CN111748839A - Preparation method of medium-high voltage corrosion foil for aluminum electrolytic capacitor and anode foil - Google Patents
Preparation method of medium-high voltage corrosion foil for aluminum electrolytic capacitor and anode foil Download PDFInfo
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- 239000011888 foil Substances 0.000 title claims abstract description 180
- 238000005260 corrosion Methods 0.000 title claims abstract description 155
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 127
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000003990 capacitor Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 33
- 230000002238 attenuated Effects 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000007864 aqueous solution Substances 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 239000000654 additive Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 230000000996 additive Effects 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-Hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 8
- GCLGEJMYGQKIIW-UHFFFAOYSA-H Sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 8
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N Hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 229960004011 Methenamine Drugs 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- BRRSNXCXLSVPFC-UHFFFAOYSA-N 2,3,4-Trihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1O BRRSNXCXLSVPFC-UHFFFAOYSA-N 0.000 claims description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 4
- SLAMLWHELXOEJZ-UHFFFAOYSA-N o-Nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 229960004365 benzoic acid Drugs 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 235000019794 sodium silicate Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000002829 reduced Effects 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010586 diagram Methods 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000670 limiting Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000011030 bottleneck Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 231100000078 corrosive Toxicity 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/04—Etching of light metals
-
- H—ELECTRICITY
- H01—BASIC ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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—BASIC ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
Abstract
The invention belongs to the technical field of aluminum electrolytic capacitors, and particularly discloses a preparation method of a medium-high voltage corrosion foil for an aluminum electrolytic capacitor and an anode foil. The preparation method adopts a power-on mode that current is increased firstly and then attenuated in the step of the pore-forming corrosion treatment to carry out more than two times of pore-forming corrosion treatment on the aluminum foil. The front small half part of the electrified current curve is an abrupt increased current, so that enough power required for the aperture expansion and growth of the newly-germinated etching holes is provided, the appearance consistency of the newly-germinated etching holes is ensured, and a foundation is laid for the consistent growth of the etching holes; then, attenuation current is adopted in the majority part after the current curve is applied, so that enough energy is provided for maintaining the growth of the etching holes, excessive etching holes can be prevented from being generated, branch holes are reduced, the uniformity of the length of the etching holes is improved, the appearance of the etching holes of the corrosion foil is improved, and the capacity and the bending performance of the corrosion foil are improved.
Description
Technical Field
The invention belongs to the technical field of aluminum electrolytic capacitors, and particularly relates to a preparation method of a medium-high voltage corrosion foil for an aluminum electrolytic capacitor and an anode foil prepared from the corrosion foil.
Background
The anode foil is a key material of the aluminum electrolytic capacitor and plays a role in determining the capacity index of the capacitor. With the rapid development of the information industry and the integration and miniaturization of electrical products, the demand of small-volume and large-capacity aluminum electrolytic capacitors is driven, and therefore, the improvement of the electrostatic capacity of the anode foil is urgently needed.
According to the capacitance C of the anode foil0 rS/d indicates that the anode foil capacity can be increased by increasing the anode foil surface area. The anode foil for medium and high voltage is generally formed with tunnel-type etching holes by electrochemical etching to increase the specific surface area, and then formed into an oxide film layer having dielectric properties. The conventional medium-high voltage corrosion process comprises pretreatment, primary hole forming, secondary hole expanding and post-treatment, and firstly, oil stains, an oxide film layer and the like on the surface of a plain foil are removed through the pretreatment; carrying out electrochemical corrosion on the primary hair holes to form tunnel holes with certain hole density and hole depth; the secondary reaming further expands the aperture of the etching hole and increases the capacity of the etching foil; finally, the residual impurities such as chloride ions and the like are removed through post-treatment. The first-level pore-forming corrosion is the key of the corrosion process, the capacity performance of the corrosion foil is determined, and tunnel holes with certain hole density, uniform distribution and consistent hole length are generated by adjusting parameters such as temperature, components, current, electric quantity and the like of corrosion bath solution, so that the aims of improving specific volume and mechanical performance are fulfilled. The control of the uniformity of the etching holes is the key to the performance of the etched foil and also the bottleneck of the etched foil process technology.
At present, the constant current adopted for corrosion of the hair holes is the most common in China, for example, a constant current power-up curve adopted by the corrosion process shown in fig. 1, in the hair hole corrosion process, because the applied current value is large, the aluminum foil is always in the process of hole initiation and hole growth in the whole power-up period, and the obtained corrosion foil has poor tunnel hole length uniformity. In addition, because the aluminum foil is always in a hole-forming state when the constant-current hole-forming corrosion is adopted, the number of ineffective short holes generated subsequently is increased, a large number of parallel holes are formed on the surface of the aluminum foil, the aluminum foil is thinned, and the mechanical strength of the electrode foil is reduced.
Japanese patent document No. JP5170163B2 discloses a decaying current curve, a waveform diagram of the decaying current is shown in fig. 2, and a corrosion foil having a high specific volume and a high mechanical strength with a suitable pore diameter for a formation voltage of 500V or more can be prepared. By adopting the attenuation current curve, the generation of new holes can be reduced to a certain extent at the later stage of electrification, but the difference of the surface state of the aluminum foil and the like causes different diameters of newly-initiated corrosion holes and different growth rates of the corrosion holes, the limit length of the large-diameter corrosion holes is longer, the limit length of the small-diameter corrosion holes is shorter, finally prepared corrosion holes of the corrosion foil are different in length, the mass transfer of corrosion products is not facilitated in the small-diameter corrosion holes, and the top ends of the corrosion holes are easily passivated to generate branch holes.
Disclosure of Invention
The present invention was made based on the following knowledge:
the traditional medium-high voltage corrosion process adopts constant current to carry out pitting corrosion, new corrosion holes continuously sprout on the surface of an aluminum foil under the condition of constant current, so that the hole density is overlarge, the holes are serious, and the growth time of the corrosion holes growing in the late stage of the pitting corrosion is not enough, so that the uniformity of the length of a tunnel hole is poor. On one hand, a large number of transverse branch holes exist in a corroded foil obtained by a traditional holing corrosion process, the mechanical property of the corroded foil is not favorably improved, and in the subsequent formation process, mass transfer of electrolyte in the transverse branch holes is difficult, so that the mechanical strength of the formed foil is poor; the winding process of electrolytic capacitor requires anode foil with certain thickness to ensure the tensile strength and bending performance of anode foil, so that the average hole length of etched hole is limited. The tunnel holes with different lengths are not beneficial to improving the capacity of the etched holes and the bending performance, the contribution of the shorter tunnel holes to the capacity is limited, the capacity is limited to be improved, and the bending performance of the etched foil is poor due to the overlong etched holes. Therefore, the invention improves the power-on mode of the traditional open pore corrosion, adopts a novel open pore corrosion current curve which is increased and then attenuated, obviously improves the uniformity of the length of the open pore and obviously reduces the transverse branch pores on the premise of ensuring the average length of the open pore so as to improve the capacity and the mechanical property of the corrosion foil.
Specifically, an aspect of the present invention provides a method for preparing a medium-high voltage etched foil for an aluminum electrolytic capacitor, comprising subjecting an aluminum foil toA step of corrosion treatment of the holes, wherein the corrosion treatment of the holes adopts a power-on mode that the current is increased firstly and then attenuated to carry out corrosion treatment of the holes on the aluminum foil for more than two times, and the power is applied firstly from the initial current density I when the holes are corroded0At first, suddenly changing to a high current density I1Then decayed to a current density I2In which I0＜I1＞I2。
According to some embodiments of the present invention, the applied current curve is an increasing and then decreasing current curve, and the waveform diagram is shown in fig. 3. During the corrosion treatment of the hair holes, a current curve with current increasing first and then attenuating is adopted, the first half part of the current curve is increased current with sudden change, and the current curve is at t1Within time from I0Increase to I1Then at t2-t1Within time from I1Attenuation to I2。
According to some embodiments of the invention, I00.001 to 1A/cm2Preferably 0.02 to 0.5A/cm2；
In particular, the I0Examples thereof include: 0.02A/cm2、0.03A/cm2、0.04A/cm2、0.05A/cm2、0.06A/cm2、0.07A/cm2、0.08A/cm2、0.1A/cm2、0.12A/cm2、0.15A/cm2、0.18A/cm2、0.2A/cm2、0.22A/cm2、0.25A/cm2、0.28A/cm2、0.3A/cm2、0.32A/cm2、0.35A/cm2、0.38A/cm2、0.4A/cm2、0.42A/cm2、0.45A/cm2、0.48A/cm2、0.5A/cm2And so on.
According to some embodiments of the invention, I10.6 to 8A/cm2Preferably 0.8 to 4A/cm2。
In particular, the I1Examples thereof include: 0.8A/cm2、1A/cm2、1.2A/cm2、1.5/cm2、1.8A/cm2、2A/cm2、2.3A/cm2、2.5A/cm2、2.8A/cm2、3A/cm2、3.2A/cm2、3.5A/cm2、3.8A/cm2、4A/cm2And so on.
According to some embodiments of the invention, I2Is 0 to 1A/cm2Preferably 0.02 to 0.5A/cm2。
In particular, the I2Examples thereof include: 0.02A/cm2、0.03A/cm2、0.04A/cm2、0.05A/cm2、0.08A/cm2、0.1A/cm2、0.12/cm2、0.15A/cm2、0.18A/cm2、0.2A/cm2、0.22/cm2、0.25A/cm2、0.28A/cm2、0.3A/cm2、0.32A/cm2、0.35A/cm2、0.38A/cm2、0.4A/cm2、0.42A/cm2、0.45A/cm2、0.48A/cm2、0.5A/cm2And so on.
According to some embodiments provided by the present invention, the power-up mode in which the current is increased first and then attenuated when the hair hole is corroded is specifically as follows: when the hole is corroded, the initial current density is 0.001-1A/cm after the hole is electrified2At the beginning, the temperature is suddenly changed to a high current density of 0.6 to 8A/cm2Then, the current is attenuated to a current density of 0 to 1A/cm2。
According to some embodiments provided by the present invention, the power-up mode in which the current is increased first and then attenuated when the hair hole is corroded is specifically as follows: when the hole is corroded, the power is added to the hole, the initial current density is 0.02-0.5A/cm2At first, the temperature is suddenly changed to a high current density of 0.8-4A/cm2Then, the current is attenuated to a current density of 0.02-0.5A/cm2。
According to some embodiments of the invention, the t is1Is 0.01 to 4 seconds.
In particular, the t1Examples thereof include: 0.01s, 0.05s, 0.1s, 0.2s, 0.3s, 0.4s, 0.5s, 0.6s, 0.7s, 0.8s, 0.9s, 1.0s, 1.2s, 1.5s, 1.8s, 2s, 2.2s, 2.5s, 2.8s, 3s, 3.2s, 3.5s, 3.8s, 4s, and so forth.
According to some embodiments of the invention, the t is2-t1Is 10 to 40 seconds.
In particular, the t2-t1Examples thereof include: 10s, 11s, 12s, 13s, 14s, 15, 16s, 17s, 18s, 19s, 20s, 21s, 22s, 23s, 24s, 25s, 26s, 27s, 28s, 29s, 30s, 31s, 32s, 33s, 34s, 35, 36s, 37s, 38s, 39s, 40s, and so forth.
According to some embodiments provided by the present invention, the power-up mode in which the current is increased first and then attenuated when the hair hole is corroded is specifically as follows: when the hole is corroded, the initial current density is 0.001-1A/cm after the hole is electrified2Starting with a current density of 0.6-8A/cm within 0.01-4 s2Then, the temperature is attenuated to 0 to 1A/cm within 10 to 40s2。
According to some embodiments provided by the present invention, the power-up mode in which the current is increased first and then attenuated when the hair hole is corroded is specifically as follows: when the hole is corroded, the power is added to the hole, the initial current density is 0.02-0.5A/cm2Starting with a current density of 0.8-4A/cm within 0.01-4 s2Then, the temperature is attenuated to 0.02-0.5A/cm within 10-40 s2。
In some embodiments, the method for preparing the medium-high voltage etched foil for the aluminum electrolytic capacitor uses an energization mode in which current is increased first and then attenuated, and performs the holing etching treatment on the aluminum foil 2 to 7 times, for example: 2 times, 3 times, 4 times, 5 times, 6 times and 7 times. The number of times of pitting corrosion is not limited to the above-mentioned number of times, and may be adjusted according to actual needs.
According to some embodiments of the present invention, the pitting corrosion treatment is performed by placing the aluminum foil in an aqueous solution containing hydrochloric acid and sulfuric acid, preferably, the concentrations of the hydrochloric acid and the sulfuric acid in the aqueous solution containing hydrochloric acid and sulfuric acid are 2 to 5 wt% and 30 to 40 wt%, respectively; more preferably, the temperature of the aqueous solution containing hydrochloric acid and sulfuric acid is 60-80 ℃.
According to some embodiments of the present invention, the aluminum foil is pretreated with an acidic solution before the pitting corrosion treatment, and preferably, the pretreatment comprises: soaking the aluminum foil in an acid solution at the temperature of 30-60 ℃ for 0.2-3 min, and then washing with water; more preferably, the acidic solution is H3PO4Dissolving in waterLiquid, more preferably 0.5 to 6 wt% of H3PO4An aqueous solution.
According to some embodiments of the present invention, the preparation method further comprises a step of performing a hole-expanding corrosion treatment on the aluminum foil after the hole-expanding corrosion treatment, preferably, the hole-expanding corrosion treatment is performed in a nitric acid aqueous solution by applying a constant current density to electricity; more preferably, the concentration of the nitric acid aqueous solution is 2-6 wt%, and the temperature is 60-80 ℃; and/or the constant current density for electrification is 0.1-0.2A/cm2The power-up time is 420-720 s.
In the traditional corrosion process, the reaming corrosion is a general corrosion process, which easily causes serious surface denudation and is not beneficial to the improvement of the performance of the corrosion foil. Therefore, the additive is added into the reaming corrosive liquid. The additive is at least one of hexamethylenetetramine, benzoic acid and derivatives thereof, sodium silicate and sodium hexametaphosphate. The additive, namely the hexamine, the benzoic acid and the derivatives thereof, can be adsorbed on the surface of the aluminum foil, and the additive, namely the sodium silicate and the sodium hexametaphosphate react with the aluminum to form a reaction product covering the surface of the aluminum, so that the corrosion inhibition effect on the aluminum foil is achieved, the surface degradation condition of a corrosion foil is improved, and the current efficiency is improved.
According to some embodiments provided herein, the reaming corrosion treatment is performed in an aqueous solution containing nitric acid and an additive, with constant current density energization; the additive is at least one of hexamethylenetetramine, benzoic acid and derivatives thereof, sodium silicate and sodium hexametaphosphate. Preferably, the benzoic acid derivative is at least one of trihydroxybenzoic acid, p-hydroxybenzoic acid and nitrobenzoic acid.
According to some embodiments of the present invention, the concentration of the additive in the aqueous solution is 0.05 to 20 wt%, preferably 0.1 to 10 wt%, and more preferably 0.5 to 10 wt%.
Specifically, the concentration of the additive in the aqueous solution may be exemplified by: 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 12 wt%, 2.2 wt%, 2.4 wt%, 2.6 wt%, 3.2 wt%, 3.4 wt%, 3.6 wt%, 3.8 wt%, 4.2 wt%, 4.4 wt%, 4.6 wt%, 4.8 wt%, 5 wt%, 5.2 wt%, 5.4 wt%, 5.6 wt%, 6 wt%, 7.8 wt%, 6 wt%, 7.6 wt%, 8 wt%, 6 wt%, 7.8 wt%, 6 wt%, 8 wt%, 7.8 wt%, 6 wt%, 8 wt%, 6 wt%, 7.8 wt%, 8 wt%, 6 wt%, 8 wt%, 6 wt%, 7.8 wt%, etc.
In some embodiments, the concentration of the additive in the aqueous solution is 0.05 to 5 wt% o; in some embodiments, the concentration of the additive in the aqueous solution is 0.05 to 3 wt% o; in some embodiments, the concentration of the additive in the aqueous solution is 0.08 to 2 wt%.
According to some embodiments of the present invention, the preparation method further comprises a step of post-treating the aluminum foil after the hole-expanding corrosion treatment; preferably, the post-processing comprises: soaking in nitric acid water solution, and then washing with water; more preferably, the temperature of the nitric acid aqueous solution is 55-75 ℃, the concentration is 2-8 wt%, and the soaking time is 30-120 s.
According to some embodiments of the present invention, the aluminum foil obtained by the treatment is dried to obtain a corrosion foil; preferably, the drying treatment is carried out in an oven at 60-95 ℃.
On the other hand, the invention also provides the corrosion foil prepared by the preparation method, which is particularly suitable for medium-high pressure stages.
On the other hand, the invention also provides the anode foil obtained after the etched foil is formed. The method of formation is not particularly limited, and any method known in the art may be used.
In another aspect, the present invention further provides an aluminum electrolytic capacitor comprising the anode foil described above.
The invention has the beneficial effects that:
(1) according to the preparation method of the medium-high voltage corrosion foil for the aluminum electrolytic capacitor, the current curve which is shown in figure 3 and is increased firstly and then attenuated is adopted during the holing corrosion treatment, the small part in the front of the current curve is added with the increased current which is suddenly changed, so that enough power required for the aperture expansion and growth of newly emerged etching holes is provided, the appearance consistency of the newly emerged etching holes is ensured, and a foundation is laid for the consistent growth of the etching holes; then, attenuation current is adopted in the majority part after the current curve is applied, so that enough energy is provided for maintaining the growth of the etching holes, excessive etching holes are prevented from being generated, branch holes are reduced, and the length of the etching holes and the aperture consistency are improved.
(2) According to the preparation method of the medium-high voltage corrosion foil for the aluminum electrolytic capacitor, provided by the invention, the additive is added into the reaming corrosion liquid, and the additive can be adsorbed on the surface of the aluminum foil, so that the corrosion inhibition effect on the aluminum foil is realized, the surface degradation condition of the corrosion foil is favorably improved, and the current efficiency is improved.
(3) On one hand, the transverse branch holes of the corrosion foil obtained by the invention are obviously reduced, the mass transfer of the electrolyte in the corrosion holes in the subsequent formation process can be improved, the heating is reduced, and the loss is reduced; on the other hand, the invention improves the consistency of the hole length of the corrosion foil, effectively reduces the denudation of the surface of the corrosion foil and is beneficial to improving the capacity and the bending performance of the corrosion foil.
Drawings
FIG. 1 is a constant current power-up curve commonly used in domestic constant current corrosion of hair holes;
FIG. 2 is a waveform diagram of a decaying current curve disclosed in the Japanese patent publication;
FIG. 3 is a graph of increasing and then decreasing power-up current provided by the present invention;
FIG. 4 is a cross-sectional SEM image of a pitting corrosion foil prepared in example 1 of the present invention;
FIG. 5 is a cross-sectional SEM image of a pitting corrosion foil prepared in comparative example 1;
fig. 6 is a cross-sectional SEM image of the pitting corrosion foil prepared in comparative example 2.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
The following describes the composition of the electrolyte solution according to the present invention, based on examples. It is to be noted that the following description is for the purpose of making the invention clearer and should not be construed as limiting the invention.
According to some embodiments provided herein, the method for preparing a medium-high voltage etched foil for an aluminum electrolytic capacitor includes:
(1) pretreatment: putting the aluminum foil into 0.5-6 wt% of H at 30-60 DEG C3PO4Soaking in the solution for 0.2-3 min, and then washing with water;
(2) and (3) corrosion of the hair holes: placing the pretreated aluminum foil in a container containing 2-5 wt% of HCl and 30-40 wt% of H2SO4In the aqueous solution, an increasing and then attenuating power-up mode is adopted to carry out the holing corrosion treatment on the aluminum foil for 2-7 times (for example, 2 times, 3 times, 4 times, 5 times, 6 times and 7 times), and a waveform diagram is shown in FIG. 3, wherein the specific power-up method is as follows; firstly, the initial current density is 0.001-1A/cm2Starting with a current density of 0.6-8A/cm within 0.01-4 s2Then, the temperature is attenuated to 0 to 1A/cm within 10 to 40s2After power-up, washing with water;
(3) reaming and corroding: putting the aluminum foil subjected to the pitting corrosion in a nitric acid aqueous solution with the temperature of 60-80 ℃ and the weight of 2-6 wt%, and electrifying by adopting a constant current density, wherein the current density is 0.1-0.2A/cm2Electrifying for 420-720 s, and then washing with water;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into a nitric acid aqueous solution with the temperature of 55-75 ℃ and the weight percent of 2-8 for 30-120 s, and then washing with water;
(5) and (3) drying treatment: and drying the aluminum foil obtained by post-treatment in an oven at the temperature of 60-95 ℃.
According to other embodiments provided by the present invention, a method for preparing a medium-high voltage etched foil for an aluminum electrolytic capacitor includes:
(1) pretreatment: putting the aluminum foil into 0.5-6 wt% of H at 30-60 DEG C3PO4Soaking in the solution for 0.2-3 minThen washing with water;
(2) and (3) corrosion of the hair holes: placing the pretreated aluminum foil in a container containing 2-5 wt% of HCl and 30-40 wt% of H2SO4In the aqueous solution, an increasing and then attenuating power-up mode is adopted to carry out the holing corrosion treatment on the aluminum foil for 2-7 times (for example, 2 times, 3 times, 4 times, 5 times, 6 times and 7 times), and a waveform diagram is shown in FIG. 3, wherein the specific power-up method is as follows; firstly, the initial current density is 0.001-1A/cm2Starting with a current density of 0.6-8A/cm within 0.01-4 s2Then, the temperature is attenuated to 0 to 1A/cm within 10 to 40s2After power-up, washing with water;
(3) reaming and corroding: putting the aluminum foil subjected to the holing corrosion in an aqueous solution containing 2-6 wt% of nitric acid and 0.05-20 wt% of additives at the temperature of 60-80 ℃, and electrifying by adopting a constant current density, wherein the current density is 0.1-0.2A/cm2Electrifying for 420-720 s, and then washing with water;
the additive is at least one of hexamethylenetetramine, benzoic acid and derivatives thereof, sodium silicate and sodium hexametaphosphate; preferably, the benzoic acid derivative is at least one of trihydroxybenzoic acid, p-hydroxybenzoic acid and nitrobenzoic acid;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into a nitric acid aqueous solution with the temperature of 55-75 ℃ and the weight percent of 2-8 for 30-120 s, and then washing with water;
(5) and (3) drying treatment: and drying the aluminum foil obtained by post-treatment in an oven at the temperature of 60-95 ℃.
In some embodiments, the method for preparing a medium-high voltage etched foil for an aluminum electrolytic capacitor includes:
(1) pretreatment: putting the aluminum foil into 0.5-6 wt% of H at 30-60 DEG C3PO4Soaking in the solution for 0.2-3 min, and then washing with water;
(2) and (3) corrosion of the hair holes: placing the pretreated aluminum foil in a container containing 2-5 wt% of HCl and 30-40 wt% of H2SO4In the aqueous solution, an increasing and then attenuating power-up mode is adopted to carry out the holing corrosion treatment on the aluminum foil for 2-7 times (for example, 2 times, 3 times, 4 times, 5 times, 6 times and 7 times), and a waveform diagram is shown in FIG. 3, wherein the specific power-up method isIs as follows; firstly, the initial current density is 0.02-0.5A/cm2Starting with a current density of 0.8-4A/cm within 0.01-4 s2Then, the temperature is attenuated to 0.02-0.5A/cm within 10-40 s2After power-up, washing with water;
(3) reaming and corroding: putting the aluminum foil subjected to the pitting corrosion in a nitric acid aqueous solution with the temperature of 60-80 ℃ and the weight of 2-6 wt%, and electrifying by adopting a constant current density, wherein the current density is 0.1-0.2A/cm2Electrifying for 420-720 s, and then washing with water;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into a nitric acid aqueous solution with the temperature of 55-75 ℃ and the weight percent of 2-8 for 30-120 s, and then washing with water;
(5) and (3) drying treatment: and drying the aluminum foil obtained by post-treatment in an oven at the temperature of 60-95 ℃.
In other embodiments, a method for preparing a medium-high voltage etched foil for an aluminum electrolytic capacitor includes:
(1) pretreatment: putting the aluminum foil into 0.5-6 wt% of H at 30-60 DEG C3PO4Soaking in the solution for 0.2-3 min, and then washing with water;
(2) and (3) corrosion of the hair holes: placing the pretreated aluminum foil in a container containing 2-5 wt% of HCl and 30-40 wt% of H2SO4In the aqueous solution, an increasing and then attenuating power-up mode is adopted to carry out the holing corrosion treatment on the aluminum foil for 2-7 times (for example, 2 times, 3 times, 4 times, 5 times, 6 times and 7 times), and a waveform diagram is shown in FIG. 3, wherein the specific power-up method is as follows; firstly, the initial current density is 0.02-0.5A/cm2Starting with a current density of 0.8-4A/cm within 0.01-4 s2Then, the temperature is attenuated to 0.02-0.5A/cm within 10-40 s2After power-up, washing with water;
(3) reaming and corroding: putting the aluminum foil subjected to the holing corrosion in an aqueous solution containing 2-6 wt% of nitric acid and 0.05-20 wt% of additives at the temperature of 60-80 ℃, and electrifying by adopting a constant current density, wherein the current density is 0.1-0.2A/cm2Electrifying for 420-720 s, and then washing with water;
the additive is at least one of hexamethylenetetramine, benzoic acid and derivatives thereof, sodium silicate and sodium hexametaphosphate; preferably, the benzoic acid derivative is at least one of trihydroxybenzoic acid, p-hydroxybenzoic acid and nitrobenzoic acid;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into a nitric acid aqueous solution with the temperature of 55-75 ℃ and the weight percent of 2-8 for 30-120 s, and then washing with water;
(5) and (3) drying treatment: and drying the aluminum foil obtained by post-treatment in an oven at the temperature of 60-95 ℃.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples were carried out under conditions described in the specification, under conventional conditions or under conditions recommended by the manufacturer, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the corrosion foil for the aluminum electrolytic capacitor provided by the embodiment comprises the following steps:
(1) pretreatment: aluminum foil was treated at 4 wt% of H3PO4Soaking in the solution at 60 deg.C for 2min, and cleaning with deionized water at room temperature;
(2) and (3) corrosion of the hair holes: the pretreated aluminum foil contained 3 wt% HCl and 35 wt% H at 69 deg.C2SO4In the aqueous solution, the aluminum foil is subjected to three times of pitting corrosion treatment by adopting a power-on mode of increasing current first and then attenuating, a wave form diagram is shown in figure 3, and when the pitting corrosion is carried out, power is applied first from the initial current density of 0.2A/cm2Initially, the current density was abruptly changed to 3.6A/cm within 1s2Then decays to 0.18A/cm within 30s2After power-up, the battery is cleaned by deionized water;
(3) reaming and corroding: subjecting the aluminum foil subjected to pitting corrosion to a solution containing 3.5 wt% of HNO3The current density is 0.12A/cm2The etching temperature is 70 ℃, the etching time is 700s, and then deionized water is used for cleaning at room temperature;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into the aluminum foil5wt％HNO3Treating in water solution at 60 deg.C for 60s, and cleaning with deionized water at room temperature;
(5) and (3) drying treatment: and drying the post-treated aluminum foil in an oven at 75 ℃ for 30min to obtain the etched foil.
Example 2
The preparation method of the medium-high voltage corrosion foil for the aluminum electrolytic capacitor provided by the embodiment comprises the following steps:
(1) pretreatment: aluminum foil was treated at 4 wt% of H3PO4Soaking in the solution at 60 deg.C for 2min, and cleaning with deionized water at room temperature;
(2) and (3) corrosion of the hair holes: the pretreated aluminum foil contained 3 wt% HCl and 35 wt% H at 69 deg.C2SO4In the aqueous solution, the aluminum foil is subjected to three times of holing corrosion treatment by adopting a power-on mode of increasing current first and then attenuating, a wave form diagram is shown in figure 3, and when the holing corrosion is carried out, power is applied first from the initial current density of 0.08A/cm2Initially, the current density was varied to 1.4A/cm within 1s2Then decays to 0.06A/cm within 30s2After power-up, the battery is cleaned by deionized water;
(3) reaming and corroding: the aluminum foil subjected to the first-level pore-forming corrosion contains 3.5wt percent of HNO3The current density is 0.12A/cm2The etching temperature is 70 ℃, the etching time is 700s, and then deionized water is used for cleaning at room temperature;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into 5 wt% of HNO3Treating in water solution at 60 deg.C for 60s, and cleaning with deionized water at room temperature;
(5) and (3) drying treatment: and drying the post-treated aluminum foil in an oven at 75 ℃ for 30min to obtain the etched foil.
Example 3
The preparation method of the medium-high voltage corrosion foil for the aluminum electrolytic capacitor provided by the embodiment comprises the following steps:
(1) pretreatment: aluminum foil was treated at 4 wt% of H3PO4Soaking in the solution at 60 deg.C for 2min, and cleaning with deionized water at room temperature;
(2) and (3) corrosion of the hair holes:the pretreated aluminum foil contained 3 wt% HCl and 35 wt% H at 69 deg.C2SO4In the aqueous solution, the aluminum foil is subjected to three times of pitting corrosion treatment by adopting a power-on mode of increasing current first and then attenuating, a wave form diagram is shown in figure 3, and when the pitting corrosion is carried out, power is applied first from the initial current density of 0.2A/cm2Initially, the current density was abruptly changed to 3.6A/cm within 1s2Then decays to 0.18A/cm within 30s2After power-up, the battery is cleaned by deionized water;
(3) reaming and corroding: the aluminum foil subjected to the first-level pore-forming corrosion contains 3.5wt percent of HNO32 wt% trihydroxybenzoic acid solution for reaming corrosion with current density of 0.12A/cm2The etching temperature is 70 ℃, the etching time is 700s, and then deionized water is used for cleaning at room temperature;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into 5 wt% of HNO3Treating in water solution at 60 deg.C for 60s, and cleaning with deionized water at room temperature;
(5) and (3) drying treatment: and drying the post-treated aluminum foil in an oven at 75 ℃ for 30min to obtain the etched foil.
Example 4
The preparation method of the medium-high voltage corrosion foil for the aluminum electrolytic capacitor provided by the embodiment comprises the following steps:
(1) pretreatment: aluminum foil was treated at 4 wt% of H3PO4Soaking in the solution at 60 deg.C for 2min, and cleaning with deionized water at room temperature;
(2) and (3) corrosion of the hair holes: the pretreated aluminum foil contained 3 wt% HCl and 35 wt% H at 69 deg.C2SO4In the aqueous solution, the aluminum foil is subjected to three times of pitting corrosion treatment by adopting a power-on mode of increasing current first and then attenuating, a wave form diagram is shown in figure 3, and when the pitting corrosion is carried out, power is applied first from the initial current density of 0.2A/cm2Initially, the current density was abruptly changed to 3.6A/cm within 1s2Then decays to 0.18A/cm within 30s2After power-up, the battery is cleaned by deionized water;
(3) reaming and corroding: the aluminum foil subjected to the first-level pore-forming corrosion contains 3.5wt percent of HNO32 wt% nitrobenzoic acidReaming corrosion is carried out in liquid, and the current density is 0.12A/cm2The etching temperature is 70 ℃, the etching time is 700s, and then deionized water is used for cleaning at room temperature;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into 5 wt% of HNO3Treating in water solution at 60 deg.C for 60s, and cleaning with deionized water at room temperature;
(5) and (3) drying treatment: and drying the post-treated aluminum foil in an oven at 75 ℃ for 30min to obtain the etched foil.
Example 5
The preparation method of the medium-high voltage corrosion foil for the aluminum electrolytic capacitor provided by the embodiment comprises the following steps:
(1) pretreatment: aluminum foil was treated at 4 wt% of H3PO4Soaking in the solution at 60 deg.C for 2min, and cleaning with deionized water at room temperature;
(2) and (3) corrosion of the hair holes: the pretreated aluminum foil contained 3 wt% HCl and 35 wt% H at 69 deg.C2SO4In the aqueous solution, the aluminum foil is subjected to three times of holing corrosion treatment by adopting a power-on mode of increasing current first and then attenuating, a wave form diagram is shown in figure 3, and when the holing corrosion is carried out, power is applied first from the initial current density of 0.2A/cm2Initially, the current density was abruptly changed to 3.6A/cm within 1s2Then decays to 0.18A/cm within 30s2After power-up, the battery is cleaned by deionized water;
(3) reaming and corroding: the aluminum foil subjected to the first-level pore-forming corrosion contains 3.5wt percent of HNO3And 2 wt% sodium hexametaphosphate aqueous solution for reaming corrosion, with current density of 0.12A/cm2The etching temperature is 70 ℃, the etching time is 700s, and then deionized water is used for cleaning at room temperature;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into 5 wt% of HNO3Treating in water solution at 60 deg.C for 60s, and cleaning with deionized water at room temperature;
(5) and (3) drying treatment: and drying the post-treated aluminum foil in an oven at 75 ℃ for 30min to obtain the etched foil.
Example 6
The preparation method of the medium-high voltage corrosion foil for the aluminum electrolytic capacitor provided by the embodiment comprises the following steps:
(1) pretreatment: aluminum foil was treated at 4 wt% of H3PO4Soaking in the solution at 60 deg.C for 2min, and cleaning with deionized water at room temperature;
(2) and (3) corrosion of the hair holes: the pretreated aluminum foil contained 3 wt% HCl and 35 wt% H at 69 deg.C2SO4In the aqueous solution, the aluminum foil is subjected to the three times of pitting corrosion treatment by an electrifying mode of increasing and then attenuating, a wave form diagram is shown in FIG. 3, and when the pitting corrosion is carried out, the initial current density is 0.2A/cm firstly after electrifying2Initially, the current density was abruptly changed to 3.6A/cm within 1s2Then decays to 0.18A/cm within 30s2After power-up, the battery is cleaned by deionized water;
(3) reaming and corroding: the aluminum foil subjected to the first-level pore-forming corrosion contains 3.5wt percent of HNO3And 0.8 wt% sodium hexametaphosphate in water solution, with current density of 0.12A/cm2The etching temperature is 70 ℃, the etching time is 700s, and then deionized water is used for cleaning at room temperature;
(4) and (3) post-treatment: immersing the aluminum foil subjected to hole expanding corrosion into 5 wt% of HNO3Treating in water solution at 60 deg.C for 60s, and cleaning with deionized water at room temperature;
(5) and (3) drying treatment: and drying the post-treated aluminum foil in an oven at 75 ℃ for 30min to obtain the etched foil.
Comparative example 1
This comparative example is different from example 1 only in the step (2), i.e., the pitting corrosion treatment step, and other steps such as the pretreatment step, the reaming corrosion treatment step, the post-treatment step and the drying treatment step are completely the same as those of example 1.
The power hole of the comparative example adopts the traditional power-up mode, only once power-up power hole is carried out, and the total applied electric quantity is equal to the electric quantity of three times of power-up of the example 1. The pitting corrosion treatment of this comparative example was:
placing the pretreated aluminum foil at 69 ℃ and containing 3 wt% HCl and 35 wt% H2SO4The applied current curve in the aqueous solution is a constant current curve shown in figure 1The corrosion of the horizontal hair holes, the total electricity quantity of the hair holes is the same as that of the embodiment 1, the constant current is adopted for electrifying once, and the current density is 0.64A/cm2And the electrifying time is 80s, and after electrifying is finished, the water is cleaned by deionized water.
Comparative example 2
This comparative example is different from example 1 only in the step (2), i.e., the pitting corrosion treatment step, and other steps such as the pretreatment step, the reaming corrosion treatment step, the post-treatment step and the drying treatment step are completely the same as those of example 1.
This comparative example also used three power-up holes, the total amount of power applied by the power-up holes being equal to the three power-up power of example 1. The pitting corrosion treatment of this comparative example was:
placing the pretreated aluminum foil at 69 ℃ and containing 3 wt% HCl and 35 wt% H2SO4In the aqueous solution, the pore-forming corrosion is carried out by adopting a decaying current waveform with an energizing current curve as shown in figure 2, and the initial current Ia value of the pore-forming current curve is 1.3A/cm2Gradually decays to a constant current Ib value of 0.14A/cm2The decay time ta is 25s, and then the constant current Ib value is kept at 0.14A/cm2Hold time (t)b-ta) After the power is added, the aluminum foil is washed with pure water at normal temperature for 5s, and the power is added for the first time to complete the power generation; and repeating the steps twice to perform secondary power-on hole processing and third power-on hole processing to obtain the corrosion foil.
Performance testing
The electrostatic capacity and the number of times of bending were measured after formation of the etched foils prepared in examples and comparative examples, and the results are shown in table 1, and the formation conditions were as follows: 10% boric acid at 90 deg.C and current density of 5A/dm2The formation voltage is Vfe-520V.
TABLE 1
It can be seen from the comparison of performance data in table 1 that the hole-forming corrosion is performed by using the power-on waveform with the first increase and the second decay, and meanwhile, through the mutual matching of corrosion process parameters, the electrostatic capacity of the prepared anode foil 520Vf is effectively improved, the mechanical strength is good, after the additive is added during the hole-expanding corrosion, the thickness reduction of the aluminum foil obtained by corrosion is obviously improved, and the electrostatic capacity and the mechanical strength are improved to a certain extent.
Fig. 4-6 provide SEM images of cross-sections of the etched foil prepared in example 1 of the present invention, the etched foil prepared in comparative example 1, and the etched foil prepared in comparative example 2, respectively. Comparing SEM images of all sections, the method greatly improves the length uniformity of the corrosion holes of the corrosion foil prepared by the method, and is beneficial to the improvement of specific volume and mechanical strength of the corrosion foil.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes in the method can be made without departing from the spirit of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Claims (10)
1. A preparation method of a medium-high voltage corrosion foil for an aluminum electrolytic capacitor is characterized by comprising the step of carrying out holing corrosion treatment on an aluminum foil, wherein the holing corrosion treatment adopts a power-on mode that current is increased firstly and then attenuated, the holing corrosion treatment is carried out on the aluminum foil for more than two times, and power is applied firstly from an initial current density I when holing is corroded0At first, suddenly changing to a high current density I1Then decayed to a current density I2Wherein, I0＜I1＞I2。
2. The method for producing a medium-high voltage etched foil for an aluminum electrolytic capacitor as recited in claim 1, wherein said I is00.001 to 1A/cm2Preferably 0.02 to 0.5A/cm2(ii) a Said I10.6 to 8A/cm2Preferably 0.8 to 4A/cm2(ii) a Said I2Is 0 to 1A/cm2Preferably 0.02 to 0.5A/cm2。
3. The method for preparing a medium-high voltage etched foil for an aluminum electrolytic capacitor according to claim 2, wherein the energization manner in which the current is increased first and then attenuated during pitting corrosion is specifically as follows: when the hair hole is corroded, the power is firstly applied from the initial current density I0Initially, the current density is suddenly changed within 0.01 to 4s1Then decaying to a current density I within 10-40 s2。
4. The method for producing a medium-high voltage etched foil for an aluminum electrolytic capacitor according to any one of claims 1 to 3, wherein the pitting corrosion treatment is carried out by placing an aluminum foil in an aqueous solution containing hydrochloric acid and sulfuric acid, preferably, the concentrations of hydrochloric acid and sulfuric acid in the aqueous solution containing hydrochloric acid and sulfuric acid are 2 to 5 wt% and 30 to 40 wt%, respectively; more preferably, the temperature of the aqueous solution containing hydrochloric acid and sulfuric acid is 60-80 ℃.
5. The method for preparing a medium-high voltage etched foil for an aluminum electrolytic capacitor according to claim 4, wherein the aluminum foil is subjected to a pretreatment with an acidic solution before the pitting corrosion treatment, preferably the pretreatment comprising: soaking the aluminum foil in an acid solution at the temperature of 30-60 ℃ for 0.2-3 min, and then washing with water; more preferably, the acidic solution is H3PO4An aqueous solution, more preferably 0.5 to 6 wt% of H3PO4An aqueous solution.
6. The method for producing a medium-high voltage etched foil for an aluminum electrolytic capacitor according to claim 4 or 5, further comprising a step of subjecting the aluminum foil after the pitting corrosion treatment to a reaming corrosion treatment, preferably, the reaming corrosion treatment is carried out in an aqueous nitric acid solution by applying a constant current density; more preferably, the concentration of the nitric acid aqueous solution is 2-6 wt%, and the temperature is 60-80 ℃; and/or the constant current density for electrification is 0.1-0.2A/cm2The power-up time is 420-720 s.
7. The method for producing a medium-high voltage etched foil for an aluminum electrolytic capacitor according to claim 6, wherein the hole-expanding etching treatment is carried out in an aqueous solution containing nitric acid and an additive by constant current density energization; the additive is at least one of sodium silicate, sodium hexametaphosphate, hexamethylenetetramine, benzoic acid and derivatives thereof; preferably, the benzoic acid derivative is at least one of trihydroxybenzoic acid, p-hydroxybenzoic acid and nitrobenzoic acid; preferably, the concentration of the additive in the nitric acid aqueous solution is 0.05-20 wt%, and more preferably 0.05-10 wt%.
8. The method for producing a medium-high voltage etched foil for an aluminum electrolytic capacitor as recited in claim 6, further comprising a step of post-treating the aluminum foil after the hole-expanding etching treatment; preferably, the post-processing comprises: soaking in nitric acid water solution, and then washing with water; more preferably, the temperature of the nitric acid aqueous solution is 55-75 ℃, the concentration is 2-8 wt%, and the soaking time is 30-120 s;
and/or drying the aluminum foil obtained by post-treatment to obtain a corrosion foil; preferably, the drying treatment is carried out in an oven at 60-95 ℃.
9. An anode foil obtained by chemical conversion of the etched foil produced by the production method according to any one of claims 1 to 8.
10. An aluminum electrolytic capacitor comprising the anode foil according to claim 9.
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| CN114164481A (en) * | 2021-11-12 | 2022-03-11 | 乳源瑶族自治县东阳光化成箔有限公司 | Holing corrosion method, medium-high voltage corrosion foil and preparation method thereof |
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Application publication date: 20201009 |