JP2001035251A - High polymer solid electrolyte and electrochemical element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high polymer solid electrolyte having high ion conductivity, excellent uniformity and sufficient solid strength for use as a solid electrolyte for an electrochemical element, and provide a electrochemical element using it. SOLUTION: This high polymer solid electrolyte is composed of a matrix component (A) of a cross-linking high polymer and electrolyte salt (B) and is produced by polymerizing reaction of the matrix component (A). The high polymer solid electrolyte contains at least urethane (metha-)acrylate compound (A1) as the matrix component (A), and is used in this electrochemical element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel solid polymer electrolyte, and more particularly to a solid polymer electrolyte having high ionic conductivity and little change with time, and an electrochemical device using the same, particularly a secondary battery. Things.

[0002]

2. Description of the Related Art In recent years, there has been remarkable progress in making electronic devices smaller, lighter, and thinner. Particularly in the OA field, the size and weight of electronic devices have been reduced from desktop types to laptop types and notebook types. In addition, the field of new small electronic devices such as electronic notebooks and electronic still cameras has emerged, and in addition to the miniaturization of conventional hard disks and floppy disks, the development of memory cards, which are new small memories, has been promoted. I have. In the wave of downsizing, lightening, and thinning of such electronic devices, secondary batteries supporting these electric powers are also required to have high performance such as high energy density, high voltage, and high output.

In response to such demands, development of a sheet-type secondary battery using a polymer solid electrolyte as an electrolyte as a thin, high-energy-density battery has been advanced, and a secondary battery using a polymer solid electrolyte has been developed. , High reliability because there is no liquid leakage,
It has many features not found in conventional cylindrical and prismatic batteries, such as being freely shaped, large area, and extremely thin. However, secondary batteries using solid polymer electrolytes have not yet been put to practical use, and one of the major factors is that
Since the interface resistance between the electrode and the polymer solid electrolyte is higher than the resistance of the electrode and the polymer solid electrolyte bulk, the internal impedance is higher than that of a normal secondary battery using an electrolyte,
It has been pointed out that charging and discharging with a large current is difficult, and that the interface resistance increases with time.

For the purpose of reducing the interface resistance, for example, Japanese Patent Application Laid-Open No. 5-290615 proposes a method of depositing a solid polymer electrolyte on an electrode by a cluster ion beam method. The prepared polymer solid electrolyte had an ionic conductivity of at least two orders of magnitude lower than that of the electrolytic solution, and had low productivity. In addition, Japanese Unexamined Patent Publication
No. 15199 proposes that an electrolyte be contained in the electrode and that it be bonded to a solid polymer electrolyte.
Since the electrolyte contained in the electrodes was absorbed by the solid polymer electrolyte, the interface resistance increased with the passage of time.

Further, Japanese Patent Application Laid-Open No. 63-94501 proposes a solid polymer electrolyte obtained by curing a composition comprising an acryloyl-modified polyalkylene oxide, an electrolyte salt and a solvent by irradiating the composition with ultraviolet rays. Since this polymer solid electrolyte has a high ionic conductivity and the precursor before irradiation with ultraviolet rays is a liquid, if this precursor is cast on an electrode and irradiated with ultraviolet rays to produce a polymer solid electrolyte, It was expected that an interface close to the state between the electrolyte and the electrode could be produced. However, the interface resistance between the polymer solid electrolyte and the electrode is higher than expected, and tends to increase with time, and the strength of the polymer solid electrolyte is low, so that the manufactured electrochemical element is satisfactory. It was not performance.

In order to reduce the interfacial resistance and improve the ionic conductivity, Japanese Patent Application Laid-Open No. 9-235479 discloses a polymer solid electrolyte comprising an electrolyte salt and a cross-linked polymer. It has been proposed to use a composite of a type polymer, and further, in Japanese Patent Application Laid-Open No. 10-218913, an unreacted polymerizable monomer and a polymer solid electrolyte comprising an electrolyte salt and a polymerizable monomer and / or a polymerizable oligomer are disclosed. Or 30% by weight of polymerizable oligomer
The following is proposed, and a photopolymerizable monomer polymerized by actinic light is disclosed as a polymerizable monomer.

[0007]

However, in consideration of the recent advancement of technology, the above-mentioned Japanese Patent Application Laid-Open No. 9-23547 has been proposed.
No. 9 and Japanese Patent Application Laid-Open No. 10-218913 are not yet satisfactory, and further improvements such as ionic conductivity and solid strength sufficient for use as a solid electrolyte for electrochemical devices are desired. In addition, there are concerns about problems such as leakage of the electrolyte solution and leakage due to deformation due to external stress. Under such circumstances, the present invention has a high ionic conductivity, excellent uniformity, and a solid strength sufficient for use as a solid electrolyte for electrochemical devices without causing electrolyte leakage or the like under such a background. It is an object of the present invention to provide a molecular solid electrolyte and an electrochemical device using the same, particularly a secondary battery.

[0008]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, have found that a matrix component (A) of a crosslinked type polymer and an electrolyte salt (B) are used. In the solid polymer electrolyte produced by the polymerization reaction of (A), the matrix component (A)
As a result, the present inventors have found that a solid polymer electrolyte containing at least a urethane (meth) acrylate compound (A1) satisfies the above object and completed the present invention.

In the present invention, it is preferable that a mixture comprising a matrix component (A) of a crosslinked type polymer and an electrolyte salt (B) is irradiated with actinic rays to obtain a solid polymer electrolyte. Further, a urethane acrylate compound (A1)
Is preferably a urethane (meth) acrylate obtained by reacting a polyol, a polyisocyanate and a hydroxy (meth) acrylate, and particularly, the polyol has a molecular weight of 200 to 6000, and is a polyethylene oxide, a polypropylene oxide, an ethylene oxide / It is preferably a polyether polyol having at least one structure of a block of propylene oxide or a random copolymer. Further, in the present invention, the photopolymerization initiator (C) is used as a matrix component (A) of a crosslinked type polymer.
When the content is 0.5% by weight or more based on the whole, the effect of the present invention is remarkably exhibited.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The solid polymer electrolyte of the present invention is a solid polymer electrolyte made of a matrix component (A) of a crosslinked polymer and an electrolyte salt (B), and crosslinked by a polymerization reaction of the matrix component (A). Also, a cross-linked polymer and an electrolyte salt (B)
A non-aqueous solvent is added to the resulting polymer solid electrolyte gel, which has the ionic conductivity comparable to that of the electrolytic solution, and is therefore most preferable for manufacturing an electrochemical device having a low internal resistance. There is no problem if the polymer solid electrolyte of the present invention is used alone in an electrochemical device, but it may be used in combination with a separator in order to completely prevent a short circuit.

As the matrix component (A) of the crosslinked polymer, it is necessary to use at least a urethane (meth) acrylate compound (A1). Such a urethane (meth) acrylate compound (A1) is particularly preferable. Although not limited, urethane (meth) acrylate obtained by reacting polyol, polyisocyanate and hydroxy (meth) acrylate is preferable.

The polyol is not particularly limited and includes, for example, ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated Bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, polyhydric alcohols such as glycerin, polyglycerin, diethylene glycol, triethylene glycol, tetraethylene glycol , Dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene Polyether polyol having at least one structure of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymer, and polyhydric alcohol or polyether polyol, maleic anhydride, maleic acid, etc. , Fumaric acid, itaconic anhydride, itaconic acid, adipic acid, polycondensates with polybasic acids such as isophthalic acid, polyester polyols, caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, polyolefin polyols, hydrogenated polybutadiene polyols Polybutadiene-based polyols and the like, among others, among others,
Molecular weight of 200-6000, preferably 500-500
0, more preferably 800 to 4000, and a polyether polyol having at least one structure of polyethylene oxide, polypropylene oxide, a block of ethylene oxide / propylene oxide or a random copolymer. If the molecular weight is less than 200, the obtained cured product of the urethane (meth) acrylate compound (A1) is brittle and does not show elongation, so that it cannot follow deformation due to stress and is likely to cause cracking or chipping. The curability of the obtained urethane (meth) acrylate compound (A1) becomes poor, and it becomes difficult to maintain the outer shape of the cured product, which is not preferable.

The polyisocyanate is not particularly restricted but includes, for example, aromatic, aliphatic, cycloaliphatic and alicyclic polyisocyanates. Among them, tolylene diisocyanate (TDI), Diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), tetramethylxylylene diisocyanate (m-TMXDI), isophorone diisocyanate ( PDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI) polyisocyanate or trimer compounds of these polyisocyanates, such as,
Reaction products of these polyisocyanates and polyols are preferably used.

Further, the hydroxy (meth) acrylate is not particularly restricted but includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, -Hydroxyethylacryloyl phosphate, 4-butylhydroxy (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, caprolactone-modified 2- Hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include dipentaerythritol penta (meth) acrylate, and among them, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferably used.

The method for producing the urethane (meth) acrylate is not particularly limited as long as it is a method of reacting a polyol, a polyisocyanate, and hydroxy (meth) acrylate, and a known method is employed. For example,
A method in which three components of polyol, polyisocyanate and hydroxy (meth) acrylate are mixed and reacted at once, and a polyol and polyisocyanate are reacted to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule. And reacting the intermediate with hydroxy (meth) acrylate to form a urethane (meth) acrylate intermediate containing one or more isocyanate groups per molecule by reacting polyisocyanate with hydroxy (meth) acrylate. Later, a method of reacting the intermediate with a polyol may be used. In the above reaction, it is also preferable to use a catalyst such as dibutyltin dilaurate for the purpose of accelerating the reaction.

In the present invention, the urethane (meth) acrylate compound (A1) is preferably contained in an amount of 5% by weight or more, more preferably 10% by weight, based on the whole matrix component (A) of the crosslinked polymer. The content is particularly preferably 15% by weight or more. If the content is less than 15% by weight, the gel-like substance obtained by the cross-linking reaction with active energy rays is brittle, and does not follow deformation due to stress, which is not preferable.

Further, in the present invention, as the matrix component (A) of the crosslinked polymer, one or more ethylenically unsaturated groups are present in one molecule in addition to the urethane (meth) acrylate compound (A1). A monomer (A2) may be contained.

The monomer (A2) having one or more ethylenically unsaturated groups in one molecule includes, for example, 2
Monofunctional monomers such as -hydroxyethyl (meth) acrylate, 2-vinylpyrrolidone, acryloyl morpholine, and 2-hydroxybutyl vinyl ether; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A type di (Meth) acrylate, propylene oxide-modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxy Bifunctional monomers such as pivalic acid-modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Trifunctional such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate Examples include the above monomers.

Other (meth) acrylates include, for example, methylethylene glycol (meth) acrylate, ethylethylene glycol (meth) acrylate, propylethylene glycol (meth) acrylate, phenylethylene glycol (meth) acrylate, ethoxydiethylene glycol ( Alkyl ethylene glycols such as meth) acrylate, methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxytetraethylene glycol (meth) acrylate; Ethyl propylene glycol (meth) acrylate, butyl propylene glycol (meth) acrylate Alkyl propylene glycol (meth) acrylates such as methoxy dipropylene glycol (meth) acrylate it may also be mentioned. Among them, ethoxydiethylene glycol (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and the like are particularly preferably used.

The electrolyte salt (B) used in the present invention includes:
There is no particular limitation as long as it is used as a normal electrolyte.
No, but for example, LiBR_Four(R is a phenyl group, alkyl
Group), LiPF₆, LiSbF₆, LiAsF₆, Li
BF_Four, LiCIO_Four, CF_ThreeSO_ThreeLi, (CF_ThreeSO_Two)
_TwoNLi, (CF_ThreeSO_Two)_ThreeCLi, C₆F₉SO_ThreeLi,
C₈F₁₇SO_ThreeLi, LiAlCl_Four, Lithium tetraki
[3,5-bis (trifluoromethyl) phenyl] bo
Rate or the like alone or as a mixture. Inside
Also CF_ThreeSO_ThreeLi, (CF_ThreeSO_Two)_TwoNLi, (CF_Three
SO_Two)_ThreeCLi, C ₆F₉SO_ThreeLi, C₈F_l7SO_ThreeLi
Sulfonic acid-based anion electrolytes are preferably used
You.

Furthermore, in the present invention, a non-aqueous electrolyte is prepared using a non-aqueous solvent.
Carbonate solvents (propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate), amide solvents (N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N-methylacetamide, N-ethylacetamide, N -Methylpyrrolilinone), lactone solvents (γ-butyl lactone, γ-valerolactone, 5
Valerolactone, 3-methyl-1,3 oxazolidin-2-one, etc.), alcohol solvents (ethylene glycol, propylene glycol, glycerin, methyl cellosolve, 1,2 butanediol, 1,3 butanediol,
1,4 butanediol, diglycerin, polyoxyalkylene glycol cyclohexanediol, xylene glycol, etc.), ether solvents (methylal, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy-2-methoxyethane, Alkoxylalkylene ethers, etc.), nitrile solvents (benzonitrile, acetonitrile, 3-methoxypropionitrile, etc.), phosphates and phosphate esters solvents (normal phosphoric acid, metaphosphoric acid, pyrophosphoric acid,
Polyphosphoric acid, phosphorous acid, trimethyl phosphate, etc.), 2-
Imidazolidinones (1,3-dimethyl-2-imidazolidinone etc.), pyrrolidones, sulfolane solvents (sulfolane, tetramethylene sulfolane), furan solvents (tetrahydrofuran, 2-methyltetrahydrofuran, 2,2
5-dimethoxytetrahydrofuran), dioxolane,
A single solvent of dioxane and dichloroethane or a mixture of two or more solvents can be used. Of these, carbonates, ethers and furan solvents are preferred.

The concentration of the electrolyte salt in the non-aqueous electrolyte is preferably from 1.0 to 7.0 mol / l, more preferably from 1.0 to 5.0 mol / l, in the non-aqueous solvent. It is. If the ratio is less than 1.0 mol / l, a solid electrolyte having a sufficient solid strength cannot be obtained, and if it exceeds 7.0 mol / l, it becomes difficult to dissolve the electrolyte salt, which is not preferable. The non-aqueous electrolyte is usually preferably 200% by weight or more, more preferably 400 to 900% by weight, particularly preferably 500 to 900% by weight, based on the whole matrix component (A) of the crosslinked type polymer.
800% by weight. If the proportion is less than 200% by weight, a sufficiently high ionic conductivity cannot be obtained, and if it exceeds 900% by weight, it is difficult to solidify the non-aqueous electrolyte, which is not preferable.

The solidification of the electrolytic solution according to the present invention can be carried out by injecting a non-aqueous electrolytic solution containing the matrix component (A) of the cross-linked polymer and the electrolyte salt (B) into a sealed container or a support (for example, Film, metal, metal oxide, glass, etc.)
And then polymerized by heat or actinic radiation. When polymerization is carried out by such heat, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, etc. Although a thermal polymerization initiator such as peroxydicarbonate is used, in the present invention, polymerization is preferably performed by irradiation with actinic rays, and usually, light, ultraviolet light, an electron beam,
It is irradiated with X-rays or the like.

When polymerizing by irradiation with actinic rays, the photopolymerization initiator (C) is used in an amount of 0.5% by weight or more, preferably 1.0 to 10% by weight, based on the whole matrix component (A) of the crosslinked polymer. %. When the photopolymerization initiator (C) is less than 0.5% by weight, the curing is insufficient and the uncured material is included, so that the shape stability is reduced, and
The internal resistance as an electrochemical element is also undesirably increased.

The photopolymerization initiator (C) is not particularly limited, and known photopolymerization initiators can be used.
For example, benzophenone, P, P'-bis (dimethylamino) benzophenone, P, P'-bis (diethylamino) benzophenone, P, P'-bis (dibutylamino) benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoylbenzoic acid, methyl benzoylbenzoate,
Benzyldiphenyldisulfide, benzyldimethylketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3′-dimethyl-4-methoxybenzophenone, dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2, 2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzosparone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1- Propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone, and further 2,4,6- [to Scan (trichloromethyl)] - 1,3,5-triazine, 2,4 [bis (trichloromethyl) - 6- (4'-methoxyphenyl)
-1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (4′-methoxynaphthyl) -1,
3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (piperonyl) -1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6
Triazine derivatives such as (4'-methoxystyryl) -1,3,5-triazine, acridine derivatives such as acridine and 9-phenylacridine, 2,2'-bis (o-
(Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-
(Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (o-
Fluorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,1′-biimidazole, 2,2′-bis (o
-Methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (p-methoxyphenyl) -4,5,4', 5'-tetra Phenyl-1,1′-biimidazole, 2,4
2 ', 4'-bis [bi (p-methoxyphenyl)]-
5,5′-diphenyl-1,1′-biimidazole,
2,2′-bis (2,4-dimethoxyphenyl) -4,
5,4 ′, 5′-diphenyl-1,1′-biimidazole, 2,2′-bis (p-methylthiophenyl) -4,
5,4 ', 5'-diphenyl-1,1'-biimidazole, bis (2,4,5-triphenyl) -1,1'-biimidazole and the like and disclosed in JP-B-45-37377. Hexaarylbiimidazole derivatives such as tautomers covalently bonded at 1,2′-, 1,4′- and 2,4′-, triphenylphosphine, and 2-
Benzoyl-2-dimethylamino-1- [4-morpholinophenyl] -butane and the like, and one or more of these are used.

Further, if necessary, a sensitizer, a storage stabilizer and the like are used in combination. Examples of the sensitizer include urea, nitrile compounds (N, N-disubstituted-P-aminobenzonitrile, etc.),
Phosphorus compounds (such as tri-n-butylphosphine) are preferred, and quaternary ammonium chloride, benzothiazole, and hydroquinone are preferred as storage stabilizers.

Thus, a polymer solid electrolyte comprising the matrix component (A) of the crosslinked type polymer and the electrolyte salt (B) and produced by the polymerization reaction of the matrix component (A) is obtained. The molecular solid electrolyte can reduce the interface resistance with the electrode without causing liquid leakage, etc., has high ionic conductivity, and has excellent solid strength, so that primary batteries, secondary batteries, sensors, electrochromic devices, It can be used for an electrochemical device utilizing an electrochemical reaction such as an electrochemical FET, and particularly when applied to a secondary battery, a great effect is exhibited.

The electrode used in the electrochemical device of the present invention is molded by using a binder and a conductive agent as required. Examples of the binder include, but are not limited to, organic fluoropolymers such as polytetrafluoroethylene and polyvinylidene fluoride, polyolefins such as polyethylene and polypropylene, and soluble conductive polymers such as polyaniline and polyalkylthiophene. . As a conductive agent, conductive carbon such as graphite, carbon black, acetylene black, ketchen black, nickel,
Metals or alloys such as copper, titanium, and stainless steel; conductive oxides such as titanium oxide and indium oxide; and conductive polymer materials such as polypyrrole, and the like. It can be improved and is preferable.

The secondary battery of the present invention basically comprises a positive electrode, a negative electrode and a solid polymer electrolyte, and may use a separator if necessary. As the separator, a separator having low resistance to ion migration of the electrolyte solution and having excellent solution retention properties is used, for example, polyester, polytetrafluoroethylene, polypropylene, polyethylene, polyvinyl alcohol, and ethylene-vinyl acetate. Nonwoven fabrics or woven fabrics selected from one or more materials such as saponified copolymers can be used to completely prevent short circuits. These are unnecessary when the polymer solid electrolyte of the present invention itself has a function as a separator.

As the positive electrode active material of the secondary battery of the present invention,
Examples thereof include an inorganic active material, an organic active material, and a composite thereof. However, an inorganic active material or a composite of an inorganic active material and an organic active material is preferable because the energy density is particularly increased.

As the inorganic active material, MnO_Two, Mn_TwoO
_Three, CoO_Two, NiO_Two, TiO_Two, V _TwoO_Five, V_ThreeO₈, Cr
_TwoO_Three, Fe_Two(SO_Four)_Three, Fe_Two(MoO_Two)_Three, Fe
_Two(WO_Two)_ThreeMetal oxides such as TiS_Two, MoS_Two, Fe
Metal sulfides such as S, complex acid of these compounds and lithium
Compounds. Polyacetylene as an organic active material
Polyaniline, polypyrrole, polythiophene,
Lialkylthiophene, polycarbazole, polyazure
Conductive polymers such as polystyrene, polydiphenylbenzine, carbon
One or more complexes selected from
You.

As the negative electrode active material of the secondary battery of the present invention,
Alkali metals such as lithium and sodium; alloys of lithium with metals such as aluminum, lead, silicon and magnesium; polypyridine, polyacetylene, polythiophene or conductive polymers capable of cation doping of these derivatives, and carbon bodies capable of storing lithium , SnO ₂ , T
Metal oxides such as iO ₂ are exemplified, and among them, carbon bodies are most preferable in terms of cycle life and energy density. Examples of carbon bodies include natural graphite, coal coke, and petroleum coke, as well as pyrolytic carbon made from organic compounds, natural polymers,
A carbon body obtained by calcining a synthetic polymer is exemplified. Although the form of the secondary battery of the present invention is not particularly limited, it can be mounted on various forms of batteries such as coins, sheets, cylinders, gums, and the like.

[0033]

The present invention will be specifically described below with reference to examples. In the examples, “%” and “part” mean on a weight basis unless otherwise specified.

Urethane (meth) acrylate compound
Production of (A1-1) After introducing dry air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, isophorone diisocyanate (VEST, manufactured by Daicel Huls Co., Ltd.)
160 parts of ANAT IPDI), and 755 parts of ethylene oxide / propylene oxide block polyether polyol (manufactured by Asahi Denka Kogyo Co., Ltd., "CM-211", weight average molecular weight of about 2100).
-85 parts of hydroxyethyl acrylate, 0.4 parts of hydroquinone monomethyl ether, and dibutyltin dilaurate ("LIOI" manufactured by Tokyo Fine Chemical Co., Ltd.)
0.1 part of the mixed liquid was uniformly dropped over 3 hours to carry out a reaction. After the completion of the dropwise addition, the reaction was continued for about 5 hours. After the disappearance of the isocyanate was confirmed by the result of IR measurement, the reaction was terminated, and the urethane (meth) acrylate compound (A1-
1) (solid content: 99.8%, number average molecular weight: 30)
00).

Urethane (meth) acrylate compound
Production of (A1-2) After introducing dry air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, isophorone diisocyanate (VEST, manufactured by Daicel Huls Co., Ltd.)
ANAT IPDI ") 115 parts, ethylene oxide / propylene oxide block polyether polyol (manufactured by Asahi Denka Kogyo Co., Ltd.," AM-505 ", weight average molecular weight about 4800) 825 parts, and after heating to 70 ° C, 2 parts were added.
-60 parts of hydroxyethyl acrylate, 0.4 parts of hydroquinone monomethyl ether, and dibutyltin dilaurate ("LIOI" manufactured by Tokyo Fine Chemical Co., Ltd.)
0.1 part of the mixed liquid was uniformly dropped over 3 hours to carry out a reaction. After the completion of the dropwise addition, the reaction was continued for about 5 hours. After the disappearance of the isocyanate was confirmed by the result of IR measurement, the reaction was terminated, and the urethane (meth) acrylate compound (A1-
2) (solid content: 99.7%, number average molecular weight: 58)
00).

Urethane (meth) acrylate compounds
Production of (A1-3) After introducing dry air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, isophorone diisocyanate (VEST, manufactured by Daicel Huls Co., Ltd.)
ANAT IPDI ") 101 parts, 681 parts of ethylene oxide / propylene oxide random polyether polyol (" PR-3007 ", weight average molecular weight about 3000, manufactured by Asahi Denka Kogyo Co., Ltd.), and after heating to 70 ° C,
218 parts of pentaerythritol triacrylate (“Biscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.4 parts of hydroquinone monomethyl ether, and dibutyltin dilaurate (manufactured by Tokyo Fine Chemical Company, “LIO”
I ") 0.1 part of the mixed liquid was dripped uniformly over 3 hours,
The reaction was performed. After the completion of dropping, the reaction was continued for about 5 hours.
The disappearance of the isocyanate was confirmed by the result of IR measurement, and the reaction was terminated to obtain a urethane (meth) acrylate compound (A1-3) (solid content: 98.0%, number average molecular weight: 4400).

Urethane (meth) acrylate compounds
Production of (A1-4) After introducing dry air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, isophorone diisocyanate (“VEST” manufactured by Daicel Huls Co., Ltd.)
ANAT IPDI ") 61 parts, ethylene oxide /
857 parts of a propylene oxide block polyether polyol (manufactured by Asahi Denka Kogyo Co., Ltd., "PR-5007", weight average molecular weight of about 4700) was charged, the temperature was raised to 70 ° C., and pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry, Inc. 82 parts of Viscoat # 300, 0.4 parts of hydroquinone monomethyl ether, and dibutyltin dilaurate ("LIO", manufactured by Tokyo Fine Chemical Co., Ltd.)
I ") 0.1 part of the mixed liquid was dripped uniformly over 3 hours,
The reaction was performed. After the completion of dropping, the reaction was continued for about 5 hours.
The disappearance of the isocyanate was confirmed by the result of IR measurement, and the reaction was terminated to obtain a urethane (meth) acrylate compound (A1-4) (solid content: 98.0%, number average molecular weight: 11000).

Urethane (meth) acrylate compounds
Production of (A1-5) After introducing dry air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, isophorone diisocyanate (VEST, manufactured by Daicel Huls Co., Ltd.)
ANAT IPDI "), 137 parts, a polyester polyol composed of ethylene glycol / 1,4-butanediol / adipic acid (manufactured by Asahi Denka Kogyo KK," V14-9 ").
0 ", weight average molecular weight about 1800) 815 parts,
After the temperature was raised to 70 ° C, 2-hydroxyethyl acrylate 4
A mixed liquid of 8 parts, 0.4 part of hydroquinone monomethyl ether, and 0.1 part of dibutyltin dilaurate ("LIOI", manufactured by Tokyo Fine Chemical Co., Ltd.) was dropped uniformly over 3 hours to carry out a reaction. After completion of the dropping, the reaction was continued for about 5 hours, and the disappearance of the isocyanate was confirmed by the result of IR measurement. The reaction was terminated to obtain a urethane (meth) acrylate compound (A1-5) (solid content: 97. 0%,
Number average molecular weight: 4500).

Example 1 1.8 mol / l LiN (CF ₃ S) dissolved in a non-aqueous solvent consisting of propylene carbonate / ethylene carbonate / dimethyl carbonate (volume ratio = 2/5/3)
To 70 parts of an equivalent mixture (I) of an O ₂ ) ₂ solution and a 0.2 mol / l LiBF ₄ solution, 9 parts of ethoxydiethylene glycol acrylate as a monofunctional monomer and 2.5 parts of urethane (meth) acrylate (A1-1) 2.5 Parts, benzoin isopropyl ether (0.2 parts) as a photopolymerization initiator (C) was added, mixed and dissolved to prepare a photopolymerizable solution (a-1).

Then, the photopolymerizable solution (a-1) was placed in a cell for measuring ionic conductivity, and irradiated with a high-pressure mercury lamp equipped with a cold mirror condensing device to solidify the electrolytic solution. The ionic conductivity of the obtained solid polymer electrolyte was measured.
It was 1 × 10 ⁻³ s / cm, and the complex shear modulus was measured. As a result, it was 530 Pa, and sufficient solid strength was obtained.

Example 2 In Example 1, the urethane (meth) acrylate (A
1-1) is a urethane (meth) acrylate (A1-2)
Photopolymerizable solution (a-2) except that was changed to
Was prepared and solidified in the same manner as in Example 1 to obtain a solid polymer electrolyte. When the ionic conductivity of the obtained solid polymer electrolyte was measured, it was 1.9 × 10 ⁻³ s / cm.
When the complex shear modulus was measured, it was 950 Pa, and sufficient solid strength was obtained.

Example 3 In Example 1, the urethane (meth) acrylate (A
1-1) is a urethane (meth) acrylate (A1-3)
Photopolymerizable solution (a-3)
Was prepared and solidified in the same manner as in Example 1 to obtain a solid polymer electrolyte. When the ionic conductivity of the obtained solid polymer electrolyte was measured, it was 4.2 × 10 ⁻³ s / cm.
When the complex shear modulus was measured, it was 420 Pa, and sufficient solid strength was obtained.

Example 4 2 mol / l LiN (CF ₃ SO ₂ ) ₂ dissolved in a non-aqueous solvent consisting of propylene carbonate / ethylene carbonate / dimethyl carbonate (volume ratio = 2/5/3)
To 70 parts of the solution, 12 parts of ethoxydiethylene glycol acrylate as a monofunctional monomer, 3 parts of urethane (meth) acrylate (A1-4), and 0.2 part of benzoin isopropyl ether as a photopolymerization initiator (C) are added, mixed and dissolved. After preparing a photopolymerizable solution (a-4), the solidification was performed in the same manner as in Example 1 to obtain a polymer solid electrolyte.

When the ionic conductivity of the obtained solid polymer electrolyte was measured, it was 3.7 × 10 ⁻³ s / cm.
When the complex shear modulus was measured, it was 450 Pa and sufficient solid strength was obtained.

Example 5 In Example 1, the urethane acrylate (A1-1) was used.
Was changed to urethane acrylate (A1-5), and the photopolymerization initiator (C) was changed to benzoin ethyl ether in the same manner to prepare a photopolymerizable solution (a-5). To obtain a solid polymer electrolyte. When the ionic conductivity of the obtained polymer solid electrolyte was measured, it was 1.1 × 10 ⁻³ s / cm, and when the complex shear modulus was measured, it was 1200 Pa, indicating that sufficient solid strength was obtained. Was.

Comparative Example 1 In Example 1, the urethane (meth) acrylate (A
A photopolymerizable solution (a-6) was prepared and solidified in the same manner as in Example 1, except that 1-1) was changed to trimethylolpropane triacrylate, to obtain a solid polymer electrolyte. The ionic conductivity of the obtained polymer solid electrolyte was measured to be 6.8 × 10 ⁻⁴ s / cm, and the complex shear modulus was measured to be 3500 Pa. This was sufficient for solid strength,
The ionic conductivity was rather poor.

The ion conductivity was measured at a measurement temperature of 25.
At ℃, as a counter electrode, using a SUS cylindrical container (20 mm inner diameter) whose inner peripheral surface except for the bottom surface was covered with insulating tape,
This container was filled with a solid electrolyte, and a SUS cylindrical body having a diameter of 18 mm was pressed as a working electrode on the surface of the solid electrolyte (cell for measuring ion conductivity). The complex shear modulus is obtained from the following equation from the storage modulus (G ₁ ) and the loss modulus (G ₂ ). (TA Inst
The measurement was performed at a measurement temperature of 30 ° C. and a measurement frequency of 10 ⁻² to 1 (Hz) using AR-1000 manufactured by R.R. )

Example 6 Preparation of Electrochemical Element / Preparation of Positive Electrode 12 parts of polyaniline synthesized by chemical polymerization using sulfuric acid and ammonium persulfate as an oxidizing agent were dissolved in 60 parts of N-methylpyrrolidone, Vanadium oxide (average particle size: 2.5 μm) was added, and mixed and dispersed by a roll lamination method under an inert atmosphere to prepare a coating for a positive electrode. This was applied on a 20 μm aluminum electrolytic foil in the air using a wire bar, and dried at 100 ° C. for 15 minutes to produce a 30 μm-thick positive electrode.

Preparation of Negative Electrode Polyvinylidene Fluoride (Kureha Chemical KF-1000) 15
Was dissolved in 35 parts of N-methylpyrrolidone, and a solution obtained by adding 50 parts of natural graphite to the solution was mixed and dispersed under an inert atmosphere by a roll mill method to prepare a paint for a negative electrode. This was applied on a 20 μm copper foil with a wire bar in the air and dried at 80 ° C. for 20 minutes to produce an electrode having a thickness of 60 μm.

A photopolymerizable solution (I-
1) was permeated and irradiated with a high-pressure mercury lamp to solidify the electrolytic solution. The battery was fabricated by sealing the three sides while uniformly applying pressure to the power generating element, and sealing the remaining side under reduced pressure. The charge / discharge test was carried out using a Hokuto Denko HJ-201B charge / discharge measurement device at a current of 0.7 mA and a battery voltage of 0.
After charging for 1 hour, the battery voltage was discharged to 0.8 V at a current of 0.7 mA, and the charging and discharging were repeated. At this time, the discharge capacity at the initial stage and the 100th cycle was 12.6 mAh in the initial stage, and 1 after the 100th cycle.
It was 2.4 mAh. In addition, an electrochemical device having sufficient solid strength without short circuit was produced.

[0051]

According to the present invention, there is provided a polymer solid electrolyte comprising a crosslinked polymer matrix component (A) and an electrolyte salt (B), which is crosslinked by a polymerization reaction of the matrix component (A). Since it contains at least a urethane (meth) acrylate-based compound (A1) as the matrix component (A), it has high ionic conductivity and excellent uniformity without causing liquid leakage or the like, and is used as a solid electrolyte for electrochemical devices. Thus, a polymer solid electrolyte having a solid strength sufficient for the use of a polymer solid electrolyte can be obtained, and an electrochemical device using the polymer solid electrolyte, particularly a secondary battery, is very useful.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4J027 AC03 AC04 AC06 AE04 AG03 AG04 AG05 AG09 AG12 AG13 AG14 AG15 AG23 AG24 AG27 AJ01 AJ08 BA07 BA08 BA19 BA20 BA21 BA23 BA24 BA26 CA13 CA14 CA15 CA16 CB03 CB09 CB10 CC02 CC05 CC06 CC08 CD00 5G301 CA16 CA30 CD01 5H024 FF21 FF31 5H029 AJ02 AM02 AM07 AM16 EJ14

Claims (9)

[Claims] 1. A polymer solid electrolyte comprising a matrix component (A) of a crosslinked type polymer and an electrolyte salt (B) produced by a polymerization reaction of the matrix component (A), wherein the matrix component (A) A polymer solid electrolyte comprising at least a urethane (meth) acrylate compound (A1). 2. The polymer solid electrolyte according to claim 1, wherein the mixture comprising the matrix component (A) of the cross-linked polymer and the electrolyte salt (B) is irradiated with an actinic ray. 3. The composition according to claim 1, wherein the content of the urethane (meth) acrylate compound (A1) is at least 5% by weight based on the whole matrix component (A) of the crosslinked polymer. The solid polymer electrolyte according to the above. 4. The urethane (meth) acrylate compound according to claim 1, wherein the urethane (meth) acrylate compound (A1) is a urethane (meth) acrylate obtained by reacting a polyol, a polyisocyanate and a hydroxy (meth) acrylate.
4. The polymer solid electrolyte according to any one of claims 1 to 3. 5. A polyol having a molecular weight of 200 to 600.
5. The polymer solid electrolyte according to claim 4, which is a polyether polyol having a structure of at least one of polyethylene oxide, polypropylene oxide, an ethylene oxide / propylene oxide block or a random copolymer. 6. The cross-linkable polymer matrix component (A) further comprises a monomer (A2) having one or more ethylenically unsaturated groups in one molecule. 6. The solid polymer electrolyte according to any one of claims 5 to 5. 7. The method according to claim 1, wherein the photopolymerization initiator (C) is contained in an amount of 0.5% by weight or more based on the whole matrix component (A) of the crosslinked polymer. The solid polymer electrolyte according to any one of the above. 8. An electrochemical device comprising the polymer solid electrolyte according to claim 1 as a constituent element. 9. A secondary battery comprising the polymer solid electrolyte according to claim 1.