WO2014073410A1 - Metal-air cell - Google Patents

Abstract

This metal-air cell is characterized in comprising a first liquid-electrolyte chamber for storing a liquid electrolyte, a metal electrode provided in the first liquid-electrolyte chamber and serving as an anode, an air electrode serving as a cathode, a second liquid-electrolyte chamber for storing a liquid electrolyte, and a drive part for delivering the liquid electrolyte; the first and second liquid-electrolyte chambers and the drive part being provided so that the liquid electrolyte flows in at a variable flow rate from the second liquid-electrolyte chamber to the first liquid-electrolyte chamber, or the liquid electrolyte flows out at a variable flow rate from the first liquid-electrolyte chamber and flows to the second liquid-electrolyte chamber.

Description

Metal air battery

The present invention relates to a metal-air battery.

A metal-air battery using a metal electrode having an electrode active material made of metal as an anode and an air electrode as a cathode has a high energy density, and thus has attracted attention as a next-generation battery.
When a metal-air battery is used as a secondary battery, dendritic dendrites may be generated from the metal electrode toward the air electrode inside the battery during charging, which may cause a short circuit. For this reason, a system has been proposed in which a metal-air battery is used as a primary battery and a metal oxide, which is a by-product, is reduced to produce an electrode active material made of metal and supplied to the metal-air battery ( For example, see Patent Documents 1 and 2).

A zinc-air battery is an example of a metal-air battery used as a primary battery. FIG. 13 is a schematic cross-sectional view for explaining the discharge reaction of the zinc-air battery. As shown in FIG. 13, the zinc-air battery has a structure in which a zinc electrode 101 containing metallic zinc as an electrode active material is provided in an alkaline electrolyte 103 and an air electrode 105 is provided on an anion exchange membrane 106 in contact with the electrolyte 103. As the discharge reaction proceeds, electric power is output from the zinc electrode 101 and the air electrode 105. The air electrode 105 is generally a carbon carrier carrying an air electrode catalyst.

In the discharge reaction of the zinc-air battery, the metal zinc of the zinc electrode 101 reacts with hydroxide ions in the alkaline electrolyte 103 to form tetrahydroxozinc (II) acid ions, and electrons are released into the zinc electrode 101. Thereafter, this tetrahydroxo zinc (II) ion is dehydrated and deposited as zinc hydroxide or zinc oxide in the electrolytic solution or on the zinc electrode 101. Further, hydroxide ions are generated by the reaction of electrons, water, and oxygen in the air electrode 105, and the hydroxide ions conduct through the anion exchange membrane 106 and move to the alkaline electrolyte 103. When such a discharge reaction proceeds, the zinc metal of the zinc electrode 101 is consumed, so that zinc metal, which is an electrode active material, is supplied to the zinc-air battery.

JP 2004-14173 A JP 2005-509262 A

However, in the conventional metal-air battery, the metal compound deposited or deposited on the metal electrode may hinder the progress of the electrode reaction, thereby reducing the performance of the metal-air battery.
The present invention has been made in view of such circumstances, and can easily remove a metal compound deposited or adhered on a metal electrode, and can suppress a decrease in performance of the metal-air battery. An air battery is provided.

The present invention includes a first electrolyte tank that stores an electrolyte, a metal electrode that is provided in the first electrolyte tank and serves as an anode, an air electrode that serves as a cathode, a second electrolyte tank that stores an electrolyte, The first and second electrolyte baths, and the drive unit flows in at a flow rate at which the electrolyte changes from the second electrolyte bath to the first electrolyte bath. Provides a metal-air battery characterized in that it is provided so as to flow out from the first electrolyte tank and flow into the second electrolyte tank.

According to the present invention, since the first electrolyte tank that stores the electrolyte, the metal electrode that is provided in the first electrolyte tank and serves as the anode, and the air electrode that serves as the cathode, the battery reaction is allowed to proceed. Thus, electric power can be output from the metal electrode and the air electrode.
According to the present invention, a second electrolytic solution tank that stores an electrolytic solution and a drive unit that sends the electrolytic solution are provided, and the first and second electrolytic solution tanks and the drive unit are configured so that the electrolytic solution is the second electrolytic solution Since it is provided so that it flows in from the tank to the first electrolyte tank or flows out from the first electrolyte tank to flow out to the second electrolyte tank, the electrolyte flows into the second electrolyte tank. The flow which changes in the electrolyte solution to be stored can be generated, and the deposit of the metal compound on the surface of the metal electrode can be separated from the surface of the metal electrode by the flow of the electrolyte solution. Moreover, it can suppress that the deposit of a metal compound is produced | generated on the surface of a metal electrode. Thereby, it can suppress that the electrode reaction in the surface of a metal electrode is inhibited by the deposit on the surface of a metal electrode, and can suppress the fall of the performance of a metal air battery.

It is a schematic top view of the metal air battery of one Embodiment of this invention. FIG. 2 is a schematic sectional view of the metal-air battery taken along a dotted line AA in FIG. It is a schematic sectional drawing of the metal air battery in the range B enclosed with the dotted line of FIG. It is a schematic sectional drawing of a part of metal air battery of one embodiment of the present invention. It is a schematic sectional drawing of a part of metal air battery of one embodiment of the present invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is a schematic sectional drawing of the metal air battery of one Embodiment of this invention. It is typical sectional drawing for demonstrating the discharge reaction of a zinc air battery.

The metal-air battery of the present invention includes a first electrolyte tank that stores an electrolyte, a metal electrode that is provided in the first electrolyte tank and serves as an anode, an air electrode that serves as a cathode, and a second electrolysis that stores the electrolyte. A liquid tank; and a drive unit for feeding the electrolyte solution. The first and second electrolyte tanks and the drive unit flow in at a flow rate at which the electrolyte solution changes from the second electrolyte tank to the first electrolyte tank. Or the electrolytic solution is provided so as to flow out from the first electrolytic solution tank and flow into the second electrolytic solution tank.

In the metal-air battery of the present invention, the first and second electrolyte baths are configured such that the electrolyte stored in the second electrolyte bath flows into the electrolyte stored in the first electrolyte bath due to gravity, and the electrode active material portion and It is preferable that the air electrode is provided so that the electrolyte flowing into the first electrolyte solution tank from the second electrolyte solution tank flows between the electrode active material portion and the air electrode.
According to such a configuration, the electrolyte flowing into the first electrolyte bath from the second electrolyte bath can flow between the electrode active material portion and the air electrode, and the surface of the electrode active material portion The deposit of the metal compound can be separated from the surface of the electrode active material portion by the flow of the electrolytic solution. Moreover, it can suppress that the deposit of a metal compound is produced | generated on the surface of an electrode active material part.
In the metal-air battery of the present invention, the electrode active material portion has a main surface that contacts the electrolyte stored in the first electrolyte bath, and the electrolyte solution is stored in the first electrolyte bath. Preferably, the air electrode is provided so as to be substantially perpendicular to the surface, and the air electrode has a main surface facing the main surface of the electrode active material portion.
According to such a configuration, the main surface where the electrode reaction of the electrode active material portion proceeds can be provided substantially vertically, and it is possible to suppress the deposit of the metal compound on the main surface. it can. Moreover, the deposit of the metal compound deposited or adhered on the main surface can be easily removed by gravity and the flow of the electrolyte.
In the metal-air battery of the present invention, the second electrolyte bath includes a first discharge port that allows the electrolyte stored in the second electrolyte bath to flow into the first electrolyte bath, and a first discharge port provided at the first discharge port. The first valve is preferably provided so as to open when the amount of the electrolyte stored in the second electrolyte tank exceeds a predetermined amount.
According to such a configuration, a relatively large amount of electrolytic solution can be allowed to flow from the second electrolytic solution tank to the first electrolytic solution tank at time intervals, and the electrode activity can be changed by changing the flow and flow rate of the electrolytic solution. The deposit of the metal compound on the surface of the substance part can be effectively removed. In addition, a relatively large amount of electrolyte with low power consumption can be allowed to flow into the first electrolyte bath.

In the metal-air battery of the present invention, it is preferable that the first electrolyte bath has an inclined bottom portion and an opening at the lowest portion of the bottom portion.
According to such a structure, the deposit of the metal compound deposited in the electrolyte solution in the first electrolyte bath can be collected in the lowest part of the bottom, and the collected precipitate can be recovered from the opening of the lowest part. Can do.
The metal-air battery of the present invention further includes a third electrolyte tank provided at a lower portion of the first electrolyte tank, and the first electrolyte tank stores the electrolyte stored in the first electrolyte tank. A second discharge port that flows into the second discharge port and a second valve provided in the second discharge port, and the second valve opens when the amount of the electrolyte stored in the first electrolyte tank exceeds a predetermined amount It is preferable that it is provided.
According to such a configuration, a relatively large amount of electrolyte can be discharged from the first electrolyte tank to the third electrolyte tank at time intervals, and the electrode activity can be changed by changing the flow and flow rate of the electrolyte. The deposit of the metal compound on the surface of the substance part can be effectively removed. In addition, a relatively large amount of electrolyte with low power consumption can be discharged from the first electrolyte bath.

The metal-air battery of the present invention further includes a levitation unit connected to the metal electrode and a fourth electrolyte bath provided at a lower portion of the first electrolyte bath, and the first electrolyte bath is a first electrolyte bath. A third discharge port is provided for allowing the electrolyte stored in the tank to flow into the fourth electrolyte tank, and the levitation unit floats the metal electrode when the electrolyte stored in the first electrolyte tank exceeds a predetermined amount. The metal electrode has a closed portion, and the closed portion is provided to close the third discharge port when the metal electrode sinks, and to be detached from the third discharge port when the metal electrode floats. It is preferable.
According to such a configuration, a relatively large amount of electrolyte can be discharged from the first electrolyte tank to the fourth electrolyte tank at time intervals, and the electrode activity can be changed by changing the flow and flow rate of the electrolyte. The deposit of the metal compound on the surface of the substance part can be effectively removed. In addition, a relatively large amount of electrolyte with low power consumption can be discharged from the first electrolyte bath.
In the metal-air battery of the present invention, it is preferable that the second electrolyte bath has a filter that is detachably provided on the bottom.
According to such a structure, the deposit of a metal compound can be deposited on a filter, and the deposit of a metal compound can be collect | recovered by replacing a filter.

In the metal-air battery of the present invention, the second electrolyte bath has a wheel shaft and two or more electrolyte chambers provided around the wheel shaft, and the drive unit includes the two or more electrolyte solutions. The electrolyte solution is provided so that the electrolyte solution flows into one of the chambers, and the two or more electrolyte solution chambers rotate about the wheel shaft by the weight of the electrolyte solution introduced by the driving unit. It is preferable to be provided.
According to such a configuration, a relatively large amount of electrolytic solution can be allowed to flow from the second electrolytic solution tank to the first electrolytic solution tank at time intervals, and the electrode activity can be changed by changing the flow and flow rate of the electrolytic solution. The deposit of the metal compound on the surface of the substance part can be effectively removed. In addition, a relatively large amount of electrolyte with low power consumption can be allowed to flow into the first electrolyte bath.
In the metal-air battery of the present invention, it is preferable that the metal electrode has a current collector, and the electrode active material portion is provided on the current collector.
According to such a structure, the electric charge produced | generated by the electrode reaction in an electrode active material part can be collected with an electrical power collector, and the performance of a metal air battery can be improved. Moreover, an electrode active material part can be supported by a collector, and it can suppress that a part of electrode active material part collapses by progress of an electrode reaction.

In the metal-air battery of the present invention, it is preferable that the current collector has a plate shape, and the electrode active material portion is provided on a main surface of the current collector.
According to such a configuration, the amount of the electrode active material supported by the current collector can be increased, and the amount of the electrode active material contained in the metal electrode can be increased. Further, the distance between the surface of the electrode active material portion where the electrode reaction proceeds and the current collector can be shortened, and the charges generated by the electrode reaction can be collected efficiently.
In the metal-air battery of the present invention, the electrode active material part is preferably made of metallic zinc, and the electrolytic solution is preferably an alkaline aqueous solution.
According to such a configuration, power can be generated by a metal air battery using metal zinc as an electrode active material.

The metal-air battery of the present invention further includes an ion exchange membrane having first and second main surfaces, wherein the ion exchange membrane is in contact with the electrolyte stored in the first electrolyte bath and second. It is preferable that the main surface is provided in contact with the air electrode.
According to such a structure, the ion species which move between an air electrode and electrolyte solution can be limited, and it can suppress that a metal and a carbonate compound precipitate in an air electrode.
In the metal-air battery of the present invention, it is preferable that the ion exchange membrane is an anion exchange membrane, and the air electrode includes a carbon support and an air electrode catalyst supported on the carbon support.
According to such a configuration, in the air electrode catalyst, electrons supplied from the carbon support, oxygen gas supplied from the atmosphere, water supplied from the atmosphere or the anion exchange membrane can coexist, and from these Hydroxide ions can be formed. Further, the formed hydroxide ions can be transferred to the electrolytic solution through the anion exchange membrane. By these things, the discharge reaction of a metal air battery can be advanced.
Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The configurations shown in the drawings and the following description are merely examples, and the scope of the present invention is not limited to those shown in the drawings and the following description.

Diagram 1 of a metal-air battery is a schematic top view of a metal-air battery of this embodiment, FIG. 2 is a schematic sectional view of a metal-air battery in a dotted line A-A of FIG. 1, dotted line in FIG. 3 FIG. 2 It is a schematic sectional drawing of the metal air battery in the range B enclosed by. 4 and 5 are schematic cross-sectional views of a part of the metal-air battery of the present embodiment, and correspond to the cross-sectional view of the range B surrounded by the dotted line in FIG. 6 to 12 are schematic cross-sectional views of the metal-air battery of this embodiment, and correspond to the cross-sectional view taken along the dotted line AA in FIG.

The metal-air battery 45 of the present embodiment includes a first electrolyte tank 1a for storing the electrolyte 3, a metal electrode 5 provided in the first electrolyte tank 1a and serving as an anode, an air electrode 6 serving as a cathode, A second electrolytic solution tank 1b for storing the electrolytic solution 3 and a drive unit (pump 15) for feeding the electrolytic solution are provided, and the first and second electrolytic solution tanks 1a, 1b and the drive unit include the second electrolytic solution tank 1b. It is provided so that it flows in from the 2 electrolyte tank 1b to the first electrolyte tank 1a at a changing flow rate or the electrolyte solution 3 flows out from the first electrolyte tank 1a and flows to the second electrolyte tank 1b. It is characterized by that.
Moreover, the metal electrode 5 can have the electrode active material part 4 which consists of an electrode active material.
Moreover, the air electrode 6 can be provided so that the electrolyte solution 3 stored in the 1st electrolyte solution tank 1a with the electrode active material part 4 may be pinched | interposed.
Further, the driving unit is not particularly limited as long as the electrolytic solution can be fed, and is, for example, a pump 15.
Hereinafter, the metal-air battery 45 of the present embodiment will be described.

1. Metal-air battery The metal-air battery 45 of the present embodiment is a battery having the metal electrode 5 as a negative electrode (anode) and the air electrode 6 as a positive electrode (cathode). For example, a zinc air battery, a lithium air battery, a sodium air battery, a calcium air battery, a magnesium air battery, an aluminum air battery, and an iron air battery. Further, the metal-air battery 45 of the present embodiment may be a primary battery or a secondary battery, but a primary battery is more preferable. By using the metal-air battery 45 of the present embodiment as a primary battery, it is possible to avoid the formation of dendritic dendrites from the metal electrode 5 toward the air electrode 6, which is a problem when used as a secondary battery. A short circuit between the electrode 5 and the air electrode 6 can be suppressed.

The metal-air battery 45 of this embodiment can have a plurality of cells including the metal electrode 5 and the air electrode 6. For example, the metal-air battery 45 shown in FIGS. 2 and 6 to 12 has three cells. The first cell includes a metal electrode 5a and air electrodes 6 on both sides thereof, and the second cell is a metal. The electrode 5b and the air electrodes 6 on both sides thereof are included, and the third cell includes the metal electrode 5c and the air electrodes 6 on both sides thereof.
The plurality of cells included in the metal-air battery 45 may be connected in series or may be connected in parallel.

2. Metal electrode The metal electrode 5 is provided in the first electrolyte bath 1 and serves as an anode of the metal-air battery 45. Moreover, the metal electrode 5 has the electrode active material part 4, and the electrode active material part 4 consists of a metal which is an electrode active material.
With such a configuration, the electrolytic solution 3 a stored in the first electrolytic solution tank 1 can be brought into contact with the surface of the electrode active material part 4, and the electrode reaction can be advanced on the surface of the electrode active material part 4. By this electrode reaction, the metal which is the electrode active material constituting the electrode active material part 4 is consumed, and the electrode active material part 4 is gradually reduced. In addition, the consumed metal is deposited as a metal compound precipitate 23 in the electrolytic solution or on the electrode active material portion 4.

When the deposit 23 adheres to the electrode active material part 4, the surface of the electrode active material part 4 on which the deposit 23 adheres cannot contact with the electrolytic solution, so that the progress of the electrode reaction is inhibited in this part. For this reason, when the deposit 23 adheres to the surface of the electrode active material part 4, the performance of the metal-air battery 45 may deteriorate. Moreover, the metal which comprises the electrode active material part 4 may be consumed unevenly, and the metal piece which comprises the electrode active material part 4 may peel from the electrode active material part.
The metal-air battery 45 of the present embodiment includes an electrolytic solution circulation mechanism that removes the metal compound deposits 23 from the surface of the electrode active material portion 4 in order to suppress a decrease in performance of the metal-air battery 45. . This mechanism will be described later.

The electrode active material part 4 can have a main surface that contacts the electrolyte stored in the first electrolyte bath 1a. As a result, the electrode reaction can proceed on the main surface of the electrode active material portion 4. Moreover, the electrode active material part 4 can be provided so that this main surface may become substantially perpendicular | vertical with respect to the liquid level of the electrolyte solution which accumulates in a 1st electrolyte solution tank. Thereby, the deposit of the metal compound deposited on the main surface of the electrode active material part 4 or the deposit of the metal compound deposited on the main surface of the electrode active material part 4 is detached from the main surface by gravity. It can be made easier.

The electrode active material portion 4 is made of a metal that becomes an electrode active material of the metal-air battery 45. For example, in the case of a zinc-air battery, the electrode active material part 4 is made of metallic zinc, in the case of an aluminum air battery, the electrode active material part 4 is made of metallic aluminum, and in the case of an iron-air battery, the electrode active material part 4 is made of metallic iron, In the case of a magnesium air battery, the electrode active material portion 4 is made of metallic magnesium.
Moreover, in the case of a lithium metal battery, a sodium air battery, and a calcium air battery, the metal electrode 5 consists of metallic lithium, metallic sodium, and metallic calcium, respectively.
In addition, although the metal which consists of a kind of metal element was mentioned in said example as a metal which comprises the electrode active material part 4, the electrode active material part 4 may consist of alloys.

The metal constituting the electrode active material part 4 is produced, for example, by refining ore or the like, or reduction of a metal oxide by a dry method or a wet method. In addition, when manufacturing the metal used as an electrode active material by electrolytic deposition, you may electrolytically deposit a metal on the electrical power collector 10. FIG.
The electrode active material portion 4 may be a metal layer that is electrolytically deposited on the current collector 10 or may be a metal lump formed by drying a metal slurry. It may be a metal lump molded by pressing.
For example, the current collector 10 is immersed as a cathode in an electrolytic solution containing metal ions as an electrolyte, and a voltage is applied between the anode and the cathode, so that the metal is electrolytically deposited on the current collector 10. it can.

The metal electrode 5 may have a current collector 10, and the electrode active material portion 4 may be provided on the main surface of the current collector 10. The current collector 10 is a member that collects charges generated by an electrode reaction on the surface of the electrode active material portion 4 and conducts the collected charges to an external circuit. The current collector 10 can also function as a support member that supports the electrode active material portion 4.
The current collector 10 is made of a material that has conductivity and has corrosion resistance to the electrolytic solution.
The current collector 10 may be plate-shaped. The current collector 10 may be made of, for example, a metal plate such as stainless steel or nickel, or may be made of a net-like metal wire made of stainless steel or nickel. When the metal electrode 5 has the current collector 10, the electrode active material portion 4 can be prevented from collapsing when the electrode reaction proceeds and the metal as the electrode active material is consumed.

When the current collector 10 is plate-shaped, the electrode active material portion 4 can be provided on the first main surface and the second main surface of the current collector 10. As a result, the amount of the electrode active material contained in the metal electrode 5 can be increased, and the amount of the electrode active material supplied to the metal air battery 45 can be increased by incorporating the metal electrode 5 into the metal air battery 45. Can do.
Further, the electrode active material portion 4 can be provided so that the surface thereof is substantially parallel to the surface of the current collector 10. As a result, it is possible to suppress the occurrence of a portion on the surface of the electrode active material portion 4 where the charge generated by the electrode reaction is easily collected and the portion where the charge is not easily collected. Moreover, the electrode active material part 4 can be provided so that the main surface of the electrode active material part 4 is substantially perpendicular to the liquid level of the electrolyte stored in the first electrolyte bath.

3. Air Electrode, Ion Exchange Membrane The air electrode 6 is an electrode that generates hydroxide ions (OH ⁻ ) from oxygen gas, water, and electrons in the atmosphere. The air electrode 6 includes, for example, a conductive porous carrier and an air electrode catalyst supported on the porous carrier. As a result, oxygen gas, water, and electrons can coexist on the air electrode catalyst, and an electrode reaction (cathode reaction) can be advanced. The water used for the electrode reaction may be supplied from the atmosphere or may be supplied from the electrolytic solution 3a.
Moreover, the air electrode 6 is provided so that the electrolyte solution 3a collected in the 1st electrolyte solution tank 1a with the electrode active material part 4 may be pinched | interposed. As a result, the distance between the air electrode 6 where the cathode reaction proceeds and the surface of the electrode active material portion 4 where the anode reaction proceeds can be shortened, and the ion conduction distance between the cathode and the anode can be shortened. it can. As a result, the performance of the metal-air battery 45 can be improved.

In addition, as shown in FIGS. 2 and 6 to 12, air electrodes 6 may be provided on both sides of the metal electrode 5, respectively. As a result, the electrode reaction can proceed on the surfaces on both sides of the metal electrode 5, and the performance of the metal-air battery 45 can be improved.
Moreover, when the electrode active material part 4 has a main surface substantially perpendicular to the liquid surface of the electrolytic solution stored in the first electrolytic solution tank 1a, the air electrode 6 has a main surface opposite to the main surface. Can do. Thereby, the flow path of the electrolyte solution 3 a can be formed between the main surface of the electrode active material 4 and the main surface of the air electrode 6. Further, the main surface of the opposing electrode active material portion 4 and the main surface of the air electrode 6 may be substantially parallel.

Examples of the porous carrier contained in the air electrode 6 include carbon black such as acetylene black, furnace black, channel black and ketjen black, and conductive carbon particles such as graphite and activated carbon. In addition, carbon fibers such as vapor grown carbon fiber (VGCF), carbon nanotube, carbon nanowire, and the like can be used.
Examples of the air electrode catalyst include fine particles made of platinum, iron, cobalt, nickel, palladium, silver, ruthenium, iridium, molybdenum, manganese, a metal compound thereof, and an alloy containing two or more of these metals. . This alloy is preferably an alloy containing at least two of platinum, iron, cobalt, and nickel. For example, platinum-iron alloy, platinum-cobalt alloy, iron-cobalt alloy, cobalt-nickel alloy, iron-nickel alloy And iron-cobalt-nickel alloy.
Further, the porous carrier contained in the air electrode 6 may be subjected to a surface treatment so that a cationic group exists as a fixed ion on the surface thereof. As a result, hydroxide ions can be conducted on the surface of the porous carrier, so that the hydroxide ions generated on the air electrode catalyst can easily move.
The air electrode 6 may have an anion exchange resin supported on a porous carrier. Thereby, since hydroxide ions can be conducted through the anion exchange resin, the hydroxide ions generated on the air electrode catalyst are easily moved.

The air electrode 6 may be provided so as to be in direct contact with the atmosphere or may be provided in contact with the air flow path 26. As a result, oxygen gas can be supplied to the air electrode 6. In addition, when the air flow path 26 is provided, water can be supplied to the air electrode 6 together with oxygen gas by flowing humidified air through the air flow path 26. The air flow path 26 can be provided in the flow path member 25 included in the metal-air battery 45 shown in FIGS. 2 and 6 to 12, for example. When the air electrode 6 is provided on both sides of the flow path member 25, the flow path member 25 may form two air flow paths 26 that supply oxygen gas to the two air electrodes 6, respectively.
The flow path member 25 may be made of a conductive material or an insulating material. When the flow path member 25 is made of a conductive material, the air flow path 26 can be formed by the flow path member 25, and the air electrode 6 and an external circuit can be connected via the flow path member 25. The electric power of the air battery 45 can be output to an external circuit.

When the air electrode 6 is provided on both sides of the flow path member 25 and the flow path member 25 is made of a conductive material, the air electrodes 6 on both sides can be electrically connected. As a result, when the metal-air battery 45 has a plurality of cells as shown in FIGS. 2 and 6 to 12, a plurality of cells can be connected in parallel.
Moreover, when the air electrode 6 is provided on both sides of the flow path member 25 and the flow path member 25 is made of an insulating material, the air electrodes 6 on both sides can be electrically separated. As a result, when the metal-air battery 45 has a plurality of cells as shown in FIGS. 2 and 6 to 12, a plurality of cells can be connected in parallel.

The air electrode 6 may be provided so as to be in contact with the electrolytic solution 3a stored in the first electrolytic solution tank 1a. Thus, hydroxide ions generated at the air electrode 6 can easily move to the electrolytic solution 3a. Further, water necessary for the electrode reaction at the air electrode 6 is easily supplied to the air electrode 6 from the electrolyte 3a.
Moreover, you may provide the air electrode 6 so that the ion exchange membrane 8 which contacts the electrolyte solution 3a stored in the 1st electrolyte tank 1a may be contacted. The ion exchange membrane 8 may be an anion exchange membrane. As a result, hydroxide ions generated at the air electrode 6 can conduct through the anion exchange membrane and move to the electrolytic solution.

By providing the ion exchange membrane 8, the ion species conducted between the air electrode 6 and the electrolyte solution 3a can be limited. When the ion exchange membrane 8 is an anion exchange membrane, since the anion exchange membrane has a cation group that is a fixed ion, the cation in the electrolytic solution cannot be conducted to the air electrode 6. On the other hand, since the hydroxide ion generated at the air electrode 6 is an anion, it can be conducted to the electrolytic solution. As a result, the battery reaction of the metal-air battery 45 can proceed, and the cations in the electrolyte 3 can be prevented from moving to the air electrode 6. Thereby, precipitation of the metal and carbonate compound in the air electrode 6 can be suppressed.

Further, by providing the ion exchange membrane 8, it is possible to suppress excessive supply of water contained in the electrolytic solution to the air electrode 6.
Examples of the ion exchange membrane 8 include perfluorosulfonic acid, perfluorocarboxylic acid, styrene vinyl benzene, and quaternary ammonium solid polymer electrolyte membranes (anion exchange membranes).

4). Electrolytic solution tank, electrolytic solution, drive unit, electrolytic solution circulation mechanism The electrolytic solution tank 1 is an electrolytic cell for storing the electrolytic solution 3 and is made of a material having corrosion resistance to the electrolytic solution. The metal-air battery 45 may have a first electrolyte tank 1a and a second electrolyte tank 1b like the metal-air battery 45 shown in FIG. 1, FIG. 2, FIG. 6, FIG. Like the metal-air battery 45 shown in FIGS. 7 and 8, the first electrolyte tank 1a, the second electrolyte tank 1b, and the third electrolyte tank 1c may be provided, and the metal shown in FIGS. Like the air battery 45, you may have the 1st electrolyte solution tank 1a, the 2nd electrolyte solution tank 1b, and the 4th electrolyte solution tank 1d.
Moreover, the 1st electrolyte solution tank a has a structure which can install the metal electrode 5 in it. The first electrolyte bath a has a structure in which ions contained in the stored electrolyte 3 a can move to the air electrode 6. As a result, ions can be conducted between the metal electrode 5 and the air electrode 6 through the electrolytic solution 3a stored in the first electrolytic solution tank a. Further, a part of the inner wall of the first electrolytic solution tank 1 a may be constituted by the ion exchange membrane 8. As a result, ions contained in the electrolytic solution 3 a can move to the air electrode 6 through the ion exchange membrane 8.

The electrolytic solution 3 is a liquid having an ionic conductivity by dissolving an electrolyte in a solvent. The type of the electrolytic solution 3 varies depending on the type of metal constituting the electrode active material part 4, but may be an electrolytic solution (aqueous electrolyte solution) using an aqueous solvent, or an electrolytic solution (organic electrolytic solution) using an organic solvent. ).
For example, in the case of a zinc-air battery, an aluminum-air battery, an iron-air battery, or a magnesium-air battery, the electrolyte includes an alkaline aqueous solution such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, or a near-neutral electrolytic solution such as a sodium chloride aqueous solution. Can be used. In the case of a lithium metal battery, a sodium air battery, or a calcium air battery, an organic electrolyte can be used.
Moreover, the 1st electrolyte solution tank 1a has a partition which consists of solid electrolytes, electrolyte aqueous solution may be stored by one side divided by the partition, and organic electrolyte solution may be stored by the other side.

The first and second electrolytic solution tanks 1a and 1b and the drive unit (pump 15) are configured such that the electrolyte flows into the first electrolytic solution tank 1a from the second electrolytic solution tank 1b or the electrolytic solution is subjected to the first electrolysis. The liquid tank 1a is provided so as to flow out at a changing flow rate and to flow to the second electrolytic solution tank 1b. As a result, a flow that changes in the electrolytic solution stored in the first electrolytic solution tank can be generated, and the deposit of the metal compound on the surface of the electrode active material portion is caused to flow in the electrode active material portion by the flow of the electrolytic solution. It can be detached from the surface. Moreover, it can suppress that the deposit of a metal compound is produced | generated on the surface of an electrode active material part.
The change in the flow rate of the electrolytic solution may be caused by utilizing the weight of the electrolytic solution, may be caused by changing the amount of the electrolytic solution discharged by the pump 15, and is adjusted by a flow rate control valve. You may change by.

The first electrolyte tank 1a and the second electrolyte tank 1b are provided such that the electrolyte stored in the second electrolyte tank 1b flows into the electrolyte stored in the first electrolyte tank 1a due to its gravity. The electrolytic solution stored in the first electrolytic solution tank 1a can be provided so as to flow into the electrolytic solution stored in the second electrolytic solution tank 1b by the pump 15. Thereby, the electrolytic solution 3a stored in the first electrolytic solution tank 1a and the electrolytic solution 3b stored in the second electrolytic solution tank 1b can be circulated, and a flow can be generated in the electrolytic solution 3a. Note that the pump 15 can pump the electrolytic solution at a constant flow rate.
Moreover, since the electrode active material part 4 and the air electrode 6 are provided so that the flow path of the electrolyte solution 3a is formed between them, the electrolyte solution 3a and the second electrolyte solution tank 1b stored in the first electrolyte solution tank 1a are provided. A flow of the electrolytic solution 3 a generated by circulating the accumulated electrolytic solution 3 b can be generated between the electrode active material portion 4 and the air electrode 6. Thus, the metal oxide precipitate or metal hydroxide precipitate on the surface of the electrode active material portion 4 can be separated from the surface of the electrode active material portion 4 by the flow of the electrolytic solution 3a.
When the ion exchange membrane 8 is provided, the flow path of the electrolytic solution formed between the electrode active material portion 4 and the air electrode 6 is formed between the ion exchange membrane 8 and the air electrode 6.
In addition, the 2nd electrolyte solution tank 1b can be provided in the upper part of the 1st electrolyte solution tank 1a.

Next, an electrolytic solution circulation mechanism and the like will be described with reference to the drawings.
The metal-air battery 45 shown in FIGS. 1 to 3 has three cells each provided with an air electrode 6 on both sides of the metal electrode 5, and ion exchange is performed between the air electrode 6 and the electrolyte 3a. A membrane 8 is provided. The main surface of the ion exchange membrane 8 and the main surface of the electrode active material part 4 included in the metal electrode 5 are provided to face each other, and are provided substantially perpendicular to the liquid surface of the electrolytic solution 3a. Yes. Furthermore, it is provided between the ion exchange membrane 8 and the electrode active material part 4 so as to be a flow path of the electrolytic solution 3a.

The drive unit (pump 15) is provided so as to suck the electrolyte solution 3a in the first electrolyte solution tank 1a through the suction channel 16 and discharge the electrolyte solution 3 into the second electrolyte solution tank 1b through the discharge channel 17. It has been. With such a configuration, the electrolytic solution 3a in the first electrolytic solution tank 1a can be pumped to the second electrolytic solution tank 1b.
The second electrolyte bath 1b is provided with a plurality of first discharge ports 20a at the bottom. The first discharge port 20 a is provided in the upper part of the electrolytic solution 3 a between the electrode active material part 4 and the ion exchange membrane 8.
As shown in FIG. 3, the electrolytic solution 3b in the second electrolytic solution tank 1b is discharged from the first discharge port 20a by gravity, and the electrode active material portion 4 and the ion exchange membrane 8 in the first electrolytic solution tank 1a It flows into the electrolytic solution 3a on the upper part of the electrolytic solution 3a. The electrolytic solution 3a that has flowed into the first electrolytic solution tank 1a flows down between the electrode active material portion 4 and the ion exchange membrane 8. Due to the flow of the electrolytic solution 3a, the metal compound deposit 23 deposited or adhered to the surface of the electrode active material portion 4 is detached from the surface of the electrode active material portion 4 and descends together with the electrolytic solution. In addition, the precipitate 23 can be easily separated by matching the direction in which the electrolyte flows and the direction of gravity.
The flow rate of the electrolyte flowing into the first electrolyte tank 1a from the second electrolyte tank 1b is changed by changing the discharge amount of the pump 15.

Thus, the deposit 23 can be removed from the surface of the electrode active material part 4 by generating the flow of the electrolyte solution 3a between the electrode active material part 4 and the ion exchange membrane 8, and the metal-air battery The decrease in the performance of 45 can be suppressed.
Note that the amount of the electrolyte 3 that is pumped from the first electrolyte tank 1a into the second electrolyte tank 1b by the pump, and the electrolyte that is discharged from the second electrolyte tank 1b and flows into the first electrolyte tank 1a. The diameter and number of the first outlets 20a and the pumping capacity of the pump 15 can be set so that the amount of the liquid 3 is substantially the same. Thereby, the electrolyte solution 3 can be circulated continuously.

The precipitate 23 that has fallen together with the electrolytic solution accumulates at the bottom of the first electrolytic solution tank 1a, and the lowered electrolytic solution 3a is pumped to the second electrolytic solution tank 1b by the pump 15.
Thus, the electrolytic solution 3a in the first electrolytic solution tank 1a and the electrolytic solution 3b in the second electrolytic solution tank 1b circulate, and precipitates 23 are formed from the surface of the electrode active material part 4 by the flow of the circulating electrolytic solution. Can be removed.

Note that the metal-air battery 45 shown in FIG. 2 has an inclined bottom portion and an opening at the bottom of the bottom portion. This opening communicates with the valve 31. By having such a configuration, the metal compound deposits 23 accumulated at the bottom of the first electrolyte bath 1a are collected at the lowest part due to the inclination of the bottom. Then, by opening the valve 31, the deposit 23 accumulated at the bottom can be discharged and collected together with the electrolyte from the first electrolyte bath 1a.
Although the inclination of the bottom part of the electrolytic solution tank 1 will not be limited if the deposit 23 can be collected, it can be set to 60 degree | times or more, for example.

Also, the metal compound precipitate 23 may be collected by a filter 14 that is detachably provided on the bottom of the second electrolyte bath 1b, as in the metal-air battery 45 shown in FIG. The filter 14 is, for example, filter paper. In the metal-air battery 45 shown in FIG. 6, the electrolytic solution 3 a in the first electrolytic solution tank 1 a is pumped into the second electrolytic solution tank 1 b together with the precipitate 23. The electrolytic solution 3b in the second electrolytic solution tank 1b is discharged from the first discharge port 20a and flows into the first electrolytic solution tank 1a, but the precipitate 23 is deposited on the filter 14. After the deposit 23 is deposited, the precipitate 23 can be recovered from the metal-air battery 45 by replacing the filter 14.

The metal-air battery 45 shown in FIGS. 4 and 5 has the same configuration as the metal-air battery 45 shown in FIGS. 1 to 3 except that the first valve 13a is provided at the first outlet 20a. ing.
The first valve 13a is connected to the second electrolyte bath 1b via an elastic member such as a spring. The first valve 13a is provided with a seal member so that the electrolyte 3b in the second electrolyte tank 1b does not leak.
The first valve 13a is provided such that the elastic member deforms and opens when the amount of the electrolyte 3b in the second electrolyte tank 1b exceeds a predetermined amount and the water pressure applied to the first valve 13a increases. .

In the metal-air battery 45 shown in FIGS. 4 and 5, when the electrolyte 3a in the first electrolyte tank 1a is pumped into the second electrolyte tank 1b by the pump 15, the pumped liquid as shown in FIG. The electrolytic solution 3 thus accumulated accumulates in the second electrolytic solution tank 1b, and the level of the electrolytic solution 3b in the second electrolytic solution tank rises. As the liquid level of the electrolytic solution 3b rises, the water pressure applied to the first valve 13a increases, and when the amount of the electrolytic solution 3b in the second electrolytic solution tank 1b exceeds a predetermined amount, the first pressure as shown in FIG. The valve 13a opens. When the first valve 13a is opened, the electrolytic solution 3b in the second electrolytic solution tank 1b is discharged from the first discharge port 20a and flows into the first electrolytic solution tank 1a. When the electrolytic solution 3 flows into the first electrolytic solution tank 1a and the water pressure applied to the first valve 13a decreases, the first valve 13a is closed by the elasticity of the elastic member, and the first discharge port 20a is closed by the first valve 13a. . Thereafter, the electrolytic solution 3 pumped by the pump 15 is accumulated in the second electrolytic solution tank 1b. When the electrolytic solution 3b exceeds a predetermined amount, the first valve 13a is opened.
As described above, the first valve 13a has a structure that opens at a time interval. When the first valve 13a is opened, a relatively large amount of the electrolyte 3 flows into the first electrolyte tank. . In addition, the flow rate of the electrolyte flowing from the second electrolytic solution tank 1b into the first electrolytic solution tank 1a can be made larger than the flow rate of the electrolytic solution pumped by the pump 15.

The electrolytic solution 3a flowing into the first electrolytic solution tank 1a flows down between the electrode active material portion 4 and the ion exchange membrane 8. Further, the flow rate of the electrolytic solution 3a changes greatly. Due to the flow and flow rate change of the electrolytic solution 3a, the metal compound deposit 23 deposited or adhered to the surface of the electrode active material portion 4 is detached from the surface of the electrode active material portion 4 and descends together with the electrolytic solution. Moreover, according to the structure provided with the 1st valve 13a, since comparatively much electrolyte solution 3 flows in into a 1st electrolyte solution tank, the electrolyte solution 3 between the electrode active material part 4 and the ion exchange membrane 8 is used. The flow becomes faster, and the precipitate 23 is easily detached from the surface of the electrode active material portion 4. Thereby, the deposit 23 can be more effectively removed from the surface of the electrode active material portion 4.

The metal-air battery 45 shown in FIGS. 7 and 8 has three cells each provided with the air electrode 6 on both sides of the metal electrode 5 like the metal-air battery 45 shown in FIGS. The liquid 3 has a structure that flows into the first electrolytic solution tank 1a from the second electrolytic solution tank 1b provided on the upper part of the first electrolytic solution tank 1a.
In the metal-air battery 45 shown in FIGS. 7 and 8, a third electrolyte tank 1c is provided below the first electrolyte tank 1a. The 1st electrolyte tank 1a and the 3rd electrolyte tank 1c are divided by the 2nd valve 13b provided in the 2nd discharge port 20b of the bottom part of the 1st electrolyte tank 1a. Moreover, the pump 15 is provided so that the electrolyte solution 3c in the 3rd electrolyte solution tank 1c may be pumped into the 2nd electrolyte solution tank 1b.

The second valve 13b is connected to the first electrolyte bath 1a through an elastic member such as a spring. The second valve 13b is provided with a seal member so that the electrolyte solution 3a in the first electrolyte solution tank 1a does not leak.
The second valve 13b is provided such that the elastic member deforms and opens when the amount of the electrolyte 3a in the first electrolyte tank 1a exceeds a predetermined amount and the water pressure applied to the second valve 13b increases. .

7 and 8, in the metal-air battery 45, the pump 15 lifts the electrolytic solution 3c in the third electrolytic solution tank 1c into the second electrolytic solution tank 1b. As shown in FIG. 7, the electrolytic solution 3b in the second electrolytic solution tank 1b is discharged from the first discharge port 20a by gravity, and the electrode active material portion 4 and the ion exchange membrane 8 in the first electrolytic solution tank 1a It flows into the electrolytic solution 3a on the upper part of the electrolytic solution 3a between, and the level of the electrolytic solution 3a rises. When the liquid level of the electrolytic solution 3a rises, the water pressure applied from the electrolytic solution 3a in the first electrolytic solution tank 1a to the second valve 13b becomes higher than the hydraulic pressure applied from the electrolytic solution 3c in the third electrolytic solution tank 1c. When the amount of the electrolytic solution 3a in the first electrolytic solution tank 1a exceeds a predetermined amount, the second valve 13b opens as shown in FIG. When the second valve 13b is opened, the electrolytic solution 3a in the first electrolytic solution tank 1a is discharged from the second discharge port 20b and flows into the third electrolytic solution tank 1c. The electrolyte 3 flows into the third electrolyte tank 1a and the water pressure applied to the second valve 13b from the electrolyte 3a in the first electrolyte tank 1a, and the water pressure applied from the electrolyte 3c in the third electrolyte tank 1c, When the difference becomes small, the second valve 13b is closed by the elasticity of the elastic member, and the second discharge port 20b is closed by the second valve 13b. Thereafter, the electrolytic solution in the second electrolytic solution tank 1b flows into the first electrolytic solution tank. When the electrolytic solution 3a in the first electrolytic solution tank 1a exceeds a predetermined amount, the second valve 13b is opened.

Thus, the second valve 13b has a structure that opens at a time interval. When the second valve 13b is opened, a relatively large amount of the electrolytic solution 3 is supplied from the first electrolytic solution tank 1a. It flows into the 3 electrolyte bath 1c. In addition, the metal compound deposit 23 moves together with the electrolytic solution 3 from the first electrolytic solution tank 1a into the third electrolytic solution tank 1c.
Further, the flow rate of the electrolyte flowing from the first electrolyte bath 1a to the third electrolyte bath 1c can be made larger than the flow rate of the electrolyte pumped by the pump 15.

When the second valve 13b is opened and a relatively large amount of the electrolytic solution 3 flows from the first electrolytic solution tank 1a to the third electrolytic solution tank 1c, the upper electrolytic solution 3a in the first electrolytic solution tank 1a is It flows between the electrode active material part 4 and the ion exchange membrane 8 and descends. Further, the flow rate of the electrolytic solution 3a changes greatly. Due to the flow and flow rate change of the electrolytic solution 3a, the metal compound deposit 23 deposited or adhered to the surface of the electrode active material portion 4 is detached from the surface of the electrode active material portion 4 and descends together with the electrolytic solution. Further, according to the structure provided with the second valve 13b, the flow of the electrolytic solution 3 between the electrode active material part 4 and the ion exchange membrane 8 becomes faster, and the precipitate 23 is detached from the surface of the electrode active material part 4. It becomes easy. Thereby, the deposit 23 can be more effectively removed from the surface of the electrode active material portion 4.

In the metal-air battery 45 shown in FIGS. 7 and 8, since the third electrolyte tank 1c is provided under the first electrolyte tank 1a, the power generation by the metal-air battery 45 is maintained while the power generation by the metal-air battery 45 is maintained. The deposit 23 of the metal compound can be removed and recovered. That is, the second discharge port 20b is closed by the second valve 13b and the power generation by the metal-air battery 45 is maintained in a state where the electrolytic solution 3a is stored in the first electrolytic solution tank 1a, and the valve 31 is opened to open the third electrolytic solution tank 1c. The electrolyte 3c inside is discharged. At this time, the deposit 23 in the third electrolytic solution tank 1c is also discharged from the metal-air battery 45 together with the electrolytic solution. Thereafter, the deposit removing door 32 is opened, and the deposit 23 remaining on the bottom of the third electrolyte bath 1c is scraped and collected. In this way, precipitates can be removed and recovered.

The metal-air battery 45 shown in FIGS. 9 and 10 has three cells each provided with the air electrode 6 on both sides of the metal electrode 5 like the metal-air battery 45 shown in FIGS. The liquid 3 has a structure that flows into the first electrolytic solution tank 1a from the second electrolytic solution tank 1b provided on the upper part of the first electrolytic solution tank 1a.
In the metal-air battery 45 shown in FIGS. 9 and 10, a fourth electrolyte tank 1d is provided below the first electrolyte tank 1a. The 1st electrolyte tank 1a and the 4th electrolyte tank 1d are connected by the 3rd discharge port 20c of the bottom part of the 1st electrolyte tank 1a. Moreover, the pump 15 is provided so that the electrolyte solution 3d in the fourth electrolyte solution tank 1d is pumped into the second electrolyte solution tank 1b. Each metal electrode 5 has a closing portion 34 provided so as to close the third discharge port 20 c, and a floating portion 36 is connected to the metal electrode 5.

When the amount of the electrolyte 3a in the first electrolyte bath 1a is less than a predetermined amount, the levitation unit 36 sinks the metal electrode 5 in the electrolyte 3a, and the amount of the electrolyte 3a in the first electrolyte bath 1a When the amount is higher than the fixed amount, the metal electrode 5 is provided so as to float on the electrolytic solution 3a. The levitation unit 36 has a large buoyancy.
The closing part 34 is provided below the metal electrode 5. The blocking portion 34 is provided so as to block the third discharge port 20c in a state where the metal electrode 5 is submerged in the electrolyte solution 3a as shown in FIG. 9, and the metal electrode 5 floats on the electrolyte solution 3a as shown in FIG. In this state, it is provided so as to be detached from the third discharge port 20c.

In the metal-air battery 45 shown in FIGS. 9 and 10, the pump 15 pumps the electrolyte 3d in the fourth electrolyte bath 1d into the second electrolyte bath 1b. As shown in FIG. 9, the electrolytic solution 3b in the second electrolytic solution tank 1b is discharged from the first discharge port 20a by gravity, and the electrode active material portion 4 and the ion exchange membrane 8 in the first electrolytic solution tank 1a It flows into the electrolytic solution 3a on the upper part of the electrolytic solution 3a between, and the level of the electrolytic solution 3a rises. When the electrolyte 3 a in the first electrolyte tank 1 a exceeds a predetermined amount and the buoyancy of the levitation unit 36 increases, the levitation unit 36 floats in the electrolyte 3 together with the metal electrode 5 as shown in FIG. 10. When the metal electrode 5 floats, the blocking portion 34 is detached from the third discharge port 20c, and the electrolyte solution 3a in the first electrolyte bath 1a is discharged from the third discharge port 20c and into the fourth electrolyte bath 1d. Inflow. When the electrolytic solution 3 flows into the fourth electrolytic solution tank 1d and the water level of the electrolytic solution 3a in the first electrolytic solution tank 1a is lowered, the metal electrode 5 sinks into the electrolytic solution 3a, and the blocking portion 34 has the third discharge port 20c. Block. Thereafter, the electrolytic solution in the second electrolytic solution tank 1b flows into the first electrolytic solution tank. When the electrolytic solution 3a in the first electrolytic solution tank 1a exceeds a predetermined amount, the metal electrode 5 becomes the electrolytic solution 3c. The floating blocking portion 34 is detached from the third outlet 20c.
As described above, the blocking portion 34 has a structure that is separated from the third discharge port 20c with a time interval. When the blocking portion 34 is removed from the third discharge port 20c, a relatively large amount of the electrolyte 3 is obtained. Flows from the first electrolyte bath 1a to the fourth electrolyte bath 1d. Further, the deposit 23 of the metal compound moves together with the electrolytic solution 3 from the first electrolytic solution tank 1a to the fourth electrolytic solution tank 1d.
In addition, the flow rate of the electrolyte flowing from the first electrolyte tank 1a to the fourth electrolyte tank 1d can be made larger than the flow rate of the electrolyte pumped by the pump 15.

When the blocking part 34 is removed from the third discharge port 20c, and a relatively large amount of the electrolyte 3 flows from the first electrolyte tank 1a into the fourth electrolyte tank 1d, the upper part in the first electrolyte tank 1a The electrolytic solution 3a flows between the electrode active material part 4 and the ion exchange membrane 8 and descends. Further, the flow rate of the electrolytic solution 3a changes greatly. Due to the flow and flow rate change of the electrolytic solution 3a, the metal compound deposit 23 deposited or adhered to the surface of the electrode active material portion 4 is detached from the surface of the electrode active material portion 4 and descends together with the electrolytic solution. In addition, according to such a structure, the flow of the electrolytic solution 3 between the electrode active material portion 4 and the ion exchange membrane 8 becomes faster, and the precipitate 23 is easily detached from the surface of the electrode active material portion 4. Thereby, the deposit 23 can be more effectively removed from the surface of the electrode active material portion 4.

In the metal-air battery 45 shown in FIGS. 9 and 10, since the fourth electrolyte tank 1d is provided under the first electrolyte tank 1a, the power generation by the metal-air battery 45 is maintained while maintaining the power generation. The deposit 23 of the metal compound can be removed and recovered. That is, the third discharge port 20c is closed by the closing portion 34, and the power generation by the metal-air battery 45 is maintained in a state where the electrolytic solution 3a is stored in the first electrolytic solution tank 1a, and the valve 31 is opened to open the third electrolytic solution tank 1c. The electrolyte solution 3c is discharged. At this time, the deposit 23 in the third electrolytic solution tank 1c is also discharged from the metal-air battery 45 together with the electrolytic solution. In this way, precipitates can be removed and recovered.

The metal-air battery 45 shown in FIGS. 11 and 12 has three cells in which the air electrode 6 is provided on both sides of the metal electrode 5 in the same manner as the metal-air battery 45 shown in FIGS.
In the metal-air battery 45 shown in FIG. 11 and FIG. 12, the second electrolyte tank 1b having the wheel shaft 41 and the three electrolyte chambers 37 around the wheel shaft 41 is rotatably provided. It is provided in the upper part of 1a. The three electrolyte chambers 37 each have a first discharge port 20a, and an elastic member 38 is provided in the vicinity of the first discharge port 20a.
The pump 15 is provided so as to pump the electrolytic solution in the first electrolytic solution tank 1 a into one of the three electrolytic solution chambers 37.

In the metal-air battery 45 shown in FIG. 11, the pump 15 causes the electrolytic solution 3a in the first electrolytic solution tank 1a to be pumped into the electrolytic solution chamber 37a of the second electrolytic solution tank 1b. At this time, the elastic member 38 attached in the vicinity of the first discharge port 20a of the electrolyte chamber 37c of the second electrolyte tank 1b comes into contact with the tray 39 to stop the rotation of the second electrolyte tank 1b. Yes.
When the electrolytic solution 3b in the electrolytic solution chamber 37a accumulates, the weight of the electrolytic solution 3b causes a force that causes the second electrolytic solution tank 1b to rotate about the wheel shaft 41, and the elastic member 38 that is in contact with the receiving tray 39 is removed. Deform. When the amount of the electrolytic solution in the electrolytic solution chamber 37a exceeds a predetermined amount, the elastic member 38 is detached from the tray 39, and the electrolytic solution chamber 37a in which the electrolytic solution is accumulated moves downward as shown in FIG. The 2 electrolyte bath 1b rotates. When the electrolytic solution chamber 37a moves downward, the electrolytic solution 3b in the electrolytic solution chamber 37a flows out from the first discharge port 20a to the tray 39. The electrolytic solution 3 in the tray 39 flows through the electrolytic solution flow path 40 and flows into the electrolytic solution 3a above the electrolytic solution 3a between the electrode active material portion 4 and the ion exchange membrane 8 in the first electrolytic solution tank 1a. To do.

The metal-air battery 45 shown in FIGS. 11 and 12 is configured such that the electrolyte stored in one electrolyte chamber 37 flows between the electrode active material portion 4 and the ion exchange membrane 8 of each cell. However, the number of cells and the number of electrolyte chambers 37 included in the second electrolyte bath 1b are the same, and the electrolyte stored in one electrolyte chamber is ion-exchanged with the electrode active material portion 4 of the corresponding one cell. You may comprise so that it may flow in between the membranes 8.
When the second electrolytic solution tank 1b rotates, the pump 15 pumps the electrolytic solution 3a in the first electrolytic solution tank 1a into the electrolytic solution chamber 37b of the second electrolytic solution tank 1b. At this time, the elastic member 38 attached in the vicinity of the first discharge port 20a of the electrolyte chamber 37a of the second electrolyte bath 1b is in contact with the tray 39 and stops the rotation of the second electrolyte bath 1b. When the amount of the electrolytic solution in the electrolytic solution chamber 37b exceeds a predetermined amount, the elastic member 38 is detached from the tray 39, and the second electrolytic solution tank 1b is moved so that the electrolytic solution chamber 37b in which the electrolytic solution is accumulated moves downward. Rotate. When the electrolytic solution chamber 37b moves downward, the electrolytic solution 3b in the electrolytic solution chamber 37b flows out from the first discharge port 20a to the tray 39. The electrolytic solution 3 in the tray 39 flows through the electrolytic solution flow path 40 and flows into the first electrolytic solution tank 1a.
As described above, the second electrolytic solution tank 1b has a structure in which a relatively large amount of the electrolytic solution 3 flows into the first electrolytic solution tank 1a at time intervals by rotating. In addition, the flow rate of the electrolyte flowing from the second electrolytic solution tank 1b into the first electrolytic solution tank 1a can be made larger than the flow rate of the electrolytic solution pumped by the pump 15.

The electrolytic solution 3a flowing into the first electrolytic solution tank 1a flows down between the electrode active material portion 4 and the ion exchange membrane 8. Further, the flow rate of the electrolytic solution 3a changes greatly. Due to the flow and flow rate change of the electrolytic solution 3a, the metal compound deposit 23 deposited or adhered to the surface of the electrode active material portion 4 is detached from the surface of the electrode active material portion 4 and descends together with the electrolytic solution. In addition, according to such a structure, a relatively large amount of the electrolyte 3 flows into the first electrolyte bath, so that the flow of the electrolyte 3 between the electrode active material portion 4 and the ion exchange membrane 8 becomes faster. The precipitates 23 are easily detached from the surface of the electrode active material part 4. Thereby, the deposit 23 can be more effectively removed from the surface of the electrode active material portion 4.

1: Electrolytic solution tank 1a: First electrolytic solution tank 1b: Second electrolytic solution tank 1c: Third electrolytic solution tank 1d: Fourth electrolytic solution tank 3: Electrolytic solution 3a: Electrolytic solution in the first electrolytic solution tank 3b: Electrolytic solution in the second electrolytic bath 3c: Electrolytic solution in the third electrolytic bath 3d: Electrolytic solution in the fourth electrolytic bath 4, 4a, 4b, 4c: Electrode active material portions 5, 5a, 5b, 5c : Metal electrode 6: Air electrode 8: Ion exchange membrane 10, 10a, 10b, 10c: Current collector 12, 12a, 12b, 12c: Lid member 13a: First valve 13b: Second valve 14: Filter 15: Pump ( Drive unit) 16: suction channel 17: discharge channel 20: discharge port 20a: first discharge port 20b: second discharge port 20c: third discharge port 23: precipitate of metal compound 25: flow channel member 26: air Flow path 30: Insulating member 31: Valve 32: For deposit removal 34: Blocking part 36: Floating part 37a: First electrolytic solution chamber 37b: Second electrolytic solution chamber 37c: Third electrolytic solution chamber 38: Elastic member 39: Receptacle 40: Electrolyte flow path 41: Wheel shaft 45: Metal-air battery 101: Zinc electrode 103: Alkaline electrolyte 105: Air electrode 106: Anion exchange membrane

Claims (15)

A first electrolyte tank for storing an electrolyte, a metal electrode provided in the first electrolyte tank and serving as an anode, an air electrode serving as a cathode, a second electrolyte tank for storing the electrolyte, and an electrolyte A liquid drive unit,
The first and second electrolyte baths and the drive unit flow out at a flow rate at which the electrolyte solution changes from the second electrolyte bath to the first electrolyte bath or at a flow rate at which the electrolyte solution changes from the first electrolyte bath. And a metal-air battery, wherein the metal-air battery is provided to flow to the second electrolyte bath. The metal electrode has an electrode active material portion made of an electrode active material,
2. The metal-air battery according to claim 1, wherein the air electrode is provided so as to sandwich an electrolytic solution stored in a first electrolytic solution tank together with the electrode active material portion. The first and second electrolyte tanks are provided such that the electrolyte stored in the second electrolyte tank flows into the electrolyte stored in the first electrolyte tank by gravity.
The electrode active material part and the air electrode are provided such that the electrolyte flowing into the first electrolyte tank from the second electrolyte tank flows between the electrode active material part and the air electrode. Metal-air battery as described in 2. The electrode active material portion has a main surface that contacts the electrolyte solution stored in the first electrolyte bath, and the main surface is substantially perpendicular to the liquid surface of the electrolyte solution stored in the first electrolyte bath. Provided,
4. The metal-air battery according to claim 2, wherein the air electrode has a main surface facing a main surface of the electrode active material portion. The second electrolyte tank includes a first discharge port for flowing the electrolyte stored in the second electrolyte tank into the first electrolyte tank, and a first valve provided at the first discharge port,
The metal-air battery according to any one of claims 1 to 4, wherein the first valve is provided so as to open when an amount of the electrolyte stored in the second electrolyte tank exceeds a predetermined amount. The metal-air battery according to any one of claims 1 to 5, wherein the first electrolyte bath has an inclined bottom portion and an opening at a lowest portion of the bottom portion. A third electrolyte bath provided at the lower portion of the first electrolyte bath;
The first electrolyte bath has a second discharge port for flowing the electrolyte stored in the first electrolyte bath into the third electrolyte bath, and a second valve provided at the second discharge port,
The metal-air battery according to any one of claims 1 to 4, wherein the second valve is provided so as to open when an amount of the electrolyte stored in the first electrolyte tank exceeds a predetermined amount. The second electrolyte bath has a wheel shaft and two or more electrolyte chambers provided around the wheel shaft,
The drive unit is provided such that the electrolyte flows into one of the two or more electrolyte chambers,
The metal air according to any one of claims 1 to 4, wherein the two or more electrolyte chambers are provided so as to rotate about the wheel shaft depending on a weight of the electrolyte introduced by the driving unit. battery. A levitation unit connected to the metal electrode, and a fourth electrolyte bath provided at a lower portion of the first electrolyte bath,
The first electrolyte bath has a third outlet for flowing the electrolyte stored in the first electrolyte bath into the fourth electrolyte bath,
The levitation unit is provided such that the metal electrode floats when the amount of electrolyte stored in the first electrolyte tank exceeds a predetermined amount.
The metal electrode has a blocking portion;
The metal air according to any one of claims 1 to 4, wherein the closing portion is provided so as to close the third discharge port when the metal electrode sinks and to come off the third discharge port when the metal electrode floats. battery. The metal-air battery according to any one of claims 1 to 9, wherein the second electrolyte bath has a filter that is detachably provided on the bottom. The metal electrode has a current collector,
The metal-air battery according to any one of claims 2 to 4, wherein the electrode active material portion is provided on the current collector. The current collector is plate-shaped,
The metal-air battery according to claim 11, wherein the electrode active material portion is provided on a main surface of the current collector. The electrode active material part is made of metallic zinc,
The metal-air battery according to claim 11 or 12, wherein the electrolytic solution is an alkaline aqueous solution. An ion exchange membrane having first and second major surfaces;
The ion exchange membrane is provided such that a first main surface is in contact with an electrolyte stored in a first electrolyte bath and a second main surface is in contact with the air electrode. Metal-air battery as described in 2. The ion exchange membrane comprises an anion exchange membrane,
The metal-air battery according to claim 14, wherein the air electrode includes a carbon support and an air electrode catalyst supported on the carbon support.

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