JP3141362B2 - Battery manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery which operates reversibly at ambient temperature, and more particularly to an improvement of an electrolyte, a positive electrode, a negative electrode, and a method of manufacturing a battery.

[0002]

2. Description of the Related Art Recent microelectronics are
As typified by the power supply for memory backup of various electronic devices, as batteries are stored in electronic devices and integrated with electronic elements and circuits, batteries have become smaller, lighter, thinner and have higher energy density. There is a strong demand for such batteries. In recent years, in the field of primary batteries, small and lightweight batteries such as lithium batteries have already been put into practical use, but their application fields are limited. Therefore, as a battery that replaces the conventional lead battery and nickel-cadmium battery, a secondary battery using a non-aqueous electrolyte that can be reduced in size and weight has attracted more attention. Currently, many research institutions are examining the lack of a material that satisfies practical properties such as characteristics.

On the other hand, conventionally, as a battery or a non-battery electrochemical device utilizing an electrochemical reaction, that is, an electrolyte such as an electric double layer capacitor or an electrochromic element, a liquid electrolyte, particularly an organic electrolyte, is generally ionic. Although a solution in which a compound is dissolved has been used, the above-mentioned liquid electrolyte is liable to cause leakage of liquid to the outside of the component, elution of an electrode substance, and further volatilization of the liquid electrolyte itself. And the like, and scattering of the electrolytic solution in the sealing step have been problems.

[0004] Therefore, in order to improve the liquid leakage resistance and the long-term storage property, ion conductive polymer compounds having high ion conductivity have been reported, and further research has been conducted as one of means for solving the above problems. Is underway.

[0005] The ion conductive polymer compounds that are currently being studied are homopolymer or copolymer linear polymers, network crosslinked polymers or comb polymers having ethylene oxide as a basic unit. In order to increase the ionic conductivity of the polymer, it has been proposed and practiced to use a crosslinked polymer or comb polymer to prevent crystallization of the ion-conductive polymer compound. In particular, an ion conductive polymer compound using the above network crosslinked polymer is useful because it has high mechanical strength and good ionic conductivity at low temperatures.

[0006] In designing a battery that is smaller and lighter and has a high energy density, the present inventor has studied a battery called a thin battery (having a thickness of 100 to 500 µm per unit cell (or a sheet battery)). did. However, when the above-mentioned ion-conductive polymer compound is used in the form of a thin film as an electrolyte, it is technically difficult to produce a thin-film metallic lithium having a quality sufficiently comparable to that, and the manufacturing process of the battery becomes complicated. Has become a problem. Further, when used as a secondary battery, there has been a problem that the use of metallic lithium is limited due to problems such as generation of lithium dendrites and passivation of the interface.

[0007] Therefore, researches on lithium metal-containing alloys represented by lithium-aluminum, lithium-lead, and lithium-tin alloys have been actively conducted. However, as represented by a lithium-aluminum alloy,
Since these alloys have low strength, the electrodes are cracked or miniaturized by repeated charge / discharge, and the cycle characteristics are not improved.

As other methods for suppressing the formation of dendrites of lithium, studies have been made on the selection of an electrolyte salt and improvement of a separator, and among these, a polypropylene nonwoven fabric which has been conventionally used is used. By laminating nonwoven fabric made of glass fiber etc., suppression of lithium dendrite has been attempted,
The essential solution has not been reached.

Therefore, at present, many research institutes are particularly studying electrode active materials that utilize intercalation or doping of a layered compound, and these are used for electrochemical reactions in charge and discharge. In this case, since a complicated chemical reaction does not theoretically occur, extremely excellent charge / discharge cycle performance is expected.

The use of a carbonaceous material as an electrode active material has also emerged as a solution to problems such as cycle characteristics and self-discharge characteristics of the electrode active material. This carbonaceous material is characterized by high doping capacity, low self-discharge rate, excellent cycling characteristics, and most notably, having a base potential very close to lithium metal.

Further, when the above-mentioned ion conductive polymer compound is applied as an electrolyte of an electrochemical device, it is necessary to make the electrolyte thinner in order to lower the internal resistance. In the case of the above-mentioned ion-conductive polymer compound, a uniform thin film can be easily processed into an arbitrary shape, but this method poses a problem. For example, a method of evaporating and removing a solvent by casting a solution of an ion-conductive polymer compound, or a method of applying a polymerizable monomer or macromer on a substrate and heating and polymerizing, or curing by irradiation with actinic rays There is a way.

Conventionally, a method of mainly performing heat polymerization has been used simply and frequently. However, the heat polymerization time is very long, and it is difficult to improve the production speed.
There is a problem that a temperature gradient is easily generated in the heating furnace, and that the heating furnace and incidental facilities become large due to the necessity of heating in an inert gas atmosphere.

Further, the inventors of the present invention provided a single electrolyte layer made of the above-mentioned ion-conductive polymer compound between a composite cathode and a composite anode composed of the above-mentioned ion-conductive polymer compound and an electrochemically active substance. An attempt was made to produce a thin battery (sheet-shaped battery) by arranging it in a sheet shape.
However, according to the above-described method, there is a problem in a method of improving the contact at the interface between the composite electrode and the electrolyte layer. Usually, the contact interface resistance is increased, so that the battery characteristics, especially the cycle characteristics and the charge / recharge after long-term storage, are increased. It had a great adverse effect on the discharge characteristics.

Therefore, an attempt was made to apply the above-mentioned composition of the ion-conductive polymer compound onto the surface of the composite positive electrode or the surface of the composite negative electrode and to carry out heat polymerization or to cure the composition by irradiation with ultraviolet rays. Compared with the above-described method, it has become possible to make the contact of the interface between the composite electrode and the electrolyte layer better, but in the above-described method, when applied to the surface of the composite electrode, It is difficult to completely cure the penetrating ion-conducting polymer compound liquid, and even in a thin battery cured by irradiation with ultraviolet rays, considering the charge / discharge characteristics after long-term storage,
It was not perfect.

When the above-mentioned method is applied to the curing method by heat polymerization, the heat polymerization time is long and, in addition, the polymerization initiator is biased in the composition of the ion-conductive polymer compound. However, there is a problem that the crosslinked network has a more irregular structure, and this has been a serious problem in addition to the above-mentioned problems of the production speed and facilities.

[0016]

SUMMARY OF THE INVENTION In view of the above-mentioned problems of the prior art, an object of the present invention is to improve battery characteristics and produce a high-performance electrode. It provides a battery with very high workability, no long-term liquid leakage, and high long-term reliability and safety. In addition, small size and light weight with high performance and high energy density It is intended to provide a method for producing a sheet-shaped battery.

[0017]

According to the present invention, there is provided an ion-conductive polymer compound composed of a polymer in which at least one ionic compound is dissolved. At least one of a composite positive electrode (A) and a composite negative electrode (B) composed of a polymer compound having a structure and having ion conductivity, an electrochemically active substance, and optionally an electron conductive substance; In a method for producing a battery comprising an electrolyte (C) comprising an ion-conductive polymer compound composed of a polymer substance in which an ionic compound is dissolved, a surface of the composite positive electrode (A) and a surface of the composite negative electrode (B) A first aspect of the present invention is to form an electrolyte layer (C) made of the above-described ion-conductive polymer compound by irradiation with ionizing radiation.

Further, as a method for forming the composite positive electrode (A) and the composite negative electrode (B) on the positive electrode current collector and the negative electrode current collector, at least one is disposed by a roller coating method or a screen coating method, A second invention is to form an electrode and an electrolyte by irradiation with ionizing radiation. As a method for forming an electrolyte layer (C) on the surface of the composite positive electrode (A) and the surface of the composite negative electrode (B), roller coating is used. The third invention is to dispose the electrolyte layer by a method or a screen coating method and form the electrolyte layer by irradiation with ionizing radiation.

Further, the above-mentioned ion-conductive polymer compound is a polymer compound which is a polyether having a reactive double bond in which at least one ionic compound is dissolved. A fourth invention is characterized in that the ion conductive polymer compound is a molecular compound, and the ion conductive polymer compound contains a substance capable of dissolving the ionic compound. By providing the composite positive electrode (A) and the composite negative electrode (B) composed of a chemically active substance and an ion-conductive polymer compound, and the electrolyte layer (C) composed of the ion-conductive polymer compound. The above object has been achieved.

By providing an electrolyte layer (C) composed of the ion-conductive polymer compound on both electrode surfaces of the composite positive electrode (A) and the composite negative electrode (B), good contact at the electrode interface is obtained. And the contact interface resistance is reduced.
This eliminates the conventional problem that the lithium deposition state when metal lithium is used for the negative electrode is uniformly distributed and the lithium deposition is partially concentrated to cause an internal short circuit.

Further, when the sheet-shaped battery is assembled, since the electrolyte layer (C) composed of the above-mentioned ion-conductive polymer has a double structure, an internal short circuit due to a pinhole or the like can be prevented. . Further, since the electrolyte layers are in contact with each other, the contact interface resistance is extremely small.

It should be noted that an ion-conductive polymer obtained by dissolving a metal salt in a polymer obtained by cross-linking a polyether is a cross-linked polymer formed by an ether bond. It has a low structure, and the migration of dissolved metal salt ions becomes extremely easy.

For example, a polymer having a crosslinked network structure obtained by reacting a mixture of polyethylene glycol dimethacrylate or diacrylate with polyethylene glycol monomethacrylate or monoacrylate may be used.

Next, as the ionic compound dissolved in the polymer compound thus obtained, for example, LiCl
O ₄ , LiBF ₄ , LIASF ₆ , LiPF ₆ , LiI, LiBr, Li ₂ B ₁₀ C
_{l 10, LiCF 3 SO 3,} LiCF 3 CO 2, LiSCN, NaI, NaSCN, NaB
r, an inorganic ion salt containing one kind of Li, Na, or K such as NaClO ₄ , KClO ₄ , KSCN, (CH ₃ ) ₄ NBF ₄ , (CH ₃ ) ₄ NBr, (C
_{2 H 5) 4 NClO 4,} (C 2 H 5) 4 NI, (C 3 H 7) 4 NBr, (nC 4 H 9) 4 NCl
O ₄ , (nC ₄ H ₉ ) ₄ NI, (C ₂ H ₅ ) ₄ N-maleate, (C ₂ H ₅ ) ₄ N-benzo
quaternary ammonium salts such as ate and (C ₂ H ₅ ) ₄ N-phtalate; and organic ion salts such as lithium stearylsulfonate, sodium octylsulfonate and lithium dodecylbenzenesulfonate. These ionic compounds are 2
More than one species may be used in combination.

The mixing ratio of such an ionic compound is as follows:
The ratio of the ionic compound is 0.0001 to 5.0 mol, preferably 0.005 to 2.0 mol, based on the ether bond oxygen of the polymer compound. If the amount of the ionic compound is too large, an excessive amount of the ionic compound, for example, an inorganic ionic salt is not dissociated, but merely mixed, resulting in a reduction in ionic conductivity.

The mixing ratio of the ionic compound is as follows:
The appropriate compounding ratio differs depending on the electrode active material. For example,
In a battery using intercalation of a layered compound, the vicinity where the ionic conductivity of the electrolyte is maximized is preferable, and in a battery using a conductive polymer utilizing a doping phenomenon as an electrode active material, the charge is sufficient. It is necessary that the ion concentration in the electrolyte can respond to the change due to the discharge.

The method of containing the ionic compound is not particularly limited. For example, a method of dissolving the compound in an organic solvent such as methyl ethyl ketone or tetrahydrofuran, uniformly mixing the compound with the organic compound, and removing the organic solvent by vacuum reduction. And the like.

Next, in the present invention, a substance capable of dissolving the ionic compound contained in the ion-conductive polymer compound may be contained in the ion-conductive polymer compound, and such a substance may be contained. Thereby, the ionic conductivity can be significantly improved without changing the basic skeleton of the polymer compound.

Examples of the substance capable of dissolving the ionic compound include cyclic carbonates such as propylene carbonate and ethylene carbonate, cyclic esters such as γ-butyrolactone, tetrahydrofuran or derivatives thereof,
Ethers such as 1,3-dioxane, 1,2-dimethoxyethane, and methyldiglyme; nitriles such as acetonitrile and benzonitrile; dioxalane or a derivative thereof; sulfolane or a derivative thereof; alone or a mixture of two or more thereof; Is mentioned. However, it is not limited to these. The mixing ratio and the mixing method are arbitrary.

The method of arranging the ion-conductive polymer compound of the present invention on the surface of the composite positive electrode and on the surface of the composite negative electrode is as described in the claims. In addition, they can be arranged in any thickness and any shape.

Further, by using the above-mentioned ion conductive polymer compound as an electrolyte layer (separator), it is possible to suppress the generation of lithium dendrites in the periphery of the composite negative electrode, and it is excellent in mechanical strength and heat resistance. It is possible to provide a stable and electrochemically stable electrolyte layer.

As the positive electrode active material used in the composite positive electrode of the present invention, the following battery electrode materials can be mentioned.

That is, CuO, Cu ₂ O, Ag ₂ O, CuS, CuSO
Group I metal compounds such as _{4, TiS 2, SiO 2,} IV group metal compounds such as _{SnO, V 2 O 5, V} 6 O 12, VO X, Nb 2 O 5, Bi 2 O 3, Sb
Group V metal compounds such as ₂ O ₃ , CrO ₃ , Cr ₂ O ₃ , MoO ₃ , W
Group VI metal compounds such as O ₃ and SeO _2, and V such as MnO ₂ and Mn ₂ O ₃
Group II metal _{compound, Fe 2 O 3, FeO,} Fe 3 O 4, Ni 2 O 3, Ni
Group VIII metal compounds such as O, CoO ₃ , CoO, or general formulas Li _X MX ₂ , Li _X MN _Y X ₂ (M and N are metals of Group I to VIII, X is a chalcogen compound such as oxygen and sulfur For example, a metal compound such as a lithium-cobalt-based composite oxide or a lithium-manganese-based composite oxide, and a conductive material such as polypyrrole, polyaniline, polyparaphenylene, polyacetylene, and polyacene-based material. Examples include, but are not limited to, polymer compounds and pseudo-graphite structured carbonaceous materials.

Further, examples of the negative electrode active material used in the composite negative electrode include the following battery electrode materials.

That is, a carbonaceous material such as carbon; [For example, the above carbonaceous material is analyzed by X-ray diffraction or the like; lattice spacing (d002) 3.35 to 3.40Å; crystallite size in the a-axis direction La 200Å More than crystallite size in c-axis direction Lc 200 mm or more True density 2.00 to 2.25 g / cm
^{3 Further} , carbon powder (an average particle diameter of 15 μm or less) or carbon fiber obtained by calcining anisotropic pitch at a temperature of 2000 ° C. or higher is desirable, but is not limited to these ranges. Or lithium metal, lithium-aluminum, lithium-lead, lithium-tin, lithium-aluminum-tin, lithium-gallium, and lithium metal-containing alloys such as wood alloys, but are not limited thereto. These negative electrode active materials can be used alone or in combination of two or more.

The method of arranging the composite positive electrode and the composite negative electrode of the present invention on the positive electrode current collector and the negative electrode current collector is as described in the claims. It is possible to increase the actual surface area of the electrochemically active material in contact with the electrolyte layer and the current collector.

The composite cathode and the composite anode of the present invention can be arranged in an arbitrary thickness and an arbitrary shape by using the method described in the claims.

In these cases, if necessary, carbon such as graphite, carbon black, acetylene black or the like (carbon having a completely different characteristic from carbon in the above-described negative electrode active material). ) And a conductive material such as a metal powder and a conductive metal oxide can be mixed in the composite positive electrode and the composite negative electrode to improve electron conduction.

In producing the above composite positive electrode and composite negative electrode, several kinds of dispersants and dispersion media can be added to obtain a uniform mixed dispersion system. Further, it is also possible to add a thickener, a bulking agent, a tackifier and the like.

The ionizing radiation described in the claims is γ
Ray, X-ray, electron beam, neutron beam and the like. The method using these ionizing radiations when cross-linking the ion-conductive polymer compound is very efficient. That is,
Not only the energy efficiency of the ionizing radiation, but also, for example, when forming various composite positive electrodes, composite negative electrodes and electrolytes, the degree of crosslinking of the ion-conductive polymer compound can be easily controlled. By controlling the irradiation dose of radiation, it becomes possible to produce electrochemically optimal electrodes and electrolytes.

Materials such as aluminum, stainless steel, titanium, and copper are preferable for the positive electrode current collector plate, and materials such as stainless steel, iron, nickel, and copper are preferable for the negative electrode current collector plate. is not.

[0042]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 A sheet-shaped battery of the present invention was manufactured according to the following procedure. a) LiCoO ₂ was used as a positive electrode active material of a battery, acetylene black was used as a conductive agent, and polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) were used.
A mixture mixed with an organic compound mixed at a weight ratio of 4 was used as a composite positive electrode.

The method for producing the composite positive electrode is as follows. That is, LiCoO ₂ and acetylene black
In a mixture of 5:15 by weight, 10 parts by weight of the organic compound, 1 part by weight of lithium tetrafluoroborate, 1,
A mixture of 10 parts by weight of 2-dimethoxyethane and 10 parts by weight of γ-butyrolactone was mixed in a dry inert gas atmosphere at a weight ratio of 10: 3. These mixtures were cast by roller coating on a current collector having a conductive carbon film formed on the surface of a positive electrode current collector plate made of aluminum. Then, in a dry inert gas atmosphere,
The composite positive electrode was cured by irradiating an electron beam with an electron dose of 12 Mrad. The thickness of the composite positive electrode film formed on the positive electrode current collector was 60 μm.

Next, 30 parts by weight of the organic compound, 6 parts by weight of lithium tetrafluoroborate, 32 parts by weight of 1,2-dimethoxyethane, and γ A mixture of 32 parts by weight of butyrolactone is cast on the composite positive electrode by roller coating in a dry inert gas atmosphere, and then irradiated with an electron beam at an electron dose of 8 Mrad in a dry inert gas atmosphere. The conductive polymer layer was cured. The thickness of the electrolyte layer thus obtained is 2
It was 5 μm.

B) Carbon powder was used as the negative electrode active material of the battery, and mixed with an organic compound in which polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) were mixed in a weight ratio of 6: 4. This was used as a composite negative electrode.

The method for producing this composite negative electrode is as follows. That is, 1 part by weight of lithium tetrafluoroborate, 10 parts by weight of 1,2-dimethoxyethane and 10 parts by weight of γ-butyrolactone
A mixture of parts by weight is placed in a dry inert gas atmosphere,
They were mixed at a weight ratio of 8: 2. These mixtures were cast on a negative electrode current collector made of stainless steel by roller coating. Thereafter, the composite negative electrode was cured by irradiating it with an electron beam having an electron dose of 15 Mrad in a dry inert gas atmosphere. The thickness of the composite negative electrode formed on the negative electrode current collector was 30 μm.

Next, 30 parts by weight of the above organic compound, 6 parts by weight of lithium tetrafluoroborate, 32 parts by weight of 1,2-dimethoxyethane, and γ -A mixture of 32 parts by weight of butyrolactone is cast by roller coating on the composite negative electrode in a dry inert gas atmosphere, and then irradiated with an electron beam at an electron dose of 8 Mrad in a dry inert gas atmosphere. The conductive polymer layer was cured. The thickness of the electrolyte layer thus obtained is 2
It was 5 μm.

C) The electrolyte layer obtained in b) / composite negative electrode /
Negative electrode current collector, positive electrode current collector obtained in a) / composite positive electrode /
By bringing the electrolyte layers into contact, a sheet-like battery of Example 1 of the present invention was produced.

FIG. 1 is a sectional view of a sheet-shaped battery of the present invention. In the figure, reference numeral 1 denotes a positive electrode current collector made of aluminum, which also serves as an exterior. 2 is a composite positive electrode, which is used as a positive electrode active material.
LiCoO ₂ , acetylene black as a conductive agent,
An organic compound obtained by mixing polyethylene glycol diacrylate and polyethylene glycol monoacrylate was used as a binder. Reference numeral 3 denotes an electrolyte layer made of the ion-conductive polymer compound of the present invention. Reference numeral 4 denotes a composite negative electrode, which used carbon powder as a negative electrode active material and the above-mentioned organic compound as a binder. Reference numeral 5 denotes a negative electrode current collector made of stainless steel, which also serves as an exterior. Reference numeral 6 denotes a sealing agent made of modified polypropylene.

(Example 2) In Example 1, the method of arranging the above composite positive electrode / composite negative electrode on the positive electrode current collector / on the negative electrode current collector, A sheet-like battery of Example 2 of the present invention was produced in the same procedure as in Example 1, except that a screen coating was used instead of the roller coating as a method of disposing an electrolyte layer made of a conductive polymer compound. .

(Comparative Example 1) A sheet-like battery of Comparative Example 1 was manufactured according to the following procedure. a) LiCoO ₂ was used as a positive electrode active material of a battery, acetylene black was used as a conductive agent, and polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) were used.
A mixture mixed with an organic compound mixed at a weight ratio of 4 was used as a composite positive electrode.

The composite positive electrode of Comparative Example 1 was produced in the same manner as in Example 1. In addition, the thickness of the composite positive electrode film formed on the positive electrode current collector was 60 μm.

B) Carbon powder was used as the negative electrode active material of the battery, and mixed with an organic compound in which polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) were mixed at a weight ratio of 6: 4. This was used as a composite negative electrode.

The composite negative electrode of Comparative Example 1 was produced in the same manner as in Example 1. The thickness of the composite negative electrode formed on the negative electrode current collector was 30 μm.

Next, in order to form an ion conductive polymer compound on the composite negative electrode, 30 parts by weight of the organic compound, 6 parts by weight of lithium tetrafluoroborate, 32 parts by weight of 1,2-dimethoxyethane and γ -A mixture of 32 parts by weight of butyrolactone is cast by roller coating on the composite negative electrode in a dry inert gas atmosphere, and then irradiated with an electron beam at an electron dose of 8 Mrad in a dry inert gas atmosphere. The conductive polymer layer was cured. The thickness of the electrolyte layer thus obtained is 5
It was 0 μm.

C) The electrolyte layer obtained in b) / composite negative electrode /
By bringing the negative electrode current collector into contact with the positive electrode current collector / composite positive electrode obtained in a), a sheet-shaped battery of Comparative Example 1 was produced.

(Comparative Example 2) In Comparative Example 1, the method of disposing the composite positive electrode / composite negative electrode on the positive electrode current collector / on the negative electrode current collector and the method of disposing the ion conductive polymer compound on the composite negative electrode surface Comparative Example 2 was carried out in the same manner as in Comparative Example 1 except that a screen coating was used instead of the roller coating as a method of disposing an electrolyte layer composed of
Was produced.

Comparative Example 3 The composite positive electrode of Comparative Example 3 was produced in the same manner as in Example 1. In addition, the thickness of the composite positive electrode film formed on the positive electrode current collector was 60 μm.

The composite negative electrode of Comparative Example 3 was produced in the same manner as in Example 1. The thickness of the composite negative electrode formed on the negative electrode current collector was 30 μm.

Next, 30 parts by weight of the above organic compound, 6 parts by weight of lithium tetrafluoroborate, 32 parts by weight of 1,2-dimethoxyethane and 32 parts by weight of γ-butyrolactone, and 0.03 part by weight of benzyl methyl ketal were added. The mixture is cast on the composite negative electrode by roller coating in a dry inert gas atmosphere, and then irradiated with 20 mW / cm ² ultraviolet ray in a dry inert gas atmosphere for 60 seconds to form the ion conductive polymer. The compound layer was cured. The thickness of the electrolyte layer thus obtained was 50 μm.

C) The electrolyte layer obtained in b) / composite negative electrode /
By bringing the negative electrode current collector into contact with the positive electrode current collector / composite positive electrode obtained in a), a sheet-shaped battery of Comparative Example 1 was produced.

The electrode area of the sheet batteries of Examples 1 and 2 and Comparative Examples 1, 2, and 3 can be variously changed depending on the manufacturing process. One having an area of 100 cm ² was produced.

Using this sheet-shaped battery, 50 μA at 25 ° C.
/ Cm ² constant current charge / discharge cycle test. In addition,
The above charge / discharge cycle test was performed with a charge end voltage of 4.1 V and a discharge end voltage of 2.7 V. FIG. 2 shows the relationship between the number of charge / discharge cycles and the battery capacity. 2. As can be seen from FIG. 2, the sheet-shaped battery according to the present invention shows superior charge-discharge cycle characteristics as compared with the sheet-shaped battery of the comparative example.

As is apparent from the above description, the present invention is an ion conductive polymer compound composed of a polymer in which at least one ionic compound is dissolved, and has a polyether structure, Composite positive electrode (A) and composite negative electrode (B) composed of a polymer compound having ion conductivity, an electrochemically active substance and optionally an electron conductive substance
And a method for producing a battery comprising an electrolyte (C) composed of an ion-conductive polymer compound composed of a polymer substance in which at least one ionic compound is dissolved. An electrolyte layer (C) composed of the above-mentioned ion-conductive polymer compound on the surface of the negative electrode (B),
By forming by irradiation of ionizing radiation, workability is remarkably improved and uniformity of quality can be achieved as compared with a conventional thermal method and a curing method by irradiation with ultraviolet rays. From this, it is possible to improve the battery characteristics and the production of high-performance electrodes, improve the workability of the battery manufacturing process and the battery performance, and have no concern about leakage to the outside, and long-term reliability In addition, it is possible to provide a highly safe battery.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a sheet-shaped battery of the present invention.

FIG. 2 is a graph showing the relationship between the number of charge / discharge cycles of a sheet-shaped battery and the battery capacity.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 positive electrode current collector 2 composite positive electrode 3 electrolyte layer 4 composite negative electrode 5 negative electrode current collector 6 sealing agent

Claims (5)

(57) [Claims] 1. An ion-conductive polymer compound composed of a polymer substance in which at least one ionic compound is dissolved, having a polyether structure and having ion conductivity. Composed of a composite positive electrode (A) and a composite negative electrode (B) composed of a molecular compound, an electrochemically active substance and optionally an electron conductive substance, and a polymer substance in which at least one ionic compound is dissolved. In the method for producing a battery comprising the electrolyte (C) made of the ion-conductive polymer compound, the electrolyte layer made of the ion-conductive polymer compound is formed on the surface of the composite positive electrode (A) and the surface of the composite anode (B) ( C) is formed by irradiation with ionizing radiation
And an electrolyte layer formed on the composite positive electrode and the composite negative electrode.
Facing and contacting the electrolyte layer formed on the pole surface
Preparation of the battery, wherein the assembly Rukoto. 2. As a method for forming the composite positive electrode (A) and the composite negative electrode (B) on the positive electrode current collector and the negative electrode current collector, at least one is disposed by a roller coating method or a screen coating method, The method for producing a battery according to claim 1, wherein the electrode and the electrolyte are formed by irradiation with ionizing radiation. 3. A method of forming an electrolyte layer (C) on the surface of the composite positive electrode (A) and the surface of the composite negative electrode (B) by disposing the electrolyte layer by a roller coating method or a screen coating method, 2. The method for producing a battery according to claim 1, wherein the electrolyte layer is formed by irradiating the electrolyte layer. 4. The high molecular compound, wherein the ion conductive polymer compound is a polyether having a reactive double bond in which at least one ionic compound is dissolved, and forms a crosslinked network structure by a polymerization reaction. 4. The method for producing a battery according to claim 1, wherein the battery is a molecular compound. 5. The method according to claim 1, wherein the ion-conductive polymer compound contains a substance capable of dissolving the ionic compound.