CN116598141A - Preparation method of surface hydroxylation sintered foil - Google Patents

Preparation method of surface hydroxylation sintered foil Download PDF

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Publication number
CN116598141A
CN116598141A CN202310820613.9A CN202310820613A CN116598141A CN 116598141 A CN116598141 A CN 116598141A CN 202310820613 A CN202310820613 A CN 202310820613A CN 116598141 A CN116598141 A CN 116598141A
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foil
aluminum foil
sintered
aluminum
treatment
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CN116598141B (en
Inventor
王建中
濮钰
王贵州
冒慧敏
徐中均
何桂丽
程恒洋
谢贵明
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Sichuan Zhongya Technology Co ltd
Nantong Haixing Electronics LLC
Nantong Haiyi Electronics Co Ltd
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Sichuan Zhongya Technology Co ltd
Nantong Haixing Electronics LLC
Nantong Haiyi Electronics Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/04—Drying; Impregnating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • H01G9/0525—Powder therefor
    • 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
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention provides a preparation method of a surface hydroxylation sintered foil, which belongs to the field of electrolytic aluminum foil preparation and comprises the following steps: treating the surface of the electronic aluminum foil by mechanical polishing, plasma gas treatment, liquid soaking and other modes; mixing aluminum powder or aluminum alloy powder, an organic solvent and an adhesive together, and uniformly mixing by high-speed ball milling; coating aluminum foil with slurry and drying; rolling and hydroxylating the surface of the aluminum foil after being coated with the slurry; finally, adopting a traditional chemical process to form; according to the invention, the contact area between the aluminum foil and the aluminum powder is increased through the surface treatment of the aluminum foil, and the surface hydroxylation treatment of the aluminum foil after coating enables hydrogen bonds to be formed between the aluminum powder and the aluminum powder, so that the acting force between the aluminum powder before sintering is enhanced, the sintering effect is further improved, and the powder dropping condition of the sintered foil is greatly reduced; meanwhile, a hydrated oxide film layer exists on the surface after hydroxylation treatment, so that agglomeration of aluminum powder in the sintering process is inhibited to a certain extent.

Description

Preparation method of surface hydroxylation sintered foil
Technical Field
The invention relates to the technical field of electrolytic aluminum foil preparation, in particular to a preparation method of a surface hydroxylation sintered foil.
Background
The aluminum electrolytic capacitor is widely applied to the fields of industrial frequency conversion, inverters, 5G base stations, new energy charging piles and the like, and is an important electronic device. The anode foil is used as a key component of the aluminum electrolytic capacitor, and has a decisive effect on the quality control of the aluminum electrolytic capacitor. At present, most of domestic high-voltage anode foil manufacture adopts a corrosion process, a sulfuric acid-hydrochloric acid system is required to carry out chemical corrosion or electrochemical corrosion on the aluminum foil, and tunnel holes with certain density are formed on the surface of the aluminum foil so as to increase the specific surface area of the aluminum foil. The method has been widely studied by a plurality of scholars, the specific surface area of the method is improved to be close to the theoretical limit, and a large amount of waste acid is generated while the sulfuric acid-hydrochloric acid system is utilized for production, so that the method has a large environmental protection pressure.
The aluminum powder sintered foil formed by stacking aluminum powder on two sides of the aluminum foil and sintering has higher specific surface area, no waste acid and waste liquid are generated in the preparation process, and at present, the process is still in a starting stage in China, so that the sintering effect has a great improvement space (the powder falling phenomenon of the sintered foil produced by the prior art is heavier).
Disclosure of Invention
The invention aims to provide a preparation method of a surface hydroxylation sintered foil, which aims to solve the problem of larger environmental protection pressure caused by increasing the specific surface area of an aluminum foil by using sulfuric acid-hydrochloric acid in the prior art.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme: a method for preparing a surface hydroxylated sintered foil, comprising the steps of:
s1, aluminum foil surface treatment: treating the surface of the electronic aluminum foil by mechanical polishing, plasma gas treatment, liquid soaking and other modes;
s2, preparing mixed slurry: mixing aluminum powder, an organic solvent and an adhesive together, and uniformly mixing by high-speed ball milling;
s3, coating the mixed slurry prepared in the step S2 on the surface of the electronic aluminum foil, and then drying the coated electronic aluminum foil;
s4, rolling the electronic aluminum foil dried in the S3, and then carrying out surface hydroxylation treatment;
s5, preparing a sintered foil: the electronic aluminum foil subjected to hydroxylation treatment in the step S4 is subjected to the following steps of segmentation and temperature control sintering;
the front section is slowly heated to 300-450 ℃ for 3-4 hours to remove the adhesive, and the rear section is heated to 550-640 ℃ under inert gas or vacuum condition to sinter for 3-4 hours, so that aluminum powder is slightly sintered to form sintered foil;
s6, performing chemical treatment on the sintered foil prepared in the step S5.
The purity of the electronic aluminum foil in the step S1 is more than 99.99%, and the mechanical polishing adopts one of sand paper polishing and sand blasting polishing.
The ionic gas in S1 is O 2 、H 2 O、O 3 、H 2 O 2 One or more of air, water, naOH, H 2 O 2 Ammonia water, H 2 SO 4 One or more of them, when electronicWhen the aluminum foil is soaked in liquid, the liquid temperature is controlled to be 60-120 ℃, and the soaking time is controlled to be 10 min-12 h.
The organic solvent in the S2 is one or a mixture of more of ethanol, glycol, acetone, N-methyl pyrrolidone and N, N-dimethylformamide; the adhesive is one or a mixture of more of epoxy resin, polyvinyl alcohol, polycarbosilane, polyacrylamide, phenolic resin, cyanoacrylate, polyurethane, polyvinylidene fluoride and acrylic resin.
The thickness of the mixed slurry coating in the step S3 is between 10 and 100 mu m, and the mixed slurry is subjected to temperature control and drying; the drying temperature is increased to 60-120 ℃ at 2-3 ℃/min, and the drying time is 1-6 h in vacuum, air and nitrogen.
The hydroxylation treatment in S4 is as follows:
using O 2 、H 2 O、O 3 、H 2 O 2 Carrying out plasma treatment on the electronic aluminum foil treated in the step S3 by using one or more mixed gases in the air, or using water, naOH and H 2 O 2 Ammonia water, H 2 SO 4 One or more of the above materials are mixed and soaked at the temperature of 60-120 ℃ for 10 min-12 h.
The temperature rising speed of the sintering at the S5 sintering front stage is 2-3 ℃/min, and the slow heating speed can effectively preheat the electronic aluminum foil, so that the final sintering effect is ensured.
The sintering front stage is carried out under the condition of air, nitrogen, argon or vacuum, and the sintering rear stage is carried out under the condition of nitrogen, argon or vacuum.
The ball milling in the step S2 is performed by using a ball mill, the effective volume of the ball mill is 5-10 m < 3 >, the ball mill is provided with a steel ball with the diameter of 50-80 mm, and the power range is controlled to be 80-210 KW.
According to the technical scheme, the invention has at least the following effects:
compared with the prior art, the aluminum foil surface treatment method has the advantages that the contact area between the aluminum foils is increased through the surface treatment of the aluminum foils, meanwhile, the tightness between the aluminum foils is improved through the rolling treatment, the surface hydroxylation treatment of the aluminum foils after coating enables hydrogen bonds to be formed between the aluminum foils and the aluminum foils, the acting force between the aluminum foils before sintering is enhanced, and the sintering effect is further improved;
meanwhile, as the hydrated oxide film layer exists on the surface of the aluminum powder or the aluminum alloy powder after hydroxylation treatment, agglomeration of the aluminum powder in the sintering process is inhibited to a certain extent, and compared with the prior sintered foil, the phenomenon that the agglomeration particles of the aluminum powder or the aluminum alloy powder become large due to excessive sintering is avoided;
in addition, the hydroxide layer can be converted into crystalline alumina in the subsequent formation process, so that the formation electricity consumption is reduced and the formation efficiency is improved.
Drawings
FIG. 1 is a diagram of a sintered foil electron microscope produced in example 1 of the present invention;
FIG. 2 is a diagram of a sintered foil electron microscope produced in example 2 of the present invention;
FIG. 3 is a diagram of a sintered foil electron microscope produced by the prior art.
Detailed Description
The invention is further described in connection with the following detailed description, in order to make the technical means, the creation characteristics, the achievement of the purpose and the effect of the invention easy to understand.
Comparative example of the prior art:
s1: uniformly stirring 1g of aluminum powder, 2ml of N-methyl pyrrolidone (NMP) solvent and 0.2g of epoxy resin adhesive, and performing high-speed ball milling to form uniform slurry;
s2: then coating the aluminum powder slurry prepared in the step S1 on the surface of an aluminum foil substrate, wherein the coating thickness is 50 mu m;
s3: heating the aluminum foil matrix after coating aluminum powder slurry to 120 ℃ in 1h to remove the solvent on the surface, heating to 360 ℃ in 2h to remove the adhesive on the surface, and finally sintering at 640 ℃ for 4h, wherein N2 is used for protection in the sintering process;
s4: the sintered aluminum foil is cleaned by pure water and then is formed by adopting a traditional formation process.
The sintering foil produced by the prior art is tested by related experiments to obtain data, the pressure resistance reaches 523.4V, and the CV performance reaches 543.2 mu F.V.cm -2 Specific volume of 1.038μF·cm -2 The weight loss ratio after ultrasonic treatment is reduced to 1.08 percent.
Example 1:
s1: carrying out sandblasting or sand paper polishing on the surface of the electronic aluminum foil with the purity of more than 99.99%;
s2: 1g of aluminum powder, 2ml of N-methyl pyrrolidone (NMP) solvent and 0.2g of epoxy resin adhesive are uniformly stirred to form uniform slurry under high-speed ball milling, a stirrer can be used for stirring before ball milling in actual mass production, electromagnetic stirring operation is carried out on the uniformly mixed slurry, the duration is 2-3 min, the stirring frequency is controlled at 100Hz, the power range is 45-55 KW, the magnetic induction intensity of the coil center in an idle period is controlled at 1000-1500A/m, then the ball milling is carried out by using a ball mill, and the effective volume of the ball mill is 5-10 m 3 The steel balls with the diameters of 50-80 mm are used, the power range is controlled to be 80-210 KW, the capacities of the stirrer and the ball mill are correspondingly adjusted according to the quantity of the prepared materials, wherein the aluminum powder is also pure aluminum, the following examples are pure aluminum powder, and the diameter of powder particles is smaller than 0.1mm;
s3: coating the aluminum powder slurry prepared in the step S2 on the surface of an aluminum foil substrate, wherein the average thickness of the aluminum powder slurry is 50 mu m; then drying the electronic aluminum foil after coating, wherein the drying time in the air is 6 hours;
s4: rolling the electronic aluminum foil dried in the step S3, and then carrying out surface hydroxylation treatment, namely placing the dried electronic aluminum foil in H with the solubility of 2 percent and the temperature of 80 DEG C 2 O 2 Soaking in the water for 20min; then washing for multiple times by using ionized water, and then putting the washed water into an oven at 80 ℃ for drying;
s5: heating the hydroxylated aluminum foil in S4 to 360 ℃ in 2h to remove solvent and binder on the surface, and then sintering at 640 ℃ for 4h, wherein N is used in the corrosion sintering process 2 Protecting;
s6: and S5, cleaning the aluminum foil sintered in the step of cleaning by pure water, and adopting a traditional formation process to form the aluminum foil.
The sintering foil produced in the embodiment is tested by related experiments to obtain data, the pressure resistance reaches 538.7V, and the CV performance reaches 552.7 mu F.V.cm -2 Specific volume of 1.026 mu F cm -2 Weight loss after ultrasoundThe ratio was reduced to 0.13%.
The method is characterized in that the electronic aluminum foil is polished in a mechanical polishing mode, the contact area of the surface of the electronic aluminum foil is increased, so that a subsequent coating mixed solution can be used for making a pad more tightly, then aluminum powder, N-methylpyrrolidone (NMP) solvent and epoxy resin adhesive are uniformly stirred and then form uniform slurry under high-speed ball milling, the coating tightness of the fine slurry with the polished electronic aluminum foil can be improved, hydrogen bonds are formed between the aluminum powder and the aluminum powder through surface hydroxylation treatment of the aluminum foil after coating, the acting force between the aluminum powder and the aluminum powder before sintering is enhanced, and the occurrence of powder dropping after forming of the sintered foil can be greatly reduced, namely the ultrasonic back weightlessness of the sintered foil is lower;
in addition, the hydrated oxide film layer exists on the surface of the aluminum powder after hydroxylation treatment, so that agglomeration of the aluminum powder in the sintering process can be inhibited to a certain extent, the phenomenon of excessive sintering of the sintered foil can be effectively avoided, the uniformity degree of a sintered layer on the surface of the sintered foil can be effectively ensured, and the sintered layer is uniformly distributed on the surface of the electronic aluminum foil substrate;
in addition, the surface energy of the aluminum foil subjected to hydroxylation treatment forms a hydroxide layer, and the hydroxide layer can be converted into crystalline alumina in the S6 sintering process, so that the power consumption for converting the hydrated oxide layer into crystalline alumina is less than that for converting pure aluminum into crystalline alumina, and the sintering efficiency is improved.
Example 2
S1: carrying out sandblasting or sand paper polishing on the surface of the electronic aluminum foil with the purity of more than 99.99%;
s2: uniformly stirring 1g of aluminum powder, 2ml of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) mixed solvent and 0.2g of polyurethane adhesive, forming uniform slurry under high-speed ball milling, wherein the mixed slurry after uniform mixing can be stirred by a stirrer before ball milling in actual mass production, electromagnetic stirring operation is carried out on the mixed slurry after uniform mixing for 2-3 min, stirring frequency is controlled to be 100Hz, power range is 45-55 KW, magnetic induction intensity of the coil center in no-load period is controlled to be 1000-1500A/m, ball milling is carried out by a ball mill, and effective volume of the ball mill is 5-10 m 3 The diameter is 50 to the wholeThe power range of the steel ball with the diameter of 80mm is controlled to be 80-210 KW, and the capacities of the stirrer and the ball mill are correspondingly adjusted according to the quantity of the prepared materials;
s3: coating the aluminum powder slurry prepared in the step S2 on the surface of an aluminum foil substrate, wherein the thickness of the aluminum powder slurry is 60 mu m on average; then drying the electronic aluminum foil after coating, wherein the drying time in the air is 5 hours;
s4: rolling the electronic aluminum foil dried in the step S3, and then carrying out surface hydroxylation treatment, namely placing the dried electronic aluminum foil in H with the solubility of 2 percent and the temperature of 80 DEG C 2 O 2 Soaking in the water for 20min; then washing for multiple times by using ionized water, and then putting the washed water into an oven at 80 ℃ for drying;
s5: the hydroxylated aluminum foil in S4 is heated to 400 ℃ in 2 hours to remove the solvent and binder on the surface, the process is carried out in air, and then sintered for 4 hours at 640 ℃, and N is used in the process 2 Protecting;
s6: and S5, cleaning the aluminum foil sintered in the step of cleaning by pure water, and adopting a traditional formation process to form the aluminum foil.
The sintering foil produced in the embodiment is tested by related experiments to obtain data, the pressure resistance reaches 536.6V, and the CV performance reaches 552.5 mu F.V.cm -2 Specific volume of 1.031 mu F cm -2 The weight loss ratio after ultrasonic treatment is reduced to 0.16 percent.
Example 3
S1: carrying out sandblasting or sand paper polishing on the surface of the electronic aluminum foil with the purity of more than 99.99%;
s2: uniformly stirring 1g of aluminum powder, 2ml of ethylene glycol, N-Dimethylformamide (DMF), an acetone mixed solvent and 0.2g of polyurethane adhesive, forming uniform slurry under high-speed ball milling, wherein a stirrer can be used for stirring before ball milling in actual mass production, electromagnetic stirring operation is carried out on the uniformly mixed slurry after uniform mixing, the duration is 2-3 min, the stirring frequency is controlled to be 100Hz, the power range is 45-55 KW, the magnetic induction intensity of the coil center in an idle period is controlled to be 1000-1500A/m, then ball milling is carried out by using a ball mill, and the effective volume of the ball mill is 5-10 m 3 The steel ball with the diameter of 50-80 mm is used, the power range is controlled to be 80-210 KW, and the capacities of the stirrer and the ball mill are according toThe amount of the prepared material is correspondingly adjusted.
S3: coating the aluminum powder slurry prepared in the step S2 on the surface of an aluminum foil substrate, wherein the thickness of the aluminum powder slurry is 60 mu m on average; then drying the electronic aluminum foil after coating, wherein the drying time in the air is 5 hours;
s4: rolling the electronic aluminum foil dried in the step S3, and then carrying out surface hydroxylation treatment, namely placing the dried electronic aluminum foil in H with the solubility of 2 percent and the temperature of 80 DEG C 2 O 2 Soaking in the water for 20min; then washing for multiple times by using ionized water, and then putting the washed water into an oven at 80 ℃ for drying;
s5: the hydroxylated aluminum foil in S4 is heated to 400 ℃ in 2 hours to remove the solvent and binder on the surface, the process is carried out in air, and then sintered for 4 hours at 640 ℃, and N is used in the process 2 Protecting;
s6: and S5, cleaning the aluminum foil sintered in the step of cleaning by pure water, and adopting a traditional formation process to form the aluminum foil.
The sintering foil produced in the embodiment is tested by related experiments to obtain data, the pressure resistance reaches 543.2V, and the CV performance reaches 552.6 mu F.V.cm -2 Specific volume of 1.028 mu F cm -2 The weight loss ratio after ultrasonic treatment is reduced to 0.15 percent.
Example 4
S1: carrying out sandblasting or sand paper polishing on the surface of the electronic aluminum foil with the purity of more than 99.99%;
s2: uniformly stirring 1g of aluminum powder, 2ml of ethylene glycol, N-Dimethylformamide (DMF), 0.2g of polyvinyl alcohol and polyurethane mixed adhesive, forming uniform slurry under high-speed ball milling, wherein a stirrer can be used for stirring before ball milling in actual mass production, electromagnetic stirring operation is carried out on the uniformly mixed slurry after uniform mixing, the duration is 2-3 min, the stirring frequency is controlled to be 100Hz, the power range is 45-55 KW, the magnetic induction intensity of the coil center in an idle period is controlled to be 1000-1500A/m, then ball milling is carried out by using a ball mill, and the effective volume of the ball mill is 5-10 m 3 The steel balls with the diameters of 50-80 mm are used, the power range is controlled to be 80-210 KW, and the capacities of the stirrer and the ball mill are correspondingly adjusted according to the quantity of the prepared materials;
s3: coating the aluminum powder slurry prepared in the step S2 on the surface of an aluminum foil substrate, wherein the average thickness is 80 mu m; then drying the electronic aluminum foil after coating, wherein the drying time in the air is 5 hours;
s4: rolling the electronic aluminum foil dried in the step S3, and then carrying out surface hydroxylation treatment, namely placing the dried electronic aluminum foil in H with the solubility of 2 percent and the temperature of 80 DEG C 2 O 2 Soaking in the water for 20min; then washing for multiple times by using ionized water, and then putting the washed water into an oven at 80 ℃ for drying;
s5: heating the hydroxylated aluminum foil in the step S4 to 380 ℃ within 2 hours to remove the solvent and the adhesive on the surface, and then sintering for 4 hours at 600 ℃, wherein the two steps are carried out in argon;
s6: and S5, cleaning the aluminum foil sintered in the step of cleaning by pure water, and adopting a traditional formation process to form the aluminum foil.
The sintering foil produced in the embodiment is tested by related experiments to obtain data, the pressure resistance reaches 541.6V, and the CV performance reaches 552.3 mu F.V.cm -2 Specific volume of 1.033 mu F cm -2 The weight loss ratio after ultrasonic treatment is reduced to 0.14 percent.
Looking at the table below, the ultrasonic weight loss ratio of the sintered foils produced in examples 1 to 4 is far smaller than that of the sintered foils produced by the prior art, so that the powder dropping condition of the sintered foils produced by the process can be greatly reduced; in the mass production, one or more metals such as copper, iron, cobalt, nickel, manganese, magnesium, titanium, tantalum, zirconium, niobium and the like can be added into the aluminum powder according to the order requirement for production, so that the customer requirement is met.
It will be appreciated by those skilled in the art that the present invention can be carried out in other embodiments without departing from the spirit or essential characteristics thereof. Accordingly, the above disclosed embodiments are illustrative in all respects, and not exclusive. All changes that come within the scope of the invention or equivalents thereto are intended to be embraced therein.

Claims (9)

1. A method for preparing a surface hydroxylated sintered foil, comprising the steps of:
s1, aluminum foil surface treatment: treating the surface of the electronic aluminum foil by mechanical polishing, plasma gas treatment, liquid soaking and other modes;
s2, preparing mixed slurry: mixing aluminum powder, an organic solvent and an adhesive together, and uniformly mixing by high-speed ball milling;
s3, coating the mixed slurry prepared in the step S2 on the surface of the electronic aluminum foil, and then drying the coated electronic aluminum foil;
s4, rolling the electronic aluminum foil dried in the S3, and then carrying out surface hydroxylation treatment;
s5, preparing a sintered foil: the electronic aluminum foil subjected to hydroxylation treatment in the step S4 is subjected to the following steps of segmentation and temperature control sintering;
the front section is slowly heated to 300-450 ℃ for 3-4 hours to remove the adhesive, and the rear section is heated to 550-640 ℃ under inert gas or vacuum condition to sinter for 3-4 hours, so that aluminum powder is slightly sintered to form sintered foil;
s6, performing chemical treatment on the sintered foil prepared in the step S5.
2. The method for preparing a surface hydroxylation sintered foil as claimed in claim 1, wherein the purity of the electronic aluminum foil in S1 is greater than 99.99%, and the mechanical polishing is one of sanding and sandblasting.
3. The method for preparing a surface-hydroxylated sintered foil according to claim 1 or 2, wherein the ionic gas in S1 is O 2 、H 2 O、O 3 、H 2 O 2 One or more of air, water, naOH, H 2 O 2 Ammonia water, H 2 SO 4 When the electronic aluminum foil is soaked in the liquid, the temperature of the liquid is controlled to be 60-120 ℃, and the soaking time is controlled to be 10 min-12 h.
4. The method for preparing a surface hydroxylation sintered foil according to claim 1, wherein the organic solvent in S2 is one or more of ethanol, ethylene glycol, acetone, N-methylpyrrolidone, N-dimethylformamide; the adhesive is one or a mixture of more of epoxy resin, polyvinyl alcohol, polycarbosilane, polyacrylamide, phenolic resin, cyanoacrylate, polyurethane, polyvinylidene fluoride and acrylic resin.
5. The method for preparing a surface hydroxylation sintered foil according to claim 1, wherein the thickness of the mixed slurry coating in S3 is 10-100 μm, and the mixed slurry is baked at a controlled temperature; the drying temperature is increased to 60-120 ℃ at 2-3 ℃/min, and the drying time is 1-6 h in vacuum, air and nitrogen.
6. The method for preparing a surface-hydroxylated sintered foil according to claim 1, characterized in that the hydroxylation treatment in S4 is as follows:
using O 2 、H 2 O、O 3 、H 2 O 2 Carrying out plasma treatment on the electronic aluminum foil treated in the step S3 by using one or more mixed gases in the air, or using water, naOH and H 2 O 2 Ammonia water, H 2 SO 4 One or more of the above materials are mixed and soaked at the temperature of 60-120 ℃ for 10 min-12 h.
7. The method for preparing a surface hydroxylation sintered foil according to claim 1, wherein the sintering temperature rising speed of the S5 pre-sintering stage is 2-3 ℃/min.
8. The method of producing a surface-hydroxylated sintered foil according to claim 7, wherein the pre-sintering stage is carried out under air, nitrogen, argon or vacuum conditions and the post-sintering stage is carried out under nitrogen, argon or vacuum conditions.
9. The method for preparing the surface hydroxylation sintered foil according to claim 1, wherein the ball milling in the step S2 is performed by using a ball mill, the effective volume of the ball mill is 5-10 m < 3 >, steel balls with the diameters of 50-80 mm are used, and the power range is controlled to be 80-210 KW.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116875973A (en) * 2023-09-07 2023-10-13 南通海星电子股份有限公司 Preparation method of sintered foil for electrolytic capacitor

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