CN115188597A - Preparation method of sintered anode material based on multi-particle size matching - Google Patents
Preparation method of sintered anode material based on multi-particle size matching Download PDFInfo
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—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
-
- 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
- H01G9/145—Liquid electrolytic capacitors
-
- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of a sintered anode material based on multi-particle size matching, which comprises the following steps: 1. selecting aluminum powder or aluminum alloy powder with large grain size and small grain size, mixing, adding a solvent, a binder and a dispersant, and stirring; 2. coating the aluminum powder slurry on the surface of an aluminum foil matrix; 3. sintering the precursor; 4. boiling the sintering precursor in water; 5. and carrying out formation treatment on the boiled precursor to obtain the anode foil of the aluminum electrolytic capacitor. The invention utilizes the aluminum powder or the aluminum alloy powder with large grain diameter and small grain diameter to form more irregular holes, so that more electrolyte can enter the holes, thereby more effectively utilizing the specific surface area of the aluminum powder with small grain diameter to improve the specific capacitance performance of the anode material, and simultaneously utilizing a certain number of irregular holes reserved in the later anodic oxidation process to improve the strength of the anode material, thereby meeting the requirements of high specific volume and high strength of the anode material for the medium-high voltage aluminum electrolytic capacitor.
Description
Technical Field
The invention belongs to the technical field of aluminum electrolytic capacitors, and particularly relates to a preparation method of a sintered anode material based on multi-particle size matching.
Background
The aluminum electrolytic capacitor is one of the most important basic electronic elements, can be used as a filter and a bypass of an electronic circuit, and can also play roles in coupling, decoupling and the like. Because of its wide usability, aluminum electrolytic capacitors are widely used in fields such as electrical equipment, communication equipment, automotive equipment, and aerospace. The high-voltage anode electronic aluminum foil is an important component of an aluminum electrolytic capacitor, is a barrier type oxide film which grows on the surface of an aluminum electrode foil through anodic oxidation and is used as a dielectric layer of the aluminum electrolytic capacitor. At present, the high-voltage anode electronic aluminum foil is mainly obtained by carrying out electrochemical corrosion or chemical corrosion on the surface of an aluminum foil with a high cubic texture by using sulfuric acid-hydrochloric acid. The corrosion process of the high-voltage anode electronic aluminum foil is generally complex, and mainly relates to the technical processes of aluminum foil raw materials, aluminum foil pretreatment, a first stage (aluminum foil hole forming stage), a second stage (aluminum foil hole forming stage), post-treatment, cleaning, drying and the like. The complex preparation process of the high-voltage anode electronic aluminum foil not only increases the processing cost, but also is difficult to reduce the cost for maintaining the quality stability, and simultaneously, the treatment of harmful substances such as waste acid, waste alkali and the like generated in the preparation process of the high-voltage anode electronic aluminum foil is difficult. Different from the traditional corrosion process, the current market has a method (powder layer electronic aluminum foil technology) for preparing the high-voltage anode electronic aluminum foil of the aluminum electrolytic capacitor by adopting a sintering method, and the method enables aluminum powder to be sintered on the surface of an aluminum matrix to form a sandwich structure with a porous structure. The method saves the traditional corrosion link, and has the characteristics of simple process, low processing cost and environmental protection.
In recent years, many patents relating to powder layer electronic aluminum foil technology have been filed and disclosed, such as patent publication nos. CN 103563028 b, CN 110828183 a, CN 110993347A. From these patents, it can be found that the prepared powder layer electronic aluminum foil has high specific capacitance performance, but the bending performance is not mentioned. The analysis reasons can be easily found, in the patents, the applicant adopts the aluminum powder with single particle size in the process of preparing the powder layer electronic aluminum foil; although aluminum powder with a single particle size is sintered on the surface of an aluminum matrix to form a porous structure with a certain porosity, the small amount of limited and ordered porous structure is easily reduced along with the growth of an oxide film in the later-stage powder layer electronic aluminum foil anodic oxidation process, so that closed pores are formed or the pores completely disappear. Therefore, the change of the limited and ordered porous structure in the anodic oxidation process is very little to the change of the specific capacitance performance of the powder layer electronic aluminum foil, but the bending performance is seriously lost, so that the standard performance of the winding for manufacturing the capacitor is difficult to achieve. In addition, the aluminum powder of a single particle diameter is difficult to be classified from the viewpoint of processing cost, and the production cost thereof is also high.
Therefore, a method for preparing a sintered anode material based on a multi-particle size matching is needed.
Disclosure of Invention
The present invention provides a method for preparing a sintered anode material based on a plurality of particle sizes, which is to solve the technical problem of the prior art. The method comprises the steps of mixing aluminum powder/aluminum alloy powder with different particle sizes to prepare slurry, and reasonably matching the aluminum powder/aluminum alloy powder with large particle size and small particle size to form more and irregular pores compared with the aluminum powder/aluminum alloy powder with single particle size, so that more electrolyte can enter the pores, and the specific surface area of the aluminum powder with small particle size is effectively utilized to improve the specific capacitance performance of the anode material; meanwhile, the strength of the anode material is improved by using a certain amount of irregular pores reserved in the later-stage anodic oxidation process, so that the requirements of high specific volume and high strength of the anode material for the medium-high voltage aluminum electrolytic capacitor are met.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a sintered anode material based on multi-particle size matching is characterized by comprising the following steps:
step one, respectively selecting aluminum-containing powder with large particle size and small particle size, uniformly mixing, adding a solvent, a binder and a dispersant, and stirring to obtain aluminum powder slurry;
coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor;
and step five, carrying out chemical treatment on the water-boiling precursor obtained in the step four to obtain the sintered anode material.
The aluminum powder or aluminum alloy powder with different particle sizes is matched to prepare the slurry, the aluminum powder with different particle sizes is reasonably matched to form a certain number of irregular pores, the electrolyte can quickly enter the inside of the anode material through the pores so as to more effectively utilize the specific surface area of the aluminum powder with small particle size, and meanwhile, a certain pore can be still kept inside the anode material after the anode material is subjected to anodic oxidation so as to ensure that the anode material has high strength; the solvent and the binder are removed by sintering, the aluminum powder with the matched particle size on the surface of the aluminum foil substrate and the aluminum foil substrate are fully combined together, a hydration film is formed on the surface of the anode material by water boiling, and an oxidation film is formed on the surface of the anode material by formation treatment, so that the performance of the anode material is improved.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that in the first step, the large particle size is 10-50 microns, the small particle size is not more than 1 micron, and the aluminum-containing powder is aluminum powder or aluminum alloy powder with the mass purity of more than 99.99%; the mass ratio of the aluminum powder containing with large particle size to the aluminum powder containing with small particle size in the aluminum powder slurry is 1 to 99. The invention ensures that the aluminum powder with the particle size can be reasonably matched to obtain the anode material with certain pores by controlling the particle size of the aluminum powder or the aluminum alloy powder, can provide higher specific surface area, improves the electrical and mechanical properties, prevents impurities from being introduced by controlling the quality purity, and achieves the purpose of controlling the specific surface area of the anode material by controlling the mass ratio of the aluminum powder or the aluminum alloy powder with the particle sizes of large size and small size.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that the mixing mode in the step one is mechanical mixing, pneumatic mixing or impulse mixing; the particle size of the aluminum-containing powder with large particle size and small particle size is two or more than two. The aluminum powder or the aluminum alloy powder with different particle sizes is uniformly mixed by adopting mechanical, pneumatic or impulse equipment, the uniformly mixed aluminum powder or the aluminum alloy powder is easy to sinter an aluminum film with uniform pores on the surface of an aluminum substrate, and an anode material with stable electrical and mechanical properties is easy to obtain.
The preparation method of the sintering anode material based on multi-particle size matching is characterized in that in the first step, the solvent is one or more of tributyl citrate, glycerol, glycol and terpineol, the binder is one of ethyl cellulose, polyvinyl alcohol, polymethacrylate and carboxymethyl cellulose, and the dispersant is one of lecithin, oleic acid, span-85 and triethanolamine. The aluminum raw material slurry has the advantages that the solvent and the dispersing agent are adopted to uniformly disperse irregular aluminum powder in the aluminum powder slurry, the binder is dissolved, the binder and the aluminum raw material are uniformly mixed, meanwhile, the aluminum raw material is loaded, the aluminum raw material is uniformly dispersed by controlling the type of the solvent, the volatilization speed is high, the boiling point is low, the pollution is small, and the price is low.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that in the second step, the aluminum foil substrate is subjected to oxidation film removal treatment before coating, and the oxidation film removal treatment process is soaking in NaOH solution with the mass concentration of 0.1% -10%. According to the invention, the oxide layer on the surface of the aluminum foil substrate is removed through the oxide film removing treatment, and the aluminum foil substrate has degreasing and dust removing effects, so that the coating layer is easy to combine, the aluminum raw material is better combined on the surface of the substrate in the sintering process, and the oxide layer is fully removed through soaking in a NaOH solution with the mass concentration of 0.1% -10%.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that in the second step, the thickness of the aluminum foil substrate is 30-60 mu m, and the thickness of the coated single surface is 40-100 mu m. According to the invention, the thickness of the aluminum foil substrate is controlled, the thickness of the coating layer is increased, the use of the aluminum substrate is reduced, the cost is saved, the mechanical strength is influenced due to the excessively thin aluminum foil substrate, the curling and winding of the anode foil in the later period are influenced, the specific capacitance of the anode foil is influenced due to the excessively thick aluminum foil substrate, the double-sided coating is carried out on the sheet-shaped aluminum foil substrate when the slurry is coated, and the thickness of the prepared sintered anode foil added with the nano high-dielectric fiber is controlled to be 130-230 mu m by controlling the thickness of the single side of the aluminum raw material slurry, so that the specific capacitance cannot be ensured when the thickness is too small, and the later period use cannot be ensured when the thickness is too large.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that in the second step, the aluminum raw material slurry is coated in a double-sided coating mode by adopting a scraper; the temperature of the vacuum drying treatment is 80-200 ℃. According to the invention, the two sides are coated by adopting the scraper, so that the aluminum electrolytic capacitor anode foil with high smoothness and glossiness is obtained, the adjustment precision is high compared with other coating modes, other impurities are prevented from being introduced by controlling the drying condition and temperature, and the solvent, the binder and the dispersing agent in the aluminum raw material slurry are primarily removed to enable the aluminum raw material slurry to be solidified to form the powder layer electronic aluminum foil, so that the subsequent treatment is convenient to carry out.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that the sintering treatment process in the third step is as follows: heating to 250-300 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 1h-4h, heating to 350-500 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 2h-8h, heating to 600-650 ℃ at a heating rate of 1-20 ℃/min, preserving heat for 1h-24h, cooling along with a furnace, and adopting nitrogen or argon as a protective gas or a vacuum environment in the sintering process. According to the invention, calcination is carried out by three-stage heating, residual solvent, binder and dispersant are removed at lower temperature in the first two stages, and the electronic aluminum foil of the powder layer on the surface of the aluminum foil substrate and the aluminum foil substrate are fully combined together at higher temperature in the third stage, so that the structural strength of the anode foil is enhanced.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that deionized water is adopted for boiling the aluminum foil in the fourth step, and the boiling is carried out for 10min to 20min. According to the invention, deionized water is adopted to prevent other impurities from being introduced, a hydration film with proper thickness is formed on the surface of the anode foil by controlling boiling time, and chemical formation treatment is utilized.
The preparation method of the sintered anode material based on multi-particle size matching is characterized in that boric acid solution with the mass concentration of 10% is adopted in the formation treatment in the fifth step, and the formation voltage is 520V. The invention forms an oxide film on the surface of the anode material through chemical conversion treatment, thereby improving the performance of the material.
Compared with the prior art, the invention has the following advantages:
1. the aluminum powder/aluminum alloy powder with different particle sizes is mixed with each other to prepare the slurry, and the aluminum powder/aluminum alloy powder with large particle size and small particle size is reasonably matched to form more and irregular pores compared with the aluminum powder/aluminum alloy powder with single particle size, so that more electrolyte can enter the pores, and the specific surface area of the aluminum powder with small particle size is more effectively utilized to improve the specific capacitance performance of the anode material; meanwhile, the strength of the anode material is improved by utilizing a certain amount of irregular pores reserved in the later anodic oxidation process, so that the requirements of high specific volume and high strength of the electrode material for the medium-high voltage aluminum electrolytic capacitor are met.
2. The invention controls the specific surface area and the number of the pores of the anode material by controlling the adding amount of the aluminum powder or the aluminum alloy powder, the specific surface area of the anode material and the number of the pores form a negative correlation relationship, and when the number of the pores reaches a certain specific value, the anode material of the aluminum electrolytic capacitor with the bending strength and the specific capacity meeting the requirements of the use in the medium-high voltage environment can be obtained.
3. The aluminum powder or the aluminum alloy powder with different particle sizes is uniformly mixed by adopting mechanical, pneumatic or impulse equipment, the uniformly mixed aluminum powder or the aluminum alloy powder is easy to sinter an aluminum film with uniform pores on the surface of an aluminum matrix, and the anode material with stable electrical and mechanical properties is easy to obtain.
4. The static specific capacity of the anode material prepared by the invention can reach 1.109 mu F/cm at most 2 The bending times can reach 157 times, the bending times are parameters for inspecting the winding performance of the anode material and are indexes for determining whether the anode material can be used for winding to produce the aluminum electrolytic capacitor, and the bending times of the anode material are far higher than those of like products.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, selecting 20 mu m-sized and 0.5 mu m-sized aluminum powder with the mass purity of more than 99.99 percent, uniformly mixing the aluminum powder with the mass ratio of 1; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
step two, coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in a NaOH solution with the mass concentration of 0.1% before being coated; the thickness of the aluminum foil substrate is 30 micrometers, and the thickness of the coated single surface is 100 micrometers; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 150 ℃;
sintering the precursor obtained in the step two to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 250 ℃ at a heating rate of 20 ℃/min under the protection of argon, then preserving heat for 1h, then heating to 400 ℃ at a heating rate of 20 ℃/min, then preserving heat for 2h, then heating to 600 ℃ at a heating rate of 20 ℃/min, preserving heat for 24h, and then cooling along with the furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; the aluminum foil is boiled by deionized water for 15min;
fifthly, carrying out chemical treatment on the water-boiled precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts a boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
The static specific capacity of the anode material prepared in the embodiment is detected to be 0.891 mu F/cm 2 The number of bending times was 122.
Comparative example 1
This comparative example comprises the following steps:
step one, selecting aluminum powder with the particle size of 10 microns and the mass purity of more than 99.99 percent, adding a solvent, a binder and a dispersant, and stirring to obtain aluminum powder slurry; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in a NaOH solution with the mass concentration of 0.1% before being coated; the thickness of the aluminum foil substrate is 30 micrometers, and the thickness of the coated single surface is 100 micrometers; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 150 ℃;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 250 ℃ at a heating rate of 20 ℃/min under the protection of argon, then preserving heat for 1h, then heating to 400 ℃ at a heating rate of 20 ℃/min, then preserving heat for 2h, then heating to 600 ℃ at a heating rate of 20 ℃/min, preserving heat for 24h, and then cooling along with the furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; the aluminum foil is boiled by deionized water for 15min;
fifthly, carrying out formation treatment on the water-boiling precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared by the comparative example is 0.909 mu F/cm 2 The number of bending times was 11.
It can be seen from comparison between comparative example 1 and example 1 that the use of aluminum powder with a single particle size in comparative example 1 results in a very low porosity in the anode material prepared in comparative example 1, and thus cannot withstand multiple bending, and the anode material prepared by matching multiple particle sizes in example 1 ensures the bending performance of the anode material.
Example 2
The embodiment comprises the following steps:
step one, selecting aluminum powder with the particle size of 10 microns and the particle size of 0.1 micron and the mass purity of more than 99.99 percent, uniformly mixing the aluminum powder and the aluminum powder by a mechanical method according to the mass ratio of 1; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
step two, coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in a NaOH solution with the mass concentration of 6% before being coated; the thickness of the aluminum foil substrate is 60 mu m, and the thickness of the coated single surface is 60 mu m; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 100 ℃;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 275 ℃ at a heating rate of 10 ℃/min under the protection of argon, then preserving heat for 4h, then heating to 350 ℃ at a heating rate of 10 ℃/min, then preserving heat for 8h, then heating to 650 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling along with a furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; deionized water is adopted for water boiling of the aluminum foil, and the water boiling is boiling for 10min;
fifthly, carrying out chemical treatment on the water-boiled precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts a boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared in the embodiment is 1.019 mu F/cm 2 The number of bending times was 127.
Example 3
The embodiment comprises the following steps:
step one, selecting aluminum powder with the particle size of 50 microns and the particle size of 1 micron and the mass purity of more than 99.99 percent, uniformly mixing the aluminum powder and the aluminum powder by a mechanical method according to the mass ratio of 99 to obtain aluminum powder slurry after adding a solvent, a binder and a dispersant; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in NaOH solution with the mass concentration of 4% before being coated; the thickness of the aluminum foil substrate is 50 μm, and the thickness of the coated single surface is 90 μm; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 100 ℃;
sintering the precursor obtained in the step two to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 275 ℃ at a heating rate of 10 ℃/min under the protection of argon, then preserving heat for 4h, then heating to 350 ℃ at a heating rate of 10 ℃/min, then preserving heat for 8h, then heating to 650 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling along with the furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; deionized water is adopted for water boiling of the aluminum foil, and the water boiling is boiling for 20min;
fifthly, carrying out formation treatment on the water-boiling precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared in the embodiment is 0.905 mu F/cm 2 The number of bending times was 132.
Example 4
The embodiment comprises the following steps:
selecting Al-Mg-Si powder with the particle size of 30 microns, the particle size of 10 microns and the particle size of 0.1 micron and the mass purity of more than 99.99 percent, uniformly mixing the Al-Mg-Si powder with the particle size of 0.1 micron by utilizing an impulse type according to the mass ratio of 1; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in a NaOH solution with the mass concentration of 8% before being coated; the thickness of the aluminum foil substrate is 40 mu m, and the thickness of the coated single surface is 70 mu m; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 120 ℃;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 275 ℃ at a heating rate of 10 ℃/min under the protection of argon, then preserving heat for 4h, then heating to 350 ℃ at a heating rate of 10 ℃/min, then preserving heat for 8h, then heating to 650 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling along with a furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; deionized water is adopted for water boiling of the aluminum foil, and the water boiling is boiling for 15min;
fifthly, carrying out formation treatment on the water-boiling precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts a boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
The static specific capacity of the anode material prepared in the embodiment is detected to be 0.829 mu F/cm 2 The number of bending times was 154.
Example 5
The embodiment comprises the following steps:
step one, selecting aluminum powder with the particle size of 50 microns, the particle size of 30 microns, the particle size of 1 micron and the particle size of 0.5 micron and the mass purity of more than 99.99 percent, uniformly mixing the aluminum powder and the aluminum powder by utilizing an impulse, adding a solvent, a binder and a dispersant, and stirring to obtain aluminum powder slurry, wherein the mass ratio of the aluminum powder to the solvent is as follows; the solvent is terpineol and glycol, the binder is carboxymethyl fiber, and the dispersant is lecithin, wherein the mass ratio of the terpineol to the glycol to the carboxymethyl fiber to the lecithin is 65;
step two, coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in NaOH solution with the mass concentration of 0.1% before being coated; the thickness of the aluminum foil substrate is 60 mu m, and the thickness of the coated single surface is 40 mu m; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 80 ℃;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 275 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, then preserving heat for 4h, then heating to 350 ℃ at a heating rate of 10 ℃/min, then preserving heat for 8h, then heating to 650 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, and then cooling along with the furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; the aluminum foil is boiled by deionized water for 10min;
fifthly, carrying out formation treatment on the water-boiling precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared in the embodiment is 0.790 mu F/cm 2 The number of bending times was 149.
Example 6
The embodiment comprises the following steps:
step one, selecting Al-Mg-Cu powder with the particle size of 20 microns and the particle size of 0.5 microns and the mass purity of more than 99.99%, uniformly mixing the Al-Mg-Cu powder and the Al-Mg-Cu powder in a mechanical mode according to the mass ratio of 1 to 99, and then adding a solvent, a binder and a dispersing agent and stirring to obtain aluminum powder slurry; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
step two, coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; soaking the aluminum foil substrate in a NaOH solution with the mass concentration of 5% before coating; the thickness of the aluminum foil substrate is 40 μm, and the thickness of the coated single surface is 80 μm; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 200 ℃;
sintering the precursor obtained in the step two to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 270 ℃ at a heating rate of 8 ℃/min under the protection of argon, then preserving heat for 3h, then heating to 420 ℃ at a heating rate of 8 ℃/min, then preserving heat for 3h, then heating to 610 ℃ at a heating rate of 8 ℃/min, preserving heat for 20h, and then cooling along with a furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; deionized water is adopted for water boiling of the aluminum foil, and the water boiling is boiling for 20min;
fifthly, carrying out chemical treatment on the water-boiled precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared in the embodiment is 0.951 mu F/cm 2 The number of bending was 157.
Example 7
The embodiment comprises the following steps:
step one, selecting Al-Mg powder with the particle size of 20 microns and the particle size of 0.5 microns and the mass purity of more than 99.99%, uniformly mixing the Al-Mg powder and the Mg-Mg powder in a mechanical mode according to the mass ratio of 1; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in a NaOH solution with the mass concentration of 10% before coating; the thickness of the aluminum foil substrate is 30 micrometers, and the thickness of the coated single surface is 60 micrometers; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 100 ℃;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 260 ℃ at a heating rate of 15 ℃/min under the protection of argon, then preserving heat for 2h, then heating to 380 ℃ at a heating rate of 15 ℃/min, then preserving heat for 6h, then heating to 640 ℃ at a heating rate of 15 ℃/min, preserving heat for 5h, and then cooling along with a furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; deionized water is adopted for water boiling of the aluminum foil, and the water boiling is boiling for 10min;
fifthly, carrying out chemical treatment on the water-boiled precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts a boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared in the embodiment is 0.826 muF/cm 2 The number of bending times was 124.
Example 8
The embodiment comprises the following steps:
selecting Al-Si-Cu-Mg powder with the particle size of 20 microns and the particle size of 0.5 microns and the mass purity of more than 99.99 percent, uniformly mixing the Al-Si-Cu-Mg powder and the Al-Si-Cu-Mg powder in a mechanical mode according to the mass ratio of 1 to 99, and then adding a solvent, a binder and a dispersing agent and stirring to obtain aluminum powder slurry; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in a NaOH solution with the mass concentration of 1% before being coated; the thickness of the aluminum foil substrate is 50 μm, and the thickness of the coated single surface is 90 μm; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 180 ℃;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 300 ℃ at a heating rate of 1 ℃/min under vacuum, then preserving heat for 2h, then heating to 500 ℃ at a heating rate of 1 ℃/min, then preserving heat for 4h, then heating to 630 ℃ at a heating rate of 1 ℃/min, then preserving heat for 12h, and then cooling along with the furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; deionized water is adopted for water boiling of the aluminum foil, and the water boiling is boiling for 10min;
fifthly, carrying out chemical treatment on the water-boiled precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts a boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared in the embodiment is 0.877 muF/cm 2 The number of bending times was 148.
Example 9
The embodiment comprises the following steps:
step one, selecting aluminum powder with the particle size of 20 microns and the particle size of 0.5 microns and the mass purity of more than 99.99 percent, uniformly mixing the aluminum powder and the aluminum powder by a mechanical method according to the mass ratio of 1; the solvent is terpineol, the binder is ethyl cellulose, and the dispersant is oleic acid, wherein the mass ratio of the terpineol to the ethyl cellulose to the oleic acid is 96;
step two, coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor; the aluminum foil substrate is soaked in a NaOH solution with the mass concentration of 2% before being coated; the thickness of the aluminum foil substrate is 40 μm, and the thickness of the coated single surface is 50 μm; the coating mode of the aluminum raw material slurry is to adopt a scraper to carry out double-sided coating; the temperature of the vacuum drying treatment is 120 ℃;
thirdly, sintering the precursor obtained in the second step to obtain a sintered precursor; the sintering treatment process comprises the following steps: firstly, heating to 280 ℃ at a heating rate of 5 ℃/min under the protection of argon, then preserving heat for 3h, then heating to 450 ℃ at a heating rate of 5 ℃/min, then preserving heat for 5h, then heating to 620 ℃ at a heating rate of 5 ℃/min, preserving heat for 15h, and then cooling along with the furnace;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor; deionized water is adopted for water boiling of the aluminum foil, and the water boiling is boiling for 20min;
fifthly, carrying out formation treatment on the water-boiling precursor obtained in the fourth step to obtain a sintered anode material; the formation treatment adopts a boric acid solution with the mass concentration of 10%, and the formation voltage is 520V.
Through detection, the static specific capacity of the anode material prepared in the embodiment is 1.109 mu F/cm 2 Number of bending of 128Next, the process is carried out.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (10)
1. A preparation method of a sintered anode material based on multi-particle size matching is characterized by comprising the following steps:
step one, respectively selecting aluminum-containing powder with large particle size and aluminum-containing powder with small particle size, uniformly mixing, adding a solvent, a binder and a dispersant, and stirring to obtain aluminum powder slurry;
coating the aluminum powder slurry obtained in the step one on the surface of an aluminum foil matrix, and then carrying out vacuum drying to obtain a precursor;
sintering the precursor obtained in the step two to obtain a sintered precursor;
step four, carrying out water boiling treatment on the sintering precursor obtained in the step three to obtain a water boiling precursor;
and step five, carrying out chemical treatment on the water-boiling precursor obtained in the step four to obtain the sintered anode material.
2. The method for sintering the anode material based on the collocation of multiple particle sizes as claimed in claim 1, wherein in the step one, the large particle size is 10 μm to 50 μm, the small particle size is not more than 1 μm, and the aluminum-containing powder is aluminum powder or aluminum alloy powder with mass purity of more than 99.99%; the mass ratio of the aluminum powder containing large and small particle sizes in the aluminum powder slurry is 1 to 99.
3. The method of claim 1, wherein the mixing in the first step is mechanical mixing, pneumatic mixing or impulse mixing; the particle size of the aluminum-containing powder with large particle size and small particle size is two or more than two.
4. The method for sintering anode material based on multi-particle size collocation according to claim 1, wherein in the first step, the solvent is one or more than two of tributyl citrate, glycerol, ethylene glycol and terpineol, the binder is one of ethyl cellulose, polyvinyl alcohol, polymethacrylate and carboxymethyl cellulose, and the dispersant is one of lecithin, oleic acid, span-85 and triethanolamine.
5. The method for sintering the anode material based on the multi-particle size matching as claimed in claim 1, wherein the aluminum foil substrate is subjected to a de-oxidation film treatment before coating in the second step, and the de-oxidation film treatment is performed by soaking in a NaOH solution with a mass concentration of 0.1% -10%.
6. The method for sintering anode material based on multi-particle size collocation according to claim 1, wherein the thickness of the aluminum foil substrate in the second step is 30 μm to 60 μm, and the thickness of the coated single surface is 40 μm to 100 μm.
7. The method for sintering anode material based on multi-particle size matching as claimed in claim 1, wherein the aluminum raw material slurry is coated by double-sided coating with a doctor blade in step two; the temperature of the vacuum drying treatment is 80-200 ℃.
8. The method for sintering anode material based on multi-particle size matching as claimed in claim 1, wherein the sintering process in step three is as follows: firstly, heating to 250-300 ℃ at a heating rate of 1-20 ℃/min, then preserving heat for 1h-4h, then heating to 350-500 ℃ at a heating rate of 1-20 ℃/min, then preserving heat for 2h-8h, then heating to 600-650 ℃ at a heating rate of 1-20 ℃/min, then preserving heat for 1h-24h, and then cooling along with a furnace, wherein nitrogen or argon is used as a protective gas in the sintering process, or a vacuum environment is adopted.
9. The method for sintering the anode material based on the multi-particle size matching as claimed in claim 1, wherein the aluminum foil is boiled with deionized water in the fourth step, and the boiling is carried out for 10min to 20min.
10. The method as claimed in claim 1, wherein the formation treatment in step five is performed with a boric acid solution with a mass concentration of 10%, and the formation voltage is 520V.
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