CN111244582B - Zinc-air battery positive electrode structure, assembly method and zinc-air battery - Google Patents
Zinc-air battery positive electrode structure, assembly method and zinc-air battery Download PDFInfo
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- CN111244582B CN111244582B CN202010029562.4A CN202010029562A CN111244582B CN 111244582 B CN111244582 B CN 111244582B CN 202010029562 A CN202010029562 A CN 202010029562A CN 111244582 B CN111244582 B CN 111244582B
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- positive electrode
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- air battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
- H01M12/085—Zinc-halogen cells or batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/102—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure
- H01M50/109—Primary casings, jackets or wrappings of a single cell or a single battery characterised by their shape or physical structure of button or coin shape
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a zinc-air battery positive electrode structure, an assembling method and a zinc-air battery. The positive electrode structure of the zinc-air battery comprises a positive electrode shell and a positive electrode plate. The positive electrode shell comprises a bottom wall and a side wall formed around the bottom wall, the inner surface of the bottom wall comprises a central area and an edge area surrounding the central area, the central area is sunken downwards relative to the edge area, an air hole of the positive electrode shell is located in the central area, the positive electrode sheet is arranged in the positive electrode shell, and the lower surface of the positive electrode sheet is attached to the edge area. The technical scheme that this application provided can solve current button zinc-air battery's weeping problem.
Description
Technical Field
The application relates to the technical field of zinc-air batteries, in particular to a zinc-air battery anode structure, an assembly method and a zinc-air battery.
Background
Zinc air battery (zinc air battery) is a galvanic cell which uses active carbon to adsorb oxygen in the air as positive active material, zinc as negative electrode and caustic soda or caustic alkali solution as electrolyte.
Because the positive pole reactant of the zinc-air battery is oxygen from the air, and the negative pole reactant is zinc powder, the one-time button zinc-air battery has the advantages of high energy density and stable discharging platform, and is widely applied to portable equipment such as hearing aids, bluetooth earphones and the like. Because the zinc-air battery needs to obtain oxygen from the air continuously, 1-5 air holes with the diameter of 0.1mm-0.5mm are distributed at the bottom of the positive shell of the button zinc-air battery, and the button zinc-air battery has one more electrolyte leakage path than the traditional alkaline zinc-manganese battery due to the air holes, and the alkaline electrolyte of the zinc-air battery is easier to leak from the air holes at the bottom of the positive shell. The zinc-air battery steel shell is unreasonable in design, the negative electrode zinc slurry generates serious gas, and liquid leakage of the battery in the storage process or the discharge process is easily caused by poor assembly or packaging. The electrolyte of the zinc-air battery is strong alkaline solution, and the electrolyte is easy to corrode an expensive hearing aid when leaking, so that the leakage problem is the most serious safety problem of the button zinc-air battery at present.
Disclosure of Invention
The application provides a zinc-air battery positive electrode structure, an assembly method and a zinc-air battery. The positive electrode structure and the assembly method of the zinc-air battery and the zinc-air battery can solve the problem of liquid leakage of the conventional button zinc-air battery.
In a first aspect, the present application provides a zinc-air battery positive electrode structure. The positive electrode structure of the zinc-air battery comprises a positive electrode shell and a positive electrode plate. The positive electrode shell comprises a bottom wall and a side wall formed around the bottom wall, the inner surface of the bottom wall comprises a central area and an edge area surrounding the central area, the central area is sunken downwards relative to the edge area, the air hole of the positive electrode shell is located in the central area, the positive electrode sheet is arranged in the positive electrode shell, and the lower surface of the positive electrode sheet is attached to the edge area.
In the scheme, a zinc-air battery anode structure is provided. When the zinc-air battery has the positive electrode structure of the zinc-air battery, the problem of leakage of the existing zinc-air battery can be solved. The zinc-air battery positive electrode structure comprises a positive electrode shell and a positive electrode plate, wherein an air hole of the positive electrode shell is located in a central area, and the lower surface of the positive electrode plate is attached to an edge area, so that the lower surface of the positive electrode plate can be in sealing fit with a part protruding from the central area. In the prior art, the negative electrode zinc slurry of the zinc-air battery is easy to generate gas through self reaction in the storage process, so that the internal pressure of the battery is increased, zinc powder of the negative electrode can be converted into zinc oxide to generate volume expansion in the discharging process of the zinc-air battery, when the internal pressure is increased and the volume is expanded to a certain degree, the sealing ring is not pressed against the positive plate and the bottom of the positive shell tightly, and electrolyte can flow out of a gap between the positive plate and the positive shell through the gap between the sealing ring and the positive plate, so that the electrolyte leaks out of an air hole. In order to make electrolyte not reveal, this technical scheme is the concave-convex structure with the diapire design of positive plate for the lower surface of positive plate forms sealedly with relative convex marginal area, so electrolyte can be by the separation in the lower surface of positive plate and relative convex marginal area department, thereby has avoided electrolyte to spill by the gas pocket that is located central area department.
In a possible implementation mode, the positive plate comprises a current collector net, a catalyst layer and a waterproof breathable layer, the current collector net is embedded in the catalyst layer, the waterproof breathable layer is arranged on the lower surface of the catalyst layer, and the waterproof breathable layer is in a compressed state and is attached to the edge area.
Optionally, in one possible implementation, the edge portion of the waterproof breathable layer is attached to the edge region, and a gap exists between the central portion and the central region of the waterproof breathable layer.
Optionally, in one possible implementation, the positive electrode structure of the zinc-air battery further comprises diffusion paper, the diffusion paper is positioned in a gap between the central part and the central area of the waterproof breathable layer, and covers the air holes.
Optionally, in one possible implementation, the diameter of the central region is five-eighths to three-quarters of the diameter of the bottom wall of the positive can.
In a second aspect, the present application provides a method of assembling a positive electrode structure for a zinc-air battery.
The method comprises the following steps:
providing a positive electrode can, the positive electrode can including a bottom wall and a side wall formed around the bottom wall, an inner surface of the bottom wall including a central region and a peripheral region surrounding the central region, the central region being recessed relative to the peripheral region;
placing the positive plate into the positive shell;
and pressurizing the positive plate so that the lower surface of the positive plate is attached to the edge area.
Optionally, in a possible implementation, the step of pressing the positive electrode plate so that the lower surface of the positive electrode plate is attached to the edge area includes:
applying 2-5kgf pressure to the positive plate for 0.1-0.5s.
Optionally, in a possible implementation, the step of pressing the positive electrode plate so that the lower surface of the positive electrode plate is attached to the edge area includes:
the positive electrode plate is pressed by a cylindrical elastic resin.
Alternatively, in one possible implementation, the diameter of the cylindrical elastic resin is the same as the diameter of the positive electrode tab.
In a third aspect, the present application provides a zinc-air battery, which includes a negative electrode cover, a zinc paste, a sealing ring, a diaphragm and the positive electrode structure of the zinc-air battery provided in any one of the first aspect. The lateral wall of negative pole lid and positive plate passes through sealing washer sealing connection, and the accommodation space is injectd jointly to the negative pole lid and positive plate, and the diaphragm separates accommodation space for anodal chamber and negative pole chamber, and anodal intracavity is located to the positive plate, and the negative pole intracavity is located to the zinc thick liquid, the upper surface butt of sealing washer and positive plate.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a schematic structural diagram of a positive electrode structure of a zinc-air battery in the embodiment;
fig. 2 is a schematic structural diagram of a conventional button zinc-air battery in this embodiment;
FIG. 3 is an indication diagram of the positive electrode sheet pressing process in the present embodiment;
fig. 4 is a state diagram of the positive electrode sheet in this embodiment after pressurization;
fig. 5 is a schematic structural view of the zinc-air battery in this embodiment.
Icon: a 10-zinc-air battery positive electrode structure; 11-positive electrode case; 12-positive plate; 80-diffusion paper; 90-a central region; 91-edge area; 92-air holes; 110-a bottom wall; 111-side walls; 120-a current collector mesh; 121-a catalyst layer; 122-waterproof breathable layer;
20-button zinc-air battery; 21-a positive electrode shell; 22-a sealing ring; 23-positive plate; 24-zinc paste; 230-waterproof breathable layer;
30-cylindrical elastic resin;
a 40-zinc-air cell; 41-negative electrode cover; 42-zinc slurry; 43-sealing ring; 44-membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined or explained in subsequent figures.
In the description of the embodiments of the present application, it is to be understood that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like, refer to the orientation or positional relationship as shown in the drawings, or as conventionally placed in use of the product of the application, or as conventionally understood by those skilled in the art, and are used merely for convenience of description and for simplicity of description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed in a particular orientation, and be operated, and therefore should not be considered as limiting the present application.
In the description of the embodiments of the present application, it should also be noted that, unless otherwise explicitly stated or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict.
The technical solution in the present application will be described below with reference to the accompanying drawings.
The present embodiment provides a positive electrode structure 10 of a zinc-air battery, which can solve the problem of liquid leakage of the existing button zinc-air battery.
Referring to fig. 1, fig. 1 shows a specific structure of a positive electrode structure 10 of a zinc-air battery in the present embodiment.
The positive electrode structure 10 of the zinc-air battery comprises a positive electrode shell 11 and a positive electrode sheet 12. Positive electrode can 11 includes a bottom wall 110 and a side wall 111 formed around bottom wall 110, the inner surface of bottom wall 110 includes a central region 90 and an edge region 91 surrounding central region 90, central region 90 is recessed downward with respect to edge region 91, air vent 92 of positive electrode can 11 is located in central region 90, positive electrode tab 12 is disposed in positive electrode can 11, and the lower surface of positive electrode tab 12 is fitted to edge region 91.
In the above embodiment, a zinc-air battery positive electrode structure 10 is provided. When the zinc-air battery has the positive electrode structure 10 of the zinc-air battery, the problem of liquid leakage of the existing zinc-air battery can be solved. The positive electrode structure 10 of the zinc-air battery comprises a positive electrode shell 11 and a positive electrode plate 12, wherein an air hole 92 of the positive electrode shell 11 is positioned in a central area 90, and the lower surface of the positive electrode plate 12 is attached to an edge area 91, so that the lower surface of the positive electrode plate 12 can be in sealing fit with a part protruding from the central area 90.
Fig. 2 shows a specific structure of a conventional button type zinc-air battery 20 for clearly explaining the effect thereof.
The bottom of the positive electrode shell 21 of the existing button-type zinc-air battery 20 is flat, and the sealing ring 22, the positive electrode plate 23 and the inner bottom of the positive electrode shell 21 are tightly pressed together, so that the electrolyte is prevented from leaking from the edge of the bottom of the positive electrode shell 21 through the side edge of the positive electrode plate 23. In the storage process of the button zinc-air battery 20, the negative electrode zinc paste 24 is easy to generate gas through self reaction, so that the internal pressure of the battery rises, the zinc powder of the negative electrode in the discharging process of the button zinc-air battery 20 can be converted into zinc oxide to generate volume expansion, when the internal pressure rises and the volume expands to a certain degree, the sealing ring 22 does not tightly press the positive plate 23 and the bottom of the positive shell 21 any more, at the moment, the electrolyte can easily flow out to the gap between the positive plate 23 and the positive shell 21 through the gap between the sealing ring 22 and the positive plate 23, and the waterproof breathable layer 230 in the positive plate 23 cannot be completely adhered to the bottom of the positive shell 21 (the waterproof breathable layer 230 of the positive plate 23 is generally made of a PTFE film which has the characteristic of being deformed under pressure without rebounding), the electrolyte can easily leak out from the air hole 92 in the long-term storage and discharging process or after discharging, namely, so as to leak the electrolyte.
In order to make electrolyte not reveal, this technical scheme for bottom wall 110 of positive plate 12 designs into the concavo-convex structure for the lower surface of positive plate 12 forms sealedly with relative convex marginal zone 91, so electrolyte can be by the separation in the lower surface of positive plate 12 and relative convex marginal zone 91 department, thereby has avoided electrolyte to get into central region 90, thereby avoids electrolyte to spill by gas pocket 92.
Referring to fig. 1 again, the positive plate 12 includes a current collector net 120, a catalyst layer 121, and a waterproof air-permeable layer 122, the current collector net 120 is embedded in the catalyst layer 121, the waterproof air-permeable layer 122 is disposed on the lower surface of the catalyst layer 121, and the waterproof air-permeable layer 122 is in a compressed state and is attached to the edge region 91.
Wherein, waterproof ventilative layer 122 is in compression state, closely laminates with the border area 91 of the diapire 110 of positive electrode can 11 after the deformation promptly, because waterproof ventilative layer 122 has the characteristic that the compression deformation does not kick-back, so waterproof ventilative layer 122 and the border area 91 of the diapire 110 of positive electrode can 11 form good sealed relation, electrolyte can be separated in waterproof ventilative layer 122 and the relative convex border area 91 department of positive plate 12, thereby electrolyte entering central zone 90 has been avoided, thereby avoid electrolyte to spill by gas pocket 92.
Optionally, in one possible implementation, the edge portions of the waterproof breathable layer 122 are conformed to the edge regions 91, with a gap between the central portion of the waterproof breathable layer 122 and the central region 90.
Optionally, in one possible implementation, the zinc-air battery positive electrode structure 10 further includes a diffusion paper 80, the diffusion paper 80 being located in the gap between the central portion of the waterproof breathable layer 122 and the central region 90 and covering the air holes 92.
Alternatively, in the present embodiment, the diameter of the central region 90 is five-eighths to three-fourths of the diameter of the bottom wall 110 of the positive electrode can 11.
It should be noted that too small a diameter of the central region 90 may reduce the effective reaction area of the positive electrode, whereas too large a diameter of the central region 90 may result in a position mismatch with the sealing ring, which is not favorable for packaging.
It should be noted that this embodiment also provides an assembly method of the positive electrode structure of the zinc-air battery.
The method comprises the following steps:
providing a positive electrode can 11, the positive electrode can 11 including a bottom wall 110 and a side wall 111 formed around the bottom wall 110, an inner surface of the bottom wall 110 including a central region 90 and an edge region 91 surrounding the central region 90, the central region 90 being recessed downward relative to the edge region 91;
placing the positive plate 12 into the positive shell 11;
the positive electrode sheet 12 is pressed so that the lower surface of the positive electrode sheet 12 is fitted to the edge area 91.
Alternatively, in one possible implementation, the step of pressing the positive electrode sheet 12 so that the lower surface of the positive electrode sheet 12 is fitted to the edge region 91 includes:
applying a pressure of 2-5kgf to the positive electrode sheet 12 for 0.1-0.5s.
Alternatively, in one possible implementation, the step of pressing the positive electrode sheet 12 so that the lower surface of the positive electrode sheet 12 fits to the edge area 91 includes:
the positive electrode sheet 12 is pressed by a cylindrical elastic resin 30.
Alternatively, in one possible implementation, the diameter of cylindrical elastic resin 30 is the same as the diameter of positive electrode tab 12.
In one particular assembly method, as illustrated in fig. 3 and 4, among others:
providing a positive electrode can 11;
placing the positive plate 12 into the positive shell 11;
a pressure of 3kgf was applied to the positive electrode sheet 12 through the cylindrical elastic resin 30 for 0.3s, so that the lower surface of the positive electrode sheet 12, i.e., the waterproof and breathable layer 122 in the positive electrode sheet 12 in this embodiment, was deformed to be attached to the edge region 91 of the inner surface of the bottom wall 110.
In other embodiments, the pressure applied to the positive electrode sheet 12 may have other values, for example, 2, 4, or 5kgf, and the pressing time may have other values, for example, 0.1, 0.2, 0.4, or 0.5s.
It should be noted that this embodiment also provides comparison data:
comparative example: 20 PR41 cells in the prior art (i.e., fabricated by the original process);
example (b): 20 PR41 batteries comprising the positive electrode structure 10 of the zinc-air battery manufactured by the assembling method of the positive electrode structure of the zinc-air battery.
It is to be noted that the conditions of the comparative example and the example were the same except that the positive electrode structure 10 of the zinc-air battery was different.
The leakage of the PR41 batteries of comparative example and example was confirmed after aging the batteries in an oven at 60 degrees celsius for 20 days at high temperature, and the leakage data are shown in table 1.
| Amount of leakage after aging at 60 deg.C for 20 days | |
| Comparative example | 4/20 (granule) |
| Examples | 0/20 (granule) |
TABLE 1
As can be seen from table 1, the positive electrode structure 10 of the zinc-air battery manufactured by the method for assembling the positive electrode structure of the zinc-air battery provided in this embodiment can effectively improve the sealing performance of the existing button zinc-air battery, and solve the problem of liquid leakage of the existing button zinc-air battery.
It should be noted that this embodiment also provides a zinc-air battery. As shown in fig. 5.
The zinc-air battery 40 comprises a negative electrode cover 41, a zinc paste 42, a sealing ring 43, a diaphragm 44 and the zinc-air battery positive electrode structure 10 provided above.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (5)
1. A positive electrode structure of a zinc-air battery is characterized by comprising a positive electrode shell and a positive electrode plate;
the positive electrode can comprises a bottom wall and a side wall formed around the bottom wall, the inner surface of the bottom wall comprises a central area and an edge area surrounding the central area, the central area is recessed downwards relative to the edge area, the air hole of the positive electrode can is located in the central area, and the positive electrode sheet is arranged in the positive electrode can;
the positive plate comprises a current collector net, a catalyst layer and a waterproof and breathable layer which does not rebound after being deformed under pressure, the current collector net is embedded in the catalyst layer, the waterproof and breathable layer is arranged on the lower surface of the catalyst layer, the positive plate is configured to be applied with pressure of 2-5kgf by cylindrical elastic resin with the same diameter as that of the positive plate, the application time is 0.1-0.5s, so that the waterproof and breathable layer is in a compressed state, the edge part of the waterproof and breathable layer is attached to the edge area to form sealing with the edge area, the sealing formed by the waterproof and breathable layer and the edge area is used for preventing electrolyte from entering the central area, and a gap exists between the central part of the waterproof and breathable layer and the central area;
the diameter of the central area is five-eighths to three-fourths of the diameter of the bottom wall of the positive electrode can.
2. The positive electrode structure of a zinc-air battery according to claim 1,
the positive electrode structure of the zinc-air battery further comprises diffusion paper, wherein the diffusion paper is positioned in a gap between the central part of the waterproof breathable layer and the central area and covers the air holes.
3. A method for assembling a positive electrode structure of a zinc-air battery is characterized in that,
the method comprises the following steps:
providing a positive electrode can comprising a bottom wall and a side wall formed around the bottom wall, an inner surface of the bottom wall comprising a central region and a peripheral region surrounding the central region, the central region being recessed downwardly relative to the peripheral region;
placing a positive plate into the positive shell;
and pressurizing the positive plate by cylindrical elastic resin, wherein the pressure is 2-5kgf, and the pressurizing time is 0.1-0.5s, so that the waterproof and breathable layer which is deformed under pressure and does not rebound is deformed to be attached to the edge area, a seal is formed to prevent the electrolyte from entering the central area, and the diameter of the cylindrical elastic resin is the same as that of the positive plate.
4. The method of assembling a positive electrode structure for a zinc-air battery according to claim 3,
the step of pressing the positive plate so that the lower surface of the positive plate is attached to the edge area includes:
applying a pressure of 2-5kgf to the positive plate for 0.1-0.5s.
5. A zinc-air cell, comprising:
a negative electrode cover;
zinc slurry;
a seal ring;
a diaphragm; and
a zinc-air battery positive electrode structure according to any one of claims 1 to 2;
the negative pole lid with the lateral wall of positive plate passes through sealing washer sealing connection, the negative pole lid with the accommodation space is injectd jointly to positive plate, the diaphragm will accommodation space separates for anodal chamber and negative pole chamber, positive plate locates anodal intracavity, the zinc thick liquid is located the negative pole intracavity, the sealing washer with the upper surface butt of positive plate.
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| CN202010029562.4A CN111244582B (en) | 2020-01-10 | 2020-01-10 | Zinc-air battery positive electrode structure, assembly method and zinc-air battery |
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| CN202010029562.4A CN111244582B (en) | 2020-01-10 | 2020-01-10 | Zinc-air battery positive electrode structure, assembly method and zinc-air battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0982315A (en) * | 1995-09-14 | 1997-03-28 | Matsushita Electric Ind Co Ltd | Button type zinc air battery |
| JP2001068170A (en) * | 1999-08-30 | 2001-03-16 | Toshiba Battery Co Ltd | Zinc air battery |
| JP2002343450A (en) * | 2001-05-11 | 2002-11-29 | Toshiba Battery Co Ltd | Zinc air battery |
| CN202678479U (en) * | 2012-06-25 | 2013-01-16 | 无锡耐克赛尔电池有限公司 | Button zinc-air battery capable of preventing solution from being leaked |
| CN202678480U (en) * | 2012-06-25 | 2013-01-16 | 无锡耐克赛尔电池有限公司 | Button zinc-air battery with improved shell structure |
| CN205282614U (en) * | 2016-01-18 | 2016-06-01 | 方倩 | Prevention of liquid leakage zinc air battery unit |
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