CN117418284A - Valve metal anodic oxidation method, capacitor and electronic equipment - Google Patents
Valve metal anodic oxidation method, capacitor and electronic equipment Download PDFInfo
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- CN117418284A CN117418284A CN202311356499.5A CN202311356499A CN117418284A CN 117418284 A CN117418284 A CN 117418284A CN 202311356499 A CN202311356499 A CN 202311356499A CN 117418284 A CN117418284 A CN 117418284A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 121
- 230000003647 oxidation Effects 0.000 title claims abstract description 119
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 89
- 239000002184 metal Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003990 capacitor Substances 0.000 title claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 118
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 33
- 238000004140 cleaning Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 15
- 230000000295 complement effect Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000007781 pre-processing Methods 0.000 claims description 6
- 238000007743 anodising Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KEXXDMPEUZTTIS-UHFFFAOYSA-N ethane-1,2-diol;phosphoric acid Chemical compound OCCO.OP(O)(O)=O KEXXDMPEUZTTIS-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
Abstract
The application provides an anodic oxidation method of valve metal, a capacitor and electronic equipment, and relates to the technical field of capacitors. The anodic oxidation method comprises the following steps: performing first-stage oxidation treatment on the valve metal anode sample in the first mixed solution to obtain a target anode sample; performing second-stage oxidation treatment on the target anode sample in a second mixed solution to obtain a required anode sample; the electric conductivity of the first mixed solution is higher than that of the second mixed solution, the temperature of the first mixed solution is lower than that of the second mixed solution, and the polyol content of the first mixed solution is lower than that of the second mixed solution. According to the method, the valve metal anode sample is subjected to two times of oxidation treatment, so that the leakage current of the valve metal anode oxide film is reduced, and the density and reliability of the oxide film are improved.
Description
Technical Field
The application relates to the technical field of capacitors, in particular to an anodic oxidation method of valve metal, a capacitor and electronic equipment.
Background
The quality of the anodic oxide film of the capacitor directly affects the reliability of the capacitor in application, in the related art, the reliability of the high-voltage capacitor is poor, the direct current leakage current is large, and in high-temperature application, the defect of the anodic oxide film of the high-voltage capacitor is easily amplified.
Disclosure of Invention
In order to improve the reliability of valve metal anode samples and prolong the service life of capacitors, the application provides a valve metal anode oxidation method, a capacitor and electronic equipment.
In a first aspect, embodiments of the present application provide a method for anodic oxidation of a valve metal, the method comprising: performing first-stage oxidation treatment on the valve metal anode sample in the first mixed solution to obtain a target anode sample; performing second-stage oxidation treatment on the target anode sample in a second mixed solution to obtain a required anode sample; the electric conductivity of the first mixed solution is higher than that of the second mixed solution, the temperature of the first mixed solution is lower than that of the second mixed solution, and the polyol content of the first mixed solution is lower than that of the second mixed solution.
In the implementation manner, the valve metal anode sample is subjected to the oxidation treatment twice, so that the insulating property of the valve metal anode sample is effectively improved. The valve metal anode sample is oxidized twice to generate a compact oxide film, and the leakage current of the valve metal anode sample is reduced through oxidation treatment, so that the reliability of the valve metal anode sample can be improved. And the conductivity of the first mixed solution used in the first oxidation treatment is higher than that of the second mixed solution used in the second oxidation treatment, the temperature of the first mixed solution is lower than that of the second mixed solution, and the polyol content of the first mixed solution is lower than that of the second mixed solution. In the mixed solution with low conductivity, high temperature and high polyol content, the oxidation treatment can be more sufficient, and the valve metal anode sample is favorable for forming a compact oxide film. According to the scheme, the leakage current performance of the valve metal anode sample can be improved, and the reliability of the valve metal anode sample is improved.
Optionally, the first stage oxidation treatment of the valve metal anode sample in the first mixed solution includes: placing the valve metal anode sample into the first mixed solution with the temperature of a first temperature and the electrical conductivity of the first mixed solution for oxidation treatment until the voltage flowing through the valve metal anode sample is a first voltage, wherein the first voltage is the voltage required by the valve metal anode sample to oxidize to form an oxide film with a specified thickness; and carrying out pretreatment on the valve metal anode sample with the oxide film formed to a specified thickness to obtain the target anode sample.
In the above implementation, the valve metal anode sample generates an oxide film by the first stage oxidation treatment. The first stage oxidation treatment is carried out in the first mixed solution with the temperature of the first temperature and the first conductivity, so that the voltage of the valve metal anode sample can be directly increased to the first voltage, and the valve metal anode sample can form an oxide film with the required thickness.
Optionally, the performing a second stage oxidation treatment on the target anode sample in a second mixed solution includes: placing the target anode sample in the second mixed solution with the second temperature and the second conductivity for oxidation treatment until the voltage flowing through the target anode sample is a second voltage, wherein the second voltage is the voltage required by the target anode sample to form a compact oxide film with uniform thickness; and (3) preprocessing the target anode sample with the uniform-thickness compact oxide film to obtain the required anode sample.
In the implementation manner, the target anode sample is subjected to the oxidation treatment, and the second-stage oxidation treatment is performed in the second mixed solution with the second temperature and the second conductivity, so that defects of an oxide film formed by the target anode sample after the first-stage oxidation treatment can be repaired, and the density of the oxide film formed by the valve metal anode sample is higher.
Optionally, the preprocessing includes: the method comprises the steps of sequentially carrying out constant voltage maintaining treatment, first cleaning treatment, heat treatment, complementary forming treatment, second cleaning treatment and drying treatment on a sample for a specified duration, wherein the duration of the constant voltage maintaining treatment of the first-stage oxidation treatment is longer than that of the constant voltage maintaining treatment of the second-stage oxidation treatment.
In the implementation mode, the defects in the sample can be made up by preprocessing the sample, and the performance of the sample is improved.
Optionally, the temperature of the heat treatment is any one of 360-400 ℃ and the treatment time is any one of 5-30 min, wherein the second-stage heat treatment time is lower than the first-stage heat treatment time.
In the above implementation, the heat treatment of the sample under high temperature conditions can increase the heat resistance and stability of the valve metal anodized film.
Optionally, the first voltage formed during the first stage oxidation process is higher than the second voltage formed during the second stage oxidation process.
In the above implementation manner, the first voltage formed during the first stage oxidation treatment is higher than the second voltage formed during the second stage oxidation treatment, so that the leakage current of the valve metal and the leakage current characteristic of the poppet valve metal anode sample can be reduced.
Optionally, the temperature of the first mixed solution is any one of 35-70 ℃, and the temperature of the second mixed solution is any one of 70-150 ℃.
In the above implementation, the valve metal anode sample can be subjected to the first stage oxidation treatment more fully in the temperature range of 35-70 ℃; the valve metal anode sample can be more fully subjected to the second stage oxidation treatment in the temperature range of 70 to 150 ℃.
Optionally, the first mixed solution comprises four solutions of an organic acid, an inorganic acid, deionized water and a polyol, and the second mixed solution comprises at least one solution of an organic acid, an inorganic acid, deionized water and a polyol.
In the above implementation manner, the polyol content of the first mixed solution is lower than the polyol content of the second mixed solution, so that the temperature of the first mixed solution is lower than that of the second mixed solution, the conductivity of the second mixed solution is lower than that of the first mixed solution, and a denser oxide film is generated by using the target anode sample.
In a second aspect, embodiments of the present application further provide a capacitor, including: the valve metal anode is obtained by performing second-stage oxidation treatment on a target anode sample in a second mixed solution, wherein the target anode sample is obtained by performing first-stage oxidation treatment on an initial valve metal anode in a first mixed solution, the conductivity of the first mixed solution is higher than that of the second mixed solution, the temperature of the first mixed solution is lower than that of the second mixed solution, and the polyol content of the first mixed solution is lower than that of the second mixed solution.
In a third aspect, embodiments of the present application further provide an electronic device, including: the capacitor as in the second aspect embodiment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below. It is to be understood that the following drawings illustrate only certain embodiments of the present application and are therefore not to be considered limiting of scope, for other related drawings may also be obtained by those of ordinary skill in the art based on these drawings.
FIG. 1 is a flow chart of two stages of anodic oxidation of valve metal provided in an embodiment of the present application;
FIG. 2 is a flow chart of a first stage of anodic oxidation of valve metal provided in an embodiment of the present application;
fig. 3 is a flow chart of the second stage of anodic oxidation of the valve metal provided in the embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be described below with reference to the drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. The components of the embodiments of the present application, which are generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, as provided in the accompanying drawings, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to be within the scope of the present application.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
As shown in fig. 1, an embodiment of the present application provides a valve metal anodizing method, which includes the steps of: S100-S200.
S100: and (3) carrying out first-stage oxidation treatment on the valve metal anode sample in the first mixed solution to obtain a target anode sample.
S200: and (3) carrying out second-stage oxidation treatment on the target anode sample in the second mixed solution to obtain the required anode sample. Wherein the conductivity of the first mixed solution is higher than the conductivity of the second mixed solution, the temperature of the first mixed solution is lower than the temperature of the second mixed solution, and the polyol content of the first mixed solution is lower than the polyol content of the second mixed solution.
Optionally, the valve metal anode sample is an anode sample, and the anode sample may be valve metal with any specific volume, and the first mixed solution and the second mixed solution are mixed solutions with different components, temperatures, conductivities and polyol contents. Specifically, a valve metal anode sample is placed in a first mixed solution for oxidation treatment to generate an oxide film, and a target anode sample is obtained. And (3) placing the target anode sample in a second mixed solution for oxidation treatment to obtain the required anode sample. The second mixed liquid has a temperature higher than that of the first mixed liquid, the second mixed liquid has a conductivity lower than that of the first mixed liquid, and the first mixed liquid has a polyol content lower than that of the second mixed liquid. Under the conditions of low conductivity, high temperature and high polyol content, the oxidation treatment can be more sufficient, and the valve metal anode sample is favorable for forming a compact oxide film. According to the scheme, the leakage current performance of the valve metal anode sample can be improved, and the reliability of the valve metal anode sample is improved.
As an alternative implementation, the valve metal anode sample is subjected to a first stage oxidation treatment in a first mixed solution, including the steps of: S101-S102.
S101: and (3) placing the valve metal anode sample in a first mixed solution with the temperature of a first temperature and the conductivity of a first conductivity for oxidation treatment until the voltage flowing through the valve metal anode sample is a first voltage. The first voltage is a voltage required by the valve metal anode sample to be oxidized to form an oxide film with a specified thickness.
S102: and (3) preprocessing the valve metal anode sample for forming the oxide film with the specified thickness to obtain a target anode sample.
Optionally, for the first stage oxidation treatment, the first temperature is a temperature of the first mixed liquor, and the first conductivity is a conductivity of the first mixed liquor. The first voltage is the voltage required by the valve metal anode sample to oxidize to form an oxide film with a specified thickness, the thickness of the oxide film can be set according to the requirement, and the first voltages corresponding to different thicknesses are also different.
In some alternative implementations, the valve metal anode sample is used as the anode, the device containing the first mixed liquor is used as the cathode, and the first mixed liquor is used as the electrolyte solution. The valve metal anode sample is placed in an electrolyte solution (i.e., a first mixed solution), and the valve metal anode sample, the device containing the first mixed solution, and the electrolyte solution are connected into a single passage by an external current source. When the valve metal anode sample is electrified with the electrifying requirement of a certain current density, the valve metal anode sample can perform oxidation reaction in an electrolyte solution (namely a first mixed solution), so that the voltage of the valve metal anode sample flowing through the valve metal anode sample is increased to a first voltage, and an oxide film with a specified thickness is formed on the valve metal anode sample.
Alternatively, the current density is between 30mA/g and 300mA/g, such as, but not limited to, any one point value or range value between any two of 30mA/g, 95mA/g, 160mA/g, 215mA/g and 300 mA/g.
As an alternative implementation manner, the target anode sample is subjected to a second stage oxidation treatment in a second mixed solution, which comprises the following steps: S201-S202.
S201: and (3) placing the target anode sample into a second mixed solution with the second temperature and the second conductivity for oxidation treatment until the voltage flowing through the target anode sample is the second voltage. The second voltage is the voltage required by the target anode sample to form a compact oxide film with uniform thickness.
S202: and (3) preprocessing the target anode sample for forming the compact oxide film with uniform thickness to obtain the required anode sample.
Optionally, for the second stage oxidation treatment, the second temperature is a temperature of the second mixed liquor, and the second temperature is higher than the first temperature. The second conductivity is the conductivity of the second mixed solution, the second conductivity is lower than the first conductivity, the second polyol content is the polyol content of the second mixed solution, and the second polyol content is higher than the first polyol content. The second voltage is a voltage required for forming a dense oxide film of uniform thickness for the target anode sample, wherein the uniform thickness is expressed as that of the oxide film formed by the target anode sample being relatively uniform, for example, the difference between the maximum thickness of the oxide film and the minimum thickness of the oxide film is within a specified thickness range, and the thickness of the oxide film is considered to be uniform. The specified thickness range may be set according to specific needs.
In some alternative implementations, the target anode sample is used as the anode, the device containing the second mixed liquor is used as the cathode, and the second mixed liquor is used as the electrolyte solution. The target anode sample is placed in an electrolyte solution (i.e., a second mixed solution), and the target anode sample, the device containing the second mixed solution, and the electrolyte solution are connected into a single passage by an external current source. When the current is supplied according to the current supply requirement of a certain current density, the target anode sample can undergo an oxidation reaction in the electrolyte solution (namely the second mixed solution), so that the voltage of the target anode sample flowing through the target anode sample is increased to the second voltage, and a compact oxide film with uniform thickness can be formed on the target anode sample.
As an alternative implementation, the pretreatment involved in the first stage oxidation treatment and the second stage oxidation treatment may include: and sequentially performing constant voltage holding treatment, first cleaning treatment, heat treatment, complementary forming treatment, second cleaning treatment and drying treatment on the sample for a specified duration, wherein the constant voltage holding time of the first-stage oxidation treatment is longer than the constant voltage holding time of the second-stage oxidation treatment.
For the constant voltage holding process, in some alternative embodiments, the specified duration of the constant voltage holding is 1h to 8h, such as, but not limited to, any one point value or range value between any two of 1h, 4h, 6h, and 8h. As an example, the constant pressure time is 2h. The constant voltage holding time period of the first stage oxidation treatment is longer than that of the second stage oxidation treatment. For example, in the first-stage oxidation treatment, the specified period of time for which the constant voltage is maintained may be 3 hours to 8 hours. In the second stage oxidation treatment, the specified duration of constant voltage holding may be 1h to 3h.
For the cleaning process, in some alternative embodiments, the cleaning solution involved in the cleaning process in the first stage oxidation process, the second stage oxidation process may be deionized water, with the temperature of the cleaning solution being greater than 80 ℃, such as, but not limited to, 85 ℃, 90 ℃, 95 ℃, and the like. The washing duration includes, but is not limited to, 2 hours.
For the drying process, in some alternative embodiments, the temperature of the drying process involved in the first stage oxidation process, the second stage oxidation process may be a temperature greater than 100 ℃, such as, but not limited to, 110 ℃, 120 ℃, 130 ℃, and the like. The drying process time includes, but is not limited to, 20 minutes.
For the heat treatment, in some alternative embodiments, the temperature of the heat treatment involved in the first stage oxidation treatment, the second stage oxidation treatment is any one of 360-400 ℃, such as, but not limited to, 360 ℃, 380 ℃, 400 ℃, and the like. The heat treatment time is any one of 5 to 30 minutes, such as, but not limited to, 5 minutes, 10 minutes, 30 minutes, etc. Optionally, the heat treatment time in the second stage oxidation treatment is lower than the heat treatment time in the first stage oxidation treatment. As an example, the first stage heat treatment time is 15 to 30 minutes, and the second stage heat treatment time is 5 to 15 minutes.
For the complementary formation process, in some alternative embodiments, the complementary formation voltage involved in the complementary formation process in the first stage oxidation process and the second stage oxidation process may each be a voltage less than or equal to the constant voltage holding process of the oxidation process stage, and the constant voltage time of the complementary formation process may be less than or equal to the constant voltage time of the oxidation process stage.
Pretreatment is required in both the first stage oxidation treatment and the second stage oxidation treatment. For the pretreatment of the first stage oxidation treatment, in some alternative embodiments, when the voltage flowing through the valve metal sample is the first voltage, the constant voltage holding treatment is performed at the first voltage, that is, the voltage flowing through the valve metal sample is held at the first voltage for a specified time. And performing first cleaning treatment on the valve metal sample subjected to the constant voltage holding treatment, and sequentially performing heat treatment, compensation forming treatment, second cleaning treatment and drying treatment on the valve metal sample subjected to the first cleaning treatment to obtain a target anode sample.
For the pretreatment of the second stage oxidation treatment, in some alternative embodiments, when the voltage flowing through the target anode sample is the second voltage, the constant voltage holding treatment is performed at the second voltage, that is, the voltage flowing through the target anode sample is held at the second voltage for a specified time. And performing first cleaning treatment on the target anode sample subjected to the constant voltage holding treatment, and sequentially performing heat treatment, complementary forming treatment, second cleaning treatment and drying treatment on the target anode sample subjected to the first cleaning treatment to obtain the target anode sample. The dielectric oxide film generated by the target anode sample has better thickness uniformity, density and insulating strength through pretreatment.
As an alternative implementation, the first voltage developed during the first stage oxidation process is higher than the second voltage developed during the second stage oxidation process.
Alternatively, in the first stage oxidation process, the voltage of the valve metal sample is raised to the first voltage with the energization requirement of the specified current density value, which may be set according to specific needs. In the second stage oxidation process, the voltage is raised to the second voltage with the energization requirement of an arbitrary current density value. The specified current density in the first stage oxidation process may be any of 30mA/g to 300mA/g, such as, but not limited to, 30mA/g, 240mA/g, 300mA/g, etc. The current density in the second stage oxidation process may be a current density greater than 0mA/g, such as, but not limited to, 10mA/g, 20mA/g, 100mA/g, etc.
As an alternative implementation, the first mixed solution includes four solutions of an organic acid, an inorganic acid, deionized water, and a polyol, and the second mixed solution includes at least one solution of an organic acid, an inorganic acid, deionized water, and a polyol.
Alternatively, the polyol may be ethylene glycol, propylene glycol, glycerin, sorbitol, a mixed polyol of ethylene glycol and polyethylene glycol, or the like. The organic acid may be citric acid, malic acid, acetic acid, etc. The inorganic acid may be phosphoric acid, nitric acid, etc. Alternatively, the first mixed solution may be a mixed solution including four solutions of an organic acid, an inorganic acid, deionized water, and a polyol. The second mixed liquid may be a mixed liquid including one or more solutions of an organic acid, an inorganic acid, deionized water, and a polyol, for example, the second mixed liquid may be a mixed liquid including three solutions of an organic acid, an inorganic acid, and a polyol.
In some alternative embodiments, the first mixed solution and the second mixed solution are both deionized water-phosphoric acid-ethylene glycol-citric acid mixed solution. Optionally, the ethylene glycol content of the deionized water-phosphoric acid-ethylene glycol-citric acid mixture in the second stage oxidation process is higher than the ethylene glycol content of the deionized water-phosphoric acid-ethylene glycol-citric acid mixture in the first stage oxidation process. The ethylene glycol content affects the conductivity of the deionized water-phosphoric acid-ethylene glycol-citric acid mixture. The electrical conductivity of the deionized water-phosphoric acid-ethylene glycol-citric acid mixture in the second stage oxidation treatment is lower than that of the deionized water-phosphoric acid-ethylene glycol-citric acid mixture in the first stage oxidation treatment. The lower the conductivity of the mixed liquor, the lower the leakage current. The phosphoric acid solution has good crystallization inhibition capability and good formation, and the solution with high polyol content is used for the second stage oxidation treatment, so that the further formed dielectric oxide film has better density.
In order to more clearly illustrate the oxidation method provided in the embodiments of the present application, the following description is given by way of specific examples:
in the first embodiment, an anode sample was prepared using tantalum powder having a specific volume of 2000. Mu.F.V/g, and the anode sample was sintered at 2050℃to obtain an anode sample having a size of Φ2.3X3.0 mm. The anode sample is placed in water with the temperature of 50 ℃ and the conductivity of 4.0mS/cm and 30% glycol-phosphoric acid-citric acid mixed solution for first stage oxidation treatment, the voltage of the anode sample is increased to 310V according to the electrifying requirement of the current density of 70mA/g, and the voltage of the tantalum powder anode sample is kept to 310V within 2 hours. And sequentially performing primary cleaning, heat treatment, complementary formation, secondary cleaning and drying treatment on the tantalum powder anode sample with the voltage of 310V to obtain a target anode sample. Then, the target anode sample having a voltage of 310V was subjected to a second stage oxidation treatment in a water-50% ethylene glycol-phosphoric acid mixture having a temperature of 85℃and a conductivity of 2.0mS/cm, and the voltage of the target anode sample was raised to 280V at a current density of 30 mA/g. And maintaining the voltage of the target anode sample at 280V within 1h, and then sequentially performing first cleaning, heat treatment, complementary formation, second cleaning and drying treatment on the target anode sample with the voltage of 280V to obtain the required anode sample.
In a second embodiment, tantalum powder with a specific volume of 20000 muF.V/g is used to prepare an anode sample, and the anode sample is sintered at 1500 ℃ to obtain an anode sample with a size of phi 8 x 20 mm. The anode sample was placed in a water-60% glycol-phosphoric acid-citric acid mixture at a temperature of 70 c and a conductivity of 2.5mS/cm for a first stage oxidation treatment, and the voltage was raised to 150V with a current density of 50mA/g for energization. And (3) maintaining the voltage of the anode sample at 150V within 5 hours, and then sequentially performing first cleaning, heat treatment, complementary formation, second cleaning and drying treatment on the anode sample with the voltage of 150V to obtain a target anode sample. The target anode sample was subjected to a second stage oxidation treatment in a mixed solution of ethylene glycol-phosphoric acid having a temperature of 120℃and a conductivity of 1.5 mS/cm. Energizing at a current density of 20mA/g requires that the voltage of the target anode sample be raised to 120V. And (3) keeping the voltage of the target anode sample at 120V within 4 hours, and then sequentially performing first cleaning, heat treatment, complementary formation, second cleaning and drying treatment on the target anode sample with the voltage of 120V to obtain the required anode sample.
In the third example, a tantalum powder having a specific volume of 3500. Mu.F.V/g was used to prepare an anode sample. The anode samples were sintered at 1900℃to obtain anode samples of 3X 8X 4mm in size. The anode sample was subjected to a first stage oxidation treatment at 65℃in a water-25% glycol-phosphoric acid-citric acid mixed electrolyte having a conductivity of 5mS/cm, and the voltage of the anode sample was raised to 300V at the current-carrying requirement of a current density of 65 mA/g. The voltage of the anode sample was maintained at 300V for 3 hours. Then, sequentially performing first cleaning, heat treatment, complementary formation, second cleaning and drying treatment on the anode sample with the voltage of 300V to obtain a target anode sample. The target anode sample was subjected to a second stage oxidation treatment in a water-60% ethylene glycol-phosphoric acid mixed electrolyte having a temperature of 75 ℃ and a conductivity of 1.0mS/cm, and the voltage of the target anode sample was raised to 285V at the energization requirement of a current density of 30 mA/g. The voltage of the target anode sample was maintained at 285V over 1 h. Then, the target anode sample with the voltage of 285V is sequentially subjected to first cleaning, heat treatment, complementary formation, second cleaning and drying treatment to obtain the required anode sample.
The first, second and third embodiments described above are only some of the examples in the present application, and do not represent all the embodiments of the present application.
The embodiment of the application also provides a capacitor, which comprises: and the valve metal anode is obtained by performing second-stage oxidation treatment on the target anode sample in the second mixed solution. The target anode sample is obtained by performing first-stage oxidation treatment on the initial valve metal anode in a first mixed solution. Wherein the conductivity of the first mixed solution is higher than the conductivity of the second mixed solution, the temperature of the first mixed solution is lower than the temperature of the second mixed solution, and the polyol content of the first mixed solution is lower than the polyol content of the second mixed solution.
In the implementation manner, the anode of the capacitor is prepared by adopting valve metal, and the valve metal anode of the capacitor is placed in the first mixed solution and the second mixed solution for oxidation treatment, so that a required anode sample is obtained. The first mixed solution and the second mixed solution are mixed solutions with different components, temperatures, conductivities and polyol contents. According to the embodiment of the application, through the oxidation treatment of the first stage, the oxide film is generated on the valve metal anode, so that the valve metal anode has better insulating property. And then the anode sample obtained by the first stage oxidation treatment is subjected to the second stage oxidation treatment, so that defects of the oxide film generated by the first stage oxidation treatment can be repaired, and the valve metal sample can generate a denser oxide film. By performing the oxidation treatment twice on the valve metal anode sample, the leakage current characteristic of the valve metal anode can be improved, and further the reliability of the capacitor prepared from the valve metal sample can be improved.
The embodiment of the application also provides electronic equipment which comprises the capacitor. The electronic device includes, but is not limited to, a mobile phone, a tablet, a computer, a game machine, a vehicle-mounted device, and the like, which include an electronic product of a capacitor.
In summary, the application provides an anodic oxidation method of valve metal, a capacitor and an electronic device, wherein the valve metal anode sample is subjected to two times of oxidation treatment, so that a compact oxide film with uniform thickness is formed on the valve metal anode, the quality of the valve metal anode sample is improved, meanwhile, the reliability of the capacitor prepared by the valve metal anode sample is improved, and the service life of the capacitor is prolonged.
The foregoing is merely exemplary of the present application and is not intended to limit the invention, and various modifications and variations may be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method of anodic oxidation of valve metal, comprising:
performing first-stage oxidation treatment on the valve metal anode sample in the first mixed solution to obtain a target anode sample;
performing second-stage oxidation treatment on the target anode sample in a second mixed solution to obtain a required anode sample; the electric conductivity of the first mixed solution is higher than that of the second mixed solution, the temperature of the first mixed solution is lower than that of the second mixed solution, and the polyol content of the first mixed solution is lower than that of the second mixed solution.
2. The method according to claim 1, wherein the first-stage oxidation treatment of the valve metal anode sample in the first mixed solution comprises:
placing the valve metal anode sample into the first mixed solution with the temperature of a first temperature and the electrical conductivity of the first mixed solution for oxidation treatment until the voltage flowing through the valve metal anode sample is a first voltage, wherein the first voltage is the voltage required by the valve metal anode sample to oxidize to form an oxide film with a specified thickness;
and carrying out pretreatment on the valve metal anode sample with the oxide film formed to a specified thickness to obtain the target anode sample.
3. The method according to claim 1, wherein the subjecting the target anode sample to the second stage oxidation treatment in the second mixed solution comprises:
placing the target anode sample in the second mixed solution with the second temperature and the second conductivity for oxidation treatment until the voltage flowing through the target anode sample is a second voltage, wherein the second voltage is the voltage required by the target anode sample to form a compact oxide film with uniform thickness;
and (3) preprocessing the target anode sample with the uniform-thickness compact oxide film to obtain the required anode sample.
4. A method of anodic oxidation according to claim 2 or 3, wherein the pre-treatment comprises: the method comprises the steps of sequentially carrying out constant voltage maintaining treatment, first cleaning treatment, heat treatment, complementary forming treatment, second cleaning treatment and drying treatment on a sample for a specified duration, wherein the duration of the constant voltage maintaining treatment of the first-stage oxidation treatment is longer than that of the constant voltage maintaining treatment of the second-stage oxidation treatment.
5. The anodizing method according to claim 4, wherein the temperature of said heat treatment is any one of 360 to 400 ℃ and the treatment time is any one of 5 to 30 minutes, and wherein the heat treatment time of the second stage oxidation treatment is lower than the heat treatment time of the first stage oxidation treatment.
6. The method according to claim 1, wherein a first voltage formed at the time of the first stage oxidation treatment is higher than a second voltage formed at the time of the second stage oxidation treatment.
7. The anodizing method according to claim 1, wherein a temperature of said first mixed solution is any one of 35 to 70 ℃ and a temperature of said second mixed solution is any one of 70 to 150 ℃.
8. The method of anodic oxidation according to any one of claims 1-7, wherein the first mixed liquor comprises four solutions of an organic acid, an inorganic acid, deionized water, and a polyol, and the second mixed liquor comprises at least one solution of an organic acid, an inorganic acid, deionized water, and a polyol.
9. A capacitor, comprising:
the valve metal anode is obtained by performing second-stage oxidation treatment on a target anode sample in a second mixed solution, wherein the target anode sample is obtained by performing first-stage oxidation treatment on an initial valve metal anode in a first mixed solution, the conductivity of the first mixed solution is higher than that of the second mixed solution, the temperature of the first mixed solution is lower than that of the second mixed solution, and the polyol content of the first mixed solution is lower than that of the second mixed solution.
10. An electronic device, comprising: the capacitor of claim 9.
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