WO2001043150A1 - Feuille a gainage en alliage d'aluminium pour anode moyenne et haute tension de condensateur electrolytique - Google Patents

Feuille a gainage en alliage d'aluminium pour anode moyenne et haute tension de condensateur electrolytique Download PDF

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Publication number
WO2001043150A1
WO2001043150A1 PCT/JP2000/008724 JP0008724W WO0143150A1 WO 2001043150 A1 WO2001043150 A1 WO 2001043150A1 JP 0008724 W JP0008724 W JP 0008724W WO 0143150 A1 WO0143150 A1 WO 0143150A1
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WO
WIPO (PCT)
Prior art keywords
foil
aluminum
etching
aluminum alloy
core layer
Prior art date
Application number
PCT/JP2000/008724
Other languages
English (en)
Japanese (ja)
Inventor
Jun Shimizu
Atsushi Konishi
Original Assignee
Toyo Aluminium Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Aluminium Kabushiki Kaisha filed Critical Toyo Aluminium Kabushiki Kaisha
Priority to JP2001543748A priority Critical patent/JP4428902B2/ja
Publication of WO2001043150A1 publication Critical patent/WO2001043150A1/fr

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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
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes

Definitions

  • the present invention relates to an aluminum alloy foil for an electrolytic capacitor anode, and more particularly to an aluminum clad foil having three layers. More specifically, the present invention relates to an aluminum alloy foil for a medium-to-high pressure electrolytic capacitor having both high capacitance and high mechanical strength after DC electrolytic etching.
  • % and ppm mean “% by weight” and “weight ppm”, respectively.
  • the aluminum alloy foil for the anode for electrolytic capacitor medium- and high-pressure anodes has a purity of 99.8% or more with the addition of a small amount of Cu as necessary, while minimizing the content of impurities such as Fe and Si.
  • High-purity aluminum foil is used. Since the capacitance as a capacitor is proportional to its surface area, the aluminum alloy foil is electrochemically etched in an acidic solution such as hydrochloric acid to enlarge the surface.
  • the aluminum foil (etched foil) that has been enlarged by etching has aluminum oxide that has a withstand voltage due to the subsequent anodic oxidation.
  • a film (chemical conversion film) is formed. This is called a formation process, and the formed etched foil is called a formation foil.
  • this composite foil is rolled up together with a separator paper impregnated with an electrolyte and a cathode foil and stored in a capacitor tube (container).
  • An aluminum foil for an anode for medium and high pressure is required. Since the withstand voltage is about 200 V or more, and the chemical conversion film after etching is thick (about 250 A or more), the diameter of the etching pit is not so large as to prevent the etching pit from being blocked by the chemical conversion film during chemical formation.
  • a tunnel shape of about 1 m is formed by direct current electrolytic etching in an acidic solution containing chlorine ions. The etching pit formed in this manner is generally called a tunnel pit.
  • the aluminum foil for an electrode used for a capacitor has a small etched foil in spite of a high capacitance per unit area, that is, a large surface area after etching. High mechanical strength is required for the etched foil to be involved.
  • etching methods Conventionally, a penetration type DC etching method mainly using hydrochloric acid has been adopted to increase the area coverage of the anode foil for medium and high pressures.However, in order to obtain a higher strength etched foil, Type DC etching, which is a core residue obtained by adding hydrochloric acid to sulfuric acid, has been developed to improve the strength of the etched foil.
  • the penetrating type etching is an etching method in which a tunnel bit is generated by penetrating in a cross-sectional direction perpendicular to the foil surface.
  • the pits are present on almost the entire cross section of the foil, so the area coverage is high, but the mechanical strength of the etched foil is low.
  • core residue type etching is the same as generating through holes perpendicular to the foil surface in the same manner as through penetration, but etching that stops the progress of the pits in the direction of the foil cross section. Is the way. Since there is an unetched part near the center, the mechanical strength is superior to the penetration type.
  • Japanese Patent Application Laid-Open No. 49-13666 discloses that a core having substantially the same purity as a coated aluminum is provided between two pieces of high-purity aluminum of 99.9% or more.
  • Aluminum foil is interposed between the coated aluminum foil and the rolling direction so that the rolling direction intersects, or aluminum foil coated between two 99.9% or more high-purity coated aluminum foils
  • An aluminum foil for an electrolytic capacitor is disclosed in which an aluminum foil having a slightly lower purity is interposed.
  • the ratio of the thickness of the core aluminum material to the total thickness of the aluminum foil (cladding ratio) must be increased. Has limitations. That is, the higher the clad ratio, the more the capacitance is sacrificed.
  • Japanese Unexamined Patent Publication (Kokai) No. 55-77986 discloses that a core of a relatively low-purity aluminum-based alloy having an iron content and a silicon content of 0.03% or more, respectively, The core is made of a relatively high-purity aluminum-based alloy containing 0.2% or less of iron and silicon, each of which is clad on both sides of the core. Discloses a composite aluminum foil for an electrolytic capacitor having a thickness of 20% or less of the thickness of the composite.
  • Japanese Patent Application Laid-Open No. 62-47110 discloses a core layer made of an aluminum alloy of less than 99.4% between two outer layers of 99.8% or more. There is disclosed a cladding foil that intervenes.
  • Japanese Patent Publication No. 2-587675 discloses that an aluminum core layer having a purity of 99.995% or more is provided on both sides of the core layer with a purity of 99.0 to 99.9%.
  • An aluminum alloy foil for an electrolytic capacitor electrode rich in cubic crystals formed by cladding with an aluminum outer layer is disclosed.
  • Japanese Patent Application Laid-Open No. HEI 4-120235 discloses that the outer layer of two aluminum layers having an aluminum purity of 99.9% or more and a cubic orientation occupancy of 80% or more is not provided. Cube Orientation There is disclosed an aluminum foil for an electrolytic capacitor electrode formed by cladding a foil having a prevalence of 40% or more.
  • this technique only utilizes the fact that the tunneling stops when the core material has a low cubic orientation, and has not been able to simultaneously improve the capacitance and mechanical strength.
  • Japanese Patent Application Laid-Open No. HEI 4-120234 discloses that aluminum core containing one or more of ZnIn, Sn, and Pb in the core material and 999 in the outer layer. There is disclosed an aluminum foil for electrolytic capacitor electrodes in which 9% or more of aluminum is clad.
  • Zn, In, Sn, Pb, and the like have a high diffusion rate in aluminum, and the effect cannot be expected when annealing is performed at around 500 as in an anode foil for medium and high pressure. This is exactly the same for Si, Cu, and Mg added to the core. If these elements are added excessively, the amount of dissolution during etching increases and the capacitance decreases.
  • FIG. 1 shows the cross-sections (images) of Sample 2 (Example (a)) of Example and Sample 1 (Comparative (b)), respectively.
  • FIG. 2 shows Sample 2 (Example of the present invention). The surfaces (images) of the product (a)) and sample 1 (comparative product (b)) after electropolishing are shown.
  • an object of the present invention is to provide an aluminum alloy foil for a medium- and high-pressure anode of an electrolytic capacitor capable of expressing high mechanical strength while maintaining a capacitance equal to or higher than that of the conventional technology.
  • the present inventors have conducted intensive studies in view of the problems of the prior art, and as a result, have found that a clad foil having a specific configuration can achieve the above object, and finally completed the present invention. It has been reached.
  • the present invention provides an aluminum outer layer—aluminum
  • An aluminum alloy cladding foil for a high-pressure anode in an electrolytic capacitor consisting of three layers: an aluminum core layer and an aluminum outer layer.
  • the thickness of the core layer is 2 to 30% of the thickness of the cladding foil
  • the cubic orientation occupancy of the outer layer is 80% or more
  • the present invention relates to an aluminum alloy clad foil for a high-pressure anode in an electrolytic capacitor, which is characterized by this feature.
  • the aluminum alloy cladding foil for the electrolytic capacitor medium and high pressure anode is an aluminum alloy clad for the electrolytic capacitor medium and high voltage anode composed of three layers: an aluminum outer layer, an aluminum core layer and an aluminum outer layer. Is a metal foil,
  • the thickness of the core layer is 2 to 30% of the thickness of the cladding foil
  • the clad foil of the present invention has a three-layer structure in which an aluminum core layer is sandwiched between two aluminum outer layers.
  • the features (1) to (4) will be described in order.
  • the thickness of the aluminum core layer is usually about 2 to 30%, preferably 5 to 10% of the thickness of the clad foil of the present invention (total of 3 layers). If it is less than 2%, even if the strength of the core layer is high, it is not possible to expect a significant improvement in the etched foil strength. If it exceeds 30%, the proportion of the portion where no tunnel bit exists is increased, and the desired capacitance cannot be obtained.
  • the thickness of the clad foil of the present invention can be appropriately set according to the use of the final product and the like, but is usually about 70 to 120 / zm, preferably 75 to 1 / zm. It should be 15 m. Also, the thickness of the two aluminum outer layers may be the same or different from each other.
  • the tensile strength of the clad foil of the present invention is usually 2 S NZmm 2 or more, preferably 30 NZ mm 2 or more. In the case of 2 8 N Zmm 2 less than the strength Ri is Do insufficient, and a call involving the small diameter becomes difficult.
  • Such strength is, for example, aluminum It can be obtained by using a known high-strength material (A1 material) having an appropriate thickness as the core layer. This strength corresponds to the strength of the soft foil annealed at around 500 ° C. in the case of the anode foil for middle and high schools.
  • the cubic orientation occupancy of the aluminum outer layer is usually at least 80%, preferably at least 85%, and most preferably at least 90%. If it is less than 80%, sufficient capacitance cannot be obtained.
  • Such cubic orientation occupancy may be adjusted, for example, by adjusting the thickness of the aluminum core layer, controlling the total thickness of the clad foil, heat treatment conditions for the aluminum core layer, intermediate annealing conditions, and after the intermediate annealing. Control by adopting rolling (light rolling) be able to.
  • the tunnel bit formed by electrolytic etching does not penetrate the core layer.
  • the tunnel pit does not penetrate the aluminum core layer '.
  • the above-mentioned DC electrolytic etching conditions may be publicly known conditions. However, at least when DC electrolytic etching is performed under the etching conditions in the examples described later, it is preferable that there is no tunnel hole penetrating the aluminum core layer.
  • the 1 2 0 seconds at a current density of 3 0 0 mA / cm 2 with a mixed aqueous solution of hydrochloric acid 1 mol l and sulfuric acid 3 mol l a (8 0 ° C) as the etching solution
  • the first etching is performed, and then the second etching is performed at a current density of 200 mA / cm 2 for 22 seconds using a 1.3 mol / l nitric acid aqueous solution (75 ° C) as an etching solution. It is desirable that there is no tunnel bit penetrating the aluminum core layer after the DC electrolytic etching to be performed.
  • the clad foil of the present invention has the features as described above.
  • the outer layer particularly has an Fe of 0.0005 to 0.05% (preferably 0.05%). 0.6 to 0.005%, more preferably 0.08 to 0.002%), and the core layer contains Mn, V, Cr, It is desirable that at least one of Fe, Ti and Ni be contained in an amount of 0.3 to 5%. The presence of these components can further promote the improvement of the strength of the clad foil of the present invention in particular.
  • the core layer in an amount of 1 to 5% (preferably 1.3 to 4.7%). Again, up to a total of 5%, including Mn, including at least one of V, Cr, Fe, Ti and Ni (preferably Fe). You may be there.
  • the clad foil of the present invention preferably further contains Cu, Si and Pb.
  • the improvement of the capacitance of the clad foil of the present invention can be further promoted.
  • the Cu content is usually 0.0015 to 0.015% (preferably 0.002 to 0.08%)
  • the Si content is usually 0.05%.
  • 0 0 5 to 0.015% preferably 0.006 to 0.08%
  • the Pb content is usually 0.001 to 0.004% (preferably In this case, it may be set to 0.0000 to 0.02%).
  • Cu, Si, and Pb may be present in at least one of the aluminum outer layer and the aluminum core layer, and all of the components are contained in aluminum. Because of its high diffusion rate, it usually exists in any layer after annealing at around 500 ° C., and this case is also included in the present invention.
  • the Cu content (C (Cu)), the Si content (C (Si)), and the Pb content (C (Pb)) in the present invention are respectively represented by the following equations.
  • C (Cu) ti C i (Cu) c. + (t .—) C 2 (Cu) / to (where t. is the thickness of the cladding foil (xm), is the thickness of the aluminum core layer (m), and C is (Cu) Represents the Cu content (% by weight) in the aluminum core layer, and C 2 (Cu) represents the Cu content (% by weight) in the aluminum outer layer.)
  • t is the thickness of the cladding foil (m), is the thickness of the aluminum core layer ( ⁇ m), and C i (Si) is the Si content in the aluminum core layer ( Wt%), C 2 (Si) is the aluminum outer layer Shows the Si content (% by weight) in the sample. )
  • t is the thickness of the cladding foil (m)
  • ti is the thickness of the aluminum core layer (im)
  • C! (Pb) is the Pb content in the aluminum core layer ( % By weight) and C 2 (Pb) indicate the Pb content (% by weight) in the aluminum outer layer.
  • Pb is present at a Pb content of 0.004 to 0.2% in the surface layer from the surface of the cladding foil to a depth of 0.1 m.
  • Pb content is determined by, for example, heat treatment (annealing, etc.) of the clad foil having the above-mentioned Pb content (0.00001 to 0.004%) at 450 or more. You can get it by doing.
  • the production method itself of the clad foil of the present invention is not particularly limited as long as the above-described configuration can be obtained. Therefore, except for the composition particularly defined in the present invention, for example, it can be produced by appropriately employing known production conditions and processing conditions for a clad foil.
  • an aluminum core layer slab and an aluminum outer layer slab having a predetermined composition are prepared, and these are cold-rolled as they are, or these slabs are laminated and soaked, and then hot-rolled.
  • the laminate is manufactured by rolling. Also, during the hot rolling of the aluminum outer layer slab, it was cut into two parts, It is also possible to obtain a laminate by sandwiching the aluminum core layer slab between these two aluminum outer layer slabs and further performing hot rolling.
  • these laminates are rolled into a foil, and the foil is annealed in an inert gas (Ar gas, N 2 gas, etc.) to obtain the clad foil of the present invention. Can be.
  • an etching treatment, a chemical conversion treatment, or the like may be performed under the same conditions as those for a known clad foil.
  • the clad foil of the present invention is an etched foil obtained by subjecting the clad foil to direct-current electrolytic etching, and that there is no tunnel bit penetrating the aluminum core layer of the clad foil. It also includes the etched foil.
  • At least a current density of 300 mA / cm 2 is used by using a mixed aqueous solution (80 ° C.) of 1 mol / liter of hydrochloric acid and 3 mol / liter of sulfuric acid as an etching solution. in for 1 2 0 seconds in the first etching, and then nitric acid 1.3
  • Morunori Tsu current density torr aqueous solution (7 5 ° C) as the or falling edge of quenching fluid 2 0 0 NIA / c ra 2 2 2 5 Perform second etching for 2 s. After direct current electrolytic etching, penetrate the aluminum core layer.
  • Preferred is an etched foil that does not have a large tunnel pitch.
  • a voltage of 150 to 600 V is applied to form an oxide film with a thickness of 200 to 100 nm on the foil surface and the inner surface of the tunnel pit.
  • New The chemically treated foil subjected to these treatments may be finally housed in a capacitor tube (container) together with the cathode foil, the separator and the like by a known method.
  • the electrolytic capacitor medium pressure anode / aluminum alloy metal foil of the present invention a mechanical strength higher than that of the conventional product can be obtained while securing the same or higher capacitance as that of the conventional product. Can be fired.
  • the coil can be wound into a smaller diameter than ever before, which can greatly contribute to miniaturization of the capacitor.
  • the chemical conversion treatment after the etching and the subsequent cutting and winding steps can be performed smoothly, which can contribute to an improvement in productivity.
  • Aluminum outer layer (FeZSi / C C) and aluminum Slabs having the composition shown in Table 1 were prepared as a rubber core layer (Fe / SiZCuZX (X is Mn, V, Cr, Fe, 1 or 1 ⁇ 1)). Each slab was subjected to ordinary soaking, hot rolling and cold rolling to form a plate having a thickness of 0.05 to 1 mm. These were superimposed on three sheets of the outer layer, the core layer Z and the outer layer, and heat-treated in an air furnace at 300, and immediately after being discharged from the furnace, rolled at a rolling reduction of 50% to obtain a three-layer clad material.
  • the above-mentioned clad foil and comparative foil were cold-rolled to a thickness of 130 m, heat-treated at 200 to 300 for 6 hours, and then cold-rolled to a thickness of 110 m.
  • the obtained foil was subjected to DC electrolytic etching under the etching conditions shown in Table 2, and the weight loss before and after the etching was used to determine the dissolution loss, and the bending strength of the etched foil was measured as M.
  • Table 4 shows the production conditions of the cladding foil, the core material ratio of the cladding foil, the tensile strength, the cubic orientation occupancy, the loss on melting during etching, the bending strength of the etched foil, and the capacitance after formation. Show. In Table 4, the dissolution weight loss and the capacitance are shown as relative values when the result of an uncladded comparative foil having a thickness of 110 / xm is 100.
  • FIG. 1 shows the cross-sections (images) of Sample 2 (Example product (a)) and Sample 1 (Comparative product (b)) of the example.
  • FIG. 2 shows the surface (image) of the sample 2 (Example product (a)) and the sample 1 (comparative product (b)) of the example after electrolytic polishing.
  • the pit density of the product of the present invention is comparative Higher and more evenly

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)

Abstract

L'invention concerne une feuille en alliage d'aluminium pour anode moyenne et haute tension dont la résistance mécanique est élevée, sa capacitance demeurant équivalente à celle de la technique actuelle. Une feuille à gainage en alliage d'aluminium pour anode moyenne et haute tension d'un condensateur électrolytique comporte trois couches: une couche extérieure en aluminium, une couche centrale en aluminium et une couche extérieure en aluminium. (1) L'épaisseur de la couche centrale représente 2 à 30 % de l'épaisseur de la feuille à gainage; (2) la résistance à la traction de la feuille à gainage est d'au moins 28 N/mm2; (3) le facteur d'occupation d'orientation cubique des couches extérieures est d'au moins 80 %; et (4) aucun puits en tunnel ne traverse la couche centrale après gravure électrolytique à courant continu.
PCT/JP2000/008724 1999-12-08 2000-12-08 Feuille a gainage en alliage d'aluminium pour anode moyenne et haute tension de condensateur electrolytique WO2001043150A1 (fr)

Priority Applications (1)

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JP2001543748A JP4428902B2 (ja) 1999-12-08 2000-12-08 電解コンデンサ中高圧陽極用アルミニウム合金クラッド箔

Applications Claiming Priority (2)

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JP34890099 1999-12-08
JP11-348900 1999-12-08

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101329954B (zh) * 2008-07-14 2011-05-25 钰邦电子（无锡）有限公司 芯片型固态电解电容器
CN110033947A (zh) * 2019-05-13 2019-07-19 南通海星电子股份有限公司 一种高强度电子光箔及其制造工艺

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021134524A1 (de) * 2021-12-23 2023-06-29 Tdk Electronics Ag Gekoppeltes Ätz- und Abscheideverfahren

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51113154A (en) * 1975-03-28 1976-10-06 Toyo Aluminium Kk Aluminum foil for elecrolytic capacitor electrode
JPS5577986A (en) * 1978-12-01 1980-06-12 Alusuisse Compound aluminum foil for improved condenser
JPS6242370B2 (fr) * 1981-05-26 1987-09-08 Toyo Aluminium Kk
JPS63288008A (ja) * 1987-05-20 1988-11-25 Sumitomo Light Metal Ind Ltd 電解コンデンサ用アルミニウム箔
JPH03257913A (ja) * 1990-03-08 1991-11-18 Sumitomo Light Metal Ind Ltd 電解コンデンサ用アルミニウム箔
JPH04120234A (ja) * 1990-09-10 1992-04-21 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH04120235A (ja) * 1990-09-10 1992-04-21 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔の製造方法
JPH04250612A (ja) * 1991-01-25 1992-09-07 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH04250613A (ja) * 1991-01-25 1992-09-07 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH08264391A (ja) * 1995-03-28 1996-10-11 Nippon Chikudenki Kogyo Kk 電解コンデンサ用アルミニウム箔のエッチング方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51113154A (en) * 1975-03-28 1976-10-06 Toyo Aluminium Kk Aluminum foil for elecrolytic capacitor electrode
JPS5577986A (en) * 1978-12-01 1980-06-12 Alusuisse Compound aluminum foil for improved condenser
JPS6242370B2 (fr) * 1981-05-26 1987-09-08 Toyo Aluminium Kk
JPS63288008A (ja) * 1987-05-20 1988-11-25 Sumitomo Light Metal Ind Ltd 電解コンデンサ用アルミニウム箔
JPH03257913A (ja) * 1990-03-08 1991-11-18 Sumitomo Light Metal Ind Ltd 電解コンデンサ用アルミニウム箔
JPH04120234A (ja) * 1990-09-10 1992-04-21 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH04120235A (ja) * 1990-09-10 1992-04-21 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔の製造方法
JPH04250612A (ja) * 1991-01-25 1992-09-07 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH04250613A (ja) * 1991-01-25 1992-09-07 Showa Alum Corp 電解コンデンサ電極用アルミニウム箔
JPH08264391A (ja) * 1995-03-28 1996-10-11 Nippon Chikudenki Kogyo Kk 電解コンデンサ用アルミニウム箔のエッチング方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101329954B (zh) * 2008-07-14 2011-05-25 钰邦电子（无锡）有限公司 芯片型固态电解电容器
CN110033947A (zh) * 2019-05-13 2019-07-19 南通海星电子股份有限公司 一种高强度电子光箔及其制造工艺

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