CN112017865B - Hydration treatment method for reducing leakage current of formed foil - Google Patents
Hydration treatment method for reducing leakage current of formed foil Download PDFInfo
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- 239000011888 foil Substances 0.000 title claims abstract description 60
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 57
- 230000036571 hydration Effects 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 235000006408 oxalic acid Nutrition 0.000 claims description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000000887 hydrating effect Effects 0.000 claims description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 13
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 239000001741 Ammonium adipate Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019293 ammonium adipate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 2
- 150000001535 azelaic acid derivatives Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 235000011083 sodium citrates Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000019794 sodium silicate Nutrition 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036619 pore blockages Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention provides a method for reducing leakage current of formed foil, and more particularly relates to a solution for hydration treatment of formed foil and a hydration treatment method. The solution is an aqueous solution containing a component A, a component B and a component C, wherein the component A contains SO4 2‑The component B is weak acid, and the component C is weak acid salt. The formed foil obtained by hydration treatment in the aqueous solution generates a more compact hydrated alumina layer, solves the problem of hole blockage caused by the thickness of the alumina film in the ultrahigh pressure forming process, reduces leakage current, improves specific volume and prolongs the service life of the aluminum electrolytic capacitor.
Description
Technical Field
The invention belongs to the technical field of electrode materials for capacitors, particularly relates to a method for reducing leakage current of formed foil, and more particularly relates to a solution for hydration treatment of formed foil and a hydration treatment method.
Background
In the conventional method for manufacturing an extra-high voltage electrode foil for an aluminum electrolytic capacitor, a step of boiling pure water is required before the electrochemical conversion treatment. By boiling pure water, the power consumption required for electrochemical conversion can be reduced, and the capacitance after electrochemical conversion can be made high. However, the reaction activity between aluminum and water is high, and the hydration reaction between the aluminum electrode and water when pure water is boiled is severe. Therefore, the hydrated film produced by boiling with pure water is porous and has many drawbacks. At present, loose porous alumina is repaired by means of dipping treatment in ammonium dihydrogen phosphate solution, high-temperature heat treatment and the like. However, after the electrode foil prepared by the formation process is used for manufacturing an aluminum electrolytic capacitor, the leakage current is large, the ripple current resistance is poor, and the service life of the capacitor is short.
At present, the methods of dissolution, high-temperature annealing and repair are adopted to reduce and convert the loose porous alumina layer, so that a compact alumina crystal structure is generated, and the leakage current is reduced. For example, CN108335925B discloses a method for improving leakage current performance of medium and high voltage electronic aluminum foil, which adds boric acid soaking treatment, ammonia soaking treatment, oxalic acid soaking treatment and other steps in the manufacturing process of electronic aluminum foil, wherein the acid treatment steps are more, the process flow is longer, and the generated foil still has larger leakage current. For another example, CN107502937B provides a method for forming a 3, 5-dihydroxybenzoic acid by combining a solution of impregnating with azelaic acid salt, a solution of mixture of azelaic acid salt and strontium phosphate, and a solution of strontium phosphate, thereby reducing the leakage current, but the formation process is complicated and is not good for improving the formation efficiency. For another example, CN108155016A discloses a method using a silane coupling agent, which is hydrolyzed to generate silanol during the treatment process, and then the silanol is combined with the hydroxyl group of the hydrated alumina film to modify the hydrated alumina; meanwhile, current is applied under an acidic condition to promote the hydrated alumina film to be converted into a compact porous alumina film, and then the hydrated alumina generated in the later period is modified, so that the leakage current is reduced, the process flow is long and complex, the hydrolysis process is uncontrollable, the influence caused by agglomeration of a silane coupling agent and the like cannot be eliminated, and the performance of the electrode foil in the later period has certain influence.
Therefore, the current methods for reducing the leakage current of the formed foil still need to be improved.
Disclosure of Invention
Aiming at the problem that the formed foil for the aluminum electrolytic capacitor in the prior art has larger leakage current, especially the problems of hole reduction and blockage in later formation caused by the existence of a hydrated film in the ultrahigh pressure formation process, the invention provides a method for reducing the leakage current of the formed foil through hydration treatment.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
in a first aspect, the present invention provides a solution for hydration treatment of formed foil, the solution being an aqueous solution comprising a component A, a component B and a component C, the component A being a solution containing SO4 2-The component B is weak acid, and the component C is weak acid salt.
In the hydration treatment, on the one hand, the anionic SO contained in the aqueous solution4 2-Covering the oxide film to inhibit the growth rate of the hydrated oxide film and make it grow more compact; on the other hand, small amounts of H in aqueous solutions+The outermost loose alumina film generated in the hydration process can be dissolved, so that the density of the film layer is further improved; the existence of weak acid salt in the aqueous solution can play a role in buffering and adjusting in the process of weak acid hydrolysis and ionization, thereby ensuring that the hydration reaction is carried out orderly and stably. Through the coating and dissolving action, the generated hydrated aluminum oxide layer is more compact, and the problem is solvedThe problem of hole blockage caused by the thickness of the alumina film in the ultrahigh pressure formation process is solved, the leakage current is reduced, the specific volume is improved, and the service life of the aluminum electrolytic capacitor is prolonged.
As a preferred embodiment of the present invention, the component a is sulfuric acid or/and a sulfate. The sulfate may be exemplified by ammonium sulfate, aluminum sulfate, sodium sulfate and the like, but is not limited thereto.
According to an embodiment of the present invention, the component a is at least one of sulfuric acid, ammonium sulfate, aluminum sulfate, and sodium sulfate.
In a more preferred embodiment of the present invention, the concentration of sulfuric acid in the aqueous solution is 0.001 to 0.003ml/L, for example: 0.001ml/L, 0.0015ml/L, 0.0016ml/L, 0.0017ml/L, 0.0018ml/L, 0.0019ml/L, 0.002ml/L, 0.0021ml/L, 0.0022ml/L, 0.0023ml/L, 0.0024ml/L, 0.0025ml/L, 0.0026ml/L, 0.0027ml/L, 0.0028ml/L, 0.0029ml/L, 0.003ml/L, and so forth. If the concentration of the sulfate ions is too high, the generation rate of the hydration film is influenced, and the formation under the later formation voltage is not facilitated; if the concentration is too low, the coating effect is not satisfactory.
In a more preferred embodiment of the present invention, the concentration of sulfate in the aqueous solution is 3 to 15g/L, for example: 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, and so forth.
In some embodiments, the sulfate salt is ammonium sulfate, and the concentration of the ammonium sulfate in the aqueous solution is 3-15 g/L.
As a preferred embodiment of the present invention, the component B is at least one of oxalic acid, acetic acid, succinic acid, benzoic acid, citric acid, tartaric acid, adipic acid, silicic acid, and carbonic acid.
As a preferred embodiment of the present invention, the concentration of component B in the aqueous solution is from 0.03 to 0.08g/L, for example: 0.03g/L, 0.035g/L, 0.04g/L, 0.045g/L, 0.05g/L, 0.055g/L, 0.06g/L, 0.065g/L, 0.07g/L, 0.075g/L, 0.08g/L, and the like.
In a preferred embodiment of the present invention, the component C is at least one of oxalate, acetate, succinate, benzoate, citrate, tartrate, silicate, adipate and carbonate, and the salts include sodium salt, potassium salt, ammonium salt and the like.
According to an embodiment of the present invention, the component C is at least one of ammonium oxalate, ammonium acetate, ammonium succinate, sodium benzoate, sodium citrate, sodium tartrate, sodium silicate, ammonium adipate, sodium carbonate, potassium carbonate, and ammonium carbonate.
As a preferred embodiment of the present invention, the concentration of component C in the aqueous solution is 3 to 10g/L, for example: 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, and the like.
In some embodiments, component C is ammonium oxalate at a concentration of 3 to 10g/L in aqueous solution.
In another aspect, the present invention provides a method of hydration using the above aqueous solution during formation foil preparation.
As a preferred embodiment of the present invention, the temperature of the hydration treatment is 80 to 100 ℃, for example: 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, etc.
As a preferred embodiment of the present invention, the time of the hydration treatment is 10 to 18min, for example: 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, and so on.
As a preferred embodiment of the present invention, the hydration treatment method does not include a step of boiling the etched foil in pure water.
In another aspect, the present invention provides a formed foil subjected to hydration treatment using the above hydration treatment method.
In another aspect, the present invention also provides an aluminum electrolytic capacitor comprising the above formed foil.
Compared with the prior art, the invention has the following technical effects:
in the hydration treatment, on the one hand, the anionic SO contained in the aqueous solution4 2-Combined with the hydrolysis process of aluminum, aluminum sulfate polymer is easily generated, similar to colloid, and covers the generated oxide film,thereby inhibiting the growth speed of the hydrated oxide film and enabling the hydrated oxide film to grow more compactly; on the other hand, small amounts of H in aqueous solutions+The outermost loose alumina film generated in the hydration process can be dissolved, so that the compactness of the film layer is further improved. Through the coating and dissolving action, the generated hydrated aluminum oxide layer is more compact, so that the pore diameter of a pore channel is increased, the problem of pore blockage caused by the thickness of the aluminum oxide film in the ultrahigh pressure formation process is solved, the leakage current is reduced, the specific volume is improved, and the service life of the aluminum electrolytic capacitor is prolonged.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The terms "comprising", "containing" or "including" are open-ended expressions that include what is specified in the present invention, but do not exclude other aspects.
According to an embodiment of the present invention, there is provided a method for preparing a formed foil, including: hydrating the corrosion foil, then carrying out four-stage formation,
the hydration treatment is as follows: putting the etched foil into an aqueous solution containing a component A, a component B and a component C, wherein the component A contains SO4 2-The component B is weak acid, and the component C is weak acid salt.
In a preferred embodiment of the present invention, the component a is sulfuric acid or/and sulfate, and the sulfate may be ammonium sulfate, aluminum sulfate, sodium sulfate, and the like, but is not limited thereto.
According to an embodiment of the present invention, the component a is at least one of sulfuric acid, ammonium sulfate, aluminum sulfate, and sodium sulfate.
In a more preferred embodiment of the present invention, the concentration of sulfuric acid in the aqueous solution is 0.001 to 0.003ml/L, for example: 0.001ml/L, 0.0015ml/L, 0.0016ml/L, 0.0017ml/L, 0.0018ml/L, 0.0019ml/L, 0.002ml/L, 0.0021ml/L, 0.0022ml/L, 0.0023ml/L, 0.0024ml/L, 0.0025ml/L, 0.0026ml/L, 0.0027ml/L, 0.0028ml/L, 0.0029ml/L, 0.003ml/L, and so forth.
In a more preferred embodiment of the present invention, the concentration of sulfate in the aqueous solution is 3 to 15g/L, for example: 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, and the like.
As a preferred embodiment of the present invention, the component B is at least one of oxalic acid, acetic acid, succinic acid, benzoic acid, citric acid, tartaric acid, adipic acid, silicic acid, and carbonic acid.
As a preferred embodiment of the present invention, the concentration of component B in the aqueous solution is from 0.03 to 0.08g/L, for example: 0.03g/L, 0.035g/L, 0.04g/L, 0.045g/L, 0.05g/L, 0.055g/L, 0.06g/L, 0.065g/L, 0.07g/L, 0.075g/L, 0.08g/L, and the like.
In a preferred embodiment of the present invention, the component C is at least one of oxalate, acetate, succinate, benzoate, citrate, tartrate, silicate, adipate and carbonate, and the salts include sodium salt, potassium salt, ammonium salt and the like.
According to an embodiment of the present invention, the component C is at least one of ammonium oxalate, ammonium acetate, ammonium succinate, sodium benzoate, sodium citrate, sodium tartrate, sodium silicate, ammonium adipate, sodium carbonate, potassium carbonate, and ammonium carbonate.
In another aspect, the present invention provides a method for performing hydration treatment using the above aqueous solution during formation foil preparation.
As a preferred embodiment of the present invention, the temperature of the hydration treatment is 80 to 100 ℃, for example: 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, etc.
As a preferred embodiment of the present invention, the time of the hydration treatment is 10 to 18min, for example: 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, and so on.
The quaternization can be carried out according to methods known in the art.
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples were carried out under conditions described in the specification, under conventional conditions or under conditions recommended by the manufacturer, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
In this embodiment, the method for preparing the formed foil includes: carrying out hydration treatment on the corrosion foil and then carrying out four-stage formation; wherein the hydration treatment process is as follows:
putting the corrosion foil into an aqueous solution of sulfuric acid, oxalic acid and ammonium oxalate for hydration treatment, wherein the concentration of the sulfuric acid is 0.002mL/L, the concentration of the oxalic acid is 0.05g/L, and the concentration of the ammonium oxalate is 5 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Example 2
In this embodiment, the method for preparing the formed foil includes: hydrating the etched foil and then carrying out four-stage formation; wherein the hydration treatment process is as follows:
placing the corrosion foil in an aqueous solution of ammonium sulfate, oxalic acid and ammonium oxalate for hydration treatment, wherein the concentration of the ammonium sulfate is 5g/L, the concentration of the oxalic acid is 0.05g/L, and the concentration of the ammonium oxalate is 5 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Example 3
In this embodiment, the method for preparing the formed foil includes: hydrating the etched foil and then carrying out four-stage formation; wherein the hydration treatment process is as follows:
placing the corrosion foil in an aqueous solution of sulfuric acid, ammonium sulfate, oxalic acid and ammonium oxalate for hydration treatment, wherein the concentration of the sulfuric acid is 0.001mL/L, the concentration of the ammonium sulfate is 3g/L, the concentration of the oxalic acid is 0.07g/L, and the concentration of the ammonium oxalate is 10 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Example 4
In this embodiment, the method for preparing the formed foil includes: hydrating the etched foil and then carrying out four-stage formation; wherein the hydration treatment process is as follows:
putting the corrosion foil into an aqueous solution of sulfuric acid, oxalic acid and ammonium oxalate for hydration treatment, wherein the concentration of the sulfuric acid is 0.002mL/L, the concentration of the oxalic acid is 0.05g/L, and the concentration of the ammonium oxalate is 3 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Example 5
In this embodiment, the method for preparing the formed foil includes: hydrating the etched foil and then carrying out four-stage formation; wherein the hydration treatment process is as follows:
placing the corrosion foil in an aqueous solution of ammonium sulfate, oxalic acid and ammonium oxalate for hydration treatment, wherein the concentration of the ammonium sulfate is 15g/L, the concentration of the oxalic acid is 0.05g/L, and the concentration of the ammonium oxalate is 10 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Comparative example 1
In this comparative example, the difference from the examples is that the hydration treatment is carried out in pure water, specifically: the etched foil is placed in pure water and boiled in water at 95 ℃ for 12 min.
Comparative example 2
In this comparative example, the difference from example 1 is that the hydration treatment process is as follows: putting the etched foil into an aqueous solution of sulfuric acid and oxalic acid for hydration treatment, wherein the concentration of the sulfuric acid is 0.002mL/L, and the concentration of the oxalic acid is 0.05 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Comparative example 3
In this comparative example, the difference from example 1 is that the hydration treatment process is as follows: placing the corrosion foil in an aqueous solution of oxalic acid and ammonium oxalate for hydration treatment, wherein the concentration of the oxalic acid is 0.05g/L, and the concentration of the ammonium oxalate is 5 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Comparative example 4
In this comparative example, the difference from example 1 is that the hydration treatment process is as follows: placing the corrosion foil in an aqueous solution of sulfuric acid and ammonium oxalate for hydration treatment, wherein the concentration of the sulfuric acid is 0.002mL/L, and the concentration of the ammonium oxalate is 5 g/L; the treatment conditions were: decocting in water at 95 deg.C for 12 min.
Performance testing
The formed foils prepared in the examples and the comparative examples were subjected to a leakage test using a TS2611 aluminum foil electrical property tester, and the test results are shown in table 1 after 1800s leakage test.
TABLE 1
As can be seen from the results of table 1, when the hydration treatment is performed in an aqueous solution containing component a, component B, and component C at the same time, the leakage current of the resultant formed foil is significantly reduced, as compared with the formed foil subjected to the hydration treatment in pure water (conventional hydration method), and when one of component a, component B, and component C is absent in the aqueous solution, the effect of reducing the leakage current of the formed foil is insignificant.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes in the method can be made without departing from the spirit of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Claims (9)
1. The solution for the hydration treatment of the formed foil is characterized by comprising a component A, a component B and a component C, wherein the component A contains SO4 2-The component B is a weak acid, and the component C is a weak acid salt;
wherein the component A is sulfuric acid or/and sulfate, the concentration of the sulfuric acid in the aqueous solution is 0.001-0.003mL/L, or/and the concentration of the sulfate is 3-15g/L, the concentration of the component B is 0.03-0.08g/L, and the concentration of the component C is 3-10 g/L.
2. The solution for use in the formation of foil by hydration treatment of claim 1, wherein the component a is at least one of sulfuric acid, ammonium sulfate, aluminum sulfate, and sodium sulfate.
3. The solution for forming foil hydration treatment of claim 1, wherein the component B is at least one of oxalic acid, acetic acid, succinic acid, benzoic acid, citric acid, tartaric acid, adipic acid, silicic acid, and carbonic acid.
4. The solution for forming foil hydration treatment of claim 1, wherein the component C is at least one of oxalate, acetate, succinate, benzoate, citrate, tartrate, adipate, silicate, and carbonate.
5. A hydration treatment method for a formed foil, comprising: hydrating etched foil by placing it in the solution for hydrating formed foil according to any one of claims 1 to 4.
6. A hydration treatment method according to claim 5, characterised in that said hydration treatment is carried out at a temperature of 80-100 ℃ for a time of 10-18 min.
7. A hydration treatment method according to claim 5, characterised in that said hydration treatment method does not comprise the step of boiling the etched foil in pure water.
8. A formed foil, characterized in that it is produced by a process comprising hydrating a etched foil according to the hydration method of any one of claims 5 to 7.
9. An aluminum electrolytic capacitor comprising the formed foil of claim 8.
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