JP6680544B2 - Metal electrode cartridge accommodation item, metal electrode cartridge storage method, and metal electrode cartridge transportation method - Google Patents

Description

The present invention relates to a metal electrode cartridge container, a method for storing a metal electrode cartridge, and a method for carrying a metal electrode cartridge. More specifically, the present invention relates to a metal electrode cartridge accommodation item in which a metal electrode cartridge used for attaching a metal electrode to a battery is stored, a storage method of the metal electrode cartridge, and a transportation method of the metal electrode cartridge.

A metal-air battery is an example of a battery in which a positive electrode (cathode) and a negative electrode (anode) are provided in an electrolytic solution (see, for example, Patent Documents 1 and 2). The metal-air battery is a battery in which the negative electrode is composed of a metal electrode and the positive electrode is composed of an air electrode. Since it has a high energy density, development and research for practical use are being promoted.

A zinc air battery is mentioned as an example of a metal air battery. FIG. 17 is a schematic sectional view for explaining a discharge reaction in a zinc-air battery. As shown in FIG. 17, the zinc-air battery 100 was provided between the alkaline electrolyte 120, the zinc electrode (negative electrode) 121 provided in the electrolyte 120, and the electrolyte 120 and the air flow path. And an air electrode (positive electrode) 122. According to the zinc-air battery 100, electric power is output (discharged) from the zinc electrode 121 and the air electrode 122 as the discharge reaction proceeds.

In the discharge reaction of the zinc-air battery 100, the metallic zinc forming the zinc electrode 121 reacts with the hydroxide ion in the electrolytic solution 120 to become tetrahydroxozincate ion, and emits an electron into the zinc electrode 121. Then, the tetrahydroxozinc acid ion is decomposed into zinc oxide or zinc hydroxide, which is deposited in the electrolytic solution 120. Further, at the air electrode 122, hydroxide ions are generated by the reaction of electrons, water, and oxygen, and the hydroxide ions move into the electrolytic solution 120. When such a discharge reaction proceeds, zinc metal that constitutes the zinc electrode 121 is consumed, and zinc oxide and zinc hydroxide are accumulated in the electrolytic solution 120. Therefore, in order to stably maintain the output of electric power (discharge) by the zinc-air battery 100, it is required to supply metallic zinc to the zinc electrode 121.

As illustrated in the zinc-air battery, in the metal-air battery, the metal electrode is oxidized and consumed with discharge. On the other hand, it has been proposed to make the negative electrode structure including the metal electrode into a cartridge (metal electrode cartridge) that can be attached to and detached from the battery housing. In such a metal-air battery, discharging is performed by attaching the metal electrode cartridge to a battery housing (discharger) provided with an air electrode. After discharging, the used metal electrode cartridge can be replaced with a new metal electrode cartridge to perform re-discharge. In addition, the used metal electrode cartridge is attached to a charging device and is charged (regenerated) by reducing the metal oxide forming the negative electrode (mechanical charging method). In the mechanical charging method, the used or charged metal electrode cartridge is stored and transported between the discharging device and the charging device.

Japanese Patent Publication No. 2005-509262 JP, 11-345633, A

However, the capacity of the negative electrode may decrease during storage and transportation of the charged metal electrode cartridge before attachment to the battery housing (discharge device). As a result, when the metal electrode cartridge is attached to the battery housing and discharged, it may not be possible to output (discharge) the power of the assumed capacity. Therefore, as a result of various studies by the present inventors, it was found that such a decrease in the capacity of the negative electrode occurs due to the following reasons. In addition, although the case where the metal electrode is a zinc electrode will be described below, the same applies to the case where the metal electrode is another type of metal electrode.

[Cause 1] Oxidation of Negative Electrode As shown in the following formula (A), metallic zinc forming the zinc electrode (negative electrode) is oxidized and becomes passive (zinc oxide). As a result, the capacity of the zinc electrode is reduced.
Zn + 1 / 2O ₂ → ZnO (A)

[Cause 2] Self-corrosion of negative electrode As shown in the following formulas (B-1) and (B-2), a zinc electrode (negative electrode) comes into contact with an electrolytic solution (for example, an aqueous electrolyte solution) leached from itself. , Self-corrosive. As a result, the capacity of the zinc electrode is reduced.
_{^{Zn + 2OH - + 2H 2 O}} → Zn (OH) 4 2- + H 2 (B-1)
Zn + 2H ₂ O → Zn (OH) ₂ + H ₂ (B-2)

As described above, when the metal electrode cartridge is stored and transported, there is a problem of suppressing a decrease in discharge capacity due to a decrease in capacity of the negative electrode, and there is a strong demand for its solution.

The above-mentioned Patent Document 1 describes that an additive is used to prevent corrosion of the negative electrode. However, in the invention described in Patent Document 1 described above, this additive is used for the purpose of preventing corrosion of the negative electrode that occurs due to contact with the electrolytic solution during charge / discharge of the metal electrode cartridge, and It didn't settle.

Patent Document 2 discloses a button type zinc-air battery. However, the invention described in Patent Document 2 is not related to the metal electrode cartridge and does not solve the above problems.

The present invention has been made in view of the above circumstances, and provides a metal electrode cartridge container, a method of storing a metal electrode cartridge, and a method of transporting a metal electrode cartridge, which can suppress a decrease in discharge capacity. The purpose is.

The inventors of the present invention have made various studies on a metal electrode cartridge containing material capable of suppressing a decrease in discharge capacity, and have the following configuration in consideration of the above [Cause 1] and [Cause 2]. Found.
(1) At least a part of the metal electrode cartridge is covered with an oxygen permeation suppression member.
(2) A space for accumulating the electrolytic solution is provided in at least a part of a region between the surface of the metal electrode cartridge other than the accommodation port side of the oxygen permeation suppression member and the oxygen permeation suppression member.
Therefore, according to the above configuration (1), it has been found that the invasion of oxygen into the metal electrode cartridge is suppressed, so that the oxidation of the negative electrode (the above [Cause 1]) is suppressed. Further, according to the configuration of (2) above, it has been found that the contact between the electrolyte leached from the negative electrode and the negative electrode is suppressed, so that the self-corrosion of the negative electrode (the above [Cause 2]) is suppressed. . As described above, the present invention has been accomplished, and has arrived at the present invention, realizing that the above problems can be solved satisfactorily.

That is, one aspect of the present invention includes a metal electrode cartridge and an oxygen permeation suppression member that covers at least a part of the metal electrode cartridge, wherein the metal electrode cartridge includes a metal electrode containing an electrode active material, and the metal electrode. And a current collector electrically connected to the oxygen permeation suppression member, the metal electrode cartridge has a storage port that can be taken in and out, a surface other than the storage port side of the metal electrode cartridge, It may be a metal electrode cartridge accommodation item in which a space for accumulating an electrolytic solution is provided in at least a part of a region between the oxygen permeation suppression member.

Another aspect of the present invention may be a method for storing a metal electrode cartridge, which stores the metal electrode cartridge after charging, which is taken out from a charging device, by using the metal electrode cartridge container.

Yet another aspect of the present invention is a method for carrying a metal electrode cartridge, which carries the charged metal electrode cartridge taken out of a charging device to a battery housing to which the metal electrode cartridge is attached, by the metal electrode cartridge contents. It may be.

ADVANTAGE OF THE INVENTION According to this invention, the metal electrode cartridge accommodation thing which can suppress a fall of discharge capacity, the storage method of a metal electrode cartridge, and the transportation method of a metal electrode cartridge can be provided.

FIG. 3 is a schematic cross-sectional view showing a metal electrode cartridge container according to the first embodiment. It is a schematic diagram which shows the flow from charge to discharge, (a) shows a mode that a metal electrode cartridge is taken out from a charging device, (b) shows a mode that a metal electrode cartridge after charging is stored and transported, (c) ) Shows how the metal electrode cartridge after charging is attached to the battery housing. FIG. 7 is a schematic cross-sectional view showing a metal electrode cartridge container according to the second embodiment. FIG. 9 is a schematic cross-sectional view showing a metal electrode cartridge container according to the third embodiment. FIG. 13 is a schematic cross-sectional view showing a metal electrode cartridge accommodation item of Modification 1 of Embodiment 3. FIG. 11 is a schematic cross-sectional view showing a metal electrode cartridge container according to a modified example 2 of the third embodiment. FIG. 13 is a schematic cross-sectional view showing a metal electrode cartridge container according to Modification 3 of Embodiment 3. FIG. 13 is a schematic cross-sectional view showing a metal electrode cartridge accommodation item of Modification 4 of Embodiment 3. It is a cross-sectional schematic diagram which shows the metal electrode cartridge accommodation object of Embodiment 4. FIG. 13 is a schematic cross-sectional view showing a metal electrode cartridge accommodation item of Modification 1 of Embodiment 4. It is a cross-sectional schematic diagram which shows the metal electrode cartridge accommodation object of Embodiment 5. It is a cross-sectional schematic diagram which shows the metal electrode cartridge accommodation object of Embodiment 6. It is a cross-sectional schematic diagram which shows the metal electrode cartridge accommodation object of Embodiment 7. It is a cross-sectional schematic diagram which shows the metal electrode cartridge accommodation object of the modified example 1 of Embodiment 7. It is a cross-sectional schematic diagram which shows the metal electrode cartridge accommodation object of Embodiment 8. It is a cross-sectional schematic diagram which shows the metal electrode cartridge accommodation object of Embodiment 9. It is a cross-sectional schematic diagram for demonstrating the discharge reaction in a zinc air battery.

Hereinafter, the present invention will be described in more detail with reference to embodiments, but the present invention is not limited to these embodiments. Note that, in the following description, the same parts or parts having the same function will be denoted by the same reference numerals in different drawings except that alphabets are attached, and repeated description thereof will be appropriately omitted. Further, 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]
The metal electrode cartridge container according to the first embodiment will be described with reference to FIG. FIG. 1 is a schematic cross-sectional view showing a metal electrode cartridge container according to the first embodiment.

The metal electrode cartridge container 1a includes a metal electrode cartridge 2 and an oxygen permeation suppression member 3a.

The metal electrode cartridge 2 has a metal electrode 4 and a current collector 5 (hereinafter, both are collectively referred to as a negative electrode).

The metal electrode 4 covers a part of the current collector 5. The current collector 5 is used as a current collecting structure for extracting electric power from the metal electrode 4, and is electrically connected to the metal electrode 4. Although the bottom of the current collector 5 is covered with the metal electrode 4 in FIG. 1, it does not have to be covered with the metal electrode 4. For example, if the metal electrode 4 is placed under pressure on the side surface of the current collector 5, a structure in which the bottom of the current collector 5 is not covered with the metal electrode 4 can be manufactured.

The metal electrode cartridge 2 may further include an ion selection member 6, a porous member 7a, and a negative electrode housing 8.

The negative electrode housing 8 accommodates the negative electrode, and covers the metal electrode 4 via the ion selection member 6 and the porous member 7a. The negative electrode housing 8 is provided with a plurality of openings 9 at positions overlapping the ion selection member 6 and the porous member 7a. Further, a part of the surface of the negative electrode housing 8 is provided with a power take-out portion 10 for taking out electric power from the metal electrode 4 to the outside of the metal electrode cartridge 2 during discharging. The power take-out unit 10 is electrically connected to the current collector 5.

The oxygen permeation suppression member 3a houses the metal electrode cartridge 2. The oxygen permeation suppression member 3a may cover at least a part of the metal electrode cartridge 2. The oxygen permeation suppression member 3a is provided with a storage port 11 (closed state in FIG. 1) through which the metal electrode cartridge 2 can be inserted and removed. Further, the oxygen permeation suppression member 3a has a protrusion 12. The protrusion 12 is in direct contact with the metal electrode cartridge 2.

A space 13 is provided between the surface of the metal electrode cartridge 2 opposite to the accommodation port 11 (the surface of the metal electrode cartridge 2 opposite to the power take-out portion 10) and the oxygen permeation suppression member 3a. There is. The space 13 is provided in at least a part of a region between the surface of the metal electrode cartridge 2 other than the accommodation port 11 side (the surface of the metal electrode cartridge 2 other than the power take-out portion 10 side) and the oxygen permeation suppression member 3a. If you have. In the first embodiment, the space 13 is formed by the protrusion 12 directly contacting the metal electrode cartridge 2.

Next, each constituent member of the metal electrode cartridge accommodation item 1a will be described below.

The metal electrode 4 contains an electrode active material and is a component of the negative electrode. The electrode active material is composed of at least one of a plurality of metal particles and a plurality of metal oxide particles. When the electrode active material contains a plurality of metal oxide particles, the metal electrode cartridge 2 can be put in a high energy state by attaching the metal electrode cartridge 2 to a charging device and charging. Inside the electrode active material, there are voids (pores) in which the above-mentioned particles (including the additives described below) do not come into contact with each other. The electrode active material may include the following materials.
-Binder for binding the above-mentioned particles to each other-Additive for suppressing corrosion and shape change of the electrode active material-Conductive agent for maintaining and improving electric conductivity of the electrode active material-Electrode Ion conductor for ensuring the ionic conductivity of the active material (for example, ion exchange resin, layered double hydroxide, etc.)

Examples of the electrode active material contained in the metal electrode 4 include metals such as zinc, lithium, sodium, calcium, aluminum, magnesium, iron, copper, cobalt, cadmium, and palladium; and two or more of these metals. Alloys; mixtures of these metals and / or alloys; oxides of these metals. In particular, when the metal electrode 4 constitutes the negative electrode of a metal-air battery, it can be operated at room temperature by using zinc, lithium, aluminum, or iron as the electrode active material. Moreover, zinc, iron, aluminum, and copper are excellent in handleability (safety). From the above viewpoints, as the metal electrode 4, a zinc electrode containing zinc as a main component is particularly preferably used. The metal electrode 4 may be formed by depositing a metal species on the current collector 5.

The shape of the metal electrode 4 is not particularly limited, and examples thereof include a flat plate shape and a rod shape. Among them, a flat plate is preferably used.

The thickness of the metal electrode 4 is preferably 0.1 mm or more from the viewpoint of increasing the battery capacity, and is preferably 50 mm or less from the viewpoint of improving handleability and reaction resistance. When the thickness of the metal electrode 4 is larger than 50 mm, the resistance increases due to the long distance between the positive electrode and the current collector 5, and the charge / discharge efficiency may decrease.

The current collector 5 is a component of the negative electrode like the metal electrode 4. Examples of the material of the current collector 5 include nickel, copper, iron, aluminum, stainless steel, platinum, carbon and the like. These materials are preferably plated with nickel, tin, indium, bismuth or the like in order to improve the corrosion resistance.

The shape of the current collector 5 is not particularly limited, and examples thereof include a foil shape, a mesh shape, and a flat plate shape. As the current collector 5, for example, a foil obtained by press punching or a foil or a flat plate subjected to etching may be used.

The ion selection member 6 is a member that allows only hydroxide ions and water to pass therethrough and does not allow other anions (for example, tetrahydroxozincate ions and the like) to pass through.

Examples of the material of the ion selection member 6 include zeolite and layered double hydroxide.

The shape of the ion selection member 6 is not particularly limited, but it is preferably a film shape or a bag shape.

The thickness of the ion selection member 6 is preferably 0.03 mm or more and 1 mm or less. When the thickness of the ion selection member 6 is less than 0.03 mm, there is a concern that the ion selection member 6 may be easily damaged by impact (vibration), dendrite generated during charging, or the like. If the thickness of the ion selection member 6 is larger than 1 mm, the metal electrode cartridge 2 becomes too thick, which is not preferable.

The porous member 7a has hydrophilicity and diffuses the electrolytic solution throughout the negative electrode. For example, when the porous member 7a is immersed in the alkaline aqueous solution for up to 12 hours, if the alkaline aqueous solution penetrates into the porous member 7a, it is considered to be hydrophilic. The porous member 7a can realize uniform charge / discharge.

Examples of the material of the porous member 7a include polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride and the like, and those obtained by subjecting these materials to hydrophilic treatment are preferable. As the porous member 7a, for example, a non-woven fabric or a woven fabric made of these materials (fibrous) can be used. Further, the porous member 7a is preferably made of a material having electrolytic solution resistance (particularly alkali resistance).

The thickness of the porous member 7a is preferably 0.1 mm or more and 1 mm or less. When the thickness of the porous member 7a is less than 0.1 mm, there is a concern that the porous member 7a is easily damaged by impact (vibration). Further, the electrolyte solution that passes through the plurality of openings 9 of the negative electrode housing 8 during charging / discharging cannot be sufficiently diffused in the plane direction of the porous member 7a, and as a result, the area usable as the negative electrode (electrode reaction range). ) Is small. If the thickness of the porous member 7a is larger than 1 mm, the metal electrode cartridge 2 becomes too thick, which is not preferable.

The negative electrode housing 8 is provided with a plurality of openings 9 at positions overlapping the ion selection member 6 and the porous member 7a. With such a configuration, it is possible to ensure ionic conduction between the negative electrode and the outside thereof (for example, the electrolytic solution). In the present specification, the opening indicates a through hole or a communication hole provided in the thickness direction (left and right direction in FIG. 1). The through-hole is a space (through) that is open from one surface to the opposite surface. The communication port is a space in which a continuous space is formed in one direction (thickness direction). The negative electrode housing 8 may be, for example, one in which two frames provided with a plurality of openings 9 are fixed by a clip or the like and integrated.

Examples of the material of the negative electrode housing 8 include resin, metal, ceramics and the like. From the viewpoint of safety, the negative electrode housing 8 is preferably made of an insulating material. Examples of the resin include polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyphenylene sulfide (PPS), polyvinyl acetate, ABS, vinylidene chloride, polyacetal, polyethylene (PE), polypropylene, polyisobutylene, fluororesin, and epoxy. Resin etc. are mentioned. Examples of the metal include nickel and stainless steel. Examples of ceramics include aluminum oxide (alumina). A porous material may be used as the material of the negative electrode housing 8. Examples of the porous material include porous ceramics and glass fibers. Here, when the negative electrode housing 8 is made of a conductive material (for example, a metal), if the negative electrode and the negative electrode housing 8 are electrically connected, the metal-containing ions are charged on the surface of the negative electrode housing 8 during charging. The metal collects at the. As a result, there is a concern that a short circuit may occur between the negative electrode and the positive electrode. Therefore, when the negative electrode housing 8 is made of a conductive material, the negative electrode and the negative electrode housing 8 are preferably electrically insulated. Further, the negative electrode housing 8 is preferably made of a material having electrolytic solution resistance (particularly alkali resistance).

The thickness of the negative electrode housing 8 is preferably 0.5 mm or more and 3 mm or less. If the thickness of the negative electrode housing 8 is less than 0.5 mm, the durability of the negative electrode housing 8 against impact (vibration) may be reduced. If the thickness of the negative electrode housing 8 is larger than 3 mm, the metal electrode cartridge 2 becomes too thick, and as a result, the weight energy density and the volume energy density may decrease.

The aperture ratio of the negative electrode housing 8 is preferably 30% or more and 70% or less. When the aperture ratio of the negative electrode housing 8 is less than 30%, there is a concern that the characteristics of the negative electrode during charge / discharge may deteriorate. If the aperture ratio of the negative electrode housing 8 is larger than 70%, the strength of the negative electrode housing 8 may be reduced. In the present specification, the opening ratio of the negative electrode housing is the total area of the plurality of openings 9 (when viewed from the thickness direction) with respect to the area (cross-sectional area when viewed from the thickness direction) of the metal electrode 4 which is the electrode reaction range. The total area) is shown. Although the number of the openings 9 is plural in FIG. 1, it may be one. When the material of the negative electrode housing 8 is a porous material, the opening ratio may be replaced with the porosity.

The shape of the opening 9 is not particularly limited, and examples thereof include a circular shape, an elliptical shape, and a polygonal shape. When the opening 9 has a circular shape or an elliptical shape, bubbles (gas) are less likely to stay in the opening 9. Such air bubbles are, for example, caused by air (mainly oxygen) invading from the outside (charging electrode etc.) at the time of charging, air caused by invading when the metal electrode cartridge 2 is inserted into the battery housing, etc. Is. When the opening 9 has a polygonal shape (for example, a square shape, a rectangular shape, a hexagonal shape, a rhombic shape, etc.), the aperture ratio of the negative electrode housing 8 can be increased.

The diameter of the opening 9 is preferably 3 mm or more and 10 mm or less. In the present specification, the diameter of the opening indicates the maximum length of the opening in all directions when viewed from the thickness direction. For example, when the opening 9 has a circular shape, the diameter of the opening 9 indicates the diameter. When the opening 9 has an elliptical shape, the diameter of the opening 9 indicates the length of the major axis. When the opening 9 has a polygonal shape, the diameter of the opening 9 indicates the length of the diagonal line.

After the metal electrode cartridge 2 is immersed in the electrolytic solution during charging / discharging, the electrolytic solution may be attached to the metal electrode cartridge 2 (for example, the negative electrode).

The electrolytic solution is a solution of an electrolyte in a solvent and is a liquid having ion conductivity. The type of the electrolytic solution is not particularly limited as long as it is a commonly used electrolytic solution, and may be selected according to the type of the metal (electrode active material) forming the metal electrode 4, and the electrolytic solution using an aqueous solvent ( It may be an aqueous electrolyte solution) or an electrolytic solution using an organic solvent (organic electrolytic solution). Examples of the combination of the metal electrode 4 and the electrolytic solution include the following. When the metal electrode 4 mainly contains zinc, aluminum, or iron, an alkaline electrolytic solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used as the electrolytic solution. When the metal electrode 4 mainly contains magnesium, a neutral electrolytic solution such as a sodium chloride aqueous solution can be used as the electrolytic solution. When the metal electrode 4 mainly contains lithium, sodium, and calcium, an acidic electrolytic solution can be used as the electrolytic solution. When the metal electrode 4 mainly contains lithium, it is preferable to use an organic electrolytic solution as the electrolytic solution. Examples of the organic electrolytic solution 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. A known lithium salt dissolved in an aprotic organic solvent having no chain structure (ethylene carbonate, tetrahydrofuran, etc.) can be used.

The electrolytic solution may contain a gelling agent and may be gelled. The gelling agent is not particularly limited as long as it is a gelling agent generally used for gelling an electrolytic solution, and examples thereof include polyacrylates such as potassium polyacrylate and sodium polyacrylate; hydrophilic groups Examples thereof include 2-acrylamido-2 methylpropane sulfonic acid having a sulfo group. Further, the electrolytic solution may contain other additives.

The oxygen permeation suppression member 3 a accommodates the metal electrode cartridge 2 and suppresses the invasion of oxygen into the metal electrode cartridge 2. According to the oxygen permeation suppression member 3a, it is possible to suppress the oxidation (passivation) of the negative electrode.

As a material for the oxygen permeation suppression member 3a, a material that has low solvent permeability in addition to oxygen permeability and is thin, lightweight, and high strength is suitable. Specifically, as the oxygen permeation suppression member 3a, a laminated film in which a metal foil is arranged between each of a plurality of plastic films is preferably used. For example, when the number of layers is three, the laminated film has a configuration in which one metal foil is arranged between two plastic films.

The laminated film can be formed by stacking the materials of the respective layers (plastic film and metal foil) and heat-sealing them.

As the plastic film, it is possible to use a film which is composed of a material such as polyamide, polyester, or polyolefin and can be heat-sealed to the metal foil. Of the plurality of plastic films, the plastic film disposed closest to the metal electrode cartridge 2 side is preferably made of a material having electrolytic solution resistance (particularly alkali resistance) such as polyolefin. The thickness of the plastic film is preferably 10 μm or more and 100 μm or less.

As the metal foil, for example, foil of aluminum, copper, iron, stainless steel or the like can be used. The thickness of the metal foil is preferably 1 μm or more and 100 μm or less.

As the oxygen permeation suppression member 3a, a laminated packaging material is preferably used in addition to the above-mentioned laminated film. The laminated packaging material is a laminate of a plurality of films having different properties. Typical examples of the bonding method include extrusion lamination (extrusion lamination) and dry lamination. Extrusion lamination is a method in which molten PE is poured into each film in a slit shape, wound after pressure bonding and cooling. Dry lamination is a method of bonding a plurality of films to each other via an adhesive.

Examples of the laminate packaging material include OPP (oriented polypropylene: oriented polypropylene) / EVOH (ethylene-vinyl alcohol copolymer: ethylene-vinyl alcohol copolymer) / PE (polyethylene: polyethylene), OPP / VMPET (vacuum polyethylene). Vapor-deposited polyethylene terephthalate) / CPP (cast polypropylene: unstretched polypropylene), KOP (K coated oriented polypropylene: K-coated polypropylene) / PE, KOP / EVA (ethylene-vinyl acetate copolymer). (Ren-vinyl acetate copolymer), KOP / LLDPE (linear low density polyethylene: linear low density polyethylene), KOP / CPP, PET (polyethylene terephthalate) / PE, PET / EVA, PET / LLDPE, PET / CPP, KPET (K coated polyethylene terephthalate) / PE, KPET / EVA, KPET / LLDPE, KPET / CPP, ON (oriented nylon: stretched nylon) / PE, ON / EVA, ON / LLDPE, ON / CPP, KON (K coated oriented nylon) / P E, KON / CPP, PET / VMPET / PE, PET / VMPET / EVA, PET / VMPET / LLDPE, etc. are mentioned. In addition, the above "/" means that the layers described on the left and right sides thereof are laminated. For example, “Layer A / Layer B” indicates a state in which Layer A and Layer B are stacked, and “Layer A / Layer B / Layer C” is formed by stacking Layer A, Layer B, and Layer C in this order. Indicates that

The shape of the oxygen permeation suppression member 3a is not particularly limited, but it is preferably a bag shape from the viewpoint of efficiently storing and transporting the metal electrode cartridge 2. For example, the bag-like oxygen permeation suppression member 3a as shown in FIG. 1 can be formed by heat-sealing the above-mentioned laminated films. Examples of a method of sealing the metal electrode cartridge 2 after putting it in the bag-shaped oxygen permeation suppression member 3a include a method using heat fusion, a chuck, a clip, or the like. Among them, the method using heat fusion is preferably used.

The oxygen permeation suppression member 3a may further have an oxygen absorbent layer on the surface on the metal electrode cartridge 2 side. Thereby, the invasion of oxygen into the metal electrode cartridge 2 is sufficiently suppressed.

The protrusion 12 forms a space 13 by directly contacting the metal electrode cartridge 2. In the first embodiment, the protrusion 12 corresponds to the heat-sealing portion between the laminated films described above. The shape of the protrusion 12 is not particularly limited, and may be, for example, a quadrangle or a triangle when viewed in cross section. Although the number of the protrusions 12 is one in FIG. 1, it may be more than one.

The space 13 is a space for storing the electrolyte leached from the negative electrode when the metal electrode cartridge 2 is stored and transported. By storing the electrolytic solution in the space 13, contact between the electrolytic solution and the negative electrode can be suppressed. As a result, self-corrosion of the negative electrode can be suppressed.

The greater the amount of the electrolytic solution that contacts the negative electrode, the greater the degree of capacity decrease due to self-corrosion of the negative electrode. Therefore, it is desirable that the electrolytic solution does not exist at all inside the oxygen permeation suppression member 3a. However, if the electrolytic solution does not exist at all, it takes time for the electrolytic solution to soak into the metal electrode cartridge 2 after the metal electrode cartridge 2 is attached to the battery housing. As a result, the startability of the battery (for example, a metal-air battery) at the time of discharging is deteriorated. Considering the above, it is considered desirable that a minimum amount of electrolytic solution be present in the pores of the electrode active material. Therefore, after charging, a work of removing the excess electrolytic solution from the negative electrode may be performed, but this work takes time and is inefficient. On the other hand, according to the first embodiment, after the metal electrode cartridge 2 is put into the oxygen permeation suppression member 3a, the metal electrode cartridge 2 is placed vertically as shown in FIG. 1 (the accommodation port 11 is arranged vertically above). When stored and transported in a state), the excess electrolytic solution can be gradually moved to the space 13 (downward in the vertical direction) by the action of gravity. That is, during storage and transportation of the metal electrode cartridge 2, the work of removing the excess electrolytic solution from the negative electrode can be naturally performed. In this case, it is considered that a minimum amount of the electrolytic solution remains in the pores of the electrode active material due to the capillary phenomenon.

Next, a method for storing the metal electrode cartridge 2 and a method for carrying the metal electrode cartridge 2 will be described with reference to FIG. FIG. 2 is a schematic diagram showing a flow from charging to discharging, (a) shows a state of taking out the metal electrode cartridge from the charging device, and (b) shows a state of storing and carrying the metal electrode cartridge after charging. 9C shows a state in which the charged metal electrode cartridge is attached to the battery housing.

(A) Charging-Removal of Metal Electrode Cartridge First, the metal electrode cartridge 2 is attached to the charging device 14 to perform charging. After that, as shown in FIG. 2A, the charged metal electrode cartridge 2 is taken out from the charging device 14. The charging device 14 is provided with a charging electrode facing the negative electrode.

(B) Storage and Transport of Metal Electrode Cartridge The metal electrode cartridge 2 after charging is put in the oxygen permeation suppression member 3a. As a result, as shown in FIG. 2B, the metal electrode cartridge housing 1a is formed. The charged metal electrode cartridge 2 is stored in the metal electrode cartridge housing 1a. Then, the charged metal electrode cartridge 2 is carried to the battery housing 15 described later by the metal electrode cartridge housing 1a.

(C) Attachment of metal electrode cartridge to metal electrode cartridge 2 after discharge charging is taken out from the oxygen permeation suppression member 3a. After that, as shown in FIG. 2C, the charged metal electrode cartridge 2 is attached to the battery housing 15 and discharged. The battery housing 15 is provided with a positive electrode facing the negative electrode. As the material for the positive electrode, a material having a higher electronegativity than the metal forming the negative electrode can be used. Examples of the material of the positive electrode include oxygen, nitrogen, chlorine and the like in the case of gas, carbon tetrachloride, hydrogen peroxide and the like in the case of liquid, and metal sulfide and metal in the case of solid. Examples thereof include chloride. Depending on the type of metal forming the negative electrode, the positive electrode may be the metal electrode. When the positive electrode is an air electrode, a metal-air battery is constructed. In this case, the metal electrode 4 and the current collector 5 form the negative electrode of the metal-air battery. The air electrode is an electrode that produces hydroxide ions from electrons, water, and oxygen.

According to the first embodiment, the following effects can be achieved.
(1) Since the metal electrode cartridge 2 is housed in the oxygen permeation suppression member 3a, the invasion of oxygen into the metal electrode cartridge 2 is suppressed, and as a result, the oxidation (passivation) of the negative electrode is suppressed.
(2) Since the space 13 is provided, contact between the electrolyte leached from the negative electrode and the negative electrode is suppressed, and as a result, self-corrosion of the negative electrode is suppressed.
As described above, it is possible to suppress the decrease in the capacity of the negative electrode during the storage and transportation of the charged metal electrode cartridge 2 before attaching the metal electrode cartridge 2 to the battery housing. As a result, reduction in discharge capacity can be suppressed.

[Embodiment 2]
FIG. 3 is a schematic cross-sectional view showing a metal electrode cartridge container according to the second embodiment. The second embodiment is the same as the first embodiment except that the porous member is arranged between the metal electrode cartridge and the oxygen permeation suppression member, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1b, the porous member 7b is arranged between the metal electrode cartridge 2 and the oxygen permeation suppression member 3a. The porous member 7b is arranged on the surface of the metal electrode cartridge 2 and is in direct contact with the metal electrode cartridge 2. The porous member 7b should just be arrange | positioned at least one part between the metal electrode cartridge 2 and the oxygen permeation suppression member 3a. For example, the porous member 7b may be disposed in the space 13 and directly contact the metal electrode cartridge 2, and the space 13 may include the void of the porous member 7b. The porous member 7b is the same as the porous member 7a described above.

In the first embodiment, the electrolytic solution leached from the negative electrode stays in the gap between the metal electrode cartridge 2 and the oxygen permeation suppression member 3a, and it takes time for the electrolytic solution to move to the space 13. I have a concern. On the other hand, according to the second embodiment, the electrolytic solution leached from the negative electrode permeates into the inside of the porous member 7b and is easily moved to the space 13 by the action of gravity.

According to the second embodiment, the following effects can be achieved in addition to the effects of the first embodiment.
(1) The porous member 7b facilitates movement of the electrolytic solution leached from the negative electrode into the space 13.
(2) Since the porous member 7b holds the electrolyte leached from the negative electrode, self-corrosion of the negative electrode is sufficiently suppressed.
(3) Even if the metal electrode cartridge accommodation item 1b is placed horizontally (the accommodation port 11 is arranged in the horizontal direction: the state where the accommodation port 11 is rotated 90 ° from the state shown in FIG. 3), the porous member 7b remains Since the electrolytic solution leached from the negative electrode is retained, contact between the negative electrode and the electrolytic solution is suppressed.
(4) Since the porous member 7b holds the electrolytic solution leached from the negative electrode even when the metal electrode cartridge accommodation item 1b is placed horizontally, electrolysis of the surface of the metal electrode cartridge 2 on the accommodation port 11 side is performed. Liquid adhesion is prevented. As a result, when handling the metal electrode cartridge 2, contact with the electrolytic solution is prevented.
(5) Since the porous member 7b holds the electrolytic solution that has leached out from the negative electrode even when the metal electrode cartridge housing 1b is placed horizontally, the electrolytic solution is prevented from adhering to the power take-out portion 10. . As a result, the corrosion of the power take-out portion 10 due to the electrolytic solution is prevented.
(6) Since the porous member 7b holds the electrolytic solution leached from the negative electrode, the metal electrode cartridge 2 is kept in an appropriate wet state. As a result, the startability of the battery during discharging is improved.

[Third Embodiment]
FIG. 4 is a schematic cross-sectional view showing a metal electrode cartridge container according to the third embodiment. The third embodiment is the same as the second embodiment except that the electrode shape holding member that covers the oxygen permeation suppression member is arranged, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge accommodation item 1c, a part of the surface (hereinafter, also referred to as the first surface) except the surface of the oxygen permeation suppression member 3a on the accommodation port 11 side and the surface opposite to the accommodation port 11 is covered. The electrode shape holding member 16a is arranged at the position. The electrode shape holding member 16a should just be arrange | positioned in the position which covers at least one part of the oxygen permeation suppression member 3a. For example, two electrode shape holding members may be arranged to face each other at a position that covers a part of the first surface of the oxygen permeation suppression member 3a. In this case, the two electrode shape holding members may be fixed with a clip or a vise.

When the metal electrode cartridge is stored and transported by the conventional method, the metal electrode expands due to the gas generated due to the self-corrosion of the negative electrode, or the metal electrode peels off from the current collector due to the shock received during storage and transportation. Sometimes. As a result, the electron conduction path disappears inside the negative electrode, that is, a portion that cannot be used for discharging is generated in the metal electrode, and the discharge capacity decreases. On the other hand, according to the third embodiment, since the electrode shape holding member 16a presses the negative electrode, expansion and peeling of the metal electrode 4 are suppressed. As a result, the generation of a portion of the metal electrode 4 that cannot be used for discharging is suppressed, and the decrease in discharge capacity is sufficiently suppressed.

Examples of the material of the electrode shape holding member 16a include resin, metal, metal oxide and the like. From the viewpoint of pressing down the negative electrode more strongly, it is preferable to select a material having higher rigidity (for example, Young's modulus) as the electrode shape holding member 16a.

The Young's modulus of the electrode shape holding member 16a is preferably 2.0 GPa or more at a temperature of 25 ° C. The Young's modulus can be measured using, for example, a free-resonance type Young's modulus measuring device (product name: JE-RT) manufactured by Japan Technoplus Co., which adopts the free-resonance type natural vibration method.

The electrode shape holding member 16a preferably has a thickness of 1 mm or more. When the thickness of the electrode shape holding member 16a is 1 mm or more, the rigidity of the electrode shape holding member 16a is sufficiently increased, so that the negative electrode can be pressed more strongly.

According to the third embodiment, the following effects can be obtained in addition to the effects of the second embodiment.
(1) Since the electrode shape holding member 16a holds down the negative electrode, expansion and peeling of the metal electrode 4 are suppressed. As a result, the generation of a portion of the metal electrode 4 that cannot be used for discharging is suppressed, and the decrease in discharge capacity is sufficiently suppressed.
(2) Since the electrode shape holding member 16a holds down the negative electrode, the excess electrolytic solution is efficiently removed from the negative electrode, and the decrease in the capacity of the negative electrode is suppressed.
(3) Since the electrode shape holding member 16a holds down the negative electrode, it becomes difficult for the air inside the oxygen permeation suppression member 3a to reach the surface of the negative electrode. As a result, the oxidation of the negative electrode is sufficiently suppressed.
(4) Since the electrode shape holding member 16a presses the negative electrode, the metal electrode cartridge 2 is sufficiently kept in an appropriate wet state.
(5) The electrode shape holding member 16a prevents the oxygen permeation suppression member 3a from being damaged.
(6) The electrode shape holding member 16a prevents the metal electrode 4, the negative electrode housing 8 and the like from being damaged.
(7) Since the porous member 7b contracts by the pressure applied by the metal electrode cartridge 2 and the electrode shape holding member 16a, the electrolytic solution held by the porous member 7b is squeezed out, and the space 13 is efficiently evacuated. It is stored.
(8) Since the porous member 7b can contract, the electrode shape holding member 16a can be easily attached.

[Modification 1 of Embodiment 3]
FIG. 5 is a schematic cross-sectional view showing a metal electrode cartridge container according to the modified example 1 of the third embodiment. The first modification of the third embodiment is the same as the third embodiment except that the shape of the electrode shape holding member is different, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge accommodation item 1d, in addition to a part of the first surface of the oxygen permeation suppression member 3a, a position (hereinafter, also referred to as a second surface) opposite to the accommodation port 11 is covered. The electrode shape holding member 16b is arranged. That is, the electrode shape holding member 16b has a container shape.

According to the first modification of the third embodiment, the following effects can be obtained in addition to the effects of the third embodiment.
(1) Since the electrode shape holding member 16b covers the second surface in addition to a part of the first surface of the oxygen permeation suppression member 3a, the oxygen permeation suppression member 3a is sufficiently prevented from being damaged.
(2) Since the electrode shape holding member 16b covers not only a part of the first surface of the oxygen permeation suppression member 3a but also the second surface thereof, the metal electrode cartridge housing 1d is placed vertically (FIG. 5). The stability under the condition (1) is improved.

[Modification 2 of Embodiment 3]
FIG. 6 is a schematic cross-sectional view showing a metal electrode cartridge container of Modification 2 of Embodiment 3. The second modification of the third embodiment is the same as the first modification of the third embodiment except that the shape of the electrode shape holding member is different, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1e, the electrode shape holding member 16c is arranged at a position that covers a part of the surface of the oxygen permeation suppression member 3b other than the housing port 11 side. The surface of the electrode shape holding member 16c on the bottom side of the oxygen permeation suppression member 3b (on the side opposite to the accommodation port 11 of the oxygen permeation suppression member 3b) projects toward the oxygen permeation suppression member 3b. Along with this, the bottom portion of the oxygen permeation suppression member 3b projects toward the metal electrode cartridge 2. The space 13 is provided between the metal electrode cartridge 2 and the bottom of the oxygen permeation suppression member 3b. At least a part of the surface of the electrode shape holding member 16c on the bottom side of the oxygen permeation suppression member 3b may be projected toward the oxygen permeation suppression member 3b.

According to the second modification of the third embodiment, the same effect as that of the first modification of the third embodiment can be obtained.

[Modification 3 of Embodiment 3]
FIG. 7 is a schematic cross-sectional view showing a metal electrode cartridge container of Modification 3 of Embodiment 3. The third modification of the third embodiment is the same as the first modification of the third embodiment except that the shape of the electrode shape holding member is different. Therefore, the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing item 1f, the electrode shape holding member 16d is arranged at a position that covers a part of the surface of the oxygen permeation suppression member 3c other than the housing port 11 side. A part of the surface of the electrode shape holding member 16d on the bottom side of the oxygen permeation suppression member 3c (the side opposite to the accommodation port 11 of the oxygen permeation suppression member 3c) is inclined and is opposite to the oxygen permeation suppression member 3c. It is depressed toward the side. Along with this, a part of the bottom of the oxygen permeation suppression member 3c is inclined and is recessed toward the side opposite to the metal electrode cartridge 2. The space 13 is provided between the metal electrode cartridge 2 and the bottom of the oxygen permeation suppression member 3c. At least a part of the surface of the electrode shape holding member 16d on the bottom side of the oxygen permeation suppression member 3c may be recessed toward the side opposite to the oxygen permeation suppression member 3c.

According to the modified example 3 of the third embodiment, the same effect as that of the modified example 1 of the third embodiment can be obtained.

[Modification 4 of Embodiment 3]
FIG. 8 is a schematic cross-sectional view showing a metal electrode cartridge container according to a modified example 4 of the third embodiment. Modification 4 of Embodiment 3 is the same as Modification 1 of Embodiment 3 except that the shape of the electrode shape holding member is different, and therefore the description of overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1g, the electrode shape holding member 16e is arranged at a position that covers a part of the surface of the oxygen permeation suppression member 3d other than the housing port 11 side. A part of the surface of the electrode shape holding member 16e on the bottom side of the oxygen permeation suppression member 3d (on the side opposite to the accommodation port 11 of the oxygen permeation suppression member 3d) is recessed toward the side opposite to the oxygen permeation suppression member 3d. I'm out. Along with this, a part of the bottom of the oxygen permeation suppression member 3d is recessed toward the side opposite to the metal electrode cartridge 2. The space 13 is provided between the metal electrode cartridge 2 and the bottom of the oxygen permeation suppression member 3d.

According to Modification 4 of Embodiment 3, the same effect as that of Modification 1 of Embodiment 3 can be obtained.

[Embodiment 4]
FIG. 9 is a schematic sectional view showing a metal electrode cartridge container according to the fourth embodiment. The fourth embodiment is the same as the first modified example of the third embodiment except that the oxygen permeation suppression member and the porous member are bonded together, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1h, the oxygen permeation suppression member 3a and the porous member 7b are bonded together via the adhesive member 17. In FIG. 9, the adhesive member 17 is arranged between the oxygen permeation suppression member 3a and the porous member 7b, but may be arranged so as to cover the end of the porous member 7b.

As described above, the porous member 7b facilitates movement of the electrolytic solution leached from the negative electrode into the space 13. However, when the metal electrode cartridge 2 is taken out from the oxygen permeation suppression member 3a, there is a concern that the porous member 7b may be taken out in a state of being attached to the metal electrode cartridge 2. In this case, the work of removing the porous member 7b from the metal electrode cartridge 2 occurs, resulting in poor efficiency. On the other hand, according to the fourth embodiment, since the oxygen permeation suppression member 3a and the porous member 7b are bonded together via the adhesive member 17, when the metal electrode cartridge 2 is taken out from the oxygen permeation suppression member 3a. The porous member 7b is not taken out in the state where it is attached to the metal electrode cartridge 2. Further, since the position of the porous member 7b is fixed, the metal electrode cartridge 2 can be easily put in the oxygen permeation suppression member 3a.

Examples of the adhesive member 17 include an adhesive such as glue and a double-sided tape having an adhesive layer. The adhesive member 17 preferably contains an adhesive material or an adhesive material having electrolytic solution resistance (particularly alkali resistance).

According to the fourth embodiment, the following effects can be obtained in addition to the effects of the first modification of the third embodiment.
(1) Since the oxygen permeation suppression member 3a and the porous member 7b are bonded together via the adhesive member 17, the metal electrode cartridge 2 can be easily taken in and out of the oxygen permeation suppression member 3a, and the workability is improved.

[Modification 1 of Embodiment 4]
FIG. 10 is a schematic cross-sectional view showing a metal electrode cartridge accommodation item of the first modification of the fourth embodiment. The first modification of the fourth embodiment is the same as the fourth embodiment except that the shape of the porous member is different, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1j, the porous member 7c is arranged between the metal electrode cartridge 2 and the oxygen permeation suppression member 3a. The porous member 7c is arranged on the surface of the metal electrode cartridge 2 and is in direct contact with the metal electrode cartridge 2. The porous member 7c has a shape that follows the outer shape of the metal electrode cartridge 2. The porous member 7c has on its surface a plurality of convex portions that match the plurality of openings 9 of the negative electrode housing 8. The plurality of convex portions may be provided in advance on the surface of the porous member 7c, or the porous member 7c is pressed by the electrode shape holding member 16b via the oxygen permeation suppression member 3a, and the plurality of openings 9 are formed. It may be formed by entering.

As described above, the porous member 7c facilitates movement of the electrolytic solution leached from the negative electrode into the space 13. However, there is a concern that the electrolytic solution leached from the negative electrode may stay in the plurality of openings 9 of the negative electrode housing 8, and it may take time for the electrolytic solution to move to the space 13. On the other hand, according to the first modification of the fourth embodiment, since the contact area between the porous member 7c and the metal electrode cartridge 2 is large, the electrolyte leached from the negative electrode is efficiently transferred to the inside of the porous member 7c. It penetrates well and becomes easy to move into the space 13 by the action of gravity.

According to the first modification of the fourth embodiment, the following effects can be obtained in addition to the effects of the fourth embodiment.
(1) The electrolyte leached from the negative electrode efficiently moves to the space 13 by the porous member 7c.

[Fifth Embodiment]
FIG. 11 is a schematic sectional view showing a metal electrode cartridge container according to the fifth embodiment. The fifth embodiment is the same as the first embodiment except that the method of placing the metal electrode cartridge contents is different, and thus the description of the overlapping points will be appropriately omitted.

The metal electrode cartridge accommodation item 1k corresponds to a state in which the metal electrode cartridge accommodation item 1a according to the first embodiment is horizontally placed (a state rotated by 90 ° from the state shown in FIG. 1). The difference between the two is the position of the protrusion 12 and the position of the space 13.

The oxygen permeation suppression member 3e has a plurality of protrusions 12. The plurality of protrusions 12 are in direct contact with the metal electrode cartridge 2. In FIG. 11, the plurality of protrusions 12 are provided on both sides (the upper side and the lower side in FIG. 11) of the metal electrode cartridge 2, but they may be provided on only one side. In this case, the portion provided with the plurality of protrusions 12 may be arranged on the lower side (lower side in the vertical direction). Thereby, the electrolytic solution can be stored in the space 13 described later.

Of the region between the surface of the metal electrode cartridge 2 other than the accommodation port 11 side and the oxygen permeation suppression member 3e, other than between the surface of the metal electrode cartridge 2 opposite to the accommodation port 11 and the oxygen permeation suppression member 3e. A space 13 is provided in a part (lower part in the vertical direction) of the. In the fifth embodiment, the space 13 is formed by the plurality of protrusions 12 directly contacting the metal electrode cartridge 2.

The space 13 is a space for storing the electrolyte leached from the negative electrode when the metal electrode cartridge 2 is stored and transported. By storing the electrolytic solution in the space 13, contact between the electrolytic solution and the negative electrode can be suppressed. As a result, self-corrosion of the negative electrode can be suppressed. According to the fifth embodiment, when the metal electrode cartridge 2 is put into the oxygen permeation suppression member 3e and then stored and transported in a horizontal state as shown in FIG. It can be gradually moved (downward in the vertical direction).

According to the fifth embodiment, the following effects can be obtained in addition to the effects of the first embodiment.
(1) Since the metal electrode cartridge contents 1k can be horizontally placed and are easily stacked, the efficiency in storage and transportation is better than that in the vertically placed state (for example, Embodiment 1).

[Sixth Embodiment]
FIG. 12 is a schematic sectional view showing a metal electrode cartridge container according to the sixth embodiment. The sixth embodiment is the same as the fifth embodiment except that the porous member is arranged between the metal electrode cartridge and the oxygen permeation suppression member, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1m, the porous member 7b is arranged between the metal electrode cartridge 2 and the oxygen permeation suppression member 3e. The porous member 7b is arranged on the surface of the metal electrode cartridge 2 and is in direct contact with the metal electrode cartridge 2. Further, the space 13 includes a void of the porous member 7b (the void of the porous member 7b also serves as the space 13).

In the fifth embodiment, the electrolytic solution leached from the negative electrode is stored in the space 13, but if the metal electrode cartridge housing 1k is largely shaken, the electrolytic solution may come into contact with the negative electrode. On the other hand, according to the sixth embodiment, since the porous member 7b holds the electrolytic solution leached from the negative electrode, the contact between the negative electrode and the electrolytic solution is sufficiently suppressed. As a result, the self-corrosion of the negative electrode is sufficiently suppressed.

According to the sixth embodiment, the following effects can be obtained in addition to the effects of the fifth embodiment.
(1) Since the porous member 7b holds the electrolytic solution leached from the negative electrode, the self-corrosion of the negative electrode is sufficiently suppressed.
(2) Since the porous member 7b holds the electrolytic solution leached from the negative electrode even when the placement of the metal electrode cartridge-containing item 1m is changed (for example, when it is placed vertically), the negative electrode and the electrolytic Contact with the liquid is suppressed.
(3) Since the porous member 7b holds the electrolytic solution leached from the negative electrode, the electrolytic solution is prevented from adhering to the surface of the metal electrode cartridge 2 on the accommodation port 11 side. As a result, when handling the metal electrode cartridge 2, contact with the electrolytic solution is prevented.
(4) Since the porous member 7b holds the electrolytic solution leached from the negative electrode, the electrolytic solution is prevented from adhering to the power take-out portion 10. As a result, the corrosion of the power take-out portion 10 due to the electrolytic solution is prevented.
(5) Since the porous member 7b holds the electrolytic solution leached from the negative electrode, the metal electrode cartridge 2 is kept in an appropriate wet state. As a result, the startability of the battery during discharging is improved.

[Embodiment 7]
FIG. 13 is a schematic cross-sectional view showing a metal electrode cartridge container according to the seventh embodiment. The seventh embodiment is the same as the sixth embodiment except that the electrode shape holding member that covers the oxygen permeation suppression member is arranged, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge accommodation item 1n, a part of the surface (hereinafter, also referred to as a third surface) except the surface of the oxygen permeation suppressing member 3e on the side of the accommodation port 11 and the surface on the side opposite to the accommodation port 11 is covered. The electrode shape holding member 16a is arranged at the position.

According to the seventh embodiment, the following effects can be achieved in addition to the effects of the sixth embodiment.
(1) Since the electrode shape holding member 16a holds down the negative electrode, expansion and peeling of the metal electrode 4 are suppressed. As a result, the generation of a portion of the metal electrode 4 that cannot be used for discharging is suppressed, and the decrease in discharge capacity is sufficiently suppressed.
(2) Since the electrode shape holding member 16a holds down the negative electrode, the excess electrolytic solution is efficiently removed from the negative electrode, and the decrease in the capacity of the negative electrode is suppressed.
(3) Since the electrode shape holding member 16a holds down the negative electrode, the air inside the oxygen permeation suppression member 3e is less likely to reach the surface of the negative electrode. As a result, the oxidation of the negative electrode is sufficiently suppressed.
(4) Since the electrode shape holding member 16a presses the negative electrode, the metal electrode cartridge 2 is sufficiently kept in an appropriate wet state.
(5) The electrode shape holding member 16a prevents damage to the oxygen permeation suppression member 3e.
(6) The electrode shape holding member 16a prevents the metal electrode 4, the negative electrode housing 8 and the like from being damaged.
(7) Since the porous member 7b contracts by the pressure applied by the metal electrode cartridge 2 and the electrode shape holding member 16a, the electrolytic solution held by the porous member 7b is squeezed out, and the space 13 is efficiently evacuated. It is stored.
(8) Since the porous member 7b can contract, the electrode shape holding member 16a can be easily attached.

[Modification 1 of Embodiment 7]
FIG. 14 is a schematic cross-sectional view showing a metal electrode cartridge accommodation item of the first modification of the seventh embodiment. The first modification of the seventh embodiment is the same as the seventh embodiment except that the shape of the electrode shape holding member is different, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge accommodation item 1p, in addition to a part of the third surface of the oxygen permeation suppressing member 3e, a position (hereinafter, also referred to as a fourth surface) opposite to the accommodation port 11 is covered. The electrode shape holding member 16b is arranged. That is, the electrode shape holding member 16b has a container shape.

According to the first modification of the seventh embodiment, the following effects can be obtained in addition to the effects of the seventh embodiment.
(1) The electrode shape holding member 16b sufficiently prevents the oxygen permeation suppression member 3e from being damaged.
(2) Since the electrode shape holding member 16b covers the fourth surface in addition to a part of the third surface of the oxygen permeation suppression member 3e, the metal electrode cartridge container 1p is placed vertically. Improves stability.

[Embodiment 8]
FIG. 15 is a schematic cross-sectional view showing a metal electrode cartridge container according to the eighth embodiment. The eighth embodiment is the same as the first modified example of the seventh embodiment except that the oxygen permeation suppression member and the porous member are bonded together, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1q, the oxygen permeation suppression member 3e and the porous member 7b are bonded together via the adhesive member 17. Although the adhesive member 17 is arranged between the oxygen permeation suppression member 3e and the porous member 7b in FIG. 15, it may be arranged so as to cover the end of the porous member 7b.

According to the eighth embodiment, the following effects can be obtained in addition to the effects of the first modification of the seventh embodiment.
(1) Since the oxygen permeation suppression member 3e and the porous member 7b are bonded together via the adhesive member 17, the metal electrode cartridge 2 can be easily taken in and out of the oxygen permeation suppression member 3e, and workability is improved.

[Embodiment 9]
FIG. 16 is a schematic sectional view showing a metal electrode cartridge container according to the ninth embodiment. The ninth embodiment is the same as the fourth embodiment except that a plurality of metal electrode cartridges are housed in one oxygen permeation suppression member, and thus the description of the overlapping points will be appropriately omitted.

In the metal electrode cartridge housing 1r, the plurality of metal electrode cartridges 2 are arranged by being partitioned by the oxygen permeation suppression member 3f. Further, an electrode shape holding member 16f is arranged at a position that covers the oxygen permeation suppression member 3f. Further, each metal electrode cartridge 2 is connected to the modularization member 18. Thereby, the plurality of metal electrode cartridges 2 can be handled in an integrated state (a modularized state).

The metal-air battery has a low voltage in a single state (single cell). Therefore, in practice, the total voltage is often increased by connecting a plurality of metal-air batteries in series. In this case, if a plurality of metal electrode cartridges are handled one by one, it takes time and effort to remove all the metal electrode cartridges from the charging device and to attach all the metal electrode cartridges to the battery housing (discharge device). It will take. Furthermore, the number of oxygen permeation suppression members and electrode shape holding members is large, which causes problems such as hindering work. On the other hand, according to the ninth embodiment, since the plurality of metal electrode cartridges 2 are handled in a modularized state by the modularizing member 18, the above-mentioned problem is solved.

The material of the modularization member 18 may be a material having an insulating property or a material having a conductive property, and can be appropriately selected according to the use situation.

The electrode shape holding member 16f and the modularization member 18 may be fixed by a fixing member. As a result, the airtightness of the metal electrode cartridge container 1r is enhanced, and the invasion of oxygen into each metal electrode cartridge 2 can be sufficiently suppressed. Further, since the metal electrode cartridge contents 1r have a rectangular parallelepiped shape and are easily stacked, the efficiency in storage and transportation is improved.

The oxygen permeation suppression member 3f and the modularization member 18 may be attached to each other via a seal member. As a result, the airtightness of the metal electrode cartridge container 1r is enhanced, and the invasion of oxygen into each metal electrode cartridge 2 can be sufficiently suppressed.

According to the ninth embodiment, the following effects can be obtained in addition to the effects of the fourth embodiment.
(1) Even when the plurality of metal electrode cartridges 2 are modularized, a decrease in the capacity of the negative electrode during storage and transportation is suppressed.
(2) Since the plurality of metal electrode cartridges 2 are modularized, the work of taking out all the metal electrode cartridges 2 from the charging device and the work of attaching all the metal electrode cartridges 2 to the battery housing are facilitated, and the work is performed. The property is improved.
(3) Since there is only one oxygen permeation suppression member 3f and one electrode shape holding member 16f, it is easy to secure a work space and workability is improved.

The ninth embodiment has a configuration in which a plurality of metal electrode cartridges are housed in one oxygen permeation suppression member and modularized as compared with the fourth embodiment, but a plurality of metal electrodes are provided in comparison with other embodiments and modifications. The electrode cartridge may be housed in one oxygen permeation suppression member to be modularized.

[Appendix]
One aspect of the present invention includes a metal electrode cartridge 2 and an oxygen permeation suppression member 3a that covers at least a part of the metal electrode cartridge 2, and the metal electrode cartridge 2 includes a metal electrode 4 containing an electrode active material, The oxygen permeation suppression member 3 a has a current collector 5 electrically connected to the metal electrode 4, the oxygen permeation suppression member 3 a has an accommodation port 11 into which the metal electrode cartridge 2 can be inserted and withdrawn, and It may be a metal electrode cartridge accommodation item 1a in which a space 13 for accumulating an electrolytic solution is provided in at least a part of a region between the surface other than the accommodation port 11 side and the oxygen permeation suppression member 3a. According to this aspect, the following effects can be achieved.
(1) Since the metal electrode cartridge 2 is housed in the oxygen permeation suppression member 3a, invasion of oxygen into the metal electrode cartridge 2 is suppressed, and as a result, the negative electrode (the metal electrode 4 and the current collector 5) Oxidation (passivation) is suppressed.
(2) Since the space 13 is provided, contact between the electrolyte leached from the negative electrode and the negative electrode is suppressed, and as a result, self-corrosion of the negative electrode is suppressed.

In the above aspect, the space 13 may be provided between the oxygen permeation suppression member 3a and the surface of the metal electrode cartridge 2 on the side opposite to the accommodation port 11 in the region. With such a configuration, the metal electrode cartridge accommodation item 1a can be stored and transported in a vertically placed state.

In the above aspect, the space 13 is at least one of the regions other than between the surface of the metal electrode cartridge 2 on the opposite side of the accommodation port 11 and the oxygen permeation suppression member (oxygen permeation suppression member 3e). It may be provided in the section. With such a configuration, the metal electrode cartridge accommodation item 1k can be stored and transported in a horizontal state.

In the above aspect, the oxygen permeation suppression member 3a may have a protrusion 12, and the protrusion 12 may directly contact the metal electrode cartridge 2 to form the space 13. With this structure, the space 13 is preferably formed.

In the above aspect, the porous member 7b having hydrophilicity may be arranged at least at a part between the metal electrode cartridge 2 and the oxygen permeation suppression member 3a. With such a configuration, the following effects can be achieved.
(1) The porous member 7b facilitates movement of the electrolytic solution leached from the negative electrode into the space 13.
(2) Since the porous member 7b holds the electrolyte leached from the negative electrode, self-corrosion of the negative electrode is sufficiently suppressed.
(3) Since the porous member 7b holds the electrolytic solution leached from the negative electrode even when the metal electrode cartridge housing 1b is placed horizontally, contact between the negative electrode and the electrolytic solution is suppressed.
(4) Since the porous member 7b holds the electrolytic solution leached from the negative electrode even when the metal electrode cartridge accommodation item 1b is placed horizontally, electrolysis of the surface of the metal electrode cartridge 2 on the accommodation port 11 side is performed. Liquid adhesion is prevented. As a result, when handling the metal electrode cartridge 2, contact with the electrolytic solution is prevented.
(5) Since the porous member 7b holds the electrolytic solution that has leached out from the negative electrode even when the metal electrode cartridge housing 1b is placed horizontally, the electrolytic solution is prevented from adhering to the power take-out portion 10. . As a result, the corrosion of the power take-out portion 10 due to the electrolytic solution is prevented.
(6) Since the porous member 7b holds the electrolytic solution leached from the negative electrode, the metal electrode cartridge 2 is kept in an appropriate wet state. As a result, the startability of the battery during discharging is improved.

In the above aspect, the porous member 7b may be arranged on the surface of the metal electrode cartridge 2. With such a configuration, the porous member 7b can be effectively used.

In the above aspect, the porous member 7b may be in direct contact with the metal electrode cartridge 2, and the space 13 may include a void of the porous member 7b. With such a configuration, the porous member 7b can be effectively used.

In the above aspect, the oxygen permeation suppression member 3a and the porous member 7b may be bonded to each other via the adhesive member 17. With such a configuration, the metal electrode cartridge 2 can be easily taken in and out of the oxygen permeation suppression member 3a, and the workability is improved.

In the above aspect, the porous member (porous member 7c) may have a shape along the outer shape of the metal electrode cartridge 2. With such a configuration, since the contact area between the porous member 7c and the metal electrode cartridge 2 is large, the electrolytic solution leached from the negative electrode efficiently permeates into the porous member 7c and moves to the space 13. Easier to do.

In the above aspect, the oxygen permeation suppression member 3a may have a bag shape. With such a configuration, the metal electrode cartridge 2 can be efficiently stored and transported.

In the above aspect, the electrode shape holding member 16a may be arranged at a position that covers at least a part of the oxygen permeation suppression member 3a. With such a configuration, the following effects can be achieved.
(1) Since the electrode shape holding member 16a holds down the negative electrode, expansion and peeling of the metal electrode 4 are suppressed. As a result, the generation of a portion of the metal electrode 4 that cannot be used for discharging is suppressed, and the decrease in discharge capacity is sufficiently suppressed.
(2) Since the electrode shape holding member 16a holds down the negative electrode, the excess electrolytic solution is efficiently removed from the negative electrode, and the decrease in the capacity of the negative electrode is suppressed.
(3) Since the electrode shape holding member 16a holds down the negative electrode, it becomes difficult for the air inside the oxygen permeation suppression member 3a to reach the surface of the negative electrode. As a result, the oxidation of the negative electrode is sufficiently suppressed.
(4) Since the electrode shape holding member 16a presses the negative electrode, the metal electrode cartridge 2 is sufficiently kept in an appropriate wet state.
(5) The electrode shape holding member 16a prevents the oxygen permeation suppression member 3a from being damaged.
(6) The electrode shape holding member 16a prevents the metal electrode 4, the negative electrode housing 8 and the like from being damaged.
(7) Since the porous member 7b contracts by the pressure applied by the metal electrode cartridge 2 and the electrode shape holding member 16a, the electrolytic solution held by the porous member 7b is squeezed out, and the space 13 is efficiently evacuated. It is stored.
(8) Since the porous member 7b can contract, the electrode shape holding member 16a can be easily attached.

In the above aspect, the electrode shape holding member (electrode shape holding member 16b) may cover the surface of the oxygen permeation suppression member 3a on the side opposite to the accommodation port 11. With such a configuration, the following effects can be achieved.
(1) The electrode shape holding member 16b sufficiently prevents the oxygen permeation suppression member 3a from being damaged.
(2) The stability of the metal electrode cartridge accommodation item 1d in a vertically placed state is improved.

In the above aspect, at least a part of the surface of the electrode shape holding member (electrode shape holding member 16c) on the oxygen permeation suppression member (oxygen permeation suppression member 3b) side is the oxygen permeation suppression member (oxygen permeation suppression member 3b). May project toward. With such a configuration, the electrode shape holding member 16c can be effectively used, and the space 13 is preferably formed.

In the above aspect, at least the surface of the electrode shape holding member (electrode shape holding member 16d or electrode shape holding member 16e) on the oxygen permeation suppression member (oxygen permeation suppression member 3c or oxygen permeation suppression member 3d) side. A part may be recessed toward the side opposite to the oxygen permeation suppression member (oxygen permeation suppression member 3c or oxygen permeation suppression member 3d). With this configuration, the electrode shape holding member 16d (electrode shape holding member 16e) can be effectively used, and the space 13 is preferably formed.

In the above aspect, the metal electrode cartridge 2 and at least one metal electrode cartridge different from the metal electrode cartridge 2 may be arranged so as to be partitioned by the oxygen permeation suppression member (oxygen permeation suppression member 3f). Good. With such a configuration, the following effects can be achieved.
(1) Even when the plurality of metal electrode cartridges 2 are modularized, a decrease in the capacity of the negative electrode during storage and transportation is suppressed.
(2) Since the plurality of metal electrode cartridges 2 are modularized, the work of taking out all the metal electrode cartridges 2 from the charging device and the work of attaching all the metal electrode cartridges 2 to the battery housing are facilitated, and the work is performed. The property is improved.
(3) Since there is only one oxygen permeation suppression member 3f and one electrode shape holding member 16f, it is easy to secure a work space and workability is improved.

In the above aspect, the metal electrode 4 and the current collector 5 may constitute a negative electrode of a metal-air battery. With such a configuration, a metal-air battery can be configured by using the metal electrode cartridge 2.

Another aspect of the present invention may be a method of storing the metal electrode cartridge 2 for storing the charged metal electrode cartridge 2 taken out of the charging device 14 by the metal electrode cartridge container 1a. According to this aspect, the capacity reduction of the negative electrode during the storage of the metal electrode cartridge 2 is suppressed. As a result, the decrease in discharge capacity is suppressed.

Still another aspect of the present invention is a metal electrode for carrying the charged metal electrode cartridge 2 taken out of the charging device 14 to the battery housing 15 to which the metal electrode cartridge 2 is attached, by the metal electrode cartridge container 1a. It may be a method of carrying the cartridge 2. According to this aspect, the capacity reduction of the negative electrode during the transportation of the metal electrode cartridge 2 is suppressed. As a result, the decrease in discharge capacity is suppressed.

1a, 1b, 1c, 1d, 1e, 1f, 1g, 1h, 1j, 1k, 1m, 1n, 1p, 1q, 1r: Metal electrode cartridge container 2: Metal electrode cartridge 3a, 3b, 3c, 3d, 3e, 3f: Oxygen permeation suppression member 4: Metal electrode 5: Current collector 6: Ion selection members 7a, 7b, 7c: Porous member 8: Negative electrode housing 9: Opening 10: Power extraction part 11: Storage port 12: Projection part 13 : Space 14: Charging device 15: Battery housings 16a, 16b, 16c, 16d, 16e, 16f: Electrode shape holding member 17: Adhesive member 18: Modularization member 100: Zinc-air battery 120: Electrolyte 121: Zinc electrode 122: Air pole

Claims (20)

A metal electrode cartridge,
An oxygen permeation suppressing member that covers at least a part of the metal electrode cartridge;
The metal electrode cartridge has a metal electrode containing an electrode active material, a current collector electrically connected to the metal electrode, and a housing that houses the metal electrode and the current collector .
The oxygen permeation suppression member has a storage port into / from which the metal electrode cartridge can be inserted / removed,
The housing has a through hole provided in the thickness direction of the housing,
Said receiving port other than the side surface of the casing, the oxygen in at least a portion of the region between the transmission suppressing member, a metal electrode cartridge receiving product and a space is provided for storing an electrolytic solution. The metal electrode cartridge housing according to claim 1, wherein the space is provided between the oxygen permeation suppression member and a surface of the region opposite to the housing port of the metal electrode cartridge. Stuff. The space is provided in at least a part of the area other than between the surface of the metal electrode cartridge opposite to the accommodation port and the oxygen permeation suppression member. Metal electrode cartridge contents of. The oxygen permeation suppression member has a protrusion,
The metal electrode cartridge accommodation object according to any one of claims 1 to 3, wherein the protrusion forms the space by directly contacting the metal electrode cartridge. The metal electrode cartridge accommodation article according to claim 4, wherein a hydrophilic porous member is disposed at least at a part between the metal electrode cartridge and the oxygen permeation suppression member. The metal electrode cartridge container according to claim 5, wherein the porous member is disposed on a surface of the metal electrode cartridge. The porous member is in direct contact with the metal electrode cartridge,
The metal electrode cartridge container according to claim 5 or 6, wherein the space includes a void of the porous member. The metal electrode cartridge container according to any one of claims 5 to 7, wherein the oxygen permeation suppression member and the porous member are attached to each other via an adhesive member. The metal electrode cartridge accommodation object according to any one of claims 5 to 8, wherein the porous member has a shape that follows the outer shape of the metal electrode cartridge. The metal electrode cartridge container according to any one of claims 1 to 9, wherein the oxygen permeation suppressing member has a bag shape. The electrode shape holding member is arranged at a position that covers at least a part of the oxygen permeation suppression member, and the metal electrode cartridge accommodation object according to any one of claims 1 to 10. The metal electrode cartridge container according to claim 11, wherein the electrode shape holding member covers a surface of the oxygen permeation suppression member on a side opposite to the housing port. At least a part of the surface of the electrode shape holding member on the oxygen permeation suppression member side projects toward the oxygen permeation suppression member. 13. The metal electrode cartridge according to claim 11, wherein at least a part of the surface of the electrode shape holding member on the oxygen permeation suppression member side is recessed toward the side opposite to the oxygen permeation suppression member. Containment. 15. The metal electrode cartridge and at least one metal electrode cartridge other than the metal electrode cartridge are arranged by being partitioned by the oxygen permeation suppression member. Metal electrode cartridge contents of. The metal electrode cartridge accommodation object according to any one of claims 1 to 15, wherein the metal electrode and the current collector constitute a negative electrode of a metal-air battery. The metal electrode cartridge accommodation object according to any one of claims 1 to 16, wherein an opening ratio of the casing is 30% or more. The metal electrode cartridge accommodation object according to any one of claims 1 to 17, wherein the diameter of the opening of the through hole is 3 mm or more. A method for storing a metal electrode cartridge, characterized in that the metal electrode cartridge accommodated in any one of claims 1 to 18 stores the charged metal electrode cartridge taken out from a charging device. A metal electrode, comprising: the metal electrode cartridge contained in any one of claims 1 to 18 for transporting the charged metal electrode cartridge taken out of a charging device to a battery housing to which the metal electrode cartridge is attached. Cartridge transportation method.

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