JPH06168739A - Secondary battery - Google Patents

Abstract

PURPOSE:To increase a cycle life by coating a front surface of a positive electrode with a thin film of insulation or semiconductor capable of transmitting ions relating to battery reaction without electron transmission. CONSTITUTION:A secondary battery is formed of a negative electrode 101, a separator 108, a positive electrode 103, electrolyte 105, a positive electrode collector 102, and a battery case 109. A surface of the positive electrode 103 facing the negative electrode 101 is coated with one layer or more than two layers of a coating layer 104 selected among insulation, semiconductor, and insulation and semiconductor capable of transmitting ions relating to battery reaction. The positive electrode 103 is mainly composed of positive electrode active material, and the negative electrode 101 is mainly composed of negative electrode active material. If lithium or zinc dendrite is grown in charging, shortcircuitting of the negative electrode 101 and the positive electrode 103 can be restricted, and a lithium secondary battery, nickel-zinc secondary battery, or an air zinc secondary of a long charge/discharge cycle life can be manufactured. In addition, because metal lithium can be used for the negative electrode active material, energy density can be set high.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery using lithium as a negative electrode, a nickel zinc secondary battery using zinc as a negative electrode, and an air zinc secondary battery. In particular, the present invention relates to a secondary battery in which lithium or zinc dendrites generated by repeated charging and discharging are suppressed.

[0002]

2. Description of the Related Art Recently, it is expected that global warming will occur due to the greenhouse effect caused by an increase in CO ₂ , and it will become difficult to construct a new thermal power plant. It has been devised to carry out so-called load leveling, in which the load is leveled by accumulating in the secondary battery installed in. In addition, there is a demand for the development of high energy density secondary batteries for electric vehicles that do not emit air pollutants, and high-performance secondary batteries for powering portable devices such as book-type personal computers, word processors, video cameras, and mobile phones. The demand for is increasing.

As the above high performance secondary battery, a rocking chair type lithium ion battery in which lithium ion is introduced into an intercalation compound as a positive electrode active material and carbon as a negative electrode active material has been developed and partially put into practical use. It's starting. However, the lithium-ion battery has not achieved the high energy density that is an original feature of a lithium battery that uses metallic lithium as a positive electrode active material. High-capacity lithium storage batteries that use lithium metal for the positive electrode have not yet been put to practical use because they have not succeeded in suppressing the generation of lithium dendrites that are the main cause of short circuits that occur due to repeated charging and discharging. Is. When lithium dendrite grows and the negative electrode and the positive electrode are short-circuited inside the battery, charging cannot be performed.

Further, when the degree of short circuit is large, the energy possessed by the battery is consumed in a short time, so that heat is generated,
There is a possibility that an accident such as an explosion or ignition may occur in the end when the solvent of the electrolytic solution is decomposed to generate gas and the internal pressure is increased. Therefore, there is a demand for the development of a long-life lithium storage battery in which an internal short circuit is unlikely to occur even when the charging and discharging are repeated. Further, also in the nickel-zinc battery and the zinc-air battery, since the dendrite of zinc is generated by the repeated charging and discharging, the zinc negative electrode and the positive electrode are short-circuited because they penetrate the separator.
The cycle life was very short.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a lithium secondary battery, a nickel-zinc secondary battery and an air-zinc secondary battery having a long cycle life by solving the above-mentioned conventional drawbacks. .

[0006]

Means for Solving the Problems The present inventor has conducted extensive studies in order to solve the above-mentioned drawbacks, and as a result, an insulator capable of transmitting ions involved in a battery reaction without electron conduction to the surface of the positive electrode. It was also found that by coating with a semiconductor thin film, the negative electrode and the positive electrode are not short-circuited inside the battery even if dendrite occurs in the negative electrode.

According to the present invention, in a secondary battery including at least a negative electrode, a separator, a positive electrode, an electrolyte, a current collector, and a battery case, at least the surface of the positive electrode facing the negative electrode permeates ions involved in the battery reaction. Insulator that can
A secondary battery characterized by being coated with one or more layers of a thin film selected from semiconductors, insulators and semiconductors.

(Structure of Battery) The basic structure of the secondary battery of the present invention is at least a negative electrode, a separator, a positive electrode, an electrolyte,
It consists of a current collector. FIG. 1 shows a basic configuration diagram of the secondary battery of the present invention. In FIG. 1, 100 is a negative electrode current collector, 10
1 is a negative electrode, 102 is a positive electrode current collector, 103 is a positive electrode, 104
Is an ion-permeable coating film, 105 is an electrolyte, 106 is a negative electrode terminal, 107 is a positive electrode terminal, 108 is a separator, 1
09 is a battery case. The positive electrode 103 is mainly composed of a positive electrode active material, and the negative electrode 101 is mainly composed of a negative electrode active material.

In the case of a lithium battery in which the negative electrode active material of the negative electrode 101 is lithium or a lithium alloy, the lithium ions in the electrolyte 105 are covered with the coating film 104 by the discharge reaction.
Permeate into the interlayer of the positive electrode active material of the positive electrode 103, and at the same time, lithium ions are dissolved from the negative electrode active material into the electrolyte 105. On the other hand, in the charging reaction, lithium ions in the electrolyte 105 are deposited as lithium metal on the negative electrode active material (at this time, dendrite growth is likely to occur), and at the same time, lithium between the layers of the positive electrode active material 103 is dissolved in the electrolyte 105.

In the case of an alkaline battery in which the negative electrode active material is zinc or a zinc alloy, the hydroxide ion in the electrolyte 105 reacts with the negative electrode active material of the negative electrode 101 in the discharge reaction, and at the same time, the positive electrode active material of the positive electrode 103. 103 to the coating film 10
Hydroxide ions come out into the electrolyte 105 after passing through 4.
On the other hand, in the charging reaction, hydroxide ions in the electrolyte 105 come out from the negative electrode into the electrolyte (at this time, zinc ions in the electrolyte easily grow dendrite at the negative electrode), and at the same time, the positive electrode 1
From 03, hydroxide ions are released into the electrolyte 105.

When the negative electrode active material is lithium or a lithium alloy, the ions involved in the battery reaction are lithium ions, and when the negative electrode active material is an alkaline battery of zinc, they are hydroxide ions. When the negative electrode active material is zinc, a typical battery is a nickel zinc battery or a zinc air battery. In the above-described repeated charge / discharge reactions, the surface of the positive electrode 103 of the battery is covered with an insulator or semiconductor film 104 that can permeate ions involved in the battery reaction without electron conduction, so that the negative electrode 101 can be repeatedly charged and discharged. Even if a lithium or zinc dendrite grows through the separator 108, the dendrite hardly contacts the conductor or the current collector in the positive electrode 103. As a result, it is possible to suppress a short circuit inside the battery, extend the life of the secondary battery, and improve safety.

(Coating of Positive Electrode for Secondary Battery) As an insulator of the coating material of the positive electrode of the secondary battery, a macrocyclic compound derivative polymer, an aromatic hydrocarbon derivative polymer, a fluororesin,
Silicone resin, titanium resin, polyolefin, or inorganic oxide, nitride, carbide, halide, etc. can be used. The polymer of the macrocyclic compound derivative, the polymer of the aromatic hydrocarbon derivative, the coating of the positive electrode with the fluororesin,
It is particularly effective for lithium secondary batteries.

Polymer of Macrocyclic Compound Derivative In the above macrocyclic compound, the heteroatoms are oxygen, nitrogen, sulfur,
A cyclic polyamine, which is a cyclic compound consisting of at least one or more kinds of atoms selected from phosphorus, and which is a cyclic polyether having pores with a radius equal to or larger than the radius of the lithium ion in order to improve the permeation of the lithium ion. Cyclic polythioether, azacrown ether, cyclic thioether, thiocrown ether, cryptand, cyclam, nonactin, variomycin, one selected from silacrown, which is a crown ether having a silicon atom, cyclodextrin, cyclophane, phthalocyanine, and porphyrin compound. A compound having a structure of at least one kind is used.

The surface coating of the macrocyclic compound on the surface of the positive electrode comprises a. Coating with a coating method such as dipping, spraying, screen printing, or coater of a solution of a polymer obtained by polymerizing the derivative of the macrocyclic compound, b. After coating a mixture of the macrocyclic compound derivative with a polymer serving as a binder, the polymer is crosslinked to form a film. C. Dissolving the above macrocyclic compound derivative as a monomer in an electrolytic solution and applying an electric field to form a film on the surface of the positive electrode by electrolytic polymerization. D. Forming a polymerized film by immersing the molded positive electrode in a solution of a macrocyclic compound derivative that undergoes anionic polymerization, e. Coating a polymer obtained by heat-condensing a macrocyclic compound having an aromatic ring and formaldehyde in formic acid, f. A method such as sputtering a macrocyclic compound or a polymer of a macrocyclic compound derivative or forming a film by plasma polymerization of the macrocyclic compound can be used.

An electrolyte may be mixed at the time of forming the film. This improves the wettability of the electrolyte and the film,
Ions easily pass through the film. The polymer used in the coating solution is poly [(dibenzo-18-crown-
6) -co-formaldehyde] and the like can be used. The following polymerization reactions are utilized to make the polymer for new coatings. In the condensation polymerization of a macrocyclic compound having a carboxyl group, an amino group or a hydroxyl group at the terminal group, a polyamide is obtained in the case of the reaction between the carboxyl group and the amino group, and a polyester is obtained in the case of the reaction between the carboxyl group and the hydroxyl group. Further, the vinyl compound as the macrocyclic compound or the diene as the macrocyclic compound can be obtained as an addition-polymerized polymer by radical polymerization, cationic polymerization or anionic polymerization. Azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), t-butyl hydroperoxide, or the like is used as a radical polymerization initiator. As an initiator of the cationic polymerization, acids such as H ₂ SO ₄ , H ₃ PO ₄ , HClO ₄ , CCl ₃ CO ₂ H, Friedel-Crafts catalysts such as BF ₃ , AlCl ₃ , TiCl ₄ , SnCl ₄ and the like are used. . Further, the macrocyclic compound having an aromatic ring is the above-mentioned Fri.
Polymerization can be performed by a dehydrogenation reaction with a combination of an edel-Crafts catalyst and an oxidant. As the anionic polymerization initiator, an alkali metal compound or an organic metal compound is used.

The monomer of the macrocyclic compound used for the polymerization is crown ether / (+)-18-crown-6.
-Tetracarboxylic acid, 1,5,9,13,17,21-
Hexathiacyclotetracosane-3,11,19-triol, 1,5,9,13-tetrathiacyclohexadecane-3,11-diol, 1-aza-12-crown-4, 1-aza-15-crown -5, 1-aza-18
-Crown-6,1,4,10,13-tetraoxa-
7,16-diazacyclooctadecane, 1,4,10-
Trioxa 7,13-diazacyclopentadecane,
6,8-Dioxabicyclo [3.2.1] octane-7
In addition, dibenzocrown ethers can be used.

In the above-mentioned polymerization, other than the polymerization of macrocyclic compound derivatives, it is possible to copolymerize two or more macrocyclic compound derivatives or a macrocyclic compound derivative and another monomer. Further, polymers obtained by introducing a macrocyclic compound derivative into various polymers by a substitution reaction can also be used.
When manufacturing a battery, it is necessary to select a polymer that does not dissolve in the solvent of the electrolytic solution, or to promote a crosslinking reaction of the polymer so that the polymer does not dissolve in the electrolytic solution.

Further, a macrocyclic compound derivative having a carboxyl group, an amino group or a hydroxyl group at the terminal group or having a vinyl bond or a diene bond in a polymer as a binder is mixed and cured. At this time, a promoter may also be mixed. As the cross-linking agent, diisocyanate, polyisocyanate prepolymer, block isocyanate, organic peroxide, polyamine, oximes, nitroso compound, sulfur and sulfur compounds, selenium, magnesium oxide, lead oxide, zinc oxide, etc. are used. To be done. Examples of organic peroxides include di-cumyl-peroxide, 2,
5-dimethyl-2,5 di- (t-butyl-peroxy)
Hexane, 1,3-bis- (t-butyl-peroxy-isopropyl) benzene, 1,1-bis- (t-butyl-peroxy) -3,3,5-trimethyl-cyclohexane, n-butyl-4,4. -Bis- (t-butylperoxy) valerate, 2,2-bis- (t-butyl-peroxy) butane, t-butyl-peroxy-benzene,
Vinyl-tris- (t-butyl-peroxy) silane and the like are used. As the accelerator, guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, xanthate-based and the like are used.

As another coating method using a binder polymer, there is also a method in which a binder polymer mixed with a macrocyclic compound is applied and cross-linked by irradiation with radiation, electron beams or ultraviolet rays. As a method of coating the positive electrode by electrolytic polymerization, a monomer such as dibenzocrown ether is mixed with an electrolytic solution, and then electrolytic polymerization is performed using the positive electrode as an anode. As the solvent of the electrolyte,
Acetonitrile: CH ₃ CN, benzonitrile: C ₆ H ₅
CN, propylene carbonate: PC, dimethylformamide: DMF, tetrahydrofuran: THF, nitrobenzene: C ₆ H ₅ NO ₂ , dichloroethane, diethoxyethane, chlorobenzene, γ-butyrolactone, dioxolane, etc., and mixtures thereof can be used. .

The solvent is dehydrated with activated alumina, molecular sieves, phosphorus pentoxide, calcium chloride or the like, or depending on the solvent, it is distilled in an inert gas in the presence of an alkali metal to remove impurities and dehydrate. Is good. The supporting electrolyte is an acid such as H ₂ SO ₄ , HCl or HNO ₃ , a monovalent metal ion (Li ⁺ , K ⁺ , Na ⁺ , Rb ⁺ , Ag ⁺ ) or a tetraammonium ion (tetrabutylammonium ion: TBA ⁺ , Tetraethylammonium ion: TEA ⁺ ) and Lewis acid ion (BF ₄ ⁻ , PF ₆ ⁻ , A)
A salt consisting of sF ₆ ⁻ , ClO ₄ ⁻ ) and a mixed salt thereof are used. It is desirable that the above-mentioned salt is recrystallized and purified, and that it is sufficiently dehydrated and deoxidized by heating under reduced pressure.

Examples of the monomer include crown ether / benzo-15-crown-5, crown ether / benzo-18-crown-6, crown ether / N-phenylaza-15-crown-5, crown ether / dibenzo-18-crown. -6, crown ether / dibenzopyridino-18-crown-6, crown ether / dibenzo-24-crown-8,1,13-bis (8
-Quinolyl) -1,4,7,10,13-pentaoxatridecane, 5,6-benzo-4,7,13,16,2
1,24-Hexaoxa-1,10-diazabicyclo [8.8.8] -hexacosane, 5,6-14,15-
Dibenzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] -hexacosane, bis [(benzo-15-crown-5)-
15-ylmethyl] pimelate, crown ether / dibenzo-30-crown-10, N, N′-dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, dilithium phthalocyanine,
4'-nitrobenzo-15-crown-5,3,6
9,14-Tetrathiabicyclo [9.2.1] tetradeca-11,13-diene and the like, and mixtures thereof can be used.

The polymer coating film for coating the surface of the positive electrode, when dissolved in the organic solvent of the electrolytic solution, causes a decrease in battery performance, and therefore is preferably crosslinked. The thickness of the film formed on the lithium surface is preferably in the range of 10 Å to 100 μm, more preferably in the range of 50 Å to 10 μm. The optimum film thickness of the coating depends on the density or porosity of the coating, and also on the type of electrolyte used. The film thickness of the film can be adjusted by changing the concentration of the film forming main material in the coating liquid.

Polymer of Aromatic Hydrocarbon Conductor As the aromatic hydrocarbon derivative which forms a charge transfer complex with lithium, at least naphthalene, anthracene, phenanthrene, naphthacene, pyrene, triphenylene, berylene, picene, benzopyrene, coronene and ovalen are selected. It is characterized by being one or more kinds of selected derivatives.

The method of forming the polymer used in the coating material is
It is obtained by polymerizing or copolymerizing monomers such as vinyl monomer, acetylene derivative monomer, dicarboxylic acid and diamine, dicarboxylic acid and glycol. The vinyl monomer can be polymerized by radical or ionic polymerization. The acetylene derivative monomer can be polymerized using molybdenum or a chloride of tungsten as a catalyst. Polycondensation of dicarboxylic acid and diamine, or dicarboxylic acid and glycol is possible.

Examples of the aromatic derivative monomer forming the above polymer include 2-vinylnaphthalene, 2-vinylpyridine, 9-vinylanthracene, 9,10-anthracene dipropionic acid, and 9,10-bis (phenylethynyl). ) Anthracene, 5,12-bis (phenylethynyl) naphthalene and the like can be used. As a radical polymerization initiator, azobisisobutyronitrile (AIB
N), benzoyl peroxide (BPO), t-butyl hydroperoxide and the like are used. As an initiator of the cationic polymerization, H ₂ SO ₄ , H ₂ PO ₄ , HClO ₄ , CC
acid such as l ₃ CO ₂ H, BF ₃ , AlCl ₃ , TiCl ₄ ,
A Friedel-Crafts catalyst such as SnCl ₄ is used. Further, the macrocyclic compound having an aromatic ring can be polymerized by a dehydrogenation reaction with a combination of the above Friedel-Crafts catalyst and an oxidizing agent. As the anionic polymerization initiator, an alkali metal compound or an organic metal compound is used.

In addition to the above method, a polymer having an aromatic group introduced therein can be obtained by causing a substitution reaction of the side chain of various polymers with an aromatic compound derivative. It is also possible to cause an electrolytic polymerization reaction in an electrolytic solution containing a monomer to directly coat the surface of the positive electrode with the aromatic compound polymer. Using a solution of the polymer,
When coating the surface of the positive electrode, it is desirable to use a polymer solution that has been sufficiently dehydrated and deoxidized in an inert gas that has been sufficiently dehydrated. The solvent used in the above solution is activated alumina, molecular sieve, phosphorus pentoxide,
It is preferable to dehydrate with calcium chloride or the like, or, depending on the solvent, to remove impurities and dehydrate by distilling in an inert gas in the presence of an alkali metal.

An electrolyte may be mixed at the time of forming the film. This improves the wettability of the electrolyte and the film,
Ions easily pass through the film. When the polymer coating film is dissolved in the organic solvent of the electrolytic solution, it causes a decrease in battery performance, and thus it is preferable that the polymer coating film be crosslinked. Examples of the cross-linking method include irradiation with ultraviolet rays, electron beams, and radiation, and the use of a cross-linking agent such as a radical generator.

Fluororesin As the fluororesin for coating the positive electrode surface, tetrafluoroethylene-ethylene copolymer, trifluoroethylene chloride resin, tetrafluoroethylene-perfluoroalkylvinylether copolymer, tetrafluoroethylene Fluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride resin, vinyl fluoride resin, tetrafluoroethylene resin, etc. are common,
Since most of them are not dissolved in a solvent, it is preferable to use a method such as sputtering or plasma polymerization to coat the surface of the positive electrode with the above fluororesin.

Among the fluororesins, those having an ether bond are more preferable because they are easily dissolved in a solvent to facilitate surface coating and the affinity with lithium ions is increased. Specific examples of the fluorocarbon resin having an ether bond include copolymers of fluorinated ethylene and a vinyl monomer having an ether bond such as vinyl ether, dioxol, dioxine, dioxene, or a diene monomer derivative, or a diene such as ethylene. A copolymer of a compound with a vinyl monomer having a fluorinated ether bond, a vinyl monomer such as dioxole, dioxine, or dioxene or a diene monomer derivative is used. As ethylene fluoride, tetrafluoroethylene, trifluoroethylene chloride, vinylidene fluoride, vinyl fluoride,
Fluorinated ethylene derivatives such as As a method for polymerizing the fluorinated ethylene copolymer containing an ether bond, solution, suspension, bulk or emulsion polymerization is possible, and as the initiator, peroxide, alkylboron, light or radiation is used.

The coating of the fluorine resin having an ether bond on the lithium metal is performed by applying a solution of the fluorine resin by spraying, screen printing, coater, dipping, or the like. B. Directly coating the surface of lithium with a fluororesin by a vacuum deposition method such as sputtering, c. A method of directly forming a polymerized film by plasma polymerization in an atmosphere of a monomer that is a raw material of the fluororesin can be used.

When the lithium surface is coated with a fluororesin solution, it is desirable to use a fluororesin solution that has been sufficiently dehydrated and deoxidized in an inert gas that has been sufficiently dehydrated. The solvent used for the fluororesin solution is dehydrated with activated alumina, molecular sieves, phosphorus pentoxide, calcium chloride or the like, or depending on the solvent, distilled in the presence of an alkali metal in an inert gas to remove impurities and dehydrate. Good to do.

An electrolyte may be mixed at the time of forming the film. This improves the wettability of the electrolyte and the film,
Ions easily pass through the film. It is preferable that the coating film of the fluororesin is cross-linked because it dissolves in the organic solvent of the electrolytic solution and causes deterioration of battery performance. In addition to the surface coating method using the above-mentioned fluororesin solution having an ether bond, a method in which fluorinated ethylene and a vinyl monomer are plasma-polymerized as main raw materials for coating can also be used. Easily causes plasma polymerization, or
In order to enhance the adhesion and strength of the film, it is desirable to mix oxygen, hydrogen, helium, argon, nitrogen, hydrocarbons, silane, etc. with the fluorine compound as the main raw material. As a method for generating plasma, glow discharge by direct current or high frequency, microwave discharge, laser, etc. are effective.
It is also possible to cover the positive electrode surface by spattering a fluororesin having an ether bond.

The thickness of the film formed on the lithium surface is 1
The range of 0 angstroms to 100 microns is preferred, and the range of 50 angstroms to 10 microns is more preferred. The optimum film thickness of the coating differs depending on the density or porosity of the coating and the type of electrolyte used. The film thickness of the film can be adjusted by changing the concentration of the film forming main material in the coating liquid, and in the case of plasma polymerization and sputtering, controlling the deposition time.

As the silicone resin organic silicon compound, alkoxysilane, alkylsilane, halogenated silane, siloxane, vinyl group, amino group, epoxy group, methacryl group, mercapto group-introduced silane, hydrogen modification, vinyl modification, Hydroxyl-modified, amino-modified, carboxyl-modified, chlorine-modified, epoxy-modified, methacryloxy-modified, mercapto-modified, fluorine-modified, long-chain alkyl-modified, phenyl-modified, etc. Silicone resins formed from polysiloxanes, alkylene oxide-modified siloxane copolymers ( Copolymer), silicone modified copolymer, alkoxysilane modified polymer,
Materials such as silicone-modified urethane and silicone-modified nylon can be used.

As a method for forming a film, when the above organic compound is a liquid, it can be applied directly or after being diluted with a solvent. When the organic compound is solid, a solution dissolved in a solvent can be applied. As a coating method, a method such as dipping, screen printing, spraying or roll coating can be adopted. The viscosity of the coating liquid needs to be appropriately adjusted according to the coating method.

[0036] Chitanporima - Titanium polymers acting organic titanium compound in an organic polymer can be used. Examples thereof include a tyranopolymer, which is a silicone polymer in which a main chain of a polycarbosilane skeleton is crosslinked with a titanium organic compound. In addition to the titanium polymer, various polymers obtained by introducing another organometallic compound derivative such as an organoaluminum compound by a substitution reaction can also be used as the coating material.

[0037] Phosphorus polyphosphazene phosphorus atoms and nitrogen atoms are alternately - polymer bound-nitrogen double bond - can be polyphosphazene heats the dichlorophosphazene trimer to 200 to 300 [° C., obtained by ring-opening polymerization To be Dichlorophosphazene trimer is synthesized from phosphorus pentachloride and ammonium chloride or ammonia. Examples of the catalyst used during the polymerization include benzoic acid, sodium benzoate, 2,6-di-p-cresol, water, methanol, ethanol, nitromethane, ether, heteropoly acid, sulfur, zinc, tin and sodium.

Various polyorganophosphazenes can be obtained by substituting the chlorine atom of polydichlorophosphazene with an organic reagent or an organometallic reagent. When the positive electrode surface is coated with the polyphosphazene solution, it is desirable to use a polymer solution that has been dehydrated and deoxidized sufficiently in an inert gas that has been dehydrated sufficiently. The solvent used in the above solution may be dehydrated with activated alumina, molecular sieves, phosphorus pentoxide, calcium chloride or the like, or depending on the solvent, distilled in the presence of an alkali metal in an inert gas to remove impurities and dehydrate. Is good.

The electrolyte may be mixed at the time of forming the film. This improves the wettability between the electrolytic solution and the coating, making it easier for ions to pass through the coating. The coating film of the polymer is
Dissolution in the organic solvent of the electrolytic solution causes deterioration of battery performance, and thus it is preferably crosslinked. Examples of the cross-linking method include irradiation with ultraviolet rays, electron beams, and radiation, and the use of a cross-linking agent such as a radical generator.

The thickness of the film formed on the lithium surface is 1
The range of 0 angstroms to 100 microns is preferred, and the range of 50 angstroms to 10 microns is more preferred. The optimum film thickness of the coating varies depending on the density or porosity of the coating and the type of electrolyte used. The film thickness of the film can be adjusted by changing the concentration of the film forming main material in the coating liquid.

Polyethylene, polypropylene and the like are used as the polyolefin polyolefin. Polyolefins are cross-linked by a method such as reaction of a cross-linking agent, UV irradiation, electron beam irradiation, and radiation irradiation after dipping the positive electrode into a solution dissolved in a solvent such as tetrahydrofuran or o-dichlorobenzene and drying. Then, a film is formed on the surface of the positive electrode.

The film can also be formed by sputtering or plasma CVD. Plasma CV
As the raw material of D, ethylene gas or propylene gas can be used. Inorganic oxide As an example of the material of the inorganic glass, silica, titanium oxide, alumina, zirconia oxide, magnesium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, tin oxide, indium oxide, iron oxide, chromium oxide, aluminum phosphate, Mention may be made of metal oxides such as iron phosphate, silicon phosphate, and mixtures thereof. The sol-gel method is one of the suitable methods for forming the above-mentioned inorganic glass. The raw material of the film having an inorganic glass structure is a solution of a metal organic compound such as a metal alkoxide such as alcohol in which an acid or a base and water are added and hydrolyzed to form a colloid of fine particles having a metal atom-oxygen atom bond. After that, the surface coating of the positive electrode is performed by directly applying this colloidal solution or by applying a solution of a monomer, an organic polymer, or an organic polymer and a crosslinking agent dissolved in the colloidal solution, and then polymerizing or drying and curing the same. Form.
By compounding the organic polymer, the strength against cracking and peeling can be improved. Furthermore, when the electrolyte forming the lithium battery is dissolved in the colloidal solution to form a film, the wettability with the electrolytic solution is improved and the migration of ions becomes easier.

As metal organic compounds other than alkoxides, acetylacetone complex salts, alkyl metal compounds, acetylacetone metal salts, naphthenic acid metal salts, octylic acid metal salts and the like can be used. Examples of organic polymers for forming a composite include epoxy resin, polyester, polyimide, polyethylene, polypropylene, polyurethane,
Examples thereof include polystyrene, polyethylene glycol, nylon, fluororesin, and silicone resin.

As the cross-linking agent for the above-mentioned polymer, diisocyanate, polyisocyanate prepolymer, block isocyanate, organic peroxide, polyamine, oxime, nitroso compound, sulfur and sulfur compound, selenium, magnesium oxide, lead oxide. , Zinc oxide, etc. are used.
Besides the method of using a crosslinking agent, there is a method of polymerizing or crosslinking the polymer by irradiating radiation, electron beam or ultraviolet ray.

As a coating method, a method such as dipping, screen printing, spraying or roll coating can be adopted. The viscosity of the coating liquid needs to be appropriately adjusted according to the coating method. Other methods for forming a glassy inorganic oxide film include sputtering, electron beam evaporation, and plasma CVD (Chemical Vap).
or Deposition), various vapor deposition methods such as laser CVD, and CVD methods are effective.

As the sputtering and electron beam evaporation methods, there are a method of directly depositing an oxide material and a method of reacting silicon or metal vapor with oxygen gas to form a film. As the plasma CVD and laser CVD methods, oxygen gas and hydrides of silicon or metal, halides, and organometallic compounds are used as raw materials and decomposed by discharge or laser to form a film.

As another method for forming a film of an inorganic oxide,
There is an electrochemical method, in which a metal film of aluminum, titanium, tantalum, niobium, etc. is formed by sputtering or electron beam evaporation, and then oxalic acid, phosphoric acid or ammonium borate is anodized and oxidized. There is a method of forming a film. In addition, a film formation method that deposits and grows an oxide film on the surface of the immersed substrate by utilizing the equilibrium reaction in an aqueous solution can be used to form a film of silica (silicon oxide), titanium oxide, vanadium oxide, etc. it can. As a specific method of forming the silica film, the positive electrode is dipped in a solution in which silica is saturated in an aqueous solution of hydrosilicofluoric acid to form the film.

[0048] As the material of the nitride nitride, silicon nitride, titanium nitride, aluminum nitride, and boron nitride can be used. As a method for forming a nitride film on the positive electrode, methods such as sputtering, electron beam evaporation, plasma CVD, laser CVD are effective. As the sputtering and electron beam evaporation methods, there are a method of directly evaporating the above-mentioned nitride material and a method of reacting vapor of silicon, titanium, aluminum with nitrogen plasma generated from nitrogen gas or ammonia gas to form a film. is there.

As the plasma CVD and laser CVD methods, as raw materials, nitrogen raw materials such as nitrogen gas, ammonia gas and nitrogen trifluoride, and hydrides such as silicon, titanium and aluminum, halides and organometallic compounds are used. Decomposes by discharge or laser to form a film. As the material of the carbide, amorphous carbon, silicon carbide, titanium carbide, vanadium carbide, tungsten carbide or the like can be used.

As the method for forming the carbide film, the same method as the method for forming the nitride can be used. As the sputtering method and the electron beam evaporation method, there are a method of directly evaporating the above-mentioned carbide material and a method of forming a film using carbon such as silicon, titanium, vanadium, and tungsten as a raw material. As plasma CVD and laser CVD methods, carbon materials such as hydrocarbons and hydrides such as silicon, titanium, vanadium, and tungsten, halides, and organometallic compounds are decomposed by discharge or laser to form a film. To do.

[0051] Lithium fluoride as a material of the halide halides, magnesium fluoride, sodium fluoride, calcium fluoride, barium fluoride, materials such as lithium chloride can be used.
The halide film can be formed by sputtering and electron beam evaporation. A CVD technique such as plasma CVD or laser CVD can also be used.

[Semiconductor] As the material of the semiconductor for coating the positive electrode, there are metal oxides such as nickel oxide, copper oxide, vanadium oxide, tin oxide and zinc oxide in addition to diamond (carbon) and silicon. An element such as an alkali metal or phosphorus or boron may be added as an impurity to the semiconductor.

As the method for forming the semiconductor film, in addition to the above-mentioned method for forming the inorganic oxide film, sputtering, electron beam evaporation, and CVD methods such as plasma CVD and laser CVD can be used. (Coating of Positive Electrode of Nickel-Zinc Secondary Battery or Air-Zinc Secondary Battery) The coating material and coating method of the positive electrode of the nickel-zinc secondary battery or air-zinc secondary battery are the same as the above-mentioned coating of the positive electrode of the lithium secondary battery. Any material and method can be used. Further, as the coating material, a polymer which is soluble in an organic solvent but insoluble in water can be used. When the coating material has water repellency, it is necessary to introduce a hydrophilic group or perform hydrophilic treatment with a silane coupling agent or the like.

(Thickness of coating film on positive electrode surface) The thickness of the coating film on the positive electrode surface is adjusted by adjusting the concentration of the solution when coating is performed by using a liquid layer reaction such as a polymer solution or a sol-gel method. This is possible by adjusting the deposition time when using sputtering, battery beam evaporation, CVD method or plasma polymerization.

(Porosity of coating film on positive electrode surface) The fine pores and porosity of the coating film on the positive electrode surface can be adjusted by using a polymer solution or a sol.
In the case of coating using a liquid layer reaction such as a gel method, it can be performed by adjusting the concentration of the solution or the drying conditions. Other methods include adjusting the concentration of the foaming agent to form a film while foaming, forming a film with an adjusted electrolyte content to dissolve the electrolyte, controlling the vapor deposition rate, and mixing the reactants. There is a method of adjusting the ratio, and the like.

(Positive Electrode) The positive electrode is formed by mixing a positive electrode active material, conductive powder, a binder and the like on a current collector. In a lithium battery in which the negative electrode active material is lithium or a lithium alloy, a transition metal oxide or a transition metal sulfide is generally used as the positive electrode active material. The transition metal element of the transition metal oxide or the transition metal sulfide is partially d-shell or f
Shell element, Sc, Y, lanthanoid, actinide, Ti, Zr, Hf, V, Nb, Ta, Cr, M
o, W, Mn, Tc, Re, Fe, Ru, Os, Co,
Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au are used. Mainly, Ti, V, Cr, M of the first transition series metals
n, Fe, Co, Ni, Cu are used.

In a nickel-zinc battery in which the negative electrode active material is zinc, nickel oxide hydroxide is used as the positive electrode active material. In an air zinc battery in which the negative electrode active material is zinc, the positive electrode active material is oxygen, and the positive electrode is composed of a current collector, a catalyst and a water repellent material. Porous carbon, porous nickel, copper oxide, etc. are used for the catalyst. As the water repellent material, a fluororesin such as a porous tetrafluoroethylene resin is used.

(Coating of Negative Electrode) When the negative electrode is coated with the above-mentioned coating material of the positive electrode, it is possible to suppress the growth of dendrite growing from the negative electrode. The effect of suppressing the internal short circuit is promoted, and the cycle life of the battery can be significantly extended.

(Electrolyte) In addition to the case where the electrolyte is used as it is, a solution dissolved in a solvent or a solution prepared by adding a gelling agent such as a polymer to a solution and fixing the solution is used. Generally, an electrolyte solution obtained by dissolving an electrolyte in a solvent is used by holding it in a porous separator. The higher the conductivity of the electrolyte is, the more preferable, and the conductivity at 25 ° C. is preferably 1 × 10 ⁻³ S / cm or more.
It is more preferable that the concentration is x10 ^-3 S / cm or more.

When the negative electrode active material is lithium or a lithium alloy
If electrolyte, H ₂ SO _4, HCl, acids such as HNO _3, lithium ion (Li ⁺⁾ and Lewis acid ion (BF ₄ ^-, PF _{6
^{-, AsF 6 -, ClO 4}} - salt consisting of), and use of these mixed salts. In addition to the above supporting electrolyte, a salt of a cation such as sodium ion, potassium ion, tetraalkylammonium ion and Lewis acid ion can be used. It is desirable that the salt be heated under reduced pressure to be sufficiently dehydrated and deoxidized.

The electrolyte solvent is acetonitrile:
CH₃CN, benzonitrile: C₆H _FiveCN, propylene
Carbonate: PC, Ethylene carbonate: EC, Di
Methylformamide: DMF, Tetrahydrofuran: T
HF, nitrobenzene: C₆H_FiveNO₂, Dichloroethane
Benzene, diethoxyethane, chlorobenzene, γ-butyrola
Kuton, dioxolane, sulfolane, nitromethane, di
Methyl sulfide, dimethyl sulphoxide, dimethoxide
Cietane, Methyl formate, 3-Methyl-2-Oxazolide
Non-, 2-methyltetrahydrofuran, sulfur dioxide,
Phosphoryl chloride, thionyl chloride, sulfuryl chloride, etc.
And mixtures of these can be used. The solvent is active
Alumina, molecular sieve, phosphorus pentoxide, calcium chloride
Dehydrate with sium, etc., or depending on the solvent, inert gas
Distillation in the presence of alkali metal to remove impurities and dehydrate
Also good to do.

Gelation is preferable in order to prevent leakage of the electrolytic solution. As the gelling agent, it is desirable to use a polymer that absorbs the solvent of the electrolytic solution and swells,
Polymers such as polyethylene oxide, polyvinyl alcohol and polyacrylamide are used. When the negative electrode active material is zinc or a zinc alloy, the electrolyte is potassium hydroxide, sodium hydroxide,
An alkali such as lithium hydroxide is used.

Gelation is preferable in order to prevent leakage of the electrolytic solution. As the gelling agent, it is desirable to use a polymer that absorbs the solvent of the electrolytic solution and swells,
Polymers such as polyethylene oxide, polyvinyl alcohol, polyacrylamide and starch are used. As the current collectors 100 and 102, fibrous, porous or mesh carbon, stainless steel, titanium, nickel, copper, platinum, gold or the like is used.

Separator The separator 108 has a role of preventing a short circuit between the negative electrode and the positive electrode. It may also have a role of holding the electrolytic solution. Since the separator has pores through which lithium ions can move and must be insoluble and stable in the electrolytic solution, a nonwoven fabric such as glass, polypropylene, polyethylene, fluororesin, or polyamide, or a material having a micropore structure is used.

(Battery Shape and Structure) Actual battery shapes include flat type, cylindrical type, rectangular type and sheet type batteries. In the spiral cylindrical type, the electrode area can be increased by winding a separator between the negative electrode and the positive electrode, and a large current can be passed during charging and discharging. Further, in the rectangular parallelepiped type, it is possible to effectively use the storage space of the device that stores the secondary battery. As for the structure, there are structures such as a single layer type and a multilayer type.

2 and 3 are examples of schematic cross-sectional views of a single-layer flat type battery and a spiral structure cylindrical battery, respectively. 2 and 3, 200 and 300 are negative electrode current collectors, 201 and 301 are negative electrode active materials, 203 and 303 are positive electrode active materials, 205 and 305 are negative electrode terminals (negative electrode caps), 206 and 306 are positive electrode cans, 207 and 307 are electrolyte and separator, 210 and 310 are insulating packing,
311 is an insulating plate. As an example of assembling the battery of FIGS. 2 and 3, after the separators 207 and 307 are sandwiched between the negative electrode active materials 201 and 301 and the molded positive electrode active materials 203 and 303, and the electrolyte is injected into the positive electrode cans 206 and 306, Negative electrode cap 205, 305 and insulating packing 21
0, 310 are assembled and caulked to produce a battery.

It is desirable that the preparation of the lithium battery material and the assembly of the battery be performed in dry air from which water has been sufficiently removed or in a dry inert gas. Insulating packing As materials for the insulating packings 210 and 310, fluorocarbon resin, polyamide resin, polysulfone resin and various rubbers can be used. As a sealing method, besides caulking using a gasket such as an insulating packing as shown in FIGS. 2 and 3, a glass sealing tube, an adhesive, welding, soldering, or the like is used.

Various organic resin materials and ceramics are used as the material of the insulating plate shown in FIG. Outer can (battery case) Positive electrode cans 206, 306 and negative electrode cap 20 of the actual battery
As the material of 5,305, stainless steel, particularly titanium clad stainless steel, copper clad stainless steel, nickel-plated steel plate, or the like is used.

2 and 3, the positive electrode cans 206 and 306 also serve as a battery case.
Other than stainless steel, a metal such as zinc, a plastic such as polypropylene, or a composite material of metal or glass fiber and plastic can be used. Safety valve Although not shown in FIGS. 2 and 3, a safety valve is generally provided as a safety measure when the internal pressure of the battery increases.

[0070]

EXAMPLES The present invention will be described in detail below based on examples. The present invention is not limited to these examples. (Example 1) A lithium secondary battery having a schematic sectional structure shown in FIG.

As the positive electrode active material 204, electrolytic manganese dioxide and lithium carbonate were mixed at a ratio of 1: 0.4 and heated at 800 ° C. to prepare a lithium-manganese oxide. Graphite and tetrafluoroethylene polymer powder were mixed with the prepared lithium-manganese oxide and then pressure-molded into a nickel mesh to form a positive electrode.
Next, the positive electrode is dipped in a solution of Teflon AF manufactured by DUPONT Co., which is a copolymer of tetrafluoroethylene and 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole, and dried to obtain fluorine. A positive electrode 204 coated with resin was prepared.

After a titanium mesh current collector 200 was pressure-bonded to the lithium metal foil from the back side in a dry argon gas atmosphere, a solution of Lumiflon manufactured by Asahi Glass Co., Ltd., which is a copolymer of ethylene tetrafluoride and vinyl ether, was applied. The lithium metal foil was dipped, dried and cured to prepare a lithium negative electrode 201 coated with a fluororesin. The electrolytic solution 208 contains propylene carbonate (PC) and dimethoxyethane (DM).
1) of tetrafluoroboric acid lithium salt is added to an equal amount of mixed solvent of E).
What was melt | dissolved in M (mol / l) was used.

As the separator 208, a polypropylene nonwoven fabric sandwiched with polypropylene micropore separators was used. Assembling is performed by inserting a separator 208 between the negative electrode 201 and the positive electrode 204, inserting the positive electrode can 207 made of a titanium clad stainless material, and injecting an electrolytic solution, and then making a negative electrode cap 20 made of a titanium clad stainless material.
6 and a fluororubber insulating packing 210 were sealed to produce a lithium secondary battery.

(Example 2) A lithium secondary battery having a schematic sectional structure shown in FIG. A lithium battery was produced in the same manner as in Example 1, except that the coating operation of the positive electrode was omitted. The positive electrode was prepared in the same manner as in Example 1. Next, the positive electrode was immersed in an acetonitrile solution in which 0.1M of monomer benzo-15-crown-5 and 0.2M of tetrabutylammonium tetrafluoroammonium tetrafluoride as an electrolyte were dissolved, and the platinum electrode was used as the cathode electrode. Then, a voltage of 3 V was applied to form a macrocyclic compound polymer coating film on the positive electrode surface by electrolytic polymerization.

Next, the titanium mesh current collector 200 was pressure-bonded to the lithium metal foil in a dry argon gas atmosphere to form a negative electrode. Then, a lithium secondary battery was produced in the same manner as in Example 1. (Example 3) A lithium secondary battery having a schematic sectional structure shown in FIG.

The positive electrode was prepared in the same manner as in Example 1. Next, Aldrich Chemical Compa
ny, Inc. Benzoyl peroxide and lithium tetrafluoroborate are dissolved in a solution of poly (2-vinylnaphthalene) in tetrahydrofuran, the positive electrode is dipped, and then heat-treated at 100 ° C. to coat with poly (2-vinylnaphthalene). The prepared positive electrode 203 was prepared.

A lithium secondary battery was manufactured in the same manner as in Example 2 except for the above. (Example 4) A lithium secondary battery having a schematic sectional structure shown in FIG. The positive electrode is used in Example 1
It was prepared by the same operation. Next, PP made by Idemitsu Petrochemical
Lithium tetrafluoroborate salt was added to and dissolved in a toluene solution of Z-U1001, the positive electrode was dipped, pre-dried and then irradiated with ultraviolet rays to be coated with polyphosphazene.
03 was prepared.

A lithium secondary battery was manufactured in the same manner as in Example 2 except for the above. (Example 5) A lithium secondary battery having a schematic cross-sectional structure shown in Fig. 2 having a simple structure and assembly was produced. The positive electrode is used in Example 1
It was prepared by the same operation. Then, this positive electrode was put in a sputtering apparatus, mounted, and vacuum-evacuated to 2 × 10 ⁻⁶ Torr, and then argon gas was mixed with 10% nitrogen gas and 5% acetylene gas to flow at 3 × 10 ⁻³ Torr.
The internal pressure was controlled, and lithium fluoride was sputtered with a target material to form a lithium nitride film containing carbon and fluorine on the positive electrode surface.

A lithium secondary battery was manufactured in the same manner as in Example 2 except for the above. (Example 6) A nickel-zinc secondary battery having a schematic structure shown in FIG. First, the positive electrode was prepared by impregnating a sintered nickel electrode plate with zinc hydroxide.
Next, in an ethyl alcohol solution of tetraethoxylane,
After acetic acid and water were added for hydrolysis, diethylamine was added to form colloidal silica. Then, the positive electrode was immersed in a silica colloidal solution and dried at 100 ° C. to form a silica film on the positive electrode surface.

The negative electrodes were formed on both surfaces of a copper punching metal by pressure-bonding a mixture of zinc powder and zinc oxide powder with tetrafluoroethylene polymer powder as a binder.
The electrolyte used was a 30 wt% potassium hydroxide aqueous solution to which lithium hydroxide was added. The battery was assembled in the same manner as in Example 1.

In order to compare and evaluate the performance of the batteries prepared in the above examples, the following comparative batteries were prepared. (Comparative Example 1) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the surface coating treatment of the positive electrode and the lithium negative electrode was not performed.

Comparative Example 2 A nickel-zinc secondary battery was prepared in the same manner as in Example 6, except that the surface coating treatment was not performed. (Performance Evaluation of Secondary Battery) The performance evaluation of the secondary batteries manufactured in the examples and comparative examples was performed under the following conditions, and the performance was evaluated by comparing with the batteries of the comparative examples. The conditions of the cycle test were a charge / discharge of 0.2 C (a current of 0.2 times the capacity / hour), a break time of 30 minutes, and a cutoff voltage of 1.0 V. Hokuto Denko H is used as the battery charging / discharging device.
J-101M6 was used.

The charge / discharge test was started from the discharge, the battery capacity was the third discharge amount, and the cycle life was the number of cycles below 60% of the battery capacity. Table 1 shows the evaluation results of the performance regarding the cycle life of the secondary battery manufactured in the example of the present invention and the secondary battery manufactured in the comparative example, with the performance of the battery of the comparative example being 1.0.

From the evaluation results of Table 1, the comparison between Examples 1 to 5 and Comparative Example 1 and the comparison between Example 6 and Comparative Example 2 show that the cycle life is improved by adopting the secondary battery of the present invention. I found it to grow.

[0085]

[Table 1]

[0086]

EFFECTS OF THE INVENTION According to the present invention, even if lithium or zinc dendrites grow during charging, short-circuiting between the negative electrode and the positive electrode is suppressed, and the charge / discharge cycle life is long. It is possible to manufacture a zinc-air secondary battery or the like. Furthermore, since metallic lithium can be used as the negative electrode active material, a secondary battery with high energy density can be manufactured.

[Brief description of drawings]

FIG. 1 is a basic configuration diagram of a secondary battery of the present invention.

FIG. 2 is an example of a schematic cross-sectional view of a flat battery to which the present invention is applied.

FIG. 3 is an example of a schematic sectional view of a cylindrical battery to which the present invention is applied.

[Explanation of reference numerals] 100, 200, 300 ... Negative electrode current collector, 101, 201, 301 ... Negative electrode active material, 102 ... Positive electrode current collector, 103 ... Positive electrode active material, 104 ... Ion permeable coating layer, 203, 303 ... Positive electrode active material coated with ion-permeable film, 105 ... Electrolyte, 106, 206, 306 ... Negative electrode terminal, 107, 207, 307 ... Positive electrode terminal, 108 ... Separator, 208, 308 ... Electrolyte and separator, 109 ... Battery Case, 210, 310 ... Insulating packing, 311 ... Insulating plate.

Claims (21)

[Claims] 1. A negative electrode, a separator, a positive electrode active material, an electrolyte,
In a secondary battery formed at least from a current collector and a battery case, at least the positive electrode surface facing the negative electrode is permeable to ions involved in the battery reaction. A secondary battery, which is coated with one or more layers of a selected film. 2. The secondary battery according to claim 1, wherein the insulator permeable to ions is a macrocyclic compound permeable to ions involved in a battery reaction. 3. The macrocyclic compound is cyclic polyether, cyclic polyamine, cyclic polythioether, azacrown ether, cyclic thioether, thiocrown ether, cryptand, cyclam, cyclodextrin,
The secondary battery according to claim 2, which is a cyclic compound having one or more kinds of structures selected from cyclophane, phthalocyanine, and porphyrin compounds. 4. The secondary battery according to claim 1, wherein the ion-permeable insulator is a polymer of an aromatic hydrocarbon derivative. 5. The aromatic hydrocarbon derivative is at least one derivative selected from at least naphthalene, anthracene, phenanthrene, naphthacene, pyrene, triphenylene, perylene, picene, benzopyrene, coronene, and ovalen. The secondary battery according to claim 4. 6. The secondary battery according to claim 1, wherein the insulator permeable to ions is a fluororesin. 7. The secondary battery according to claim 6, wherein the fluororesin has an ether bond. 8. The secondary battery according to claim 1, wherein the insulator permeable to ions is a silicone resin which is an organic silicon compound. 9. The secondary battery according to claim 1, wherein the insulator permeable to ions is a titanium polymer which is an organic titanium compound. 10. The secondary battery according to claim 1, wherein the insulator permeable to ions is a polymer in which phosphorus atoms and nitrogen atoms are alternately bonded to a phosphorus-nitrogen double bond. 11. The secondary battery according to claim 1, wherein the insulator permeable to ions is an inorganic glass containing an inorganic oxide as a main component. 12. The secondary battery according to claim 11, wherein the inorganic glass is combined with an organic polymer. 13. The inorganic oxide contains at least an oxide of one or more elements selected from silicon, titanium, aluminum, magnesium, zirconium, lead and calcium. The secondary battery according to claim 11. 14. The secondary battery according to claim 1, wherein the insulator capable of transmitting the ions is a carbide. 15. The secondary battery according to claim 1, wherein the insulator capable of transmitting the ions is a nitride. 16. The secondary battery according to claim 1, wherein the insulator capable of transmitting the ions is a halide. 17. The secondary battery according to claim 16, wherein the halide is a fluoride. 18. The secondary battery according to claim 1, wherein the semiconductor permeable to ions contains at least one kind or two kinds of elements selected from carbon and silicon. 19. The secondary battery according to claim 1, wherein the surface of the negative electrode is covered with a film that transmits ions involved in a battery reaction. 20. The secondary battery according to claim 1, wherein the negative electrode is lithium or a lithium alloy, and the ions involved in the reaction are lithium ions. 21. The secondary battery according to claim 1, wherein the negative electrode is zinc or a zinc alloy, and the ions involved in the reaction are hydroxide ions.