JPH05303980A - Ion conductive polymer compound and its manufacture - Google Patents

Abstract

PURPOSE:To provide a battery having excellent long sheet-life property, long- term reliability, and stability by producing an ion conductive polymer compound of cross-linked network structure by the polymerizing reaction of an organic compound represented by a specified formula, and containing an insulating porous compound having a high specific surface area therein. CONSTITUTION:An organic compound represented by the formula I or II (R1-R6 are hydrogen atom or a lower alkyl group having one or more carbon atoms, m>=3, n>=0, n/m=integral number of 0-5, k>=3, 1>=0, k/1=integral number of 0-5), an ionic compound (LiClO4, etc.), a solvent (propylene carbonate, etc.), an insulating porous compound (zeolite powder, etc.) having a high specific surface area are mixed together, irradiated with electron beams, and hardened to produce an ion conductive polymer compound of cross-linked network structure. The ratio of the ionic compound to the polymer compound ether bonded oxygen is about 0.0001-2.0 mole. Thus, a small-size and light-weight sheet battery having a high energy density can be provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion-conducting polymer compound, and relates to improvement of an ion-conducting polymer compound useful as a battery having high safety and reliability.

[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, at present, in many research institutions, as electrode active materials, those using intercalation of layered compounds or doping phenomenon are particularly studied, and these are electrochemical reactions in charging and discharging. In this case, theoretically, a complicated chemical reaction does not occur, so that 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 the above-mentioned problems of internal short circuit, cycle characteristics of the electrode active material, self-discharge characteristics and the like. 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, as an electrolyte for a battery or an electrochemical device other than a battery which has conventionally utilized an electrochemical reaction, that is, an electric double layer capacitor, an electrochromic element, etc., 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 liquid 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 studied are homopolymers or copolymers of ethylene oxide as a basic unit, such as linear polymers, reticulated crosslinked polymers or comb polymers. 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.

The inventor of the present invention arranges an electrolyte layer composed of the ion conductive polymer compound between a composite positive electrode and a composite negative electrode composed of the ion conductive polymer compound and an electrochemically active substance. By doing so, 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 smaller and lighter battery having a high energy density was produced. Further, when the ion conductive polymer compound is applied as an electrolyte of an electrochemical device, it is necessary to reduce the thickness of the electrolyte to reduce the internal resistance. Especially for the inventor,
In designing the thin battery (sheet-shaped battery), it can be said that the above thinning is a very 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 coating a polymerizable monomer or macromer on a substrate,
There is a method of heat polymerization or a method of curing by irradiation with actinic rays.

Conventionally, the method of mainly heat-polymerizing has been simple and widely used. However, it is difficult to improve the production rate because the heat polymerization time becomes very long,
There is a problem that a temperature gradient is likely to occur in the heating furnace and that the heating furnace and ancillary equipment become large because it is necessary to heat in an inert gas atmosphere. Further, in the curing method by heat polymerization, since the heating time is long, a bias of the polymerization initiator occurs in the ion conductive polymer compound composition liquid during polymerization, so that the crosslinked network has a more irregular structure. However, in addition to the above-mentioned problems of manufacturing speed and equipment, it has become a big problem.

Further, although it is possible to form a uniform thin film by using the above method, when an ion conductive polymer compound thin film is actually laminated between electrodes and a battery or an electrochromic element name copper is assembled, In some cases, the electrolyte layer was damaged by compressive deformation, resulting in a slight short circuit. In particular, when increasing the surface area of the ion-conductive polymer compound layer, a slight short circuit was more likely to occur. Therefore, there has been a problem in the conventional technique for uniformly thinning the electrolyte layer.

Further, one of the above ion-conductive polymer compounds
One of the problems is that polymerization inhibitors or impurities such as chloride ions, sulfide ions, and free acids contained in the polymeric compound raw materials such as polymerizable monomers or macromers remain. For example, when lithium metal is used as a negative electrode active material in a battery, the polymerization inhibitor contained in the above ion-conductive polymer compound reacts with lithium metal to generate hydrogen gas. The rise may cause the battery to expand or burst.

Further, the reaction between the polymerization inhibitor and lithium metal produces a strong alkali such as LiOH, which causes the electrolyte layer made of the ion-conductive polymer compound to be hydrolyzed and converted into a gel. As a result, the impedance of the lithium metal / ion-conductive polymer compound layer interface rapidly rises, especially when stored for a long period of time, because an inactive film is formed on the lithium metal. Similarly, an inactive film is formed on the surface of the positive electrode active material, and the impedance at the positive electrode / ion-conductive polymer compound layer interface rapidly increases, especially when stored for a long time. ing.

[0013]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and in a battery using an ion-conductive polymer compound, a long-term storage property is improved by improving the ion-conductive polymer compound. It is a battery with long-term reliability and high safety, and also has very high workability and no worry of liquid leakage to the outside. In addition, high performance, high energy It is intended to provide a compact and lightweight sheet battery having a density.

[0014]

In order to achieve the above-mentioned object, the present invention provides an ion-conducting polymer compound composed of a polymer substance in which at least one ionic compound is dissolved. The conductive polymer compound is a polymer compound which forms a crosslinked network structure by polymerizing at least the organic compound represented by the above Chemical Formula 1 or the organic compound represented by the above Chemical Formula 2, and the ion conductive polymer. The first invention is that the compound contains at least one insulating porous compound having a high specific surface area, and the insulating porous compound having a high specific surface area is at least one active alumina, zeolite and The second invention is to be selected from silica gel. A third invention is that the ion-conductive polymer compound contains a substance capable of dissolving the ionic compound, and an electrolyte layer composed of the ion-conductive polymer compound is formed. By providing it, the said objective is achieved.

Further, at least the chemical formula 1 or the chemical formula 2
A fourth invention is a method for producing an ion-conducting polymer compound, which comprises forming a crosslinked network structure by reacting an organic compound represented by the above with irradiation of ionizing radiation.

The insulating porous compound having a high specific surface area is preferably selected from at least one active alumina, zeolite and silica gel as described in the claims, but is not limited thereto. Basically, it is a necessary condition that the polymerization inhibitor and impurities such as chloride ion, sulfide ion and free acid contained in the above-mentioned ion-conductive polymer compound raw material can be adsorbed.

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, LiI, LiBr, Li ₂ B ₁₀ Cl ₁₀ , NaI, NaSCN, NaBr,
Inorganic ionic salt containing one of Li, Na, or K such as NaClO ₄ , KSCN, KClO ₄ , (CH ₃ ) ₄ NBF ₄ , (CH ₃ ) ₄ NBr, (C ₂ H ₅ ) ₄ N
ClO ₄ , (C ₂ H ₅ ) ₄ NI, (C ₃ H ₇ ) ₄ NBr, (nC ₄ H ₉ ) ₄ NBr, (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, 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.

Further, in the present invention, the above-mentioned ion-conducting polymer compound is prepared by using a composite positive electrode and a composite negative electrode composed of the above-mentioned ion-conducting polymer compound, an electrochemically active substance and optionally an electron-conducting substance. A sheet-like battery can be formed by combining the electrolyte layer (separator) including

The electrolyte layer (separator) made of the ion-conductive polymer compound is formed into a sheet by itself, and the ion-conductive polymer compound is placed between the composite positive electrode and the composite negative electrode or a composite. It is also possible to form the sheet battery by applying the above-mentioned ion conductive polymer compound composition liquid on the surface of the positive electrode or the surface of the composite negative electrode 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 coder or the like may be used to obtain an arbitrary thickness and optional thickness. It is desirable to apply in the form of, but not limited to these.

Further, by using the above-mentioned 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 thermal. ,
It is possible to provide an electrochemically stable electrolyte layer.

Further, as the positive electrode active material used for 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 ; Group IV metal compounds such as TiS ₂ , SiO ₂ and 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 , Mo
Group VI metal compounds such as S ₂ , WO 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 and Ni
Group VIII metal compounds such as ₂ O ₃ , CoO ₃ and CoO, or general formulas Li _x MX ₂ , Li _x MN _y X ₂ (M and N are metals of groups I to VIII, X is a chalcogen such as oxygen and sulfur) Indicates a compound.)
Represented by, for example, a metal compound such as a lithium-cobalt-based composite oxide or a lithium-manganese-based composite oxide, and a conductive polymer compound such as polypyrrole, polyaniline, polyparaphenylene, polyacetylene, or a polyacene-based material. , Pseudo-graphite structure carbonaceous materials, etc., but not limited to these.

Further, examples of the negative electrode active material used for 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 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, for example, roller coating such as an applicator roll, screen coating, doctor blade method, spin coating, etc. It is desirable to apply it to any thickness and any shape by means of coating, bar coder or the like, but when these means are used, the actual surface area of the electrochemically active substance in contact with the electrolyte layer and the current collector is determined. It is possible to increase. Further, the composite positive electrode and the composite negative electrode of the present invention can be arranged in any thickness and any shape by using these methods.

When producing a composite positive electrode and a composite negative electrode, graphite, carbon black,
Carbon such as acetylene black (the carbon here has characteristics completely different from the carbon in the above-mentioned negative electrode active material) and a conductive material such as a metal powder or a conductive metal oxide are combined. It can be mixed in the positive electrode and the composite negative electrode to improve electron conduction.

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.

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.

[0038]

EXAMPLES The details of the present invention will be described below with reference to examples, but the present invention is not limited thereto.
The samples obtained in this example were evaluated by the following test methods.

[0039]

[Ion Conductivity Measurement] After punching out the ion conductive polymer compound thin film obtained in this example to 13 mmφ, an AC impedance between the electrodes was measured using a conductivity measuring cell using a Pt electrode, Complex impedance analysis was performed on the ionic conductivity of this thin film. As a measuring device, So
latorn 1286 ELECTROCHEMICAL INTERFACE, 1255 HF
FREQUENCY RESPONSE ANALYZER was used.

[0040]

[Tensile Strength Measurement] A test piece obtained by cutting out the ion conductive polymer thin film obtained in this example into a shape with a width of 4.0 mm and a thickness of 100 μm was used as an autograph DCS-2 manufactured by Shimadzu Corporation.
000 was used.

Example 1 30 parts by weight of an organic compound prepared by mixing polyethylene glycol diacrylate (molecular weight 5000) and polyethylene glycol monoacrylate (molecular weight 400) 6: 4, 6 parts by weight of lithium perchlorate, and 64 parts by weight of propylene carbonate. 100 parts by weight of the mixed powder and 5 parts by weight of zeolite powder (Zeorum F-9 Tosoh Corporation) were mixed. This composition liquid was cast on a glass plate and irradiated with an electron beam of 10 Mrad to be cured.

The thickness of the obtained ion conductive polymer compound thin film was 100 μm. The result of measurement by the complex impedance method is 1.6 × 10 ^-3 Scm ^-1 at 25 ° C and 6. at 10 ° C.
It was 9 × 10 ^-3 Scm ^-1 , and 2.1 × 10 ^-3 Scm ^-1 at -20 ° C. Regarding the flexibility of this ion-conductive polymer compound, a 90 ° bending test and a 180 ° bending test were carried out, and as a result, no cracking occurred. Furthermore, a tensile test of the above ion-conductive polymer compound thin film revealed that it was 1.9 Kg / cm ² .

Comparative Example 1 An ion conductive polymer compound thin film was prepared under the same conditions and methods as in Example 1 except that the zeolite powder was not mixed.

The thickness of the obtained ion-conductive polymer compound thin film was 100 μm. Measured by the complex impedance method: 1.4 × 10 ^-3 Scm ^-1 at 25 ° C, 6. at 0 ° C.
It was 7 × 10 ⁻³ Scm ⁻¹ and 2.0 × 10 ⁻³ Scm ⁻¹ at -20 ° C. However, when measuring the ionic conductivity using a conductivity cell with Pt electrodes, the thickness is 100 μm, so the thin film of the ion-conductive polymer compound is easily damaged, and a uniform thin film can be obtained. Problems such as difficulty occurred. Regarding the flexibility of this ion-conductive polymer compound, as a result of performing a 90 ° bending test and a 180 ° bending test, 6 out of 50 measurement samples were cracked.
Furthermore, a tensile test of the above ion-conductive polymer thin film revealed a result of 0.8 g / cm ² .

(Example 2) Using the ion-conductive polymer compound of Example 1, a sheet-shaped battery was manufactured. Less than,
A sheet-like battery was produced by the procedure of a) to c). a) Manganese dioxide 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 in a weight ratio of 6: 4. A mixture of the organic compound mixed with the above 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, 10 parts by weight of the above organic compound, 1 part by weight of lithium perchlorate and 20 parts by weight of propylene carbonate were dried. Mixing was carried out in an 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. After that, in a dry inert gas atmosphere, electron dose 1
The composite positive electrode was cured by irradiating it with an electron beam of 0 Mrad. The thickness of the composite positive electrode coating film formed on the positive electrode current collector was 60 μm.

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, polyethylene glycol diacrylate (molecular weight: 5000) and polyethylene glycol monoacrylate (molecular weight: 400) were mixed with 6: 6.
100 parts by weight of a mixture of 30 parts by weight of the organic compound mixed with 4, 6 parts by weight of lithium perchlorate, and 64 parts by weight of propylene carbonate, and zeolite powder (Zeolam F-
9 A mixture of 15 parts by weight of Tosoh Corp. was cast on the above-mentioned lithium metal and was cured by irradiating it 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 manganese dioxide 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 2) A sheet-shaped battery of Comparative Example 2 was produced under the same conditions and method as in Example 2, except that the zeolite powder was not mixed.

The electrode area of the sheet-shaped batteries of Example 2 and Comparative Example 2 can be variously changed by the manufacturing process, but in this Example, the electrode area was 100 cm ² . .. 25 ℃, load 3 of these sheet batteries
The initial discharge characteristics when discharged at kΩ and the discharge characteristics after storage at 60 ° C. for 100 days were examined. FIG. 2 shows the discharge characteristics of the above discharge test. As is clear from FIG. 2, the battery of Example 2 of the present invention is
It is recognized that the initial discharge characteristics and the discharge characteristics after storage at 60 ° C for 100 days are excellent. Regarding this cause, it is conceivable that in Example 2, the adhesion of the ion conductive polymer compound to the electrode is excellent, and a slight short circuit of the electrode does not occur due to thinning.

Example 3 A sheet-shaped battery of Example 3 was manufactured 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.

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, 30 parts by weight of the organic compound, 6 parts by weight of lithium hexafluoroarsenate, 32 parts by weight of ethylene carbonate, and 2 parts by weight of the organic compound are formed in order to form the ion conductive polymer compound layer of the present invention on the lithium metal. 32 parts by weight of methyltetrahydrofuran and zeolite powder (Zeorum F
-9 A mixture of 14 parts by weight of Tosoh Co., Ltd. was cast on the above lithium metal, and the mixture was placed in an inert gas atmosphere,
It was cured by irradiating it with an electron beam having an electron dose of 8 Mrad. The thickness of the electrolyte layer thus obtained was 20 μm.

C) A sheet-like 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).

The electrode area of the sheet-shaped batteries of Example 3 and Comparative Example 3 can be variously changed by the manufacturing process. In this Example, the electrode area was 100 cm ² . .. Use these sheet batteries at 25 ℃
50μA / cm ² constant current charge / discharge cycle test and 60
After storage at 100 ° C. for 100 days, a charge / discharge cycle test was conducted at 25 ° C. and 50 μA / cm ² constant current. A charge / discharge cycle test was conducted with a charge end voltage of 3.2 V and a discharge end voltage of 2.0 V.
FIG. 3 shows the relationship between the number of charge / discharge cycles and the electric capacity.

As can be seen from FIG. 3, the sheet-shaped battery using the ion-conductive polymer of the present invention is superior to the sheet-shaped battery of the comparative example immediately after cell preparation and after storage at 60 ° C. for 100 days. It can be seen that it exhibits excellent charge / discharge cycle characteristics.

[0060]

As is apparent from the above description, in the battery using the ion conductive polymer compound of the present invention, at least one kind of insulating material having a high specific surface area is contained in the ion conductive polymer compound. By including a porous compound,
It is possible to improve the battery characteristics (in particular, cycle characteristics and discharge characteristics after long-term storage, cycle characteristics) and to manufacture high-performance electrodes, as compared with conventional batteries, and further, by irradiation with ionizing radiation, the composite electrode and the electrolyte By forming the layer, it is possible to provide a battery having a very high workability, no fear of liquid leakage to the outside, and long-term reliability and high safety. 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.

2 is a sheet-shaped battery of Example 2 and Comparative Example 2;
60 ° C, initial discharge characteristics when discharged at 3 kΩ and 60
3 is a graph showing a discharge curve showing discharge characteristics after storage at 100 ° C. for 100 days.

FIG. 3 is a graph showing the relationship between the number of charge / discharge cycles and the discharge capacity immediately after cell production of the sheet-shaped batteries of Example 3 and Comparative Example 3 and after storage at 60 ° C. for 100 days.

[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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 33/14 LHU 7921-4J H01M 6/18 E

Claims (4)

[Claims] 1. An ion-conducting polymer compound composed of a polymer substance in which at least one ionic compound is dissolved, wherein the ion-conducting polymer compound is at least ] (R ₁ , R ₂ and R ₃ are hydrogen atoms or lower alkyl groups having 1 or more carbon atoms, m and n are m ≧ 3, n ≧ 0, n / m =
Indicates an integer in the range 0-5. ) Or an organic compound represented by the following formula: (R ₄ , R ₅ and R ₆ are hydrogen atoms or lower alkyl groups having 1 or more carbon atoms, k and l are k ≧ 3, l ≧ 0 and k / l =
Indicates an integer in the range 0-5. ) Is a polymer compound having a crosslinked network structure formed by an organic compound represented by the formula (1), wherein the ion conductive polymer compound contains at least one kind of insulating porous compound having a high specific surface area. Ion conductive polymer compound. 2. The insulating porous compound having a high specific surface area is selected from at least one active alumina, zeolite and silica gel.
The ion-conductive polymer compound described. 3. The ion conductive polymer compound according to claim 1, wherein the ion conductive polymer compound contains a substance capable of dissolving the ionic compound. 4. An ion-conductive polymer compound characterized by forming a crosslinked network structure by reacting at least the organic compound represented by Chemical Formula 1 or Chemical Formula 2 by irradiation with ionizing radiation. Production method.