JP2002305034A - Electrical power accumulating device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a power accumulating device having a high energy density and a low internal resistance by the optimum combination of current collectors. SOLUTION: This is a power accumulating device which is constituted such that a positive electrode having activated carbon as an electrode active material, a negative electrode having carbonaceous materials capable of storing and releasing lithium ion as the electrode active material, and an electrolytic solution containing lithium ions are equipped, and in which an aluminum foil or alumina foil is used as the positive electrode current collector and a copper foil or a metallic foil whose surface is covered with a copper plated film is used as a negative electrode current collector to constitute the negative electrode.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a power storage device having a high withstand voltage and a high energy density and a low internal resistance.

[0002]

2. Description of the Related Art Devices that can store electric energy by charging and discharge electric energy when necessary are called power storage devices, and typical examples thereof include nickel cadmium batteries and nickel hydride batteries. Batteries, lithium ion batteries, electric double layer capacitors, and the like. In particular, an electric double layer capacitor that can be charged and discharged with a large current is promising as an energy storage device for electric vehicles, auxiliary power supplies, midnight power storage, and the like. This electric double layer capacitor is capable of rapid charging and discharging, has high cycle durability, and has high durability when a voltage is applied, as compared with a lithium ion secondary battery which has also recently attracted attention as an energy storage device. However, there is a disadvantage that the energy density and the withstand voltage are smaller than those of the lithium ion secondary battery. Therefore,
There is a strong demand for the development of an electric double layer capacitor having high energy density and high withstand voltage while maintaining rapid charge / discharge properties and high durability.

[0003] The electric double layer capacitor is composed of a pair of polarizable electrodes. The polarizable electrode mainly comprises a carbonaceous material such as activated carbon having a very large surface area, and operates on the principle of providing electricity by physically adsorbing anions and cations in the electrolyte on the large surface of the carbonaceous material. The polarizable electrode can be obtained by applying and drying a slurry obtained by mixing a finely pulverized carbonaceous material, a binder, and a solvent on the surface of the aluminum foil, or by adding a Teflon (registered trademark) resin to the finely pulverized carbonaceous material. Such an electrode sheet is produced by mixing and kneading a polymer binder which is liable to be fibrillated, and laminating the sheet to an aluminum foil.

A pair of polarizable electrodes of a capacitor is different from a battery electrode involving a chemical reaction, and there is no distinction between a positive electrode and a negative electrode. Anions are absorbed and desorbed on the surface of the polarizable electrode serving as the positive electrode, and cations are stored on the surface of the polarizable electrode serving as the negative electrode to store electricity. Even if the positive electrode and the negative electrode are exchanged, the operation in theory is exactly the same. However, in an actual electric double layer capacitor, the surface area, density, pore distribution, pore volume of the carbonaceous material to be used are considered in consideration of the size of anions and cations in the electrolyte, the capacitance and operating voltage of the polarizable electrode, and the like. In practice, the positive electrode and the negative electrode are used while being distinguished from each other since the electrode is manufactured by optimizing the filling amount and the like for each electrode.

[0005] Here, the polarizable electrode is held in a sheet shape,
A metal foil called a current collector plays a role of extracting electric energy from the polarizable electrode. Conventionally, as the current collector of the electric double layer capacitor layer, an aluminum foil, an aluminum alloy foil, and an aluminum oxide foil are used for both the positive and negative electrodes.

On the other hand, in the electric double layer capacitor, the energy stored in the cell is represented by 1/2 CV ² (C is the capacity per cell (F), and V is the voltage (V) applicable to the cell). Since the square of the applied voltage V is reflected in the energy, it is effective to increase the voltage (withstand voltage) applied to the capacitor to improve the energy density.

Further, in order to achieve a high energy density and a high withstand voltage, activated carbon or activated carbon fiber is used for the positive electrode, a carbon material (eg, graphite) capable of inserting and extracting lithium ions in the negative electrode, and lithium ion in the electrolyte. There has been proposed an electricity storage device using the same (JP-A-60-182670, JP-A-64-14882, etc.). However, since these secondary batteries use nickel, titanium, and stainless steel as current collectors, not only has the problem of high internal resistance, but also nickel and stainless steel have a positive electrode collector during long-term use. The conductor may be eluted.

The characteristics required of the current collector are as follows: (1) A material which does not corrode or cause an electrochemical reaction in a charge / discharge voltage range to be used and which withstands a high voltage. (2) A material that can be made thin to increase the electrode area. (3) It must have sufficient strength to keep the polarizable electrode in a sheet shape even if it is thin. (4) High conductivity. (5) Inexpensive. Therefore, there is a demand for the development of a current collector for a power storage device including such a point.

The present invention has been made in view of such circumstances, and has as its object to provide a power storage device having a high energy density and a low internal resistance by using an optimal combination of current collectors.

[0010]

Means for Solving the Problems and Embodiments of the Invention As a result of intensive studies to achieve the above object, the present inventor has found that activated carbon is stored in the positive electrode and lithium ions are stored in the negative electrode.
In a power storage device using a detachable carbon material and an electrolyte containing lithium ions, an aluminum foil or an aluminum oxide foil is used for a positive electrode current collector, and a copper foil or a copper plating film is used for a negative electrode current collector. It has been found that when a metal foil coated with the above is used, a high-performance power storage device with improved energy density and low internal resistance can be obtained.

As mentioned above, activated carbon or activated carbon fiber is used for the positive electrode, a carbon material (eg, graphite) capable of occluding and releasing lithium ions for the negative electrode, and nickel and titanium are used as current collectors for a power storage device using lithium ions for the electrolyte. Although stainless steel is used, these current collectors have high resistance. The resistance is related to the shape of the substance and is expressed by the following equation. R = ρL / s (where R is the electrical resistance (Ω) and ρ is the resistance value (Ω · c
m) and s indicate a cross-sectional area (cm ³ ), L indicates a length (cm), and ρ is a value specific to the substance. )

When the resistivity of the above nickel, titanium, stainless steel, aluminum, and copper is compared, nickel is 6.
84 μΩ · cm, titanium 42 μΩ · m, stainless steel (composition Cr: Ni: Fe = 25: 20: 55) 73 μ
Ω · cm, aluminum is 2.65 μΩ · cm, copper is 1.67 μΩ · cm, and the resistivity of copper, aluminum and nickel tends to be low.

The aluminum oxide foil most commonly used in electric double layer capacitors is a foil in which pure aluminum is electrically corroded, an aluminum oxide layer is formed, and the surface is etched to increase the surface area. . Actually, the results of comparing the specific resistances of the aluminum oxide foil and the copper foil are as follows. Cut out 3 cm x 3 cm foil of aluminum oxide foil and copper foil of known thickness,
The measurement was performed using a resistivity probe Σ-10 of Company S and a four-probe probe. In the measurement, the measurement was performed ten times and the average was obtained. As a result, the volume resistivity was 3.4 μΩ · cm for aluminum oxide and 1.6 μΩ · cm for copper foil. The copper foil has a value close to the above literature value, but the aluminum oxide foil has a pure aluminum literature value of 2.8264 μΩ · cm.
The resistivity is even higher. This is thought to be higher due to the effect of the aluminum oxide layer on the aluminum foil surface, but still lower than the resistivity of nickel.

From the above results, it was considered that it is more effective to use a copper foil having higher conductivity for the positive and negative electrodes. When a cell was formed using a current collector made of copper, the copper of the current collector on the positive electrode side was reduced. Ionization, copper ions were eluted in the solvent, and reduced to copper on the negative electrode side to precipitate. As a result, as shown in FIG. 1, it was found that a significant voltage drop occurred during charging at a set voltage of 4.3 V and a charging current density of 1.59 mA / cm ² , and the battery did not function as a secondary battery.

Therefore, the present inventor examined whether or not the above-mentioned current collector can be used as a positive electrode current collector. As a result, it was found that corrosion of the current collector started at a voltage of 4.3 V or less except for titanium and aluminum. Was. In particular, in the case of copper having the highest conductivity, the ionization of copper is remarkable as apparent from the above experimental results, and it cannot be used as a positive electrode current collector at all.

On the other hand, as a current collector for the negative electrode, cells were actually prepared for copper, aluminum and nickel having low resistivity, their capacity and internal resistance were investigated, and the most suitable current collector was set. As a result, while using an aluminum foil or an aluminum oxide foil as the positive electrode current collector, it is optimal to use a copper foil or a metal foil whose surface is coated with a copper plating film as the negative electrode current collector, The present inventors have found that the internal resistance of the electric storage device is reduced and the energy density is improved, and the present invention has been accomplished.

Therefore, the present invention provides the following electricity storage device. [Claim 1]: A power storage device including a positive electrode using activated carbon as an electrode active material, a negative electrode using a carbon material capable of inserting and extracting lithium ions as an electrode active material, and an electrolyte solution containing lithium ions. An aluminum foil or an aluminum oxide foil is used as a positive electrode current collector constituting the positive electrode, and a copper foil or a metal foil whose surface is coated with a copper plating film is used as a negative electrode current collector constituting the negative electrode. An electricity storage device characterized by the above-mentioned. [Claim 2]: The power storage device according to claim 1, wherein the raw material of the activated carbon is phenol, petroleum coke, or coconut shell. [Claim 3]: The power storage device according to claim 1 or 2, wherein the maximum voltage used is 3.5 to 5V.

Hereinafter, the present invention will be described in more detail. The power storage device according to the present invention is configured to include a positive electrode using activated carbon as an electrode active material, a negative electrode using a carbon material capable of occluding and releasing lithium ions as an electrode active material, and an electrolytic solution containing lithium ions. A power storage device, wherein an aluminum foil or an aluminum oxide foil is used as a positive electrode current collector constituting the positive electrode, and a copper foil or a metal foil whose surface is coated with a copper plating film is used as a negative electrode current collector constituting the negative electrode Is used.

In this case, an aluminum foil of the positive electrode current collector,
A known aluminum oxide is used.
In addition, as the copper foil of the negative electrode current collector, normal pure copper is used, and as the metal foil whose surface is coated with a copper plating film,
A copper plating film or a nickel plating film is preferably formed on the surface of a metal foil such as aluminum or nickel by an electroplating method, an electroless plating method, or a vapor-phase plating method such as sputtering or vacuum evaporation, preferably to a thickness of about 0.1 to 20 μm, and .1 to 1
What has formed about 5 micrometers is used. The shape of the foil may be a thin foil or a sheet spread in a plane. It may be a stampable sheet having holes. In this case, the foil weight per unit area can be reduced. further,
The surface may be roughened, and may be a mesh or mesh.

The thickness is preferably about 1 to 200 μm.
If the thickness is large, the density of the carbonaceous material in the entire electrode is low. Therefore, a thin material is preferable, and a thickness of about 1 to 100 μm is more preferable. Furthermore, 1 to 30 μm is particularly preferred. If the thickness is too thin, a problem may occur in the strength. In view of this, the thickness is preferably 8 to 50 μm, and particularly preferably 8 to 30 μm.

In the present invention, phenol, petroleum coke or coconut shell is used as a raw material for the electrode composition applied on the current collector constituting the positive electrode, and these are carbonized to activate steam or alkali. It is preferable to use activated carbon obtained by performing the method.

Further, a conductive material may be added to the activated carbon for a positive electrode. The conductive material is not particularly limited as long as it can impart conductivity to the carbon material.For example, carbon black, Ketjen black, acetylene black, carbon whisker, carbon fiber, natural graphite, artificial graphite, titanium oxide, Examples thereof include metal fibers such as ruthenium oxide, aluminum, and nickel. These can be used alone or in combination of two or more.
Among them, it is preferable to use Ketjen black and acetylene black, which are one kind of carbon black.

Here, the compounding amount of the conductive material is not particularly limited.
0.1 to 20 parts by weight of the conductive material powder relative to 0 parts by weight,
Preferably from 0.5 to 10 parts by weight, more preferably from 1 to 7 parts by weight.
Preferably it is parts by weight. The average particle size of the conductive material powder is 10 nm to 10 μm, preferably 10 nm to 10 μm.
It is 100 nm, more preferably 20 nm to 40 nm. In this case, the average particle size of the conductive material powder is 1/5000 to 1/2, particularly 1/100 of the average particle size of the positive electrode carbon material.
It is preferably about 1/10.

The above-mentioned electrode composition for a positive electrode contains a carbon material for a positive electrode, a binder polymer or a solution thereof to be described later, and a solvent, if necessary, in a mixing container, and preferably rotates and revolves the mixing container. It can be obtained by wet mixing. At this time, a necessary minimum amount of a solvent is added to the positive electrode composition as needed so that the slurry has a viscosity suitable for coating. The viscosity of the positive electrode electrode composition slurry depends on the coating method.
2,000 to 20,000 mPa · s, especially 2,000 to
It is preferably 10,000 mPa · s. Also,
The addition amount of the binder polymer is preferably 0.5 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the mixed powder.

As the carbon material capable of occluding and desorbing lithium ions of the negative electrode in the present invention, a material usable for a negative electrode of a lithium ion secondary battery can be used. Specifically, natural graphite, artificial graphite, MCMB, MCF, carbon nanotube, VGCF and the like can be used.

A conductive material can be added to the carbon material for the negative electrode. The conductive material is not particularly limited as long as it can impart conductivity to the carbon material.
Carbon black, ketjen black, acetylene black, carbon whisker, carbon fiber, natural graphite, artificial graphite, titanium oxide, ruthenium oxide, aluminum,
Metal fibers such as nickel, etc .;
These can be used alone or in combination of two or more. Among them, it is preferable to use Ketjen black and acetylene black, which are one kind of carbon black.

Here, the compounding amount of the conductive material is not particularly limited.
The amount of the conductive material powder is preferably 0 to 20 parts by weight, preferably 0 to 10 parts by weight, and more preferably 0 to 6 parts by weight with respect to 0 parts by weight. The average particle size of the conductive material powder is 10 nm to 10 μm, preferably 10 nm to 100 μm.
nm, more preferably 20 nm to 40 nm. In this case, the average particle size of the conductive material powder is 1/5000 to 1/2 of the average particle size of the carbon material for the positive electrode, particularly 1/100 to 1/1.
It is preferably 0.

The above-described electrode composition for a negative electrode contains a carbon material for a negative electrode, a binder polymer or a solution thereof described below, and a solvent as necessary, in a mixing vessel, and preferably rotates and revolves the mixing vessel. It can be obtained by wet mixing. At this time, a necessary minimum amount of a solvent is added to the negative electrode composition as needed so that the slurry has a viscosity suitable for coating. The viscosity of the negative electrode composition slurry depends on the coating method.
2,000 to 20,000 mPa · s, especially 2,000 to
It is preferably 10,000 mPa · s. Also,
The amount of the binder polymer to be added is preferably 0.5 to 20 parts by weight, particularly preferably 5 to 17 parts by weight based on 100 parts by weight of the mixed powder.

Examples of the binder polymer include (I) an unsaturated polyurethane compound, (II) a polymer material having an interpenetrating network structure or a semi-interpenetrating network structure,
(III) a thermoplastic resin or (IV) a fluorine-based polymer material can be used.

Further, among the binder polymers (I) to (I)
The use of the polymer material (III) has high adhesiveness, so that the physical strength of the electrode can be improved. Further, the polymer material having the interpenetrating network structure or semi-interpenetrating network structure (II) has a high affinity for an electrolyte solvent molecule and an ionic molecule, has a high ion mobility, and has a high concentration of an electrolyte salt. And has high ionic conductivity. Since the thermoplastic resin (III) is thermoplastic, it can be easily molded and processed, absorbs an organic electrolyte moderately and swells, and exhibits high ionic conductivity. The fluorine-based polymer material (IV) has excellent thermal and electrical stability.

Specifically, the unsaturated polyurethane compound (I) includes (A) an unsaturated alcohol having at least one (meth) acryloyl group and a hydroxyl group in a molecule, (B) Those obtained by reacting the polyol compound represented by the general formula (1), the (C) polyisocyanate compound, and if necessary, the (D) chain extender are preferable. HO-[(R ¹ ) _a- (Y) _b- (R ² ) _c ] _d -OH (1) [wherein, R ¹ and R ² are the same or different amino group, nitro group, carbonyl group or A divalent hydrocarbon group having 1 to 10 carbon atoms which may contain an ether group, and Y is -COO
—, —OCOO—, —NR ³ CO— (R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), —O— or an arylene group, and a, b, and c are 0 or 1 to 10. , D represents an integer of 1 or more. ]

As the unsaturated alcohol of the component (A),
There is no particular limitation as long as it has at least one (meth) acryloyl group and a hydroxyl group in the molecule, and examples thereof include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl methacrylate. Examples thereof include propyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, and triethylene glycol monomethacrylate.

As the polyol compound of the component (B),
For example, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, ethylene glycol / propylene glycol copolymer, ethylene glycol / oxytetramethylene glycol copolymer, and polyester polyols such as polycaprolactone can be used. But,
Particularly, those represented by the following general formula (1) are preferable. HO-[(R ¹ ) _a- (Y) _b- (R ² ) _c ] _d -OH (1)

In the above formula (1), R ¹ and R ^{2 each} have the same or different amino group, nitro group, carbonyl group or ether group and may have 1 to 10 carbon atoms, preferably 1 to 10 carbon atoms.
And 6 represents a divalent hydrocarbon group, particularly an alkylene group, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, an ethylene oxide group, and a propylene oxide group.

Y is -COO-, -OCOO-, -NR ³
CO- (R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), -O-, or an arylene group such as a phenylene group. a, b, and c are 0 or an integer of 1 to 10, and d is 1 or more, preferably 5 or more, and more preferably 10 to 200.

In this case, the number average molecular weight of the polyol compound as the component (B) is preferably in the range of 400 to 10,000, more preferably 1,000 to 5,000.

As the polyisocyanate compound of the component (C), for example, tolylene diisocyanate, 4,4'-
Aromatic diisocyanates such as diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane diisocyanate, xylylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, Examples thereof include aliphatic or alicyclic diisocyanates such as 4′-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate.

It is preferable to add a chain extender to the unsaturated polyurethane compound, if necessary, in addition to the components (A) to (C). As such a chain extender, those usually used for synthesizing a thermoplastic polyurethane resin can be used. For example, ethylene glycol, diethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol;
1,4-bis (β-hydroxyethoxy) benzene,
Aromatic diols or alicyclic diols such as 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, hexamethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, Diamines such as piperazine derivatives, phenylenediamines and tolylenediamines; adipic hydrazide;
Examples thereof include amino alcohols such as isophthalic hydrazide and the like, and one of these can be used alone or in combination of two or more.

It is also possible to use a urethane prepolymer obtained by previously reacting the polyol compound (B) and the polyisocyanate compound (C).

The above components are used in an amount of 100 to 20,000 parts by weight, preferably 1,000 to 10,000 parts by weight, of the polyol compound of the component (B) per 100 parts by weight of the unsaturated alcohol of the component (A). Parts, 80 to 5,000 parts by weight, preferably 300 to 2,000 parts by weight, of the polyisocyanate compound of the component (C), and if necessary, 5 to 1,000 parts by weight of the chain extender of the component (D). And preferably 10 to 500 parts by weight.

The unsaturated polyurethane thus obtained
As the urethane compound, specifically, the compounds shown below
And the like. One of these may be used alone or two or more may be used.
It can be used in combination. CH_Two= C (CH_Three) COO-C_TwoH_FourO-CONH-C
₆H_Four-CH_TwoC₆H_Four-NHCOO-[(C_TwoH_FourO)_a(C
H_TwoCH (CH_Three) O)_c]_d-CONH-C₆H_Four-CH_Two
C₆H_Four-NHCOO-C_TwoH_FourO-COC (CH_Three) = C
H_Two (However, a = 7, c = 3, d = 5-7) (A) component: hydroxyethyl methacrylate (B) component: ethylene oxide / propylene oxide
Nandam copolymerized diol (In the general formula (1), a / c = 7/3, number average
(C molecular weight: about 3,000) (C) component: 4,4'-diphenylmethane diisocyanate
Auto CH_Two= C (CH_Three) COO-C_TwoH_FourO-CONH-C
₆H_Four-CH_TwoC₆H_Four-NHCOO-｛[(C_TwoH_FourO)
_a(CH_TwoCH (CH_Three) O)_c]_d-CONH-C₆H _Four−
CH_TwoC₆H_Four-NHCOO-C_FourH₈O｝_e-CONH-C
₆H_Four-CH_TwoC₆H_Four-NHCOO-C_TwoH_FourO-COC
(CH_Three) = CH_Two (However, a = 7, c = 3, d = 5-7, e = 2-20
(A) Component: hydroxyethyl methacrylate (B) Component: ethylene oxide / propylene oxide
Nandam copolymerized diol (In the general formula (1), a / c = 7/3, number average
(C molecular weight: about 3,000) (C) component: 4,4'-diphenylmethane diisocyanate
Component (D): 1,4-butanediol CH_Two= C (CH_Three) COO-C_TwoH_FourO-CONH-C
₆H₇(CH_Three)_Three-CH_Two-NHCOO-[(C_TwoH_FourO)_a
(CH_TwoCH (CH_Three) O)_c]_d-CONH-C₆H₇(C
H_Three)_Three-CH_Two-NHCOO-C_TwoH_FourO-COC (C
H_Three) = CH_Two (However, a = 7, c = 3, d = 5-7) (A) component: hydroxyethyl methacrylate (B) component: ethylene oxide / propylene oxide
Nandam copolymerized diol (In the general formula (1), a / c = 7/3, number average
(Molecular weight: about 3,000) (C) component: isophorone diisocyanate CH_Two= C (CH_Three) COO-C_TwoH_FourO-CONH-C
₆H_Four-CH_TwoC₆H_Four-NHCOO-CH_TwoCH_TwoO- (C
OC_FiveH_TenO)_f-CH_TwoCH_TwoO-CONH-C₆H_Four-C
H_TwoC₆H_Four-NHCOO-C_TwoH_FourO-COC (CH_Three) =
CH_Two (However, f = 20 to 30) (A) component: hydroxyethyl methacrylate (B) component: polycaprolactone diol (number average molecule)
(Amount: about 3,000) Component (C): 4,4'-diphenylmethane diisocyanate
To

The number average molecular weight of the obtained unsaturated polyurethane compound is preferably in the range of 1,000 to 50,000, more preferably in the range of 3,000 to 30,000.
If the number average molecular weight is too small, the molecular weight between cross-linking points of the cured gel becomes small, and the flexibility as a binder polymer may become too low. On the other hand, if it is too large, the viscosity of the electrode composition before curing becomes large, and it may be difficult to prepare an electrode having a uniform coating thickness.

Incidentally, a monomer copolymerizable with the unsaturated polyurethane compound may be used in combination. Examples of the monomer copolymerizable with the unsaturated polyurethane compound include acrylonitrile, methacrylonitrile, acrylates, methacrylates, and N-vinylpyrrolidone. It is preferable to use acrylonitrile and methacrylonitrile in combination, because the ionic conductivity is not impaired and the strength of the electrode coating film can be improved.

Next, as the polymer material having the interpenetrating network structure or the semi-interpenetrating network structure (II), two or more kinds capable of forming an interpenetrating network structure or a semi-interpenetrating network structure with each other can be used. (Polymers, reactive monomers, etc.) can be used.

As such two or more compounds,
(A) (a) a hydroxyalkyl polysaccharide derivative and (d)
A polymer matrix combining a compound having a crosslinkable functional group, a polymer matrix combining a (b) (b) polyvinyl alcohol derivative and (d) a compound having a crosslinkable functional group, or (c) ( Polymer matrix in which c) a polyglycidol derivative and (d) a compound having a crosslinkable functional group are combined.
In this case, it is preferable to use the unsaturated polyurethane compound of the above (I) as a part or all of the compound having a crosslinkable functional group of the component (d) from the viewpoint of improving physical strength.

As the hydroxyalkyl polysaccharide derivative of the component (a) constituting the binder polymer (a), hydroxyethyl polysaccharide obtained by reacting a naturally occurring polysaccharide such as cellulose or starch with ethylene oxide is used. Sugars, hydroxypropyl polysaccharides obtained by reacting propylene oxide, glycidol or dihydroxypropyl polysaccharides obtained by reacting 3-chloro-1,2-propanediol, and the like. Some or all of the hydroxyl groups are blocked with a substituent via an ester bond or an ether bond.

Examples of the polysaccharide include cellulose,
Examples include starch, amylose, amylopectin, pullulan, curdlan, mannan, glucomannan, arabinan, chitin, chitosan, alginic acid, carrageenan, dextran, etc. Although there is no restriction on the arrangement and the like, cellulose and pullulan are particularly preferred from the viewpoint of availability.

A method for synthesizing dihydroxypropylcellulose is described in US Pat. No. 4,096,326. Other dihydroxypropyl polysaccharides can be synthesized by known methods [Sato et al., Makr.
omol. Chem. , 193, 647 (1992),
Or Macromolecules 24, 4691
(1991)].

The hydroxyalkyl polysaccharide has a degree of molar substitution of 2 or more. When the molar substitution degree is less than 2, the ability to dissolve the ion-conductive metal salts is too low to be used. The upper limit of the degree of molar substitution is 30, preferably 20 ,. It is sometimes difficult to industrially synthesize a hydroxyalkyl polysaccharide having a degree of molar substitution higher than 30 in view of the industrial production cost and the complexity of the synthesis operation. Further, even if it is manufactured by force and the molar substitution degree is increased from 30, the increase in conductivity due to the increase in the molar substitution degree is not expected to be so much expected.

As the component (a), at least 10% of the terminal OH groups in the molecular chain of the hydroxyalkyl polysaccharide are a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, an R ⁴ CO— group (R ⁴
Unsubstituted or substituted monovalent hydrocarbon group), R ⁴ ₃ Si- groups (R
⁴ is the same as above), amino group, alkylamino group, H
(OR ⁵ ) _m -group (R ⁵ is an alkylene group having 2 to ⁵ carbon atoms,
m is an integer of 1 to 100) and a hydroxyalkyl polysaccharide derivative blocked with one or more monovalent groups selected from groups containing a phosphorus atom.

As the unsubstituted or substituted monovalent hydrocarbon group, the same groups as those described above for R ¹ and R ² can be used.
Particularly, those having 1 to 10 carbon atoms are preferable. The substituent can be blocked using a known method for introducing various groups into the terminal OH group.

Next, the polyvinyl alcohol derivative of the component (b) constituting the binder polymer (b) is a hydroxyl group of a polymer compound having a polyvinyl alcohol unit having an oxyalkylene chain (the remaining hydroxyl group derived from the polyvinyl alcohol unit, (Total of hydroxyl groups derived from the introduced oxyalkylene-containing group) is partially or entirely substituted.

Here, the polymer compound having a polyvinyl alcohol unit is a polymer compound having a polyvinyl alcohol unit in the molecule and having an average degree of polymerization of 20 or more, preferably 30 or more, more preferably 50 or more. Some or all of the hydroxyl groups therein are substituted by oxyalkylene-containing groups.
The upper limit of the average degree of polymerization is 2,000 or less, particularly 2
It is preferably at most 00. The average degree of polymerization here is a number average degree of polymerization. A polymer having an excessively high degree of polymerization has an excessively high viscosity and is difficult to handle. Therefore, the preferable range of the degree of polymerization is 20 to 500 mer.

Here, the polyvinyl alcohol unit constitutes a main chain of a polyvinyl alcohol derivative and is represented by the following general formula (2).

[0055]

Embedded image

In the above formula (2), n is at least 20, preferably at least 30, more preferably at least 50, and the upper limit is preferably at most 2,000, particularly preferably at most 200.

The high molecular compound having a polyvinyl alcohol unit is preferably a homopolymer which satisfies the above-mentioned average polymerization degree range and has a polyvinyl alcohol unit fraction of 98 mol% or more in the molecule, but is not particularly limited. A polymer compound which satisfies the above average polymerization degree range and has a polyvinyl alcohol content of preferably at least 60 mol%, more preferably at least 70 mol%, for example, a part of the hydroxyl group of the polyvinyl alcohol is formal. For example, modified polyvinyl formal, modified polyvinyl alcohol in which a part of hydroxyl groups of polyvinyl alcohol is alkylated, poly (ethylene vinyl alcohol), partially saponified polyvinyl acetate, and other modified polyvinyl alcohol can be used.

This polymer compound is an oxyalkylene-containing group in which a part or all of the hydroxyl groups in the polyvinyl alcohol unit has an average molar substitution degree of 0.3 or more (this oxyalkylene group is a part of the hydrogen atom). May be substituted with a hydroxyl group), and preferably at least 30 mol%, more preferably at least 50 mol%.

The average degree of molar substitution (MS) can be calculated by accurately measuring the charged mass and the mass of the reaction product. For example, consider a case where 10 g of PVA is reacted with ethylene oxide, and the amount of the obtained PVA derivative is 15 g. PVA is a unit of _{- (CH 2 CH (OH)} )
Therefore, the unit molecular weight is 44. On the other hand, PVA derivative is a reaction _{product, - (CH 2 CH (OH} ))
- because those -OH groups becomes _{-O- (CH 2 CH 2 O)} n -H group, their unit molecular weight is 44 + 44n. Accordingly, the mass increase accompanying the reaction corresponds to 44n, and is as follows.

[0060]

(Equation 1)

Therefore, in the above example, it can be calculated that MS = 0.5. Note that this value merely represents the average degree of molar substitution. That is, the amount of unreacted PVA units and the length of oxyethylene groups introduced by the reaction cannot be specified.

[0062]

Embedded image

Here, as a method for introducing an oxyalkylene-containing group into the polymer compound having a polyvinyl alcohol unit, a method of reacting an oxirane compound such as ethylene oxide with a polymer compound having a polyvinyl alcohol unit, A method in which a polymer compound having a unit is reacted with a polyoxyalkylene compound having a substituent having reactivity with a hydroxyl group at a terminal.

In the above method, one kind selected from ethylene oxide, propylene oxide and glycidol can be used alone or in combination of two or more kinds as the oxirane compound.

In this case, when ethylene oxide is reacted, an oxyethylene chain is introduced as shown by the following formula.

[0066]

Embedded image [However, g is preferably 1 to 10, particularly preferably 1 to 5. ]

When propylene oxide is reacted, an oxypropylene chain is usually introduced as shown by the following formula.

[0068]

Embedded image [However, h = 1 to 10, especially 1 to 5 is preferable. ]

Further, when glycidol is reacted, two branched chains are introduced as shown by the following formula.
As the reaction between the hydroxyl group of PVA and glycidol, two types of a-attack and b-attack are considered. When one glycidol reacts, two new hydroxyl groups are generated, and the hydroxyl groups react with glycidol again. As a result, the following two branched chains are introduced on the hydroxyl group of the PVA unit.

[0070]

Embedded image

The value of x + y is preferably 1 to 10,
More preferably, it is 1-5. The ratio between x and y is not particularly limited, but generally, x: y = 0.4: 0.6 to .0.
6: 0.4 is often in the range.

The reaction between the polymer compound having a polyvinyl alcohol unit and the above oxirane compound can be carried out using a basic catalyst such as sodium hydroxide, potassium hydroxide, various amine compounds and the like.

More specifically, the reaction between polyvinyl alcohol and glycidol will be described as an example. A solvent and polyvinyl alcohol are charged in a reaction vessel. In this case, the polyvinyl alcohol does not necessarily need to be dissolved in the solvent, and may be uniformly dissolved or the polyvinyl alcohol may be in a suspended state in the solvent. A predetermined amount of a basic catalyst, for example, an aqueous solution of sodium hydroxide is added to this solution, and the mixture is stirred for a while, and then glycidol diluted with a solvent is added. After reacting at a predetermined temperature for a predetermined time, polyvinyl alcohol is taken out. If the polyvinyl alcohol is not dissolved, it is filtered off using a glass filter or the like. In the case of dissolution, an alcohol or the like is poured to cause precipitation, and the precipitate is separated by filtration using a glass filter or the like. For purification, neutralization by dissolving in water and passing through an ion exchange resin or dialysis and freeze-drying can be performed to obtain dihydroxypropylated polyvinyl alcohol.

The reaction ratio between the polyvinyl alcohol and the oxirane compound is in a molar ratio of 1:10 to 1:30, preferably 1:10 to 1:20.

As the polyoxyalkylene compound having a substituent reactive with a hydroxyl group at the terminal, a compound represented by the following general formula (3) can be used.

[0076]

Embedded image

In the formula (3), A is a monovalent substituent having a reactivity with a hydroxyl group, for example, isocyanate group, epoxy group, carboxylic acid group, carboxylic acid chloride group, ester group, ester group, amide group, fluorine, Halogen atoms such as bromine and chlorine,
Examples include a silicon-containing reactive substituent and a monovalent substituent capable of reacting with another hydroxyl group. Among these, an isocyanate group, an epoxy group, and a carboxylic acid chloride group are preferable from the viewpoint of reactivity.

The carboxylic acid group may be an acid anhydride. Further, as the ester group, a methyl ester group,
Ethyl ester groups are preferred. Examples of the silicon-containing reactive substituent include those having a SiH group, a SiOH group, or the like at a terminal.

Further, the above isocyanate groups and epoxy groups
The reactive group with a hydroxyl group such as ⁷O oxyalkyl
May be bonded to an oxygen group, an oxygen atom, a sulfur atom,
Rubonyl group, carbonyloxy group, NH group, N (C
H_Three) Group, N (C_TwoH_Five) Groups, such as nitrogen-containing groups, SO_TwoGroup, and the like
Intervening, preferably 1-10 carbon atoms, especially 1-carbon
6, alkylene group, alkenylene group, arylene group, etc.
Through R⁷May be bonded to the oxyalkylene group of O
No.

For example, as such a polyoxyalkylene group having a substituent A, a substance obtained by reacting a polyisocyanate compound with a terminal hydroxyl group of the polyoxyalkylene group can be used. In this case, as the compound having an isocyanate group, for example, two or more in a molecule such as tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, biphenylene diisocyanate, diphenyl ether diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Can be used. For example, a compound obtained by the following reaction can be used.

[0081]

Embedded image

R ⁷ O is an oxyalkylene group having 2 to 5 carbon atoms, for example, —CH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ O
_{-, - CH 2 CH (CH} 3) O -, - CH 2 CH (CH 2 C
H ₃ ) O— and —CH ₂ CH ₂ CH ₂ CH ₂ O—. m represents the number of added moles of the oxyalkylene group, and the number of added moles (o) is preferably 1 to 100, and more preferably 1 to 50.

In this case, the polyoxyalkylene chain represented by the above formula (R ⁷ O) _o is, in particular, a polyethylene glycol chain, a polypropylene glycol chain, or a polyethylene oxide (EO) / polypropylene oxide (P
O) Copolymer chains are preferred. The weight average molecular weight of these polyoxyalkylene chains is preferably from 100 to 3,000.
0, more preferably those having a weight average molecular weight in the range of 200 to 1,000, which is a molecular region in a liquid state at room temperature.

R ⁶ is a one-terminal blocking group, and is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or an R ⁶ CO— group (R ⁶ is a non-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms). Substituted or substituted monovalent hydrocarbon group). As the R ⁶ CO— group, for example, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and preferably, R ⁶ is an alkyl group or a phenyl group which may be substituted with a cyano group. And an acyl group, a benzoyl group, a cyanobenzoyl group and the like are preferable.

As the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, the same groups as those described above for R ¹ and R ² can be used, and those having 1 to 8 carbon atoms are particularly preferable.

The reaction between the polymer compound having a polyvinyl alcohol unit and the polyoxyalkylene compound having a substituent having reactivity with the hydroxyl group at the terminal can be carried out in the same manner as in the case of the oxirane compound.

The reaction ratio between the polyvinyl alcohol and the polyoxyalkylene compound having a substituent having reactivity with the hydroxyl group at the terminal is preferably 1: 1 to 1 in molar ratio.
The ratio is 1:20, more preferably 1: 1 to 1:10.

The structure of a polymer compound having an oxyalkylene-containing group introduced into a polyvinyl alcohol unit has the structure of ¹³ C—N
It can be confirmed by MR.

In this case, the analysis of how many oxyalkylene groups the polymer compound having a polyvinyl alcohol unit having an oxyalkylene chain has is as follows.
It can be measured by various methods such as NMR and elemental analysis,
A simple method is to obtain from the mass increase of the polymer produced by the reaction with the charged polymer. For example, the method for obtaining from the yield is to accurately measure the charged amount of the polymer compound having a polyvinyl alcohol unit and the mass of the polymer compound having a polyvinyl alcohol unit having an oxyalkylene group obtained by the reaction, and introduce the mass from the difference. The amount (average molar substitution degree) of the oxyalkylene chain thus obtained can be determined as described above.

The average degree of molar substitution (MS) is an index indicating how many moles of oxyalkylene groups are introduced per vinyl alcohol unit. In a polymer compound, the average degree of molar substitution is 0.3 or more. It is necessary that the ratio be 0.5 or more, more preferably 0.7 or more, and still more preferably 1.0 or more.
In this case, the upper limit of the average molar substitution degree is not particularly limited, but is preferably at most 20 or less. If the average molar substitution degree is too small, the ionic conductive salt does not dissolve, the mobility of ions is low, and the ionic conductivity may be a low value. Solubility and mobility remain the same, so that too large is useless.

The above-mentioned polymer compound having a polyvinyl alcohol unit having an oxyalkylene chain changes its apparent shape from a syrupy liquid having a high viscosity at room temperature (20 ° C.) to a rubbery solid state depending on the average degree of polymerization. The higher the average degree of polymerization, the lower the fluidity at room temperature (20 ° C.), so-called solids (soft paste solids).

The above-mentioned polymer compound is not a linear polymer but an amorphous (amorphous) polymer formed by entanglement of highly branched molecular chains, regardless of the average degree of polymerization.

The above-mentioned polyvinyl alcohol derivative is partially or wholly, preferably 10 mol%, of the hydroxyl group (the total of the residual hydroxyl group derived from the polyvinyl alcohol unit and the hydroxyl group derived from the introduced oxyalkylene-containing group) in the molecule.
Halogen atoms or, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ CO- groups (R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms), R ⁴ ₃ Si-group (R ⁴
Is the same as described above), one or more monovalent substituents selected from an amino group, an alkylamino group and a group having a phosphorus atom.

As the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, the same ones as those of R ¹ and R ² can be used, and those having 1 to 8 carbon atoms are particularly preferable.

The substituent can be introduced by a known method for introducing various groups into the terminal OH group.

Next, the polyglycidol derivative of the component (c) constituting the polymer matrix of the above (c) is composed of a unit represented by the following formula (4) (hereinafter referred to as A unit) and a unit represented by the following formula (5) (Hereinafter, referred to as a B unit), and each terminal of the molecular chain is blocked with a predetermined substituent.

[0097]

Embedded image

The polyglycidol can be obtained by polymerizing glycidol or 3-chloro-1,2-propanediol.
It is recommended to carry out the polymerization using glycidol as raw material.

As the above-mentioned polymerization reaction, there are known a method using a basic catalyst such as sodium hydroxide, potassium hydroxide and various amine compounds and a method using a Lewis acid catalyst (Andrzej Dwork).
et al. , Macromol. Chem. Phys
s. 196, 1963-1970 (1995); T
oker. , Macromolecules 27,3
20-322 (1994)).

The polyglycidol has A, B in the molecule.
It is preferable that there are two or more, preferably six or more, and more preferably ten or more of the two units. In this case, although the upper limit is not particularly limited,
The number is preferably 0 or less. When fluidity as a liquid is required for polyglycidol, it is preferable that the total of the A and B units is small. On the other hand, when high viscosity is required, the total of the A and B units is preferably large.

The appearance of these A and B units has no regularity and is random. For example, -AAAA-, -AA
-B-, -ABBA-, -BAA-, -AB-
B-, -BABB-, -BBAA-, -BBB
Any combination such as-is possible.

The polyglycidol preferably has a weight average molecular weight (Mw) in terms of polyethylene glycol using gel filtration chromatography (GPC) of 200.
~ 730,000, more preferably 200 ~ 100,0
00, more preferably 600 to 20,000. In this case, polyglycidol having a weight average molecular weight of up to about 2,000 is a high-viscosity liquid flowing at room temperature, whereas polyglycidol having a weight average molecular weight exceeding 3,000 is a soft paste-like solid at room temperature. Further, the average molecular weight ratio (Mw / Mn) is 1.1 to 20, more preferably 1.
It is preferably from 1 to 10.

The apparent shape of the polyglycidol changes from a syrupy liquid having a high viscosity at room temperature (20 ° C.) to a rubbery solid state at room temperature (20 ° C.) depending on the molecular weight. It has low fluidity, so-called solid (soft paste solid).

Further, polyglycidol is not a linear polymer, regardless of the molecular weight, but is an amorphous (amorphous) polymer formed by entanglement of highly branched molecular chains. This is recognized because the result of wide-angle X-ray diffraction does not show any peak indicating the presence of crystals.

The ratio of A unit to B unit in the molecule is
A: B = 1 / 9-9 / 1, preferably 3 / 7- by molar ratio
7/3.

As the binder polymer of the present invention,
As the component (c), at least 10% of the terminal OH groups of the molecular chain of the polyglycidol are halogen atoms, unsubstituted or substituted monovalent hydrocarbon groups, R ⁴ CO— groups (R ⁴ is an unsubstituted or substituted monovalent hydrocarbon). group), R ⁴ ₃ Si- groups (R ⁴ is as defined above), an amino group, an alkylamino group, H (OR ⁵⁾ _m - group (R ⁵ represents an alkylene group having 2 to 5 carbon atoms, m is 1 An integer of 100)
And a polyglycidol derivative blocked by one or more monovalent groups selected from a group containing a phosphorus atom.

As the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, the same ones as those of R ¹ and R ² can be used, and those having 1 to 8 carbon atoms are particularly preferable.

The substituent can be blocked by a known method for introducing various groups into the terminal OH group.

Next, the compound having a crosslinkable functional group of the component (d) includes a compound having an epoxy group in a molecule and a compound having two or more active hydrogen groups capable of reacting with the epoxy group. A compound having an isocyanate group in the molecule, a compound having two or more active hydrogen groups capable of reacting with the isocyanate group, and a compound having two or more reactive double bonds in the molecule can be used.

Examples of the compound having an epoxy group in the molecule include sorbitol polyglycidyl ether,
Sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylpropane polyglycidyl ether,
Resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diglycidyl ether of ethylene / propylene glycol copolymer, polytetramethylene glycol diglycidyl ether, adipic acid diglycidyl ether Compounds having two or more epoxy groups in the molecule, such as glycidyl ether, are mentioned.

Compounds having two or more active hydrogen groups, such as amine compounds,
An alcohol compound, a carboxylic acid compound, and a phenol compound can be reacted to form a three-dimensional network structure. Examples thereof include polyethylene glycol, polypropylene glycol, polymer polyols such as ethylene glycol / propylene glycol copolymer, ethylene glycol, 1,2-propylene glycol, 1,3
-Propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 2,2-dimethyl-1,3
-Propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 1,4-bis (β-hydroxyethoxy) benzene,
p-xylylenediol, phenyldiethanolamine, methyldiethanolamine, polyethyleneimine,
Other polyfunctional amines, polyfunctional carboxylic acids and the like can be mentioned.

Examples of the compound having an isocyanate group in the molecule include tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, and the like.
Diphenylmethane diisocyanate, biphenylene diisocyanate, diphenyl ether diisocyanate,
2 in the molecule of trizine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.
Compounds having at least two isocyanate groups are exemplified.

Further, an isocyanate-terminated polyol compound obtained by reacting the above isocyanate compound with a polyhydric polyol compound can also be used. These can be obtained by reacting an isocyanate compound such as diphenylmethane diisocyanate or tolylene diisocyanate with the following polyol compounds.

In this case, the isocyanate compound [NC
O] and the stoichiometric ratio of [OH] of the polyol compound are [NCO]> [OH], and specifically, [NCO]:
[OH] = 1.03 / 1 to 10/1, preferably 1.10 / 1 to 5/1.

Examples of the polyol compound include high molecular weight polyols such as polyethylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3
-Butanediol, 1,4-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 2,2
-Dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 1,4-bis- (β-hydroxyethoxy) benzene, p-xylylenediol, phenyldiethanolamine, methyldiethanolamine,
3,9-bis- (2-hydroxy-1,1-dimethyl)
-2,4,8,10-tetraoxaspiro [5,5]-
Undecane and the like.

In place of the polyol compound, an amine compound having two or more active hydrogen groups may be reacted with the isocyanate compound. As the amine compound,
Although those having primary and secondary amino groups can be used, compounds having primary amino groups are more preferred.
For example, ethylenediamine, 1,6-diaminohexane,
Diamines such as 1,4-diaminobutane and piperazine,
Examples thereof include polyamines such as polyethyleneamine, and amino alcohols such as N-methyldiethanolamine and aminoethanol. Of these, more preferred are diamines having the same reactivity of functional groups. Also in this case, the stoichiometric ratio of [NCO] of the isocyanate compound to [NH ₂ ] and [NH] of the amine compound is [NCO]> [N
H ₂ ] + [NH].

A compound having an isocyanate group alone cannot form a three-dimensional network structure. In order to form a three-dimensional network structure, these compounds must have two
A three-dimensional network structure can be formed by reacting a compound having two or more active hydrogen groups, for example, an amine compound, an alcohol compound, a carboxylic acid compound, and a phenol compound. Such compounds having two or more active hydrogen groups include, for example, polyethylene glycol, polypropylene glycol, ethylene glycol.
Polymer polyols such as propylene glycol copolymers,
Ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-
1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, 1,4-bis (β-hydroxyethoxy) benzene, p-xylylene diol, phenyldiethanolamine, methyldiethanolamine, polyethyleneimine, and others And polyfunctional carboxylic acids.

Compounds having a reactive double bond include divinylbenzene, divinylsulfone, allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate ( Weight average molecular weight 200 to 1,000), 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate (weight average molecular weight 400), 2 -Hydroxy-1,
3-dimethacryloxypropane, 2,2-bis- [4-
(Methacryloxyethoxy) phenyl] propane, 2,
2-bis- [4- (methacryloxyethoxydiethoxy) phenyl] propane, 2,2-bis- [4- (methacryloxyethoxy / polyethoxy) phenyl] propane, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene diacrylate Ethylene glycol, polyethylene glycol diacrylate (weight average molecular weight 200 to 1,000), 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polypropylene glycol diacrylate (weight average molecular weight) 40
0), 2-hydroxy-1,3-diacryloxypropane, 2,2-bis- [4- (acryloxyethoxy) phenyl] propane, 2,2-bis- [4- (acryloxyethoxydiethoxy) Phenyl] propane, 2,2
-Bis- [4- (acryloxyethoxy / polyethoxy) phenyl] propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetetraacrylate, tricyclodecanedimethanolacrylate, hydrogenated Two reactive double bonds are present in the molecule of dicyclopentadiene diacrylate, polyester diacrylate, polyester dimethacrylate, the unsaturated polyurethane compound of the above (I), etc.
Compounds having at least one compound.

If necessary, acrylic acid or methacrylic acid ester such as glycidyl methacrylate, glycidyl acrylate, tetrahydrofurfuryl methacrylate, methacryloyl isocyanate, 2-hydroxymethyl methacrylic acid, N, N-dimethylaminoethyl methacrylic acid, etc. A compound having one acrylic acid group or methacrylic acid group in the molecule can be added. Further, acrylamide compounds such as N-methylolacrylamide, methylenebisacrylamide and diacetoneacrylamide, vinyl compounds such as vinyloxazolines and vinylene carbonate, and other compounds having a reactive double bond can be added.

Also in this case, in order to form a three-dimensional network structure, it is necessary to add a compound having two or more reactive double bonds in the molecule. That is, since a compound having only one reactive double bond such as methyl methacrylate alone cannot form a three-dimensional network structure, a compound partially having at least two reactive double bonds is used. It must be added.

Among the compounds containing a reactive double bond, particularly preferred reactive monomers include the above-mentioned (I)
And a diester compound containing a polyoxyalkylene component represented by the following general formula (6), and a monoester compound containing these and a polyoxyalkylene component represented by the following general formula (7) It is recommended to use in combination with

[0122]

Embedded image (Wherein, R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom, or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-
X represents an alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, such as a butyl group, an i-butyl group, an s-butyl group, and a t-butyl group;
≧ 1 and the condition of Y ≧ 0 is satisfied, or X ≧ 0 and the condition of Y ≧ 1 is satisfied, and X + Y is 100
Hereinafter, it is particularly preferable that it is 1 to 30. Especially R ⁸ ,
R ⁹ and R ¹⁰ represent a methyl group, an ethyl group, an n-propyl group, i
-Propyl, n-butyl, i-butyl, s-butyl and t-butyl are preferred. )

[0123]

Embedded image(However, in the formula, R¹¹, R¹², R¹³Is a hydrogen atom or methyl
Group, ethyl group, n-propyl group, i-propyl group, n
-Butyl group, i-butyl group, s-butyl group, t-butyl
Represents an alkyl group having 1 to 6, particularly 1 to 4, carbon atoms such as a group;
The condition of A ≧ 1 and B ≧ 0 is satisfied, or A ≧ 0
And the condition of B ≧ 1 is satisfied, and A + B is 10
It is preferably 0 or less, particularly preferably 1 to 30. In particular
R¹¹, R¹², R ¹³Is a methyl group, an ethyl group, n-propyl
Group, i-propyl group, n-butyl group, i-butyl group, s
-Butyl group and t-butyl group are preferred. )

The unsaturated polyurethane compound of the above (I),
Alternatively, a diester compound containing a polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component may be heated or irradiated with an electron beam, microwave, high frequency, or the like in the electrode composition, or the mixture may be heated. Thus, a three-dimensional network structure can be formed.

In this case, generally, the unsaturated polyurethane compound or the diester compound containing a polyoxyalkylene component of the above (I) can form a three-dimensional network structure by reacting it alone, but as described above. To
It is preferable to further add a monoester compound containing a polyoxyalkylene component which is a monofunctional monomer to the unsaturated polyurethane compound or a diester compound containing a polyoxyalkylene component. This is because a polyoxyalkylene branched chain can be introduced onto a three-dimensional network by adding this monoester compound.

The composition ratio of the unsaturated polyurethane compound or the diester compound containing the polyoxyalkylene component to the monoester compound containing the polyoxyalkylene component is not particularly limited. Diester compound containing oxyalkylene component / monoester compound containing polyoxyalkylene component] = 0.2 to 10, especially 0.1 to 0.1.
The range of 5 to 5 is preferable from the viewpoint of improving the electrode coating film strength.

The binder polymer containing the components (a) to (c) and (d) is heated or irradiated with an electron beam, microwave, high frequency, or the like, so that the crosslinkable functional group of the component (d) is changed. The three-dimensional network structure of the polymer obtained by reacting (polymerizing) the compound having
It forms a semi-interpenetrating polymer network in which the molecular chains of the polymer (c) are entangled with each other.

Next, as the binder polymer (III), it is preferable to use a thermoplastic resin containing a unit represented by the following general formula (8).

[0129]

Embedded image (In the formula, r represents 3 to 5, and s represents an integer of 5 or more.)

As such a thermoplastic resin, (E)
It is preferable to use a thermoplastic polyurethane resin obtained by reacting a polyol compound, (F) a polyisocyanate compound, and (G) a chain extender. The thermoplastic polyurethane-based resin includes a polyurethane urea resin having a urethane bond and a urea bond in addition to a polyurethane resin having a urethane bond.

As the polyol compound of the component (E), those obtained by a dehydration reaction or dealcoholation reaction of the following compounds (i) to (vi) are preferable. Particularly, polyester polyols, polyester polyether polyols and polyester polycarbonate polyols , Polycaprolactone polyol, or a mixture thereof. (I) a polyester polyol obtained by ring-opening polymerization of one or more cyclic esters (lactones); (ii) (a) a polyester polyol obtained by ring-opening polymerization of the cyclic ester (lactone) and a carboxylic acid;
(B) a dihydric aliphatic alcohol, a carbonate compound,
Polyester polyol obtained by reacting at least one selected from a polycarbonate polyol and a polyether polyol, respectively. (Iii) Polyester polyol obtained by reacting one or more carboxylic acids with one or more dihydric aliphatic alcohols (iv ) Polyester polycarbonate polyol obtained by reacting one or more carboxylic acids with one or more polycarbonate polyols (v) Polyester polyether polyol obtained by reacting one or more carboxylic acids with one or more polyether polyols (vi) One kind Polyester polyol obtained by reacting the above carboxylic acid with two or more kinds selected from dihydric aliphatic alcohols, polycarbonate polyols and polyether polyols

In this case, examples of the cyclic ester (lactone) include γ-butyrolactone, δ-valerolactone, ε-caprolactone and the like.

Examples of the carboxylic acid include glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
5-1 carbon atoms such as sebacic acid and dodecanedicarboxylic acid
4 linear aliphatic dicarboxylic acids; 2-methylsuccinic acid,
2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-
C5-14 branched aliphatic dicarboxylic acids such as dimethyldecandioic acid and 3,7-dimethyldecandioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid; or esters thereof. Derivatives and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, carbon number 5-14
Are preferred, and adipic acid, azelaic acid and sebacic acid are particularly preferably used.

Examples of the dihydric aliphatic alcohol include ethylene glycol, 1,3-propanediol,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, 1,7-heptanediol,
1,8-octanediol, 1,9-nonanediol,
C2-C14 linear aliphatic diols such as 1,10-decanediol; 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl C3 to C14 branched aliphatic diols such as -1,8-octanediol; cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; and the like, alone or in combination of two or more. Can be used in combination. Among them, a branched or chain aliphatic diol having 4 to 10 carbon atoms is preferable, and 3-methyl-1,5-pentanediol is particularly preferable.

Examples of the carbonate compound include dialkyl carbonate, alkylene carbonate, diaryl carbonate and the like. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate. Examples of the alkylene carbonate include ethylene carbonate. Examples of the diaryl carbonate include, for example, diphenyl carbonate.

As the polycarbonate polyol, one selected from a polyhydric alcohol and the above-mentioned carbonate compound is used.
And those obtained by a dealcoholation reaction with at least one carbonate compound. Examples of the polyhydric alcohol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octane. Examples include diol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, 1,4-cyclohexanedimethanol, and the like.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol,
EO / PO copolymer, polyoxytetramethylene glycol and the like can be mentioned, and one of these can be used alone or in combination of two or more.

The number average molecular weight of the polyol compound (E) is preferably from 1,000 to 5,000, more preferably from 1,500 to 3,000. Heat resistance of the thermoplastic polyurethane resin film obtained when the number average molecular weight of the polyol compound is too small,
Physical properties such as tensile elongation may be reduced. On the other hand, if it is too large, the viscosity at the time of synthesis increases, and the production stability of the obtained thermoplastic polyurethane resin may decrease. In addition, the number average molecular weight of the polyol compound referred to herein means a number average molecular weight calculated based on a hydroxyl value measured according to JIS K1577.

Examples of the polyisocyanate compound (F) include tolylene diisocyanate,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate And aliphatic or alicyclic diisocyanates such as 4,4'-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate.

As the chain extender of the component (G), it is preferable to use a low molecular weight compound having two active hydrogen atoms reactive with an isocyanate group in the molecule and having a molecular weight of 300 or less.

Examples of such low molecular weight compounds include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol, 1,7-heptanediol, 1,8
Aliphatic diols such as octanediol and 1,9-nonanediol; 1,4-bis (β-hydroxyethoxy)
Benzene, 1,4-cyclohexanediol, bis (β
Aromatic diols or alicyclic diols such as -hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, hexamethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, piperazine derivatives, phenylenediamine, tolylenediamine, etc. Diamines; amino alcohols such as adipic hydrazide and isophthalic hydrazide; one of these can be used alone or two or more can be used in combination.

In the thermoplastic polyurethane resin,
The polyisocyanate compound (F) is added in an amount of 5 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the polyol compound (E), and the chain extender (G) is added in an amount of 1 to 200 parts by weight. Parts by weight, preferably 5 to 10
It is preferable to add 0 parts by weight.

The swelling ratio of the thermoplastic resin obtained from the following equation is in the range of 150 to 800% by weight, preferably 250 to 500% by weight, more preferably 250 to 40% by weight.
0% by weight.

[0144]

(Equation 2)

Next, as the fluorine-based polymer material as the binder polymer of the above (IV), for example, polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (HFP) copolymer [P (VDF-H
FP)], vinylidene fluoride-ethylene trifluoride chloride (CTFE) copolymer [P (VDF-CTFE)], vinylidene fluoride-hexafluoropropylene fluororubber [P (VDF-HFP)], vinylidene fluoride- Tetrafluoroethylene-hexafluoropropylene fluoro rubber [P (VDF-TFE-HFP)], vinylidene fluoride-tetrafluoroethylene-perfluoroalkyl vinyl ether fluoro rubber, and the like. As the vinylidene fluoride-based polymer, those having a vinylidene fluoride content of 50% by weight or more, particularly 70% by weight or more (the upper limit is about 97% by weight) are preferable. Among these, polyvinylidene fluoride (PVDF), a copolymer of vinylidene fluoride and hexafluoropropylene [P (VDF-H
FP)], and a copolymer of vinylidene fluoride and ethylene chloride trifluoride [P (VDF-CTFE)] is preferred.

In this case, the weight average molecular weight of the fluoropolymer is at least 500,000, preferably 500,000.
0 to 2,000,000, more preferably 500,00
0 to 1,500,000. If the weight average molecular weight is too small, the physical strength may be significantly reduced.

By coating the polarizable electrode composition obtained as described above on a current collector, an electrode used for the electric storage device according to the present invention can be obtained.

[0148] The electricity storage device according to the present invention is one in which a separator is interposed between a pair of polarizable electrodes obtained as described above, and is filled with an electrolyte. In general, a liquid electrolyte is often used as an electrolyte, but a polymer gel electrolyte in which a polymer or a reactive compound is added to a liquid electrolyte can be used to prevent liquid leakage.

Here, the electrolyte solution is preferably a non-aqueous electrolyte solution. As the ionic conductive salt, an ionic conductive salt usually used for lithium ion secondary batteries can be used. ⁺ Cation and BF _{4
^{-, N (CF 3 SO 2}} ) 2 -, CF 3 SO 3 -, ClO 4 -, PF
₆ ^- it is preferable to use a salt which combines with anions such. Specifically, LiClO ₄ , LiBF ₄ , LiPF
₆ , LiN (CF ₃ SO ₂ ) ₂ , LiCF ₃ SO _{3 and the} like, and these can be used alone or in combination of two or more.

Solvents capable of dissolving the ionic conductive salt include dibutyl ether, 1,2-dimethoxyethane, 1,2-ethoxymethoxyethane, methyldiglyme, methyltriglyme, methyltetraglyme, and ethylglyme. , Ethyl diglyme, butyl diglyme, etc., glycol ethers (ethyl sorbitol, ethyl carbitol, butyl sorbitol, butyl carbitol, etc.), chain ethers such as, tetrahydrofuran,
Heterocyclic ethers such as 2-methyltetrahydrofuran, 1,3-dioxolan, 4,4-dimethyl-1,3-dioxane, γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3-methyl-1,3 Butyrolactones such as -oxazolidine-2-one and 3-ethyl-1,3-oxazolidine-2-one; and amide solvents (N-methylformamide, N, N-dimethyl) which are solvents generally used for electrochemical devices. Formamide, N
-Methylacetamide, N-methylpyrrolidinone, etc.),
Carbonate solvents (diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, styrene carbonate, etc.), imidazolidinone solvents (1,3-dimethyl-
2-imidazolidinone and the like, and one of these solvents may be used alone or as a mixture of two or more.

In this case, the concentration of the ionic conductive salt in the solvent of the electrolyte is 0.5 to 3.0 mol / L, preferably 0.1 to 3.0 mol / L.
It is 7 to 2.2 mol / L.

As the separator, those usually used as a separator base material for an electric double layer capacitor can be used. For example, polyethylene non-woven fabric, polypropylene non-woven fabric, polyester non-woven fabric, PTFE porous film, kraft paper, rayon fiber / sisal fiber mixed sheet, manila hemp sheet, glass fiber sheet,
Cellulose-based electrolytic paper, papermaking made of rayon fiber, mixed papermaking of cellulose and glass fiber, or a combination of these into a plurality of layers can be used.

As the separator, a separator obtained by forming the polymer binder used for the polarizable electrode for an electric double layer capacitor into a film can be used. As a result, the composition is the same as the polymer binder for the electrode, and the interface between the electrode and the separator can be integrally controlled, so that the internal resistance can be further reduced.

The electric storage device of the present invention has a maximum use voltage of 3.5 to 5 V, particularly,
Preferably, it is 4-5V.

The power storage device of the present invention described above can be used as a backup power supply for memories such as personal computers and portable terminals, as a power supply for instantaneous power failure prevention in personal computers and the like, applied to electric vehicles or hybrid vehicles, and used in combination with solar cells. It can be suitably used for various uses such as a solar power generation energy storage system, a load leveling power supply combined with a battery, and the like.

[0156]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1, Comparative Examples 1-4] Preparation of positive electrode 35 g of activated carbon (MSP-20, manufactured by Kansai Thermochemical Co., Ltd.)
Conductive material (HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd.)
92 g was put into a mixing vessel, and dry-mixing was performed three times for 5 minutes at about 1,000 rpm for both revolution and rotation using a rotation and revolution mixer (Mazellstar KK-102N, manufactured by Kurabo Industries) to obtain a positive electrode active material mixed powder. Was.

N-methyl-2-pyrrolidone (hereinafter, referred to as NMP) in which 10% by weight of this mixed powder of positive electrode active material and PVDF (average molecular weight: about 534,000 (GPC), manufactured by Aldrich) is dissolved. The solution in which PVDF was dissolved in NMP is referred to as a PVDF-NMP solution.) 21.1.
g, 86.16 g of NMP into a mixing vessel, and a rotation revolution mixer (Mazerustar KK-102N, manufactured by Kurabo Industries)
, Using both revolution and rotation at about 1,000 rpm for 5 minutes,
Then, three sets of wet mixing and defoaming at about 1,000 rpm and 270 rpm for 1 minute were performed to obtain a paste-like binder composition for a positive electrode. The obtained composition was applied on a current collector of various materials shown in Table 1 with a doctor blade, dried and cured at 80 ° C. for 2 hours, and then roll-pressed to obtain a positive electrode having a thickness of 200 μm. Was.

Preparation of Negative Electrode 34.35 g of artificial graphite, 46.9 PVDF-NMP solution
g, 63.36 g of NMP into the mixed solution, and a rotation revolving mixer (Mazerustar KK-102N, manufactured by Kurabo Industries)
Using both the revolution and the rotation at about 1,000 rpm for 5 minutes,
And around 1,000 rpm and 270 rpm
3 minutes of wet mixing and defoaming were performed to obtain a paste-like binder composition for a negative electrode. The obtained composition was applied on a current collector of various materials shown in Table 1 with a doctor blade, dried and cured at 80 ° C. for 2 hours, and then roll-pressed to obtain a 50 μm-thick negative electrode.

Preparation of Secondary Battery The positive electrode and negative electrode prepared above were punched into a disc having a diameter of 1.2 cm, and a secondary battery was prepared using a paper separator. Here, as the electrolytic solution, ethylene carbonate / diethylene carbonate = 1/1 (volume ratio) in which 1 M lithium perchlorate was dissolved was used. The cell assembly was performed at -70 ° C in an argon gas atmosphere.

[0161]

[Table 1]

With respect to the obtained secondary battery, charging and discharging were repeated 100 times at a charging voltage of 4.3 V, a charging / discharging current density of 1.6 mA / cm ² and a discharging end voltage of 3 V, and the energy density was determined. Here, the internal resistance was determined by dividing the voltage difference between the y-intercept of the approximate curve at the time of 25% from the discharge start time to the discharge end time and the charge voltage by the discharge current. The rate characteristics were measured by setting the discharge current to 10 times the discharge current.

[0163]

[Table 2]

In Table 2, the values of the energy density and the internal resistance were those at the 100th cycle. In addition, the rate was expressed by% by dividing the discharge energy density when discharging at 16 mA / cm ² by the discharging energy density when discharging at 1.6 mA / cm ² and multiplying by 100.

As shown in Table 2, when aluminum oxide was used as the positive electrode current collector and copper foil was used as the negative electrode current collector, the energy density and rate characteristics were improved as compared with the case where other current collectors were used. It can be seen that the internal resistance has decreased. In particular, it can be seen that the energy density is improved by 348% and the internal resistance is reduced by 29% as compared with Comparative Example 1 using aluminum oxide for the positive and negative electrodes.

[0166]

According to the present invention, an aluminum foil or an aluminum oxide foil is used as a positive electrode current collector constituting a positive electrode, and a copper foil or a surface is coated with a copper plating film as a negative electrode current collector constituting the negative electrode. Because the metal foil is used
A power storage device with low internal resistance and improved energy density and rate characteristics can be obtained.

[Brief description of the drawings]

FIG. 1 is a graph showing a voltage change during charging of a secondary battery using a copper foil for a positive electrode current collector and an aluminum oxide foil for a negative electrode current collector.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01M 4/58 H01G 9/00 301F 4/66 301D (72) Inventor Hiroshi Yoshida Onodai, Midori-ku, Chiba-shi, Chiba 1-2-3 Nisshin Spinning Co., Ltd. Research and Development Center (72) Inventor Hidehashi Mitsuhashi 1-2-3 Onodai, Midori-ku, Chiba City, Chiba Prefecture Nisshin Spinning Co., Ltd. Research and Development Center (72) Inventor Minami Shigenori 1-2-3 Onodai, Midori-ku, Chiba-shi, Chiba F-term in the R & D Center of Nisshinbo Industries Co., Ltd. 5H017 AA03 AS02 BB00 CC01 EE01 EE05 HH10 5H029 AJ02 AJ03 AJ06 AK08 AL06 AL07 AM02 AM03 AM04 AM05 AM07 CJ24 DJ07 EJ01 EJ05 EJ12 HJ18 5H050 AA02 AA07 AA08 BA17 CA16 CB07 CB08 DA04 DA07 DA08 EA23 GA24 HA18

Claims (3)

[Claims] 1. A power storage device comprising a positive electrode using activated carbon as an electrode active material, a negative electrode using a carbon material capable of absorbing and desorbing lithium ions as an electrode active material, and an electrolyte solution containing lithium ions. An aluminum foil or an aluminum oxide foil is used as a positive electrode current collector constituting the positive electrode, and a copper foil or a metal foil whose surface is coated with a copper plating film is used as a negative electrode current collector constituting the negative electrode. An electricity storage device characterized by the above-mentioned. 2. The power storage device according to claim 1, wherein the raw material of the activated carbon is phenol, petroleum coke, or coconut shell. 3. The power storage device according to claim 1, wherein the maximum voltage used is 3.5 to 5 V.