WO2005056885A1 - Metal-plated steel sheet for battery case, battery case using the plated steel sheet for battery case and battery using the battery case - Google Patents
Metal-plated steel sheet for battery case, battery case using the plated steel sheet for battery case and battery using the battery case Download PDFInfo
- Publication number
- WO2005056885A1 WO2005056885A1 PCT/JP2004/015165 JP2004015165W WO2005056885A1 WO 2005056885 A1 WO2005056885 A1 WO 2005056885A1 JP 2004015165 W JP2004015165 W JP 2004015165W WO 2005056885 A1 WO2005056885 A1 WO 2005056885A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- battery
- plating
- steel sheet
- battery container
- plated steel
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 46
- 239000010959 steel Substances 0.000 title claims abstract description 46
- 238000007747 plating Methods 0.000 claims abstract description 80
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000006229 carbon black Substances 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000009792 diffusion process Methods 0.000 claims description 8
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 229910001096 P alloy Inorganic materials 0.000 abstract description 6
- 229910000531 Co alloy Inorganic materials 0.000 abstract description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000521 B alloy Inorganic materials 0.000 abstract description 3
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 abstract description 3
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 235000019241 carbon black Nutrition 0.000 description 23
- 239000010439 graphite Substances 0.000 description 17
- 229910002804 graphite Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 238000000137 annealing Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 4
- 229910000655 Killed steel Inorganic materials 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
- H01M50/128—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only inorganic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/117—Inorganic material
- H01M50/119—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
- H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
-
- 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
- Plated steel plate for battery container battery container using the plated steel plate for battery container, and battery using the battery container
- the present invention relates to a plated steel plate for a battery container, and a battery container using the plated steel plate for a battery container.
- Patent Document 1 JP-A-2002-180296
- Patent Document 2 International Publication No. WO00Z05437 pamphlet
- An object of the present invention is to provide a plated steel plate for a battery container, which can be a battery having excellent discharge characteristics, a battery container using the same, and a battery using the same. Means for solving the problem
- the plated steel sheet for a battery container of the present invention that solves the above-mentioned problem is characterized in that, in the plated steel sheet for a battery container, carbon black having an average particle size of 10 to 200 nm is coated on at least the inner surface of the battery container.
- the carbon black is dispersed in the dispersion-coated layer in an amount of 0.1 to 10% by weight (claim 2), or In the plated steel sheet for a battery container according to claim 1 or 2, the plating is-plating or nickel alloy plating (claim 3); or
- the battery container of the present invention is a battery container (claim 5) obtained by forming any one of the above-mentioned (claims 14) into a tubular shape with a bottom. is there.
- the battery of the present invention is a battery (claim 6) using the battery container according to the above (claim 5).
- a dispersion-coated layer in which extremely fine carbon black having an average particle diameter of 10 to 200 nm is dispersed during plating is provided on the surface of the coated steel sheet for a battery container on the side to be the inner surface of the battery container.
- the steel sheet used as the substrate may be a general-purpose low-carbon aluminum-killed steel (carbon content 0.01 to 0.15% by weight) or a non-aging ultra-low-carbon aluminum-killed steel (carbon content 0.011%) to which niobium or titanium is added. % By weight).
- a hot rolled plate of these steels is pickled to remove surface scale, cold rolled, electrolytically cleaned, annealed, and temper rolled, and used as a substrate. Cold rolled and electrolytically cleaned, then plated as a substrate without annealing And then annealed.
- a chromium steel sheet containing 3-20% by weight of chromium can be used.
- a plated layer is formed on a steel plate as a substrate to obtain a plated steel plate for a battery container of the present invention.
- the plated steel sheet for a battery container of the present invention is characterized in that a dispersed plating layer in which fine carbon black having an average particle diameter of 10 to 200 nm is dispersed during plating is formed on at least the surface on the inner side of the battery container.
- Channel black, thermal black, furnace black, acetylene black, Ketjen black, etc. can be used as the carbon black to be dispersed during plating.
- carbon blacks are preferably dispersed in an amount of 0.1 to 10% by weight during the plating, more preferably in an amount of 0.1 to 15% by weight.
- graphite particles having an average particle size of 110 m may be mixed with these extremely fine carbon blacks and dispersed during plating. In this case, both carbon black and graphite are preferably dispersed in an amount of 0.1 to 10% by weight.
- Examples of the plating layer for dispersing carbon black include a nickel plating layer, a cobalt plating layer, and a nickel alloy plating layer such as a nickel-cobalt alloy, a nickel-cobalt-phosphorus alloy, a nickel-boron alloy, and a nickel-phosphorus alloy. . Further, it is preferable to provide a diffusion layer below the plating layer in which the carbon black is dispersed.
- these carbon black and graphite particles are hydrophobic, they are dispersed in the plating solution using a surfactant.
- a dispersed plating in which the carbon black or the graphite particles are dispersed during plating can be obtained.
- a nickel-based plating that does not disperse carbon black during plating may be performed on a steel sheet, and then the dispersion plating layer may be formed thereon.
- Nickel base plating includes matte nickel plating, semi-bright nickel plating, cobalt plating, or the above nickel-cobalt alloy, nickel-cobalt-phosphorus alloy, nickel-boron alloy, nickel-phosphorus alloy, etc. Etc. can be used.
- platings are deposited on a steel sheet by a known plating solution using an electroplating method.
- the undercoat is plated at a thickness of 0.5-2.5 / zm, then the dispersion plating is applied at a thickness of 0.1-1.5 m.
- the plating thickness shall be 11 ⁇ m.
- a similar plating layer as the above-mentioned surface to be the inner surface of the battery container may be formed on the surface to be the outer surface of the battery container. It is preferable to form a single layer of the same plating as nickel-based plating. The thickness of the plating to be attached is preferably 114 m. Similar to the inner surface side, it is preferable to form a diffusion layer by heat treatment after forming a plating layer.
- the diffusion layer is formed by plating the steel plate on the surface to be the outer surface of the battery container as described above, applying a base coat to the surface to be the inner surface of the battery container, and then performing heat treatment. If the undercoating is not applied, plating is performed on the surface that will be the outer surface of the battery container, and dispersion plating is applied to the surface that will be the inner surface of the battery container, and then heat treatment is performed.
- the diffusion layer may be formed by applying an undercoating to the surface on the side which is to be the inner surface of the battery container, and then forming the above-mentioned dispersion-coating layer thereon, followed by heat treatment.
- the substrate is heated to a temperature of 450 ° C. or more in a non-oxidizing atmosphere or a reducing atmosphere.
- the heating method used in the box-type annealing method or the continuous annealing method can be used as it is.
- the heating time is preferably 6 to 15 hours in the box annealing method and 0.5 to 2 minutes in the continuous annealing method in the above temperature range.
- the plated steel sheet for a battery container of the present invention is obtained as described above.
- the battery container of the present invention is obtained by subjecting the above-mentioned steel sheet for battery container to drawing, drawing and ironing (DI processing), drawing and stretching (DTR), or stretching after drawing and ironing. It is obtained by forming into a bottomed cylindrical shape using the combined processing method.
- the bottom surface is a circle, an ellipse, or a polygonal shape such as a rectangle and a square, and the height of the side wall is appropriately selected according to the application, and the cylindrical shape is formed.
- the battery container thus obtained is filled with a positive electrode, a negative electrode active material and the like to form a battery.
- Nickel-cobalt alloy plating conditions (indicated by "B” in Table 1)>
- Acetylene black (average particle size 120nm) 10g / L Sodium benzenesulfonate (dispersant) 20g / L Pit inhibitor (sodium lauryl sulfate) 2mL / L pH 4-4.6
- Ketzin black (average particle size 25nm) 10g / L Sodium benzenesulfonate (dispersant) 20g / L Pit inhibitor (sodium lauryl sulfate) 2mL / L pH 4-4.6
- Ketjen black (average particle size 25nm) 5 g /
- a blank with a diameter of 57 mm was punched out from the sample of the steel sheet for battery containers shown in Table 1 as sample number 1 10 so that the side with only the iron-nickel alloy layer and the nickel layer was the outer surface of the container. It was formed into a cylindrical LR6 type battery (AA battery) container with an outer diameter of 13.8 mm and a height of 49.3 mm by drawing in 10 steps.
- AA battery AA battery
- an alkaline manganese battery was prepared as follows. Manganese dioxide and graphite were collected at a ratio of 10: 1, and potassium hydroxide (10 mol) was added and mixed to prepare a positive electrode mixture. Next, the positive electrode mixture was pressurized in a mold to form a donut-shaped positive electrode mixture pellet having a predetermined size, and was press-inserted into the battery container. A mixture of graphite powder (80 parts by weight) and epoxy resin (20 parts by weight) was applied to the inner surface of the battery container. It was diluted with til ketone and applied. Next, the negative electrode plate on which the negative electrode current collector was spot-welded was mounted on the battery container.
- a separator made of vinylon woven cloth was inserted along the inner periphery of the positive electrode mixture pellet pressed into the battery container, and zinc hydroxide and potassium hydroxide were saturated with zinc oxide.
- the negative electrode gel which was strong was filled in the battery container.
- an insulator gasket was attached to the negative electrode plate, inserted into the battery container, and then subjected to a cashmere process to produce an alkaline manganese battery.
- the internal resistance ( ⁇ ) was measured by using the AC impedance method.
- the battery After leaving the battery at 80 ° C for 3 days, the battery was discharged at a constant current of 1.5A and the voltage was 0.9
- the time to reach V was measured as the discharge time. The longer the discharge time, the better the discharge characteristics.
- Table 2 shows the results of these characteristic evaluations.
- a battery using the plated steel sheet for a battery container of the present invention in which extremely fine carbon black having a particle size of 10 to 200 nm is dispersed in plating formed on the surface serving as the inner surface of the battery container, It also has better internal resistance, short-circuit current, and discharge characteristics than batteries using plating that does not disperse carbon black or plating steel sheets for battery containers in which graphite particles having a relatively large particle size are dispersed. Therefore, a high-performance battery can be provided.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
A metal-plated steel sheet for a battery case wherein the surface to be used for the inner side of the case has a dispersion plating layer in which an extremely fine carbon black powder having a particle diameter of 10 to 200 nm is dispersed in a plating layer of nickel, cobalt, a nickel-cobalt alloy, a nickel-cobalt-phosphorus alloy, a nickel-boron alloy, a nickel-phosphorus alloy, or the like; a battery case using the metal-plated steel sheet; and a battery using the case. The metal-plated steel sheet can provide a battery having excellent discharge characteristics.
Description
明 細 書 Specification
電池容器用めつき鋼板、その電池容器用めつき鋼板を用いた電池容器、 およびその電池容器を用いた電池 Plated steel plate for battery container, battery container using the plated steel plate for battery container, and battery using the battery container
技術分野 Technical field
[0001] 本発明は、電池容器用めつき鋼板、その電池容器用めつき鋼板を用いた電池容器 The present invention relates to a plated steel plate for a battery container, and a battery container using the plated steel plate for a battery container.
、およびその電池容器を用いた電池に関する。 And a battery using the battery container.
背景技術 Background art
[0002] 近年、オーディオ機器ゃモパイル電話など、多方面にお!/、て携帯用機器が用いら れ、その作動電源として一次電池であるアルカリ電池、二次電池であるニッケル水素 電池、リチウムイオン電池などが多用されている。これらの電池においては、高出力 化および長寿命化など、高出力化が常時求められおり、正極および負極活物質を充 填する電池容器も電池の重要な構成要素として性能の向上が求められている。例え ば、負極活物質と電池容器表面との密着性を向上させて接触抵抗を低減させること を目的として、鋼板表面に形成させるニッケルめっき中に黒鉛を分散析出させること により、表面に凹凸を形成させるとともに、黒鉛粒子をめつき層中に分散させ、めっき 層表面に導電性に優れる黒鉛粒子を露出させて負極活物質と電池容器表面との接 触抵抗を低減させた分散めつき層を有する表面処理鋼板が本発明者カゝら提案され て ヽる（特許文献 1および 2参照)。 [0002] In recent years, portable devices have been used in various fields, such as audio devices and mobile telephones, and their operating power sources are alkaline batteries as primary batteries, nickel-metal hydride batteries as secondary batteries, and lithium ion batteries. Batteries are frequently used. These batteries are constantly required to have high output such as high output and long life, and battery containers filled with positive and negative electrode active materials are also required to improve performance as important components of batteries. I have. For example, irregularities are formed on the surface by dispersing and depositing graphite in the nickel plating formed on the steel sheet surface in order to improve the adhesion between the negative electrode active material and the surface of the battery container and reduce the contact resistance. And a dispersed plating layer in which the graphite particles are dispersed in the plating layer to expose graphite particles having excellent conductivity on the surface of the plating layer to reduce the contact resistance between the negative electrode active material and the surface of the battery container. The present inventors have proposed a surface-treated steel sheet (see Patent Documents 1 and 2).
[0003] これらの黒鉛粒子を分散させた表面処理鋼板を電池容器に成形に成形加工し、正 極および負極活物質を充填して電池とする場合、充填する負極活物質との接触抵抗 が減少して放電特性が向上するが、さらに優れた放電特性が得られる電池容器用め つき鋼板が求められている。 [0003] When a surface-treated steel sheet in which these graphite particles are dispersed is molded into a battery container and filled with a positive electrode and a negative electrode active material to form a battery, the contact resistance with the filled negative electrode active material is reduced. However, there is a demand for a steel sheet for a battery container, which can improve the discharge characteristics, but can obtain more excellent discharge characteristics.
[0004] 本発明に関する先行技術文献として以下のものがある。 [0004] Prior art documents relating to the present invention include the following.
特許文献 1：特開 2002-180296号公報 Patent Document 1: JP-A-2002-180296
特許文献 2：国際公開第 WO00Z05437号パンフレット Patent Document 2: International Publication No. WO00Z05437 pamphlet
発明の開示 Disclosure of the invention
発明が解決しょうとする課題
[0005] 本発明は、優れた放電特性を有する電池とすることが可能な電池容器用めつき鋼 板、それを用いた電池容器、およびそれを用いた電池を提供することを目的とする。 課題を解決するための手段 Problems the invention is trying to solve [0005] An object of the present invention is to provide a plated steel plate for a battery container, which can be a battery having excellent discharge characteristics, a battery container using the same, and a battery using the same. Means for solving the problem
[0006] 上記課題を解決する本発明の電池容器用めつき鋼板は、電池容器用めつき鋼板 において、少なくとも電池容器内面となる側の面に、平均粒径が 10— 200nmのカー ボンブラックをめつき層中に分散した分散めつき層が形成されてなることを特徴とする 電池容器用めつき鋼板 (請求項 1)であり、 [0006] The plated steel sheet for a battery container of the present invention that solves the above-mentioned problem is characterized in that, in the plated steel sheet for a battery container, carbon black having an average particle size of 10 to 200 nm is coated on at least the inner surface of the battery container. A plated steel sheet for a battery container, wherein a dispersed plated layer dispersed in the plated layer is formed,
上記 (請求項 1)の電池容器用めつき鋼板において、前記分散めつき層中に、前記 カーボンブラックが 0. 1— 10重量％の量で分散されてなること (請求項 2)、または 上記 (請求項 1または 2)の電池容器用めつき鋼板において、前記めつきが、 -ッケ ルめっき、またはニッケル合金めつきであること（請求項 3)、あるいは In the above-mentioned (claim 1), the carbon black is dispersed in the dispersion-coated layer in an amount of 0.1 to 10% by weight (claim 2), or In the plated steel sheet for a battery container according to claim 1 or 2, the plating is-plating or nickel alloy plating (claim 3); or
上記 (請求項 1一 3)の電池容器用めつき鋼板において、前記めつき層の下層に拡散 層が形成されてなること (請求項 4)を特徴とする。 In the above-mentioned plated steel sheet for a battery container (claim 13), a diffusion layer is formed below the plating layer (claim 4).
[0007] さらに、本発明の電池容器は、上記 (請求項 1一 4)のいずれか電池容器用めつき 鋼板を有底の筒型形状に成形加工してなる電池容器 (請求項 5)である。 [0007] Furthermore, the battery container of the present invention is a battery container (claim 5) obtained by forming any one of the above-mentioned (claims 14) into a tubular shape with a bottom. is there.
そして本発明の電池は上記 (請求項 5)に記載の電池容器を用いてなる電池 (請求 項 6)である。 The battery of the present invention is a battery (claim 6) using the battery container according to the above (claim 5).
[0008] 本発明においては、電池容器用めつき鋼板の電池容器内面となる側の面に、平均 粒径が 10— 200nmの極く微細なカーボンブラックがめっき中に分散した分散めつき 層を形成させることにより、接触抵抗が小さぐ短絡電流が大きぐまた連続放電時間 が長くなるなど、電池性能が向上する。 [0008] In the present invention, a dispersion-coated layer in which extremely fine carbon black having an average particle diameter of 10 to 200 nm is dispersed during plating is provided on the surface of the coated steel sheet for a battery container on the side to be the inner surface of the battery container. By forming, the battery performance is improved, for example, the contact resistance is small, the short-circuit current is large, and the continuous discharge time is long.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0009] 以下、本発明を詳細に説明する。まず本発明の電池容器用鋼板の基板である鋼板 について説明する。基板となる鋼板としては、汎用の低炭素アルミキルド鋼 (炭素量 0 . 01-0. 15重量％)、またはニオブやチタンを添加した非時効性の極低炭素アルミ キルド鋼 (炭素量 0. 01重量％未満)を用いる。これらの鋼の熱間圧延板を酸洗して 表面のスケールを除去した後、冷間圧延し次いで電解洗浄、焼鈍、調質圧延したも のを基板として用いる。冷間圧延して電解洗浄後、焼鈍を施さずに基板としてめつき
を施し、その後焼鈍してもよい。また、 3— 20重量％のクロムを含有するクロム鋼板も 用!/、ることができる。 Hereinafter, the present invention will be described in detail. First, a steel sheet which is a substrate of the steel sheet for a battery container of the present invention will be described. The steel sheet used as the substrate may be a general-purpose low-carbon aluminum-killed steel (carbon content 0.01 to 0.15% by weight) or a non-aging ultra-low-carbon aluminum-killed steel (carbon content 0.011%) to which niobium or titanium is added. % By weight). A hot rolled plate of these steels is pickled to remove surface scale, cold rolled, electrolytically cleaned, annealed, and temper rolled, and used as a substrate. Cold rolled and electrolytically cleaned, then plated as a substrate without annealing And then annealed. Also, a chromium steel sheet containing 3-20% by weight of chromium can be used.
[0010] これらの基板である鋼板にめっき層を形成させて、本発明の電池容器用めつき鋼 板とする。本発明の電池容器用めつき鋼板は、少なくとも電池容器内面となる側の面 に、平均粒径が 10— 200nmの微細なカーボンブラックがめっき中に分散した分散 めっき層が形成されてなることを特徴とする。めっき中に分散させるカーボンブラック としてはチャンネルブラック、サーマルブラック、ファーネスブラック、アセチレンブラッ ク、ケッチェンブラックなどを用いることができる力 平均粒径が 10— 60nmのケツチ ェンブラックや平均粒径が 50— 200nmのアセチレンブラックを用いることが好ましい 。これらのカーボンブラックはめつき中に 0. 1— 10重量％の量で分散されていること が好ましぐ 0. 1一 5重量％の量で分散されていることがより好ましい。また、これらの 極く微細なカーボンブラックとともに、平均粒径が 1一 10 mの黒鉛粒子を混合して めっき中に分散させてもよい。この場合、カーボンブラックと黒鉛の両方で 0. 1— 10 重量％の量で分散されて 、ることが好まし 、。 [0010] A plated layer is formed on a steel plate as a substrate to obtain a plated steel plate for a battery container of the present invention. The plated steel sheet for a battery container of the present invention is characterized in that a dispersed plating layer in which fine carbon black having an average particle diameter of 10 to 200 nm is dispersed during plating is formed on at least the surface on the inner side of the battery container. Features. Channel black, thermal black, furnace black, acetylene black, Ketjen black, etc. can be used as the carbon black to be dispersed during plating. Ketjen black with an average particle size of 10 to 60 nm and an average particle size of 50 to 200 nm It is preferable to use acetylene black. These carbon blacks are preferably dispersed in an amount of 0.1 to 10% by weight during the plating, more preferably in an amount of 0.1 to 15% by weight. Also, graphite particles having an average particle size of 110 m may be mixed with these extremely fine carbon blacks and dispersed during plating. In this case, both carbon black and graphite are preferably dispersed in an amount of 0.1 to 10% by weight.
[0011] カーボンブラックを分散させるめっき層としては、ニッケルめっき層、コバルトめっき 層、またはニッケル コバルト合金、ニッケル コバルト—リン合金、ニッケル ボロン合 金、ニッケル リン合金などのニッケル合金めつき層などがある。また、これらのカーボ ンブラックを分散させるめっき層の下層に、拡散層を設けることが好ましい。 [0011] Examples of the plating layer for dispersing carbon black include a nickel plating layer, a cobalt plating layer, and a nickel alloy plating layer such as a nickel-cobalt alloy, a nickel-cobalt-phosphorus alloy, a nickel-boron alloy, and a nickel-phosphorus alloy. . Further, it is preferable to provide a diffusion layer below the plating layer in which the carbon black is dispersed.
[0012] これらのカーボンブラックや黒鉛粒子は疎水性であるので、界面活性剤を用いてめ つき液中に分散させる。このカーボンブラック、またはさらに黒鉛粒子を分散させため つき液を用いて電解処理することにより、めっき中にカーボンブラック、またはさらに黒 鉛粒子が分散してなる分散めつきが得られる。 [0012] Since these carbon black and graphite particles are hydrophobic, they are dispersed in the plating solution using a surfactant. By subjecting the carbon black or the graphite particles to an electrolytic treatment using a coating liquid for dispersing the particles, a dispersed plating in which the carbon black or the graphite particles are dispersed during plating can be obtained.
[0013] また、鋼板上にめっき中にカーボンブラックを分散させないニッケル系の下地めつき を施し、次いでその上に上記の分散めつき層を形成させてもよい。ニッケル系の下地 めっきとしては、無光沢ニッケルめっき、半光沢ニッケルめっきや、コバルトめっき、ま たは上記のニッケル コバルト合金、ニッケル コバルト—リン合金、ニッケル ボロン 合金、ニッケル リン合金などのニッケル合金めつきなどを用いることができる。 [0013] Further, a nickel-based plating that does not disperse carbon black during plating may be performed on a steel sheet, and then the dispersion plating layer may be formed thereon. Nickel base plating includes matte nickel plating, semi-bright nickel plating, cobalt plating, or the above nickel-cobalt alloy, nickel-cobalt-phosphorus alloy, nickel-boron alloy, nickel-phosphorus alloy, etc. Etc. can be used.
[0014] これらのめっきは公知のめっき液を用いて電気めつき法を用いて鋼板上に付着させ
る。めっきの厚さは 1一 3 /z mであることが好ましい。下地めつきを施す場合は、下地 めっきを 0. 5—2. 5 /z mの厚さでめっきした後、分散めつきを 0. 1— 1. 5 mの厚さ でめつきして、全めつき厚さを 1一 3 μ mとする。 [0014] These platings are deposited on a steel sheet by a known plating solution using an electroplating method. The It is preferable that the thickness of the plating is 113 / zm. When undercoating is applied, the undercoat is plated at a thickness of 0.5-2.5 / zm, then the dispersion plating is applied at a thickness of 0.1-1.5 m. The plating thickness shall be 11 μm.
[0015] 電池容器外面となる側の面には、上記の電池容器内面となる側の面と同様のめつ き層を形成させてもよいが、上記の電池容器内面となる側に形成させるニッケル系の 下地めつきと同様のめっきを単層で形成させることが好ましい。付着させるめっきの厚 さは 1一 4 mであることが好ましい。内面側と同様に、めっき層を形成させた後、熱 処理して拡散層を形成させることが好ま ヽ。 [0015] A similar plating layer as the above-mentioned surface to be the inner surface of the battery container may be formed on the surface to be the outer surface of the battery container. It is preferable to form a single layer of the same plating as nickel-based plating. The thickness of the plating to be attached is preferably 114 m. Similar to the inner surface side, it is preferable to form a diffusion layer by heat treatment after forming a plating layer.
[0016] 拡散層は、鋼板上に上記のようにして電池容器外面となる側の面にめっきし、電池 容器内面となる側の面に下地めつきを施した後に熱処理して設ける。下地めつきを施 さない場合は、電池容器外面となる側の面にめっきし、電池容器内面となる側の面に 分散めつきを施した後に熱処理して形成させる。また、電池容器内面となる側の面に 下地めつきを施し、次いでその上に上記の分散めつき層を形成させた後、熱処理し て拡散層を形成させてもよい。拡散層を形成させる熱処理としては、非酸化性雰囲 気中、または還元性中で 450°C以上の温度に加熱する。加熱方法としては箱型焼鈍 法または連続焼鈍法で用いられて 、る加熱方法をそのまま使用することができる。加 熱時間は、上記温度範囲において、箱型焼鈍法では 6— 15時間、連続焼鈍法では 0. 5— 2分であることが好ましい。 [0016] The diffusion layer is formed by plating the steel plate on the surface to be the outer surface of the battery container as described above, applying a base coat to the surface to be the inner surface of the battery container, and then performing heat treatment. If the undercoating is not applied, plating is performed on the surface that will be the outer surface of the battery container, and dispersion plating is applied to the surface that will be the inner surface of the battery container, and then heat treatment is performed. Alternatively, the diffusion layer may be formed by applying an undercoating to the surface on the side which is to be the inner surface of the battery container, and then forming the above-mentioned dispersion-coating layer thereon, followed by heat treatment. As the heat treatment for forming the diffusion layer, the substrate is heated to a temperature of 450 ° C. or more in a non-oxidizing atmosphere or a reducing atmosphere. The heating method used in the box-type annealing method or the continuous annealing method can be used as it is. The heating time is preferably 6 to 15 hours in the box annealing method and 0.5 to 2 minutes in the continuous annealing method in the above temperature range.
[0017] 本発明の電池容器用めつき鋼板は上記のようにして得られる。本発明の電池容器 は上記電池容器用めつき鋼板を、絞り加工法、絞りしごき加工法 (DI加工法）、絞りス トレツチカ卩工法 (DTR加工法）、または絞り加工後ストレッチ加工としごき加工を併用 する加工法を用いて、有底の筒型形状に成形加工して得られる。筒型形状としては 底面が円、楕円、または長方形や正方形などの多角形の形状であり、用途に応じて 側壁の高さを適宜選択した筒型形状に成形加工する。このようにして得られる電池容 器に正極、負極活物質等を充填して電池とする。 The plated steel sheet for a battery container of the present invention is obtained as described above. The battery container of the present invention is obtained by subjecting the above-mentioned steel sheet for battery container to drawing, drawing and ironing (DI processing), drawing and stretching (DTR), or stretching after drawing and ironing. It is obtained by forming into a bottomed cylindrical shape using the combined processing method. As the cylindrical shape, the bottom surface is a circle, an ellipse, or a polygonal shape such as a rectangle and a square, and the height of the side wall is appropriately selected according to the application, and the cylindrical shape is formed. The battery container thus obtained is filled with a positive electrode, a negative electrode active material and the like to form a battery.
実施例 Example
[0018] 以下、実施例にて本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
[電池容器用めつき鋼板の作成]
基板として、下記に示す化学組成を有する低炭素アルミキルド鋼を用い、下記に示 すめつき液、またはめつき液にカーボンブラックや黒鉛を含有させてなる下記に示す 分散めつき液を用いて、電気めつ法により電池容器外面となる側の面にめっき層、お よび電池容器内面となる側の面に表 1に示す下地めつき層を形成させた後、表 1に 示す条件で熱処理してそれぞれのめっき層の下に拡散層を形成させ、次いで表 1に 示す条件で電池容器内面となる側の面の下地めつき層の上に表 1に示すめっき層を 形成させ、試料番号 1一 10で示す電池容器用めっき鋼板を作成した。 [Preparation of steel sheet for battery container] Using a low-carbon aluminum-killed steel having the chemical composition shown below as the substrate, and using the following plating solution or the following dispersion plating solution containing carbon black or graphite in the plating solution, A plating layer is formed on the surface that will become the outer surface of the battery container by plating, and a base plating layer shown in Table 1 is formed on the surface that will be the inner surface of the battery container, and then heat-treated under the conditions shown in Table 1. A diffusion layer was formed under each plating layer, and then a plating layer shown in Table 1 was formed on the undercoating layer on the inner surface side of the battery container under the conditions shown in Table 1, and sample No. 11 A plated steel sheet for a battery container indicated by 10 was produced.
[0019] <鋼板の化学組成 > [0019] <Chemical composition of steel sheet>
C:0. 04重量％、 Si:0. 01重量％、 Mn:0. 023重: %、 P:0. 006重量0 /0、 S :： 0. 01重量0 /0、A1:0. 046重量0 /0、N:0. 0023重量0/ Nb :0. 001重量％、および 残部の Fe C:. 0 04 wt%, Si:. 0 01 wt%, Mn:. 0 023-fold:%, P:. 0 006 weight 0/0, S :: 0. 01 weight 0/0, A1: 0. 046 weight 0/0, N:. 0 0023 weight 0 / Nb:. 0 001 wt%, and the balance of Fe
[0020] <ニッケルめっき条件（表 1中に「A」で表示） > [0020] <Nickel plating conditions (indicated by "A" in Table 1)>
浴組成 硫酸ニッケル 300g Bath composition Nickel sulfate 300g
塩化ニッケル 40g Nickel chloride 40g
ホウ酸 30g Boric acid 30g
pH 4—4. 6 pH 4—4.6
浴温 55— 60°C Bath temperature 55-60 ° C
撹拌 空気撹拌 Stir Air stir
電流密度 20AZdm2 Current density 20AZdm 2
[0021] くニッケル コバルト合金めつき条件（表 1中に「B」で表示） > [0021] Nickel-cobalt alloy plating conditions (indicated by "B" in Table 1)>
浴組成 硫酸ニッケル 300g Bath composition Nickel sulfate 300g
硫酸コバルト 25g Cobalt sulfate 25g
塩化 ッケル 45g 45g chloride
ホウ酸 45g 45g boric acid
pH 4—4. 6 pH 4—4.6
浴温 55— 60°C Bath temperature 55-60 ° C
撹拌 空気撹拌 Stir Air stir
電流密度 5AZdm2
[0022] <カーボンブラック分散ニッケルめっき条件（表 1中に「C」で表示） > 浴組成 硫酸ニッケル 300g/ 塩化ニッケル 40g, Current density 5AZdm 2 [0022] <Carbon black dispersed nickel plating conditions (indicated by “C” in Table 1)> Bath composition Nickel sulfate 300 g / nickel chloride 40 g,
ホウ酸 30g/ Boric acid 30 g /
アセチレンブラック（平均粒径 120nm) 10g/L ベンゼンスルホン酸ナトリウム (分散剤） 20g/L ピット抑制剤 (ラウリル硫酸ナトリウム） 2mL/L pH 4—4. 6 Acetylene black (average particle size 120nm) 10g / L Sodium benzenesulfonate (dispersant) 20g / L Pit inhibitor (sodium lauryl sulfate) 2mL / L pH 4-4.6
浴温 55— 60°C Bath temperature 55-60 ° C
撹拌 空気撹拌 Stir Air stir
電流密度 5AZdm2 Current density 5AZdm 2
[0023] <カーボンブラック分散ニッケルめっき条件（表 1中に「D」で表示） > 浴組成 硫酸ニッケル 300g/ 塩化ニッケル 40g, [0023] <Carbon black dispersed nickel plating conditions (indicated by "D" in Table 1)> Bath composition Nickel sulfate 300 g / nickel chloride 40 g,
ホウ酸 30g/ Boric acid 30 g /
ケツチ ンブラック（平均粒径 25nm) 10g/L ベンゼンスルホン酸ナトリウム (分散剤） 20g/L ピット抑制剤 (ラウリル硫酸ナトリウム） 2mL/L pH 4—4. 6 Ketzin black (average particle size 25nm) 10g / L Sodium benzenesulfonate (dispersant) 20g / L Pit inhibitor (sodium lauryl sulfate) 2mL / L pH 4-4.6
浴温 55— 60°C Bath temperature 55-60 ° C
撹拌 空気撹拌 Stir Air stir
電流密度 5AZdm2 Current density 5AZdm 2
[0024] <黒鉛分散ニッケルめっき条件 (表 1中に「E」で表示） > [0024] <Graphic dispersion nickel plating conditions (indicated by "E" in Table 1)>
浴組成 硫酸ニッケル 300g/ 塩化ニッケル 40g, Bath composition Nickel sulfate 300 g / nickel chloride 40 g,
ホウ酸 30g/ Boric acid 30 g /
黒鉛 (平均粒径 1. 3 m) 10g, Graphite (average particle size 1.3 m) 10g,
ベンゼンスルホン酸ナトリウム (分散剤） 20g/L
ピット抑制剤 (ラウリル硫酸ナトリウム） 2mL/L Sodium benzenesulfonate (dispersant) 20g / L Pit inhibitor (sodium lauryl sulfate) 2mL / L
pH 4—4. 6 pH 4—4.6
浴温 55— 60°C Bath temperature 55-60 ° C
撹拌 空気撹拌 Stir Air stir
電流密度 5AZdm2 Current density 5AZdm 2
[0025] くカーボンブラックおよび黒鉛分散ニッケル コバルト合金めつき条件（表 1中に「F」 で表示） > [0025] Carbon black and graphite-dispersed nickel-cobalt alloy deposition conditions (indicated by "F" in Table 1)>
浴組成 硫酸ニッケル 300g/ Bath composition Nickel sulfate 300 g /
硫酸コバルト 25gZL Cobalt sulfate 25gZL
塩化ニッケル 45g/L Nickel chloride 45g / L
ホウ酸 45gZL Boric acid 45gZL
黒鉛 (平均粒径 1. 3 m) 10g, Graphite (average particle size 1.3 m) 10g,
ケッチェンブラック（平均粒径 25nm) 5g/ Ketjen black (average particle size 25nm) 5 g /
ベンゼンスルホン酸ナトリウム（分散剤） 30g/L Sodium benzenesulfonate (dispersant) 30g / L
ピット抑制剤 (ラウリル硫酸ナトリウム） 2mL/L Pit inhibitor (sodium lauryl sulfate) 2mL / L
pH 4—4. 6 pH 4—4.6
浴温 55— 60°C Bath temperature 55-60 ° C
撹拌 空気撹拌 Stir Air stir
電流密度 5A/dm2 Current density 5A / dm 2
[0026] [表 1]
[Table 1]
容 器 外 面 側 容器 内 面侧 熱処理 Container outer surface side Container inner surface Heat treatment
料 条 件 Fee conditions
めつ 組 めっき 下 地 め つ き 分 散 め つ き Metal plating Plating underground Dispersion
号 (めっき条件） , No. (Plating conditions),
{g m ;) めつき組成 めつき めっき組 めっき 分散粒子 温度 時間 {g m ; ) Plating composition Plating group Plating Dispersed particles Temperature Time
(めっき条件） (めっき条 (分） (Plating condition) (Plating condition (min)
( /m :) (g/m ?) 種類 ^"率 (/ M:) (? G / m) type ^ "rate
1 Ni(A) 17.8 Ni (A) 4+ fi i-AE"(C) f5.1 ΛΒ 0, 3 550 480 1 Ni (A) 17.8 Ni (A) 4+ fi i-AE "(C) f5.1 ΛΒ 0, 3 550 480
2 Κϊ (A) 17.6 Ni (Λ) 7, 8 Ni - KB1 '(D) S.2 KBLl 9, 2 550 480 2 Κϊ (A) 17.6 Ni (Λ) 7, 8 Ni-KB 1 '(D) S.2 KB Ll 9, 2 550 480
3 Ϊ(Α) 17.4 i(A) 7.6 Ni-KB"(D) 7.2 KB' 7, 3 7S0 2 3 Ϊ (Α) 17.4 i (A) 7.6 Ni-KB "(D) 7.2 KB '7, 3 7S0 2
4 Ni-32%Co( ) 16,8 Ν i (Λ) .4 Ni-GKEll(F) 6.8 G Br 4.6 780 2 4 Ni-32% Co () 16,8Ν i (Λ) .4 Ni-GKE ll (F) 6.8 GB r 4.6 780 2
5 Ni (Λ) 16.9 9.8 Ni-KB1:( ) 2, 1 KB, 1.8 550 柳 5 Ni (Λ) 16.9 9.8 Ni-KB 1: () 2, 1 KB , 1.8 550 Willow
6 Ni - 5%Co (B) 17.2 i-32%Cn(B) 3.4 Ni-AB1:(C) 8.6 ΛΗΓ' 0, 7 6 Ni-5% Co (B) 17.2 i-32% Cn (B) 3.4 Ni-AB 1: (C) 8.6 ΛΗ Γ '0, 7
7 Ni (Λ) 17.8 Ni- Bi:( ) 7.0 KB1' 6.1 780 2 7 Ni (Λ) 17.8 Ni-B i: () 7.0 KB 1 '6.1 780 2
8 Ni(A) 17.8 Ni (A) 4.6 8 Ni (A) 17.8 Ni (A) 4.6
9 Ni (A) 17.6 Ni(A) 12.8 550 480 9 Ni (A) 17.6 Ni (A) 12.8 550 480
10 Ni(A) 17. S Ni(A) 4.6 i-Gi:(£) 7.5 2.3 7S0 2 10 Ni (A) 17.S Ni (A) 4.6 iG i: (£) 7.5 2.3 7S02
注 ; - ) AE：ァ fレンフ'ラ？ク、 KB ：ケ ンフ'ラ ク、 ϋ ： 黒鉛、 GKB： ffi S +ケ ンフ Note;-) AE: afren'ra? K, KB: Ken'raq, ：: Graphite, GKB: ffi S + Kenf
[0027] 表 1において、めっき中のカーボンブラック、黒鉛などの分散粒子の含有量は、 JIS-G- 1211記載の赤外線吸収法により測定した。 In Table 1, the content of dispersed particles such as carbon black and graphite in the plating was measured by an infrared absorption method described in JIS-G-1211.
[0028] [電池容器の作成] [0028] [Preparation of battery container]
表 1に試料番号 1 10で示す電池容器用めつき鋼板の試料から 57mm径でブラン クを打ち抜 ヽた後、鉄 ニッケル合金層とニッケル層のみを設けた側が容器外面とな るようにして、 10段の絞り加工により、外径 13.8mm、高さ 49.3mmの円筒形の LR 6型電池（単三型電池)容器に成形加工した。 A blank with a diameter of 57 mm was punched out from the sample of the steel sheet for battery containers shown in Table 1 as sample number 1 10 so that the side with only the iron-nickel alloy layer and the nickel layer was the outer surface of the container. It was formed into a cylindrical LR6 type battery (AA battery) container with an outer diameter of 13.8 mm and a height of 49.3 mm by drawing in 10 steps.
[0029] [電池の作成] [0029] [Creation of battery]
この電池容器を用いて、以下のようにしてアルカリマンガン電池を作成した。二酸ィ匕 マンガンと黒鉛を 10: 1の比率で採取し、水酸ィ匕カリウム（10モル）を添加混合して正 極合剤を作成した。次いで、この正極合剤を金型中で加圧して所定寸法のドーナツ 形状の正極合剤ペレットに成形し、上記の電池容器に圧挿入した。なお、電池容器 の内面には黒鉛粉末 (80重量部）とエポキシ榭脂（20重量部）の混合物ををメチルェ
チルケトンで希釈して塗布した。次に、負極集電棒をスポット溶接した負極板を電池 容器に装着した。次いで、ビニロン製織布カゝらなるセパレータを、電池容器に圧挿入 した正極合剤ペレットの内周に沿うようにして挿入し、亜鉛粒と酸ィ匕亜鉛を飽和させ た水酸ィ匕カリウム力もなる負極ゲルを電池容器内に充填した。さらに、負極板に絶縁 体のガスケットを装着して電池容器内に挿入した後、カシメカ卩ェを施してアルカリマン ガン電池を作成した。 Using this battery container, an alkaline manganese battery was prepared as follows. Manganese dioxide and graphite were collected at a ratio of 10: 1, and potassium hydroxide (10 mol) was added and mixed to prepare a positive electrode mixture. Next, the positive electrode mixture was pressurized in a mold to form a donut-shaped positive electrode mixture pellet having a predetermined size, and was press-inserted into the battery container. A mixture of graphite powder (80 parts by weight) and epoxy resin (20 parts by weight) was applied to the inner surface of the battery container. It was diluted with til ketone and applied. Next, the negative electrode plate on which the negative electrode current collector was spot-welded was mounted on the battery container. Next, a separator made of vinylon woven cloth was inserted along the inner periphery of the positive electrode mixture pellet pressed into the battery container, and zinc hydroxide and potassium hydroxide were saturated with zinc oxide. The negative electrode gel which was strong was filled in the battery container. Further, an insulator gasket was attached to the negative electrode plate, inserted into the battery container, and then subjected to a cashmere process to produce an alkaline manganese battery.
[0030] [特性評価] [Characteristic evaluation]
以上のようにして試料番号 1一 10の試料カゝら作成した電池容器を用いて作成した 電池の特性を、以下のようにして評価した。 The characteristics of the battery prepared using the battery container prepared as described above with the sample caps of Sample Nos. 1 to 10 were evaluated as follows.
[0031] <内部抵抗 > [0031] <Internal resistance>
電池を 80°Cで 3日間放置した後、交流インピーダンス法を用いて内部抵抗 (πιΩ ) を測定した。 After the battery was left at 80 ° C. for 3 days, the internal resistance (πιΩ) was measured by using the AC impedance method.
[0032] <短絡電流 > [0032] <Short circuit current>
電池を 80°Cで 3日間放置した後、電池に電流計を接続して閉回路を設けて電流値 を測定し、これを短絡電流とした。短絡電流が大きいほど特性が良好であることを示 す。 After leaving the battery at 80 ° C for 3 days, an ammeter was connected to the battery, a closed circuit was provided, and the current value was measured. This was defined as the short-circuit current. The higher the short-circuit current, the better the characteristics.
[0033] <放電特性 > [0033] <Discharge characteristics>
電池を 80°Cで 3日間放置した後、電池を 1. 5Aの一定電流で放電し、電圧が 0. 9 After leaving the battery at 80 ° C for 3 days, the battery was discharged at a constant current of 1.5A and the voltage was 0.9
Vに到達するまでの時間を放電時間として測定した。放電時間が長!、ほど放電特性 が良好であることを示す。 The time to reach V was measured as the discharge time. The longer the discharge time, the better the discharge characteristics.
これらの特性評価結果を表 2に示す。 Table 2 shows the results of these characteristic evaluations.
[0034] [表 2]
試 料 特 性 評 価 結 果 区 分 [0034] [Table 2] Sample characteristics Evaluation results
番 号 No.
内 部 抵 抗 短 絡 電 流 1 .5 A 放 電 Internal resistance short-circuit current 1.5 A discharge
( m Ω ) ( A ) (秒） (mΩ) (A) (seconds)
1 149 8,0 363 本 発 明 1 149 8,0 363 inventions
2 .141 8.5 426 本発 明 2.141 8.5 426 Invention
3 142 8.6 422 本発 明 3 142 8.6 422 Invention
4 144 8,7 408 本発 明 4 144 8,7 408 Invention
5 146 8.3 388 本発 明 5 146 8.3 388 Invention
6 148 8.1 370 本 発 明 6 148 8.1 370 books
7 155 7.5 274 比 較例 7 155 7.5 274 Comparative example
8 162 6.3 130 比 較例 8 162 6.3 130 Comparative example
9 166 5.9 110 比 蛟例 9 166 5.9 110
10 170 6.1 128 比 校例 10 170 6.1 128 Ratio School example
[0035] 表 2に示すように、電池容器内面となる側の面に形成させるめっき中に極く微細な カーボンブラックを分散させた本発明の電池容器用めつき鋼板を用いた電池におい ては、カーボンブラックを分散させないめっきや、比較的大きな粒径の黒鉛粒子を分 散させた電池容器用めつき鋼板を用いた電池よりも内部抵抗、短絡電流、放電特性 に優れている。 [0035] As shown in Table 2, in the battery using the plated steel sheet for a battery container of the present invention in which extremely fine carbon black is dispersed in the plating formed on the surface that is to be the inner surface of the battery container. It also has better internal resistance, short-circuit current, and discharge characteristics than batteries using plating that does not disperse carbon black or plating steel sheets for battery containers in which graphite particles having a relatively large particle size are dispersed.
産業上の利用可能性 Industrial applicability
[0036] 電池容器内面となる側の面に形成させるめっき中に極く微細な 10— 200nmの粒 径のカーボンブラックを分散させてなる本発明の電池容器用めつき鋼板を用いた電 池は、カーボンブラックを分散させないめっきや、比較的大きな粒径の黒鉛粒子を分 散させた電池容器用めつき鋼板を用いた電池よりも内部抵抗、短絡電流、放電特性 に優れている。そのため、高性能な電池を提供することができる。
[0036] A battery using the plated steel sheet for a battery container of the present invention, in which extremely fine carbon black having a particle size of 10 to 200 nm is dispersed in plating formed on the surface serving as the inner surface of the battery container, It also has better internal resistance, short-circuit current, and discharge characteristics than batteries using plating that does not disperse carbon black or plating steel sheets for battery containers in which graphite particles having a relatively large particle size are dispersed. Therefore, a high-performance battery can be provided.
Claims
[1] 電池容器用めつき鋼板において、少なくとも電池容器内面となる側の面に、平均粒 径が 10— 200nmのカーボンブラックをめつき層中に分散した分散めつき層が形成さ れてなることを特徴とする電池容器用めつき鋼板。 [1] In a plating steel sheet for a battery container, a dispersion plating layer in which carbon black having an average particle diameter of 10 to 200 nm is dispersed in the plating layer is formed on at least the surface on the inner side of the battery container. A plated steel sheet for a battery container, characterized in that:
[2] 前記分散めつき層中に、前記カーボンブラックを 0. 1— 10重量％の量で分散して なることを特徴とする、請求項 1に記載の電池容器用めつき鋼板。 2. The plated steel sheet for a battery container according to claim 1, wherein the carbon black is dispersed in the dispersed plating layer in an amount of 0.1 to 10% by weight.
[3] 前記めつきが、ニッケルめっき、またはニッケル合金めつきであることを特徴とする、 請求項 1または 2に記載の電池容器用めつき鋼板。 [3] The plated steel sheet for a battery container according to claim 1 or 2, wherein the plating is nickel plating or nickel alloy plating.
[4] 前記めつき層の下層に拡散層が形成されてなることを特徴とする、請求項 1一 3の いずれか 1項に記載の電池容器用めつき鋼板。 4. The plated steel sheet for a battery container according to any one of claims 13 to 13, wherein a diffusion layer is formed below the plating layer.
[5] 請求項 1一 4のいずれか 1項に記載の電池容器用めつき鋼板を有底の筒型形状に 成形加工してなる電池容器。 [5] A battery container obtained by forming the plated steel sheet for a battery container according to any one of claims 1-4 into a cylindrical shape having a bottom.
[6] 請求項 5に記載の電池容器を用いてなる電池。
[6] A battery using the battery container according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005516059A JPWO2005056885A1 (en) | 2003-12-08 | 2004-10-14 | Plated steel sheet for battery container, battery container using the plated steel sheet for battery container, and battery using the battery container |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003408926 | 2003-12-08 | ||
| JP2003-408926 | 2003-12-08 | ||
| JP2004274169 | 2004-09-21 | ||
| JP2004-274169 | 2004-09-21 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013216971A (en) * | 2012-03-02 | 2013-10-24 | Rohm & Haas Electronic Materials Llc | Composite of carbon black and metal |
| US20140050971A1 (en) * | 2011-04-28 | 2014-02-20 | Toyo Kohan Co., Ltd. | Surface-treated steel sheet for battery cases, battery case and battery |
| EP3725921A4 (en) * | 2017-12-15 | 2021-01-27 | Takagi, Mikiharu | Method for refining crystal grains in plating film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000268783A (en) * | 1999-03-18 | 2000-09-29 | Toyo Kohan Co Ltd | Surface treated steel sheet for battery case, manufacture thereof, battery case using surface treated steel sheet for battery case and battery using them |
| JP2002530810A (en) * | 1998-11-12 | 2002-09-17 | ヒレ ウント ミュラー ゲーエムベーハー | Battery sleeve made of shaped cold rolled sheet metal and method of manufacturing battery sleeve |
| JP2003525346A (en) * | 1999-08-06 | 2003-08-26 | ヒレ ウント ミュラー ゲーエムベーハー | A method for making surface-treated cold-rolled steel sheets that can be deep drawn or drawn, and preferably cold rolled steel sheets for making cylindrical containers, especially battery containers. |
| JP2004076118A (en) * | 2002-08-20 | 2004-03-11 | Toyo Kohan Co Ltd | Surface treated steel sheet for battery case, manufacturing method therefor, battery case formed of the steel sheet, and battery using the battery case |
-
2004
- 2004-10-14 JP JP2005516059A patent/JPWO2005056885A1/en not_active Withdrawn
- 2004-10-14 WO PCT/JP2004/015165 patent/WO2005056885A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002530810A (en) * | 1998-11-12 | 2002-09-17 | ヒレ ウント ミュラー ゲーエムベーハー | Battery sleeve made of shaped cold rolled sheet metal and method of manufacturing battery sleeve |
| JP2000268783A (en) * | 1999-03-18 | 2000-09-29 | Toyo Kohan Co Ltd | Surface treated steel sheet for battery case, manufacture thereof, battery case using surface treated steel sheet for battery case and battery using them |
| JP2003525346A (en) * | 1999-08-06 | 2003-08-26 | ヒレ ウント ミュラー ゲーエムベーハー | A method for making surface-treated cold-rolled steel sheets that can be deep drawn or drawn, and preferably cold rolled steel sheets for making cylindrical containers, especially battery containers. |
| JP2004076118A (en) * | 2002-08-20 | 2004-03-11 | Toyo Kohan Co Ltd | Surface treated steel sheet for battery case, manufacturing method therefor, battery case formed of the steel sheet, and battery using the battery case |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140050971A1 (en) * | 2011-04-28 | 2014-02-20 | Toyo Kohan Co., Ltd. | Surface-treated steel sheet for battery cases, battery case and battery |
| JP2013216971A (en) * | 2012-03-02 | 2013-10-24 | Rohm & Haas Electronic Materials Llc | Composite of carbon black and metal |
| EP3725921A4 (en) * | 2017-12-15 | 2021-01-27 | Takagi, Mikiharu | Method for refining crystal grains in plating film |
| JP2021042397A (en) * | 2017-12-15 | 2021-03-18 | 幹晴 高木 | Method of micronizing crystal grains in plating film |
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| JPWO2005056885A1 (en) | 2007-07-05 |
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