JP2017079147A - Metal-air battery, electrolyte tank, and method of using metal-air battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-air battery capable of preventing the leakage of an electrolyte caused due to removal of a metal electrode cartridge.SOLUTION: A metal-air battery includes: an electrolyte tank; an air electrode forming a part of a side wall of the electrolyte tank; a metal electrode cartridge inserted from an opening of the electrolyte tank to the inside of the electrolyte tank; a first uneven part provided on an inner wall of the opening; and a first sealing member provided at a lower end of the metal electrode cartridge and in the electrolyte tank and having a second uneven part capable of being fitted to the first uneven part.SELECTED DRAWING: Figure 1

Description

The present invention relates to a metal-air battery, an electrolytic solution tank, and a method for using the metal-air battery. More specifically, the present invention relates to a metal-air battery that uses a detachable metal electrode, an electrolytic solution tank related to the metal-air battery, and a method of using the metal-air battery.

A metal-air battery is a battery in which an anode (negative electrode) is constituted by a metal electrode, and a cathode (positive electrode) is constituted by an air electrode, and has a high energy density. Therefore, development and research for practical application are advanced. ing.

An example of the metal-air battery is a zinc-air battery. FIG. 24 is a schematic cross-sectional view showing an example of the structure of a conventional zinc-air battery, and FIG. 25 is a schematic cross-sectional view for explaining a battery reaction in the zinc-air battery. The zinc-air battery 121 has a structure in which a zinc electrode (negative electrode) 111 is provided in an alkaline electrolyte 115 and an air electrode (positive electrode) 112 is provided between the air flow path 113 and the electrolyte 115, Electric power is output from the zinc electrode 111 and the air electrode 112 as the battery reaction (discharge reaction) proceeds.

In the battery reaction of the zinc-air battery 121, metallic zinc constituting the zinc electrode 111 reacts with hydroxide ions in the electrolytic solution 115 to form tetrahydroxozinate ions, and electrons are released into the zinc electrode 111. In addition, the tetrahydroxozincate ion is decomposed and zinc oxide or zinc hydroxide is precipitated in the electrolytic solution 115. Further, hydroxide ions are generated by the reaction of electrons, water, and oxygen in the air electrode 112, and these hydroxide ions move to the electrolytic solution 115. When such a battery reaction proceeds, the zinc metal of the zinc electrode 111 is consumed, and zinc oxide and zinc hydroxide accumulate in the electrolytic solution 115. Therefore, in order to maintain the power output from the zinc-air battery 121, it is necessary to supply metallic zinc to the zinc electrode 111.

As exemplified by the zinc-air battery, in the metal-air battery, the negative electrode metal is consumed along with the discharge. On the other hand, the system which enables the metal part used as a negative electrode to be inserted / extracted in a battery housing | casing is proposed (for example, refer patent document 1). In this method, discharge is performed by attaching a negative electrode to a battery housing provided with an air electrode, and re-discharge is possible by replacing the used negative electrode with a new negative electrode after the discharge. The used negative electrode is regenerated by being attached to a charging device and being reduced.

JP 2004-362869 A

As described above, in the metal-air battery, the metal electrode constituting the negative electrode is dissolved in the electrolytic solution along with the discharge. For this reason, the metal-air battery needs to periodically replace the metal electrode. Here, the metal-air battery is designed so that the metal electrode is made into a cartridge so that the metal electrode can be exchanged for continuous use. In a mechanical rechargeable metal-air battery, the metal electrode cartridge (metal electrode structure) is inserted into the electrolyte tank (battery housing) during discharge and removed during non-discharge. When the metal electrode cartridge is removed, the metal electrode There was a possibility that the electrolyte in the electrolyte bath would leak out of the battery through the opening for inserting and removing the cartridge.

When the electrolyte solution leaks and the electrolyte solution adheres to the inside of the metal-air battery, the exterior member, or the wiring member, these members are deteriorated, which causes deterioration of battery characteristics and occurrence of malfunction.

Note that Patent Document 1 describes that a cap having a sealing function is provided in the grip portion of the metal portion so that the electrolyte does not leak outside (see FIG. 3). However, the cap of Patent Document 1 can seal the opening only with the metal portion inserted, and cannot seal the opening when the metal portion is removed. For this reason, in order to move and store the electrolytic solution tank with the metal part removed, another sealing means is required to seal the opening of the electrolytic solution tank. Moreover, when the used metal part was collected from the battery body, it was not possible to prevent the electrolytic solution adhering to the metal part from being scattered.

The present invention has been made in view of the above situation, and a metal-air battery capable of preventing leakage of an electrolyte caused by taking out a metal electrode cartridge, an electrolyte tank related to the metal-air battery, and metal air It aims at providing the usage method of a battery.

As a result of various studies on the replacement method of the metal electrode cartridge in the metal-air battery, the present inventors have provided a first uneven portion on the inner wall of the opening of the electrolytic solution tank, and can be fitted to the first uneven portion. By providing the first sealing member having the second concavo-convex portion, when the opening of the electrolytic solution tank is sealed by the first sealing member when the metal electrode cartridge is pulled out, leakage of the electrolytic solution is prevented. I found out that I can do it. As a result, the present inventors have conceived that the above problems can be solved brilliantly, and have reached the present invention.

That is, the first aspect of the present invention includes an electrolyte bath, an air electrode that forms part of the side wall of the electrolyte bath, and a metal inserted into the electrolyte bath from the opening of the electrolyte bath. An electrode cartridge, a first concavo-convex portion provided on the inner wall of the opening, a second end provided in the lower end portion of the metal electrode cartridge and the electrolytic bath, and fitable with the first concavo-convex portion. And a first sealing member having a concavo-convex portion.

The electrolytic solution tank that can be used for the metal-air battery of the first aspect is also an aspect of the present invention. That is, the second aspect of the present invention includes an air electrode that forms a part of the wall portion of the electrolytic solution tank, a first uneven portion provided on the inner wall of the opening of the electrolytic solution tank, and the electrolytic solution. It is an electrolytic solution tank provided with the 1st sealing member which sealed the said opening part of the tank and was provided with the 2nd uneven | corrugated | grooved part fitted to the said 1st uneven | corrugated | grooved part.

The method of using the metal-air battery related to the replacement of the metal electrode cartridge performed in the metal-air battery of the first aspect is also an aspect of the present invention. That is, the third aspect of the present invention is a method of using a metal-air battery, wherein the metal-air battery includes a metal electrode cartridge, an electrolyte tank containing an electrolyte, and a wall portion of the electrolyte tank. An air electrode that forms a part, and a first sealing member that seals the opening of the electrolytic solution tank. The metal electrode cartridge is pushed into the electrolytic solution tank from the opening, and the sealing is performed. A step of fitting the stopper member and the metal electrode cartridge, immersing the metal electrode cartridge in the electrolyte, pulling out the metal electrode cartridge from the opening, and attaching the first sealing member together with the metal electrode cartridge A method of using the metal-air battery including a step of pulling up from the electrolytic solution and sealing the opening with the first sealing member.

The metal-air battery, the electrolytic solution tank, and the method of using the metallic battery of the present invention are all suitable for preventing leakage of the electrolytic solution caused by taking out the metal electrode cartridge.

It is the cross-sectional schematic diagram which looked at the metal air battery of Embodiment 1 of the discharge state from the side surface direction. It is the cross-sectional schematic diagram which expanded and showed the opening part vicinity of the electrolyte solution tank in FIG. It is the cross-sectional schematic diagram which expanded and showed the 1st sealing member in FIG. It is the cross-sectional schematic diagram which expanded and showed the metal electrode cartridge in FIG. FIGS. 5A and 5B are schematic cross-sectional views illustrating a method for using the metal-air battery according to the first embodiment. FIG. 5A illustrates a discharge state, and FIG. FIG. 5C shows a state immediately before removal, and FIG. 5C shows a state where the metal electrode cartridge is removed from the metal-air battery of the first embodiment. It is the cross-sectional schematic diagram which looked at the metal air battery in the state of FIG.5 (b) from the front direction. It is a cross-sectional schematic diagram explaining the dimension of a 1st sealing member. In the metal air battery of Embodiment 1, it is the cross-sectional schematic diagram seen from the side surface direction which expands and shows the mode inside an electrolyte tank when pulling up a metal electrode cartridge. FIG. 9A is a schematic cross-sectional view of the metal electrode battery according to the second embodiment as seen from the side direction, and FIG. 9A shows a state in which the metal electrode cartridge and the first sealing member are removed. (B) shows the state which the metal electrode cartridge and the 1st sealing member couple | bonded. It is the cross-sectional schematic diagram seen from the side direction which shows the metal electrode battery of Embodiment 2 typically, Fig.10 (a) shows a discharge state, FIG.10 (b) is a mode that the metal electrode cartridge was removed. Indicates. It is a figure which shows the 1st sealing member of Embodiment 3 typically, Fig.11 (a) is a top view, FIG.11 (b) is sectional drawing. It is the figure which expanded and showed the part enclosed with the dotted line in FIG. It is the cross-sectional schematic diagram which looked at the metal air battery of Embodiment 4 from the side surface direction. It is the cross-sectional schematic diagram which expanded and showed the 1st uneven | corrugated | grooved part vicinity of the electrolyte solution tank of FIG. 13 in the state which took out the metal electrode cartridge. It is the cross-sectional schematic diagram which expanded and showed the 2nd uneven | corrugated | grooved part vicinity of the electrolyte solution tank of FIG. 13 in the state which attached the metal electrode cartridge. It is the cross-sectional schematic diagram which looked at the metal air cell of Embodiment 5 from the side surface direction, Fig.16 (a) shows a discharge state, FIG.16 (b) shows the state just before removing a metal electrode cartridge. 10 is a top view schematically showing a first sealing member of Embodiment 6. FIG. 10 is a top view schematically showing an electrolytic solution tank of Embodiment 6. FIG. It is the cross-sectional schematic diagram which looked at the metal air battery of Embodiment 6 from the side surface direction. It is the cross-sectional schematic diagram which looked at the electrolyte solution tank of Embodiment 7 from the side surface direction. It is the cross-sectional schematic diagram which looked at the metal air battery of Embodiment 7 from the side surface direction, Fig.21 (a) shows a discharge state, FIG.21 (b) shows the state just before removing a metal electrode cartridge. FIGS. 22A and 22B are schematic cross-sectional views of the metal-air battery of Embodiment 8 as viewed from the side, FIG. 22A shows a discharge state, FIG. 22B shows a state immediately before removing the metal electrode cartridge, and FIG. 22 (c) shows a state in which the metal electrode cartridge is removed. It is the cross-sectional schematic diagram which looked at the metal air battery of Embodiment 9 from the side surface direction. It is the schematic cross section which showed an example of the structure of the conventional zinc air battery. It is typical sectional drawing for demonstrating the battery reaction in a zinc air battery.

Embodiments will be described below, and the present invention will be described in more detail with reference to the drawings. However, the present invention is not limited only to these embodiments. Note that in the following description, the same portions or portions having similar functions are denoted by the same reference numerals in different drawings, and description thereof is not repeated.
In addition, the configurations of the respective embodiments may be appropriately combined or changed within a range not departing from the gist of the present invention.

[Embodiment 1]
A metal-air battery according to Embodiment 1 will be described with reference to FIGS. FIG. 1 is a schematic cross-sectional view of the metal-air battery according to Embodiment 1 in a discharged state as viewed from the side. FIG. 2 is an enlarged schematic cross-sectional view showing the vicinity of the opening of the electrolytic solution tank in FIG. FIG. 3 is an enlarged schematic cross-sectional view of the first sealing member in FIG. FIG. 4 is an enlarged schematic cross-sectional view of the metal electrode cartridge in FIG. FIG. 5 is a schematic cross-sectional view illustrating a method of using the metal-air battery of Embodiment 1, FIG. 5 (a) shows a discharge state, and FIG. 5 (b) is from the metal-air battery of Embodiment 1. FIG. 5C shows a state immediately before removing the metal electrode cartridge, and FIG. 5C shows a state where the metal electrode cartridge is removed from the metal-air battery of the first embodiment. FIG. 6 is a schematic cross-sectional view of the metal-air battery in the state of FIG. FIG. 7 is a schematic cross-sectional view illustrating the dimensions of the first sealing member. FIG. 8 is a schematic cross-sectional view of the metal-air battery of Embodiment 1 as seen from the side direction, showing an enlarged view of the inside of the electrolytic solution tank when the metal electrode cartridge is pulled up. The negative electrode current collector 11a and the positive electrode current collector (air electrode current collector) 21a are not shown except for FIG.

The metal-air battery 1 of Embodiment 1 is a battery having a metal electrode cartridge 10 and an electrolytic solution tank 20 that stores an electrolytic solution 50. The electrolytic solution tank 20 includes an opening 24 for inserting the metal electrode cartridge 10, an air electrode 21 that forms a part of the side wall of the electrolytic solution tank 20, and a first electrode provided on the inner wall of the electrolytic solution tank 20. An uneven portion 23 and a first sealing member 31 provided with a second uneven portion 32 that seals the opening 24 of the electrolyte bath 20 and is fitted to the first uneven portion 23 are provided. It is characterized by that.
Hereinafter, the metal-air battery 1 of Embodiment 1 will be described in detail.

As shown in FIG. 5A, in the metal-air battery 1 of Embodiment 1, when the metal electrode cartridge 10 is installed in the electrolytic solution tank 20 containing the electrolytic solution 50, the metal electrode 11 and the electrolytic solution 50 are disposed. Will come into contact with each other and discharge by battery reaction is possible. The metal electrode cartridge (metal electrode structure) 10 includes a metal electrode 11 used as the negative electrode of the metal-air battery 1, and is detachable from the electrolytic solution tank 20. When the negative electrode active material contained in the metal electrode 11 is consumed as the battery reaction progresses, power can be generated again by replacing the metal electrode cartridge 10.

In the upper part of the electrolytic solution tank 20, there is an opening 24 for inserting the metal electrode cartridge 10. The opening 24 is provided with a first uneven portion 23. A first sealing member 31 having a second concavo-convex part 32 that can be fitted to the first concavo-convex part 23 is provided in the electrolytic solution tank 20. The metal electrode cartridge 10 is provided with a metal electrode 11 and a second sealing member 13 that supports the upper end portion of the metal electrode 11 and has a third uneven portion 14 that can be fitted to the first uneven portion 23. ing. A fourth uneven portion 16 is provided at the lower end portion of the metal electrode cartridge 10. The first sealing member 31 has a groove 33 on the upper surface. On the inner wall of the groove 33, a fifth uneven portion 34 that can be fitted to the fourth uneven portion 16 is provided.

In a state where the metal electrode cartridge 10 is attached to the electrolytic solution tank 20, the third uneven portion 14 is fitted with the first uneven portion 23, and the fourth uneven portion 16 is the fifth uneven portion in the electrolytic solution tank 20. The part 34 is fitted. In a state where the metal electrode cartridge 10 is not inserted, the second concavo-convex portion 32 is fitted with the first concavo-convex portion 23, and the first sealing member 31 seals the opening 24. When the metal electrode cartridge 10 is inserted into the electrolytic cell 20, the fourth uneven portion 16 of the metal electrode cartridge 10 is fitted with the fifth uneven portion 34 of the first sealing member 31. When the metal electrode cartridge 10 is pushed into the electrolyte bath 20, the fitting between the second uneven portion 32 and the first uneven portion 23 is released, and the first sealing member 31 is moved to the electrolyte bath 20. Move to the bottom inside. After the metal electrode cartridge 10 and the first sealing member 31 are immersed in the electrolytic solution 50, the third uneven portion 14 is fitted to the first uneven portion 23, and the second sealing member 13 is an opening. 24 is sealed.

When removing the metal electrode cartridge 10 inserted into the electrolytic solution tank 20, the metal electrode cartridge 10 is pulled up. By this operation, the fitting between the third uneven portion 14 and the first uneven portion 23 is released, and the first sealing member 31 is also pulled up. As shown in FIGS. 5B and 6, when the first sealing member 31 reaches the upper part of the electrolytic solution tank 20, the first uneven portion 23 and the second uneven portion 32 are fitted. In a state where the first uneven portion 23 and the second uneven portion 32 are fitted, the opening 24 is sealed by the first sealing member 31, and the electrolytic solution 50 in the electrolytic solution tank 20 is the electrolytic solution. Leakage to the outside of the tank 20 is suppressed. When the metal electrode cartridge 10 is further pulled up, as shown in FIG. 5C, the fitting between the fourth uneven portion 16 and the fifth uneven portion 34 is released, and only the metal electrode cartridge 10 is in the electrolytic solution tank 20. Is taken out of.

In the first embodiment, the second sealing member 13 is detachable from the metal electrode 11. However, in another embodiment, the second sealing member 13 is integrated with the metal electrode 11. Also good.

The first concavo-convex portion 23 includes a first convex portion 25 and a second convex portion 26 provided below the first convex portion. The amount of protrusion of the second convex portion 26 is the first This is smaller than the protruding amount of one convex portion 25. In addition, the second concavo-convex portion 32 includes a third convex portion 35 and a fourth convex portion 36 provided above the third convex portion 35, and the fourth convex portion 36 protrudes. The amount is smaller than the protruding amount of the third convex portion.

When the metal electrode cartridge 10 is pulled out, the metal electrode cartridge 10 is separated from the first sealing member 31 after the second uneven portion 32 and the first uneven portion 23 of the first sealing member 31 are fitted to each other. In order to do this, as shown in FIG. 7, the first sealing member 31 has a relationship between the protrusion amount a of the protrusion with respect to the first uneven portion 23 and the protrusion amount b of the protrusion with respect to the metal electrode cartridge 10. It is preferable that a ≦ b is satisfied.

The first sealing member 31 is preferably capable of moving up and down in the electrolytic solution tank 20 while being spaced from the inner wall that forms the side surface of the electrolytic solution tank 20. Accordingly, as shown in FIG. 8, when the first sealing member 31 is moved up and down in the electrolytic solution tank 20 by inserting the metal electrode cartridge 10, the electrolytic solution 50 in the electrolytic solution tank 20 is changed. The first sealing member 31 can be moved through a gap formed between the inner wall of the electrolyte bath 20 and the first sealing member 31 can be easily moved.

The material of the first sealing member 31 preferably has corrosion resistance against the electrolytic solution 50, and for example, an alkali-resistant material is used. Specific examples of the material include resin, ceramic, metal and the like.

Then, each structural member of the metal air battery 1 of Embodiment 1 is demonstrated.
In the metal electrode cartridge 10, a metal electrode 11 is used as a negative electrode (anode) of the metal-air battery 1. The metal contained in the metal electrode 11 is not particularly limited as long as it is a metal species that can be used as a negative electrode active material. For example, zinc (Zn), lithium (Li), sodium (Na), calcium (Ca), aluminum ( Al), magnesium (Mg), iron (Fe), copper (Cu), cobalt (Co), cadmium (Cd), palladium (Pd) and other metals, alloys thereof, and mixtures of these metals and / or alloys Is mentioned. Especially, if Zn, Li, Al, and Fe are used, it can be operated at room temperature. Zn, Fe, Al, Mg, and Cu are excellent in handling safety. A zinc electrode mainly composed of Zn is particularly preferably used as the metal electrode 11. The metal contained in the metal electrode 11 emits electrons by the discharge reaction of the battery, dissolves in the electrolytic solution 50, and then deposits as a metal compound such as a metal oxide or a metal hydroxide.

An additive may be added to the metal electrode 11 as necessary. For example, when the metal electrode 11 mainly composed of zinc is used, the metal electrode 11 can be prevented from self-corrosion by adding an additive such as indium, bismuth, aluminum, or calcium.

The shape of the metal electrode 11 is not particularly limited and can be, for example, a flat plate shape, a rod shape, or a slurry shape, and a flat plate shape is preferably used. Moreover, it does not specifically limit as a manufacturing method of the metal electrode 11, What shape | molded the granular metal in plate shape and rod shape may be sufficient.

The metal electrode cartridge 10 may be provided with a current collecting structure for taking out electricity from the negative electrode. For example, the metal electrode 11 may be formed by electrodepositing a metal species on the negative electrode current collector 11 a provided in the metal electrode cartridge 10. Further, a current collecting structure arranged so as to be electrically connected to the metal electrode 11 inserted into the electrolytic solution tank 20 may be provided in the electrolytic solution tank (battery casing) 20. Examples of the material constituting the negative electrode current collector 11a used in the current collecting structure include nickel, platinum, stainless steel, copper, tin, and carbon.

The arrangement of the metal electrode 11 is not particularly limited as long as ions are conducted between the electrolytic solution 50 held in the electrolytic solution tank 20 and the metal electrode 11, but in a state where the metal electrode cartridge 10 is attached to the electrolytic solution tank 20, The metal electrode 11 is preferably disposed in the electrolytic solution tank 20 so that the electrode surface is parallel to the direction of gravity, in other words, the electrode surface intersects the horizontal direction. In addition, in a state where the metal electrode cartridge 10 is attached to the electrolytic solution tank 20, the electrode surface of the metal electrode 11 is preferably opposed to the electrode surface of the air electrode 21 so that the distance between the electrodes is uniform.

Further, the metal electrode 11 may be in direct contact with the electrolytic solution 50, or an ion conductive separator may be provided between the metal electrode 11 and the electrolytic solution 50. The separator may be included in the metal electrode cartridge 10, the electrolyte bath 20, or another member independent of them. When a separator is provided between the metal electrode 11 and the electrolytic solution 50, the metal electrode 11 can be replaced while preventing leakage of the electrolytic solution 50 without limiting the insertion direction of the metal electrode cartridge 10 to the gravity direction. .
Further, when the metal electrode cartridge 10 is taken out from the electrolytic solution tank 20, the metal electrode 11 may be exposed to the air, or the metal electrode 11 may be covered with a separator.

The separator only needs to have resistance to electrolytic solution and ion conductivity, and a solid electrolyte, a porous resin film, or a nonwoven fabric can be used. Examples of the solid electrolyte include an ion conductive ceramic and an ion conductive glass. Examples of the porous resin include polyethylene, polypropylene, nylon 6, nylon 66, polyolefin, polyvinyl acetate, polyvinyl alcohol-based material, and polytetrafluoroethylene (PTFE). The separator is preferably hydrophilized so that the flow of the electrolytic solution 50 is improved. Ion conductivity may be improved by dispersing an electrolyte salt such as a zinc salt or a lithium salt in the porous resin.

In the metal-air battery 1, an air electrode 21 is used as a positive electrode (cathode). The air electrode 21 is an electrode that generates hydroxide ions from oxygen, water, and electrons in the atmosphere.

The air electrode 21 is configured to include, for example, a conductive porous carrier and an air electrode catalyst supported on the porous carrier. According to such a configuration, oxygen, water, and electrons can coexist on the air electrode catalyst, and the electrode reaction can proceed efficiently. The air electrode catalyst is preferably supported in the form of fine particles and supported on a porous carrier. The water used for the electrode reaction may be supplied from the atmosphere or supplied from the electrolytic solution 50.

Examples of porous carriers include carbon black such as acetylene black, furnace black, channel black, and ketjen black; conductive carbon particles such as graphite and activated carbon; vapor grown carbon fiber (VGCF), carbon nanotube, and carbon nanowire. Carbon fibers such as can be used.
The porous carrier may be surface-treated 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 21 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. Examples of the ion exchange group of the anion exchange resin include a strong basic group such as a quaternary ammonium base; a weak basic group having a primary, secondary or tertiary amino group. Examples of strongly basic anion exchange resins include those obtained by introducing a trialkylammonium base such as trimethylammonium and an alkylalkanolammonium base such as dimethylethanolammonium and methyldiethanolammonium into a crosslinked polymer having a styrene skeleton. . Examples of weakly basic anion exchange resins include homopolymers or copolymers having a benzimidazole unit such as polybenzimidazole and benzimidazole-polyimide copolymer; and aminated polyethersulfone.

Examples of the air electrode catalyst include metals such as platinum, iron, cobalt, nickel, palladium, silver, ruthenium, iridium, molybdenum and manganese; metal compounds containing these metal atoms; alloys containing two or more of these metals A metal oxide of these metals can be used. The 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 An alloy and an iron-cobalt-nickel alloy can be preferably used. The metal oxide is preferably a metal oxide containing at least one metal atom of ruthenium, cobalt, manganese, cerium, and iron. Specifically, ruthenium (IV) oxide (RuO ₂ ), manganese dioxide ( MnO ₂ ), cobalt (III) oxide (Co ₂ O ₃ ), and cerium (IV) oxide (CeO ₂ ) can be suitably used.

In the first embodiment, the air electrode 21 is provided as a part of the side wall of the electrolytic solution tank 20. The electrode surface of the air electrode 21 is preferably disposed to face the electrode surface of the negative electrode. Thereby, the distance between electrodes can be made uniform and short, and resistance between electrodes can be suppressed.

The air electrode 21 may be provided in direct contact with the atmosphere or may be provided in contact with the air flow path. In FIG. 1 and the like, a vent hole 22 provided in the side wall of the electrolytic solution tank 20 is shown as an example of an air flow path. The vent hole 22 is not particularly limited as long as it can vent such as a mesh or a hole. The vent hole 22 may be openable and closable. In the case where an openable / closable device is provided, the vent hole 22 is opened when the metal-air battery 1 is operated, and the vent hole 22 is closed when the metal electrode 11 is removed from the electrolytic solution 50. Thereby, it is possible to prevent the electrolyte solution 50 from leaking from the vent hole 22 when the metal electrode 11 is taken out. When the air flow path is provided, not only oxygen but also water can be supplied to the air electrode 21 by flowing the humidified air through the air flow path.

The method of installing the air flow path is not particularly limited. For example, a positive electrode current collector (air electrode current collector) 21a is disposed on the side of the air electrode 21 opposite to the side in contact with the electrolyte solution 50, and the positive electrode current collector is provided. 21a may be formed. If the air electrode 21 and the external circuit are electrically connected via the positive electrode current collector 21a, the power of the metal-air battery 1 can be efficiently output to the external circuit.

The air electrode 21 may be provided so as to contact the electrolytic solution 50 in the electrolytic solution tank 20. Thus, hydroxide ions generated at the air electrode 21 can easily move to the electrolytic solution 50. Further, water necessary for the electrode reaction in the air electrode 21 is easily supplied from the electrolytic solution 50 to the air electrode 21.

Further, the air electrode 21 may be provided in contact with a separator provided so as to be in contact with the electrolytic solution 50 in the electrolytic solution tank 20. By providing, for example, an ion exchange membrane as the separator, the ion species that move between the air electrode 21 and the electrolytic solution 50 can be limited. The ion exchange membrane may be an anion exchange membrane. As a result, hydroxide ions generated at the air electrode 21 can be transferred to the electrolytic solution 50 through the anion exchange membrane, and the cations in the electrolytic solution 50 are prevented from moving to the air electrode 21. can do.

The electrolytic solution 50 is a liquid having ionic conductivity by dissolving an electrolyte in a solvent. The type of the electrolytic solution 50 is not particularly limited as long as it is an electrolytic solution used in a general metal-air battery, and may be selected according to the type of metal constituting the negative electrode. The electrolytic solution using an aqueous solvent (electrolyte aqueous solution) Or an electrolytic solution using an organic solvent (organic electrolytic solution).
For example, when the metal electrode 11 mainly contains zinc, aluminum, and iron, an alkaline electrolyte such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution can be used. When the metal electrode 11 mainly contains magnesium, a sodium chloride aqueous solution or the like can be used. In the case of mainly containing lithium, sodium and calcium, an acidic electrolyte can be used. Moreover, when the metal electrode 11 mainly contains lithium, it is preferable to use an organic electrolyte. Examples of the organic electrolyte include LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₃ ), LiN (C ₂ F ₅ SO ₂ ) _{2, and the} like. And a known lithium salt dissolved in an aprotic organic solvent having no chain structure (ethylene carbonate, tetrahydrofuran, etc.) can be used.

Moreover, the electrolyte solution 50 contains a gelatinizer and may be gelatinized. The gelling agent is not particularly limited and may be any gelling agent generally used for gelling an electrolyte in the field of batteries. For example, potassium polyacrylate, sodium polyacrylate, etc. Polyacrylic acid salt or 2-acrylamido-2-methylpropanesulfonic acid having a sulfo group as a hydrophilic group can be used.

Since the electrolytic solution tank 20 for storing the electrolytic solution 50 is a container in which the electrolytic solution 50 is stored, the electrolytic solution tank 20 is preferably formed of a material having corrosion resistance to the electrolytic solution 50. The electrolytic solution tank 20 may have any shape that can store the electrolytic solution 50 such as a cylindrical shape or a rectangular parallelepiped shape, and the volume and shape thereof are not particularly limited. The electrolytic solution tank 20 is provided with an opening 24 having a size capable of inserting the metal electrode 11. The arrangement of the opening 24 is not particularly limited as long as the metal electrode 11 can be brought into contact with the electrolytic solution 50 held in the electrolytic solution tank 20, but is preferably provided on the upper surface of the electrolytic solution tank 20.

The electrolytic solution tank 20 may be provided with a flow path for circulating the electrolytic solution 50. Further, the replacement (electrolyte or waste liquid) of the electrolytic solution 50 may be performed from the opening 24, or the electrolytic solution tank 20 may be provided with a liquid supply port or a waste liquid port for replacing the electrolytic solution 50, and from there. .

Note that the metal-air battery 1 of Embodiment 1 has at least one electrolytic solution tank 20. When a plurality of electrolytic solution tanks 20 are provided, the air electrode 21 of each electrolytic solution tank 20 and the metal electrode cartridge 10 attached to each electrolytic solution tank 20 are electrically connected to each other.

The metal-air battery 1 according to Embodiment 1 having the above-described configuration has the following advantages.
(1) The opening 24 of the electrolytic solution tank 20 can be sealed only by the attachment / detachment operation of the metal electrode cartridge 10. Thereby, it is possible to always prevent leakage and scattering of the electrolyte solution 50 from the opening 24 regardless of whether or not the metal electrode cartridge 10 is inserted.
(2) By fitting the first sealing member 31, the strength of the upper part of the electrolytic solution tank 20 provided with the opening 24 can be increased.
(3) Since there is a gap between the first sealing member 31 and the inner wall constituting the side surface of the electrolytic solution tank 20, the electrolytic solution 50 is hardly pushed out by the movement of the first sealing member 31. Moreover, the first sealing member 31 is prevented from coming into contact with the inner wall and the air electrode 21 constituting the side surface of the electrolytic solution tank 20.

[Embodiment 2]
A metal-air battery according to Embodiment 2 will be described with reference to FIGS. FIG. 9 is a schematic cross-sectional view of the metal electrode battery according to the second embodiment as seen from the side direction. FIG. 9A shows the metal electrode cartridge 10 and the first sealing member 31 removed. FIG. 9B shows a state where the metal electrode cartridge 10 and the first sealing member 31 are coupled. FIG. 10 is a schematic cross-sectional view of the metal electrode battery according to the second embodiment as seen from the side direction. FIG. 10A shows a discharge state, and FIG. 10B shows the metal electrode cartridge 10. Shows the state of being removed. In the second and subsequent embodiments, descriptions of matters common to the first embodiment are omitted.

In the second embodiment, the inner periphery of the first uneven portion 23 of the electrolytic solution tank 20 and the outer periphery of the first sealing member 31 are tapered. 9A, the first uneven portion 23 of the electrolytic solution tank 20 is provided with a first tapered portion 23a having a large inner diameter toward the bottom surface side of the electrolytic solution tank 20, as shown by being surrounded by a dotted line. It has been. 9B, the first sealing member 31 is provided with a second tapered portion 31a having a large outer diameter toward the bottom surface side of the electrolytic solution tank 20. As shown in FIG. ing. As shown in FIG. 10, the first tapered portion 23 a and the second tapered portion 31 b are configured such that their inclined surfaces are in close contact with each other and the opening 24 can be sealed. Thus, in a state where the metal electrode cartridge 10 is removed, the first uneven portion 23 of the electrolytic solution tank 20 and the first sealing member 31 come into contact with each other in a wider area than that of the first embodiment.

According to the second embodiment, in addition to the advantages of the first embodiment, the sealing performance of the electrolytic solution tank 20 when the opening 24 is sealed with the first sealing member 31 is improved, and the leakage / There is an advantage that scattering can be prevented more effectively. Moreover, the strength of the upper part of the electrolytic solution tank 20 when the first sealing member 31 and the first uneven portion 23 are fitted is improved.

[Embodiment 3]
A metal-air battery according to Embodiment 3 will be described with reference to FIGS. FIG. 11 is a diagram schematically illustrating the first sealing member 31 of the third embodiment, FIG. 11A is a top view, and FIG. 11B is a cross-sectional view. FIG. 12 is an enlarged view of a portion surrounded by a dotted line in FIG.

In the third embodiment, a cutout (electrolyte flow path) 31 b extending along the vertical direction in the electrolyte bath 20 is formed on the side surface of the first sealing member 31. When the metal electrode cartridge 10 is inserted, the electrolytic solution 50 below the bottom surface of the first sealing member 31 can escape upward through the notch 31b. On the other hand, when the metal electrode cartridge 10 is pulled out, the electrolytic solution 50 above the upper surface of the first sealing member 31 can be released downward through the notch 31b. Although the number and shape of the notches 31b provided in the first sealing member 31 are not limited, it is preferable that the first sealing member 31 is continuously provided from the upper end to the lower end.

According to the third embodiment, in addition to the advantages of the first embodiment, there is an advantage that the resistance of the electrolytic solution 50 with respect to the movement of the first sealing member 31 can be reduced and the metal electrode cartridge 10 can be easily attached and detached. is there. In addition, when the metal electrode cartridge 10 is attached or detached, it is possible to prevent the pressure (internal pressure) in the electrolyte bath 20 from increasing, and as a result, it is possible to prevent damage to the air electrode 21 and the like.

[Embodiment 4]
A metal-air battery according to Embodiment 4 will be described with reference to FIGS. FIG. 13 is a schematic cross-sectional view of the metal-air battery of Embodiment 4 as seen from the side surface direction. FIG. 14 is an enlarged schematic cross-sectional view showing the vicinity of the first uneven portion of the electrolytic solution tank 20 of FIG. 13 in a state where the metal electrode cartridge 10 is taken out. FIG. 15 is an enlarged schematic cross-sectional view showing the vicinity of the second uneven portion of the electrolytic solution tank 20 of FIG. 13 with the metal electrode cartridge 10 attached.

In the fourth embodiment, chamfers 23 b are provided at the corners of the second convex portion 26 that fits with the first sealing member 31 in the first concave-convex portion 23 of the electrolytic solution tank 20. Thereby, the 1st sealing member 31 can be attached or detached more smoothly.

According to the fourth embodiment, in addition to the advantages of the first embodiment, there is an advantage that the metal electrode cartridge 10 can be easily attached and detached. That is, it is not necessary to apply a large force when the metal electrode cartridge 10 is inserted. Further, when the metal electrode cartridge 10 is pulled out, it is possible to prevent the metal electrode cartridge 10 from coming out before the first sealing member 31 is fitted to the first uneven portion 23.

[Embodiment 5]
A metal-air battery according to Embodiment 5 will be described with reference to FIG. FIG. 16 is a schematic cross-sectional view of the metal-air battery of Embodiment 5 as viewed from the side, FIG. 16 (a) shows a discharge state, and FIG. 16 (b) shows a state immediately before the metal electrode cartridge 10 is removed. Indicates the state.

In the fifth embodiment, a close contact member 27 is provided in the opening 24 of the electrolytic solution tank 20. As the contact member 27, for example, a magnetic body (magnet) or an adhesive material can be used.
As shown in FIG. 16A, the close contact member 27 has a flat surface on the upper side of the close contact member 27 and the fourth sealing member 17 when the metal electrode cartridge 10 is inserted into the electrolyte bath 20. The lower flat surface is in close contact. On the other hand, as shown in FIG. 16B, the lower flat surface of the contact member 27 and the upper flat surface of the third sealing member 37 are in close contact with each other. Thereby, since it is not necessary to use a fixing method for fitting the concavo-convex structure to each other, the shapes of the contact member 27 and the third sealing member 37 can be simplified. Further, the shape of the fourth sealing member 17 can be simplified.

Further, the third sealing member 37 and the metal electrode cartridge 10 may be configured by the contact member 27. Since the close contact member 27 in the third sealing member 37 is disposed in the electrolytic solution 50, one having resistance to the electrolytic solution 50 (for example, alkali resistance) is suitable, and is coated with, for example, a resin. Magnetic materials and alkali-resistant adhesive materials are used.

According to the fifth embodiment, in addition to the advantages of the first embodiment, there is an advantage that the inside of the electrolytic solution tank 20 and the shape of the third sealing member 37 can be simplified. Further, the shape of the fourth sealing member 17 can be simplified.

[Embodiment 6]
A metal-air battery according to Embodiment 6 will be described with reference to FIGS. FIG. 17 is a top view schematically showing the first sealing member of the sixth embodiment. FIG. 18 is a top view schematically showing the electrolytic solution tank of the sixth embodiment. FIG. 19 is a schematic cross-sectional view of the metal-air battery of Embodiment 6 as viewed from the side.

In the sixth embodiment, as shown in FIG. 17, the first guide portion 31 d for positioning is provided on the side surface of the first sealing member 31. Further, as shown in FIG. 18, a second guide portion 20 a for positioning is provided on the inner wall surface constituting the side surface of the electrolytic solution tank 20. The first guide part 31d of the first sealing member 31 and the second guide part 20a of the electrolytic solution tank 20 are both along the direction in which the first sealing member 31 moves in the electrolytic solution tank 20. The first guide part 31d and the second guide part 20a are formed so as to be fitted. That is, the first sealing member 31 is in a state where the first guide portion 31d of the first sealing member 31 and the second guide portion 20a of the electrolytic solution tank 20 are fitted (see FIG. 19). The electrolyte tank 20 is moved up and down. Thereby, the metal electrode cartridge 10 can be attached and detached at a fixed position. The number and shape of the first guide part 31d and the second guide part 20a are not limited, but the second guide part 20a is preferably provided continuously from the upper end to the lower end of the electrolytic solution tank 20.

According to the sixth embodiment, in addition to the advantages of the first embodiment, there is an advantage that the first sealing member 31 can be prevented from being displaced and the distance between the metal electrode 11 and the air electrode 21 can be appropriately maintained. . Therefore, it is possible to prevent the battery reaction from being uniformly generated on the electrode surface and to prevent the first sealing member 31 from contacting the air electrode 21.

[Embodiment 7]
A metal-air battery according to Embodiment 7 will be described with reference to FIGS. FIG. 20 is a schematic cross-sectional view of the electrolytic solution tank of the seventh embodiment when viewed from the side surface direction. FIG. 21 is a schematic cross-sectional view of the metal-air battery of Embodiment 7 as seen from the side, FIG. 21 (a) shows a discharged state, and FIG. 21 (b) shows a state immediately before removing the metal electrode cartridge. Indicates.

In the seventh embodiment, a gasket 23e is provided on a surface of the first concavo-convex portion 23 of the electrolytic solution tank 20 that is in contact with the second sealing member 13 or the first sealing member 31. Sealing performance is further improved by sealing between the first sealing member 31 and the first uneven portion 23 by the gasket 23e. The gasket 23e is not particularly limited, and may be made of rubber or resin.

According to the seventh embodiment, in addition to the advantages of the first embodiment, there is an advantage that leakage / scattering of the electrolytic solution 50 can be more effectively prevented.

[Embodiment 8]
A metal-air battery according to Embodiment 8 will be described with reference to FIG. FIG. 22 is a schematic cross-sectional view of the metal-air battery of Embodiment 8 as viewed from the side, FIG. 22 (a) shows a discharge state, and FIG. 22 (b) shows a state immediately before the metal electrode cartridge 10 is removed. A state is shown and FIG.22 (c) shows a mode that the metal electrode cartridge 10 was removed.

In the eighth embodiment, a removal unit 13 b that removes the electrolytic solution 50 attached to the metal electrode cartridge 10 and the first sealing member 31 is provided. The removing unit 13b absorbs the electrolytic solution 50 attached to the metal electrode cartridge 10 and the first sealing member 31 and the function of scraping off the electrolytic solution 50 attached to the metal electrode cartridge 10 drawn from the electrolytic solution tank 20. Although it has both functions, in this invention, you may have only any one function. The removal portion 13b can be made of resin or rubber. The removal portion 13b having a function of scraping off the electrolytic solution 50 is preferably disposed at a position in contact with the metal electrode cartridge 10 drawn from the electrolytic solution tank 20. The removal portion 13b made of an absorbent material having a function of absorbing the electrolytic solution 50 is in a state where the first sealing member 31 is coupled to the first uneven portion 23, and the electrolytic solution tank 20 of the first sealing member 31. It is preferable that the coating | coated part which contact | connects the surface of the outer side of is included. In the eighth embodiment, since the electrolytic solution 50 in the electrolytic solution tank 20 can be sealed by the first sealing member 31, the absorbent does not need to absorb a large amount of the electrolytic solution 50, and the metal electrode A sufficient effect can be obtained as long as a small amount of the electrolytic solution 50 adhering to the surface of the cartridge 10 can be absorbed. The absorbent material is made of, for example, a porous or non-woven resin. As the resin, for example, polyolefin such as polypropylene is used. As the rubber, vinyl chloride or the like is used.

As shown in FIG. 22A, the removal portion 13 b is preferably located above the first sealing member 31 and can be bent according to the movement of the metal electrode cartridge 10. As shown in FIG. 22B, when the metal electrode cartridge 10 is pulled out from the electrolytic solution tank 20, the removing unit 13b rubs the surface of the metal electrode cartridge 10 to remove the electrolytic solution 50 attached to the surface. To do. As shown in FIG. 22C, when the removal portion 13 b is an absorbent material, the removal portion 13 b is more in the electrolyte tank 20 than the first sealing member 31 in the state where the metal electrode cartridge 10 is taken out. The electrolyte solution 50 adhering to the upper surface can be absorbed by being located on the outer side and covering the first sealing member 31 in contact with the upper surface.

In the metal-air battery 1 of the eighth embodiment, in a state where the metal electrode cartridge 10 is inserted, the first protrusion 25 of the first uneven portion 23 disposed above the removal portion 13b and the first of the metal electrode cartridge 10 are arranged. In the state where the three concavo-convex portions 14 are coupled (see FIG. 22A) and the metal electrode cartridge 10 is taken out, the second concavo-convex portion 23 disposed below the removal portion 13b It is preferable that the portion 26 and the second concavo-convex portion 32 are coupled to each other, and the removal portion 13b covers and covers the upper surface of the first sealing member 31 (see FIG. 22C).

According to the eighth embodiment, in addition to the advantages of the first embodiment, it is possible to more effectively prevent leakage and scattering of the electrolytic solution 50 by more reliably removing the electrolytic solution 50 attached to the metal electrode cartridge 10. There are advantages.

[Embodiment 9]
A metal-air battery according to Embodiment 9 will be described with reference to FIG. FIG. 23 is a schematic cross-sectional view of the metal-air battery of Embodiment 9 as seen from the side surface direction.

In the ninth embodiment, the ion adsorbent 15 is provided on at least a part of the outer surface of the metal electrode cartridge 10. The ion adsorbent 15 adsorbs metal ions eluted from the metal electrode 11 into the electrolytic solution 50. In the case of a zinc-air battery, the ion adsorbent 15 adsorbs zinc ions, so that precipitation of a zinc compound in the electrolytic solution tank 20 can be suppressed. Zinc ions adsorbed on the ion adsorbent 15 are taken out of the electrolytic solution tank 20 by replacing the metal electrode cartridge 10. The ion adsorbent 15 is not particularly limited, and for example, an ion exchange resin, a chelate resin, or the like is used.

According to the ninth embodiment, in addition to the advantages of the first embodiment, the generation of precipitates in the electrolytic solution tank 20 can be suppressed. Accordingly, there is an advantage that it is possible to prevent deposits from being deposited on the upper surface of the first sealing member 31 and to prevent poor fitting between the second uneven portion 32 and the first uneven portion 23. Moreover, deterioration of the power generation characteristics of the battery can be prevented.

In addition, although the electrolytic solution tank 20 of Embodiment 1-9 was described as the electrolytic solution tank 20 used for the metal air battery 1, it can be used also as electrolytic solution tanks other than the metal air battery 1. FIG. Specifically, instead of the air electrode 21 forming a part of the wall portion of the electrolytic solution tank 20, a positive electrode generally used in the battery field can be used. Specifically, nickel, stainless steel, platinum, a carbon rod, or the like can be used as the positive electrode instead of the air electrode 21. The electrolytic solution tank 20 that does not use the air electrode 21 for the positive electrode can be used as the electrolytic solution tank 20 of a device that charges the discharged (used) metal electrode cartridge 10. By inserting the discharged metal electrode cartridge 10 into the electrolytic solution tank 20 that does not use the air electrode 21 as the positive electrode, a charging device that charges the discharged metal electrode cartridge 10 is obtained. The metal electrode 11 of the discharged metal electrode cartridge 10 contains a large amount of negative electrode active material oxidized by the discharge reaction. By inserting the discharged metal electrode cartridge 10 into the electrolyte bath 20 that does not use the air electrode 21 for the positive electrode and applying a voltage between the positive electrode and the metal electrode, the oxidized negative electrode active material is changed from oxide to metal. Reduced. After applying the voltage, the charged metal electrode cartridge 10 is extracted from the electrolytic solution tank 20 that does not use the air electrode 21 for the positive electrode, and the charged metal electrode cartridge 10 is inserted again into the electrolytic solution tank 20 that uses the air electrode 21 for the positive electrode. As a result, the metal-air battery 1 can be discharged.

[Appendix]
The first aspect of the present invention is that the electrolytic solution tank 20, the air electrode 21 that forms a part of the side wall of the electrolytic solution tank 20, and the opening 24 of the electrolytic solution tank 20 enter the electrolytic solution tank 20. The inserted metal electrode cartridge 10, the first uneven portion 23 provided on the inner wall of the opening 24, the lower end portion of the metal electrode cartridge 10, and the electrolyte bath 20, The metal-air battery 1 includes a first sealing member 31 having a second uneven portion 32 that can be fitted to the uneven portion 23.

In the first aspect, the second sealing member 13 provided at the upper end of the metal electrode cartridge 10 and the outer wall of the second sealing member 13 are provided, and the first uneven portion 23 is provided. And a third concavo-convex portion 14 that is fitted to the second concavo-convex portion 14.

In the first aspect, the lower end portion of the metal electrode cartridge 10 has a fourth uneven portion 16, and the first sealing member 31 can be inserted and removed from the lower end portion of the metal electrode cartridge 10. The groove 33 may have a fifth uneven portion 34 that can be fitted to the fourth uneven portion 16 on the inner wall of the groove 33.

In the first aspect, the first concavo-convex portion 23 has a first tapered portion 23a having a large inner diameter toward the bottom surface side of the electrolytic solution tank 20, and the first sealing member 31 includes: You may have the 2nd taper part 31a which has an inclined surface which has an outer diameter large toward the bottom face side of the said electrolyte tank 20, and fits the inclined surface of the said 1st taper part 23a.

In the first aspect, a cutout portion 31 b extending vertically may be provided on the side wall of the first sealing member 31.

In the first aspect, the first uneven portion 23 includes a first convex portion 25 and a second convex portion 26 provided below the first convex portion 25, and The protrusion amount of the second protrusion 26 may be smaller than the protrusion amount of the first protrusion 25.

In the first aspect, the second uneven portion 32 includes a third convex portion 35 and a fourth convex portion 36 provided above the third convex portion 35, and The protrusion amount of the fourth protrusion 36 may be smaller than the protrusion amount of the third protrusion 35.

In the first aspect, the first contact area where the first convex portion 25 and the fourth convex portion 36 are in contact is such that the second convex portion 26 and the third convex portion 35 are in contact with each other. The contact area may be smaller than the second contact area.

The second aspect of the present invention includes an air electrode 21 that forms a part of the wall portion of the electrolytic solution tank 20, a first uneven portion 25 provided on the inner wall of the opening 24 of the electrolytic solution tank 20, Electrolyte tank provided with the 1st sealing member 31 in which the said opening part 24 of the said electrolyte tank was sealed, and the 2nd uneven part 32 fitted to the said 1st uneven part 23 was provided 20.

In the second aspect, a groove 33 may be provided on the upper surface of the first sealing member 31.

A third aspect of the present invention is a method of using the metal-air battery 1, wherein the metal-air battery 1 includes a metal electrode cartridge 10, an electrolyte bath 20 that contains an electrolyte 50, and the electrolyte bath 20. An air electrode 21 that forms a part of the wall portion of the first electrolyte member 20 and a first sealing member 31 that seals the opening portion 24 of the electrolytic solution tank 20, and the metal electrode cartridge 10 is inserted into the opening portion 24 from the opening portion 24. A step of inserting the first sealing member 31 and the metal electrode cartridge 10 into the electrolytic solution tank 20 and immersing the metal electrode cartridge 10 in the electrolytic solution 50; and The first sealing member 31 is pulled out from the opening 24, the first sealing member 31 is pulled up from the electrolytic solution 50 together with the metal electrode cartridge 10, and the opening 24 is sealed with the first sealing member 31. A method using a metal-air battery 1 including and.

1: Metal-air battery 10: Metal electrode cartridge 11: Metal electrode 11a: Negative electrode current collector 13: Second sealing member 13b: Removal part 14: Third uneven part 15: Ion adsorbent 16: Fourth uneven part Part 17: Fourth sealing member 20: Electrolyte tank 20a: Second guide part 21: Air electrode 21a: Positive electrode current collector 22: Air hole 23: First uneven part 23a: First taper part 23b : Chamfer 23e: Gasket 24: Opening 25: 1st convex part 26: 2nd convex part 27: Contact | adherence member 31: 1st sealing member 31a: 2nd taper part 31b: Notch 31d: 1st Guide part 32: second uneven part 33: groove 34: fifth uneven part 35: third convex part 36: fourth convex part 37: third sealing member 50: electrolyte 111: zinc electrode 112: Air electrode 113: Air flow path 115: Electrolytic solution 121: Zinc-air battery

Claims (11)

An electrolyte bath;
An air electrode that forms part of the side wall of the electrolyte bath;
A metal electrode cartridge inserted into the electrolyte bath from the opening of the electrolyte bath,
A first uneven portion provided on an inner wall of the opening;
A first sealing member provided in a lower end portion of the metal electrode cartridge and in the electrolytic solution tank and having a second concavo-convex portion that can be fitted to the first concavo-convex portion; Metal air battery to do. A second sealing member provided at the upper end of the metal electrode cartridge;
The metal-air battery according to claim 1, further comprising a third uneven portion provided on an outer wall of the second sealing member and fitted to the first uneven portion. The lower end portion of the metal electrode cartridge has a fourth uneven portion,
The first sealing member has a groove in which a lower end portion of the metal electrode cartridge can be inserted and removed,
3. The metal-air battery according to claim 1, wherein the inner wall of the groove has a fifth uneven portion that can be fitted to the fourth uneven portion. 4. The first concavo-convex portion has a first tapered portion having a large inner diameter toward the bottom surface side of the electrolytic solution tank,
The first sealing member has a second tapered portion having an inclined surface that has a large outer diameter toward the bottom surface side of the electrolytic solution tank and that fits the inclined surface of the first tapered portion. The metal-air battery according to any one of claims 1 to 3, characterized in that The metal-air battery according to any one of claims 1 to 4, wherein a cutout portion extending vertically is provided on a side wall of the first sealing member. The first uneven portion includes a first convex portion and a second convex portion provided below the first convex portion,
The metal-air battery according to any one of claims 1 to 5, wherein a protruding amount of the second convex portion is smaller than a protruding amount of the first convex portion. The second concavo-convex portion includes a third convex portion and a fourth convex portion provided above the third convex portion,
7. The metal-air battery according to claim 1, wherein a protruding amount of the fourth convex portion is smaller than a protruding amount of the third convex portion. The first contact area where the first convex portion and the fourth convex portion are in contact with each other is as follows:
The metal-air battery according to claim 7, wherein the metal-air battery is smaller than a second contact area where the second protrusion and the third protrusion are in contact with each other. An air electrode that forms part of the wall of the electrolyte bath;
A first concavo-convex portion provided on the inner wall of the opening of the electrolyte bath;
An electrolyte solution comprising: a first sealing member that seals the opening of the electrolyte bath and is provided with a second concavo-convex portion that is fitted to the first concavo-convex portion. Tank. The electrolytic solution tank according to claim 9, wherein a groove is provided on an upper surface of the first sealing member. A method of using a metal-air battery,
The metal-air battery is
A metal electrode cartridge;
An electrolytic bath containing the electrolytic solution;
An air electrode that forms part of the wall of the electrolyte bath;
A first sealing member for sealing the opening of the electrolytic solution tank,
Pushing the metal electrode cartridge into the electrolyte bath from the opening, fitting the first sealing member and the metal electrode cartridge, and immersing the metal electrode cartridge in the electrolyte; and
Extracting the metal electrode cartridge from the opening, pulling the first sealing member together with the metal electrode cartridge from the electrolyte, and sealing the opening with the first sealing member. A method of using a metal-air battery.

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