WO2024111573A1 - 亜鉛電極 - Google Patents

亜鉛電極 Download PDF

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Publication number
WO2024111573A1
WO2024111573A1 PCT/JP2023/041776 JP2023041776W WO2024111573A1 WO 2024111573 A1 WO2024111573 A1 WO 2024111573A1 JP 2023041776 W JP2023041776 W JP 2023041776W WO 2024111573 A1 WO2024111573 A1 WO 2024111573A1
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Prior art keywords
zinc
mass
conductive layer
metal
layer
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Ceased
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PCT/JP2023/041776
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English (en)
French (fr)
Japanese (ja)
Inventor
弘子 原田
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2024560156A priority Critical patent/JPWO2024111573A1/ja
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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
    • H01M4/02—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 invention relates to a zinc electrode. More specifically, the present invention relates to a zinc electrode used in a battery and a battery comprising the zinc electrode.
  • Zinc anodes which use zinc-containing substances as the anode active material, have long been researched as batteries have become more widespread, and in particular, air-zinc primary batteries, manganese-zinc primary batteries, and silver-zinc primary batteries have been put to practical use and are widely used around the world.
  • Patent No. 3386805 Japanese Patent Application Laid-Open No. 3-130393 Japanese Patent Application Laid-Open No. 3-130395 Japanese Patent Application Laid-Open No. 3-130394 Japanese Patent Application Laid-Open No. 61-208756 JP 2007-234484 A JP 2008-66145 A JP 2008-305698 A JP 2008-71533 A JP 2008-159497 A JP 2009-140676 A
  • zinc electrodes have issues specific to zinc electrodes, such as the dissolution and precipitation reaction of zinc-containing substances occurring near the active material layer, and repeated charging and discharging over a long period of time can cause the battery reaction to become uneven, or additives such as conductive additives to become unevenly distributed and lose their effectiveness, resulting in a shortened lifespan.
  • the present invention was made in consideration of the above-mentioned current situation, and aims to provide a method for extending the life of a battery comprising a zinc electrode and improving the weight energy density.
  • the inventors have investigated various methods for extending the life of zinc batteries, and have focused on making the current collector fibrous.
  • the inventors have discovered that if a current collector is made up of resin fibers and a conductive layer covering the surface of the resin fibers, and a zinc electrode is made up of a zinc-containing material as the active material, the electrolyte can be impregnated well even in a thick film, making the battery reaction uniform and stable, thereby extending the life of the zinc battery and providing excellent energy density by weight. They have come up with the idea of brilliantly solving the above problems, and have arrived at the present invention.
  • the present invention (1) is a current collector including resin fibers and a conductive layer covering the surface thereof, and a zinc electrode including a zinc-containing material as an active material.
  • the present invention (2) is a zinc electrode of the present invention (1), in which the conductive layer contains a metal and/or a metal oxide.
  • the present invention (3) is a zinc electrode of the present invention (2), in which the metal and/or metal oxide contains at least one metal element selected from the group consisting of zinc, tin, bismuth, indium, lead, cadmium, gold, copper, and silver.
  • the present invention (4) is a zinc electrode in any combination with any of the present inventions (1) to (3), in which the conductive layer includes a top surface layer containing at least one metal selected from the group consisting of zinc, tin, bismuth, indium, lead, and cadmium and/or its metal oxide.
  • the present invention (5) is a zinc electrode in any combination with any of the present inventions (1) to (4), in which the conductive layer includes a top surface layer and an intermediate layer between the top surface layer and the resin fiber, and the intermediate layer includes at least one metal selected from the group consisting of gold, copper, silver, and tin and/or a metal oxide thereof.
  • the present invention (6) is a zinc electrode in any combination with any of the present inventions (1) to (5) in which the conductive layer contains a metal.
  • the present invention (7) is a zinc electrode in any combination with any of the present inventions (1) to (6), in which the average thickness of the conductive layer is 0.1 to 40 ⁇ m.
  • the current collector is a porous current collector
  • the zinc electrode is a zinc electrode in any combination with any of the present inventions (1) to (7), which contains a zinc-containing material as an active material in the pores of the porous current collector.
  • the present invention (9) is a battery comprising a zinc electrode according to any one of the present inventions (1) to (8).
  • the zinc electrode of the present invention has the above-mentioned configuration, and can extend the life of a battery that includes a zinc electrode and improve the weight energy density.
  • FIG. 1 is a graph showing charge/discharge curves at the 100th cycle of the battery of the example and the battery of the comparative example.
  • the zinc electrode of the present invention comprises a current collector including resin fibers and a conductive layer covering the surface of the current collector, and a zinc-containing material as an active material.
  • the current collector includes a resin fiber (core material) and a conductive layer covering the surface of the resin fiber.
  • the conductive layer may completely cover the resin fiber, but may not completely cover the resin fiber, and a part of the resin fiber may be exposed.
  • the conductive layer is a layer made of a conductive material having an electrical conductivity of 1 ⁇ 10 6 S/m or more at 0° C.
  • the electrical conductivity is preferably 5 ⁇ 10 6 S/m or more.
  • the electrical resistance is obtained by measuring the electrical resistance in the thickness direction of the conductive layer using a tester.
  • the conductive material may be any material that exhibits the above-mentioned specific electrical conductivity in the conductive layer, and may be, for example, one or more of metals such as zinc, tin, bismuth, indium, lead, cadmium, gold, copper, brass, silver, and tin, metal compounds such as metal oxides, conductive carbon, conductive ceramics, and conductive polymers.
  • metals such as zinc, tin, bismuth, indium, lead, cadmium, gold, copper, brass, silver, and tin
  • metal compounds such as metal oxides, conductive carbon, conductive ceramics, and conductive polymers.
  • the conductive layer contains a metal and/or a metal oxide, and it is more preferable that the conductive layer is a metal layer made of a metal, a metal oxide layer made of a metal oxide, or a laminate of a metal layer and/or a metal oxide layer.
  • the conductive layer contains a metal, and it is particularly preferable that the conductive layer is a metal layer made of a metal or a laminate thereof.
  • the metal when simply referring to a metal, the metal means a simple metal or an alloy.
  • the metal oxide is not particularly limited as long as the conductive layer exhibits the above-mentioned specific electrical conductivity, but indium tin oxide (ITO) and the like are preferred from the viewpoint of improving electronic conductivity.
  • the metal oxide may be a low-valent metal oxide (e.g., Cu 2 O, Ag 2 O, SnO, etc.) formed by forming a conductive layer made of an easily oxidizable metal (e.g., a metal with a high ionization tendency such as zinc or tin, or copper , silver, etc.) and then oxidizing the surface or the entire conductive layer with oxygen in the outside air.
  • an easily oxidizable metal e.g., a metal with a high ionization tendency such as zinc or tin, or copper , silver, etc.
  • the above metals and/or metal oxides are not particularly limited as long as they have the above electrical conductivity, but preferably contain at least one metal element selected from the group consisting of zinc, tin, bismuth, indium, lead, cadmium, gold, copper, and silver.
  • the conductive layer preferably includes a top surface layer containing at least one metal selected from the group consisting of zinc, tin, bismuth, indium, lead, and cadmium and/or a metal oxide thereof, and more preferably includes a top surface layer containing at least one metal selected from the group consisting of zinc, tin, bismuth, indium, lead, and cadmium and/or a metal oxide thereof.
  • the conductive layer further preferably includes a top surface layer containing at least one metal selected from the group consisting of zinc, tin, bismuth, indium, lead, and cadmium, and particularly preferably includes a top surface layer containing at least one metal selected from the group consisting of zinc, tin, bismuth, indium, lead, and cadmium.
  • These metals have a high hydrogen overvoltage, and can sufficiently suppress the generation of hydrogen by forming a mixed potential with the zinc-containing material, which is an active material, and can further suppress the self-discharge of the zinc-containing material.
  • the metal element constituting the metal or metal oxide of the outermost surface layer from the viewpoint of improving safety, zinc, tin, bismuth, and indium are more preferable. Also, from the viewpoint of reducing costs, zinc, tin, bismuth, lead, and cadmium are more preferable. From both of these viewpoints, zinc, tin, and bismuth are particularly preferable.
  • the conductive layer preferably does not contain nickel, iron, or steel (SUS) in the outermost layer. More preferably, the conductive layer further does not contain copper in the outermost layer.
  • These metals have low hydrogen overvoltage, and by not using these metals in the outermost layer, it is possible to sufficiently suppress the generation of hydrogen by forming a mixed potential between these metals and the zinc-containing material, which is an active material, and to further suppress the self-discharge of the zinc-containing material.
  • the conductive layer is only one layer, the conductive layer itself becomes the outermost layer.
  • the conductive layer includes an outermost layer and an intermediate layer between the outermost layer and the resin fiber, and the intermediate layer preferably includes at least one metal selected from the group consisting of gold, copper, silver, and tin and/or its metal oxide, and more preferably includes a metal layer including at least one metal selected from the group consisting of gold, copper, silver, and tin, a metal oxide layer including its metal oxide, or a laminate including the metal layer and/or the metal oxide layer (a laminate of the metal layers, a laminate of the metal oxide layers, or a laminate of the metal layer and the metal oxide layer).
  • the intermediate layer further preferably includes at least one metal selected from the group consisting of gold, copper, silver, and tin, and is particularly preferably a metal layer including at least one metal selected from the group consisting of gold, copper, silver, and tin.
  • the metal element constituting the metal or metal oxide of the intermediate layer copper and tin are more preferable from the viewpoint of cost reduction, and gold, copper and silver are more preferable from the viewpoint of electronic conductivity, and copper is particularly preferable from both of these viewpoints.
  • the conductive layer When a metal with low hydrogen overvoltage such as gold, copper, cobalt, or iron is used in the conductive layer, it is preferable to further laminate a metal with high hydrogen overvoltage such as zinc, tin, bismuth, indium, lead, or cadmium on the surface in order to suppress self-discharge of the zinc-containing material.
  • a metal with high hydrogen overvoltage such as zinc, tin, bismuth, indium, lead, or cadmium
  • the intermediate layer in the conductive layer contains copper and the outermost layer contains zinc and/or tin. Zinc and tin are easier to plate when the base material is copper than when the base material is resin fiber, which is also advantageous in terms of production.
  • the outermost layer is zinc, the zinc in the outermost layer is not in a particle form like zinc active material, so its function as an active material is limited.
  • the top surface layer may completely cover the intermediate layer, or may not completely cover the intermediate layer, leaving part of the intermediate layer exposed.
  • the conductive layer is a layer of a metal with a high hydrogen overvoltage laminated on the surface of a metal with a low hydrogen overvoltage, it is particularly preferable that the top surface layer substantially completely covers the intermediate layer.
  • each layer When the conductive layer is formed by laminating multiple layers, the composition and thickness of each layer may be the same or different. Also, the outermost layer is usually only one layer, but the intermediate layer may be one or more layers. When the intermediate layer is made up of multiple layers, each layer may or may not completely cover the layer or resin fiber below it.
  • the total content of metal and metal oxide (more preferably, the content of metal) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. It is particularly preferable that the conductive layer is substantially composed of metal or metal and metal oxide, and most preferably substantially composed of metal.
  • the conductive layer preferably has an average thickness of 0.1 ⁇ m or more.
  • the conductive layer preferably has an average thickness of 40 ⁇ m or less.
  • the conductive layer preferably has an average thickness of 0.1 to 40 ⁇ m.
  • the conductive layer has better electronic conductivity.
  • the conductive layer has an average thickness of 40 ⁇ m or less, the generation of cracks can be more sufficiently prevented.
  • the average thickness is more preferably 0.2 ⁇ m or more.
  • the average thickness is more preferably 35 ⁇ m or less.
  • the average thickness is more preferably 0.2 to 35 ⁇ m.
  • the average thickness is measured by observing a cross section of the current collector under an electron microscope and calculating the simple average of thicknesses at any ten points of the conductive layer. Specifically, it can be determined as follows. 1) The current collector (porous body) is cut in the thickness direction, and the resulting cross section is observed with a scanning electron microscope. Cross-sectional images of 10 locations in the thickness direction of the fibers on which the conductive layer is formed are arbitrarily selected. 2) Next, in each of the 10 selected cross-sectional images, the thickness of the conductive layer is measured at 10 arbitrarily selected locations, and the simple average of the obtained 10 measured values is regarded as the thickness of the conductive layer in each cross-sectional image.
  • the thicknesses of the conductive layer in each cross-sectional image are simply averaged, and the obtained value is regarded as the average thickness of the conductive layer in the current collector.
  • the method for cutting the current collector (porous body) in the thickness direction is not particularly limited, but may be a method of mechanically cutting with a razor or a method of further subjecting the cross section obtained after mechanical cutting to an ion milling treatment, etc.
  • a razor T5332 TEFLON (registered trademark) COATED) manufactured by JEOL Ltd. may be used.
  • the scanning electron microscope is not particularly limited, but for example, a TM3000 Miniscope manufactured by Hitachi Technologies, Ltd. can be used.
  • each layer can be measured in the same manner.
  • the average thickness of the conductive layer of the current collector in the zinc electrode can be determined in a similar manner.
  • the ratio of the average thickness of the outermost layer to the average thickness of the intermediate layer can be, for example, 1:100 to 100:1, preferably 1:40 to 40:1, more preferably 1:20 to 20:1, even more preferably 1:10 to 10:1, even more preferably 1:5 to 5:1, even more preferably 1:2 to 5:1, even more preferably 1:1 to 4:1, and particularly preferably 4:3 to 3:1.
  • the mass proportion of the conductive layer is preferably 0.5 mass% or more, more preferably 1 mass% or more, even more preferably 3 mass% or more, and particularly preferably 5 mass% or more, based on 100 mass% of the zinc electrode of the present invention.
  • the mass proportion of the conductive layer is preferably 40 mass % or less, more preferably 35 mass % or less, and even more preferably 30 mass % or less, based on 100 mass % of the zinc electrode of the present invention.
  • the mass proportion of the conductive layer is preferably 0.5 to 40 mass%, more preferably 1 to 35 mass%, even more preferably 3 to 30 mass%, and particularly preferably 5 to 30 mass%, based on 100 mass% of the zinc electrode of the present invention.
  • the mass ratio of the conductive layer can be determined by combining ICP optical emission spectroscopy with, as necessary, EDX analysis (energy dispersive X-ray analysis) such as SEM-EDX analysis and TEM-EDX analysis.
  • EDX analysis energy dispersive X-ray analysis
  • SEM-EDX analysis energy dispersive X-ray analysis
  • TEM-EDX analysis energy dispersive X-ray analysis
  • the measurement sample a solution obtained by acid decomposing (for example, using a microwave decomposition device) a predetermined amount of zinc electrode.
  • the ICPE-9000 manufactured by Shimadzu Corporation can be used as the ICP optical emission spectroscopy device
  • the ETHOS One manufactured by Milestone General can be used as the microwave decomposition device.
  • resin fibers examples include hydrocarbon moiety-containing polymers such as polyethylene and polypropylene, polytetrafluoroethylene moiety-containing polymers, polyvinylidene fluoride moiety-containing polymers, cellulose-based polymers such as cellulose, fibrillated cellulose, viscose rayon, cellulose acetate, hydroxyalkyl cellulose, and carboxymethyl cellulose, polyvinyl alcohol-based polymers such as polyvinyl alcohol and partial acetalization products of polyvinyl alcohol (for example, vinylon), aromatic ring moiety-containing polymers such as cellophane, polystyrene, and polyphenylene sulfide, polyacrylonitrile moiety-containing polymers, polyacrylamide moiety-containing polymers, polyvinyl halide moiety-containing polymers, nylon, and the like.
  • hydrocarbon moiety-containing polymers such as polyethylene and polypropylene
  • polytetrafluoroethylene moiety-containing polymers such as cellulose, fibrillated
  • the fiber examples include polyamide-containing polymers such as polyisoprenol, polyimide-containing polymers, ester-containing polymers, poly(meth)acrylic acid-containing polymers, poly(meth)acrylate-containing polymers, hydroxyl-containing polymers such as polyisoprenol and poly(meth)allyl alcohol, carbonate-containing polymers such as polycarbonate, ester-containing polymers such as polyester, carbamate- or carbamide-containing polymers such as polyurethane, agar, gel compounds, organic-inorganic hybrid (composite) compounds, ion-exchangeable polymers, cyclized polymers, sulfonate-containing polymers, quaternary ammonium salt-containing polymers, quaternary phosphonium salt-containing polymers, and ether-containing polymers.
  • polyamide-containing polymers such as polyisoprenol, polyimide-containing polymers, ester-containing polymers, poly(meth)acrylic acid-containing polymers,
  • hydrocarbon-containing polymers such as polypropylene, polyvinyl alcohol-based polymers, aromatic ring-containing polymers, and polyamide-containing polymers are more preferable.
  • These fibers may be used alone or in combination of two or more.
  • the zinc electrode can be made flexible, which is thought to contribute to preventing cracks and the like from occurring in the zinc electrode.
  • the resin fibers may be an insulating material that does not substantially conduct electricity.
  • the resin fibers may be hydrophilized by a method of adding a surfactant, a method of sulfonation, fluorination, grafting, or the like using chemicals such as fuming sulfuric acid or chlorosulfonic acid, or a method using corona discharge or plasma discharge.
  • a surfactant e.g., a surfactant for sulfonation
  • fluorination e.g., fluorination
  • grafting e.g., grafting, or the like using chemicals such as fuming sulfuric acid or chlorosulfonic acid, or a method using corona discharge or plasma discharge.
  • the resin fiber is a polymer containing a hydrocarbon moiety
  • it is preferable that the resin fiber has been subjected to a hydrophilization treatment.
  • the resin fiber include nonwoven fabric, woven fabric, mesh, felt, etc., and among these, nonwoven fabric and mesh are preferred.
  • the resin fibers preferably have a density of 0.01 g/cm 3 or more, more preferably 0.03 g/cm 3 or more, even more preferably 0.05 g/cm 3 or more, and particularly preferably 0.1 g/cm 3 or more.
  • the upper limit of the density is not particularly limited, but is preferably 1 g/cm 3 or less, more preferably 0.7 g/cm 3 or less, and even more preferably 0.5 g/cm 3 or less.
  • the density is preferably 0.01 to 1 g/cm 3 , more preferably 0.03 to 0.7 g/cm 3 , further preferably 0.05 to 0.5 g/cm 3 , and particularly preferably 0.1 to 0.5 g/cm 3 .
  • the density is calculated by measuring the mass and the volume, including the surface irregularities and the internal space, of the resin fiber and dividing the mass by the volume.
  • the average fiber diameter of the resin fibers is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more.
  • the average fiber diameter is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the average fiber diameter is preferably 1 to 200 ⁇ m, more preferably 5 to 150 ⁇ m, and even more preferably 10 to 100 ⁇ m.
  • the resin fiber is cut in the thickness direction, the cross section obtained is observed with a scanning electron microscope, 10 points are arbitrarily selected from the cross section images in the thickness direction of each fiber constituting the resin fiber, the major axis at the selected 10 points is measured, and the simple average of the 10 measured values is calculated, and the obtained value can be regarded as the average fiber diameter of the resin fiber.
  • the above-mentioned major axis means the length of the longest line segment among the line segments connecting two points on the periphery in the cross section image in the thickness direction.
  • the method of cutting the resin fibers in the thickness direction is not particularly limited, but may include a method of mechanically cutting the fibers with a razor or the like, a method of further subjecting the cross section obtained after mechanical cutting to an ion milling treatment, etc.
  • a razor T5332 TEFLON (registered trademark) COATED) manufactured by JEOL Ltd. may be used.
  • the scanning electron microscope is not particularly limited, but for example, a TM3000 Miniscope manufactured by Hitachi Technologies, Ltd. can be used.
  • the average fiber diameter of the resin fibers in the current collector and the average fiber diameter of the resin fibers constituting the current collector in the zinc electrode can also be determined in a similar manner.
  • the average thickness of the resin fiber is not particularly limited, but is preferably 25 ⁇ m or more, more preferably 30 ⁇ m or more, even more preferably 40 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
  • the average thickness is preferably 10 mm or less, more preferably 1000 ⁇ m or less, even more preferably 500 ⁇ m or less, and particularly preferably 200 ⁇ m or less.
  • the average thickness is preferably 25 to 10,000 ⁇ m, more preferably 30 to 1000 ⁇ m, even more preferably 40 to 500 ⁇ m, and particularly preferably 50 to 200 ⁇ m.
  • the average thickness of the resin fibers can be measured using a micrometer, and the thickness is measured at any ten positions, and the simple average value thereof can be adopted as the average thickness of the resin fibers.
  • the mass ratio of the resin fiber is not particularly limited, but for example, in 100% by mass of the zinc electrode of the present invention, it is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. Moreover, the mass ratio is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less. For example, the mass ratio is preferably 1 to 40% by mass, more preferably 3 to 35% by mass, and even more preferably 5 to 30% by mass.
  • the mass proportion of the resin fibers can be determined as follows.
  • the conductive layer content (% by mass) in the current collector is determined by ICP atomic emission spectrometry of the current collector, the remainder is taken as the resin fiber content (% by mass) in the current collector, and the mass ratio X of the resin fiber content to the conductive layer content (resin fiber content/conductive layer content) is determined.
  • the conductive layer content Y (mass%) in the zinc electrode is determined by ICP atomic emission spectrometry of the zinc electrode, and Z (mass%) obtained by the following formula can be used as the mass proportion of the resin fiber in the zinc electrode.
  • Z Y x X
  • the method of preparing the measurement sample, the ICP emission spectrometer, and the microwave decomposition device to be used may preferably be the same as those for the mass ratio of the conductive layer in the zinc electrode described above.
  • the current collector is usually a porous current collector.
  • a porous current collector By using a porous current collector, it is possible to obtain a current collector that has ion conductivity in the direction through which it penetrates (thickness direction or current direction). In addition, it is possible to reduce the weight of the current collector.
  • the density of the current collector is preferably 0.01 g/ cm3 or more, more preferably 0.03 g/ cm3 or more, even more preferably 0.05 g/ cm3 or more, still more preferably 0.1 g/ cm3 or more, even more preferably 0.3 g/ cm3 or more, still more preferably 0.5 g/ cm3 or more, and particularly preferably 1 g/ cm3 or more.
  • the upper limit of the density is not particularly limited, but is preferably 10 g/cm 3 or less, more preferably 7 g/cm 3 or less, and even more preferably 5 g/cm 3 or less.
  • the density is preferably 0.01 to 10 g/ cm3 , more preferably 0.03 to 7 g/ cm3 , even more preferably 0.05 to 5 g/ cm3 , still more preferably 0.1 to 5 g/ cm3 , even more preferably 0.3 to 5 g/ cm3 , even more preferably 0.5 to 5 g/ cm3 , and particularly preferably 1 to 5 g/ cm3 .
  • the density is calculated by measuring the mass and the volume, including the surface irregularities and the internal space, of the resin fiber and dividing the mass by the volume.
  • a current collector (porous body) is cut in the planar direction to a specific size (e.g., 40 mm ⁇ 40 mm) to obtain a rectangular parallelepiped (whose thickness remains the same as that of the porous body), and the weight of the obtained rectangular parallelepiped is weighed.
  • the value obtained by the following formula can be regarded as the density of the current collector (porous body).
  • Density [g/cm 3 ] (mass of rectangular solid [g])/(volume of rectangular solid [cm 3 ])
  • the volume of the rectangular parallelepiped is calculated from the length, width, and thickness of the rectangular parallelepiped, and the thickness of the rectangular parallelepiped is measured at 10 points using a micrometer and the average value is used.
  • the zinc electrode of the present invention comprises a zinc-containing material as an active material.
  • the zinc electrode of the present invention preferably contains a zinc-containing material as an active material in the pores of the porous current collector. By disposing the active material three-dimensionally in the zinc electrode in this way, a uniform reaction is possible, and good performance is obtained.
  • the zinc-containing substance may be metallic zinc (zinc alone), an alloy containing zinc, or a compound containing zinc as a constituent element (hereinafter also referred to as a zinc-containing compound).
  • the zinc element may function as a conductive assistant, but it also functions as an active material by undergoing an oxidation-reduction reaction during the use of the battery. In this specification, zinc element, as well as an alloy containing zinc and a zinc-containing compound, which will be described later, are referred to as active materials and are distinguished from conductive assistants.
  • the zinc-containing alloy may be a zinc alloy used in an (alkaline) dry battery or an air battery, and examples thereof include alloys of zinc and at least one selected from the group consisting of magnesium, lithium, manganese, aluminum, bismuth, and indium.
  • the zinc-containing compound may be any compound that can be used as an active material, and examples thereof include zinc oxide (e.g., type 1/type 2/type 3 as specified in JIS K1410 (2006)), zinc hydroxide, zinc sulfide, zinc tetrahydroxyl alkali metal salts, zinc tetrahydroxyl alkaline earth metal salts, zinc chloride and other zinc halide compounds, zinc acetate and other zinc carboxylate compounds, zinc borate, zinc phosphate, zinc hydrogen phosphate, zinc silicate, zinc aluminate, basic zinc carbonate, zinc carbonate, zinc nitrate, zinc sulfate and other zinc compounds; composite oxides of zinc and other metal elements; metal oxides that form a solid solution with the zinc element, and
  • the active material is usually in a particulate form, and the average particle diameter is preferably 1 nm or more. More preferably, it is 10 nm or more, even more preferably, it is 50 nm or more, and particularly preferably, it is 100 nm or more.
  • the average particle diameter is preferably 500 ⁇ m or less. More preferably, it is 400 ⁇ m or less, even more preferably, it is 200 ⁇ m or less, and particularly preferably, it is 100 ⁇ m or less.
  • the average particle diameter is preferably 1 nm to 500 ⁇ m.
  • the average particle size refers to the average particle size in a volume-based particle size distribution obtained by particle size distribution measurement using a dynamic light scattering method.
  • the active material particles are diluted with a dispersion medium (ion-exchanged water containing 0.2% sodium hexametaphosphate) to prepare a measurement sample.
  • a particle size distribution measuring device using the dynamic light scattering method for example, a concentrated particle size analyzer FPAR-1000AS manufactured by Otsuka Electronics Co., Ltd. can be used.
  • the active material may have an aspect ratio (length/width) of 1 or more.
  • the aspect ratio (length/width) is preferably 10 or less.
  • the aspect ratio (length/width) is more preferably 8 or less, even more preferably 5 or less, even more preferably 4 or less, even more preferably 2 or less, and particularly preferably 1.5 or less.
  • the aspect ratio (length/width) is preferably 1 to 10. It is more preferably 1 to 8, even more preferably 1 to 5, even more preferably 1 to 4, even more preferably 1 to 2, and particularly preferably 1 to 1.5.
  • the aspect ratio (length/width) can be determined from the shape of the particle observed by SEM.
  • the active material is observed with a SEM (scanning electron microscope), the major axis and minor axis are measured for 10 particles selected arbitrarily in the SEM image, the major axis/minor axis ratio is calculated, and the simple average value of the major axis/minor axis ratio can be adopted as the aspect ratio of the active material.
  • the major axis means the length of the longest line segment (A) among the line segments connecting two points on the periphery in each particle image
  • the minor axis means the distance (length of the line segment) between two intersection points between the periphery and a straight line that passes through the midpoint of the longest line segment (A) and is perpendicular to the line segment (A).
  • the mass ratio of zinc alone to zinc-containing substances other than zinc alone is preferably 1:99 to 100:0, more preferably 2:98 to 80:20, even more preferably 3:97 to 50:50, even more preferably 5:95 to 35:65, and particularly preferably 8:92 to 25:75.
  • the mass ratio of the active material is preferably 50% by mass or more relative to the total of 100% by mass of the active material and polymer (solid content) contained in the zinc electrode of the present invention.
  • the mass ratio of the active material is preferably 99.9% by mass or less.
  • the mass ratio of the active material is preferably 50 to 99.9% by mass.
  • the mass ratio of the active material is more preferably 55% by mass or more, and even more preferably 60% by mass or more.
  • the mass ratio of the active material is more preferably 99.5% by mass or less, and even more preferably 99% by mass or less.
  • the mass ratio of the active material is more preferably 55 to 99.5% by mass, and even more preferably 60 to 99% by mass.
  • the polymer refers to a polymer that the zinc electrode of the present invention may contain in addition to the current collector and active material described above, which will be described later.
  • the mass ratio of the current collector to the active material is preferably 1:9 to 5:4, more preferably 1:7 to 1:1, and even more preferably 1:5 to 4:5.
  • the zinc electrode of the present invention preferably contains a polymer in addition to the above-mentioned current collector and active material.
  • the polymer include hydrocarbon moiety-containing polymers such as polyethylene and polypropylene, aromatic group-containing polymers such as polystyrene; ether group-containing polymers such as alkylene glycol; hydroxyl group-containing polymers such as polyvinyl alcohol and poly( ⁇ -hydroxymethyl acrylate); amide bond-containing polymers such as polyamide, nylon, polyacrylamide, polyvinylpyrrolidone and N-substituted polyacrylamide; imide bond-containing polymers such as polymaleimide; carboxyl group-containing polymers such as poly(meth)acrylic acid, polymaleic acid, polyitaconic acid and polymethylene glutaric acid; carboxylate-containing polymers such as poly(meth)acrylate, polymaleate, polyitaconate and polymethylene glutarate; polyvinyl chloride, polyvinylidene fluoride, poly
  • polymers examples include halogen-containing polymers such as ethylene; epoxy resins; sulfonate moiety-containing polymers; quaternary ammonium salt or quaternary phosphonium salt-containing polymers; ion-exchangeable polymers used in cation/anion exchange membranes; conjugated diene-based polymers such as styrene-butadiene-based polymers; sugars such as cellulose, cellulose acetate, hydroxyalkyl cellulose (e.g., hydroxyethyl cellulose), carboxymethyl cellulose, chitin, chitosan, and alginic acid (salt); amino group-containing polymers such as polyethyleneimine; carbamate group moiety-containing polymers; carbamide group moiety-containing polymers; epoxy group moiety-containing polymers; heterocyclic and/or ionized heterocyclic moiety-containing polymers; polymer alloys; heteroatom-containing polymers; and low molecular weight surfactants.
  • the above polymer is preferably a carboxyl group-containing polymer, a carboxylate-containing polymer, or a conjugated diene-based polymer, more preferably a carboxylate-containing polymer or a conjugated diene-based polymer, and particularly preferably a conjugated diene-based polymer. It is also preferable to use two or more of these preferred polymers in combination.
  • the polymer can be obtained from the monomers corresponding to the constituent units thereof by radical polymerization, radical (alternating) copolymerization, anionic polymerization, anionic (alternating) copolymerization, cationic polymerization, cationic (alternating) copolymerization, graft polymerization, graft (alternating) copolymerization, living polymerization, living (alternating) copolymerization, dispersion polymerization, emulsion polymerization, suspension polymerization, ring-opening polymerization, cyclization polymerization, polymerization by light, ultraviolet light or electron beam irradiation, metathesis polymerization, electrolytic polymerization, etc.
  • these polymers may have functional groups, they may have them in the main chain and/or side chain, or may exist as a binding site with a crosslinking agent. These polymers may be used alone or in combination of two or more. The polymer may be crosslinked.
  • the polymer preferably has a weight average molecular weight of 200 or more.
  • the weight average molecular weight is preferably 7,000,000 or less.
  • the weight average molecular weight is preferably 200 to 7,000,000. This allows the ionic conductivity, flexibility, and the like of the resulting zinc electrode to be adjusted.
  • the weight average molecular weight of the polymer is more preferably 1,000 or more, and even more preferably 5,000 or more.
  • the weight average molecular weight of the polymer is more preferably 2,000,000 or less, and even more preferably 800,000 or less.
  • the weight average molecular weight of the polymer is more preferably 1,000 to 2,000,000, and even more preferably 5,000 to 800,000.
  • the weight average molecular weight can be measured as a polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC) under the following conditions.
  • GPC gel permeation chromatography
  • Apparatus Tosoh Corporation HCL-8220GPC Column: TSKgel Super AWM-H Eluent (LiBr.H 2 O, NMP containing phosphoric acid): 0.01 mol/L
  • the mass ratio of the polymer is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, based on 100% by mass of the total of the active material and polymer (solid content) contained in the zinc electrode.
  • the mass ratio of the polymer is preferably 30% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on 100% by mass of the total of the active material and polymer (solid content) contained in the zinc electrode.
  • the mass ratio of the polymer is preferably 0.1 to 30 mass% relative to 100 mass% of the total of the active material and polymer (solid content) contained in the zinc electrode, more preferably 0.3 to 15 mass%, even more preferably 0.5 to 10 mass%, and particularly preferably 1 to 5 mass%.
  • the zinc electrode of the present invention may contain elements or compounds containing these elements as constituent elements in order to suppress the side reaction of water decomposition that may occur when a water-containing electrolyte is used in a battery such as a secondary battery made using the zinc electrode.
  • Specific elements include Al, B, Ba, Bi, Br, C, Ca, Cd, Ce, Cl, Cu, Eu, F, Ga, Hg, In, La, Mg, Mn, N, Nb, Nd, Ni, P, Pb, S, Sb, Sc, Si, Sm, Sn, Sr, Ti, Tl, Y, Zr, etc.
  • the mass ratio of the conductive assistant can be 0.0001 mass% or more relative to 100 mass% of the active material in the zinc electrode. Preferably, it is 0.0005 mass% or more, and more preferably, it is 0.001 mass% or more.
  • the mass ratio of the conductive assistant can be 80 mass% or less relative to 100 mass% of the active material in the zinc electrode. Preferably, it is 60 mass% or less, and more preferably, it is 40 mass% or less.
  • the mass ratio of the conductive assistant can be 0.0001 to 80 mass% relative to 100 mass% of the active material in the zinc electrode. Preferably, it is 0.0005 to 60 mass%, and more preferably, it is 0.001 to 40 mass%.
  • the zinc electrode of the present invention may contain, in addition to the current collector and active material, a polymer, a conductive assistant, etc., and may further contain one or more other components other than these.
  • the other components are not particularly limited, and examples thereof include alumina, silica, etc.
  • the other components can function to assist ion conductivity, etc.
  • the mass ratio of other components is preferably 1 mass % or less, and more preferably 0.1 mass % or less, relative to 100 mass % of the active material.
  • the zinc electrode of the present invention preferably has an average thickness of 25 ⁇ m or more, more preferably 30 ⁇ m or more, even more preferably 40 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
  • the zinc electrode of the present invention is relatively light even as a thick film, and is capable of a uniform reaction.
  • the average thickness of the zinc electrode is preferably 10 mm or less.
  • the average thickness of the zinc electrode is preferably 25 ⁇ m to 10 mm, more preferably 30 ⁇ m to 10 mm, even more preferably 40 ⁇ m to 10 mm, and particularly preferably 50 ⁇ m to 10 mm.
  • the average thickness of the zinc electrode of the present invention can be calculated by measuring the thickness at any ten points with a micrometer or the like and calculating the simple average value thereof.
  • the zinc electrode of the present invention is preferably obtained by impregnating a current collector including resin fibers and a conductive layer covering the surface thereof with a composition including a zinc active material and a polymer, thereby making it possible to suitably obtain an electrode including a zinc-containing material as an active material in the pores of the porous current collector.
  • the zinc electrode of the present invention is obtained, for example, by contacting and impregnating the above-mentioned current collector with a slurry or paste-like (hereinafter also referred to as a slurry-like) composition containing the active material of the present invention and a polymer.
  • a slurry or paste-like hereinafter also referred to as a slurry-like composition containing the active material of the present invention and a polymer.
  • the composition contains a volatile component such as a solvent, it may be further dried.
  • the composition after the composition is brought into contact with and impregnated into the current collector, if necessary, it may be dried to evaporate a part or all of the volatile components such as the solvent contained in the composition to obtain a zinc electrode.
  • rolling may be performed as necessary.
  • the voids are reduced by rolling when obtaining the zinc electrode of the present invention, the occurrence of cracks due to the voids can be further suppressed.
  • the film thickness can be made uniform, and the electrode density can be increased to increase the volumetric capacity density.
  • the impregnation and rolling may be repeated two or more times.
  • the zinc electrode of the present invention may be formed by coating, pressing, adhering, piezoelectrically applying, rolling, stretching, melting, etc., the above composition onto a current collector.
  • the present invention also relates to a battery comprising the zinc electrode of the present invention described above.
  • the battery of the present invention is configured to include the zinc electrode of the present invention, and therefore can be driven sufficiently, has a long life, and is excellent in weight energy density.
  • the positive electrode active material can be one that is usually used as a positive electrode active material for primary batteries or secondary batteries, and is not particularly limited, but examples thereof include oxygen (when oxygen is the positive electrode active material, the positive electrode becomes an air electrode composed of a perovskite-type compound capable of reducing oxygen and oxidizing water, a cobalt-containing compound, an iron-containing compound, a copper-containing compound, a manganese-containing compound, a platinum-containing compound, etc.), nickel compounds such as nickel oxyhydroxide, nickel hydroxide, and cobalt-containing nickel hydroxide, and silver oxide.
  • oxygen when oxygen is the positive electrode active material, the positive electrode becomes an air electrode composed of a perovskite-type compound capable of reducing oxygen and oxidizing water, a cobalt-containing compound, an iron-containing compound, a copper-containing compound, a manganese-containing compound, a platinum-containing compound, etc.
  • nickel compounds such as nickel oxyhydroxide, nickel hydroxide, and cobalt-
  • the positive electrode active material is a nickel compound.
  • the positive electrode may also include a collector including resin fibers and a conductive layer covering its surface, and an active material, which is also a preferred form of the present invention.
  • the form of a battery using the zinc electrode of the present invention as a negative electrode may be any form, such as a primary battery, a secondary battery that can be charged and discharged, a mechanical charge (mechanical replacement of the zinc negative electrode), or a third electrode other than a positive electrode composed of the negative electrode of the present invention and the positive electrode active material as described above.
  • the electrolyte used in the battery of the present invention can be any electrolyte that is commonly used as an electrolyte for batteries, and is not particularly limited.
  • Examples of the electrolyte include organic solvent-based electrolytes, aqueous electrolytes, and solid electrolytes.
  • organic solvent-based electrolytes include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyltetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, benzonitrile, ionic liquids, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, and fluorine-containing polyethylene glycols. These can be used alone or in combination of two or more.
  • aqueous electrolytes examples include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, zinc sulfate aqueous solution, zinc nitrate aqueous solution, zinc phosphate aqueous solution, and zinc acetate aqueous solution.
  • alkaline electrolytes such as potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, and lithium hydroxide aqueous solution are preferred.
  • the above aqueous electrolytes can be used alone or in combination of two or more.
  • the aqueous electrolyte may contain the organic solvent electrolyte.
  • the battery of the present invention may further include a separator.
  • the separator may be any material that isolates the positive electrode and the negative electrode, retains the electrolyte, and ensures ionic conductivity between the positive electrode and the negative electrode.
  • There are no particular limitations on the separator and examples thereof include nonwoven fabrics, filter paper, and microporous membranes.
  • Materials constituting these include hydrocarbon-containing polymers such as polyethylene and polypropylene, polytetrafluoroethylene-containing polymers, polyvinylidene fluoride-containing polymers, cellulose-based polymers such as cellulose, fibrillated cellulose, viscose rayon, cellulose acetate, hydroxyalkyl cellulose, and carboxymethyl cellulose, polyvinyl alcohol-based polymers such as polyvinyl alcohol and partially acetalized polyvinyl alcohol, aromatic ring-containing polymers such as cellophane and polystyrene, polyacrylonitrile-containing polymers, polyacrylamide-containing polymers, polyvinyl halide-containing polymers, and polyamides such as nylon.
  • hydrocarbon-containing polymers such as polyethylene and polypropylene
  • polytetrafluoroethylene-containing polymers such as polytetrafluoroethylene-containing polymers
  • polyvinylidene fluoride-containing polymers such as cellulose, fibrillated cellulose, viscose
  • polymeric materials include various polymer materials such as amide moiety-containing polymers, polyimide moiety-containing polymers, ester moiety-containing polymers, poly(meth)acrylic acid moiety-containing polymers, poly(meth)acrylate moiety-containing polymers, hydroxyl group-containing polymers such as polyisoprenol and poly(meth)allyl alcohol, carbonate group-containing polymers such as polycarbonate, ester group-containing polymers such as polyester, carbamate and carbamide group-containing polymers such as polyurethane, agar, gel compounds, ion exchange polymers, cyclized polymers, sulfonate-containing polymers, quaternary ammonium salt-containing polymers, quaternary phosphonium salt polymers, cyclic hydrocarbon group-containing polymers, and ether group-containing polymers.
  • polymer materials such as amide moiety-containing polymers, polyimide moiety-containing polymers, ester moiety-containing polymers, poly(meth)acrylic
  • the separator may be an inorganic membrane having ion conductivity such as layered double hydroxides such as hydrotalcite, or an organic-inorganic composite membrane (ion-conductive membrane) containing the above polymer material and an inorganic compound.
  • the separator may be one of these, or may be a combination of two or more types by lamination or the like.
  • the battery of the present invention can be obtained using known methods. For example, a separator and a positive electrode are stacked on top of a negative electrode, inserted into a battery cell of an appropriate size, and an electrolyte solution is introduced into the battery cell to produce a battery.
  • the battery of the present invention has a long life and excellent weight energy density, making it suitable for use in a wide range of applications, from small portable devices to large applications such as automobiles.
  • the average particle size of the active material (zinc metal) used in each example was determined as follows.
  • the active material was added to a dispersion medium (ion-exchanged water containing 0.2% sodium hexametaphosphate) and mixed to prepare a measurement sample.
  • the volume-based particle size distribution was measured using a concentrated particle size analyzer FPAR-1000AS manufactured by Otsuka Electronics Co., Ltd., and the 50% particle size was taken as the average particle size of the active material.
  • the aspect ratio of the active material (zinc metal) used in each example was determined as follows. The active material was observed under a scanning electron microscope, and the major axis and minor axis of 10 randomly selected particles in the electron microscope image were measured to determine the major axis/minor axis ratio. The simple average of the major axis/minor axis ratios obtained for the 10 particles was regarded as the aspect ratio of the active material.
  • the above-mentioned major axis refers to the length of the longest line segment (A) among the line segments connecting two points on the periphery of each particle image
  • the above-mentioned minor axis refers to the distance (length of the line segment) between the two intersection points between the periphery and a straight line that passes through the midpoint of the longest line segment (A) and is perpendicular to the line segment (A).
  • the resin fiber used in each example was cut in the thickness direction with a razor (T5332 TEFLON (registered trademark) COATED) manufactured by JEOL Ltd., and the obtained cross section was observed with a scanning electron microscope.
  • 10 cross-sectional images in the thickness direction of each fiber constituting the resin fiber were arbitrarily selected, the major axis at the selected 10 points was measured, and the simple average of the 10 measured values was obtained, and the obtained value was the average fiber diameter of the resin fiber.
  • the length of the longest line segment among the line segments connecting two points on the periphery in the cross-sectional image in the thickness direction was adopted as the above-mentioned major axis.
  • the scanning electron microscope used was a TM3000 Miniscope manufactured by Hitachi Technologies, Ltd.
  • the average thickness of the resin fiber used in each Example was measured at 10 points using a micrometer, and the simple average value was taken as the average thickness of the resin fiber.
  • the current collector (porous body) obtained in each Example was cut in the thickness direction with a razor (T5332 TEFLON (registered trademark) COATED) manufactured by JEOL Ltd., and the obtained cross section was observed with a scanning electron microscope, and 10 cross-sectional images in the thickness direction of the fiber on which the conductive layer (plating layer) was formed were arbitrarily selected. Next, in each of the selected 10 cross-sectional images, the thickness of the conductive layer was arbitrarily selected and measured at 10 points, and the simple average of the obtained 10 measured values was taken as the thickness of the conductive layer in each cross-sectional image.
  • the thicknesses of the conductive layer in each cross-sectional image thus obtained (10 in total) were simply averaged, and the obtained value was taken as the average thickness of the conductive layer (plating layer) in the current collector.
  • the scanning electron microscope used was a TM3000 Miniscope manufactured by Hitachi Technologies, Ltd. When there were a plurality of conductive layers, such as an intermediate layer and an outermost surface layer, the same measurement was performed for each layer.
  • the current collector (porous body) obtained in each Example was cut in the planar direction to a specific size (for example, 40 mm ⁇ 40 mm) to obtain a rectangular parallelepiped (the thickness of the current collector was the same as that of the current collector).
  • the weight of the obtained rectangular parallelepiped was weighed, and the value obtained by the following formula was regarded as the density of the current collector.
  • Density [g/cm 3 ] (mass of rectangular solid [g])/(volume of rectangular solid [cm 3 ])
  • the volume of the rectangular parallelepiped in the above formula is a value calculated from the length, width, and thickness of the rectangular parallelepiped, and the thickness of the rectangular parallelepiped is a simple average value measured at 10 points using a micrometer.
  • the average thickness of the zinc negative electrode obtained in each Example was determined by measuring the thickness at 10 points using a micrometer and taking the simple average value of the measurements as the average thickness of the zinc negative electrode.
  • Example 1 Zinc metal (average particle size 75 ⁇ m), styrene-butadiene rubber, and sodium polyacrylate were mixed in a mass ratio of 98:1:1 and stirred to obtain paint (1).
  • a mesh made of nylon resin was plated with Cu and Sn in this order to obtain a porous body (1) in which the surface of the nylon resin was covered with a Cu-plated layer (intermediate layer) and a Sn-plated layer (outermost layer).
  • the coating material (1) was impregnated into the porous body (1), and then the porous body (1) was dried and rolled to obtain a zinc negative electrode (1).
  • the average thickness of the obtained zinc negative electrode (1) was 140 ⁇ m.
  • Example 2 Zinc oxide (average particle size: 1 ⁇ m), polytetrafluoroethylene, and sodium polyacrylate were mixed in a mass ratio of 95:4:1 and stirred to obtain a coating material (2).
  • the zinc negative electrode (1) obtained in Example 1 was impregnated with the paint (2), dried and rolled to obtain a zinc negative electrode (2).
  • the zinc negative electrode had an average thickness of 250 ⁇ m.
  • the weight energy density was calculated for each zinc negative electrode obtained in each Example and Comparative Example. The results are shown in Tables 1 and 2.
  • the gravimetric energy density was calculated as follows. (How to calculate gravimetric energy density) The weight energy density of the zinc negative electrode obtained in each of the Examples and Comparative Examples was calculated according to the following formula.
  • Comparative Example 2 A charge-discharge cycle test was performed using the zinc negative electrode (c1) obtained in Comparative Example 1, a carbon electrode as a positive electrode, and a nonwoven fabric and an anion conductor between the positive and negative electrodes, and an 8M potassium hydroxide aqueous solution saturated with zinc oxide as an electrolyte.
  • the current value was 1 mA/ cm2 (charge-discharge voltage 1.35V, discharge voltage 0.35V). As a result, a cycle life of more than 1000 cycles was obtained.
  • Example 3 In Comparative Example 2, a charge-discharge cycle test was performed in the same manner as in Comparative Example 2, except that the zinc negative electrode (c1) was replaced with the zinc negative electrode (1) obtained in Example 1. As a result, a cycle life of 1000 cycles or more was obtained.
  • Example 4 Paint (4) was obtained by mixing and stirring zinc metal (average particle size 75 ⁇ m, aspect ratio 3.0), styrene-butadiene rubber, and sodium polyacrylate in a mass ratio of 95:3:2 using water as a solvent.
  • a mesh average thickness 160 ⁇ m
  • polypropylene resin fibers average fiber diameter 87 ⁇ m
  • Cu copper
  • Sn silver
  • the density of the resulting porous body (4) was 0.48 g/ cm3 .
  • the porous body (4) was impregnated with the coating material (4), and then dried and rolled to obtain a zinc negative electrode (4).
  • the average thickness of the obtained zinc negative electrode (4) was 210 ⁇ m.
  • the mass percentage of the conductive layer was 8.8 mass%, and the mass percentage of the resin fiber was 9.5 mass%.
  • the mass ratio of the conductive layer and the mass ratio of the resin fiber in the zinc negative electrode (4) obtained in Example 4 were determined by ICP emission spectrometry.
  • a predetermined amount of the zinc electrode (4) was subjected to acid decomposition using a microwave decomposition device (ETHOS One manufactured by Milestone General Co.), and the obtained solution was used as a measurement sample.
  • the measurement sample was used to perform quantitative analysis of Sn and Cu using an ICP emission spectrometer, and the mass ratio of the conductive layer in the zinc negative electrode (4) was calculated from the obtained Sn and Cu contents.
  • the ICP emission spectrometer used was ICPE-9000 manufactured by Shimadzu Corporation.
  • Example 5 In Example 4, instead of the mesh made of polypropylene resin fiber (average fiber diameter 87 ⁇ m), a nonwoven fabric (average thickness 90 ⁇ m) made of polypropylene resin fiber/high-density polyethylene resin fiber (average fiber diameter 35 ⁇ m) and polypropylene ultrafine fiber (average fiber diameter 14 ⁇ m) that had been hydrophilized with fluorine gas was used, the average thickness of the Cu plating layer (intermediate layer) was set to 3 ⁇ m, the average thickness of the Sn plating layer (outermost layer) was set to 4 ⁇ m, and the amount of paint (4) was changed. A zinc negative electrode (5) was obtained in the same manner as in Example 4. The average thickness of the obtained zinc negative electrode (5) was 140 ⁇ m.
  • Example 6 In Example 4, a nonwoven fabric (average thickness 90 ⁇ m) made of polypropylene resin fiber/polyethylene resin fiber (average fiber diameter 18 ⁇ m) was used instead of the mesh made of polypropylene resin fiber (average fiber diameter 87 ⁇ m), the average thickness of the Cu plating layer (intermediate layer) was set to 3 ⁇ m, the average thickness of the Sn plating layer (outermost layer) was set to 6 ⁇ m, and the amount of paint (4) was changed. A zinc negative electrode (6) was obtained in the same manner as in Example 4. The average thickness of the obtained zinc negative electrode (6) was 140 ⁇ m.
  • Example 7 A zinc negative electrode (7) was obtained in the same manner as in Example 4, except that a nonwoven fabric (average thickness 90 ⁇ m) made of vinylon resin fiber (average fiber diameter 10 ⁇ m) was used instead of a mesh made of polypropylene resin fiber (average fiber diameter 87 ⁇ m), the average thickness of the Cu plating layer (intermediate layer) was set to 4 ⁇ m, the average thickness of the Sn plating layer (outermost layer) was set to 10 ⁇ m, and the amount of paint (4) was changed. The average thickness of the obtained zinc negative electrode (7) was 140 ⁇ m.
  • Example 8 In Example 4, a mesh (average thickness 100 ⁇ m) made of polyphenylene sulfide resin fiber (average fiber diameter 55 ⁇ m) was used instead of the mesh made of polypropylene resin fiber (average fiber diameter 87 ⁇ m), the average thickness of the Cu plating layer (intermediate layer) was set to 7 ⁇ m, the average thickness of the Sn plating layer (outermost layer) was set to 20 ⁇ m, and the amount of paint (4) was changed. A zinc negative electrode (8) was obtained in the same manner as in Example 4. The average thickness of the zinc negative electrode (8) was 150 ⁇ m.
  • the charge/discharge cycle test described in Comparative Example 2 was performed using the zinc negative electrodes obtained in Examples 4 to 8, and the cycle life was 1000 cycles or more in all cases. It was confirmed that even when a zinc negative electrode using a porous body in which the surface of various resin fibers is covered with a Cu plating layer (middle layer) and a Sn plating layer (outermost layer) as a current collector was used, the life was 1000 cycles or more, just like when a brass mesh current collector was used.

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JPS5946759A (ja) * 1982-06-11 1984-03-16 ソシエテ・シビル・デ・コンポジト・ゼレクトロリチク 複合材料陽極およびそれを用いた蓄電池
JP2015520914A (ja) * 2012-05-04 2015-07-23 ナノ−ヌーヴェル プロプライエタリー リミテッドＮａｎｏ−Ｎｏｕｖｅｌｌｅ Ｐｔｙ Ｌｔｄ． 電池電極材料
CN114267827A (zh) * 2020-09-16 2022-04-01 松山湖材料实验室 一种锌电极及其制备方法、二次电池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5946759A (ja) * 1982-06-11 1984-03-16 ソシエテ・シビル・デ・コンポジト・ゼレクトロリチク 複合材料陽極およびそれを用いた蓄電池
JP2015520914A (ja) * 2012-05-04 2015-07-23 ナノ−ヌーヴェル プロプライエタリー リミテッドＮａｎｏ−Ｎｏｕｖｅｌｌｅ Ｐｔｙ Ｌｔｄ． 電池電極材料
CN114267827A (zh) * 2020-09-16 2022-04-01 松山湖材料实验室 一种锌电极及其制备方法、二次电池

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