic sectional view of the solid polymer electrolyte of the present invention, wherein 1 is a polymer matrix, 2 is polymer fine particles constituting the polymer matrix, and 3 is continuous in the polymer matrix 1. The ion conduction path is formed in a mesh shape, and is formed by being phase-separated from the polymer matrix 1. The black circles in FIG. 1 are, for example, Li ⁺ ions.

The ion conduction path 3 according to the present invention is characterized in that a polar member is impregnated with a metal salt electrolyte comprising a highly polar metal salt and an electrolyte solvent. The dissociated metal ions move in the solvent. It should be noted that the fine structure of the polymer solid electrolyte of the present invention is composed of a polymer matrix 1 composed of an aggregate of polymer fine particles and an ion conduction path 3 phase-separated from the polymer matrix by TEM (transmission). It was verified and confirmed by observation using a scanning electron microscope.

The polar member includes a polymer soluble in a polar solvent, a surfactant, a polar organic component partially or entirely covalently bonded to polymer fine particles, and a crosslinked structure formed between the polymer fine particles. Parts or mixtures thereof can be applied. These polar members stabilize the dispersion of the polymer fine particles in the dispersion medium and can be a precursor of the ion conduction path when a polymer solid electrolyte is produced.

The polymer soluble in the polar solvent varies depending on the type of the dispersion medium of the polymer fine particles in the following process for producing a polymer solid electrolyte. Acrylonitrile, hydroxyethylcellulose, polyvinyl alcohol, metal polyacrylate, methylcellulose, polyvinylpyrrolidone, poly-4-vinylpyridine, polystyrenesulfonic acid, etc. can be used alone or in a complex form, but are not particularly limited to these. Instead, even when another polar solvent is used as the dispersion medium, any other polymer that can be dissolved in the dispersion medium can be used. In the present invention, the proportion of the polar member in the polymer matrix is increased by actively introducing such a polymer soluble in the polar solvent as the polar member.

Examples of the surfactant include fatty acids and their metal salts, alkylbenzenesulfonic acids and their metal salts, alkylsulfuric acids and their metal salts, dioctylsulfosuccinic acid and their metal salts, polyoxyethylene stearate, and polyoxyethylene sorbitan monolaurin. Acid esters, polyoxyethylene nonyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymers, polyether-modified silicone oils and the like can be used alone or in a complex form, provided that they have a surfactant activity. However, there is no particular limitation.

The polar solvent component is not particularly limited. For example, acrylic acid and its metal salt, methacrylic acid and its metal salt, ethacrylic acid and its metal salt, itaconic acid and its metal salt, styrenesulfonic acid and its metal Salts, ethylenesulfonic acid and its metal salts, unsaturated fatty acids and its metal salts, and the like can be used as the raw material of the polar organic component. These polar organic components are incorporated into and bonded to the polymer fine particles in the form of copolymerization, graft polymerization, or directly react with the functional groups of the main components of the polymer fine particles. Alternatively, the main component of the polymer fine particles may be oxidized with sulfuric acid or the like to introduce a carboxyl group or a metal salt substituent thereof. Note that such a polar organic component does not necessarily need to be bonded to the polymer fine particles in a copolymerized form, and can be a precursor of an ion conduction path even if it is a raw material. Further, a polymer soluble in the polar solvent, a surfactant, and a polar organic component may be used in any desired combination.

The crosslinked structure can be realized by covalently bonding two or more kinds of polar organic components to the molecular chains constituting the polymer fine particles. That is, by heating polymer fine particles having two or more types of polar organic components, a cross-linking reaction occurs in the polymer fine particles and between the polymer fine particles to form a cross-linked structure. Crosslinking within the polymer particles provides a polymer solid electrolyte with high mechanical strength,
Crosslinking between polymer fine particles can continuously form aggregated portions having a network-like crosslinked structure that is a precursor of an ion conduction path.

Examples of such a crosslinking reaction include an esterification reaction, an amidation reaction, and an epoxy group ring-opening reaction. In order to perform this crosslinking by self-crosslinking, that is, between polymer fine particles or within polymer fine particles, , Amide group, hydroxyl group,
What is necessary is just to give two or more types of polar organic components, such as a carboxyl group, an epoxy group, and a sulfonic acid group, to a polymer chain.
For example, a self-crosslinking polymer can be obtained by copolymerizing two or more of the main component monomers of the polymer fine particles and the following crosslinking component monomers. That is, although not particularly limited, acrylamide, diacetone acrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, acrylic acid, methacrylic acid, itaconic acid, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, allyl benzene sulfone Crosslinking component monomers such as acids can be applied.

The metal salt constituting the metal salt electrolyte varies depending on the use of the solid polymer electrolyte. For example, considering application to a lithium battery, LiClO ₄ , LiAlCl
_{4, LiBF 4, LiPF 6,} LiAsF 6, LiNb
F ₆ , LiSCN, LiCl, Li (CF ₃ SO ₃ ),
Lithium salts such as Li (C ₆ H ₅ SO ₃ ) and mixtures thereof can be applied, but are not limited thereto, and other lithium salts can also be applied.

The electrolyte solvent for dissolving such a metal salt to form an electrolyte also varies depending on the use of the solid polymer electrolyte, and is not particularly limited. Considering the application of propylene carbonate, ethylene carbonate, γ-butyrolactone, dimethyl carbonate, dimethyl sulfoxide, acetonitrile, sulfolane, dimethylformamide, dimethylacetamide, 1,2-diethoxyethane, 1,2-dimethoxyethane, tetrahydrofuran,
-Aprotic polar solvents such as -methyltetrahydrofuran, dioxolan, methyl acetate and the like, and polyethylene oxide derivatives represented by the following general formula (Chemical Formula 1) can be used, and these are used alone or in a mixture.

[0023]

Embedded image A- (CH ₂ —CH ₂ —O) _n —B

In the formula, A represents an alkyl group, an alkoxy group,
An aryl group, an aryloxy group, or an aliphatic / aromatic organic group containing an ether bond, an ester bond, an amide bond, a siloxane bond, a urethane bond, a phosphazene bond, or a halogen, a hydroxyl group, or a carboxylic acid of the above organic groups A monovalent organic group such as a group or an amino group-substituted product, or an H group, an OH group, or B is a monovalent organic group or an H group represented by A, and n is an integer of at least 2 or more. Such polyethylene oxide derivatives are used alone or in a combination of two or more.

The polymer matrix 1 according to the present invention comprises:
Polymer fine particles 2 are formed by fusing each other.

The polymer fine particles 2 can be used to stably phase-separate the ion conduction path 3 composed of a highly polar metal salt electrolyte and a polar member from the polymer matrix 1 when a polymer solid electrolyte is manufactured. Although not limited, preferably the following low-polarity polymers, namely, polystyrene, polypropylene, polyisobutene, polyethylene,
Polybutadiene, polyisoprene, poly (α-methylstyrene), polybutyl methacrylate, polybutyl acrylate, poly (2-ethylhexyl acrylate),
Polydibutyl phthalate, polyvinyl butyl ether,
Polymer fine particles made of inexpensive hydrocarbon polymers such as polyvinyl butyral and polyvinyl formal or copolymers containing these components are suitable, and these low-polar polymers are used alone or in a composite form. . In particular, a polymer solid electrolyte made of a low-polarity rubber-based polymer containing a conjugated diene-based component such as butadiene or isoprene, for example, a styrene-butadiene copolymer or a styrene-isoprene copolymer, is soft and elastic. Is very suitable because it has good adhesion to the electrode. Also,
The particle size of the polymer fine particles 2 is 0.01 to
50 μm is preferred.

As described above, in the solid polymer electrolyte of the present invention, the ionic conduction path 3 composed of the metal salt electrolyte and the polar member has the polymer fine particles 2 constituting the polymer matrix 1.
During this process, the polymer matrix 1 is phase-separated and formed into a continuous network.

Therefore, the metal salt electrolyte having a high ionic conductivity plays a role in ionic conduction, and excellent ionic conductivity can be expected. Further, since the ion conduction path 3 is phase-separated from the polymer matrix 1, unlike the conventional electrolyte-impregnated polymer solid electrolyte in which the electrolyte is dispersed at the molecular level in the polymer matrix, Even if the impregnation amount is large, the polymer matrix 1 is not plasticized, so that a decrease in mechanical strength of the solid electrolyte can be suppressed.

Here, the method for producing a solid polymer electrolyte according to the present invention can be roughly classified into the following three methods. In addition, these manufacturing methods are distinguished by focusing on a method of forming an ion conduction path,
The manufacturing method numbers are used in the embodiments of the present invention.

[Manufacturing method 1] A solution in which a polar member which can be a precursor of an ion conduction path is dissolved in a polar solvent in which polymer fine particles are uniformly dispersed is used as a polymer fine particle dispersion. In this case, a polymer soluble in a polar solvent, a surfactant, or a mixture thereof can be used as the polar member. In addition, when using polymer fine particles in which a part or all of the polar organic components are covalently bonded or polymer fine particles in which a cross-linking component is covalently bonded, these polar organic components and the cross-linking component are also precursors of the ion conduction path. Therefore, these can be used alone or in a complexed form, or further in a complexed form with a polymer or a surfactant soluble in the polar solvent. Further, although the polar solvent as the dispersion medium is preferably water, a polar organic solvent such as an alcohol can be used alone or in combination with water as needed, and such a dispersion medium is used in the present invention. It can be applied to all manufacturing methods. In the step of preparing the polymer fine particle dispersion, the polar member has a function of stabilizing the dispersion of the polymer fine particles in the dispersion medium.

The dispersion of the polymer fine particles in the dispersion medium can be performed by the following two methods. First, a first method is to dissolve a solution in which a low-polar polymer for polymer fine particles is dissolved in a low-polar solvent, a polymer or a surfactant soluble in the polar solvent,
Alternatively, this is a method in which a low-polar polymer is made into fine particles by adding the mixture of both to a dissolved polar solvent with stirring. The second method is a known emulsion polymerization method as follows [for example, Soichi Muroi, Introduction to Polymer Latex (First Edition, First Printing) (Kobunsha, issued July 29, 1980)
Reference].

That is, when a surfactant is added to the aqueous dispersion medium at a concentration higher than the critical micelle concentration and the main monomer of the polymer fine particles is introduced, a part of the main monomer is taken into the surfactant micelle. Next, when a water-soluble polymerization initiator (for example, metal persulfate) is added and heated, radicals of the polymerization initiator are generated. When the polymerization initiator radicals enter micelles filled with the main component monomer, the main component monomer is polymerized to synthesize a polymer and form polymer fine particles. Here, when the main component monomer inside the micelle is consumed due to the progress of the polymerization reaction, the main component monomer dissolved in water is supplied to the micelle in the reaction field in order to maintain the equilibrium. The diameter of the produced polymer fine particles can be controlled by adjusting the polymerization time of the main component monomer that has entered the micelle.

In this case, a polymer soluble in a polar solvent is dissolved in the polymer fine particle dispersion, or a polar solvent component or a cross-linking component monomer is added during the reaction to add a polar organic component or a polymer to the polymer fine particles. By introducing a crosslinking component, different dispersions can be stabilized.

Among them, the same emulsion polymerization method is preferably applied as a method for introducing a polar organic component or a crosslinking component into the polymer fine particles. That is, when the monomer of the polar organic component or the cross-linking component is dissolved in the dispersion medium, a polymerization reaction occurs with the main monomer of the polymer fine particles in the surfactant micelle of the reaction field, and a copolymer of the main component of the polymer fine particles is formed. Is obtained. Since the polar organic component and the cross-linking component described above have low compatibility with the main component of the polymer fine particles, the polar organic component and the crosslinking component are distributed more to the peripheral portion of the polymer fine particles.

Next, by heating and evaporating the solvent from the dispersion liquid of the polymer fine particles produced in this way, the polymer fine particles are fused with each other to form a polymer matrix, and the high-molecular weight particles soluble in the polar solvent are formed. A polar member made of a molecule, a surfactant, a polar organic component or a cross-linking component, or a composite thereof forms a continuous network-like aggregate between polymer fine particles constituting a polymer matrix. In this case, in order to completely remove the polar solvent, it is necessary to heat the solvent to a temperature higher than the boiling point of the polar solvent or to perform the treatment in combination with a reduced pressure treatment. It is preferable to heat the matrix to a temperature higher than the glass transition temperature of the main component.

In the case where the self-crosslinkable polymer fine particles having a crosslinkable component are used, the crosslinking reaction in the polymer fine particles or between the polymer fine particles is performed in the heating step for removing the dispersion medium as described above. Will wake up. In the cross-linking reaction between polymer fine particles, since a cross-linked structure serving as a polar member is formed between the polymer fine particles, the polar member moves inside due to the influence of an external electric field or a dialysis effect,
There is no need to worry about seepage to the outside, and the ion conduction path can be stably held. In this case, in order to cause a cross-linking reaction, it is preferable to heat the mixture to 100 ° C. or higher. If necessary, the polymer matrix can be formed into an arbitrary shape by hot pressing. Also,
The effect of such a crosslinked structure is similarly exhibited in the case of a polar organic component.

The composition ratio between the main component of the polymer fine particles and the polar organic component or the cross-linking component is such that the dispersion of the polymer fine particles in the polar solvent is stabilized, and when the polymer solid electrolyte is produced, the polymer matrix and the ion Any material that can sufficiently secure the mechanical strength of the solid polymer electrolyte when the conductive path is phase-separated and causes a cross-linking reaction may be used. It is preferred that this be done.

Finally, by immersing the polymer matrix film thus prepared in the separately prepared metal salt electrolyte, the polar member continuously formed in a network in the polymer matrix is formed. Is impregnated with the metal salt electrolyte solution to obtain a polymer solid electrolyte having a continuous ion conduction path phase-separated from the polymer matrix.

In this case, since the metal salt electrolyte has a high polarity, the metal salt electrolyte is selectively impregnated in a polar member having a high polarity, and the low-polarity polymer matrix is hardly impregnated. Therefore, a stable and continuous ion conduction path can be ensured, and a decrease in mechanical strength due to plasticization of the polymer matrix does not occur. The amount of impregnation of the metal salt electrolyte can be controlled by the immersion time, but it is preferable to impregnate the solid polymer electrolyte at a rate of 30% by weight or more. Further, it is desirable to adjust the mixing ratio of the metal salt and the solvent in the metal salt electrolyte so that the metal salt concentration in the formed ion conduction path is 0.01 to 5 mol / l.

As described above, the polar member promotes the selective impregnation of the polar member with the metal salt electrolyte to form an ion conduction path, and also serves as a holding member for the metal salt electrolyte after the impregnation. Play. In addition, the detailed manufacturing process described in the manufacturing method 1 will be omitted in the following respective manufacturing methods of a solid polymer electrolyte, if they overlap.

[Production Method 2] The metal salt constituting the metal salt electrolyte is dissolved in the polymer fine particle dispersion containing the various polar members described in Production Method 1. Next, by heating and evaporating the polar solvent from the polymer fine particle dispersion thus prepared, the polymer fine particles are fused with each other to form a polymer matrix, and the polar member and the metal salt are A network-like continuous agglomerated part is formed between the polymer fine particles constituting the polymer matrix. Finally, by immersing the polymer matrix film thus prepared in an electrolytic solution solvent dissolving the metal salt, the polar member and the metal salt formed continuously in a network in the polymer matrix. Is selectively impregnated with the electrolyte solution solvent to obtain a polymer solid electrolyte having a continuous ion conduction path phase-separated from the polymer matrix. According to such a method, the impregnation of the aggregating portion of the polar member and the metal salt with the electrolytic solvent is more excellent in terms of the osmotic pressure than in the case of the metal salt electrolytic solution in the production method 1, and therefore, excellent. Ion conductivity can be obtained.

[Production Method 3] The metal salt is dissolved in the polymer fine particle dispersion containing various polar members described in Production Method 1, and the boiling point is higher than that of the polar solvent. An electrolytic solution solvent to be dissolved is mixed to prepare a polymer fine particle dispersion. Next, when the polar solvent is heated and evaporated from the polymer fine particle dispersion thus prepared,
The polymer microparticles are fused together to form a polymer matrix, and the polar member containing the metal salt electrolyte is a continuous polymer phase-separated from the polymer matrix between the polymer microparticles constituting the polymer matrix. A simple mesh-like ion conduction path is formed, and it becomes a polymer solid electrolyte. in this case,
Electrolyte solvent is a polar solvent, for example, has a higher boiling point than water, so even if the dispersion is heated, only the water which is the dispersion medium evaporates and the electrolyte solvent does not evaporate, even after the polar solvent is removed. In the polymer matrix, the metal salt is held by the polar member in the form of a metal salt electrolyte solution in which the metal salt is dissolved, thereby forming an ion conduction path. Such a production method is particularly effective when an electrolyte solvent having a large viscosity and a high boiling point, such as a polyethylene oxide derivative, is used. That is, in the manufacturing methods 1 and 2,
When an electrolyte solvent having a large viscosity such as a polyethylene oxide derivative is used, there is a possibility that the impregnation of the polar member in the polymer matrix with the metal salt electrolyte or the electrolyte solvent is reduced. Therefore, if the metal salt is previously dissolved in a polar solvent as a dispersion medium, and further mixed with an electrolyte solvent, after forming the polymer matrix film, without impregnating the metal salt electrolyte or the electrolyte solvent. , An ion conduction path can be formed. In this case, it is desirable to adjust so that the polyethylene oxide derivative is 10 parts by weight or more based on 100 parts by weight of the polymer fine particles in the dispersion medium.

[0043]

According to the solid polymer electrolyte of the present invention, since the metal salt electrolyte having a high ionic conductivity plays a role in ionic conduction, excellent ionic conductivity can be expected as a solid polymer electrolyte. In addition, since the ion conduction path composed of the metal salt electrolyte is formed separately in the polymer matrix, the mechanical strength of the polymer solid electrolyte is reduced despite the large amount of impregnation of the metal salt electrolyte. Can be suppressed. Further, by forming the polymer matrix into a crosslinked structure, the protection of the ion conduction path and the strength of the polymer solid electrolyte can be further improved. Furthermore, since the manufacturing method is simple, a low manufacturing cost can be expected, and an inexpensive polymer solid electrolyte can be obtained.

[0044]

The present invention will now be described in detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 Unmodified styrene (S) -butadiene (B) copolymer (S: B = 20: 80, NS11 manufactured by Zeon Corporation)
6) 10 g was taken and dissolved in 100 g of benzene. This solution was gradually added with stirring to a 500 g aqueous solution in which 1 g of polyethylene oxide, a polymer soluble in a polar solvent, was dissolved to obtain a polymer fine particle dispersion. The dispersion was pre-dried at 95 ° C. under normal pressure until the solid content became 95% by weight. Further, at 100 ° C and 0.1 Torr, 2
After drying for 0 hour under reduced pressure, a polymer matrix film was obtained. Next, γ-butyrolactone /
A LiClO ₄ solution (1 mol / l) of a mixed solvent of 1,2-dimethoxyethane was prepared, and the prepared polymer matrix film was immersed therein for 2 hours to be impregnated with a metal salt electrolyte, thereby obtaining a polymer solid of the present invention. An electrolyte was obtained. The concentration of the metal salt in the metal salt electrolyte in the following examples is the same as in this example.

Example 2 A benzene solution of the unmodified styrene-butadiene copolymer (NS116 manufactured by Zeon Corporation) used in Example 1 was mixed with 1 g of polyethylene oxide and 4 g of LiClO _4.
Was slowly added with stirring to a 500 g aqueous solution to obtain a polymer fine particle dispersion. This dispersion was dried under the same conditions as in Example 1 to produce a polymer matrix film.
-Impregnated by immersion in a butyrolactone / 1,2-dimethoxyethane mixed solvent to obtain a solid polymer electrolyte of the present invention.

Example 3 Polyethylene oxide dimethyl ether (weight average molecular weight: 400) was added to the polyethylene oxide-containing polymer fine particle dispersion prepared in Example 1, stirred well, and dried under the same conditions as in Example 1. The solid polymer electrolyte of the present invention was obtained.

Example 4 A solid polymer electrolyte of the present invention was obtained by replacing the polar polymer polyethylene oxide of Example 1 with 1 g of polyethylene glycol (n = 20) nonylphenyl ether as a surfactant.

Example 5 10 g and 1 g of the unmodified styrene-butadiene copolymer (NS116 manufactured by Zeon Corporation) used in Example 1
Was taken and dissolved in 100 g of benzene. This solution is slowly added to 500 g of water while stirring,
A polymer fine particle dispersion was obtained. This dispersion was dried under the same conditions as in Example 1 to prepare a polymer matrix film, and impregnated with a LiClO ₄ solution of a mixed solvent of ethylene carbonate / 1,2-dimethoxyethane to obtain a polymer solid electrolyte of the present invention. Obtained. In all of Examples 1 to 5, the dispersion state of the polymer fine particles in the dispersion was good, and the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength. Was.

Example 6 A non-modified styrene (S) -butadiene (B) type latex containing a surfactant (S: B = 30: 70, average particle size 0.05 μm, Japan) was used as a polymer fine particle dispersion. An aqueous solution of Nipol LX110 (Zeon) was prepared. First,
10 g of this polymer fine particle dispersion was taken and further diluted with 10 g of water. Next, the dispersion was passed through an ion-exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) in which lithium ions were replaced, to replace alkali metal ions in the latex with lithium ions. afterwards,
A polymer matrix film was prepared by drying under the same conditions as in Example 1, and propylene carbonate / 1,2-
A LiClO ₄ solution of a dimethoxyethane mixed solvent was impregnated to obtain a solid polymer electrolyte of the present invention.

Examples 7 to 12 A polymer matrix film prepared in the same manner as in Example 6 was impregnated with various metal salt electrolytes obtained by changing the metal salt and the electrolyte solvent shown in Table 1 below. The solid polymer electrolyte of the invention was obtained. In all of Examples 6 to 12, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 13 A non-modified styrene (S) -butadiene (B) type latex containing a surfactant (S: B = 30: 70, average particle size 0.20 μm, Japan) After preparing an aqueous solution of Nipol LX4850 (manufactured by ZEON) and substituting the alkali metal ions in the latex with lithium ions in the same manner as in Example 6, the polymer was dried under the same conditions as in Example 1 to produce a polymer matrix film. A polymer solid electrolyte of the present invention was obtained by impregnation with a LiClO ₄ solution of a propylene carbonate / 1,2-dimethoxyethane mixed solvent.

Examples 14 to 19 A polymer matrix film prepared in the same manner as in Example 13 was impregnated with various metal salt electrolytes obtained by changing the metal salt and the electrolyte solvent shown in Table 1 to obtain six kinds of the present invention. Was obtained. In all of Examples 13 to 19, the obtained solid polymer electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 20 A benzene solution of the non-modified styrene-butadiene copolymer prepared in Example 1 was mixed with 500 g of 1 g of polyethylene glycol (n = 20) -nonylphenyl ether and 1 g of LiClO ₄ . The mixture was gradually added to water while stirring to obtain a polymer fine particle dispersion. This dispersion was dried under the same conditions as in Example 1 to prepare a polymer matrix film, and this film was impregnated with a mixed solvent of γ-butyrolactone / 1,2-dimethoxyethane to obtain a polymer solid electrolyte of the present invention. Obtained.

Example 21 A solution of the unmodified styrene-butadiene copolymer prepared in Example 5 and a benzene solution of polyethylene glycol (n = 20) / nonylphenyl ether was added to 1 g of LiC
lO ₄ was gradually added stirring to 500g of water containing dissolved to obtain a polymer fine particle dispersion. This dispersion was dried under the same conditions as in Example 1 to prepare a polymer matrix film, and this film was impregnated with a mixed solvent of propylene carbonate / ethylene carbonate to obtain a polymer solid electrolyte of the present invention. In both Examples 20 and 21, the dispersion state of the polymer fine particles in the dispersion was good, and the obtained polymer solid electrolyte was also a flexible rubber-like sheet and had sufficient mechanical strength. Was.

Example 22 In a pressure vessel, 25 g of styrene, 0.5 g of n-dodecyl mercaptan, 0.28 g of lithium persulfate, 4.0 g of lithium oleate, polyethylene glycol (n = 20)
-After charging 0.5 g of nonylphenyl ether and 180 g of water, 78 g of butadiene was added thereto, and the mixture was sealed.
After reacting for 4 hours, the reaction was stopped by adding 0.1 g of hydroquinone to obtain a polymer fine particle dispersion (the volume ratio of styrene-butadiene in the obtained polymer fine particles was 40:60). After dissolving 3 g of LiClO _{4 in} this dispersion, the polymer was dried under the same conditions as in Example 1 to produce a polymer matrix film.
The polymer solid electrolyte of the present invention was obtained by impregnation with a mixed solvent of 1,2-dimethoxyethane.

Examples 23 to 28 Six kinds of solid polymer electrolytes of the present invention were obtained by changing the metal salt and the electrolyte solution solvent in Example 22 so as to obtain the combinations shown in Table 2. In all of Examples 22 to 28, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 29 LiClO ₄ was dissolved in the non-modified type polymer fine particle dispersion used in Example 6, and polyethylene oxide dimethyl ether (weight average molecular weight 400) was mixed. Drying was carried out under the conditions to obtain a solid polymer electrolyte of the present invention.

Example 30 1 g of polyethylene oxide was further dissolved in the non-denatured polymer fine particle dispersion used in Example 6 to prepare a dispersion, which was then dried under the same conditions as in Example 1. A polymer matrix film was prepared, and a propylene carbonate / 1,2-dimethoxyethane mixed solvent LiCl was used.
The solid polymer electrolyte of the present invention was obtained by impregnation with an O ₄ solution.

Example 31 ₄ g of LiClO 4 was dissolved in the non-modified type polymer fine particle dispersion prepared in Example 30, and then dried under the same conditions as in Example 1 to produce a polymer matrix film. Then, the mixture was impregnated with a propylene carbonate / 1,2-dimethoxyethane mixed solvent to obtain a solid polymer electrolyte of the present invention.

Example 32 4 g of LiClO ₄ was dissolved in the dispersion of the unmodified polymer fine particles prepared in Example 30, and the mixture was further dissolved in polyethylene oxide dimethyl ether (weight average molecular weight: 40%).
After adding 0) and stirring well, the mixture was dried under the same conditions as in Example 1 to obtain a solid polymer electrolyte of the present invention. In all of Examples 29 to 32, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

The ionic conductivity of the solid polymer electrolytes obtained in Examples 1 to 32 (non-modified type) was examined. The measurement of the ionic conductivity was performed by an AC impedance method using a measurement cell including the obtained solid polymer electrolyte and two stainless steel electrodes. The results are shown in Tables 1 and 2.

The notes in Tables 1 and 2 are as follows. * 1: Polymer fine particles, main component SBR (styrene-butadiene copolymer) * 2: No polar organic component added, that is, non-modified type. * 3: Additive SA (surfactant) PEO (polyethylene oxide) * 4: Electrolyte solvent (volume ratio:%) PC / DME; propylene carbonate (40) / 1
2-dimethoxyethane (60) PC / DO; propylene carbonate (40) / dioxolane (60) PC / EC; propylene carbonate (50) / ethylene carbonate (50) γBL / DME; γ-butyrolactone (50) / 1,2
-Dimethoxyethane (50) EC / DME; ethylene carbonate (40) / 1,2
-Dimethoxyethane (60) PEODME; polyethylene oxide dimethyl ether (liquid) * 5: Production method Based on the production method number in the above-mentioned "Production method". * 6: Filling amount Weight% of filled electrolyte solvent

[0064]

[Table 1]

[0065]

[Table 2]

From the viewpoint of the production method, the ionic conductivity of the solid polymer electrolyte produced by the method of Production Method 3 is higher than that of the metal salt electrolyte impregnated type of Production Method 1 and the electrolyte solvent impregnated type of Production Method 2. Small and not very advantageous.

Further, the ionic conductivity of the solid polymer electrolyte using γ-butyrolactone / 1,2-ditoximesiethane as the electrolyte solvent is larger than that when other electrolyte solvents are used, and γ-butyrolactone / 1 , 2-Dimethoxyethane is also considerably increased.

Further, Examples 1 and 2 and Examples 30 and 31
As shown in the figure, the ionic conductivity of a polymer solid electrolyte in which a polar polymer, polyethylene oxide, is positively introduced as a polar member shows a much larger value than a system using only a surfactant as a polar member. I have.

From the above results, in order to increase the ionic conductivity of the solid polymer electrolyte, the methods of Production Methods 1 and 2 were used, and γ-butyrolactone / 1,2-
Active introduction of a polar polymer such as polyethylene oxide using dimethoxyethane can be an effective means.

Example 33 In a pressure vessel, 25 g of styrene, 1 g of n-dodecyl mercaptan, 0.6 g of lithium persulfate, 1 g of lithium dodecylbenzene sulfate, polyethylene glycol (n = 20)
After charging 1 g of nonylphenyl ether and 180 g of water, 78 g of butadiene was added and sealed, and the mixture was reacted at 50 ° C. for 60 hours while stirring the reaction system. Then, 0.1 g of hydroquinone was added to stop the reaction. A molecular fine particle dispersion was obtained. During the reaction, 10 g of acrylic acid was gradually added, and the pH of the reaction system was adjusted to 7 to 8 with an aqueous solution of lithium hydroxide or an aqueous solution of perchloric acid so that the carboxyl modification of the polymer particles was performed. (The volume ratio of styrene-butadiene in the obtained polymer fine particles was 40:60). Next, a polymer matrix film was prepared by drying under the same conditions as in Example 1, and impregnated with a LiClO ₄ solution of a mixed solvent of propylene carbonate / 1,2-dimethoxyethane to obtain a polymer solid electrolyte of the present invention. Was.

Examples 34 to 39 A polymer matrix film prepared in the same manner as in Example 33 was impregnated with various metal salt electrolytes obtained by changing the metal salt and the electrolyte solvent shown in Table 3 to obtain six types of the present invention. Was obtained. In all of Examples 33 to 39, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 40 As a polymer fine particle dispersion, a styrene (S) -butadiene (B) -based latex containing a surfactant and modified with a carboxyl group, which is a polar organic component (S: B = 5)
0:50, average particle size 0.12 μm, Nip manufactured by Zeon Corporation
olLX424) An aqueous solution was prepared and dried under the same conditions as in Example 1 to prepare a polymer matrix, and the propylene carbonate / 1,2-dimethoxyethane mixed solvent L
The solid polymer electrolyte of the present invention was obtained by impregnation with an iClO ₄ solution.

Examples 41 and 42 Propylene carbonate / 1,2-
The dimethoxyethane mixed solvent is ethylene carbonate /
A solid polymer electrolyte of the present invention was obtained in place of the mixed solvent of 1,2-dimethoxyethane and the mixed solvent of γ-butyrolactone / 1,2-dimethoxyethane. In all of Examples 40 to 42, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 43 3 g of LiClO ₄ was further dissolved in the carboxyl group-modified type polymer fine particle dispersion used in Example 33, and dried under the same conditions as in Example 1 to obtain a polymer matrix film. And propylene carbonate / 1,
The solid polymer electrolyte of the present invention was obtained by impregnation with a mixed solvent of 2-dimethoxyethane.

Examples 44 to 54 The metal salt and the electrolyte solvent in Example 43 were changed as shown in Tables 3 and 4 to obtain 11 kinds of solid polymer electrolytes of the present invention. In all of Examples 43 to 54, the obtained solid polymer electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 55 A styrene (S) -butadiene (B) -based latex (S: B = 3) containing a surfactant and modified with a carboxyl group, which is a polar organic component, was used as a polymer fine particle dispersion.
0:70, average particle size 0.12 μm, Nip manufactured by Zeon Corporation
olLX426) An aqueous solution was prepared, and 4 g of LiBF ₄ was further dissolved in the polymer fine particle dispersion, and dried under the same conditions as in Example 1 to prepare a polymer matrix film, and a γ-butyrolactone solvent was prepared. To obtain a solid polymer electrolyte of the present invention.

Examples 56 to 58 Three kinds of solid polymer electrolytes of the present invention were obtained by changing the metal salt and the electrolyte solvent in Example 55 as shown in Table 4. In all of Examples 55 to 58, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 59 A polymer matrix film was obtained by dissolving ₄ g of LiClO ₄ in the carboxyl group-modified type polymer fine particle dispersion used in Example 40 and drying under the same conditions as in Example 1. And propylene carbonate / 1,
The solid polymer electrolyte of the present invention was obtained by impregnation with a mixed solvent of 2-dimethoxyethane.

Examples 60 to 63 The metal salt and the electrolyte solvent in Example 59 were changed as shown in Table 4 to obtain four kinds of solid polymer electrolytes of the present invention.

Example 64 After dissolving ₄ g of LiClO _{4 in} the carboxyl group-modified type polymer fine particle dispersion used in Example 40, polyethylene oxide dimethyl ether (weight average molecular weight 400) was further added, and the mixture was stirred well. Drying was performed under the same conditions as in Example 1 to obtain a solid polymer electrolyte of the present invention.

Examples 65 and 66 The LiClO ₄ of Example 64 was replaced with LiBF ₄ and Li
A solid polymer electrolyte of the present invention was obtained in place of CF ₃ SO ₃ .

Example 67 A polymer matrix film was prepared by dissolving 1 g of polyethylene oxide in the carboxyl group-modified type polymer fine particle dispersion used in Example 40 and drying under the same conditions as in Example 1. And propylene carbonate /
A polymer solid electrolyte of the present invention was obtained by impregnation with a LiClO ₄ solution of a 1,2-dimethoxyethane mixed solvent.

Example 68 1 g of polyethylene oxide and LiCl were added to the polymer fine particle dispersion of the carboxyl group-modified type used in Example 40.
After dissolving ₄ g of O _4, it was dried under the same conditions as in Example 1 to prepare a polymer matrix film, and impregnated with a mixed solvent of propylene carbonate / 1,2-dimethoxyethane to obtain a polymer solid electrolyte of the present invention. I got

Example 69 After dissolving ₄ g of LiClO _{4 in} the carboxyl group-modified type polymer fine particle dispersion used in Example 40, polyethylene oxide dimethyl ether (weight average molecular weight: 400) was further added, and the mixture was stirred well. By drying under the same conditions as in Example 1, a polymer solid electrolyte of the present invention was obtained. In all of Examples 59 to 69, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

The ionic conductivity of the solid polymer electrolytes obtained in Examples 33 to 69 (carboxyl group-modified type) was examined in the same manner as in Examples 1 to 32. The results are shown in Tables 3 and 4.

Note that the numbers of the notes in Tables 3 and 4 that are the same as those in Tables 1 and 2 have the same meanings as in Tables 1 and 2.
* 7 has the following meaning. * 7: Modification 1 COOH modification

[0087]

[Table 3]

[0088]

[Table 4]

Tables 3 and 4 show the results of Examples 1 to 3 using the non-modified type polymer fine particles shown in Tables 1 and 2.
The results are similar to those in Table 2, but the ionic conductivity is generally larger than those in Tables 1 and 2 because the carboxyl group-modified type polymer fine particles are used.

In Examples 33 to 69, the carboxyl group-modified type was used as the polymer fine particles.
In this invention, it carried out similarly, replacing the carboxyl group with the alkali metal (Li, Na etc.) salt substituent of a carboxyl group. Also in this case, the same ionic conductivity as that of the carboxyl group-modified type was obtained.

Example 70 As a polymer fine particle dispersion, a self-crosslinking styrene (S) -butadiene (B) type latex (S: B = 2) modified with a carboxyl group and a hydroxyl group containing a surfactant was used.
0:80, average particle size 0.13 μm, Nip manufactured by Zeon Corporation
olLX432A) An aqueous solution was prepared and dried under the same conditions as in Example 1 to produce a polymer matrix film.
A polymer solid electrolyte of the present invention was obtained by impregnation with a LiClO ₄ solution of a propylene carbonate / 1,2-dimethoxyethane mixed solvent.

Examples 71 and 72 Propylene carbonate / 1,2-
The dimethoxyethane mixed solvent is ethylene carbonate /
A solid polymer electrolyte of the present invention was obtained in place of the mixed solvent of 1,2-dimethoxyethane and the mixed solvent of γ-butyrolactone / 1,2-dimethoxyethane. Examples 70-72,
The obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 73 As a polymer fine particle dispersion, a self-crosslinking styrene (S) -butadiene (B) latex (S: B = 5) modified with a carboxyl group and a hydroxyl group containing a surfactant was used.
0:50, average particle size 0.1 μm, Nipol manufactured by Zeon Corporation
LX2570 × 5) An aqueous solution was prepared, dried under the same conditions as in Example 1 to prepare a polymer matrix film, and impregnated with a LiClO ₄ solution of a mixed solvent of propylene carbonate / 1,2-dimethoxyethane to obtain the present invention. A solid polymer electrolyte was obtained.

Examples 74 and 75 Propylene carbonate / 1,2-
The dimethoxyethane mixed solvent is ethylene carbonate /
A solid polymer electrolyte of the present invention was obtained in place of the mixed solvent of 1,2-dimethoxyethane and the mixed solvent of γ-butyrolactone / 1,2-dimethoxyethane. Examples 73-75,
The obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 76 ₄ g of LiClO 4 was dissolved in the self-crosslinking type polymer fine particle dispersion used in Example 70, and dried under the same conditions as in Example 1 to produce a polymer matrix film. And a mixed solvent of propylene carbonate / 1,2-dimethoxyethane to obtain a solid polymer electrolyte of the present invention.

Examples 77 to 82 Six kinds of solid polymer electrolytes of the present invention were obtained by changing the metal salt and the electrolyte solvent in Example 76 so as to obtain the combinations shown in Table 5. In each of Examples 76 to 82, the obtained polymer solid electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 83 A polymer matrix film was prepared by dissolving ₄ g of LiClO _{4 in} the self-crosslinking type polymer fine particle dispersion used in Example 73 and drying it under the same conditions as in Example 1. And a mixed solvent of propylene carbonate / 1,2-dimethoxyethane to obtain a solid polymer electrolyte of the present invention.

Examples 84 to 87 Four kinds of solid polymer electrolytes of the present invention were obtained by changing the metal salt and the electrolyte solution solvent in Example 83 so as to obtain the combinations shown in Table 5. In all of Examples 83 to 87, the obtained solid polymer electrolyte was a flexible rubber-like sheet and had sufficient mechanical strength.

Example 88 ₄ g of LiClO 4 was dissolved in the dispersion of the polymer particles of the self-crosslinking type used in Example 70, and then polyethylene oxide dimethyl ether (weight average molecular weight 40
After adding 0) and stirring well, the mixture was dried under the same conditions as in Example 1 to obtain a solid polymer electrolyte of the present invention.

Example 89 1 g of polyethylene oxide was further dissolved in the self-crosslinking type polymer fine particle dispersion used in Example 70, and dried under the same conditions as in Example 1 to obtain a polymer matrix film. Produced, propylene carbonate / 1,
A LiClO ₄ solution of a mixed solvent of 2-dimethoxyethane was impregnated to obtain a solid polymer electrolyte of the present invention.

Example 90 The self-crosslinking type polymer fine particle dispersion used in Example 70 was further added with 1 g of polyethylene oxide and 4 g of LiC
After dissolving 10 ₄ , it was dried under the same conditions as in Example 1 to prepare a polymer matrix film, and impregnated with a mixed solvent of propylene carbonate / 1,2-dimethoxyethane to obtain a polymer solid electrolyte of the present invention. Obtained.

Example 91 The self-crosslinking type polymer fine particle dispersion used in Example 70 was mixed with 1 g of polyethylene oxide and 4 g of LiClO.
₄ was dissolved, and polyethylene oxide dimethyl ether (weight average molecular weight: 400) was further added thereto, stirred well, and dried under the same conditions as in Example 1 to obtain a solid polymer electrolyte of the present invention.

The ionic conductivity of the solid polymer electrolytes obtained in Examples 70 to 91 (self-crosslinking type) was measured in Examples 1 to 32.
Investigation was performed by the same method as described above. The results are shown in Tables 5 and 6.

Note that the numbers of the notes in Tables 5 and 6 which are the same as those in Tables 1 to 4 are synonymous with Tables 1 to 4,
Has the following meaning. * 8: Modification 2 COOH, OH modification (self-crosslinking)

[0105]

[Table 5]

[0106]

[Table 6]

The results in Tables 5 and 6 show the results of Examples 1 to 3 using the unmodified polymer fine particles shown in Tables 1 and 2.
The results are similar to those of Table 2, but the self-crosslinking type polymer fine particles are used, so that the ionic conductivity is generally larger than those of Tables 1 and 2 as in Tables 3 and 4. ing.

[0108]

According to the solid polymer electrolyte of the present invention, since the metal salt electrolyte having a high ionic conductivity plays a role in ionic conduction, the polymer solid electrolyte exhibits excellent ionic conductivity as a solid polymer electrolyte. In addition, since the ion conduction path composed of the metal salt electrolyte is formed separately in the polymer matrix,
Despite the large content of the metal salt electrolyte, a decrease in the mechanical strength of the solid polymer electrolyte can be suppressed. In addition, by making the polymer matrix a crosslinked structure,
The protection of the ion conduction path and the strength of the solid polymer electrolyte can be further improved. Furthermore, since the manufacturing method is simple, low manufacturing cost can be expected, and an inexpensive solid polymer electrolyte can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of the structure of a solid polymer electrolyte of the present invention.

[Explanation of symbols]

1: Polymer matrix, 2: Polymer fine particles, 3: Ion conduction path

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 3-354393 (32) Priority date December 20, 1991 (December 20, 1991) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-354408 (32) Priority date December 20, 1991 (December 20, 1991) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-354409 (32) Priority date December 20, 1991 (December 20, 1991) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-73164 ( 32) Priority date February 25, 1992 (19.2.2.25) (33) Priority country Japan (JP) (72) Inventor Shigeo Sugihara 1-6-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nippon Telegraph and Telephone Inside (72) Inventor Takahisa Masayo Inside Nippon Telegraph and Telephone Corporation 1-6-1, Uchisaiwaicho, Chiyoda-ku, Tokyo (72) Inventor Take Mikio 1-6-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nippon Telegraph and Telephone Corporation (56) References JP-A-1-294768 (JP, A) JP-A-3-95802 (JP, A) JP-A-2- 34660 (JP, A) JP-A-3-95871 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01M 6/18 H01B 1/06 H01M 10/40

Claims (20)

(57) [Claims] 1. A fused body of polymer fine particles, and the polymer fine particles
In fusion adherend child, and fusion adherend and phase separation of the polymer particles, polymer solid electrolyte, comprising the ion conductive path formed continuously in a network form. 2. The solid polymer electrolyte according to claim 1, wherein the ion conduction path comprises a metal salt electrolyte and a polar member. 3. The polar member according to claim 2, wherein the polymer is a polymer or a surfactant soluble in a polar solvent or the polymer fine particles.
A polymer solid electrolyte comprising a polar organic component or a crosslinked structure part or all of which is fixed to a fused body by a covalent bond, or a composite of any combination thereof. 4. A polymer solid electrolyte according to claim 3, wherein the polar organic component is a carboxyl group or a metal salt substituent thereof. 5. The metal salt electrolyte according to claim 2, wherein
A solid polymer electrolyte comprising a liquid polyethylene oxide derivative represented by the following general formula (Formula 1) and a metal salt dissolved therein. Embedded image Wherein A is a monovalent organic group or H or OH, and B is 1
Organic group or H and n are integers of at least 2] 6. The polymer particle according to claim 1 to 5,
A polymer solid electrolyte comprising a crosslinking component. 7. A polymer particle according to claim 1 to 5,
A polymer solid electrolyte characterized by being a rubber member. 8. A polymer solid electrolyte, wherein the rubber member according to claim 7 is a styrene-butadiene copolymer. 9. A solution in which a low-polar polymer is dissolved in a low-polar solvent is added to a polar solvent in which a polymer or a surfactant soluble in the polar solvent, or a mixture of both are dissolved, with stirring. To produce a polymer fine particle dispersion,
By heating and evaporating the low-polarity solvent and the polar solvent from the polymer fine particle dispersion, the polymer fine particles are fused with each other to form a fused body of the polymer fine particles , and further the fusion of the polymer fine particles is performed. a step of forming a polar member made of aggregation of the soluble polymer or surfactant in a polar solvent, or a mixture of both which are continuously in the body and distributed in a network form, in said polar member, metal salts A process for impregnating a metal salt electrolyte comprising an electrolyte solution and an electrolyte solvent to form an ion conduction path phase-separated from the fused body of the polymer fine particles . 10. A solution in which a low-polar polymer is dissolved in a low-polar solvent is added to a polar solvent in which a polymer or a surfactant soluble in the polar solvent, or a mixture of both is dissolved, with stirring. Producing a first polymer fine particle dispersion by dissolving a metal salt in the first polymer fine particle dispersion to produce a second polymer fine particle dispersion; by heating evaporating the low polar solvent and a polar solvent from the polymer particle dispersion, the polymer fine particles was allowed to fuse to form a fusion adherend polymer particles, further fusion adherend of the polymer particles Forming a polar member comprising a polymer or a surfactant which is soluble in the polar solvent continuously distributed in a network or a flocculation portion of a metal salt and a flocculation portion of a metal salt; and And dissolve the metal salt in the aggregation portion of the metal salt. A method for producing a solid polymer electrolyte comprising a step of impregnating an electrolyte solvent to be dissolved to form an ion conduction path which is phase-separated from the fused body of polymer particles . 11. A solution in which a low-polar polymer is dissolved in a low-polar solvent is added to a polar solvent in which a polymer or a surfactant soluble in the polar solvent, or a mixture of both is dissolved, with stirring. Producing a first polymer fine particle dispersion by dissolving a metal salt in the first polymer fine particle dispersion, further having a boiling point higher than that of the polar solvent, and dissolving the metal salt. Mixing a liquid solvent to produce a second polymer fine particle dispersion, and heating and evaporating the low-polar solvent and the polar solvent from the second polymer fine particle dispersion, thereby separating the polymer fine particles from each other. Fused to polymer fine particles
Continuous to form a fusion adherend child, further fusion within adherend of the polymer particles, and fusion adherend and phase separation of the polymer particles, containing a metal salt electrolyte consisting of an electrolyte solvent and the metal salt Forming a ionic conduction path composed of a network-like polymer or surfactant soluble in the polar solvent or a mixture of both. 12. The method according to claim 1, wherein the low-polarity polymer particles are uniformly dispersed in a polar solvent containing a polymer soluble in a polar solvent or a surfactant, or a mixture of both. by solvent is heated evaporation, the polymer fine particles are fused with to form a fusion adherend polymer particles, further fusion within adherend of the polymer particles, distributed continuously in a network form the A polar member composed of an aggregation portion of a surfactant is formed, and the polar member is impregnated with a metal salt electrolyte to form an ion conduction path which is phase-separated from the fused body of the polymer fine particles. A method for producing a polymer solid electrolyte. 13. A polymer fine particle dispersion obtained by uniformly dispersing low-polarity polymer fine particles in a polar solvent in which a polymer or a surfactant soluble in a polar solvent, or a mixture of both, and a metal salt are dissolved. By heating and evaporating the polar solvent, the polymer fine particles are fused together to form polymer fine particles.
To form a fusion adherend child, further fusion within adherend of the polymer particles, aggregation of contiguous soluble polymer or surfactant to the polar solvent distributed in a mesh shape, or a mixture of both Forming an agglomerated portion of the polar member and the metal salt, and impregnating the agglomerated portion of the polar member and the metal salt with an electrolytic solution solvent for dissolving the metal salt to form a phase with the fused body of the polymer fine particles. A method for producing a solid polymer electrolyte characterized by forming a separate ion conduction path. 14. A polymer fine particle dispersion in which low-polarity polymer fine particles are uniformly dispersed in a polar solvent in which a polymer or a surfactant soluble in a polar solvent, or a mixture of both, and a metal salt are dissolved, By mixing an electrolyte solvent having a higher boiling point than the polar solvent and dissolving the metal salt, and heating and evaporating the polar solvent from the polymer fine particle dispersion,
Fusion of polymer particles by fusing the polymer particles
Body is formed, further fusion within adherend of the polymer particles, and fusion adherend and phase separation of the polymer fine particles, a continuous mesh containing a metal salt electrolyte consisting of an electrolyte solvent and the metal salt A method for producing a solid polymer electrolyte, comprising forming an ion conduction path comprising a polymer or a surfactant soluble in the polar solvent, or a mixture of both. 15. As polymer particle according to claim 12-14, polar organic component part or process for producing a polymer solid electrolyte which comprises using the polymer fine particles obtained by covalent binding of the whole. 16. The polar organic component according to claim 15 ,
A method for producing a solid polymer electrolyte comprising a carboxyl group or a metal salt substituent thereof. 17. The polymer particle according to claims 12 to 14 having a self-crosslinking component, by heating with the heating evaporation of the polar solvent, the polymer particles be crosslinked reaction between fine particles inside and particulates A method for producing a solid polymer electrolyte, comprising: 18. A solvent comprising the metal salt electrolyte according to claim 9 to 16 , wherein the solvent is a polyethylene oxide derivative represented by the general formula (1) according to claim 5. A method for producing a molecular solid electrolyte. 19. The polymer particle according to claim 9 to 18, a manufacturing method of the solid polymer electrolyte, which is a rubber member. 20. A method for producing a polymer solid electrolyte, wherein the rubber member according to claim 19 is a styrene-butadiene copolymer.