JPH05290885A - Battery - Google Patents

Abstract

(57) [Abstract] [Purpose] A battery using an ion-conductive polymer compound has extremely high workability, and there is no worry of liquid leakage to the outside, and long-term reliability and safety are high. The battery is a small and lightweight battery having high performance and high energy density in addition to the above. An ion-conductive polymer compound composed of a polymer substance in which at least one ionic compound is dissolved, the polymer compound having a polyether structure and having ion conductivity A composite positive electrode (A) and a composite negative electrode (B) composed of an electrochemically active substance and optionally an electronically conductive substance: a polymer substance in which at least one ionic compound is dissolved A secondary battery comprising an electrolyte (C) composed of an ion-conductive polymer compound, and at least (B) or () as a method for forming the composite positive electrode (A), the composite negative electrode (B) and the electrolyte (C). Electrodes are formed by irradiation of ionizing radiation with A), (B) and (C).

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Recently, as microelectronics has been used, as represented by a memory backup power source for various electronic devices, batteries are stored in electronic devices and integrated with electronic elements and circuits. There is a demand for a battery having smaller size, lighter weight, thinner shape and higher energy density. In the field of primary batteries, small and lightweight batteries such as lithium batteries have already been put into practical use, but their fields of use are limited. Therefore, as an alternative to the conventional lead battery and nickel-cadmium battery,
Secondary batteries using non-aqueous electrolytes, which can be made smaller and lighter, are drawing attention, but the reason is that no one satisfying practical physical properties such as cycle characteristics and self-discharge characteristics of electrode active materials has been found. Is still being considered by many research institutions.

When designing batteries that are smaller, lighter and have higher energy density, the present inventors have studied batteries called thin batteries (thickness per unit cell is 100 to 500 μm). However, when the above-mentioned ion-conductive polymer compound is used as a thin film as an electrolyte, it is technically somewhat difficult to produce thin-film metallic lithium having a quality sufficiently comparable to that, and the battery manufacturing process is complicated. Has become a problem. Furthermore, when used as a secondary battery, there has been a problem that the use of metallic lithium is restricted due to problems such as generation of dendrite of lithium and passivation of the interface. Therefore, research on lithium metal-containing alloys represented by lithium-aluminum, lithium-lead, and lithium-tin alloys has been actively conducted. However, as represented by lithium-aluminum alloys, these alloys have low alloy strength, and the cycle characteristics are not improved because the electrodes are cracked and miniaturized by repeated charging and discharging.

As another method for suppressing dendrite formation of lithium, attempts have been made to study the selection of an electrolyte salt and the improvement of a separator. Among them, the separator is made of polypropylene, which has been conventionally used. It has been attempted to suppress lithium dendrites by laminating non-woven fabrics and non-woven fabrics made of glass fiber.
The essential solution has not been reached.

Therefore, as the above-mentioned electrode active material, it is ideal to use intercalation of a layered compound or a doping phenomenon, and these are theoretically used during an electrochemical reaction in charging and discharging. Since it does not cause a complicated chemical reaction, extremely excellent charge / discharge cycle performance is expected.

An example of using a carbonaceous material as an electrode active material in the above concept has also appeared as a solution to problems such as cycle characteristics and self-discharge characteristics of the electrode active material. The characteristics of this carbonaceous material are high doping capacity,
It has a low self-discharge rate, excellent cycling characteristics, and most notably, it has a base potential very close to that of metallic lithium.

On the other hand, conventionally, as an electrolyte for a battery utilizing an electrochemical reaction or an electrochemical device other than a battery, that is, an electric double layer capacitor, an electrochromic element, etc., a liquid electrolyte, particularly an organic electrolyte, is ionic. Liquid electrolytes have been used, but liquid electrolytes are prone to liquid leakage to the outside of parts, elution of electrode substances, volatilization, etc., which causes problems such as long-term reliability and electrolyte solution in the sealing process. There was a problem such as the scattering of.

Therefore, in order to improve the leakage resistance and the long-term storage stability, an ion-conductive polymer compound having high ion-conductivity has been reported, and further research is being conducted as one of the means for solving the above problems. It is being advanced.

The ion-conducting polymer compounds currently being researched are homopolymers or copolymers of ethylene oxide as a basic unit, such as linear polymers, reticulated crosslinked polymers or comb polymers. For the purpose of increasing the ionic conductivity in the above, it has been proposed and practiced to prevent crystallization by using a crosslinked polymer or a comb polymer. In particular, the ion-conductive polymer compound using the above-mentioned network cross-linked polymer is useful because it has high mechanical strength and good ionic conductivity at low temperature.

When the above ion-conductive polymer compound is applied to an electrolyte of an electrochemical device, it is necessary to make the electrolyte thin so as to reduce the internal resistance. In the case of an ion conductive polymer compound, a uniform thin film can be easily processed into an arbitrary shape, but that method becomes a problem. For example, a method of casting a solution of an ion-conductive polymer compound to evaporate and remove the solvent, a method of coating a polymerizable monomer or macromer on a substrate and heating polymerization, or curing by irradiation with actinic rays. There is a way. Conventionally, the method of mainly heat-polymerizing is simple and has been widely used. However, the heating polymerization time becomes very long, it is difficult to improve the forming rate, a temperature gradient is likely to occur in the heating furnace, and heating is performed in an inert gas atmosphere, so the heating furnace and auxiliary equipment are large. There was a problem such as becoming.

Further, in addition to the above-mentioned problems, the curing method by heat polymerization has a problem that the cross-linking network has an irregular structure due to the bending of the polymerization inhibitor in the ion-conductive polymer compound composition liquid. However, in addition to the above-mentioned problems of manufacturing speed and equipment, it has become a big problem.

Further, even in the curing method by irradiation of ultraviolet rays, the curing time can be shortened by adding an ultraviolet irradiation lamp, but there is a serious problem of a larger inert gas atmosphere area and heat generated from the ultraviolet irradiation lamp. It was supposed to be. Therefore, in addition to the ultraviolet irradiation equipment, the increase in the size of the auxiliary equipment has been a problem.

[0013]

In view of the above problems of the prior art, therefore, the present invention aims to improve battery characteristics and produce high-performance electrodes. In the present invention, in a battery using an ion-conductive polymer compound, It is a small and lightweight battery that has extremely high work efficiency, has no fear of leaking liquid to the outside, has high long-term reliability and safety, and has high performance and high energy density. Is provided.

[0014]

SUMMARY OF THE INVENTION The present invention comprises at least one
An ion-conducting polymer compound composed of a polymer substance in which a certain ionic compound is dissolved, which has a polyether structure and has ion-conducting property and electrochemical activity. A composite positive electrode (A) and a composite negative electrode (B) composed of a substance and optionally an electronically conductive substance: a high ion conductivity composed of a polymer substance in which at least one ionic compound is dissolved A secondary battery composed of an electrolyte (C) composed of a molecular compound, wherein at least (B) or (A), (B) is used as a method for forming the composite positive electrode (A), the composite negative electrode (B) and the electrolyte (C). ),
The first invention is to form an electrode by irradiation with ionizing radiation together with (C). Further, the ion conductive polymer compound is a polymer compound which is a polyether having a reactive double bond in which at least one kind of ionic compound is dissolved, and is reacted by irradiation with the above-mentioned actinic rays to give a crosslinked network. In the second invention, a polymer compound having a structure is used. In the irradiation of the ionizing radiation, particularly when an electron beam is used, the electron beam is irradiated with an accelerating voltage of at least 100 kV or more. Invention.

Further, the above-mentioned ion conductive polymer compound is characterized in that it contains a substance capable of dissolving an ionic chemical substance.

By forming the composite positive electrode (A), the composite negative electrode (B) and the electrolyte (C) by the irradiation of the ionizing radiation, it becomes possible to carry out the treatment at a low temperature and in a short time. Workability is significantly improved compared to the thermal method or the method using visible or ultraviolet irradiation,
It is possible to achieve uniform quality. In this case, since the composite positive electrode (A) and the electrolyte (C) have better curability than the composite negative electrode (B), they may be formed thermally or by visible or ultraviolet irradiation.

Further, since the composite positive electrode, the composite negative electrode and the electrolyte (separator) are formed by irradiation with actinic rays such as ionizing radiation, the degree of crosslinking of the ion conductive polymer compound can be easily controlled. For,
When various composite positive electrodes, composite negative electrodes and electrolytes are formed, it is possible to produce electrochemically optimal electrodes and electrolytes by controlling the irradiation dose.

Further, by using an ion conductive polymer compound as an electrolyte (separator), it is possible to suppress the generation of dendrite of lithium in the peripheral portion of the composite negative electrode, and it is excellent in mechanical strength, thermal and electric properties. It is possible to provide a chemically stable separator.

The above-mentioned ionizing radiation means γ rays, X
Rays, electron beams, neutron rays and the like can be mentioned. The method of using these ionizing radiations in cross-linking the ion conductive polymer compound is very efficient.

Since the ion conductive polymer compound in which a metal salt is dissolved in a polymer compound obtained by crosslinking polyether is a crosslinked polymer formed by an ether bond, it has no intermolecular hydrogen bond and has a glass transition temperature of The low structure makes migration of dissolved metal salt ions extremely easy.

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

Next, as the ionic compound contained in the polymer compound thus obtained, for example, LiClO ₄ ,
LiSCN, LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , N
Inorganic ion salt containing one of Li, Na, or K such as aI, NaSCN, NaBr, 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 NClO ₄ , (nC
₄ H ₉ ) ₄ NI, (C ₂ H ₅ ) ₄ N-maleate, (C ₂ H ₅ ) ₄ N-benzoate, (C ₂ H
₅ ) Quaternary ammonium salts such as ₄ N-phtalate, and organic ionic salts such as lithium stearyl sulfonate, sodium octyl sulfonate and lithium dodecylbenzene sulfonate. Two or more kinds of these ionic compounds may be used in combination.

If the amount of the ionic compound used is too large, an excess ionic compound, for example, an inorganic ionic salt will not be dissociated, but will only be mixed, resulting in a decrease in ionic conductivity. Further, the compounding ratio of the ionic compound varies depending on the electrode active material. For example, in a battery using intercalation of a layered compound, it is preferable that the vicinity of the maximum conductivity of the electrolyte is used, and in a battery using a conductive polymer that utilizes a doping phenomenon as an electrode active material, It is necessary that the ion concentration in the electrolyte can be changed by the discharge.

The method of containing the ionic compound is not particularly limited, but for example, it is dissolved in an organic solvent such as methyl ethyl ketone or tetrahydrofuran and uniformly mixed with the organic compound, and then the organic solvent is vacuum-decompressed. A method of removing it may be mentioned.

Next, in the present invention, the ion conductive polymer compound may contain a substance capable of dissolving the ionic compound contained in the ion conductive polymer compound, and this kind of substance is contained therein. As a result, the conductivity can be remarkably improved without changing the basic skeleton of the polymer compound.

As the substance capable of dissolving the ionic compound, cyclic carbonate such as propylene carbonate and ethylene carbonate, cyclic ester such as γ-butyrolactone, tetrahydrofuran or its derivative, 1,
Examples thereof include ethers such as 3-dioxane and 1,2-dimethoxyethane, nitriles such as acetonitrile and benzonitrile, dioxolane or a derivative thereof, sulfolane or a derivative thereof, or a mixture of two or more thereof. However, it is not limited to these. Moreover, the mixing ratio and the mixing method are arbitrary.

Regarding the method for applying the ion-conductive polymer compound of the present invention, for example, a roller coating such as an applicator roll, a screen coating, a doctor blade method, a spin coating, a bar coder or the like is used to obtain a uniform thickness. However, it is not limited thereto.

Further, 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 ₄
Group I metal compounds such as TiS ₂ , SiO ₂ , SnO and the like Group IV metal compounds, V ₂ O ₅ , V ₆ O ₁₂ , VO _X , Nb ₂ O ₅ , Bi ₂ O ₃ , Sb ₂ O ₃
Group V metal compounds such as CrO ₃ , Cr ₂ O ₃ , MoO ₃ , MoS ₂ , W
Group VI metal compounds such as O ₃ and SeO ₂ , Group VII metal compounds such as MnO ₂ and Mn ₂ O ₃ , Fe ₂ O ₃ , FeO, Fe ₃ O ₄ , Ni ₂ O ₃ , and Ni
Group VIII metal compounds such as O, CoO ₃ , and CoO, or general formulas Li _X MX _U , Li _X MN _U X ₂ (M and N are metals of groups I to VIII,
X represents a chalcogen compound such as oxygen or sulfur. ) And the like, for example, a metal compound such as a lithium-cobalt-based composite oxide or a lithium-manganese-based composite oxide, a conductive polymer compound such as polypyrrole, polyaniline, polyparaphenylene, polyacetylene, a polyacene-based material, and pseudo graphite. Structural carbonaceous materials, etc., are not limited to these.

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-mentioned carbonaceous material is analyzed by X-ray diffraction; lattice spacing (dOO2) 3.35 to 3.40 A Size of crystallite in the a-axis direction La 200 A or more Size of crystallite in the c-axis direction Lc 200 A True density 2.00 to 2.25 g / cm ³ Also, carbon powder (average particle size 15 μm or less) or carbon fiber obtained by firing an anisotropic pitch at a temperature of 2000 ° C. or higher is preferable, but of course within these ranges. It is not limited. ] Or lithium alloys such as lithium metal, lithium-aluminum, lithium-lead, lithium-tin, lithium-aluminum-tin, lithium-gallium, and wood alloys, but are not limited to these. Alternatively, the one used as the positive electrode active material may be used.

Regarding the method for applying the composite positive electrode and the composite negative electrode of the present invention, for example, a roller coating such as an applicator roll, a screen coating, a doctor blade method, a spin coating, a bar coater or the like is used to obtain a uniform thickness. It is desirable to apply, but it is not limited thereto. When these means are used, it is possible to increase the actual surface area of the electrochemically active substance that contacts the electrolyte layer and the current collector.

In these cases, carbon such as graphite or carbon black acetylene black is used as needed (the carbon here has completely different characteristics from the carbon in the above-mentioned negative electrode active material).
Also, a conductive material such as a metal powder or a conductive metal oxide can be mixed in the composite positive electrode or the composite negative electrode to improve electron conduction. Further, when manufacturing the composite positive electrode and the composite negative electrode, several kinds of dispersants and dispersion media can be added in order to obtain a uniform mixed dispersion system. Further, it is also possible to add a thickener, a bulking agent, an adhesion aid and the like.

As the separator, the ion-conductive polymer compound alone is formed into a sheet and is placed between the composite positive electrode and the composite negative electrode, or the ion-conductive polymer compound liquid is applied to the surface of the composite positive electrode or the surface of the composite negative electrode. It is also possible to apply and cure to form a battery.

The positive electrode current collector plate is preferably made of a material such as aluminum, stainless steel, titanium or copper, and the negative electrode current collector plate is preferably made of a material such as stainless steel, iron, nickel or copper, but is not particularly limited thereto. Absent.

[0036]

EXAMPLES Details of the present invention will be described below with reference to examples, but the present invention is not limited thereto.

[0037]

Example 1 A sheet-shaped battery of Example 1 of the present invention was manufactured according to the following procedure.

A) LiCoO 2 as the positive electrode active material of the battery
₂ using acetylene black as a conductive agent, and polyethylene glycol diacrylate (molecular weight: 50
00) and an organic compound obtained by mixing polyethylene glycol monoacrylate (molecular weight: 400) at 6: 4 were used as a composite positive electrode. The method for producing this composite positive electrode is as follows.

That is, LiCoO ₂ and acetylene black were mixed in a weight ratio of 85:15, 10 parts by weight of the above organic compound, 1 part by weight of lithium tetrafluoroborate, 10 parts by weight of 1,2-dimethoxyethane and A mixture of 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 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, an accelerating voltage of 25
It was cured by irradiation with an electron beam of 0 kV and an electron dose of 12 Mrad. The thickness of the composite positive electrode coating film formed on the stainless current collector was 60 μm.

B) Carbon powder used as the negative electrode active material of the battery, and a mixture of polyethylene glycol diacrylate (molecular weight: 5000) and an organic compound obtained by mixing polyethylene glycol monoacrylate (molecular weight: 400) in a ratio of 6: 4. Was used as the composite negative electrode.

The method for producing this composite negative electrode is as follows. That is, a mixture of carbon powder and 10 parts by weight of the above organic compound with 1 part by weight of lithium tetrafluoroborate, 10 parts by weight of 1,2-dimethoxyethane and 10 parts by weight of γ-butyrolactone was mixed with a dry inert gas atmosphere. During,
Mixed in a weight ratio of 7: 3. These mixtures were cast on a current collector in which a conductive carbon film was formed on the surface of a negative electrode current collector plate made of stainless steel. Then, in a dry inert gas atmosphere, an acceleration voltage of 250 kV and an electron dose of 1
It was cured by irradiation with an electron beam of 0 Mrad.
The thickness of the composite negative electrode coating formed on the stainless current collector is
It was 30 μm.

Next, in order to form the ion conductive polymer compound layer of the present invention on the composite negative electrode, the organic compound 3
0 parts by weight and 6 parts by weight of lithium tetrafluoroborate, 1,2-
A mixture of 32 parts by weight of dimethoxyethane and 32 parts by weight of γ-butyrolactone was cast on the above composite negative electrode, and cured by irradiation with an electron beam having an acceleration voltage of 250 kV and an electron dose of 8 Mrad in a dry inert gas atmosphere. The thickness of the electrolyte layer thus obtained was 25 μm.

C) Electrolyte / composite negative electrode obtained in b) /
A sheet battery was produced by bringing the negative electrode current collector and the positive electrode current collector / composite negative electrode obtained in a) into contact with each other. FIG. 1 is a sectional view of the sheet-shaped battery of the present invention.
In the figure, 1 is a positive electrode current collector plate made of aluminum, 2 is a composite positive electrode, LiCoO ₂ is a positive electrode active material, acetylene black is a conductive agent, and polyethylene glycol diacrylate and polyethylene glycol monoacrylate are a binder. Mixed organic compounds were used. Also,
3 is an electrolyte layer composed of the ion conductive polymer compound of the present invention. Reference numeral 4 denotes a composite negative electrode in which carbon powder was used as the negative electrode active material and the above organic compound was used as the binder.
Reference numeral 5 is a negative electrode current collector plate made of stainless steel, which also serves as an exterior. 6 is a sealing material made of modified polypropylene.

[0044]

Comparative Example 1 The procedure of Comparative Example 1 was followed according to the following procedure.
A toroidal battery was produced.

A) LiCoC as the positive electrode active material of the battery
₂ , using acetylene black as a conductive agent, and polyethylene glycol diacrylate (molecular weight: 50
00) and an organic compound obtained by mixing polyethylene glycol monoacrylate (molecular weight: 400) at 6: 4 were used as a composite positive electrode.

The method for producing this 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 above organic compound, 1 part by weight of lithium tetrafluoroborate, 0.05 part by weight of azobisisobutyronitrile, 10 parts by weight of 1,2-dimethoxyethane. Parts and γ-butyrolactone 10
Mixing parts by weight, in a dry inert gas atmosphere,
Mixed in a weight ratio of 10: 3. These mixtures were cast on a current collector having a conductive carbon film formed on the surface of a positive electrode current collector plate made of aluminum. Then, it was cured by leaving it at 100 ° C. for 1 hour in a dry inert gas atmosphere. The thickness of the composite positive electrode coating film formed on the stainless current collector was 60 μm.

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

The method for producing this composite negative electrode is as follows.

That is, carbon powder and the above organic compound 1
A mixture of 0 parts by weight of lithium tetrafluoroborate (1 part by weight), azobisisobutyronitrile (0.05 parts by weight), 1,2-dimethoxyethane (10 parts by weight) and γ-butyrolactone (10 parts by weight) was used. In a dry inert gas atmosphere,
Mixed in a weight ratio of 7: 3. These mixtures were cast on a current collector in which a conductive carbon film was formed on the surface of a negative electrode current collector plate made of stainless steel. Then, it was cured by leaving it at 100 ° C. for 3 hours in a dry inert gas atmosphere. The thickness of the composite negative electrode coating film formed on the stainless current collector was 30 μm.

Next, in order to form the ion conductive polymer compound layer of the present invention on the composite negative electrode, the organic compound 30 is added.
A mixture of 1 part by weight, 6 parts by weight of lithium tetrafluoroborate, 0.05 parts by weight of azobisisobutyronitrile, 32 parts by weight of 1,2-dimethoxyethane and 32 parts by weight of γ-butyrolactone is used as the composite negative electrode. It was cast and cured by standing at 100 ° C. for 1 hour in a dry inert gas atmosphere. The thickness of the electrolyte layer thus obtained is
It was 25 μm.

C) Electrolyte / composite negative electrode obtained in b) /
A sheet-shaped battery was produced by bringing the negative electrode current collector and the positive electrode current collector / composite positive electrode obtained in a) into contact with each other.

[0052]

Comparative Example 2 A sheet-shaped battery of Comparative Example 2 was manufactured according to the following procedure.

A) The composite positive electrode of Comparative Example 2 was manufactured by the same method as in Comparative Example 1. The thickness of the composite positive electrode coating film formed on the stainless current collector was 60 μm.

B) The composite negative electrode of Comparative Example 2 was produced in the same manner as in Comparative Example 1. The thickness of the composite negative electrode coating film formed on the stainless current collector was 30 μm.

Next, in order to form the ion conductive polymer compound layer of the present invention on the above composite negative electrode, 30 parts by weight of the same organic compound as in Comparative Example 1 and 6 parts by weight of lithium tetrafluoroborate, 1,2- 32 parts by weight of dimethoxyethane, 32 parts by weight of γ-butyrolactone and 0.
A mixture of 03 parts by weight was cast on the above composite negative electrode, and cured by irradiating with ultraviolet rays of 20 mW / cm ² for 60 seconds in a dry inert gas atmosphere. The thickness of the electrolyte layer thus obtained was 25 μm.

C) Electrolyte / composite negative electrode obtained in b) /
A sheet-shaped battery was produced by bringing the negative electrode current collector and the positive electrode current collector / composite positive electrode obtained in a) into contact with each other. The electrode area of the sheet-shaped batteries of Example 1, Comparative Example 1 and Comparative Example 2 can be variously changed by the manufacturing process, but in this Example, the electrode area is 100 cm.
² was produced.

Using these sheet batteries, a charge / discharge cycle test was conducted at 25 ° C. and a constant current of 50 μA / cm ² . In addition, the charge end voltage 4.1V and the discharge end voltage 2.7.
A charging / discharging cycle test was performed as V. FIG. 2 shows the relationship between the number of charge / discharge cycles and the battery capacity. Second
As can be seen from the figure, the sheet-shaped battery using the ion-conductive polymer compound of the present invention exhibits excellent charge / discharge cycle characteristics as compared with the sheet-shaped battery of the comparative example.

[0058]

As is apparent from the above description, the ion-conductive polymer compound composed of the polymer substance in which at least one ionic compound is dissolved, the electrochemically active substance, and optionally the electron-conductive substance. A composite positive electrode (A) and a composite negative electrode (B) composed of a ionic substance, and an electrolyte composed of an ion conductive polymer compound composed of a polymer substance in which at least one ionic compound is dissolved ( C)
At least the composite negative electrode (B) or (A), (B),
By forming together with (C) by irradiation of ionizing radiation, it becomes possible to process at a low temperature in a short time, workability is markedly improved as compared with the conventional thermal method, and uniformity of quality is achieved. It is possible.

As a result, the workability of the battery manufacturing process and the battery performance can be improved.

[Brief description of 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 and the battery capacity of the sheet-shaped battery of Example 1 and the sheet-shaped batteries of Comparative Example 1 and Comparative Example 2.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Positive electrode collector, 2 ... Composite positive electrode, 3 ... Electrolyte, 4 ... Composite negative electrode, 5 ... Negative electrode collector, 6 ...
-Sealing material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Issei Takeda 6-6 Josaimachi, Takatsuki City, Osaka Prefecture Yuasa Battery Co., Ltd. (72) Inventor Shuichi Ido 6-6 Josaimachi, Takatsuki City, Osaka Yuasa Battery Stock company

Claims (4)

[Claims] 1. An ion-conducting polymer compound composed of a polymer substance in which at least one ionic compound is dissolved, which has a polyether structure and high ionic conductivity. A composite positive electrode (A) and a composite negative electrode (B) composed of a molecular compound, an electrochemically active substance, and optionally an electronically conductive substance: a polymer substance in which at least one ionic compound is dissolved A battery comprising an electrolyte (C) composed of an ion-conductive polymer compound constituted, and as a method for forming the composite positive electrode (A), the composite negative electrode (B) and the electrolyte (C), at least (B) or ( A battery formed by irradiation with ionizing radiation together with A), (B) and (C). 2. A polymer compound in which the ion-conductive polymer compound is a polyether having a reactive double bond in which at least one ionic compound is dissolved, and is reacted by irradiation with the ionizing radiation. 2. The battery according to claim 1, wherein the polymer compound has a crosslinked network structure. 3. In the irradiation of the ionizing radiation, particularly when an electron beam is used, the electron beam is at least 100 k.
The battery according to claim 1, wherein the battery is irradiated with an acceleration voltage of V or higher. 4. The battery according to claim 1, 2 or 3, wherein the ion conductive polymer compound contains a substance capable of dissolving the ionic compound.