JPH05290883A - Battery - Google Patents

Abstract

PURPOSE:To provide a battery allowing to improve a battery characteristic and manufacture a high-performance electrode further to have high workability, the long time reliability and safety with no liquid leakage to the outside by fixed a water content in a composite positive electrode and a composite negative electrode. CONSTITUTION:A battery using an ion conductive high-molecular compound consists of composite positive and negative electrodes composed of a high-molecular compound which is an ion high-molecular compound composed of a high-molecular material, in which at least one kind of ionicity compounds is dissolved while having the polyether structure and ion conductivity, an electrochemical active material and an electronic conductive material, an electrolyte of an ion-conductive high-molecular compound composed of a high-molecular material wherein at least one kind of ionic compounds is dissolved, and the like. When water content in these comosite positive and negative electrodes is made to be 0.01% or less, a battery characteristic can be heightened and a high-performance electrode can be manufactured. Further, the battery being formed of composite electrodes and an electrolytic layer has high workability with irradiation of active rays and no liquid leakage as well as the long time reliability and stability can be obtained.

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 improvement of electrolyte, positive electrode and negative electrode.

[0002]

2. Description of the Related Art Recent microelectronics is
As typified by power supplies for memory backup of various electronic devices, by accommodating batteries inside electronic devices and integrating them with electronic elements and circuits, batteries can be made smaller, lighter, thinner, and have higher energy density. There is a strong demand for batteries that have them. In recent years, small and lightweight batteries such as lithium batteries have already been put into practical use in the field of primary batteries, but the fields of application thereof are limited. Therefore, secondary batteries using non-aqueous electrolytes, which can be made smaller and lighter, are drawing more attention as batteries that replace conventional lead batteries and nickel-cadmium batteries. Many research institutions are currently studying it because of the fact that nothing satisfying practical properties such as characteristics has been found. Therefore, as an electrode active material, a material utilizing intercalation of a layered compound or a doping phenomenon has been particularly studied, and these are theoretically complicated during an electrochemical reaction during charging and discharging. Since no chemical reaction occurs, extremely excellent charge / discharge cycle performance is expected.

An example of using a carbonaceous material as an electrode active material 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 dope capacity, low self-discharge rate, excellent cycle characteristics, and most notably, a base potential very close to that of metallic lithium.

On the other hand, as an electrolyte for a battery or an electrochemical device other than a battery using a conventional electrochemical reaction, that is, an electric double layer capacitor, an electrochromic element, etc., generally, a liquid electrolyte, particularly an organic electrolyte is ionic. Although the one in which the compound is dissolved has been used, the liquid electrolyte is likely to cause liquid leakage to the outside of the component, elution of the electrode substance, and further volatilization of the liquid electrolyte itself, so that the long-term reliability of the electrochemical device is high. However, there have been problems such as scattering of the electrolytic solution in the sealing process.

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

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

Further, when the above ion-conductive polymer compound is applied as an electrolyte of an electrochemical device, it is necessary to make the electrolyte thin so as to reduce the internal resistance. In particular, in designing a battery called a thin battery (having a thickness per unit cell of 100 to 500 μm (or a sheet-shaped battery)) which is a battery having a smaller size, a lighter weight, and a higher energy density, the present inventors have described above. It can be said that thinning is an extremely important issue. In the case of the above 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, or a method of applying a polymerizable monomer or macromer on a substrate and performing heat polymerization,
Alternatively, there is a method of curing by irradiation with actinic rays.

Further, the present inventors arranged an electrolyte layer made of the ion conductive polymer compound between a composite positive electrode and a composite negative electrode composed of the ion conductive polymer compound and the electrochemically active substance. By doing so, the above thin battery (sheet-shaped battery) was produced.

However, when the above ion-conductive polymer compound was applied to a battery, the following occurred. That is, when the charge-discharge cycle is repeated, water is extracted from the composite electrode with the repetition, passes through the separator layer composed of the ion-conductive polymer compound, and reaches the lithium metal which is the negative electrode. Lithium metal and water react with each other to generate hydrogen gas, which causes expansion and rupture of the battery due to increase in internal pressure of the battery.

A further problem is that the water extracted from the composite electrode as the charge and discharge cycles are repeated reacts with the lithium metal, which is the negative electrode, to form a strong alkali such as LiOH, and the strong alkali is generated. Due to the presence of alkali,
As a result, the separator layer made of the ion-conductive polymer compound was hydrolyzed and changed into a gel.

Therefore, not only the leakage resistance and the long-term storage property cannot be improved by applying the ion-conductive polymer compound to the battery, but also the internal resistance of the battery is increased due to the decrease of the ionic conductivity, and the battery characteristics are thereby increased. (In particular, cycle characteristics and cycle characteristics after long-term storage) are deteriorated.
Further, due to the above-mentioned phenomenon, the mechanical strength of the separator layer is remarkably reduced, which causes problems such as frequent occurrence of internal short circuit between the electrodes.

On the other hand, as a method for forming the composite positive electrode, the composite negative electrode and the electrolyte layer in the production of the sheet-like battery, a method of mainly heat-polymerizing has heretofore been simple and often used. However, the heating polymerization time becomes very long and it is difficult to improve the production rate, a temperature gradient is likely to occur in the heating furnace, and it is necessary to heat in an inert gas atmosphere. There was a problem of becoming large.

[0013]

In view of the above problems of the prior art, the present invention aims at improving battery characteristics and producing a high-performance electrode. The present invention provides a battery using an ion-conductive polymer compound. It has a very high workability, there is no fear of liquid leakage to the outside, and it provides a battery with long-term reliability and safety. In addition, it has high performance, high energy density, and is small and lightweight. A sheet-shaped battery is provided.

[0014]

In order to achieve the above-mentioned object, the present invention is an ion-conducting polymer compound composed of a polymer substance in which at least one ionic compound is dissolved, which is a polyether. At least one of a composite positive electrode (A) and a composite negative electrode (B), which are composed of a polymer compound having a structure and ion conductivity, an electrochemically active substance, and optionally an electron conductive substance In a battery composed of an electrolyte (C) composed of an ion-conductive polymer compound composed of a polymer substance in which the ionic compound is dissolved, the amount of water in the composite positive electrode (A) and the composite negative electrode (B) is 0. The first invention is to set the range to 10% or less.

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, and which forms a crosslinked network structure by a polymerization reaction. The second aspect of the present invention is to obtain a polymer compound characterized in that, and a method of forming the composite positive electrode (A), the composite negative electrode (B) and the electrolyte layer (C) is as follows. The third invention is to form the composite electrode and the electrolyte layer by irradiation with actinic rays such as radiation.

A fourth aspect of the present invention is that the composite negative electrode is composed of a carbonaceous material and the ion-conductive polymer compound, and the ion-conductive polymer compound dissolves the ionic compound. The composite positive electrode (A), the composite negative electrode (B), and the ion composed of the electrochemically active material and the ion-conductive polymer compound. The above object is achieved by providing an electrolyte layer (C) composed of a conductive polymer compound.

Since the ion conductive polymer compound in which a metal salt is dissolved in a polymer compound obtained by crosslinking a 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.

Further, 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 which is soluble in the polymer compound thus obtained, for example, LiCl
O ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , Li
SCN, LiBr, LiI, Li ₂ B ₁₀ Cl ₁₀ , NaClO ₄ , NaI, NaSCN
, NaBr, KClO ₄ , KSCN, etc. 1 of Li, Na, or K
Inorganic ion salt containing species, (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
, Quaternary ammonium salts such as (C ₂ H ₅ ) ₄ N-phtalate, and organic ionic salts such as lithium stearyl sulfonate, lithium octyl sulfonate, and lithium dodecylbenzene sulfonate. Two or more kinds of these ionic compounds may be used in combination.

The mixing ratio of such an ionic compound is
The ratio of the ionic compound to the ether-bonded oxygen of the polymer compound is 0.0001 to 5.0 mol, and preferably 0.005 to 2.0 mol. If the amount of the ionic compound used is too large, an excess ionic compound, for example, an inorganic ionic salt does not dissociate, but simply mixes, resulting in a decrease in ionic conductivity.

The mixing ratio of the ionic compound is
The appropriate compounding ratio differs depending on the electrode active material. For example,
In the battery using intercalation of the layered compound, it is preferable that the ionic conductivity of the electrolyte is around the maximum, and in the battery using the conductive polymer that utilizes the doping phenomenon as the 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. For example, a method of dissolving the ionic compound in an organic solvent such as methyl ethyl ketone or tetrahydrofuran, uniformly mixing with the organic compound, and then removing the organic solvent by vacuum decompression. And so on.

Next, in the present invention, the ion-conducting polymer compound may contain a substance capable of dissolving the ionic compound contained in the ion-conducting polymer compound. As a result, the ionic conductivity can be remarkably improved without changing the basic skeleton of the polymer compound.

As the substances capable of dissolving the above ionic compounds, cyclic carbonates such as propylene carbonate and ethylene carbonate; cyclic esters such as γ-butyrolactone; tetrahydrofuran or its derivatives,
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. Moreover, the mixing ratio and the mixing method are arbitrary.

Consisting of the above ion-conductive polymer compound,
The electrolyte layer (separator) is a sheet of the ion-conductive polymer compound, and is placed between the composite positive electrode and the composite negative electrode, or the ion-conductive polymer compound is formed on the surface of the composite positive electrode or the surface of the composite negative electrode. It is also possible to form a sheet-like battery by applying a liquid crystalline polymer compound composition and curing it.

Regarding the method for applying the ion-conductive polymer compound, for example, roller coating such as an applicator roll, screen coating, doctor blade method, spin coating, bar coater, etc. may be used to obtain an arbitrary thickness and arbitrary thickness. It is desirable to apply in the form of, but not limited to these.

Furthermore, by using the above ion-conductive polymer compound as an electrolyte layer (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 and heat. It is possible to provide a chemically and electrochemically stable electrolyte layer.

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
Group I metal compounds such as ₄ and IVs such as TiS ₂ , SiO ₂ and SnO
Group metal compound, V ₂ O ₅ , V ₆ O ₁₂ , VOx, Nb ₂ O ₅ , Bi ₂ O ₃ ,
Group V metal compounds such as Sb ₂ O ₃ , CrO ₃ , Cr ₂ O ₃ , MoO ₃ , Mo
Group VI metal compounds such as S ₂ , WO ₃ , and SeO ₂ , MnO ₂ , Mn ₂ O ₃
VII-series metal compounds such as Fe ₂ O ₃ , FeO, Fe ₃ O ₄ , Ni
Group VIII metal compounds such as ₂ O ₃ , NiO, CoO ₃ and CoO,
Alternatively, a compound represented by the general formula Li _x MX ₂ , Li _x MN _y X ₂ (M and N are metals of groups I to VIII, and X is a chalcogen compound such as oxygen or sulfur), for example, lithium- Metal compounds such as cobalt-based composite oxides or lithium-manganese-based composite oxides, and further conductive polymer compounds such as polypyrrole, polyaniline, polyparaphenylene, polyacetylene, polyacene-based materials, and pseudo-graphite carbonaceous materials. However, it is not limited thereto.

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 carbonaceous material is analyzed by X-ray diffraction or the like; lattice spacing (d002) 3.35 to 3.40 Å a-axis crystallite size La 200 Å or more c-axis crystallite size Lc 200 Å or more True density 2.00 to 2.25 g / cm
³ Also, carbon powder (average particle diameter of 15 μm or less) obtained by firing an anisotropic pitch at a temperature of 2000 ° C. or higher, or carbon fiber is preferable, but it is not limited to these ranges. ] Or lithium metal-containing 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. These negative electrode active materials can be used alone or in combination of two or more.

Regarding the method for applying the composite positive electrode and the composite negative electrode of the present invention, for example, roller coating such as an applicator roll, screen coating,
It is desirable to use a means such as a doctor blade method, spin coating, or a bar coder to apply it in an arbitrary thickness and an arbitrary shape, but it is not limited thereto. In addition, when these means are used, it is possible to increase the actual surface area of the electrochemically active substance in contact with the electrolyte layer and the current collector.

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

When producing 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.

The ionizing radiation described in the claims is γ
Rays, X-rays, electron rays, 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. That is,
Not only the energy efficiency of the ionizing radiation, for example, when forming various composite positive electrodes, composite negative electrodes and electrolytes, it is possible to easily control the degree of cross-linking of the ion conductive polymer compound, and thus the ionizing property By controlling the dose of radiation, it becomes possible to prepare electrochemically optimal electrodes and electrolytes.

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. is not.

[0037]

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

Example 1 A sheet-shaped battery of Example 1 was produced according to the following procedure. a) Vanadium pentoxide was used as the positive electrode active material of the battery, acetylene black was used as the conductive agent, and polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) were weighed 6: 4. A mixture of an organic compound mixed in a ratio was used as a composite positive electrode.

The method for producing this composite positive electrode is as follows. That is, a mixture of vanadium pentoxide and acetylene black in a weight ratio of 85:15 was added to 10 parts by weight of the above organic compound, 1 part by weight of lithium hexafluoroarsenate, 10 parts by weight of ethylene carbonate, and 10 parts of 2-methyltetrahydrofuran. The mixture of parts by weight 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 stainless steel.
Then, in a dry inert gas atmosphere, the electron dose is 10 Mra.
The composite positive electrode was cured by irradiating the electron beam of d. The thickness of the composite positive electrode coating formed on the positive electrode current collector is
It was 60 μm. The amount of water contained in the composite positive electrode of Example 1 was measured and found to be 0.04%.

B) Lithium metal was used as the negative electrode active material of the battery, and this was pressed onto a negative electrode current collector plate made of stainless steel.

Next, in order to form the ion conductive polymer compound layer of the present invention on the lithium metal, 30 parts by weight of the organic compound, 6 parts by weight of lithium hexafluoroarsenate, 32 parts by weight of ethylene carbonate, and A mixture of 32 parts by weight of 2-methyltetrahydrofuran was cast on the above lithium metal, and cured by irradiation with an electron beam having an electron dose of 8 Mrad in an inert gas atmosphere. The thickness of the electrolyte layer thus obtained was 20 μm.

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

FIG. 1 is a sectional view of the sheet-like battery of the present invention. In the figure, 1 is a positive electrode current collector plate made of stainless steel,
It also serves as the exterior. Reference numeral 2 denotes a composite positive electrode, in which vanadium pentoxide was used as a positive electrode active material, acetylene black was used as a conductive agent, and the ion conductive polymer compound of the present invention was used as a binder. Further, 3 is an electrolyte layer made of the ion conductive polymer compound of the present invention. 4 is metallic lithium,
Reference numeral 5 is a negative electrode current collector plate made of stainless steel, which also serves as an exterior. 6 is a sealing agent made of modified polypropylene.

Comparative Example 1 The composite positive electrode of Example 1 has the same manufacturing method and cell structure as the sheet-shaped battery of Example 1 except that the water content in the composite positive electrode is 0.22%. A sheet-shaped battery of Comparative Example 1 was produced.

The electrode area of the sheet-shaped batteries of Example 1 and Comparative Example 1 can be variously changed by the manufacturing process. In Example 1 and Comparative Example 1, the electrode area is 100 cm ² Was produced.

(Experiment 1) Using the sheet-shaped batteries of Example 1 and Comparative Example 1, a charge / discharge cycle test was performed immediately after the production and a charge / discharge cycle test was carried out at 60 ° C. for 100 days. 25 ° C
A 50 μA / cm ² constant current charge / discharge cycle test was carried out. The charge / discharge cycle test conditions were a charge end voltage of 3.2 V and a discharge end voltage of 2.0 V. FIG. 2 shows the relationship between the number of charge / discharge cycles and the battery capacity. Figure 2
As can be seen, the sheet battery according to the present invention exhibits excellent charge / discharge cycle characteristics as compared with the sheet battery of the comparative example.

(Experiment 2) Using the sheet-shaped batteries of Example 1 and Comparative Example 1, a 90 ° bending test was carried out after 100 days at 60 ° C. When the charge / discharge cycle test was performed after the 90 ° bending test, as shown in Table 1, Comparative Example 1
In the sheet-shaped battery of, the total short circuit cell, which is a combination of the short circuit before the charge / discharge cycle test and the minute short circuit during the test, was about 50% of the 90 ° bending test sample.

Example 2 A sheet-shaped battery of the present invention was manufactured according to the following procedure. a) LiCoO ₂ is used as the positive electrode active material of the battery, acetylene black is used as the conductive agent, and polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) are added in a ratio of 6:
The mixture with the organic compound mixed in the weight ratio of 4 was used as the composite positive electrode.

The method for producing this composite positive electrode is as follows. That is, LiCoO ₂ and acetylene black 8
In a mixture of 5:15 by weight, 10 parts by weight of the above 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 on a current collector having a conductive carbon film formed on the surface of a positive electrode current collector plate made of aluminum. Then, the composite positive electrode was cured by irradiating it with an electron beam having an electron dose of 12 Mrad in a dry inert gas atmosphere. The thickness of the composite positive electrode coating formed on the positive electrode current collector is 6
It was 0 μm. The water content contained in the composite positive electrode of Example 2 was measured and found to be 0.06%.

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 were formed in order to form an ion conductive polymer compound on the above composite positive electrode. -A mixture of 32 parts by weight of butyrolactone was cast on the above composite positive electrode in a dry inert gas atmosphere, and then irradiated with an electron beam with an electron dose of 8 Mrad in a dry inert gas atmosphere to obtain the above high ionic conductivity. The molecular compound layer was cured. The thickness of the electrolyte layer thus obtained was 25 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, carbon powder, 10 parts by weight of the organic compound, 1 part by weight of lithium tetrafluoroborate, 10 parts by weight of 1,2-dimethoxyethane and 10 parts of γ-butyrolactone.
Mixing parts by weight in a dry inert gas atmosphere,
Mixed in a weight ratio of 8: 2. These mixtures were cast on a negative electrode current collector plate made of stainless steel. Then, 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 is 30 μm.
It was m. The amount of water contained in the composite positive electrode of Example 2 was measured and found to be 0.03%.

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 were formed in order to form an ion conductive polymer compound on the above composite negative electrode. -A mixture of 32 parts by weight of butyrolactone was cast on the above composite negative electrode in a dry inert gas atmosphere, and then irradiated with an electron beam with an electron dose of 8 Mrad in a dry inert gas atmosphere to obtain a high ionic conductivity. The molecular compound layer was cured. The thickness of the electrolyte layer thus obtained was 25 μm.

C) Electrolyte layer / composite negative electrode obtained in b) /
Negative electrode current collector and positive electrode current collector / composite positive electrode / obtained in a)
The sheet-shaped battery of Example 2 of the present invention was produced by bringing the electrolyte layer into contact with each other.

Comparative Example 2 In the composite positive electrode and the composite negative electrode of Example 2, the moisture contents in the composite positive electrode and the composite negative electrode were 0.25% and 0.19%, respectively. A sheet-shaped battery of Comparative Example 1 was produced with the same manufacturing method and cell structure as the sheet-shaped battery of Example 1.

The electrode area of the sheet-shaped batteries of Example 2 and Comparative Example 2 can be variously changed by the manufacturing process. In Example 2 and Comparative Example 2, the electrode area is 100 cm ² Was produced.

(Experiment 3) Using the sheet-shaped batteries of Example 2 and Comparative Example 2, a charge / discharge cycle test was carried out at a constant current of 50 μA / cm ² at 25 ° C. and a charge / discharge cycle test was carried out after 100 days at 60 ° C. .. The above charge / discharge cycle test was carried out with a charge end voltage of 4.1 V and a discharge end voltage of 2.7 V. Figure 3
Shows the relationship between the number of charge / discharge cycles and the battery capacity. As can be seen from FIG. 3, the sheet-shaped battery according to the present invention exhibits excellent charge / discharge cycle characteristics as compared with the sheet-shaped battery of the comparative example.

(Experiment 4) In the same manner as in Experiment 2, the sheet-shaped batteries of Example 2 and Comparative Example 2 were used and the temperature was 60 ° C. and 100 ° C.
When a 90 ° bending test was performed after a day, as shown in Table 2, in the sheet-shaped battery of Comparative Example 2, the short circuit before the charge / discharge cycle test and the short circuit during the test were combined.
tal short-circuit cell has about 43% of 90 ° bending test sample
Became.

[0059]

As is apparent from the above description, in the battery using the ion conductive polymer compound of the present invention, the water content in the composite positive electrode (A) and the composite negative electrode (B) is 0.1.
Batteries in the range of 0% or less are capable of improving their battery characteristics (in particular, cycle characteristics and cycle characteristics after long-term storage) and producing high-performance electrodes, as compared with conventional batteries, and further ultraviolet and ionizing radiation. By forming the composite electrode and the electrolyte layer by irradiating with actinic rays, etc., the battery has very high workability, and there is no fear of liquid leakage to the outside, and the battery has high long-term reliability and safety. It has become possible to provide. From these facts, it is possible to improve the performance of a battery, particularly a small and lightweight sheet battery having high performance and high energy density.

[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 batteries of Example 1 and Comparative Example 1.

FIG. 3 is a graph showing the relationship between the number of charge / discharge cycles and the battery capacity of the sheet-shaped batteries of Example 2 and Comparative Example 2.

[Explanation of symbols]

 1 Positive Electrode Current Collector 2 Composite Positive Electrode 3 Electrolyte Layer 4 Metal Lithium 5 Negative Electrode Current Collector 6 Sealant

Claims (5)

[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. Consisting 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 A battery comprising an electrolyte (C) comprising the ion-conductive polymer compound described above, wherein the water content in the composite positive electrode (A) and the composite negative electrode (B) is in the range of 0.10% or less. .. 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 which has a high degree of forming a crosslinked network structure by a polymerization reaction. The battery according to claim 1, wherein the battery is a high molecular compound which is a molecular compound. 3. A battery according to claim 1, wherein the composite positive electrode (A), the composite negative electrode (B) and the electrolyte layer (C) are formed by irradiation with actinic rays. 4. The battery according to claim 1, 2 or 3, wherein the composite negative electrode is composed of a carbonaceous material and the ion conductive polymer compound. 5. The battery according to claim 1, wherein the ion-conductive polymer compound contains a substance capable of dissolving the ionic compound.