JPH08295713A - Solid polymer electrolyte, battery and solid electric double layer capacitor containing same, their production and material for solid polymer electrolyte - Google Patents

Abstract

PURPOSE: To obtain a solid polymer electrolyte which can give a membrane having good strengths, improved room-temperature and low-temperature inoic conductivity and processability by composing it of at least a polymer of a specified compound and/or a copolymer containing the compound and at least one electrolyte. CONSTITUTION: A solid polymer electrolyte comprising a complex containing at least one polymer of a compound containing units of the formula [wherein R<1> is H or methyl; R<2> is a linear, branched or cyclic group and may contain at least one element other than C, H and O; (x) and (y) are each an integer of 0-5; (z) is an integer of 0-10; provided that z=0 when (x) and (y) are 0; and (CH2 ) groups and (CH(CH3 )) groups may be bonded to each other at random, provided that R<1> , R<2> , (x), (y) and (z) in a plurality of units of the formula are independent of each other in the same molecule] and/or a copolymer containing the above compound as a comonomer and at least one molecule, per 1-100 carbonate groups in the side chains or in the bridging chains of the polymer, of at least one electrolyte.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymer solid electrolyte having high ion conductivity using a polymer having a carbonate side chain and / or a cross-linked chain having a urethane bond, and an electrode using the polymer. Manufacturing method thereof, battery using the polymer solid electrolyte or the electrode and manufacturing method thereof, electric double layer capacitor using the polymer solid electrolyte and manufacturing method thereof,
The present invention relates to the polymer and a monomer of the polymer.

[0002]

2. Description of the Related Art Solid electrolytes are used as new ion conductors in place of conventional electrolyte solutions in the field of downsizing and solidification in the field of ionics, and are used as all-solid-state primary batteries, secondary batteries, and electric double layer capacitors. The application to is being actively attempted. Current batteries using electrolyte solutions have a problem in long-term reliability because liquid leakage to the outside of parts or elution of electrode substances is likely to occur. On the other hand, the product using the solid electrolyte does not have such a problem and can be easily thinned. Furthermore, the solid electrolyte is also excellent in heat resistance and is advantageous in the manufacturing process of products such as batteries.

In particular, the one using a solid electrolyte containing a polymer as a main component has an advantage that the flexibility of the battery is increased and it can be processed into various shapes as compared with an inorganic substance. However, what has been studied so far has a problem that the extraction current is small because the ionic conductivity of the solid polymer electrolyte is low.

Examples of these polyelectrolytes include “British Polymer Journal (Br. Polym. J.),
319, p. 137, 1975 ", it is described that a composite of polyethylene oxide and an inorganic alkali metal salt exhibits ionic conductivity, but the ionic conductivity at room temperature is 10 ^-7 S. / Cm is low.

Recently, it has been reported that a comb polymer having oligooxyethylene introduced into its side chain enhances the thermal mobility of the oxyethylene chain, which is responsible for the ionic conductivity, and improves the ionic conductivity. There is. For example, “J. Phys. Chem., Vol. 89, p. 987, 1984” in “Journal of Physical Chemistry. The example which compounded is described. further,
"Journal of American Chemical Society, J. Am. Chem. Soc., Vol. 106, p. 6854,
"1984" describes an example in which a polyphosphazene having an oligooxyethylene side chain is complexed with an alkali metal salt.

Recently, LiCoO ₂ , LiNiO ₂ , Li
Many studies have been made on lithium secondary batteries using a metal oxide such as MnO ₂ or MoS ₂ or a metal sulfide as a positive electrode. For example, “Journal of Electrochemical Society (J. Electrochem. Soc.), Volume 138 (No.
3), p. 665, 1991 ", a battery having MnO ₂ or NiO ₂ as a positive electrode is reported. These have attracted attention because of their high capacity per weight or volume.

Many reports have been made 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
3rd Battery Discussion Session, 3A05L and 3A06L, 1986
As reported in "Year", it has already been put on the market as a coin-type battery for use as a backup power source by Bridgestone and Seiko. Polyaniline has been attracting attention as a positive electrode active material having a high capacity and excellent flexibility.

Further, 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 them has been widely used for a memory backup power source or the like. . For example, "Functional Materials, February 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 issue, 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, the current electric double layer capacitor using the electrolyte solution is liable to leak to the outside of the capacitor for a long period of time during abnormal conditions such as long-term use or application of high voltage. There is a problem in use and reliability. 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 Unexamined Patent Publication (Kokai) No. 4-253771 proposes to use a polyphosphazene type polymer as an ion conductive substance of a battery or an electric double layer capacitor. A material using a conductive substance has a merit that it has a higher output voltage than an inorganic ion conductive material, can be processed into various shapes, and can be easily sealed.

However, in this case, the ionic conductivity of the solid polymer electrolyte is not sufficient at 10 ^-4 to 10 ^-6 S / cm, and there is a drawback that the extraction current is small.
It is also possible to add a plasticizer to the polymer solid electrolyte to increase the ionic conductivity, but since it adds fluidity, it cannot be handled as a perfect solid, resulting in poor film strength and film formability. When it is applied to an electric double layer capacitor or a battery, a short circuit is likely to occur, and a sealing problem occurs like the liquid ion conductive material. On the other hand, when assembling a solid electrolyte together with a polarizable electrode into a capacitor, there is a problem that it is difficult to uniformly compound a carbon material having a large specific surface area because the solids are mixed with each other.

The ionic conductivity of polymer solid electrolytes generally studied is 10 ⁻⁴ to 10 ⁻⁵ S at room temperature.
Although it has been improved to about / cm, the level is still lower by two digits or more as compared with the liquid ion conductive material. Also,
At a low temperature of 0 ° C. or lower, the ionic conductivity further deteriorates. Furthermore, when incorporating these solid electrolytes into an element such as an electric double layer capacitor, or when incorporating these solid electrolytes into a thin film into a battery, it is difficult to process such as compounding with electrodes and securing contactability, and even in the manufacturing method. There was a problem. The present inventors have found that by introducing a urethane bond into a side chain and / or a crosslinked chain in a polymer, a polymer solid electrolyte having good membrane strength and high ionic conductivity can be obtained ( JP-A-6-187822). However, the dielectric constant of the polymer is still insufficient, and the ionic conductivity is insufficient for practical use in batteries and the like, and it was necessary to add a low molecular weight compound having a high dielectric constant.

[0013]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a polymer solid electrolyte which has good strength even when formed into a film, has high ionic conductivity at room temperature and low temperature, and is excellent in processability. And Further, the present invention, by using this polymer solid electrolyte, thin film is easy, high capacity, high current can be operated, good cycleability, excellent reliability primary battery and secondary Intended to develop batteries. Another object of the present invention is to provide an electrode having high electrochemical activity and flexibility, and a secondary battery using the electrode.

Another object of the present invention is to provide an electrode used in an electric double layer capacitor, which has good polarizability, good strength when formed into a film, and good contact with a solid electrolyte. And Furthermore, the present invention uses a polymer solid electrolyte having high ionic conductivity even at room temperature or lower temperature, and having excellent membrane strength and processability, so that the output voltage is high and the extraction current is large. Another object of the present invention is to provide an electric double layer capacitor having excellent workability and reliability.

[0015]

Means for Solving the Problems The present inventors have promoted ionic dissociation of an electrolyte salt by using a compound in which a carbonate having a high dielectric constant is further introduced into the side chain and / or the cross-linked chain, and the ion dissociation is promoted. It has been found that the addition of other high dielectric constant compounds for promoting the reaction can be eliminated or reduced, and a polymer solid electrolyte having more excellent ionic conductivity, thermal stability or membrane strength can be obtained.

Further, it has been found that by using this polymer solid electrolyte, a battery having a high output voltage, a large extraction current, a long cycle life, and excellent workability and reliability can be obtained. Furthermore, the present inventors, for example, when recognizing that the thinning of the electrode is important when manufacturing a thin solid battery using this polymer solid electrolyte, the electrode active material As a conductive polymer, polyaniline and its derivatives, that is, aniline-based polymers soluble in organic solvents, or other conductive polymers, metal oxides, metal sulfides or carbon By using a material or another electrode active material (positive electrode active material or negative electrode active material) and a polymer into which a carbonate side chain having a urethane bond and / or a cross-linked chain is introduced, the electrochemical activity of the electrode active material can be improved. It is possible to obtain an electrode having high electrochemical activity and flexibility without deteriorating the activity, and further, for example, thinning the electrode by a solvent casting method or another method. It was found that the deposition is possible.

Further, the present inventors have introduced a carbon material as described below, which is a polarizable material used as a polarizable electrode of an electric double layer capacitor, and a carbonate side chain and / or a crosslinked chain having a urethane bond. By using such a polymer, it is possible to form a polarizable electrode suitable for the capacitor without impairing the polarization characteristics of the polarizable material. Further, for example, a thin film formation of the electrode is performed by a solvent casting method or another method. We have found that a membrane is possible.

Furthermore, the inventors of the present invention can obtain an electric double layer capacitor having a high output voltage, a large extraction current, excellent workability and reliability by using the above-mentioned polymer solid electrolyte. , And found that it can be an all-solid-state electric double layer capacitor.

That is, the present invention provides the following. 1) General formula (I)

[Chemical 15] [In the formula, R ¹ represents hydrogen or a methyl group, and R ² represents an organic group. The organic group may have 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.
Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, R ¹ , R ² and x, y in a plurality of units represented by the above general formula (I) in the same molecule,
The values of z are independent of each other and need not be the same. ] The polymer solid electrolyte which consists of a polymer obtained from at least 1 type of the compound which has a unit represented by, and / or a copolymer which uses this compound as a copolymerization component, and a complex containing at least 1 type of electrolyte.

2) General formula (II)

Embedded image [In the formula, R ¹ represents hydrogen or a methyl group, and R ² , R ³
Represents an organic group. The organic group may have a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y are 0 or an integer of 1 to 5, respectively, and z is 0 or 1 to 10.
Represents the numerical value of. However, when x = 0 and y = 0, z = 0. Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. ] A polymer solid electrolyte comprising a polymer obtained from at least one compound having a structure represented by: and / or a copolymer containing the compound as a copolymerization component, and a composite containing at least one electrolyte.

3) At least one of the electrolytes is an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt,
Alternatively, the polymer solid electrolyte according to 1) or 2) above, which is a transition metal salt. 4) The polymer solid electrolyte as described in 1) to 3) above, wherein a plasticizer is added. 5) A battery containing the polymer solid electrolyte described in 1) to 4) above. 6) The battery according to 5), which has a negative electrode containing a carbon material capable of inserting and extracting lithium, a lithium alloy, or lithium ions. 7) The battery according to 5) above, which has a positive electrode containing an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material.

8) General formula (I)

[Chemical 17] [The symbols in the formula are the same as those in 1) above. ] A polymerizable monomer mixture containing at least one compound having a unit represented by the following formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added thereto is placed in a structure for battery construction or supported. A method for producing a battery, comprising a step of disposing the mixture on the body and polymerizing the polymerizable monomer mixture. 9) General formula (II)

Embedded image [The symbols in the formula are the same as those in 2) above. ] A polymerizable monomer mixture containing at least one compound having a structure represented by the formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added to the polymerizable monomer mixture, is placed in a structure for battery construction or supported. A method for producing a battery, comprising a step of disposing the mixture on the body and polymerizing the polymerizable monomer mixture.

10) General formula (I)

[Chemical 19] [The symbols in the formula are the same as those in 1) above. ] The polymer obtained from at least 1 type of the compound which has a unit represented by this, and / or the copolymer which uses this compound as a copolymerization component, and an electrode characterized by including an electrode active material or a polarizable material. 11) General formula (II)

Embedded image [The symbols in the formula are the same as those in 2) above. ] And a polymer obtained from at least one compound having a structure represented by
Alternatively, an electrode comprising a copolymer containing the compound as a copolymerization component, and an electrode active material or a polarizable material.

12) The electrode active material or polarizable material is
The electrode according to 10) or 11) above, which is an organic solvent-soluble aniline polymer or other conductive polymer, metal oxide, metal sulfide, or carbon material. 13) An electric double layer capacitor in which polarizable electrodes are arranged via an ion conductive substance, wherein the ion conductive substance is the polymer solid electrolyte described in 1) to 4) above. Capacitors.

14) General formula (I)

[Chemical 21] [The symbols in the formula are the same as those in 1) above. ] A polymerizable monomer mixture containing at least one compound having a unit represented by the following formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added thereto is placed in a structure for constructing an electric double layer capacitor. Or a step of polymerizing the polymerizable monomer mixture, which is arranged on a support, and a method for producing an electric double layer capacitor. 15) General formula (II)

[Chemical formula 22] [The symbols in the formula are the same as those in 2) above. ] A polymerizable monomer mixture containing at least one compound having a structure represented by the formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added thereto is placed in a structure for constructing an electric double layer capacitor. Or a step of polymerizing the polymerizable monomer mixture, which is arranged on a support, and a method for producing an electric double layer capacitor.

16) An electric double layer capacitor in which polarizable electrodes are arranged via an ion conductive substance, wherein the polarizable electrodes are of the general formula (I).

[Chemical formula 23] [The symbols in the formula are the same as those in 1) above. ] An electric double layer capacitor comprising a polymer obtained from at least one kind of a compound having a unit represented by and a composite containing a carbon material and a copolymer having the compound as a copolymerization component. 17) An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the polarizable electrode is represented by the general formula (II).

[Chemical formula 24] [The symbols in the formula are the same as those in 2) above. ] And a polymer obtained from at least one compound having a structure represented by
Alternatively, an electric double layer capacitor comprising a composite containing a copolymer containing the compound as a copolymerization component and a carbon material.

18) General formula (I)

[Chemical 25] [In the formula, R ¹ represents hydrogen or a methyl group, and R ² represents an organic group. The organic group may have 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.
Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, R ¹ , R ² and x, y in a plurality of units represented by the above general formula (I) in the same molecule,
The values of z are independent of each other and need not be the same. ] The polymer obtained from at least 1 type of the compound which has the unit represented by these, or the copolymer which uses this compound as a copolymerization component.

19) Formula (II)

[Chemical formula 26] [In the formula, R ¹ represents hydrogen or a methyl group, and R ² , R ³
Represents an organic group. The organic group may have a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y are 0 or an integer of 1 to 5, respectively, and z is 0 or 1 to 10.
Represents the numerical value of. However, when x = 0 and y = 0, z = 0. Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. ] The polymer obtained from at least 1 type of the compound which has a structure represented by these, or the copolymer which uses this compound as a copolymerization component.

20) General formula (I)

[Chemical 27] [In the formula, R ¹ represents hydrogen or a methyl group, and R ² represents an organic group. The organic group may have 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.
Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, R ¹ , R ² and x, y in a plurality of units represented by the above general formula (I) in the same molecule,
The values of z are independent of each other and need not be the same. ] The compound which has a unit represented by these.

21) General formula (II)

[Chemical 28] [In the formula, R ¹ represents hydrogen or a methyl group, and R ² , R ³
Represents an organic group. The organic group may have a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y are 0 or an integer of 1 to 5, respectively, and z is 0 or 1 to 10.
Represents the numerical value of. However, when x = 0 and y = 0, z = 0. Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. ] The compound which has a structure represented by these.

The present invention will be described in detail below. In the present invention, the carbonate group refers to an atomic group represented by the chemical formula —OCOO—, and the carbonate (side) chain is represented by the chemical formula —
A (side) chain having an atomic group represented by OCOO- is shown.
The compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II), which is a monomer for producing the polymer solid electrolyte of the present invention, can be prepared by the reaction of the following formula. Obtainable. CH ₂ = C (R ¹ ) CO (O (CH ₂ ) _x (CH (CH
₃ )) _y ) _z NCO +

[Chemical 29] →

Embedded image

As an example, as in the reaction of the following formula, 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as MOI) and propylene hydroxycarbonate are heated and reacted at a molar ratio of 1: 1 under a tin-based catalyst. By 2-
Methacryloyloxyethylcarbamic acid carbonic acid propylene ester is obtained. _{CH 2 = C (CH 3)} COO (CH 2) 2 NCO +

[Chemical 31] →

Embedded image

The polymer contained in the solid polymer electrolyte of the present invention is at least one selected from the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II). It is obtained by polymerizing the compound (1) or by using the compound as a copolymerization component. For the polymerization, a general method utilizing the polymerizability of the acryloyl group or methacryloyl group of these monomers can be adopted. That is, a radical polymerization catalyst such as azobisisobutyronitrile or benzoyl peroxide, a protonic acid such as CF ₃ COOH, BF ₃ , AlCl ₃ or the like is prepared by mixing these monomers or a mixture of these monomers with another polymerizable compound. Radical, cationic or anionic polymerization can be carried out using a cationic polymerization catalyst such as Lewis acid or an anionic polymerization catalyst such as butyllithium, sodium naphthalene or lithium alkoxide.

It is also possible to polymerize such a polymerizable monomer mixture after being formed into a film-like shape. When the polymer solid electrolyte is used in a battery or an electric double layer capacitor as in the present invention, it is particularly advantageous to polymerize the polymerizable monomer mixture after the film formation as described above.

That is, at least one compound selected from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by (II), an alkali metal salt, a quaternary ammonium salt, At least one electrolyte such as a quaternary phosphonium salt or a transition metal salt is mixed, and the polymerizable monomer mixture is irradiated with electromagnetic waves such as heating and / or light in the presence or absence of the catalyst. To polymerize. In particular,
After molding the polymerizable monomer mixture into a film-like shape, for example, irradiation with an electromagnetic wave such as heating and / or light to polymerize the mixture to obtain a film-like polymer, thereby increasing the degree of freedom in the processed surface. This is a great application advantage.

Polymerization by mixing with a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by (II), which is a monomer for producing the solid polymer electrolyte of the present invention. There is no particular limitation on the compound, and any compound having a unit represented by the general formula (I) and / or a compound having a structure represented by (II) can be used. For example, the following general formula _{(III) (CH 2 = C} (R 1) CO (O (CH 2) x (CH (CH 3)) y) z NHCO OR 2 -) (III) ( In the formula, R ¹ Represents a hydrogen atom or a methyl group, and R ² represents a divalent organic chain containing an oxyalkylene group, which organic chain may have a linear, branched or cyclic structure, and includes carbon, hydrogen and oxygen. And x may represent an integer of 0 or 1 to 5, and z may represent an integer of 0 or 1 to 10. However, x = 0.
And when y = 0, z = 0. Also (CH ₂ ) and (C
H (CH ₃ )) may be randomly arranged. However, the values of R ¹ , R ² and x, y, and z in a plurality of units represented by the above general formula (III) in the same molecule are independent and need not be the same. ) Urethane (meth) having an oxyalkylene chain such as (meth) acryloylcarbamate having one or more units represented by
Having an oxyalkylene chain such as acrylate or methacrylic acid ω-methyl oligooxyethyl ester (meth)
(Meth) acrylic acid alkyl ester such as acrylic acid ester, methyl methacrylate, and n-butyl acrylate,
(Meth) acrylamide compounds such as methacrylamide, acrylamide, N, N-dimethylmethacrylamide, acryloylmorpholine, methacryloylmorpholine, N, N-dimethylaminopropyl (meth) acrylamide, styrene compounds such as styrene and α-methylstyrene. Examples thereof include N-vinylamide compounds such as N-vinylacetamide and N-vinylformamide, alkyl vinyl ethers such as ethyl vinyl ether, and cyclic vinyl compounds such as vinylene carbonate, vinylpyrrolidone and maleimide.

Among them, urethane (meth) acrylate and (meth) acrylic acid ester having an oxyalkylene chain are preferable in view of the fact that the polymer has a high dielectric constant and a low glass transition point, and has an oxyalkylene chain. Urethane (meth) acrylate is particularly preferred.

When a solvent is used, the polymerization depends on the kind of the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II) and the presence or absence of a polymerization catalyst. Any solvent may be used as long as it does not inhibit the above, and for example, tetrahydrofuran, acetonitrile, toluene and the like can be used.

The temperature at which the polymerization is carried out is a compound having a unit represented by the general formula (I) and / or (II)
It depends on the kind of the compound having the structure represented by, but it may be carried out at a temperature at which the polymerization occurs, and it is usually carried out in the range of 0 ° C to 200 ° C. When polymerized by electromagnetic wave irradiation, it depends on the kind of the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II). An initiator can be used to polymerize by irradiating with ultraviolet light of several mW or more, γ rays, or the like.

The polymer used in the solid polymer electrolyte of the present invention is a homopolymer of a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by (II). Also, it may be a copolymer of two or more kinds of compounds having a unit represented by the general formula (I) and / or a compound having a structure represented by the (II), or at least one general formula (I). A compound having a unit represented by (4) and / or a compound having a structure represented by (II) and another polymerizable compound may be a copolymer or a mixture thereof.

The polymer used in the solid polymer electrolyte of the present invention is a homopolymer of a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by (II). Or a copolymer of a compound having two or more types of units represented by general formula (I) and / or a compound having a structure represented by (II), or at least one type of At least one kind of copolymers of a compound having a unit represented by the formula (I) and / or a compound having a structure represented by (II) and another polymerizable compound, and another polymer It may be a mixture. Examples of the other polymer include one or more polymers selected from polyethylene oxide, polyacrylonitrile, polybutadiene, polymethacrylic (or acrylic) acid esters, polyphosphazenes, polysiloxane, polysilane and the like.

Amount of the structural unit derived from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by (II) contained in the above-mentioned copolymer or polymer mixture. It is preferable that the content of the copolymer or the polymer mixture is 20% by weight or more because the characteristics of the carbonate chain having a urethane bond can be sufficiently exhibited. The molecular weight of the polymer used in the solid polymer electrolyte of the present invention is preferably 1,000 or more and 1,000,000 or less,
It is particularly preferably 5,000 or more and 50,000 or less. When the molecular weight of the polymer becomes high, the film properties such as the film strength after processing are improved, but on the other hand, the thermal motion that is important for carrier ion transfer is restricted, the ion conductivity is lowered, and it becomes difficult to dissolve in a solvent. It is disadvantageous in terms of processing. On the other hand, if the molecular weight is too low, the film-forming property, the film strength, etc. deteriorate, and the basic physical properties deteriorate.

It is preferable to add an organic compound which is usually used as a so-called plasticizer (referred to as a plasticizer in the present invention) to the polymer solid electrolyte of the present invention because the ionic conductivity of the solid electrolyte is further improved. . As the plasticizer that can be used, a compound having good compatibility with the monomer used in the solid polymer electrolyte of the present invention, a large dielectric constant, a boiling point of 100 ° C. or higher, and a wide electrochemical stability range is suitable. . Such plasticizers include oligoethers such as triethylene glycol methyl ether and tetraethylene glycol dimethyl ether, carbonates such as ethylene carbonate, propylene carbonate, diethyl carbonate, vinylene carbonate, and aromatic nitriles such as benzonitrile and tolunitrile. , Sulfur compounds such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-vinylpyrrolidone and sulfolane, and phosphoric acid esters. Of these, oligoethers and carbonates are preferable, and carbonates are particularly preferable. The larger the amount of the plasticizer added, the higher the ionic conductivity of the solid polymer electrolyte, but if it is too large, the mechanical strength of the solid polymer electrolyte decreases. The preferable addition amount is not more than 5 times the weight of the (M) ACE polymer.

The composite ratio of the polymer in the solid polymer electrolyte of the present invention and the electrolyte used for the composite is preferably one electrolyte molecule to one to 100 side chain or cross-linked carbonate groups. If the electrolyte used for the composite is present at a ratio of 1 or more of the carbonate groups, the migration of ions is greatly inhibited, and conversely, at a ratio of 1/100 or less, the absolute amount of ions is insufficient and the ionic conductivity is reduced. , Not preferable.

The type of electrolyte used for the composite is not particularly limited, and an electrolyte containing ions which are desired to be used as carriers by electric charge may be used, but it is desirable that the dissociation constant in the solid polymer electrolyte is large, Metal salt,
(CH ₃ ) ₄ NBF _{4 and} other quaternary ammonium salts, (CH
₃ ) ₄ Quaternary phosphonium salts such as PBF ₄ , AgClO ₄
A transition metal salt such as or a protic acid such as hydrochloric acid, perchloric acid, or fluoroboric acid is recommended.

Examples of the negative electrode active material used in the battery of the present invention include alkali metals, alkali metal alloys, and
By using a material with a low redox potential that uses an alkali metal ion as a carrier, such as a carbon material, a high voltage,
It is preferable because a high capacity battery can be obtained. Therefore, an alkali metal salt is required as an electrolyte in the polymer solid electrolyte when using such a negative electrode in a battery using alkali metal ions as a carrier. Examples of the alkali metal salt include, for example, LiN (CF ₃ SO ₂ ) ₂ and Li.
CF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiI, L
iBF ₄ , LiSCN, LiAsF ₆ , NaCF ₃ SO
₃ , NaPF ₆ , NaClO ₄ , NaI, NaBF ₄ ,
NaAsF _6, KCF ₃ SO _3, can be mentioned KPF _6, KI, or the like. Among these, as the alkali metal,
High voltage when using lithium or lithium alloy,
It is most preferable because it has a high capacity and can be thinned. In the case of a carbonaceous material negative electrode, not only alkali metal ions but also quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and various protic acids can be used.

The kind of the electrolyte used for the composite in the case of the solid electric double layer capacitor is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used, but the dissociation constant in the polymer solid electrolyte is It is desirable to contain ions that are large in size and easily form a polarizable electrode and an electric double layer. Such compounds include (CH ₃ ) ₄
NBF ₄ , quaternary ammonium salts such as (CH ₃ CH ₂ ) ₄ NClO ₄ , transition metal salts such as AgClO ₄ , (CH ₃ )
₄ Quaternary phosphonium salt such as PBF ₄ , LiCF ₃ SO
₃ , LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ ,
LiSCN, LiAsF ₆ , NaCF ₃ SO ₃ , NaP
F ₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF ₆
, KCF ₃ SO ₃ , KPF ₆ , and KI, alkali metal salts, organic acids such as paratoluenesulfonic acid and salts thereof, inorganic acids such as hydrochloric acid and sulfuric acid, and the like. Among these, a quaternary ammonium salt, a quaternary phosphonium salt, and an alkali metal salt are preferable from the viewpoints of high output voltage and large dissociation constant. 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 CH ₂ ) ₃ NBF ₄ have a large solubility in the solid polymer electrolyte or a large dissociation constant. preferable.

In the structure of the battery of the present invention, an electrode active material (negative electrode active material) having a low redox potential, which uses as a carrier an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material, or a conductive polymer for the negative electrode. The use of is preferable because a high voltage and high capacity battery can be obtained. Among such electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, lithium / antimony alloy and the like are particularly preferable because they have the lowest redox potential. Also, the carbon material is Li
It is particularly preferable in that it has a low redox potential when occluding ions and is stable and safe. Examples of the carbon material capable of occluding and releasing Li ions include natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal coke, pitch carbon, polyacene, and fullerenes such as C ₆₀ and C ₇₀ .

In the structure of the battery of the present invention, by using an electrode active material (positive electrode active material) having a high redox potential such as a metal oxide, a metal sulfide, a conductive polymer or a carbon material for the positive electrode, This is preferable because a battery having a high voltage and a high capacity 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 molybdenum sulfide are included in terms of high packing density and high volume capacity density.
Metal sulfides such as titanium sulfide and vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable from the viewpoint of high capacity and high voltage. In addition, a conductive polymer such as polyaniline is particularly preferable because it is flexible and can be easily formed into a thin film.

The method for producing the metal oxide or the metal sulfide is not particularly limited, and for example, “Electrochemistry, Vol. 22, 57”.
4 page, 1954 ”, it is manufactured by a general electrolytic method or heating method. When these are used for a lithium battery as an electrode active material, Li element is inserted into a metal oxide or a metal sulfide in the form of Li _x CoO ₂ or Li _x MnO ₂ (composite) at the time of manufacturing the battery. It is preferable to use it in the prepared state. Like this
The method of inserting the i element is not particularly limited, and examples thereof include a method of electrochemically inserting Li ions and US Pat.
As described in Japanese Patent No. 57215, it can be carried out by mixing a salt such as Li ₂ CO ₃ and a metal oxide and heating the mixture.

Examples of the conductive polymer include polyaniline, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polypyrrolylene and its derivatives, polythienylene and its derivatives, polypyridinediyl and its derivatives, polyisothianaphthenylene and its derivatives. Derivatives, polyfrillene and its derivatives, polyselenophene and its derivatives, polyparaphenylene vinylene, polythienylene vinylene, polyfrillene vinylene, polynaphthenylene vinylene, polyselenophene vinylene, polypyridine diyl vinylene, and other polyarylene vinylenes and the like. 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 by a chemical or electrochemical method as described below or another known method.

Examples of the carbon material include natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal coke, fluorinated graphite, pitch carbon and polyacene. Further, as the carbon material used as an electrode active material in the battery or electrode of the present invention, a commercially available carbon material can be used, or it can be produced according to a known method. The use of an organic solvent-soluble aniline polymer as the positive electrode active material in the electrode or battery of the present invention is advantageous because molding can be performed by solution coating, and is particularly advantageous when a thin film battery is produced. . Examples of the aniline-based polymer include polyaniline, poly-o-toluidine, and poly-m.
-Toluidine, poly-o-anisidine, poly-m-anisidine, polyxylidines, poly-2,5-dimethoxyaniline, poly-2,6-dimethoxyaniline, poly-
2,5-diethoxyaniline, poly-2,6-diethoxyaniline, poly-o-ethoxyaniline, poly-m-
Examples thereof include ethoxyaniline and copolymers thereof, but are not particularly limited thereto, and any polymer having a repeating unit derived from an aniline derivative may be used. Further, the introduction amount of the side chain in the organic solvent-soluble aniline-based polymer is more convenient in terms of solubility, but as the introduction amount increases, the capacity per weight of the positive electrode decreases. The surface appears. Therefore, preferable aniline-based polymers include, for example, polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, and polyxylidines.

The polymerization method of the aniline polymer used in the present invention is not particularly limited, but generally, for example, "Journal of Chemical Society, Chemical Communication, page 1784 (1.
987) "and the like, aniline, o-
Examples thereof include a method of electrochemically or chemically oxidizing and oxidizing an aniline derivative such as anisidine.

The electrochemical oxidative polymerization is carried out by anodic oxidation, and the current density is about 0.01 to 50 mA / cm ₂ , and the electrolysis voltage is 0.1 to 30 V. Any method can be used.
The pH of the electrolytic solution is not particularly limited, but preferably p
H is 3 or less, particularly preferably 2 or less. Specific examples of the acid used for pH adjustment include HCl, HBF ₄ , CF ₃
Strong acids such as COOH, H ₂ SO ₄ , HNO ₃ and paratoluenesulfonic acid can be mentioned, but the acid is not particularly limited thereto. In the case of chemical oxidative polymerization, for example, the aniline derivative can be oxidatively polymerized in an acidic solution with an oxidizing agent such as peroxide or persulfate. As the acid used in this case, the same acid as that used in the electrochemical oxidative polymerization can be used, but the acid is not limited thereto.

The molecular weight of the aniline polymer used in the present invention obtained by such a method is not particularly limited, but it is usually preferably 2000 or more. The aniline-based polymer obtained by such a method is generally obtained in a state where the anion in the polymerization solution is contained as a dopant, which is disadvantageous in terms of solubility and capacity per weight. Therefore, by, for example, a film forming method, dedoping these anions before forming the electrode,
The reduced form is preferred. The dedoping method is not particularly limited, but a method of treating with a base such as aqueous ammonia or sodium hydroxide is generally used. The reduction method is not particularly limited, and general chemical or electrochemical reduction may be performed. For example, regarding the chemical reduction method, the aniline-based polymer treated with a base in a hydrazine or phenylhydrazine solution can be easily reduced by immersion or stirring at room temperature.

The dedoped or reduced aniline-based polymer thus obtained is soluble in various organic solvents, and a compound having a unit represented by the above general formula (I) in a solution state and / Or a polymerizable monomer solution containing at least one compound having a structure represented by (II), and using the mixture prepared as described above, for example, by a coating method, various supports, for example, The electrode can be manufactured by forming a thin film on the electrode or molding it into another shape. The solvent in which the aniline-based polymer is dissolved depends on the kind of the substituent on the benzene ring, and is not particularly limited, but pyrrolidones such as N-methylpyrrolidone, amides such as dimethylformamide, m-cresol and dimethyl. Examples include polar solvents such as propylene urea.

According to the present invention, as described above, even if a soluble conductive polymer such as an organic solvent-soluble aniline polymer is used, it is possible to use the polymer used for the solid polymer electrolyte of the present invention. Since the flexible thin film electrode can be manufactured, the conductive polymer that can be used in the electrode or the battery of the present invention may be soluble or insoluble in an organic solvent.

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 comprises, for example, at least one compound selected from the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II), and optionally other compound. A polymerizable compound and / or a plasticizer is added and mixed with the above electrode active material (positive electrode active material or negative electrode active material). In that case, the ratio of each component to be mixed should be appropriate for the intended battery. The polymerizable monomer / electrode active material mixture thus obtained is molded into a film-like shape and then polymerized to produce an electrode. In this method, the polymerization is carried out in the case of obtaining a polymer obtained from at least one compound selected from the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II). The same polymerization method as described above can be used, and for example, the polymerization can be performed by heating and / or electromagnetic wave irradiation. When the electrode active material provides a mixture of polymerizable monomer / electrode active material having high fluidity such as an organic solvent-soluble aniline polymer, the mixture is supported on a collector or other glass. An electrode is manufactured by polymerizing after molding by a method such as coating on the body to form a film.

The electrode containing the above-mentioned electrode active material produced in this manner is used as at least one electrode, and the electrode containing the other electrode active material produced in the same manner or another commonly used electrode is used as the other electrode. , Both electrodes are placed in a battery structure structure or placed on a support so that they do not contact each other. For example, the positive electrode and the negative electrode are attached to each other through a spacer having an appropriate thickness at the end of the electrode and placed in the structure, and then the unit represented by the general formula (I) is provided between the positive electrode and the negative electrode. Compound and / or at least one compound selected from compounds having a structure represented by (II) and at least one electrolyte selected from the above-mentioned electrolytes such as alkali metal salts are mixed, and in some cases further polymerization After injecting a polymerizable monomer mixture prepared by adding and mixing a polymerizable compound and / or a plasticizer,
For example, from at least one compound selected from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by (II), which is polymerized by heating and / or electromagnetic wave irradiation. Polymerization by the same method as in the case of obtaining the obtained polymer and / or a copolymer having the compound as a copolymerization component, or after the polymerization, if necessary, a polyolefin resin, an epoxy resin, etc. By sealing with an insulating resin, a battery in which the electrode and the electrolyte are in good contact can be obtained. When an electrode obtained by polymerizing the above-mentioned polymerizable monomer mixture is used, a battery in which the electrode and the electrolyte are in excellent contact can be obtained. In addition, when preparing such a polymerizable monomer mixture, the ratio of each component to be mixed should be appropriate depending on the intended battery. The battery structure or the support is a metal such as SUS, polypropylene,
A resin such as polyimide or a ceramic material such as conductive or insulating glass is preferable, but the material is not particularly limited to those made of these materials, and the shape thereof is cylindrical, box-shaped, sheet-shaped or any other shape. It may have a shape.

As described above, a monomer mixture containing at least one compound selected from the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II) and at least one compound. By polymerizing a mixed solution obtained by mixing an electrolyte, at least one compound selected from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by (II) The method for producing a polymer solid electrolyte composed of the obtained polymer and / or a copolymer containing the copolymer as a copolymerization component and at least one electrolyte is particularly useful when producing a thin film battery. is there.

FIG. 1 shows a schematic sectional view of an example of a thin film solid secondary battery as an example of the battery of the present invention manufactured in this way. In the figure, 1 is a positive electrode, 2 is a solid polymer electrolyte, 3
Is a negative electrode, 4 is a stainless steel foil which is a current collector, 5 is an insulating polyimide film which is a spacer, and 6 is an insulating resin sealant.

In the case of producing a wound type battery, a polymer solid electrolyte sheet prepared in advance is used to
A method is also possible in which the positive electrode and the negative electrode are laminated, wound, inserted into the structure for battery construction, and then the polymerizable monomer mixture is further injected and polymerized. Next, the solid-state 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 extraction current, or excellent processability and reliability. To be done.

FIG. 2 shows a schematic sectional view of an example of the solid-state electric double layer capacitor of the present invention. This example is 1 cm in size
A thin cell having a size of 1 cm and a thickness of about 0.5 mm, 8 is a current collector, a pair of polarizable electrodes 7 is arranged inside the current collector, and a solid polymer electrolyte membrane 9 is arranged between them. ing. 10 is 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 electronic conductivity and electrochemical corrosion resistance, and a material having a large specific surface area as much 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 an electrode made of a polarizable material such as a carbon material usually used in an electric double layer capacitor, but a composite of the polymer solid electrolyte of the present invention with such a carbon material is preferable. The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area, but the larger the specific surface area, the larger the capacity of the electric double layer, which is preferable. For example, carbon blacks such as furnace black, thermal black (including acetylene black) and channel black, activated carbon such as coconut palm charcoal, natural graphite, artificial graphite, so-called pyrolytic graphite produced by a vapor phase method, polyacene and C ₆₀ and C ₇₀ can be mentioned.

Next, an example of a method for manufacturing the solid electric double layer capacitor of the present invention will be described. As described above, when at least one compound selected from the compound having the unit represented by the general formula (I) and / or the compound having the structure represented by (II) is mixed with at least one electrolyte, Depending on the other polymerizable compound and /
Alternatively, a compound having a unit represented by the general formula (I) and / or a compound having a structure represented by (II) is selected by polymerizing a polymerizable monomer mixture obtained by adding and mixing a plasticizer. A polymer obtained from at least one compound and / or a composite containing a copolymer having the compound as a copolymerization component and at least one electrolyte can be obtained, and this method produces the solid electric double layer capacitor of the present invention. It is especially useful when

A polarizable material such as a carbon material, a compound having a unit represented by the general formula (I) and / or a structure represented by (II), which are preferably used in the solid electric double layer capacitor of the present invention, are prepared. In the case of producing a polarizable electrode containing a polymer obtained from at least one compound selected from the compounds having and / or a copolymer having the compound as a copolymerization component, first, for example, a polarizable electrode represented by the general formula (I) At least one compound selected from the group consisting of a compound having a unit and / or a compound having a structure represented by (II), and optionally a polymerizable compound and / or a plasticizer may be added to the polarizable material. Mix with. In that case, the ratio of each component to be mixed should be appropriate depending on the intended condenser. The polymerizable monomer / polarizable material mixture thus obtained is formed into a film on a support, for example, a current collector, and then heated and / or
Alternatively, a polarizable electrode is produced by polymerizing by the same method as the above-mentioned polymerizing method for obtaining the polymer, such as polymerizing by irradiation of electromagnetic waves. 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 in this manner are placed in a structure for forming a capacitor or arranged on a support so as not to contact each other. For example, attach both electrodes to the end of the electrode through a spacer of appropriate thickness,
It is selected from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by (II) between the two polarizable electrodes which are placed in the structure. A polymerizable monomer mixture prepared by mixing at least one compound and at least one electrolyte selected from the above electrolytes such as alkali metal salts, and optionally further adding and mixing another polymerizable compound and / or a plasticizer. After injecting, by polymerizing by the same method as above, or by further sealing after polymerization with an insulating resin such as a polyolefin resin or an epoxy resin as necessary, the electrode and the electrolyte are in good contact with each other. The obtained electric double layer capacitor is obtained. When preparing such a monomer mixture, the ratio of each component to be mixed should be appropriate for the intended condenser. By this method, a particularly thin all-solid-state electric double layer capacitor can be manufactured. The capacitor structure 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 insulative glass, but is particularly composed of these materials. However, the shape is not limited to the above, and may be any shape such as a tubular shape, a box shape, and a sheet 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 type laminated body of a polarizable electrode and a polymer solid electrolyte is wound into a cylindrical shape to form a cylindrical tubular shape. Put it in the structure for capacitor construction,
It may be a cylindrical type manufactured by sealing. In the case of producing a wound-type capacitor, the polarizable electrodes are bonded together via a polymer solid electrolyte sheet prepared in advance, wound, and inserted into the structure for constructing a capacitor, and then the polymerizable monomer mixture is further added. It is also possible to inject and polymerize.

[0068]

The function of the solid polymer electrolyte of the present invention is as described above.
A film can be easily formed from the polymerizable monomer mixture that is the raw material.
It is a solid electrolyte of high ion conductivity made of a high dielectric constant polymer having a side chain of a carbonate group having a urethane bond capable of being compounded, and has good film strength and excellent thin film processability.

In the battery of the present invention, by using the polymer solid electrolyte as the ion conductive material, it is easy to process it into a thin film, there is no fear of short circuit even in the thin film, the extraction current is large and the reliability is high. It is a battery, and can be an all-solid-state battery in particular. Further, the battery of the present invention, in which the negative electrode is composed of 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. It is a battery that is easy to process, has no fear of short-circuiting even with a thin film, has a large extraction current, and has high reliability, and in particular can be an all-solid-state battery.

Further, the positive electrode of the present invention has the general formula (I)
A compound having a unit represented by and / or (I
A polymer obtained from at least one compound selected from the compounds having the structure represented by I) and / or a copolymer containing the compound as a copolymerization component and an organic solvent-soluble aniline-based polymer or other conductive materials. A battery comprising an electrode containing an active material such as a polymer, a metal oxide, a metal sulfide or a carbon material and characterized by using the polymer solid electrolyte as an electrolyte is easy to process such as thin film, However, there is no risk of short circuit, the current for extraction is large, the capacity is high, and the reliability is high. In particular, it can be an all-solid-state battery. Furthermore, a polymer obtained from at least one compound selected from the compound having a unit represented by the general formula (I) and / or the compound having a structure represented by (II) of the present invention, And / or an electrode containing a copolymer containing the compound as a copolymerization component and an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or an electrode active material such as a carbon material, and the like. The method for producing an electrode is to provide an electrode having flexibility as necessary without impairing the electrochemical activity of the electrode active material having excellent activity as an electrode, for example, a thin film Electrodes can be provided, which are useful as electrodes in various batteries.

Further, according to the battery manufacturing method of the present invention,
It is possible to manufacture batteries of various shapes, in particular, it is easy to make the battery thin, and it is possible to manufacture batteries with high capacity, high current operation, or excellent cycleability and excellent reliability, In particular, all-solid-state batteries can be manufactured.

The electric double layer capacitor of the present invention can be easily formed into a film from a mixture of polymerizable monomers and can be composited to form a comb polymer or a network polymer in which an oxyalkyl group having a urethane bond is introduced into a side chain. Polymerized by dissolving an electrolyte in a monomer mixture, produced by using as a high ion conductivity and good polymer solid electrolyte polymer solid electrolyte as an ion conductive material, there is no short circuit even in a thin film, It is an electric double layer capacitor having a high output voltage and a large extraction current and high reliability, and in particular, it can be an all-solid-state electric double layer capacitor. Particularly, according to the electric double layer capacitor of the present invention and the manufacturing method thereof,
Good contact between the polarizable electrode and the solid polymer electrolyte, which is an ion-conducting substance, has no short circuit even in a thin film.
An electric double layer capacitor having high output voltage and extraction current and high reliability is provided, and in particular, an all-solid-state electric double layer capacitor is provided.

[0073]

The present invention will be described in more detail below by showing typical examples. Note that these are merely examples for description, and the present invention is not limited to these. Example 1 <Synthesis of methacryloyloxyethyl carbamic acid carbonic acid propylene ester (MOECP)> Carbon dioxide gas was added to 34.2 g of allyl glycidyl ether at 100 ° C. for 14 hours under high pressure of 10 to 15 kg / cm ² using triphenyl phosphorus as a catalyst. By doing so, 42.3 g of allyloxy propylene carbonate was obtained. Next, a platinum catalyst was added and the reaction was carried out at 40 ° C. for 5 hours to deallylate the carboxylic acid to obtain 25 g of propylene hydroxycarbonate.

This propylene hydroxycarbonate 0.1 mo
1 (= 11.8 g) and 2-methacryloyloxyethyl isocyanate (MOI) 0.1 mol (= 15.5)
g) was dissolved in 100 ml of well-purified THF in a nitrogen atmosphere and then 0.33 g of dibutyltin dilaurate was added. Then, by reacting at 50 ° C. for about 3 hours, 27 g of MOECP was obtained as a colorless liquid. The product was confirmed to be MOECP by the following analysis. (1) Melting point: 60 ° C (3) Infrared absorption spectrum: (KBr tablet, cm ⁻¹ ) 3362, 2960, 2267, 1798, 1716,
1638, 1537, 1455, 1398, 1322
1299, 1255, 1171, 1091, 1055
952,851,816,773,715,605 (4) Nuclear magnetic resonance spectrum: (CDCl ₃ ) δ = 2.0 (s, 3H), 3.5 (m, 2H), 4.2
(T, 2H), 4.3 (m, 3H), 4.6 (m, 1)
H), 4.9 (m, 1H), 5.3 (t, 1H), 5.
6 (s, 1H), 6.1 (s, 1H) (5) FAB-MS spectrum: 296 ([M + Na]
⁺ ), 274 ([M + H] ⁺ ), 188, 69 From the above results, the MOI and the propylene hydroxycarbonate react in a one-to-one manner, and the isocyanate group of the MOI disappears to form a urethane bond. I understood.

Example 2 <Preparation and Evaluation of MOECP Polymer Solid Electrolyte> 1.5 g of MOECP synthesized in Example 1 was added to 10 c of THF.
It was dissolved in c, and 0.15 g of LiCF ₃ SO ₃ was added and mixed well. Then THF was removed at room temperature under reduced pressure and MO
An ECP / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. After coating this mixture on a glass plate in an argon atmosphere and heating at 80 ° C. for 1 hour, MOECP / Li
The CF ₃ SO ₃ composite was obtained as a transparent film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 3 × 10 ⁻⁵ S /
It was cm.

Example 3 Instead of LiCF ₃ SO ₃ used in Example 2, LiBF ₃ was used.
_A solid electrolyte was prepared in the same manner as in Example 2 except that 0.20 g of _{4 was} used. The ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method to be 4 × 10.
It was ^-5 S / cm. When the temperature change of the ionic conductivity of this solid electrolyte film was measured by the impedance method, it was as shown in FIG. The ordinate of FIG. 3 shows the ionic conductivity in logarithm, and the abscissa shows the Arrhenius plot showing the temperature in 1000 / absolute temperature, the slope of which is MOECP polymer /
It represents the activation energy of ion transfer in a LiBF ₄ based solid electrolyte.

Example 4 <Synthesis of 2-methacryloyloxyethylcarbamic acid 2-methacryloyloxyethylcarbamoyloligooxyethyl / oxypropyl ester (MCMC (800))> MOI 0.2 mol (= 31.0 g), average molecular weight 80
After dissolving 0.1 mol (= 80 g) of an oligoethylene glycol / propylene glycol copolymer of 0 in 100 ml of well-purified THF in a nitrogen atmosphere, 0.66 g
Of dibutyltin dilaurate was added. Then 50
MCMC (800) was obtained as a colorless gel-like solid by reacting at 0 ° C. for about 3 hours. Its H1-NMR,
From the results of IR and elemental analysis, it was found that the MOI and the oligoethylene glycol / propylene glycol copolymer reacted in a ratio of 2 to 1, the isocyanate group of the MOI disappeared, and a urethane bond was formed.

Example 5 <MOECP / MCMC (80
0) Preparation and Evaluation of Copolymer Solid Electrolyte> MOECP (1.50 g) synthesized in Example 1 and MCMC (800) (1.50 g) synthesized in Example 4 were added to THF 20c.
It was dissolved in c and 0.30 g of LiCF ₃ SO ₃ was added and mixed well. The THF is then removed at room temperature under reduced pressure and M
An OECP / MCMC (800) / LiCF ₃ SO ₃ mixture was obtained as a viscous liquid. After coating this mixture on a glass plate in an argon atmosphere and heating at 80 ° C. for 1 hour, MOECP / MCMC (800) copolymer / LiC
The F ₃ SO ₃ composite was obtained as a transparent free-standing film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 2 × 10 ⁻⁴ S
Was / cm. When the temperature change of the ionic conductivity of this solid electrolyte film was measured by the impedance method,
It looks like Figure 3. The vertical axis of FIG. 3 is an Arrhenius plot in which the ionic conductivity is logarithmic and the horizontal axis is temperature 1000 / absolute temperature, and the slope thereof is MOECP / MCMC.
It represents the activation energy of ion transfer in the (800) copolymer / LiCF ₃ SO ₃ based solid electrolyte.

Example 6 Instead of LiCF ₃ SO ₃ used in Example 5, LiPF
_A solid electrolyte was produced in the same manner as in Example 5 except that 0.30 g of ₆ was used. The ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method to be 3 × 1.
It was 0 ⁻⁴ S / cm.

Example 7 Instead of LiCF ₃ SO ₃ used in Example 5, NaCF was used.
_A solid electrolyte was produced in the same manner as in Example 5 except that 0.26 g of ₃ SO ₃ was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method, it was 8 × 10 ⁻⁵ S / cm.

Example 8 A solid electrolyte was prepared in the same manner as in Example 5 except that 0.60 g of AgI was used instead of LiCF ₃ SO ₃ used in Example 5. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method, it was 5 × 10 5.
It was ^-4 S / cm.

Example 9 Instead of LiCF ₃ SO ₃ used in Example 5, tetraethylammonium tetrafluoroborate (TEAB) was used.
A solid electrolyte was produced in the same manner as in Example 5 except that 0.43 g of was used. When the ionic conductivity of this solid electrolyte at 25 ° C. was measured by the impedance method, it was 2 × 1.
It was 0 ⁻⁴ S / cm.

Example 10 <Synthesis of 2-methacryloyloxyethylcarbamic acid ω-methyloligooxyethyl ester (MECME (550))> Methacryloyloxyethyl isocyanate (MOI)
0.1 mol (= 15.5 g), 0.1 mol (= 5) of monomethyl oligoethylene glycol having an average molecular weight of 550
5 g) was thoroughly purified in a nitrogen atmosphere and 100 m of THF was used.
After dissolving in 1, 0.66 g of dibutyltin dilaurate is added. Then, by reacting at 50 ° C. for about 3 hours, MECME (550) was obtained as a colorless viscous liquid.
I got From the results of the H1-NMR, IR and elemental analysis, MOI and monomethyl oligoethylene glycol were 1
It was found that the reaction was carried out in a pair of 1, the isocyanate group of MOI disappeared, and a urethane bond was formed.

Example 11 <MOECP / MECMC (5
50) Preparation and Evaluation of Copolymer Polymer Solid Electrolyte> MOECP (1.50 g) synthesized in Example 1 and Example 10
1.50 g of MECMC (550) synthesized in
It was dissolved in 0 cc, 0.20 g of LiBF ₄ was added and mixed well. Then THF was removed at room temperature under reduced pressure and MO
An ECP / MECMC (550) / LiBF ₄ mixture was obtained as a viscous liquid. This mixture was coated on a glass plate in an argon atmosphere and heated at 80 ° C. for 1 hour.
OECP / MECMC (550) copolymer / LiBCF
_{The 4} composite was obtained as a transparent free-standing film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 3 × 10 ⁻⁴ S / cm.

Comparative Example 1 <Preparation and Evaluation of MCMC (800) -based Polymer Solid Electrolyte> 1.5 g of MCMC (800) synthesized in Example 4 was used as TH.
It was dissolved in F10 cc, 0.15 g of LiCF ₃ SO ₃ was added and mixed well. Then THF was removed under reduced pressure at room temperature to give the _{MCMC (800) / LiCF 3 SO} 3 mixture as a viscous liquid. This mixture was coated on a glass plate in an argon atmosphere and heated at 80 ° C. for 1 hour.
CMC (800) / LiCF ₃ SO ₃ composite is about 50μ
m as a transparent film. 2 of this film
When the ionic conductivity at 5 ° C. was measured by the impedance method, it was 8 × 10 ⁻⁶ S / cm.

Example 12 <Synthesis of N-methacryloylcarbamic acid carbonic acid propylene ester (NMCP)> 0.1 m of propylene hydroxycarbonate synthesized in Example 1
ol (= 11.8 g) and N-methacryloyl isocyanate (MAI) 0.1 mol (= 11.1 g) were dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and then 0.33 g of dibutyltin dilaurate was added. . After that, by reacting at 50 ° C. for about 3 hours,
22 g of NMCP was obtained as a colorless liquid. The product is NM
It was confirmed to be CP by the following analysis. (1) Melting point: 56 ° C (3) Infrared absorption spectrum: (KBr tablet, cm ⁻¹ ) 3290, 2988, 2257, 1780, 1708,
1636, 1509, 1458, 1400, 1292,
1218, 1172, 1098, 1057, 999, 9
47,890,803,771,716,666,60
3,483 (4) Nuclear magnetic resonance spectrum: (CDCl ₃ ) δ = 1.9 (s, 3H), 4.3 to 4.6 (m, 4)
H), 5.0 (m, 1H), 5.6 (s, 1H), 5.
9 (s, 1H), 8.6 (s, 1H) (5) FAB-MS spectrum: 252 ([M + Na]
⁺ ), 230 ([M + H] ⁺ ), 69 From the above results, it is clear that MAI and propylene hydroxycarbonate react in a one-to-one manner, and the isocyanate group of MAI disappears to form a urethane bond. It was

Example 13 <Preparation and Evaluation of NMCP-based Polymer Solid Electrolyte> 1.5 g of NMCP synthesized in Example 12 was added to THF10c.
Dissolved in c to obtain a LiBF ₄ mixture as a viscous liquid. After coating this mixture on a glass plate in an argon atmosphere and heating at 80 ° C. for 1 hour, NMCP / LiB
The F ₄ composite was obtained as a transparent film of about 50 μm. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 1 × 10 ⁻⁵ S / cm.

Example 14 <NMCP / MCMC (80
0) Preparation and Evaluation of Copolymer Solid Electrolyte> 1.50 g of NMCP synthesized in Example 12 and 1.50 g of MCMC (800) synthesized in Example 4 were added to THF 20c.
After dissolving in c, 0.20 g of LiBF ₄ was added and mixed well. Then THF was removed at room temperature under reduced pressure to remove NMCP
A / MCMC (800) / LiBF ₄ mixture was obtained as a viscous liquid. When this mixture was applied to a glass plate in an argon atmosphere and heated at 80 ° C. for 1 hour, NMCP /
MCMC (800) copolymer / LiBF ₄ composite is about 5
It was obtained as a 0 μm transparent self-supporting film. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 1 × 10 ⁻⁴ S / cm.

Example 15 <MOECP / MC with plasticizer added
Preparation and Evaluation of MC (800) Copolymer Solid Electrolyte> MOECP 1.80 g synthesized in Example 1 and MCMC (800) 1.80 g synthesized in Example 4, LiBF ₄
0.63 g, propylene carbonate (PC) 3.6 g
Well mixed in argon atmosphere, MOECP / MCM
A polymerizable monomer solution which was a C (800) / PC / LiBF ₄ mixture was obtained as a viscous liquid. After coating this polymerizable monomer solution on a glass plate in an argon atmosphere, 100
When heated at ℃ for 1 hour, MOECP / MCMC (8
00) Copolymer / PC / LiBF ₄ composite is about 50 μm
Obtained as a transparent self-supporting film. The ionic conductivities of this film at 25 ° C. and −10 ° C. were measured by the impedance method to be 3.5 × 10 ⁻³ and 1.5, respectively.
It was × 10 ^-3 S / cm.

Example 16 Instead of the propylene carbonate used in Example 15,
A MOECP / MCMC (800) copolymer / TG / LiBF ₄ composite was obtained as a transparent self-supporting film of about 50 μm in the same manner as in Example 15 except that tetraglyme (TG) was used. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 9
It was × 10 ^-4 S / cm.

Example 17 Instead of the propylene carbonate used in Example 15,
Except for using diethyl carbonate (DEC), the MOECP / MCMC (8
00) Copolymer / DEC / LiBF ₄ composite at about 50μ
Obtained as a transparent free-standing film of m 2. 2 of this film
When the ionic conductivity at 5 ° C. was measured by the impedance method, it was 1.5 × 10 ⁻³ S / cm.

Example 18 Instead of 0.63 g of LiBF ₄ used in Example 15, L was used.
A MOECP / MCMC (800) copolymer / PC / LiPF ₆ composite was obtained as a transparent self-supporting film of about 50 μm in the same manner as in Example 15 except that 0.95 g of iPF ₆ was used. The ionic conductivity of this film at 25 ° C. was measured by the impedance method to be 4 × 1.
It was 0 ^-3 S / cm.

Comparative Example 2 <MCMC (800) with plasticizer added
And Evaluation of Polymer Polymer Solid Electrolyte> MCMC (800) 3.60 g, L synthesized in Example 4
iBF ₄ 0.63 g, propylene carbonate (PC)
Mix well with 3.6g in an argon atmosphere, and MCMC
A polymerizable monomer solution that was a (800) / PC / LiBF ₄ mixture was obtained as a viscous liquid. After coating this polymerizable monomer solution on a glass plate in an argon atmosphere, 100 ° C
After heating for 1 hour, MCMC (800) polymer /
The PC / LiBF ₄ composite was obtained as a transparent free-standing film of about 50 μm. 25 ℃, -10 ℃ of this film
The ionic conductivity at room temperature was measured by an impedance method to find that it was 8.0 × 10 ⁻⁴ and 3.2 × 10 ⁻⁴ S / cm, respectively.
Met.

Example 19 <Preparation of Polymerizable Monomer Solution> 1.80 g of MOECP synthesized in Example 1, 1.80 g of MCMC (800) synthesized in Example 4, LiBF ₄
0.63 g, propylene carbonate (PC) 1.8
g and ethylene carbonate (EC) 1.8 g were mixed well in an argon atmosphere, and MOECP / MCMC (80
A polymerizable monomer solution of 0) / PC / EC / LiBF ₄ mixture was obtained as a viscous liquid. After coating this polymerizable monomer solution on a glass plate in an argon atmosphere, 100 ° C
After heating for 1 hour, MOECP (550) / MC
The MC (800) copolymer / PC / EC / LiBF ₄ composite was obtained as a transparent self-supporting film of about 50 μm.
The ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by the impedance method to be 4.0 ×, respectively.
It was 10 ⁻³ and 1.5 × 10 ⁻³ S / cm.

Example 20 <Production of cobalt oxide positive electrode> 11 g of Li ₂ CO ₃ and 24 g of Co ₃ O ₄ were mixed well,
LiCoO ₂ powder was obtained by heating in an oxygen atmosphere at 800 ° C. for 24 hours and then pulverizing. This LiCoO ₂ powder and the polymerizable monomer solution prepared in Example 19 were mixed in an argon atmosphere at a weight ratio of 7: 3 and applied onto a stainless steel foil at a thickness of 1 × 1 cm and a thickness of about 200 μm. Further, by heat-polymerizing at about 100 ° C. for 1 hour, a cobalt oxide / polymer solid electrolyte composite positive electrode (70 mg) was obtained.

Example 21 <Manufacture of Polymer Solid Electrolyte Secondary Battery> In an argon atmosphere glove box, a 75 μm thick lithium foil was cut into 1 × 1 cm (5.3 mg), and about 1 mm square at its end was 5 μm. Of polyimide film as a spacer. Next, the polymerizable monomer solution prepared in Example 19 was applied on a lithium foil, and the cobalt oxide positive electrode prepared in Example 20 was laminated thereon.
After heating at 00 ° C. for 1 hour, the battery end was sealed with an epoxy resin to obtain a lithium / cobalt oxide solid secondary battery. A cross-sectional view of the obtained battery is shown in FIG. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.3 V and a current of 0.3 mA, the maximum discharge capacity was 4.0 mAh and the capacity was 50%.
The cycle life before it decreased to 200 was 200 times. A battery manufactured by the same method was used, and the operating voltage was 2.0 to 4.3.
When charging and discharging were repeated at V and a current of 0.3 mA, the maximum discharge capacity was 3.8 mAh, and the cycle life until the capacity decreased to 50% was 251 times.

Example 22 <Production of vapor-phase graphite negative electrode> Showa Denko vapor-phase graphite fiber (average fiber diameter, 0.3 μm,
Average fiber length, 2.0μm, 2700 ℃ heat treated product) 10g
And 2.5 M butyllithium-containing hexane solution 200 ml
Were mixed and stirred at room temperature for 8 hours. Then, it was washed with hexane and dried to obtain a graphite fiber in which lithium ions were preliminarily inserted. The C / Li atomic ratio determined by elemental analysis was 12/1. 6 g of the lithium-containing graphite fiber thus obtained and the polymerizable monomer mixture prepared in Example 19
4 g was mixed under an argon atmosphere, and a part thereof was taken and applied on a stainless steel foil to a thickness of 1 × 1 cm and a thickness of about 150 μm. Furthermore, by heat-polymerizing at about 100 ° C. for 1 hour, a vapor-phase method graphite / polymer solid electrolyte composite negative electrode (25
mg).

Example 23 <Manufacture of polymer solid electrolyte secondary battery> The same procedure as in Example 21 was repeated except that the negative electrode for the vapor phase graphite prepared in Example 22 was used instead of the lithium foil. / Cobalt oxide solid secondary battery was obtained. When this battery was repeatedly charged and discharged with an operating voltage of 1.5 to 4.3 V and a current of 0.3 mA, the maximum discharge capacity was 4.0 mAh, and the cycle life until the capacity decreased to 50% was 323 times. there were.

Example 24 <Synthesis of Organic Solvent-Soluble Polyaniline> A 1 L four-necked flask was equipped with a thermometer, a stirrer, and a condenser, and 500 ml of 1N HCl aqueous solution was added. Dissolved aniline. Then, with stirring, while nitrogen bubbled, 11.5
g of ammonium persulfate was added as a solid over about 30 minutes. The reaction temperature was maintained at about 22 ° C. After the addition, the mixture was further reacted for 22 hours and then filtered, and the filter residue was washed with 500 ml of distilled water. Then, the product was transferred to a beaker and stirred with 500 ml of 5% aqueous ammonia for about 1 hour,
By filtering, washing with distilled water and drying under reduced pressure, about 16 g of polyaniline powder in a de-doped state was obtained.

Next, 150 ml of hydrazine monohydrate was added to a 300 ml three-necked flask, and the above-mentioned dedoped polyaniline powder was added at room temperature under a nitrogen stream while stirring for about 1 hour. After stirring under a nitrogen stream for about 10 hours at room temperature, the mixture was filtered in a nitrogen atmosphere and dried under reduced pressure. Furthermore, under a nitrogen atmosphere, the product was washed with purified THF and purified ether and dried under reduced pressure to obtain about 14 g of reduced polyaniline powder. The elemental analysis value of the reduced polyaniline powder was 98% of the total of carbon, hydrogen and nitrogen, and the element ratio of carbon / hydrogen / nitrogen was 6.00 / 4.95 /
It was almost the same as the theoretical value of 1.01. This powder was added to purified N-methylpyrrolidone (NMP) in an argon atmosphere at a concentration of about 5%.
Dissolved to a concentration of wt%. The number average molecular weight of polyaniline determined by GPC measurement of this solution was about 20,000 in terms of polystyrene.

Example 25 <Production of Polyaniline Positive Electrode> The polymerizable monomer solution produced in Example 19 was prepared in Example 24 in a glove box in an argon atmosphere, and 5w was prepared in Example 24.
The t% polyaniline / NMP solution was mixed so that the weight ratio of polyaniline and the polymerizable monomer solution was 1: 1. This mixed solution was applied onto a stainless steel foil so as to have a thickness of 10 × 10 mm and a thickness of 200 μm. Then 60 ℃,
By heating at 80 ° C. and 100 ° C. for 1 hour each, drying and polymerization were performed to obtain a polyaniline / polymer solid electrolyte composite positive electrode (20 mg).

Example 26 <Production of Polymer Solid Electrolyte Secondary Battery> A 25 μm thick lithium foil was cut into 12 × 12 mm (2.6 mg) in an argon atmosphere glove box,
A thickness of 10μ is used as a spacer at the end of about 2mm square.
m polyimide film. Next, Example 19
The polymerizable monomer solution prepared in 1. was applied onto a lithium foil, and the polyaniline / polymer solid electrolyte composite positive electrode prepared in Example 25 was attached to the foil. After heating at 100 ° C. for 1 hour, the battery end was sealed with an epoxy resin. A lithium / polyaniline solid state secondary battery having the same structure as in FIG. 1 was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2 to 4 V and a current of 0.3 mA, the maximum discharge capacity was 1.2 mAh.
And the cycle life is 38 until the capacity is reduced to 50%.
It was 0 times.

Example 27 <Preparation of Polymerizable Monomer Solution> 1.80 g of MOECP synthesized in Example 1, 1.80 g of MCMC (800) synthesized in Example 4, tetraethylammonium tetrafluoroborate (TEAB) 1.
35 g and propylene carbonate (PC) 3.6 g were mixed well in an argon atmosphere, and MOECP / MCMC
A polymerizable monomer solution that was a (800) / PC / TEAB mixture was obtained as a viscous liquid. This polymerizable monomer solution was coated on a glass plate in an argon atmosphere and heated at 100 ° C. for 1 hour. MOECP (550) / MCM
C (800) copolymer / PC / TEAB composite is about 50
It was obtained as a transparent self-supporting film of μm. The ionic conductivity of this film at 25 ° C. and −10 ° C. was measured by an impedance method to be 3.8 × 10 ⁻³ ,
It was 1.2 × 10 ⁻³ S / cm.

Example 28 <Production of Activated Carbon Electrode> Coconut shell activated carbon and the polymerizable monomer solution prepared in Example 27 were mixed in an argon atmosphere at a weight ratio of 1: 1 and the mixture was placed on a stainless steel foil to a size of 1 cm × 1 cm. About 150 μm
Applied to the thickness of. Further, by heating at about 100 ° C. for 1 hour to polymerize, an activated carbon / polymer solid electrolyte composite electrode (15 mg) was obtained.

Example 29 <Manufacture of solid-state electric double layer capacitor> In an argon atmosphere glove box, the activated carbon electrode (15 mg) manufactured in Example 28 was 1 cm × 1 cm, and the end was about 1 m.
The m square was covered with a polyimide film having a thickness of 10 μm as a spacer. Next, the polymerizable monomer solution prepared in Example 27 was applied on the electrodes, another electrode was attached to the electrodes, heated at 100 ° C. for 1 hour, and the ends of the capacitors were sealed with epoxy resin. A solid-state electric double layer capacitor as shown in 2 was manufactured. When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.3 mA, the maximum capacity was 230 mF. In addition, even if the charge and discharge were repeated 50 times under these conditions, there was almost no change in the capacity.

Example 30 <Production of solid electric double layer capacitor> Salt T used in the polymerizable monomer solution produced in Example 27
A polymerizable monomer solution was prepared by using 0.63 g of LiBF ₄ instead of EAB. A solid electric double layer capacitor was manufactured by the same method as in Example 29 except that this polymerizable monomer solution was used. When this capacitor was charged and discharged at an operating voltage of 0 to 2.0 V and a current of 0.3 mA, the maximum capacity was 173 mF. In addition, even if the charge and discharge were repeated 50 times under these conditions, there was almost no change in the capacity.

Example 31 <Production of acetylene black electrode> Acetylene black and the polymerizable monomer solution produced in Example 27 were mixed in an argon atmosphere at a weight ratio of 6: 4, and the mixture was sized on a stainless steel foil to a size of 1 cm × 1 cm. Now, about 1
It was applied to a thickness of 50 μm. Further, acetylene black / polymer solid electrolyte composite electrode (15 mg) was obtained by heat polymerization at about 100 ° C. for 1 hour.

Example 32 <Manufacture of Solid-state Electric Double Layer Capacitor> The acetylene black electrode manufactured in Example 31 (15 m
A solid-state electric double layer capacitor was manufactured by the same method as in Example 29 except that g) was used. When this capacitor was charged and discharged at an operating voltage of 0 to 2.5 V and a current of 0.3 mA, the maximum capacity was 55 mF. In addition, even if the charge and discharge were repeated 50 times under these conditions, there was almost no change in the capacity.

[0109]

The polymer solid electrolyte of the present invention comprises a composite of a polymer having a carbonate group in its side chain bonded by a urethane bond and at least one electrolyte, and is a thin film having good film strength. It is easy to obtain and has a feature of high ionic conductivity. Batteries and capacitors using the polymer solid electrolyte of the present invention can be used stably for a long period of time without risk of liquid leakage because the ion conductive material is solid, and by using this solid electrolyte, it is thin. It is possible to manufacture batteries and capacitors.

The polymer of the present invention having a carbonate group bonded by a urethane bond in the side chain and the organic solvent-soluble polyaniline polymer or other conductive polymer, metal oxide, metal sulfide, carbon material, etc. An electrode containing an electrode active material or a polarizable material and a method for manufacturing the same are
We can provide electrodes with high electrochemical activity and flexibility,
In particular, a thin electrode can be provided, and it is useful as an electrode used in various batteries or electric double layer capacitors, and a manufacturing method thereof.

Further, the battery of the present invention is an all-solid-state battery which can operate at high capacity and high current, has good cycleability, and is excellent in safety and reliability. It can be used as a power supply for electric products such as backup power supply, a large power supply for electric vehicles, and load leveling. Further, since it can be easily made into a thin film, it can be used as a paper battery such as an identification card. Furthermore, the electric double layer capacitor of the present invention has high voltage, high capacity,
It is an electric double layer capacitor that can operate at high current or has good cycleability, and is excellent in safety and reliability, and can be an all-solid-state electric double layer capacitor having such characteristics. Therefore, it can be used not only as a backup power source but also as a power source for various electric products when used together with a small battery. Further, since it has excellent workability such as thinning, it can be expected to be used in applications other than the conventional solid-state electric double layer capacitors.

[Brief description of 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-state electric double layer capacitor of the present invention.

FIG. 3 MOECP system and MOECP / MCMC (80
0) Temperature change of ionic conductivity of copolymer type polymer solid electrolyte film.

[Explanation of symbols]

 1 Positive Electrode 2 Polymer Solid Electrolyte 3 Negative Electrode 4 Current Collector 5 Spacer 6 Insulating Resin Sealant 7 Polarizing Electrode 8 Current Collector 9 Polymer Solid Electrolyte Membrane 10 Spacer 11 Insulating Resin Sealant 12 Lead Wire

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01M 4/02 H01M 6/18 E 6/18 10/40 B 10/40 9375-5E H01G 9 / 00 301G (72) Inventor Eri Tamura 1-1-1, Onodai, Midori-ku, Chiba City, Chiba Prefecture Showa Denko K.K.

Claims (21)

[Claims] 1. A compound of the general formula (I) [In the formula, R ¹ represents hydrogen or a methyl group, and R ² represents an organic group. The organic group may have 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.
Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, R ¹ , R ² and x, y in a plurality of units represented by the above general formula (I) in the same molecule,
The values of z are independent of each other and need not be the same. ] The polymer solid electrolyte which consists of a polymer obtained from at least 1 type of the compound which has a unit represented by, and / or a copolymer which uses this compound as a copolymerization component, and a complex containing at least 1 type of electrolyte. 2. A compound represented by the general formula (II): [In the formula, R ¹ represents hydrogen or a methyl group, and R ² , R ³
Represents an organic group. The organic group may have a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y are 0 or an integer of 1 to 5, respectively, and z is 0 or 1 to 10.
Represents the numerical value of. However, when x = 0 and y = 0, z = 0. Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. ] A polymer solid electrolyte comprising a polymer obtained from at least one compound having a structure represented by: and / or a copolymer containing the compound as a copolymerization component, and a composite containing at least one electrolyte. 3. The polymer solid electrolyte according to claim 1, wherein at least one of the electrolytes is an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, or a transition metal salt. 4. The solid polymer electrolyte according to claim 1, wherein a plasticizer is added. 5. A battery containing the solid polymer electrolyte according to claim 1. 6. The battery according to claim 5, comprising a negative electrode containing lithium, a lithium alloy, or a carbon material capable of inserting and extracting lithium ions. 7. The battery according to claim 5, which has a positive electrode containing an organic solvent-soluble aniline-based polymer or other conductive polymer, a metal oxide, a metal sulfide, or a carbon material. 8. A compound represented by the general formula (I): [The symbols in the formula are the same as in claim 1. ] A polymerizable monomer mixture containing at least one compound having a unit represented by the following formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added thereto is placed in a structure for battery construction or supported. A method for producing a battery, comprising a step of disposing the mixture on the body and polymerizing the polymerizable monomer mixture. 9. A compound represented by the general formula (II): [The symbols in the formula are the same as in claim 2. ] A polymerizable monomer mixture containing at least one compound having a structure represented by the formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added to the polymerizable monomer mixture, is placed in a structure for battery construction or supported. A method for producing a battery, comprising a step of disposing the mixture on the body and polymerizing the polymerizable monomer mixture. 10. A compound represented by the general formula (I): [The symbols in the formula are the same as in claim 1. ] The polymer obtained from at least 1 type of the compound which has a unit represented by this, and / or the copolymer which uses this compound as a copolymerization component, and an electrode characterized by including an electrode active material or a polarizable material. 11. A compound represented by the general formula (II): [The symbols in the formula are the same as in claim 2. ] And a polymer obtained from at least one compound having a structure represented by
Alternatively, an electrode comprising a copolymer containing the compound as a copolymerization component, and an electrode active material or a polarizable material. 12. The electrode according to claim 10 or 11, wherein the electrode active material or polarizable material is an organic solvent-soluble aniline polymer or other conductive polymer, metal oxide, metal sulfide or carbon material. . 13. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the ion conductive substance is the polymer solid electrolyte according to any one of claims 1 to 4. Double layer capacitor. 14. A compound represented by the general formula (I): [The symbols in the formula are the same as in claim 1. ] A polymerizable monomer mixture containing at least one compound having a unit represented by the following formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added thereto is placed in a structure for constructing an electric double layer capacitor. Or a step of polymerizing the polymerizable monomer mixture, which is arranged on a support, and a method for producing an electric double layer capacitor. 15. A compound represented by the general formula (II): [The symbols in the formula are the same as in claim 2. ] A polymerizable monomer mixture containing at least one compound having a structure represented by the formula and at least one electrolyte, or a polymerizable monomer mixture in which a plasticizer is added thereto is placed in a structure for constructing an electric double layer capacitor. Or a step of polymerizing the polymerizable monomer mixture, which is arranged on a support, and a method for producing an electric double layer capacitor. 16. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the polarizable electrode is represented by the general formula (I): [The symbols in the formula are the same as in claim 1. ] An electric double layer capacitor comprising a polymer obtained from at least one kind of a compound having a unit represented by and a composite containing a carbon material and a copolymer having the compound as a copolymerization component. 17. An electric double layer capacitor in which a polarizable electrode is arranged via an ion conductive substance, wherein the polarizable electrode is represented by the general formula (II): [The symbols in the formula are the same as in claim 2. ] And a polymer obtained from at least one compound having a structure represented by
Alternatively, an electric double layer capacitor comprising a composite containing a copolymer containing the compound as a copolymerization component and a carbon material. 18. A compound represented by the general formula (I): [In the formula, R ¹ represents hydrogen or a methyl group, and R ² represents an organic group. The organic group may have 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.
Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However, R ¹ , R ² and x, y in a plurality of units represented by the above general formula (I) in the same molecule,
The values of z are independent of each other and need not be the same. ] The polymer obtained from at least 1 type of the compound which has the unit represented by these, or the copolymer which uses this compound as a copolymerization component. 19. A compound represented by the general formula (II): [In the formula, R ¹ represents hydrogen or a methyl group, and R ² , R ³
Represents an organic group. The organic group may have a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y are 0 or an integer of 1 to 5, respectively, and z is 0 or 1 to 10.
Represents the numerical value of. However, when x = 0 and y = 0, z = 0. Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. ] The polymer obtained from at least 1 type of the compound which has a structure represented by these, or the copolymer which uses this compound as a copolymerization component. 20. The general formula (I):[Wherein, R¹ Represents hydrogen or a methyl group, R² Is organic
Represents a group. The organic group has a linear, branched or cyclic structure
It may be composed of any of the above and may be an element other than carbon, hydrogen and oxygen.
One or more elements may be included. x and y are respectively
0 or an integer of 1 to 5, z is a numerical value of 0 or 1 to 10
Represents However, when x = 0 and y = 0, z = 0.
Also (CH₂ ) And (CH (CH₃ )) Are arranged irregularly
May be. However, a plurality of the above general formulas in the same molecule
R in the unit represented by (I)¹ , R ² And x, y,
The values of z are independent and need not be the same.
Yes. ] The compound which has a unit represented by these. 21. A compound represented by the general formula (II): [In the formula, R ¹ represents hydrogen or a methyl group, and R ² , R ³
Represents an organic group. The organic group may have a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y are 0 or an integer of 1 to 5, respectively, and z is 0 or 1 to 10.
Represents the numerical value of. However, when x = 0 and y = 0, z = 0. Further, (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. ] The compound which has a structure represented by these.