JPH1036657A - Polymerizable monomer, solid polyelectrolyte comprising the same, and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable functional monomer for a solid polyelectrolyte excellent in ionic conductivity at room and low temperatures, membrane strengths, processability, heat stability, electric current characteristics, etc., by using a methacrylate compound having a specified functional group. SOLUTION: This heat- and/or actinic-radiation-polymerizable monomer compound is a monomer having polymerizable functional groups represented by formulas I and/or II (R<1> is H or an alkyl; R<2> is a divalent organic group; R<3> is a divalent group containing a fluoroalkylene and/or an oxyfluoroalkylene; provided that each of the divalent organic group and divalent group may have a linear, branched or cyclic structure; and x is 0 or 1-10, provided that R<1> s, R<2> s, R<3> s and xs in a plurality of the polymerizable functional group are independent of each other in the same molecule and are not necessarily the same).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer using a monomer compound having a urethane bond and a fluoroalkylene and / or oxyfluoroalkylene group, and a highly ion-conductive polymer using a composite comprising an electrolyte. Solid electrolyte, an electrode using the polymer and a method for producing the same,
The present invention relates to a battery using the polymer solid electrolyte or the electrode and a method for manufacturing the same, and an electric double layer capacitor using the polymer solid electrolyte and a method for manufacturing the same.

[0002]

2. Description of the Related Art In the field of downsizing and all-solidification in the field of ionics, all-solid primary and secondary batteries and solid-state batteries using solid electrolytes are used as new ion conductors instead of conventional electrolyte solutions. Applications to multilayer capacitors are being actively pursued. 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.

[0003] In particular, those using a solid electrolyte containing a polymer as a main component have the advantage that the flexibility of the battery is increased and that it can be processed into various shapes as compared with inorganic materials. However, those studied so far have a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low. Examples of these polyelectrolytes include the British Polymer Journal (B
r. Polym. J.), Vol. 319, p. 137, 1975
The publication describes that a composite of polyethylene oxide and an inorganic alkali metal salt exhibits ionic conductivity, but its ionic conductivity at room temperature is as low as 10 ^-7 S / cm.

[0004] Recently, it has been reported that a comb polymer in which oligooxyethylene is introduced into a side chain enhances the thermal mobility of an oxyethylene chain which is responsible for ionic conductivity and improves ionic conductivity. I have. For example, "Journal of Physical Chemistry (J. Phys. Chem.), Vol. 89, p. 987, 1984" discloses that an alkali metal salt is obtained by adding oligooxyethylene to a side chain of polymethacrylic acid. Are described. further,
"Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 106, p. 6854,
“1984” describes an example in which an alkali metal salt is complexed with polyphosphazene having an oligooxyethylene side chain, but the ionic conductivity is still insufficient at about 10 ⁻⁵ S / cm.

[0005] US Pat. No. 4,357,401 reports that a polymer solid electrolyte comprising a heteroatom-containing crosslinked polymer and an ionizable salt has reduced crystallinity, low glass transition point, and improved ionic conductivity. But
About 10 ^-5 S / cm was still insufficient. Recently, Li
Many studies have been made on lithium secondary batteries using metal oxides such as CoO ₂ , LiNiO ₂ , LiMnO ₂ , and MoS ₂ , and metal sulfides as positive electrodes. For example, see the Journal of Electrochemical Society (J. Electroche
m. Soc.), 138 (No. 3), p. 665, 19
In 1991, a battery using MnO ₂ or NiO ₂ as a positive electrode was reported. These have attracted attention because of their high capacity per weight or volume. In addition, there are many reports on batteries using a conductive polymer as an electrode active material. For example, a lithium secondary battery using a polyaniline as a positive electrode is described in, for example, “27th Battery Symposium, 3A05L and 3A06L, 1986”. As reported in
It has already been launched by Bridgestone and Seiko as a coin-type battery for backup power supply. In addition, polyaniline has attracted attention as a positive electrode active material having high capacity and excellent flexibility.

Further, in recent years, electric double layer capacitors 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 disposed therebetween for use as a memory backup power supply or the like. . For example, "Functional Materials, February 1989, p. 33"
Discloses a capacitor using a carbon-based polarizable electrode and an organic electrolyte, "173rd Electrochemical Society Meeting Atlanta Georgia, May, No.
18, 1988 "describes an electric double layer capacitor using a sulfuric acid aqueous solution. Also, JP-A-63-2
No. 44570 discloses Rb ₂ C having high electrical conductivity.
A capacitor using u 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.

Japanese Patent Application Laid-Open No. Hei 4-253771 discloses the use of a polyphosphazene-based polymer as an ion-conductive substance for batteries and electric double-layer capacitors. The use of a conductive material has the advantages that the output voltage is higher than that of an inorganic ion conductive material, that the material can be processed into various shapes, and that sealing is simple. However, in this case, the ionic conductivity of the solid polymer electrolyte is 10 ⁻⁴ to 10 ⁻⁶ S / c.
m was not sufficient, and there was a drawback that the takeout current was small. In addition, when assembling a solid electrolyte and a polarizable electrode into a capacitor, there is also a problem that it is difficult to uniformly combine the solid electrolyte with a carbon material having a large specific surface area because of mixing of solids.

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. Furthermore, when these solid electrolytes are incorporated into an element such as an electric double layer capacitor, or when these solid electrolytes are incorporated into a battery as a thin film, processing techniques such as compounding with electrodes and securing contactability are difficult, and even in a manufacturing method. There was a problem. J. Appl. Electrochem. , NO
As described in pages 5, 63 to 69 (1975), a so-called polymer gel electrolyte obtained by adding a solvent and an electrolyte to a cross-linked polymer such as polyacrylonitrile or polyvinylidene fluoride gel has a high ionic conductivity. , Because it imparts fluidity, it cannot be handled as a completely solid, has poor film strength and film formability, and when applied to electric double layer capacitors and batteries, it is easy for short circuits to occur. This causes a sealing problem.

On the other hand, in US Pat. No. 4,792,504, the use of a crosslinked polymer solid electrolyte impregnated with an electrolytic solution comprising a metal salt and an aprotic solvent in a continuous network of poly (ethylene oxide) improves the ionic conductivity. It has been proposed. However, even if a solvent is added, the ionic conductivity is still insufficient at 10 ^-4 S / cm, and there is a problem that the strength of the film is reduced due to the addition of the solvent.

[0010] In order to solve these problems, the present inventors have proposed an ionic conductivity using a polymer comprising a (meth) acrylate monomer mixture containing an oxyalkylene group having a urethane bond and a composite comprising an electrolyte. (JP-A-6-187822).
Ion conductivity of this solid polymer electrolyte is a a high level of solvent is not added 10 ^-4 S / cm (room temperature), the further addition of solvent, at room temperature or above 10 ^over even at a low temperature ³ S / cm or more, and when the film quality was thick, it was improved to such an extent that it could be obtained as a free-standing film. In addition, this monomer has good polymerizability, and when it is applied to batteries and electric double layer capacitors, there is also a processing merit that it can be polymerized after being assembled into a battery or electric double layer capacitor in a monomer state and solidified. .

[0011] However, several tens of μm in the solvent addition system.
There is room for improvement in the strength of the film when it is made into a thin film of about m and the degree of short-circuit when it is applied to electric double layer capacitors and batteries. The polymer solid electrolyte layer in a battery and a capacitor only performs ion transfer. The thinner the polymer electrolyte layer, the smaller the volume of the entire battery and the capacitor, and the higher the energy density of the battery and the capacitor. Further, when the polymer solid electrolyte layer is thinned, the electric resistance of the battery and the capacitor can be reduced, the takeout current and the charging current can be increased, and the power density of the battery can be improved. Accordingly, there has been a demand for a polymer solid electrolyte having high ionic conductivity which has as good a film strength as possible and which can be made into a thin film. Further, the oxyalkylene group contained in the polymer solid electrolyte has room for improvement in terms of heat resistance.
It deteriorates when stored for a long time at a high temperature of 0 ° C. or higher. Further, the oxyalkylene group, particularly the oxyethylene group, is liable to be complexed with ions, which hinders ion transfer when a large current is to be obtained.

[0012]

SUMMARY OF THE INVENTION The present invention has a good strength even when a thin film having a thickness of about several tens of μm is formed in a solvent-added system, has high ionic conductivity at room temperature and low temperature, and has excellent workability and heat resistance. An object of the present invention is to provide a polymer solid electrolyte having excellent high current characteristics. Another object of the present invention is to develop a primary battery and a secondary battery which can be easily formed into a thin film, can be operated at a high capacity and a high current, and have excellent reliability by using the polymer solid electrolyte. And Another object of the present invention is to provide an electrode having high electrochemical activity and flexibility, and a secondary battery having good cycleability using the electrode.
Another object of the present invention is to provide an electrode which is used in an electric double layer capacitor, has good polarizability, has good strength when formed into a film, and has good contact with a solid electrolyte. Further, the present invention has a high ionic conductivity even at room temperature or lower temperature, membrane strength,
By using a polymer solid electrolyte with excellent processability, the output voltage is high, the take-out current is large, the processability,
An object is to provide an electric double layer capacitor having excellent reliability.

[0013]

Means for Solving the Problems The present inventors have developed a composite comprising a polymer obtained from a (meth) acrylate compound having a urethane bond and a fluoromethylene group or an oxyfluoromethylene group as a monomer, and an electrolyte.
It has been found that the polymer solid electrolyte has good membrane strength, high ionic conductivity, and excellent processability, heat resistance, and high current characteristics. In addition, the present inventors have found that by using this polymer solid electrolyte, thinning is easy, and a high capacity,
It has been found that a primary battery and a secondary battery which can operate at a high current and have excellent reliability can be obtained. Further, they have found that by using this polymer solid electrolyte, an electrode having high electrochemical activity and flexibility and a secondary battery having good cycleability using the same can be obtained. Furthermore, the present inventors have obtained that by using the above-mentioned polymer solid electrolyte, an electric double layer capacitor having a high output voltage, a large take-out current, and excellent workability and reliability can be obtained. Type electric double layer capacitor.

That is, the present invention has achieved the above object by developing the following. [1] A polymerizable functional group represented by the general formula (1) and / or a general formula (2) CH ₂ = C (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ ＣC (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. And / or actinic ray-polymerizable monomer compounds having a polymerizable functional group represented by the formula: [2] The polymerizable functional group represented by the general formula (1) and / or the general formula (2) CH ₂ ＲC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ ＣC (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. ] A polymer solid electrolyte obtained by polymerizing a polymerizable composition containing a heat- and / or actinic-ray-polymerizable monomer compound having a polymerizable functional group represented by formula (1) and at least one electrolyte. [3] The polymer solid electrolyte according to the above [2], comprising at least one solvent. [4] The polymer solid electrolyte according to [2] or [3], wherein the electrolyte is at least one selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. [5] A battery using the polymer solid electrolyte according to any of [2] to [4]. [6] The battery according to the above [5], wherein the negative electrode of the battery comprises an electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions. [7] The above-mentioned [5], wherein the positive electrode of the battery comprises an electrode containing a conductive polymer, a metal oxide, a metal sulfide or a carbon material.
Or the battery according to [6].

[8] The polymerizable functional group represented by the general formula (1) and / or the general formula (2): CH ₂ ＣC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. A polymerizable composition containing at least one kind of a heat and / or actinic ray polymerizable monomer compound having a polymerizable functional group and an electrolyte represented by the following formula: And polymerizing the polymerizable composition. [9] The method for producing a battery according to the above [8], wherein the polymerizable composition contains at least one kind of solvent. [10] A polymerizable functional group represented by the general formula (1) and / or
Or CH ₂ = C (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) [Wherein, R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. A polymer obtained from at least one kind of a heat- and / or actinic-ray-polymerizable monomer compound having a polymerizable functional group represented by the formula (1) and / or a copolymer containing the compound as a copolymer component, and an electrode active material or An electrode for a battery or an electric double layer capacitor comprising a polarizable material. [11] The electrode for a battery or an electric double layer capacitor according to the above [10], wherein the electrode active material or the polarizable material is a conductive polymer, a metal oxide, a metal sulfide or a carbon material. [12] In an electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive material, the ion conductive material is the polymer solid electrolyte according to any one of the above [2] to [4]. And electric double layer capacitor.

[13] The polymerizable functional group represented by the general formula (1) and / or the general formula (2): CH ₂ ＣC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. ] A polymerizable composition containing at least one kind of a heat and / or actinic ray polymerizable monomer compound having a polymerizable functional group and an electrolyte, or a polymerizable composition obtained by adding at least one solvent thereto A method for producing an electric double-layer capacitor, comprising placing an object in a structure for forming an electric double-layer capacitor or disposing the same on a support, and polymerizing the polymerizable composition.

Hereinafter, the present invention will be described in detail. Formula (1), which is a monomer for a polymer solid electrolyte of the present invention.
The compound having a polymerizable functional group represented by the formula and / or a polymerizable functional group represented by the general formula (2) has at least one ethylenically unsaturated group and a urethane group in a molecule, and further includes a fluorocarbon Group and / or a compound having an oxyfluorocarbon group. The general formula (1)
And R ² in (2) has, for example, 20 carbon atoms.
The following alkylene, oxyalkylene, arylene, and arylene groups are exemplified, and an alkylene group or an oxyalkylene group is preferable, and the number of carbon atoms is preferably 10 or less.
The method of synthesizing the compound having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2) is not particularly limited. For example, the following chemical formula CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH
₃ )) _y ] _z It can be obtained by reacting a compound represented by NCO ₃ with a hydroxy compound having a fluorocarbon group and / or an oxyfluorocarbon group (where R ¹ is the same as in the general formula (1); x and y represents 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10, provided that x = 0.
And when y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. )

As a specific method, a compound having one ethylenically unsaturated group, that is, a compound having one polymerizable functional group represented by the general formula (1) or (2) is, for example, a methacryloyl isocyanate compound. (Hereinafter abbreviated as MIs) or an acryloyl isocyanate compound (hereinafter abbreviated as AIs) and a monool such as 2,2,3,3,4,4,4-heptafluoro-1-butanol Are reacted in a molar ratio of 1: 1 by the following reaction formula,
Obtained easily. 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

A compound having two ethylenically unsaturated groups, that is, a compound having two polymerizable functional groups represented by the general formula (1) or (2) is, for example, a compound having MI or AI and 2,2. It can be easily obtained by reacting a diol such as 2,3,3-tetrafluoro-1,4-butanediol with a molar ratio of 2: 1 by the following reaction formula. 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

A side chain polymer is obtained by polymerizing a compound having one ethylenically unsaturated group, and a crosslinked polymer is obtained by polymerizing a compound having two or more ethylenically unsaturated groups. As the monomer used for the polymer of the polymer solid electrolyte of the present invention, it is necessary to use a compound having a polymerizable functional group represented by the general formula (1) or (2). When a polymer formed by polymerizing a compound having only one polymerizable functional group represented by the general formula (1) or (2) is used together with the electrolyte as a polymer of a solid polymer electrolyte, Although it has excellent adhesiveness to electrodes and composite efficiency, it has a large risk of short-circuiting when made into a thin film due to insufficient film strength. Considering the strength of the thin film of the solid electrolyte thus formed, the general formula (1) contained in one molecule
Alternatively, the number of polymerizable functional groups represented by (2) preferably includes two or more compounds.

The polymer contained in the solid polymer electrolyte of the present invention is a polymer having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2). It can be obtained by polymerizing at least one kind or polymerizing the compound as a copolymer component. Other polymerizable compounds copolymerizable with the compound having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2) are not particularly limited. . For example, one polymerizable functional group represented by the following general formula (3) such as N-methacryloylcarbamic acid ω-methyl oligooxyethyl ester and methacryloyloxyethyl carbamic acid ω-methyl oligooxyethyl ester is included in one molecule. Compound having the above (hereinafter, this compound is referred to as urethane (meth) acrylate having an oxyalkylene chain), CH ₂ ＣC (R ⁴ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOOR ^5- (3) [wherein, R ⁴ represents hydrogen or a methyl group, and R ⁵ represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. However, when x = 0 and y = 0, z = 0. (CH ₂ ) and (C
H (CH ₃ )) may be arranged irregularly. However, the values of R ⁴ , R ⁵ and x, y, z in a plurality of polymerizable functional groups represented by the above general formula (3) in the same molecule are independent of each other, and need not be the same. Absent. (Meth) acrylic ester having an oxyalkylene chain such as methacrylic acid ω-methyloligooxyethyl ester and / or (meth) acrylic ester having an oxyfluorocarbon chain, methyl methacrylate, n-butyl acrylate and the like. Acrylic acid alkyl ester and / or (meth) acrylic acid fluorinated alkyl ester, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, vinylene carbonate, (meth) acryloyl carbonate, N-vinylpyrrolidone , Acryloyl morpholine,
(Meth) acrylamide compounds such as methacryloylmorpholine and N, N-dimethylaminopropyl (meth) acrylamide; styrene compounds such as styrene and α-methylstyrene; N-vinylamide compounds such as N-vinylacetamide and N-vinylformamide Examples thereof include compounds and alkyl vinyl ethers such as ethyl vinyl ether. Among these, urethane (meth) acrylate having an oxyalkylene chain, (meth) acryl ester having an oxyalkylene chain and / or (meth) acryl ester having an oxyfluorocarbon chain, alkyl (meth) acrylate as well as/
Alternatively, a (meth) acrylic acid fluorinated alkyl ester compound is used. Among them, (meth) acrylic ester having oxyfluorocarbon chain, (meth)
Acrylic acid fluorinated alkyl ester compounds are particularly preferred.

For the polymerization, a general method utilizing the polymerizability of an acryloyl group or a methacryloyl group in the monomer compound can be employed. That is, a radical polymerization catalyst such as azobisisobutyronitrile, benzoyl peroxide, etc.
Radical polymerization, cationic polymerization or anionic polymerization using a cationic polymerization catalyst such as a proton acid such as CF ₃ COOH, a Lewis acid such as BF ₃ or AlCl ₃ or an anionic polymerization catalyst such as butyllithium, sodium naphthalene or lithium alkoxide. be able to. Further, the total content of the compound having a polymerizable functional group represented by the general formula (1) and / or the compound having a polymerizable functional group represented by the general formula (2) is 20 wt. %, The temperature is reduced to 70 under anoxic condition.
Polymerization can be carried out only by raising the temperature to at least ° C.

It is also possible to polymerize such a polymerizable monomer mixture after forming it into a film or the like. A polymer obtained from at least one compound having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2) and / or a copolymerization component of the polymer When the copolymer is used as the polymer of the solid polymer electrolyte as in the present invention, it is particularly advantageous to polymerize the polymerizable monomer mixture after forming the film. That is, at least one compound having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2) and an alkali metal salt, a quaternary ammonium salt, and a quaternary It is mixed with at least one electrolyte such as a phosphonium salt or a transition metal salt, and if necessary, further mixed with another polymerizable compound and / or a plasticizer and / or
Alternatively, a solvent is added and mixed, and the polymerizable composition is polymerized in the presence or absence of the catalyst, if necessary, by heating and / or irradiating with an actinic ray. In particular, after forming the polymerizable composition into a film-like shape, for example, by heating and / or irradiating with an actinic ray to polymerize to form a film-like polymer, the degree of freedom in the processing surface is increased, This is a great advantage in application.

When a solvent is used, any solvent may be used as long as it does not inhibit the polymerization, for example, tetrahydrofuran, acetonitrile, toluene, etc., depending on the type of monomer and the presence or absence of a polymerization catalyst. The polymerization temperature depends on the type of the compound having a polymerizable functional group represented by the general formula (1) and / or the compound having a polymerizable functional group represented by the general formula (2). Normally, the heat treatment may be performed in the range of 0 ° C. to 200 ° C. When polymerizing by irradiation with actinic rays, it depends on the type of the compound having a polymerizable functional group represented by the general formula (1) and / or the polymerizable functional group represented by the general formula (2). Benzyl methyl ketal,
By using an initiator such as benzophenone, polymerization can be carried out by irradiating ultraviolet light of several mW or more, γ-ray, electron beam or the like.

As described above, the polymer used in the solid polymer electrolyte of the present invention is a polymerizable functional group represented by the general formula (1) and / or a polymerizable functional group represented by the general formula (2). A homopolymer of a compound having a group, a copolymer of two or more types belonging to the category, or a copolymer of at least one of the compounds and another polymerizable compound. Good. Further, the polymer used for the polymer solid electrolyte of the present invention includes at least a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2). It may be a mixture of a polymer obtained from one kind and / or a copolymer containing the compound as a copolymer component and another polymer. For example, a polymer obtained from at least one compound having a structure substituted with the polymerizable functional group represented by the general formula (1) and / or the polymerizable functional group represented by the general formula (2); And / or a mixture of a copolymer having the compound as a copolymer component and a polymer such as polyethylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic acid (or acrylic) ester, polystyrene, polyphosphazene, polysiloxane or polysilane. The polymer solid electrolyte of the present invention may be used.

When the copolymer is used, the amount of the structural unit derived from the compound having a polymerizable functional group represented by the general formula (1) and / or the polymerizable functional group represented by the general formula (2) is as follows:
Although it depends on the type of the other copolymer component or polymer mixture component, in consideration of ionic conductivity and membrane strength, heat resistance, and current characteristics when used in a solid polymer electrolyte, the weight of the copolymer is 20% by weight. %, More preferably 50% by weight or more. When the structural unit derived from the compound having a polymerizable functional group represented by the general formula (1) and / or the polymerizable functional group represented by the general formula (2) is in the above-specified amount range, the polymer is used. Can exhibit sufficient membrane strength and heat resistance, and have high ionic conductivity and current characteristics when used as a polymer solid electrolyte.

(Co) used in the solid polymer electrolyte of the present invention
A compound having a polymerizable functional group represented by the general formula (1) and / or a polymerizable functional group represented by the general formula (2) used to obtain a polymer, and having one ethylenically unsaturated group Polymerization of the compound possessed results in a comb-shaped polymer and polymerization of the compound possessing two or more results in a crosslinked polymer.
Therefore, by mixing and polymerizing a compound having one polymerizable functional group represented by the general formula (1) or (2) and a compound having two or more in one molecule, the thermal kinetic property is improved. It is also possible to obtain a polymer having a large film strength. The number of fluorocarbon chains in the side chain or the cross-linking group of the polymer is preferably in the range of 1 to 1,000, particularly preferably 1 to 50.

It is preferable to add an organic compound as a solvent to the solid polymer electrolyte of the present invention since the ionic conductivity of the solid polymer electrolyte is further improved. As the plasticizer that can be used, a compound having good compatibility with the monomer used in the polymer solid electrolyte of the present invention, a large dielectric constant, a boiling point of 70 ° C. or higher, and a wide electrochemical stability range is suitable. . Examples of such a plasticizer include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, vinylene carbonate, (meth) acryloyl carbonate, and benzo. Aromatic nitriles such as nitrile and tolunitrile; sulfur compounds such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone, and sulfolane; and phosphate esters. Among them, oligoethers and carbonates are preferable,
Carbonates are particularly preferred. Although the ionic conductivity of the polymer solid electrolyte increases as the amount of the solvent added increases, the mechanical strength of the polymer solid electrolyte decreases when the amount is too large. The preferable addition amount is 5 times or less the weight of the monomer used for the polymer solid electrolyte of the present invention.

The polymer solid electrolyte of the present invention is obtained from at least one compound having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2). The composite ratio of the polymer and / or the copolymer having the compound as a copolymer component and the electrolyte used for the composite is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the polymer and the copolymer. Is particularly preferred. When the electrolyte used in the composite is present at a ratio of 50% by weight or more, the movement of ions is greatly inhibited. On the other hand, at a ratio of 0.1% by weight or less, the absolute amount of ions becomes insufficient and the ion conductivity decreases. .

The type of electrolyte used for the composite is not particularly limited, and an electrolyte containing an ion to be used as a carrier by charge may be used. However, it is desirable that the dissociation constant in the polymer solid electrolyte is large, Metal salts,
Quaternary ammonium salts such as (CH ₃ ) ₄ NBF ₄ ;
₃ ) ₄ Quaternary phosphonium salts such as ₄ PBF ₄ , AgClO ₄
And the like, or a protic acid such as hydrochloric acid, perchloric acid, and borofluoric acid.

The negative electrode active material used in the battery of the present invention includes 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 , LiI, LiBF ₄ , LiSCN, Li
AsF ₆ , NaCF ₃ SO ₃ , NaPF ₆ , NaClO ₄
, NaI, NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃
, KPF ₆ and KI. Among them, the use of lithium or a lithium alloy as the alkali metal is the most preferable because it has a high voltage, a high capacity, and can be formed into a thin film. In the case of a carbon material negative electrode, not only alkali metal ions but also quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and various protonic acids can be used.

In the case of a solid electric double layer capacitor, the type of electrolyte used for the composite is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used. It is desirable to contain ions which are large and easily form a polarizable electrode and an electric double layer. Such compounds include (CH ₃ ) ₄
Quaternary ammonium salts such as NBF ₄ , (CH ₃ CH ₂ ) ₄ ClO ₄ , transition metal salts such as AgClO ₄ , (CH ₃ ) ₄
Quaternary phosphonium salts such as PBF ₄ , LiCF ₃ SO ₃ ,
LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , Li
SCN, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF
₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF
₆ , alkali metal salts such as KCF ₃ SO ₃ , KPF ₆ and KI, organic acids and salts thereof such as paratoluenesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. Among them, quaternary ammonium salts, quaternary phosphonium salts, and alkali metal salts are preferable in that the output voltage can be increased and the dissociation constant is large. Among the quaternary ammonium salts, (CH ₃ CH
₂ ) Those having different substituents on the nitrogen of the ammonium ion, such as (CH ₃ CH ₂ CH ₂ CH ₂ ) ₃ NBF ₄ , have a large solubility or dissociation constant in the solid polymer electrolyte. preferable.

In the structure of the battery of the present invention, a low oxidation-reduction potential electrode active material (negative electrode active material) using an alkali metal ion such as an alkali metal, an alkali metal alloy or a carbon material as a carrier is used for the negative electrode. This is preferable because a high-voltage, high-capacity battery can be obtained. Among such electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, and lithium / antimony alloy are particularly preferable 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. Carbon materials capable of inserting and extracting Li ions include natural graphite, artificial graphite, vapor-phase graphite,
Examples include petroleum coke, coal coke, pitch-based carbon, polyacene, and fullerenes such as C ₆₀ and C ₇₀ .

In the structure of the battery of the present invention, a high oxidation-reduction potential electrode active material (positive electrode active material) such as a metal oxide, a metal sulfide, a conductive polymer or a carbon material is used for the positive electrode to increase the positive electrode. It is preferable because a battery with high voltage and high capacity can be obtained. Among such electrode active materials, the packing density is high, and the volume capacity density is high.
Metal sulfides such as titanium sulfide and 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. For example, "Electrochemistry, Vol. 22, p. 574, 195
It is manufactured by a general electrolytic method or a heating method as described in “4 Years”. When these are used in a lithium battery as an electrode active material, a Li element is inserted into a metal oxide or metal sulfide in the form of, for example, Li _x CoO ₂ or Li _x MnO ₂ (composite) at the time of manufacturing the battery. It is preferable to use it in a state where it has been used. 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 form 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. The conductive polymer used as an electrode active material in these batteries or electrodes is manufactured according to a chemical or electrochemical method described later or other known methods.

Examples of the carbon material include natural graphite, artificial graphite, vapor-phase graphite, petroleum coke, coal coke, fluorinated graphite, pitch-based carbon, and polyacene. Further, as the carbon material used as the electrode active material in the battery or the electrode of the present invention, a commercially available carbon material can be used, or it is manufactured according to a known method.

Next, an example of the method for manufacturing the electrode and the battery of the present invention will be described in detail. The electrode of the present invention may further comprise, for example, at least one compound having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2). Other polymerizable compounds and / or solvents are added and mixed with the above-mentioned electrode active material (a positive electrode active material or a negative electrode active material). In that case, the ratio of each component to be mixed is determined to be more appropriate for the intended battery. The polymerizable monomer thus obtained /
The electrode is manufactured by forming the electrode active material mixture into a film shape or the like and then performing polymerization. In this method, the polymerization is performed in the same manner as when a polymer is obtained from a compound (monomer) having a polymerizable functional group represented by the general formula (1) and / or a polymerizable functional group represented by the general formula (2). A similar polymerization method can be used. For example, polymerization can be performed by heating and / or irradiation with actinic rays. When the electrode active material gives a highly flowable polymerizable monomer / electrode active material mixture, for example, as in the case of an organic solvent-soluble aniline-based polymer, the mixture is treated with a current collector or other glass or the like. An electrode is produced by forming the film by a method such as coating on a support and forming a film, and then polymerizing.

The electrode containing the above-mentioned electrode active material manufactured in this manner is used as at least one electrode, and the electrode containing another electrode active material manufactured in the same manner or another commonly used electrode is used as the other electrode. The two electrodes are placed in the structure for battery construction so as not to contact each other, or are arranged on a support. For example, a positive electrode and a negative electrode are attached to the end of the electrode via a spacer having an appropriate thickness, and the positive electrode and the negative electrode are placed in the structure. Next, a polymerizable functional compound represented by the general formula (1) is placed between the positive electrode and the negative electrode At least one compound having a group and / or a polymerizable functional group represented by the general formula (2) is mixed with at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts. After injecting the polymerizable composition prepared by adding and mixing the polymerizable compound and / or the solvent of the above, the polymerization represented by the above-mentioned general formula (1), for example, polymerization by heating and / or irradiation with actinic rays is performed. For obtaining a polymer obtained from at least one compound having a functional functional group and / or a polymerizable functional group represented by the general formula (2) and / or a copolymer containing the compound as a copolymer component Same as By polymerizing in the method, or, further, after polymerization if necessary in the polyolefin resin, followed by sealing with an insulating resin such as epoxy resin, battery electrodes and electrolyte has good contact is obtained.

The structure for the battery or the support may be a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. It is not limited to what is, and its shape is
It may be cylindrical, box-shaped, sheet-shaped or any other shape. As described above, a monomer mixture containing at least one compound having a polymerizable functional group represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2) and at least one electrolyte Is polymerized to obtain a polymerizable composition represented by the general formula (1) and / or a compound having a polymerizable functional group represented by the general formula (2). The method for producing a solid polymer electrolyte comprising a polymer obtained from at least one type of polymer and / or a copolymer containing the compound as a copolymer component and at least one type of electrolyte is particularly suitable for producing a thin film battery. Useful.

FIG. 1 shows a schematic sectional view of an example of a thin-film solid state secondary battery as an example of the battery of the present invention thus manufactured. In the figure, 1 is a positive electrode, 2 is a solid polymer electrolyte, 3
Denotes an anode, 4 denotes a current collector, 5 denotes an insulating resin film serving as a spacer, and 6 denotes an insulating resin sealant. When manufacturing a wound type battery, the above-described positive electrode and negative electrode are pasted together through a previously prepared polymer solid electrolyte sheet, wound, and inserted into the battery structure, and then the polymerizable composition is further added. It is also possible to inject a substance and polymerize it.

Next, the solid electric double layer capacitor of the present invention will be described. In the solid electric double layer capacitor of the present invention, the use of the polymer solid electrolyte of the present invention provides an all solid electric double layer capacitor having a high output voltage, a large take-out current, or excellent workability and reliability. Is done. FIG. 2 is a schematic sectional view of an example of the solid electric double layer capacitor of the present invention. This example is 1cm in size
A thin cell having a size of about 1 mm and a thickness of about 0.5 mm, 8 is a current collector, and a pair of polarizable electrodes 7 is disposed inside the current collector, and a solid polymer electrolyte membrane 9 is disposed therebetween. Have been. Reference numeral 10 denotes a spacer, an insulating film is used in this example, 11 is an insulating resin sealant, and 12 is a lead wire.

The current collector 8 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, carbon sheets and the like can be mentioned. The polarizable electrode 7 may be any electrode made of a polarizable material such as a carbon material usually used for an electric double layer capacitor. However, it is preferable that the carbon material is combined with the polymer solid electrolyte of the present invention. 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.

Next, an example of a method for manufacturing a solid electric double layer capacitor of the present invention will be described. As described above, at least one kind of the compound having the polymerizable functional group represented by the general formula (1) and / or the compound having the polymerizable functional group represented by the general formula (2) is mixed with at least one kind of electrolyte. By polymerizing the obtained polymerizable composition, it is obtained from at least one compound having a polymerizable functional group represented by the general formula (1) and / or a polymerizable functional group represented by the general formula (2). The method for producing a composite containing the obtained polymer and / or a copolymer containing the compound as a copolymer component and at least one electrolyte is particularly useful for producing the solid electric double layer capacitor of the present invention.

A polarizable material such as a carbon material and a polymerizable functional group represented by the general formula (1) and / or a general formula (2) preferably used in the solid electric double layer capacitor of the present invention. When producing a polarizable electrode containing a polymer obtained from at least one compound having a polymerizable functional group and / or a copolymer containing the compound as a copolymer component, first, for example, the following general formula (1) is used. At least one compound having a polymerizable functional group represented by the general formula (2) and / or a compound having a polymerizable functional group represented by the general formula (2), and if necessary, further adding another polymerizable compound and / or a solvent; Mix with polarizable material. In that case, the ratio of the components to be mixed is determined to be more appropriate for the intended capacitor. The polymerizable monomer / polarizable material mixture thus obtained is formed into a film on a support, for example, a current collector, and then polymerized by heating and / or irradiation with electromagnetic waves. ) And / or a polymer obtained from at least one compound having a polymerizable functional group represented by the general formula (2) and / or a copolymer containing the compound as a copolymer component The polarizable electrode is produced by polymerizing in the same manner as the polymerization method for obtaining According to this method, a composite thin-film electrode that is in good contact with the current collector can be manufactured.

The two polarizable electrodes manufactured as described above are placed in a structure for forming a capacitor so as not to be in contact with each other, or are arranged on a support. For example, by bonding both electrodes to the end of the electrode via a spacer of appropriate thickness,
A polymerizable composition prepared by placing the polymer in the structure, then mixing a monomer and an electrolyte between the two polarizable electrodes, and optionally adding and mixing another polymerizable compound and / or a solvent. After injecting the substance, by polymerizing in the same manner as described above, or further, if necessary after the polymerization, sealing with an insulating resin such as polyolefin resin, epoxy resin, etc. A contacted electric double layer capacitor is obtained. When preparing such a polymerizable composition, the ratio of each component to be mixed is determined to be appropriate for the intended capacitor. By this law,
In particular, a thin all-solid-state electric double layer capacitor can be manufactured. The structure for forming the capacitor or the support may be a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. However, the shape is not limited to this, and the shape may be cylindrical, box, sheet, or any other shape.

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 laminate of a polarizable electrode and a polymer solid electrolyte is wound into a cylindrical shape, and a cylindrical tubular shape is obtained. Put in the structure for capacitor construction,
It may be a cylindrical type or the like manufactured by sealing. In the case of manufacturing a wound capacitor, the polarizable electrode is pasted through a polymer solid electrolyte prepared in advance, wound, wound, and further inserted into the structure for forming a capacitor. Is injected and polymerized.

[0047]

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 Monomer 1> CF ₃ (CF ₂ ) ₂ CH ₂ OH + CH ₂ = C (CH ₃ ) CONCO → CF ₃ (CF ₂ ) ₂ CH ₂ OCONHCOC (CH ₃ ) = CH ₂ compound 1 MAI monomer 1 Compound 1 (2,2,3,3,4,4,4-heptafluoro-1-butanol, manufactured by Aldrich) 20 g, MAI (methacryloyl isocyanate, manufactured by Nippon Paint) 11.1 g were thoroughly mixed in a nitrogen atmosphere. After mixing with 100 ml of purified THF, 0.66 g of dibutyltin dilaurate is added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a polymerizable monomer 1 as a colorless viscous liquid. From the results of ¹ H-NMR, IR, and elemental analysis, it was found that Compound 1 and MAI reacted one-to-one, and further, the isocyanate group of MAI disappeared, and a urethane bond was formed. .

Example 2 1: 1.00 g of polymerizable monomer synthesized in Example 1, diethyl carbonate (DEC)
1.5g, ethylene carbonate (EC) 1.5g, LiP
0.40 g of F ₆ and 0.02 g of Darocure 1173 were mixed well in an argon atmosphere to obtain a polymerizable monomer solution as a polymerizable composition. This polymerizable monomer solution was coated on a PET film under an argon atmosphere, and then a mercury lamp was used.
After irradiation for 0 minutes, a monomer 1 polymer impregnated with the electrolytic solution was obtained as a transparent free-standing film of about 50 μm.
When the ionic conductivity of this film at 25 ° C. and −15 ° C. was measured by an impedance method, each was 1 × 10 5
^-3 and 0.3 × 10 ^-3 S / cm.

Example 3 <Synthesis of Monomer 2> HOCH ₂ (CF ₂ ) ₄ CH ₂ OH + 2 CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ NCO Compound 2 MOI → {-(CF ₂ ) ₂ CH ₂ OCONH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ } ₂ Monomer 2 Compound 2 (2,2,3,3,4,4,5,5, -octafluoro-1,6-hexanediol , Aldrich) 13.1g, MOI (2-
Methacryloyloxyethyl isocyanate (15.5 g, manufactured by Showa Denko KK)
After mixing to 100 ml, 0.66 g of dibutyltin dilaurate is added. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a polymerizable monomer 2 as a colorless viscous liquid. From the results of ¹ H-NMR, IR and elemental analysis, it was found that the compound 2 reacted with the MOI at a ratio of 1: 2, the isocyanate group of the MOI disappeared, and a urethane bond was formed. .

Example 4 Example 1 under an argon atmosphere
1: 0.8 g of the monomer synthesized in Example 2, 0.2 g of the monomer synthesized in Example 2, and 1.0 g of propylene carbonate (PC)
, Ethylene carbonate (EC) 2.0g, LiPF ₆
0.40 g and 0.02 g of Irgacure 500 were mixed well in an argon atmosphere to obtain a polymerizable monomer solution.
This polymerizable monomer solution was applied to a PET film under an argon atmosphere, and then irradiated with a mercury lamp for 10 minutes.
A copolymer of monomer 1 and monomer 2 impregnated with the electrolyte was obtained as a transparent free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −15 ° C. was measured by an impedance method, each was 0.8 × 1.
0 ^-3 and 0.1 × 10 ^-3 S / cm.

Example 5 Instead of LiPF ₆ , NaC
Except that 0.40 g of F ₃ SO _{3 was} used, the procedure was the same as in Example 4,
The solid polymer electrolyte was obtained as a transparent free-standing film of about 50 μm. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by an impedance method, it was 1.5 × 10 ⁻³ S / cm
Met.

Example 6 <Synthesis of Monomer 3> HOCH ₂ (OCF ₂ CF ₂ ) _2n CH ₂ OH + 2CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ NCO Compound 3 MOI → {-(OCF ₂ CF ₂ ) _n CH ₂ OCONH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ } ₂ Monomer 3 Compound 3 (AUSIMONT; FOMBLIN ZDOL-2000): 100 g,
MOI 15.5g THF 100 well purified in nitrogen atmosphere
After mixing to 0.6 ml, add 0.66 g of dibutyltin dilaurate. Thereafter, the mixture was reacted at 25 ° C. for about 15 hours to obtain a polymerizable monomer 3 as a colorless viscous liquid. From the results of ¹ H-NMR, IR and elemental analysis, Compound 3
And the MOI reacted one to two, and it was further found that the isocyanate group of the MOI disappeared and a urethane bond was formed.

Example 7 Monomer 3: synthesized in Example 6, 1.00 g, diethyl carbonate (DEC) 1.5 g,
1.5 g of ethylene carbonate (EC), LiClO ₄₀ .
40 g and 0.01 g of Irgacure 500 were mixed well in an argon atmosphere to obtain a polymerizable monomer solution. This polymerizable monomer solution was coated on a PET film in an argon atmosphere, and then irradiated with a mercury lamp for 10 minutes. As a result, a monomer 3 polymer-based polymer solid electrolyte impregnated with an electrolyte was obtained as a transparent free-standing film of about 30 μm. Was. When the ionic conductivity at 25 ° C. and −15 ° C. of the film was measured by an impedance method, they were 1.0 × 10 ⁻³ ,
It was 0.5 × 10 ⁻³ S / cm.

Example 8 Instead of LiClO ₄ , 0.50
In the same manner as in Example 7 except that g of tetraethylammonium tetrafluoroborate (TEAB) was used, a monomer 3 polymer-based polymer solid electrolyte containing an electrolytic solution was obtained as a transparent free-standing film of about 30 μm. When the ionic conductivity of this film at 25 ° C. and −15 ° C. was measured by an impedance method, they were 1.2 × 10 ⁻³ and 0.6 ×, respectively.
It was 10 ^-3 S / cm.

Example 9 Under an argon atmosphere, monomer 1: 0.50 g, monomer 2: 0.20 g, butyl acrylate (BA) 0.30 g, propylene carbonate (PC) 1.0
g, ethylene carbonate (EC) 2.0 g, LiPF ₆
0.40 g and 0.02 g of Irgacure 500 were mixed well in an argon atmosphere to obtain a polymerizable monomer solution.
This polymerizable monomer solution was applied to a PET film under an argon atmosphere, and then irradiated with a mercury lamp for 10 minutes.
A copolymer of Monomer 1, Monomer 2, and BA impregnated with the electrolytic solution was obtained as a transparent free-standing film of about 30 μm. The ionic conductivity at 25 ° C. and −15 ° C. of this film was measured by an impedance method, and was 1.
It was 8 × 10 ^-3 and 0.8 × 10 ^-3 S / cm.

Example 10 Monomer 1: 1.00 g, diethyl carbonate (DEC) 1.5 g, ethylene carbonate (EC) 1.5 g, LiBF ₄ 0.30 g, and 0.02 g of Darocure 1173 were mixed well in an argon atmosphere. A polymerizable monomer solution was obtained. This polymerizable monomer solution was impregnated and applied to a nonwoven fabric made of polypropylene (MU3005, manufactured by Japan Vilene Co., Ltd.) of about 50 μm under an argon atmosphere, and then irradiated with a mercury lamp for 10 minutes. As a composite film with a polypropylene nonwoven fabric. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 0.8 × 10 ⁻³ S / cm.

Example 11 <Production of Lithium Cobaltate Cathode> 11 g of Li ₂ CO ₃
And 24 g of Co ₃ O ₄ are mixed well, and
After heating at 0 ° C. for 24 hours, pulverization is performed to obtain LiCoO.
_Two powders were obtained. The LiCoO ₂ powder, acetylene black, and polyvinylidene fluoride were mixed at a weight ratio of 8: 1: 1, and an excess N-pyrrolidone solution was added to obtain a gel composition. This composition was placed on an aluminum foil of about 25 μm in a thickness of 1
It was applied and molded to a size of cm × 1 cm and a thickness of about 200 μm. Furthermore, by heating and vacuum drying at about 100 ° C. for 24 hours, a lithium cobaltate positive electrode (80 mg) was obtained.

Example 12 <Production of Li Secondary Battery> A 75 μm-thick lithium foil was cut into 1 cm × 1 cm (5.3 mg) in an argon atmosphere glove box, and about 1 mm square at its end was 5 μm polyimide. The film was coated as a spacer. Next, an electrolytic solution (1.5 mol / l LiPF ₆ / PC + EC) was placed on the lithium foil.
(Weight ratio 1: 2)), and the polymer solid electrolyte film (12 mm × 12 mm) prepared in Example 4 was stuck on a lithium foil, and the lithium cobaltate positive electrode (10 mm × 10 mm) in an electrolyte solution (1.5 mol / l LiPF ₆ / PC + EC (weight ratio 1:
2)) was impregnated, and the battery end was sealed with an epoxy resin to obtain a lithium / cobalt oxide secondary battery. FIG. 1 shows a cross-sectional view of the obtained battery. When the battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.5 mA, the maximum discharge capacity was 6.8 mAh, and the cycle life until the capacity was reduced to 50% was 150 times.

Example 13 <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)
Excessive N-pyrrolidone solution was added to a mixture having an average fiber length of 2.0 μm and heat treated at 2700 ° C.) and a weight ratio of polyvinylidene fluoride of 8.6: 0.4: 1.0 to obtain a gel composition. This composition was placed on a copper foil of about 15 μm in a size of 1 cm × 1 cm, about 250 cm.
It was applied and molded to a thickness of μm. Furthermore, at about 100 ° C., 24
By heating and vacuum drying for a period of time, a graphite negative electrode (30 mg) was obtained.

Example 14 <Manufacture of Li-ion secondary battery> The graphite negative electrode manufactured in Example 13 was replaced with an electrolyte (1.5 mol / l Li
A graphite / lithium cobaltate-based Li-ion secondary battery was obtained in the same manner as in Example 12, except that the battery impregnated with PF ₆ / PC + EC (weight ratio 1: 2) was used. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.5 mA, the maximum discharge capacity was 6.6 mAh, and the cycle life until the capacity was reduced to 50% was 320 times.

Example 15 Under an argon atmosphere, the monomer synthesized in Example 1 was 1: 0.8 g, the monomer 2 synthesized in Example 2 was 0.2 g, propylene carbonate (PC) 2.0
g, ethylene carbonate (EC) 4.0 g, LiPF ₆
0.70 g and 0.002 g of AIBN (azobisisobutyronitrile) were mixed well in an argon atmosphere to obtain a thermopolymerizable monomer solution. A 75 μm-thick lithium foil was cut into 1 cm × 1 cm (5.3 mg) in an argon atmosphere glove box, and about 1 mm on each end thereof was covered with a 5 μm polyimide film as a spacer. Next, the above-mentioned thermopolymerizable monomer solution was thinly applied on a lithium foil, the polymer solid electrolyte film prepared in Example 4 was adhered thereon, and the lithium cobaltate positive electrode (10 mm × 10 mm), which was impregnated with the above-mentioned thermopolymerizable monomer solution, was bonded thereto, heated at 80 ° C. for 30 minutes to polymerize the polymerizable monomer solution, and the battery end was sealed with an epoxy resin to obtain a lithium / cobalt acid solid. A lithium secondary battery was obtained. Operate the battery with an operating voltage of 2.0 to 4.2.
When charge and discharge were repeated at V and a current of 0.1 mA, the maximum discharge capacity was 6.3 mAh, and the cycle life until the capacity was reduced to 50% was 210 times.

Example 16 <Manufacture of a solid Li-ion secondary battery> Example 16 was repeated except that the graphite anode prepared in Example 13 was impregnated with the thermopolymerizable monomer solution prepared in Example 15. In the same manner as in Example 14, a graphite / lithium cobaltate solid Li-ion secondary battery was obtained. This battery is operated at an operating voltage of 2.0 to 4.2 V and a current of 0.
Repeated charge and discharge at 1mA, the maximum discharge capacity is 6.3mAh
And the cycle life until the capacity is reduced to 50% is 43
It was 0 times.

Example 17 <Production of Activated Carbon Electrode> An excess N-pyrrolidone 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 placed on a stainless steel foil in a size of 1 cm × 1 cm in a size of about 150 μm.
To a thickness of Vacuum dried at about 100 ° C for 10 hours,
An activated carbon electrode (14 mg) was obtained.

Example 18 <Manufacture of Solid Electric Double Layer Capacitor> In an argon atmosphere glove box, the activated carbon electrode (14 mg) manufactured in Example 17 was 1 cm × 1 cm, and about 1 mm square at the end was 5 mm thick.
Two electrodes coated with a polyimide film of μm and impregnated with the thermopolymerizable monomer solution prepared in Example 15 were prepared. Next, the polymer solid electrolyte film (12 mm × 12 mm) prepared in Example 4 was attached to one of the electrodes,
Further, another electrode was bonded and heated at 80 ° C. for 1 hour, and the end of the capacitor was sealed with epoxy resin to produce a solid electric double layer capacitor as shown in FIG. This capacitor is operated at an operating voltage of 0 to 2.0 V and a current of 0.1 mA.
And the maximum capacity was 410 mF. In addition, even if charging and discharging were repeated 50 times under these conditions, the capacity hardly changed.

From the above results, the solid polymer electrolyte of the present invention has good thin film strength, high ionic conductivity, and shows good physical properties when applied to batteries and solid electric double layer capacitors. You can see that.

[0066]

As described above, the polymer solid electrolyte of the present invention has a urethane bond / fluorocarbon group which can be easily formed into a film from the polymerizable composition as a raw material and is compounded into a side chain and / or a crosslinking group. A highly ion-conductive solid electrolyte made of a comb-shaped polymer or a network polymer, has a good film strength, and is excellent in thin film workability. The battery of the present invention is a highly reliable battery that can be easily processed into a thin film by using the polymer solid electrolyte as an ion conductive material, does not cause a short circuit even in a thin film, has a large take-out current, and has high reliability. In particular, an all-solid-state battery can be used. Further, the battery of the present invention, in which the negative electrode comprises an electrode containing an active material such as lithium or a lithium alloy or a carbon material capable of inserting and extracting lithium ions, can be formed into a thin film by using the polymer solid electrolyte as an ion conductive material. Such a battery is easy to process, has no danger of short circuit even in a thin film, has a large take-out current, and has high reliability. In particular, it can be an all solid-state battery.

Further, the positive electrode of the present invention can be obtained by using the general formula (1)
A polymer obtained from at least one compound having a polymerizable functional group represented by the formula and / or a polymerizable functional group represented by the general formula (2) and / or a copolymer containing the compound as a copolymer component; A battery comprising an electrode containing an active material such as a conductive polymer, a metal oxide, a metal sulfide or a carbon material, and using the polymer solid electrolyte as an electrolyte, is easy to process such as thinning. In addition, there is no danger of short-circuiting even in a thin film, a large current is taken out, the capacity is high, and the battery is highly reliable. Further, the battery of the present invention has a high capacity as an all solid type,
It is a battery that can be operated at high current or has good cycling characteristics and is excellent in safety and reliability. It is a main power supply for portable equipment, a power supply for backup and other electric products,
It can be used as a large power source for electric vehicles and road leveling. Further, since it can be easily thinned, it can be used as a paper battery for an identification card or the like.

Further, a polymer obtained from at least one of the compounds having a polymerizable functional group represented by the general formula (1) and / or a polymerizable functional group represented by the general formula (2) of the present invention. And / or an electrode containing a copolymer having the compound as a copolymer component and an electrode active material such as a conductive polymer, a metal oxide, a metal sulfide or a carbon material, and a method for producing the electrode, Without impairing the electrochemical activity of the electrode active material excellent in activity, it is intended to provide an electrode having flexibility as required, for example, it can be a thin film electrode, various It is useful as a battery electrode. Further, according to the method for producing a battery of the present invention, batteries of various shapes can be produced, particularly, the battery can be easily made thin, and can operate at high capacity and high current,
Alternatively, a battery having good cyclability and excellent reliability can be manufactured, and in particular, an all-solid-state battery can be manufactured.

The electric double layer capacitor of the present invention is a polymerizable monomer mixture which is a comb polymer or a network polymer in which a urethane bond / fluorocarbon group is introduced into a side chain and / or a crosslinkable group, which can be easily formed and combined. It is manufactured by polymerizing a polymerizable composition in which an electrolyte is dissolved into a polymer solid electrolyte having high ionic conductivity and good film strength as an ion conductive material. This is a highly reliable electric double-layer capacitor having a large output voltage and a high current, and in particular, can be an all-solid-state electric double-layer capacitor. In particular, according to the electric double layer capacitor and the method of manufacturing the same of the present invention, good contact is made between the polarizable electrode and the solid polymer electrolyte that is an ion conductive substance, there is no short circuit even in a thin film, and the output voltage and An electric double layer capacitor having a large extraction current and high reliability is provided, and particularly, an all-solid-state electric double layer capacitor is provided.

Further, the electric double layer capacitor of the present invention
Compared with conventional all solid type capacitors, it can operate at high voltage, high capacity, high current, or has good cycleability,
It is an electric double layer capacitor with excellent safety and reliability.
An all-solid-state electric double layer capacitor having such characteristics can be obtained. Therefore, not only the backup power supply,
It can be used as a power source for various electrical products when used with small batteries. Further, it is excellent in workability such as thinning, and can be expected for uses other than the use of the conventional solid type electric double layer capacitor.

[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 of an embodiment of the solid electric double layer capacitor of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Polymer solid electrolyte 3 Negative electrode 4 Current collector 5 Spacer 6 Insulating resin sealing agent 7 Polarizing electrode 8 Current collector 9 Polymer solid electrolyte membrane 10 Spacer 11 Insulating resin sealing agent 12 Lead wire

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location H01G 9/025 H01M 4/02 B 9/058 6/18 E H01M 4/02 10/40 6 / 18 C08F 299/02 10/40 H01G 9/00 301G // C08F 299/02 301A (72) Inventor Takashi Okubo 1-1-1, Onodadai, Midori-ku, Chiba-shi, Chiba Pref. Showa Denko KK

Claims (13)

[Claims] 1. A polymerizable functional group represented by the general formula (1) and / or a general formula (2): CH ₂ ＣC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. And / or actinic ray-polymerizable monomer compounds having a polymerizable functional group represented by the formula: 2. A polymerizable functional group represented by the general formula (1) and / or a general formula (2): CH ₂ ＣC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. ] A polymer solid electrolyte obtained by polymerizing a polymerizable composition containing a heat- and / or actinic-ray-polymerizable monomer compound having a polymerizable functional group represented by formula (1) and at least one electrolyte. 3. The polymer solid electrolyte according to claim 2, comprising at least one solvent. 4. The polymer solid electrolyte according to claim 2, wherein the electrolyte is at least one selected from alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and transition metal salts. 5. A battery using the polymer solid electrolyte according to claim 2. 6. The battery according to claim 5, wherein the negative electrode of the battery comprises an electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions. 7. The battery according to claim 5, wherein the positive electrode of the battery comprises an electrode containing a conductive polymer, a metal oxide, a metal sulfide, or a carbon material. 8. A polymerizable functional group represented by the general formula (1) and / or a general formula (2): CH ₂ ＣC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. A polymerizable composition containing at least one kind of a heat and / or actinic ray polymerizable monomer compound having a polymerizable functional group and an electrolyte represented by the following formula: And polymerizing the polymerizable composition. 9. The method according to claim 8, wherein the polymerizable composition contains at least one solvent. 10. The polymerizable functional group represented by the general formula (1) and / or the general formula (2): CH ₂ ＣC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. A polymer obtained from at least one kind of a heat- and / or actinic-ray-polymerizable monomer compound having a polymerizable functional group represented by the formula (1) and / or a copolymer containing the compound as a copolymer component, and an electrode active material or An electrode for a battery or an electric double layer capacitor comprising a polarizable material. 11. The electrode for a battery or an electric double layer capacitor according to claim 10, wherein the electrode active material or the polarizable material is a conductive polymer, a metal oxide, a metal sulfide or a carbon material. 12. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is the solid polymer electrolyte according to any one of claims 2 to 4. Electric double layer capacitor. 13. The polymerizable functional group represented by the general formula (1) and / or the general formula (2): CH ₂ ＣC (R ¹ ) CO [OR ² ] _x NHCOO-R ^3- (1) CH ₂ = C (R ¹ ) CO [OR ² ] _x OCONH-R ^3- (2) wherein R ¹ represents hydrogen or an alkyl group, and R ² represents 2
Represents a valent organic group. R ³ is a fluoroalkylene and / or
Or a divalent group containing oxyfluoroalkylene. The divalent organic group and the divalent group are linear, branched,
Any of a ring structure may be used. 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. ] A polymerizable composition containing at least one kind of a heat and / or actinic ray polymerizable monomer compound having a polymerizable functional group and an electrolyte, or a polymerizable composition obtained by adding at least one solvent thereto A method for producing an electric double-layer capacitor, comprising placing an object in a structure for forming an electric double-layer capacitor or disposing the same on a support, and polymerizing the polymerizable composition.