CN114703526A - Preparation method of high specific volume low-voltage electrode foil for automotive electronics - Google Patents
Preparation method of high specific volume low-voltage electrode foil for automotive electronics Download PDFInfo
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- CN114703526A CN114703526A CN202210632100.0A CN202210632100A CN114703526A CN 114703526 A CN114703526 A CN 114703526A CN 202210632100 A CN202210632100 A CN 202210632100A CN 114703526 A CN114703526 A CN 114703526A
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- 239000011888 foil Substances 0.000 title claims abstract description 202
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 63
- 238000002791 soaking Methods 0.000 claims abstract description 53
- 238000011282 treatment Methods 0.000 claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 33
- 238000007605 air drying Methods 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 21
- 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 19
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 19
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000012805 post-processing Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- -1 amine salt Chemical class 0.000 claims description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- VFZWCTYGZWDQGK-UHFFFAOYSA-N n-benzylhexan-1-amine Chemical class CCCCCCNCC1=CC=CC=C1 VFZWCTYGZWDQGK-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000010981 drying operation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000011221 initial treatment Methods 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 238000005956 quaternization reaction Methods 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 239000005696 Diammonium phosphate Substances 0.000 claims description 3
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical class C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 3
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- BTSZTGGZJQFALU-UHFFFAOYSA-N piroctone olamine Chemical compound NCCO.CC(C)(C)CC(C)CC1=CC(C)=CC(=O)N1O BTSZTGGZJQFALU-UHFFFAOYSA-N 0.000 claims description 3
- 229940081510 piroctone olamine Drugs 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VPRYEZICHXRJIW-MERQFXBCSA-N (2S)-2-[bis[(2-methylpropan-2-yl)oxycarbonyl]amino]-3-(1H-imidazol-5-yl)propanoate dicyclohexylazanium Chemical compound C1(CCCCC1)[NH2+]C1CCCCC1.C(=O)(OC(C)(C)C)N([C@@H](CC1=CNC=N1)C(=O)[O-])C(=O)OC(C)(C)C VPRYEZICHXRJIW-MERQFXBCSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000009835 boiling Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- 235000021317 phosphate Nutrition 0.000 description 11
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 3
- 239000001741 Ammonium adipate Substances 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- 235000019293 ammonium adipate Nutrition 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
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- C—CHEMISTRY; METALLURGY
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/77—Controlling or regulating of the coating process
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/12—Anodising more than once, e.g. in different baths
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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Abstract
The invention relates to a preparation method of a high specific volume low-voltage electrode foil for automotive electronics, which comprises the following steps: firstly, sequentially carrying out first-stage formation, second-stage formation, third-stage formation and fourth-stage formation operations on a corrosion foil, respectively adjusting the voltage, the temperature, the time, the components and the proportion of a formation liquid in the single-stage formation, adding an amine treatment liquid during the first-stage formation to greatly improve the content of alumina crystals in a formed oxide film, and then, soaking the formation foil in a phosphate solution for multiple times to carry out post-treatment operation to repair the residual defect points on the formed oxide film. Therefore, the boiling life of the electrode foil can be effectively prolonged, and the specific volume of the aluminum electrode foil is greatly improved to make a good cushion.
Description
Technical Field
The invention relates to the technical field of electrode foil manufacturing, in particular to a preparation method of a high specific volume low-voltage electrode foil for automotive electronics.
Background
Nowadays, the degree of global automobile electrification is continuously improved, especially along with the development of electric automobiles and automatic driving, the degree of automobile intellectualization, networking and electronization is continuously improved, so that electronic components used on automobiles are more and more. In an automobile electronic system, the capacitors matched with the automobile electronic system are various in types, large in quantity and high in quality requirement, and the development of the capacitors is improved with wide prospects. The capacitor plays an important role in the development of automotive electronic parts as a basic element in automotive electronic parts, and the capacitor with small size, long service life and high reliability assists the integration and diversification of automotive electronic design, and the improvement of the capacity of the electrode foil is the key to realizing the miniaturization and high performance of the aluminum electrolytic capacitor.
At present, the electrode foil is prepared by adopting a multi-stage formation mode on the corrosion foil, and the operation steps are as follows: four-stage formation, one-stage formation: 7% ammonium adipate and 1% borate, the temperature is 70 ℃, the time is 7min, and after water washing, secondary formation is carried out: 5% of ammonium adipate and 1% of borate, at the temperature of 70 ℃, for 6min, carrying out three-stage formation: 3% of ammonium adipate and 1% of borate, the temperature is 70 ℃, the time is 8min, and the quaternary formation is carried out after water washing: 5% phosphate, temperature 70 ℃, time 15min, the latter: 1% phosphate, the temperature is 80 ℃, the time is 12min, the mixture is washed and then put into a 7% phosphoric acid solution for 5min, the high-temperature (450-: 3% phosphate, temperature 70 ℃, time 5min, last three: 1% phosphate at 70 deg.C for 5.5min, washing with water, and drying. Although the preparation process route is simple and the cost is low, the capacitance and the water boiling life of the prepared electrode foil are low, and the defective rate is high. The reason for this is that the content of alumina crystals in the oxide film on the surface of the electrode foil is low, and a large number of defects remain on the oxide film after the formation treatment, and thus, it is necessary for the skilled person to solve the above problems.
Disclosure of Invention
Therefore, in view of the above-mentioned problems and drawbacks, the present inventors have collected relevant information, evaluated and considered in many ways, and continuously conducted experiments and modifications by technicians with many years of research and development experience in this field, which finally resulted in the appearance of the method for preparing the high specific volume and low voltage electrode foil for automotive electronics.
In order to solve the technical problem, the invention relates to a preparation method of a high specific volume low-voltage electrode foil for automobile electronics, which comprises the following steps:
s1, preparation of corrosion foil: immersing the aluminum foil with the purity of not less than 99.9% into acid liquor, and corroding the surface of the aluminum foil;
s2, multilevel formation, comprising the following substeps:
s21, first-order formation: soaking the corrosion foil obtained in the step S1 in a mixed solution containing 5-10 wt% of ammonium sulfate, 1-2 wt% of borate and 0.5-1 wt% of amine salt at the temperature of 65-85 ℃ for formation under the voltage of 20-160V for 5-10 min to prepare a first-level formed foil;
s22, surface cleaning: performing water washing and air drying operation on the primary formed foil obtained in the step S21;
s23, secondary formation: soaking the primary formed foil processed in the step S22 in a mixed solution containing 3-7 wt% of ammonium sulfate and 1-2 wt% of borate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 5-10 min to prepare a secondary formed foil;
s24, carrying out three-stage formation: soaking the secondary formed foil obtained in the step S23 in a mixed solution containing 3-5 wt% of ammonium sulfate and 1-2 wt% of borate at the temperature of 65-85 ℃, and forming at the voltage of 20-160V for 7-15 min to prepare a tertiary formed foil;
s25, surface cleaning: performing water washing and air drying operation on the three-level formed foil obtained in the step S24;
s26, intermediate processing: soaking the three-level formed foil treated in the step S25 in a quaternary ammonium salt water solution with the temperature controlled at 40-60 ℃ and the weight percent of 5-10% for 5-10 min;
s27, quaternization: soaking the three-level formed foil obtained in the step S26 in a solution containing 5-7 wt% of phosphate at the temperature of 65-85 ℃, and forming at the voltage of 20-160V for 15-20 min to obtain a four-level formed foil;
s3, post-processing, comprising the following sub-steps:
s31, primary post-processing: soaking the four-stage formed foil obtained in the step S27 in a phosphate aqueous solution with the temperature controlled at 65-85 ℃ and the weight percent of 1-5, applying a voltage of 20-160V for 10-15 min, and preparing a first-stage treated foil;
s32, surface cleaning: performing water washing and air drying operation on the primary processing foil obtained in the step S31;
s33, pickling treatment: soaking the primary treatment foil treated in the step S32 in a mixed solution containing 7-10 wt% of phosphoric acid and oxidizing acid, wherein the time duration is controlled to be 5-10 min;
s34, heat treatment: performing water washing and drying operation on the primary treated foil obtained in the step S33, wherein the drying temperature is controlled to be 450-500 ℃, and the time duration is controlled to be 1-2 min;
s35, secondary post-treatment: soaking the primary treated foil obtained in the step S34 in a phosphate aqueous solution with the temperature controlled at 65-85 ℃ and the weight percent of 1-5, applying a voltage of 20-160V for 5-10 min, and preparing a secondary treated foil;
s36, three-stage post-treatment: soaking the secondary treated foil obtained in the step S35 in a phosphate aqueous solution with the temperature controlled at 65-85 ℃ and the weight percent of 1-5, applying a voltage of 20-160V for 5-10 min, and preparing a tertiary treated foil;
s37, surface cleaning: and (5) performing water washing and air drying on the three-level treated foil obtained in the step (S36) to obtain the high specific volume low-voltage electrode foil.
As a further optimization of the technical solution disclosed in the present invention, the borate is preferably any one of borax or sodium metaborate or a mixture thereof.
As a further optimization of the technical scheme disclosed by the invention, the amine salt is preferably any one of hexylbenzylamine salt, dicyclohexylamine salt, bis (tert-butoxycarbonyl) histidine dicyclohexylamine salt, dimethylamine hydrochloride, triethanolamine, piroctone olamine or a mixture thereof.
As a further optimization of the technical scheme disclosed by the invention, the quaternary ammonium salt is preferably any one of sodium dodecyl sulfate, dodecyl trimethyl ammonium bromide and dodecyl alcohol ether ammonium sulfate or a mixture of the sodium dodecyl sulfate, the dodecyl trimethyl ammonium bromide and the dodecyl alcohol ether ammonium sulfate.
As a further optimization of the technical solution disclosed in the present invention, the phosphate is preferably any one of diammonium phosphate, sodium hexametaphosphate, disodium hydrogen phosphate, or a mixture thereof.
As the further optimization of the technical scheme disclosed by the invention, the oxidizing acid is preferably any one of nitric acid, permanganic acid and hypochloric acid, and the mixed acid ratio by weight is as follows: phosphoric acid: oxidizing acid = 2: 1.
in practical industrial application, the preparation method of the high specific volume low-voltage electrode foil for automobile electronics at least achieves the following beneficial effects:
1) in the first-stage formation stage, or the second-stage formation stage, the second-stage formation stage and the fourth-stage formation stage, current with constant density is applied to the formation bath solution to ensure that an oxide film is stably and quickly generated on the surface of the corrosion foil and the distribution forms of formed pore channels in different areas are more balanced;
2) aiming at each formation step, the voltage, the temperature and the time as well as the components and the proportion of the formation liquid are adjusted, so that the density of each layer of the formed oxide film tends to be consistent, and the water boiling life of the electrode foil is prolonged;
3) in step S21, an amine-based treating liquid is added during the first-order formation to improve the oxide film
Gamma' or gamma-Al2O3The content of (a). The reason for this is that, in a weakly alkaline environment, a boehmite deposition film is formed on the surface of the micropores of the etched foil, and is decomposed to form γ' or γ -Al by subsequent high-temperature treatment2O3；
4) In the post-treatment stage, the defects (exposed after acid soaking or high-temperature treatment) formed on the oxide film in the formation process can be repaired, and the water boiling service life of the oxide film can be prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a metallographic photograph of a formed electrode foil prepared by the conventional multi-stage formation described in the background art.
FIG. 2 is a metallographic photograph of a formed electrode foil prepared by the method in example 1.
FIG. 3 is a metallographic photograph of a formed electrode foil prepared by the method in example 2.
FIG. 4 is a metallographic photograph of a formed electrode foil prepared by the method of example 3.
FIG. 5 is a metallographic photograph of a formed electrode foil prepared by the method in example 4.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention. The methods are conventional methods, not specifically described.
Comparative example 1
The electrode foil was prepared by reference to the multi-stage formation method disclosed in the background art.
Example 1
The preparation method of the high specific volume low-voltage electrode foil for the automobile electronics comprises the following steps:
s1, preparation of corrosion foil: immersing an aluminum foil with the purity of not less than 99.9% and the thickness of 100 mu m into acid liquor, and corroding the surface of the aluminum foil;
s2, multilevel formation, comprising the following substeps:
s21, first-order formation: soaking the etched foil obtained in the step S1 in a mixed solution containing 5wt% of ammonium sulfate, 1wt% of sodium metaborate and 0.5wt% of hexyl benzylamine salt at the temperature of 65-85 ℃, and forming under the voltage of 20-160V for 10min to prepare a first-grade formed foil;
s22, surface cleaning: performing water washing and air drying operation (the air drying temperature is not more than 20 ℃) on the first-stage formed foil obtained in the step S21;
s23, secondary formation: soaking the primary formed foil processed in the step S22 in a mixed solution containing 3wt% of ammonium sulfate and 1wt% of sodium metaborate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 10min, so as to prepare a secondary formed foil;
s24, carrying out three-stage formation: soaking the secondary formed foil obtained in the step S23 in a mixed solution containing 3wt% of ammonium sulfate and 1wt% of sodium metaborate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 15min to prepare a three-level formed foil;
s25, surface cleaning: performing water washing and air drying operation on the three-level formed foil obtained in the step S24;
s26, intermediate processing: immersing the three-stage formed foil processed in the step S25 in a lauryl sodium sulfate aqueous solution with the temperature controlled at 40-60 ℃ and the weight percent of 5, and controlling the time duration to be 10 min;
s27, quaternization: soaking the three-level formed foil obtained in the step S26 in a solution containing 5wt% of sodium hexametaphosphate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 20min to prepare a four-level formed foil;
s3, post-processing, comprising the following sub-steps:
s31, primary post-processing: soaking the four-stage formed foil obtained in the step S27 in a 1wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 15min, and preparing a first-stage treated foil;
s32, surface cleaning: performing water washing and air drying operation on the primary processing foil obtained in the step S31;
s33, pickling treatment: soaking the primary treatment foil treated in the step S32 in an acid mixed solution containing 7wt% of phosphoric acid and perchloric acid in a ratio of 1:1, and controlling the time duration to be 6 min;
s34, heat treatment: performing water washing and drying operation on the primary treated foil obtained in the step S33, wherein the drying temperature is controlled to be 450-500 ℃, and the time duration is controlled to be 1.5 min;
s35, secondary post-treatment: soaking the primary treated foil obtained in the step S34 in a 1wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 10min, and preparing a secondary treated foil;
s36, three-stage post-treatment: soaking the secondary treated foil obtained in the step S35 in a 1wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 10min, and preparing a tertiary treated foil;
s37, surface cleaning: and (5) performing water washing and air drying on the three-level treated foil obtained in the step (S36) to obtain the high specific volume low-voltage electrode foil.
Example 2
The preparation method of the high specific volume low-voltage electrode foil for the automobile electronics comprises the following steps:
s1, preparation of corrosion foil: immersing an aluminum foil with the purity of not less than 99.9% and the thickness of 100 mu m into acid liquor, and corroding the surface of the aluminum foil;
s2, multilevel formation, comprising the following substeps:
s21, first-order formation: soaking the corrosion foil obtained in the step S1 in a mixed solution containing 8wt% of ammonium sulfate, 1.5wt% of sodium metaborate and 0.7wt% of hexyl benzylamine salt at the temperature of 65-85 ℃, and forming under the voltage of 20-160V for 10min to prepare a first-grade formed foil;
s22, surface cleaning: performing water washing and air drying operation (the air drying temperature is not more than 20 ℃) on the first-stage formed foil obtained in the step S21;
s23, secondary formation: soaking the primary formed foil treated in the step S22 in a mixed solution containing 5wt% of ammonium sulfate and 1.5wt% of sodium metaborate at the temperature of 65-85 ℃, and forming at the voltage of 20-160V, wherein the time is preferably controlled to be 10min, so as to prepare a secondary formed foil;
s24, carrying out three-stage formation: soaking the secondary formed foil obtained in the step S23 in a mixed solution containing 4wt% of ammonium sulfate and 1.5wt% of sodium metaborate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 15min to prepare a tertiary formed foil;
s25, surface cleaning: performing water washing and air drying operation on the three-level formed foil obtained in the step S24;
s26, intermediate processing: soaking the three-stage formed foil processed in the step S25 in 8wt% of lauryl sodium sulfate aqueous solution at the temperature of 40-60 ℃ for 10 min;
s27, quaternization: soaking the three-level formed foil obtained in the step S26 in a solution containing 6wt% of sodium hexametaphosphate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 20min to prepare a four-level formed foil;
s3, post-processing, comprising the following sub-steps:
s31, primary post-processing: soaking the four-stage formed foil obtained in the step S27 in a 3wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 15min, and preparing a first-stage treated foil;
s32, surface cleaning: performing water washing and air drying operation on the primary processing foil obtained in the step S31;
s33, pickling treatment: soaking the primary treatment foil treated in the step S32 in an acid mixed solution containing 8wt% of phosphoric acid and perchloric acid in a ratio of 1:1, and controlling the time duration to be 6 min;
s34, heat treatment: performing water washing and drying operation on the primary treated foil obtained in the step S33, wherein the drying temperature is controlled to be 450-500 ℃, and the time duration is controlled to be 1.5 min;
s35, secondary post-treatment: soaking the primary treated foil obtained in the step S34 in a 3wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 10min, and preparing a secondary treated foil;
s36, three-stage post-treatment: soaking the secondary treated foil obtained in the step S35 in a 3wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 10min, and preparing a tertiary treated foil;
s37, surface cleaning: and (5) performing water washing and air drying on the three-level treated foil obtained in the step (S36) to obtain the high specific volume low-voltage electrode foil.
Example 3
The preparation method of the high specific volume low-voltage electrode foil for the automobile electronics comprises the following steps:
s1, preparation of corrosion foil: immersing an aluminum foil with the purity of not less than 99.9% and the thickness of 100 mu m into acid liquor, and corroding the surface of the aluminum foil;
s2, multilevel formation, comprising the following substeps:
s21, first-order formation: soaking the etched foil obtained in the step S1 in a mixed solution containing 10wt% of ammonium sulfate, 2wt% of sodium metaborate and 1wt% of hexyl benzylamine salt at the temperature of 65-85 ℃, and forming at the voltage of 20-160V for 10min to prepare a first-grade formed foil;
s22, surface cleaning: performing water washing and air drying operation (the air drying temperature is not more than 20 ℃) on the first-stage formed foil obtained in the step S21;
s23, secondary formation: soaking the primary formed foil processed in the step S22 in a mixed solution containing 7wt% of ammonium sulfate and 2wt% of sodium metaborate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 10min, so as to prepare a secondary formed foil;
s24, carrying out three-stage formation: soaking the secondary formed foil obtained in the step S23 in a mixed solution containing 5wt% of ammonium sulfate and 2wt% of sodium metaborate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 15min to prepare a three-level formed foil;
s25, surface cleaning: performing water washing and air drying operation on the three-level formed foil obtained in the step S24;
s26, intermediate processing: immersing the three-stage formed foil processed in the step S25 in a 10wt% sodium dodecyl sulfate aqueous solution at the temperature of 40-60 ℃ for 10 min;
s27, quaternization: soaking the three-level formed foil obtained in the step S26 in a solution containing 7wt% of sodium hexametaphosphate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 20min to obtain a four-level formed foil;
s3, post-processing, comprising the following sub-steps:
s31, primary post-processing: soaking the four-stage formed foil obtained in the step S27 in a 5wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 15min, and preparing a first-stage treated foil;
s32, surface cleaning: performing water washing and air drying operation on the primary processing foil obtained in the step S31;
s33, pickling treatment: soaking the primary treatment foil treated in the step S32 in an acid mixed solution containing 10wt% of phosphoric acid and perchloric acid in a ratio of 1:1, and controlling the time duration to be 6 min;
s34, heat treatment: performing water washing and drying operation on the primary treated foil obtained in the step S33, wherein the drying temperature is controlled to be 450-500 ℃, and the time duration is controlled to be 1.5 min;
s35, secondary post-treatment: soaking the primary treated foil obtained in the step S34 in a 5wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 10min, and preparing a secondary treated foil;
s36, three-stage post-treatment: soaking the secondary treated foil obtained in the step S35 in a 5wt% sodium hexametaphosphate aqueous solution at a temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 10min, and preparing a tertiary treated foil;
s37, surface cleaning: and (5) performing water washing and air drying on the three-level treated foil obtained in the step (S36) to obtain the high specific volume low-voltage electrode foil.
Example 4
The preparation method of the high specific volume low-voltage electrode foil for the automobile electronics comprises the following steps:
s1, preparation of corrosion foil: immersing an aluminum foil with the purity of not less than 99.9% and the thickness of 100 mu m into acid liquor, and corroding the surface of the aluminum foil;
s2, multilevel formation, comprising the following substeps:
s21, first-order formation: soaking the etched foil obtained in the step S1 in a mixed solution containing 5wt% of ammonium sulfate, 1wt% of sodium metaborate and 0.5wt% of hexyl benzylamine salt at the temperature of 65-85 ℃, and forming under the voltage of 20-160V for 5min to prepare a first-grade formed foil;
s22, surface cleaning: performing water washing and air drying operation (the air drying temperature is not more than 20 ℃) on the first-stage formed foil obtained in the step S21;
s23, secondary formation: soaking the primary formed foil processed in the step S22 in a mixed solution containing 3wt% of ammonium sulfate and 1wt% of sodium metaborate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 5min to prepare a secondary formed foil;
s24, carrying out three-stage formation: soaking the secondary formed foil obtained in the step S23 in a mixed solution containing 3wt% of ammonium sulfate and 1wt% of sodium metaborate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 7min to prepare a three-level formed foil;
s25, surface cleaning: performing water washing and air drying operation on the three-level formed foil obtained in the step S24;
s26, intermediate processing: immersing the three-stage formed foil processed in the step S25 in a lauryl sodium sulfate aqueous solution with the temperature controlled at 40-60 ℃ and the weight percent of 5, and controlling the time duration to be 10 min;
s27, quaternization: soaking the three-level formed foil obtained in the step S26 in a solution containing 5wt% of sodium hexametaphosphate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 15min to obtain a four-level formed foil;
s3, post-processing, comprising the following sub-steps:
s31, primary post-processing: soaking the four-stage formed foil obtained in the step S27 in a 1wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 10min, and preparing a first-stage treated foil;
s32, surface cleaning: performing water washing and air drying operation on the primary processing foil obtained in the step S31;
s33, pickling treatment: soaking the primary treatment foil treated in the step S32 in an acid mixed solution containing 7wt% of phosphoric acid and perchloric acid in a ratio of 1:1, and controlling the time duration to be 6 min;
s34, heat treatment: performing water washing and drying operation on the primary treated foil obtained in the step S33, wherein the drying temperature is controlled to be 450-500 ℃, and the time duration is controlled to be 1.5 min;
s35, secondary post-treatment: soaking the primary treated foil obtained in the step S34 in a 1wt% sodium hexametaphosphate aqueous solution with the temperature controlled at 65-85 ℃, applying a voltage of 20-160V for 5min, and preparing a secondary treated foil;
s36, three-stage post-treatment: soaking the secondary treated foil obtained in the step S35 in a 1wt% sodium hexametaphosphate aqueous solution at a temperature controlled at 65-85 ℃, and applying a voltage of 20-160V for 5min to obtain a tertiary treated foil;
s37, surface cleaning: and (5) performing water washing and air drying on the three-level treated foil obtained in the step (S36) to obtain the high specific volume low-voltage electrode foil.
As can be seen from the comparative analysis of the attached drawing 1 and the attached drawings 2, 3, 4 and 5, the porosity of the prepared electrode foil is greatly improved, the average particle size is smaller, the distribution form is more uniform, and the further improvement of the electrical performance index of the electrode foil is facilitated. And the specific experimental results prove that the voltage resistance and the capacitance of the electrode foil are effectively improved, and the water boiling boosting time is obviously shortened (the specific performance test data are shown in table 1).
Table 1 summarizes the results of the performance tests of the electrode foils obtained in the comparative examples and examples 1 to 4
TABLE 1
Vfe-final voltage applied during the unformed foil forming process;
vt-withstand voltage of the formed foil;
the reason for this is that:
1) in the first-stage formation stage, or the second-stage formation stage, the second-stage formation stage and the fourth-stage formation stage, the constant-density current is applied to the formation bath solution, so that an oxide film is stably and quickly generated on the surface of the corrosion foil, and the distribution forms of formed pore channels in different areas are more balanced;
2) aiming at each formation step, the voltage, the temperature and the time as well as the components and the proportion of the formation liquid are adjusted, so that the density of each layer of the formed oxide film tends to be consistent, and the water boiling life of the electrode foil is prolonged;
3) in step S21, an amine-based treating liquid is added during the first-order formation to improve the oxide film
Gamma' or gamma-Al2O3The content of (a). The reason is that under the alkalescent environment, the micro-pore surface of the corrosion foil can form a boehmite deposition film which is decomposed to generate gamma' or gamma-Al after subsequent high-temperature treatment2O3；
It should be noted that, in the post-treatment stage, the defect points (exposed after acid soaking or high temperature treatment) formed on the oxide film during formation can be effectively and sufficiently repaired, and the specific volume of the aluminum electrode foil can be greatly increased.
The principle is briefly described as follows: post-treatment stage, in acid treatment:
anode
Cathode electrode
The cathode is a strong oxidizing acid
At the interface of the two phases, Al occurs due to the reduction of acidity3+、Mn2+The phosphate film deposition simultaneously generates the boehmite structure deposition to realize the restoration of the surface of the electrode foil;
the formed chemical conversion film still has gamma' or gamma-Al on the bottom layer even if the chemical conversion film is not subjected to high-temperature treatment2O3The components improve the content of alumina crystals in the oxide film. Due to crystalline Al2O3Has a dielectric constant higher than that of amorphous Al2O3Thereby effectively improving the crystal form Al in the dielectric film2O3The content of (A) is greatly improved for the specific capacitance of the aluminum electrode foil to make a good bedding.
Finally, the following points are to be noted:
1) in the formation treatment of the etched foil, in addition to the sodium metaborate disclosed in the above embodiments, borate such as borax and a mixture of sodium metaborate and borax may be preferably selected according to practical situations;
2) in the chemical conversion treatment of the etched foil, in addition to the hexylbenzylamine salt disclosed in the above embodiments, any one of amine salts such as dicyclohexylamine salt, bis (tert-butoxycarbonyl) histidine dicyclohexylamine salt, dimethylamine hydrochloride, triethanolamine, and piroctone olamine, or a mixture thereof may be preferably selected according to actual conditions;
3) in the chemical conversion treatment of the etched foil, in addition to the sodium dodecyl sulfate disclosed in the above embodiments, any one of quaternary ammonium salts such as dodecyl trimethyl ammonium bromide, dodecyl alcohol ether ammonium sulfate, etc. or a mixture thereof may be selected according to actual conditions;
4) in addition to the sodium hexametaphosphate disclosed in the above embodiments, any one of or a mixture of phosphates such as diammonium phosphate, disodium hydrogen phosphate, etc. may be preferably selected in the post-treatment process of the formed foil.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A preparation method of a high specific volume low-voltage electrode foil for automobile electronics is characterized by comprising the following steps:
s1, preparation of corrosion foil: immersing the aluminum foil with the purity of not less than 99.9% into acid liquor, and corroding the surface of the aluminum foil;
s2, multilevel formation, comprising the following substeps:
s21, first-order formation: immersing the corrosion foil obtained in the step S1 in a mixed solution containing 5-10 wt% of ammonium sulfate, 1-2 wt% of borate and 0.5-1 wt% of amine salt at the temperature of 65-85 ℃, and carrying out formation under the voltage of 20-160V, wherein the time is controlled to be 5-10 min, so as to prepare a first-level formation foil;
s22, surface cleaning: performing water washing and air drying operation on the primary formed foil obtained in the step S21;
s23, secondary formation: soaking the primary formed foil processed in the step S22 in a mixed solution containing 3-7 wt% of ammonium sulfate and 1-2 wt% of borate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 5-10 min to prepare a secondary formed foil;
s24, carrying out three-stage formation: soaking the secondary formed foil obtained in the step S23 in a mixed solution containing 3-5 wt% of ammonium sulfate and 1-2 wt% of borate at the temperature of 65-85 ℃, and forming at the voltage of 20-160V for 7-15 min to prepare a tertiary formed foil;
s25, surface cleaning: performing water washing and air drying operation on the three-level formed foil obtained in the step S24;
s26, intermediate processing: soaking the three-level formed foil treated in the step S25 in a quaternary ammonium salt water solution with the temperature controlled at 40-60 ℃ and the weight percent of 5-10% for 5-10 min;
s27, quaternization: soaking the three-level formed foil obtained in the step S26 in a solution containing 5-7 wt% of phosphate at the temperature of 65-85 ℃, forming at the voltage of 20-160V, and controlling the time duration to be 15-20 min to prepare a four-level formed foil;
s3, post-processing, comprising the following sub-steps:
s31, primary post-processing: soaking the four-stage formed foil obtained in the step S27 in a phosphate aqueous solution with the temperature controlled at 65-85 ℃ and the weight percent of 1-5, applying a voltage of 20-160V for 10-15 min, and preparing a first-stage treated foil;
s32, surface cleaning: performing water washing and air drying operation on the primary processing foil obtained in the step S31;
s33, pickling treatment: soaking the primary treatment foil treated in the step S32 in a mixed solution containing 7-10 wt% of phosphoric acid and oxidizing acid, wherein the time duration is controlled to be 5-10 min;
s34, heat treatment: performing water washing and drying operation on the primary treated foil obtained in the step S33, wherein the drying temperature is controlled to be 450-500 ℃, and the time duration is controlled to be 1-2 min;
s35, secondary post-treatment: soaking the primary treated foil obtained in the step S34 in a phosphate aqueous solution with the temperature controlled at 65-85 ℃ and the weight percent of 1-5, applying a voltage of 20-160V for 5-10 min, and preparing a secondary treated foil;
s36, three-stage post-treatment: soaking the secondary treated foil obtained in the step S35 in a phosphate aqueous solution with the temperature controlled at 65-85 ℃ and the weight percent of 1-5, applying a voltage of 20-160V for 5-10 min, and preparing a tertiary treated foil;
s37, surface cleaning: and (5) performing water washing and air drying on the three-level treated foil obtained in the step (S36) to obtain the high specific volume low-voltage electrode foil.
2. The method for preparing a high specific volume low voltage electrode foil for automotive electronics according to claim 1, wherein the borate is any one of borax or sodium metaborate or a mixture thereof.
3. The method for preparing a high specific volume low voltage electrode foil for automotive electronics according to claim 1, wherein the amine salt is any one of hexylbenzylamine salt, dicyclohexylamine salt, bis-tert-butoxycarbonylhistidine dicyclohexylamine salt, dimethylamine hydrochloride, triethanolamine, piroctone olamine, or a mixture thereof.
4. The method for preparing a high specific volume low voltage electrode foil for automotive electronics according to claim 1, wherein the quaternary ammonium salt is any one of sodium dodecyl sulfate, dodecyl trimethyl ammonium bromide, ammonium lauryl alcohol ether sulfate or a mixture thereof.
5. The method for preparing a high specific volume low voltage electrode foil for automotive electronics according to claim 1, wherein the phosphate is any one of diammonium phosphate, sodium hexametaphosphate, disodium hydrogen phosphate, or a mixture thereof.
6. The method for preparing the high specific volume low voltage electrode foil for the automobile electronics as claimed in claim 1, wherein the oxidizing acid is any one of nitric acid, permanganic acid and hypochloric acid, and the mixed acid ratio by weight is as follows: phosphoric acid: oxidizing acid = 2: 1.
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Also Published As
| Publication number | Publication date |
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| WO2023236573A1 (en) | 2023-12-14 |
| KR20240009387A (en) | 2024-01-22 |
| CN114703526B (en) | 2022-11-01 |
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