CN102568858B - Production method of high dielectric constant composite alumina film - Google Patents
Production method of high dielectric constant composite alumina film Download PDFInfo
- Publication number
- CN102568858B CN102568858B CN 201210010959 CN201210010959A CN102568858B CN 102568858 B CN102568858 B CN 102568858B CN 201210010959 CN201210010959 CN 201210010959 CN 201210010959 A CN201210010959 A CN 201210010959A CN 102568858 B CN102568858 B CN 102568858B
- Authority
- CN
- China
- Prior art keywords
- aluminium foil
- presoma
- immersed
- dielectric constant
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011888 foil Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000005030 aluminium foil Substances 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 34
- 239000003292 glue Substances 0.000 claims description 30
- 229910021645 metal ion Inorganic materials 0.000 claims description 30
- 238000012986 modification Methods 0.000 claims description 27
- 230000004048 modification Effects 0.000 claims description 27
- 239000002738 chelating agent Substances 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001741 Ammonium adipate Substances 0.000 claims description 6
- 235000019293 ammonium adipate Nutrition 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 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
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 4
- 229940094800 barium oxalate Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- BZRSOWBAZCOWRN-UHFFFAOYSA-N butan-1-ol;tantalum Chemical compound [Ta].CCCCO BZRSOWBAZCOWRN-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- JXLWTLZBAJWNSG-UHFFFAOYSA-N CCCC[Ti] Chemical compound CCCC[Ti] JXLWTLZBAJWNSG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- -1 enanthic acid niobium Chemical compound 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- YXADBYBKMNNRPQ-UHFFFAOYSA-N heptanoic acid;zirconium Chemical compound [Zr].CCCCCCC(O)=O YXADBYBKMNNRPQ-UHFFFAOYSA-N 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BPYXFMVJXTUYRV-UHFFFAOYSA-J octanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O BPYXFMVJXTUYRV-UHFFFAOYSA-J 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a production method of high dielectric constant composite alumina film, which can improve the specific capacity of an anode foil for an aluminum electrolysis capacitor. By improving the present industrial production line, high dielectric constant oxide is introduced on the surface of a corrosion aluminum foil, and a composite alumina film medium layer having high dielectric constant can be formed through the nanometer compounding. A layer of high dielectric constant oxide precursor is deposited on the surface of the surface modified corrosion aluminum foil through a wet chemical method, gradient heat treatment is performed on the corrosion aluminum foil after hydrolyzation, then the corrosion aluminum foil is soaked into the formation solution to be subjected to the nanometer compounding so as to obtain a layer of the nanometer composite alumina film having the high dielectric constant, so the specific capacity of the corrosion aluminum foil can be improved. Compared with the composited aluminum foil which is not treated, the aluminum foil which is treated by the method provided by the invention has the advantages that the specific capacity of the aluminum foil can be improved by 20 to 50 percent. The production method can be linked with the present industrial electrochemistry corrosion extended surface.
Description
Technical field
The invention belongs to technical field of electronic materials, be specifically related to the production method that aluminium electrolytic capacitor is used high dielectric constant composite alumina film.
Background technology
Aluminium electrolytic capacitor is one of base electronic element very important in electric, electronic system.Along with 3C (Computer, Communication, Consumer electronic) fast development of industry, electronic product constantly strides forward towards miniaturization, lightweight direction, as discrete component-aluminium electrolytic capacitor indispensable in circuit---equally also be badly in need of to miniaturization, lightweight future development.
Aluminium electrolytic capacitor forms by the anode aluminium foil that forms the alumina medium film through excessive erosion and anodic oxidation, electrolyte and through the cathode aluminum foil of excessive erosion, due to the cathode aluminum foil capacitance far above anode aluminium foil, therefore, the capacitance of aluminium electrolytic capacitor is mainly determined by anode aluminium foil.By specific volume formula C=ε Sd
-1As can be known, the Material cladding that the dielectric constant ratio aluminum oxide is high can increase the medium DIELECTRIC CONSTANT ε in alumina medium, improves the anode aluminium foil specific volume, reduces the anode aluminium foil consumption, realizes miniaturization and the lightweight of aluminium electrolytic capacitor.
At present more existing researchers apply high dielectric constant oxide to aluminium foil surface and launch research, the aluminium foil specific volume obtains certain raising, but all prepare only for the laboratory, the special supporting suitable industry technology of producing that links on a large scale of studying therewith not have to report substantially, and traditional production technology utmost point does not mate.
Summary of the invention
The purpose of this invention is to provide link the on a large scale linkage-production method of the high dielectric constant composite alumina film produced of a kind of suitable industry, to improve the aluminium electrolytic capacitor specific volume, the production method of the high dielectric constant composite alumina film that realization and the extended surface of electrochemistry in industry corrosion are at present produced.
For achieving the above object, the technical solution used in the present invention is:
1) presoma glue configuration: adopting wet chemical method is that the ratio of 1: 1 is mixed to get mixture with solubility organic metal salt and metal inorganic salt in metal ion mol ratio, then mixture is joined and get mixed solution in chelating agent, metal ion in mixture wherein: the mol ratio of chelating agent=1: 5～20, to regulate the concentration of mixed solution metal ion be 0.001～0.5mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.001～0.1mol/L that corrosive aluminum foil is immersed in concentration, and temperature is silane, mercaptan, phosphatide, sulfonate, polyethylene glycol, polyvinyl alcohol, the tween of 20～80 ℃ or takes charge of in shift report face modifier solution, soaks 60～600S;
3) aluminium foil surface applies: it is in the presoma glue of 20～80 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 10～300S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 10～300S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 0.3～3m/min, risen to 300～630 ℃ take temperature gradient as 20～150 ℃/m from room temperature, process 60～600S at the constant temp. heatings of 300～630 ℃;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 3～10%, temperature is in the ammonium adipate or boric acid of 60～95 ℃, loads 6～600V voltage, 10～100A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 0.05～10%, temperature is in phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphomolybdate or the teos solution of 20～90 ℃, soak 10～600S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
One or both in the n-butanol salt that described solubility organic metal salt is Ti, Ta, Zr, Nb, isopropoxide, caprylate, enanthate.
Described metal inorganic salt is one or both in the acetate, oxalates, nitrate of Ca, Ba, Bi, Sr.
Described chelating agent is a kind of in ethylenediamine tetra-acetic acid, acetylacetone,2,4-pentanedione, lactic acid, urea or two kinds.
The present invention adopts wet-chemical to be deposited as film method, at first to the corrosive aluminum foil surface modification, then at its superficial growth one deck high dielectric constant oxide presoma, after hydrolysis, gradient heat treatment, form high dielectric nano-oxide film, again that electrochemical nano in aluminium foil immersion formation liquid is compound, formation has the nano-filled composite film of high-k, improve the specific volume of anode aluminium foil, at last aluminium foil is immersed in the methanol treatment fluid, strengthen the water-fast and property of aluminium foil, to improve the useful life of aluminium electrolytic capacitor.Compare with untreated formed aluminum foil, the present invention can improve aluminium foil specific volume 20～50%, untreated 20Vf formed aluminum foil specific capacity 70-82 μ F/cm
2, aluminium foil specific capacity 84-123 μ F/cm of the present invention
2
Embodiment
Embodiment 1:
1) presoma glue configuration: adopting wet chemical method is that the ratio of 1: 1 is mixed to get mixture with n-butyl titanium and acetate calcium in metal ion mol ratio, then mixture is joined and get mixed solution in the chelating agent ethylenediamine tetra-acetic acid, metal ion in mixture wherein: the mol ratio of chelating agent=1: 8, to regulate the concentration of mixed solution metal ion be 0.001mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.005mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in the silane surface modified agent solution of 30 ℃, soaks 100S;
3) aluminium foil surface applies: it is in the presoma glue of 30 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 50S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 100S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 0.3m/min, risen to 500 ℃ take temperature gradient as 150 ℃/m from room temperature, process 100S at 500 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 5%, temperature is in the ammonium adipate of 75 ℃, loads 100V voltage, 10A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 3%, temperature is in the phosphoric acid solution of 30 ℃, soaks 100S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
Embodiment 2:
1) presoma glue configuration: adopting wet chemical method is that the ratio of 1: 1 is mixed to get mixture with isopropyl alcohol tantalum and barium oxalate in metal ion mol ratio, then mixture is joined and get mixed solution in the chelating agent acetylacetone,2,4-pentanedione, metal ion in mixture wherein: the mol ratio of chelating agent=1: 10, to regulate the concentration of mixed solution metal ion be 0.003mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.03mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in the mercaptan surface modification agent solution of 50 ℃, soaks 300S;
3) aluminium foil surface applies: it is in the presoma glue of 50 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 200S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 80S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 1m/min, risen to 300 ℃ take temperature gradient as 120 ℃/m from room temperature, process 300S at 300 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 7%, temperature is in the boric acid of 85 ℃, loads 300V voltage, 50A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 6%, temperature is in the ammonium dihydrogen phosphate of 50 ℃, soaks 300S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
Embodiment 3:
1) presoma glue configuration: adopting wet chemical method is that the ratio of 1: 1 is mixed to get mixture with zirconium caprylate and bismuth nitrate in metal ion mol ratio, then mixture is joined and get mixed solution in chelating agent lactic acid, metal ion in mixture wherein: the mol ratio of chelating agent=1: 5, to regulate the concentration of mixed solution metal ion be 0.005mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.001mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in the phosphatide surface modification agent solution of 20 ℃, soaks 500S;
3) aluminium foil surface applies: it is in the presoma glue of 20 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 100S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 50S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 0.5m/min, risen to 600 ℃ take temperature gradient as 135 ℃/m from room temperature, process 500S at 600 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 3%, temperature is in the ammonium adipate of 65 ℃, loads 6V voltage, 30A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 0.5%, temperature is in the ammonium phosphomolybdate solution of 20 ℃, soaks 500S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
Embodiment 4:
1) presoma glue configuration: adopting wet chemical method is that the ratio of 1: 1 is mixed to get mixture with enanthic acid niobium and strontium acetate in metal ion mol ratio, then mixture is joined and get mixed solution in chelating agent urea, metal ion in mixture wherein: the mol ratio of chelating agent=1: 12, to regulate the concentration of mixed solution metal ion be 0.1mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.08mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in the sulfonate surface modification agent solution of 40 ℃, soaks 200S;
3) aluminium foil surface applies: it is in the presoma glue of 40 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 80S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 200S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 1.6m/min, risen to 400 ℃ take temperature gradient as 100 ℃/m from room temperature, process 200S at 400 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 6%, temperature is in the boric acid of 90 ℃, loads 600V voltage, 80A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 8%, temperature is in the teos solution of 40 ℃, soaks 200S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
Embodiment 5:
1) presoma glue configuration: adopting wet chemical method is that the ratio of 0.3: 0.7: 1 is mixed to get mixture with n-butanol tantalum, isopropyl titanate and barium oxalate in metal ion mol ratio, then mixture is joined in the mixture of chelating agent ethylenediamine tetra-acetic acid and acetylacetone,2,4-pentanedione to get mixed solution, metal ion in mixture wherein: the mol ratio of chelating agent=1: 15, to regulate the concentration of mixed solution metal ion be 0.3mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.05mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in the polyethylene glycol surface modification agent solution of 60 ℃, soaks 60S;
3) aluminium foil surface applies: it is in the presoma glue of 60 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 300S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 150S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 3m/min, risen to 350 ℃ take temperature gradient as 20 ℃/m from room temperature, process 60S at 350 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 8%, temperature is in the ammonium adipate of 60 ℃, loads 200V voltage, 40A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 0.05%, temperature is in the phosphoric acid solution of 60 ℃, soaks 10S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
Embodiment 6:
1) presoma glue configuration: adopting wet chemical method is that the ratio of 1: 0.4: 0.6 is mixed to get mixture with sad niobium and calcium acetate, barium oxalate in metal ion mol ratio, then mixture is joined in the mixture of chelating agent lactic acid and urea to get mixed solution, metal ion in mixture wherein: the mol ratio of chelating agent=1: 20, to regulate the concentration of mixed solution metal ion be 0.5mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.01mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in the polyvinyl alcohol surface modification agent solution of 80 ℃, soaks 400S;
3) aluminium foil surface applies: it is in the presoma glue of 80 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 10S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 260S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 2m/min, risen to 560 ℃ take temperature gradient as 50 ℃/m from room temperature, process 400S at 560 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 10%, temperature is in the ammonium adipate of 95 ℃, loads 80V voltage, 35A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 1.5%, temperature is in the ammonium dihydrogen phosphate of 80 ℃, soaks 400S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
Embodiment 7:
1) presoma glue configuration: adopting wet chemical method is 0.8: 0.2: 0.1 with sad titanium, enanthic acid zirconium and bismuth acetate, strontium oxalate in metal ion mol ratio: 0.9 ratio is mixed to get mixture, then mixture is joined in the mixture of chelating agent ethylenediamine tetra-acetic acid and urea to get mixed solution, metal ion in mixture wherein: the mol ratio of chelating agent=1: 18, to regulate the concentration of mixed solution metal ion be 0.2mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.1mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in the tween surface modification agent solution of 70 ℃, soaks 600S;
3) aluminium foil surface applies: it is in the presoma glue of 70 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 150S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 300S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 1.3m/min, risen to 630 ℃ take temperature gradient as 80 ℃/m from room temperature, process 600S at 630 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 4%, temperature is in the boric acid of 70 ℃, loads 500V voltage, 100A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 10%, temperature is in the ammonium phosphomolybdate solution of 90 ℃, soaks 600S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
Embodiment 8:
1) presoma glue configuration: adopting wet chemical method is 0.5: 0.5: 0.6 with n-butanol tantalum, isopropyl alcohol niobium and strontium acetate, barium oxalate in metal ion mol ratio: 0.4 ratio is mixed to get mixture, then mixture is joined in the mixture of chelating agent acetylacetone,2,4-pentanedione and lactic acid to get mixed solution, metal ion in mixture wherein: the mol ratio of chelating agent=1: 16, to regulate the concentration of mixed solution metal ion be 0.4mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
2) aluminium foil surface modification: it is 0.07mol/L that corrosive aluminum foil is immersed in concentration, and temperature is in department's shift report face modifier solution of 50 ℃, soaks 350S;
3) aluminium foil surface applies: it is in the presoma glue of 50 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 260S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 10S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 2.8m/min, risen to 460 ℃ take temperature gradient as 40 ℃/m from room temperature, process 350S at 460 ℃ of constant temp. heatings;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 9%, temperature is in the boric acid of 80 ℃, loads 400V voltage, 60A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 7%, temperature is in the teos solution of 90 ℃, soaks 80S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
The invention process equipment is simple, with short production cycle, adopts water solution system fully, and is environmentally friendly, can realize interlock with present electrochemistry in industry corrosion extended surface or anodic oxidation production line.
Claims (2)
1. the production method of high dielectric constant composite alumina film is characterized in that:
1) presoma glue configuration: adopt the ratio that wet chemical method is 1:1 with solubility organic metal salt and metal inorganic salt in metal ion mol ratio to be mixed to get mixture, then mixture is joined and get mixed solution in chelating agent, the mol ratio of metal ion in mixture: chelating agent=1:5～20 wherein, to regulate the concentration of mixed solution metal ion be 0.001～0.5mol/L to water again, and regulating simultaneously pH value and be 0～5 must presoma glue;
One or both in the n-butanol salt that described solubility organic metal salt is Ti, Ta, Zr, Nb, isopropoxide, caprylate, enanthate;
Described metal inorganic salt is one or both in the acetate, oxalates, nitrate of Ca, Ba, Bi, Sr;
2) aluminium foil surface modification: it is 0.001～0.1mol/L that corrosive aluminum foil is immersed in concentration, and temperature is silane, mercaptan, phosphatide, sulfonate, polyethylene glycol, polyvinyl alcohol, the tween of 20～80 ℃ or takes charge of in shift report face modifier solution, soaks 60～600S;
3) aluminium foil surface applies: it is in the presoma glue of 20～80 ℃ that the corrosive aluminum foil after surface modification is immersed in temperature, soaks 10～300S;
4) presoma hydrolysis: have the aluminium foil of presoma to be immersed in hydrolytic tank surface-coated, hydrolysis 10～300S;
5) presoma heat treatment: aluminium foil is sent in high temperature furnace with the feeding rate of 0.3～3m/min, risen to 300～630 ℃ take temperature gradient as 20～150 ℃/m from room temperature, process 60～600S at the constant temp. heatings of 300～630 ℃;
6) nano combined: with the aluminium foil after heat treatment be immersed in that mass concentration is 3～10%, temperature is in the ammonium adipate or boric acid of 60～95 ℃, loads 6～600V voltage, 10～100A/m
2Electric current carries out anodic oxidation, forms the nano-filled composite film;
7) water-fastly close processing: with the aluminium foil after anodic oxidation be immersed in that mass concentration is 0.05～10%, temperature is in phosphoric acid, ammonium dihydrogen phosphate, ammonium phosphomolybdate or the teos solution of 20～90 ℃, soak 10～600S, then repeating step 6) the nano combined high dielectric constant composite alumina film that obtains.
2. the production method of high dielectric constant composite alumina film according to claim 1, it is characterized in that: described chelating agent is a kind of in ethylenediamine tetra-acetic acid, acetylacetone,2,4-pentanedione, lactic acid, urea or two kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210010959 CN102568858B (en) | 2012-01-13 | 2012-01-13 | Production method of high dielectric constant composite alumina film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210010959 CN102568858B (en) | 2012-01-13 | 2012-01-13 | Production method of high dielectric constant composite alumina film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102568858A CN102568858A (en) | 2012-07-11 |
| CN102568858B true CN102568858B (en) | 2013-11-06 |
Family
ID=46414026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210010959 Expired - Fee Related CN102568858B (en) | 2012-01-13 | 2012-01-13 | Production method of high dielectric constant composite alumina film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102568858B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103871747B (en) * | 2014-03-06 | 2017-01-25 | 扬州宏远电子有限公司 | Method for improving specific volume of anode foil for aluminum electrolytic condenser |
| CN103910369B (en) * | 2014-03-14 | 2016-02-10 | 开封大学 | A kind of preparation method of nano aluminium oxide |
| CN104593848A (en) * | 2014-12-27 | 2015-05-06 | 西安交通大学 | Surface modification method for enhancing specific volume of etched aluminum foil |
| CN104576066A (en) * | 2014-12-27 | 2015-04-29 | 西安交通大学 | Preparation method of composite oxide film with high dielectric constant |
| CN107275125A (en) * | 2017-05-17 | 2017-10-20 | 浙江长兴鑫启元电子科技有限公司 | The production technology of high-voltage super farad level capacitor |
| CN107221435A (en) * | 2017-05-17 | 2017-09-29 | 浙江长兴鑫启元电子科技有限公司 | A kind of novel aluminium foil nano-filled composite production technology |
| CN108447690B (en) * | 2018-03-16 | 2020-05-22 | 浙江华昱科技有限公司 | Preparation method of electrode foil for high-capacity medium-high voltage aluminum electrolytic capacitor, electrode foil and capacitor |
| CN110565140A (en) * | 2019-09-18 | 2019-12-13 | 南通海星电子股份有限公司 | Preparation method of high-dielectric-constant composite film aluminum foil |
| CN111768974B (en) * | 2020-06-22 | 2021-11-26 | 广西大学 | Method for preparing medium-low voltage laminated foil containing composite medium by surface self-assembly method |
| CN116092834B (en) * | 2023-03-31 | 2023-07-14 | 南通海星电子股份有限公司 | Preparation method of high-specific capacitance electrode foil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1731549A (en) * | 2005-06-13 | 2006-02-08 | 西安交通大学 | Method for preparing aluminum electrolytic capacitor anode foil |
| CN1766168A (en) * | 2005-10-10 | 2006-05-03 | 西安交通大学 | Titanium oxide/aluminum oxide high dielectric constant composite anode film preparation method |
| JP2006310256A (en) * | 2005-03-30 | 2006-11-09 | Dainippon Printing Co Ltd | Oxide semiconductor electrode and dye-sensitized solar cell using it |
| CN101281823A (en) * | 2008-06-03 | 2008-10-08 | 华南师范大学 | High specific volume anode aluminum foil and preparation method thereof |
| EP2148341A1 (en) * | 2007-04-20 | 2010-01-27 | Fujitsu Limited | Electrode foil, process for producing the electrode foil, and electrolytic capacitor |
-
2012
- 2012-01-13 CN CN 201210010959 patent/CN102568858B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006310256A (en) * | 2005-03-30 | 2006-11-09 | Dainippon Printing Co Ltd | Oxide semiconductor electrode and dye-sensitized solar cell using it |
| CN1731549A (en) * | 2005-06-13 | 2006-02-08 | 西安交通大学 | Method for preparing aluminum electrolytic capacitor anode foil |
| CN1766168A (en) * | 2005-10-10 | 2006-05-03 | 西安交通大学 | Titanium oxide/aluminum oxide high dielectric constant composite anode film preparation method |
| EP2148341A1 (en) * | 2007-04-20 | 2010-01-27 | Fujitsu Limited | Electrode foil, process for producing the electrode foil, and electrolytic capacitor |
| CN101281823A (en) * | 2008-06-03 | 2008-10-08 | 华南师范大学 | High specific volume anode aluminum foil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102568858A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102568858B (en) | Production method of high dielectric constant composite alumina film | |
| Chen et al. | Microwave–hydrothermal crystallization of polymorphic MnO2 for electrochemical energy storage | |
| Ghalmi et al. | Capacitance performance of NiO thin films synthesized by direct and pulse potentiostatic methods | |
| CN101651046B (en) | Preparation method of Al2O3/TiO2 compound dielectric film aluminum electrode foil | |
| CN104576066A (en) | Preparation method of composite oxide film with high dielectric constant | |
| Zhong et al. | Electrochemically conductive treatment of TiO2 nanotube arrays in AlCl3 aqueous solution for supercapacitors | |
| CN104616905B (en) | Polyaniline carbon-coating titanium nitride nano linear array composite and its preparation method and application | |
| Lu et al. | Formation and morphology evolution of anodic TiO2 nanotubes under negative pressure | |
| CN105780087B (en) | The preparation method of Electric oxidative synthesis 1-dimention nano oxide structure | |
| RU2016118529A (en) | PRODUCTION OF GRAPHENE OXIDE | |
| Chang et al. | Physicochemical factors that affect the pseudocapacitance and cyclic stability of Mn oxide electrodes | |
| CN105185598B (en) | A kind of Mn for ultracapacitor3O4/TiO2Nanometer tube composite materials and preparation method thereof | |
| CN104911629A (en) | Synthesis method of composite electrode | |
| KR20140001991A (en) | Manufacturing method for anode foil of aluminum electrolytic capacitor | |
| CN103643254A (en) | Method for synthesizing titanium dioxide/bismuth oxychloride composite electrode on FTO | |
| CN102360955B (en) | Method for improving specific volume of an aluminum electrode foil by electrochemical deposition method | |
| CN100463086C (en) | Method for preparing aluminum electrolytic capacitor anode foil | |
| CN104404566B (en) | A kind of to modify TiO 2nano-tube array is the ti-lead dioxide anode in middle layer and preparation method thereof and application | |
| CN102899701A (en) | Preparation of TiO2 nanotube ordered array on Al2O3 ceramic substrate | |
| CN104593848A (en) | Surface modification method for enhancing specific volume of etched aluminum foil | |
| CN111217361B (en) | Method for preparing graphene nanosheet through electrochemical cathode stripping | |
| CN108346517B (en) | Nanometer Nb2O5The preparation method of/carbon cloth combination electrode material | |
| Kalska-Szostko | Electrochemical methods in nanomaterials preparation | |
| CN106683881B (en) | A kind of nanostructured dielectric capacitor and preparation method thereof | |
| Bu et al. | Al 2 O 3-TiO 2 composite oxide films on etched aluminum foil fabricated by electrodeposition and anodization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131106 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |