JPH1131414A - Polymerizable composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolyte with improved strength, stability and electrically characteristic, by adding inorganic oxide fine particles having a polymerizable functional group for polymerization. SOLUTION: A polymerizable composition containing one kind of polymerizable organic compound, electrolyte salt and an inorganic oxide fine particles having polymerizable functional group expressed by formula I or II, is used. In the formula, R<1> and R<2> represent hydrogen or an alkyl group, R<3> is a bivalent group, (x) is 0 or a value 1-10, and R<1> , R<2> , R<3> and the value (x) in the polymerizable functional group in the same molecule are independent from each other. The polymer solid electrolyte with improved strength, stability and electrical characteristic is used so as to provide a non-aqueous battery and an electric double layer capacitor. A high energy and high density battery with excellent current characteristic, safety and reliability and a long lifetime, is thereby obtained, and a double layer capacitor having an excellent cycle characteristic can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymerizable composition containing a polymerizable organic compound, inorganic oxide fine particles having a polymerizable functional group and an electrolyte, a solid polymer electrolyte obtained from the polymerizable composition, an electrode, The present invention relates to a battery, an electric double layer capacitor, and a method for manufacturing the same.

[0002]

2. Description of the Related Art In the field of downsizing and solidification in the field of ionics, solid electrolytes are used as new ion conductors instead of conventional electrolyte solutions. It is widely applied to electric double layer capacitors. A battery using a current electrolyte solution has a problem in long-term reliability because liquid leakage to the outside of a component or elution of an electrode material easily occurs. On the other hand, a product using a solid electrolyte does not have such a problem, and it is easy to reduce the thickness. Further, the solid electrolyte is excellent in heat resistance, and is advantageous in a process of manufacturing a product such as a battery. In particular, those using a solid electrolyte containing a polymer as a main component have the advantages that the flexibility of the battery is increased and that the battery can be processed into various shapes as compared with inorganic materials. However, those studied so far have had a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low.

[0003] Lithium primary batteries and lithium (ion) secondary batteries, which are typical electrochemical devices, have recently been rapidly mounted on small portable devices due to their high energy density, and have shown rapid growth. For example, LiCoO ₂ ,
Lithium primary batteries and lithium secondary batteries using metal oxides and metal sulfides such as LiNiO ₂ , LiMnO ₂ , and MoS ₂ for the positive electrode and lithium, lithium alloys, carbon materials and inorganic compounds capable of inserting and extracting lithium ions for the negative electrode Many batteries have been studied. "Journal of Electrochemical Society (J. Electrochem. Soc.)
138 (No. 3), p. 665, 1991. "
Discloses a battery using MnO ₂ or NiO ₂ as a positive electrode.

[0004] A porous film such as a polyolefin nonwoven fabric or a polyolefin microporous film is used as a separator which is important as a component other than the positive and negative electrodes of these lithium primary batteries and lithium (ion) secondary batteries. The function of the separator is required to electrically isolate the positive electrode and the negative electrode from each other so as not to cause a short circuit, and to prevent the movement of ions in the electrolytic solution interposed between the positive electrode and the negative electrode. In addition, it is preferable that the battery has the above-described function, as thin as possible because the energy density of the whole battery is increased. To provide these functions, a porous thin film is currently used as a separator. Therefore, film production and processing costs are high, which is a factor of high cost. In addition, there is no ability to carry an electrolytic solution, and liquid leakage from the battery to the outside of the component or elution of the electrode material is likely to occur, so that there has been a problem in long-term reliability and safety of the battery.

In recent years, an electric double layer capacitor in which a carbon material having a large specific surface area, such as activated carbon or carbon black, is used as a polarizable electrode and an ion-conductive solution is arranged between the polarizable electrodes for use as a memory backup power supply or the like has been widely used. For example, in “Functional Materials, February 33, 1989, p. 33”, a capacitor using a carbon-based polarizable electrode and an organic electrolyte is described in “173rd Electrochemical Society Meeting Atlanta Georgia, May, No. .1
8, 1988 "describes an electric double layer capacitor using a sulfuric acid aqueous solution. Also, JP-A-63-24
Japanese Patent No. 4570 discloses Rb ₂ Cu having high electrical conductivity.
_A capacitor using ₃ I ₃ Cl ₇ as an inorganic solid electrolyte is disclosed. However, with current electric double-layer capacitors using an electrolyte solution, when the battery is used for a long period of time or abnormalities such as when a high voltage is applied, liquid leakage to the outside of the capacitor is likely to occur. There is a problem with sex. On the other hand, the electric double layer capacitor using the conventional inorganic ion conductive material has a problem that the decomposition voltage of the ion conductive material is low and the output voltage is low.

[0006] Recently, a so-called solid polymer electrolyte comprising a composite of a polyethylene oxide polymer and an alkali metal salt has attracted attention. Examples of these polymer solid electrolytes,
"The British Polymer Journal (Br. Polym.
J.), Vol. 319, p. 137, 1975 "describes that a composite of polyethylene oxide and an inorganic alkali metal salt exhibits ionic conductivity. In addition, many reports have been made that a comb-type polymer having oligooxyethylene introduced into a side chain enhances the thermal mobility of an oxyethylene chain that is responsible for ion conductivity and improves ion conductivity. For example, "Journal of Physical Chemistry (J. Phys. Chem.), Vol. 89, p. 987, 1
“984” describes an example in which an alkali metal salt is complexed with oligooxyethylene added to the side chain of polymethacrylic acid. In addition, "Journal of
American Chemical Society (J. Am. Chem. So
c.), Vol. 106, p. 6854, 1984 "describes an example in which a polyphosphazene having an oligooxyethylene side chain is complexed with an alkali metal salt. It is said that the polymer itself forms a complex with the Li salt, which is an electrolyte, and can exhibit ionic conduction by thermal motion of the polymer chain. Accordingly, there is basically no need for a hole for passing an electrolyte such as a current separator. However, these are membrane strength,
No practically satisfactory ion conductivity has been obtained.

The ionic conductivity of a polymer solid electrolyte which is generally studied is 10 ⁻⁴ to 10 ⁻⁵ S at room temperature.
/ Cm, but is still at least two orders of magnitude lower than liquid ion conductive materials. Also,
At a low temperature of 0 ° C. or lower, the ionic conductivity further decreases extremely. Further, when these solid electrolytes are formed into a thin film and incorporated into a battery, processing techniques such as compounding with electrodes and ensuring contact properties are difficult, and there is a problem in the production method. J. Appl. E
electrochem. , No. As described on pages 5, 63 to 69 (1975), a so-called polymer gel electrolyte obtained by adding a solvent and an electrolyte to a thermoplastic polymer or a cross-linked polymer such as polyacrylonitrile or polyvinylidene fluoride gel has a high ionicity. Reported conductivity. JP-B-58-36828 reports that a similar polymer gel electrolyte obtained by adding a solvent and an electrolyte to a polymethacrylate alkyl ester has a high ionic conductivity. However, although these polymer gel electrolytes have high ionic conductivity, they impart fluidity and cannot be handled as perfect solids. In addition, similar to the liquid-based ion conductive material, there is a problem in sealing.

In US Pat. No. 4,357,401, a polymer solid electrolyte comprising a heteroatom-containing crosslinked polymer and an ionizable salt reduces the crystallinity of the polymer, lowers the glass transition point, and improves the ionic conductivity. However, at room temperature, about 10 ^-5 S / cm was still insufficient. Further, U.S. Pat. No. 4,792,504 proposes a solid polymer electrolyte in which a crosslinked network of poly (ethylene oxide) is impregnated with an electrolytic solution comprising a metal salt and an aprotic solvent. These indicate that the oxyethylene chain can impregnate not only a Li salt but also an aprotic solvent, and that it can provide a uniform polymer solid electrolyte without pores impregnated with an electrolyte solution that can be used as a separator of a Li battery. Is shown. However, even in this system, the ionic conductivity was still insufficient at 10 ^-4 S / cm. Further, since the solvent was added, the strength of the film was lowered, and there was a problem that it was difficult to handle the film at the time of manufacture or when used for batteries and the like.

[0009] Japanese Patent Publication No. 3-73081, US Patent 490
No. 8283 discloses a method for forming a polymer solid electrolyte by irradiating a composition comprising an acryloyl-modified polyalkylene oxide such as polyethylene glycol diacrylate / electrolyte salt / organic solvent with active light such as ultraviolet rays. Attempts have been made to reduce time. Also, U.S. Pat. No. 4,830,939,
No. 0 also forms a solid polymer electrolyte containing an electrolyte by irradiating a composition comprising a cross-linkable polyethylene unsaturated compound / electrolyte salt / active ray inert solvent with radiation such as ultraviolet rays and electron beams. A similar method is disclosed. In these systems, the amount of the electrolyte in the solid polymer electrolyte was increased, so that the ionic conductivity was improved, but it was still insufficient, and the membrane strength tended to deteriorate.

In order to solve these problems, the present inventors have proposed an ionic conductivity using a composite comprising a polymer obtained from a (meth) acrylate prepolymer containing an oxyalkylene group having a urethane bond and an electrolyte. (JP-A-6-187822). Ion conductivity of this solid polymer electrolyte is a 10 ^-4 S / cm is (room temperature) higher levels in a solvent not added, the further addition of solvent, at room temperature or above a temperature lower by 10 ^-3 S / cm or more, and the film quality was good and improved to such an extent that it could be obtained as a free-standing film. In addition, this prepolymer has good polymerizability, and when applied to batteries,
There is also a processing advantage that it can be polymerized after being incorporated in a battery in a prepolymer state and solidified. However, these systems also have insufficient film strength to be used as separators for batteries and the like, and are difficult to handle industrially. In addition, there is also a problem that a small amount of impurities in the battery system, such as water, a decomposition product of an electrolyte salt, and an electrode material impurity, easily deteriorate a polymer, particularly an oxyalkylene moiety, and easily affect the battery life.

Solid State Ionics, 19
Issue 7, 1982, p. 75, Li, a polymer solid electrolyte
It has been reported that by further combining alumina particles with the ClO ₄ / polyethylene oxide composite, it is possible to achieve an improvement in the strength of the solid polymer electrolyte without lowering the ionic conductivity. Japanese Patent Application Laid-Open No. 6-140052 proposes a solid electrolyte in which a polyalkylene oxide / crosslinked isocyanate / inorganic oxide composite is impregnated with a non-aqueous electrolyte, and the strength of the electrolyte solid polymer electrolyte is improved. It is planned. However, these composite polymer solid electrolytes have insufficient properties of the polymer itself,
There were still problems in practical use in terms of ionic conductivity, workability, and stability.

[0012]

SUMMARY OF THE INVENTION The present invention relates to a molding process,
Good strength, easy handling, high ionic conductivity,
An object of the present invention is to provide an organic / inorganic composite polymer solid electrolyte which is stable, low cost, excellent in safety and reliability, and a polymerizable composition for obtaining the polymer solid electrolyte. Another object of the present invention is to obtain a high-performance battery or electric double-layer capacitor excellent in safety and reliability.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, have added inorganic oxide fine particles having a polymerizable functional group to a polymerizable composition for forming a solid polymer electrolyte. By polymerizing the polymerizable composition, it has been found that a solid polymer electrolyte having improved strength, stability, and electrical properties can be easily obtained. In addition, the present inventors have found that a nonaqueous battery using the polymer solid electrolyte is a high energy density battery having good current characteristics, a long life, and excellent safety and reliability. Furthermore, the present inventors have found that an electric double layer capacitor using the polymer solid electrolyte is an electric double layer capacitor having excellent current characteristics and cycle characteristics, and excellent in safety and reliability.

That is, the present invention has achieved the above object by providing the following. [1] In the polymerizable composition containing at least one polymerizable organic compound, at least one electrolyte salt, and at least one inorganic oxide fine particle, at least one inorganic oxide fine particle has the general formula (1) or the general formula (1). 2)

Embedded image

Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. ] The polymerizable composition which has a polymerizable functional group represented by these.

[2] At least one polymerizable organic compound is represented by the general formula (1) or the general formula (2)

Embedded image

Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. ] The polymerizable composition according to the above [1], having a polymerizable functional group represented by the formula:

[3] At least one polymerizable organic compound is represented by the general formula (1) or the general formula (2)

Embedded image

Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. The polymerizable composition according to the above [2], which has a polymerizable functional group represented by the formula: and has an oxyalkylene group, a fluorocarbon group and / or an oxyfluorocarbon group.

[4] At least one kind of inorganic oxide fine particles has a general formula (3)

Embedded image [Wherein, R ² represents hydrogen or an alkyl group, and R ³ represents 2
Represents a valence group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10. The polymerizable composition according to any one of the above [1] to [3], wherein the fine particles are inorganic oxide fine particles having a polymerizable functional group obtained by reacting the compound represented by the formula (1) with an inorganic oxide. Stuff.

[5] At least one of the inorganic oxide fine particles having a polymerizable functional group is an alumina-based compound, a silica-based compound, a titania-based compound, and / or a magnesia-based compound. The polymerizable composition according to any one of [4]. [6] The polymerizable composition according to any one of [1] to [5], wherein the inorganic oxide fine particles have a crystal particle diameter of 0.1 μm or less. [7] The polymerizable composition according to any one of [1] to [6], wherein the at least one electrolyte salt is a lithium salt. [8] The polymerizable composition according to any one of [1] to [7], comprising at least one organic solvent. [9] The polymerizable composition according to [8], wherein the at least one organic solvent is a cyclic or chain carbonate.

[10] A method for producing a polymer solid electrolyte, comprising curing the polymerizable composition according to any one of [1] to [9] by heating and / or irradiating with active light. [11] The method according to any one of [1] to [9], wherein the polymerizable composition according to any one of [1] to [9] is placed on a substrate made of an electrode used in an electrochemical element, and then cured by heating and / or irradiation with actinic rays. Of producing a solid polymer electrolyte composite electrode. [12] The polymerizable composition according to any one of the above [1] to [9] is placed in a structure for battery construction or placed on a support, and the polymerizable composition is heated and / or activated with light. A method for producing a battery, comprising curing by irradiation. [13] The polymerizable composition according to any one of the above [1] to [9] is placed in a structure for forming an electric double layer capacitor or placed on a support, and the polymerizable composition is heated and / or heated. Alternatively, a method for producing an electric double layer capacitor, comprising curing by irradiation with actinic light.

[14] The general formula (1) or the general formula (2)

Embedded image

Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. ] The inorganic oxide fine particle which has a polymerizable functional group represented by these.

[15] Formula (3)

Embedded image [Wherein, R ² represents hydrogen or an alkyl group, and R ³ represents 2
Represents a valence group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10. ] The inorganic oxide fine particles having a polymerizable functional group according to the above [14], which are obtained by reacting the compound represented by the formula (1) with an inorganic oxide.

[16] A polymer solid electrolyte comprising at least one kind of polymer, at least one kind of electrolyte salt, and at least one kind of inorganic oxide fine particles, wherein at least one kind of polymer is at least one kind of inorganic oxide fine particles. A solid polymer electrolyte characterized by being covalently bonded. [17] The polymer solid electrolyte according to [16], wherein at least one of the inorganic oxide fine particles covalently bonded to the polymer is an alumina-based fine particle. [18] At least one of the polymers covalently bonded to the inorganic oxide fine particles is a polymer having an oxyalkylene group, a fluorocarbon group and / or an oxyfluorocarbon group, and / or a urethane bond. 16] or the solid polymer electrolyte according to [17].

[19] The bonding portion of at least one kind of polymer and at least one kind of inorganic oxide fine particles is represented by the general formula (4) or (5):

Embedded image

Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of structures represented by the general formula (4) or (5) in the same molecule are each independent and need not be the same. Absent. [16] is characterized by having a structure represented by the following formula:
-The solid polymer electrolyte according to any one of [18] to [18]. [20] The solid polymer electrolyte according to any one of [16] to [19], comprising at least one organic solvent.

[21] A battery using the solid polymer electrolyte according to any one of [16] to [20]. [22] The polymer solid electrolyte according to any one of [16] to [20], and a carbon material, an inorganic oxide, an inorganic chalcogenide, or a conductive polymer capable of inserting and extracting lithium, a lithium alloy, or lithium ions. A lithium secondary battery using at least one negative electrode active material selected from the group consisting of: [23] An electric double layer capacitor using the solid polymer electrolyte according to any of [16] to [20]. [24] A composite electrode using the solid polymer electrolyte according to any one of [16] to [20].

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [1] Polymerizable composition The polymerizable composition of the present invention contains at least one polymerizable organic compound, at least one electrolyte salt, and at least one inorganic oxide fine particle as essential components. Further, it may further contain an organic solvent or the like. Hereinafter, each component will be described in detail. (1-a) Inorganic oxide fine particles having a polymerizable functional group The inorganic oxide fine particles contained in the polymerizable composition of the present invention contain a polymerizable functional group represented by the general formula (1) or (2). It is characterized by having. By bonding to the polymer with the polymerizable functional group of the inorganic oxide fine particles, not only the strength and the film thickness uniformity of the polymer solid electrolyte are improved, but also fine pores between the inorganic oxide fine particles and the polymer. Occurs,
The free electrolyte is dispersed through the holes, so that the ionic conductivity and the mobility can be increased.

(1-a-1) Inorganic oxide fine particles As the inorganic oxide fine particles to be used, non-electroconductive and electrochemically stable ones are selected. Further, it is more preferable that the material has ion conductivity. Specific examples thereof include alumina-based fine particles such as α, β, and γ-alumina, silica-based fine particles, titania-based fine particles, magnesia-based fine particles, and ionic conductive or non-conductive oxide fine particles such as composite oxide fine particles thereof. Can be Among these, alumina-based fine particles and silica-based fine particles are preferable because of their excellent stability and interaction with electrolyte ions. In particular, the surface of the alumina-based fine particles has a high affinity for the electrolyte anion, and in particular, can reduce binding of cations and improve cation mobility. Specific examples of the alumina-based fine particles include α, β, and γ-type Al ₂ O ₃ fine particles obtained by various production methods such as a solid phase method and a gas phase method,
LiAl reacted with various inorganic substances such as Li salt
Examples include fine particles of an alumina-based composite oxide such as O ₂ . Among these, aluminum oxide-C (trade name, manufactured by Degussa Co., Ltd.) having a large specific surface area and a large surface activity, and Showa Denko KK
Γ-type Al ₂ O ₃ fine particles such as UA-5805 and LiA
lO ₂ is suitable for the polymerizable composition of the present invention. Specific examples of the silica-based fine particles include Aerosil (trade name, manufactured by Degussa Co., Ltd.) having a large specific surface area and a large surface activity.

These inorganic oxide fine particles are preferably used in a state where the specific surface area is as large as possible and water adsorbed on the surface is removed. By making the added inorganic oxide fine particles have a high specific surface area and a high surface activity with reduced adsorbed water, impurities in the electrochemical element as well as in the electrolytic solution and / or solid polymer electrolyte, in particular, It can adsorb moisture, free acid and free base very well,
A great effect can be exhibited in reducing the deterioration of the sealing material and other materials, and as a result, the life of the battery and the capacitor can be improved. In addition, the effect of interaction with electrolyte ions is increased, and the ion mobility can be improved. Therefore,
Those having a BET method of 10 m ² / g or more are preferably used, and those having a 50 m ² / g or more are preferably used. Therefore, the smaller the crystal grain size is, the more preferable the crystal grain size is 1 μm or less, and preferably 0.1 μm or less. In addition, various shapes such as a sphere, an egg, a cube, a rectangular parallelepiped, a cylinder or a rod can be used.

(1-a-2) Method for Producing Inorganic Oxide Fine Particles Having Polymerizable Functional Group Producing Inorganic Oxide Fine Particles Having Polymerizable Functional Group Represented by General Formula (1) or (2) of the present invention The method of performing is not particularly limited. For example, it may be reacted with various compounds having a polymerizable functional group represented by the general formula (1) or (2) by utilizing the reactivity of the hydroxyl group on the surface of the inorganic oxide. As a specific example, a method of reacting a methacryloylsilane coupling agent with an inorganic oxide as described below is exemplified.

Embedded image [R ⁴ and R ⁵ are OH or O- (Al ₂ O ₃ ). ]

There is also a method of reacting with an isocyanate compound such as methacryloyloxyethyl isocyanate (MOI) as follows.

Embedded image The reaction product of the isocyanate compound and the inorganic oxide fine particles is obtained by a reaction in a non-aqueous solvent, and does not require subsequent dehydration, and is a particularly preferable material for application to the polymer solid electrolyte of the present invention. .

The inorganic oxide fine particles of the present invention are preferably heat-treated before reacting with the above-mentioned functional compound. By performing the heat treatment, the water adsorbed on the surface of the alumina-based fine particles can be reduced, and not only the side reaction between the functional compound and water can be reduced, but also, when introduced into the solid polymer electrolyte, free water diffusing into other materials can be reduced. In addition, it is possible to adsorb impurities of other materials, thereby improving the stability in the system. The temperature and time of the heat treatment vary depending on the shape and type of the inorganic oxide fine particles to be used.
It may be performed for about 0 hours, and the temperature is 500 to 1200.
The range of ° C. is particularly preferred. The heat treatment temperature is preferably as high as possible, but if it exceeds 1200 ° C., sintering of the inorganic oxide fine particles proceeds, and the surface activity is undesirably reduced. The atmosphere during the heat treatment is not particularly limited to reduced pressure, in air, or in an inert atmosphere. However, after the heat treatment, it is necessary to handle in an atmosphere having a dew point of −30 ° C. or less to prevent re-adsorption of moisture. Particularly preferred is -50 ° C or lower.

(1-a-3) Addition In the polymerizable composition of the present invention, if the addition amount of the inorganic oxide fine particles having a polymerizable functional group is too large, on the contrary, the polymer solid electrolyte obtained therefrom is There are problems that strength and ionic conductivity are reduced and that film formation is difficult. Therefore, a preferable addition amount is 1 to 50 wt% with respect to the polymer solid electrolyte obtained therefrom, and 1 to 30 w%.
A range of t% is particularly preferred.

(1-b) Polymerizable organic compound The polymerizable organic compound in the polymerizable composition of the present invention includes:
It is sufficient that at least one of them is polymerizable with the inorganic oxide fine particles having a polymerizable functional group of the present invention, and the polymerizable functional group represented by the general formula (1) or (2)

Embedded image

Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. ] Is preferable. A polymer obtained by curing these by heating and / or irradiation with actinic rays is easy to form a film in a state containing a solvent, and has good film strength. Among them, a compound containing an oxyalkylene group and / or a fluorocarbon group or an oxyfluorocarbon group in a compound having a polymerizable functional group represented by the general formula (1) or (2) is particularly preferable.

The method for synthesizing the compound having a functional group represented by the general formula (1) used in the solid polymer electrolyte of the present invention is not particularly limited. For example, by reacting with an oligooxyalkyleneol. For example, a compound having one functional group represented by the general formula (1) is obtained by reacting an acid chloride and a monoalkyl oligooxyalkylene glycol by the following reaction formula:
It is easily obtained by reacting at a molar ratio of 1. CH ₂ ＣC (R ¹ ) COCl + HO (CH ₂ CHR
⁶ O) _m R ⁷ → CH ₂ ＣC (R ¹ ) COO (CH ₂ CH
R ⁶ O) _m R ^{7 wherein} R ¹ is the same as in the general formula (1). R ⁶ is H,
Or an alkyl group having 10 or less carbon atoms. R ⁷ has 10 carbon atoms
The following alkyl groups. m is an integer of 1 or more. ]

For example, a compound having two functional groups represented by the general formula (1) can be obtained by reacting acid chloride and oligooxyalkylene glycol at a molar ratio of 2: 1 by the following reaction formula. , Easily obtained. 2CH ₂ ＣC (R ¹ ) COCl + HO (CH ₂ CH
R ⁸ O) _n H → CH ₂ ＣC (R ¹ ) COO (CH ₂ CH
R ⁸ O) _n CO (R ¹ ) CＣＨCH ₂ [wherein, R ¹ is the same as in the general formula (1). R ⁸ is H,
Or an alkyl group having 10 or less carbon atoms. n is an integer of 1 or more. ]

The method for synthesizing the compound having a polymerizable functional group represented by the general formula (2) used in the solid polymer electrolyte of the present invention is not particularly limited. For example, CH ₂ ＣC (R
² ) It can be obtained by reacting CO [OR ³ ] _x NCO with an oligoalkylene glycol (where R
² , R ³ and x are the same as in the general formula (2). ). As a specific method, a compound having one ethylenically unsaturated group is, for example, a methacryloyl isocyanate-based compound (hereinafter abbreviated as MIs) or an acryloyl isocyanate-based compound (hereinafter abbreviated as AIs) and monoalkyl. It can be easily obtained by reacting with an oligoalkylene glycol at a molar ratio of 1: 1.

The compound having two ethylenically unsaturated groups can be easily obtained, for example, by reacting an MI or an AI with an oligoalkylene glycol in a molar ratio of 2: 1. Compounds having three ethylenically unsaturated groups include, for example, MIs and / or AIs
These compounds can be easily obtained by reacting the compounds with a triol obtained by addition-polymerizing an alkylene oxide to a trihydric alcohol such as glycerin in a molar ratio of 3: 1. Further, a compound having four ethylenically unsaturated groups is, for example, MI
And / or AIs and 4 such as pentaerythritol
It can be easily obtained by reacting a tetraol obtained by addition-polymerizing an alkylene oxide with a polyhydric alcohol at a molar ratio of 4: 1.

Compounds having five ethylenically unsaturated groups include, for example, MIs and / or AIs, α-D
-Can be easily obtained by reacting pentaol obtained by addition polymerization of glucopyranose with alkylene oxide in a molar ratio of 5: 1. The compound having six ethylenically unsaturated groups can be prepared, for example, by reacting MIs and / or AIs with hexaol obtained by addition-polymerizing an alkylene oxide to mannite in a molar ratio of 6: 1. Obtained easily.

The method for synthesizing the compound having a polymerizable functional group represented by the general formula (1) or (2) having a fluorocarbon group and / or an oxyfluorocarbon group is not particularly limited. Compounds having one polymerizable functional group are MIs or AIs and 2,2
It can be easily obtained by reacting a monool such as 2,3,3,4,4,4-heptafluoro-1-butanol with a molar ratio of 1: 1 according to the following reaction formula. CH ₂ = C (R ¹ ) COO (CH ₂ ) ₂ NCO + CF
₃ (CF ₂ ) ₂ CH ₂ OH → CH ₂ ＣC (R ¹ ) COO (C
H ₂ ) ₂ NHCOOCH ₂ (CF ₂ ) ₂ CF ₃ [wherein, R ¹ is the same as in the general formula (1). ]

The compound having two polymerizable functional groups is
For example, by reacting MIs or AIs with a diol such as 2,2,3,3-tetrafluoro-1,4-butanediol in a molar ratio of 2: 1 by the following reaction formula: ,
Obtained easily. 2CH ₂ = C (R ¹ ) COO (CH ₂ ) ₂ NCO + HOCH
₂ (CF ₂ ) ₂ CH ₂ OH → ｛CH ₂ = C (R ¹ ) COO (
CH ₂ ) ₂ NHCOOCH ₂ CF _2- ｝ ₂ [wherein, R ¹ is the same as in the general formula (1). ]

A polymer obtained by polymerizing a compound having only one polymerizable functional group represented by the general formula (1) or (2) does not have a crosslinked structure and has insufficient film strength. For this reason, when a thin film is used, there is a high risk of short-circuiting, and it is better not to use it alone. Therefore, it is preferable to allow a compound having two or more polymerizable functional groups represented by the general formula (1) or (2) to coexist. Thereby, when cured, they are copolymerized and crosslinked. In consideration of the strength of the thin film of the polymer solid electrolyte, the number of polymerizable functional groups represented by the general formula (1) or (2) contained in one molecule is more preferably three or more. Further, among the compounds having a polymerizable functional group represented by the general formula (1), a polymer obtained from the compound having a polymerizable functional group represented by the general formula (2) contains a urethane group. It is preferable because it has good polymerizability and high film strength when formed into a thin film.

The polymerizable composition of the present invention includes, in addition to the organic compound having a polymerizable functional group represented by the general formula (1) or (2), other polymerizable compounds copolymerizable therewith. Compounds can also be included. The other polymerizable compound is not particularly limited. For example, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N
-(Meth) acrylamide compounds such as dimethylmethacrylamide, acryloylmorpholine, methacryloylmorpholine, N, N-dimethylaminopropyl (meth) acrylamide, styrene compounds such as styrene and α-methylstyrene, N-vinylacetamide, N- Examples thereof include N-vinylamide compounds such as vinylformamide and alkyl vinyl ethers such as ethyl vinyl ether.

(1-c) Electrolyte Salt The composite ratio of the electrolyte salt used in the polymerizable composition for obtaining the polymer solid electrolyte of the present invention is 0.1 to 50% by weight based on the weight of the polymerizable organic compound. Is preferable, and 1 to 30% by weight is particularly preferable. When the electrolyte salt used for the composite is present in a ratio of 50% by weight or more, the movement of ions is greatly inhibited,
Conversely, at a ratio of 0.1% by weight or less, the absolute amount of ions becomes insufficient and the ionic conductivity decreases. The type of electrolyte salt used for the composite is not particularly limited, and an electrolyte salt containing ions to be used as a carrier in a battery or the like may be used. However, it is preferable that the dissociation constant in the polymer solid electrolyte is large, ₃ SO ₃ , LiN (CF ₃ S
O ₂ ) ₂ , LiPF ₆ , LiClO ₄ , LiI, LiB
F ₄ , LiSCN, LiAsF ₆ , NaCF ₃ SO ₃ ,
NaPF ₆ , NaClO ₄ , NaI, NaBF ₄ , Na
Alkali metal salts such as AsF ₆ , KCF ₃ SO ₃ , KPF ₆ and KI; quaternary ammonium salts such as (CH ₃ ) ₄ NBF _4; quaternary phosphonium salts such as (CH ₃ ) ₄ PBF ₄ ;
Transition metal salts such as gClO ₄ are recommended.

As the negative electrode active material used in the battery of the present invention, an alkali metal, an alkali metal alloy,
By using a material having a low oxidation-reduction potential using an alkali metal ion such as a carbon material as a carrier, a high voltage,
This is preferable because a high-capacity battery can be obtained. Therefore, when such a negative electrode is used in a battery using an alkali metal ion as a carrier, an alkali metal salt is required as an electrolyte in the solid polymer electrolyte. Examples of the kind of the alkali metal salt include LiCF ₃ SO ₃ , LiPF ₆ ,
LiClO ₄ , LiBF ₄ , LiSCN, LiAsF
₆ , LiN (CF ₃ SO ₂ ) ₂ , NaCF ₃ SO ₃ , L
iI, NaPF ₆ , NaClO ₄ , NaI, NaBF
₄ , NaAsF ₆ , KCF ₃ SO ₃ , KPF ₆ , KI and the like. Among the negative electrodes, the use of lithium or a lithium alloy as the alkali metal is most preferable in terms of high voltage and high capacity. Therefore, a lithium salt is also used as the electrolyte salt. Among them, LiPF ₆ ,
LiCF ₃ SO ₃ , LiBF ₄ , LiAsF ₆ , LiN
Those containing a fluorine-based anion such as (CF ₃ SO ₂ ) ₂ are preferable in terms of high degree of dissociation, high ionic conductivity, and a wide electrochemical stability region, and LiPF ₆ is particularly preferable.

(1-d) Organic Solvent When the polymerizable composition for obtaining the solid polymer electrolyte of the present invention is impregnated with at least one organic solvent, the ionic conductivity of the obtained solid polymer electrolyte is improved. Is preferred. As the organic solvent that can be used, those having good compatibility with the polymer in the solid polymer electrolyte of the present invention, high boiling point, high solubility of the electrolyte salt, and having no adverse effect on the battery used are preferred. That is, a compound having a large dielectric constant, a boiling point of 60 ° C. or higher, and a wide electrochemical stability range is suitable. Examples of such a solvent include linear and cyclic ethers such as triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,2-dioxolan, and crown ether, ethylene carbonate, propylene carbonate, and dimethyl ether. Chain and cyclic carbonates such as carbonate, diethyl carbonate, ethylmethyl carbonate, vinylene carbonate, (meth) acryloyl carbonate, aromatic nitriles such as benzonitrile and tolunitrile, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N- Examples include nitrogen-containing compounds such as vinylpyrrolidone, sulfur-containing compounds such as sulfolane, and phosphate esters. Among them, ethers and carbonates are preferable, and carbonates are particularly preferable. The higher the content of the solvent in the solid polymer electrolyte, the easier the dissociation of the electrolyte salt or the diffusion of ions, and the higher the ionic conductivity in that case, but the lower the mechanical strength of the separator. The preferable addition amount is 0.5% of the polymer weight in the polymer solid electrolyte of the present invention.
The amount is preferably from 1 to 12 times, more preferably from 1 to 8 times.

(1-e) Others In the polymerizable composition of the present invention, as a polymerization initiator, for example, a thermopolymerizable initiator such as azobisisobutyronitrile and benzoyl peroxide, benzyl methyl ketal And an actinic ray initiator such as benzophenone.

[2] Solid Polymer Electrolyte The solid polymer electrolyte of the present invention contains at least one kind of polymer, at least one kind of electrolyte salt, and at least one kind of inorganic oxide fine particles, and at least one kind of polymer is at least one kind. Characterized by being covalently bonded to the inorganic oxide fine particles. Such a solid polymer electrolyte can be obtained by curing the polymerizable composition of the present invention.

(2-a) Structure of Polymer Solid Electrolyte The polymer in the polymer solid electrolyte of the present invention corresponds to the polymer of the polymerizable compound in the polymerizable composition of the present invention. That is, at least one is obtained by polymerizing the inorganic oxide fine particles having a polymerizable functional group of the present invention with a polymerizable compound. Further, a polymer which is preferable as a constituent component of the polymer solid electrolyte of the present invention is obtained by polymerizing at least one compound having a polymerizable functional group represented by the general formula (1) or (2), or Is obtained by polymerizing as a copolymer component. Therefore, even if it is a homopolymer of the compound having a polymerizable functional group represented by the general formula (1) or the general formula (2) or a copolymer of two or more kinds belonging to the category, Alternatively, it may be a copolymer of at least one of the compounds and another polymerizable compound. The electrolyte salt and the organic solvent are the same as those described in the description of the polymerizable composition of the present invention. The organic solvent is an optional component, but is preferably contained as described above.

At least one kind of the inorganic oxide fine particles in the solid polymer electrolyte of the present invention is characterized in that it is covalently bonded to at least one kind of polymer. This is the same as that described in the description of the composition. In addition, as a method for bonding to a polymer, a method using polymerization using a polymerizable functional group represented by the general formula (1) or (2) is preferable.

The polymer used in the polymer solid electrolyte of the present invention is obtained by polymerizing the polymerizable compound in the polymerizable composition of the present invention. For the polymerization, a general method utilizing the polymerizability of an acryloyl group or a methacryloyl group in a polymerizable organic compound can be employed. That is, a radical polymerization catalyst such as azobisisobutyronitrile and benzoyl peroxide, a protonic acid such as CF ₃ COOH, BF ₃ , A
Radical polymerization, cationic polymerization or anionic polymerization can be performed using a cationic polymerization catalyst such as a Lewis acid such as 1Cl ₃ or an anionic polymerization catalyst such as butyllithium, sodium naphthalene or lithium alkoxide. In addition, depending on the polymerizable compound, radical polymerization can be performed only by heating in an oxygen-free state. The polymer used for the polymer solid electrolyte of the present invention preferably contains an oxyalkylene structure, and in this case, the number of oxyalkylene repeats is preferably in the range of 1 to 1,000, and particularly preferably in the range of 5 to 100. .

(2-b) Method for Producing Polymer Solid Electrolyte As a method for producing the polymer solid electrolyte of the present invention, a method of curing the polymerizable composition of the present invention by heating and / or irradiation with actinic rays is preferable. That is, when producing the solid polymer electrolyte of the present invention, a polymerizable organic compound, at least one kind of inorganic oxide fine particles having a polymerizable functional group represented by the general formula (1) or (2), and at least one kind A polymerizable composition comprising an electrolyte salt of, or a polymerizable composition further added with at least one kind of organic solvent and / or at least one kind of polymerization initiator on a variety of substrates, applying the polymerizable composition. The method of polymerizing and curing the polymerizable organic compound having a functional group and the inorganic oxide fine particles by heating and / or irradiating with actinic rays can be recommended because a uniform film can be formed, and the control of the film thickness is simple. In addition,
The polymerizable compound is preferably a compound having a polymerizable functional group represented by the general formula (1) or (2).

The polymerization temperature depends on the type of the inorganic oxide fine particles having a polymerizable functional group represented by the general formula (1) or (2), the type of the polymerizable organic compound, and the type of the initiator. Any temperature may be used as long as it occurs, and usually, the temperature may be in the range of 0 ° C to 200 ° C. Even when the polymerization is carried out by irradiation with actinic rays, it depends on the type of the inorganic oxide fine particles having a polymerizable functional group represented by the general formula (1) or (2) and the polymerizable organic compound. Using an actinic ray initiator such as benzophenone, ultraviolet light or electron beam of several mW or more, γ
The polymerization can be performed by irradiating a line or the like.

As another method for producing the solid polymer electrolyte of the present invention, a polymerizable composition not containing an electrolyte but containing a solvent among the components of the polymerizable composition of the present invention is prepared in the same manner as described above. After polymerizing and curing the polymer, the polymer is brought into contact with a solvent in which the electrolyte is dissolved, thereby introducing the electrolyte later.

(2-c) Combination with Other Films The solid polymer electrolyte of the present invention can be used in combination with another porous polymer film to improve the strength and the like. However, depending on the type of polymer used, the shape of the film, and the composite ratio, a decrease in ionic conductivity and a deterioration in stability are caused. Examples of the porous polymer film to be used include a porous polyolefin film such as a reticulated polyolefin sheet such as a polypropylene nonwoven fabric or a polyethylene net, a polyolefin microporous film such as Celgard (trade name), a nylon nonwoven fabric, and a polyester net. However, a polyolefin porous film is preferable in terms of stability. The porosity is 10 to 90.
%, But it is preferable that the porosity is as large as possible as long as the strength allows. Therefore, the preferable range of the porosity is 40 to 90%. Although there is no particular limitation on the composite method, for example, a method of impregnating the polymerizable composition of the present invention with a porous polymer film and then polymerizing the polymerizable organic compound and the inorganic oxide fine particles contained in the polymerizable composition. However, it can be uniformly compounded, and the film thickness control is simple and recommended.

[3] Battery When the solid polymer electrolyte of the present invention is applied to a battery, the solid polymer electrolyte of the present invention has a high electrolyte retention property and has no holes, so that liquid leakage and short circuit hardly occur. Since the polymer solid electrolyte has few impurities and fast ion transfer, a battery having a long cycle life, a large take-out current, and high safety and reliability can be obtained. Further, since liquid leakage and short circuit hardly occur, the battery can be made thinner and a battery with a simple package can be obtained. FIG. 1 shows a schematic cross-sectional view of an example of a thin-film battery as a battery manufactured in this manner. In the figure, 1 is a positive electrode, 2 is a polymer solid electrolyte of the present invention, 3 is a negative electrode, 4 is a current collector, and 5 is an insulating resin sealant.

(3-a) Negative Electrode Active Material The negative electrode active material used in the battery of the present invention includes alkali metals, alkali metal alloys, carbon materials, metal oxides and metal chalcogenides, and alkali metal ions such as conductive polymers. It is preferable to use a battery having a low oxidation-reduction potential using as a carrier since a battery of high voltage and high capacity can be obtained. Among such negative electrode active materials, lithium metal or lithium / aluminum alloy, lithium / lead alloy,
Lithium alloys such as lithium / antimony alloys are particularly preferred because they have the lowest redox potential. In addition, the carbon material is particularly preferable because it has a low oxidation-reduction potential when occluding Li ions, and is stable and safe. The carbon material of Li ions can occluding and releasing, natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal coke, pitch carbon, polyacene, C _60, C ₇₀ fullerenes, such as and the like.

(3-b) Positive Electrode Active Material In the structure of the battery of the present invention, the positive electrode has a high oxidation-reduction potential electrode active material such as metal oxide, metal sulfide, conductive polymer or carbon material (positive electrode active material). The use of (substance) is preferable because a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, metal oxides such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, and molybdenum oxide, molybdenum sulfide, and sulfide Titanium,
Metal sulfides such as vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable in terms of high capacity and high voltage. The method for producing the metal oxide or metal sulfide in this case is not particularly limited, and for example, a general electrolytic method or a general electrolytic method described in “Electrochemistry, Vol. 22, pp. 574, 1954”. It is manufactured by a heating method. When these are used for a lithium battery as an electrode active material, for example, Li _x CoO
Preferably, Li is used in a state of being inserted (composite) into a metal oxide or metal sulfide in the form of Li ₂ or Li _x MnO ₂ . The method of inserting the Li element in this way is not particularly limited. For example, a method of electrochemically inserting Li ions or a method of inserting a Li ion such as Li ₂ CO ₃ as described in US Pat. No. 4,357,215. It can be carried out by mixing and heating the metal oxide.

Also, in terms of being flexible and easy to make into a thin film,
Conductive polymers are preferred. Examples of conductive polymers include:
Polyaniline, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polypyrrole and its derivatives, polythienylene and its derivatives, polypyridinediyl and its derivatives, polyisothianaphthenylene and its derivatives, polyfurylene and its derivatives, polyselenophene and its Derivatives, polyarylenevinylenes such as polyparaphenylenevinylene, polythienylenevinylene, polyfurylenevinylene, polynaphthenylenevinylene, polyselenophenvinylene, polypyridinediylvinylene, and derivatives thereof, and the like. Among them, a polymer of an aniline derivative soluble in an organic solvent is particularly preferable. Also,
Carbon materials include natural graphite, artificial graphite, vapor-phase graphite,
Examples include petroleum coke, coal coke, graphite fluoride, pitch-based carbon, polyacene, and the like.

(3-c) Current Collector The current collector is preferably made of a material having electron conductivity, electrochemical corrosion resistance, and as large a specific surface area as possible.
For example, various metals and their sintered bodies, electron conductive polymers,
A carbon sheet and the like can be mentioned. (3-d) Method for Producing Battery For the battery of the present invention, for example, the polymerizable composition of the present invention is placed in a structure for battery construction or placed on a support, and the polymerizable composition is heated and / or heated. It is obtained by curing by irradiation with actinic rays. In addition, there is a method in which a polymer solid electrolyte film obtained from the polymerizable composition is disposed between electrodes, and then placed in a battery structure.

[4] Electric Double Layer Capacitor Next, the electric double layer capacitor of the present invention will be described.
In the electric double layer capacitor of the present invention, by using the polymer solid electrolyte of the present invention, an electric double layer capacitor having a high output voltage, a large take-out current, or excellent workability and reliability is provided. FIG. 2 shows a schematic sectional view of an example of the electric double layer capacitor of the present invention.
This example is a thin cell having a size of 1 cm × 1 cm and a thickness of about 0.5 mm. Reference numeral 7 denotes a current collector, and a pair of polarizable electrodes 6 are arranged inside the current collector. A molecular solid electrolyte membrane 8 is provided. 9 is an insulating resin sealing agent,
10 is a lead wire. The current collector 7 is preferably made of a material having electron conductivity and electrochemical corrosion resistance, and having a specific surface area as large as possible. For example, various metals and their sintered bodies, electron conductive polymers, carbon sheets and the like can be mentioned.

The polarizable electrode 6 may be any electrode made of a polarizable material such as a carbon material usually used for an electric double layer capacitor. The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area. For example, carbon blacks such as furnace black, thermal black (including acetylene black), and channel black; activated carbon such as coconut charcoal; natural graphite; artificial graphite; so-called pyrolytic graphite produced by a gas phase method; mention may be made of _60, C _70. As the shape of the electric double layer capacitor, in addition to the sheet type as shown in FIG. 2, a coin type, or a sheet-like laminated body of a polarizable electrode and a polymer solid electrolyte is wound into a cylindrical shape to form a cylindrical tubular capacitor. It may be a cylindrical type or the like manufactured by sealing in a structure. In the electric double layer capacitor of the present invention, for example, the polymerizable composition of the present invention is placed in a structure for forming an electric double layer capacitor or placed on a support, and the polymerizable composition is heated and / or irradiated with actinic rays. And obtained by curing.

[5] Composite Electrode The solid polymer electrolyte of the present invention can be used as a composite electrode laminated or mixed with an electrode material used for an electrochemical device. By manufacturing such a composite electrode in advance, the preparation of an electrochemical device can be greatly facilitated. For example, a battery can be easily manufactured by pressure-bonding a positive electrode and a negative electrode laminated with the polymer solid electrolyte of the present invention. Examples of the method for producing the composite electrode of the present invention include a method in which a polymerizable composition is disposed on a substrate made of an electrode, cured by heating or irradiation with actinic rays, and laminated. Alternatively, a method of mixing the polymerizable composition with a powder as an electrode material, molding the mixture into an electrode form, curing the mixture by heating or irradiation with actinic rays, and forming a composite material may be used.

[0062]

The present invention will be described more specifically with reference to representative examples. These are merely examples for explanation, and the present invention is not limited to these.

Example 1 <Synthesis of Compound>

Embedded image

Embedded image [However, [X ¹ ] is [(CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _n ] H,
[X ² ]

Embedded image Is shown. ] Compound (average molecular weight 5000, m / n = 7 /
3) 50.0 g and 4.6 g of the compound are dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and 0.44 g of dibutyltin dilaurate is added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless viscous liquid. That
^From the results of ¹ H-NMR, IR, and elemental analysis, the compound and the compound reacted one to three, and further, the isocyanate group of the compound disappeared, and a urethane bond was formed, and the compound was formed. I understood.

Example 2 <Synthesis of Compound> CH ₃ (OCH ₂ CH (CH ₃ )) _m OH + CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ NCO (compound) (compound) → CH ₃ ( OCH ₂ CH (CH ₃ )) _m OCONHCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (Compound) 55 g of compound (average molecular weight 550) and 15.5 g of compound are dissolved in 100 ml of well-purified THF in a nitrogen atmosphere.
0.66 g of dibutyltin dilaurate are added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a colorless viscous liquid. From the results of ¹ H-NMR, IR, and elemental analysis, the compound and the compound reacted one-to-one, and further, the isocyanate group of the compound disappeared, and a urethane bond was generated, and the compound was generated. I understand.

Example 3 <Synthesis of Compound> 20 g of the compound (2,2,3,3,4,4,4,4-heptafluoro-1-butanol, manufactured by Aldrich) and 15.5 g of the compound were mixed in 100 ml of well-purified THF in a nitrogen atmosphere.
g of dibutyltin dilaurate are added. Then 2
By reacting at 5 ° C. for about 15 hours, a compound was obtained as a colorless viscous liquid. From the results of ¹ H-NMR, IR and elemental analysis, it was found that the compound and the compound reacted one-to-one, the isocyanate group of the compound disappeared, and a urethane bond was formed.

Example 4 <Modification of Alumina Fine Particles with Compound-1> Aluminum oxide C (manufactured by Degussa Co., Ltd., crystal particle diameter 0.013)
μm, secondary particle size average about 0.2 μm, specific surface area about 1
00m ² / g) in air in an electric furnace at 1000 ° C. for 1 hour, and then slowly cooled in a glove box in an argon atmosphere. This heat treated aluminum oxide C 15g
Is dispersed in 200 ml of well-purified THF in a nitrogen atmosphere, 7.5 g of compound are added, followed by 0.33 g of dibutyltin dilaurate. Then, at 25 ° C, about 15
The mixture was allowed to react for hours, filtered, and vacuum dried (24 hours) at room temperature to obtain 15.5 g of a white powder.

FIGS. 3 and 4 show Raman spectra of the aluminum oxide C powder before and after the reaction. The measurement conditions and measurement results are as follows. (Fig. 3) Before reaction Laser: 514.53 nm, 200 mW Spectrometer: F single Incident slit width: 1000 μm Number of integrations: 2 Exposure time: 60 sec Binning (offset): 109 Binning (width): 158 peak (Raman shift [cm ^-1] ], Int.) 1: 449.93, 0.1045 2: 560.33, 0.1108 3: 747.90,
0.2741 4: 843.87, 0.3396 5: 1087.90, 0.2474 6: 1563.39,
0.2573

(FIG. 4) After the reaction Laser: 514.53 nm, 200 mW Spectroscope: F single Incident slit width: 500 μm Number of integrations: 2 Exposure time: 30 sec Binning (offset): 66 Binning (width): 162 peak (Raman shift) [Cm ^-1 ], int.) 1: 739.11, 3.0443 2: 840.11, 2.9145 3: 928.56,
2.3303 4: 1065.94, 2.4957 5: 1296.79, 3.0495 6: 1392.77,
2.7969 7: 1448.60, 3.6288 8: 1562.14, 2.6436 9: 1638.67,
2.9136 10: 1717.71, 2.6914 Among these, 2,4,5,7,9,10 are peaks derived from methacrylic acid of the compound.

FIG. 5 shows IR spectra before and after the reaction.
As shown in FIG. The measurement results are as follows. (Fig. 5) Before reaction (wave number [cm ^-1 ], absorption) 1: 3459.75, 1.709 2: 1640.66, 0.879 3: 1385.06,
0.716 (FIG. 6) After the reaction (wave number [cm ^-1 ], absorption) 1: 3415.38, 1.507 2: 2960.13, 1.447 3: 2929.26,
1.474 4: 2858.85, 1.311 5: 2277.24, 0.936 6: 1716.85,
1.709 7: 1652.23, 1.635 8: 1557.71, 1.697 9: 1455.47,
1.616 The elemental analysis value of carbon after the reaction (EMIA-110 carbon analyzer) was 4.6%, which was increased from 0% before the reaction.

Example 5 <Modification of Alumina Fine Particles with Compound-2> High Purity γ
-Alumina UA5805 (manufactured by Showa Denko, crystal particle size 0.03 μm, average secondary particle size about 1.8 μm, specific surface area about 80 m ² / g) in air in a 1000 ° C. electric furnace.
After the heat treatment for an hour, the mixture was slowly cooled in a glove box in an argon atmosphere. After dispersing 15 g of this heat-treated UA5805 in 50 ml of well-purified THF in a nitrogen atmosphere, 7.5 g of the compound are added, followed by 0.33 g of dibutyltin dilaurate. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours, separated by filtration, and vacuum-dried at room temperature (24 hours) to obtain 15.3 g of a white powder.

The Raman spectra of UA5805 before and after the reaction are shown in FIGS. The measurement conditions and measurement results are as follows. (Fig. 7) Before reaction Laser: 514.53 nm, 200 mW Spectrometer: F single Incident slit width: 1000 μm Integration frequency: 2 Exposure time: 60 sec Binning (offset): 109 Binning (width): 158 peak (Raman shift [cm ^-1] ], Int.) 1: 451.18, 0.1858 2: 555.94, 0.1380 3: 626.83,
0.1172 4: 750.41, 0.3947 5: 843.25, 0.3282 6: 981.88,
0.3304 7: 1072.84, 0.1331 8: 1563.39, 0.1745

(FIG. 8) After the reaction Laser: 514.53 nm, 200 mW Spectrometer: F single Incident slit width: 500 μm Number of integrations: 2 Exposure time: 30 sec Binning (offset): 66 Binning (width): 162 peak (Raman shift) [Cm ^-1 ], int.) 1: 514.54, 4.6225 2: 738.49, 2.5501 3: 838.23,
2.7656 4: 964.32, 2.4331 5: 1050.26, 2.4662 6: 1287.38,
2.7015 7: 1452.36, 4.0138 8: 1566.53, 2.3067 9: 1634.91,
2.5233 10: 1715.20, 2.4670 Among these, 3,4,5,6,7,9,10 are peaks derived from methacrylic acid of the compound.

FIG. 9 shows IR spectra before and after the reaction.
As shown in FIG. The measurement results are as follows. (FIG. 9) Before reaction (wave number [cm ⁻¹ ], absorption) 1: 3465.54, 1.714 2: 1633.91, 1.776 3: 1372.52,
1.732 4: 1021.43, 2.277 (FIG. 10) After the reaction (wave number [cm ⁻¹ ], absorption) 1: 3408.63, 1.596 2: 2930.23, 1.505 3: 2858.85,
1.365 4: 1721.68, 1.962 5: 1651.27, 1.902 6: 1557.71,
2.045 7: 1455.47, 1.961 8: 1155.50, 2.280 9: 401.24,
2.174 The elemental analysis value of carbon after the reaction was 3.9%, which was increased from 0% before the reaction.

Example 6 <Modification of Alumina Fine Particles with Silane Coupling Agent> Silane Coupling Agent KBM503P (CH ₂ CC (CH ₃ ) C
OOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ : Shin-Etsu Silicon) 4.0g, 100% ethanol solution of 1% acetic acid, heat treatment UA5805 for 15
g After the dispersion, the mixture was reacted at 25 ° C. for about 2 hours, filtered, and dried in vacuo at room temperature (24 hours) to obtain 15.1 g of a white powder.

FIG. 11 shows a Raman spectrum of the UA5805 powder after the reaction. The measurement conditions and measurement results are as follows. (Fig. 11) Laser: 514.53 nm, 200 mW Spectrometer: F single Incident slit width: 500 μm Number of integrations: 2 Exposure time: 30 sec Binning (offset): 66 Binning (width): 162 peaks (Raman shift [cm ^-1 ]) , Int.) 1: 371.51, 2.0999 2: 746.01, 1.9767 3: 853.28,
2.0954 4: 978.12, 2.2748 5: 1051.51, 1.8874 6: 1298.67,
2.2801 7: 1388.38, 2.0061 8: 1427.27, 2.1297 9: 1562.77,
1.8638 10: 1633.03, 1.7581 Among these, 3,4,5,6,8,10 are the peaks of KBM503P derived from methacrylic acid.

FIG. 12 shows an IR spectrum after the reaction. The measurement results are as follows. (FIG. 12) After the reaction (wave number [cm ⁻¹ ], absorption) 1: 3480.97, 1.355 2: 1694.67, 1.261 3: 1640.66,
1.343 4: 1568.32, 1.388 5: 1470.90, 1.390 6: 1417.85,
1.412 7: 1329.12, 1.395 8: 1305.00, 1.422 9: 1049.40,
1.600 10: 484.19, 1.466 11: 429.21 1.485 12: 412.82
1.509 13: 405.10, 1.492 The elemental analysis value of carbon after the reaction was 0.8%, which was increased from 0% before the reaction.

Example 7 Compound synthesized in Example 1
1.0 g, 0.33 g of the modified aluminum oxide C produced in Example 4, 1.8 g of ethylene carbonate (EC), 4.2 g of diethyl carbonate (EMC), 0.60 g of LiPF ₆ (battery grade manufactured by Hashimoto Kasei), and 2,4,6 0.005 g of trimethylbenzoyldiphenylphosphine oxide (trade name Lucylin TPO, manufactured by BASF) was mixed well in an argon atmosphere to obtain a photopolymerizable composition. This photopolymerizable composition was applied on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp (FL20S.BL, manufactured by Sankyo Electric Co., Ltd.) for 10 minutes. An aluminum oxide C composite film was obtained as a free standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, each was 5.0 × 1
0 ^-3 and 1.0 × 10 ^-3 S / cm. The tensile strength (25 ° C.) of this film was 10 kg / cm ² .

Comparative Example 1 A photopolymerizable composition was prepared in the same manner as in Example 7 except that the modified aluminum oxide C was not added. As a free standing film. When the ionic conductivity at 25 ° C. and −20 ° C. of this film was measured by an impedance method,
It was 4.5 × 10 ^-3 and 0.8 × 10 ^-3 S / cm. Further, the tensile strength (25 ° C.) of this film was 5 kg / cm ^2, which was lower than that of the modified aluminum oxide C-added product.

Example 8 Compound synthesized in Example 2
1.0 g, 0.66 g of the modified UA5805 produced in Example 5,
0.9 g of EC, 2.1 g of DEC, 0.40 g of LiPF _{6 and} 0.005 g of lucilin TPO (manufactured by BASF) were mixed well in an argon atmosphere to obtain a photopolymerizable composition. This photopolymerizable composition was coated on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes.
A compound polymer / UA5805 composite film impregnated with a system electrolyte was obtained as a free-standing film of about 30 μm.
When the ionic conductivity of the film at 25 ° C. and −20 ° C. was measured by an impedance method, each was 4.0 ×
The ^{values were} 10 ⁻³ and 0.8 × 10 ⁻³ S / cm. The tensile strength (25 ° C.) of this film was 2 kg / cm ² .

Example 9 Compound synthesized in Example 2
0.5 g, the compound synthesized in Example 3 0.5 g, Example 6
UA5805 0.66g, EC 0.9g, DE manufactured by
C 2.1 g, LiPF ₆ 0.40 g, Lucirin TPO (BAS
0.005 g (manufactured by Company F) was mixed well in an argon atmosphere to obtain a photopolymerizable composition. This photopolymerizable composition was applied on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes.
Obtained as a μm freestanding film. 2 of this film
When the ionic conductivity at 5 ° C. and −20 ° C. was measured by the impedance method, they were 2.0 × 10 ⁻³ and 0.6 × 10 ⁻³ S /, respectively.
cm. Also, the tensile strength of this film (25
C) was 3 kg / cm ² .

Comparative Example 2 A photopolymerizable composition was prepared in the same manner as in Example 8 except that the modified UA5805 was not added. After coating this photopolymerizable composition on a PET film under an argon atmosphere, the film was irradiated with a chemical fluorescent lamp for 20 minutes, but no free-standing film was obtained.

Example 10 Lucilin TP as an initiator
O (BASF) 0.005g instead of Parloyl TCP
A thermopolymerizable composition was obtained in the same manner as in Example 7 except that 0.04 g (manufactured by NOF Corporation) was added. This thermopolymerizable composition was coated on a PET film under an argon atmosphere, coated with a PP film, and heated on a hot plate at 60 ° C. for 1 hour. Aluminum oxide C composite film is about 3
Obtained as a 0 μm freestanding film. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, it was 4.7 × 10 ⁻³ and 1.0 × 10 ⁻³ , respectively.
It was S / cm. Also, the tensile strength of this film (25
C) was 8 kg / cm ² .

Example 11 Lucilin TP as an initiator
A thermopolymerizable composition was obtained in the same manner as in Example 8, except that 0.04 g of Parloyl TCP (manufactured by NOF Corporation) was added instead of O. The heat-polymerizable composition is placed under an argon atmosphere under PET.
After coating on a film, the film was coated with a PP film and heated on a hot plate at 60 ° C. for 1 hour.
A compound polymer / UA5805 composite film impregnated with an EC electrolyte was obtained as a free-standing film of about 30 μm. When the ionic conductivity at 25 ° C. and −20 ° C. of this film was measured by an impedance method,
It was 4.0 × 10 ⁻³ and 0.8 × 10 ⁻³ S / cm. The tensile strength (25 ° C.) of this film was 1.5 kg / cm ² .

Example 12 A photopolymerizable composition was obtained in the same manner as in Example 7, except that 0.50 g of battery grade LiBF ₄ (manufactured by Hashimoto Kasei) was used instead of LiPF ₆ . The photopolymerizable composition was applied and irradiated with light in the same manner as in Example 7 to obtain a compound polymer / aluminum oxide C composite film impregnated with an electrolyte as a self-supporting film having a thickness of about 30 μm. The ionic conductivity at 25 ° C. and −20 ° C. of the solid electrolyte was measured by an impedance method.
0 × 10 ⁻³ and 0.6 × 10 ⁻³ S / cm. The tensile strength (25 ° C.) of this film was 11 kg / cm ² .

Example 13 Instead of LiPF ₆ , high-purity tetraethylammonium tetrafluoroborate (T
A photopolymerizable composition was obtained in the same manner as in Example 7, except that 1.00 g of EAB (manufactured by Hashimoto Kasei) and 6.0 g of propylene pyrene carbonate were used in place of EC and EMC. This photopolymerizable composition was applied and irradiated with light in the same manner as in Example 7 to obtain a compound polymer / aluminum oxide C composite film impregnated with a PC-based electrolyte as a self-supporting film having a thickness of about 30 μm. The ionic conductivity of this solid electrolyte at 25 ° C. and −20 ° C. was measured by an impedance method and found to be 10.0 × 10 ⁻³ and 1.8 × 10 ⁻³ S / cm. The tensile strength (25 ° C.) of this film was 11 kg / cm ² .

Example 14 Lucilin TP as an initiator
A thermopolymerizable composition was obtained in the same manner as in Example 13, except that 0.04 g of Parloyl TCP (manufactured by NOF Corporation) was added instead of O. This thermopolymerizable composition is placed in an argon atmosphere under PE
After coating on a T film, it was coated with a PP film and heated on a hot plate at 60 ° C for 1 hour.
A compound polymer / aluminum oxide C composite film impregnated with a DEC electrolyte was obtained as a free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method,
They were 9.0 × 10 ⁻³ and 1.8 × 10 ⁻³ S / cm, respectively. Also,
The tensile strength (25 ° C.) of this film was 8 kg / cm ² .

Example 15 Compound (CH ₃ (OCH ₂ CH ₂ ) _k
OCOC (CH ₃ ) = CH ₂ ; manufactured by NOF Corporation; Blemmer AE-40
0, Mw 400) 0.5 g, compound synthesized in Example 1
0.5 g, 0.33 g of the modified aluminum oxide C prepared in Example 5, 1.8 g of EC, 4.2 g of ethyl methyl carbonate (EMC), 0.40 g of LiPF ₆ , and lucirin TPO
0.005 g (manufactured by BASF) was mixed well in an argon atmosphere to obtain a photopolymerizable composition. This photopolymerizable composition was coated on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes. Obtained as a 30 μm freestanding film. The ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method and found to be 5.0 × 10 ⁻³ and 0.8 × 10 ⁻³ S / cm, respectively. The tensile strength (25 ° C.) of this film was 8 kg / cm ² .

Example 16 Example 15 was repeated except that 0.5 g of the compound synthesized in Example 2 was used instead of the compound.
The same photopolymerizable composition was obtained. This photopolymerizable composition was coated on a PET film under an argon atmosphere, and then irradiated with a chemical fluorescent lamp for 10 minutes. Obtained as a 30 μm freestanding film. When the ionic conductivity of this film at 25 ° C. and −20 ° C. was measured by an impedance method, it was 5.5 × 10 ⁻³ and 1.5 × 10 ⁻³ S / cm, respectively. The tensile strength (25 ° C.) of this film was 9 kg / cm ² .

Example 17 <Production of Lithium Cobaltate Cathode> 11 g of Li ₂ CO ₃
And 24 g of Co ₃ O ₄ are mixed well, and the mixture is
After heating at 0 ° C. for 24 hours, pulverization is performed to obtain LiCoO.
_Two powders were obtained. This LiCoO ₂ powder, acetylene black, and polyvinylidene fluoride were mixed at a weight ratio of 8: 1: 1, and an excess N-methylpyrrolidone solution was added to obtain a gel composition. This composition was applied and molded on an aluminum foil of about 25 μm to a thickness of 10 mm × 10 mm and a thickness of about 180 μm. Further, by heating and vacuum drying at about 100 ° C. for 24 hours, a lithium cobaltate positive electrode (75 mg) was obtained.

Example 18 <Production of Graphite Negative Electrode> MCMB graphite (manufactured by Osaka Gas), vapor phase graphite fiber (manufactured by Showa Denko KK: average fiber diameter: 0.3 μm)
An excess N-methylpyrrolidone solution was added to a mixture of polyvinylidene fluoride at a weight ratio of 8.6: 0.4: 1.0 to obtain a gel composition. This composition was coated on a copper foil of about 15 μm in a thickness of 10 mm ×
It was applied and molded to a thickness of 10 mm and a thickness of about 250 μm. further,
Heating and vacuum drying at about 100 ° C. for 24 hours gave a graphite negative electrode (35 mg).

Example 19 <Production of Li-Ion Secondary Battery> The graphite negative electrode (10 m
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + E)
MC (3: 7)), the compound prepared in Example 16 / aluminum oxide C composite film (12 mm × 12 mm) was stuck on a graphite negative electrode, and the cobalt acid prepared in Example 17 was further bonded. Electrolyte (1M LiPF ₆ ) is applied to a lithium positive electrode (10 mm × 10 mm).
/ EC + EMC (3: 7)) were bonded together, and the battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide Li-ion secondary battery. FIG. 1 shows a cross-sectional view of the obtained battery. The battery was charged and discharged at 60 ° C. and 25 ° C. with an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA.
The maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively. Also, 2
When charge and discharge were repeated at 5 ° C., operating voltage 2.75 to 4.1 V, charge 0.5 mA, and discharge 2.5 mA, the maximum discharge capacity was 7.0 mAh, and the cycle life until the capacity was reduced to 50% was 550 times. .

Example 20 <Production of Li-ion secondary battery> The graphite negative electrode (10 m
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + D)
EC (3: 7)), the compound / aluminum oxide C composite film (12 mm × 12 mm) prepared in Example 7 was adhered on a graphite negative electrode, and the lithium cobaltate produced in Example 17 was further bonded. Positive electrode (1
0 mm × 10 mm) in the electrolyte (1M LiPF ₆ / EC
+ DEC (3: 7)), and
The battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide-based Li-ion secondary battery. The battery was heated at 60 ° C, 2
When charging and discharging were performed at 5 ° C. at an operating voltage of 2.75 to 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively. Also, 25 ° C, operating voltage 2.75 ~ 4.1V, charging 0.5mA,
Repeated charge and discharge at 2.5 mA discharge, the maximum discharge capacity is
At 6.4 mAh, the cycle life before the capacity was reduced to 50% was 580 times.

Example 21 <Production of Li-Ion Secondary Battery> The graphite negative electrode (10 m) produced in Example 18 was placed in an argon atmosphere glove box.
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + D)
EC (3: 7)), and then the compound 5 / UA5805-based photopolymerizable composition prepared in Example 8 was applied to a thickness of 30.
It was applied to a thickness of μm and irradiated with a chemical fluorescent lamp for 10 minutes under an argon atmosphere. As a result, a compound polymer / UA5805 composite film impregnated with an electrolytic solution was formed directly on the graphite negative electrode. Further, the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 17 was applied to the electrolyte (1
M LiPF ₆ / EC + DEC (3: 7)) were impregnated, and the battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide Li-ion secondary battery shown in FIG. The battery is operated at a working voltage of 2.75 at 60 ° C and 25 ° C.
When charge and discharge were performed at ~ 4.1 V and a current of 0.5 mA, the maximum discharge capacities were 7.2 mAh and 7.2 mAh, respectively. When charge and discharge were repeated at 25 ° C., operating voltage 2.75 to 4.1 V, charge 0.5 mA, and discharge 2.5 mA, the maximum discharge capacity was 7.0 mAh and the capacity was 50
% Was 460 cycles.

Example 22 <Production of Li-ion secondary battery> The graphite negative electrode (10 m) produced in Example 18 was placed in an argon atmosphere glove box.
m × 10 mm) in the electrolyte (1M LiPF ₆ / EC + D)
EC (3: 7)), and then the compound / aluminum oxide C-based thermopolymerizable composition prepared in Example 10 was applied so as to have a thickness of 30 μm, and was heated to 70 μm on a hot plate under an argon atmosphere. When heated at 1 ° C. for 1 hour, a compound polymer / aluminum oxide C composite film impregnated with an electrolytic solution was formed directly on the graphite negative electrode.
Further, the lithium cobaltate positive electrode (10 mm × 10 mm) produced in Example 17 was applied to the electrolyte solution (1 M LiPF ₆ /
EC + DEC (3: 7)) was impregnated, and the battery end was sealed with an epoxy resin to obtain a graphite / cobalt oxide Li-ion secondary battery shown in FIG. The battery was operated at 60 ° C and 25 ° C with an operating voltage of 2.75 to 4.1V and a current of 0.5mA.
The maximum discharge capacity was 7.2 mAh for each,
7.2 mAh. In addition, 25 ℃, operating voltage 2.75 ~ 4.1V,
When charge and discharge were repeated at a charge of 0.5 mA and a discharge of 2.5 mA, the maximum discharge capacity was 6.6 mAh, and the cycle life until the capacity was reduced to 50% was 430 times.

Example 23 <Production of Activated Carbon Electrode> An excess N-methylpyrrolidone solution was added to a mixture of coconut palm activated carbon and polyvinylidene fluoride at a weight ratio of 9.0: 1.0 to obtain a gel composition. This composition was applied on a stainless steel foil in a size of 10 mm × 10 mm to a thickness of about 150 μm. After vacuum drying at about 100 ° C. for 10 hours, an activated carbon electrode (14.0 mg) was obtained.

Example 24 <Production of Electric Double Layer Capacitor> The activated carbon electrode (14) produced in Example 23 was placed in an argon atmosphere glove box.
mg) 10 mm x 10 mm with electrolyte (1 M TEAB /
Two electrodes impregnated with PC) were prepared. Next, the compound polymer / aluminum oxide C composite film (12 mm × 12 mm) produced in Example 13 was attached to one electrode, and another electrode was attached, and the end of the capacitor was sealed with epoxy resin. As a result, an electric double layer capacitor as shown in FIG. 2 was manufactured. This capacitor is operated at an operating voltage of 0 to 2.5 at 60 ° C. and 25 ° C.
When the battery was charged and discharged at V and a current of 0.2 mA, the maximum capacity was 470 mF and 470 mF. 25 ° C,
The maximum capacity at 2.0 mA is 420 mF and the charge and discharge is 50
There was almost no change in the capacity even after repeated times.

Example 25 <Production of Electric Double Layer Capacitor> The activated carbon electrode (14) produced in Example 23 was placed in an argon atmosphere glove box.
mg) Two electrodes of 10 mm × 10 mm impregnated with the thermopolymerizable composition prepared in Example 14 were prepared. Next, the compound polymer / aluminum oxide C composite film (12 mm × 12 mm) produced in Example 13 was attached to one electrode, and another electrode was attached, and the end of the capacitor was sealed with epoxy resin. Then, the thermopolymerizable composition was heated and polymerized at 80 ° C. for 1 hour to produce an electric double layer capacitor as shown in FIG. This capacitor is operated at an operating voltage of 0 to 2.5 at 60 ° C. and 25 ° C.
When the battery was charged and discharged at V and a current of 0.2 mA, the maximum capacity was 460 mF and 380 mF. 25 ° C,
The maximum capacity at 2.0 mA is 230 mF and the charge / discharge is 50
There was almost no change in the capacity even after repeated times.

[0098]

The polymerizable composition for a solid polymer electrolyte of the present invention comprises a polymerizable organic compound, an electrolyte salt, and inorganic oxide fine particles having a polymerizable functional group as main components. By polymerizing the polymerizable composition, a polymer solid electrolyte having improved mechanical strength, stability, and electrical properties can be easily obtained. Further, the battery of the present invention is a high energy density battery having good current characteristics, long life, excellent safety and reliability, using the polymer solid electrolyte. Further, since there is no liquid leakage, batteries having various shapes such as a thin shape can be obtained. Further, the electric double layer capacitor of the present invention uses the polymer solid electrolyte,
It is an electric double layer capacitor with good current characteristics and cycle characteristics, and excellent safety and reliability. Further, since there is no liquid leakage, various types of electric double layer capacitors such as a thin type and a chip type can be obtained. In the composite electrode of the present invention, the polymer solid electrolyte and the electrode are in close contact with each other, and only by laminating them, an electrochemical element such as a battery or an electric double layer capacitor having improved current characteristics and life can be easily obtained. be able to.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a thin solid state battery shown as an example of the battery of the present invention.

FIG. 2 is a schematic sectional view as an example of the electric double layer capacitor of the present invention.

FIG. 3 is a Raman spectrum of aluminum oxide C.

FIG. 4 is a Raman spectrum of aluminum oxide C reacted with a compound.

FIG. 5 is an IR spectrum of aluminum oxide C.

FIG. 6 is an IR spectrum of aluminum oxide C reacted with a compound.

FIG. 7 is a Raman spectrum of UA5805.

FIG. 8 is a Raman spectrum of UA5805 reacted with a compound.

FIG. 9 is an IR spectrum of UA5805.

FIG. 10 is an IR spectrum of UA5805 reacted with a compound.

FIG. 11 is a Raman spectrum of UA5805 reacted with KBM503P.

FIG. 12 is an IR spectrum of UA5805 reacted with KBM503P.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Polymer solid electrolyte 3 Negative electrode 4 Current collector 5 Insulating resin sealing agent 6 Polarized electrode 7 Current collector 8 Polymer solid electrolyte 9 Insulating resin sealing agent 10 Lead wire

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09C 3/10 C09C 3/10 H01G 9/025 H01M 10/40 H01M 10/40 C08F 20/00 // C08F 20/00 H01G 9 / 00 301G

Claims (15)

[Claims] 1. A polymerizable composition comprising at least one kind of polymerizable organic compound, at least one kind of electrolyte salt, and at least one kind of inorganic oxide fine particles, wherein at least one kind of inorganic oxide fine particles has the general formula (1) or Formula (2) Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. ] The polymerizable composition which has a polymerizable functional group represented by these. 2. The method according to claim 1, wherein the at least one polymerizable organic compound has the general formula (1) or the general formula (2). Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. The polymerizable composition according to claim 1, which has a polymerizable functional group represented by the formula: 3. The at least one polymerizable organic compound represented by the general formula (1) or the general formula (2): Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. The polymerizable composition according to claim 2, which has a polymerizable functional group represented by the formula: and has an oxyalkylene group, a fluorocarbon group and / or an oxyfluorocarbon group. 4. At least one kind of inorganic oxide fine particles,
General formula (3) [Wherein, R ² represents hydrogen or an alkyl group, and R ³ represents 2
Represents a valence group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10. The polymerizable composition according to any one of claims 1 to 3, wherein the compound is a fine particle of an inorganic oxide having a polymerizable functional group obtained by reacting the compound represented by formula (I) with an inorganic oxide. 5. The method according to claim 1, wherein at least one of the inorganic oxide fine particles having a polymerizable functional group is an alumina-based compound, a silica-based compound, a titania-based compound, and / or a magnesia-based compound. The polymerizable composition according to any one of the above. 6. The inorganic oxide fine particles having a crystal particle diameter of 0.1
The polymerizable composition according to any one of claims 1 to 5, wherein the composition is not more than μm. 7. The polymerizable composition according to claim 1, wherein the at least one electrolyte salt is a lithium salt. 8. The polymerizable composition according to claim 1, comprising at least one organic solvent. 9. The polymerizable composition according to claim 8, wherein the at least one organic solvent is a cyclic or chain carbonate. 10. A method for producing a solid polymer electrolyte, comprising curing the polymerizable composition according to claim 1 by heating and / or irradiating with active light. 11. A method comprising arranging the polymerizable composition according to claim 1 on a substrate comprising an electrode used for an electrochemical element, and then curing the composition by heating and / or irradiation with actinic rays. A method for producing a polymer solid electrolyte composite electrode. 12. The polymerizable composition according to any one of claims 1 to 9, which is placed in a structure for battery construction or placed on a support, and the polymerizable composition is heated and / or irradiated with actinic rays. A method for producing a battery, comprising: curing the battery. 13. The polymerizable composition according to claim 1, which is placed in a structure for forming an electric double layer capacitor or placed on a support, and the polymerizable composition is heated and / or heated. A method for producing an electric double layer capacitor, comprising curing by irradiation with actinic rays. 14. The general formula (1) or the general formula (2) Embedded image [Wherein R ¹ and R ² represent hydrogen or an alkyl group;
³ represents a divalent group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10.
However, the values of R ¹ , R ² , R ³ and x in a plurality of polymerizable functional groups represented by the above general formula (1) or (2) in the same molecule are independent of each other and are the same. No need to be. ] The inorganic oxide fine particle which has a polymerizable functional group represented by these. 15. A compound of the general formula (3) [Wherein, R ² represents hydrogen or an alkyl group, and R ³ represents 2
Represents a valence group. The divalent group may contain a hetero atom and may have any of a linear, branched or cyclic structure. x shows 0 or the numerical value of 1-10. The inorganic oxide fine particles having a polymerizable functional group according to claim 14, which are obtained by reacting the compound represented by the formula (1) with an inorganic oxide.