JP2013073765A - Thin positive electrode structure, method of manufacturing the same, and thin lithium air battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin positive electrode structure and a large capacity thin lithium air battery, having a lamination structure composed of a positive electrode material and a positive electrode base material, and capable of efficiently supplying a positive electrode active material made of air or oxygen gas to the positive electrode material even when laminating the positive electrode structure with a separator and a negative electrode structure.SOLUTION: The thin positive electrode structure is formed by joining a plate-like positive electrode base material 81A with positive electrode material 82A1, 82A2 of madreporic body. A thin positive electrode structure 86A arranged so that gaps or holes 15A for passage of gas leading from one side face to an opposite side face are formed on the positive electrode base material 81A or the positive electrode material 82A1, 82A2 is provided.

Description

The present invention relates to a thin positive electrode structure, a manufacturing method thereof, and a thin lithium air battery for realizing the lamination of battery cells of a lithium air battery and the increase in capacity by the lamination.

The air battery includes a solid positive electrode material (air electrode), a negative electrode material made of metal foil or metal fine particles, and a liquid or solid electrolyte, and air or oxygen flowing in a gas flow path provided in the air battery. The battery uses a gas as a positive electrode active material and the metal foil or metal fine particles as a negative electrode active material.

A plurality of air battery technologies have been proposed. In recent years, research and development of lithium air batteries have been particularly active (Patent Documents 1 to 6). This is because the secondary battery can be recharged and reused, and the energy density per unit weight can be greatly improved as compared with a lithium ion battery that has already been put into practical use.

Among air battery technologies, a zinc-air battery has been put into practical use (Patent Document 7). However, the zinc-air battery is a primary battery that cannot be recharged, and since it is lightweight but has a small capacity, it is mainly used for hearing aids, and a large capacity has not been realized.

One type of air battery is a fuel cell. In a fuel cell, a plurality of cells are stacked via a separator called a bipolar plate. The bipolar plate has a function of partitioning two flow paths of a fuel flow for the negative electrode and an air flow for the positive electrode, and a function of electrically connecting the stacked cells in series (Non-patent Document 1).
In order to increase the capacity of the stacked battery cells, it is necessary to connect them in parallel. However, the bipolar plate is not suitable for its use and is very thick and has a problem that the volume when stacked is increased.

On the other hand, a lithium ion battery that has already been widely used is a laminate film in which a plurality of negative electrode structures, separators, and positive electrode structures are alternately laminated together with an electrolytic solution in a metal container such as aluminum or a polymer film. A battery sealed in a container.

Here, the positive electrode structure is composed of a positive electrode material in which the positive electrode reaction occurs inside or on the surface thereof, and a positive electrode base material that functions to collect the electron current generated by the positive electrode reaction while structurally supporting the positive electrode material. Means a functional body that realizes a set of positive electrode functions. Hereinafter, it is used in the present invention for convenience. Similarly, the negative electrode structure is composed of a negative electrode material in which the negative electrode reaction occurs inside or on the surface, and a negative electrode base material that functions to collect the electron current generated by the negative electrode reaction while supporting the negative electrode material structurally. Means a functional body that realizes a set of negative electrode functions.

The positive electrode structure of a lithium ion battery uses a foil of several tens of μm mainly made of Al as a positive electrode base material, and a positive electrode material made of a transition metal oxide such as Co, Ni, Mn or the like is applied on both surfaces thereof. The structure of the negative electrode is the same, and a negative electrode structure in which a negative electrode material composed of graphite intercalated with Li is installed on both surfaces of a negative electrode base material mainly made of Cu and having a thickness of several tens of μm is used. The thickness of the entire battery when laminated is reduced.
The negative electrode structure and the positive electrode structure are each connected to a metal terminal called a tab, so that a plurality of stacked cells are connected in parallel to increase the capacity. (Nonpatent literature 2 (FIG. 2)).

In a lithium-air battery, when the same negative electrode structure as that of a lithium ion battery, a separator, and a positive electrode structure are alternately stacked, the positive electrode structure for a lithium ion battery is a simple plate. Therefore, it is difficult to efficiently take in air or oxygen gas that becomes the positive electrode active material.

From the above, in order to realize a large capacity by stacking cells in a lithium-air battery, the positive electrode active material can be transported to the positive electrode material in the same manner as the bipolar plate of the fuel cell, and the same thin stack as in the lithium ion battery A structure needs to be formed.

JP 2011-96492 A Special table 2008-502118 gazette JP 2010-192313 A JP 2011-96456 A JP 2011-108388 A JP 2011-108512 A JP 2011-96586 A

Hiroaki Tagawa “Solid Oxide Fuel Cell and Global Environment”, p. 60, Agne Jofusha Kazuaki Utsumi “Lithium-ion batteries for next-generation automobiles”, Motor Ring No. 28, March 2009 issue (Automobile Engineering Association of Japan)

The present invention has a positive electrode structure having a laminated structure of a positive electrode material and a positive electrode substrate, and even when laminated with a separator and a negative electrode structure, a positive electrode active material made of air or oxygen gas is efficiently used as the positive electrode material. It is an object to provide a thin positive electrode structure that can be supplied, a manufacturing method thereof, and a large-capacity thin lithium-air battery.

In view of the above circumstances, the present investigator developed a thin positive electrode structure having a laminated structure of a positive electrode material and a positive electrode base material and provided with an air or oxygen gas flow channel by trial and error. Thereby, air or oxygen gas can be efficiently supplied to the positive electrode material. Even if this thin positive electrode structure is overlapped with a thin separator and a thin negative electrode structure, the supply of air or oxygen gas to the thin positive electrode structure can be sufficiently secured. The battery capacity can be easily increased.
The present invention has the following configuration.
In the following configuration, one surface of the positive electrode base material is one of the two widest surfaces of the foil-shaped base material, and the groove has a finite width and depth and is constant in the depth direction. The hole is a tunnel-like space in which the groove is covered with a positive electrode material or a positive electrode substrate, for example.

(1) A thin-film positive electrode structure in which a positive electrode material made of a porous body is bonded to a plate-shaped positive electrode substrate, and a gas flow path that leads from one side surface to the positive electrode substrate or the positive electrode material. A thin positive electrode structure in which a groove or a hole is formed.

(2) The thin positive electrode structure according to claim 1, wherein the positive electrode material is made of carbon or a composite material thereof.
(3) The thin positive electrode structure according to (1) or (2), wherein the positive electrode base material includes any one of Ni, Al, and Cu, or an alloy thereof.
(4) The thin positive electrode structure according to any one of (1) to (3), wherein a layer made of an oil-repellent molecule is formed on an inner surface of the gas channel groove or hole.

(5) A plate-like positive electrode material is joined so as to cover a groove formed on one surface and / or the other surface of the positive electrode base material, and the groove is a hole for a gas flow path. The thin positive electrode structure according to any one of (1) to (4).

(6) The positive electrode material composed of two or more columnar members is arranged in parallel and spaced apart, and a space between the positive electrode materials is a groove for a gas flow path (1) The thin positive electrode structure according to any of (4) to (4).

(7) The positive electrode base material is made of a metal foam, has a through hole having an opening on one surface and / or the other surface, a plate-like positive electrode material is joined so as to cover the opening, and the through hole is a gas The thin-film positive electrode structure according to any one of (1) to (4), wherein the thin-film positive electrode structure is a hole for the flow path.
(8) When one surface or the other surface of the positive electrode base material has a substantially rectangular shape in plan view, when the one surface or the other surface is partitioned by a line dividing each side into three equal parts, In any one of (1) to (7), an opening of a gas flow path hole or a gas flow path groove is formed in all of the divided nine regions. Thin positive electrode structure.

(9) After forming a groove extending from one side surface to the opposite side surface on one surface or the other surface of the plate-shaped positive electrode base material, a positive electrode material made of a plate-shaped porous body is joined so as to cover the groove. A step, a step of arranging a positive electrode material composed of two or more columnar porous bodies on one side or the other side of a plate-like positive electrode substrate in parallel and spaced apart, or an opening is formed on one side and / or the other side Any one process selected from the group of processes of using a metal foam having a through-hole as a plate-like positive electrode base material and joining a positive electrode material comprising a plate-like porous body to one surface and / or the other surface thereof A method for producing a thin positive electrode structure, comprising producing the thin positive electrode structure according to any one of (1) to (8).

(10) The thin positive electrode structure according to any one of claims 1 to 8, a thin separator, and a thin negative electrode structure comprising a plate-like negative electrode substrate coated with a Li thin film or Li fine particles, A thin lithium-air battery in which a laminated body is stored in a storage container, wherein a positive electrode substrate of the thin positive electrode structure is connected to a positive electrode tab disposed outside the storage container, and the positive electrode substrate A part of the battery is exposed to the outside of the storage container through an opening provided in the storage container.
(11) The thin lithium-air battery according to (10), wherein a shielding film is attached to the positive electrode base material so that only a part of the positive electrode base material is exposed outside the storage container. .

The thin positive electrode structure of the present invention is a thin positive electrode structure in which a positive electrode material made of a porous body is joined to a plate-shaped positive electrode substrate, and the side surface facing the positive electrode substrate or the positive electrode material from one side surface Since the groove or hole for the gas flow path leading to the gas is connected to the thin electrode and the thin negative electrode structure, the positive electrode active material composed of air or oxygen gas is formed from the continuous groove or hole on the side surface. A substance can be supplied to the positive electrode material, can react with lithium ions contained in the electrolyte held in the positive electrode material, and a large-capacity thin lithium-air battery can be provided.

The method for producing a thin positive electrode structure according to the present invention is such that a groove extending from one side surface to the opposite side surface is formed on one surface or the other surface of a plate-shaped positive electrode substrate, A step of bonding a positive electrode material made of a porous body, a step of arranging a positive electrode material made of two or more columnar porous bodies in parallel and spaced apart on one side or the other side of a plate-like positive electrode base material, or Alternatively, a group of processes in which a metal foam having a through-hole having an opening formed on the other surface is used as a plate-like positive electrode substrate, and a positive electrode material made of a plate-like porous body is joined to one surface and / or the other surface Since the above-described thin positive electrode structure is manufactured by any one process selected from the above, a large-capacity thin lithium-air battery can be easily manufactured.

A thin lithium-air battery according to the present invention is formed by laminating the thin positive electrode structure described above, a thin separator, and a thin negative electrode structure including a plate-like negative electrode substrate coated with a Li thin film or Li fine particles. A thin lithium-air battery in which a laminate is stored in a storage container, wherein the positive electrode base material of the thin positive electrode structure is connected to a positive electrode tab disposed outside the storage container, and a part of the positive electrode base material However, even if it is laminated with a thin separator and a thin negative electrode structure, a positive electrode substrate is formed through the opening of the storage container. The positive electrode active material which consists of air or oxygen gas can be supplied to a positive electrode material from one side which is not in contact with a positive electrode material among these, and a large capacity thin lithium air battery can be provided.

It is a figure of the thin lithium air battery which is embodiment of this invention, Fig.1 (a) is a perspective view, FIG.1 (b) is a top view. FIG. 2 is a diagram of the thin lithium-air battery of FIG. 1, FIG. 2 (a) is a front side view, and FIG. 2 (b) is a right side view. FIG. 3 is a diagram of the thin lithium-air battery of FIG. 1, FIG. 3A is a cross-sectional view taken along line AA ′ of FIG. 1B, and FIG. 3B is BB of FIG. It is sectional drawing in a line. It is an enlarged view in the C section of Drawing 3 (b). It is a figure which shows an example of the thin positive electrode structure which is embodiment of this invention, Fig.5 (a) is a perspective view, FIG.5 (b) is a top view. FIG. 6A is a cross-sectional view taken along the line DD ′ of FIG. 5B, and FIG. 6B is a cross-sectional view taken along a line F in FIG. 6A. It is an enlarged view. It is process drawing which shows the manufacturing method of the thin positive electrode structure which is embodiment of this invention. It is process drawing which shows the manufacturing method of the thin positive electrode structure which is embodiment of this invention. It is a figure explaining the usage method of the thin lithium air battery of this invention. It is a figure explaining the usage method of the thin lithium air battery of this invention. It is a figure which shows another example of the thin positive electrode structure which is embodiment of this invention, Comprising: Fig.11 (a) is a perspective view, FIG.11 (b) is a top view. FIG. 12A is a cross-sectional view taken along the line GG ′ of FIG. 11B, and FIG. 12B is an H portion of FIG. 12A. FIG. It is process drawing of the thin positive electrode structure which is embodiment of this invention. It is a figure which shows another example of the thin positive electrode structure which is embodiment of this invention, Comprising: Fig.14 (a) is a perspective view, FIG.14 (b) is a top view. FIG. 15A is a cross-sectional view taken along the line II ′ of FIG. 14B, and FIG. 15B is a cross-sectional view taken along a line J in FIG. 15A. FIG.

(First embodiment of the present invention)
<Thin lithium-air battery>
First, a thin lithium-air battery that is an embodiment of the present invention will be described.
FIG. 1 is a view showing an example of a thin lithium-air battery according to an embodiment of the present invention, FIG. 1 (a) is a perspective view, and FIG. 1 (b) is a plan view.
2 is a diagram of the thin lithium-air battery of FIG. 1, FIG. 2 (a) is a front side view, and FIG. 2 (b) is a right side view.

As shown in FIGS. 1 (a) and 1 (b), a thin lithium-air battery 101 according to an embodiment of the present invention is formed by stacking two upper and lower film materials 91a and 91b having a substantially rectangular shape in plan view, and surrounding the periphery. The storage container 92 is configured by bonding. On the short side, plate-like tabs 97, 98 protrude outward from the inside of the storage container 92. An opening 99 is provided on the side surface of the storage container 92.
For the film materials 91a and 91b for the storage container, a material having at least an electrically insulating surface is used. This is to prevent an electrical short circuit between the two protruding tabs. For example, a laminate film in which a metal foil is coated with a polymer film having adhesiveness by heat can be used.

As shown in FIG. 2A, on the tab 97, a plurality of positive electrode bases 81 are laminated and pressure-bonded or bonded. As shown in FIG. 2B, an opening 99 having a substantially rectangular shape in plan view is provided on the side surface of the thin lithium-air battery 101.
As shown in FIGS. 2 (a) and 2 (b), the film materials 91a and 91b for the storage container having a substantially rectangular shape in plan view, which are arranged one above the other, are bonded on the one surface side and the other surface side of the peripheral portion. ing.

3 is a diagram of the thin lithium-air battery of FIG. 1, FIG. 3 (a) is a cross-sectional view taken along line AA ′ of FIG. 1 (b), and FIG. 3 (b) is FIG. 1 (b). It is sectional drawing in the BB 'line | wire. FIG. 4 is an enlarged view of a portion C in FIG.
As shown in FIGS. 3A and 3B, the storage container 92 formed by adhering two storage container film materials 91a and 91b at the periphery includes an air battery body. A certain laminated body 80 is accommodated.
As shown in FIG. 4, the laminate 80 is formed by laminating three unit structures 88 between two thin separators 83 with the thin separator 83 interposed therebetween.
The unit structure 88 is formed by laminating a thin positive electrode structure 86, a thin separator 83, and a thin negative electrode structure 87. The thin negative electrode structure 87 is formed by laminating the negative electrode material 85 on both surfaces of the negative electrode base material 84, and the thin positive electrode structure 86A is formed by forming positive electrode materials 82A1 and 82A2 on both surfaces of the positive electrode base material 81A.

The laminate 80 is filled with an electrolytic solution (not shown). The amount of the electrolyte is such that the stacked positive electrode materials 82A1 and 82A2 and the entire thin separator 83 are impregnated.

As shown in FIG. 3A, a shielding film 100 is attached to one long side of the laminate 80. The laminated body 80 is shielded from the atmosphere outside the storage container 92 by the shielding film 100. However, one long side end of the positive electrode base material 81 </ b> A having a path for transporting the positive electrode active material can be taken in outside air by the opening 99 provided in the storage container 92. Thus, air or oxygen gas, which is a positive electrode active material, can be supplied from the outside of the storage container 92 into the positive electrode base material 81A via the end portion of one long side of the positive electrode base material 81A. .

The shielding film 100 is made of an organic material or an inorganic material. For example, an insulating polyimide film is used as the organic material. As the inorganic material, insulating glass such as SiO ₂ can be used. The reason for using an insulating material is that it may come into contact with the electrolytic solution, and a metal foil coated with an insulating material may be used. Thereby, it is possible to prevent the electrolyte from leaking out of the storage container 92 through the opening 99, and at the same time, it is possible to prevent the inflow of air or oxygen gas from the outside of the storage container 92 to the thin negative electrode structure 87.

As shown in FIG. 3B, one short side end of the positive electrode base material 81 </ b> A of the thin positive electrode structure 86 </ b> A is connected to a tab 97. In addition, one short side end of the negative electrode base 84 of the thin negative electrode structure 87 is connected to the tab 98.

(Thin separator)
The thin separator 83 is made of an insulator. For example, a porous film made of fibrous polypropylene or polyethylene can be used. Thereby, since the electrolyte solution containing Li ions is impregnated, Li ions can pass through the thin separator, and a short circuit due to direct contact between the positive electrode material and the negative electrode material can be avoided.

(Thin negative electrode structure)
The negative electrode substrate 84 is made of a metal thin plate or foil. By using a metal, it can function as a current collector.
The negative electrode material 85 is made of a Li thin film or a Li foil. Thereby, Li which comprises Li thin film or Li foil can be utilized as a negative electrode active material. The Li thin film or the Li foil can be easily formed by a known method, for example, by vacuum-depositing Li on the negative electrode base material or attaching a rolled Li foil on the negative electrode base material.
In FIG. 4, the negative electrode material 85 is formed on both surfaces of the negative electrode substrate 84, but only one surface may be used.

(Thin positive electrode structure)
FIG. 5 is a view showing an example of a thin positive electrode structure according to an embodiment of the present invention, FIG. 5 (a) is a perspective view, and FIG. 5 (b) is a plan view.
6 is a diagram of the thin positive electrode structure of FIG. 5, FIG. 6 (a) is a cross-sectional view taken along the line DD ′ of FIG. 5 (b), and FIG. 6 (b) is FIG. 6 (a). It is an enlarged view in F section.

As shown in FIG. 5A, a thin positive electrode structure 86A according to an embodiment of the present invention has positive electrode materials 82A1 and 82A2 formed on both surfaces of a positive electrode base material 81A.
The positive electrode base material 81A has a substantially plate shape, and grooves are formed on one surface and the other surface. These grooves serve as gas flow passage holes 15A by arranging the positive electrode materials 82A1 and 82A2. The gas flow passage hole 15 </ b> A communicates with all the side surfaces of the positive electrode substrate 11.

As shown in FIG. 5 (b), the gas flow passage holes 15A are formed so that one surface of the positive electrode base member 81A has a substantially lattice shape in plan view. One is formed in a plurality of lines having a width l. These are arranged in parallel at regular intervals. The other is formed in a plurality of lines having a width m. These are arranged in parallel at regular intervals. The gas passage hole 15A formed in a straight line having a width l and the gas passage hole 15A formed in a straight line having a width m intersect each other vertically.
The lengths of the widths l and m may be the same or different. For example, the widths l and m are 10 nm to 500 μm, the pitch (period) of the gas flow path holes 15A is 100 μm to 1 mm, and the depth of the gas flow path holes 15A is 0.1 μm to 10 μm. .
The width, depth, pitch, and direction of the gas flow passage holes 15A do not have to be the same in the surface of the positive electrode base material 81A, and may be formed irregularly.

As shown in FIG. 5B, one surface of the positive electrode base material 81A on which the gas flow passage hole 15A is formed has a substantially rectangular shape in plan view.
One surface of the positive electrode base material 81A in which the gas flow passage holes 15A are formed is divided into nine regions in a substantially lattice shape in a plan view when each side is partitioned by lines d1, d2, d3, and d4. It is partitioned into R1, R2, R3, R4, R5, R6, R7, R8, R9.
Each of the divided nine regions R1 to R9 has a substantially rectangular shape in plan view, and at least one gas flow channel hole 15A is formed in each of these regions, and adjacent regions at the boundaries of the regions. This is communicated with a gas flow passage hole 15A. Further, in the region in contact with the end portion of the positive electrode substrate 81A, the gas flow passage hole 15A is communicated with the outside in at least a part thereof.
With the above structure, air or oxygen gas can be uniformly supplied to every corner of the positive electrode material when used as the air or oxygen gas flow path of the gas flow path hole 15A.

As shown in FIGS. 6A and 6B, the positive electrode material 82A is formed so that the one surface 82Aa of the positive electrode material 82A1 is in contact with the one surface 81Aa of the positive electrode substrate 81, and the other surface 81Ab of the positive electrode substrate 81 is contacted. Is also formed so as to contact one surface 82Aa of the positive electrode material 82A2.
The positive electrode substrate 81A is composed of silicon (Si) 11A having grooves, a metal layer 17A, and a layer 18A made of oil-repellent molecules. The groove formed in the positive electrode base material 81A is a hole 15A for a tunnel-like gas flow path by disposing the positive electrode material 82A1 so as to be in contact with 81Aa.

The metal layer 17A is formed so as to cover the surface of the silicon (Si) 11A.
The metal layer 17A is made of any metal of Ni, Al, Cu or an alloy thereof. Thereby, the electrical resistance of the positive electrode base material 81A surface can be lowered, and battery performance can be maintained. Between the metal layer 17 </ b> A and silicon (Si) 11 </ b> A, 1 to 20 nm of Ti or Ta may be disposed as an adhesion layer.

As shown in FIG. 6B, the positive electrode material 82 is made of a porous body having pores 21Ac.
As the material of the positive electrode material 82A1, carbon (C) or a composite material containing carbon as a main component is used. Examples of carbon (C) or a composite material containing carbon as a main component include carbon fine particles or carbon nanostructures such as carbon nanotubes and nanohorns. The pore diameter s is set to 1 nm or more and 1000 nm or less. By having the pore 21Ac, the electrolytic solution can be infiltrated into the pore 21Ac, and Li ions can be transported efficiently.
For example, in the case of a structure in which graphene pieces are stacked, if the distance between adjacent graphene pieces is less than 1 nm, it is almost the same as graphite, and it is difficult to operate as an air battery, and Li ion intercalation occurs instead. . In the case of 1000 nm or more, the carbon surface density becomes too small as a reaction field, and the purpose of increasing the capacity is not fulfilled.

The layer 18A made of oil-repellent molecules is formed so as to cover the surface of the metal layer 17A in the gas flow path hole 15A. Fluoroalkylsilanes are used as the material for the oil repellent molecule. As a result, even if the electrolyte stored in the pore 21Ac in the positive electrode material 82A1 is dropped into the gas flow path hole 15A, the electrolyte is turned into a droplet, and the inner surface of the gas flow path hole 15A. It does not spread upward and does not obstruct the flow of air or oxygen gas.

The positive electrode base material 81A is not limited to the configuration of the silicon (Si) 11A and the metal layer 17A formed on the surface thereof, but may be composed of only one of Ni, Al, Cu, or an alloy thereof. Good.

<Method for producing thin positive electrode structure>
7 and 8 are process cross-sectional views illustrating a method of manufacturing the thin positive electrode structure shown in FIG.
First, as shown in FIG. 7A, plate-like silicon (Si) 11A is prepared.
Next, as shown in FIG. 7B, after the adhesion improving layer 12 is formed on one surface and the other surface, a mask layer 13 is formed so as to cover the adhesion improving layer 12.
As a material for the adhesion improving layer 12, hexamethyldisilane (HMDS) or the like is used.
The thickness of the mask layer 13 is, for example, about 20 μm. Note that a photoresist or SiO ₂ is used as the mask layer 13.

Next, as shown in FIG. 7C, the mask layer 13 is patterned by photolithography.
Next, as shown in FIG. 7 (d), the adhesion improving layer 12 is removed by dry etching using the patterned mask layer 13 as a mask, and the cross-sectional width l ′ of the silicon (Si) 11 is removed. The groove 14A is formed.
Note that a wet etching method may be used instead of the dry etching method. This is because the accuracy of the shape may be low.

Next, as shown in FIG. 8A, the mask layer 13 and the adhesion improving layer 12 are removed.
Next, as shown in FIG. 8B, a metal layer 17A is formed so as to cover the inner surface, one surface, and the other surface of the groove 14A of silicon (Si) 11.
By providing the metal layer 17A, the electric resistance (internal resistance) on the surface of the positive electrode base material 81A can be reduced. For forming the metal layer 17A, a CVD method, a sputtering method, or an electrolytic plating method is used. The thickness k of the metal layer 17A may be a thickness that does not fill the groove 14A, that is, 1/2 or less of the groove depth, but the cross-sectional width l of the oxygen gas flow path is more than half of the cross-sectional width l ′ of the groove 14A. It is preferable that the thickness is not more than the remaining thickness. This is for suppressing the functional deterioration of the air or oxygen gas flow path. Between the metal layer 17A and the substrate 11A, Ti or Ta may be disposed as an adhesion layer with a thickness of 1 to 20 nm using a sputtering method or a CVD method.

Next, a layer 18A made of oil-repellent molecules is formed so as to cover the metal layer 17A.
As a film forming method, for example, a dipping method in which a substrate is immersed in a solution in which oil repellent molecules are dispersed to adsorb the surface of the oil repellent molecules, or the oil repellent polymer itself is heated in the air or in a vacuum. Phase vapor deposition can be used. In addition, a spin coating method, a brush coating method, or the like can be used. By using these film forming methods, the oil repellent molecules can be chemically adsorbed uniformly on the surface of the metal layer 17A, and the layer 18 made of oil repellent molecules can be formed.

Next, as shown in FIG. 8C, the layer 18A made of oil-repellent molecules on the inner surface of the groove 14A is left, and only the layer 18A made of oil-repellent molecules on one side and the other side is removed by etching. And the metal layer 17A on the other surface side is exposed. As the etching process, a dry etching method or the like is used. For example, it is removed by dry etching using RF or DC plasma for Ar gas of 1 to 100 mTorr.

Next, the positive electrode materials 82A1 and 82A2 are formed so as to be bonded to the metal layer 17A on the one surface side and the other surface side of the positive electrode base material and cover the upper opening of the groove 14A.
As a method for forming the positive electrode materials 82A1 and 82A2, various gas phase chemical reaction methods (CVD methods) such as a plasma CVD method or a cat-CVD method, a sputtering method, or the like is used. In the CVD method, CH ₄ , CH ₃ OH, C ₂ H ₂ , C ₂ H ₆ , or a molecule having a benzene ring is used as a hydrocarbon material.
When the plasma CVD method, hot wire CVD, or cat-CVD method is used, radicals suitable for growth can be generated from the raw material molecules by the action of plasma or catalyst, and the progress of the gas phase reaction is promoted. There is an effect that the substrate heating temperature required for the film can be lowered.
The substrate heating temperature during film formation is preferably 400 ° C. or lower.

The thickness of the positive electrode materials 82A1 and 82A2 is preferably 0.1 μm or more, and more preferably 0.8 μm or more. By setting the thickness of the positive electrode materials 82A1 and 82A2 to 0.1 μm or more, the battery internal resistance can be reduced. In addition, the situation where the metallic lithium of the negative electrode facing at the time of discharge becomes all Li ions and becomes a lithium peroxide on the surface of the positive electrode is the best balance as the positive electrode surface area of the battery. Can be realized.

As a method of forming the positive electrode materials 82A1 and 82A2, a method of dispersing, applying, and drying carbon-based secondary particles may be used as in the case of a lithium ion battery or a fuel cell.
Moreover, you may use the method of pressing and adhering plate-shaped positive electrode material 82A1, 82A2.
Through the above steps, the thin positive electrode structure 86A shown in FIG. 6A can be manufactured.

<How to use thin lithium batteries>
FIG. 9 is an explanatory diagram showing an example of how to use a thin lithium battery.
As shown in FIG. 9, the thin lithium battery 101 is stored in a storage container 201 and used.
A gas exhaust pipe 202 </ b> B and a gas supply pipe 202 </ b> A are attached to the storage container 201, and the portions other than the connection portions of 202 </ b> A and 202 </ b> B are sealed.
The inside of the storage container 201 can be decompressed by a pump 203 connected to the gas exhaust pipe 202B. After depressurizing the inside of the storage container 201, the valve 204 of the gas exhaust pipe 202B is closed, and the pump 203 is operated from a gas supply unit (not shown), whereby the storage container 201 can be filled with air or oxygen gas.
When the storage container 201 is filled with air or oxygen gas, air or oxygen gas can be supplied from the opening 99 of the storage container of the thin lithium battery 101 into the thin positive electrode structure, and the battery reaction can be started.

Within the storage container 201, the two tabs 97 and 98 of the thin lithium-air battery 101 are connected to the blades 205 and 206. The blades 205 and 206 are connected to output terminals 206 and 208, and the electric power generated in the thin lithium-air battery 101 can be taken out from the output terminals 206 and 208 to the outside.

FIG. 10 shows another example of how to use a thin lithium battery.
As shown in FIG. 10, four thin lithium-air batteries 101 according to the first embodiment of the present invention are stacked. Each thin lithium-air battery 101 has tabs 97 and 98 connected by a tab connecting member 96 so as to be connected in series.
Thus, by increasing the number of stacked layers, the output voltage can be easily increased.

(Second embodiment of the present invention)
<Thin positive electrode structure>
FIG. 11 is a diagram showing another example of a thin positive electrode structure according to an embodiment of the present invention.
As shown in FIG. 11A, in the thin positive electrode structure 86B according to the embodiment of the present invention, square columnar positive electrode materials 82B1 and 82B2 are arranged in parallel on both surfaces of a substantially rectangular positive electrode base material 81B in plan view. A layer 18B made of an oil-repellent molecule is formed so as to cover the positive electrode base material 81B and the positive electrode materials 82B1 and 82B2.
As shown in FIGS. 11A and 11B, between the adjacent positive electrode members 82B1 and 82B2, grooves 14B for a gas flow passage having a width n in a planar view are formed in parallel at regular intervals. .

As shown in FIG. 11B, one surface of the positive electrode base material 81B on which the gas flow channel groove 14B is formed has a substantially rectangular shape in plan view.
One surface of the positive electrode base material 81B on which the gas flow channel groove 14B is formed is divided into nine regions R1 to R9 when divided on lines d1, d2, d3, and d4 that divide each side into three equal parts. Are substantially rectangular in a plan view, and in all of these regions, the gas flow channel groove 14B communicates with the gas flow channel groove 14B in the adjacent region at the boundary of each region. Further, in the region in contact with the end portion of the positive electrode base member 81A, the gas flow channel groove 14B communicates with the outside at least in a part thereof.
With the above structure, it can be used as the air or oxygen gas flow path of the gas flow channel groove 14B, and air or oxygen gas can be uniformly supplied to every corner of the positive electrode material.

12 is a diagram of the thin positive electrode structure of FIG. 11, in which FIG. 12 (a) is a cross-sectional view taken along the line GG ′ of FIG. 11 (b), and FIG. 12 (b) is a diagram of FIG. FIG.
As shown in FIGS. 12A and 12B, the positive electrode base member 81B is composed of 11B made of silicon (Si) or SiO ₂ and a metal layer 17B covering the silicon (Si) 11B. On the metal layer 17B, positive electrode members 82B1 and 82B2 having a quadrangular prism shape in cross section are arranged in parallel. An insulating layer 19 is formed between the adjacent positive electrode members 82B1 and 82B2 and on the metal layer 17B. A layer 18B made of oil-repellent molecules is formed so as to cover the positive electrode materials 82B1 and 82B2 and the insulating layer 19. A gas flow channel groove 14B having a cross-sectional width n is formed between adjacent positive electrode members 82B1 and 82B2.
The gas flow channel 14B communicates from one side surface to the opposite side surface. Therefore, air or oxygen gas can be supplied into the thin positive electrode structure 86 </ b> B from one side surface from one side surface. A thin separator is disposed on one side and the other side of the thin positive electrode structure 86B, and the gas flow channel groove 14B functions as a flow channel for circulating air or oxygen gas.

As shown in FIG. 12B, the positive electrode materials 82B1 and 82B2 are made of carbon (C) having a pore 21Bc having a cross-sectional width s or a porous body 21B of a composite material thereof. Thereby, electrolyte solution can be osmose | permeated in the pore 21Bc.
As the material of the metal layer 17B, a metal of Ni, Al, or Cu or an alloy thereof is used.
The layer 18B made of oil repellent molecules is made of fluoroalkylsilanes.

With the above configuration, the oxygen ions (positive electrode active material) contained in the air or oxygen gas flowing in the gas flow channel 14B are taken into the pores 21Bc in the positive electrode material 82B1 and permeate into the pores 21Bc. The battery can be reacted with Li ions (negative electrode active material) contained in the electrolyte solution on the surface of the positive electrode material 82B1.

<Method for producing thin positive electrode structure>
FIG. 13 is a process cross-sectional view illustrating a method of manufacturing the thin positive electrode structure shown in FIG.
First, as shown in FIG. 13A, silicon (Si) 11B having a substantially rectangular shape in cross section is prepared.
Next, as shown in FIG. 13B, a metal layer 17B is formed on one surface of the silicon (Si) or SiO ₂ substrate 11B.

Next, an insulator thin film is deposited by CVD or sputtering so as to cover the metal layer 17B.
As a material of the insulator thin film, a material having a high electrical withstand voltage is preferable, and it may be an organic material or an inorganic material. In particular, such SiO _{2, Al} 2 _{O 3} is preferred. The thickness of the insulator thin film is 10 nm or more and 1 μm or less.

Next, as illustrated in FIG. 13C, the insulating thin film 19 is formed by patterning the insulator thin film into a stripe shape by a photolithography method.
The stripe width of the insulating layer 19 is 0.1 μm or more and 1 mm or less. The stripe period is 0.2 μm or more and 2 mm or less.

Next, as shown in FIG. 13D, a carbon-based material is used on the metal layer 17B exposed between the adjacent insulating layers 19 by using a carbon-based material by thermal CVD, plasma CVD, or thermal catalytic CVD. A positive electrode material 82B1 is grown. A groove 14B is formed between adjacent positive electrode materials 82B1.
When carbon-based nanostructures such as carbon nanotubes and nanohorns are used, the carbon-based nanostructures selectively grow the positive electrode material 82B mainly only on the metal layer 17B that functions as a catalyst. However, the carbon-based nanostructure does not completely grow selectively only on the metal layer 17 </ b> B, but is slightly deposited on the insulating layer 19. The carbon-based nanostructure that is slightly deposited on the insulating layer 19 is removed by dry etching in plasma using a gas such as CF ₄ , CHF _3, or SF ₆ after the growth of the positive electrode material 82B1.

Next, as shown in FIG. 13E, the other surface side of the positive electrode base material 81B is processed in the same manner as the one surface side to grow the positive electrode material 82B2.
Next, a layer 18B made of an oil repellent molecule is formed so as to cover the one surface side and the other surface side by a method similar to the method described in the first embodiment.
Note that a layer 18B made of an oil-repellent molecule may be formed in advance on the insulating layer 19 formed on the positive electrode substrate 81B and the metal layer 17B. Further, by forming the insulating layer 19 with molecules made of fluoroalkylsilanes, the insulating layer 19 may also serve as the layer 18B made of oil-repellent molecules. At this time, the positive electrode materials 82B1 and 82B2 are formed later, but the layer 18B made of oil-repellent molecules may not be provided on the surfaces of the positive electrode materials 82B1 and 82B2.
Through the above steps, the thin positive electrode structure 86B can be formed.

(Third embodiment of the present invention)
<Thin positive electrode structure>
FIG. 14 is a view showing still another example of a thin positive electrode structure according to an embodiment of the present invention, in which FIG. 14 (a) is a perspective view and FIG. 14 (b) is a plan view.
15A is a cross-sectional view taken along the line II ′ of FIG. 14B, and FIG. 15B is a cross-sectional view taken along line J in FIG. 15A. FIG.
As shown in FIGS. 14A and 15A, a thin positive electrode structure 86C according to an embodiment of the present invention is formed by forming positive electrode materials 82C1 and 82C2 on both surfaces of a positive electrode substrate 81C.

As shown in FIG. 14A, a plate-shaped foam metal is used for the positive electrode base material 81C. The foam metal is a metal porous body and has a porosity (porosity) of 75 to 99% and a pore diameter of about 10 μm to 1000 μm. As the material of the foam metal, any one of Ni, Al, and Cu or an alloy thereof is used.
The positive electrode base material 81C made of a foam metal has a hole 15C for a flow path of a three-dimensional network gas.

As shown in FIG. 14B, one surface of the positive electrode base material 81C in which the gas flow passage hole 15C is formed is substantially rectangular in plan view.
One surface of the positive electrode base material 81C in which the gas flow passage hole 15C is formed is divided into nine regions R1 to R9 when the sides are divided by lines d1, d2, d3, and d4. Are substantially rectangular in a plan view, and an opening of a gas flow path hole 15C is formed in all of these regions.
Thereby, when used as the air or oxygen gas flow path of the hole 15C for the gas flow path, air or oxygen gas can be uniformly supplied to every corner of the positive electrode material.

As shown in FIG. 15B, the positive electrode base material 81C made of a foam metal has a hole 15C for a flow path of a three-dimensional network gas having a cross-sectional width t. Although not shown in FIGS. 14 and 15, the inner surface of the gas flow passage hole 15C is covered with a layer made of oil-repellent molecules. Thus, even if the electrolyte solution leaks into the gas flow passage hole 15C, the electrolyte solution has a droplet shape and does not hinder the flow of air or oxygen gas.

<Method for producing thin positive electrode structure>
First, a commercially available plate-like foam metal material is prepared.
Next, in the same manner as in the first embodiment, positive electrode materials 82C1 and 82C2 are formed on both surfaces of the foam metal material.
Next, an oil-repellent molecular vapor is sprayed to form a layer made of oil-repellent molecules on the inner surface of the pores of the foam metal material.
The thin positive electrode structure 86C can be manufactured through the above steps.

Before forming the positive electrode materials 82C1 and 82C2, the oil-repellent molecular vapor may be sprayed on the inner walls of the three-dimensional network. In this case, under the pressure adjusted Ar gas etc. from 10 mTorr to 50 mTorr, the layer made of oil-repellent molecules near the surface of the entire surface of the foam metal is removed by DC or RF plasma to expose the surface of the metal foam material. . At this time, a part of the oil-repellent molecules inside the hole may be removed.
Thereafter, positive electrode materials 82C1 and 82C2 are formed on both surfaces of the foam metal material. It is preferable that the positive electrode materials 82C1 and 82C2 cover the regions where the oil-repellent molecules in the holes are removed by the plasma process. When the positive electrode materials 82C1 and 82C2 are formed by the CVD method, the pressure during film formation can be controlled, and when the method of dispersing, applying, and drying the carbon-based secondary particles is used, the press pressure before drying can be controlled.
The thin positive electrode structure 86C may be manufactured by this method.

When foam metal is used, since the pore diameter is 10 μm or more, the positive electrode materials 82C1 and 82C2 may enter the inside of the pores too much. In this case, two sheets in which the positive electrode materials 82C1 and 82C2 are applied in advance on one side The thin positive electrode structure 86C can be manufactured by pasting the positive electrode materials 82C1 and 82C2 to one surface or the other surface of the positive electrode base material 81C from which the oil-repellent molecules are removed only as described above. Good.

In order to make the pore diameter 10 μm or less, a metal nonwoven fabric may be used as the positive electrode substrate 81C. The hole diameter of the metal nonwoven fabric is several μm to several hundred μm.

In the thin positive electrode structures 86A, 86B, 86C according to the embodiment of the present invention, positive electrode materials 82A1, 82A2, 82B1, 82B2, 82C1, 82C2 made of a porous material are joined to plate-like positive electrode base materials 81A, 81B, 81C. The thin positive electrode structure has a structure in which grooves 14B or holes 15A and 15C for gas passages extending from one side surface to the opposite side surface of the positive electrode base material or the positive electrode material are formed. Even when laminated with the negative electrode structure, the positive electrode active material made of air or oxygen gas is efficiently supplied to the positive electrode material from one side of the positive electrode substrate that is not in contact with the positive electrode material, and the electrolytic solution in the positive electrode material Can be reacted with Li ions contained in the battery, and a large capacity can be realized by a multilayer structure, and a large-capacity thin lithium-air battery can be provided.

  The thin positive electrode structures 86A, 86B, 86C according to the embodiments of the present invention are configured such that the positive electrode material is made of carbon or a composite material thereof, so that the electrolytic solution can be held in the pores of the positive electrode material, and the grooves Alternatively, air or oxygen gas flowing through the pores can be efficiently taken into the pores of the positive electrode material, and Li ions, which are negative electrode active materials contained in the electrolyte solution in the pores of the positive electrode material, and air or Oxygen ions, which are positive electrode active materials contained in oxygen gas, can be reacted efficiently on the inner wall surfaces of the pores of the positive electrode material.

In the thin positive electrode structures 86A, 86B, 86C according to the embodiment of the present invention, since the positive electrode base material has a metal of Ni, Al, or Cu or an alloy thereof, a highly conductive metal or an alloy thereof is used. It can be used as a current collector for the current generated by the battery reaction, and the efficiency of the battery reaction can be increased.

The thin positive electrode structures 86A, 86B, 86C according to the embodiment of the present invention have a structure in which an oil repellent molecule layer is formed on the inner surface of the gas flow channel groove or hole. Intrusion of the electrolyte solution impregnated in the positive electrode material into the groove or hole serving as a path can be suppressed. Even if the electrolyte enters, it can be made into droplets. Thereby, the flow of air or oxygen gas can be secured without blocking the air or oxygen gas flow path. Furthermore, it can suppress that the droplet which consists of electrolyte solution has an electrochemical influence on battery operation.

In the thin positive electrode structure 86A according to the embodiment of the present invention, plate-like positive electrode materials 82A1 and 82A2 are joined so as to cover the groove 14A formed on one surface and / or the other surface of the positive electrode base material 11A, and the groove 14A is formed. Since it is configured as the gas flow passage hole 15A, air or oxygen gas can be sufficiently supplied to the positive electrode every corner.

In a thin positive electrode structure 86B according to an embodiment of the present invention, positive electrode materials 82B1 composed of two or more columnar members are arranged in parallel and spaced apart, and a space between the positive electrode materials 82B1 is a groove for a gas flow path. Since it is the structure made into 14B, air or oxygen gas can fully be supplied to a positive electrode material to every corner.

In the thin positive electrode structure 86C according to the embodiment of the present invention, the positive electrode base material 81C is made of a metal foam, has a through hole having an opening on one surface and / or the other surface, and has a plate shape so as to cover the opening. Since the positive electrode material is joined and the through hole is a gas channel hole, air or oxygen gas can be sufficiently supplied to the positive electrode every corner.

When one surface or the other surface of the positive electrode substrate is substantially rectangular in plan view, when the one surface or the other surface is partitioned by a line dividing each side into three equal parts, the one surface or the other surface is partitioned. Since all of the nine regions are configured to have gas channel hole openings or gas channel grooves, air or oxygen gas can be sufficiently supplied to the cathode material.

In the manufacturing method of the thin positive electrode structures 86A, 86B, 86C according to the embodiment of the present invention, a groove extending from one side surface to the side surface facing from one side surface is formed on one surface or the other surface of the plate-shaped positive electrode base material, A step of joining a positive electrode material made of a plate-like porous body so as to cover the groove, a positive electrode material made of two or more columnar porous bodies being parallel and spaced apart on one surface or the other surface of the plate-like positive electrode base material A metal foam having a through-hole forming an opening on one side and / or the other side is used as a plate-like positive electrode substrate, and the one side and / or the other side is formed from a plate-like porous body. Since the thin positive electrode structure is manufactured by any one process selected from the group of processes for joining the positive electrode materials, the thin positive electrode structure having a groove or a hole for a gas flow path can be easily obtained. Can be manufactured.

A thin lithium-air battery 101 according to an embodiment of the present invention has a thin negative electrode structure comprising thin positive electrode structures 86A, 86B, 86C, a thin separator 83, and a plate-like negative electrode substrate coated with a Li thin film or Li fine particles. A thin lithium-air battery in which a stacked body 80 is stacked in a storage container 91, and the positive electrode bases 81 A, 81 B, 81 C of the thin positive structure are disposed outside the storage container 91. Since it is connected to the positive electrode tabs 97 and 98 and a part of the positive electrode base materials 81A, 81B and 81C is exposed to the outside of the storage container 91 through the opening 99 provided in the storage container 91, the separator and Even when laminated with the negative electrode structure, the positive electrode active material made of air or oxygen gas is used as the positive electrode material from one side of the positive electrode substrate that is not in contact with the positive electrode material through the opening of the storage container. A possible paper, can provide a large volume thin lithium-air battery.

In the thin lithium-air battery 101 according to the embodiment of the present invention, the shielding film 100 is attached to the positive electrode base material so that only a part of the positive electrode base materials 81A, 81B, 81C is exposed outside the storage container 91. Therefore, leakage of the electrolyte can be prevented and air or oxygen gas can be prevented from flowing into the negative electrode structure.

The thin positive electrode structure and the thin lithium-air battery, which are embodiments of the present invention, are not limited to the above-described embodiments, and can be implemented with various modifications within the scope of the technical idea of the present invention. Specific examples of this embodiment are shown in the following examples. However, the present invention is not limited to these examples.

Example 1
<Thin positive electrode structure>
First, an adhesion improving layer made of hexamethyldisilane (HMDS) was applied on a plate-like Si substrate having a substantially rectangular shape in plan view.
Next, a photoresist was applied on the adhesion improving layer to a thickness of about 20 μm, and then patterned by photolithography to form a substantially lattice-shaped recess in plan view on one surface.
Next, grooves extending vertically and horizontally were formed on the Si substrate by dry etching. Next, the photoresist used as a mask was removed.
Next, a metal layer made of Ni was formed to a thickness of 0.1 μm by electrolytic plating to form a metal layer coated substrate.

Next, this metal layer coated substrate was immersed in a fluoroalkylsilane dispersion solution, and then pulled up and dried to form a layer made of an oil-repellent molecule made of fluoroalkylsilane on the metal layer.
Next, plasma was generated in an Ar gas of 10 to 100 mTorr by RF, and the layer made of oil-repellent molecules in the portion where the positive electrode material was disposed was removed by dry etching.
Next, using CH ₄ , the substrate heating temperature during film formation is set to 400 ° C. or less, and a carbon-based material is formed by plasma CVD so as to be in contact with the exposed surface of the metal layer and to cover the one surface side. Then, a positive electrode material was formed. Thereby, the Si groove was made a hole. Similarly, a carbon-based material was deposited on the other surface to form a positive electrode material.
Thus, the thin positive electrode structure of Example 1 was manufactured.

(Example 2)
First, an insulator thin film made of SiO ₂ was formed to a thickness of 100 nm on one surface of a substrate made of Ni by a CVD method, and then the insulator thin film was formed into a stripe pattern by a photolithography method.
Next, carbon nanotubes were used as a raw material, and a carbon-based material was selectively grown on the exposed Ni metal by catalytic CVD.
Next, dry etching was performed in plasma using CF ₄ gas to remove the carbon-based material on the insulator thin film, and a plurality of positive electrode materials having a line in plan view were formed at regular intervals.

Next, the same operation was performed on the other surface side to form a positive electrode material having a line in plan view arranged on both surfaces at a predetermined interval.
Next, a layer made of an oil-repellent molecule was applied on the insulator thin film by the same method as in Example 1.
As described above, the thin positive electrode structure of Example 2 was manufactured.

Because of the layer made of oil-repellent molecules, only the positive electrode material was impregnated with the electrolyte solution, and could be separated from the oxygen gas flow path on the insulator thin film.
Since the positive electrode material and the oxygen gas flow path are installed in the same plane, the effective electrode area is reduced. However, oxygen gas was supplied from both sides of the positive electrode material to improve the efficiency of the battery reaction.

(Example 3)
First, a plate material made of foam metal having a substantially rectangular shape in plan view was prepared as a positive electrode base material.
Next, in the same manner as in Example 1, a carbon-based material was formed on both surfaces of a plate material made of foam metal to form a positive electrode material.
Next, the vapor | steam which consists of oil-repellent molecules was poured into the board | plate material which consists of foam metal by the flow of Ar gas, and the layer which consists of oil-repellent molecules was formed in the inner wall of the pore of foam metal.
As described above, the thin positive electrode structure of Example 3 was manufactured.

Example 4
Three unit structures formed by stacking the thin positive electrode structure, the separator, and the thin negative electrode structure of Example 1 were stacked through the separator to form a stacked body.
At this time, the thin positive electrode structure, the separator, and the thin negative electrode structure were overlapped so that the opposing surfaces were in contact with each other as much as possible. Further, the two side surfaces of the positive electrode base material of the thin positive electrode structure were aligned with the two side surfaces of the separator, and the other two side surfaces of the positive electrode base material were arranged so as to protrude from the other two side surfaces of the separator. Further, the three side surfaces of the negative electrode substrate of the thin negative electrode structure were aligned with the three side surfaces of the separator, and the other one side surface of the negative electrode substrate was disposed so as to protrude from the other one side surface of the separator.
As the separator, a separator made of polyethylene fiber having a thickness of 250 μm was used.
Further, as the thin negative electrode structure, a 10 μm thick Cu foil having a Li film of 20 μm on both sides was used.

Next, a partition film was attached so as to partition one side surface of the protruded thin positive electrode structure.
Next, the other one side surface of the positive electrode base material of the protruded thin positive electrode structure is put together, crimped to the tab for the positive electrode, and the other one side surface of the negative electrode base material of the protruded thin negative electrode structure is put together. Crimped to the negative electrode tab.
Next, after the laminate was impregnated with the electrolytic solution, the laminate was stored in the storage container so that one side surface of the thin positive electrode structure protruded from the opening of the storage container was exposed. The containment vessel was completely sealed with a laminate package.
Next, the storage container was placed in the storage container, the positive electrode blade and the negative electrode blade were connected to the positive electrode tab and the negative electrode tab, respectively, and then the storage container was sealed. One gas tube of the containment vessel was connected to the oxygen cylinder and the other gas tube was connected to the pump.
Thus, a thin lithium-air battery of Example 4 was manufactured.

(Example 5)
A thin lithium-air battery of Example 5 was produced in the same manner as Example 4 except that the thin positive electrode structure of Example 2 was used.

(Example 5)
A thin lithium-air battery of Example 6 was produced in the same manner as in Example 4 except that the thin positive electrode structure of Example 3 was used.

By supplying oxygen gas to the laminate in the thin lithium-air batteries of Examples 4 to 6, the electric power generated in the laminate could be taken out from the positive electrode tab and the negative electrode tab.

The present invention has a laminated structure of a positive electrode material and a positive electrode base material, and a thin positive electrode structure capable of supplying a positive electrode active material made of air or oxygen gas to a positive electrode material even when laminated with a separator and a negative electrode structure, and The present invention relates to a large-capacity thin lithium-air battery and can be used in the battery industry, the energy industry, and the like.

11A, 11B ... Silicon (Si), 12 ... Adhesion improving layer, 13 ... Mask layer, 14A ... Groove, 14B ... Gas channel groove, 15A, 15C ... Gas channel hole, 17A, 17B ... Metal layer, 18A, 18B ... Layer made of oil-repellent molecule, 19 ... Insulating layer, 21A, 21B, 21C ... Member made of carbon material, 31 ... Foam metal, 80 ... Laminated body, 81A, 81B, 81C ... Positive electrode Base material, 82A1, 82A2, 82B1, 82B2, 82C1, 82C2 ... Positive electrode material, 21Ac, 21Bc, 21Cc ... Fine pore, 83 ... Separator, 84 ... Negative electrode base material, 85 ... Negative electrode material, 86 ... Thin positive electrode structure, 87 ... Thin negative electrode structure, 88 ... Unit structure, 91a, 91b ... (for storage container) film material, 92 ... Storage container, 96 ... Tab connecting member, 97, 98 ... Tab, 99 ... Opening, 100 ... Partition Irumu, 101 ... thin lithium-air battery, 201 ... storage container, 202 ... gas pipe, 203 ... pressure pump, 204 ... valve, 205 and 206 ... blade, 207, 208 ... output terminal.

Claims (11)

A thin positive electrode structure in which a positive electrode material made of a porous body is joined to a plate-shaped positive electrode substrate,
A thin positive electrode structure in which a groove or a hole for a gas flow path extending from one side surface to the opposite side surface is formed in the positive electrode base material or the positive electrode material.   The thin positive electrode structure according to claim 1, wherein the positive electrode material is made of carbon or a composite material thereof. The thin positive electrode structure according to claim 1, wherein the positive electrode base material includes any one of Ni, Al, and Cu, or an alloy thereof. The thin positive electrode structure according to any one of claims 1 to 3, wherein a layer made of an oil-repellent molecule is formed on an inner surface of the gas channel groove or hole. The plate-like positive electrode material is joined so as to cover a groove formed on one surface and / or the other surface of the positive electrode base material, and the groove is a hole for a gas flow path. The thin positive electrode structure according to any one of 1 to 4.   5. The positive electrode material composed of two or more columnar members is arranged in parallel and spaced apart, and a space between the positive electrode materials is a groove for a gas flow path. The thin positive electrode structure according to any one of the above. The positive electrode base material is made of a metal foam, has a through hole having an opening on one surface and / or the other surface, a plate-like positive electrode material is joined so as to cover the opening, and the through hole is a gas flow path. The thin positive electrode structure according to any one of claims 1 to 4, wherein the thin positive electrode structure is a hole for use. When one surface or the other surface of the positive electrode substrate is substantially rectangular in plan view, when the one surface or the other surface is partitioned by a line dividing each side into three equal parts, the one surface or the other surface is partitioned. The thin positive electrode structure according to any one of claims 1 to 7, wherein an opening for a gas channel or a groove for a gas channel is formed in all nine regions. body. A step of joining a positive electrode material made of a plate-shaped porous body so as to cover the groove after forming a groove that leads from one side surface to the opposite side surface on one surface or the other surface of the plate-shaped positive electrode substrate;
A step of arranging a positive electrode material made of two or more columnar porous bodies in parallel and spaced apart on one surface or the other surface of a plate-shaped positive electrode substrate, or
A metal foam having a through hole having an opening formed on one side and / or the other side is used as a plate-like positive electrode base material, and a positive electrode material made of a plate-like porous body is joined to the one side and / or the other side. A method for producing a thin positive electrode structure, comprising producing the thin positive electrode structure according to any one of claims 1 to 8 by any one step selected from a group of steps. The thin positive electrode structure according to any one of claims 1 to 8, a thin separator, and a thin negative electrode structure comprising a plate-like negative electrode substrate coated with a Li thin film or Li fine particles are laminated. A thin lithium-air battery in which a laminate is stored in a storage container, wherein the positive electrode base material of the thin positive electrode structure is connected to a positive electrode tab disposed outside the storage container, and a part of the positive electrode base material However, the thin lithium-air battery is exposed outside the storage container through an opening provided in the storage container. The thin lithium-air battery according to claim 10, wherein a shielding film is attached to the positive electrode base material so that only a part of the positive electrode base material is exposed outside the storage container.