CN117758335A - Three-dimensional laminated foil manufacturing process - Google Patents
Three-dimensional laminated foil manufacturing process Download PDFInfo
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- CN117758335A CN117758335A CN202311831331.5A CN202311831331A CN117758335A CN 117758335 A CN117758335 A CN 117758335A CN 202311831331 A CN202311831331 A CN 202311831331A CN 117758335 A CN117758335 A CN 117758335A
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- 239000011888 foil Substances 0.000 title claims abstract description 169
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 76
- 239000000243 solution Substances 0.000 claims abstract description 66
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 57
- 238000011282 treatment Methods 0.000 claims abstract description 42
- 230000003647 oxidation Effects 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 46
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 31
- 239000004327 boric acid Substances 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 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 10
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- 238000010981 drying operation Methods 0.000 claims description 5
- 238000011221 initial treatment Methods 0.000 claims description 5
- 239000006012 monoammonium phosphate Substances 0.000 claims description 5
- 238000012805 post-processing Methods 0.000 claims description 5
- 238000007781 pre-processing Methods 0.000 claims description 5
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 5
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
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- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification 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
- 239000010452 phosphate Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 fatty alcohol sulfate Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of electrode foil manufacturing, in particular to a three-dimensional laminated foil manufacturing process which comprises the steps of generating a gel compound, pre-treating, multilevel formation treatment and post-treating. AlCl is added in the gel compound formation stage 3 The solution and polyethylene glycol 600 are mixed to obtain a primary mixed solution, ammonia water is dropped toward the primary mixed solution to obtain a secondary mixed solution, precipitate is separated out, and immersed in pure water, and a nitric acid solution is dropped, so that a gel compound is produced. In the pre-treatment stage, constant pressure oxidation treatment is performed on the laminated foil, and at the same time, a gel compound is added to the formation liquid,until it is fully encapsulated by the gel compound. On the one hand, the dielectric film generated on the surface of the laminated foil is ensured to have good molding quality, and the thickness values in different areas are basically consistent; on the other hand, in the formation process, the generated y' -alumina has better density distribution form, and the occurrence rate of the phenomenon that pores are blocked can be reduced.
Description
Technical Field
The invention relates to the technical field of electrode foil manufacturing, in particular to a three-dimensional laminated foil manufacturing process.
Background
The three-dimensional laminated foil has the characteristics of ultra-high capacity, less pollution and the like, and is gradually becoming a main material for manufacturing the anode aluminum foil of the high-performance capacitor. The current preparation process of the three-dimensional laminated foil is continuously perfected, but the subsequent formation process still has a large room for improvement.
The formation process of three-dimensional laminated foils has been generally as follows for many years: and (3) electroplating on the three-dimensional laminated foil to form a coating, directly performing first-step formation, performing high-temperature heat treatment to form a composite oxide film, performing second-step formation, and drying to obtain the finished foil. However, the above-mentioned process has the following problems, specifically: in the electroplating stage, the three-dimensional laminated foil material characteristics and the fine surface characteristics are limited, a plating layer is difficult to generate on the surface of the three-dimensional laminated foil material, the generated plating layer has extremely poor uniform distribution, and the original small pores are easily blocked by an oxide film with poor growth state, so that the surface smoothness and capacitance of the finished foil are finally affected.
In recent years, various companies have developed a method of forming a plating film by using an anodic aluminum oxide template, and although an oxide film substrate can be formed by three-dimensional lamination of foils, the surface quality of a dielectric layer formed subsequently is good, and the capacitance is high, the following problems are also involved, specifically: 1) The anodic aluminum oxide plate has higher brittleness and is extremely easy to damage in the practical application process; 2) The generated coating film is extremely easy to collect dust, and is difficult to realize good cleaning by adopting a traditional cleaning mode; 3) The electric energy consumption is extremely high and the pollution is high. Thus, a technician is required to solve the above problems.
Disclosure of Invention
Accordingly, in view of the above-mentioned problems and drawbacks, the present inventors have collected related data, and have conducted many experiments and modifications by those skilled in the art, which are conducted in many years of research and development, to finally result in the three-dimensional laminated foil manufacturing process.
In order to solve the technical problems, the invention relates to a three-dimensional laminated foil manufacturing process, which comprises the following steps:
s1, preparing a gel compound, which comprises the following substeps:
s11, mixing 2-3 mol/L AlCl 3 Mixing the solution with 0.5-1wt% of polyethylene glycol 600, and stirring thoroughly to obtain a first-stage mixed solution;
s12, 2-3 mol/L ammonia water is dripped into the primary mixed solution, and the mixture is heated to 90-95 ℃ to obtain a secondary mixed solution;
s13, fully stirring the secondary mixed solution until a precipitate is separated out;
s14, immersing the precipitate into pure water at 80-90 ℃, and continuously dripping into nitric acid solution with the concentration of 0.2-0.5 mol/L for fully stirring, so that gel compounds are generated;
s2, pre-processing, which comprises the following sub-steps:
s21, cleaning the three-dimensional laminated foil;
s22, immersing the three-dimensional laminated foil into an oxalic acid solution with the temperature of between 95 and 98 ℃ and the constant pressure oxidation for 15 to 20 minutes under the condition of 40 to 50V, and simultaneously adding a gel compound into the oxalic acid solution until the three-dimensional laminated foil is fully wrapped by the gel compound;
s23, cleaning the three-dimensional laminated foil again;
s3, formation, comprising the following substeps:
s31, immersing the three-dimensional laminated foil into a primary formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 10-13min under the condition of 160-170V;
the primary formation liquid is preferably formed by mixing 9.5-10 wt% of boric acid, 0.3-0.5 wt% of ammonium hypophosphite, 0.8-1.5 wt% of citric acid and 2-3 wt% of ammonium citrate;
s32, immersing the three-dimensional laminated foil into secondary formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 6-8min under the condition of 300-320V;
the secondary formation liquid is preferably formed by mixing 2-3 wt% of hexamethylenediamine and 7-8 wt% of boric acid;
s33, immersing the three-dimensional laminated foil into a three-time formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 6-8min under the condition of 400-450V;
the tertiary formation liquid is preferably formed by mixing 1.2-1.5 wt percent of hexamethylenediamine and 7-8 wt percent of boric acid;
s34, immersing the three-dimensional laminated foil into a four-time formation liquid with the temperature controlled at 80-85 ℃, and oxidizing for 8-12min at a constant pressure under the condition of 500-505V;
the fourth chemical solution is preferably prepared by mixing 0.5-1.5 wt% of hexamethylenediamine and 10-15 wt% of boric acid; s35, immersing the three-dimensional laminated foil into a five-time formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 10-15min under the condition of 540-600V;
the penta-chemical solution is preferably formed by mixing 16-20 wt% of boric acid and 2-3 wt% of ammonium pentaborate;
s36, immersing the three-dimensional laminated foil in primary treatment liquid at the temperature of 40-60 ℃ for 2-3min;
the primary medium treatment solution is preferably 4-5wt% phosphoric acid solution;
s37, performing high-temperature treatment on the three-dimensional laminated foil, wherein the temperature is controlled to be 300-400 ℃ and the time is controlled to be 1-2min;
s38, repeating the steps S35-S37 for at least two times on the three-dimensional laminated foil;
s39, immersing the three-dimensional laminated foil into a six-time formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 4-8min under the condition of 540-600V; then, immersing the three-dimensional laminated foil into secondary medium treatment liquid with the temperature controlled at 60-80 ℃ for 5-7min;
the sextuple formation liquid is also preferably formed by mixing 16-20 wt% of boric acid and 2-3 wt% of ammonium pentaborate;
the secondary medium treatment solution is preferably a phosphoric acid solution with the weight percent of 0.2-0.3;
s4, post-processing, which comprises the following substeps:
s41, immersing the three-dimensional laminated foil into a primary post-treatment liquid with the temperature controlled at 60-65 ℃ and washing for 5-8min by ultrasonic waves;
the primary post-treatment liquid is preferably formed by mixing 1-2 wt% of benzenesulfonic acid and 2-3 wt% of sodium benzenesulfonate;
s42, immersing the three-dimensional laminated foil into a secondary post-treatment liquid with the temperature controlled at 70-72 ℃ and washing for 10-12min by ultrasonic waves;
the secondary post-treatment liquid is preferably formed by mixing 1-2 wt% of phosphoric acid and 1-5 wt% of monoammonium phosphate;
s43, performing pure water cleaning operation on the three-dimensional laminated foil;
and S44, performing drying operation on the three-dimensional laminated foil to obtain the finished foil.
As a further improvement of the disclosed technical solution, in step S21, the thickness of the selected three-dimensional laminated foil is controlled to be 115-125 μm; step S21 comprises the following sub-steps:
s211, immersing the three-dimensional laminated foil into a sodium hydroxide solution with the mol/L of 0.15-0.2 and the temperature of 40-45 ℃ to execute ultrasonic cleaning operation;
s212, flushing the three-dimensional laminated foil by using clear water, and draining; in step 23, the three-dimensional laminated foil is immersed in pure water at 95 ℃ and the immersion time period is controlled to 15-20min.
As a further improvement of the technical scheme disclosed by the invention, in the step S44, the drying temperature is controlled to be 70-80 ℃ and the duration is controlled to be 5-8min.
As a further improvement of the technical scheme disclosed by the invention, in the step S13, after the sediment is collected, the sediment is washed at least 3-5 times by pure water with the temperature controlled at 80-90 ℃.
In practical implementation, the three-dimensional laminated foil manufacturing process disclosed by the invention has at least the following beneficial technical effects:
1) In view of the large specific surface area of the three-dimensional laminated foil and the abrupt features, the relatively large surface tension of the laminated foil results in the gel compound being prone to form a large number of air pockets during the surface attachment process of the three-dimensional laminated foil. In the cavitation morphology, the ion concentration is in an unbalanced state, A1 3+ Is difficult to diffuse freely therethrough, but OH - But can freely pass through the cavitation channel and simultaneously with the decomposition of A1 on the laminated foil 3+ Continuing the process, the cavitation pressure is gradually increased, and finally the morphology of the cavitation is destroyed, so that the oxalic acid solution is further immersed;
2） A1 3+ cause and C 2 O 4 2- 、PO 4 3- The plasma combines to precipitate out alumina crystals, i.e., the as-spun dielectric layer. Along with the continuous progress of the process, internal stress is generated on the dielectric layers attached to the surface of the three-dimensional laminated foil, and the dielectric layers on different spherical surfaces are always subjected to coulomb force, so that the growth speed of the dielectric layers in each area is basically ensured to be consistent, the thickness values in different areas are basically consistent, and the growth form and the order of distribution areas are promoted;
3) The growth thickness of the dielectric layer can be controlled by controlling the concentration of oxalic acid and phosphate radical, and the y' -alumina grown along the dielectric layer is better in density distribution form by five subsequent formation procedures, so that the occurrence probability of blocking phenomena of pores can be effectively reduced, the improvement of the porosity is facilitated, and a good bedding is provided for further improvement of the electrical property of the finished foil.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a cross-sectional representation (x 400) of a finished foil prepared using a conventional formation process.
Fig. 2 is a surface characterization graph (x 3000) of a finished foil prepared using a conventional chemical process.
FIG. 3 is a cross-sectional representation (500) of a finished foil prepared using example one of the disclosed three-dimensional laminated foil fabrication processes.
FIG. 4 is a cross-sectional representation (x 3000) of a finished foil prepared using an embodiment of the disclosed three-dimensional laminated foil manufacturing process.
Description of the embodiments
The present invention will be further described in detail with reference to examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the present invention. The methods are conventional methods unless otherwise specified.
Comparative example
The existing three-dimensional laminated foil manufacturing process comprises the following steps:
s1, placing the laminated foil into a 40 ℃ aqueous solution obtained by uniformly mixing 0.05 wt percent of titanium tetrachloride and 5wt per mill of fatty alcohol sulfate, and connecting the negative electrode with the laminated foil at a ratio of 0.5 mA/cm 2 After the constant current density is electrified for 15min, taking out pure water for washing;
s2. The laminated foil obtained in S1 was put into an aqueous solution of 10wt% boric acid and 0.1 wt% citric acid at a voltage of 580V at 70℃and 5mA/cm 2 After the current density is electrified for 20min, taking out pure water for washing;
s3, placing the laminated foil obtained in the S2 in a muffle furnace at 600 ℃, keeping the temperature for 2min, taking out, and cooling;
s4, repeating the step S2 on the laminated foil obtained in the step S3, wherein the electrifying time is 7min;
s5, soaking the laminated foil obtained in the S4 in 2wt% ammonium dihydrogen phosphate aqueous solution at 60 ℃ for 5min, taking out the laminated foil, drying at 170 ℃, and cooling to obtain the finished laminated foil.
Example 1
The three-dimensional laminated foil manufacturing process comprises the following steps:
s1, preparing a gel compound, which comprises the following substeps:
s11, 2mol/L AlCl 3 Solution and 0.5wt% PolymerMixing ethylene glycol 600, and stirring thoroughly to obtain a first-stage mixed solution;
s12, 2mol/L ammonia water is dripped into the primary mixed solution, and the temperature is raised to 90 ℃ to obtain a secondary mixed solution;
s13, fully stirring the secondary mixed solution until precipitate is separated out, and flushing the secondary mixed solution at least 3-5 times by pure water with the temperature controlled at 80 ℃ after the precipitate is collected;
s14, immersing the precipitate in pure water at 80 ℃, and continuously dripping the precipitate into a 0.2 mol/L nitric acid solution to be fully stirred, so that a gel compound is generated;
s2, pre-processing, which comprises the following sub-steps:
s21, cleaning the three-dimensional laminated foil, which comprises the following substeps:
s211, immersing the three-dimensional laminated foil in a sodium hydroxide solution with the mol/L of 0.15 and the temperature controlled at 40 ℃ to execute ultrasonic cleaning operation;
s212, flushing the three-dimensional laminated foil by using clear water, and draining;
s22, immersing the three-dimensional laminated foil with the thickness of 115 mu m into an oxalic acid solution with the temperature controlled at 95 ℃ and constant pressure oxidation for 20min under the condition of 40V, and meanwhile, adding a gel compound into the oxalic acid solution until the three-dimensional laminated foil is fully wrapped by the gel compound;
s23, cleaning the three-dimensional laminated foil again, namely immersing the three-dimensional laminated foil in pure water at 95 ℃ for 20 minutes;
s3, formation, comprising the following substeps:
s31, immersing the three-dimensional laminated foil into a primary formation liquid with the temperature controlled at 80 ℃, and carrying out constant-pressure oxidation for 13min under 160V;
the primary chemical solution is preferably formed by mixing 9.5 weight percent of boric acid, 0.3 weight percent of ammonium hypophosphite, 0.8 weight percent of citric acid and 2 weight percent of ammonium citrate;
s32, immersing the three-dimensional laminated foil into secondary formation liquid with the temperature controlled at 80 ℃, and oxidizing for 8 minutes at a constant pressure under 300V;
the secondary chemical solution is preferably formed by mixing 2 weight percent of hexamethylenediamine and 7 weight percent of boric acid;
s33, immersing the three-dimensional laminated foil into a three-time formation liquid with the temperature controlled at 80 ℃, and carrying out constant-pressure oxidation for 8min under the condition of 400V;
the tertiary chemical solution is preferably formed by mixing 1.2 weight percent of hexamethylenediamine and 7 weight percent of boric acid;
s34, immersing the three-dimensional laminated foil into a four-time formation liquid with the temperature controlled at 80 ℃, and carrying out constant-pressure oxidation for 12min under the condition of 500V;
the fourth chemical conversion solution is preferably formed by mixing 0.5 weight percent of hexamethylenediamine and 10 weight percent of boric acid;
s35, immersing the three-dimensional laminated foil into a five-time formation liquid with the temperature controlled at 80 ℃, and carrying out constant-pressure oxidation for 15min under the condition of 540V;
the penta-chemical solution is formed by mixing 16wt% of boric acid and 2wt% of ammonium pentaborate;
s36, immersing the three-dimensional laminated foil in the primary treatment liquid with the temperature controlled at 40 ℃ for 3min;
the primary medium treatment solution is 4wt% phosphoric acid solution;
s37, performing high-temperature treatment on the three-dimensional laminated foil, wherein the temperature is controlled to be 300 ℃ and the time is controlled to be 2min;
s38, repeating the steps S35-S37 for two times on the three-dimensional laminated foil;
s39, immersing the three-dimensional laminated foil into a six-time formation liquid with the temperature controlled at 80 ℃, and carrying out constant-pressure oxidation for 8min under the condition of 540V; subsequently, immersing the three-dimensional laminated foil in a secondary treatment liquid with the temperature controlled at 60 ℃ for 7min;
the sixth chemical solution is also formed by mixing 16 percent wt percent boric acid and 2 percent by weight of ammonium pentaborate;
the secondary medium treatment solution is 0.2wt% phosphoric acid solution;
s4, post-processing, which comprises the following substeps:
s41, immersing the three-dimensional laminated foil into a primary post-treatment liquid with the temperature controlled at 60 ℃, and washing for 8min by ultrasonic waves;
the primary post-treatment liquid is preferably formed by mixing 1 weight percent of benzenesulfonic acid and 2 weight percent of sodium benzenesulfonate;
s42, immersing the three-dimensional laminated foil into a secondary post-treatment liquid with the temperature controlled at 70 ℃, and washing for 12min by ultrasonic waves;
the secondary post-treatment liquid is preferably formed by mixing 1 weight percent of phosphoric acid and 1 weight percent of monoammonium phosphate;
s43, performing pure water cleaning operation on the three-dimensional laminated foil;
s44, performing drying operation on the three-dimensional laminated foil, wherein the drying temperature is controlled to be 70 ℃, and the time length is controlled to be 8min, so that the finished foil is obtained.
Example 2
The three-dimensional laminated foil manufacturing process comprises the following steps:
s1, preparing a gel compound, which comprises the following substeps:
s11, 2.5mol/L AlCl 3 Mixing the solution with 0.7wt% of polyethylene glycol 600, and stirring thoroughly to obtain a first-stage mixed solution;
s12, 2.5mol/L ammonia water is dripped into the primary mixed solution, and the temperature is raised to 95 ℃ to obtain a secondary mixed solution;
s13, fully stirring the secondary mixed solution until precipitate is separated out, and flushing the precipitate for at least 3-5 times by pure water with the temperature controlled at 90 ℃ after the precipitate is collected;
s14, immersing the precipitate in pure water at 90 ℃, and continuously dripping the precipitate into a 0.35 mol/L nitric acid solution to be fully stirred, so that a gel compound is generated;
s2, pre-processing, which comprises the following sub-steps:
s21, cleaning the three-dimensional laminated foil, which comprises the following substeps:
s211, immersing the three-dimensional laminated foil in a sodium hydroxide solution with the mol/L of 0.17 and the temperature controlled at 45 ℃ to execute ultrasonic cleaning operation;
s212, flushing the three-dimensional laminated foil by using clear water, and draining;
s22, immersing the three-dimensional laminated foil with the thickness of 115 mu m into an oxalic acid solution with the temperature of 98 ℃ and constant pressure oxidation for 18min under the condition of 45V, and meanwhile, adding a gel compound into the oxalic acid solution until the three-dimensional laminated foil is fully wrapped by the gel compound;
s23, cleaning the three-dimensional laminated foil again, namely immersing the three-dimensional laminated foil in pure water at 95 ℃ for 15min;
s3, formation, comprising the following substeps:
s31, immersing the three-dimensional laminated foil into a primary formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 12min under the condition of 165V;
the primary chemical solution is preferably formed by mixing 9.7 weight percent of boric acid, 0.4 weight percent of ammonium hypophosphite, 1.2 weight percent of citric acid and 2.5 weight percent of ammonium citrate;
s32, immersing the three-dimensional laminated foil into secondary formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 7min under the condition of 310V;
the secondary chemical solution is preferably formed by mixing 2.5 weight percent of hexamethylenediamine and 7.5 weight percent of boric acid;
s33, immersing the three-dimensional laminated foil into a three-time formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 7min under the condition of 420V;
the tertiary formation liquid is preferably formed by mixing 1.4 weight percent of hexamethylenediamine and 7.5 weight percent of boric acid;
s34, immersing the three-dimensional laminated foil into a four-time formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 10min under the condition of 503V;
the fourth chemical conversion solution is preferably formed by mixing 1 weight percent of hexamethylenediamine and 12 weight percent of boric acid;
s35, immersing the three-dimensional laminated foil into a five-time formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 10min under the condition of 600V;
the quintic liquid is formed by mixing 20 wt% of boric acid and 3wt% of ammonium pentaborate;
s36, immersing the three-dimensional laminated foil in the primary treatment liquid with the temperature controlled at 60 ℃ for 3min;
the primary medium treatment solution is 5wt% phosphoric acid solution;
s37, performing high-temperature treatment on the three-dimensional laminated foil, wherein the temperature is controlled at 400 ℃ and the time is controlled at 1min;
s38, repeating the steps S35-S37 for two times on the three-dimensional laminated foil;
s39, immersing the three-dimensional laminated foil into a six-time formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 4min under the condition of 600V; subsequently, immersing the three-dimensional laminated foil in a secondary treatment liquid with the temperature controlled at 80 ℃ for 5min;
the sixth chemical solution is also formed by mixing 20 wt% boric acid and 3wt% ammonium pentaborate;
the secondary medium treatment solution is 0.3wt% phosphoric acid solution;
s4, post-processing, which comprises the following substeps:
s41, immersing the three-dimensional laminated foil into a primary post-treatment liquid with the temperature controlled at 65 ℃, and washing by ultrasonic waves for 5min;
the primary post-treatment liquid is preferably formed by mixing 1.5 weight percent of benzenesulfonic acid and 2.5 weight percent of sodium benzenesulfonate;
s42, immersing the three-dimensional laminated foil into a secondary post-treatment liquid with the temperature controlled at 72 ℃, and washing by ultrasonic waves for 10min;
the secondary post-treatment liquid is preferably formed by mixing 1.5 weight percent of phosphoric acid and 3 weight percent of monoammonium phosphate;
s43, performing pure water cleaning operation on the three-dimensional laminated foil;
s44, performing drying operation on the three-dimensional laminated foil, wherein the drying temperature is controlled to be 80 ℃, and the time duration is controlled to be 5min, so that the finished foil is obtained.
Example 3
The three-dimensional laminated foil manufacturing process comprises the following steps:
s1, preparing a gel compound, which comprises the following substeps:
s11, 3 mol/L AlCl 3 Mixing the solution with 1wt% polyethylene glycol 600, and stirring thoroughly to obtain a first-stage mixed solution;
s12, 3 mol/L ammonia water is dripped into the primary mixed solution, and the temperature is raised to 95 ℃ to obtain a secondary mixed solution;
s13, fully stirring the secondary mixed solution until precipitate is separated out, and flushing the precipitate for at least 3-5 times by pure water with the temperature controlled at 90 ℃ after the precipitate is collected;
s14, immersing the precipitate in pure water at 90 ℃, and continuously dripping the precipitate into a 0.5 mol/L nitric acid solution to be fully stirred, so that a gel compound is generated;
s2, pre-processing, which comprises the following sub-steps:
s21, cleaning the three-dimensional laminated foil, which comprises the following substeps:
s211, immersing the three-dimensional laminated foil in a sodium hydroxide solution with the mol/L of 0.2 and the temperature controlled at 45 ℃ to execute ultrasonic cleaning operation;
s212, flushing the three-dimensional laminated foil by using clear water, and draining;
s22, immersing the three-dimensional laminated foil with the thickness of 115 mu m into oxalic acid solution with the temperature of 0.5 mol/L and the temperature of 98 ℃ for constant-pressure oxidation for 15min under the condition of 50V, and simultaneously adding a gel compound into the oxalic acid solution until the three-dimensional laminated foil is fully wrapped by the gel compound;
s23, cleaning the three-dimensional laminated foil again, namely immersing the three-dimensional laminated foil in pure water at 95 ℃ for 18 minutes;
s3, formation, comprising the following substeps:
s31, immersing the three-dimensional laminated foil into a primary formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 10min under 170V;
the primary chemical solution is preferably formed by mixing 10wt% of boric acid, 0.5wt% of ammonium hypophosphite, 1.5wt% of citric acid and 3wt% of ammonium citrate;
s32, immersing the three-dimensional laminated foil into secondary formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 6min under the condition of 320V;
the secondary formation liquid is preferably formed by mixing 3wt% of hexamethylenediamine and 8wt% of boric acid;
s33, immersing the three-dimensional laminated foil into a three-time formation liquid with the temperature controlled at 85 ℃, and carrying out constant-pressure oxidation for 6min under the condition of 450V;
the tertiary formation liquid is preferably formed by mixing 1.5wt percent of hexamethylenediamine and 8wt percent of boric acid;
s34, immersing the three-dimensional laminated foil into a four-time formation liquid with the temperature controlled at 85 ℃, and oxidizing for 8 minutes at constant pressure under the condition of 505V;
the fourth chemical conversion solution is preferably formed by mixing 1.5wt percent of hexamethylenediamine and 15 wt percent of boric acid;
s35, immersing the three-dimensional laminated foil into a five-time formation liquid with the temperature controlled at 82 ℃, and carrying out constant-pressure oxidation for 12min under the condition of 580V;
the quintic liquid is formed by mixing 18. 18wt percent of boric acid and 2.5 percent of ammonium pentaborate by weight;
s36, immersing the three-dimensional laminated foil in the primary treatment liquid with the temperature controlled at 50 ℃ for 2.5min;
the primary medium treatment solution is 4.2 weight percent phosphoric acid solution;
s37, performing high-temperature treatment on the three-dimensional laminated foil, wherein the temperature is controlled to be 350 ℃ and the time is controlled to be 1.5min;
s38, repeating the steps S35-S37 for two times on the three-dimensional laminated foil;
s39, immersing the three-dimensional laminated foil into a six-time formation liquid with the temperature controlled at 83 ℃, and carrying out constant-pressure oxidation for 6min under the condition of 580V; subsequently, immersing the three-dimensional laminated foil in a secondary treatment liquid with the temperature controlled at 70 ℃ for 6min;
the sextuple formation liquid is also mixed by 18 weight percent of boric acid and 2.5 weight percent of ammonium pentaborate;
the secondary medium treatment solution is 0.25wt% phosphoric acid solution;
s4, post-processing, which comprises the following substeps:
s41, immersing the three-dimensional laminated foil into a primary post-treatment liquid with the temperature controlled at 65 ℃, and washing by ultrasonic waves for 5min;
the primary post-treatment liquid is preferably formed by mixing 2wt% of benzenesulfonic acid and 3wt% of sodium benzenesulfonate;
s42, immersing the three-dimensional laminated foil into a secondary post-treatment liquid with the temperature controlled at 72 ℃, and washing by ultrasonic waves for 10min;
the secondary post-treatment liquid is preferably formed by mixing 2wt% of phosphoric acid and 5wt% of monoammonium phosphate;
s43, performing pure water cleaning operation on the three-dimensional laminated foil;
s44, performing drying operation on the three-dimensional laminated foil, wherein the drying temperature is controlled to be 80 ℃, and the time duration is controlled to be 5min, so that the finished foil is obtained.
Table 1 shows the results of the performance tests of the finished foils obtained using the prior art and examples 1 to 3.
TABLE 1
In practical implementation, the three-dimensional laminated foil manufacturing process disclosed by the invention has at least the following beneficial technical effects:
1) In view of the large specific surface area of the three-dimensional laminated foil and the abrupt features, the relatively large surface tension of the laminated foil results in the gel compound being prone to form a large number of air pockets during the surface attachment process of the three-dimensional laminated foil. In the cavitation morphology, the ion concentration is in an unbalanced state, A1 3+ Is difficult to diffuse freely therethrough, but OH - But can freely pass through the cavitation pore canal and the sameIn this case, A1 is decomposed from the laminated foil 3+ Continuing the process, the cavitation pressure is gradually increased, and finally the morphology of the cavitation is destroyed, so that the oxalic acid solution is further immersed;
2） A1 3+ cause and C 2 O 4 2- 、PO 4 3- The plasma combines to precipitate out alumina crystals, i.e., the as-spun dielectric layer. Along with the continuous progress of the process, internal stress is generated on the dielectric layers attached to the surface of the three-dimensional laminated foil, and the dielectric layers on different spherical surfaces are always subjected to coulomb force, so that the growth speed of the dielectric layers in each area is basically ensured to be consistent, the thickness values in different areas are basically consistent, and the growth form and the order of distribution areas are promoted;
3) The growth thickness of the dielectric layer can be controlled by controlling the concentration of oxalic acid and phosphate radical, and the y' -alumina grown along the dielectric layer is better in density distribution form by five subsequent formation procedures, so that the occurrence probability of blocking phenomena of pores can be effectively reduced, the improvement of the porosity is facilitated, and a good bedding is provided for further improvement of the electrical property of the finished foil.
It should be noted that, in the first embodiment, compared with the conventional embodiments, the growth form of the dielectric layer prepared by the new process is better than that of the conventional embodiments, and the number of small blocked pores is very small, so that the dielectric layer formed on the finished foil has better surface quality and the thickness and thinness of different regions tend to be consistent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A process for producing a three-dimensional laminated foil, comprising the steps of:
s1, preparing a gel compound, which comprises the following substeps:
s11, mixing 2-3 mol/L AlCl 3 Mixing the solution with 0.5-1wt% of polyethylene glycol 600, and stirring thoroughly to obtain a first-stage mixed solution;
s12, dropwise adding 2-3 mol/L ammonia water into the primary mixed solution, and heating to 90-95 ℃ to obtain a secondary mixed solution;
s13, fully stirring the secondary mixed solution until a precipitate is separated out;
s14, immersing the precipitate into pure water at 80-90 ℃, and continuously dripping into nitric acid solution with the concentration of 0.2-0.5 mol/L for fully stirring, so that gel compounds are generated;
s2, pre-processing, which comprises the following sub-steps:
s21, cleaning the three-dimensional laminated foil;
s22, immersing the three-dimensional laminated foil into an oxalic acid solution with the temperature controlled at 95-98 ℃ and constant pressure oxidation for 15-20min under the condition of 40-50V, and meanwhile, adding the gel compound into the oxalic acid solution until the three-dimensional laminated foil is fully wrapped by the gel compound;
s23, cleaning the three-dimensional laminated foil again;
s3, formation, comprising the following substeps:
s31, immersing the three-dimensional laminated foil into a primary formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 10-13min under the condition of 160-170V;
the primary formation liquid is formed by mixing 9.5-10 wt% of boric acid, 0.3-0.5 wt% of ammonium hypophosphite, 0.8-1.5 wt% of citric acid and 2-3 wt% of ammonium citrate;
s32, immersing the three-dimensional laminated foil into secondary formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 6-8min under the condition of 300-320V;
the secondary formation liquid is formed by mixing 2-3 wt% of hexamethylenediamine and 7-8 wt% of boric acid;
s33, immersing the three-dimensional laminated foil into a three-time formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 6-8min under the condition of 400-450V;
the tertiary formation liquid is formed by mixing 1.2-1.5 wt% of hexamethylenediamine and 7-8 wt% of boric acid;
s34, immersing the three-dimensional laminated foil into a four-time formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 8-12min under the condition of 500-505V;
the four-time chemical solution is formed by mixing 0.5-1.5 wt% of hexamethylenediamine and 10-15 wt% of boric acid;
s35, immersing the three-dimensional laminated foil into a five-time formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 10-15min under the condition of 540-600V;
the pentachemical liquid is formed by mixing 16-20 wt% of boric acid and 2-3 wt% of ammonium pentaborate;
s36, immersing the three-dimensional laminated foil in primary treatment liquid with the temperature controlled at 40-60 ℃ for 2-3min;
the primary medium treatment liquid is 4-5wt% phosphoric acid solution;
s37, performing high-temperature treatment on the three-dimensional laminated foil, wherein the temperature is controlled to be 300-400 ℃ and the time is controlled to be 1-2min;
s38, repeating the steps S35-S37 for at least two times on the three-dimensional laminated foil;
s39, immersing the three-dimensional laminated foil into a six-time formation liquid with the temperature controlled at 80-85 ℃, and carrying out constant-pressure oxidation for 4-8min under the condition of 540-600V; subsequently, immersing the three-dimensional laminated foil into a secondary medium treatment liquid with the temperature controlled at 60-80 ℃ for 5-7min;
the sextupling chemical solution is also formed by mixing 16-20 wt% of boric acid and 2-3 wt% of ammonium pentaborate;
the secondary medium treatment solution is a phosphoric acid solution with the weight percent of 0.2-0.3;
s4, post-processing, which comprises the following substeps:
s41, immersing the three-dimensional laminated foil into a primary post-treatment liquid with the temperature controlled at 60-65 ℃ and washing for 5-8min by ultrasonic waves;
the primary post-treatment liquid is formed by mixing 1-2 wt% of benzenesulfonic acid and 2-3 wt% of sodium benzenesulfonate;
s42, immersing the three-dimensional laminated foil into secondary post-treatment liquid with the temperature controlled at 70-72 ℃ and washing for 10-12min by ultrasonic waves;
the secondary post-treatment liquid is formed by mixing 1-2 wt% of phosphoric acid and 1-5 wt% of monoammonium phosphate;
s43, performing pure water cleaning operation on the three-dimensional laminated foil;
and S44, performing drying operation on the three-dimensional laminated foil to obtain a finished foil.
2. The three-dimensional laminated foil manufacturing process according to claim 1, wherein in step S21, the thickness of the three-dimensional laminated foil selected is controlled to be 115-125 μm; step S21 comprises the following sub-steps:
s211, immersing the three-dimensional laminated foil into a sodium hydroxide solution with the mol/L of 0.15-0.2 and the temperature of 40-45 ℃ to execute ultrasonic cleaning operation;
s212, flushing the three-dimensional laminated foil by using clear water, and draining;
in step 23, the three-dimensional laminated foil is immersed in pure water at 95 ℃ and the immersion time is controlled to be 15-20min.
3. The process of claim 1, wherein in step S44, the drying temperature is controlled to be 70-80 ℃ and the duration is controlled to be 5-8min.
4. The process for producing a three-dimensional laminated foil according to claim 1, wherein in step S13, after the sediment is collected, the sediment is rinsed at least 3 to 5 times with pure water having a temperature controlled at 80 to 90 ℃.
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