JP5876327B2 - Electrolyte material and battery material and secondary battery using the same - Google Patents

Description

The present invention relates to an electrolyte material. More specifically, the present invention relates to an electrolyte material that can be suitably used as an electrolyte or binder for a lithium ion battery or the like.

In recent years, with the growing interest in environmental issues, the conversion of energy resources from fossil fuels such as oil and coal has been progressing, and batteries are attracting attention as an alternative energy source. Among them, secondary batteries that can be repeatedly charged and discharged are used not only in electronic devices such as mobile phones and laptop computers, but also in various fields such as automobiles and airplanes. Research and development are being conducted on materials used in secondary batteries. In particular, a large-capacity and light-weight lithium ion battery is a secondary battery that is most expected to expand in the future, and is a battery that is most actively researched and developed.

As a material used for such a secondary battery, various solid electrolytes that are less likely to cause an abnormal reaction at the electrode interface than a liquid electrolyte and have high safety have been recently studied. Specifically, for example, a solid electrolyte using a polymer has been studied, and a high concentration in which a lithium salt is dissolved in a copolymer having a specific ratio of ethylene oxide, glycidyl ether, and allyl glycidyl ether and having a specified weight average molecular weight. A lithium polymer battery including a polymer solid electrolyte membrane in which a molecular solid electrolyte is held in a nonwoven fabric is disclosed (for example, see Patent Document 1). In addition, after placing a polymer solid electrolyte sheet obtained by impregnating a porous film or a nonwoven fabric with a prepolymer composition, a positive electrode active material layer, and a negative electrode active material layer, the prepolymer composition is cured by thermal polymerization to increase the thickness. A method for producing a polymer solid electrolyte battery that is changed to a molecular solid electrolyte is disclosed (for example, see Patent Document 2). Patent Document 2 describes that an organic polymer solution containing polyethylene glycol dimethacrylate, methoxypolyethylene glycol monomethacrylate and LiClO ₄ is used as a prepolymer composition.

Japanese Patent No. 4559587 (first page) Japanese Patent No. 3416375 specification (first page)

By the way, secondary batteries such as lithium ion batteries are expected to be used in various fields, and since the conditions for use are various, high charge / discharge characteristics at temperatures around room temperature (room temperature) ( In addition to exhibiting cycle characteristics), it is required to exhibit charge / discharge characteristics not only at room temperature but also in a low temperature region where the temperature is 0 ° C. or lower. For this reason, electrolytes used in such batteries are required to exhibit high ionic conductivity at room temperature and low temperature. In addition, in order to apply an electrolyte to a battery, not only high safety but also mechanical strength that can withstand mounting on the battery is required. As described above, various studies have been made on the electrolyte used in the secondary battery. However, in the conventional technology, a material satisfying both high ionic conductivity and mechanical strength at a high level has not been obtained. For example, the technique described in Patent Document 1 described above assumes a high temperature range of 40 to 100 ° C. as an operating temperature, and can be said to endure use in a low temperature range near room temperature or lower. Absent. Patent Document 2 describes that the mechanical strength of the solid polymer electrolyte layer is improved by the technique described in the document, but ion conductivity in a wide temperature range including a low temperature range has been studied. Absent. Therefore, there is room for devising to develop an electrolyte material having mechanical strength that can withstand mounting on a battery and capable of exhibiting high ionic conductivity even in the vicinity of room temperature or lower temperature region.

The present invention has been made in view of the above situation, and is a material for a lithium ion battery that is excellent in mechanical strength, exhibits high ion conductivity even in the low temperature region around room temperature or lower, and has excellent charge / discharge characteristics. It is an object of the present invention to provide a stable electrolyte material that can be suitably used.

The present inventors have made various studies on solid electrolyte materials that can be used as solid electrolytes that exhibit good ionic conductivity even at temperatures below room temperature. As a result, the oxyalkylene structure has a double bond portion between carbons via an ether bond. An electrolyte material combining a polymer obtained from a monomer having a structure bonded to the electrolyte and an electrolyte salt exhibits excellent lithium ion conductivity due to the fact that the polymer has an oxyalkylene structure. I found something to do. It has also been found that when the electrolyte material further includes a support, and the support supports the polymer and / or the electrolyte salt, the electrolyte material has excellent mechanical strength. Furthermore, by making the electrolyte salt contained in this electrolyte material a specific ionic compound, or by specifying the material and thickness of the support, this electrolyte material is further superior in ion conductivity and mechanical strength in the low temperature region. I have found that A battery equipped with the electrolyte material as described above exhibits excellent charge / discharge characteristics at room temperature and low temperature, and such an electrolyte material is suitably used as a material for a battery such as a lithium ion battery. It has been found that the material can be obtained, and the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is an electrolyte material having an essential component of a polymer having an ether bond in the side chain and an electrolyte salt, wherein the polymer has the following general formula (1);

(In the formula, R ¹ represents a hydrogen atom or a methyl group. X represents a methylene group or a direct bond. R ^a is the same or different and is a carbon atom having a linear or branched chain having 1 to 4 carbon atoms. R ² represents a hydrocarbon group having 1 to 18 carbon atoms having a linear, branched or cyclic structure, and n represents the average number of moles added of the group represented by R ^a O. ), And the electrolyte material further includes a support for supporting the polymer and / or the electrolyte salt. It is an electrolyte material characterized by this.
The present invention is described in detail below.

The electrolyte material of the present invention includes a polymer having an ether bond in the side chain, an electrolyte salt, and a support, and includes a polymer having an ether bond in the side chain, an electrolyte salt, and a support. Other components may be included as long as it is unnecessary.

The polymer having an ether bond in the side chain is represented by the following general formula (1);

(In the formula, R ¹ represents a hydrogen atom or a methyl group. X represents a methylene group or a direct bond. R ^a is the same or different and is a carbon atom having a linear or branched chain having 1 to 4 carbon atoms. R ² represents a hydrocarbon group having 1 to 18 carbon atoms having a linear, branched or cyclic structure, and n represents the average number of moles added of the group represented by R ^a O. The polymer obtained by superposing | polymerizing the monomer component containing the monomer represented by this is included. A polymer obtained from such a monomer unit has an oxyalkylene structure bonded to the side chain via an ether bond. Since the polymer having such a structure has an oxyalkylene structure, it can exhibit good ionic conductivity, and can exhibit ionic conductivity even in a low temperature region below room temperature. In addition, excellent ion conductivity can be exhibited even in a high temperature region exceeding room temperature, and ion conductivity can be exhibited in a wide temperature range from a low temperature region to a high temperature region. In addition, when the polymer has a carbonyl structure in the structure, the interaction with lithium becomes too strong and the ionic conductivity is reduced. However, as in the monomer of the general formula (1), an ether bond When the compound has an ether bondable functional group having an oxyalkylene structure bonded thereto, this interaction is moderately suppressed and it can be suitably used as a material for a lithium ion battery.
The monomer component for obtaining the polymer contained in the electrolyte material of the present invention may contain one type of monomer represented by the general formula (1), or may contain two or more types. In addition, the electrolyte material of the present invention is a polymer having an ether bond having another structure in the side chain as long as it contains a polymer obtained from a monomer component containing the monomer represented by the general formula (1). Coalescence may be included.
The detail of the polymer (henceforth a polymer (A)) obtained from the monomer component containing the monomer represented by the said General formula (1) is mentioned later.

The electrolyte material of the present invention also includes a support for supporting the polymer (A) and / or the electrolyte salt. By supporting the polymer (A) and / or the electrolyte salt by the support, the mechanical strength of the obtained electrolyte membrane can be improved and can be mounted on a secondary battery such as a lithium ion battery. It becomes possible.
The support is not particularly limited as long as it can support the polymer (A) and / or the electrolyte salt, but is selected from the group consisting of a woven fabric, a nonwoven fabric, a porous membrane, and a glass molded body. It is preferable that it consists of at least one kind. When the support is in such a form, the polymer (A) and / or the electrolyte salt can be impregnated in the support, so that the obtained electrolyte membrane has a more excellent ion conductivity.

Specific examples of the woven fabric and the nonwoven fabric include polyolefin resins such as polypropylene, polyethylene, and polymethylpentene, polyester resins such as polyethylene terephthalate, polyamide resins such as nylon, and aramid resins such as polyparaphenylene terephthalamide. Examples thereof include resins such as resins, acrylic resins, polyvinyl alcohol resins, and cellulose resins; those made of alumina fibers, ceramic fibers, glass fibers, and the like.
Examples of the porous film include polyolefin resins such as polypropylene, polyethylene, and ethylene-propylene copolymers, fluororesins such as polyester resins and tetrafluoroethylene-perfluoroalkoxyethylene copolymers, and polyetheretherketone. And those made of a resin such as polybutylene terephthalate, polyphenylene sulfide, and polyamide resin.
A glass cloth etc. can be mentioned as said glass molded object.
As these supports, in order to further improve the hydrophilicity, a method of imparting a surfactant, a method of sulfonation with a chemical such as fuming sulfuric acid or chlorosulfonic acid, a fluorination, a grafting treatment or the like, or a corona You may use what hydrophilized by the method by discharge, plasma discharge, etc. FIG.
The support to be used is not limited to these, but the support to be used is preferably a polyester resin, an aramid resin, a polyvinyl alcohol resin, a cellulose resin, a woven fabric made of glass fiber, and A porous membrane made of a nonwoven fabric or a polyester resin, more preferably a woven fabric or a nonwoven fabric made of a polyester resin, a cellulose resin, or a glass fiber.

The support preferably has a water retention rate of 100% or more. When the water retention ratio is in such a range, the support can be easily impregnated with the polymer (A) and / or the electrolyte salt, and the retention force on the support is also increased. The mechanical strength of the material becomes even better. In addition, by using such a support, the obtained electrolyte membrane has good cycle characteristics that allow more stable charge and discharge while maintaining a high discharge capacity. These are considered to be caused by the high affinity between the polymer contained in the electrolyte material of the present invention and the support having such a water retention rate.
The water retention rate is more preferably 150% or more, and still more preferably 200% or more. Particularly preferably, it is 300% or more.
The water retention rate of the support was determined by immersing the support cut to a certain size in water for a certain period of time, measuring the water retention weight after draining, and the weight of water contained in the support (water retention weight-water The weight of the support before being immersed in water) can be determined from the ratio of the weight of the support before being immersed in water.

The support preferably has a thickness of 1 to 200 μm. When the thickness of the support is in such a range, when the support is impregnated with the polymer (A) and / or the electrolyte salt, the ratio of those components in the electrolyte membrane can be increased and obtained. The ionic conductivity of the electrolyte membrane can be further improved.
More preferably, it is 1-100 micrometers as thickness of the said support body, More preferably, it is 5-70 micrometers, Most preferably, it is 10-50 micrometers.

The electrolyte salt used in the present ^{_{invention, R 3 SO 2 N - SO}} 2 R 4 (. R 3 and ^{R 4} are the same or _different, F, represent any one of _{CF 3, C 2 F 5)} , PF ₆ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , [B (CN) _4−m (R ⁵ ) _m ] ⁻ (wherein R ⁵ is independently a hydrogen atom, a halogen atom, or an atom number of 1 to 30 And m represents an integer of 0 to 3.) It is preferable to include an ionic compound composed of at least one anion selected from the group consisting of an alkali metal cation.
As said electrolyte salt, 1 type of the said ionic compound may be included, and 2 or more types may be included. Moreover, the electrolyte material of the present invention may contain other electrolyte salts other than the ionic compound.
Examples of the anion include R ³ SO ₂ N ^— SO ₂ R ⁴ (R ³ and R ⁴ are the same or different and each represents F, CF ₃ , or C ₂ F ₅ ), PF ₆ ⁻ , and ^{_{, [B (CN) 4-}} m (R 5) m] - ( wherein, ^{R 5} independently represents a hydrogen atom, an organic substituent of a halogen atom or atoms 1 to 30, m is 0 to 3 more preferably at least one member of selected from the group consisting of) represents an ^{_{integer, R 3'SO 2 N -.}} SO 2 R 4'(R 3' and ^{R 4'are} the same or different, Represents F or CF ₃ ), and [B (CN) _4-m (R ⁵ ) _m ] ^— (wherein R ⁵ is independently a hydrogen atom, a halogen atom, or an organic compound having 1 to 30 atoms). Represents a substituent, and m represents an integer of 0 to 3.) is at least one selected from the group consisting of Theft is more preferable.

As the alkali metal cation, a lithium cation is preferably used. When such an ionic compound is used, the electrolyte material of the present invention can be more suitably used as an electrolyte. Specific examples of the ionic compound include lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium difluorosulfonylimide (LiFSI), and lithium tetracyanoborate (LiTCB).

It is preferable that content of the said ionic compound is 1-50 mass% with respect to 100 mass% of polymers which have the ether bond used in this invention in a side chain. When the content of the ionic compound is within such a range, an electrolyte exhibiting better ionic conductivity is obtained. More preferably, it is 1-40 mass% with respect to 100 mass% of the polymer which has an ether bond used in this invention in a side chain, More preferably, it is 1-30 mass%.

In the electrolyte material of the present invention, the polymer (A) and / or the electrolyte salt is preferably impregnated and held on the support. Thereby, since a polymer (A) and / or electrolyte salt can be made to exist also in a support body, the ratio of those components in a support body can be raised, and the ionic conductivity of the electrolyte membrane obtained is improved. This can be further improved. More preferably, the polymer (A) and the electrolyte salt are impregnated and held on the support.

Below, the preferable form of the said polymer (A) is explained in full detail.
In the general formula (1), examples of the hydrocarbon group having a linear or branched chain having 1 to 4 carbon atoms represented by R ^a include methylene (—CH ₂ —), ethylene (—CH ₂ CH ₂ —), trimethylene ( A linear alkylene group such as —CH ₂ CH ₂ CH ₂ —) or tetramethylene (—CH ₂ CH ₂ CH ₂ CH ₂ —); ethylidene [—CH (CH ₃ ) —], propylene [—CH (CH _{3) CH} 2 -], propylidene _{[-CH (CH 3 CH 2)} -], isopropylidene _{[-C (CH 3) 2 -} ], butylene _{[-CH (CH 3 CH 2)} CH 2 -], isobutylene [ Branched chain alkylene groups such as —C (CH ₃ ) ₂ CH ₂ —], butylidene [—CH (CH ₃ CH ₂ CH ₂ ) —], isobutylidene [—CH (CH (CH ₃ ) ₂ ) —], etc. Can be mentioned.
Among these, a linear alkylene group such as methylene, ethylene, trimethylene and tetramethylene, and a branched alkylene group such as propylene, propylidene, butylene and butylidene are preferable. More preferred are ethylene, trimethylene, tetramethylene, propylene, propylidene and butylene.
In the general formula (1), ^Ra may be one type or two or more types. When R ^a is 2 or more, the addition form of the oxyalkylene group represented by — (R ^a O) — may be any form such as block form or random form.

N representing an average molar number of addition of the groups represented by R ^{a O} in the above general formula (1) varies depending on the type of the oxyalkylene group constituting the group represented by R a ^O, 1 to 50 of A range is preferable. When the average number of repeating oxyalkylene structures is 1 to 50, the crystallization temperature of the polymer becomes lower, and the ionic conductivity in a low temperature region below room temperature is more satisfactorily exhibited. When the number of repetitions exceeds 50, the influence of the polyether structure becomes strong, and problems such as easy crystallization occur. n is more preferably 2 to 30, still more preferably 4 to 30, and most preferably 6 to 30. In particular, when the group represented by R ^a O is an oxyethylene group, n is more preferably 2 to 30, still more preferably 4 to 20, and most preferably 6 to 14.
Thus, when the average number of repetitions of the oxyalkylene structure is somewhat large, the ionic conductivity in the low temperature region below room temperature of the polymer is further improved. This effect is that when the average number of repeating oxyalkylene structures in the polymer increases, the contribution of the oxyalkylene structure to the physical properties of the polymer increases and the performance decreases due to freezing at low temperatures. On the contrary, it is an unexpected effect in that it exhibited better ionic conductivity.

In the general formula (1), the hydrocarbon group having 1 to 18 carbon atoms having a linear, branched or cyclic structure represented by R ² is methyl, ethyl, n-propyl, isopropyl, n-butyl, n- An aliphatic or alicyclic alkyl group having 1 to 18 carbon atoms such as hexyl, n-octyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc .; phenyl, naphthyl, anthryl, An aryl group having 6 to 18 carbon atoms such as phenanthryl; an aryl group substituted with an alkyl group such as o-, m- or p-tolyl, 2,3- or 2,4-xylyl, mesityl; , Aryl groups substituted with (alkyl) phenyl groups; substituted with aryl groups such as benzyl, phenethyl, benzhydryl, trityl, etc. An alkyl group etc. are mentioned.
When the number of carbon atoms in R ² is too large, the glass transition temperature of the resulting polymer is lowered, but the hydrophobicity is improved, which is not preferable. Among these, aliphatic having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, isobutyl, sec-butyl, tert-butyl and the like are preferable. More preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl and n-octyl.
Further, in order to increase the dielectric constant of the polymer, it is effective to contain a polar substituent such as a carbonate group and an ester group in R ^2.

In the general formula (1), when X is a direct bond, the monomer represented by the general formula (1) is a vinyl ether monomer, and in the general formula (1), X is a methylene group. In some cases, the monomer represented by the general formula (1) is a (meth) allyl monomer. Any of these structures exhibit the above characteristics and can be suitably used as a monomer component of a polymer used in an electrolyte material. That is, it is one of preferred embodiments of the present invention that X in the general formula (1) is a direct bond. Furthermore, it is one of the preferred embodiments of the present invention that X in the general formula (1) is a methylene group.

The production method of the monomer represented by the general formula (1) is not particularly limited, but a halide containing a vinyl ether group or a (meth) allyl group, and a hydrogen atom of a hydroxyl group at one end of the polyether diol are a hydrocarbon group. And a method of subjecting the compound substituted with a desalting reaction in the presence of a basic compound. In addition, as a method for producing a monomer in which X is a direct bond in the above general formula (1), a compound obtained by substituting a hydrogen atom of a hydroxyl group at one end of a polyether diol with a hydrocarbon group is formed in the molecule in the presence of a basic catalyst. Examples include a method of dehydrating. In addition, in the case of producing a monomer having a large number of n in the general formula (1), that is, a large number of repeating oxyalkylene structures, one end of a polyether diol having a small number of repeating oxyalkylene structures is used. Alkylene oxide is added to a compound having a structure in which the hydrogen of the hydroxyl group is substituted with a vinyl ether group or a (meth) allyl group in the presence of an addition reaction catalyst, and the resulting adduct and an alkyl halide are present in the presence of a basic compound. Below, the method of desalting reaction etc. are mentioned.

The basic compound to be desalted is not particularly limited, and specific examples include alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, and calcium hydroxide. (Earth) Metal hydroxides and the like can be mentioned. As the basic catalyst used for intramolecular dehydration, in addition to the alkali (earth) metal hydroxide, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate , Cesium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, alkali (earth) metal carbonates such as cesium carbonate, magnesium carbonate, calcium carbonate; lithium acetate, sodium acetate, potassium acetate, Alkali (earth) metal cals such as cesium acetate, magnesium acetate, calcium acetate Sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium butoxide and other alkali (earth) metal alkoxides; ammonia, methylamine, ethylamine, butylamine, ethanolamine, dimethylamine, Diethylamine, dibutylamine, diethanolamine, trimethylamine, triethylamine, tributylamine, tris (2-ethylhexyl) amine, triethanolamine, ethylenediamine, tetramethylethylenediamine, tolene, 1,4-diazabicyclo [2,2,2] octane, aniline, Methylaniline, dimethylaniline, pyridine, piperidine, picoline, N, N-dimethyl-p-toluidine, lutidine, quinoline, isoquinoline , Amines such as collidine; and the like are.
Examples of the addition reaction catalyst include metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and magnesium hydroxide, metal hydrides such as sodium hydride and potassium hydride, butyl lithium, methyl lithium, Organic metal compounds such as phenyl lithium, Lewis acids such as boron trifluoride and titanium tetrachloride, metal alkoxides such as sodium methoxide and potassium methoxide, and the like can be used.
The usage-amount of a basic compound, a basic catalyst, and an addition reaction catalyst can be suitably set according to the quantity of the reaction raw material, etc.

The polymer used in the present invention is obtained from the monomer component containing the monomer represented by the general formula (1), but the monomer component is represented by the general formula (1). In the case where the monomer represented by the general formula (1) is a vinyl ether monomer, the other monomer may be included. It preferably includes a body.
Other monomers include radically copolymerizable polymerizable compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) Cyclohexyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, 2- (acetoacetoxy) ethyl (meth) acrylate, (meth ) (Meth) acrylic acid esters such as acrylic acid; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4- Hydroxybutyl, methyl (α-hydroxymethyl) acrylate, ethyl (α-hydroxymethyl) (Meth) acrylic acid esters such as (til) acrylate, caprolactone-modified hydroxy (meth) acrylate, (meth) acrylic acid 4-hydroxymethylcyclohexylmethyl; acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, Acidic functional group-containing polymerizable monomers such as itaconic acid, maleic anhydride, carboxyl-terminated caprolactone-modified (meth) acrylate, sulfoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate; styrene, α -Vinyl compounds such as methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate, vinyl chloride, vinylidene chloride; silicon-containing heavy metals such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane Containing monomers: Halogen containing (meth) acrylic acid trifluoroethyl, (meth) acrylic acid octafluoropentyl, (meth) acrylic acid heptadodecafluorodecyl, (meth) acrylic acid perfluorooctyl ethyl ) Acrylic acid esters; (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid N, N′-dimethyl Contains nitrogen atoms such as aminoethyl, N-methyl-N-vinylformamide, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, N-phenylmaleimide, N-cyclohexylmaleimide, 2-isopropenyl-2-oxazoline Polymerizable monomers; ethylene Recall di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( Multifunctional polymerizable monomers such as (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, vinyloxyethyl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate; (meth) acryl Epoxy group-containing polymerizable monomers such as glycidyl acid, α-methylglycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate; 2- (meth) acryloyloxyethyl isocyanate Isocyanate-containing polymerizable monomers such as nate, (meth) acryloyl isocyanate, m-isopropenyl-α, α dimethylbenzyl isocyanate; 4- (meth) acryloyloxy-2,2,6,6-tetramethyl Examples include UV-stable polymerizable monomers such as piperidine and 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine. 1 type (s) or 2 or more types can be used.

Further, as polymerizable compounds capable of cationic copolymerization, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxy Monofunctional vinyl ethers such as ethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, chloroethyl vinyl ether; styrene, α-methylstyrene, vinyltoluene, Acetic acid Monofunctional vinyl compounds such as benzene, vinyl acetate, vinyl propionate, vinyl benzoate; methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, cyclohexyl glycidyl ether, methoxyethyl glycidyl ether Monofunctional epoxy compounds such as ethoxyethyl glycidyl ether, methoxyethoxyethyl glycidyl ether, ethoxyethoxyethyl glycidyl ether, methoxypolyethylene glycol glycidyl ether; 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane 3-methyl-3-phenoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-methyl Monofunctional alicyclic ether compounds such as ru-3- (2-ethylhexyloxymethyl) oxetane and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene Polyfunctional vinyl ethers such as glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether; polyfunctional vinyl compounds such as divinylbenzene; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl Polyfunctional epoxy compounds such as ether and propylene glycol diglycidyl ether; di [1-methyl (3-oxetanyl)] Tilether, di [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis {[(3-methyl-3-oxetanyl) methoxy] methyl} benzene, 1,4-bis {[(3-ethyl- 3-oxetanyl) methoxy] methyl} benzene, bis {4-[(3-methyl-3-oxetanyl) methoxy] methyl} benzyl ether, bis {4-[(3-ethyl-3-oxetanyl) methoxy] methyl} benzyl Polyfunctional alicyclic ether compounds such as ether; cyclic ethers such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran can be used, and one or more of these can be used.

Among the other monomers, a polyfunctional monomer is preferable. When the monomer component contains a polyfunctional monomer, the resulting polymer has a crosslinkable functional group in the molecule. Such a polymer having a crosslinkable functional group in the molecule can be suitably used as a component of an electrolyte material as it is, but it can be further cured by forming a crosslinked structure in the polymer. It can be made excellent in properties such as properties and coating properties.
That is, it is one of the preferred embodiments of the present invention that the polymer used in the present invention is a crosslinkable polymer having a crosslinkable functional group in the molecule.
Further, as the monomer component of the polymer used in the present invention, among the monomers represented by the general formula (1), those having a large average number of repeating oxyalkylene structures and polyfunctional monomers are used. When obtained, the resulting polymer can exhibit particularly good ionic conductivity, and can exhibit high ionic conductivity even in a low temperature region below room temperature. That is, the said polymer contains the polymer obtained from the monomer component containing the monomer represented by the said General formula (1), n in the said General formula (1) is 6-30, A form in which the polymer is a crosslinkable polymer having a crosslinkable functional group in the molecule is also one preferred embodiment of the present invention.

Among the other monomers, vinyl ether group-containing (meth) acrylic acid esters such as vinyloxyethyl (meth) acrylate and vinyloxyethoxyethyl (meth) acrylate are particularly preferable. Most preferred is vinyloxyethoxyethyl acrylate.
Thus, it is one of the suitable embodiments of the present invention that the crosslinkable polymer is a polymer obtained from a monomer component containing a vinyl ether group-containing (meth) acrylic acid ester. is there.
In addition, a form in which the polymer is a polymer obtained from a monomer component containing the monomer represented by the general formula (1) and vinyloxyethoxyethyl acrylate is also suitable for the present invention. This is one of the embodiments.

The polymer contained in the electrolyte material of the present invention preferably has a crosslinked structure. By having a crosslinked structure, it is possible to further improve the properties such as curability and coating properties as described above. The polymer having a cross-linked structure is not particularly limited as long as it has a cross-linked structure. However, in the polymer having a cross-linkable functional group in the molecule, the cross-linkable functional group possessed by the polymer is allowed to react. Polymers that form the structure are preferred.
That is, it is one of the preferred embodiments of the present invention that the electrolyte material of the present invention contains a crosslinked polymer obtained by reacting a crosslinkable functional group in the polymer molecule.
In the present invention, the “electrolyte material” means that when a polymer having an ether bond as a side chain as a constituent component is a polymer having a crosslinkable functional group in the molecule, the polymer undergoes a crosslinking reaction. It represents a polymer having a crosslinkable functional group in the molecule before it is released, and a polymer (crosslinked product) in a state in which the crosslinking reaction of the polymer is completed to form a crosslinked structure. In particular, a material containing a polymer having a crosslinkable functional group in the molecule before the crosslinking reaction of the polymer is referred to as “electrolyte material raw material composition”, and the crosslinking reaction of the polymer is completed to form a crosslinked structure. It is also possible to distinguish by including the formed polymer as “electrolyte material”.

When the monomer component includes other monomers, the proportion of the monomer represented by the general formula (1) is 10% by mass or more and 99.9% with respect to 100% by mass of the whole monomer component. It is preferable that it is below mass%. When the ratio of the monomer represented by the general formula (1) is within such a range, the obtained polymer is excellent in ionic conductivity, and is a material that exhibits ionic conductivity even in a low temperature region. Become. More preferably, they are 30 mass% or more and 99.9 mass% or less, More preferably, they are 50 mass% or more and 99.9 mass% or less.

When the monomer component contains a polyfunctional monomer as another monomer, the ratio of the polyfunctional monomer is 0.1% by mass or more and 90% by mass or less with respect to 100% by mass of the whole monomer component. It is preferable that When the ratio of the polyfunctional monomer is within such a range, the obtained polymer becomes a material excellent in ion conductivity. More preferably, it is 0.1 mass% or more and 70 mass% or less, More preferably, it is 0.1 mass% or more and 50 mass% or less.

The weight average molecular weight of the polymer in the present invention is preferably 2 million or less. When the weight average molecular weight of the polymer is in such a range, the viscosity becomes easy to handle. More preferably, it is 500,000 or less, More preferably, it is 400-200,000, Most preferably, it is 500-100,000.
The weight average molecular weight can be determined by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120
Molecular weight columns: G5000HXL and GMHXL-L (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran calibration curve standard material: Polystyrene Measuring method: Solid content of measurement object in eluent is 0.3 mass % Dissolved and filtered through a filter.

The polymer preferably has a glass transition temperature (Tg) of 20 ° C. or lower and −150 ° C. or higher. When the glass transition temperature is in such a range, the ion conductivity can be exhibited even in a low temperature region such as a temperature of 0 ° C. or lower, and the electrolyte material exhibits ion conductivity in a wide temperature region. can do. More preferably, it is -40 degrees C or less, More preferably, it is -60 degrees C or less.
The glass transition temperature of the polymer may be determined based on the knowledge already obtained, and may be controlled by the type and use ratio of the monomer component, but in theory, from the following calculation formula: Can be calculated.

In the formula, Tg ′ is Tg (absolute temperature) of the copolymer. W ₁ ′, W ₂ ′,... W _n ′ are mass fractions of the respective monomers with respect to the total monomer components. T ₁ , T ₂ ,..., T _n are glass transition temperatures (absolute temperatures) of a homopolymer (homopolymer) composed of each monomer component.

The crystallization temperature of the polymer depends on the weight average molecular weight of the polymer, and can be adjusted by the average number of added moles of the oxyalkylene group of the monomer represented by the general formula (1). Moreover, when a monomer component contains other monomers other than the monomer represented by General formula (1), it can also adjust by increasing the content rate. Most preferably, the polymer is in an amorphous state.

When the polymer having an ether bond in the side chain contained in the electrolyte material of the present invention has a crosslinkable functional group in the molecule, first a prepolymer is produced, and then a crosslinked structure is formed by performing a crosslinking reaction. It is preferable to produce the polymer which has. A polymer having a crosslinked structure produced by such a production method is advantageous in that processability is improved, such as good coating molding and formation of a good interface with the negative electrode.

The polymer used in the present invention can be synthesized by the following polymerization method. The following polymerization method can be used not only for a polymer having a crosslinked structure obtained by forming a crosslinked structure after producing the prepolymer, but also for all polymers used in the present invention.
(1) When polymerizing the radically polymerizable monomer component, a polymerization initiator can be used. Examples of the radical polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, Examples include benzoyl peroxide and di-tert-butyl peroxide, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator may be appropriately set according to the desired physical properties of the resulting acrylic polymer, but is usually 0.01 to 50% by mass, preferably 100 to 50% by mass, per 100% by mass of the monomer component. Preferably it is 0.05-20 mass%.
The polymerization conditions for polymerizing the monomer components may be set as appropriate according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably room temperature (25 ° C.) to 200 ° C., more preferably room temperature (25 ° C.) to 140 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of a monomer component may be completed.

(2) Cationic polymerization Cationic polymerization can be carried out by a commonly used method. Cationic polymerization initiators include heteropolyacids, thermal latent cationic polymerization initiators, protons such as perchloric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, picrylsulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, trifluoroacetic acid, etc. Acids; Lewis acids such as boron trifluoride, aluminum bromide, aluminum chloride, antimony pentachloride, ferric chloride, tin tetrachloride, titanium tetrachloride, mercury chloride, zinc chloride; others include iodine, triphenylchloromethane Etc. can be used.

As the heteropolyacid, for example, a central atom of the skeletal acid is selected from tungsten, molybdenum, vanadium, etc., and the heteroatom is formed from an atom selected from phosphorus, silicon, germanium, titanium, zirconium, boron, arsenic, cobalt, etc. A polyacid having a structure, for example, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, borotungstic acid, boromolybdic acid, cobalt molybdic acid, cobalt tungstic acid, arsenic tungstic acid, germanium tungstic acid, Examples thereof include phosphomolybdotungstic acid and boromolybdotungstic acid. Among these, phosphotungstic acid is particularly preferable in terms of no coloring, solubility, and polymerization initiation ability.
The heteropolyacid used in the present invention can also be used as a partially neutralized salt. Examples of these partially neutralized salts include sodium salts, potassium salts, cesium salts, organic amine salts, ammonium salts, and the like. The partially neutralized salt of the heteropolyacid may be prepared and then added to the reaction system, but may be formed by reacting the heteropolyacid with a base in vinyl ether.

Examples of the thermal latent curing catalyst include the following general formula (2);
_{^{(R 5 a R 6 b R}} 7 c R 8 d Z) + m (AX n) -m (2)
(In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements. R ⁵ , R ⁶ , R ⁷ and R ⁸ is the same or different and represents an organic group, a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. Cation (R ⁵ _a R ⁶ _b R ⁷ _c R ⁸ _d Z) ^{+ m} represents an onium salt, A represents a metal element or metalloid which is a central atom of a halide complex, and B, P, As, Al, It is at least one selected from the group consisting of Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halogen element, and m is the net charge of the halide complex ion. N is the number of halogen elements in the halide complex ion Is preferred).

Specific examples of the anion (AX _n ) ^-m of the general formula (2) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexa Examples include fluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ), and the like. Further general formula _AX n (OH) ^- can also be used anion represented by. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzenesulfone. An acid ion etc. are mentioned.

Specific examples of the thermal latent curing catalyst include the following products. Diazonium salt types: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemical Industries), iodonium salt types: UVE series (General Electric), FC series ( 3M), UV9310C (GE Toshiba Silicone), Photoinitiator 2074 (Rhone-Poulenc), WPI series (Wako Pure Chemical Industries), sulfonium salt type: CYRACURE series (Union Carbide), UVI series ( General Electric Co., Ltd.), FC Series (manufactured by 3M), CD Series (manufactured by Satomer), Optomer SP Series, Optmer CP Series (manufactured by Adeka), Sun Aid SI Series (Sanshin Chemical) Made by the company), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San-Apro Ltd.), and the like.

In addition to the above cationic polymerization initiators, it is also possible to use so-called photocationic polymerization initiators that generate cationic species by the action of light and initiate polymerization. As the photocationic polymerization initiator, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, (2,4 An onium salt of Lewis acid such as -cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron-hexafluorophosphate can be used.

The cationic polymerization initiator and / or the cationic photopolymerization initiator may be used alone or in combination of two or more. In the present invention, the initiator is used in an amount of 1 ppm to 30% by mass, preferably 5 ppm to 20% by mass, particularly preferably 10 ppm to 10% by mass, based on the monomer used for the raw material. If the amount used is less than 1 ppm, the polymerization may not start. If the amount used exceeds 30% by mass, the polymerization becomes too intense and the reaction cannot be controlled, the molecular weight of the resulting polymer becomes low, or the product is colored. May happen.

When polymerizing the monomer, polymerization may be carried out in bulk, and a solvent may be used to control the reaction temperature and viscosity. When a polymer is produced using a polymerization catalyst and a polymerization solvent, polymerization is performed while stirring the monomer composition in the solvent. Examples of such a polymerization method include a solution polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these, the solution polymerization method is more preferable because of its excellent productivity. Furthermore, a solution polymerization method in which polymerization is performed while supplying a monomer composition as a raw material to a previously charged solvent is particularly preferable from the viewpoint of safety such as easy removal of reaction heat.

The solvent used for polymerizing the monomer is not particularly limited, but is an aromatic solvent such as toluene or xylene; propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, 1 Ether solvents such as 1,4-dioxane; ester solvents such as ethyl acetate, butyl acetate and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; amide solvents such as dimethylformamide; chloroform , Halogenated hydrocarbons such as trichlorethylene; nitriles such as acetonitrile and benzonitrile; aliphatic hydrocarbons such as hexane and octane; saturated cyclic carbonization such as cyclohexane and methylcyclohexane Including but organic solvents such as iodine, the present invention is not limited only to those exemplified. These solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, the composition of the monomer components, the concentration of the resulting acrylic polymer, and the like. In order to obtain a high molecular weight polymer, it is preferable to use a solvent that does not contain active hydrogen, such as aromatic hydrocarbons, aliphatic hydrocarbons, saturated cyclic hydrocarbons, and esters.

In order to obtain the high molecular weight polymer, it is preferable that impurities such as moisture and alcohol in the reaction system are small. In the present invention, the temperature for polymerizing the polymer is not particularly limited, but is preferably -70 to 120 ° C. In particular, in order to obtain a high molecular weight polymer, it is preferable to adjust the polymerization initiation temperature to −10 to 90 ° C. and the maximum temperature during polymerization to 20 to 80 ° C. by heating or cooling. When the polymerization temperature exceeds 120 ° C, the molecular weight of the resulting polymer may be low.
The reaction pressure may be normal pressure or increased pressure, but is usually carried out at normal pressure.

In the polymerization of the monomer, after the polymerization reaction, the reaction may be stopped by adding an organic base such as ammonia and amine or an inorganic base such as NaOH and KOH, if necessary. However, for the stability of the product, it is preferable to stop the reaction using the above base.

In the case of making a crosslinked polymer (crosslinked product) by reacting the crosslinkable functional group of the polymer, a polymer (prepolymer), a polymerization initiator, an ionic compound, and a solvent (if necessary) After preparing a mixture solution containing the above, the support is impregnated into the above support, and when a solvent is used, the solvent is removed by drying, and then the UV-irradiated or heated to form a crosslinkable functional group. And the like can be used in a chain addition reaction. For example, in the case of forming a film-like cross-linked body (polymer cross-linked film), the polymer, ionic compound and polymerization initiator were dissolved in a solvent, and then impregnated into a support such as a nonwoven fabric and dried. The film can be reacted by UV light irradiation or heating to form a crosslinked film.
As a method of forming a crosslinked product by reacting a crosslinkable functional group present in the molecule of the polymer, in addition to the method of chain addition reaction of the crosslinkable functional group of the polymer, the polymer has Examples thereof include a method of forming a crosslinked structure by adding a compound having two or more functional groups capable of reacting with a crosslinkable functional group (crosslinking agent). Among these, the crosslinkable functional groups possessed by the polymer are linked. It is preferable to form a crosslinked structure by the addition reaction method.

The polymerization initiator used in the method of chain addition reaction of crosslinkable functional groups by UV light irradiation or heating is a photo radical polymerization initiator, a thermal radical initiator, an anionic polymerization initiator, photo anion polymerization initiation Agents. The photo radical polymerization initiator generates a polymerization initiating radical by irradiation with active energy rays, the thermal radical polymerization initiator generates a polymerization initiating radical by heating, and the photo anion polymerization initiator starts polymerization by irradiation with active energy rays. It is a component necessary for initiating a polymerization reaction to generate an anionic species. Moreover, after forming a polymer and an organic acid lithium salt into a thin film by kneading extrusion, a crosslinked structure may be formed by making a crosslinking reaction utilizing the reactivity of the polymer.
The anionic polymerization initiator referred to here is a component that initiates a polymerization reaction that generates a polymerization initiating anion species, and does not correspond to a photoanionic polymerization initiator.

The photo radical polymerization initiator is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2- Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer, 2,2-dimethoxy-1,2-diphenylethane- 1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2 Methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-dimethylamino Acetophenones such as -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholyl) phenyl] -1-butanone; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4- Benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl- N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-vinyl Benzoylones such as zoylbenzyl) trimethylammonium chloride; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, Thioxanthones such as 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone-9-one mesochloride; 2 Acylphosphineoxy such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide , Titanocenes such as bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium; Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- Oxime esters such as 1- (O-acetyloxime); oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester, etc. Oxyphenyl acetate esters; and the like. These photopolymerization initiators may be used alone or in combination of two or more. Of these photopolymerization initiators, acetophenones and benzophenones are preferred, and 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2 -Morpholino (4-thiomethylphenyl) propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one are particularly preferred.

The thermal radical polymerization initiator is not particularly limited. For example, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (T-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) cyclo Dodecane, 1,1-bis (t-butylperoxy) bu 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide , Cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5 -Bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl Luperoxide, 3,5,5-trimethylhexanoyl peroxy Id, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropylperoxydicarbonate, bis (4 -T-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-s-butylpercarbonate Oxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1, , 3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2 -Ethylhexanoyperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexa Noate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisobuty Tate, t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexylmonic carbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2 , 5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyl Trimethylsilyl peroxide, 3,3 ', 4,4'- Organic peroxide initiators such as tetra (t-butylperoxycarbonyl) benzophenone and 2,3-dimethyl-2,3-diphenylbutane;

2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2, 2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2 '-Azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-H Rophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2 -Propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2- Imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (4,5,6, 7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- 3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane ] Dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazoline- 2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] 2,2′-azobis (2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane), dimethyl 2,2 ′ -Azo initiators such as azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl) propionitrile];

Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl- Acetophenones such as 1- [4- (1-methylvinyl) phenyl] polopanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzoyl Methyl perfume, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone Benzophenones such as 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; Isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl- 9H-thioxanthone-9 Thioxanthones such Onmesokurorido; and the like. These thermal radical polymerization initiators may be used alone or in combination of two or more. Of these thermal radical polymerization initiators, organic peroxide initiators and azo initiators are preferred.

Although it does not specifically limit as said anionic polymerization initiator, For example, alkali metal compounds which have alkali metals and carbon anions, such as sodium naphthalene, n-butyllithium, and t-butyllithium; trimethylaluminum, triethylaluminum, Trialkylaluminums such as tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum; chlorodialkylaluminum, chlorodiethylaluminum, chlorodipropylaluminum, chlorodiisopropylaluminum, chlorodibutylaluminum, chlorodiisobutylaluminum, bispentamethyl Examples include cyclopentadienyl samarium and methyl-bispentamethylcyclopentadienyl samarium. It is.

The photoanionic polymerization initiator is not particularly limited, and examples thereof include alkoxytitanium and p-chlorophenyl-o-nitrobenzyl ether.
These anionic polymerization initiators and / or photoanionic polymerization initiators may be used alone or in combination of two or more.

The blending amount of the radical polymerization initiator is preferably 0.01% by mass, more preferably 0.05% by mass, and still more preferably 0.1% by mass with respect to the amount of the prepolymer, The upper limit is preferably 20% by mass, more preferably 15% by mass, and still more preferably 10% by mass. If the blending amount is less than 0.01% by mass, sufficient curing cannot be obtained, and the strength of the film may be lowered. On the contrary, if the blending amount exceeds 20% by mass, the characteristics of the film will not be further improved, and rather adverse effects may be caused and the economy may be impaired.
Moreover, 0.01-30 mass% is normally used for the compounding quantity of the said anionic polymerization initiator and / or photoanionic polymerization initiator with respect to the amount of prepolymers.

When the electrolyte membrane is formed from the electrolyte material of the present invention, it is preferably formed so that the film thickness (thickness including the support) is 5 to 300 μm. More preferably, it is 10-200 micrometers, More preferably, it is 20-100 micrometers.
In addition, it is preferable that the ratio (α / β) of the thickness (α) including the support in the electrolyte membrane of the present invention and the thickness (β) of the support is 1 to 10. . When the thickness of the electrolyte including the support is the same as the thickness of the support alone (= the electrolyte component is completely absorbed in the support and the electrolyte component does not come out on the surface), the performance as an electrolyte is sufficient. There is a possibility that it cannot be demonstrated. Moreover, when the film thickness of the electrolyte containing a support exceeds 10 times the thickness of only a support, mechanical strength becomes inadequate and cycling characteristics will fall. The ratio (α / β) of the film thickness (α) including the support in the electrolyte membrane of the present invention and the film thickness (β) of the support is more preferably 1 to 8, and still more preferably. 1-5.

The electrolyte material of the present invention includes a polymer having the ether bond in the side chain (polymer (A)), an electrolyte salt, and a support, and is excellent in mechanical strength and ion conductivity. Since the charge / discharge characteristics in the room temperature and low temperature regions can be made excellent, in addition to the electrolyte, it can also be suitably used as a conductive additive, a positive electrode binder, a negative electrode binder, an inorganic solid electrolyte binder, The binder can improve moldability without impairing electrochemical characteristics. Such a binder for an electrode using the electrolyte material of the present invention is also one aspect of the present invention. Furthermore, a battery material using the electrolyte material of the present invention that can be suitably used as various materials for such a battery is also one aspect of the present invention.

The electrolyte material of the present invention may contain other components (impurities) other than the polymer (A) and the ionic compound in the electrolyte component (component obtained by removing the support from the electrolyte material). The content is preferably 5% by mass or less with respect to 100% by mass of the electrolyte component. When the content of impurities is more than 5% by mass, ion conductivity is lowered or performance is deteriorated with time due to electrochemical reaction. More preferably, it is 1 mass% or less.
The impurities referred to here include polymerization inhibitors, chain transfer agents, solvents, unreacted reaction materials, and by-products formed by decomposition of the reaction materials used in the production of the polymer having an ether bond in the side chain in the present invention. Etc. are included.

The electrolyte material of the present invention may contain an organic solvent for improving plasticity, coating properties and flame retardancy. Examples of the organic solvent include the following general formula (3);
M (= O) _m (OR ⁹ ) ₃ (3)
(In the formula, R ⁹ represents any one of a hydrocarbon group having 1 to 18 carbon atoms and an alkylene carbonate group having a linear, branched or cyclic structure. M represents any element of Al, B and P. When M is Al, m = 0 and becomes an aluminate ester, when M is B, m = 0 and becomes a borate ester, and when M is P, m = 1 and phosphoric acid A compound represented by an ester);

1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, crown ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1,4-dioxane, 1,3-dioxolane, 2,6-dimethyltetrahydrofuran, tetrahydropyran, triethylene Ethers such as glycol methyl ether and tetraethylene glycol dimethyl ether; chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate and methyl phenyl carbonate; ethylene carbonate, propylene carbonate, 2,3-dimethyl ethylene carbonate Cyclic carbonates such as butylene carbonate, vinylene carbonate, 2-vinylethylene carbonate; methyl formate, methyl acetate, methyl propionate, ethyl acetate, propyl acetate, Aliphatic carboxylic acid esters such as butyl acid and amyl acetate; Aromatic carboxylic acid esters such as methyl benzoate and ethyl benzoate; Cyclic carboxylic acid esters such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone Nitriles such as acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile and 2-methylglutaronitrile; aromatic nitriles such as benzonitrile and tolunitrile; N-methylformamide, N-ethylformamide, Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone, N-methylpyrrolidone, N-vinylpyrrolidone; dimethylsulfone, ethylmethylsulfone, diethylsulfone, sulfolane, 3-methylsulfolane Sulfur compounds such as 2,4-dimethylsulfolane, dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide; alcohols such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; nitromethane, 1,3-dimethyl -2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazolidinone, etc., and one or two of these More than seeds can be used. Among these, aluminate esters, borate esters, phosphate esters, carbonate esters, aliphatic esters, cyclic esters, ethers are preferred, and aluminate esters, borate esters, phosphate esters are preferred. , Carbonic acid esters, and cyclic esters such as γ-butyrolactone and γ-valerolactone are more preferable.
When the electrolyte material of this invention contains a solvent, it is preferable that the content is 1-500 mass% with respect to 100 mass% of electrolyte components. More preferably, it is 1-100 mass%.

The electrolyte material preferably has a viscosity at 25 ° C. of 100 to 100,000 cps (0.1 to 100 Pa · s). When the viscosity is in such a range, the binder ability and the workability for preparing the coating film are improved. More preferably, it is 300-50000 cps (0.3-50 Pa.s).
The viscosity of the electrolyte material can be measured by, for example, a commercially available B-type viscometer or E-type viscometer.

The electrolyte material preferably has an ionic conductivity at 25 ° C. of 10 ⁻⁶ S / cm or more. More preferably, it is 10 ⁻⁵ S / cm or more, and further preferably 3 × 10 ⁻⁵ S / cm or more.

As described above, the electrolyte material of the present invention exhibits excellent characteristics as an electrolyte, and can be suitably used as an electrolyte constituting a secondary battery. In particular, not only at room temperature, but also polyethylene glycol, which is currently widely studied as an electrolyte for secondary batteries, can exhibit good performance even in a low temperature region where good battery performance cannot be exhibited. . Therefore, when the electrolyte material of the present invention is used in a low temperature region, its superiority becomes remarkable. That is, it is also one of the preferred embodiments of the present invention that the operating temperature region of the electrolyte material includes 0 to 30 ° C.
The electrolyte material of the present invention exhibits excellent ionic conductivity even in a wide temperature range outside the operating temperature range of 0 to 30 ° C., and can be used.

In addition to the electrolyte, the electrolyte material of the present invention can also be suitably used as various battery materials such as a conductive additive, a positive electrode binder, a negative electrode binder, and an inorganic solid electrolyte binder. It is also a battery material. A secondary battery configured using such a battery material of the present invention is also one aspect of the present invention.

The secondary battery is mainly composed of a positive electrode, an electrolyte, and a negative electrode. As the positive electrode in the secondary battery, a slurry made of a positive electrode material including a solvent, a positive electrode active material, a conductive additive, and a binder as necessary. What is obtained by coating and drying the substrate on a substrate can be used. Moreover, what is obtained by apply | coating and drying the slurry which consists of a negative electrode material containing a solvent, a negative electrode active material, a conductive support agent, and a binder as needed as a negative electrode can be used.
Among these, the secondary battery using the electrolyte material of the present invention as at least one of an electrolyte, a conductive additive, and a binder is the secondary battery of the present invention.

As the positive electrode active material, lithium-manganese composite oxide, lithium cobaltate, vanadium pentoxide, a compound having an olivine structure, polyacetylene, polypyrene, polyaniline, polyphenylene, polyphenylene sulfide, polyphenylene oxide, polypyrrole, polyfuran, polyazulene, etc. are used. be able to.
The compound having an olivine structure is the following general formula (4);
_{Li x A y D z PO 4} (4)
(In the formula, A is one or more selected from the group consisting of Cr, Mn, Fe, Co, Ni and Cu, and D is Mg, Ca, Sr, Ba, Ti, Zn, B, It is one or more selected from the group consisting of Al, Ga, In, Si, Ge, Sc, Y and rare earth elements, where x, y and z are 0 <x <2, 0 <y <1.5. And a number satisfying 0 ≦ z ≦ 1.5.). When such a positive electrode active material is used, an oxygen atom in the structure is bonded to phosphorus to form a (PO ₄ ) ³ -polyanion, and in principle, oxygen is immobilized in the crystal structure. Since the combustion reaction does not occur and the safety is excellent, it is preferable in consideration of the use for a medium-sized and large-scale power source. The component A is preferably Fe, Mn, or Ni, and particularly preferably Fe. The D component is preferably Mg, Ca, Ti, or Al.
Specific examples of these compounds having an olivine structure include lithium iron phosphate and lithium manganese phosphate, and the positive electrode active material preferably contains these compounds. More preferred is carbon-coated lithium iron phosphate. Lithium iron phosphate has high safety and stability against overcharge, and is inexpensive because it uses abundant resources such as iron and phosphorus, and is also preferable in terms of manufacturing cost.
The proportion of the positive electrode active material containing the compound having an olivine structure is preferably 70% by mass or more of the compound having an olivine structure with respect to 100% by mass of the entire positive electrode active material. More preferably, it is 90 mass% or more, and most preferably, the positive electrode active material is composed of only a compound having an olivine structure.
As described above, it is one of the preferred embodiments of the present invention that the secondary battery is configured using the lithium salt of olivine-type iron phosphate as the positive electrode active material.

As the conductive aid, in addition to the battery material of the present invention, conductive carbon is mainly used. Examples of the conductive carbon include carbon black, fiber carbon, and graphite. Among these, the battery material of the present invention, ketjen black, acetylene black, graphite and the like are preferable.

As the solvent, an aromatic hydrocarbon compound such as toluene or a polar compound containing no active hydrogen such as acetonitrile, acetone, or tetrahydrofuran can be used.
It is preferable that content of the solvent in the said positive electrode material is 50-300 mass% with respect to 100 mass% of positive electrode active materials. When the content of the solvent is within this range, a slurry having an appropriate viscosity can be produced. More preferably, it is 70-200 mass%.

The positive electrode material preferably further uses a dispersant. When a dispersant is used, the dispersant is not particularly limited, and various dispersants such as an anionic, nonionic or cationic surfactant, or a polymer dispersant can be used. A more stable conductivity of the positive electrode film can be achieved by promoting the formation of fine particles of the positive electrode active material and the conductive auxiliary agent and improving the dispersibility.
It is preferable that content of a dispersing agent is 5-20 mass% with respect to 100 mass% of conductive support agents. When the content of the dispersant is in such a range, the positive electrode active material and the conductive additive can be sufficiently uniformly dispersed. More preferably, it is 6-15 mass% with respect to 100 mass% of conductive support agents.

As the negative electrode active material, those generally used as a negative electrode active material can be used. In the case of a lithium ion battery, carbon obtained by firing a polymer, organic matter, pitch, etc., or vapor grown carbon Graphite materials such as natural graphite and artificial graphite, graphite, coke, Li metal, or at least one selected from Al, Si, Ge, Sn, Pb, In, Zn and Ti, or an alloy containing each element, or An oxide containing each element, a material capable of reversibly occluding and releasing lithium, such as lithium titanate, and the like can be used.
As the conductive additive, solvent, and dispersant contained in the negative electrode material, the same materials as those described above can be used.

As the electrolyte, in addition to the battery material of the present invention, an organic electrolytic solution (consisting of an electrolyte salt and an organic solvent), a polymer solid electrolyte, an inorganic solid electrolyte, a molten salt, and the like can be used in combination. Among these, it is preferable to use the battery material of the present invention.

The electrode composition can further contain a binder. As the binder, in addition to the electrode binder of the present invention, a modified polymer obtained by introducing a functional group such as a carboxyl group into a hydrogenated diene polymer, a fluorine-containing polymer, and a functional group such as a carboxyl group An aqueous dispersion of a composite polymer obtained by combining an acrylic polymer can be used in combination. Among these, it is preferable to use the binder for electrodes of the present invention.

The electrolyte material of the present invention has the above-described configuration, and not only exhibits excellent ion conductivity at room temperature, but also exhibits good ion conductivity even in a low temperature region below room temperature, and has excellent mechanical strength. Furthermore, the charge / discharge characteristics of the battery can be made excellent. In addition to the electrolyte of a battery such as a lithium ion battery, it is an electrolyte material that can be suitably used as a conductive additive or an electrode binder.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

The measurement was performed under the following conditions.
(Weight average molecular weight)
It determined by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120
Molecular weight columns: G5000HXL and GMHXL-L (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran calibration curve standard material: Polystyrene Measuring method: Solid content of measurement object in eluent is 0.3 mass % Dissolved and filtered through a filter.

(Water retention rate)
A support specimen having a square of 50 mm on one side was weighed and designated as M1. Next, the test piece was immersed in a container containing ion exchange water maintained at 25 ± 2 ° C. After 10 minutes, remove the test piece from the water, leave it for 1 minute at a temperature of 25 ± 2 ° C and a humidity of 65 ± 20%, remove excess water droplets adhering to the surface with dry filter paper, and weigh it. Was M2, and the water retention rate was determined by the following equation.
Water retention rate (%) = (M2-M1) / M1 × 100

(Ionic conductivity)
The ionic conductivity of the prepared electrolyte membrane was measured by the following method.
A sample (electrolyte membrane) was sandwiched between SUS electrodes having an electrode area of 12φ, and the resistance was measured by an AC impedance method (0.1 V, frequency 10 Hz to 10 MHz) to calculate ion conductivity. The measurement device used was an impedance analyzer SI1260 (manufactured by Solartron), and the following measurement cell was used.
A sample (electrolyte membrane) was sandwiched between SUS electrodes having an electrode area of 12φ, and the resistance was measured by an AC impedance method (0.1 V, frequency 10 Hz to 10 MHz) to calculate ion conductivity.

[Manufacture of monomers]
(Synthesis Example 1)
A 1 liter SUS autoclave reaction vessel equipped with a thermometer, stirrer, raw material introduction tube and nitrogen introduction tube was charged with 277 parts of diethylene glycol monovinyl ether and 4.1 parts of sodium hydroxide as an addition reaction catalyst. Was replaced with nitrogen, and the temperature was raised to 100 ° C. Next, 735 parts of ethylene oxide was introduced into the reactor over 4 hours while maintaining 100 ° C. under a safe pressure, and after completion of the introduction, aging was performed at an internal temperature of 100 ° C. for 0.5 hours. The total amount of ethylene oxide reacted, and the resulting reaction product was decaethylene glycol vinyl ether in which an average of 10 moles of ethylene oxide was added to vinyl alcohol.
Subsequently, 500 parts of the resulting decaethylene glycol vinyl ether and 80 parts of sodium hydroxide were charged into a 1 liter flask equipped with a stirrer, a dropping funnel, a thermometer, a cooling pipe and a nitrogen gas inlet. The temperature was raised to 40 ° C. with stirring in a nitrogen atmosphere, and then 287 parts of methyl iodide was slowly added dropwise while maintaining the internal temperature at 40 ° C. or lower. After completion of the dropwise addition, the mixture was aged for 5 hours and distilled under reduced pressure to remove unreacted methyl iodide. Furthermore, in order to remove excess sodium hydroxide and water and sodium iodide produced after the reaction, adsorption treatment with an adsorbent was carried out to obtain decaethylene glycol methyl vinyl ether.
The purity of the decaethylene glycol methyl vinyl ether thus obtained was 99% or more, and the yield based on diethylene glycol monovinyl ether used as a raw material was about 40%.

[Production of polymer]
(Synthesis Example 2)
150 parts of butyl acetate and 40 parts of decaethylene glycol methyl vinyl ether were charged into a 0.5 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet. The reaction solution was cooled to −5 ° C. by stirring for 10 minutes while cooling in an acetone-dry ice bath. As a polymerization initiator, a mixture of 0.01 part of picrylsulfonic acid and 1 part of butyl acetate was put into the flask, and the temperature was raised by self-heating. After 15 minutes, since no increase in the liquid temperature was observed, 0.04 part of triethylamine was added for neutralization, and then a solution having a polymer non-volatile content of 21.0% was obtained. The weight average molecular weight of the obtained polymer was 11,000. After concentrating the polymer solution with a rotary evaporator, the volatile component was removed with a vacuum dryer to obtain a polymer.

[Manufacture of electrolyte membrane]
(Production Example 1)
In a 0.5 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 150 parts of butyl acetate, 40 parts of decaethylene glycol methyl vinyl ether, 0.3 part of vinyloxyethoxyethyl acrylate Was charged. The reaction solution was cooled to −5 ° C. by stirring for 10 minutes while cooling in an acetone-dry ice bath. As a polymerization initiator, a mixture of 0.01 part of picrylsulfonic acid and 1 part of butyl acetate was put into the flask, and the temperature was raised by self-heating. After 15 minutes, since no increase in the liquid temperature was observed, 0.04 part of triethylamine was added for neutralization, and then a solution having a polymer non-volatile content of 21.0% was obtained. The weight average molecular weight of the obtained polymer was 12,000. After concentrating the polymer solution with a rotary evaporator, volatile components were removed with a vacuum dryer, and 10 parts of the resulting polymer was added with 2.5 parts of LiTFSI (lithium bistrifluoromethanesulfonylimide) and a radical photopolymerization initiator KTO46. 0.05 part (made by DKSH Japan) was dissolved and the mixture was obtained. The obtained mixture solution was applied and impregnated on a PET non-woven fabric A (Nippon Paper Papillia Co., Ltd., film thickness: 10 μm) as a support using an applicator 6 mil on a Teflon (registered trademark) sheet. The coating film is irradiated with UV (UV irradiator: manufactured by Ushio Inc., light source device URM-100 for printing, UV irradiation conditions: (output) 450 W, (irradiation time) 80 seconds), and a thickness of 98 μm made of a polymer composition An electrolyte membrane (1) of (film thickness of electrolyte including support) was obtained. In addition, the water retention of PET nonwoven fabric A was 701%.

(Production Examples 2 to 6)
In Production Example 1, an electrolyte membrane (in the same manner as in Production Example 1 except that the applicator used, the material of the support, the thickness of the support, and the thickness of the electrolyte membrane are as shown in Table 1). 2) to (6) were obtained. Table 1 also shows the measurement results of the water retention rate of each support.

(Production Example 7)
In a 0.3 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 50 parts of butyl acetate, 12.8 parts of decaethylene glycol methyl vinyl ether, 0. 25 parts were charged. The reaction solution was cooled to −5 ° C. by stirring for 10 minutes while cooling in an acetone-dry ice bath. As a polymerization initiator, a mixture of 0.001 part of picrylsulfonic acid and 1 part of ethyl acetate was put into the flask, and the temperature was raised by self-heating. After 15 minutes, since no increase in the liquid temperature was observed, 0.03 part of triethylamine was added for neutralization, and then a solution having a polymer non-volatile content of 20.5% was obtained. The weight average molecular weight of the obtained polymer was 10,000. After concentrating the polymer solution with a rotary evaporator, volatile components were removed with a vacuum dryer, and 10 parts of the resulting polymer was added with 2.5 parts of LiTFSI (lithium bistrifluoromethanesulfonylimide) and a radical photopolymerization initiator KTO46. 0.05 part (made by DKSH Japan) was dissolved and the mixture was obtained. The obtained mixture solution was applied and impregnated on a PET non-woven fabric A (Nippon Paper Papillia Co., Ltd., film thickness: 10 μm) using a 2 mil applicator on a Teflon (registered trademark) sheet. The coating film is irradiated with UV (UV irradiation machine: Ushio Electric Co., Ltd., light source device URM-100 for printing, UV irradiation conditions: (output) 450 W, (irradiation time) 80 seconds), and 50 μm thick composed of a polymer composition An electrolyte membrane (7) of (film thickness of electrolyte including support) was obtained.

(Production Example 8)
In Production Example 7, the same procedure as in Production Example 7 was used except that the applicator used, the material of the support, the thickness of the support, and the thickness of the electrolyte membrane were as shown in Table 1. 8) was obtained.

(Examples 1-8)
Preparation of positive electrode 0.09 part of LiTFSI, 0.04 part of acetylene black, 0.85 part of lithium iron phosphate, 0.42 part of the polymer obtained in Synthesis Example 2 and 1.2 part of acetonitrile were charged in a sealed container. The slurry of the positive electrode composition obtained by mixing and dispersing with a mixer was applied on an aluminum current collector with 10 mil of applicator. Subsequently, it dried at 60 degreeC * 30 minutes with the vacuum dryer, and produced the positive electrode sheet.

Cell assembly The positive electrode sheet, the electrolyte membrane prepared in Production Examples 1 to 8, and the metal Li foil were punched out with a punch. Here, for the positive electrode film, the weight of the current collector with the cathode was measured with a precision balance.
Lamination is done in the order of Li foil / electrolyte membrane / positive electrode sheet, taking care not to allow air to enter between the layers, and after placing the laminate in the coin battery, it is caulked with a caulking machine while crimping with a spring. The lithium ion batteries of Examples 1 to 8 were produced.

Battery evaluation 1 (initial discharge capacity evaluation)
About Battery of Examples 1-8 produced, using Battery Labo System [BS2501 Series] (manufactured by Instrument Center Co., Ltd.) at 60 ° C. or 30 ° C., charge / discharge rate up to 3.7 V up to 1 / 24C Table 1 shows the results of measuring the initial discharge capacity at the first cycle of the electrolyte membrane using the support after charging and discharging to 2.5V.

Battery evaluation 2 (cycle characteristics evaluation)
The batteries of Examples 1 to 8 were subjected to charge / discharge cycle tests under the evaluation conditions (temperature and charge / discharge rate) shown in Table 2. The results are shown in Table 2.

(Comparative Example 1)
In the above production example 1, without applying the polymer mixture solution to the support, it was applied on a Teflon (registered trademark) sheet with an applicator 2 mil, and the coating film was irradiated with UV (UV irradiation machine: manufactured by USHIO INC.) A 50 μm-thick electrolyte membrane made of a polymer composition was produced. (Lighting device URM-100 for printing, UV irradiation conditions: (output) 450 W, (irradiation time) 80 seconds)). The electrolyte membrane was peeled from the Teflon (registered trademark) sheet and an attempt was made to make a battery in the same manner as in Example 1. However, the strength of the electrolyte membrane was weak and it was difficult to mount it on the battery.

(Comparative Example 2)
In the above production example 1, instead of impregnating the support with the polymer mixture solution, the polymer mixture solution was directly applied on the positive electrode sheet prepared in Example 1 with an applicator 2 mil, and the coating film was irradiated with UV. (UV irradiation machine: manufactured by Ushio Electric Co., Ltd., light source device URM-100 for printing, UV irradiation conditions: (output) 450 W, (irradiation time) 80 seconds), a 50 μm-thick electrolyte membrane made of a polymer composition on the electrode The composite positive electrode sheet was produced. The composite positive electrode sheet and the metal Li foil were punched out with a punch, and a battery was produced in the same manner as in Example 1. However, a short circuit occurred and battery evaluation was impossible.

(Examples 9 to 15)
About electrolyte membrane (2)-(8) obtained in the said manufacture examples 2-8, temperature was changed and ion conductivity was measured. The results are shown in Table 3.

The following was found from the results of the examples and comparative examples.
The polymer obtained from the monomer component containing the monomer represented by the general formula (1) of the present invention, the electrolyte material containing the electrolyte salt and the support has sufficient mechanical strength to withstand mounting on a battery. In addition, the lithium ion battery produced using the electrolyte material exhibits good ion conductivity in a wide temperature range from a low temperature of −20 ° C. to a high temperature range of 60 ° C. It was confirmed that it exhibited excellent charge / discharge characteristics.
Note that, in the above-mentioned examples, there are shown examples in which an electrolyte material containing a specific polymer is evaluated. However, the electrolyte material of the present invention exhibits excellent ion conductivity in a wide temperature range, and The mechanism in which the battery using the electrolyte material exhibits excellent charge / discharge characteristics in a wide temperature range is a polymer obtained from the monomer component containing the monomer represented by the general formula (1) of the present invention. Since all are the same, from the results of the above-described embodiments, the present invention can be applied in various technical forms of the present invention and in various forms disclosed in the present specification, and exhibit advantageous effects. Can be said.

Claims (9)

An electrolyte material containing a polymer having an ether bond in the side chain and an electrolyte salt as essential components,
The polymer has the following general formula (1);

(In the formula, R ¹ represents a hydrogen atom or a methyl group. X represents a methylene group or a direct bond. R ^a is the same or different and is a carbon atom having a linear or branched chain having 1 to 4 carbon atoms. R ² represents a hydrocarbon group having 1 to 18 carbon atoms having a linear, branched or cyclic structure, and n represents the average number of moles added of the group represented by R ^a O. ) And a monomer component containing a vinyl ether group-containing (meth) acrylic acid ester, having a crosslinkable functional group in the molecule, and reacting the crosslinkable functional group Including a cross-linked polymer obtained by
The electrolyte material further comprises a support for supporting the polymer and / or the electrolyte salt. The electrolyte salt is R ³ SO ₂ N ^— SO ₂ R ⁴ (R ³ and R ⁴ are the same or different and each represents F, CF ₃ , C ₂ F ₅ ), PF ₆ ⁻ , BF. _{^{4 -, CF 3 SO 3 -}} , [B (CN) 4-m (R 5) m] - ( wherein, ^{R 5} is independently hydrogen atom, an organic substituent of a halogen atom or atoms of 1 to 30 And m represents an integer of 0 to 3. The ionic compound comprises at least one anion selected from the group consisting of an alkali metal cation and an ionic compound. Electrolyte material. The said support body consists of at least 1 sort (s) selected from the group which consists of a woven fabric, a nonwoven fabric, a porous membrane, and a glass molded object, The thickness is 1-200 micrometers, It is characterized by the above-mentioned. 2. The electrolyte material according to 2. The electrolyte material according to any one of claims 1 to 3, wherein the polymer and the electrolyte salt are impregnated and held on the support. The electrolyte material according to any one of claims 1 to 4 , wherein n representing the average number of added moles of the group represented by R ^a O in the general formula (1) is 1 to 50. The electrolyte material, the electrolyte material according to any one of claims 1 to 5, operating temperature range, characterized in that it comprises a 0 to 30 ° C.. The battery material using the electrolyte material in any one of Claims 1-6 . A secondary battery comprising the battery material according to claim 7 . The secondary battery according to claim 8 , comprising a olivine-type iron phosphate lithium salt as the positive electrode active material.