WO2023181552A1 - Corps poreux métallique, batterie nickel-zinc et batterie zinc-air - Google Patents

Corps poreux métallique, batterie nickel-zinc et batterie zinc-air Download PDF

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Publication number
WO2023181552A1
WO2023181552A1 PCT/JP2022/047445 JP2022047445W WO2023181552A1 WO 2023181552 A1 WO2023181552 A1 WO 2023181552A1 JP 2022047445 W JP2022047445 W JP 2022047445W WO 2023181552 A1 WO2023181552 A1 WO 2023181552A1
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Prior art keywords
metal
porous
skeleton
layer
zinc
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PCT/JP2022/047445
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English (en)
Japanese (ja)
Inventor
知陽 竹山
一樹 奥野
光靖 小川
晃久 細江
斉 土田
正利 真嶋
淳一 西村
慧大 藤巻
Original Assignee
住友電気工業株式会社
富山住友電工株式会社
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Publication of WO2023181552A1 publication Critical patent/WO2023181552A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H01M10/30—Nickel accumulators
    • 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
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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

Definitions

  • the present disclosure relates to a porous metal body, a nickel-zinc battery, and a zinc-air battery.
  • This application claims priority based on Japanese Patent Application No. 2022-048337, which is a Japanese patent application filed on March 24, 2022. All contents described in the Japanese patent application are incorporated herein by reference.
  • Patent Document 1 a metal mesh is described in Publication No. 2021-501446 (Patent Document 1).
  • the metal mesh described in Patent Document 1 is used, for example, in the negative electrode of a nickel-zinc battery.
  • the metal mesh described in Patent Document 1 has a metal skeleton made of copper and a tin layer coated on the surface of the metal skeleton.
  • the metal porous body of the present disclosure includes a metal skeleton.
  • the inside of the metal skeleton is hollow.
  • the metal skeleton has a tin content of 99.99 mass percent or more.
  • FIG. 1 is a perspective view of a porous metal body 10.
  • FIG. 2 is a schematic cross-sectional view showing the internal structure of the metal porous body 10.
  • FIG. 3 is a schematic cross-sectional view taken along III-III in FIG.
  • FIG. 4 is a schematic perspective view of the cell 14.
  • FIG. 5 is a process diagram showing a method for manufacturing the metal porous body 10.
  • FIG. 6 is a schematic cross-sectional view of the resin molded body 20.
  • FIG. 7 is a process diagram showing a method for manufacturing a porous metal body 10 according to Modification Example 1.
  • FIG. 8 is a process diagram showing a method for manufacturing a porous metal body 10 according to Modification Example 2.
  • FIG. 9 is a schematic cross-sectional view of the nickel-zinc battery 100.
  • FIG. 1 is a perspective view of a porous metal body 10.
  • FIG. 2 is a schematic cross-sectional view showing the internal structure of the metal porous body 10.
  • FIG. 3 is a
  • FIG. 10 is a schematic cross-sectional view of a zinc-air battery 110.
  • FIG. 11 is a graph showing the relationship between the number of charging and discharging cycles and the discharge capacity in Samples 1 to 3.
  • FIG. 12 is a schematic cross-sectional view showing the internal structure of the porous metal body 10B.
  • FIG. 13 is a process diagram showing a method for manufacturing the porous metal body 10B.
  • the present disclosure has been made in view of the problems of the prior art as described above. More specifically, the present disclosure provides a metal porous body that can suppress the generation of zinc dendrites and hydrogen when used in the negative electrode of a nickel-zinc battery or a zinc-air battery.
  • the metal porous body according to the embodiment includes a metal skeleton.
  • the inside of the metal skeleton is hollow.
  • the metal skeleton has a tin content of 99.99 mass percent or more.
  • the metal porous body of (1) above it is possible to suppress the generation of zinc dendrites and hydrogen when used in the negative electrode of a nickel-zinc battery or a zinc-air battery.
  • the metal skeleton may be composed of an electrolytic tin plating layer.
  • the amount of carbon in the metal skeleton may be 100 mg/m 2 or less.
  • the metal skeleton has a first layer including a first surface facing the inside of the metal skeleton and a second surface opposite to the first surface; and a second layer disposed on the surface.
  • the first layer may be a layer of fired tin particles.
  • the second layer may be an electrolytic tin-plated layer.
  • the metal skeleton may be made of a layer of fired tin particles.
  • the metal skeleton may have a three-dimensional network structure.
  • a plurality of continuous pores defined by the metal skeleton may exist inside the metal porous body.
  • the porous metal body may have a porosity of 50% or more.
  • the thickness of the metal skeleton may be 0.3 ⁇ m or more and 100 ⁇ m or less.
  • the metal porous body of (8) above even if the metal skeleton is soft, the rigidity of the metal porous body can be ensured.
  • the nickel-zinc battery according to the embodiment includes a positive electrode and a negative electrode.
  • the negative electrode is formed of the metal porous bodies described in (1) to (8) above.
  • the zinc-air battery according to the embodiment includes a positive electrode and a negative electrode.
  • the negative electrode is formed of the metal porous bodies described in (1) to (8) above.
  • a metal porous body includes a metal skeleton and a core material.
  • the metal skeleton is made of a metal material having a Vickers hardness of 600 Hv or less.
  • the core material is filled inside the metal skeleton.
  • the metal porous body of (11) above even if the metal skeleton is formed of a soft metal material, the rigidity of the metal porous body can be ensured.
  • the tin content of the metal material may be 99.99 mass percent or more.
  • the core material may be formed of a resin material.
  • the content of the core material in the metal porous body may be 5 g/m 2 or more and 100 g/m 2 or less.
  • the metal skeleton may have a three-dimensional network structure.
  • a plurality of continuous pores defined by the metal skeleton may exist inside the metal porous body.
  • the porous metal body may have a porosity of 50% or more.
  • FIG. 1 is a perspective view of a porous metal body 10.
  • the metal porous body 10 has a sheet shape, for example.
  • the thickness of the metal porous body 10 is defined as thickness T1.
  • the thickness T1 is, for example, 0.1 mm or more and 3.0 mm or less. However, the thickness T1 is not limited to this.
  • FIG. 2 is a schematic cross-sectional view showing the internal structure of the porous metal body 10.
  • FIG. 3 is a schematic cross-sectional view taken along III-III in FIG. As shown in FIGS. 2 and 3, the metal porous body 10 has a metal skeleton 11.
  • the metal skeleton 11 has, for example, a three-dimensional network structure. That is, the metal skeleton 11 is integrally and continuously formed.
  • the metal skeleton 11 has a metal layer 12 and a hollow part 13.
  • Metal layer 12 is on the surface of metal skeleton 11 .
  • Hollow portion 13 is located inside metal skeleton 11 . That is, the metal skeleton 11 is hollow inside.
  • the metal skeleton 11 has, for example, a substantially triangular shape in a cross-sectional view perpendicular to its extending direction.
  • the metal layer 12 is formed of a metal material having a tin (Sn) content of 99.99% by mass or more.
  • the metal layer 12 may be formed of a metal material having a tin content of 99.9% by mass or more.
  • the remainder other than tin in the metal layer 12 is, for example, carbon (C), nitrogen (N), copper (Cu), sodium (Na), iron (Fe), lead (Pb), bismuth (Bi), antimony ( Sb), arsenic (As), zinc (Zn), etc.
  • the amount of carbon in the metal skeleton 11 (metal layer 12) is, for example, 100 mg/m 2 or less.
  • the monomer content in the metal skeleton 11 is the value obtained by dividing the mass of carbon contained in the metal skeleton 11 by the apparent area of the metal porous body 10.
  • the apparent area of the metal porous body 10 is the surface area when the metal porous body 10 is regarded as a plate material without considering the internal structure. More specifically, the porous metal body 10 is regarded as a plate material, and the sum of the area of the two main surfaces of the plate material and the area of the four side surfaces of the plate material is the apparent area of the porous metal body 10.
  • the tin content in the metal layer 12 is measured by the following method.
  • ICP inductively coupled plasma
  • the content of tin in the metal layer 12 can be obtained by dividing the mass of tin in this solution by the mass of the porous metal body 10 dissolved in this solution.
  • the amount of carbon in the metal skeleton 11 can be obtained by dividing the mass of carbon in the metal skeleton 11 obtained by non-dispersive infrared analysis using a carbon-in-metal analyzer by the apparent area of the porous metal body 10. .
  • the metal layer 12 may have a first layer 12a and a second layer 12b.
  • the first layer 12a is a layer on the hollow portion 13 side.
  • the second layer 12b is a layer on the surface side of the metal skeleton 11 (that is, on the pore 15 side, which will be described later).
  • the first layer 12a is a sputtering layer formed by sputtering, for example.
  • the first layer 12a has a first surface and a second surface.
  • the first surface is a surface facing the hollow portion 13 side.
  • the second surface is the opposite surface to the first surface.
  • the second layer 12b is arranged on the second surface of the first layer 12a.
  • the second layer 12b is an electrolytic tin plating layer formed by electrolytic plating, for example.
  • the metal layer 12 may consist of an electrolytic tin plating layer.
  • the metal layer 12 may consist of a layer of fired tin particles. In the metal layer 12, a plurality of tin particles are necked together.
  • the first layer 12a may be a layer of fired tin particles, and the second layer 12b may be an electrolytic tin plating layer formed by electrolytic plating.
  • the thickness of the metal skeleton 11 (thickness of the metal layer 12) is defined as thickness T2. From the viewpoint of ensuring the rigidity of the metal skeleton 11, the thickness T2 is preferably 0.3 ⁇ m or more and 100 ⁇ m or less.
  • a cross-sectional image of the metal skeleton 11 perpendicular to the extending direction of the metal skeleton 11 is acquired using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the thickness of the metal layer 12 is measured based on this cross-sectional image. At this time, the thickness of the metal layer 12 is measured at the location where it has the minimum value. This measured value becomes the thickness T2.
  • the metal porous body 10 is composed of a plurality of cells 14.
  • FIG. 4 is a schematic perspective view of the cell 14. Only one cell 14 is shown in FIG. As shown in FIG. 4, the cell 14 has a polyhedral structure, and the metal skeleton 11 corresponds to each side of the polyhedral structure.
  • the polyhedral structure of the cell 14 is, for example, a dodecahedral structure. However, the polyhedral structure of the cell 14 is not limited to this.
  • the polyhedral structure of the cell 14 may be a cubic structure, an icosahedral structure, or the like.
  • the metal porous body 10 is composed of a plurality of cells 14, a plurality of pores 15 are present inside the metal porous body 10.
  • the cell 14 has a plurality of holes 16.
  • the periphery of the hole 16 is surrounded by the metal skeleton 11.
  • the pores 16 communicate with the pores 15. Therefore, the pores 15 of each of the two adjacent cells 14 are continuous pores.
  • the porosity of the metal porous body 10 is, for example, 50% or more.
  • the porous metal body 10 preferably has a porosity of 70% or more, more preferably 90% or more.
  • the porosity of the porous metal body 10 is calculated as follows: ⁇ 1-A/(B ⁇ C ) ⁇ 100.
  • the apparent volume of the metal porous body 10 is calculated by width ⁇ length ⁇ thickness T1.
  • the average diameter of the pores 15 is, for example, 200 ⁇ m or more and 1000 ⁇ m or less.
  • a cross-sectional image of the porous metal body 10 is acquired using a SEM.
  • the value obtained by dividing 25.4 mm by the number of counted cells 14 becomes the average diameter of the pores 15.
  • FIG. 5 is a process diagram showing a method for manufacturing the porous metal body 10.
  • the method for manufacturing the porous metal body 10 includes a preparation step S1, a conductive treatment step S2, a plating step S3, and a resin molded body removal step S4.
  • the conductive treatment step S2 is performed after the preparation step S1.
  • the plating step S3 is performed after the conductive treatment step S2.
  • the resin molded body removal step S4 is performed after the plating step S3.
  • the resin molded body 20 is prepared.
  • the resin molded body 20 is a foamed resin.
  • the resin molded body 20 is made of a resin material such as urethane.
  • FIG. 6 is a schematic cross-sectional view of the resin molded body 20. As shown in FIG. 6, the resin molded body 20 has a skeleton 21. As shown in FIG. The skeleton 21 has a three-dimensional network structure. The skeleton 21 is solid.
  • a plurality of pores 22 exist inside the resin molded body 20.
  • the pores 22 are defined by the skeleton 21 .
  • the resin molded body 20 has been subjected to film removal treatment (for example, removal of partition walls between two adjacent pores 22 by performing an explosion treatment). Therefore, the plurality of pores 22 are continuous pores.
  • the porosity of the resin molded body 20 and the average diameter of the pores 22 are appropriately selected according to the porosity of the metal porous body 10 and the average diameter of the pores 15.
  • conductive treatment is performed on the surface of the skeleton 21.
  • This conductive treatment is performed, for example, by sputtering tin onto the surface of the skeleton 21.
  • a conductive layer is formed on the surface of the skeleton 21. Note that by performing the above conductive treatment, a conductive layer is also formed on the surface of the partition between two adjacent pores 22.
  • an electrolytic plating layer is formed on the conductive layer by applying electricity to the conductive layer formed in the conductive treatment step S2 to perform electrolytic plating.
  • the resin molded body 20 is removed.
  • the resin molded body 20 is made of an ionic liquid at a temperature lower than the melting point of the constituent material (tin) of the conductive layer and the plating layer (for example, 175° C. when the conductive layer and the plating layer are formed of tin). (e.g. diethanolamine).
  • the above-mentioned conductive layer and plating layer become the metal layer 12.
  • the conductive treatment step S2 may be performed by applying carbon to the surface of the skeleton 21. In this case, only the plating layer formed in the plating step S3 constitutes the metal layer 12.
  • FIG. 7 is a process diagram showing a method for manufacturing a porous metal body 10 according to Modification Example 1. As shown in FIG. 7, a fired layer forming step S5 may be performed instead of the conductive treatment step S2 and the plating step S3.
  • a paste containing tin particles and a binder is applied onto the surface of the skeleton 21 and the surface of the partition between two adjacent pores 22.
  • the binder is, for example, carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • the applied paste is fired. This calcination takes place at a temperature below the melting point of tin. As a result, adjacent tin particles in the applied paste are necked and metallurgically bonded, and the applied paste becomes a layer of fired tin particles. This layer of fired tin particles becomes the metal layer 12 after the resin molded body removal step S4.
  • FIG. 8 is a process diagram showing a method for manufacturing a porous metal body 10 according to Modification 2.
  • the method for manufacturing the porous metal body 10 may include a fired layer forming step S5 instead of the conductive treatment step S2.
  • the layer of fired tin particles becomes a conductive layer
  • electrolytic plating is performed by applying electricity to the layer of fired tin particles.
  • the fired tin particle layer and the plating layer formed in the plating step S3 become the metal layer 12.
  • the porous metal body 10 is used, for example, in a nickel-zinc battery 100 or a zinc-air battery 110.
  • FIG. 9 is a schematic cross-sectional view of the nickel-zinc battery 100.
  • the nickel-zinc battery 100 includes a negative electrode 101 (zinc negative electrode), a positive electrode 102 (nickel hydroxide positive electrode), and a separator 103.
  • a metal porous body 10 whose interior is filled with a negative electrode active material is used.
  • the negative electrode active material contains zinc oxide.
  • a porous metal body filled with a positive electrode active material is used.
  • the positive electrode active material contains nickel hydroxide.
  • Separator 103 is sandwiched between negative electrode 101 and positive electrode 102. Separator 103 is made of a material that is permeable to hydroxide ions.
  • the electrolytic solution is, for example, a potassium hydroxide aqueous solution in which zinc oxide is dissolved.
  • nickel hydroxide and hydroxide ions in the electrolytic solution react to emit electrons and generate nickel oxyhydroxide.
  • electrons released from the positive electrode 102, zinc oxide, hydroxide ions in the electrolytic solution, and water in the electrolytic solution react to generate zinc.
  • discharge a reaction opposite to the above occurs, and current flows from the positive electrode 102 to the negative electrode 101.
  • FIG. 10 is a schematic cross-sectional view of the zinc-air battery 110.
  • the zinc-air battery 110 includes a negative electrode 111 (zinc negative electrode), a positive electrode 112 (air electrode), and a separator 113.
  • a metal porous body 10 whose interior is filled with a negative electrode active material is used.
  • the negative electrode active material contains zinc oxide.
  • a porous metal body is used for the positive electrode 112.
  • Separator 113 is sandwiched between negative electrode 111 and positive electrode 112.
  • the separator 113 is made of a material that is permeable to hydroxide ions.
  • the negative electrode 111 is immersed in an electrolytic solution.
  • hydroxide ions react at the positive electrode 112 to release electrons and generate oxygen and water. Further, during charging, at the negative electrode 111, electrons released from the positive electrode 112, zinc oxide, hydroxide ions in the electrolytic solution, and water in the electrolytic solution react to generate zinc. On the other hand, when discharge is occurring, a reaction opposite to the above occurs, and current flows from the positive electrode 112 to the negative electrode 111.
  • a porous metal body according to a comparative example is referred to as a porous metal body 10A.
  • the porous metal body 10A differs from the porous metal body 10 in that the metal skeleton 11 is made of copper, and the surface of the metal skeleton 11 is coated with a tin layer.
  • the tin layer is merely coated on the surface of the metal skeleton 11 formed of copper. Therefore, if the surface of the metal skeleton 11 is exposed due to defects in the tin layer, etc., that portion becomes a starting point for dendrite or hydrogen generation. In this way, when the metal porous body 10A is used as the negative electrode of the nickel-zinc battery 100 or the zinc-air battery 110, generation of zinc dendrites or hydrogen on the surface of the negative electrode of the nickel-zinc battery 100 or the zinc-air battery 110 can be effectively suppressed. Sometimes that's enough.
  • the metal skeleton 11 is formed almost entirely of tin, so materials other than tin are not exposed on the surface of the negative electrode, and the generation of zinc dendrites or hydrogen is suppressed. It turns out.
  • Samples 1 to 3 were prepared as samples of nickel-zinc batteries.
  • porous metal bodies made of nickel porous nickel bodies
  • the inside of the nickel porous body was filled with positive electrode active material slurry.
  • the composition of the positive electrode active material slurry after drying is 90% by mass of nickel hydroxide, 7% by mass of cobalt hydroxide, 0.3% by mass of CMC (granulated binder), and 2.7% by mass of SBR (styrene butadiene rubber). Ta.
  • the fixed content ratio in the positive electrode active material was 78% by mass.
  • a nickel porous body with a thickness of 1.2 mm and a metal content of 300 g/m 2 was prepared.
  • the inside of the nickel porous body was filled with the positive electrode active material slurry.
  • the nickel porous body filled with the positive electrode active material slurry was dried at 100° C. and then roll pressed to make it densified.
  • a positive electrode with an electrode area of 30 mm x 30 mm, a thickness of 0.45 mm, and a calculated capacity of 240 mAh was obtained. Note that a lead made of nickel was attached to the positive electrode by welding.
  • a metal porous body (copper porous body) made of copper is used, and for the negative electrode of sample 2, a metal porous body (copper porous body) made of copper and whose surface is tin-plated is used. Tin-plated copper porous body) is used.
  • porous metal body 10 was used. In the metal porous bodies of Samples 1 to 3, the amount of metal was 200 g/m 2 and the thickness was 1.0 mm. The porous metal bodies of Samples 1 to 3 had porosity of 97.8%, 97.8%, and 97.2%, respectively.
  • the metal porous bodies used in Samples 1 to 3 are shown in Table 1.
  • the inside of the metal porous body was filled with the negative electrode active material slurry.
  • the composition of the negative electrode active material slurry after drying is 90% by mass of zinc oxide, 5% by mass of AB (acetylene black), 0.5% by mass of CMC, 1.5% by mass of PTFE (polytetrafluoroethylene), and 3% by mass of SBR. Ta.
  • the fixed content ratio in the negative electrode active material was 60% by mass.
  • the porous bodies shown in Table 2 were prepared.
  • the inside of the metal porous body was filled with the negative electrode active material slurry.
  • the metal porous body filled with the negative electrode active material slurry was dried at 100° C. and then roll pressed to make it dense.
  • a negative electrode with an electrode area of 30 mm x 30 mm and a calculated capacity of 400 mAh was obtained.
  • a lead made of nickel was attached to the negative electrode by welding.
  • an electrode group was obtained by interposing an anionic conductive film with a thickness of 150 ⁇ m as a separator between the above-mentioned positive electrode and negative electrode. This electrode group was placed inside a polypropylene bag, and the bag was sandwiched and fixed between acrylic plates from the outside.
  • As the electrolytic solution a 1 mol/L potassium hydroxide aqueous solution in which zinc oxide was saturated and dissolved was used. The electrolytic solution was supplied into the bag until the electrode group was completely immersed, and the electrode group was impregnated under reduced pressure.
  • Samples 1 to 3 were activated prior to evaluation. In this activation, a cycle of first charging to 1.9V at 0.1C and then discharging to 1.5V at 0.1C was repeated three times. Second, a cycle of charging to 1.9V at 0.2C and then discharging to 1.5V at 0.2C was repeated three times. Thirdly, a cycle of charging to 1.9V at 0.5C and then discharging to 1.5V at 0.5C was repeated three times.
  • the discharge capacities of the negative electrodes of Samples 1 to 3 were compared.
  • charging was performed at 0.5C to 1.9V in a constant temperature bath at 30°C.
  • the cutoff during CV was set at 5 hours or 10 mA in current value.
  • discharge was performed at 0.2C, 0.5C, and 1C until the voltage reached 1.5V.
  • samples 1 to 3 were charged in the same manner as in the first test. After charging was completed, samples 1 to 3 were stored in a constant temperature bath at 45° C. for 15 days. After this storage, Samples 1 to 3 were discharged at 0.2C until the voltage reached 1.5V, and the remaining capacities were compared.
  • the results of the second test are shown in Table 3.
  • the remaining capacity of Sample 3 was greater than the remaining capacity of Sample 1 and the remaining capacity of Sample 2. From this, it was confirmed that the use of the metal porous body 10 as the negative electrode of a nickel-zinc battery exhibits excellent self-discharge characteristics.
  • porous metal body 10B porous metal body 10B according to a second embodiment will be described.
  • the points different from the metal porous body 10 will be mainly explained, and redundant explanations will not be repeated.
  • the metal porous body 10B has a metal skeleton 11.
  • the metal skeleton 11 has a metal layer 12 and a hollow part 13. Regarding these points, the configuration of the metal porous body 10B is common to the configuration of the metal porous body 10.
  • the Vickers hardness of the metal material constituting the metal layer 12 is 600 Hv or less. That is, in the metal porous body 10B, the tin content of the metal layer 12 may be 99.99 mass percent or more (or 99.9 mass percent or more), but it does not have to be.
  • Specific examples of metal materials having a Vickers hardness of 600 Hv or less include aluminum, copper, nickel, etc. in addition to tin.
  • the Vickers hardness of the metal material constituting the metal layer 12 is measured according to the Vickers hardness test method defined in JIS Z 2244.
  • FIG. 12 is a schematic cross-sectional view showing the internal structure of the porous metal body 10B.
  • the metal porous body 10B further includes a core material 17.
  • the core material 17 is made of a resin material such as urethane.
  • the core material 17 is filled in the hollow portion 13.
  • the content of the core material 17 in the metal porous body 10B is preferably 5 g/m 2 or more and 100 g/m 2 or less.
  • the content of the core material 17 in the porous metal body 10B is obtained by dividing the mass of the core material 17 measured by total organic carbon (TOC) measurement by the apparent area of the porous metal body 10. .
  • TOC total organic carbon
  • FIG. 13 is a process diagram showing a method for manufacturing the porous metal body 10B.
  • the method for manufacturing the porous metal body 10B includes a preparation step S1, a conductive treatment step S2, and a plating step S3.
  • the method for manufacturing the metal porous body 10B may include a fired layer forming step S5 in place of the conductive treatment step S2 and the plating step S3, and a fired layer forming step in place of the conductive treatment step S2. It may have S5. Regarding these points, the method for manufacturing the porous metal body 10B is common to the method for manufacturing the porous metal body 10.
  • the method for manufacturing the metal porous body 10B does not include the resin molded body removal step S4. Therefore, the resin molded body 20 remains in the metal porous body 10B as the core material 17. In this regard, the method for manufacturing the porous metal body 10B is different from the method for manufacturing the porous metal body 10.
  • the metal porous body 10 When a load is applied to the porous metal body 10 from the outside, the load is supported only by the metal skeleton 11. Therefore, the metal porous body 10 is easily deformed by external loads and may have low rigidity.
  • the metal porous body 10B when a load is applied from the outside, the load is supported not only by the metal skeleton 11 but also by the core material 17, so that it is difficult to deform under the load. Therefore, according to the metal porous body 10B, the rigidity is improved.
  • the porous metal body 10 may have too low rigidity to become a self-supporting body.
  • the core material 17 improves the rigidity, it is possible to make it a self-supporting body even when the metal skeleton 11 is formed of a soft metal such as tin.

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Abstract

Ce corps poreux métallique est pourvu d'un squelette métallique. L'intérieur du squelette métallique est creux. Le squelette métallique contient de l'étain dans une quantité égale ou supérieure à 99,99 % en masse.
PCT/JP2022/047445 2022-03-24 2022-12-22 Corps poreux métallique, batterie nickel-zinc et batterie zinc-air WO2023181552A1 (fr)

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JPH07138792A (ja) * 1993-09-14 1995-05-30 Katayama Tokushu Kogyo Kk 金属多孔体および該金属多孔体の製造方法
JPH07326358A (ja) * 1994-06-02 1995-12-12 Matsushita Electric Ind Co Ltd アルカリ電池
CN101824619A (zh) * 2010-06-01 2010-09-08 武汉银泰科技电源股份有限公司 一种泡沫锡材料的制备方法
JP2011246779A (ja) * 2010-05-28 2011-12-08 Sumitomo Electric Ind Ltd アルミニウム構造体の製造方法およびアルミニウム構造体
WO2012049991A1 (fr) * 2010-10-13 2012-04-19 住友電気工業株式会社 Corps métallique poreux, son procédé de production et batterie à sels fondus
JP2012132083A (ja) * 2010-12-24 2012-07-12 Sumitomo Electric Ind Ltd 高耐食性を有する金属多孔体及びその製造方法
CN109609795A (zh) * 2018-11-30 2019-04-12 常德力元新材料有限责任公司 一种三维多孔锡材料的制备方法
WO2019116631A1 (fr) * 2017-12-15 2019-06-20 富山住友電工株式会社 Procédé de fabrication d'un corps métallique poreux, et dispositif de placage

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07138792A (ja) * 1993-09-14 1995-05-30 Katayama Tokushu Kogyo Kk 金属多孔体および該金属多孔体の製造方法
JPH07326358A (ja) * 1994-06-02 1995-12-12 Matsushita Electric Ind Co Ltd アルカリ電池
JP2011246779A (ja) * 2010-05-28 2011-12-08 Sumitomo Electric Ind Ltd アルミニウム構造体の製造方法およびアルミニウム構造体
CN101824619A (zh) * 2010-06-01 2010-09-08 武汉银泰科技电源股份有限公司 一种泡沫锡材料的制备方法
WO2012049991A1 (fr) * 2010-10-13 2012-04-19 住友電気工業株式会社 Corps métallique poreux, son procédé de production et batterie à sels fondus
JP2012132083A (ja) * 2010-12-24 2012-07-12 Sumitomo Electric Ind Ltd 高耐食性を有する金属多孔体及びその製造方法
WO2019116631A1 (fr) * 2017-12-15 2019-06-20 富山住友電工株式会社 Procédé de fabrication d'un corps métallique poreux, et dispositif de placage
CN109609795A (zh) * 2018-11-30 2019-04-12 常德力元新材料有限责任公司 一种三维多孔锡材料的制备方法

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