CN113921282B - Medium-high voltage formation foil low-loss formation process for aluminum electrolytic capacitor - Google Patents
Medium-high voltage formation foil low-loss formation process for aluminum electrolytic capacitor Download PDFInfo
- Publication number
- CN113921282B CN113921282B CN202111130106.XA CN202111130106A CN113921282B CN 113921282 B CN113921282 B CN 113921282B CN 202111130106 A CN202111130106 A CN 202111130106A CN 113921282 B CN113921282 B CN 113921282B
- Authority
- CN
- China
- Prior art keywords
- formation
- concentration
- minutes
- stage
- foil
- 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.)
- Active
Links
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 288
- 239000011888 foil Substances 0.000 title claims abstract description 147
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 96
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003990 capacitor Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 56
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000001632 sodium acetate Substances 0.000 claims abstract description 34
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 34
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 30
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 15
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 15
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 15
- 230000000887 hydrating effect Effects 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 14
- 239000012670 alkaline solution Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 8
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims description 88
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 87
- 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 claims description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 238000006703 hydration reaction Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000036571 hydration Effects 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/055—Etched foil electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the technical field of medium-high voltage formation foil, in particular to a low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor, which comprises the steps of immersing an aluminum foil subjected to electrolytic corrosion treatment in an NaOH alkaline solution at 30-40 ℃; hydrating in pure water at 60-90 deg.c; taking out, pre-forming in pre-forming solution with ammonium oxalate as main solute, adding sodium acetate and ascorbic acid as supplementary additive into the pre-forming solution, washing with pure water after pre-forming, and performing four-stage formation treatment, adding sodium acetate or ammonium acetate as supplementary additive into the primary forming solution, and adding EDTA disodium as supplementary additive into the four-stage forming solution. The effect is that the loss of the formed foil is reduced by 40-50%. The invention reduces the formation foil loss, needs that the porous layer on the surface of the aluminum foil is not blocked, avoids or reduces the crystalline alumina component, and greatly reduces the component properties of the hydrated alumina and the crystalline alumina in the oxide film.
Description
Technical Field
The invention relates to the technical field of medium-high voltage formation foil, in particular to a low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor.
Background
Aluminum electrolytic capacitors are the most widely used capacitor products, and are applied to the fields of consumption, industry, communication and the like for a long time, and formed foil is a key raw material for manufacturing the aluminum electrolytic capacitors, and the industrial chain is as follows: high purity aluminum-electronic aluminum foil (photo foil) -etched foil-formed foil-aluminum electrolytic capacitor-electronic complete machine. The formation technology is mainly to obtain a compact voltage-resistant film through anodic oxidation (commonly called formation) on the surface of an aluminum foil in inorganic or organic oxygen acid, and the quality of the film is related to a plurality of performance indexes of the aluminum electrolytic capacitor such as capacitance, leakage current, loss, storage, service life and the like.
With the development of society and the advancement of electronic industry technology, aluminum electrolytic capacitors are subdivided according to application occasions, and diversified requirements are put on formation foils. Taking aluminum electrolytic capacitors as an example of the frequent charge and discharge occasions of emerging special-purpose products such as strobe lamps, alternating current motors and the like, the products are increasingly applied to the fields of the industries such as the military industry, the aerospace industry, the automobile industry and the like, and the market demand is increasing year by year. Such special applications require that the formed foil has low loss properties, thereby reducing rapid circuit temperature rise during frequent capacitor charging and discharging. But at present, the field is mainly occupied by foreign factories, and domestic batch capacity is limited. The conventional formation foil market in the current market has tended to be saturated and competitive, and the formation process with reduced loss can provide a new product category with market demand.
The formation foil for the aluminum electrolytic capacitor is manufactured by a series of formation processes such as electrochemical anodic oxidation and the like on the high-purity aluminum foil after corrosion and surface expansion, and the product characteristic is the technical trend of the formation foil industry to meet the electronic technology and the future social demands. Before the process, the formation process flow of the formation foil for the high-voltage aluminum electrolytic capacitor is as follows: firstly, placing the high-purity aluminum foil subjected to corrosion surface expansion in deionized water at 90-100 ℃ for soaking for 6-30 minutes, and then performing four-stage or multi-stage formation treatment, wherein the formation liquid adopts a combined solution of boric acid and ammonium pentaborate, and the depolarization treatment adopts a heat treatment and phosphoric acid treatment method. The formed foil for the aluminum electrolytic capacitor manufactured by the process has the advantages that the surface porous layer is blocked by hydrated alumina, the crystalline alumina component is higher, the loss can not meet the requirements of special application occasions, the circuit temperature rise is faster when the formed foil is applied to frequent charge and discharge occasions, and the charge and discharge times or time are limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a middle-high voltage formation foil low-loss formation process for an aluminum electrolytic capacitor, which is characterized in that an aluminum foil subjected to electrolytic corrosion treatment is immersed in an alkaline solution to remove natural oxide film components on the surface of the aluminum foil, so that hydration treatment with lower temperature in the subsequent traditional formation is smoothly carried out, a porous layer on the surface of the aluminum foil is controlled not to be blocked by combining with low-temperature hydration treatment, the conversion of an oxide film layer to a crystal form state is avoided or reduced, then a short carbon chain oxygen-containing organic acid is adopted for carrying out pre-formation, a high-concentration boric acid material is adopted for carrying out formation, hydrated alumina and crystal form alumina components in the oxide film are greatly reduced, sodium acetate or ammonium acetate is added into primary formation liquid as a supplement additive, EDTA disodium is added into quaternary formation liquid as a supplement additive, and the original capacity characteristic is maintained through metal chelation. The formed foil for the aluminum electrolytic capacitor manufactured by the method has obviously reduced loss and maintains the original capacity characteristic.
The technical scheme adopted by the invention is as follows:
a low-loss formation process of a medium-high voltage formation foil for an aluminum electrolytic capacitor, comprising the steps of:
s1: immersing the aluminum foil subjected to electrolytic corrosion treatment in an alkaline solution;
s2: performing hydration treatment in pure water after the aluminum foil dipping treatment;
s3: taking out the mixture after hydration treatment and then carrying out pre-formation in a pre-formation solution;
s4: and cleaning with pure water, and performing four-stage formation treatment to complete the medium-high voltage formation foil low-loss formation process for the aluminum electrolytic capacitor.
Preferably, in the step S1: the alkaline solution is NaOH alkaline solution, and can also be KOH, ammonia water or other alkaline solutions or combinations thereof.
Preferably, in the step S1: the concentration of the alkaline solution is 0.05-2.5g/L, the dipping treatment temperature is 30-40 ℃ and the time is 0.5-3 minutes.
Preferably, in the step S2: the hydration treatment temperature in pure water is 60-90 ℃ and the time is 3-15 minutes.
Preferably, in the step S3: the pre-formed solution is prepared by adding sodium acetate and ascorbic acid as supplementary additives into the pre-formed solution with ammonium oxalate or oxalic acid as main solute.
Further preferably, the concentration of the ammonium oxalate or oxalic acid is 5-100g/L, the concentration of sodium acetate is 0.2-2g/L, the concentration of ascorbic acid is 0.01-1.0g/L, and the temperature of the pre-formed solution is 30-50 ℃.
Preferably, in the step S3: the pre-forming condition is that the voltage is 5-30V and the current density is 40-300mA/cm 2 The pre-forming time is 3-20 minutes.
Preferably, in the step S4: sodium acetate or ammonium acetate is added into the primary formation liquid as a supplementary additive, and EDTA disodium is added into the quaternary formation liquid as a supplementary additive.
Further preferably, sodium acetate or ammonium acetate is added to the primary formation liquid at a concentration of 0.1-1.5g/L; EDTA disodium is added into the four-stage formation liquid to the concentration of 0.05-3g/L.
Preferably, the process specifically comprises the following steps:
the first step is dipping: immersing the aluminum foil subjected to electrolytic corrosion treatment in NaOH alkaline solution at 30-40 ℃ for 0.5-3 minutes; the concentration of NaOH is 0.05-2.5g/L;
and a second step of hydration: hydrating in pure water at 60-90deg.C for 3-15 min;
and thirdly, preforming: the concentration of ammonium oxalate is 5-100g/L, the concentration of sodium acetate is 0.2-2g/L, the concentration of ascorbic acid is 0.01-1.0g/L, and the temperature of the solution is 30-50 ℃; the formation voltage is 5-30V, and the current density is 40-300mA/cm 2 The formation time is 3-20 minutes;
fourth step, primary formation: the concentration of boric acid is 100-150g/L, the concentration of sodium acetate is 0.1-1.5g/L, the concentration of ammonium pentaborate is 5-30g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 100-400V, and the current density is 10-50mA/cm 2 The formation time is 5-20 minutes;
and fifthly, carrying out secondary formation: the concentration of boric acid is 100-150g/L, the concentration of ammonium pentaborate is 5-20g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 200-500V, and the current density is 10-50mA/cm 2 The formation time is 5-20 minutes;
sixth step, three-stage formation: the concentration of boric acid is 100-150g/L, the concentration of ammonium pentaborate is 0.2-5g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 300-600V, and the current density is 10-50mA/cm 2 The formation time is 8-30 minutes;
fourth step of four-stage formation: the concentration of four-stage primary formation boric acid is 100-150g/L, the concentration of EDTA disodium is 0.05-3g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 400-700V, and the current density is 10-50mA/cm 2 The formation time is 15-60 minutes, and four-stage aluminum foils subjected to primary formation are obtained;
eighth step, first high temperature treatment: treating the aluminum foil subjected to the four-stage primary formation at 200-500 ℃ for 0.5-5 minutes;
ninth step four-stage second chemical synthesis: the foil treated at the first high temperature is converted into a film with the boric acid concentration of 100-150g/L, EDTA disodium concentration of 0.05-3g/L, the bath solution temperature of 50-85 ℃ and the voltage of 400-700V and the current density10-50mA/cm 2 The formation time is 5-15 minutes, and a four-stage second formed aluminum foil is obtained;
tenth step of phosphoric acid treatment: immersing the fourth-stage second-formed foil in 30-60deg.C phosphoric acid water solution with concentration of 30-100ml/L for 2-12 min;
eleventh step, fourth stage third formation: the foil after phosphoric acid treatment is formed into a film with the boric acid concentration of 100-150g/L, EDTA disodium concentration of 0.05-3g/L, the bath solution temperature of 50-85 ℃ and the current density of 10-50mA/cm at 400-700V 2 The formation time is 5-15 minutes, and a fourth-stage aluminum foil subjected to third formation is obtained;
twelfth step, second high temperature treatment: treating the aluminum foil subjected to the third formation of the fourth stage at 200-500 ℃ for 0.5-5 minutes;
fourth-stage fourth-time formation: the foil treated at the second high temperature is subjected to chemical treatment at boric acid concentration of 100-150g/L, EDTA disodium concentration of 0.05-3g/L, bath solution temperature of 50-85deg.C, voltage of 400-700V and current density of 10-50mA/cm 2 The formation time is 5-15 minutes;
the fourth-order formed foil is washed with pure water and then treated at 60-150 ℃ for 2-5 minutes.
The beneficial effects of the invention are as follows:
reducing formation foil losses requires that the porous layer of the aluminum foil surface is not blocked and that the crystalline alumina component is avoided or reduced, so the following process projects are all carried out around the following objectives: greatly reduces the components of hydrated alumina and crystal alumina in the oxide film; meanwhile, when changing the state of the oxide film, the original capacity characteristic needs to be ensured.
1. The conventional hydration treatment of the formed foil adopts high-temperature treatment above 90 ℃, most of the porous layer on the surface of the aluminum foil is blocked by hydrated alumina, the oxide film layer part is converted into a crystal form state in the high-temperature state, the state is changed by reducing the hydration reaction temperature, and meanwhile, the normal reaction of aluminum and pure water can be ensured by the temperature.
2. The natural oxide film is easy to generate on the surface layer of the aluminum foil, and the influence of the natural oxide film is small in the conventional formation foil hydration treatment, but the influence of the natural oxide film on the hydration reaction is obvious in the hydration treatment with lower temperature, and the influence can be improved by adopting the alkaline solution dipping treatment before the hydration reaction.
3. The short carbon chain oxygen-containing organic acid is adopted for preforming, and meanwhile, high-concentration boric acid substances are matched for forming, so that the beneficial effect of limiting the conversion of amorphous alumina into crystal alumina is achieved.
4. Sodium acetate or ammonium acetate is added into the primary formation liquid as a supplementary additive, EDTA disodium is added into the quaternary formation liquid as a supplementary additive, metal chelation is promoted, aluminum oxygen migration balance in an anodic oxidation reaction is changed, aluminum migration efficiency of the surface of the aluminum foil is improved, partially-closed defect positions which do not generate aluminum oxide are exposed to continuously form aluminum oxide, and projection area of the surface layer of the aluminum foil is fully utilized, so that the original capacity characteristic can be maintained. The formed foil for the aluminum electrolytic capacitor manufactured by the method has obviously reduced loss, maintains the original capacity characteristic, can be applied to occasions with faster circuit temperature rise when frequent charge and discharge occasions, and ensures the charge and discharge times or time.
Drawings
FIG. 1 is a foil SEM image (a, b are SEM images of comparative example 1, c, d are SEM images of example 1);
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It should be apparent to those skilled in the art that the examples are merely provided to aid in understanding the present invention and should not be construed as limiting the invention in any way.
Example 1
A low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor comprises the following steps:
the first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 2 minutes; naOH concentration is 1g/L;
and a second step of: hydrating in pure water at 70 ℃ for 5 minutes;
and a third step of: the concentration of ammonium oxalate for the pre-forming is 10g/L, the concentration of sodium acetate is 0.3g/L, and the concentration of ascorbic acid is0.02g/L, bath solution temperature 40 ℃, formation voltage 25V and current density 200mA/cm 2 The formation time is 12 minutes;
fourth step: the concentration of the primary boric acid is 130g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: in the second stage, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
sixth step: in the three stages, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
seventh step: in the four-stage primary formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.8g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
eighth step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
ninth step: in the secondary four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
tenth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
eleventh step: in the third four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
twelfth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
thirteenth step: in the fourth-stage chemical reaction, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the chemical reaction voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
fourteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes.
Comparative example 1
Comparative example 1 is based on a conventional chemical scheme:
the first step: taking 99.99% aluminum foil subjected to electrolytic corrosion treatment, and hydrating the aluminum foil in pure water at 97 ℃ for 16 minutes;
and a second step of: the concentration of the primary boric acid is 50g/L, the concentration of the ammonium pentaborate is 20g/L, the temperature of the tank liquor is 86 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
and a third step of: in the second stage, the concentration of boric acid is 50g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 86 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fourth step: in the three stages, the concentration of boric acid is 50g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 86 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
fifth step: the concentration of boric acid used for the first four-stage formation is 50g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 86 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
sixth step: treating the four-stage first-formed aluminum foil at 500 ℃ for 3 minutes;
seventh step: in the secondary four-stage formation, the concentration of boric acid is 50g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 86 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
eighth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
ninth step: in the third four-stage formation, the concentration of boric acid is 50g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 86 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
tenth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
eleventh step:in the fourth-stage chemical conversion, the concentration of boric acid is 50g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 86 ℃, the chemical conversion voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
thirteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes. Relevant parameters and morphology graphs are measured, and measurement results are shown in table 1 and fig. 1.
TABLE 1 comparison of electrical properties of formed foils prepared in examples and comparative examples of the present invention
As can be seen from table 1, the loss of the formation foil in example 1 was 40% or more lower than that in comparative example 1, and the capacitance at 600V at the voltage was comparable to that in comparative example 1, indicating that the loss performance of the formation foil prepared by the present invention was significantly improved; as seen from fig. 1, the porous layer on the surface of the anode foil in example 1 was not plugged compared with comparative example 1, indicating that the present invention can achieve control of the porous layer on the surface of the aluminum foil not to be plugged, thereby reducing the conversion of the oxide film layer to the crystalline state.
Example 2
A low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor comprises the following steps:
the first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 1 minute; naOH concentration is 1.5g/L;
and a second step of: hydrating in pure water at 65 ℃ for 10 minutes;
and a third step of: the concentration of ammonium oxalate for the pre-formation is 10g/L, the concentration of sodium acetate is 0.3g/L, the concentration of ascorbic acid is 0.05g/L, the temperature of the bath solution is 40 ℃, the formation voltage is 25V, and the current density is 200mA/cm 2 The formation time is 12 minutes;
fourth step: the concentration of the primary boric acid is 130g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 0.5g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: in the second stage, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
sixth step: in the three stages, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
seventh step: in the four-stage primary formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.8g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
eighth step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
ninth step: in the secondary four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
tenth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
eleventh step: in the third four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
twelfth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
thirteenth step: in the fourth-stage chemical reaction, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the chemical reaction voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
fourteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes.
Comparative example 2
Comparative example 2 is based on example 2: the electrolytic corrosion foil was directly subjected to high Wen Shuige treatment without being immersed in NaOH solution.
The first step: taking 99.99% aluminum foil subjected to electrolytic corrosion treatment, and hydrating in pure water at 98 ℃ for 15 minutes;
and a second step of: the concentration of ammonium oxalate for the pre-formation is 10g/L, the concentration of sodium acetate is 0.3g/L, the concentration of ascorbic acid is 0.05g/L, the temperature of the bath solution is 40 ℃, the formation voltage is 25V, and the current density is 200mA/cm 2 The formation time is 12 minutes;
and a third step of: the concentration of the primary boric acid is 130g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 0.5g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fourth step: in the second stage, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: in the three stages, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
sixth step: in the four-stage primary formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.8g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
seventh step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
eighth step: in the secondary four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
ninth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
tenth step: in the third four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
eleventh step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
twelfth step: fourth formation in fourth stageThe boric acid concentration is 130g/L, the EDTA disodium concentration is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
thirteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes. Relevant parameters were measured and the measurement results are shown in table 2.
TABLE 2 comparison of electrical properties of formed foils prepared in examples and comparative examples of the present invention
As shown in table 2, the loss of the formed foil in example 2 is lower than that in comparative example 2, the capacitance at the reaching voltage and 600V is equivalent to that in comparative example 2, and the boost time of the formed foil in example 2 is smaller than that in comparative example 2, which indicates that the present invention can prevent or reduce the conversion of the oxide film layer to the crystalline form by removing the natural oxide film component on the aluminum foil surface and reducing the hydration reaction temperature through the dipping treatment in the alkaline solution.
Example 3
A low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor comprises the following steps:
the first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 2 minutes; naOH concentration is 1g/L;
and a second step of: hydrating in pure water at 70 ℃ for 10 minutes;
and a third step of: the concentration of ammonium oxalate for the pre-formation is 90g/L, the concentration of sodium acetate is 0.5g/L, the concentration of ascorbic acid is 1.0g/L, the temperature of the bath solution is 40 ℃, the formation voltage is 25V, and the current density is 260mA/cm 2 The formation time is 18 minutes;
fourth step: the concentration of the primary boric acid is 130g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: at the position ofThe concentration of the secondary boric acid is 130g/L, the concentration of the ammonium pentaborate is 8g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
sixth step: in the three stages, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
seventh step: in the four-stage primary formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.8g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
eighth step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
ninth step: in the secondary four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
tenth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
eleventh step: in the third four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
twelfth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
thirteenth step: in the fourth-stage chemical reaction, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the chemical reaction voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
fourteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes.
Comparative example 3
Comparative example 3 is based on example 3: the process was otherwise identical to that of example 3 without the pretreatment.
The first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 2 minutes; naOH concentration is 1g/L;
and a second step of: hydrating in pure water at 70 ℃ for 10 minutes;
and a third step of: the concentration of the primary boric acid is 50g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 1.0g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fourth step: in the second stage, the concentration of boric acid is 50g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: in the three stages, the concentration of boric acid is 50g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
sixth step: in the four-stage primary formation, the concentration of boric acid is 50g/L, the concentration of EDTA disodium is 0.8g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
seventh step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
eighth step: in the secondary four-stage formation, the concentration of boric acid is 50g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
ninth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
tenth step: in the third four-stage formation, the concentration of boric acid is 50g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
eleventh step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
twelfth step: in the fourth-stage chemical reaction, the concentration of boric acid is 50g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the chemical reaction voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
thirteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes. Relevant parameters were measured and the measurement results are shown in table 3.
TABLE 3 comparison of electrical properties of formed foils prepared in examples and comparative examples of the present invention
As shown in table 3, the loss of the formed foil in example 3 was lower than that in comparative example 3, the reaching voltage was equivalent to that in comparative example 3, and the capacitance at 600V was higher than that at 600V in comparative example 3, indicating that the hydrated alumina and the crystalline alumina components in the oxide film were greatly reduced by the formation by the pretreatment with the short carbon chain oxygen-containing organic acid and the formation by the incorporation of the high concentration boric acid substance.
Example 4
A low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor comprises the following steps:
the first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 2 minutes; naOH concentration is 1.5g/L;
and a second step of: hydrating in pure water at 70 ℃ for 4 minutes;
and a third step of: the concentration of ammonium oxalate for the pre-formation is 10g/L, the concentration of sodium acetate is 0.3g/L, the concentration of ascorbic acid is 0.05g/L, the temperature of the bath solution is 40 ℃, the formation voltage is 25V, and the current density is 200mA/cm 2 The formation time is 12 minutes;
fourth step: the concentration of the primary boric acid is 130g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 1g/L, the temperature of the tank liquor is 80 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: in the second stage, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 80 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
sixth step: the concentration of boric acid used in the third stage is 130g/L, the concentration of ammonium pentaborate is 1g/L,the temperature of the bath solution is 80 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
seventh step: in the four-stage primary formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.8g/L, the temperature of the bath solution is 80 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
eighth step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
ninth step: in the secondary four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 80 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
tenth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
eleventh step: in the third four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 80 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
twelfth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
thirteenth step: in the fourth-stage chemical reaction, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 80 ℃, the chemical reaction voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
fourteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes.
Comparative example 4
Comparative example 4 is based on example 4: sodium acetate is not added into the primary formation liquid, and EDTA disodium additive is not added into the quaternary formation liquid.
The first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 2 minutes; naOH concentration is 1.5g/L;
and a second step of: hydrating in pure water at 70 ℃ for 4 minutes;
and a third step of: the concentration of ammonium oxalate for the pre-forming is 10g/L, the concentration of sodium acetate is 0.3g/L,the concentration of ascorbic acid is 0.05g/L, the temperature of the bath solution is 40 ℃, the formation voltage is 25V, and the current density is 200mA/cm 2 The formation time is 12 minutes;
fourth step: the concentration of the primary boric acid is 130g/L, the concentration of the ammonium pentaborate is 20g/L, the temperature of the tank liquor is 80 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: in the second stage, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 80 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
sixth step: in the three stages, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 80 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
seventh step: the concentration of boric acid for the first four-stage chemical conversion is 130g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 80 ℃, the chemical conversion voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
eighth step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
ninth step: in the secondary four-stage formation, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 80 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
tenth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
eleventh step: in the third four-stage formation, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 80 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
twelfth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
thirteenth step: in the fourth-stage chemical conversion, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 0.5g/L, the temperature of the tank liquor is 80 ℃, the chemical conversion voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
fourteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes. Relevant parameters were measured and the measurement results are shown in table 4.
TABLE 4 comparison of electrical properties of formed foils prepared in examples and comparative examples of the present invention
As shown in table 4, the electrostatic capacity of the formed foil in example 4 is 6% higher than that of comparative example 4, which indicates that sodium acetate or ammonium acetate added to the primary formation liquid in the scheme of the present invention, disodium EDTA added to the quaternary formation liquid has the effect of promoting metal chelation and improving the aluminum migration efficiency on the surface of the aluminum foil, thereby maintaining the original high capacity characteristics. The aluminum electrolytic capacitor prepared by the method has low formation foil loss and maintains the original capacity characteristic.
Example 5
A low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor comprises the following steps:
the first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 2 minutes; naOH concentration is 1.2g/L;
and a second step of: hydrating in pure water at 70 ℃ for 5 minutes;
and a third step of: the concentration of ammonium oxalate for the pre-formation is 10g/L, the concentration of sodium acetate is 0.3g/L, the concentration of ascorbic acid is 0.02g/L, the temperature of the bath solution is 40 ℃, the formation voltage is 25V, and the current density is 200mA/cm 2 The formation time is 12 minutes;
fourth step: the concentration of the primary boric acid is 130g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 160V, and the current density is 50mA/cm 2 The formation time is 10 minutes;
fifth step: the concentration of boric acid used in the second stage is 130g/L, fiveThe concentration of ammonium borate is 8g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 300V, and the current density is 50mA/cm 2 The formation time is 10 minutes;
sixth step: in the three stages, the concentration of boric acid is 130g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 400V, and the current density is 50mA/cm 2 The formation time is 12 minutes;
seventh step: in the four-stage primary formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 450V, and the current density is 50mA/cm 2 The formation time is 45 minutes;
eighth step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
ninth step: in the secondary four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.2g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 450V, and the current density is 50mA/cm 2 Forming for 10 minutes;
tenth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
eleventh step: in the third four-stage formation, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.2g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 50mA/cm 2 Forming for 10 minutes;
twelfth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
thirteenth step: in the fourth-stage chemical reaction, the concentration of boric acid is 130g/L, the concentration of EDTA disodium is 0.2g/L, the temperature of the bath solution is 75 ℃, the chemical reaction voltage is 450V, and the current density is 50mA/cm 2 Forming for 10 minutes;
fourteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes. Relevant parameters were measured and the measurement results are shown in table 5.
Example 6
A low-loss formation process of medium-high voltage formation foil for an aluminum electrolytic capacitor comprises the following steps:
the first step: immersing 99.99% aluminum foil subjected to electrolytic corrosion treatment in NaOH solution at 35 ℃ for 2 minutes; naOH concentration is 2g/L;
and a second step of: hydrating in pure water at 70 ℃ for 5 minutes;
and a third step of: the concentration of ammonium oxalate for the pre-formation is 10g/L, the concentration of sodium acetate is 0.3g/L, the concentration of ascorbic acid is 0.01g/L, the temperature of the bath solution is 40 ℃, the formation voltage is 25V, and the current density is 200mA/cm 2 The formation time is 12 minutes;
fourth step: the concentration of the primary boric acid is 100g/L, the concentration of the ammonium pentaborate is 20g/L, the concentration of the sodium acetate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 160V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
fifth step: in the second stage, the concentration of boric acid is 100g/L, the concentration of ammonium pentaborate is 8g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 300V, and the current density is 30mA/cm 2 The formation time is 10 minutes;
sixth step: in the three stages, the concentration of boric acid is 100g/L, the concentration of ammonium pentaborate is 1g/L, the temperature of the tank liquor is 75 ℃, the formation voltage is 400V, and the current density is 30mA/cm 2 The formation time is 12 minutes;
seventh step: in the four-stage primary formation, the concentration of boric acid is 100g/L, the concentration of EDTA disodium is 0.8g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 The formation time is 45 minutes;
eighth step: treating the four-stage first-formed aluminum foil at 450 ℃ for 3 minutes;
ninth step: in the secondary four-stage formation, the concentration of boric acid is 100g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
tenth step: immersing the fourth-stage second-formed foil in 35ml/L phosphoric acid aqueous solution at 35 ℃ for 8 minutes;
eleventh step: in the third four-stage formation, the concentration of boric acid is 100g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the formation voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
twelfth step: treating the aluminum foil subjected to the third formation of the fourth stage at 450 ℃ for 3 minutes;
thirteenth step: in the fourth-stage chemical conversion, the concentration of boric acid is 100g/L, the concentration of EDTA disodium is 0.6g/L, the temperature of the bath solution is 75 ℃, the chemical conversion voltage is 450V, and the current density is 30mA/cm 2 Forming for 10 minutes;
fourteenth step: the fourth-order formed foil is washed with pure water and then dried at 100 ℃ for 2 minutes. Relevant parameters were measured and the measurement results are shown in table 5.
TABLE 5 comparison of electrical properties of formed foils prepared in examples and comparative examples of the present invention
As can be seen from Table 5, the formed foils of example 5 and example 6 have very low loss, indicating that the formed foils prepared according to the present invention have good loss properties.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (3)
1. A low-loss formation process of a medium-high voltage formation foil for an aluminum electrolytic capacitor, which is characterized by comprising the following steps of:
s1: immersing the aluminum foil subjected to electrolytic corrosion treatment in an alkaline solution, wherein the alkaline solution is a NaOH solution, a KOH solution, ammonia water or a combination thereof, the concentration of the alkaline solution is 0.05-2.5g/L, the immersion treatment temperature is 30-40 ℃ and the immersion treatment time is 0.5-3 minutes;
s2: hydrating the aluminum foil in pure water after the impregnation treatment, wherein the hydrating temperature in the pure water is 60-70 ℃ and the time is 3-15 minutes;
s3: taking out the mixture after hydration treatment, and performing pretreatment in a pretreatment solution, wherein the pretreatment solution is prepared by taking ammonium oxalate or oxalic acid as a main solute, adding sodium acetate and ascorbic acid as supplementary additives into the pretreatment solution, wherein the concentration of the ammonium oxalate or oxalic acid is 5-100g/L, the concentration of the sodium acetate is 0.2-2g/L, the concentration of the ascorbic acid is 0.01-1.0g/L, and the temperature of the pretreatment solution is 30-50 ℃;
s4: cleaning with pure water, and performing four-stage formation treatment to complete a medium-high voltage formation foil low-loss formation process for the aluminum electrolytic capacitor;
in the step S4: sodium acetate or ammonium acetate is added into the primary formation liquid to serve as a supplementary additive, and EDTA disodium is added into the quaternary formation liquid to serve as a supplementary additive;
sodium acetate or ammonium acetate with the concentration of 0.1-1.5g/L is added into the primary formation liquid; EDTA disodium is added into the four-stage formation liquid to the concentration of 0.05-3g/L.
2. The medium-high voltage forming foil low-loss forming process for aluminum electrolytic capacitors as recited in claim 1, wherein in said step S3: the pre-forming condition is that the voltage is 5-30V and the current density is 40-300mA/cm 2 The pre-forming time is 3-20 minutes.
3. The medium-high voltage formation foil low-loss formation process for an aluminum electrolytic capacitor as recited in claim 1, wherein the process specifically comprises the steps of:
the first step is dipping: immersing the aluminum foil subjected to electrolytic corrosion treatment in a NaOH solution at 30-40 ℃ for 0.5-3 minutes; the concentration of the NaOH solution is 0.05-2.5g/L;
and a second step of hydration: hydrating in pure water at 60-70deg.C for 3-15 min;
and thirdly, preforming: the concentration of ammonium oxalate is 5-100g/L, the concentration of sodium acetate is 0.2-2g/L, the concentration of ascorbic acid is 0.01-1.0g/L, and the temperature of the solution is 30-50 ℃; the formation voltage is 5-30V, and the current density is 40-300mA/cm 2 The formation time is 3-20 minutes;
fourth step, primary formation: the concentration of boric acid is 100-150g/L, the concentration of sodium acetate is 0.1-1.5g/L, the concentration of ammonium pentaborate is 5-30g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 100-400V, and the current density is 10-50mA/cm 2 The formation time is 5-20 minutes;
and fifthly, carrying out secondary formation: boric acid concentration is 100-150g/L, pentaboronThe concentration of the ammonium acid is 5-20g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 200-500V, and the current density is 10-50mA/cm 2 The formation time is 5-20 minutes;
sixth step, three-stage formation: the concentration of boric acid is 100-150g/L, the concentration of ammonium pentaborate is 0.2-5g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 300-600V, and the current density is 10-50mA/cm 2 The formation time is 8-30 minutes;
fourth step of four-stage formation: the concentration of four-stage primary formation boric acid is 100-150g/L, the concentration of EDTA disodium is 0.05-3g/L, the temperature of the tank liquor is 50-85 ℃, the formation voltage is 400-700V, and the current density is 10-50mA/cm 2 The formation time is 15-60 minutes, and four-stage aluminum foils subjected to primary formation are obtained;
eighth step, first high temperature treatment: treating the aluminum foil subjected to the four-stage primary formation at 200-500 ℃ for 0.5-5 minutes;
ninth step four-stage second chemical synthesis: the foil treated at the first high temperature is converted into a film with the boric acid concentration of 100-150g/L, EDTA disodium concentration of 0.05-3g/L, the bath solution temperature of 50-85 ℃ and the voltage of 400-700V and the current density of 10-50mA/cm 2 The formation time is 5-15 minutes, and a four-stage second formed aluminum foil is obtained;
tenth step of phosphoric acid treatment: immersing the fourth-stage second-formed foil in 30-60deg.C phosphoric acid water solution with concentration of 30-100ml/L for 2-12 min;
eleventh step, fourth stage third formation: the foil after phosphoric acid treatment is formed into a film with the boric acid concentration of 100-150g/L, EDTA disodium concentration of 0.05-3g/L, the bath solution temperature of 50-85 ℃ and the current density of 10-50mA/cm at 400-700V 2 The formation time is 5-15 minutes, and a fourth-stage aluminum foil subjected to third formation is obtained;
twelfth step, second high temperature treatment: treating the aluminum foil subjected to the third formation of the fourth stage at 200-500 ℃ for 0.5-5 minutes;
fourth-stage fourth-time formation: the foil treated at the second high temperature is subjected to chemical treatment at boric acid concentration of 100-150g/L, EDTA disodium concentration of 0.05-3g/L, bath solution temperature of 50-85deg.C, voltage of 400-700V and current density of 10-50mA/cm 2 The formation time is 5-15 minutes;
the fourth-order formed foil is washed with pure water and then treated at 60-150 ℃ for 2-5 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111130106.XA CN113921282B (en) | 2021-09-26 | 2021-09-26 | Medium-high voltage formation foil low-loss formation process for aluminum electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111130106.XA CN113921282B (en) | 2021-09-26 | 2021-09-26 | Medium-high voltage formation foil low-loss formation process for aluminum electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113921282A CN113921282A (en) | 2022-01-11 |
| CN113921282B true CN113921282B (en) | 2023-11-17 |
Family
ID=79236424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111130106.XA Active CN113921282B (en) | 2021-09-26 | 2021-09-26 | Medium-high voltage formation foil low-loss formation process for aluminum electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113921282B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115050591B (en) * | 2022-07-21 | 2023-06-27 | 新疆金泰新材料技术股份有限公司 | Long-life high-pressure formed foil processing device and method |
| CN115198330B (en) * | 2022-07-21 | 2023-06-27 | 新疆金泰新材料技术股份有限公司 | Multistage formation treatment device and method for medium-high pressure formation foil |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101651049A (en) * | 2009-06-24 | 2010-02-17 | 吴江飞乐天和电子材料有限公司 | Method for increasing specific volume of electrode foil of low-voltage aluminum electrolytic capacitor |
| CN108505094A (en) * | 2017-02-24 | 2018-09-07 | 宜都东阳光化成箔有限公司 | A kind of chemical synthesizing method reducing electrode foil current-leakage |
| CN109609991A (en) * | 2018-12-26 | 2019-04-12 | 东莞东阳光科研发有限公司 | Waste Acid From Hua Cheng Foil, preparation method and applications |
| CN109859949A (en) * | 2018-01-26 | 2019-06-07 | 东莞东阳光科研发有限公司 | A method of reducing medium-high pressure chemical foil leakage current |
| CN110055571A (en) * | 2019-04-18 | 2019-07-26 | 宜都东阳光化成箔有限公司 | A kind of preprocessing solution and chemical synthesis technology improving aluminium electrolutic capacitor medium-high pressure chemical foil capacity |
| WO2019166034A1 (en) * | 2018-03-02 | 2019-09-06 | 乳源瑶族自治县东阳光化成箔有限公司 | Anode foil etching process for aluminium electrolytic capacitor |
| CN111613446A (en) * | 2020-06-05 | 2020-09-01 | 南通海星电子股份有限公司 | Formation treatment method of high-water-resistance low-pressure aluminum foil |
| CN112941592A (en) * | 2021-01-28 | 2021-06-11 | 恒扬（韶关）工业有限公司 | Low-voltage formed foil production process for aluminum electrolytic capacitor |
-
2021
- 2021-09-26 CN CN202111130106.XA patent/CN113921282B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101651049A (en) * | 2009-06-24 | 2010-02-17 | 吴江飞乐天和电子材料有限公司 | Method for increasing specific volume of electrode foil of low-voltage aluminum electrolytic capacitor |
| CN108505094A (en) * | 2017-02-24 | 2018-09-07 | 宜都东阳光化成箔有限公司 | A kind of chemical synthesizing method reducing electrode foil current-leakage |
| CN109859949A (en) * | 2018-01-26 | 2019-06-07 | 东莞东阳光科研发有限公司 | A method of reducing medium-high pressure chemical foil leakage current |
| WO2019166034A1 (en) * | 2018-03-02 | 2019-09-06 | 乳源瑶族自治县东阳光化成箔有限公司 | Anode foil etching process for aluminium electrolytic capacitor |
| CN109609991A (en) * | 2018-12-26 | 2019-04-12 | 东莞东阳光科研发有限公司 | Waste Acid From Hua Cheng Foil, preparation method and applications |
| CN110055571A (en) * | 2019-04-18 | 2019-07-26 | 宜都东阳光化成箔有限公司 | A kind of preprocessing solution and chemical synthesis technology improving aluminium electrolutic capacitor medium-high pressure chemical foil capacity |
| CN111613446A (en) * | 2020-06-05 | 2020-09-01 | 南通海星电子股份有限公司 | Formation treatment method of high-water-resistance low-pressure aluminum foil |
| CN112941592A (en) * | 2021-01-28 | 2021-06-11 | 恒扬（韶关）工业有限公司 | Low-voltage formed foil production process for aluminum electrolytic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113921282A (en) | 2022-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113921282B (en) | Medium-high voltage formation foil low-loss formation process for aluminum electrolytic capacitor | |
| CN110993347B (en) | High-voltage anode foil of sintered aluminum electrolytic capacitor and preparation method thereof | |
| CN111146005B (en) | Sintered low-voltage anode foil of aluminum electrolytic capacitor and preparation method thereof | |
| CN106653373B (en) | A kind of aluminium electrolutic capacitor Waste Acid From Hua Cheng Foil and its production technology | |
| CN110219032A (en) | A kind of chemical synthesizing method of extra-high voltage aluminum electrolysis capacitor anode foil | |
| CN109609991B (en) | Formed foil, preparation method and application thereof | |
| CN110993348B (en) | Sintered aluminum electrolytic capacitor ultrahigh-voltage anode foil and preparation method thereof | |
| CN112117129B (en) | Mixed acidification formation process of high-voltage high-capacity low-defect anode foil | |
| CN103400694B (en) | A kind of manufacture method of high-voltage electrolysis capacitor | |
| CN107354498A (en) | A kind of manufacture method of the electrode foil for aluminum electrolytic capacitors of high pressure high power capacity | |
| CN112582177A (en) | Method for improving specific volume and hydration resistance of high-voltage anodized formed foil in aluminum electrolytic capacitor | |
| KR20220160539A (en) | Manufacturing method of nano-microporous structure aluminum electrode foil for automotive electronics | |
| CN100576389C (en) | The preparation method of the conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor | |
| CN109859949A (en) | A method of reducing medium-high pressure chemical foil leakage current | |
| CN108505094B (en) | Formation method for reducing leakage current of electrode foil | |
| CN110016702A (en) | A kind of aluminium electrolutic capacitor super-pressure Waste Acid From Hua Cheng Foil chemical synthesis technology | |
| CN115172054B (en) | Medium-high voltage anodic oxidation pretreatment method, aluminum foil and aluminum electrolytic capacitor | |
| CN104103428B (en) | A kind of manufacture method of aluminium electrolutic capacitor high pressure high-dielectric formed foil | |
| CN113436891A (en) | Method for inducing medium-high voltage anode foil to uniformly corrode and form pores by adopting nano pits after anodic oxidation | |
| KR101415641B1 (en) | Producting method for electrode foil for stacked type aluminium capacitor | |
| CN112582176B (en) | Method for improving specific volume and hydration resistance of low-voltage anodized formed foil of aluminum electrolytic capacitor | |
| CN112133563B (en) | Six-stage formation process of high-capacity low-leakage medium-voltage anode foil | |
| CN103714974A (en) | Method for preparing aluminum electrolytic capacitor anode material | |
| CN114808076A (en) | Preparation method of electrode foil with good bending performance | |
| CN103151174A (en) | Manufacturing method of electrode foil for high-voltage aluminium electrolytic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |