CN114678222A - Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs - Google Patents

Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs Download PDF

Info

Publication number
CN114678222A
CN114678222A CN202210215040.2A CN202210215040A CN114678222A CN 114678222 A CN114678222 A CN 114678222A CN 202210215040 A CN202210215040 A CN 202210215040A CN 114678222 A CN114678222 A CN 114678222A
Authority
CN
China
Prior art keywords
aluminum foil
mofs
hydrothermal
metal
high voltage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210215040.2A
Other languages
Chinese (zh)
Inventor
胡传彬
李永春
刘挺
龙周国
孙晓涛
袁小清
陈家进
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi Zhengrun New Material Technology Co ltd
Original Assignee
Guangxi Zhengrun New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangxi Zhengrun New Material Technology Co ltd filed Critical Guangxi Zhengrun New Material Technology Co ltd
Priority to CN202210215040.2A priority Critical patent/CN114678222A/en
Publication of CN114678222A publication Critical patent/CN114678222A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes

Abstract

The invention discloses a method for inducing uniform hole formation of a medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs. According to the invention, the medium-high voltage anode aluminum foil with the surface enriched with trace elements such as Fe, Cu, Sn, Pb and the like with higher electrode potential than aluminum is fully annealed, and the occupancy rate of {100} cubic texture of the medium-high voltage anode aluminum foil exceeds 95% by adopting a hydrothermal in-situ synthesis method, polymetallic MOFs of the trace elements such as Fe, Cu, Sn, Pb and the like in highly ordered distribution is generated on the surface of the aluminum foil, the defects of uniform distribution in acidic pore-forming solution are easily generated by utilizing the instability of metal ions in the polymetallic MOFs on the surface of the aluminum foil, and the tunnel pore-shaped nuclear position of the aluminum foil during pore-forming corrosion is regulated and controlled by utilizing the defects. The invention can obviously improve the distribution uniformity of generated tunnel holes and reduce the merging of the tunnel holes, thereby improving the specific capacitance of the aluminum foil.

Description

Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs
Technical Field
The invention relates to a method for preparing a high-voltage anode aluminum foil material in an aluminum electrolytic capacitor, which can remarkably improve the capability of corroding and forming holes of an anode aluminum foil by a multi-metal MOFs technology and a corrosion and hole forming technology which are hydrothermally synthesized on the surface of the aluminum foil enriched with trace elements such as Fe, Cu, Sn, Pb and the like.
Background
With the increasing demand of people for portable electronic devices, aluminum electrolytic capacitors have been rapidly growing due to their advantages of low cost, small size, high energy storage and conversion rate, etc. Aluminum electrolytic capacitors generally comprise an anodic aluminum foil, a cathodic aluminum foil and a separator between the two electrodes, as well as an organic electrolyte additive. According to the formula of the plate capacitor, the specific capacitance of the aluminum electrolytic capacitor is mainly determined by the specific surface area of the anode aluminum foil. An anode aluminum foil of a medium-high voltage aluminum electrolytic capacitor is generally formed with a large number of tunnel holes on the surface thereof by an electrochemical etching method to enlarge the specific surface area of a high-purity aluminum foil, thereby increasing the specific capacitance, and high capacity and miniaturization of the capacitor are achieved by the method.
The process for corroding and perforating the medium-high voltage anode aluminum foil mainly comprises the following steps: pretreatment before corrosion, perforation treatment and reaming treatment. When the holes are corroded, the shape and distribution mode of the tunnel holes are mainly determined by the surface state of the aluminum foil, and the surface state of the high-purity aluminum foil is mainly determined by the pretreatment step before corrosion. At present, the pretreatment technology for the surface of the aluminum foil at home and abroad mainly comprises heat treatment, acid and alkali treatment, cathode polarization treatment, oxidation treatment, deposited metal treatment and the like. In order to promote uniform hole forming and overcome the problems of inconsistent oxide film thickness, poor uniformity of surface tissue structure, more residual oil stain and the like of domestic aluminum foil during the corrosion of the traditional anode foil during the production, trace elements such as Fe, Cu, Sn, Pb and the like are often added during the production of the foil, the trace elements are enriched on the surface of the aluminum foil through an annealing heat treatment process, and the enriched trace elements form a large number of corrosion micro-batteries with an aluminum substrate during the subsequent corrosion hole forming of the aluminum foil, so that the uniformity of the corrosion hole forming of the aluminum foil is improved. The result of this approach is that although the uniformity of the generated tunnel holes is improved, at the same time, due to the too high areal density of the etched microcells, the generated tunnel holes and holes are also increased severely, the former improves the specific capacitance of the etched aluminum foil, while the latter limits the further improvement of the specific capacitance. In order to optimize the comprehensive performance of the aluminum foil after corrosion, in the electrolytic corrosion process, the uniformity of the distribution of the tunnel holes on the surface of the anode aluminum foil needs to be improved, and the occurrence of tunnel merging is avoided as much as possible.
Chinese patent ZL201210391778.0 discloses a method for generating a hydrated oxidation film by hydration of a medium-high voltage aluminum foil in pure water, ammonia water and amine aqueous solution at the temperature of 70-100 ℃, and guiding corrosion and hole formation of the aluminum foil through defects of the hydrated oxidation film, and the method has the effects of improving distribution uniformity of tunnel holes and improving specific capacitance. However, we have found that the above patent directly adopts the method of oxygen hydrate, and the obtained hydrated oxide film has poor defect distribution uniformity and size uniformity, and is prone to have tunnel holes and holes in local areas when the aluminum foil is corroded to generate holes, which can significantly reduce the mechanical properties of the aluminum foil and limit further improvement of the specific capacitance of the aluminum foil. The same patent ZL201711360884.1 discloses a method and a system for in-situ deposition of tin crystal nucleus on the surface of an aluminum foil by a sol-gel method to improve the merging of tunnel holes, but the self-corrosion of the surface of the aluminum foil is aggravated along with the gradual accumulation of metal elements in a solution due to the introduction of other metal elements, so that the thickness of the corroded aluminum foil is seriously reduced. Based on the problems, the method can obtain a positive effect by generating the orderly-distributed multi-metal MOFs on the surface of the aluminum foil to regulate and control the tunnel hole nucleation position when the aluminum foil is corroded to generate holes, and a better research result is obtained.
Disclosure of Invention
The key technology of the invention is to adopt a hydrothermal in-situ synthesis polymetallic MOFs technology to obtain polymetallic MOFs with ordered distribution and consistent size on the surface of the aluminum foil enriched with trace elements such as Fe, Cu, Sn, Pb and the like, as shown in figure 1, and the polymetallic MOFs is a scanning electron microscope topography map of the polymetallic MOFs synthesized on the surface of the aluminum foil enriched with trace elements such as Fe, Cu, Sn, Pb and the like in situ through hydrothermal.
The method is characterized in that the surface is enriched with trace elements such as Fe, Cu, Sn, Pb and the like with higher electrode potential than aluminum, a high-purity medium-high voltage aluminum foil with {100} cubic texture occupancy rate of more than 95% after full annealing is adopted, a multi-metal MOFs technology of hydrothermal in-situ synthesis is adopted to generate orderly distributed multi-metal MOFs on the surface of the aluminum foil, the defects of uniform distribution of the highly ordered multi-metal MOFs on the surface of the aluminum foil in an acidic pore-forming solution are easily generated by utilizing the instability of metal ions in the multi-metal MOFs, and then the tunnel pore-shaped nuclear position of the aluminum foil during corrosion pore-forming is regulated and controlled by utilizing the defects. The process of uniformly forming the holes on the anode foil comprises hydrothermal in-situ synthesis of the multi-metal MOFs, defect formation induced by metal ions of the multi-metal MOFs and defect regulation and control of nuclear hole forming.
The specific process is as follows: the method comprises the steps of enriching trace elements such as Fe, Cu, Sn and Pb with higher electrode potential than aluminum on the surface, fully annealing, and then carrying out hydrothermal reaction on a medium-high voltage anode aluminum foil with {100} cubic texture occupancy rate of more than 95% in a polytetrafluoroethylene high-pressure kettle containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution (1.54-4.61 g of terephthalic acid is dissolved in 120ml of DMF) for 6-12 h, wherein the hydrothermal temperature is 150-180 ℃, orderly-distributed multi-metal MOFs are generated on the surface of the aluminum foil, the instability of metal ions in the multi-metal MOFs is utilized, the highly-ordered multi-metal MOFs on the surface of the aluminum foil are easy to generate uniformly-distributed defects in an acidic pore-forming solution, and then the defects are utilized to regulate and control the tunnel pore-shaped nuclear positions when the aluminum foil corrodes pores, so as to obtain the orderly-distributed tunnel pores.
The invention aims at solving the problems that the trace elements such as Fe, Cu, Sn, Pb and the like are added during the production of the plain foil, the trace elements are enriched on the surface of the aluminum foil through an annealing heat treatment process, and the enriched trace elements form a large amount of corrosion microcells with an aluminum matrix during the subsequent corrosion pore-forming of the aluminum foil, so that the uniformity of the corrosion pore-forming of the aluminum foil is improved, and due to the fact that the surface density of the corrosion microcells is too high, the generated tunnel hole combination is also seriously increased, the former improves the specific capacitance of the corrosion aluminum foil, and the latter limits the further improvement of the specific capacitance, and invents a novel method for synthesizing the multi-metal MOFs on the surface of the anode aluminum foil by adopting hydrothermal in situ. Compared with a large amount of corrosion micro-batteries formed by trace elements and an aluminum matrix, the multi-metal MOFs synthesized in situ by hydrothermal has ordered distribution and more uniform size, and can solve the problems that the surface density of the trace elements and the aluminum matrix corrosion micro-batteries is too high, and the generated tunnel holes and holes are also seriously increased, thereby further improving the specific capacitance of the corrosion aluminum foil.
Drawings
FIG. 1 is a scanning electron microscope topography of polymetallic MOFs synthesized on the surface of an aluminum foil in situ by hydrothermal.
Detailed Description
The invention is further described by the following examples.
According to the invention, the highly ordered and distributed multi-metal MOFs is synthesized in situ by surface hydrothermal, the defects that the highly ordered multi-metal MOFs on the surface of the aluminum foil is easy to generate uniform distribution in an acidic pore forming solution are easily generated by utilizing the instability of metal ions in the multi-metal MOFs, and then the defects are utilized to regulate and control the nuclear positions of the tunnel pores when the aluminum foil corrodes the pores, so that the tunnel pores in ordered distribution are obtained. The pore solution was 0.6M HCl +7.4M H2SO4+0.8M Al3+The mixed solution is subjected to reaming corrosion at the temperature of 72 ℃, and the reaming solution is 3 wt.% of HNO3The solution is processed into nitric acid solution at the temperature of 70 ℃, and finally cleaned, dried and finally subjected to 520V formation according to the industry standard.
Comparative example
The lead-containing aluminum foil with the purity of 99.99 percent, the thickness of 120 mu M and the cubic texture occupancy rate of more than 95 percent adopts the traditional mixed acid pretreatment process, and the used pretreatment solution is 1M HCl +7M H2SO4At a temperature of 80 ℃ to prepare aluminumThe foil is directly soaked in the pretreatment solution for 120s, and then the perforation corrosion, the reaming corrosion, the post-treatment and the 520V formation treatment are carried out.
Example 1
The method comprises the steps of carrying out hydrothermal reaction on a medium-high voltage anode aluminum foil with {100} cubic texture occupancy rate of more than 95% after fully annealing by enriching trace elements such as Fe, Cu, Sn, Pb and the like with electrode potential higher than that of aluminum on the surface, in a polytetrafluoroethylene autoclave containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution (1.54g of terephthalic acid is dissolved in 120ml of DMF), wherein the hydrothermal temperature is 150 ℃, and orderly distributed multi-metal MOFs are generated on the surface of the aluminum foil.
The instability of metal ions in the polymetallic MOFs is utilized, the polymetallic MOFs with ordered height on the surface of the aluminum foil is easy to generate uniformly distributed defects in an acidic pore-forming solution, and then the defects are utilized to regulate and control the tunnel pore nucleus positions when the aluminum foil corrodes the pores. And carrying out pore-forming corrosion on the aluminum foil of the multi-metal MOFs with the ordered distribution on the surface by a hydrothermal in-situ synthesis method, wherein a pore-forming solution is a mixed solution of 0.6M HCl +7.4M H2SO4+0.8M Al3+, the temperature is 75 ℃, and then carrying out reaming corrosion, post-treatment and 520V formation treatment which are the same as those of the comparative example.
Example 2
The method comprises the steps of carrying out hydrothermal reaction on a medium-high voltage anode aluminum foil with {100} cubic texture occupancy rate of more than 95% after fully annealing by enriching trace elements such as Fe, Cu, Sn, Pb and the like with electrode potential higher than that of aluminum on the surface, in a polytetrafluoroethylene autoclave containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution (3.07g of terephthalic acid is dissolved in 120ml of DMF), wherein the hydrothermal temperature is 150 ℃, and orderly distributed multi-metal MOFs are generated on the surface of the aluminum foil.
The instability of metal ions in the polymetallic MOFs is utilized, the polymetallic MOFs with ordered height on the surface of the aluminum foil is easy to generate uniformly distributed defects in an acidic pore-forming solution, and then the defects are utilized to regulate and control the tunnel pore nucleus positions when the aluminum foil corrodes the pores. Carrying out pore-forming corrosion on an aluminum foil of which the surface is provided with orderly-distributed multi-metal MOFs by a hydrothermal in-situ synthesis method, wherein the pore-forming solution is 0.6M HCl +7.4M H 2SO4+0.8M Al3+The temperature of the mixed solution is 75 ℃, and then the hole expanding corrosion, the post-treatment and the 520V formation treatment which are the same as the comparative example are carried out.
Example 3
The method comprises the steps of carrying out hydrothermal reaction on a medium-high voltage anode aluminum foil with {100} cubic texture occupancy rate of more than 95% after fully annealing by enriching trace elements such as Fe, Cu, Sn, Pb and the like with electrode potential higher than that of aluminum on the surface, in a polytetrafluoroethylene autoclave containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution (4.61g of terephthalic acid is dissolved in 120ml of DMF), wherein the hydrothermal temperature is 150 ℃, and orderly distributed multi-metal MOFs are generated on the surface of the aluminum foil.
The instability of metal ions in the polymetallic MOFs is utilized, the polymetallic MOFs with ordered height on the surface of the aluminum foil is easy to generate uniformly distributed defects in an acidic pore-forming solution, and then the defects are utilized to regulate and control the tunnel pore nucleus positions when the aluminum foil corrodes the pores. Carrying out pore-forming corrosion on the aluminum foil of the polymetallic MOFs (metal-organic frameworks) with the surface orderly distributed by a hydrothermal in-situ synthesis method, wherein the pore-forming solution is 0.6M HCl +7.4M H2SO4+0.8M Al3+The temperature of the mixed solution is 75 ℃, and then the hole expanding corrosion, the post-treatment and the 520V formation treatment which are the same as the comparative example are carried out.
Example 4
The method comprises the steps of carrying out hydrothermal reaction on a medium-high voltage anode aluminum foil with {100} cubic texture occupancy rate of more than 95% after fully annealing by enriching trace elements such as Fe, Cu, Sn, Pb and the like with electrode potential higher than that of aluminum on the surface, in a polytetrafluoroethylene autoclave containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution (1.54g of terephthalic acid is dissolved in 120ml of DMF), wherein the hydrothermal temperature is 180 ℃, and orderly distributed multi-metal MOFs are generated on the surface of the aluminum foil.
The method is characterized in that the defects of uniform distribution of polymetallic MOFs with ordered height on the surface of the aluminum foil in an acidic pore-forming solution are easily generated by utilizing the instability of metal ions in the polymetallic MOFs, and then the tunnel pore nucleation position of the aluminum foil during pore-forming corrosion is regulated and controlled by utilizing the defects. Carrying out pore-forming corrosion and pore-forming dissolution on the aluminum foil of the polymetallic MOFs which is obtained by the hydrothermal in-situ synthesis method and is distributed orderly on the surfaceThe solution was 0.6M HCl +7.4M H2SO4+0.8M Al3+The mixed solution of (2) was subjected to pore-enlarging etching, post-treatment and 520V formation treatment at a temperature of 75 ℃.
Example 5
The method comprises the steps of carrying out hydrothermal reaction on a medium-high voltage anode aluminum foil with {100} cubic texture occupancy rate of more than 95% after fully annealing by enriching trace elements such as Fe, Cu, Sn, Pb and the like with electrode potential higher than that of aluminum on the surface, in a polytetrafluoroethylene autoclave containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution (3.07g of terephthalic acid is dissolved in 120ml of DMF), wherein the hydrothermal temperature is 180 ℃, and orderly distributed multi-metal MOFs are generated on the surface of the aluminum foil.
The instability of metal ions in the polymetallic MOFs is utilized, the polymetallic MOFs with ordered height on the surface of the aluminum foil is easy to generate uniformly distributed defects in an acidic pore-forming solution, and then the defects are utilized to regulate and control the tunnel pore nucleus positions when the aluminum foil corrodes the pores. Carrying out pore-forming corrosion on an aluminum foil of which the surface is provided with orderly-distributed multi-metal MOFs by a hydrothermal in-situ synthesis method, wherein the pore-forming solution is 0.6M HCl +7.4M H 2SO4+0.8M Al3+The mixed solution of (2) was subjected to pore-enlarging etching, post-treatment and 520V formation treatment at a temperature of 75 ℃.
Example 6
The method comprises the steps of carrying out hydrothermal reaction on a medium-high voltage anode aluminum foil with {100} cubic texture occupancy rate of more than 95% after fully annealing by enriching trace elements such as Fe, Cu, Sn, Pb and the like with electrode potential higher than that of aluminum on the surface, in a polytetrafluoroethylene autoclave containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution (4.61g of terephthalic acid is dissolved in 120ml of DMF), wherein the hydrothermal temperature is 180 ℃, and orderly distributed multi-metal MOFs are generated on the surface of the aluminum foil.
The instability of metal ions in the polymetallic MOFs is utilized, the polymetallic MOFs with ordered height on the surface of the aluminum foil is easy to generate uniformly distributed defects in an acidic pore-forming solution, and then the defects are utilized to regulate and control the tunnel pore nucleus positions when the aluminum foil corrodes the pores. Obtaining orderly distributed polymetallic on the surface by a hydrothermal in-situ synthesis methodPerforming pore-forming corrosion on the aluminum foil of the MOFs, wherein the pore-forming solution is 0.6M HCl +7.4M H2SO4+0.8M Al3+The temperature of the mixed solution is 75 ℃, and then the hole expanding corrosion, the post-treatment and the 520V formation treatment which are the same as the comparative example are carried out.
Table 1 shows that the specific capacitance and the bending times of the aluminum foil with the multi-metal MOFs synthesized in situ by using the surface hydrothermal method of the present invention are compared after the aluminum foil with the multi-metal MOFs synthesized in situ by using the surface hydrothermal method of the present invention is subjected to anodic electrolytic corrosion and formation, and it can be seen that the specific capacitance of the aluminum foil with the multi-metal MOFs synthesized in situ by using the surface hydrothermal method of the present invention is increased by 4% to 9%, and the bending times are increased by about 30%.
TABLE 1 specific capacitance and number of bends of anode aluminum foils of comparative examples and examples
Figure BDA0003534090890000091
Table 1.

Claims (2)

1. A method for inducing medium-high voltage anode foil to uniformly generate holes by adopting hydrothermal in-situ synthesis of multi-metal MOFs is characterized in that trace elements such as Fe, Cu, Sn and Pb, the electrode potential of which is higher than that of aluminum, are enriched on the surface of the medium-high voltage anode foil, the {100} cubic texture occupancy rate of which exceeds 95% after annealing is carried out, the multi-metal MOFs containing the trace elements such as Fe, Cu, Sn and Pb, which are distributed in a highly ordered mode, are generated on the surface of the aluminum foil by adopting the hydrothermal in-situ synthesis method, the defects of uniform distribution of the multi-metal MOFs on the surface of the aluminum foil in an acidic hole forming solution are easily generated by utilizing the instability of metal ions in the multi-metal MOFs, and the tunnel hole-shaped nuclear position when the aluminum foil corrodes the holes is regulated and controlled by utilizing the defects.
2. The method of claim 1, which employs hydrothermal in-situ synthesis of multi-metal MOFs to induce uniform pore formation of the medium-high voltage anode foil, the method is characterized in that the medium-high voltage anode aluminum foil with the {100} cubic texture occupancy rate of more than 95% is subjected to hydrothermal reaction for 6-12 h in a polytetrafluoroethylene autoclave containing 10ml of distilled water, 10ml of absolute ethyl alcohol and 15ml of A solution after annealing by enriching trace elements such as Fe, Cu, Sn, Pb and the like with higher electrode potential than aluminum on the surface, wherein the hydrothermal temperature is 150-180 ℃, orderly-distributed multi-metal MOFs are generated on the surface of the aluminum foil, and the defects that the highly-ordered multi-metal MOFs on the surface of the aluminum foil is easy to generate uniform distribution in an acidic pore-forming solution are overcome by utilizing the instability of metal ions in the multi-metal MOFs, then, the defect is utilized to regulate and control the nuclear position of the tunnel hole when the aluminum foil is corroded to generate the hole, and the tunnel holes which are distributed orderly are obtained; the solution A is prepared by dissolving 1.54g to 4.61g of terephthalic acid in 120ml of DMF.
CN202210215040.2A 2022-03-07 2022-03-07 Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs Pending CN114678222A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210215040.2A CN114678222A (en) 2022-03-07 2022-03-07 Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210215040.2A CN114678222A (en) 2022-03-07 2022-03-07 Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs

Publications (1)

Publication Number Publication Date
CN114678222A true CN114678222A (en) 2022-06-28

Family

ID=82072099

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210215040.2A Pending CN114678222A (en) 2022-03-07 2022-03-07 Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs

Country Status (1)

Country Link
CN (1) CN114678222A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117612867A (en) * 2024-01-24 2024-02-27 南通南辉电子材料股份有限公司 Medium-pressure foil formation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117612867A (en) * 2024-01-24 2024-02-27 南通南辉电子材料股份有限公司 Medium-pressure foil formation method
CN117612867B (en) * 2024-01-24 2024-04-26 南通南辉电子材料股份有限公司 Medium-pressure foil formation method

Similar Documents

Publication Publication Date Title
US9928967B2 (en) Three-dimensional composites of nickel cobalt oxide/ graphene on nickel foam for supercapacitor electrodes, and preparation method thereof
CN105097286B (en) A kind of caustic solution of super-pressure energy storage material
CN105869924B (en) A kind of preparation method of graphene-based thick cipher telegram pole
CN101425390B (en) Medium high voltage anode aluminum foil corrosion method
CN105405658A (en) Pure inorganic acid formation process for positive electrode foil for high-voltage bolt type aluminium electrolytic capacitor
Shi et al. Fabrication of IrO2 decorated vertical aligned self-doped TiO2 nanotube arrays for oxygen evolution in water electrolysis
CN114678222A (en) Method for inducing uniform pore formation of medium-high voltage anode foil by hydrothermal in-situ synthesis of multi-metal MOFs
CN101345137A (en) Anode foil corrosion technology of electrolytic capacitor
CN113436891A (en) Method for inducing medium-high voltage anode foil to uniformly corrode and form pores by adopting nano pits after anodic oxidation
Peng et al. Effect of tunnel structure on the specific capacitance of etched aluminum foil
CN104878441B (en) A kind of aluminium electrolutic capacitor etching process of the anode aluminium foil with tunnel branch hole
CN104357886B (en) The method that mesohigh anode deposits disperse tin, zinc nucleus with high-purity aluminum foil surface chemistry
CN108172402A (en) The preparation method of aluminium electrolutic capacitor high voltage anodization film
CN103774193B (en) A kind of method of mesohigh electric aluminum foil surface electro-deposition disperse zinc nucleus
CN102915847A (en) Medium-high voltage electronic aluminum foil corrosion pretreatment method
CN1975949A (en) Aluminium foil for electrolytic capacitor low-voltage anode use and producing method thereof
CN112267114A (en) Method for improving compactness and corrosion resistance of hydrotalcite coating on surface of magnesium alloy
Bu et al. Al 2 O 3-TiO 2 composite oxide films on etched aluminum foil fabricated by electrodeposition and anodization
CN108493000B (en) Flexible nano porous metal/oxide supercapacitor electrode material and preparation method thereof
CN101029411A (en) Electrochemical corrosive process of anode aluminum foil
CN110085429B (en) Method for pulse deposition of nano tin dots on medium-high voltage anode aluminum foil for aluminum electrolytic capacitor
CN114229964B (en) With Ti 4 O 7 Preparation method and application of anode for surface etching and fluorination of substrate
CN108183034A (en) The preparation method of aluminium electrolutic capacitor high voltage anodization film
CN116275057B (en) Corrosion pretreatment method for preparing electronic aluminum foil with micro-couple based on powder sintering
Protsenko et al. Anodic treatment of Ni-Cu alloy in a deep eutectic solvent to improve electrocatalytic activity in the hydrogen evolution reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 542899 No. 3, Tianhe Avenue, electronic science and Technology Park, Hezhou City, Guangxi Zhuang Autonomous Region

Applicant after: Guangxi Guangtou Zhengrun New Material Technology Co.,Ltd.

Address before: 542899 No. 3, Tianhe Avenue, Electronic Science Park, Hezhou City, Pinggui District, Hezhou City, Guangxi Zhuang Autonomous Region

Applicant before: Guangxi Zhengrun New Material Technology Co.,Ltd.