WO2022014720A1 - 金属層被覆亜鉛箔及びその製造方法 - Google Patents

金属層被覆亜鉛箔及びその製造方法 Download PDF

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Publication number
WO2022014720A1
WO2022014720A1 PCT/JP2021/026995 JP2021026995W WO2022014720A1 WO 2022014720 A1 WO2022014720 A1 WO 2022014720A1 JP 2021026995 W JP2021026995 W JP 2021026995W WO 2022014720 A1 WO2022014720 A1 WO 2022014720A1
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Prior art keywords
metal layer
foil
zinc
bismuth
foil body
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PCT/JP2021/026995
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English (en)
French (fr)
Japanese (ja)
Inventor
裕樹 澤本
秀利 井上
拓也 來間
昌嗣 松藤
貴将 椛島
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三井金属鉱業株式会社
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Priority to JP2022536471A priority Critical patent/JPWO2022014720A1/ja
Publication of WO2022014720A1 publication Critical patent/WO2022014720A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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 metal layer-coated zinc foil and a method for producing the same, and more particularly to a metal layer-coated zinc foil and a method for producing the same, which can be suitably used as a negative electrode active material for a primary battery or a secondary battery.
  • the applicant has previously proposed a zinc foil containing bismuth as a base material and a negative electrode active material for a primary battery using the zinc foil (see Patent Document 1).
  • the content ratio of bismuth is 100 ppm or more and 10000 ppm or less on a mass basis, and the size of zinc crystal grains is 0.2 ⁇ m or more and 8 ⁇ m or less.
  • this zinc foil is used as a negative electrode active material, there is an advantage that the amount of gas generated during long-term storage of the battery is suppressed more than before.
  • an object of the present invention is to provide a zinc foil for a negative electrode active material in which the amount of gas generated is suppressed more than before in the battery, particularly when used as a negative electrode active material in a thin battery. ..
  • the present invention is a metal layer-coated zinc foil having a foil body using zinc as a base material and a metal layer arranged on the surface of the foil body, and the metal element contained in the metal layer is bismuth.
  • a metal layer-coated zinc foil which is at least one selected from the group consisting of indium, aluminum, gallium, tin, silver and manganese.
  • FIG. 1 is a schematic diagram showing the area between electrodes used to calculate the circulation rate of the electrolytic solution.
  • FIG. 2 is a captured image of software used when determining the size of zinc crystal grains.
  • the metal layer-coated zinc foil of the present invention has a zinc-based foil body and a metal layer arranged on the surface (one side or both sides) of the foil body.
  • 1. Foil body made of zinc as a base material
  • a preferred embodiment of a foil body (hereinafter, also referred to as “zinc foil”) using zinc as a base material will be described.
  • the above-mentioned "using zinc as a base material” means that the zinc element is preferably contained in the foil body in an amount of 80% by mass or more.
  • the zinc element content can be measured by ICP emission spectroscopy.
  • the size of the crystal grains of the zinc foil One of the features of the foil body used in the present invention is that the size of the zinc crystal grains in the zinc foil is smaller than that of the conventionally known zinc foil. As a result, gas generation during storage of the battery is suppressed as compared with the conventional zinc foil. The reason for this is not completely clear, but the present inventors think that it may be because the hydrogen overvoltage is changed due to the distribution of small-sized zinc crystal grains and the existence of a large number of grain boundaries. ing. From the viewpoint of further enhancing this advantage, the size of zinc crystal grains is preferably 0.2 ⁇ m or more and 50.0 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 50.0 ⁇ m or less.
  • crystal grain size is a concept different from the crystallite size obtained from the XRD pattern.
  • the size of zinc crystal grains in the foil body used in the present invention is measured by the following method.
  • an FE gun-type scanning electron microscope (OIM Data Collection Ver. 7.2.0, manufactured by TSL Solutions Co., Ltd.) equipped with an electron backscatter diffraction (hereinafter also referred to as “EBSD”) evaluation device (OIM Data Collection Ver. 7.2.0) SUPRA 55VP, manufactured by Karl Zeiss Co., Ltd.) and the attached EBSD analyzer are used.
  • EBSD electron backscatter diffraction
  • a sample whose cross section is cut out is prepared using an ultramicrotome, and for this sample, data on grain size in a cross-sectional view in which the thickness of the entire sample can be measured is obtained according to the EBSD method.
  • background processing of EBSD measurement data "Background Subtraction”, “Normalize Integrity Histogram”, “Dynamic Background” in “Image Processing” of the EBSD evaluation device, "Dynamic Baccground”, “Dynamic Baccground” It is carried out under the condition of 160x120).
  • the conditions of "Gain” and “Exposure” may be appropriately changed so that the image in "Camera” is in a state where the Kikuchi pattern is not observed by electron diffraction and is 30 ⁇ 1 fps as shown in FIG.
  • the background information is acquired by "Capture Bkd”.
  • the WD value when measuring the crystal grain size was set to 15 ⁇ 1 mm, and "Background Subtraction”, “Normalize Integrity Histogram” in "Image Processing", “Dynamic Baccground Checked” in the “Dynamic Background” state, and checked in the "Dynamic Background” position.
  • This crystal grain size (average) is taken as the size of zinc crystal grains in the present invention.
  • 1-3 Crystal structure of zinc foil
  • an orientation difference of 15 ° or more is regarded as a grain boundary.
  • the orientation difference at a certain grain boundary is expressed by the rotation axis and the angle of rotation in consideration of the twin grain boundaries, and the rotation axis is the following (1).
  • the rotation angles are represented by 94.8 ⁇ 1 ° and 57 ⁇ 1 °, and the rotation axis is represented by (2) below, and the rotation angles are 34.8 ⁇ 1 ° and 64.3 ⁇ 1 °. In the case, it was not regarded as a grain boundary.
  • the conditions of the scanning electron microscope at the time of observation are an acceleration voltage: 20 kV, an aperture diameter: 60 ⁇ m, a High Current mode, and a sample angle: 70 °.
  • the conditions of the observation magnification, the measurement area, and the step size may be appropriately changed according to the size of the crystal grains.
  • Metal elements contained in zinc foil The foil body used in the present invention is based on zinc as described above, and may contain 100% by mass of zinc, but contains a small amount of other metal elements other than zinc. It is preferable to be. As a result, gas generation during storage of the battery is effectively suppressed. From this point of view, it is advantageous to use a metal element having a hydrogen overvoltage higher than that of zinc or a redox potential higher than that of zinc.
  • Such metal elements include at least one selected from the group consisting of bismuth, indium, aluminum, magnesium, calcium, gallium, tin, barium, strontium, silver and manganese.
  • metal elements it is preferable to use at least one selected from the group consisting of bismuth, indium, aluminum, tin, silver and gallium from the viewpoint of further suppressing gas generation, and bismuth, indium, tin and silver. It is more preferable to use at least one selected from the group consisting of, from the viewpoint of further suppressing gas generation. In particular, it is even more preferable to use bismuth.
  • the content ratio of metal elements in the foil body is expressed as the total amount of metal elements, and is 10 ppm or more and 10,000 ppm on a mass basis. It is preferably 15 ppm or more and 8000 ppm or less, more preferably 20 ppm or more and 7000 ppm or less, further preferably 30 ppm or more and 6500 ppm or less, and particularly preferably 40 ppm or more and 6000 ppm or less. preferable.
  • the content ratio of metal elements in the foil body can be measured by ICP emission spectroscopy.
  • a method compliant with JIS H1111 can be adopted for the measurement by the ICP emission spectroscopic analysis method. Specifically, after dissolving the foil body in an acidic aqueous solution such as hydrochloric acid, the concentration of contained metals other than zinc is measured by ICP emission spectroscopic analysis, and the concentration of all metals is set to 1 to contain various metal elements. Is converted as mass.
  • the content ratio of bismuth in the foil body is preferably 10 ppm or more and 10000 ppm or less, more preferably 15 ppm or more and 8000 ppm or less, and 20 ppm or more and 6000 ppm. It is more preferably 30 ppm or more and 3000 ppm or less, and further preferably 40 ppm or more and 1200 ppm or less.
  • the foil body used in the present invention may contain lead or cadmium as unavoidable impurities. However, it is desirable that lead is not contained from the viewpoint of reducing the environmental load. Even if the foil body contains lead, it is desirable that the content ratio is as low as possible. Specifically, the lead content is preferably 60 ppm or less, more preferably 50 ppm or less, and even more preferably 40 ppm or less on a mass basis. The lead content in the foil body is measured by ICP emission spectroscopy. Similarly, it is desirable that cadmium is not contained, or even if it is contained, the ratio thereof is as low as possible. In particular, the cadmium content is preferably 10 ppm or less on a mass basis.
  • the metal elements in the foil body are as uniform as possible. Whether or not the existence state is uniform can be confirmed by observing the mapping image of the metal element described later. As a result, gas generation during storage of the battery is further suppressed as compared with the conventional zinc foil containing a metal element. In order to realize the existence state of such a metal element, it is advantageous to reduce the size of zinc crystal grains in the foil body as described above. In particular, when the metal element and zinc are not compatible with each other, the metal element tends to segregate in the vicinity of the grain boundaries of the zinc crystal grains due to this.
  • zinc foil containing a metal element has been manufactured by rolling a casting of zinc containing a metal element.
  • zinc containing a metal element was produced by casting, the growth of zinc crystal grains proceeded due to the cooling conditions, and it was not easy to produce small size crystal grains.
  • the metal element was deposited near the grain boundary of the large-sized zinc crystal grain, and when the metal element was magnified and observed to the extent that the existence of the grain boundary could be recognized, the metal element was in a state of non-uniformity.
  • the foil body is preferably manufactured by the electrolysis method described later. Due to this, small-sized zinc crystal grains can be easily generated, and it is possible for the first time to make the existence state of metal elements as uniform as possible.
  • the state of existence of the metal element in the foil body used in the present invention is the metal element using energy dispersion type X-ray spectroscopy (hereinafter also referred to as “EDS”) by a scanning electron microscope (hereinafter also referred to as “SEM”). It can be judged based on the mapping image of. Specifically, when a plurality of squares having a side of 300 nm are virtually set in the mapping image, the number is preferably 2% or more, more preferably 5 with respect to the total number of the plurality of squares.
  • the presence state of the metal element is uniform to the extent that the metal element is observed in the squares of% or more, more preferably 10% by number or more.
  • the number of squares shall be 48 or more.
  • Apparent density of zinc foil One of the features of the foil body used in the present invention is that the apparent density is lower than that of a conventionally known zinc foil, for example, a zinc foil produced by a rolling method. This also suppresses gas generation during storage of the battery, as compared with the conventional zinc foil.
  • the value of the apparent density of the foil body is preferably 3.0 g / cm 3 or more and 7.0 g / cm 3 or less, and 4.0 g / cm 3 or more and 7.0 g / cm 3 or less. Is more preferable, and 5.0 g / cm 3 or more and 7.0 g / cm 3 or less is further preferable.
  • the above-mentioned apparent density is a value calculated from the volume obtained by measuring the outer shape of the foil body and the mass of the foil body.
  • the method for obtaining the volume by measuring the outer shape of the foil body is as follows.
  • the area of the foil body in a plan view is calculated from the vertical and horizontal dimensions of the foil body.
  • the thickness of the foil body is measured with a micrometer.
  • the thickness shall be the arithmetic mean value of the measurement results at 15 points.
  • the mass of the sample whose volume is obtained from the area and thickness is measured, and the apparent density is calculated from the volume and mass.
  • the apparent density calculated in this way is also referred to as the apparent density measured by external shape measurement.
  • the apparent density of the zinc foil and the apparent density of the foil body are strictly different, the metal layer provided on the surface of the foil body is extremely thin, so that the apparent density of the zinc foil and the apparent density of the foil body are extremely thin. Can be substantially identified with.
  • the thickness of the foil body is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 15 ⁇ m or more and 400 ⁇ m or less, still more preferably 20 ⁇ m or more and 400 ⁇ m or less, and particularly preferably. It is a thin type with a thickness of 20 ⁇ m or more and 300 ⁇ m or less. The thickness of the foil body is measured by a micrometer as described above.
  • the foil body can be manufactured by the rolling method described above, but it is preferably manufactured by an electrolytic method.
  • Electrolysis method In the electrolysis method, the anode and cathode are immersed in an electrolytic solution containing a zinc source, and a zinc foil is deposited on the cathode.
  • the foil obtained by the electrolytic method is also referred to as "electrolytic foil".
  • the electrolytic solution containing a zinc source include an aqueous solution of zinc sulfate, an aqueous solution of zinc nitrate, and an aqueous solution of zinc chloride.
  • the concentration of zinc contained in the electrolytic solution is preferably 30 g / L or more and 100 g / L or less from the viewpoint that a foil body having a small crystal grain size can be easily obtained.
  • the anode used for electrolysis it is preferable to use a known dimensional stabilization electrode (DSE).
  • DSE for example, a titanium electrode coated with iridium oxide, a titanium electrode coated with ruthenium oxide, or the like is preferably used.
  • the type of cathode is not particularly limited, and a material that does not affect the reduction of zinc is appropriately selected. For example, aluminum can be used.
  • the electrolytic solution contains the above-mentioned metal element source in addition to the zinc source, if necessary.
  • the concentration of the metal element source contained in the electrolytic solution is preferably such that the ratio of the mass of the metal element to the total mass of zinc and the metal element in the electrolytic solution is 10 ppm or more and 10000 ppm or less, and 15 ppm or more and 8000 ppm or less. It is more preferably 20 ppm or more and 7,000 ppm or less, further preferably 30 ppm or more and 6500 ppm or less, particularly preferably 30 ppm or more and 6000 ppm or less, and particularly preferably 400 ppm or more and 6000 ppm or less. ..
  • the electrolytic solution may further contain other compounds.
  • sulfuric acid can be added for the purpose of adjusting the pH of the electrolytic solution.
  • a pump equipped with a closed flow path, an electrolytic cell arranged in the flow path, and a pump arranged in the flow path is used. May be driven to direct the electrolytic solution in one direction and circulate in the electrolytic cell.
  • the anode and cathode used for electrolysis may be immersed in an electrolytic cell with the two facing each other. It is preferable that the anode and the cathode are arranged in the electrolytic cell so that their facing surfaces (electroplated surfaces in the case of the cathode) are parallel to the flow direction of the electrolytic solution.
  • Circulation rate When performing electrolysis while circulating the electrolytic solution, it is advantageous to adjust the flow rate of the electrolytic solution, that is, the circulation rate, from the viewpoint of successfully obtaining the foil body having the desired apparent density.
  • the circulation speed is calculated by dividing the flow rate (L / min) of the electrolytic solution by the area between electrodes (mm 2). As shown in FIG. 1, the area between electrodes is represented by the product of the distance between electrodes (mm) and the length of electrodeposited electrodes (mm). In FIG. 1, it is preferable to distribute the electrolytic solution in a direction orthogonal to the paper surface.
  • the current density during electrolysis is one of the factors that affect the size of zinc crystal grains in the obtained foil body and the apparent density of the foil body. Specifically, by increasing the current density above the conditions of normal zinc electrolysis, a large number of fine crystals can be generated, whereby a foil body having a small crystal grain size can be easily obtained. From this viewpoint, it is preferable to set the current density to below 1000A / m 2 or more 10000 A / m 2, further preferably set to below 1000A / m 2 or more 6000A / m 2, 1000A / m 2 or more 4000A / m It is more preferable to set it to 2 or less. On the other hand, conventionally, the current density when manufacturing the electrolytic zinc foil is as low as about 500 A / m 2.
  • the electrolytic solution can be subjected to electrolysis in a non-heated state or a heated state.
  • the temperature of the electrolytic solution is preferably set to 10 ° C. or higher and 90 ° C. or lower.
  • the temperature of the electrolytic solution is more preferably 20 ° C. or higher and 90 ° C. or lower, further preferably 30 ° C. or higher and 80 ° C. or lower, and further preferably 30 ° C. or higher and 70 ° C. or lower. This is done until the thickness of the foil body reaches the desired value.
  • Electrolysis is performed under the above conditions, and zinc is reduced and precipitated on the cathode immersed in the electrolytic solution to obtain the desired foil body.
  • a coating metal layer (hereinafter, also simply referred to as “metal layer”) arranged on the surface of the foil body described above will be described.
  • This metal layer is arranged on one side or both sides of the surface of the foil body by a coating forming means described later.
  • Metal elements contained in the coated metal layer examples include at least one selected from the group consisting of bismuth, indium, aluminum, gallium, tin, silver and manganese. Among these metal elements, it is preferable to use at least one of bismuth and indium from the viewpoint of further suppressing gas generation.
  • the thickness of the metal layer is preferably 5.0 ⁇ 10 -1 nm or more and 3.0 ⁇ 10 3 nm or less. It is more preferably 1.0 nm or more and 1.0 ⁇ 10 3 nm or less, and further preferably 1.0 ⁇ 10 1 nm or more and 5.0 ⁇ 10 2 nm or less. By forming the coated metal layer in this range, gas generation can be effectively suppressed.
  • the thickness of the metal layer is measured by a light emitting surface analyzer described later.
  • the metal layer is arranged on one side or both sides of the surface of the foil body.
  • the thickness (T S of the other surface than the thickness of one surface (T C) ) Is larger.
  • the ratio of the thickness (T S / T C) is 2 or more, more preferably 2.3 or more.
  • the upper limit of T S / T C is preferably 5.0.
  • the foil body is composed of, for example, an electrolytic foil
  • one surface is an electrode surface of the foil body (hereinafter, also referred to as “C surface”)
  • the other surface is a precipitation surface in contact with the electrolytic solution (hereinafter, “S”). Also called “face”).
  • the thickness of the metal layer in this case, towards the thickness of the S-plane than the thickness of the C-plane (T C) (T S) that is greater, from the viewpoint of the effect of the becomes more pronounced.
  • Which of the surfaces of the foil body is the C surface and which is the S surface can be determined by surface observation.
  • the C-plane is smoother than the S-plane and has a small specific surface area. Further, the size of the crystal grains is smaller on the C plane than on the S plane.
  • the thickness of the metal layer coated zinc foil having the coated metal layer and the foil body is preferably 1 ⁇ m or more and 1000 ⁇ m or less, more preferably 3 ⁇ m or more and 800 ⁇ m or less, and further preferably 10 ⁇ m or more and 500 ⁇ m or less. It is thin.
  • the thickness of the metal layer-coated zinc foil is measured by the same method as the thickness of the foil body.
  • Such a thin metal layer-coated zinc foil is particularly suitable as a negative electrode material for a thin primary battery or a secondary battery.
  • a method for manufacturing a coated metal layer that is, a method for forming a metal layer coating on a foil body will be described.
  • the coating forming means a sputtering method, a PVD method, a CVD method, a reduction plating method, an electroplating method, a substitution plating method, or the like can be used.
  • the substitution plating method it is preferable to use the substitution plating method from the viewpoint of the continuity of the process when the foil body is manufactured by the electrolytic method.
  • substitution plating method is a plating method that utilizes the difference in ionization tendency, and is an excellent method for forming a metal layer.
  • a preferred embodiment of the substitution plating method will be described below.
  • a substitution plating solution for the substitution plating method a nitric acid aqueous solution of a metal element having an arbitrary concentration or another acidic aqueous solution is prepared and dissolved in ion-exchanged water.
  • the metal element includes at least one selected from the group consisting of bismuth, indium, aluminum, gallium, tin, silver and manganese. Among these metal elements, it is preferable to use at least one of bismuth and indium from the viewpoint of further suppressing gas generation.
  • the concentration of the metal element in the replacement plating solution can be appropriately selected depending on the type of the target metal element, the thickness of the coating metal layer, and other conditions.
  • concentration of bismuth in the replacement plating solution is preferably adjusted to 0.1 mg / L or more and 10,0000.0 mg / L or less.
  • bismuth nitrate can be used as the bismuth compound.
  • concentration of indium in the replacement plating solution is preferably adjusted to 0.1 mg / L or more and 10,0000.0 mg / L or less.
  • Various complexing agents such as a chelating agent such as ethylenediaminetetraacetic acid may be added to the replacement plating solution, if necessary.
  • the pH of the replacement plating solution may be adjusted to a predetermined range by adding an alkaline solution such as aqueous ammonia or sodium hydroxide solution to the replacement plating solution.
  • an alkaline solution such as aqueous ammonia or sodium hydroxide solution
  • the immersion temperature and the immersion time may be appropriately adjusted according to the thickness of the metal layer.
  • the electroplating method is a plating method using an electric current, and is an excellent method for forming a metal layer.
  • a preferred embodiment of the electroplating method will be described below.
  • the electroplating solution for the electroplating method a nitric acid aqueous solution of a metal element having an arbitrary concentration or another acidic aqueous solution is prepared.
  • the metal element includes at least one selected from the group consisting of bismuth, indium, aluminum, gallium, tin, silver and manganese.
  • the concentration of the metal element in the electroplating solution can be appropriately selected depending on the type of the target metal element, the thickness of the coating metal layer, and other conditions.
  • the tin concentration in the electroplating solution is preferably adjusted to 1.0 g / L or more and 100.0 g / L or less.
  • tin nitrate can be used as the tin compound.
  • the concentration of indium in the electroplating solution is preferably adjusted to 1.0 g / L or more and 100.0 g / L or less.
  • various complexing agents such as a chelating agent such as ethylenediaminetetraacetic acid may be added to the electroplating solution.
  • the pH of the electroplating solution may be adjusted to a predetermined range by adding an alkaline solution such as aqueous ammonia or sodium hydroxide solution to the electroplating solution.
  • an alkaline solution such as aqueous ammonia or sodium hydroxide solution
  • a foil body coated with a metal layer can be obtained.
  • the current density, immersion temperature and time at the time of energization may be appropriately adjusted according to the surface condition and thickness of the target metal layer.
  • the foil body immersed in the electroplating solution is used as the cathode, and the counter electrode is used as the anode.
  • the counter electrode it is preferable to use a flat plate made of the same type of metal as the metal layer covering the foil body. As a result, the concentration of the metal element in the electroplating can be kept constant during energization.
  • Negative electrode active material for batteries The metal layer-coated zinc foil obtained as described above is suitably used as a negative electrode active material for batteries in primary batteries and secondary batteries.
  • the primary battery include a manganese zinc battery and a zinc air battery.
  • the secondary battery include a nickel-zinc battery and a zinc-air battery.
  • the zinc foil coated with a metal layer of the present invention is particularly preferably used as a negative electrode active material for a thin battery. Further, since the metal layer-coated zinc foil itself has conductivity, the zinc foil also functions as a current collector. This makes it possible to use the metal layer-coated zinc foil itself as the negative electrode without using a current collector.
  • the thin battery has a thickness of, for example, several millimeters or less at the maximum.
  • Many thin batteries have an outer case made of a softer material than a conventional battery (for example, a cylindrical nickel-plated iron outer case), for example, a resin such as a metal laminated resin film or a heat-resistant resin film.
  • a battery having a power generation element having a positive electrode, an electrolyte, and a negative electrode as one unit and a resin exterior body accommodating the power generation element can be mentioned.
  • expansion of the battery due to gas generation is likely to occur, and the use of the metal layer-coated zinc foil of the present invention can effectively suppress gas generation.
  • the thickness of the structure containing one unit of the positive electrode, the electrolyte and the negative electrode is generally as thin as 5 mm or less. In a thin battery, it is preferable to use the unit as a single unit.
  • Example 1 Preparation of electrolytic solution
  • Zinc oxide was used as the zinc compound. This was dissolved in water together with sulfuric acid to prepare an electrolytic solution. The concentration of zinc in the electrolytic solution was 50 g / L. The concentration of sulfuric acid was set to 200 g / L as a value obtained by converting the total amount of sulfate ions into H 2 SO 4. Bismuth nitrate was added here. The concentration of bismuth was adjusted so that the content ratio of bismuth contained in the target zinc foil was 750 ppm.
  • (2) Reduction and precipitation of zinc As an anode, a DSE made of a titanium electrode coated with iridium oxide was used. An aluminum plate was used as the cathode.
  • Example 2 A replacement plating solution was prepared in the same manner as in Example 1 except that the bismuth concentration of the surface treatment solution was 50 mg / L and ethylenediaminetetraacetic acid was added in an equimolar amount with bismuth nitrate. Further, a zinc foil coated with a metal bismuth layer was obtained in the same manner as in Example 1 except that the immersion time of the foil body was set to 10 minutes.
  • Example 3 The replacement plating solution was used in the same manner as in Example 1 except that the indium concentration was adjusted to 960 mg / L by changing to indium nitrate instead of bismuth nitrate, and sodium hydroxide was added to adjust the pH to 6.5. Prepared. Further, a metal indium layer-coated zinc foil was obtained in the same manner as in Example 1 except that the immersion time of the foil body was 30 seconds.
  • Example 4 As the electroplating solution, an electroplating solution DAIN IN-161 (manufactured by Daiwa Kasei Co., Ltd.) adjusted to have an indium concentration of 30,000 mg / L was used. An indium plate (manufactured by Niraco) was used as the anode. The foil body obtained in (2) above was used as the cathode. A cathode was placed between the two anodes. Under the condition that the electroplating liquid is kept at 30 ° C., energization is applied between the anode and the cathode so that a metal layer having a predetermined thickness is formed on the surface of the foil body, and the zinc foil coated with the metal indium layer is formed. Obtained. The current density was 1 A / cm 2 .
  • Example 5 As the electroplating solution, DAIN TINGOOD 101 (manufactured by Daiwa Kasei Co., Ltd.), which was adjusted so that the tin concentration was 20000 mg / L, was used. A tin plate (manufactured by Niraco) was used as the anode. The current density was set to 2 A / cm 2 and energization was performed while the electroplating solution was kept at 25 ° C. A zinc foil coated with a metallic tin layer was obtained in the same manner as in Example 4 except for these.
  • the metal element seven kinds of elements such as bismuth, indium, aluminum, gallium, tin, silver and manganese were measured. From the depth profile of each of the obtained elements, an element having a strength of 0.2 Volt or more and having a peak top was determined to be a metal element contained in the coated metal layer. The thickness of the metal layer was calculated using the above-mentioned sputter rate based on the depth profile of the discriminated metal element, starting from the outermost surface, and based on the time when the strength decreased to 1/5 with respect to the maximum strength.
  • the peak top position is not always located only on the outermost surface of the metal layer-coated zinc foil, and may be located between the outermost surface and the zinc layer.
  • the thickness of the metal layer starts from the outermost surface and is closest to the zinc layer among the multiple times when the intensity of the metal element becomes 1/5 of the peak top.
  • the time can be selected as the end point and the thickness of the metal layer can be calculated using the sputter rate based on the time.
  • a zinc foil for a negative electrode active material in which the amount of gas generated is suppressed more than before in the battery, particularly when used as the negative electrode active material of a thin battery.

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JP7466069B1 (ja) 2023-03-13 2024-04-11 三井金属鉱業株式会社 亜鉛箔及びその製造方法
WO2024189937A1 (ja) * 2023-03-13 2024-09-19 三井金属鉱業株式会社 亜鉛箔及びその製造方法

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JPS62241260A (ja) * 1986-04-10 1987-10-21 Matsushita Electric Ind Co Ltd アルカリ電池
JPH05174813A (ja) * 1991-12-26 1993-07-13 Shin Kobe Electric Mach Co Ltd 亜鉛陰極板及びその製造方法並びに亜鉛−二酸化鉛蓄電池
JP2010504428A (ja) * 2006-09-20 2010-02-12 ザ クイーンズ ユニバーシティ オブ ベルファスト 金属品を調整された濡れ性を有する表面で被覆する方法
JP2010518585A (ja) * 2007-02-12 2010-05-27 パワージェニックス システムズ， インコーポレーテッド 金属亜鉛型電流コレクタ
JP2015072832A (ja) * 2013-10-03 2015-04-16 株式会社日本触媒 亜鉛負極用組成物及び亜鉛負極
WO2020071350A1 (ja) * 2018-10-03 2020-04-09 三井金属鉱業株式会社 亜鉛箔、これを用いた一次電池用負極活物質材料及び亜鉛箔の製造方法

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JPS62241260A (ja) * 1986-04-10 1987-10-21 Matsushita Electric Ind Co Ltd アルカリ電池
JPH05174813A (ja) * 1991-12-26 1993-07-13 Shin Kobe Electric Mach Co Ltd 亜鉛陰極板及びその製造方法並びに亜鉛−二酸化鉛蓄電池
JP2010504428A (ja) * 2006-09-20 2010-02-12 ザ クイーンズ ユニバーシティ オブ ベルファスト 金属品を調整された濡れ性を有する表面で被覆する方法
JP2010518585A (ja) * 2007-02-12 2010-05-27 パワージェニックス システムズ， インコーポレーテッド 金属亜鉛型電流コレクタ
JP2015072832A (ja) * 2013-10-03 2015-04-16 株式会社日本触媒 亜鉛負極用組成物及び亜鉛負極
WO2020071350A1 (ja) * 2018-10-03 2020-04-09 三井金属鉱業株式会社 亜鉛箔、これを用いた一次電池用負極活物質材料及び亜鉛箔の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7466069B1 (ja) 2023-03-13 2024-04-11 三井金属鉱業株式会社 亜鉛箔及びその製造方法
WO2024189937A1 (ja) * 2023-03-13 2024-09-19 三井金属鉱業株式会社 亜鉛箔及びその製造方法

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