JP2943127B2 - 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 dendrite for a lithium secondary battery using lithium metal or a lithium alloy as a negative electrode active material, or an alkaline secondary battery or a zinc bromine secondary battery using zinc or a zinc alloy as a negative electrode active material. inhibit the growth, but about the secondary <br/> batteries having improved charge-discharge cycle characteristics.

[0002]

2. Description of the Related Art In recent years, devices have become more portable and cordless, and a battery as a power source for driving the device has been required to be small, light, and have a high energy density. Lithium secondary batteries, nickel zinc secondary batteries, air zinc secondary batteries, and the like are expected as batteries that meet this demand. However, these secondary batteries have a disadvantage that the charge / discharge cycle life is short. The following can be considered as the reason for this.

[0003] During charging, lithium or zinc is deposited on the surface of the negative electrode. At this time, the current density locally increases on the negative electrode surface depending on the surface state,
At this location, lithium or zinc is selectively deposited.
These metals are grown resinous with progress of charge-discharge cycles (dendrite) through the separators by reaching the positive electrode, in order to short-circuit.

[0004] The reaction mechanism of dendrite is considered as follows.

[0005] Since lithium or zinc precipitated during charging has high reactivity, it reacts with the electrolytic solution or moisture in the electrolytic solution to form an insulator film. Since the insulation film has a high resistance, the current density in the film portion is increased at the time of the next charge, and the dendrite is easily grown.

[0006]

As described above, in a secondary battery using lithium or zinc as a negative electrode active material, when charge and discharge are repeated, dendrites grow on the surface of the negative electrode, and the dendrites penetrate the separator. However, there has been a problem that the contact with the positive electrode by contact with the positive electrode or the contact with the positive electrode by dropping from the negative electrode surface causes a short circuit and a short charge / discharge cycle life, and has not been put to practical use.

An object of the present invention is to provide a secondary battery which is safe and has an excellent charge / discharge cycle life by solving such problems.

[0008]

In order to solve these problems, a first secondary battery according to the present invention comprises at least a negative electrode made of lithium or a lithium alloy, an electrolyte, a separator, and a positive electrode. Ni, Ti, P between the negative electrode and the separator.
t, Al, Pb, Cr, Cu, V, Mo, W, Fe, C
o, Zn, a metal conductive layer made of a material selected from the group consisting of Mg, diamond, Si, nickel oxide, copper oxide, titanium oxide, manganese oxide, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide, vanadium oxide At least one selected from the group consisting of
At least one of a semiconductor layer made of the above material and an insulator layer made of at least one material selected from the group consisting of lithium fluoride, magnesium fluoride, nitride, carbide, and fluororesin. It is characterized by having. As such a metal conductor layer, a semiconductor layer, and an insulator layer, a layer through which at least lithium ions can pass is used. Further, the second secondary battery according to the present invention is a negative electrode made of zinc or a zinc alloy, an electrolyte, a separator, and a secondary battery at least composed of a positive electrode, between the negative electrode and the separator, diamond, A semiconductor layer made of at least one material selected from the group consisting of Si, nickel oxide, copper oxide, manganese oxide, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide, and vanadium oxide; At least one insulating layer made of at least one material selected from the group consisting of lithium oxide, magnesium fluoride, nitride, carbide, and fluororesin is provided. For such a semiconductor layer and an insulator layer, a layer having microscopic pores through which hydroxyl ions can pass is used.

[0009] pores transmitted through the ion are those derived from the molecular structure of the material, or may be due to the manufacturing method. One example of easily forming pores is a method in which an electrolyte is put into a layer at the time of forming the above-mentioned layer and the battery is made, and then the electrolyte is eluted to form micropores. There is also a method of adding a foaming material at the time of forming the above-mentioned layer, and then forming a micropore by heat treatment or the like.

On the other hand, according to the present invention, as a third secondary battery, in a secondary battery comprising at least a negative electrode, an electrolyte, a separator, and a positive electrode, a conductive layer is provided between the negative electrode and the separator. Alternatively, a laminated film of a semiconductor layer and an insulator layer is provided , and the conductor layer is made of carbon, Ni, Ti, Pt, A
1, Pb, Cr, Cu, V, Mo, W, Fe, Co, Z
at least one selected from the group consisting of n and Mg
A metal layer containing the material of
, Si, nickel oxide, copper oxide, manganese oxide, oxidation
Titanium, zinc oxide, zirconium oxide, tungsten oxide
, Molybdenum oxide, and vanadium oxide
A secondary battery is provided , which is a layer containing at least one or more materials selected . In addition, the present invention
According to the fourth secondary battery, in a secondary battery comprising at least a negative electrode, an electrolyte, a separator, and a positive electrode, between the negative electrode and the separator, a conductor, a semiconductor, and an insulator are selected. A secondary battery provided with a composite layer of two or more materials is provided.

[0011] Figure 1 is a secondary battery of the present invention, between the negative electrode and the separator, the conductive layer or a semiconductor layer, provided with an insulating layer, an example of a product layer pattern. In Figure 1, 001 is a negative electrode, 002 dendrites, 003 conductive layer or a semiconductor layer, 004 separators, 005
Denotes an insulator layer, 006 denotes an electrolytic solution, and 007 denotes a positive electrode.

In particular, FIG. 1 is an example of a schematic diagram showing the effect of the present invention when an insulator layer and a conductor layer capable of transmitting lithium ions are laminated on the surface of a lithium negative electrode.

At the time of charging, lithium (or zinc) is deposited on the negative electrode 001. At this time, a portion having a high current density is locally formed on the negative electrode 001 due to surface irregularities and the thickness of the insulating film.
Is selectively deposited, so that dendrite 002 grows. The dendrite 002 reaches the conductor layer 003 as the charge / discharge cycle progresses. Dendrite 0
02 and the conductive layer 003 are short-circuited, the current density of the negative electrode decreases during charging, and the dendrite 002 cannot grow further, so that the dendrite 002 passes through the separator 004 and reaches the positive electrode 007. Can be suppressed.

An ion-permeable insulator layer 0 is formed on the negative electrode.
By coating with 05, active lithium (or zinc) deposited during charging becomes less likely to react with the electrolytic solution, and the formation of the above-mentioned insulator film can be suppressed.

[0015] FIG. 2 (a) ~ (h), the negative electrode and the separators
In this case, one or more layers selected from an ion-permeable conductor, a semiconductor, and an insulator are provided. The reference numerals in FIG. 2 are the same as those in FIG. Note that the present invention is not limited to the example of FIG. 2 (b), (d), (e),
In (f), the layer 003 or the layer 005 is defined in the fourth invention.
Selected from conductors or semiconductors as described above and insulators
Or more (same material, for example, two or more conductive materials
May be a layer of a composite of the above materials.

[0016] In the first secondary battery of the present invention, as the conductive layer provided between the negative electrode and the separator, N i, T
i, Pt, Al, Pb, Cr, Cu, V, Mo, W, F
e, Co, Zn, Mg, etc., and carbon, Ni, Ti, etc. are desirable.

[0017] Even when the conductor layer is replaced with a semiconductor layer, the same effect as the above-described conductor layer is obtained. When using a semiconductor layer, the current density during dendrite growth is larger than the conductor layer, and base specific conductivity conductor layer is lowered,
There is an advantage that conduction with the positive electrode is difficult.

As the semiconductor layer, diamond, Si,
Nickel oxide, copper oxide, manganese oxide, titanium oxide, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide, vanadium oxide, or the like is used. Third and third
In the secondary battery of No. 4, the metal listed above as a conductor
The element, as well as carbon, can be employed. These secondary power
As the semiconductor of the pond, it is possible to use the semiconductor material described above.
it can. As a material for the semiconductor layer in the second secondary battery
Are diamond, Si, nickel oxide, copper oxide, oxide
Manganese, zinc oxide, zirconium oxide, tungsten oxide
Ten, molybdenum oxide, and vanadium oxide are used.

In the case where an insulator layer is used in the first and second secondary batteries of the present invention, halides such as lithium fluoride and magnesium fluoride, nitrides such as silicon nitride, and silicon carbide etc. Use carbide . Third and fourth rechargeable batteries
Now, the insulator material in the insulator layer or composite layer
And in addition to the above materials, polyethylene , polypropylene
And the like .

Hereinafter, a conductor layer, a semiconductor layer, an insulator layer,
The production method and raw materials of the composite layer are shown. However, the material of the negative electrode
When lithium metal is used, attention should be paid to the following two points.

If water remains in the raw material, water reacts with lithium metal, and this water must be removed in advance. As a method for removal, dehydration using activated alumina, molecular sieve, phosphorus pentoxide, calcium chloride, or the like, or when using a solvent, distillation in an inert atmosphere in the presence of an alkali metal to remove impurities and dehydration. Sometimes it is better to do it.

The temperature at which the above layer is coated on the surface of the negative electrode by the CVD method or the like must be lower than the temperature at which the negative electrode active material is melted.

[0023] Representative examples of the conductor layer conductor layer, carbon,
Alternatively, a method for producing a metal such as Ni and Ti will be described below.

[Carbon] The crystal form of carbon may be crystalline, amorphous or a mixed crystal of crystalline and amorphous. As the carbon to be coated, carbon powder, carbon fiber, carbon paper obtained by paper-making carbon fiber, or the like can be used.

As a method for coating the carbon on the negative electrode surface, there is the following method.

(1) A liquid obtained by uniformly dispersing carbon powder or carbon fiber in an organic solvent such as toluene or xylene under an inert atmosphere of Ar is applied to the surface of the negative electrode by a method such as spraying, screen printing, a coater, or dipping and drying. Then, crimp.

(2) After laminating carbon paper on the surface of the negative electrode, pressure bonding is performed.

(3) Using a carbon as a target, carbon is coated on the negative electrode surface by a vacuum deposition method such as sputtering.

(4) Carbon is coated on the negative electrode surface by a CVD (Chemicai Vapor Deposition) method in the presence of the organic compound serving as the carbon raw material.

In the coating method by coating, the negative electrode and the carbon powder or carbon fiber are pressure-bonded to increase the adhesion.
As the pressure bonding method, there are a pressure press, a roller press and the like. It is necessary to perform the pressure bonding at a temperature lower than the temperature at which the negative electrode active material melts. The thickness to cover is 10
The range is preferably from 100 to 100 μm, and more preferably 50 μm or less in order to suppress a decrease in the active material content of the negative electrode.

[0031] As compression method after laminating the carbon paper, pressing the press, other such roller press, or wound positive and negative electrode plates via a separator <br/> over data, when stacking There is a method in which carbon paper is sandwiched and pressed by a winding pressure or a laminating pressure. Particularly the latter method is not needed a step of crimping the carbon page path over to advance the negative electrode, there is an advantage that compression of the carbon paper in winding or laminating process can be. Those in the range of 150~300μm A thickness of the carbon page path over is preferably used and pressed to 75-150.

Next, in the coating method by the sputtering method, carbon is coated on the negative electrode surface by performing discharge by direct current or high frequency by using carbon as a target in an inert atmosphere of Ar.

[0033] As raw material with a coating of a carbon by a CVD method, a saturated hydrocarbon such as methane, acetylene, ethylene and <br/> pro pin Ren, unsaturated hydrocarbons such as benzene, carbon monoxide, alcohols, acetone and the like . Examples of the excitation method include plasma, laser, and filament heating.
The thickness of the carbon coated by these methods is preferably 1 μm or less, more preferably 100 nm or less.

In the case of plasma CVD, a high frequency or direct current (DC) can be used as a power source for causing glow discharge.
As a high frequency, a radio frequency (RF), a VHF, a microwave or the like is generally used. 13.56 MHz is used as a typical wavelength of radio waves, and 2.45 GHz is used as a typical wavelength of microwaves.

In the case of the laser CVD, an ArF excimer laser over or infrared of CO ₂ ultraviolet as the laser light source.

[Metal such as Ni and Ti] As a method for coating the surface of the negative electrode with a metal such as Ni and Ti, a sputtering method, a CVD method, an electron beam evaporation method, a cluster ion beam evaporation method, or the like is used in the same manner as carbon. Used.

As targets of the sputtering method,
Ni, Ti or the like is used. When a composite film is formed, two or more types of targets are prepared and sputtering is performed simultaneously or one by one. As a method of sputtering,
This is performed in an Ar inert atmosphere in the same manner as the above-mentioned carbon.

In the coating by the CVD method, the following materials are used as raw materials.

As a raw material of Ni or Ti, a solution in which an organic metal such as an acetylacetone complex of nickel (or titanium) is dissolved in a non-aqueous solvent such as hexane, acetone or toluene, or a halide such as nickel chloride (or titanium) is used. Is dissolved in a non-aqueous solvent such as ethanol, and the like is bubbled with a carrier gas (hydrogen or the like).
It is introduced into a VD reaction chamber, where a CVD reaction occurs to perform coating.

When forming a composite film of Ni and carbon, a hydrocarbon such as methane is used together with a metal compound.

Semiconductor Layer In the secondary battery of the present invention, the semiconductor layer may be, for example, diamond, Si, nickel oxide, copper oxide, cobalt oxide, or the like.
Manganese oxide, titanium oxide, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide, vanadium oxide, or the like is selected and used. Examples of the coating method include sputtering, electron beam evaporation, plasma CVD, and light CV.
D method, laser CVD method, thermal CVD method, or the like is used.

[Si] As a sputtering target, Si or the like is used.

In the CVD method, SiH is used as a raw material for Si.
_4, Si ₂ H or hydride-based gas such as _6, SiHF _3, SiH
₂ F _2, SiH ₃ or fluorine-based gas such as F, SiHCl _3, S
A chloride gas such as iH ₂ Cl ₂ or SiHCl ₃ is used.
In the above-mentioned raw materials, when a liquid is used, it is heated to be a vapor, or is introduced by bubbling with a carrier gas. When forming a composite film of Si and a carbon material, a hydrocarbon such as methane is used together with the above gas. Further, compounds such as carbon and P and B may be appropriately mixed.

[Oxides of Nickel Oxide, Titanium Oxide, etc.] As a method of producing oxides of nickel oxide, titanium oxide, etc., a sol-gel in which an alkoxide of nickel or titanium, an organic metal or the like is dissolved in alcohol and then hydrolyzed. There is a method in which oxygen gas is introduced into a reaction chamber by using a method, anodization in which electrolysis is performed in a solution in which a salt of nickel or titanium is dissolved, or a CVD method or an electron beam evaporation method.

Insulator Layer In the secondary battery of the present invention, the insulator may be a halide,
A nitride, carbide, or a resin such as polyethylene (PE), polypropylene (PP), or fluororesin is selected and used as a coating method, such as a sputtering method, a plasma CVD method, or a coating method. .

Further, as the resin other than the above, an organic polymer monomer may be vaporized and polymerized by plasma, an organic polymer sputtered, or an organic polymer film may be used. However, it is necessary to have pores through which ions can pass and not to react with the electrolytic solution.

[Nitride] In the sputtering method, a nitride such as silicon nitride and lithium nitride is used as a target.
Using i or Li as a target, sputtering is performed in a nitrogen gas or ammonia as a reaction gas.

In the plasma CVD method, Si is used as a raw material.
H ₄ , Si ₂ H ₆ and the like are used together with ammonia, nitrogen gas, NF _{3 and the} like.

[PE, PP] In the sputtering method, PE, PP is used as a target.
Is used to perform sputtering to cover the insulator layer.

In the plasma polymerization method, as a raw material, ethylene is used for PE, and propylene is used for PP.

[Fluororesin] In the sputtering method, as a target, polytetrafluoroethylene, polytrifluoroethylene, or a polymer or copolymer of vinyl fluoride, vinylidene fluoride, dichlorodifluoroethylene, or the like is used.

As raw materials for the plasma polymerization method, tetrafluoroethylene, trifluoroethylene, vinyl fluoride, vinylidene fluoride, dichlorodifluoroethylene and the like are used.

A fluororesin film having micropores can also be used.

[0054] composite layer composite layer conductor as described above, the semiconductor is selected from the insulator, by using two or more kinds of raw material, a sputtering method, to prepare a CVD method. Further, a film prepared by mixing two or more kinds of conductor powder, semiconductor powder, and insulator powder in a molten or dissolved resin is used.

It is also preferable that the concentrations (contents) of the conductor, semiconductor, and insulator in the composite layer be different continuously or discontinuously in the thickness direction.

As an example of a method for preparing the pores in the layer, when the above conductor, semiconductor and insulator are coated by a sputtering method or a CVD method, an electrolyte is mixed with the raw material to form the conductor layer. An electrolyte is added to the semiconductor layer and the insulator layer. The electrolyte in these dissolves into the electrolyte solution of the battery and forms a micropore structure in the conductor, semiconductor, and insulator. In the micropores, the entrance and exit of lithium ions and hydroxyl ions are improved, so that the charge / discharge efficiency is improved. In addition, since these pores are small, dendrite does not easily grow. Therefore, the charge / discharge cycle life is also improved.

Laminated Structure The laminated structure of the conductor layer, the semiconductor layer, and the insulator layer is as follows .
A multilayer structure of more than one type is used.

[0058] As lamination method is, conductor, semiconductor, a film selected from the insulator laminated between the negative electrode and the separators. The film or laminated on the negative electrode surface, or laminated without contacting the negative electrode and the separators are laminated to separator <br/> rate data table surface. In addition, the negative electrode or separators
Oh Rui is the substrate material that passes through the ion, conductor,
A semiconductor and an insulator stacked by a sputtering method or a CVD method can be used.

The film thickness is selected from the above-mentioned conductor layer, semiconductor layer, and insulator layer.
The optimum film thickness of one or two or more single layers, multilayers, and composite layers depends on the porosity, pore distribution, material, and number of layers. When the material of the layer is a material having many gaps in the structure, such as a polymer resin material, the thickness is preferably 10 μm or less,
1 μm or less is more preferable. In the case of a dense material such as an inorganic compound, the thickness is desirably 1 μm or less, and 100 nm or less.
The following is more preferred.

[0060] Secondary batteries Figure 3 is an example showing the basic configuration of a secondary battery of the present invention.

In FIG. 3, reference numeral 100 denotes a negative electrode current collector, 10
Reference numeral 1 denotes a negative electrode active material; 102, one or more layers selected from a conductor layer, a semiconductor layer, and an insulator layer;
03 is a positive electrode current collector, 104 is a positive electrode active material, 105 is an electrolyte solution, 106 is a negative electrode terminal, 107 is a positive electrode terminal, 108
Separators, the 109 is a battery case.

In the case where lithium is used as the negative electrode active material, in the discharge reaction, lithium ions in the electrolyte solution 105 enter between layers of the positive electrode active material 104, while on the negative electrode side,
From the negative electrode active material 101 through the layer 102, the electrolyte solution 1
Dissolves as lithium ions in 05. In the charging reaction, lithium in the electrolyte solution 105 is deposited as lithium metal between the surface of the negative electrode and the layer 102. On the other hand, on the positive electrode side, lithium in the interlayer of the positive electrode active material 104 dissolves into the electrolyte solution 105 as lithium ions.

As the negative electrode active material of the negative electrode lithium secondary battery, lithium metal and lithium alloy can be used. As lithium alloys, magnesium, aluminum, lead, tin, indium, boron,
An alloy of lithium with at least one or more elements selected from gallium, titanium, potassium, sodium, calcium, zinc and the like.

As the negative electrode active material of the alkaline zinc battery,
A zinc or zinc alloy, zinc oxide, with zinc hydroxide or the like, a paste obtained by uniformly kneaded together with binder and mixing solution,
It is applied to a current collector and dried to obtain a negative electrode plate.

As the zinc alloy, indium, tin, lead,
There are lithium, magnesium, mercury and the like.

As the binder, polyvinyl alcohol,
Examples include cellulose-based materials such as methylcellulose and carboxymethylcellulose, polyolefin-based materials such as polyethylene, fluororesin-based materials such as polytetrafluoroethylene, and polyamide resin-based materials such as nylon.

[0067] As kneading liquid, and organic solvents such as ethylene glycol, water containing oxo acid salts of sodium phosphate and the like, etc. are used.

[0068] as a current collector, nickel-plated iron perforated plate, expanded metal, there is a Nikkerume Tsu Pradesh, and the like.

[0069] As the positive electrode the positive electrode active material 104 <positive electrode for a lithium secondary battery> lithium secondary battery, the compound lithium ions can enter and exit the interlayer, raised the following. Examples of the transition metal oxide include manganese oxide, vanadium oxide, molybdenum oxide, chromium oxide, cobalt oxide, nickel oxide, titanium oxide, iron oxide, and tungsten oxide. As the metal sulfide, titanium sulfide, molybdenum sulfide, iron sulfide, Chevrel phase sulfide _{(M y Mo 6 S 8-} z (M: copper, cobalt, and nickel)) and the like. Niobium selenide is used as the metal selenide. Examples of metal hydroxides include oxyhydroxide. The conductive polymer over, polyacetylene, polyparaphenylene phosphorus, polyaniline, polythiophene, polypyrrole, poly triphenylamine. Examples of the composite oxide include LiMn _2-x M _x O ₄ and LiCo _x Ni _1-x O ₂ .

[0070] As a manufacturing method of the positive electrode is carried out above the positive electrode active material 104, a polyethylene, Poripurobiren, a paste obtained by adding a binder such as a fluorine resin and pressed on the cathode current collector 100. Further, in order to improve the current collecting performance of the positive electrode, it is preferable to add a conductive material powder to the paste.

As the conductive powder, a carbon material such as acetylene black and a metal such as copper, nickel and titanium are used.
For the current collector 100, a fibrous, porous or mesh carbon material, stainless steel, titanium, nickel, copper, platinum, gold, or the like is used.

[0072] The positive electrode of <positive electrode for a nickel-zinc battery> nickel-zinc batteries, impregnating a paste type of filling directly nickel hydroxide powder to the current collector, the nickel hydroxide in the pores of the sintered plate of nickel There is a sintering method.

[0073] In the paste-type nickel hydroxide and additives of nickel and cobalt, a paste obtained by uniformly kneaded together with binder and mixing solution, coated on a current collector, dried positive electrode plate Get.

For the binder and the current collector, the same material as that of the zinc negative electrode plate is used.

On the other hand, in the sintering method, a sintered plate obtained by sintering a nickel powder on a nickel-plated iron perforated plate is mixed with a mixed solution of a nickel salt as a main active material and a cobalt salt as an additive. After the impregnation, the sintered plate is reacted with an alkali solution such as sodium hydroxide to impregnate nickel hydroxide into the sintered plate.

<Positive Electrode for Zinc Air Secondary Battery> The positive electrode of the zinc secondary air battery is composed of an air electrode, a water-repellent film, and diffusion paper.

Examples of the catalyst material for the air electrode include activated carbon, carbon black, etc., having a specific surface area of 200 to 1000 m ² / g.
A material obtained by adding silver, manganese dioxide, nickel-cobalt composite oxide, platinum, or the like to the above carbon material is used.

Here, the function of the water-repellent film is to prevent the electrolyte passed through the air electrode from leaking out of the battery, and a fluororesin such as polytetrafluoroethylene is used as a material. Can be The diffusion paper is for uniformly supplying oxygen to the entire surface of the air electrode, and cellophane or the like is used.

[0079] Separator separators (108) has a function to prevent short-circuiting between the positive electrode and the negative electrode, also to retain the electrolyte solution. The conditions should include Te and separators <br/> (1) be stable insoluble to the electrolyte solution (2) large liquid absorption of the electrolyte solution, also possible retaining force larger (3) Having pores through which lithium ions and hydroxyl ions can pass (4) Having pores small enough to prevent penetration of dendrites (5)
It has high mechanical strength, and may not be cut at the time of winding or have significant deformation. As a material that satisfies the above conditions, a nonwoven fabric of glass, polypropylene, polyethylene, or fluororesin or a material having a micropore structure is used.

Here, in the case of an alkaline zinc secondary battery,
The electrolytic solution is an aqueous solvent, Ru <br/> using separators hydrophilic. As its separators are nylon, used as the nonwoven fabric or microporous structure such as polypropylene or polypropylene hydrophilic treatment.

[0081] The electrolyte electrolyte, or used as it is, is used as an electrolyte solution in a solvent. Further, a solution obtained by adding a gelling agent such as a polymer material to a dissolved solution is also used. Generally, an electrolyte solution dissolved in a solvent is used.

As the electrolyte solution of the lithium secondary battery, a solution obtained by dissolving an electrolyte salt in a non-aqueous solvent is used. Since the conductivity of the electrolyte solution is related to the internal resistance of the battery and greatly affects the current density during charge and discharge, it is preferably as high as possible. The conductivity at 25 ° C. is 1 × 10 ⁻³ S · cm ⁻¹ or more. Desirably, it is more preferably 5 × 10 ⁻³ S · cm ⁻¹ or more. Examples of the electrolyte salt include LiClO ₄ , LiB
F ₄ , LiPF ₆ , LiAsF ₆ , LiCF ₃ SO _{3 and the} like are used. Before dissolving these salts in a non-aqueous solvent, it is desirable to perform sufficient dehydration and deoxygenation by heating under reduced pressure. Also in the above non-aqueous solvent, acetonitrile high dielectric constant solvent, base Nzonitoriru, propylene carbonate, ethylene carbonate, dimethyl formaldehyde, nitrobenzene, and γ- butyrolactone, tetrahydrofuran low viscosity solvent, dichloroethane, diethoxyethane, chlorobenzene , Dioxolane, etc., which are used alone or in combination. Water in the solvent is activated alumina, molecular sieve, phosphorus pentoxide,
Dehydration with calcium chloride or the like, or depending on the solvent, it may be better to remove impurities and dehydrate by distillation in an inert atmosphere in the presence of an alkali metal.

Further, as the electrolyte, a solid electrolyte can be used. In this production method, a polyethylene oxide (PEO) -based polymer compound and an electrolyte salt are dissolved in the above-mentioned non-aqueous solvent and gelled, and then developed on, for example, a flat substrate, and the non-aqueous solvent is evaporated. To obtain a solid electrolyte membrane. As the empty PEO-based polymer compound, polyethylene oxide, polyethylene oxide cross-linked with isocyanate, poly (methoxyethoxide phosphazene) and the like are used.

As the electrolyte for the alkaline zinc secondary battery,
A single or mixed aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide or the like is used.

Battery When testing the secondary battery of the present invention with a sealed battery, the shape of the battery includes a flat type, a cylindrical type, a square type, a sheet type and the like. Positive in spiral cylindrical, the negative electrode plate can be the electrode area is increased by winding through <br/> the separators, it is characterized in that can flow a large current during charging and discharging. In the square, positive, for laminated via separators to the negative electrode plate, is characterized in that high volumetric efficiency than spiral cylindrical to wound, also it can be effectively utilized storage space of the device.

FIG. 4 shows an example of a single-layer flat battery, and FIG. 5 shows an example of a schematic sectional view of a spiral cylindrical battery. 4 and 5, 200 and 300 are negative electrode current collectors, 201 and 301 are negative electrode active materials, 204 and 304 are positive electrode active materials,
06 and 306 are negative terminal (negative electrode cap), 207 and 3
07 is a battery can, 208 and 308 are electrolyte solutions and separators, 210 and 310 are insulating packings, and 311 is an insulating plate. Method of assembling a battery, the positive electrode and the negative electrode (201, 301), stacked via separators (208, 308) (FIG. 4) or winding (Fig. 5), and then the battery can (20
7, 307). Next, after adding the electrolyte solution,
Negative electrode gap (206, 306) and insulating packing (2
10, 310) and caulked to form a battery.

Battery can (battery case) (207, 307)
As the material of the negative electrode cap (206, 306), stainless steel, particularly titanium clad stainless steel, copper clad stainless steel, nickel plated steel plate, or the like is used, and plastic such as polypropylene or a composite material of metal or glass fiber and plastic is used. I can do things. As the material of the insulating Pas Kkingu (210, 310), fluorine resin, polyamide resin, polysulfone resin, various rubber. As a sealing method, a method such as adhesive, welding, glass sealing, soldering, or the like is used in addition to caulking using a gasket such as an insulating packing as shown in FIGS. As the material of the insulating plate in FIG. 5, various organic resin materials, ceramics, and the like are used. Also not shown in FIG. 4 and 5, but the add a safety valve as a safety device when the internal pressure of the battery was over technique increases are common. As this safety valve, a spring, rubber for an organic solvent resistant or the like is used.

The preparation of the battery material and the assembly of the battery are preferably performed in dry air or an inert atmosphere from which water has been sufficiently removed.

By providing a single layer, multilayer, or composite layer such as a conductor layer, a semiconductor layer, and an insulator layer between the negative electrode and the separator , the growth of dendrite during charging is suppressed, and the charge / discharge cycle life is improved. it can.

[0090]

EXAMPLES Examples of the lithium secondary battery of the present invention will be described below.
One had to be explained. Note that the present invention is not limited to the following embodiments.

Example 1 A test was performed using the liquid-rich test cell shown in FIG.

Preparation and assembly of the materials was performed in dry Ar.
RF metal lithium metal foil with titanium mesh current collector
After being inserted into the chamber of the plasma CVD apparatus, the chamber is evacuated to a vacuum degree of 2 × 10 ⁻⁶ Torr. Tetrafluoroethylene, ethylene, hydrogen, helium, and oxygen were introduced into the chamber, and the internal pressure was maintained at 0.8 Torr. Next, a high frequency power of 200 W was supplied to the parallel plate electrode, and a plasma polymerized film of a fluororesin was formed on the sample by 10 n.
m . Next, acetylene gas was introduced into the chamber as a source gas, and the pressure in the chamber was reduced to 0.1 Ton.
A carbon film was coated on the surface of the lithium metal foil to a thickness of 20 nm by controlling the rr and performing RF discharge, and this was used as a sample negative electrode (FIG. 2A).

As a positive electrode active material, a lithium-manganese composite oxide prepared by heat-treating a mixture of dehydrated electrolytic manganese dioxide, lithium carbonate, and graphite was mixed with a tetrafluoroethylene polymer powder, and then mixed with a titanium mesh. Was press-formed to obtain a positive electrode.

[0094] The Se Pas rate data was used to sandwich the microporous separators of polypropylene nonwoven and polypropylene.

As the electrolyte solution, a solution prepared by dissolving 1 M of lithium arsenide hexafluoride in a mixed solvent of an equal amount of propylene carbonate and dimethoxyethane, which was dehydrated with a molecular sieve, was used.

As shown in FIG. 3, a lithium secondary battery was manufactured.

[0097] (Example 2) In Example 1, full Tsu lithium metal foil coated with a plasma polymerized film of fluororesin, it was inserted into the chamber in the RF plasma CVD apparatus, the vacuum degree 2 × 10 ^- Exhaust to ⁶ Torr. After introducing a monosilane gas into the chamber as a source gas, the pressure in the chamber is reduced to 0.1 Torr.
r, and an RF discharge was performed to coat an amorphous silicon film on the surface of the lithium metal foil to a thickness of 10 nm , which was used as a sample electrode. Example 1 except that this sample electrode was used as the negative electrode
A battery was manufactured under the same conditions as in FIG. 2 (d).
) .

( Reference Example 1 ) Graphite fibers having a specific surface area of 10 m ² / g by spinning petroleum-based pitch by a gliding method and heat-treating in an inert atmosphere were used. After water was completely removed by heating the fiber, the fiber was dispersed in toluene that had been dehydrated with a molecular sieve, applied on a lithium metal foil, dried, and then pressed by a pressure press to obtain a sample ( Fibrous layer thickness 50 μm). A negative electrode was obtained by pressing a titanium mesh current collector on this sample from the back side. A battery was manufactured under the same conditions as in Example 1 except that this negative electrode was used (the structure shown in FIG. 2D) .

(Example 3) The graphite fiber (fibrous graphite) of Example 1 was mixed with a solvent (xylene).
A liquid dispersed in emissions), a solution of Asahi Glass Co., Ltd. fluororesin paint Lumifron hexafluoride lithium salt, it was coated and dried on the surface of the separator, and pressed by the press. A battery was manufactured under the same conditions as in Example 1 except that this separator was arranged as shown in FIG.

( Reference Example 2 ) Graphite paper (200 μm thick) obtained by making graphite fibers having a specific surface area of 10 m ² / g or more was prepared as shown in FIG.
Except that disposed between the negative electrode and the separator as in (b) is a battery was prepared under the same conditions as in Example 1.

Example 4 The preparation and assembly of the materials were performed in dry Ar. RF plasma CV using lithium metal foil with titanium mesh current collector pressed
After inserting into the chamber in the D apparatus, the degree of vacuum is 2 × 10
Exhaust to ^-6 Torr. Using hexane acetylacetone complex of nickel as a raw material, which is introduced into the chamber by the server blanking ring with hydrogen gas.
The pressure in the chamber was controlled to 1 Torr, and the nickel film was deposited on the surface of the lithium metal foil by RF discharge.
0 nm was coated, and this was used as a sample electrode. A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as a negative electrode (the structure shown in FIG. 2D) .

[0102] (Example 5) raw material, except for using an oxygen gas with F hexa <br/> down solution of acetylacetone complexes of nickel, by the RF discharge under the same conditions as in Example 6, the nickel oxide film 5 nm was coated on the surface of the lithium metal foil, and this was used as a sample electrode. A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as a negative electrode (the structure shown in FIG. 2D) .

Example 6 Preparation and assembly of materials were performed in dry Ar. RF plasma CV using lithium metal foil with titanium mesh current collector pressed
After inserting into the chamber in the D apparatus, the degree of vacuum is 2 × 10
Exhaust to ^-6 Torr. After introducing monosilane gas and ammonia gas into the chamber as source gases, the pressure in the chamber is reduced to 0. The silicon nitride film was formed on the lithium metal foil surface by controlling the pressure to 1 Torr and performing RF discharge.
0 nm was coated, and this was used as a sample electrode. A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as the negative electrode (the structure shown in FIG. 2D) .

[0104] (Example 7) starting material, by RF discharge under the same conditions as in Example 4 except that using methane gas with hexane solution of acetylacetone complex of titanium, lithium metal foil surface a composite layer of titanium and carbon The top was coated with 25 nm to form a sample electrode. A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as a negative electrode (the structure shown in FIG. 2D) .

Example 8 After inserting a polypropylene separator into a chamber in an RF plasma CVD apparatus, the degree of vacuum was 2 × 10 ⁻⁶ T.
Exhaust to orr. After acetylene gas is introduced into the chamber as a source gas, the pressure in the chamber is reduced to 0.
Controlled to 1 Torr, used was 20 nm coated with a carbon film to separators table plane by RF discharge.
Except that arranged as in FIG. 2 (f) using the separators, a battery was prepared under the same conditions as in Example 1.

(Example 9 ) In Example 8 , a monosilane gas was used as a raw material gas.
The upper separators coated with amorphous silicon film. The separator <br/> except that arranged as in FIG. 2 (f) using the laser data is a battery was prepared under the same conditions as in Example 1.

Example 10 Preparation and assembly of materials were performed in dry Ar. After inserting the polypropylene separators into a chamber in the RF plasma CVD apparatus is evacuated to a vacuum degree 10 ^-5 Torr. Tetrafluoroethylene, ethylene, H ₂ , and helium oxygen are introduced into the chamber, and the internal pressure is set to 0.8 To
rr was maintained. Next, high frequency power is applied to the parallel plate electrodes for 2
And 00 watts supplied, coated with plasma polymerized film of a fluorine resin on the separators. Then after introducing acetylene gas into the Chi catcher members as a material gas, to control the pressure in the chamber to 0.1 Torr, it was coated 20 nm carbon by RF discharge. The separator using data other than be arranged as in FIG. 2 (g) is a battery was prepared under the same conditions as in Example 1.

Example 11 Preparation and assembly of materials were performed in dry Ar. After inserting a fluororesin film having micropores into a chamber in an RF plasma CVD apparatus, the degree of vacuum is 2 × 10 ⁻⁶ Torr.
Exhaust to r. Using hexane solution of acetylacetone complex of nickel as a raw material, which is introduced into the chamber by bubbling with hydrogen gas. Controlling the pressure in the chamber to 1 Torr, and 30 nm coated separators table plane of the nickel film by the RF discharge. Using this film, a battery was fabricated under the same conditions as in Example 1 except that the battery was arranged as shown in FIG.

Example 12 In Example 11 , the fluororesin film having micropores was covered with an amorphous silicon film by using monosilane gas as a raw material gas. Using this film, Figure 2
A battery was manufactured under the same conditions as in Example 1 except that the arrangement was as shown in (c).

Example 13 Preparation and assembly of materials were performed in dry Ar. RF plasma CV using lithium metal foil with titanium mesh current collector pressed
After inserting into the chamber in the D apparatus, the degree of vacuum is 2 × 10
Exhaust to ^-6 Torr. After a monosilane gas and an acetylene gas are introduced into the chamber as source gases, the pressure in the chamber is controlled to 0.1 Torr, and RF discharge is performed to reduce the surface of the lithium metal foil to 3 with a silicon carbide film.
0 nm was coated, and this was used as a sample electrode. A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as a negative electrode (the structure shown in FIG. 2D) .

Example 14 Preparation and assembly of the materials were performed in dry Ar. After inserting a lithium metal foil on which a titanium mesh current collector has been pressed into a chamber in a sputtering apparatus, the degree of vacuum is 5 × 10 ⁻⁶ T.
The chamber was evacuated to orr, and Ar gas was flown to make the inside of the chamber inert. Next, the pressure in the chamber was increased to 3 × 10
^-3 Torr, using graphite and Si as targets, RF
Discharge. At this time, in the early stage of the discharge, sputtering was performed from the Si side, and by gradually increasing the sputtering ratio of the graphite side, a composite layer of carbon and Si was coated on the lithium metal foil surface to a thickness of 30 nm. Pole.
A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as the negative electrode (the structure shown in FIG. 2D) .

[0112] (Example 15) Example 14 above, graphite as a target, using the Si and polytetrafluoroethylene, except that laminating these composite film on the lithium metal foil surface Example 1 under the same conditions A battery was manufactured in the manner described above (the structure shown in FIG. 2D) .

Example 16 Preparation and assembly of materials were performed in dry Ar. After inserting the sample manufactured in Example 1 into a chamber in an RF plasma CVD apparatus, the sample is evacuated to a degree of vacuum of 10 ⁻⁵ Torr. Tetrafluoroethylene, ethylene, hydrogen, helium, and oxygen were introduced into the chamber, and the internal pressure was maintained at 0.8 Torr. Next, 200 watts of high-frequency power was supplied to the parallel plate electrode to coat a fluoropolymer plasma-polymerized film on the sample, which was used as a sample electrode. A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as a negative electrode.
(Structure shown in FIG . 2E) .

Example 17 Preparation and assembly of materials were performed in dry Ar. After inserting a lithium metal foil on which a titanium mesh current collector has been pressed into a chamber in a sputtering apparatus, the degree of vacuum is 5 × 10 ⁻⁶ T.
The chamber was evacuated to orr, and Ar gas was flown to make the inside of the chamber an inert atmosphere. Next, the pressure in the chamber was increased to 3 × 10
To ^-3 Torr, a graphite and LiAsF ₆ used in the target, the carbon and LiAsF ₆ to 30 nm coated on the lithium metal foil surface by the RF discharge, which was used as a sample electrode. A battery was manufactured under the same conditions as in Example 1 except that this sample electrode was used as the negative electrode (the structure shown in FIG. 2D) .

[0115] prepared in Example 18 Example 8, it had <br/> use the separators coated with carbon, a fluororesin film having micropores on the coated carbon as in FIG. 2 (h) Laminated. A battery was produced under the same conditions as in Example 1 except that this film was used.

Example 19 A test was performed using the spiral cylindrical battery shown in FIG. The battery in KR-A type, cell size profile 1 7.
0 mm and a total height of 50.5 mm.

A paste obtained by kneading together with ethylene glycol using zinc oxide and metallic zinc as main active materials and polyvinyl alcohol as a binder is applied to a nickel-plated iron perforated plate, dried and pressed. To obtain a zinc plate.

This zinc electrode plate was inserted into a chamber in an RF plasma CVD apparatus. In Example 1, the ratio of tetrafluoroethylene was high at the beginning of discharge and the ratio of acetylene to oxygen was increased at the end of discharge. by RF discharge, and fluorine resins 20 nm coated on the surface of the zinc plate, which was used as a sample electrode.

For the positive electrode plate, a paste obtained by adding nickel and cobalt to nickel hydroxide, carboxymethyl cellulose as a binder, and water to a kneading solution was used to form a paste from foamed metal (Celmet manufactured by Sumitomo Electric Industries, Ltd.). ) After filling
What was dried and pressed was used.

As the separator, a nonwoven fabric made of polypropylene and having a microporous film attached thereto (Celanese Corporation (US)
A) Cell Guard).

As the electrolytic solution, a 30 wt% potassium hydroxide solution was used.

[0122] assembly, after the group is wound through <br/> the separators between the negative electrode and the positive electrode was inserted into a stainless steel battery can titanium clad, was injected an electrolytic solution, a titanium clad The nickel-zinc secondary battery was manufactured by inserting the stainless steel negative electrode cap and insulating packing made of fluororubber and caulking (the structure shown in FIG. 2A) .

Example 20 A test was performed using the flat battery shown in FIG.

After mixing zinc oxide and zinc metal with tetrafluoroethylene polymer powder, the mixture was pressed into a nickel mesh to obtain a zinc electrode plate. After the zinc negative electrode was inserted into an RF plasma CVD chamber, the surface of the zinc electrode plate was coated with 5 nm of a fluororesin and 20 nm of carbon under the same conditions as in Example 19 to form a negative electrode.

The positive electrode catalyst layer was prepared by adding manganese dioxide to activated carbon, and the layer formed by laminating a water repellent film made of polytetrafluoroethylene and a diffusion paper made of cellulose was used as the positive electrode catalyst layer.
The positive electrode was used. In addition, the separators cellophane, using a 30 wt% potassium hydroxide solution in the electrolyte.

[0126] assembly, and through <br/> the separators between the anode and cathode is inserted into the pores with the battery can of stainless material of titanium clad, it was injected an electrolytic solution, a titanium clad stainless steel The battery was sealed with a negative electrode cap made of a material and an insulating packing made of fluororubber to produce an air zinc secondary battery (FIG. 2A).
Structure shown in) .

[0127] (Comparative Example 1) Example 1, those which do not perform the coating of the carbon film on the lithium metal foil, except for using the negative electrode, a battery was fabricated under the same conditions as in Example 1.

[0128] (Comparative Example 2) Example 19 above, those on the zinc electrode plate does not perform the coating of the fluororesin and the composite film of carbon, except that used for the negative electrode, the battery under the same conditions as in Example 18 Produced.

[0129] (Comparative Example 3) In the above-described Example 20, those on the zinc electrode plate does not perform the coating of the fluororesin and the composite film of carbon, but using the negative electrode, the battery under the same conditions as in Example 20 Produced.

The batteries prepared in Examples 1 to 18, Reference Examples 1 and 2 and Comparative Example 1 were charged to 4.0 V at a current of 0.2 C, and after a 30-minute pause, at a current of 0.2 C. 2.8
Discharge to V. The results of repeating this test are shown in Table 1.

The batteries prepared in Examples 19 and 20 and Comparative Examples 2 and 3 were charged at 150% with a current of 0.2 C, and after a rest of 30 minutes, discharged to 1.0 V at a current of 0.2 C. Do.

When the cycle life of the batteries of Comparative Examples 1, 2, and 3 was set to 1, the results of the cycle life of each example for each comparative example are shown in Table 1. The results in Table 1, the comparative example, between the negative electrode and the separators, carbon or nickel as the conductive layer, titanium, silicon and the like as a semiconductor layer, a metal oxide, a halide or a nitride as an insulator layer It has been found that the provision of a single layer, a multilayer, and a composite layer of carbon, carbide, organic polymer, etc. (Example) significantly improves the charge / discharge cycle life.

[0133]

[Table 1]

[0134]

According to the present invention as described above, according to the present invention, the conductive material layer between the negative electrode and the separator, the semiconductor layer, a single layer of the insulating layer, multi-layer, by providing the composite layer or the like, the growth of dendrite Since it can be suppressed, a secondary battery having high safety and a long charge / discharge cycle life can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic diagram for explaining an effect of the present invention.

Between the Figure 2 negative electrode and the separator, the conductive layer, a semiconductor layer, provided with an insulating layer, an example of a laminate pattern of the present invention.

FIG. 3 is a basic configuration diagram of a secondary battery of the present invention.

FIG. 4 is a view showing a flat battery to which the present invention is applied.

FIG. 5 is a view showing a cylindrical battery to which the present invention is applied.

[EXPLANATION OF SYMBOLS] 001 negative electrode plate, 002 dendrites, 003 conductive layer or a semiconductor layer, 004 separators, 005
Chloroplast layer, 006 electrolyte, 007 positive electrode plate, 100,
200, 300 Negative electrode current collector, 101, 201, 301
Negative electrode active material, one or more single layer, multilayer, composite layer selected from conductor layer, semiconductor layer, insulator layer, 104, 204, 304 Positive electrode active material,
05 electrolyte solution, 106, 206, 306 negative electrode terminal (negative electrode cap), 107 positive electrode terminal, 207, 307
Battery can 108 separators, 208, 308 electrolytic solution and separators, 109 battery case, 210,3
10 insulating Pas Kkingu, 311 insulating plate.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-289069 (JP, A) JP-A-3-263758 (JP, A) JP-A-4-229562 (JP, A) JP-A-57- 69677 (JP, A) JP-A-57-126068 (JP, A) JP-A-58-142771 (JP, A) JP-A-4-28172 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) H01M 10/38 H01M 10/40

Claims (25)

(57) [Claims] 1. A secondary battery comprising at least a negative electrode made of lithium or a lithium alloy, an electrolyte, a separator, and a positive electrode, wherein Ni, Ti, Pt, Al, Pb, Cr are provided between the negative electrode and the separator. , Cu, V, M
o, W, Fe, Co, Zn, a metal conductor layer made of at least one material selected from the group consisting of Mg, diamond, Si, nickel oxide, copper oxide, titanium oxide, manganese oxide, zinc oxide, A semiconductor layer made of at least one material selected from the group consisting of zirconium oxide, tungsten oxide, molybdenum oxide, and vanadium oxide; and a group consisting of lithium fluoride, magnesium fluoride, nitride, carbide, and fluororesin. At least one selected
A rechargeable battery comprising at least one of an insulator layer made of at least one kind of material. 2. The secondary battery according to claim 1, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer contacts a negative electrode active material. 3. The secondary battery according to claim 1, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer contacts a separator. 4. The secondary battery according to claim 1, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer covers at least the surface of the negative electrode active material on the separator side. . 5. The secondary battery according to claim 1, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer is pressed on the surface of the negative electrode active material. 6. The secondary battery according to claim 1, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer covers at least the surface of the separator on the negative electrode side. 7. The secondary battery according to claim 3, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer is pressure-bonded to a separator. 8. A secondary battery comprising at least a negative electrode made of zinc or a zinc alloy, an electrolyte, a separator, and a positive electrode, wherein diamond, Si, nickel oxide, copper oxide, oxide, A semiconductor layer composed of at least one material selected from the group consisting of manganese, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide, and vanadium oxide; lithium fluoride, magnesium fluoride, nitride, carbide, and fluorine At least one selected from the group consisting of resins
A rechargeable battery comprising at least one of an insulator layer made of at least one kind of material. 9. The secondary battery according to claim 8, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer contacts a negative electrode active material. 10. The secondary battery according to claim 8, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer contacts a separator. 11. The secondary battery according to claim 8, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer covers at least the surface of the negative electrode active material on the separator side. . 12. The secondary battery according to claim 8, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer is pressed on the surface of the negative electrode active material. 13. The secondary battery according to claim 8, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer covers at least the surface of the separator on the negative electrode side. 14. The secondary battery according to claim 10, wherein a layer selected from the conductor layer, the semiconductor layer, and the insulator layer is pressure-bonded to a separator. 15. A secondary battery comprising at least a negative electrode, an electrolyte, a separator, and a positive electrode, wherein a laminated film of a conductor layer or a semiconductor layer and an insulator layer is provided between the negative electrode and the separator , The conductor layer is made of carbon, Ni, Ti, Pt, Al, Pb,
Cr, Cu, V, Mo, W, Fe, Co, Zn, Mg
At least one material selected from the group consisting of
A semiconductor layer formed of diamond, Si, nickel oxide, acid,
Copper oxide, manganese oxide, titanium oxide, zinc oxide, jill oxide
Conium, tungsten oxide, molybdenum oxide,
At least one selected from the group consisting of nadium
A secondary battery comprising: a layer containing the material described in (1) . 16. The secondary battery according to claim 15, wherein the negative electrode is made of lithium, a lithium alloy, zinc, or a zinc alloy. 17. The insulator layer, halides, nitrides, carbides, little is selected from the group consisting of a polymer material
The secondary battery according to claim 15, wherein the secondary battery is an insulator layer made of at least one material. 18. The method according to claim 15, wherein the laminated film has a structure in which an insulator layer, a conductor layer, or a semiconductor layer is laminated in this order on a surface of the negative electrode which faces the separator. Rechargeable battery. 19. The structure according to claim 15, wherein the laminated film has a structure in which an insulator layer, a conductor layer, or a semiconductor layer is laminated in this order on a surface of the separator facing the negative electrode. Rechargeable battery. 20. The structure according to claim 15, wherein the laminated film has a structure in which a conductor layer or a semiconductor layer and an insulator layer are laminated in this order on a surface of the separator facing the negative electrode. Rechargeable battery. 21. A secondary battery comprising at least a negative electrode, an electrolyte, a separator, and a positive electrode, wherein between the negative electrode and the separator, two or more materials selected from a conductor, a semiconductor, and an insulator are provided. A secondary battery provided with a composite layer. 22. The secondary battery according to claim 21 , wherein the concentrations of the conductor, the semiconductor, and the insulator in the composite layer vary in the layer thickness direction. 23. The method according to claim 20, wherein the conductor is carbon, Ni, Ti, P
t, Al, Pb, Cr, Cu, V, Mo, W, Fe, C
o, Zn, Mg, diamond, secondary battery according to claim 21, characterized in that a metal containing at least one selected from the group consisting of Si. 24. The method according to claim 24, wherein the semiconductor is diamond, Si,
A small metal selected from the group consisting of nickel oxide, copper oxide, manganese oxide, titanium oxide, zinc oxide, zirconium oxide, tungsten oxide, molybdenum oxide, and vanadium oxide.
Claims characterized by at least one material
22. The secondary battery according to 21 . 25. The secondary battery according to claim 21 , wherein the insulator is a material containing at least one selected from the group consisting of a halide, a nitride, a carbide, and a polymer.