JPH0737604A - Battery - Google Patents

Abstract

PURPOSE:To increase current density by using a solid electrolyte obtained by the action of a supporting electrolyte to a polyimide thin film as an electrolyte separator. CONSTITUTION:A positive active material 12 and a negative active material 13 are arranged on each side of an electrode separator, and a positive current collector 14 and a negative current collector 15 are arranged on the outside of the active materials respectively. As the electrode separator 11, a solid electrolyte prepared by doping a supporting electrolyte such as hydrogen chloride in a polyimide thin film formed in a thickness of 1mum or less by an LB process is used. The active materials 12, 13 are prepared, for example, by doping hydrogen chloride in a conductive polymer deposited on both sides of the electrode separator 11 by an LB process of polyaniline. The current collectors 14, 15 are formed by sputtering, for example, gold on the outsides of the active materials 12, 13.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a battery having excellent characteristics such as an all-solid battery or a paper battery to which a polymer solid electrolyte is applied.

[0002]

2. Description of the Related Art Batteries (particularly secondary batteries) are one of the important products that support the modern society as a power source that can easily store electricity and extract it again. In particular, the recent miniaturization and cordlessness of electronic devices is remarkable, and batteries as their energy sources are required to have higher performance, smaller size, longer life, lighter weight, and safety. . However, the rate of technological innovation of batteries is slower than the rate of technological innovation of electronic devices, and the importance of developing batteries having excellent characteristics in electronic devices tends to increase year by year. Further, it is considered that the demand for the small power source capable of supplying a weak current for a long period of time will be further increased in the future. For example, as an implantable power supply for (artificial) organs such as a cardiac pacemaker, as a power supply for micromechanics that can be applied to internal drug release devices, as a backup power supply for nonvolatile memory (inserted in a package), And I
Application as a power source for C cards can be considered. By the way, the batteries which have been put into practical use conventionally use liquid electrolytes including lead batteries. The dry battery is also a wet battery in which the electrolyte is in the form of gel.

On the other hand, solid-state batteries having a solid electrolyte have been studied extensively in recent years because various advantages can be considered. In particular, a polymer solid electrolyte battery using a polymer such as polyether as an electrolyte is very useful from the following points. (1) A very thin solid battery can be obtained: That is, it can be expected to be used as a battery for an extremely thin electronic device such as a battery in an IC card and an IC backup package. or,
Generally, the chemical reaction inside the battery is a solid-phase reaction and is very inefficient, but due to the thinning of the active material, the effect due to the very slow ion diffusion becomes small, and the actual energy density is higher than the theoretical energy density. Could be. (2) Flexible and strong mechanical strength: That is, as the solid electrolyte, not only polymer solid electrolytes but also inorganic solid electrolytes can be mentioned. However, from the viewpoint of mechanical strength, deformability, moldability, plasticity, etc. Solid electrolytes are better. (3) Safe without liquid leakage: That is, since there is no liquid leakage and no heavy metals are contained, it is highly safe in use and can be used for implantable devices. Furthermore, since the electrolyte does not evaporate, it is also suitable for space development. (4) It can be easily formed into a film and can have a large area. That is, in a normal secondary battery (lead battery, Ni-Cd battery), the cost increases exponentially as the electrode area increases. Therefore, in recent years, while the battery for large power storage, such as a power load leveling has been expected, from the increase in cost due to an increase of the electrode area is the current situation is not just the prospect of yet practical . (5) Molding is easy and the shape can be freely selected. That is, the battery shape can be easily changed according to the shape of the electronic device. (6) Disposal is easy: In other words, since it does not contain heavy metals such as cadmium and lead, it can be disposed of in the same manner as normal waste at the time of disposal.

However, as described above, the solid electrolyte has a problem that the ionic conductivity at room temperature is poor and the current density cannot be large. For example, the ionic conductivity of a solid polymer electrolyte is about two orders of magnitude lower than that of an organic solvent-based electrolyte that has been put into practical use. Ionic conduction in polymers is
Since it is said to be due to the segmental motion of the polymer,
As long as this is used, the ionic conductivity has an upper limit. That is, in the case of polyether, which is generally represented by a polymer solid electrolyte, a value higher than the ionic conductivity exhibited by an oligooxyethylene solution of an inorganic salt is not expressed. The value is said to be around 10 ⁻⁴ S / cm at room temperature. Therefore, in order to achieve faster ionic conductivity, it has been attempted to thin the solid polymer electrolyte used for the electrode diaphragm. This is because if the thickness of the polymer solid electrolyte can be reduced by an order of magnitude, the same effect that the ionic conductivity is improved by an order of magnitude is produced.

[0005]

However, in order to reduce the thickness of the solid polymer electrolyte used for the electrode diaphragm,
There are various problems as listed below. (1) In the case of a battery whose supporting electrolyte concentration changes with charge and discharge, it is necessary to hold a supporting electrolyte that increases and decreases with charge and discharge, and thus a solid polymer electrolyte capable of dissolving the maximum amount of supporting electrolyte is required. . Generally, the solubility of the supporting electrolyte in the solid polymer electrolyte is low, and thus a large amount of the solid polymer electrolyte is required. Therefore, the energy capacity per volume is reduced, and further, the thickness of the solid polymer electrolyte is increased,
Ionic conductivity also deteriorates. (2) The thinning of the solid electrolyte deteriorates mechanical strength and electronic insulation. (3) Since the cushioning property of the solid electrolyte is reduced, there is a high possibility that the active material and the polymer solid electrolyte will be separated from each other. (4) It is difficult to stack batteries because the performance of the unit cells tends to vary. Therefore, the object of the present invention is to solve various problems associated with the thinning of the solid electrolyte used for the above electrode diaphragm, despite using an ultrathin film for the solid electrolyte, excellent in ion conductivity, It is an object of the present invention to provide a high-performance battery having a high current density, mechanical strength, electronic insulation, and no peeling in the bond between the active material and the solid polymer electrolyte. Further, another object of the present invention is to provide a battery having a large electromotive force, which allows easy stacking of single cells.

[0006]

The above objects can be achieved by the present invention described below. That is, the present invention is a negative electrode active material,
In a battery that includes an electrode diaphragm, a positive electrode active material, a supporting electrolyte, and a current collector, and uses electromotive force due to a difference in the concentration of the supporting electrolyte between the positive electrode active material and the negative electrode active material, the thickness of the electrode diaphragm is 1 μm or less. Is a battery characterized by.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The battery of the present invention is a concentration-difference battery that exerts an electromotive force due to the difference in the concentration of the supporting electrolyte between the positive electrode active material and the negative electrode active material, and a very thin ultrathin film for the solid electrolyte, for example, polyimide that is a polymer electrolyte. It is characterized by using an ultra-thin film. The primary battery is
Since it is considered that the secondary battery is only discharged without being charged, it is functionally the same as the case of the secondary battery.
It deals with secondary batteries. FIG. 1 is a schematic diagram showing an example of a battery of the present invention (hereinafter, referred to as a concentration difference battery) that utilizes a concentration difference of a supporting electrolyte, and uses an ultrathin film of polyimide, which is a polymer electrolyte, as an electrode diaphragm. . In the figure, 15 is a negative electrode active material, 14 is a positive electrode active material, 13 is a negative electrode active material, 12 is a positive electrode active material, and 11 is an electrode diaphragm made of a solid electrolyte. Note that FIG. 1 is merely an example of an embodiment of the present invention, and does not limit the structure of the battery of the present invention. For example, in order to further improve the adhesion between the solid electrolyte and the active material, it is also a preferred embodiment of the present invention to insert a mixed film of the solid electrolyte and the active material between them.

As the constituent materials of the positive electrode active material 12 and the negative electrode active material 13 of the battery of the present invention, the following conductive polymer compounds are preferably used in the present invention. Examples of the conductive compound include polyaniline, polypyrrole, polyacetylene, polythiophene, polyparaphenylene, polyazulene, disulfide polymer, polyacene and poly (2,5-pyridinediyl), and any of them is preferably used. I can. In the present invention, it is particularly preferable to use polyaniline.

As the electrode diaphragm constituting the battery of the present invention, any polymer solid electrolyte can be used, but the most preferable one is as shown in the following formula (2). It is a polyimide thin film. Of course, the polyimide used in the present invention is not particularly limited to the compound of the formula (2) shown below.

[Chemical 1]

The above-mentioned polyimide can be formed into a very thin film. For example, the thickness of a single molecule can be set to -10 nm when applied by the spin coating method, and can be set to -0.4 nm which is the thickness of a single molecule when applied by the LB method. If a supporting electrolyte is made to act on this, it can be made to have a function as an ion conductor and an electronic insulator like a normal solid electrolyte. Hydrogen chloride is used as the supporting electrolyte at this time, but it is not particularly limited thereto, and ammonium chloride, sulfuric acid, or the like may be used. or,
The supporting electrolyte is discharged from one of the positive and negative polar active materials and absorbed by the other as the charge and discharge are performed. Therefore, it is not necessary to hold all the supporting electrolyte required for charge / discharge in the solid electrolyte. Therefore, in the present invention, as described above, by using a pseudo solid electrolyte in which a supporting electrolyte is made to act on a polyimide ultrathin film (hereinafter, this is referred to as a solid electrolyte without distinguishing it from the solid electrolyte), the solid electrolyte can be significantly reduced. It becomes possible to form a very thin film (1 μm or less, preferably 400 nm to 4 nm), and an effect equivalent to that the ionic conductivity is increased by several orders of magnitude can be obtained.

The concentration difference battery having a very thin solid electrolyte usually has various problems as described below. In the present invention, by using a solid electrolyte composed of the above polyimide ultra-thin film and a supporting electrolyte, the following measures can be taken.

(A) For the problem of deterioration of the electronic insulation of the solid electrolyte. Since a polyimide thin film is used, the electron conductivity is very low (about 10 ^-16 S / cm at a thickness of 4 to 20 nm), which is convenient. Since a thin film of polyimide can be easily formed by the Langmuir-Blodgett method (hereinafter abbreviated as LB method), the film thickness can be adjusted in the sub-nano order, and a desired electron conduction value can be arbitrarily set. You can get it.

(B) For the problem of deterioration of the adhesion between the active material and the solid polymer electrolyte. When the electrolyte is liquid, the exchange of ions between the active material (solid) and the electrolyte (liquid) proceeds smoothly. On the other hand, when the electrolyte is a solid, ions are exchanged between the solid (active material) and the solid (electrolyte), so that the quality of the adhesion of both directly affects the efficiency of the electrochemical reaction. .
Particularly in the case of secondary batteries, peeling may occur at the junction between the active material (generally a metal such as lithium) and the polymer solid electrolyte due to repeated charging / discharging, or thinning of the polymer solid electrolyte may occur. Since the voids are generated due to the decrease in the cushioning property, the battery performance may be significantly adversely affected. However, in the battery of the present invention, the positive electrode active material 12 and the negative electrode active material 13 shown in FIG.
Since it is a conductive compound such as polyaniline having a high compatibility with, it is possible to prevent peeling and voids from being easily generated at the joint between the active material and the solid polymer electrolyte. Furthermore, when both the active material and the solid electrolyte are produced by the LB method, the LB film surface is extremely smooth, which is advantageous for bonding.
Further, by continuously forming the active material and the solid electrolyte by the LB method, it is possible to manufacture a battery having a very high adhesiveness at the bonding portion on a molecular order.

(C) With respect to the problems of a decrease in the dielectric breakdown voltage and mechanical strength of the solid electrolyte that accompany the thinning of the film. Although pinholes are easily generated when the film is thinned by the spin coating method, the polyimide LB film formed by the LB method is very dense and has no pinhole. Further, the dielectric breakdown voltage of polyimide is 10 ⁺⁶ V / cm or more, and even when two layers of polyimide LB film (0.8 nm in thickness) are used as one layer of MIM (metal / insulator / metal element), It has been confirmed that it can withstand a voltage of several volts. Further, the supporting electrolyte is released from either one of the positive and negative polar active materials as it is charged and discharged, and is absorbed by the other. Therefore, the volume contraction / expansion of the active material due to the release / absorption of the supporting electrolyte has an advantage of being offset, but the solid polymer electrolyte between them has a tensile strain, which makes it resistant. Need to have. On the other hand, the polyimide thin film preferably used in the battery of the present invention generally has high tensile strength (10 Kg / mm ² or more), and therefore has resistance to breakage and breakage.

(D) With respect to the problem of difficulty in stacking the unit cells due to variation in the performance of the unit cells. The performance of a laminated battery in which the cells are stacked and used depends on the worst of the stacked cells. Therefore, in order to produce a laminated battery, it is required to produce a unit cell as homogeneous as possible. On the other hand, regarding a battery using a conventional solid electrolyte, it is difficult to homogenize the performance of a single battery because a clear manufacturing method has not been established yet. In the case of the battery of the present invention, the active material is LB
Since it can be manufactured by the method, the scale reliability is improved especially in the thickness direction, and the bondability is also improved as described above, so that the variation in the performance of the unit cell is less likely to occur, Has the advantage of being easy to stack.

(E) To the problem relating to the small electromotive force of the unit cell. In the present invention, the active material and the solid polymer electrolyte can be formed into a film by the LB method as described above. Further, it is possible to form the current collector by the LB method. When all layers are manufactured by the LB method, the adhesiveness of the joint portion and the productivity of the laminated battery are improved, and due to the reason described in (D) above, the performance of the unit cell is more varied than that when the layers are separately manufactured. It gets harder. Therefore, a laminated battery can be manufactured relatively easily, and a high-potential battery can be manufactured. Generally, the concentration difference battery as in the present invention has a problem that the electromotive force of a single cell is small, but this can be solved by using it as a laminated battery.

[0018]

EXAMPLES The present invention will be described in more detail below with reference to examples. <Example 1> N, N'-dimethylacetamide (hereinafter referred to as DM) so that the concentration of polyaniline in terms of monomer was 1 mM.
AC), and then mixed with a separately prepared 1 mM solution of stearic acid in the same solvent at a volume ratio of 1: 1,
A developing solution was prepared. This solution was spread on pure water having a water temperature of 20 ° C. to form a monomolecular film on the water surface. After evaporating and removing the solvent, the surface pressure was raised to 25 mN / m, and the substrate electrode (a current collector obtained by vapor-depositing a gold electrode on a glass substrate) was moved across the water surface while keeping the surface thickness constant. Speed 5mm
After gently immersing the film at the same speed / min, the film was gently pulled up at the same speed to form a two-layer Y-type monomolecular cumulative film. The same operation was repeated to produce a 100-layer monomolecular cumulative film. Next, this substrate is depressurized (up to 1 mmHg) at 80 ° C.
And baked for 10 minutes to distill off stearic acid and form a cumulative film of the active material polyaniline.

Next, after the polyamic acid is dissolved in DMAC As will 1mM in monomer concentration in terms, N- methyl -N separately prepared, N ^'- volume 2mM solution by dialkyl DMAC ratio of 1: 1 and mixed to prepare a developing solution of a polyamic acid alkylamine salt represented by the following formula (1).

[0020]

[Chemical 2]

The developing solution obtained as described above is treated at a water temperature of 20 ° C.
It was developed on pure water, and a monomolecular film was formed on the water surface. After the solvent was removed by evaporation, the surface pressure was raised to 30 mN / m, and the substrate electrode on which the polyaniline was accumulated while keeping the surface thickness constant was gently immersed in a direction across the water surface at a speed of 5 mm / min, and then, Gently pull up at the same speed, 2
A Y-type monomolecular cumulative film of layers was created. The same operation was repeated to form 10 layers of a monomolecular polyamic acid alkylamine salt monomolecular film. This substrate is decompressed (up to 1 mmH
g), and heat-baking at 250 ° C. for 10 minutes to imidize the polyamic acid alkylamine salt (see the following formula (2)),
A polyimide monomolecular cumulative film was formed as an electrode diaphragm.

[0022]

[Chemical 3]

On the polyimide monomolecular cumulative film forming substrate formed as described above, 100 layers of polyaniline monomolecular cumulative film were further deposited by the same method as described above, and as shown in (2) of FIG. It was configured. This was left to act in a hydrochloric acid gas atmosphere for 1 hour to act to dope the supporting electrolyte and fix it in an 80 ° C. constant temperature layer for 10 minutes. Finally, gold was vapor-deposited on this substrate to obtain a collector for the other electrode.
When the charge and discharge characteristics of the battery obtained by the above method were examined, good results were obtained that the self-discharge was small and the current density was large.

Example 2 The same as Example 1 except that a mixed film of polyimide and polyaniline was inserted between polyimide, which is a solid electrolyte, and polyaniline, which is an active material, in order to improve adhesion. As a result, a battery having the configuration shown in (2) of FIG. 2 was created. When the charge and discharge characteristics of this battery were examined, good results were obtained as in Example 1.
The details of the method for producing the mixed film of polyimide and polyaniline used in this example are shown below. First, polyaniline was dissolved in DMAC to a monomer conversion concentration of 1 mM, and then 1 mM of separately prepared stearic acid was added using the same solvent.
The solutions were mixed in a volume ratio of 1: 1. Next, the polyamic acid was dissolved in DMAC to a monomer conversion concentration of 1 mM, and then a separately prepared 2 mM solution of N-methyl-N, N′-dialkyl in the same solvent was added at a volume ratio of 1: 1. And mixed to prepare a developing solution. This solution was spread on pure water having a water temperature of 20 ° C. to form a monomolecular film on the water surface. After removing the solvent by evaporation, increase the surface pressure to 30 mN / m, keep the surface thickness constant, and move the substrate electrode across the water surface at a speed of 5
After gently soaking at mm / min, the film was gently pulled up at the same speed to form a two-layer Y-type monomolecular cumulative film. The same operation was repeated to form a mixed monomolecular cumulative film composed of four layers of polyaniline and polyamic acid. After the completion of all depositions, the substrate is put under reduced pressure (~ 1 mmHg) at 250
The polyamic acid alkylamine salt was imidized by heating at 10 ° C. for 10 minutes to remove stearic acid.

Example 3 Polyaniline, which is an active material, was dissolved in DMAC to a monomer conversion concentration of 100 mM, and then a film was formed by spin coating under the condition of 1500 rpm / 1 μm, and the polyaniline was formed thereon. 2 was prepared in the same manner as in Example 1 except that polyimide was deposited / imidized by the LB method as shown in Example 1, and polyaniline was similarly formed thereon by the spin coating method. A battery having the configuration shown in (3) was produced. When the charge and discharge characteristics of this battery were examined, good results were obtained as in Example 1.

Example 4 Example 2 was repeated except that polyaniline, which was an active material, was dissolved in DMAC to a monomer conversion concentration of 100 mM, and then a film was formed by spin coating under the condition of 1500 rpm / 1 μm. Similarly to the above, a battery having a structure having a mixed film of polyimide and polyaniline shown in (4) of FIG. 2 was produced. When the charge and discharge characteristics of this battery were examined, good results were obtained as in Example 2.

Example 5 A polyaniline layer produced by the LB method similar to that of Example 1 is interposed between a polyaniline layer which is an active material produced by the spin coating method and a polyimide layer which is an electrode diaphragm produced by the LB method. A battery having the configuration shown in (5) of FIG. 2 was produced in the same manner as in Example 3 except that four layers were inserted. When the charge / discharge characteristics of this battery were examined, good results were obtained as in Example 3.

<Example 6> Between (polyaniline + polyimide mixed layer) / polyimide layer / (polyaniline + polyimide mixed layer), which is an electrode diaphragm, produced by the LB method, and polyaniline layer produced by the spin coating method,
A battery having a structure as shown in (6) of FIG. 2 was produced in the same manner as in Example 4 except that four polyaniline layers produced by the same LB method as in Example 1 were inserted. When the charge and discharge characteristics of this battery were examined, good results were obtained as in Example 4.

<Examples 7 to 12> A conductive (ion insulating) material (polyisobutyromethylmethacrylate (hereinafter abbreviated as PIBM) + C60) was used as a current collector between the cells, and Example 1 was used. -The unit cells obtained in Example 6 were laminated to produce a laminated battery. When the charge / discharge characteristics of these laminated batteries were examined, good results were obtained as in the case of the unit cells of Examples 1 to 6. FIG. 3 shows an example in which three unit cells of Example 1 are stacked. In this case, all of the active material, the solid polymer electrolyte (electrode diaphragm), and the current collector between the single cells can be continuously manufactured by the LB method. The method for producing the current collector will be described in detail below. An equal volume of a 1 mM benzene solution of PIBM and a 1 mM benzene solution of C60 were mixed to prepare a developing solution. The solution was spread on pure water having a water temperature of 20 ° C. to form a monomolecular film on the water surface. After removing the solvent by evaporation, the surface pressure is 30mN / m
The substrate electrode is gently immersed in a direction crossing the water surface at a speed of 5 mm / min, and then gently pulled up at the same speed to form a two-layer Y-type monomolecular cumulative film. A film was formed. The same operation was repeated to form 10 layers of a mixed monomolecular cumulative film of PIBM and C60, which was used as a current collector.

<Examples 13 to 24> The batteries of the present invention were prepared in the same manner as in Examples 1 to 12 except that soluble polypyrrole was used instead of polyaniline as the positive electrode active material and the negative electrode active material. did. When the charge and discharge characteristics of these batteries were examined, good results were obtained as in Examples 1 to 12.

<Examples 25 to 36> The batteries of the present invention were manufactured in the same manner as in Examples 1 to 12 except that polyaniline was used as the positive electrode active material and soluble polypyrrole was used as the negative electrode active material. When the charge and discharge characteristics of these batteries were examined, good results were obtained as in Examples 1 to 12.

<Examples 37 to 38> Batteries of the present invention were produced in the same manner as in Examples 1 and 3 except that polyaniline was used as the positive electrode active material and polythiophene was used as the negative electrode active material. When the charge / discharge characteristics of these fabricated batteries were examined, good results were obtained as in Examples 1 and 3.

<Examples 39 to 40> Active material / electrode diaphragm produced in the same manner as in Examples 1 and 3
A battery was manufactured by press-bonding a lithium thin film having a thickness of 50 μm to a polyaniline / polyimide thin film. When the charge and discharge characteristics of these batteries were examined, Example 1 and Example 3 were obtained.
Similar good results were obtained.

[0034]

As described above, the present invention has the following excellent effects. (1) Since the electrode diaphragm (polymer solid electrolyte) can be made into an ultrathin film, ionic conductivity is improved and current density is improved. (2) The adhesion between the active material and the electrode diaphragm (polymer solid electrolyte) is improved, and problems such as peeling of the joint are solved. (3) High mechanical strength and electronic insulation can be provided by using a polymer solid electrolyte such as polyimide as an electrode diaphragm. (4) Since there is less variation in the performance of the unit cell, an ultra-thin layered battery can be manufactured, and thus a battery having high electromotive force can be easily obtained. (5) A battery having less self-discharge can be obtained by using a film forming method having a high electron insulating property of the electrode diaphragm (polymer solid electrolyte) and in which impurities are less likely to enter. (6) Solid electrolytes are expected to find applications in areas such as small power supplies, sensors, capacitors and displays. Although the present invention has been shown for a battery as an application technique using a solid electrolyte, it is suggested that the performance of a solid electrolyte other than a battery expected to be applied may be improved by using a polyimide thin film.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a battery of the present invention using a solid electrolyte.

FIG. 2 is a diagram showing a configuration of batteries of Examples 1 to 6.

FIG. 3 is a schematic diagram showing a laminated battery configuration of Example 7.

[Explanation of symbols]

 11, 11a, 11b, 11c: Electrode diaphragm 12, 12a, 12b, 12c: Active material (positive electrode) 13, 13a, 13b, 13c: Active material (negative electrode) 14: Current collector (positive electrode) 15: Current collector ( Negative electrode) 16a, 16b: current collector between single cells

Claims (8)

[Claims] 1. A battery comprising an anode active material, an electrode diaphragm, a cathode active material, a supporting electrolyte, and a current collector, which utilizes an electromotive force due to a difference in the concentration of the supporting electrolyte between the cathode active material and the anode active material. A battery having a thickness of 1 μm or less. 2. The battery according to claim 1, wherein the electrode diaphragm has a thickness of 100 nm or less. 3. The electrode diaphragm is 10 nm or less.
The battery described in. 4. The battery according to claim 1, wherein the negative electrode active material and / or the positive electrode active material is a conductive polymer compound. 5. A negative electrode active material and / or a positive electrode active material and / or
Alternatively, the battery according to claim 1, wherein the electrode diaphragm is formed by the Langmuir-Blodgett method. 6. The battery according to claim 1, wherein the electrode diaphragm is a polyimide thin film having a thickness of 100 nm or less. 7. The battery according to claim 1, wherein the current collector is formed by a Langmuir-Blodgett method. 8. A negative electrode active material, an electrode diaphragm having a thickness of 1 μm or less, a positive electrode active material, and a current collector as one unit, and a plurality of these are laminated, and all are formed by a Langmuir-Blodgett method. A battery characterized by.