JP3530544B2 - Rechargeable battery - Google Patents

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, an air zinc secondary battery, and a bromine zinc secondary battery. In particular, the present invention relates to a secondary battery in which a short circuit due to dendrite of lithium or zinc that occurs due to repeated charge and discharge is 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 a secondary battery installed in a home is used to level the load.

Further, there has been a demand for the development of a high energy density secondary battery for electric vehicles that does not emit air pollutants. Furthermore, there is an increasing demand for the development of high-performance secondary batteries for powering portable devices such as book-type personal computers, word processors, video cameras and mobile phones.

As a high-performance secondary battery, a rocking chair type lithium-ion battery in which lithium ions are 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 which is the original feature of the lithium battery using metallic lithium as the 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 the dendrite of lithium 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 explosion or ignition may occur infrequently as the solvent of the electrolytic solution is decomposed to generate gas to increase the internal pressure. 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.

In nickel-zinc batteries and zinc-air batteries as well, dendrites of zinc are generated by repeated charging and discharging, which penetrates the separator and short-circuits the zinc negative electrode and the positive electrode, resulting in extremely long cycle life. It was short.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned conventional drawbacks and to provide a secondary battery having a long cycle life, in which the negative electrode active material is lithium or a lithium alloy or zinc or a zinc alloy. And

[0010]

The present inventor has conducted extensive studies to solve the above-mentioned conventional drawbacks, and as a result, formed a film having a structure capable of transmitting ions involved in a battery reaction on the surface of a negative electrode. , Found that the generation of lithium and zinc dendrites can be suppressed.

The present invention includes a secondary electrode formed of at least a negative electrode made of lithium or a lithium alloy , a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a collecting electrode, and a battery case. In the battery,
A structure in which the negative electrode surface is permeable to ions involved in battery reaction, a negative electrode composed of a negative electrode active material, a separator, a positive electrode composed of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution),
In a secondary battery formed at least from a current collector and a battery case, the negative electrode surface has a structure capable of transmitting ions involved in the battery reaction, and is coated with a film that is stable without reacting or dissolving in an electrolyte or an electrolytic solution. , The film is naphthalene, anthracene, phenanthrene, naphthacene,
It is characterized in that it is a polymer film of a derivative of one or more kinds of aromatic hydrocarbon compounds selected from pyrene, triphenylene, perylene, picene, benzopyrene, coronene and ovalen. The present invention relates to lithium or lithium
In a secondary battery formed at least from a negative electrode made of an alloy , a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case,
The negative electrode surface has a structure capable of transmitting ions involved in the battery reaction, and is covered with a film that is stable without reacting or dissolving in the electrolyte or the electrolytic solution, and the film has a radius not less than the radius of the ions participating in the battery reaction. It is characterized in that it is a polymer film of a macrocyclic compound derivative having pores of. The present invention is a negative electrode made of lithium or a lithium alloy,
In a secondary battery including at least a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte), a current collector, and a battery case, the negative electrode surface has a structure that allows ions involved in a battery reaction to permeate. Alternatively, it is characterized in that it is covered with a film which is stable without reacting or dissolving in the electrolytic solution, and the film is a fluororesin film having an ether bond. The present invention relates to a secondary battery including at least a negative electrode made of lithium or a lithium alloy, a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case. It has a structure capable of transmitting ions involved in the reaction, and is coated with a film that is stable without reacting or dissolving in an electrolyte or an electrolytic solution, and the film is titanium, aluminum, silicon, zirconium, tantalum, magnesium, indium, tin. , A metal alkoxide, an alkyl metal compound, a metal salt of acetylacetone, a metal salt of naphthenic acid, a metal salt of octylate, and lithium of a metal selected from the group consisting of metal, molybdenum, tungsten, and germanium, and lithium. Characterized by being a film formed by reacting That.
The present invention relates to a secondary battery including at least a negative electrode made of lithium or a lithium alloy, a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case. in the structure that can penetrate the ion involved in the reaction, Yes coated with a stable coating does not react or dissolve in the electrolyte or electrolyte solution, is said coating Gaga lath metal oxide, the
The film is characterized by being combined with an organic polymer .

The material of the above-mentioned film is characterized by having a molecular structure or pores through which the negative electrode active material deposited on the negative electrode during charging does not permeate but the ions involved in the battery reaction can permeate.

Further, the present invention is characterized in that the coating material has an electron-donating element or group so that ions involved in the battery reaction can be easily conducted in the coating.

Examples of the electron-donating element include an oxygen atom having a pair electron, an unpaired electron, and a d electron, a nitrogen atom, a sulfur atom, a transition metal atom and the like. In addition, examples of the electron-donating group include a cyclic compound, a compound having a carbon-carbon double bond having π electrons and an aromatic ring.

Further, the film on the surface of the negative electrode of the present invention comprises:
Another feature is that it does not dissolve in the electrolyte.

[0016]

[Action]

(Battery Structure) The basic structure of the secondary battery of the present invention comprises at least a negative electrode, a separator, a positive electrode, an electrolyte, and 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, 101 is a negative electrode made of a negative electrode active material, 102 is a film, 103 is a positive electrode current collector,
104 is a positive electrode made of a positive electrode active material, 105 is an electrolyte solution (electrolyte), 106 is a negative electrode terminal, 107 is a positive electrode terminal, 1
Reference numeral 09 is a battery case, and 108 is a separator.

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 electrolytic solution 105 enter the layers of the positive electrode active material of the positive electrode 104 by the discharge reaction, and at the same time, the negative electrode active material. Lithium ions are dissolved from 101 into the electrolyte 105 through the film 102. On the other hand, in the charging reaction, lithium ions in the electrolytic solution 105 permeate the film 102 and are deposited as lithium metal on the negative electrode active material (at this time, dendrite easily grows without the film 102), and at the same time, between the positive electrode active material 104 layers. Of lithium dissolves into the electrolyte solution 105. Lithium deposited by the charging reaction is very active and easily reacts with a trace amount of water, oxygen, impurities or solvent in the electrolytic solution to form an insulating reaction film, but the surface of the negative electrode 101 is film 1.
Since it is covered with 02, the deposited lithium does not come into direct contact with the electrolytic solution, and the generation of dendrites that cause a short circuit of the battery is suppressed.

In the case of an alkaline battery in which the negative electrode active material 101 is zinc or a zinc alloy, an electrolytic solution 1 is produced by a discharge reaction.
Hydroxide ions in 05 react with the negative electrode active material of the negative electrode 101 through the film 102, and at the same time, hydroxide ions come out of the positive electrode active material of the positive electrode 104 into the electrolytic solution 105. On the other hand, in the charging reaction, hydroxide ions are transferred from the negative electrode 101 to the film 1.
02 through the electrolyte solution (in this case, if there is no film 102, zinc ions in the electrolyte solution tend to grow dendrites at the negative electrode), and at the same time, hydroxide ions in the electrolyte solution react with the positive electrode 104. Similar to the case where the negative electrode active material is lithium, the formation of zinc dendrite is suppressed during charging because of the coating 102.

Therefore, according to the present invention, as a result, it is possible to suppress a short circuit inside the battery, extend the life of the secondary battery, and enhance the safety.

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, hydroxide ions. When the negative electrode active material is zinc, typical batteries include nickel-zinc batteries, zinc-air batteries, and bromine-zinc batteries. (However, in the case of a bromine zinc battery, the ions on the negative electrode side that contribute to the battery reaction are zinc ions.) (Method for forming negative electrode) Dipping the surface of the negative electrode active material
Besides the method of directly coating the coating material with a coating agent by a spray method or a CVD method to form the negative electrode, the following method can be adopted.

A porous conductive matrix (base material), for example, a sponge-like or fibrous metal or carbon is coated with a coating material capable of transmitting ions involved in a battery reaction at the communicating holes, and then the negative electrode active material A method of electrochemically depositing and depositing lithium or zinc to form a negative electrode is also very effective. In particular, when a porous conductive matrix having a high specific surface area is used, the current density per unit area during charging / discharging can be reduced, the growth of dendrites can be suppressed, and the charging / discharging efficiency can be increased. Another alternative method for forming the negative electrode is to directly immerse the porous conductive matrix in the molten negative electrode active material and pull it up to coat the surface of the conductive matrix with the negative electrode active material or electrochemically form the surface of the conductive matrix. After coating with a negative electrode active material,
A method of coating with a coating material that is permeable to ions involved in the battery reaction is also effective.

FIG. 4 is a schematic diagram showing a partial structure of the negative electrode formed by coating the conductive matrix 400 with the negative electrode active material 401 and the coating material 402 that allows the ions involved in the battery reaction to pass therethrough.

(Coating Material for Negative Electrode Surface) Here, the coating material for the negative electrode surface will be described in detail in 1 to 7.

1. By coating the surface of the negative electrode active material with a film having an inorganic glass structure that allows ions involved in a battery reaction to pass through the film having an inorganic glass structure,
When the negative electrode active material is lithium, the reaction with the moisture or oxygen of lithium is suppressed to facilitate handling, and furthermore, the lithium metal does not come into direct contact with the electrolytic solution, and the lithium surface is formed from the solvent of the electrolytic solution. It is possible to suppress the growth of the polymerized film . As a result, the formation of dendrite is suppressed, it is possible to extend the charge-discharge cycle life. Further, since the film having the inorganic glass structure is flame-retardant or non-flammable, it is possible to enhance the safety even if the battery should be damaged. Examples of the inorganic glass material include silica, titanium oxide, alumina, zirconia oxide, magnesium oxide, tantalum oxide, molybdenum oxide, tungsten oxide, tin oxide, indium oxide,
Iron oxide, chromium oxide, aluminum phosphate, iron phosphate,
Mention may be made of metal oxides such as silicon phosphate, and mixtures thereof. In particular, silica, titanium oxide, alumina, zirconia oxide, aluminum phosphate and the like are preferable.

The sol-gel method is one of the suitable methods for forming the above-mentioned inorganic glass. However, since the melting point of lithium is as low as 181 ° C., when coating these materials directly on the lithium surface, it must be performed at a low temperature. Moreover, lithium reacts with water and alcohol, so it must be operated in an environment free of water and alcohol. (This does not apply when the conductive matrix is first coated with inorganic glass or when the negative electrode active material is zinc.) Therefore, to apply the sol-gel method, which is a typical method of inorganic coating at low temperature, Requires some ingenuity. 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 bond between a metal atom and an oxygen atom. After that, the solvent is replaced with a non-aqueous solvent other than alcohol to obtain.

To coat the surface of the negative electrode active material, the colloidal solution is directly applied, or a solution of a monomer, an organic polymer, or an organic polymer and a crosslinking agent is dissolved in the colloidal solution, followed by polymerization or dry curing. Let it form. By compounding the organic polymer, the strength against cracking and peeling can be improved. Furthermore, when the electrolyte forming the 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 are epoxy resin, polyester, polyimide, polyethylene, polypropylene, polyurethane, polystyrene, polyethylene glycol, nylon, fluororesin,
Silicone resin etc. are mentioned.

Examples of the cross-linking agent for the above polymer include diisocyanate, polyisocyanate prepolymer, block isocyanate, organic peroxide, polyamine, oxime, nitroso compound, sulfur and sulfur compound, selenium, magnesium oxide and 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.

Further, at the time of forming the film, in order to facilitate the transfer of electric charge during charging, powder or fibers or whiskers of a conductor such as carbon or titanium may be mixed with the above film forming solution.

The film thickness of the film formed on the surface of the negative electrode active material is
The range of 50 angstroms to 100 microns is preferred, and the range of 100 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.

2. About polymer film of aromatic hydrocarbon compound derivative By coating the metal surface of the negative electrode active material with the polymer film of aromatic hydrocarbon compound derivative, when the negative electrode active material is lithium, the reaction of lithium with moisture or oxygen is suppressed. Further, the handling is facilitated, and further, the lithium metal does not come into direct contact with the electrolytic solution, and the growth of the polymer film formed on the lithium surface from the solvent of the electrolytic solution can be suppressed. Further, when the negative electrode active material is zinc, elution of zinc into the electrolytic solution is suppressed by the coating.

As a result, the formation of dendrites is suppressed, and the charge / discharge cycle life can be extended. As the aromatic hydrocarbon derivative forming a charge transfer complex with lithium, at least naphthalene, anthracene, phenanthrene, naphthacene, pyrene, triphenylene, perylene, picene, benzopyrene, coronene,
It is characterized by being one or more kinds of derivatives selected from Ovalene. The method of forming the polymer used for the coating material is a vinyl monomer, an acetylene derivative monomer,
Dicarboxylic acid and diamine, dicarboxylic acid and glycol,
It is obtained by polymerization or copolymerization of monomers such as. The vinyl monomer can be polymerized by radical or ionic polymerization. The acetylene derivative monomer can be polymerized by using a chloride of molybdenum or 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 polymer include
2-vinylnaphthalene, 2-vinylpyridine, 9-vinylanthracene, 9,10-anthracene dipropionic acid, 9,10-bis (phenylethynyl) anthracene, 5,12-bis (phenylethynyl) naphthalene and the like can be used. . In particular, 2-vinylnaphthalene, 9-
Vinyl anthracene and the like are preferable.

As the radical polymerization initiator, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), t-butyl hydroperoxide and the like are used. As an initiator of cationic polymerization, H ₂ SO ₄ , H
Acids such as ₃ PO ₄ , HClO ₄ , CCl ₃ and CO ₂ H, B
Frie such as F ₃ , AlCl ₃ , TiCl ₄ , SnCl ₄
A del-Crafts catalyst or the like is used. Further, the macrocyclic compound having an aromatic ring is the above-mentioned Friedel-C.
Polymerization can be performed by a dehydrogenation reaction using a combination of a Rafts 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-mentioned method, a polymer having an aromatic group introduced therein can be obtained by subjecting the side chains of various polymers to a substitution reaction 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 lithium with the aromatic compound polymer.

When the lithium surface is coated with the polymer 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. (However, when the conductive matrix is first coated with the above polymer, or when the negative electrode active material is zinc, it is not necessary to strictly control the water content.) An electrolyte is mixed during the film formation. Good. This improves the wettability between the electrolytic solution and the film, and facilitates the permeation of ions through the film. Further, in order to facilitate the transfer of electric charges during charging, powder or fibers of electric conductors such as carbon or titanium, or whiskers may be mixed during the formation of the film.

If the polymer coating film is dissolved in the organic solvent of the electrolytic solution, it may cause deterioration of battery performance.
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 surface of the negative electrode active material is
The range of 50 angstroms to 100 microns is preferred, and the range of 100 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.

3. About organometallic compounds When a lithium surface reacts with an organometallic compound, it forms a bond with a lithium atom and a film is formed on the surface of which an organic bond is formed, and the wettability (lipophilicity) with the non-aqueous electrolyte is increased, resulting in charging. It becomes easy for lithium ions to come and go with the discharge. In addition, since the lithium metal and the organic solvent do not come into direct contact with each other due to the surface coating film, formation of a polymer film of the organic solvent that increases the internal resistance of the battery on the lithium surface is suppressed. As a result, the formation of dendrites is suppressed, and the charge / discharge cycle life can be extended. Further, during the manufacturing process, the reaction between lithium and water is suppressed, and the handling is facilitated. In the lithium battery according to the present invention, when the metal content of the lithium film is high, it is possible to suppress a rapid reaction of lithium in the event of damage.

Examples of the organometallic compound include metal alkoxides of metals such as titanium, aluminum, silicon, zirconium, tantalum, magnesium, indium, tin, molybdenum, tungsten and germanium.
It can be selected from alkyl metal compounds, acetylacetone metal salts, naphthenic acid metal salts, octylic acid metal salts and the like. Among the above organometallic compounds, it is desirable to use a metal compound of silicon, titanium, or aluminum that is easy to handle, easy to form a film, and stable in the formed film.

Examples of the organic silicon compound include alkoxysilane, alkylsilane, halogenated silane, siloxane, vinyl group, amino group, epoxy group, methacryl group,
Mercapto group-introduced silane, hydrogen modified, vinyl modified, hydroxyl modified, amino modified, carboxyl modified, chlor modified, epoxy modified, methacryloxy modified, mercapto modified, fluorine modified, long chain alkyl modified, phenyl modified, and other polysiloxanes, Materials such as alkylene oxide-modified siloxane copolymer (copolymer), silicone-modified copolymer, alkoxysilane-modified polymer, silicone-modified urethane, and silicone-modified nylon can be used.

As the organic titanium compound, alkoxy titanium, titanium chelate, titanium acylate, titanium polymer and the like can be used.

As the organoaluminum compound, alkoxyaluminum, alkylaluminum, aluminum halide and the like can be used.

Further, examples of the organosilicon-titanium compound include a tyranopolymer, which is a silicone polymer in which a main chain of a polycarbosilane skeleton is crosslinked with a titanium organic compound.

Also, various polymers prepared by introducing an organometallic compound derivative into the polymer by a substitution reaction can be used as the coating material.

As a method for forming a film, when the 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.

Further, by mixing with the organometallic compound at the time of forming the film, the wettability with the electrolytic solution is improved, and ions can easily come in and out at the time of charging and discharging. Further, in order to facilitate the transfer of electric charge during charging, powder or fibers or whiskers of a conductor such as carbon or titanium may be mixed when the organometallic compound is applied.

The thickness of the film formed on the lithium surface is 5
The range of 0 angstroms to 100 microns is preferred, and the range of 100 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.

4. Fluororesin coating By using a fluororesin having an ether bond as the fluororesin for coating the lithium surface, the surface coating step is facilitated, and the one having good adhesion between the lithium metal and the film can be obtained.

That is, the presence of the ether-bonded oxygen atom of the fluororesin facilitates coordination of lithium ions and facilitates movement of lithium ions in the fluororesin.

Further, since the surface coating film prevents the lithium metal and the organic solvent from directly contacting with each other, formation of a polymer film of the organic solvent which increases the internal resistance of the battery on the lithium surface can be suppressed.

As a result, the formation of dendrites is suppressed, and the charge / discharge cycle life can be extended.

Further, by coating the surface of the lithium metal with the above-mentioned fluororesin, the reaction of lithium with moisture or oxygen is suppressed to facilitate handling.

Further, since the fluororesin film is flame retardant,
Safety in case of a fire accident can be improved.

Specific examples of the fluororesin for coating the lithium metal surface include copolymers of fluoroethylene and vinyl monomers having an ether bond, such as vinyl ether, dioxole, dioxine and dioxene, or diene monomer derivatives. Or a copolymer of a diene compound such as ethylene and a vinyl monomer having a fluorinated ether bond, such as vinyl ether, dioxole, dioxine, or dioxene, or a diene monomer derivative. Particularly preferred is a copolymer of fluoroethylene and vinyl ether having an ether bond. As the fluoroethylene, a fluoroethylene derivative such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride or vinyl fluoride is used. As a method for polymerizing a fluoroethylene copolymer containing an ether bond, solution, suspension, bulk or emulsion polymerization can be performed, and a peroxide can be used as an initiator.
Alkyl boron, light or radiation is used.

The coating of the above-mentioned fluororesin on lithium metal is carried out by a. Apply the solution of fluororesin by spraying, screen printing, coater, dipping, etc. 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 a lithium surface is coated with a fluororesin solution, it is desirable to use a fluororesin solution that has been dehydrated and deoxidized sufficiently in an inert gas that has been dehydrated sufficiently. 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. However, when lithium is electrochemically inserted and adhered between the fluororesin and the conductive matrix after the conductive matrix is first coated with the fluororesin, strict moisture management may not be required.

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. Further, in order to facilitate the transfer of electric charges during charging, powder or fibers of electric conductors such as carbon or titanium, or whiskers may be mixed during the formation of the film.

If the fluororesin film is dissolved in the organic solvent of the electrolytic solution, it may cause deterioration of battery performance.
It is preferably crosslinked.

In addition to the method for coating the surface of lithium metal with the above-mentioned fluororesin solution, a method of plasma-polymerizing a fluorine compound such as tetrafluoroethylene as a main raw material for coating can also be used. It is desirable to mix oxygen, hydrogen, helium argon, nitrogen, hydrocarbon silane, etc. with the fluorine compound as the main raw material in order to easily cause plasma polymerization or to enhance the adhesion and strength of the film. As a method for generating plasma, glow discharge by direct current or high frequency, microwave discharge, laser, etc. are effective.

The thickness of the film formed on the lithium surface is 5
The range of 0 angstroms to 100 microns is preferred, and the range of 100 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.

5. Polymers of derivatives of macrocycles that are permeable to macrocycles that are permeable to ions involved in battery reactions .
By coating the surface of the negative electrode active material with a polymer of a derivative, when the negative electrode active material is lithium, the reaction with the moisture or oxygen of lithium can be suppressed to facilitate the handling. Can be prevented from contacting with each other, and the growth of a polymer film formed on the lithium surface from the solvent of the electrolytic solution can be suppressed. Further, when the negative electrode active material is zinc, it is possible to suppress dissolution of zinc in the electrolytic solution. As a result, the formation of dendrites is suppressed, and the charge / discharge cycle life can be extended.

In the above macrocycle, the hetero atom is oxygen,
It is a cyclic compound consisting of at least one or two or more kinds of atoms selected from nitrogen, sulfur, and phosphorus, and in order to improve the permeation of ions participating in the battery reaction, it must have a radius equal to or larger than the radius of the ions participating in the battery reaction. Cyclic polyethers with radial pores, cyclic polyamines, cyclic polythioethers, azacrown ethers, cyclic thioethers, thiocrown ethers, cryptands, cyclams, nonactins, variomycins, silacrowns, which are crown ethers with silicon atoms, cyclodextrins. , A compound having one or more structures selected from cyclophane, phthalocyanine, and porphyrin compounds are used. Particularly, crown ether polymer, variomycin, phthalocyanine and porphyrin are preferable.

[0065] induction of the surface of the negative electrode active material of the macrocyclic compound
By coating with the polymer of the conductor, the movement of the ions involved in the battery reaction of the solid solution between the electrolyte solution (electrolyte solution) and the negative electrode active material is made smooth, and the dendrite of lithium or zinc is locally generated on the negative electrode. It is possible to prevent this from occurring and to prevent the reaction of the fresh lithium or zinc generated during charging with the solvent of the electrolytic solution.

The surface coating of the polymer of the derivative of the macrocyclic compound on the surface of the negative electrode active material 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 macrocyclic compound derivative as a monomer in an electrolytic solution and applying an electric field to form a film on the surface of the negative electrode active material or the surface of the conductive matrix by electrolytic polymerization. D. Forming a polymer film by immersing lithium in a solution of a macrocyclic compound derivative which undergoes anionic polymerization with lithium, e. Coating a polymer obtained by heat-condensing a macrocyclic compound having an aromatic ring and formaldehyde in formic acid, f. A method of forming a film by sputtering a polymer of a macrocyclic compound or a macrocyclic compound derivative or plasma polymerizing 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. Further, in order to facilitate the transfer of electric charges during charging, powder or fibers of electric conductors such as carbon or titanium, or whiskers may be mixed during the formation of the film.

The polymer used in the coating solution may be poly [(dibenzo-18-crown-6) -coformaldehyde] or the like. 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 (B
PO) and t-butyl hydroperoxide are used. H ₂ SO ₄ , H ₃ P as an initiator of cationic polymerization
Acids such as O ₄ , HClO ₄ , CCl ₃ , and CO ₂ H, BF ₃ ,
Friede such as AlCl ₃ , TiCl ₄ , SnCl ₄
An l-Crafts catalyst or the like is used. Further, the macrocyclic compound having an aromatic ring is the above-mentioned Friedel-Cr.
Polymerization can be carried out by a dehydrogenation reaction with a combination of an AFTS catalyst and an oxidizing agent. As the anionic polymerization initiator, an alkali metal compound or an organic metal compound is used.

The macrocyclic compound monomer used in 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-one, etc., and other dibenzocrown ethers can be used.

In the above-mentioned polymerization, it is possible to copolymerize two or more kinds of macrocyclic compound derivatives other than the polymerization of macrocyclic compound derivatives with each other and copolymerize the macrocyclic compound derivative with other monomers. 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 which is not dissolved in the solvent of the electrolytic solution or to promote the crosslinking reaction of the polymer so as not to dissolve it 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 peroxides, polyamines, oximes, nitroso compounds, sulfur and sulfur compounds, selenium, magnesium oxide,
Lead oxide, zinc oxide, etc. are used. 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 or the like is 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 negative electrode active material electrode by electrolytic polymerization, a monomer such as dibenzocrown ether is mixed with an electrolytic solution, and then electrolytic polymerization is performed using the negative electrode active material or the conductive matrix as an anode.
As the solvent of the electrolytic solution, 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 a mixture thereof can be used. The solvent may be dehydrated with activated alumina, molecular sieves, phosphorus pentoxide, calcium chloride or the like, or depending on the solvent, it may be distilled to remove impurities and dehydrate in the presence of an alkali metal in an inert gas. The supporting electrolyte is an acid such as H ₂ SO ₄ , HCl or HNO ₃ or a monovalent metal ion (Li ⁺ , K ⁺ , Na ⁺ , Rb ⁺ , Ag).
⁺⁾ Or tetrabutylammonium ion (tetrabutylammonium ion: TBA ^+, tetraethylammonium ion: TEA ⁺⁾ and Lewis acid ion (BF ₄ ^-, P
F ₆ ⁻ , AsF ₆ ⁻ , ClO ₄ ⁻ ) and a mixed salt thereof are used. The salt is recrystallized and purified,
It is desirable to perform sufficient dehydration and deoxidation by heating under depressurization.

As the monomer, crown ether / benzo-15-crown-5, crown ether / benzo-18-crown-6, crown ether / N-phenylaza-15-crown-5, crown ether / dibenzo-18 are used. -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] tetradec-11,13-diene, and the like, and mixtures thereof can be used.

The polymer film for coating the surface of the negative electrode active material dissolves in the electrolytic solution and causes deterioration of battery performance. Therefore, it is preferable that the polymer film is crosslinked.

The thickness of the film formed on the lithium surface is 5
The range of 0 angstroms to 100 microns is preferred, and the range of 100 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.

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

7. Regarding other organic polymer coatings The surface of the negative electrode is coated with an organic polymer material that contains one or more elements selected from oxygen, nitrogen and sulfur elements and is permeable to the ions involved in the battery reaction. . By this coating, the fresh negative electrode active material deposited by the charging reaction does not come into direct contact with the electrolytic solution, so that it is not covered with a low-conductivity reaction product formed by reacting with the electrolytic solution. Dendrite growth is less likely to occur.

[0084] As the organic polymer material containing elemental oxygen, cellulose, alkyl cellulose, nitrocellulose, acetyl cellulose, chitin, chitosan, Po polyvinyl alcohol, polyvinyl acetate, polylactides, polylactones, poly 3-hydroxyalkanoate, poly Glycolic acid, polylactic acid, polydioxanone, glycolic acid-lactic acid copolymer, polyethylene terephthalate, polyphenylene oxide, polyether ether ketone and the like can be mentioned. In particular, acetyl cellulose, chitin, polyvinyl alcohol and the like are preferable.

Examples of the organic polymer material containing a nitrogen element include collagen, chitin, chitosan, polyurethane, polyimide, polyamide, polyetherimide and the like. The organic polymer material containing sulfur, Po Lisle <br/> phone, and polyether sulfone.

As a method for coating the surface of the negative electrode with the organic polymer material, a solution of the organic polymer material is applied and dried, and then a cross-linking reaction is caused to form a film, or sputtering is performed with the organic polymer as a target. There is a method of forming a film by a method or a method of forming a film by plasma-polymerizing a monomer which is a raw material of an organic polymer material.

As a coating method, there are methods such as dipping, spraying and screen printing.

As a method of causing a crosslinking reaction, ultraviolet rays,
There are methods such as irradiation with electron beams and radiation, or decomposition of radical generators such as azobisbutyronitrile and benzoyl peroxide. The reason why the organic polymer material of the coating is crosslinked is to prevent the coating from dissolving into the electrolytic solution.

The thickness of the film is preferably in a range where the ions involved in the battery reaction in the electrolytic solution can permeate, and it varies depending on the material and the porosity of the film and the type of ions, but it is 1 on average.
The range of 0 angstroms to 100 microns is preferred, and the range of 100 angstroms to 10 microns is more preferred. When the film has poor ion permeability, an electrolyte may be mixed during the film formation.

When the electrolytic solution of the battery is an aqueous solution and the organic polymer film is not hydrophilic, it is preferable to treat it with a silane coupling agent or a titanate coupling agent to impart hydrophilicity.

As described above, with respect to various coating materials and coating methods,
Although the method of directly coating the negative electrode active material has been mainly described, the negative electrode active material may be introduced after first coating the conductive matrix with the coating material.

(Negative Electrode Active Material) As the negative electrode active material 101, metallic lithium and a lithium alloy, or zinc and a zinc alloy are used. As the lithium alloy, a lithium alloy containing one or more elements selected from magnesium, aluminum, potassium, sodium, calcium, zinc and lead can also be used. Zinc alloys include aluminum, indium, magnesium, tin,
A zinc alloy containing one or more elements selected from titanium, copper and lead can also be used.

(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 order to facilitate the molding of the positive electrode active material, a solvent resistant resin such as polypropylene, polyethylene or fluororesin is used as a binder in some cases. Conductor powder is mixed at the time of molding in order to facilitate current collection. As the material of the conductor powder, various kinds of carbon, copper, nickel, titanium, etc. are used.

When the negative electrode active material is lithium, as the positive electrode active material 104, lithium intercalates lithium, nickel oxide, cobalt oxide, titanium oxide, iron oxide, vanadium oxide, manganese oxide, molybdenum oxide, chromium oxide. Metal oxides such as tungsten oxide, metal sulfides such as molybdenum sulfide, iron sulfide, and titanium sulfide, hydroxides such as iron oxyhydroxide, and conductive polymers such as polyacetylene, polyaniline, polypyrrole, and polythiophene can be 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 a water repellent material,
A fluororesin such as a porous tetrafluoroethylene resin is used.

In a zinc bromine battery in which the negative electrode active material is zinc, bromine is used as the positive electrode active material.

(Coating of positive electrode) In order to prevent generation of dendrite which causes a short circuit at the time of charging, the surface of the positive electrode is
The cycle life of the battery can be extended by coating it with a film that allows the ions involved in the battery reaction to pass therethrough.

As the coating material, a macrocyclic compound derivative polymer, an aromatic hydrocarbon derivative polymer, a fluororesin, a silicone resin, a titanium resin, a polyolefin, or an inorganic oxide, a nitride, a carbide or a halide can be used. . Covering with a flame-retardant material or non-combustible material such as fluororesin, polyphosphazene, inorganic oxides, nitrides, carbides, and halides is effective for further improving the safety of the lithium secondary battery.

(Electrolyte) In addition to the case where the electrolyte is used as it is, a solution dissolved in a solvent or a solution in which a gelling agent such as a polymer is added and immobilized 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. The conductivity at 25 ° C. is preferably 1 × 10 ⁻³ S / cm or more, and more preferably 5 × 10 ⁻³ S / cm or more. preferable.

[When the Negative Electrode Active Material is Lithium or a Lithium Alloy] The electrolyte is an acid such as H ₂ SO ₄ , HCl or HNO ₃ , lithium ion (Li ⁺ ) and Lewis acid ion (B).
F ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , ClO ₄ ⁻ ) and mixed salts thereof are used. 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.

As the solvent of the electrolyte, acetonitrile:
CH₃CN, benzonitrile: C₆H _FiveCN, propylene
Carbonate: PC, Ethylene carbonate: EC, Di
Methylformamide: DMF, Tetrahydrofuran: T
HF, nitrobenzene: C₆H_FiveNO₂, Dichloroethane
Amine, diethoxyethane, chlorobenzene, γ-butyral
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 may be dehydrated with activated alumina, molecular sieve, phosphorus pentoxide, calcium chloride or the like, or depending on the solvent, it may be distilled in an inert gas in the presence of an alkali metal to remove impurities and dehydrate. Is good.

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 Negative Electrode Active Material is Zinc or Zinc Alloy] As the electrolyte, alkali salts such as potassium hydroxide, sodium hydroxide, lithium hydroxide and ammonium hydroxide, and salts such as zinc bromide are 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.

In the case of batteries other than alkaline batteries such as zinc bromine batteries, salts such as zinc bromide are used.

(Separator) As the separator,
It also has the role of preventing a short circuit between the negative and positive electrodes. It may also have a role of holding the electrolytic solution. Since the separator has pores through which the ions involved in the battery reaction can move and must be insoluble and stable in the electrolyte, it must be made of a non-woven fabric such as glass, polypropylene, polyethylene, fluororesin, or polyamide, or a material with a micropore structure. Is used. Further, a metal oxide film having fine pores or a resin film in which a metal oxide is composited can also be used. In particular, when a metal oxide film having a multi-layered structure is used, it is difficult for dendrites to penetrate, which is effective in preventing short circuits. When a fluororesin film which is a flame retardant material or a glass or metal oxide film which is a nonflammable material is used, the safety can be further enhanced.

(Current Collector) As the current collectors 100 and 103, fibrous, porous or mesh carbon, stainless steel, titanium, nickel, copper, platinum, gold or the like is used.

(Battery Shape and Structure) Actual battery shapes include flat type, cylindrical type, rectangular type and sheet type batteries. In the spiral structure cylindrical type, by sandwiching a separator between the negative electrode and the positive electrode, the electrode area can be increased, and a large current can be passed during charge / discharge. 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.

FIG. 2 and FIG. 3 are examples of schematic sectional views of a single-layer flat type battery and a spiral structure cylindrical battery, respectively. 2 and 3, 201 and 301 are negative electrodes coated with a film, 200 and 300 are negative electrode current collectors, 203 and 303 are positive electrode active material positive electrodes, 304 is a positive electrode current collector, and 206 and 306 are negative electrodes. Terminal (negative electrode cap), 20
7 and 307 are outer cans (positive electrode can and battery case), 208 and 308 are separators holding an electrolytic solution, 210 and 31
Reference numeral 0 is an insulating packing, and 311 is an insulating plate.

As an example of assembling the battery of FIGS. 2 and 3,
Surface-treated negative electrodes 201, 301 and positive electrodes 203, 3
Positive electrode can 20 with separators 208 and 308 sandwiched by 03
7 and 307, and after injecting an electrolytic solution, the negative electrode caps 206 and 306 and the insulating packings 210 and 310 are assembled and caulked to produce a battery.

In the case of a lithium battery, it is desirable to prepare the materials and assemble the battery in dry air from which water is sufficiently removed or in dry inert gas.

(Battery Case (Exterior Can)) As the battery case, a plastic resin material case is used in addition to a metallic outer can that also serves as an output terminal.

As the material of the positive electrode cans 207 and 307 and the negative electrode caps 206 and 306 of the actual battery, stainless steel, particularly titanium clad stainless steel, copper clad stainless steel, nickel plated steel plate and the like are used.

2 and 3, the positive electrode cans 207 and 307 also serve as the battery case and the output terminal, but as the material of the battery case, in addition to stainless steel, metal such as aluminum, plastic such as polypropylene, or metal. Alternatively, a composite material of glass fiber and plastic can be used.

(Insulating packing) Insulating packing 21
As the material of 0,310, fluororesin, polyamide resin, polysulfone resin, various rubbers, etc. can be used.

(Sealing) As a sealing method, in addition to caulking using a gasket such as an insulating packing, an adhesive,
Methods such as welding, soldering, and glass sealing tubes are used.

(Insulating Plate) As the material of the insulating plate 311 used for insulation and isolation in the battery, various organic resin materials and ceramics are used.

(Safety valve) Although not shown in FIGS. 2 and 3, as a safety measure when the internal pressure of the battery increases, a safety valve using rubber, springs, metal balls or the like is provided.

[0122]

EXAMPLES The present invention will be described in detail below based on examples. The present invention is not limited to these examples.

(Embodiment 1-1) FIG. 2 showing a simple structure and assembly.
The flat type battery having the schematic cross-sectional structure shown in Fig. 3 was assembled, and the characteristics of the secondary battery were evaluated centering on the cycle life.

First, in a dry argon gas atmosphere, hydrophobized colloidal silica manufactured by Catalysis Co., Ltd. was treated with N, N.
The solution dispersed in dimethylformamide was dehydrated on activated alumina. Next, the lithium metal foil to which the titanium mesh current collector 200 was pressed from the back surface side was dipped in the solution of colloidal silica prepared by the above method and dried at 120 ° C. to prepare a lithium electrode 201 coated with silica. .

As the positive electrode active material 203, a lithium-manganese composite oxide was prepared by heat treatment of a mixture of dehydrated electrolytic manganese dioxide, lithium carbonate and graphite. Then, after mixing the tetrafluoroethylene polymer powder, it was pressure molded into a titanium mesh.

As the electrolyte solution 208, 1M (mol / l) of hexafluoroarsenic acid lithium salt was dissolved in an equal amount mixed solvent of propylene carbonate (PC) and dimethoxyethane (DME).

As the separator 208, a polypropylene nonwoven fabric sandwiched with polypropylene micropore separators was used.

For assembly, a separator 208 is sandwiched between the negative electrode 201 and the positive electrode 203, inserted into a positive electrode can 207 made of a titanium clad stainless material, an electrolyte is injected, and then a negative electrode cap 206 made of a titanium clad stainless material is formed. A lithium secondary battery was produced by sealing with an insulating packing 210 of fluororubber.

(Comparative Example 1-1) In Example 1-1,
Except that the surface coating of metallic lithium foil is not applied,
A lithium secondary battery was produced by the same method.

Example 1-2 A battery similar to that of Example 1-1 was prepared.

Materials were prepared and assembled as in Example 1-1 in dry argon.

First, aluminum trichloride and phosphoric acid are reacted in ethyl alcohol and gradually heated to 100 ° C. to obtain glassy aluminum phosphate, and then n-
It was dispersed in hexane to prepare a film forming liquid. This film forming liquid was applied to a lithium metal foil to which a titanium mesh current collector was pressure bonded, and a film was formed at 120 ° C. After that, a lithium battery was produced in the same manner as in Example 1-1.

Example 1-3 A battery similar to that of Example 1-1 was prepared.

Materials were prepared and assembled as in Example 1-1 in dry argon.

First, acetic acid and water were added to an ethyl alcohol solution of tetrabutoxy titanium for hydrolysis,
Diethylamine was added to form colloidal titanium oxide. Then, a colloidal titanium oxide was dispersed in a polyethylene xylene solution to prepare a film-forming solution. This film-forming solution was applied to a lithium metal foil to which a stainless mesh current collector was pressure bonded, dried at 100 ° C., and then irradiated with an electron beam to crosslink polyethylene to form a film. After that,
A lithium battery was produced in the same manner as in Example 1-1.

Example 1-4 A battery similar to that of Example 1-1 was prepared.

Materials were prepared and assembled as in Example 1-1 in dry argon.

First, a solution of tetrabutoxytitanium in isopropyl alcohol was mixed with a solution of triethylaluminum in toluene, and acetic acid and water were added for hydrolysis.
Diethylamine was added to form colloidal titanium oxide-alumina. Then, colloidal titanium oxide-alumina was dispersed in a toluene solution in which an acrylic resin and an epoxy resin were dissolved to prepare a film forming solution. This film forming liquid was applied to a lithium metal foil to which a stainless mesh current collector was pressure bonded, and then a film was formed at 80 ° C. After that, a lithium battery was produced in the same manner as in Example 1-1.

Example 1-5 A battery similar to that in Example 1-1 was prepared. Material preparation and assembly was performed in dry argon as in Example 1-1.

First, acetic acid and water were added to an ethyl alcohol solution of tetraethoxylane for hydrolysis, and then diethylamine was added to form colloidal silica oxide. Then, colloidal silica was dispersed in a solution of polyethylene glycol in acetonitrile, and azobisisobutyronitrile and lithium hexafluoroarsenate salt were added to prepare a film forming solution. This film-forming solution is applied to a lithium metal foil to which a stainless mesh current collector is pressure bonded,
After drying at ℃, ultraviolet rays were irradiated to crosslink polyethylene glycol to form a film. After that, a lithium battery was produced in the same manner as in Example 1-1.

Example 1-6 A battery similar to that in Example 1-1 was prepared.

Material preparation and assembly was done in dry air.

First, felt-like carbon was dipped in a silica coating solution NT-G326 manufactured by Nissan Chemical Industries, Ltd., to which lithium tetrafluoroborate salt was added, and the temperature was raised to 110 ° C.
After curing and coating for 20 minutes at 300 ° C. for 30 minutes, the obtained silica-coated felt-like carbon is used as a cathode, and lithium metal is used as an anode, in an equal amount of a mixed solvent of propylene carbonate and dimethoxyethane that is sufficiently dehydrated in an electrolytic solution. A negative electrode 201 was produced by introducing and adhering lithium to silica-coated felt-like carbon using a solution of lithium hexafluoroacid salt dissolved in 1 M (mol / l).

After that, a lithium battery was produced in the same manner as in Example 1-1.

Example 1-7 A battery similar to that of Example 1-1 was prepared.

First, foamed nickel (Celmet) manufactured by Sumitomo Electric Industries, Ltd. was filled with a paste obtained by mixing zinc oxide powder, metallic zinc powder and water glass, and then at 80 ° C. for 20 minutes at 200 ° C.
The negative electrode 201 was formed by curing under the condition of 30 minutes.

Next, nickel hydroxide, nickel powder and cobalt powder, carboxymethyl cellulose as a binder,
A paste obtained by mixing ethylene glycol and water was filled in a Celmet manufactured by Sumitomo Electric Industries, and then dried and pressed to form a positive electrode 203.

As the separator 208, a hydrophilic microporous polypropylene film sandwiched with polyamide non-woven cloth was used. 30% by weight in the electrolyte
A potassium hydroxide solution was used. A nickel-zinc secondary battery was produced in the same manner as in Example 1-1.

(Comparative Example 1-2) In Example 1-7,
A nickel-zinc secondary battery was produced in the same manner except that the negative electrode was produced by mixing polyethylene as a binder and ethylene glycol instead of water glass.

Example 1-8 A battery having the same structure as in Example 1-1 was prepared. However, a positive electrode can having pores for taking in oxygen in the air was adopted.

As the negative electrode 201, the same one as in Example 1-7 was used.

The positive electrode 203 was formed by adding manganese dioxide to activated carbon as a positive electrode catalyst layer, and laminating a water repellent film of polytetrafluoroethylene and cellulosic diffusion paper on the positive electrode catalyst layer.

A cellophane film was used as the separator 208, and a 30 wt% potassium hydroxide solution was used as the electrolytic solution.

For assembly, the separator 208 was sandwiched between the negative electrode 201 and the positive electrode 203, and the separator 208 was inserted into a positive electrode can 207 made of a titanium clad stainless material with pores as an inlet for oxygen in the air, and the electrolyte was poured. After that, the titanium-clad negative electrode cap 206 made of a stainless steel material and an insulating packing 210 made of fluororubber were hermetically sealed to manufacture an air-zinc secondary battery.

Comparative Example 1-3 In Example 1-8,
An air-zinc secondary battery was produced in the same manner except that the negative electrode produced in Comparative Example 1-2 was used as the negative electrode.

(Evaluation of Performance of Secondary Battery) Examples 1-1 to 1
-6 and the lithium secondary battery produced in Comparative Example 1-1,
Nickel produced in Example 1-7 and Comparative Example 1-2
The performance evaluation of the zinc secondary battery, the air-zinc secondary battery produced in Example 1-8 and the comparative example 1-3 was performed a charge / discharge cycle test under the following conditions, and comparative examples 1-1, 1-2, 1-3
The performance was evaluated by comparing with the cycle life of the battery. The conditions of the cycle test were a charge / discharge of 0.2 C (0.2 times the capacity / time), a break time of 30 minutes, and a cutoff voltage of 1.0 V. Hokuto Denko HJ-101M6 was used as the battery charging / discharging device. The charge / discharge test was started from discharging, the battery capacity was the third discharge amount, and the cycle life was the number of cycles below 60% of the battery capacity.

When the cycle life of the battery of Comparative Example 1-1 was 1, the cycle life of the batteries of the respective Examples was as shown in Table 1.

As described above, Examples 1-1 to 1-6 and Comparative Example 1-
From the comparison between 1, Example 1-7 and Comparative Example 1-2, and Example 1-8 and Comparative Example 1-3, a negative electrode active material whose surface is coated with a film having an inorganic glass structure that permeates the lithium ion of the present invention. It was found that the use of the material foil for the negative electrode significantly extends the cycle life.

[0159]

[Table 1] (Example 2-1) A flat battery having a schematic cross-sectional structure shown in FIG. 2 which is easy in structure and assembly was assembled, and the characteristics of the secondary battery were evaluated centering on the cycle life.

First, in a dry argon gas atmosphere, Al
drich Chemical Company, In
c. Benzoyl peroxide was dissolved in a toluene solution of poly (2-vinylnaphthalene), and the lithium metal foil to which the titanium mesh current collector 200 was pressure-bonded was dipped from the back surface side,
Heat treated at 100 ℃ to poly (2-vinylnaphthalene)
A lithium electrode 201 coated with was prepared.

As the positive electrode active material 204, a lithium-manganese composite oxide was prepared by heat treatment of a mixture of dehydrated electrolytic manganese dioxide, lithium carbonate and graphite. Then, it was formed by mixing tetrafluoroethylene polymer powder and press-molding it into a titanium mesh.

As the electrolytic solution 208, 1M (mol / l) of hexafluoroarsenic acid lithium salt was dissolved in a mixed solvent of equal amounts of propylene carbonate (PC) and dimethoxyethane (DME).

As the separator 208, a polypropylene nonwoven fabric sandwiched with polypropylene micropore separators was used.

Assembling was performed by inserting a separator 208 between the negative electrode 201 and the positive electrode 203, inserting it into a positive electrode can 207 made of a titanium clad stainless material, and injecting an electrolytic solution.
A lithium secondary battery was produced by sealing with a negative electrode cap 206 made of a titanium clad stainless material and an insulating packing 210 made of fluororubber.

(Comparative Example 2-1) In Example 2-1,
Except that the surface coating of metallic lithium foil is not applied,
A lithium secondary battery was produced by the same method.

(Example 2-2) A battery similar to that of Example 2-1 was prepared.

The materials were prepared and assembled in the same manner as in Example 2-1 in dry-dried argon.

First, 0.03 M of azobisisobutyronitrile was added to a 5 M solution of 9-vinylanthracene in tetrahydrofuran, and polymerization was carried out at 45 ° C. to obtain a polymer solution. Next, a polymer solution was applied to a lithium metal foil to which a titanium mesh current collector was pressure-bonded, dried, and then irradiated with ultraviolet rays to produce a lithium electrode having a film of polyvinylanthracene formed thereon. Hereinafter, a lithium secondary battery was produced in the same manner as in Example 2-1.

Example 2-3 A battery similar to that of Example 2-1 was prepared.

Material preparation and assembly was performed in dry argon as in Example 2-1.

First, equimolar amounts of 9,10-anthracene dipropionic acid, ethylene glycol and a small amount of zinc acetate were added to a reaction vessel, and a dehydration condensation reaction was carried out at 200 ° C. under an argon stream, and then azobisisobutyric acid was added. Ronitrile was added, and the lithium metal foil to which the stainless steel mesh current collector was pressure-bonded was dipped, pulled up and heated to 100 ° C. to form a film on the lithium surface. Hereinafter, a lithium secondary battery was produced in the same manner as in Example 2-1.

(Example 2-4) A battery similar to that of Example 2-1 was prepared.

Materials were prepared and assembled as in Example 2-1 in dry argon.

Tantalum pentachloride was dissolved in toluene under heating at 80 ° C., a toluene solution of 5,12-bis (phenylethynyl) naphthalene was added, and the mixture was polymerized at a temperature of 80 ° C. The obtained polymer was methylated. It was washed with alcohol, dried, and dissolved again in toluene to prepare a film forming liquid. Next, the lithium metal foil to which the stainless steel mesh current collector was pressure-bonded was dipped, pulled up and dried, and then irradiated with an electron beam to be crosslinked to form a film on the lithium surface. Hereinafter, a lithium secondary battery was produced in the same manner as in Example 2-1.

(Example 2-5) In Example 2-1,
A lithium secondary battery was produced by the same operation except that benzoyl peroxide was dissolved in a toluene solution of poly (2-vinylnaphthalene) and lithium hexafluoroarsenate was added to prepare a film-forming solution. did.

Example 2-6 A battery similar to that of Example 2-1 was produced.

Preparation and assembly of materials were carried out in dry argon as in Example 2-1.

Lithium dissolved in the stainless steel container,
After the dehydrated and dried felt-like carbon was immersed and cooled to prepare a lithium-coated felt-like carbon, it was immersed in a toluene solution of poly (2-vinylnaphthalene) to which azobisisobutyronitrile was added, and was pulled up at 80 ° C. A negative electrode 201 was manufactured by drying and irradiating with ultraviolet rays to crosslink. Otherwise, a lithium secondary battery was assembled and manufactured by the same method as in Example 2-1.

(Evaluation of Performance of Lithium Secondary Battery) Example 2
-1 to 2-5 and the performance evaluation of the lithium secondary battery produced in Comparative Example 2-1 was performed under a charge / discharge cycle test under the following conditions, and the performance was compared with the cycle life of the battery of Comparative Example 2-1. evaluated. The conditions of the cycle test were a charge / discharge of 0.2 C (0.2 times the capacity / time), a break time of 30 minutes, and a cutoff voltage of 1.0 V. Hokuto Denko HJ-101M6 was used as the battery charging / discharging device. 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.

When the cycle life of the battery of Comparative Example 2-1 was set to 1, the cycle life of the batteries of the respective Examples are shown in Table 2.

As described above, Examples 2-1 to 2-5 and Comparative Example 2-1
From the comparison, it was found that the cycle life is considerably extended by using the lithium foil whose surface is coated with the polymer of the aromatic hydrocarbon compound derivative of the present invention as the negative electrode.

[0182]

[Table 2] (Example 3-1) A flat-type battery having a schematic cross-sectional structure shown in FIG. 2 which is easy in structure and assembly was assembled, and the characteristics of the secondary battery were evaluated centering on the cycle life.

First, in a dry argon gas atmosphere, the titanium metal current collector 200 was pressure-bonded to the lithium metal foil from the back side, and then the lithium metal foil was dipped in a dioxane solution of tetrabutoxytitanium and dried to form a film. A lithium electrode 201 having the above structure was prepared.

As the positive electrode active material 204, a lithium-manganese composite oxide was prepared by heat treatment of a mixture of dehydrated electrolytic manganese dioxide and lithium carbonate and graphite. Then, it was formed by mixing tetrafluoroethylene polymer powder and press-molding it into a titanium mesh.

As the electrolytic solution 208, 1M (mol / l) of hexafluoroarsenic acid lithium salt was dissolved in an equal amount mixed solvent of propylene carbonate (PC) and dimethoxyethane (DME).

As the separator 208, a polypropylene nonwoven fabric sandwiched with polypropylene micropore separators was used.

For assembly, a separator 208 is sandwiched between the negative electrode 201 and the positive electrode 203, the titanium clad is inserted into a positive electrode can 207 made of a stainless steel material, and an electrolytic solution is injected.
A lithium secondary battery was produced by sealing with a negative electrode cap 206 made of a titanium clad stainless material and an insulating packing 210 made of fluororubber.

(Comparative Example 3-1) In Example 3-1,
Except that the surface coating of metallic lithium foil is not applied,
A lithium secondary battery was produced by the same method.

(Example 3-2) A battery similar to that in Example 3-1 was produced.

Material preparation and assembly was performed in dry argon as in Example 3-1. Ube Industries, Ltd. Tyranno coat (polytitanocarbosilane) hexane solution was added to the solution of benzoyl peroxide is applied to a titanium metal current collector pressure-bonded lithium metal foil, dried, and then heated to 80 ° C. Then, heat treatment was performed at 150 ° C. to prepare a lithium electrode having a tyrano coat film formed thereon.

After that, a lithium secondary battery was produced in the same manner as in Example 3-1.

(Example 3-3) A battery similar to that in Example 3-1 was produced.

Material preparation and assembly was performed in dry argon as in Example 3-1.

First, 2,4,6-trimethyl-tris (3,3,3-trifluoropropyl) cyclotrisiloxane was heated to 76 ° C. in an argon stream and a potassium silarate catalyst was added to polymerize the polymer. Obtained. After adding benzoyl peroxide to this, a lithium metal foil with a stainless steel mesh current collector pressure-bonded was dipped and pulled up, and then heat-treated at 100 ° C. to prepare a lithium electrode having a polysiloxane film formed thereon.

Thereafter, a lithium secondary battery was produced in the same manner as in Example 3-1.

(Example 3-4) A battery similar to that in Example 3-1 was produced.

Material preparation and assembly was performed in dry argon as in Example 3-1.

First, azobisisobutyronitrile was added to tetramethyldivinyldisiloxane, the lithium metal foil to which the stainless steel mesh current collector had been pressure-bonded was dipped, and after pulling up, ultraviolet rays were radiated to produce polysiloxane. A lithium electrode having a film formed was prepared.

Thereafter, a lithium secondary battery was produced in the same manner as in Example 3-1.

(Example 3-5) A battery similar to that in Example 3-1 was produced.

Materials were prepared and assembled as in Example 3-1 in dry argon.

In Example 3-2, except that lithium hexafluoroarsenate was added to a solution prepared by adding benzoyl peroxide to a hexane solution of Tyranno Coat (polytitanocarbosilane) manufactured by Ube Industries, and immersing lithium in the solution. Manufactured a lithium secondary battery by the same operation.

(Evaluation of Performance of Lithium Secondary Battery) Example 3
-1, 3-2, 3-3, 3-4, 3-5 and Comparative Example 3
For the performance evaluation of the lithium secondary battery manufactured in No. 1, a charge / discharge cycle test was performed under the following conditions, and the performance was evaluated by comparing with the cycle life of the battery of Comparative Example 3-1. The conditions of the cycle test were a charge / discharge of 0.2 C (0.2 times the capacity / time), a break time of 30 minutes, and a cutoff voltage of 1.0 V. Hokuto Denko HJ-101M6 was used as the battery charging / discharging device. The charge / discharge test was started from discharge, the battery capacity was the third discharge amount, and the cycle life was the number of cycles below 60% of the battery capacity.

When the cycle life of the battery of Comparative Example 3-1 was set to 1, the cycle life of the batteries of the respective Examples is shown in Table 3.

The above Examples 3-1, 3-2, 3-3, 3-
From the comparison between Nos. 4 and 3-5 and Comparative Example 3-1, it was found that the cycle life was considerably extended by using the lithium foil whose surface was coated with the organometallic compound of the present invention as the negative electrode.

[0206]

[Table 3] (Example 4-1) A flat battery having a schematic cross-sectional structure shown in FIG. 2 having a simple structure and assembly was assembled, and the characteristics of the secondary battery were evaluated centering on the cycle life.

First, in a dry argon gas atmosphere, after a titanium mesh current collector 200 was pressure-bonded to the lithium metal foil from the back surface side, tetrafluoroethylene and 2,2-bistrifluoromethyl-4,5-difluoro-1, Teflon A manufactured by DUPONT, which is a copolymer of 3-dioxole
The lithium metal foil was immersed in the solution of F and dried to prepare a lithium electrode 201 coated with an amorphous fluororesin. As the positive electrode active material 204, a lithium-manganese composite oxide was prepared by heat treatment of a mixture of dehydrated electrolytic manganese dioxide, lithium carbonate, and graphite. Then, it was formed by mixing tetrafluoroethylene polymer powder and press-molding it into a titanium mesh. As the electrolytic solution 208, a solution obtained by dissolving 1M (mol / l) of lithium hexafluoroarsenate salt in an equal amount mixed solvent of propylene carbonate (PC) and dimethoxyethane (DME) 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 203, 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.

(Comparative Example 4-1) In Example 4-1,
Except that the surface coating of metallic lithium foil is not applied,
A lithium secondary battery was produced by the same method.

(Example 4-2) A battery similar to that in Example 4-1 was produced.

Materials were prepared and assembled as in Example 4-1 in dry argon. After inserting the lithium metal foil to which the titanium mesh current collector was pressure-bonded into the chamber of the sputtering apparatus, after exhausting to a vacuum degree of 5 × 10 ⁻⁶ Torr, argon gas was flown and the internal pressure was 3 × 10 ⁻³ Torr.
Under control, plasma was generated by RF discharge to target a neoflon PFA manufactured by Daikin Industries, Ltd., which is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, as a target to prepare a lithium electrode having a film formed thereon by sputtering. A lithium secondary battery was produced in the same manner as in Example 4-1.

(Example 4-3) A battery similar to that in Example 4-1 was produced.

Materials were prepared and assembled as in Example 4-1 in dry argon. A lithium metal foil with a stainless steel mesh current collector pressure-bonded was inserted into the chamber of an RF (radio wave) plasma CVD apparatus, and 2 × 10 ⁻⁶ T
After evacuation to a vacuum of orr, vinylidene fluoride was introduced into the champer, and isobutyl vinyl ether was introduced into the chamber using hydrogen gas as a carrier gas.
While controlling the internal pressure to 1 Torr, RF discharge was generated to form a plasma polymerized film on the lithium surface. A lithium secondary battery was produced in the same manner as in Example 4-1.

(Example 4-4) A battery similar to that in Example 4-1 was produced.

Materials were prepared and assembled as in Example 4-1 in dry argon. In Example 4-1, after the lithium metal foil was pressure-bonded with a titanium mesh current collector from the back surface side, isocyanate and graphite powder were added to a xylene solution of Lumiflon manufactured by Asahi Glass Co., Ltd., which is a copolymer of tetrafluoroethylene and a non-fluorinated vinyl ether. Was mixed, the lithium metal foil was dipped, and the mixture was dried at 140 ° C. for 10 minutes to prepare a lithium electrode coated with an amorphous fluororesin, and the same operation was performed to produce a lithium secondary battery.

(Example 4-5) A battery similar to that in Example 4-1 was produced.

Materials were prepared and assembled in dry argon as in Example 4-1. First, a fluororesin for coating was prepared. 2 in autoclave with stirrer
00 parts pure, 40 parts vinyl fluoride, 60 parts ethyl vinyl ether, 0.6 parts perfluorocarboxylic acid,
0.2 part of ammonium persulfate and 3 parts of water glass are added, heated to 46 ° C. and kept at 42.5 atm, and polymerization is carried out for 8 hours. The polymer obtained was washed with hot methanol and dried, then dissolved in sufficiently dehydrated tetrahydrofuran in argon gas, benzoyl peroxide was added, and then a lithium metal foil with a stainless steel mesh current collector pressure-bonded It was soaked and pulled up and heat-treated at 100 ° C. to prepare a lithium electrode coated with a fluororesin.

After that, a lithium secondary battery was produced in the same manner as in Example 4-1.

Example 4-6 A battery similar to that in Example 4-1 was produced.

First, a lithium electrode was prepared. 13.
A lithium metal foil with a stainless steel mesh current collector pressure-bonded was placed in a vacuum chamber of a parallel plate type plasma CVD apparatus connected to a high frequency power source of 56 MHz, and the parallel plate electrodes were mounted vertically, and then a vacuum of 10 ^-5 Torr was applied. Degassed to tetrafluoroethylene 10sccm, ethylene 2sccm, hydrogen 2sccm, helium 1scc
m and oxygen of 1 sccm were introduced into the vacuum chamber as a reaction chamber, and the internal pressure was maintained at 0.8 Torr. Next, 200 watts of high frequency power was supplied to the parallel plate electrodes to form a plasma polymerized film of fluororesin on the surface of the lithium metal. Using the fluororesin-coated lithium electrode prepared by the above method,
A lithium secondary battery was produced in the same manner as in Example 4-1.

(Evaluation of Performance of Lithium Secondary Battery) Example 4
-1, 4-2, 4-3, 4-4, 4-5, 4-6 and the performance evaluation of the lithium secondary battery produced in Comparative Example 4-1 was performed a charge-discharge cycle test under the following conditions, Comparative Example 4-1
The performance was evaluated by comparing with the cycle life of the battery. The conditions of the cycle test were a charge / discharge of 0.2 C (0.2 times the capacity / time), a break time of 30 minutes, and a cutoff voltage of 1.0 V. Hokuto Denko HJ-101M6 was used as the battery charging / discharging device. The charge / discharge test was started from discharge, the battery capacity was the third discharge amount, and the cycle life was the number of cycles below 60% of the battery capacity.

When the cycle life of the battery of Comparative Example 4-1 was set to 1, the cycle life of the batteries of the respective examples are shown in Table 4.

The above Examples 4-1, 4-2, 4-3, 4-
From the comparison between 4, 4-5, 4-6 and Comparative Example 4-1, it was found that the cycle life is considerably extended by using the lithium foil whose surface is coated with the fluororesin having the ether bond of the present invention as the negative electrode. It was

[0223]

[Table 4] (Example 5-1) A flat battery having a schematic cross-sectional structure shown in FIG. 2 that has a simple structure and easy assembly was assembled, and the characteristics of the secondary battery were evaluated centering on the cycle life.

First, in a dry argon gas atmosphere, after the titanium metal collector electrode 200 was pressure-bonded to the lithium metal foil from the back surface side, E. Merc
Kryptofix 222 B Polymer made by k company
The above lithium metal foil was immersed in a tetrahydrofuran solution of, dried and heat-treated at 150 ° C. to prepare a lithium electrode 201 coated with a macrocyclic compound polymer.

As the positive electrode active material, a lithium-manganese composite oxide was prepared by heat treatment of a mixture of dehydrated electrolytic manganese dioxide and lithium carbonate and graphite. Then, it was formed by mixing tetrafluoroethylene polymer powder and press-molding it on a stainless steel mesh.

As the separator 208, a polypropylene nonwoven fabric sandwiched with polypropylene micropore separators was used.

The electrolyte solution contains propylene carbonate (P
C) and dimethoxyethane (DME) in an equal amount mixed solvent,
A solution of lithium hexafluoroarsenate salt dissolved in 1 M (mol / l) was used as a stool.

Assembling is performed by inserting a separator 208 between the negative electrode 201 and the positive electrode 203, inserting it into a positive electrode can 207 made of a titanium clad stainless material, and injecting an electrolytic solution.
A lithium secondary battery was produced by sealing with a negative electrode cap 206 made of a titanium clad stainless material and an insulating packing 210 made of fluororubber.

(Comparative Example 5-1) In Example 5-1,
Except that the surface coating of metallic lithium foil is not applied,
A lithium secondary battery was produced by the same method.

Example 5-2 A battery similar to that in Example 5-1 was prepared.

Materials were prepared and assembled as in Example 5-1 in dry argon. The lithium metal foil to which the titanium mesh electrode is pressure-bonded is dissolved in an acetonitrile solution in which 0.1 M of benzo-15-crown-5 as a monomer and 0.2 M of tetrabutylammonium tetrafluoroborate as an electrolyte are dissolved, and a platinum electrode is used as a cathode electrode. Then, a voltage of 3 V was applied to prepare a lithium electrode on which a macrocyclic compound polymer film was formed by electrolytic polymerization.

A lithium secondary battery was made in the same manner as in Example 5-1.

(Example 5-3) A battery similar to that in Example 5-1 was produced.

Materials were prepared and assembled as in Example 5-1 in dry argon. (+)-18-crown-6
-After mixing tetracarboxylic acid (0.4 mol), 1,4-butanediol (0.8 mol), titanic acid tetra-n-butyl ester (0.08 g) and butylhydroxytin oxide (0.03 g), Distillation was carried out for 60 minutes while maintaining the temperature at 220 ° C. to remove products such as water. Next, this reaction product and titanic acid tetra-n-butyl ester (0.02 g) were placed in an autoclave, decompressed, and heated at 250 ° C. for 22 hours to obtain a polymer.

Tolylene diisocyanate was added to the polymer obtained in the above reaction, and the lithium metal foil to which a titanium mesh electrode had been pressure-bonded was dipped in the polymer and then pulled up at 80 ° C.
Then, the surface of the lithium foil was coated with the macrocyclic compound polymer.

A lithium secondary battery was made in the same manner as in Example 5-1.

Example 5-4 A battery similar to that in Example 5-1 was prepared.

Materials were prepared and assembled as in Example 5-1 in dry argon. Lithium metal to which a titanium mesh electrode was pressure-bonded, polystyrene to which azobisisobutyronitrile and lithium hexafluoroarsenate were added, and 3,3 '
The surface of the lithium metal foil was coated by immersing it in a toluene solution of dibenzyl-1,4,8,11-tetraoxacyclotetradecane, pulling it up, drying it, and then irradiating it with ultraviolet rays to crosslink it.

A lithium secondary battery was made in the same manner as in Example 5-1.

Example 5-5 A battery similar to that in Example 5-1 was prepared.

Materials were prepared and assembled as in Example 5-1 in dry argon. Sufficient degassed and dehydrated naphthalene in tetrahydrofuran solution, styrene and 4,
7,13,16,21,24-hexaoxa-1,10
-Diazabicyclo [8.8.8] hexacosane is dissolved, graphite powder is mixed, lithium metal pressed with titanium mesh electrode is soaked to cause polymerization reaction, dried and cured, and lithium surface is macrocyclic compound polymer. Coated.

A lithium secondary battery was made in the same manner as in Example 5-1.

(Experimental Example 5-6) A battery similar to that of Experimental Example 5-1 was prepared.

Material preparation and assembly was done in dry air.

After dehydrating and drying a porous nickel sheet manufactured by Osaka Gas Co., Ltd., an anode was used, a platinum electrode was used as a cathode, and 0.1 M of benzo-18-crown-6 and tetrabutylammonium tetrafluoroborate salt were added to 0.2 M. Electrolytic polymerization was performed with the dissolved acetonitrile solution to prepare a porous nickel sheet coated with a crown ether polymer. Then, 1 M of tetrafluoroboric acid lithium salt dissolved in an equal amount mixed solvent of propylene carbonate and dimethoxyethane was used as an electrolytic solution, and the obtained coated porous nickel sheet was used as a cathode and lithium metal was used as an anode. A negative electrode 203 was formed by inserting and adhering lithium between the coating of the high quality nickel sheet and nickel.

Thereafter, a lithium secondary battery was produced in the same manner as in Example 5-1.

(Example 5-7) A nickel zinc battery having the same structure as that of Example 5-1 was produced.

First, polyvinyl alcohol, zinc phthalocyanine, zinc oxide powder, zinc powder, formaldehyde, formic acid, and water were mixed to prepare a paste, and this paste was applied to a nickel mesh and then reacted by heating to produce a negative electrode 2.
01 was produced.

Next, nickel hydroxide, nickel powder and cobalt powder, carboxymethyl cellulose as a binder,
A paste obtained by mixing ethylene glycol and water was filled in foamed nickel (Celmet) manufactured by Sumitomo Electric Co., Ltd., and dried and pressed to form a positive electrode 203.

As the separator 208, a hydrophilic microporous polyamide film sandwiched between polyamide nonwoven fabrics was used. A 30 wt% potassium hydroxide solution was used as the electrolytic solution. A nickel-zinc secondary battery was prepared in the same manner as in Example 5-1.

(Comparative Example 5-2) In Example 5-7,
A nickel-zinc secondary battery was produced in the same procedure except that a paste obtained by mixing zinc oxide powder, zinc powder, polyvinyl alcohol, and ethylene glycol was applied onto a nickel mesh and dried to form the negative electrode 201.

Example 5-8 A battery having the same structure as that of Example 5-1 was produced. However, a positive electrode can having pores for taking in oxygen in the air was used.

As the negative electrode 201, a paste obtained by mixing zinc oxide powder, zinc powder, polyacrylamide, water, formaldehyde, lithium hydroxide, and zinc phthalocyanine was applied on a nickel mesh and then dried by heating.

The positive electrode 203 was formed by adding manganese dioxide to activated carbon as a positive electrode catalyst layer, and laminating a water repellent film of polytetrafluoroethylene and a diffusion paper made of cellulose on the positive electrode catalyst layer. As the separator 209,
A 30% by weight potassium hydroxide solution was used as the cellophane film and the electrolytic solution.

For assembly, a separator 208 was sandwiched between the negative electrode 201 and the positive electrode 203, and the separator 208 was inserted into a positive electrode can 207 made of a titanium clad stainless material with pores as an oxygen intake in the air, and the electrolyte was poured. After that, a titanium-clad negative electrode cap 206 made of a stainless material and an insulating packing 210 made of fluororubber were hermetically sealed to produce an air-zinc secondary battery.

(Comparative Example 5-3) In Example 5-8,
An air-zinc secondary battery was produced in the same manner except that the negative electrode produced in Comparative Example 5-2 was used as the negative electrode.

(Evaluation of Performance of Lithium Secondary Battery) Example 5
-1, 5-2, 5-3, 5-4, 5-5 and Comparative Example 5
For the performance evaluation of the lithium secondary battery manufactured in No. 1, a charge / discharge cycle test was performed under the following conditions, and the performance was evaluated by comparing with the cycle life of the battery of Comparative Example 1. The conditions of the cycle test are: 0.2 C (0.2 times the capacity / hour of current) charge / discharge, 30 minutes break time, 2.0 V cut-off voltage, 1
The depth of discharge was 00%. The battery charging / discharging device is HJ. 101M6 was used. The charge / discharge test starts from the discharge, and the battery capacity is the third discharge amount,
The cycle life was defined as the number of cycles when the battery capacity was less than 60%.

When the cycle life of the battery of Comparative Example 5-1 was set to 1, the cycle life of the batteries of Examples was as shown in Table 5.

The above Examples 5-1, 5-2, 5-3, 5-
4, 5-5, 5-6 and Comparative Example 5-1 and Example 5-7 and Comparative Example 5-2, and Example 5-8 and Comparative Example 5-3, the macrocyclic compound of the present invention It was found that the cycle life is considerably extended by using lithium or zinc coated on the surface for the negative electrode.

[0260]

[Table 5]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270] to a lithium secondary battery of (Example 6-1) flat type of assembly easy Figure 2 configuration. The materials were prepared and assembled in dry argon.

First, in a dry argon gas atmosphere, a leaded titanium mesh current collector 200 was pressure-bonded to a lithium metal foil from the back side, and acetyl cellulose obtained by adding azobisisobutyronitrile and lithium tetrafluoroborate lithium salt was added. After immersing in a nitromethane solution of 110 ° C., it was dried at 110 ° C. and irradiated with ultraviolet rays to form a film to prepare a lithium negative electrode 201.

As the positive electrode active material, electrolytic manganese dioxide and lithium carbonate were mixed in a ratio of 1: 0.4, and then 80
A lithium-manganese oxide was prepared by heating at 0 ° C.
The prepared lithium-manganese oxide was mixed with Ketjen black and Nippon Oil &Fat's powder fluororesin coating material Super Konak, and then pressure-molded on a nickel mesh and heat-treated at 170 ° C. to form a positive electrode 203.

As the separator 208, a sandwich of a porous layered alumina film, a polypropylene non-woven fabric and a polypropylene fine pore separator was used.

The electrolytic solution contains propylene carbonate (P
C) and dimethoxyethane (DME) in an equal amount mixed solvent,
A solution obtained by dissolving 1M (mol / l) of lithium tetrafluoroborate salt was used.

For assembly, the negative electrode 201, the positive electrode 203, and the separator 208 are sandwiched, the titanium clad stainless steel positive electrode can 207 is inserted, the electrolytic solution is injected, and then the titanium clad stainless steel negative electrode cap 206 and fluororubber. A lithium secondary battery was manufactured by hermetically sealing with an insulating packing 210.

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284] (Example 6 - 2) A battery was produced in the same manner as in Example 6-1 Fig.

[0285] Preparation and assembly of the materials was carried out in Example 6-1 Similarly dry argon.

First, a lithium foil, to which a nickel mesh current collector 200 was pressure-bonded, was attached to a sputtering apparatus with a lithium surface coating, and degassed to a vacuum degree of 1.5 × 10 ⁻⁴ Pascal, followed by argon gas at 5 sccm. Is introduced, the internal pressure of the film forming chamber is maintained at 6 × 10 ⁻¹ Pascal, and polyether sulfone is sputtered on the target.
A lithium negative electrode 201 coated with chitosan having a thickness of 500 Å was obtained.

As the positive electrode active material, electrolytic manganese dioxide is used.
And lithium carbonate at a ratio of 1: 0.4, then 80
Lithium-manganese oxide was prepared by heating at 0 ° C.
The lithium-manganese oxide prepared was used to
After mixing the powder with tetrafluoroethylene polymer powder,
Pressure molding into nickel mesh and heat treatment at 250 ℃
The positive electrode 203 was formed. The separator 208 is a polypro
Pyrene non-woven fabric and polypropylene micropore separator
I used the one that was ditched. Use propylene carbonate as the electrolyte.
Carbonate (PC) solvent, lithium tetrafluoroborate salt
Was dissolved in 1M (mol / l). After that,
A lithium secondary battery was produced in the same manner as in Example 6-1.
did.

[0288] (Example 6 - 3) Example 6 - In 2, the nickel mesh current collector 200
Attach the lithium foil with pressure bonded to the sputter device, and
After degassing to a vacuum degree of × 10 ^-4 Pascal under a reduced pressure, argon gas was introduced at a flow rate of 5 sccm, the internal pressure of the film forming champer was maintained at 6 × 10 ^-1 Pascal, and chitosan was sputtered on the target to a thickness of 1000. A lithium negative electrode 201 coated with Angstrom chitosan was prepared.

[0289] After, to prepare a lithium secondary battery in the same manner as in Example 6-2.

[0290] (Example 6 - 4) was prepared flat type nickel-zinc secondary battery schematic cross-sectional structure structure and assembly is illustrated in simplified FIG.

First, the negative electrode was formed by press-bonding a mixture of zinc powder and zinc oxide powder with tetrafluoroethylene polymer powder as a binder on both surfaces of a copper punching metal. This negative electrode was dipped in an acetone-ethyl alcohol solution of acetylcellulose to which azobisisobutyronitrile was added, dried, heat-treated at 110 ° C., and irradiated with ultraviolet rays to form a film, thereby preparing a zinc negative electrode 201.

The positive electrode 203 was prepared by impregnating a sintered nickel electrode plate with nickel hydroxide and then coating it with a film of acetyl cellulose in the same manner as the negative electrode.

As the separator 208, a sandwich of hydrophilic non-woven fabric and microporous nylon film was used.

[0294] The electrolytic solution was 30 w to which lithium hydroxide was added.
A t% aqueous potassium hydroxide solution was used.

[0295] Assembly of the battery was carried out in the same manner as in Example 6-1.

[0296] (Example 6 - 5) to produce structural and nickel-zinc secondary battery schematic cross-sectional structure assembly shown in simplified FIG.

[0297] Example 6 - In 4, the molded zinc anode mounted in the sputtering apparatus, after deaeration under reduced pressure to a vacuum degree of 1.5 × 10 ^-4 Pa, argon gas flow rate introduced in the 5 sccm, the film formation The internal pressure of the champer was maintained at 6 × 10 ⁻¹ Pascal, and collagen was sputtered on the target to obtain a zinc negative electrode coated with collagen having a thickness of 1000 Å.

The positive electrode 203 was prepared by impregnating a sintered nickel electrode plate with nickel hydroxide.

[0299] After the Example 6 - was produced nickel-zinc secondary battery in the same manner as 4.

In order to compare and evaluate the performance of the batteries produced in the above examples, the batteries of the following comparative examples were produced.

First, in a dry argon gas atmosphere,
Um metal foil with lead from the back side titanium mesh current collector
The body 200 was pressure-bonded to prepare a lithium negative electrode 201.
As the positive electrode active material, electrolytic dioxide was used as in Example 6-2.
Manganese and lithium carbonate were mixed in a ratio of 1: 0.4
Then, heat at 800 ° C to prepare lithium manganese oxide.
Made To the prepared lithium-manganese oxide,
Black and tetrafluoroethylene polymer powder mixed
After that, it is pressed into a nickel mesh and heat treated at 250 ° C.
Then, the positive electrode 203 was formed. The separator 208 is
Polypropylene nonwoven fabric and polypropylene micropore separation
A sandwich of seaweed was used. The electrolyte should be a professional
Pyrocarbonate (PC) solvent, tetrafluoroboric acid
Use a solution containing 1M (mol / l) of thium salt.
It was After that, by the same operation as in Example 6-1, lithium secondary
A battery was made.

[0302] (Comparative Example 6-2) Example 6 - In 5, except that not subjected to surface coating treatment of the zinc anode, to produce a nickel-zinc secondary battery in the same way.

(Evaluation of Performance of Secondary Battery) A lithium secondary battery and a nickel-zinc secondary battery produced in Examples and Comparative Examples were subjected to a performance evaluation under the following conditions to evaluate the performance.
The performance was evaluated in comparison with the battery of the comparative example.

The condition of the cycle test is 0.2 C (capacity /
Charge / discharge of 0.2 times the time), break time of 30 minutes,
The cutoff voltage was 1.0 V. Hokuto Denko HJ-101M6 was used for the battery charging / discharging device. In addition,
The charge / discharge test was started from 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 6 summarizes the evaluation results of the cycle life performance of the secondary batteries prepared in the examples of the present invention and the secondary batteries prepared in the comparative examples, with the performance of the comparative battery as 1.0. Indicated.

[0306]

[Table 6] Evaluation of the results of Table 6, Examples 6 - 16 - 3 and Comparative Example 6
Comparison of -1, Example 6 - 4 and Example 6 - 5 and Comparative Example 6
From the comparison of -2, it was found that the cycle life was extended by adopting the secondary battery having the constitution of the present invention.

[0307]

According to the present invention, by suppressing the growth of lithium or zinc dendrites during charging, it is possible to prevent a short circuit between the negative electrode and the positive electrode, and to have a long charge / discharge cycle life. It is possible to manufacture nickel-zinc secondary batteries, zinc-air secondary batteries, zinc-bromine secondary batteries, and the like. Furthermore, since lithium metal can be used for the negative electrode, 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.

FIG. 4 is an example of a schematic view showing a partial structure of a negative electrode formed by coating with a film permeable to ions involved in the battery reaction of the present invention.

[Explanation of symbols]

100, 200, 300, 400 Negative electrode current collector, 101, 401 negative electrode active material, 102, 402 ion-permeable film, 201,301 coated negative electrode, 103, 304 positive electrode current collector, 104, 203, 303 positive electrode, 105 electrolyte, 106, 206, 306 negative electrode terminal, 107, 207, 307 positive electrode terminal, 108 separator, 208,308 separator holding electrolyte, 109 battery case, 210,310 insulation packing, 311 Insulation plate.

─────────────────────────────────────────────────── ─── Continuation of front page (31) Priority claim number Japanese Patent Application No. 4-245324 (32) Priority date September 14, 1992 (September 14, 1992) (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-245325 (32) Priority date September 14, 1992 (September 14, 1992) (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-245326 (32) Priority date September 14, 1992 (September 14, 1992) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-13721 ( 32) Priority date January 29, 1993 (January 29, 1993) (33) Priority claiming country Japan (JP) (56) Reference JP-A-2-215043 (JP, A) JP-A-59- 873 (JP, A) JP 4-248276 (JP, A) JP 59-173977 (JP, A) JP 6-60871 (JP, A) JP 4-28173 (JP, A) JP-A-58-163187 (JP, A) JP-A-58-111276 (JP, A) JP-A-58-163188 (JP, A) JP-A-63-289759 (JP, A) JP-A-4-22072 ( JP, A) JP 4-28172 (JP, A) JP 2-284358 (JP, A) JP 57-163963 (JP, A) JP 2-215048 (JP, A) JP 47-15648 (JP, A) JP-B 47-25207 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01M 4/02-4/04 H01M 4/36-4 / 62 H01M 10/36-10/40

Claims (9)

(57) [Claims] 1. A secondary battery comprising at least a negative electrode made of lithium or a lithium alloy , a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case. The structure is permeable to ions involved in battery reaction, and is coated with a stable film that does not react or dissolve in an electrolyte or an electrolytic solution, and the film is naphthalene, anthracene,
A secondary battery comprising a polymer film of a derivative of one or more aromatic hydrocarbon compounds selected from phenanthrene, naphthacene, pyrene, triphenylene, perylene, picene, benzopyrene, coronene, and ovalen. 2. A secondary battery comprising at least a negative electrode made of lithium or a lithium alloy , a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case. It has a structure that allows the ions involved in the battery reaction to permeate, and is covered with a film that is stable without reacting or dissolving in the electrolyte or electrolytic solution, and the film has pores with a radius greater than the radius of the ions participating in the battery reaction. A secondary battery comprising a polymer film of a macrocyclic compound derivative having: 3. A secondary battery comprising at least a negative electrode made of lithium or a lithium alloy, a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case. A structure capable of transmitting ions involved in a battery reaction, coated with a film that does not react or dissolve in an electrolyte or an electrolytic solution and is stable, and the film is a fluororesin film having an ether bond. Secondary battery. 4. A secondary battery comprising at least a negative electrode made of lithium or a lithium alloy, a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case. It has a structure capable of transmitting ions involved in a battery reaction, and is coated with a film that does not react or dissolve in an electrolyte or an electrolytic solution and is stable, and the film is titanium, aluminum, silicon, zirconium, tantalum, magnesium, indium, One or more organometallic compounds selected from the group consisting of metal alkoxides, alkyl metal compounds, acetylacetone metal salts, naphthenic acid metal salts, and octylic acid metal salts, of metals selected from tin, molybdenum, tungsten, and germanium. Characterized by a film formed by reacting lithium And a secondary battery. 5. A secondary battery comprising at least a negative electrode made of lithium or a lithium alloy, a separator, a positive electrode made of a positive electrode active material, an electrolyte or an electrolyte solution (electrolyte solution), a current collector, and a battery case. in the structure that can penetrate the ion involved in the cell reaction, Yes coated with a stable coating does not react or dissolve in the electrolyte or electrolyte solution, is said coating Gaga lath metal oxide,
A secondary battery in which the film is combined with an organic polymer . Wherein said coating is a secondary battery of any one of claims 1 to 5, characterized in that it has a molecular structure or pore with a large gap than ions involved in the battery reaction . 7. The coating, to claim 1, characterized in that an ion involved in the cell reaction is transmitted has a molecular structure or pore does not transmit a negative electrode active material deposited on the negative electrode during charging The secondary battery according to any one of 6 above. 8. The coating, a secondary battery of any one of claims 1 to 5, characterized in that a crosslinked polymer structure. 9. A said film in the secondary battery of any one of claims 1 to 5, characterized in that by dispersing conductive powder.