JP2015153490A - air battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-quality, high-capacity, compact and lightweight air battery for offering an intended voltage, which is arranged by laminating, electrically in series, cells each making a smallest unit capable of forming a primary element serving as a metal air battery so that an electrolytic solution is allowed to infiltrate into lamination parts of the laminated cells, and stabilized in output by preventing the occurrence of a galvanic corrosion or gap corrosion in the lamination parts.SOLUTION: A high-quality, high-capacity, compact and lightweight air battery comprises: unit cells laminated electrically in series so as to form parts which enables the offering of an intended voltage. Each unit cell is arranged by putting a negative electrode metal 100, a separator 200 and an air electrode layer 300 making a reaction layer of a positive electrode in close contact together with the separator 200 sandwiched between the air electrode layer 300 and the negative electrode metal 100. The negative electrode metal 100 of each unit cell having a lamination face on the negative electrode side is covered with a conductive material 110 on the side of the lamination face, so water or electrolytic solution is prevented from touching the surface of the negative electrode metal 100 on the lamination face side, thereby preventing the occurrence of a counter electromotive voltage at the contact faces of the adjacent unit cells.

Description

The present invention relates to an air battery having a laminated structure for increasing output stability in an air battery in which a plurality of metal air batteries are stacked to obtain a desired voltage.

Magnesium is abundant in seawater, the eighth most abundant metal on earth, and its specific gravity is 1.74, the lightest of all metals. This magnesium air battery using magnesium has a high energy density, and there is a possibility that the storage period without using an electrolyte is unused for several decades. A magnesium-air battery is a battery using oxygen in the air as a positive electrode active material and magnesium or a magnesium alloy (hereinafter, both magnesium and magnesium alloy may be collectively referred to as magnesium) as a negative electrode active material. Since oxygen-containing air can be taken in from the atmosphere as necessary, it can be significantly reduced in size and weight as compared with other batteries having a positive electrode active material in the battery container.

Magnesium has high specific value as a battery because of its low specific gravity and abundance on the earth, and many attempts have been made to commercialize resource-saving magnesium-air batteries that use magnesium and oxygen in the air. It has been done, but the current situation is still not satisfactory.

Always carry or store and save light, small, long-term storage, high safety when urgently needed in the event of a disaster or emergency response, or when wearing in a place where a disaster is expected From the standpoint that it can be used anywhere if there is moisture, the magnesium-air battery can exhibit a very good overall capacity.

Against this background, research on magnesium-air batteries has recently become active, and many patents have been issued. The contents of the patent are conductive materials for increasing the reaction rate at the positive electrode, conductive assistant, catalyst and structure, oxygen supply method, reaction area expansion method, temperature control, oxygen supply method, etc. The main content of the negative electrode is related to an electrolyte component and an alloy component for improving the sustainability and stability of the reaction at the negative electrode.

Regarding the reaction on the magnesium surface which is the negative electrode active material, Japanese Patent Application Laid-Open No. 2010-182435 uses a polycarboxylic acid aqueous solution as an aqueous electrolyte for enabling continuous electrolysis, and prevents self-discharge of the negative electrode material, Patent document WO2012144301A1 discloses an alloy component of a magnesium alloy that allows electricity to flow for a long time.

Regarding the improvement of the positive electrode reaction, JP 2009-252637 discloses that a fluorine-containing compound is used as an electrolytic solution to increase the oxygen solubility of the electrolytic solution, thereby increasing the oxygen transfer rate at the air electrode surface and improving the output characteristics. The content of providing modified carbon nanotubes suitable for an air electrode catalyst is disclosed in Japanese Patent Application Laid-Open No. 2012-164492, and the solid surface is painted with a pencil, and the obtained metal-free graphene is effective as an air electrode catalyst in Japanese Patent Application Laid-Open No. 2012-182052. Japanese Patent Application Laid-Open No. 2012-174655 discloses that the air electrode catalyst contains a magnet to improve the function of the catalyst.

Japanese Patent Application Laid-Open No. 2012-256547 discloses a structure in which a positive electrode is arranged on both sides of magnesium for the purpose of extending the life and output, and the positive electrode current collector is uneven for introducing air. Japanese Patent Application Laid-Open No. 2011-181382 discloses a structure in which a surface other than the surface facing the positive electrode is covered with an insulator to realize a uniform electrolytic reaction on the surface of the negative electrode active material.

A structure that increases the capacity per unit volume by stacking a plurality of electrode bodies in which the positive electrode and the negative electrode are arranged via separators, and prevents adverse effects on battery performance caused by insufficient introduction of air when stacked. No. 2013-45684.

In a battery formed by stacking a plurality of basic battery cells formed by stacking four negative electrode active materials, magnesium, separator, air electrode layer, and air electrode current collector, an insulating member is inserted between adjacent basic battery cells. A structure for preventing the occurrence of galvanic corrosion and crevice corrosion is disclosed in published patent WO2013018769A1.

As described above, many studies have been made on metal-air batteries in order to achieve higher density, higher capacity, and higher output, but the main focus of the research is on improving the reaction between the positive and negative electrodes. Some literatures have also been published regarding methods for increasing the reaction area, but no new method for high output and high quality by improving the battery configuration has been found.

As described above, a method of stacking a plurality of batteries and increasing the capacity by efficiently using a space is described in JP2013-45684A and published patent WO2013018769A1, but in JP2013-45684A, There is no detailed description of the laminated portion of the electrode body, that is, the contact portion between the positive electrode and the negative electrode of the electrode body, and at least the contact portion cannot contain an electrolyte.

In the published patent application WO2013018769A1, a basic battery cell (hereinafter referred to as one unit battery consisting of four members) composed of four members of a negative electrode, a separator, a positive electrode catalyst layer, and a positive electrode current collector described in claim 13. In a battery in which a plurality of batteries are stacked in a straight line (sometimes referred to as a “basic battery cell”), the battery is stacked in a straight line with an insulator sandwiched between the basic battery cells. As is clear from the description in the specification of the published patent WO20130181769A1, in the existing technology, an insulator is placed between the stacked batteries to prevent direct contact between the batteries and the galvanic corrosion or crevice corrosion is prevented. It was the only way.

The published patent WO2013018769A1 assumes that water or electrolyte enters between adjacent basic battery cells, and an insulator for the purpose of preventing the occurrence of galvanic corrosion and crevice corrosion when water or electrolyte enters. Is inserted.

In the case of the published patent WO2013018769A1, for example, the positive electrode and the lead, and the negative electrode and the lead are taken out after being joined by a method such as welding and taken out from the positive electrode of one of the neighboring basic battery cells with respect to all the neighboring basic battery cells. A complicated process of electrically connecting the lead and the lead taken out from the negative electrode of the other basic battery cell prevents the entry of electrolyte into the electrical connection part, and copes with galvanic corrosion and crevice corrosion. There must be.

In the metal-air battery including the magnesium-air battery as described above, various techniques other than the technical literature cited for the reaction at the negative electrode part, the reaction at the positive electrode, or the densification have been studied. However, in a structure in which a plurality of basic battery cells are directly and electrically connected in series, there is no effective technique on the premise that water or an electrolyte enters between the positive electrode and the negative electrode of adjacent batteries.

JP2010-182435 Published patent WO2012144301A1 JP2009-252637 JP2012-164492 JP2012-182052 JP2012-174655 JP2012-256547 JP2011-181382A JP 2013-45684 A Published patent WO2013018769A1

The present invention has been made in view of the current state-of-the-art technology of metal-air batteries in general including the magnesium-air battery as described above, and is based on the premise that the electrolyte enters the most basic air battery unit. This is related to a laminated metal-air battery (hereinafter also referred to as “laminated battery”) for obtaining a desired voltage by stacking a plurality of layers, and prevents the occurrence of galvanic corrosion and crevice corrosion and back electromotive force in the laminated part. In addition to stabilizing the quality of the product, the extra features and features of the metal-air battery are eliminated, eliminating the need for extra parts and processing, realizing a high-output, high-capacity metal-air battery, and simplifying the manufacturing method. It is something to try.

A laminated battery in which a plurality of metal air batteries (hereinafter referred to as “single cells”), which are the most basic units composed of flat plate members, are electrically stacked in series to form a battery having a desired voltage. As described in claim 1, by covering the negative electrode side surface of all the unit cells whose negative electrode side is a laminate surface with a conductive material, the negative electrode metal surface of the unit cell on the laminate surface side is covered. By preventing the direct contact of water and electrolyte solution, it is possible to prevent the generation of counter electromotive force in the layered portion, and to suppress the occurrence of galvanic corrosion and crevice corrosion, realizing a high output and high capacity stacked battery. To do. A cell can be said to be a minimum assembly having a function capable of generating electromotive force by air and metal.

The details of the present invention will be described below. In particular, in recent years, many studies have been made on metal-air batteries, and many patents have been filed. The basic structure of the battery is a structure that has a separator placed between the positive electrode and the negative electrode, in addition to the air electrode that serves as the positive electrode, the electrolyte, and the metal electrode that serves as the negative electrode. Since the expressions are different, the terms used in the present invention will be explained while clarifying their meanings.

The most basic minimum unit battery according to the present invention (previously referred to as “single cell”) is a reaction of oxygen in the air as the positive electrode active material, as shown in claim 1 of the claims. It is configured by laminating an air electrode layer as a field and a metal as a negative electrode active material with a separator interposed therebetween. The unit cell is a battery in which an electrolyte is held in a separator when in use, an air electrode layer that is an oxygen reaction field, a separator for holding an electrolyte, a negative electrode active material (hereinafter referred to as “negative electrode metal”). It is the most basic battery composed of the minimum three members necessary for a certain battery, and is assumed to be unused, and in the following description, it is assumed that water and electrolyte are not included in the constituent elements.

The air battery shown in the prior art document may or may not include the positive electrode current collector in the air electrode layer as described below, but the reaction layer corresponding to the air electrode layer of the present invention has a positive electrode current collector. In the case of being regarded as being integral with the body, the present invention includes both cases in the air electrode layer.

The separator has the same purpose as that described in many of the prior art documents described above, and prevents the short-circuit between the air electrode layer and the negative electrode metal, and plays a role of retaining water and electrolyte. As materials, there are many materials as shown in the prior art documents, but coffee filters and filter papers, natural materials and nonwoven fabrics made of various resins such as polyethylene, fibers made of various resins, glass fibers, etc. are used. be able to.

The disclosed metal-air battery includes a primary battery and a secondary battery, and an aqueous electrolyte and a non-aqueous electrolyte are used as the electrolyte. However, the basic configuration is similar, and it may be considered that the reaction layer of the positive electrode and the negative electrode are almost similar. In addition, the constituent members of the battery that is the subject of the present invention are basically flat members, and the flat portions of the flat plates are used as overlapping batteries, and have a predetermined curvature within a range that does not hinder the close contact between the flat plates. You may do it.

The present invention is convenient for carrying and is for a battery that can be easily operated by adding moisture when necessary, and is a magnesium air primary battery intended to be used for lighting or charging in an emergency or without electricity, When not in use, the battery does not hold the electrolyte inside. However, the present invention can also be used for general metal-air primary batteries and secondary batteries using metals other than magnesium.

Generally, the positive electrode of a metal-air battery is a positive electrode current collector, a catalyst for promoting the reaction between oxygen in the air, which is a positive electrode active material, and water, a conductor for supplying electrons necessary for the reaction, and a conductive auxiliary agent. And a binder to form a positive electrode reaction layer, and in order to obtain a large number of reaction fields, there are three materials: a catalyst, a conductor, and a conductive auxiliary agent used in the positive electrode reaction layer (hereinafter also referred to as “air electrode layer”). In many cases, powder is used, and the specific surface area is made as large as possible by binding with a binder while maintaining a mesh-like space where air and water easily enter between the powders.

In many cases, a porous sheet is used to make the powder into a plate shape, and three types of powders of catalyst, conductor, and conductive auxiliary agent are kneaded on both sides or the surface of the porous sheet, and in a binder. Three types of powders are uniformly dispersed and bound to form a plate. The porous sheet may be a conductor or a non-conductor, but in the case of a conductor, the porous sheet may be used as a positive electrode current collector.

  The conductor of the air electrode layer may be a metal as long as it is a conductive substance. However, various carbon material powders are often used together with a conductive additive, and as a catalyst, the effect has recently been clarified along with noble metals such as manganese dioxide and platinum. Carbon materials such as graphene and feralene that have been used are listed. Since some carbon material powders having a catalytic effect such as graphene are naturally mixed during the production process, three types of powders can be substituted with one carbon material.

In the present invention, a bonding layer in which powder is bound in a plate shape using a porous sheet is referred to as an air electrode layer. The three types of powders are kneaded and bound on both surfaces or one surface of the positive electrode current collector. Include one integrated with the extreme layers.

The reason for using a porous sheet is to provide a large number of reaction fields by allowing air and water to easily enter the entire inside of the air electrode layer. In some cases, the air electrode layer is directly attached to the surface of the body.

Since the function of the positive electrode current collector is to supply electrons over the entire surface of the air electrode layer as much as possible, a material having a small electric resistance in the direction parallel to the laminated surface is preferable. Therefore, in many cases, a metal material is used as the positive electrode current collector. In the case of using a carbon material or the like, a material having a high density and a large thickness is preferable in order to reduce the resistance in the direction parallel to the laminated surface.

The purpose of using the negative electrode current collector is the same as the positive electrode current collector, and is intended to efficiently collect electrons from the entire surface of the negative electrode active material, and has high conductivity in the direction parallel to the laminated surface. Material is preferred. Therefore, a metal material is also preferable when using a negative electrode current collector.

As described above, the positive electrode is roughly classified into three types, the first having the positive electrode current collector inside the air electrode layer, and the second having the air electrode layer on one side of the positive electrode current collector. The third is the one in which the positive electrode current collector is pressed and adhered to the air electrode layer, and the present invention functions effectively for both.

The present invention will be described in more detail. The first required function is that the negative electrode metal of one of the two adjacent unit cells is adjacent to the adjacent unit cell, as shown in claim 1 of the claims. When the battery is located on the contact surface side with the positive electrode, a conductive material is coated on the contact surface side of the negative electrode metal with the adjacent unit cell, and the surface of the negative electrode metal on the contact surface side with water or By preventing the electrolytic solution from directly touching, it is possible to suppress the generation of a counter electromotive voltage at the contact surface between the single cells.

The second required function is to prevent direct contact between the negative electrode active material of one of the adjacent unit cells and the positive electrode of the other unit cell, and when galvanic corrosion and water are injected. It does not cause crevice corrosion.

A unit cell in which a negative electrode metal is coated with a conductive material is arranged such that one of the two surfaces of the negative electrode metal that is not coated with a conductive material is disposed on the contact surface side with the separator, and the air electrode layer is sandwiched between the separators. The battery is configured to be in close contact with each other. The present invention can be said to be a laminated battery in which the number of single cells necessary for securing a target voltage is laminated by using a surface coated with a conductive material as a contact surface to be in close contact with the adjacent single cells.

The effect of the present invention of stacking unit cells that do not have a positive electrode current collector will be described. The unit cell without the positive electrode current collector cannot be supplied with electrons all over the entire surface of the air electrode layer. A battery that does not have a positive electrode current collector has not been put into practical use, but a single battery that does not have a positive electrode current collector is effective in a laminated battery that is formed by stacking single cells.

In order for a single battery not having a positive electrode current collector to function as the laminated battery of the present invention, the single cell on the highest potential side of the laminated battery must be in contact with the air electrode layer and provided with no positive electrode current collector. As a result, the function is significantly reduced.

In both the air electrode layer and the negative electrode inside the unit cell, the redox reaction does not proceed uniformly over the entire surface. Therefore, in order to make the reaction as uniform as possible, all the unit cells constituting the stacked cell have a positive current collector. The present invention is based on the new idea that the function of the positive electrode current collector of one unit cell is assigned to the negative electrode metal of the adjacent unit cell, together with a new idea for the corrosion prevention method. is there.

  The negative electrode metal is often a metal with high conductivity, the reaction proceeds and the consumable part increases, and even if the metal part becomes thin, it functions sufficiently as a current collector. Also works.

In contrast to such a laminated battery, conventionally, an attempt has been made to laminate a basic battery cell by adhering a positive electrode current collector to an air electrode layer, so that a metal that is a positive electrode current collector and a negative electrode active material. Carbanic corrosion and crevice corrosion occurred when the electrolyte entered the metal contact area.

In order to stabilize the quality of the laminated battery, the basic battery cells cannot be directly laminated, and as disclosed in the published patent WO2013018769A1, an insulative material is inserted between adjacent basic battery cells so as to form a straight line. Has been made.

  Batteries with direct stacking of basic battery cells also exist, but the output is unstable due to the influence of the corrosive layer generated on the laminated surface, the life varies greatly, and the manufacturing method for reducing the influence of the corrosive layer is complicated. Become.

Since the negative electrode metal of the cell on the lowest potential side of the laminated battery has no contact with other cells, this non-contact surface must always be coated with a conductive material to prevent contact with water and electrolyte There is no. However, when the negative electrode current collector is brought into close contact with the negative electrode metal of the unit cell on the lowest potential side, or when the lead terminal for taking out electrons is brought into close contact with the negative electrode metal, the negative electrode current collector or lead terminal of the negative electrode metal It is desirable to coat the contact surface.

  The use of various conductive resins is effective as a conductive material that covers the surface of the negative electrode metal in terms of preventing the permeation of the liquid. This is a preferred material because it often uses carbon materials, and when the positive electrode current collector is integrated with the air electrode layer and the metal surface is exposed, metal-to-metal contact does not occur. .

  Other coating methods include metal plating, particularly copper plating and the use of copper clad materials. Further, even a resin having a low conductivity such as an ordinary resin can be used as a conductive material as long as it can be coated with a thin film having a thickness of nanometer order or micrometer order.

  In order to make it easy to take air in the air into the air electrode layer, it is also effective that the coating surface of the negative electrode metal has water repellency. It is also an effective method to use a water-repellent resin having a property of impervious to liquid and liquid as a coating material for the negative electrode metal.

  In the present invention, when the negative electrode metal of one of the two adjacent unit cells is located on the contact surface side with the positive electrode of the adjacent unit cell, the contact surface of the negative electrode with the adjacent unit cell A conductive material is coated on the side of the negative electrode metal so that water or an electrolyte does not touch the surface of the negative electrode metal on the contact surface side. Even when water or an electrolyte enters the contact portion, the surface of the negative electrode metal is not touched, so that generation of a counter electromotive voltage between adjacent air electrode layers of the battery is prevented, and the air electrode layer Can prevent galvanic corrosion and crevice corrosion at the contact area. Furthermore, the negative electrode metal of one unit cell also serves as the positive electrode current collector of the adjacent unit cell, so that the desired voltage can be easily obtained with a stable output voltage of a simple structure with a small number of parts to assemble. It is possible to obtain an air battery that can be secured to

FIG. 1 is an explanatory view showing a stacked state of a stacked battery in which four unit cells are electrically connected in series according to one embodiment of the present invention. It is the figure which can see the plate | board thickness and length of a battery which adhere | attach the planes of a plate-shaped rectangular member. The dimensions are not proportional to the actual product. (Example 1)

  In the present invention, a plate-like air electrode layer, a separator, and a negative electrode metal are stacked to form a single cell, and the cells are electrically connected in series to obtain a high voltage. The lamination | stacking state of the laminated battery which connected the 4 cell was shown. The laminated battery of the present invention will be described based on FIG.

  The four members of the negative electrode metal 100, the separator 200, the air electrode layer 300, and the positive electrode current collector 400 constituting the laminated battery are all flat plate members having the same length and width. The flat portions of the separator 200 and the air electrode layer 300 are in close contact to form a single cell, and the single cells are stacked to constitute a laminated battery. Therefore, FIG. 1 is a view showing the thickness of the members laminated by viewing the laminated state of all the members of the laminated battery from the side. However, as described above, the dimensions are not proportional.

  In order to make the configuration of the four unit cells easy to understand, the constituent members of each unit cell are collectively shown in curly brackets at the top of FIG. 1 and displayed as unit cell 1, unit cell 2, unit cell 3, unit cell 4. .

  The basic configuration of the unit cell is three flat plates of the negative electrode metal 100, the separator 200, and the air electrode layer 300. For the single cell 2, the single cell 3, and the single cell 4, the surface 100a of the negative electrode metal 100 is covered with the conductive material 110. Further, the penetration of water and electrolyte into the surface 100a of the negative electrode metal 100 of the unit cell 2, the unit cell 3, and the unit cell 4 is prevented.

  In Example 1, the magnesium material AZ31B having a thickness of 0.6 mm, a width of 25 mm, and a length of 50 mm as the negative electrode material 100, the conductive material 110 is copper-plated, the vegetable fiber-based nonwoven fabric as the separator 200, and the resin as the air electrode layer 300 Good results were obtained using a porous nonwoven fabric coated with a carbon material powder containing a catalyst with a binder.

  The conductive material 110 is a material that does not allow water or an electrolyte to pass therethrough and good adhesion to the negative electrode metal 100, but does not need a function as a positive electrode current collector. Therefore, the conductive material 110 does not need to be conductive in the direction parallel to the contact surface, and the thickness should be as thin as possible.

The thinner the conductive material 110 is, the easier it is to move electrons through the coating layer of the conductive material 110 because the electric resistance in the direction perpendicular to the adhesion surface decreases.

  The function of the positive electrode current collector will be described with the single battery 1 and the single battery 2 of FIG. In an air battery, the inside of the air electrode layer and the surface of the negative electrode metal do not always react uniformly as viewed from the surface. In particular, regarding the air electrode layer, it is necessary to easily distribute a necessary amount of electrons to necessary portions over the entire surface.

It is the role of the current collector to easily collect and distribute electrons. The current collector is required to be made of a material having low resistance in the direction parallel to the laminated surface, and a metal material is particularly suitable.

The function of the positive electrode current collector will be described with the single battery 1 and the single battery 2 of FIG. Electrons generated by the reaction on the surface of the negative electrode metal 100 of the unit cell 2 facing the separator 200 move in the conductive material 110 in the direction perpendicular to the stacking surface and move to the air electrode layer 300 of the unit cell 1. .

In order to supply a necessary amount of electrons to a necessary portion in the plane of the air electrode layer 300 in accordance with a reaction inside the air electrode layer 300 of the unit cell 1, electrons generated in the unit cell 2 are stacked on the laminated surface. A material corresponding to a positive electrode current collector that can easily move in a parallel direction is required, and in the battery of this configuration, the negative electrode metal 100 of the unit cell 2 serves as the positive electrode current collector.

  Furthermore, the reaction on the surface of the negative electrode metal 100 of the unit cell 2 in contact with the separator 200 of the unit cell 2 cannot be said to be uniform, and electrons generated by the reaction must be able to easily move in the direction parallel to the laminated surface.

The negative electrode metal 100 of the unit cell 2 also functions as a negative electrode current collector that takes in electrons generated on its surface and moves them easily in a direction parallel to the laminated surface. However, when the negative electrode metal 100 is made of powder, a separate negative electrode current collector is required, but the concept is the same and the negative electrode current collector plays the role of the positive electrode current collector.

  As the reaction of the negative electrode metal 100 of the unit cell 2 progresses and the thickness decreases, the resistance in the direction parallel to the laminated surface increases, but the function as a current collector is effectively maintained unless the plate is exhausted.

The point of time when the negative electrode metal 100 of the unit cell 2 loses its function as a current collector is the life of the battery of this configuration, but the life of the metal-air battery provided with the positive electrode current collector is not much different from that of the battery of the present invention.

  Even in a battery equipped with a positive electrode current collector, the reaction of the negative electrode metal is not uniform over the entire surface, and the negative electrode metal is partially consumed at the final stage. This is because it may be considered that the battery deteriorates significantly and the life of the battery itself is reached.

  The positive electrode current collector has been described by taking the contact portion between the unit cell 1 and the unit cell 2 as an example, but the negative electrode metal 100 at the contact portion between the unit cell 2 and the unit cell 3 and at the contact portion between the unit cell 3 and the unit cell 4 is described. The function of the positive electrode current collector is the same as the contact portion between the single cell 1 and the single cell 2.

  The conductive material 110 is preferably a material having a natural electrode potential close to that of the carbon material forming the air electrode layer 300, and functions as long as it is thin or thick as long as it has good conductivity such as copper. In the case of copper, plating or a clad material of the negative electrode material 100 and copper can be used. However, it is desirable that the thickness is thin from the viewpoint of resource saving, and the feature of the present invention is that the thickness can be reduced.

  When the conductive material 110 is a resin containing a conductive material, the contained conductive material is preferably a carbon material. If it is a carbon material, since the natural electrode potential is close to the carbon material constituting the air electrode layer 300 of the adjacent unit cell, a good battery can be obtained with little formation of local batteries.

  As indicated by a minus sign above the negative electrode metal 100 of the unit cell 1 in FIG. 1, in the present Example 1, the negative electrode metal 100 of the unit cell 1 is used as it is as a negative electrode current collector as the whole laminated battery. . When the negative electrode current collector or the lead wire terminal is in close contact with each other, the unit cell 1 is also made by using the negative electrode metal 100 coated with the conductive material 110 in the same manner as the unit cell 2, unit cell 3 and unit cell 4. Is good.

  As a whole battery, the voltage generating part is composed of four single cells, and the positive electrode current collector 400 is closely attached to the air electrode layer 300 of the single cell 4, and this positive electrode current collector 400 is attached to the positive electrode terminal of the entire laminated battery. A laminate type air battery is configured using the member or the positive electrode current collector 400 itself as a positive electrode terminal. In Example 1, stainless steel was used as the positive electrode current collector 400, but other carbon materials and metals having a natural electrode potential may be used.

  When the battery of FIG. 1 is actually used, the separator 200 sucks up and holds the water by immersing the extremely small length portion of the battery shown in FIG. Functions as a battery with a lifetime.

  In Example 1, a stacked battery in which four single cells are stacked as shown in FIG. 1 is used. However, the number of stacked single cells is possible from two. To obtain a higher voltage, the number of stacked layers is increased to four or more. Good. Further, the laminated flat plates may have a shape other than a rectangle.

  By covering the surface of the negative electrode metal that is in close contact with the adjacent battery with a conductive material, even if the cells are connected in series and water or electrolyte enters the contact portion, Generation of counter electromotive force and occurrence of galvanic corrosion and crevice corrosion can be prevented. By preventing the occurrence of corrosion, the variation in potential, internal resistance and life caused by uneven oxide film is reduced, the output is stabilized, and the back electromotive force is prevented from occurring in the laminated part. A lightweight, high-power, high-capacity, high-quality laminated battery can be realized, and an air battery that can be used safely in an emergency or the like can be supplied. In particular, the air battery of the present invention is effective as a battery for long-term storage in an unused state.

100 negative electrode metal 110 conductive material 200 separator 300 air electrode layer 100a negative electrode metal surface

Claims (4)

There is a unit cell unit (unit cell) in which an air electrode layer, which is a reaction field for oxygen in the air, which is a positive electrode active material, and a metal, which is a negative electrode active material, are stacked with a separator in between. In the air battery in which the air electrode layer of one unit battery unit to be stacked and the metal of the other unit battery unit to be stacked are adjacent to each other, on the surface of the metal that is the adjacent negative electrode active material, An air battery in which a film satisfying the following conditions is formed. (1) It has a characteristic that electrons can move between the air electrode layer and the metal.
(2) Protect and shield the metal from the electrolyte for the air battery. The air battery according to claim 1, wherein the metal that is the negative electrode active material is one of magnesium, aluminum, lithium, or an alloy thereof. The air battery according to claim 1 or 2, wherein the coating film covering the surface of the metal that is the negative electrode active material is made of a material having conductivity. The coating film covering the surface of the metal as the negative electrode active material is made of a polymer resin material, and the thickness thereof is thin enough to satisfy the condition (1). Air battery.

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