Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/004—Details
  • H01G9/04—Electrodes or formation of dielectric layers thereon
  • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
  • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/004—Details
  • H01G9/04—Electrodes or formation of dielectric layers thereon
  • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C21/00—Alloys based on aluminium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
  • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
  • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
  • B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
  • B21B2003/001—Aluminium or its alloys
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
  • B21B45/004—Heating the product

Definitions

• the present invention relates to a method for producing an aluminum material and an aluminum foil used as an electrode of an electrolytic capacitor, and an electrolytic capacitor.
• the aluminum material used for the electrolytic capacitor electrode is subjected to an etching treatment to increase the surface area and improve the capacitance. Since the area coverage increases as the depth of the etching pit formed by the etching process increases, various proposals have been made to improve the etching characteristics. For example, with regard to the manufacturing process, degreasing and cleaning before final annealing, hydration treatment before final annealing, formation of a crystalline oxide film during final annealing, and oxidation treatment before final annealing have been proposed. No. 58-34949, Japanese Unexamined Patent Publication No. 3-122620, etc.).
• the present invention provides an aluminum for an electrolytic capacitor electrode capable of generating deep etching pits with high density and uniformity, reliably increasing the area coverage, and further increasing the capacitance.
• An object of the present invention is to provide a method for producing aluminum foil for a material and an electrode for an electrolytic capacitor, and an electrolytic capacitor.
• the term “aluminum” is used to include both aluminum and its alloys.
• the present invention provides an electrolysis having a specific composition:
• the aluminum material for an electrolytic capacitor electrode according to claims 1 to 2 has a chemical composition in which A1 purity is 99.9% or more, Si: 2 to 50 ppm, and Fe: 2 to 5 O. p'pm, Cu: 15-: L 50 ppm, Zn: l-80 ppm and Pb: 0.1-3 ppm, and at least one of Z. r, V More than 11 ppm of seeds and in total: I.:! Contains ⁇ 10 Oppm and B! : Is regulated to 2j? Pm or less, and the basic point is that the balance consists of aluminum and impurities.
• the Si content is 5 to 20 pp Fe content is 5 to 20 ppm
• the Cu content is 30 to 100 ppm
• the Zn content is 10 to 10 ppm. 50 ppm
• the Pb content is 0.3 to 2 ppm
• the content of at least one of Zr, V is 20 p or more
• Zr and V The total content is preferably 20 to 70 ppm
• the B content is preferably 1 ppm or less.
• the aluminum material for an electrolytic capacitor electrode according to claims 3 to 5 is characterized in that: 1 Purity: 99.9% or more, Si: 2 to 50 ppm, Fe: 2 to 50 ppm, Cu: 15 to: L50 ppm, Zn: 1 to 80 ppm and Pb: 0.1 to 3 p, pm, at least one of Zr and V is 11 ppm or more and a total of 11 to: L 0 0 ppm, and Ti: contains l to 30 ppm, B content is regulated to 2
• the Ti content is preferably 5 to 2 ° ppm.
• the aluminum material for an electrolytic capacitor electrode according to any one of claims 6 to 8 is, in chemical composition, A1 purity: 9.9.9% or more, Si: 2 to 50 ppm, Fe: 2 to 50 pp: m, Cu: 15—150 ppra, ⁇ : l to 80 ppm and P. b: 0.1 to 3 ppm, and at least one of Zr and V is 11 p pm or more and 1. 1 to 1 00 p mu contain a total of further M n, containing G a, M g, 1 ⁇ 5 0 ppm at least one or more 1 ppm and the total of C a, B-containing
• the basic gist is that the amount is restricted to 2 ppm or less and the balance consists of and impurities.
• the Si content is 5 to 20 p. pm, Fe content 5 to 20 ppm, Cu content 30 to: L 0 ppm, 2 n content 10 to 50 ppm, Pb content 0.3 to 2 ppm
• the content of at least one of Zr and V is 20 ppm or more, the total content of Zr and V is 20 to 70 ppm, and the B content is 1 pm
• the content of at least 3 ppm or more of Mn, Ga, Mg, and Ca; and the total content of Mn, Ga, Mg, and Ca is 3 to 30 ppm.
• the Si content is 5 to 20 ppm
• the Fe content is 5 to .20 ppm
• the Cu content is 30 to 100 ppm
• the Zn content Is 10 to 50 ppm
• the P'b content is 0: 3 to 2 ppm
• the content of at least one of Zr and V is 20 ppm or more
• the total content of Z ′ r and V is 20 to 70 ppm
• the B content is 1 ppm or less.
• at least one of In, Sn, and Sb] is 2 ppm or more
• the total content of In, Sn, and Sb is 2 to 15 p. Is preferred.
• the aluminum material for an electrolytic capacitor electrode according to claims 12 to 16 has a chemical composition, A1 purity: 99.9% or more, Si: 2 to 50 ppm, Fe: 2 to 50 ppm, Cu: 15 to 5].
• the basic point is that the balance consists of aluminum and impurities.
• the electrolytic capacitor electrode aluminum material S i content of 5 ⁇ 2 0 p pm, F e content of 5 ⁇ 20 ppm, C u content 3 0 ⁇ : L 00 ppm, Z n contains chromatic weight 10 to 50 ppm, the Pb content is 0.3 to 2 ppm, the content of at least one of Zr and V is 20 ppm or more, and the sum of Zr and V It is preferable that the content is 20 to 70 ppm and the B content is 1 ppm or less. Further, the Ti content is preferably 5 to 20 ppm.
• the content of at least one of V [n, G a, M g, and C a is 3 ppm or more, and the total content of M n, G a, M g, and C a is 3 to 30 It is preferably ppm.
• the aluminum material for an electrode of an electrolytic capacitor according to claims 17 to 21 has a chemical composition of A1 purity: 99.9. /. S i: 2 to 0.50 PP ra., F e.: 2 to 50 p.pm, Cu: 15 to 150 ppm, Z n: 1 to 8 +0 ppm and Pb: 0.1 to 3.
• ppm at least one of Zr and V is 11 pp.m or more and a total of 11 'to 1 Q 0 ppm, and Ti: ⁇ to 3 ppm, and at least one of In, Sn, and Sb at 1 pm or more and a total of 30 to 30 ppra, with a B content of 2 ppm or less
• the basic point is that it is regulated and the balance consists of aluminum and impurities.
• the Si content is 5 to 20 ppm
• the Fe content is 5 to 20 ppm
• the Cu content is 30 to 100 ppm
• the Zn content is The content is 10 to 50 ppm
• the Pb content is 0.3 to 2 ppm
• the content of at least one of Zr and V is 20 ppm or more and Zr
• the total content of V and V is 20 to 70 ppm
• the B content is 1 ppm or less.
• the Ti content is preferably 5 to 2 ° ppm.
• the content of at least one of In, Sn, and Sb is 2 p or more, and the total content of In, Sn, and Sb is 2 to 15 ppm. preferable.
• the aluminum material for an electrode of an electrolytic capacitor according to Claims 2, 2 to 26 has an A1 purity of 99.9% or more in chemical composition, Si: 2 to 50 ppm, and Fe: 2 to 50 ppm, Cu: 15 to 150 ppm, Zn:;! . ⁇ 80 ppro and Pb: 0.1 ⁇ 3 ppm, and at least one of Zr and V at least 11 ppm and a total of 11 ...
• the basic gist is that both contain 1 ppm or more and contain 1 to 30 ppm in total, the B content is regulated to 2 ppm or less, and the balance consists of aluminum and impurities.
• the content of Si is 5 to 20 ppm
• the content of Fe is 5 to 20 ppm
• the content of Cu is 30 to 00 ppm
• the content of Zn is The amount is 1: Q to 50 ppm
• the Pb content is 0.3 to 2 ppm
• the content of at least one of Zr and V is 20 ppm or more
• the total content of Z ⁇ and V is 20 to 70 ppm
• the B content is 1 ppm or less.
• the content of at least one of Mn, Ga, Mg, and Ca is 3 ppm or more
• the total content of ⁇ , Ga, Mg, and Ca is 3 to 30 ppm. That's good ,.
• the content of at least one of In, Sn, and Sb is 2 ppm or more, and the total content of In, Sn, and Sb is 2 to 15 ppm. .
• the anode material for an electrolytic capacitor electrode according to claims 27 to 38 has an A.1 purity of 99.9 in view of the composition. /. S i: 2 to 50 ppm, F e: 2 to 50 p pin, Cu: 15 to: I. 50 ppm, Z n: l to 80 ppm, and P b: 0. It contains 1 to 3 ppm and at least one of Zr and V is 11 ppm or more and contains 11 to 1 in total; L 0 0 pp in, and Ti: l to 30 ppm At least one of Mn, Ga, Mg, and Ca at lppm or more and a total of 1 to 50 ppm, and at least one of In, Sn, and Sb.
• the basic gist is that the content is 1 ppm or more and 1 to 30 ppm in total, the B content is regulated to 2 ppm or less, and the balance consists of aluminum and impurities.
• the Si content is 5 to 20 ppm
• the Fe content is 5 to 20 ppm
• the Cu content is 3 ° to 100 ppm
• the Zn content is Is 10 to 50 ppm
• the Pb content is 0.3 to 2 ppm
• the content of at least one of Z ⁇ and V is 20 Vpm or more
• Zr And the total content of V is preferably 20 to 70 ppm
• the B content is preferably 1 ppm or less.
• the Ti content is preferably from 5 to 20 ppm.
• the content of at least one of Mn, .Ga, Mg, and Ca is 3 ppm or more, and the total content of Mn, Ga, Mg, and Ca is 3 to 30 pp: m is preferred. Further, the content of at least one of In, Sn, and Sb is 2 ppm or more, and the total content of I.'n, 'Sn and Sb is 2 to 15 It is preferably p p.nr. Also, a method for producing an aluminum foil for an electrolytic capacitor electrode according to claims 39 to 46 is disclosed in claim 1, 3, '6, 9, 12, 17, 17, 22, 27. This is a method of manufacturing foil using a tamper material.
• At least one of the anode and the cathode is an aluminum foil having a chemical composition corresponding to claims 1, 3, 6, 9, 12, 17, 22, 22. It is characterized by comprising.
• the common elements that are added to the high-purity aluminum and whose content is controlled are the essential added elements Si, Fe, Cu, and P? And Zr and V, which are selectively added from the two types, and B whose content is suppressed.
• the purity of the base aluminum is 99.9% or more, over 99.9%, the amount of impurities increases, and even if the content of trace added elements is controlled, overdissolution is likely to occur during etching. This is because the etching characteristics deteriorate.
• Preferred aluminum purity is 99, 98% or more.
• Si, Fe, Cu, Zn and Pb are essential additive elements and are included in all the aluminum materials according to claims 1 to 38.
• Si has the effect of preventing the crystal grains from becoming coarse during 'recrystallization'. If the content is less than 2 ppm, the above effect is poor, and if it exceeds 50 ppm, the distribution of etching pits becomes non-uniform, so that the content is set to 2 to 50 ppm.
• a preferred lower limit of the Si content is 5 ppm, and a preferred upper limit is 20 ppm.
• Fe is an element inevitably contained in aluminum, and if it is contained in a large amount, depending on the final annealing temperature, it may form ⁇ -Fe-based precipitates, which may be dissolved during etching. Excessive increase in the amount of erosion and uneven distribution of etching pits.
• the preferred lower limit of the Fe content is 5 ppm, the preferred upper limit is 20 ppm, and the most preferred upper limit is 15 ppm.
• Cu is an element that contributes to the improvement of the etching characteristics. If the content is less than 15 ppm, the effect is poor. If the content exceeds 1.5 ppm, the formation of cubic orientation is inhibited in the crystal yarn I ability, and the etching characteristics are deteriorated. Specified within the range.
• a preferred lower limit of the Cu content is 30 ppm, and a preferred upper limit is 100 ⁇ pm.
• Z. Has the effect of uniformly generating etch pits. If the content is less than 1 ppm, the effect is poor, and if it exceeds 80 p, the surface dissolution increases and the capacitance decreases rather, so the content is specified in the range of 1 to 80 ppm.
• a preferred lower limit of the Zn content is 10 ppm, and a preferred upper limit ⁇ tt is 50 ppm.
• Pb concentrates on the foil surface during final annealing, makes the generation of etching bits in the initial stage of etching uniform, and suppresses the occurrence of local etching pits. If the Pb content is less than 0.1 ppm, the above effect is poor, and if it exceeds 3 ppm, the melting of the foil surface becomes severe and the capacitance is rather lowered, so that the Pb content is in the range of 0.1 to 3 ppm.
• the preferred lower limit of the Pb content is 0.3 pp, and the preferred upper limit is 2 pm.
• Zr and V are optional and optional elements, and all aluminum materials according to claims 1 to 38 contain at least one of them.
• Each of Zr and V has an effect of increasing the generation of etching pits, and the above effect can be obtained by at least containing one kind.
• the content of these elements have poor the effect is less than 1 1 p P m at least one kind alone, because the total exceeds 1 0 0 p in the distribution of etch pits becomes uneven.
• Alone 1 1 ppm or more and the total content is in the range of 11 to 10 ° p ⁇ .
• the preferable lower limit of these elements is 20 ppm, alone and in total, and the preferable upper limit is 70 ppm in total.
• B When B forms a compound with Zr or V, these compounds may locally concentrate the etching pit or cause overdissolution, so that it is preferably as small as possible.
• 3 Restrict the content of all aluminum materials to 2 ppm or less. The preferred upper limit of the B content is 1.
• the etching pit can be increased without causing excessive dissolution during the etching.
• the density and uniformity can be increased to increase the area coverage.
• the capacitance can be improved by such an increase in the surface area.
• Ti has the effect of increasing the generation of etching pits, and is added to the aluminum material according to claims 3 to 5, 12 to: L 6, 17 to 21 27 to 38. If the Ti content is less than 1 ppm, the above effect is poor, and if it exceeds 30 ppm, grain boundary etching becomes strong and the generation of pits becomes non-uniform. Therefore, the Ti content is specified in the range of 1 to 30 ppm. A preferred lower limit for the Ti content is 5 ppm and a preferred upper limit is 20 ppm:>
• the Mn group elements Mn, G a, M g, and C 'a have an effect of uniformizing the distribution of the generation of etching pits, and claims 6 to 8, 12 to: 16, 22, and It is added to 26, 27-38 aluminum materials. These effects can be obtained by containing at least one of these elements. If at least one of these elements alone is less than 1 ppm, the above effect is poor, and if the total exceeds 5 O ppm, surface melting occurs. Decrease in capacitance In order to achieve this, the content should be at least 1 ppm alone and the total content should be in the range of 1 to 50 ppm. The lower limit of these elements is 3 ppm alone and in total, and the upper limit is 30 p ⁇ m in total.
• the distribution of the etching pits is further uniformed, and the area coverage can be increased.
• an In group element, In, 51, and 31 are concentrated on the foil surface during final annealing, making the distribution of etching pits generated at the beginning of etching uniform, and causing localized etching pits. And is added to the aluminum material of claims 9-11, 17-2.1, 22-26, 27-38.
• These elements can achieve the above-mentioned effects by containing at least one kind. At least] .
• the effect is poor when the species is less than 1 ppm alone, and when the total exceeds 30 ppm, the foil becomes less effective.
• the total content should be in the range of 1 to 30 ppo, since the surface will be severely dissolved and the capacitance will be reduced.
• the aluminum material for an electrode of an electrolytic capacitor of the present invention defines a chemical composition as an electrode material for an electrolytic capacitor, and its shape is the same as that of a foil obtained by rolling. Includes stages.
• the aluminum material of the present invention is a foil, it is suitably manufactured by the method of the present invention.
• the method for producing an aluminum foil for an electrolytic capacitor electrode of the present invention To 4330-580.
• C is used for final annealing.
• the final annealing is performed in a temperature range of 430 to 580 ° C. If the temperature is lower than 430 C, A1-Fe-based precipitates are formed, and the precipitates are preferentially etched, so that the generation of pits becomes uneven. On the other hand, if it exceeds 580 C, the foils adhere to each other.
• the preferred lower limit of the annealing temperature is 500 ° C. and the upper limit is 560.
• the annealing is preferably performed in a non-oxidizing atmosphere in a vacuum or an inert gas.
• the annealing time is preferably from 1 to 24 hours, and particularly preferably from 4 to 12 hours.
• the present invention does not limit the steps up to final annealing, and these steps are performed according to a conventional method.
• Examples of general foil manufacturing processes up to final annealing include manufacturing of the required composition of aluminum slab, facing, soaking, hot rolling, cold rolling including intermediate annealing, foil rolling, degreasing cleaning. .
• the electrolytic capacitor according to the present invention since aluminum foil having a specific chemical composition is used as an electrode material, pitting pits are formed with high density and uniformity, and the area coverage can be increased. Then, a high capacitance can be obtained by such an increase in the surface area.
• the capacitor includes an anode and a cathode, one of which is composed of an aluminum foil having the above composition, and both electrodes which are composed of an aluminum foil of the above composition.
• conditions other than the chemical composition of the aluminum-foil, such as the thickness of the foil, the etching method, and the composition of the chemical conversion film, are not limited at all.
• the aluminum material for an electrolytic capacitor electrode of the present invention and the aluminum foil for an electrolytic capacitor electrode manufactured by the method of the present invention provide high capacitance by increasing the surface area. It is suitable as an electrode material for electrolytic capacitors used in electronic equipment, especially miniaturized electronic equipment.
• the terms and expressions used herein are used for description, not for limiting interpretation, and are not equivalent to any of the particulars shown and described herein. It should be recognized that they do not exclude things and also allow various modifications within the claimed scope of the invention.

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