CN116206901A - Preparation method of anode foil of titanium electrolytic capacitor - Google Patents
Preparation method of anode foil of titanium electrolytic capacitor Download PDFInfo
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- CN116206901A CN116206901A CN202310144664.4A CN202310144664A CN116206901A CN 116206901 A CN116206901 A CN 116206901A CN 202310144664 A CN202310144664 A CN 202310144664A CN 116206901 A CN116206901 A CN 116206901A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 239000010936 titanium Substances 0.000 title claims abstract description 68
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 68
- 239000011888 foil Substances 0.000 title claims abstract description 52
- 239000003990 capacitor Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010408 film Substances 0.000 claims abstract description 126
- 238000004140 cleaning Methods 0.000 claims abstract description 121
- 230000003647 oxidation Effects 0.000 claims abstract description 101
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 101
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 38
- 238000003980 solgel method Methods 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000000137 annealing Methods 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 25
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 25
- 239000010935 stainless steel Substances 0.000 claims abstract description 25
- 230000001502 supplementing effect Effects 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 173
- 239000000243 solution Substances 0.000 claims description 121
- 238000001035 drying Methods 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 239000002243 precursor Substances 0.000 claims description 56
- 235000019441 ethanol Nutrition 0.000 claims description 53
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 238000009792 diffusion process Methods 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 239000010955 niobium Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- -1 aluminum alkoxide Chemical class 0.000 claims description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- OPZULYDYSMWNFK-UHFFFAOYSA-I butan-1-ol tantalum(5+) pentachloride Chemical compound [Cl-].C(CCC)O.[Ta+5].[Cl-].[Cl-].[Cl-].[Cl-] OPZULYDYSMWNFK-UHFFFAOYSA-I 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 238000003618 dip coating Methods 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims 2
- 239000001361 adipic acid Substances 0.000 claims 1
- 235000011037 adipic acid Nutrition 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 63
- 239000012498 ultrapure water Substances 0.000 description 63
- 238000004321 preservation Methods 0.000 description 32
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 27
- 239000001741 Ammonium adipate Substances 0.000 description 27
- 235000019293 ammonium adipate Nutrition 0.000 description 27
- 238000009413 insulation Methods 0.000 description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 10
- OTRAYOBSWCVTIN-UHFFFAOYSA-N OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N Chemical compound OB(O)O.OB(O)O.OB(O)O.OB(O)O.OB(O)O.N.N.N.N.N.N.N.N.N.N.N.N.N.N.N OTRAYOBSWCVTIN-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 238000001259 photo etching Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- PCIBVZXUNDZWRL-UHFFFAOYSA-N ethylene glycol monophosphate Chemical compound OCCOP(O)(O)=O PCIBVZXUNDZWRL-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- H01G9/0029—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemically Coating (AREA)
Abstract
The invention relates to a preparation method of anode foil of a titanium electrolytic capacitor, which comprises the steps of ultrasonically cleaning the titanium foil, and then preparing valve metal oxides-M with different thicknesses on the surface of the titanium foil by an atomic layer deposition or sol-gel method x O y A film; heat-treating the titanium foil forming the valve metal oxide thin film in vacuum or inert atmosphere; the heat treatment temperature is 500-1500 ℃ and the heat treatment time is 3-72h; performing anodic oxidation, annealing and shape supplementing on the titanium foil subjected to heat treatment to obtain the titanium foil with TiO 2 ‑M x O y Titanium anode foil of composite dielectric film, conditions of anodic oxidation: taking the heat-treated titanium foil as an anode and a stainless steel forming groove as a cathode, and performing anodic oxidation in a saline solution or a weakly corrosive electrolyte to form a constant-voltage anodic oxidation time of 1-60min at a voltage of 5-300V; firstly, adopts atomic layer deposition technology, sol-gel method, heat treatment and anodic oxidation to prepare titanium electrobathElectrolytic capacitor anode foil TiO 2 ‑M x O y A composite oxide film; so that it is possible to produce a titanium electrolytic capacitor having a small leakage current and a large capacitance.
Description
Technical Field
The invention belongs to the field of electrolytic capacitors, and particularly relates to a preparation method of an anode foil of a titanium electrolytic capacitor.
Background
With the rapid development of electronic technology,the miniaturization of electronic devices and the integration of circuits place higher demands on capacitors, which are moving toward higher capacities, miniaturization, lower costs, etc. Hitherto, aluminum electrolytic capacitors and tantalum electrolytic capacitors, which are represented by large-capacity capacitors, have been widely used in various fields of home appliances, communications, automobiles, instruments, military industry, aerospace, and the like. However, dielectric film Al of aluminum electrolytic capacitor 2 O 3 Is easy to deteriorate, resulting in reduced insulating property, large leakage current, short service life, and Al 2 O 3 The dielectric constant of the tantalum electrolytic capacitor is low, the capacity improvement is limited, and the tantalum electrolytic capacitor has the problem that the high-purity tantalum powder is expensive, so that the electrolytic capacitor which is put into practical application at present inevitably has some inherent defects.
Compared with other valve metals, titanium metal has a rich reserve, low cost and its oxide (TiO 2 ) Since there are many researches on the development of a high-performance low-cost titanium electrolytic capacitor by using valve titanium as an anode material of the electrolytic capacitor and titanium oxide or a composite dielectric film formed on the valve titanium as a dielectric of the electrolytic capacitor, the present technology has been attempted. The prior patent CN1419520a provides a method for forming an oxide film on a metal titanium substrate, which comprises calcining a metal titanium substrate having an oxide film with a thickness of 50 nm or more on the surface thereof under vacuum or inert gas atmosphere, and then forming a titanium oxide film with a relatively high dielectric constant on the surface of the metal titanium by oxidizing treatment to form an oxide film, but the titanium oxide film prepared by the method has the problems of poor compactness and stability, and large leakage current when applied to electrolytic capacitors, and cannot be sufficiently used in practical circuits.
Disclosure of Invention
In order to solve the problems in the prior art, the present invention provides a method for preparing an anode foil of a titanium electrolytic capacitor by depositing a valve metal oxide (M x O y ) Thin film, then heat treatment and anodic oxidation of M x O y The dielectric material is introduced into the dielectric medium of the titanium electrolytic capacitor, thereby forming the dielectric constant on the surface of the metallic titanium substrateTiO with large leakage current 2 -M x O y Composite oxide film for solving TiO growing directly by anodic oxidation on valve metal titanium 2 The dielectric film has poor compactness and larger leakage current.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the preparation method of the anode foil of the titanium electrolytic capacitor comprises the following steps:
step 1: ultrasonic cleaning titanium foil with purity over 99.9%, and preparing valve metal oxide-M with different thickness on the surface of titanium foil by atomic layer deposition or sol-gel method x O y A film;
step 2: heat-treating the titanium foil forming the valve metal oxide thin film in vacuum or inert atmosphere; the heat treatment temperature is 500-1500 ℃ and the heat treatment time is 3-72h;
step 3: performing anodic oxidation, annealing and shape supplementing on the titanium foil subjected to heat treatment to obtain the titanium foil with TiO 2 -M x O y Titanium anode foil of composite dielectric film, conditions of anodic oxidation: taking the heat-treated titanium foil as an anode and a stainless steel forming tank as a cathode, and performing anodic oxidation in a salt solution or a weakly corrosive electrolyte; the voltage is 5-300V during the shape compensation, and the constant-voltage anodic oxidation time is 1-60min.
The process of cleaning the titanium foil in step 1: respectively ultrasonically cleaning the titanium foil in NaOH solution, acetone solution, ethanol solution and deionized water, wherein the mass concentration of the NaOH aqueous solution is 3% -15%, the ultrasonic time is 30-90min, the ultrasonic cleaning time in the acetone solution is 10-60min, and the ultrasonic time in the ethanol and the deionized water is 10-60min; and then drying to obtain the clean titanium foil.
The valve metal oxide being Al 2 O 3 、Ta 2 O 5 、ZrO 2 Or Nb (Nb) 2 O 5 。
The thickness of the valve metal oxide film is 1-100nm.
The electrolyte adopts phosphoric acid, monoammonium phosphate, borate or adipic acid salt water solution or ammonium borate, sodium acetate or ethylene glycol solution of phosphoric acid.
And in the step 3, the annealing condition is that the annealing is carried out for 2-15min at 100-500 ℃ in an air atmosphere.
Atomic layer deposition method for forming Al in step 1 2 O 3 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor adopts trimethylaluminum, the source temperature of TMA is 10-100 ℃, the charging time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; al (Al) 2 O 3 The number of deposition cycles is 10-1000;
step 1 of forming Al by a sol-gel method 2 O 3 Specific conditions of the film: aluminum alkoxide or inorganic salt is selected as a precursor, deionized water is used as a solvent, nitric acid is used as a peptizing agent, aluminum isopropoxide and water are uniformly mixed according to the molar ratio of 1:100-250, the water bath is kept at the constant temperature of 60-90 ℃, nitric acid with the molar ratio of 1:0.1-0.8 to aluminum isopropoxide is added after uniform stirring, reflux stirring is carried out for 5-25 hours, finally, standing and aging are carried out, and a dipping and pulling method is adopted to coat a sample: immersing the sample in the sol for 3-10min, slowly lifting, drying the sol film at 60-150deg.C for 10-60min, coating the sample by dip-coating method, repeating the process for 3-10 times, and sintering at 300-1500deg.C for 0.5-5 hr.
Ta formation by atomic layer deposition in step 1 2 O 5 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor is Ta (OCH) 3 ) 5 、Ta(OC 2 H 5 ) 5 Or Ta [ N (CH) 3 ) 2 ] 5 When Ta (OC) 2 H 5 ) 5 Ta (OC) 2 H 5 ) 5 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; ta 2 O 5 The number of deposition cycles is 10-1000;
ta formation by Sol-gel method in step 1 2 O 5 Specific conditions of the film: tantalum alkoxide or inorganic salt is selected as a precursor, ethanol is taken as a solvent, diethanolamine is taken as a stabilizer, tantalum butanol pentachloride and ethanol are uniformly mixed according to the molar ratio of 1:100-250, and stirred at room temperature1-8h, and then the precursor is subjected to 100-1000 r.min on the titanium substrate -1 Homogenizing for 3-20s, standing for 1-10min, standing for 1-15min, oven drying, and roasting at 300-1000deg.C for 30-90min.
Forming ZrO by atomic layer deposition in step 1 2 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor is Zr (EMA) (Me) 3 Or Zr (DMA) (Me) 2 (Cp) is a precursor when Zr (EMA) (Me) is used 3 Zr (EMA) (Me) when in use 3 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; zrO (ZrO) 2 The number of deposition cycles is 10-1000;
ZrO formation by sol-gel method in step 1 2 Specific conditions of the film: zirconium alkoxide or inorganic salt is selected as a precursor, ethanol and deionized water are used as solvents, zirconium oxychloride is firstly added into a mixed aqueous solution of ethanol and deionized water in a ratio of 1:1-1:3, stirring is carried out to dissolve the zirconium oxychloride, then a set amount of yttrium nitrate is added, the solution is in a transparent state, then concentrated ammonia water is dropwise added into the solution, the pH value is regulated to 9-11, the gel reaction is completed, a few drops of nitric acid are added into pasty gel with chloride ions removed as a dispergator, the pH value is reduced to 1-2, the temperature is continuously heated to 80 ℃, stirring is carried out uniformly, and finally a polyvinyl alcohol aqueous solution is added to prepare the ZrO 2 The solution is coated by adopting a dipping pulling method, the coated film is dried in air at 40-70 ℃, and then is heat-treated for 20-40min at 400-600 ℃.
Atomic layer deposition method for forming Nb in step 1 2 O 5 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor may be Nb (OEt) 5 ，Nb(OEt) 5 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; nb (Nb) 2 O 5 The number of deposition cycles is 10-1000;
forming Nb by sol-gel method in step 1 2 O 5 Specific conditions of the film: niobium alkoxide or inorganic salt is used as precursorForming Nb on the cleaned and dried titanium foil by adopting a sol-gel method by taking aqueous ethanol as a solvent 2 O 5 A film. The specific operating conditions are as follows: with Nb (OEt) 5 As a precursor, nb (OEt) is first introduced into a nitrogen glove box by using absolute ethyl alcohol as a solvent 5 Dissolving in absolute ethyl alcohol, adding 0.5-2 mol/L hydrochloric acid ethanol solution and 1-3 mol/LH 2 O ethanol solution, water and catalyst amount and alkoxide molar ratio are respectively 1:1-4:1 and 0.125:1-0.725:1, the mixed solution is stirred for 2-8 h and then is kept stand for standby, and the pH value is controlled at 3-6; the dipping and pulling method is adopted for coating, the vertical pulling speed is 2-15 cm/min, the substrate is dried at room temperature after coating, then the substrate is treated for 5-15 min at 100-150 ℃ and then the coating is repeated, and finally different samples are respectively treated for 1-5 h at 300-500 ℃.
Compared with the prior art, the invention has at least the following beneficial effects: the invention firstly provides the preparation of the anode foil TiO of the titanium electrolytic capacitor by adopting an atomic layer deposition technology, a sol-gel method, heat treatment and anodic oxidation 2 -M x O y Compared with the anode foil of the aluminum electrolytic capacitor, the titanium anode foil has higher dielectric constant and unit area capacity; compared with the anode foil of the tantalum electrolytic capacitor, the titanium anode foil has the advantages of rich resources and low price; compared with the anode foil of the titanium electrolytic capacitor which is formed by anodic oxidation of a pure titanium sheet, the TiO of the invention 2 -M x O y The composite oxide film greatly reduces the leakage current of the titanium anode foil, improves the compactness of the titanium anode foil, and makes the titanium metal possible to be used as the anode material of the electrolytic capacitor.
Drawings
FIG. 1 is a schematic diagram of the present invention for preparing an anode foil of a titanium electrolytic capacitor.
Detailed Description
The invention adjusts and controls Al 2 O 3 、Ta 2 O 5 、ZrO 2 、Nb 2 O 5 The parameters of the preparation process, the heat treatment condition and the anodic oxidation process of the isovalve metal oxide are changed to change the internal structure and components of the composite dielectric film, and the TiO with high dielectric constant and small leakage current is prepared 2 -M X O y And compounding the dielectric film to obtain the titanium anode foil with excellent performance. The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Atomic layer deposition to form Al 2 O 3 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor adopts trimethylaluminum, the source temperature of TMA is 10-100 ℃, the charging time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; al (Al) 2 O 3 The number of deposited cycles is 10-1000 (1 cycle. Apprxeq.0.1 nm).
Formation of Ta by atomic layer deposition 2 O 5 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor is Ta (OCH) 3 ) 5 、Ta(OC 2 H 5 ) 5 Or Ta [ N (CH) 3 ) 2 ] 5 When Ta (OC) 2 H 5 ) 5 Ta (OC) 2 H 5 ) 5 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; ta 2 O 5 The number of deposited cycles is 10-1000 (1 cycle. Apprxeq.1-3 nm).
Atomic layer deposition to form ZrO 2 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor is Zr (EMA) (Me) 3 Or Zr (DMA) (Me) 2 (Cp) is a precursor when Zr (EMA) (Me) is used 3 Zr (EMA) (Me) when in use 3 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; zrO (ZrO) 2 The number of deposited cycles is 10-1000 (1 cycle. Apprxeq.1.8-2 nm).
Atomic layer deposition method for forming Nb 2 O 5 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor may be Nb (OEt) 5 ，Nb(OEt) 5 Is the source temperature ofThe introducing time is 0.1-5s at 10-100 ℃ and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; nb (Nb) 2 O 5 The number of deposited cycles is 10-1000 (1 cycle. Apprxeq.2-2.5 nm).
Step 1 of forming Al by a sol-gel method 2 O 3 Specific conditions of the film: aluminum alkoxide or inorganic salt is selected as a precursor, deionized water is used as a solvent, nitric acid is used as a peptizing agent, aluminum isopropoxide and water are uniformly mixed according to the molar ratio of 1:100-250, the water bath is kept constant at 60-90 ℃, the stirring is carried out for 0.5-3 hours, nitric acid with the molar ratio of 1:0.1-0.8 to aluminum isopropoxide is added, the mixture is refluxed and stirred for 5-25 hours, finally, the mixture is kept stand and aged for 12-48 hours, and a dipping and pulling method is adopted to coat a sample: immersing the sample in the sol for 3-10min, slowly lifting, drying the sol film at 60-150deg.C for 10-60min, coating the sample by dip-coating method, repeating the process for 3-10 times, and sintering at 300-1500deg.C for 0.5-5 hr.
Formation of Ta by sol-gel method 2 O 5 Specific conditions of the film: tantalum alkoxide or inorganic salt is selected as a precursor, preferably tantalum butanol pentachloride solution, ethanol is used as a solvent, diethanolamine is used as a stabilizer, tantalum butanol pentachloride and ethanol are uniformly mixed according to the molar ratio of 1:100-250, stirring is carried out for 1-8h at room temperature, and then a photoetching machine is used for carrying out 100-1000 r.min on the precursor on a titanium substrate -1 Homogenizing for 3-20s, standing for 1-10min, standing for 1-15min, drying in oven at 80deg.C for 1-5 hr, and roasting in muffle furnace at 300-1000deg.C for 30-90min.
ZrO formation by sol-gel method 2 Specific conditions of the film: zirconium alkoxide or inorganic salt is selected as precursor, preferably ZrOCl 2 Adding zirconium oxychloride into a solvent of ethanol and deionized water, wherein the solvent is 1:1 to 1:3, stirring to dissolve the solution, adding a set amount of yttrium nitrate into the solution to reach a transparent state, then dropwise adding concentrated ammonia water into the solution, adjusting the pH to 9-11, completing the gel reaction, adding a few drops of nitric acid serving as a dispergator into the pasty gel with chloride ions removed, reducing the pH to 1-2, continuously heating to 80 ℃, and stirring for 3-4 days. Finally adding polyvinyl alcohol waterPreparing the solution to obtain ZrO 2 Coating the solution by adopting a dipping and pulling method, drying the coated film in air at 40-70 ℃ for 10-30min, and then performing heat treatment in a muffle furnace at 400-600 ℃ for 20-40min
Sol gel process for forming Nb 2 O 5 Specific conditions of the film: niobium alkoxide or inorganic salt is selected as precursor, preferably Nb (OEt) 5 Forming Nb on the cleaned and dried titanium foil by adopting a sol-gel method by taking absolute ethyl alcohol as a solvent 2 O 5 A film. The specific operating conditions are as follows: with Nb (OEt) 5 As a precursor, nb (OEt) is first introduced into a nitrogen glove box by using absolute ethyl alcohol as a solvent 5 Dissolving in absolute ethyl alcohol, adding 0.5-2 mol/L hydrochloric acid ethanol solution and 1-3 mol/LH 2 O ethanol solution, water and catalyst amount and alkoxide molar ratio are respectively 1:1-4:1 and 0.125:1-0.725:1, the mixed solution is stirred for 2-8 h and then is kept stand for standby, and the pH value is controlled at 3-6; the dipping and pulling method is adopted for coating, the vertical pulling speed is 2-15 cm/min, the substrate is dried for 5-30 min at room temperature after coating, then the substrate is treated for 5-15 min at 100-150 ℃ and then the coating is repeated, and finally different samples are respectively treated for 1-5 h at 300-500 ℃.
In the invention, the titanium foil is heated to a set temperature along with the furnace during the heat treatment of the titanium foil.
The heat treatment temperature in step 2 is preferably 700-900 ℃.
Example 1
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 3% for 30min, repeatedly cleaning with ultrapure water for three times, ultrasonically treating with acetone solution for 10min, respectively cleaning in ethanol solution and deionized water for 10min, finally preserving heat in an oven at 60 ℃ for 30min, and drying.
(2) Atomic Layer Deposition (ALD) of 10cycles of Al on cleaned and baked titanium foil 2 O 3 A film. The specific deposition conditions are as follows: the growth temperature is 100 ℃; the precursor is Trimethylaluminum (TMA), the source temperature of the TMA is 10 ℃, the introducing time is 0.1s, and the diffusion time is 0.1s; the reactant is H 2 O is introduced for 0.1s, and the diffusion time is0.1s。
(3) Will finish Al 2 O 3 The deposited titanium foil was heat treated at 500 c in vacuum or in an inert gas for 3 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the mass fraction of 10wt%, performing constant-pressure anodic oxidation for 1min at the voltage of 5V, then cleaning with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 100 ℃ for 2min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 1min under the voltage of 5V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Comparative example 1:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 3% for 30min, repeatedly cleaning with ultrapure water for three times, ultrasonically treating with acetone solution for 10min, respectively cleaning in ethanol solution and deionized water for 10min, finally preserving heat in an oven at 60 ℃ for 30min, and drying.
(2) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the mass fraction of 10wt%, performing constant-pressure anodic oxidation for 1min at the voltage of 10V, then cleaning with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 150 ℃ for 2min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 1min under the voltage of 10V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 Titanium anode foil of dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 2:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 10% for 50min, repeatedly cleaning with ultrapure water for three times, ultrasonically treating with acetone solution for 20min, respectively cleaning in ethanol solution and deionized water for 20min, and finally heat-preserving in an oven at 60 ℃ for 50min and drying.
(2) Atomic Layer Deposition (ALD) of 60cycles of Al on cleaned and baked titanium foil 2 O 3 . The specific deposition conditions are as follows: the growth temperature is 200 ℃; the precursor is Trimethylaluminum (TMA), the source temperature of the TMA is 50 ℃, the introducing time is 2s, and the diffusion time is 7s; reactant H 2 The O-in time was 1s and the diffusion time was 4s.
(3) Will finish Al 2 O 3 The deposited titanium foil was heat treated at 700 c in vacuum or in an inert gas for 24 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the mass fraction of 10wt%, performing constant-pressure anodic oxidation for 15min at the voltage of 10V, then cleaning with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 150 ℃ for 5min; and (3) shape supplementing: taking 1.0wt% phosphoric acid aqueous solution as electrolyte, performing constant-pressure anodic oxidation at 10V for 5min, cleaning with ultrapure water for three times, and oven-drying at 60deg.C for 30min to obtain TiO-containing material 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 3:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 10% for 50min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 20min, respectively cleaning in ethanol solution and deionized water for 20min, and finally heat-preserving in an oven at 60 ℃ for 50min and drying.
(2) Atomic Layer Deposition (ALD) of 60cycles of Al on cleaned and baked titanium foil 2 O 3 . The specific deposition conditions are as follows: the growth temperature is 200 ℃; precursor bodyTrimethylaluminum (TMA), wherein the source temperature of TMA is 50 ℃, the charging time is 2s, and the diffusion time is 7s; reactant H 2 The O-in time was 1s and the diffusion time was 4s.
(3) Will finish Al 2 O 3 The deposited titanium foil was heat treated at 700 c in vacuum or in an inert gas for 24 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, carrying out anodic oxidation in a 3.5wt% ammonium dihydrogen phosphate aqueous solution at a voltage of 30V, carrying out constant-pressure anodic oxidation for 15min, then cleaning with ultrapure water for three times, and carrying out heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 150 ℃ for 5min; and (3) shape supplementing: taking 3.5wt% of monoammonium phosphate aqueous solution as electrolyte, performing constant-pressure anodic oxidation for 5min at a voltage of 30V, then washing with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min and drying to obtain the catalyst with TiO 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 4
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 12% for 70min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 40min, respectively cleaning in ethanol solution and deionized water for 40min, and finally performing heat preservation in an oven at 80 ℃ for 70min and drying.
(2) Atomic Layer Deposition (ALD) of 100cycles of Al on cleaned and baked titanium foil 2 O 3 . The specific deposition conditions are as follows: the growth temperature is 200 ℃; the precursor is Trimethylaluminum (TMA), the source temperature of the TMA is 70 ℃, the introducing time is 3s, and the diffusion time is 8s; reactant H 2 The O-in time was 1.5s and the diffusion time was 6s.
(3) Will finish Al 2 O 3 The deposited titanium foil was heat treated at 700 c in vacuum or in an inert gas for 48 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a tank as a cathode, and adding 10wt% of ammonium pentaborate aqueous solutionPerforming anodic oxidation at a voltage of 80V for 20min at constant pressure, cleaning with ultrapure water for three times, and keeping the temperature in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 200 ℃ for 10min; and (3) shape supplementing: 10wt% ammonium pentaborate aqueous solution is used as electrolyte, constant-pressure anodic oxidation is carried out for 10min under the voltage of 80V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 5:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 12% for 70min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 40min, respectively cleaning in ethanol solution and deionized water for 40min, and finally performing heat preservation in an oven at 80 ℃ for 70min and drying.
(2) Depositing 400cycles of Al by Atomic Layer Deposition (ALD) on cleaned and baked titanium foil 2 O 3 . The specific deposition conditions are as follows: the growth temperature is 200 ℃; the precursor is Trimethylaluminum (TMA), the source temperature of the TMA is 70 ℃, the introducing time is 3s, and the diffusion time is 8s; reactant H 2 The O-in time was 1.5s and the diffusion time was 6s.
(3) Will finish Al 2 O 3 The deposited titanium foil was heat treated at 1000 c in vacuum or in an inert gas for 48 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate glycol solution with the weight of 10 percent, performing constant-pressure anodic oxidation for 20 minutes at the voltage of 120V, then cleaning with ultrapure water for three times, and performing heat preservation in an oven at 60 ℃ for 30 minutes and drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 200 ℃ for 10min; and (3) shape supplementing: 10wt% ammonium adipate glycol solution is used as electrolyte, constant-pressure anodic oxidation is carried out for 10min under the voltage of 120V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Al 2 O 3 Composite mediumTitanium anode foil of plasma membrane. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 6:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in 15% NaOH solution for 90min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 60min, respectively cleaning in ethanol solution and deionized water for 60min, and finally performing heat preservation in a 100 ℃ oven for 90min and drying.
(2) Depositing 1000cycles of Al by Atomic Layer Deposition (ALD) on cleaned and baked titanium foil 2 O 3 . The specific deposition conditions are as follows: the growth temperature is 500 ℃; the precursor is Trimethylaluminum (TMA), the source temperature of the TMA is 200 ℃, the introducing time is 5s, and the diffusion time is 10s; reactant H 2 The O-in time was 2s and the diffusion time was 10s.
(3) Will finish Al 2 O 3 The deposited titanium foil was heat treated at 1500 c in vacuum or in an inert gas for 72 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in 10wt% sodium acetate aqueous solution at 300V for 60min under constant pressure, cleaning with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min for drying; annealing: heat-treating the titanium foil subjected to anodic oxidation in an air furnace at 300 ℃ for 15min; and (3) shape supplementing: 10wt% sodium acetate aqueous solution is used as electrolyte, constant-pressure anodic oxidation is carried out for 30min under 300V voltage, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 7:
(1) The procedure for cleaning the titanium foil was the same as in example 1
(2) Deposition of 10cycles of Ta by Atomic Layer Deposition (ALD) on cleaned and baked titanium foil 2 O 5 A film. The specific deposition conditions are as follows: the growth temperature is 100 ℃; the precursor is Ta (O)C 2 H 5 ) 5 ，Ta(OC 2 H 5 ) 5 The source temperature is 10 ℃, the introducing time is 0.1s, and the diffusion time is 0.1s; the reactant is H 2 O was introduced for 0.1s and diffused for 0.1s.
(3) Will finish Ta 2 O 5 The deposited titanium foil was heat treated at 500 c in vacuum or in an inert gas for 3 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, carrying out anodic oxidation in a glycol phosphate solution with the mass fraction of 5wt%, carrying out constant-pressure anodic oxidation for 1min at the voltage of 5V, then cleaning with ultrapure water for three times, and carrying out heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 100 ℃ for 2min; and (3) shape supplementing: taking 5wt% of ethylene glycol phosphate solution as electrolyte, performing constant-pressure anodic oxidation for 1min at a voltage of 5V, then washing with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min and drying to obtain the catalyst with TiO 2 -Ta 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Examples 8 to 16:
similar to the procedure of example 7, the invention prepares TiO by atomic layer deposition based on the parameters described in Table 1 2 -Ta 2 O 5 Films, while providing performance parameters under different parameter films.
TABLE 1
Example 16:
(1) The procedure for cleaning the titanium foil was the same as in example 1
(2) Deposition of 10cycles of ZrO on cleaned and baked titanium foil using Atomic Layer Deposition (ALD) method 2 A film. The specific deposition conditions are as follows: the growth temperature is 100 ℃; the precursor is Zr (EMA) (Me) 3 The source temperature is 10 ℃, the introducing time is 0.1s, and the diffusion time is 0.1s; the reactant is H 2 O, when it is introduced intoThe interval is 0.1s, and the diffusion time is 0.1s.
(3) Will finish ZrO 2 The deposited titanium foil was heat treated at 500 c in vacuum or in an inert gas for 3 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the mass fraction of 10wt%, performing constant-pressure anodic oxidation for 1min at the voltage of 5V, then cleaning with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 100 ℃ for 2min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 1min under the voltage of 5V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -ZrO 2 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Examples 17 to 24:
similar to the procedure of example 16, the present application prepares TiO by atomic layer deposition based on the parameters described in Table 2 2 -ZrO 2 A film.
TABLE 2
Example 25:
(1) The procedure for cleaning the titanium foil was the same as in example 1;
(2) Deposition of 10cycles of Nb by Atomic Layer Deposition (ALD) on cleaned and baked titanium foil 2 O 5 A film. The specific deposition conditions are as follows: the growth temperature is 100 ℃; the precursor is Nb (OEt) 5 The source temperature is 10 ℃, the introducing time is 0.1s, and the diffusion time is 0.1s; the reactant is H 2 O was introduced for 0.1s and diffused for 0.1s.
(3) Will finish Nb 2 O 5 The deposited titanium foil was heat treated at 500 c in vacuum or in an inert gas for 3 hours.
(4) After heat treatmentThe titanium foil is used as an anode, a stainless steel forming groove is used as a cathode, anodic oxidation is carried out in an ammonium adipate aqueous solution with the mass fraction of 10wt%, the voltage is 5V, the constant-pressure anodic oxidation is carried out for 1min, then the titanium foil is washed three times by ultrapure water, and the titanium foil is preserved for 30min in a 60 ℃ oven for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 100 ℃ for 2min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 1min under the voltage of 5V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Nb 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Examples 26 to 33:
similar to the procedure of example 25, the present application prepares TiO by atomic layer deposition based on the parameters described in Table 3 2 -Nb 2 O 5 Films, while providing performance parameters under different parameter films.
TABLE 3 Table 3
Example 34:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 10% for 50min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 20min, respectively cleaning in ethanol solution and deionized water for 20min, and finally heat-preserving in an oven at 60 ℃ for 50min and drying.
(2) Forming Al on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 3 Film thickness 100+ -10 nm. The specific operating conditions are as follows: aluminum isopropoxide [ Al (C) 3 H 7 O) 3 ]As a precursor, deionized water is used as a solvent, nitric acid is used as a peptizing agent, and aluminum isopropoxide is firstly preparedAnd water at 1:150, water bath constant temperature 70 ℃, stirring for 1.5h, then adding aluminum isopropoxide with the molar ratio of 1: nitric acid with the molar ratio of 0.2, reflux stirring for 10 hours, standing and aging for 24 hours, and coating a sample by adopting a dip-coating method: the test piece was immersed in the sol completely, slowly lifted after 5min, the sol film was dried at 80℃and the procedure was repeated 5 times, followed by sintering at 500℃for 1.5h.
(3) Will form Al 2 O 3 The titanium foil of the film was heat treated in vacuum at 700 c for 24 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, carrying out anodic oxidation in a 10wt% ammonium pentaborate aqueous solution at a voltage of 30V, carrying out constant-pressure anodic oxidation for 15min, then cleaning with ultrapure water for three times, and carrying out heat preservation in a 60 ℃ oven for 30min and drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 150 ℃ for 5min; and (3) shape supplementing: 10wt% ammonium pentaborate aqueous solution is used as electrolyte, constant-pressure anodic oxidation is carried out for 5min under the voltage of 30V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 35:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 12% for 70min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 40min, respectively cleaning in ethanol solution and deionized water for 40min, and finally performing heat preservation in an oven at 80 ℃ for 70min and drying.
(2) Forming Al on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 3 Thin film (thickness 600.+ -.100 nm). The specific operating conditions are as follows: aluminum isopropoxide [ Al (C) 3 H 7 O) 3 ]As a precursor, deionized water is used as a solvent, nitric acid is used as a peptizing agent, aluminum isopropoxide and water are firstly mixed according to the molar ratio of 1:200, the water bath is kept at a constant temperature of 80 ℃, stirring is carried out for 2 hours, then nitric acid with the molar ratio of 1:0.4 to aluminum isopropoxide is added, reflux stirring is carried out for 15 hours, finally standing and ageing are carried out for 36 hours, and then the preparation method comprises the steps ofCoating the test pieces by dip-coating: the test piece was immersed in the sol completely, slowly lifted after 7min, the sol film was dried at 100℃and the procedure was repeated 7 times, followed by sintering at 700℃for 2h.
(3) Will form Al 2 O 3 The titanium foil of the film was heat treated in vacuum at 1000 c for 48 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in 10wt% sodium acetate aqueous solution with the voltage of 120V, performing constant-pressure anodic oxidation for 20min, then cleaning with ultrapure water for three times, and performing heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 200 ℃ for 10min; and (3) shape supplementing: 10wt% sodium acetate aqueous solution is used as electrolyte, constant-pressure anodic oxidation is carried out for 10min under the voltage of 120V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 36:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in 15% NaOH solution for 90min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 60min, respectively cleaning in ethanol solution and deionized water for 60min, and finally performing heat preservation in a 100 ℃ oven for 90min and drying.
(2) Forming Al on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 3 Thin film (thickness 900.+ -.100 nm). The specific operating conditions are as follows: aluminum isopropoxide [ Al (C) 3 H 7 O) 3 ]As a precursor, deionized water is used as a solvent, nitric acid is used as a peptizing agent, aluminum isopropoxide and water are mixed according to the molar ratio of 1:230, the water bath is kept at a constant temperature of 90 ℃, stirring is carried out for 2.5 hours, then nitric acid with the molar ratio of 1:0.6 to aluminum isopropoxide is added, reflux stirring is carried out for 20 hours, finally standing and aging are carried out for 40 hours, and a dipping and pulling method is adopted to coat a sample: the sample was immersed in the sol completely, slowly lifted up after 9min, the sol film was dried at 120 ℃, the procedure was repeated 8 times, and then sintered at 1000 ℃ for 3h.
(3) Will form Al 2 O 3 The titanium foil of the film was heat treated in vacuum at 1500 c for 72 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the weight percentage of 10%, wherein the voltage is 300V, the constant-voltage anodic oxidation time is 60min, then cleaning with ultrapure water for three times, and performing heat preservation in a baking oven at the temperature of 60 ℃ for 30min and drying; annealing: heat-treating the titanium foil subjected to anodic oxidation in an air furnace at 300 ℃ for 15min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 30min under 300V voltage, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Al 2 O 3 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 37:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 10% for 50min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 20min, respectively cleaning in ethanol solution and deionized water for 20min, and finally heat-preserving in an oven at 60 ℃ for 50min and drying.
(2) Ta is formed on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 5 Thin film (thickness 100.+ -.10 nm). The specific operating conditions are as follows: the precursor is tantalum butanol pentachloride solution, ethanol is used as solvent, diethanolamine is used as stabilizer, tantalum butanol pentachloride and ethanol are uniformly mixed according to the molar ratio of 1:100, stirring is carried out for 1-8h at room temperature, and then the precursor is carried out on a titanium substrate by a photoetching machine for 100 r.min -1 Homogenizing for 3s, standing for 1min, drying at 80deg.C in oven for 1 hr, and roasting at 300deg.C in muffle furnace for 30min.
(3) Will form Ta 2 O 5 The titanium foil of the film was heat treated in vacuum at 700 c for 24 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, and adding 10wt% of ammonium adipate waterAnodizing in the solution at 30V under constant pressure for 15min, cleaning with ultrapure water for three times, and keeping the temperature in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 150 ℃ for 5min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 5min under the voltage of 30V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Ta 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 38:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 12% for 70min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 40min, respectively cleaning in ethanol solution and deionized water for 40min, and finally performing heat preservation in an oven at 80 ℃ for 70min and drying.
(2) Ta is formed on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 5 Thin film (thickness 600.+ -.100 nm). The specific operating conditions are as follows: selecting tantalum butanol pentachloride solution as a precursor, using ethanol as a solvent and diethanolamine as a stabilizer, firstly uniformly mixing tantalum butanol pentachloride and ethanol in a molar ratio of 1:125, stirring at room temperature for 4, and then using a photoetching machine to carry out 300 r.min on the precursor on a titanium substrate -1 Homogenizing for 10s, standing for 1min, standing for 5min, drying, baking in oven at 80deg.C for 2 hr, and baking in muffle furnace at 400deg.C for 40min.
(3) Will form Ta 2 O 5 The titanium foil of the film was heat treated in vacuum at 1000 c for 48 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the weight percentage of 10%, performing constant-pressure anodic oxidation for 20min at the voltage of 120V, then cleaning with ultrapure water for three times, and performing heat preservation in an oven at the temperature of 60 ℃ for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 200 ℃ for 10min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is used as electrolyte, and 120V of electricity is usedConstant pressure anodic oxidation under pressure for 10min, washing with ultrapure water for three times, and oven drying at 60deg.C for 30min to obtain TiO-containing material 2 -Ta 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 39:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in 15% NaOH solution for 90min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 60min, respectively cleaning in ethanol solution and deionized water for 60min, and finally performing heat preservation in a 100 ℃ oven for 90min and drying.
(2) Ta is formed on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 5 Thin film (thickness 900.+ -.100 nm). The specific operating conditions are as follows: selecting tantalum butanol pentachloride solution as a precursor, using ethanol as a solvent and diethanolamine as a stabilizer, firstly uniformly mixing tantalum butanol pentachloride and ethanol in a molar ratio of 1:200, stirring for 6 hours at room temperature, and then using a photoetching machine to make the precursor pass through a titanium substrate with a temperature of 500 r.min -1 Homogenizing for 15s, standing for 8min, standing for 10min, drying at 80deg.C in oven for 4 hr, and roasting at 700deg.C in muffle furnace for 60min.
(3) Will form Ta 2 O 5 The titanium foil of the film was heat treated in vacuum at 1500 c for 72 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the weight percentage of 10%, wherein the voltage is 300V, the constant-voltage anodic oxidation time is 60min, then cleaning with ultrapure water for three times, and performing heat preservation in a baking oven at the temperature of 60 ℃ for 30min and drying; annealing: heat-treating the titanium foil subjected to anodic oxidation in an air furnace at 300 ℃ for 15min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 30min under 300V voltage, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Ta 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation and measured for capacity, and the results are shown in Table 3Shown.
Example 40:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 10% for 50min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 20min, respectively cleaning in ethanol solution and deionized water for 20min, and finally heat-preserving in an oven at 60 ℃ for 50min and drying.
(2) ZrO formation by sol-gel method on cleaned and dried titanium foil 2 Thin film (thickness 100.+ -.10 nm). The specific operating conditions are as follows: zrOCl is selected as the precursor 2 Adding zirconium oxychloride into a 1:1 aqueous solution of ethanol and deionized water, stirring to dissolve the zirconium oxychloride, adding yttrium nitrate to enable the solution to reach a transparent state, then dropwise adding concentrated ammonia water into the solution, adjusting the pH to 9, and completing the gel reaction. Then, a few drops of nitric acid as a dispergator was added to the chloride ion-removed paste gel, the pH was lowered to 1, and the heating was continued to 70℃and stirring was continued for 1 day. Finally adding the polyvinyl alcohol aqueous solution and finally adding the polyvinyl alcohol aqueous solution to prepare the ZrO 2 The solution was coated by dip-coating, and the coated film was dried in air at 40℃for 10 minutes, and then heat-treated in a muffle furnace at 400℃for 20 minutes.
(3) Will form ZrO 2 The titanium foil of the film was heat treated in vacuum at 700 c for 24 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the weight percentage of 10%, performing constant-pressure anodic oxidation for 15min at the voltage of 30V, then cleaning with ultrapure water for three times, and performing heat preservation in an oven at the temperature of 60 ℃ for 30min and drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 150 ℃ for 5min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 5min under the voltage of 30V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -ZrO 2 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 41:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in 15% NaOH solution for 90min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 60min, respectively cleaning in ethanol solution and deionized water for 60min, and finally performing heat preservation in a 100 ℃ oven for 90min and drying.
(2) ZrO formation by sol-gel method on cleaned and dried titanium foil 2 Thin film (thickness 600.+ -.100 nm). The specific operating conditions are as follows: zrOCl is selected as the precursor 2 Adding zirconium oxychloride into a 1:2 aqueous solution of ethanol and deionized water, stirring to dissolve the zirconium oxychloride, adding yttrium nitrate to enable the solution to reach a transparent state, then dropwise adding concentrated ammonia water into the solution, adjusting the pH to 10, and completing the gel reaction. Then, a few drops of nitric acid as a dispergator was added to the chloride ion-removed paste gel, the pH was lowered to 1, and the heating was continued to 80℃and stirring was continued for 2 days. Finally adding the polyvinyl alcohol aqueous solution and finally adding the polyvinyl alcohol aqueous solution to prepare the ZrO 2 The solution was coated by dip-coating, and the coated film was dried in air at 50℃for 20 minutes, and then heat-treated in a muffle furnace at 500℃for 30 minutes.
(3) Will form ZrO 2 The titanium foil of the film was heat treated in vacuum at 1000 c for 48 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the weight percentage of 10%, performing constant-pressure anodic oxidation for 20min at the voltage of 120V, then cleaning with ultrapure water for three times, and performing heat preservation in an oven at the temperature of 60 ℃ for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 200 ℃ for 10min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 10min under the voltage of 120V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -ZrO 2 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 42:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in 15% NaOH solution for 90min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 60min, respectively cleaning in ethanol solution and deionized water for 60min, and finally performing heat preservation in a 100 ℃ oven for 90min and drying.
(2) ZrO formation by sol-gel method on cleaned and dried titanium foil 2 Film (thickness 900+ -100 nm. Specific operation condition is that ZrOCl is selected as precursor 2 Adding zirconium oxychloride into a 1:3 aqueous solution of ethanol and deionized water, stirring to dissolve the zirconium oxychloride, adding yttrium nitrate to enable the solution to reach a transparent state, then dropwise adding concentrated ammonia water into the solution, adjusting the pH to 11, and completing the gel reaction. Then, a few drops of nitric acid as a dispergator was added to the chloride ion-removed paste gel, the pH was lowered to 1, and the heating was continued to 90℃and stirring was continued for 4 days. Finally adding polyvinyl alcohol aqueous solution to prepare ZrO 2 The solution was coated by dip-coating, and the coated film was dried in air at 70℃for 30 minutes, and then heat-treated in a muffle furnace at 600℃for 40 minutes.
(3) Will form ZrO 2 The titanium foil of the film was heat treated in vacuum at 1500 c for 72 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the weight percentage of 10%, wherein the voltage is 300V, the constant-voltage anodic oxidation time is 60min, then cleaning with ultrapure water for three times, and performing heat preservation in a baking oven at the temperature of 60 ℃ for 30min and drying; annealing: heat-treating the titanium foil subjected to anodic oxidation in an air furnace at 300 ℃ for 15min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 30min under 300V voltage, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -ZrO 2 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 43:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in NaOH solution with mass fraction of 10% for 50min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 20min, respectively cleaning in ethanol solution and deionized water for 20min, and finally heat-preserving in an oven at 60 ℃ for 50min and drying.
(2) Forming Nb on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 5 Thin film (thickness 100.+ -.10 nm). The specific operating conditions are as follows: with Nb (OEt) 5 As a precursor, nb (OEt) is first introduced into a nitrogen glove box by using absolute ethyl alcohol as a solvent 5 Dissolving in absolute ethanol, adding 0.5mol/L ethanol solution of hydrochloric acid and 1/LH 2 O ethanol solution, water and catalyst amount and alkoxide molar ratio are respectively 1:1 and 0.125:1, the mixed solution is stirred for 2 hours and then is kept stand for standby, and the pH value is controlled at 3; coating is carried out by dipping and pulling, the vertical pulling speed is 2cm/min, the substrate is dried for 5min at room temperature after coating, then the substrate is treated for 5min at 100 ℃, the coating is repeated, and finally the different samples are respectively treated for 1h at 300 ℃.
(3) Will form Nb 2 O 5 The titanium foil of the film was heat treated in vacuum at 700 c for 24 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, performing anodic oxidation in an ammonium adipate water solution with the weight percentage of 10%, performing constant-pressure anodic oxidation for 15min at the voltage of 30V, then cleaning with ultrapure water for three times, and performing heat preservation in an oven at the temperature of 60 ℃ for 30min and drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 150 ℃ for 5min; and (3) shape supplementing: 10wt% ammonium adipate aqueous solution is taken as electrolyte, constant-pressure anodic oxidation is carried out for 5min under the voltage of 30V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Nb 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 44:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in 15% NaOH solution for 90min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 60min, respectively cleaning in ethanol solution and deionized water for 60min, and finally performing heat preservation in a 100 ℃ oven for 90min and drying.
(2) Forming Nb on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 5 Thin film (thickness 600.+ -.100 nm). The specific operating conditions are as follows: with Nb (OEt) 5 As a precursor, nb (OEt) is first introduced into a nitrogen glove box by using absolute ethyl alcohol as a solvent 5 Dissolving in absolute ethanol, adding 1.5mol/L ethanol solution of hydrochloric acid and 2mol/LH 2 O ethanol solution, water and catalyst amount and alkoxide molar ratio are respectively 2:1 and 0.425:1, the mixed solution is stirred for 6 hours and then is kept stand for standby, and the pH value is controlled at 4; coating is carried out by dipping and pulling, the vertical pulling speed is 8cm/min, the substrate is dried for 15min at room temperature after coating, then the substrate is treated for 10min at 120 ℃, the coating is repeated, and finally the different samples are respectively treated for 3h at 400 ℃.
(3) Will form Nb 2 O 5 The titanium foil of the film was heat treated in vacuum at 1000 c for 48 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, carrying out anodic oxidation in a 10wt% ammonium pentaborate aqueous solution at a voltage of 120V, carrying out constant-pressure anodic oxidation for 20min, then cleaning with ultrapure water for three times, and carrying out heat preservation in a 60 ℃ oven for 30min for drying; annealing: carrying out heat treatment on the titanium foil subjected to anodic oxidation in an air furnace at 200 ℃ for 10min; and (3) shape supplementing: 10wt% ammonium pentaborate aqueous solution is used as electrolyte, constant-pressure anodic oxidation is carried out for 10min under the voltage of 120V, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Nb 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
Example 45:
(1) Ultrasonically cleaning titanium foil with purity of over 99.9% in 15% NaOH solution for 90min, repeatedly cleaning with ultrapure water for three times, ultrasonically cleaning with acetone solution for 60min, respectively cleaning in ethanol solution and deionized water for 60min, and finally performing heat preservation in a 100 ℃ oven for 90min and drying.
(2) Forming Nb on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 5 Thin film (thickness 900.+ -.100 nm). The specific operating conditions are as follows: with Nb (OEt) 5 As a precursor, nb (OEt) is first introduced into a nitrogen glove box by using absolute ethyl alcohol as a solvent 5 Dissolving in absolute ethanol, adding ethanol solution of 2mol/L hydrochloric acid and 3mol/LH 2 O ethanol solution, water and catalyst amount and alkoxide molar ratio are respectively 4:1 and 0.725:1, the mixed solution is stirred for 8 hours and then is kept stand for standby, and the pH value is controlled at 6; coating is carried out by dipping and pulling, the vertical pulling speed is 15cm/min, the substrate is dried for 30min at room temperature after coating, then the substrate is treated for 15min at 150 ℃, the coating is repeated, and finally the different samples are respectively treated for 5h at 500 ℃.
(3) Will form Nb 2 O 5 The titanium foil of the film was heat treated in vacuum at 1500 c for 72 hours.
(4) Taking the heat-treated titanium foil as an anode, stainless steel into a groove as a cathode, carrying out anodic oxidation in 10wt% of ammonium pentaborate aqueous solution at 300V for 60min under constant pressure, then cleaning with ultrapure water for three times, and carrying out heat preservation in a 60 ℃ oven for 30min for drying; annealing: heat-treating the titanium foil subjected to anodic oxidation in an air furnace at 300 ℃ for 15min; and (3) shape supplementing: 10wt% ammonium pentaborate aqueous solution is used as electrolyte, constant-pressure anodic oxidation is carried out for 30min under 300V voltage, then ultra-pure water is used for cleaning for three times, and the temperature is kept for 30min in a 60 ℃ oven for drying, thus obtaining the catalyst with TiO 2 -Nb 2 O 5 Titanium anode foil of composite dielectric film. The oxide film was evaluated for insulation properties and measured for capacity, and the results are shown in table 3.
TABLE 3 Table 3
Claims (10)
1. The preparation method of the anode foil of the titanium electrolytic capacitor is characterized by comprising the following steps of:
step 1: ultrasonic cleaning titanium foil with purity over 99.9%, and preparing valve metal oxide-M with different thickness on the surface of titanium foil by atomic layer deposition or sol-gel method x O y A film;
step 2: heat-treating the titanium foil forming the valve metal oxide thin film in vacuum or inert atmosphere; the heat treatment temperature is 500-1500 ℃ and the heat treatment time is 3-72h;
step 3: performing anodic oxidation, annealing and shape supplementing on the titanium foil subjected to heat treatment to obtain the titanium foil with TiO 2 -M x O y The conditions of the anodic oxidation of the titanium anode foil of the composite dielectric film are as follows: taking the heat-treated titanium foil as an anode and a stainless steel forming tank as a cathode, and performing anodic oxidation in a salt solution or a weakly corrosive electrolyte; the voltage is 5-300V during the shape compensation, and the constant-voltage anodic oxidation time is 1-60min.
2. The method for producing a titanium electrolytic capacitor anode foil according to claim 1, wherein the process of cleaning the titanium foil in step 1: respectively ultrasonically cleaning the titanium foil in NaOH solution, acetone solution, ethanol solution and deionized water, wherein the mass concentration of the NaOH aqueous solution is 3% -15%, the ultrasonic time is 30-90min, the ultrasonic cleaning time in the acetone solution is 10-60min, and the ultrasonic time in the ethanol and the deionized water is 10-60min; and then drying to obtain the clean titanium foil.
3. The method for producing an anode foil for a titanium electrolytic capacitor according to claim 1, wherein the valve metal oxide is Al 2 O 3 、Ta 2 O 5 、ZrO 2 Or Nb (Nb) 2 O 5 。
4. The method for producing an anode foil for a titanium electrolytic capacitor according to claim 1, wherein the thickness of the valve metal oxide film is 1 to 100nm.
5. The method for producing an anode foil for a titanium electrolytic capacitor according to claim 1, wherein the electrolyte is phosphoric acid, monoammonium phosphate, borate or adipic acid aqueous solution or ammonium borate, sodium acetate or phosphoric acid glycol solution.
6. The method for producing a titanium electrolytic capacitor anode foil according to claim 1, wherein the annealing conditions in step 3 are: heat treatment is carried out for 2-15min at 100-500 ℃ in air atmosphere.
7. The method for producing an anode foil for a titanium electrolytic capacitor according to claim 1, wherein Al is formed by atomic layer deposition in step 1 2 O 3 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor adopts trimethylaluminum, the source temperature of TMA is 10-100 ℃, the charging time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; al (Al) 2 O 3 The number of deposition cycles is 10-1000;
Step 1 of forming Al by a sol-gel method 2 O 3 Specific conditions of the film: aluminum alkoxide or inorganic salt is selected as a precursor, deionized water is used as a solvent, nitric acid is used as a peptizing agent, aluminum isopropoxide and water are uniformly mixed according to the molar ratio of 1:100-250, the water bath is kept at the constant temperature of 60-90 ℃, nitric acid with the molar ratio of 1:0.1-0.8 to aluminum isopropoxide is added after uniform stirring, reflux stirring is carried out for 5-25 hours, finally, standing and aging are carried out, and a dipping and pulling method is adopted to coat a sample: immersing the sample in sol for 3-10min, slowly lifting, and drying the sol film at 60-150deg.C for 10-60min; the sample is coated by the dip-coating method, the process is repeated 3-10 times, and then sintered for 0.5-5 hours at 300-1500 ℃.
8. The method for producing an anode foil for a titanium electrolytic capacitor according to claim 1, wherein Ta is formed by atomic layer deposition in step 1 2 O 5 Specific conditions of the film:the growth temperature is 100-500 ℃; the precursor is Ta (OCH) 3 ) 5 、Ta(OC 2 H 5 ) 5 Or Ta [ N (CH) 3 ) 2 ] 5 When Ta (OC) 2 H 5 ) 5 Ta (OC) 2 H 5 ) 5 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; ta 2 O 5 The number of deposition cycles is 10-1000;
ta formation by Sol-gel method in step 1 2 O 5 Specific conditions of the film: tantalum alkoxide or inorganic salt is selected as a precursor, ethanol is taken as a solvent, diethanolamine is taken as a stabilizer, tantalum butanol pentachloride and ethanol are uniformly mixed according to the molar ratio of 1:100-250, stirring is carried out for 1-8h at room temperature, and then the precursor is subjected to 100-1000 r.min on a titanium substrate -1 Homogenizing for 3-20s, standing for 1-10min, standing for 1-15min, oven drying, and roasting at 300-1000deg.C for 30-90min.
9. The method for producing an anode foil for a titanium electrolytic capacitor according to claim 1, wherein ZrO is formed by atomic layer deposition in step 1 2 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor is Zr (EMA) (Me) 3 Or Zr (DMA) (Me) 2 (Cp) is a precursor when Zr (EMA) (Me) is used 3 Zr (EMA) (Me) when in use 3 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; zrO (ZrO) 2 The number of deposition cycles is 10-1000;
ZrO formation by sol-gel method in step 1 2 Specific conditions of the film: zirconium alkoxide or inorganic salt is selected as a precursor, ethanol and deionized water are used as solvents, zirconium oxychloride is firstly added into an aqueous solution of ethanol and deionized water which are mixed in a ratio of 1:1-1:3, stirring is carried out to dissolve the zirconium oxychloride, then a set amount of yttrium nitrate is added, the solution is in a transparent state, then concentrated ammonia water is dropwise added into the solution, the pH value is regulated to 9-11, and the gel reaction is completed Adding a few drops of nitric acid as a dispergator into the pasty gel with chloride ions removed, reducing the pH to 1-2, continuously heating to 80 ℃, stirring uniformly, and finally adding a polyvinyl alcohol aqueous solution to prepare the ZrO 2 The solution is coated by adopting a dipping pulling method, the coated film is dried in air at 40-70 ℃, and then is heat-treated for 20-40min at 400-600 ℃.
10. The method for producing an anode foil for a titanium electrolytic capacitor according to claim 1, wherein Nb is formed by atomic layer deposition in step 1 2 O 5 Specific conditions of the film: the growth temperature is 100-500 ℃; the precursor may be Nb (OEt) 5 ，Nb(OEt) 5 The source temperature is 10-100 ℃, the introducing time is 0.1-5s, and the diffusion time is 0.1-10s; the reactant is H 2 O，H 2 The introducing time of O is 0.1-2s, and the diffusion time is 0.1-10s; nb (Nb) 2 O 5 The number of deposition cycles is 10-1000;
forming Nb by sol-gel method in step 1 2 O 5 Specific conditions of the film: selecting niobium alkoxide or inorganic salt as a precursor, using absolute ethyl alcohol as a solvent, and forming Nb on the cleaned and dried titanium foil by adopting a sol-gel method 2 O 5 The specific operation conditions of the film are as follows: with Nb (OEt) 5 As a precursor, nb (OEt) is first introduced into a nitrogen glove box by using absolute ethyl alcohol as a solvent 5 Dissolving in absolute ethyl alcohol, adding 0.5-2 mol/L hydrochloric acid ethanol solution and 1-3 mol/LH 2 O ethanol solution, water and catalyst amount and alkoxide molar ratio are respectively 1:1-4:1 and 0.125:1-0.725:1, the mixed solution is stirred for 2-8 h and then is kept stand for standby, and the pH value is controlled at 3-6; the dipping and pulling method is adopted for coating, the vertical pulling speed is 2-15 cm/min, the substrate is dried at room temperature after coating, then the substrate is treated for 5-15 min at 100-150 ℃ and then the coating is repeated, and finally different samples are respectively treated for 1-5 h at 300-500 ℃.
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