EP4028580A2 - Électrode et son procédé de fabrication et utilisation associée - Google Patents

Électrode et son procédé de fabrication et utilisation associée

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Publication number
EP4028580A2
EP4028580A2 EP20864249.6A EP20864249A EP4028580A2 EP 4028580 A2 EP4028580 A2 EP 4028580A2 EP 20864249 A EP20864249 A EP 20864249A EP 4028580 A2 EP4028580 A2 EP 4028580A2
Authority
EP
European Patent Office
Prior art keywords
catalytic layer
metal element
layer
substrate
electrode
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
EP20864249.6A
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German (de)
English (en)
Other versions
EP4028580A4 (fr
Inventor
Hongyuan Chen
Qite ZHAO
Junwei XUE
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.)
Magneto Special Anodes Suzhou Co Ltd
Original Assignee
Magneto Special Anodes Suzhou 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.)
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Publication date
Application filed by Magneto Special Anodes Suzhou Co Ltd filed Critical Magneto Special Anodes Suzhou Co Ltd
Publication of EP4028580A2 publication Critical patent/EP4028580A2/fr
Publication of EP4028580A4 publication Critical patent/EP4028580A4/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury

Definitions

  • the application relates to, but is not limited to, the field of electrochemistry, in particular to, but is not limited to, an electrode and a preparation method and use thereof.
  • Electrometallurgy is an important part of the electrochemical industry, which is mainly used for the electrolytic extraction and purification of metals from their solutions.
  • an aqueous solution containing a certain concentration of fluoride ion is usually used as an electrolyte.
  • This electrometallurgy process requires insoluble anodes to form a stable circuit and a continuous electrolytic current.
  • the lead-based alloy electrodes mainly used are characterized by large weight, heavy pollution, and high energy consumption, etc. With the increasing environmental protection standards, it is urgent to find environmentally friendly substitutes.
  • An oxygen-evolution titanium electrode as an environment-friendly insoluble anode, has been widely used in electrochemical industry, mainly focusing on electrochemical water treatment, metal element extraction, electroplating and other fine finishing processes.
  • the oxygen-evolution titanium electrode is mainly composed of pure metal titanium or titanium alloy substrate and noble metal oxide catalytic layer on its surface.
  • the substrate provides conductive and mechanical support.
  • the catalytic layer can greatly reduce the oxygen-evolution potential in aqueous solution through its own redox process to achieve the effect of energy saving, while the anode has a long service life depending on its extremely low electrochemical consumption rate.
  • the oxygen-evolution catalyst is mainly iridium oxide, which is mixed with tantalum or titanium oxide to make the coating denser to protect the substrate from quick passivation. Sometimes titanium or tantalum or an alloy or oxide of the two is also used as an intermediate layer interposed between the catalytic layer and the substrate to protect the substrate.
  • the most widely used catalytic layer for the oxygen-evolution titanium electrode is iridium-tantalum composite oxide.
  • This kind of coating usually has a long service life in purer acidic electrolyte.
  • the oxygen-evolution overpotential of this electrode is significantly lower than that of lead alloy electrode commonly used in electrometallurgy (about 0.3V lower) , so it has a characteristic of more energy saving.
  • lead alloy electrode commonly used in electrometallurgy about 0.3V lower
  • it is light in weight and convenient to operate, and will not produce harmful substances to pollute the environment and affect the purity of the product.
  • the aqueous electrolyte used for metal electrolytic extraction usually comes from mineral leaching and contains a certain amount of fluoride ions, which have a fatal corrosion effect on titanium electrodes.
  • US5407556 states that when the electrolyte contains 5 mg of fluoride ions per liter, the service life of the oxygen-evolution titanium oxide electrode will be drastically reduced to about 12%of the service life of an oxygen-evolution titanium oxide electrode under the condition without fluoride ions.
  • the fluoride ion content in the electrolyte used in the electrolytic extraction of metals such as electrolyzing metal zinc and electrolyzing metal manganese is usually as high as 20 mg/L to 200 mg/L (even higher than 200 mg/L) .
  • a titanium electrode with a fluoride ion corrosion resistant coating is required.
  • the inventors of the application have carefully studied for many years to improve the fluoride ion corrosion resistance of the valve-type metal-substrated coated electrode for the electrolytic metal extraction process when the valve-type metal-substrated coated electrode is applied to an aqueous solution containing high concentration of fluoride ion.
  • the application provides an electrode, including a substrate and a catalytic layer; the catalytic layer being positioned on the upper surface and/or the lower surface of the substrate, and the catalytic layer including a plurality of catalytic layer units with different chemical compositions; wherein an outermost catalytic layer unit in the catalytic layer that is away from the direction of the substrate is an oxide layer containing a first metal element; other catalytic layer units except the outermost catalytic layer unit are oxide composite layers containing a first metal element and a second metal element; the first metal element is selected from one or more of iridium, platinum, rhodium, palladium and ruthenium, and the second metal element is selected from one or more of titanium, tantalum, niobium, tungsten and zirconium; and, the mole percentage of the first metal element in each layer of the catalytic layer units accounted for a total of metal elements in each layer of the catalytic layer units increases layer by layer along the direction away from the substrate, and the mo
  • the molar content of the first metal element may be greater than the molar content of the second metal element in an innermost catalytic layer unit in the catalytic layer that is near the direction of the substrate.
  • the mole percentage of the first metal element accounted for a total of metal elements in the innermost catalytic layer unit may be 65%to 95%, and may also be 80%.
  • the outermost catalytic layer unit may be an oxide composite layer containing a first metal element and a second metal element.
  • the loading capacity of the first metal element in each layer of the catalytic layer units may be greater than 3 g/m 2 , and may also be 6 g/m 2 to 50 g/m 2 .
  • the first metal element may be iridium and the second metal element may be tantalum.
  • the catalytic layer may be two layers of the catalytic layer unit.
  • the substrate may be a valve-type metal or an alloy of valve-type metals; the valve-type metal may be selected from one of titanium, tantalum, niobium, zirconium, hafnium, vanadium, molybdenum and tungsten; and the substrate may be titanium or titanium alloy.
  • the electrode may include an intermediate protective layer between the substrate and the catalytic layer.
  • the intermediate protective layer may be selected from the group consisting of following metals or alloys or oxides thereof: tantalum, titanium, tungsten, tin, antimony, niobium, zirconium, or combinations thereof.
  • the application also provides a method for preparing the electrode as described above, wherein the catalytic layer is formed by coating a precursor solution containing corresponding elements, drying and then sintering.
  • the application also provides use of the electrode as described above.
  • the electrode may be used as an insoluble anode for electrometallurgy.
  • electrometallurgy may include electrolyzing zinc and electrolyzing manganese in a sulfate electrolyte system.
  • electrolyte in electrometallurgy may contain fluoride ions with a concentration of not less than 20 mg/L and not more than 500 mg/L.
  • the catalytic layer unit at the inner side has oxides with a higher content of the second metal element, has better compactness, and can play a role of shielding fluoride ions and thus protecting a substrate;
  • the catalytic layer unit at the outer side has oxides with a lower content of the second metal element, which is beneficial to slowing down the consumption of the first metal element and has a good electrocatalytic effect, and can effectively protect the catalytic layer unit at the inner side from being corroded by fluoride ions due to participating in oxygen evolution reaction prematurely;
  • Fig. 1 is a schematic diagram of an electrode structure according to an Example of the present application
  • Fig. 2 is an X-ray photoelectron spectrum of the electrode prepared in the Example of the application.
  • Fig. 3 is an X-ray photoelectron spectrum of an electrode prepared in Comparative Example of the application.
  • Substrate 1.
  • Catalytic layer 3.
  • Intermediate protective layer 21.
  • First catalytic layer unit 1.
  • an example of the application provides an electrode, for example, as shown in Fig. 1, the electrode includes a substrate 1, an intermediate protective layer 3, a first catalytic layer unit 22 and a second catalytic layer unit 21 which are sequentially stacked from bottom to top, wherein the first catalytic layer unit 22 and the second catalytic layer unit 21 form a catalytic layer 2.
  • An intermediate protective layer 3 and a catalytic layer 2 may also be symmetrically arranged on both sides of the substrate 1; alternatively, an intermediate protective layer 3 and a catalytic layer 2 may be provided on one side of the substrate 1, and only the catalytic layer 2 may be provided on the other side of the substrate 1; alternatively, the intermediate protective layer 3 may not be provided on both sides of the substrate 1.
  • the intermediate protective layer 3 may be an oxide layer, metal layer or and alloy layer consisting of one or more metals of tantalum, titanium, tungsten, tin, antimony, niobium and zirconium, and the intermediate protective layer 3 can slow down the trend of forming an insulating oxide layer and avoid increasing the oxygen evolution resistance.
  • the catalytic layer 2 may include a plurality of catalytic layer units, for example, it may be arranged to include two catalytic layer units, i.e., a first catalytic layer unit 22 and a second catalytic layer unit 21.
  • the second catalytic layer unit 21 at the outer side has a lower fluoride ion corrosion rate while exerting the advantage of low oxygen-evolution potential, which can prolong the service life of the coating.
  • the first catalytic layer unit 22 at the inner side has better compactness, which can prevent electrolyte and fluoride ions therein from contacting the titanium substrate, thus delaying passivation of the electrode.
  • the catalytic layer 2 may also be provided to include three catalytic layer units, four catalytic layer units or more catalytic layer units. The number of units of the catalytic layer 2 on both sides of the substrate may be the same or different.
  • the unit loading capacity of the first metal element in each catalytic layer unit may be 10 g/m 2 to 50 g/m 2 . This is because too low loading capacity will not be conducive for ensuring the life of the electrode, while too high loading capacity will lead to a too high electrode cost.
  • the first metal element may be iridium and the second metal element may be tantalum. Because iridium oxide has the characteristics of low oxygen-evolution potential and long service life compared with other metal oxides, the combination of tantalum oxide the iridium oxide will further improve the compactness of the catalytic layer and prevent electrolyte and harmful ions (such as fluoride ions, etc. ) therein from contacting the titanium substrate.
  • the material of the substrate 1 may be titanium, the material of the intermediate protective layer 3 may be titanium tantalum oxide or its alloy, and the material of the first catalytic layer unit 22 may be iridium tantalum oxide; the material of the second catalytic layer unit 21 may be iridium oxide or iridium tantalum oxide; the molar content of iridium in the first catalytic layer unit 22 may account for 65%to 95%of the total molar content of iridium and tantalum, and the molar content of tantalum may account for 5%to 35%of the total molar content of iridium and tantalum; the molar content of iridium in the second catalytic layer unit 21 may account for 95%to 100%of the total molar content of iridium and tantalum, and the molar content of tantalum may account for 0%to 5%of the total molar content of iridium and tantalum. It can be ensured that the second catalytic layer unit 21 at the outer
  • the molar ratio of the second metal element of the catalytic layer unit located at the inner side is larger than the molar ratio of the second metal element of the outer layer, so that the compactness of the inner layer can be improved, thereby being beneficial to further improving the overall compactness of the catalytic layer unit and improving the shielding effect of fluoride ions.
  • the surface of a 50 ⁇ 50 mm 2 first-grade titanium sheet was oxidized and soaked in 3 wt%of oxalic acid aqueous solution at 90 °C for 15h to obtain a rough surface with a roughness Ra of 4 ⁇ m-7 ⁇ m.
  • the rough surface was washed with deionized water and dried to obtain a metallic titanium substrate 1 suitable for coating a catalytic layer.
  • 0.2 mol/L tetra-n-butyl titanate and 0.05 mol/L tantalum ethoxide were dissolved in n-butanol, then 50 ml of hydrochloric acid with a concentration of 37%was added for acidification to prepare a precursor solution of an intermediate protective layer; the prepared precursor solution of the intermediate protective layer was coated on one side surface of the substrate 1 prepared in the step 1) , wherein the total loading capacity of the metal titanium and tantalum elements is 1 g/m 2 , then air dried, and sintered in an air atmosphere at 500 °C; the above-mentioned procedures of coating, air drying and sintering were repeated once, and coating was carried out twice in total; the intermediate protective layer 3 was obtained by the twice coating, thereby obtaining the titanium tantalum oxide intermediate protective layer 3 with a molar ratio of titanium to tantalum elements of 4: 1.
  • the metal elements contained in the first catalytic layer unit 22 were iridium and tantalum with the molar ratio of iridium to tantalum of 65: 35; the application method was as follows: 0.035 mol of tantalum ethoxide was dissolved in 200 ml of n-butanol solution and acidified with 50 ml of hydrochloric acid with a concentration of 37%; after that, 0.065 mol of chloroiridium acid crystal was dissolved in 200 ml of n-butanol and acidified with 50 ml of hydrochloric acid with a concentration of 37%; the two salt solutions were mixed according to a volume ratio of 1: 1 to obtain a precursor solution of the first catalytic layer unit with an element molar ratio of iridium to tantalum of 65: 35; the precursor solution of the first catalytic layer unit was coated on the surface of the intermediate protective layer 3 prepared in step 2) , wherein the coating amount of iridium was 1 g/m 2 based on
  • the metal element contained in the second catalytic layer unit 21 was iridium; the application method was as follows: 0.065 mol of chloroiridium acid crystal was dissolved in 200 ml of n-butanol and acidified with 50 ml of hydrochloric acid with a concentration of 37%to prepare a precursor solution of the second catalytic layer unit; the precursor solution of the second catalytic layer unit was coated on the surface of the first catalytic layer unit 22, wherein the coating amount was determined based on the weight of the metal element iridium where the ratio of the weight of iridium to the coating area is 1g/m 2 , then dried, and sintered in an air atmosphere at 450 °C; the above-mentioned coating, drying and sintering processes were repeated four times, and the coating was carried out five times in total, and the second catalytic layer unit 21 was obtained by the above-mentioned five times of coating, thereby preparing and obtaining the required electrode.
  • the electrode prepared above was cut into three samples with a size of 25 ⁇ 25 mm 2 , and electrometallurgy was carried out in an electrolytic zinc system: the electrolyte contains 150 g/L sulfuric acid, 60 g/L zinc ion, 7 g/L divalent manganese ion, 20 mg/L industrial bovine bone glue and 0.221 g/L sodium fluoride (converted into 100 mg/L of fluoride ion concentration) , the test temperature was 43 °C, the current density was 500 A/m 2 , and the electrode deactivation was determined by setting the cell voltage to rise by 0.5 V (based on the sensitivity of electrometallurgy to cell voltage) .
  • the average cumulative overcharge of the three samples to deactivation was 12.3 MAh/m 2
  • the residual iridium content of the noble metal-containing catalytic layer (including the first catalytic layer unit and the second catalytic layer unit) to deactivation amounted to 7 g/m 2 , i.e. the consumption rate of iridium element was 0.65 g/MAh/m 2 .
  • the intermediate protective layer was prepared as a titanium tantalum oxide layer with a molar ratio of titanium to tantalum of 4: 1 using a magnetron sputtering method; except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Example 1, the average accumulated overcharge of the three samples to the deactivation was 12.7 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 7.5 g/m 2 , i.e. the consumption rate of iridium element was 0.59 g/MAh/m 2 .
  • step 1) a rough surface with a roughness Ra of 4 ⁇ m ⁇ 7 ⁇ m was obtained by soaking the surface in 30 wt%sulfuric acid aqueous solution at 85 °C for 1.5 hours; in step 2) , a tantalum oxide intermediate protective layer was applied, wherein the loading capacity of each layer of tantalum element is 1.0 g/m 2 , and the intermediate protective layer was coated three times; in step 3) the first catalytic layer unit was coated seven times; in step 4) the second catalytic layer unit was coated eight times; except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Example 1, the average accumulated overcharge of the three samples to the deactivation was 12.6 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 8.3 g/m 2 , i.e. the consumption rate of iridium element was 0.53 g/MAh/m 2 .
  • the metal elements contained in the first catalytic layer unit were iridium and tantalum with the molar ratio of the iridium to tantalum elements of 80: 20; except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Example 1, the average accumulated overcharge of the three samples to the deactivation was 15.9 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 6.7 g/m 2 , i.e. the consumption rate of iridium element was 0.52 g/MAh/m 2 .
  • step 1) a rough surface with a roughness Ra of 7 ⁇ m ⁇ 9 ⁇ m was obtained by sand blasting with brown corundum and then soaking in 3 wt%oxalic acid aqueous solution at 90 °C for 1 hour; in step 2) a titanium tantalum oxide intermediate protective layer with a molar ratio of titanium to tantalum of 3: 2 was applied, wherein the total loading capacity of the titanium and tantalum elements is 0.5 g/m 2 , and the intermediate protective layer was coated twice; in step 3) the metal elements contained in the first catalytic layer unit were iridium and tantalum with the molar ratio of iridium to tantalum of 80: 20; except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Example 1, the average accumulated overcharge of the three samples to the deactivation was 16.6 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 5.7 g/m 2 , i.e. the consumption rate of iridium element was 0.56 g/MAh/m 2 .
  • step 1) a rough surface with a roughness Ra of 11 ⁇ m ⁇ 13 ⁇ m was obtained by sand blasting and then soaking in boiling 37 wt%hydrochloric acid for 1 hour; in step 2) , the intermediate protective layer was coated three times; in step 3) , the metal elements contained in the first catalytic layer unit were iridium and tantalum with the molar ratio of iridium to tantalum of 80: 20, and the first catalytic layer unit was coated five times; in step 4) , the second catalytic layer unit was coated ten times; except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Example 1, the average accumulated overcharge of the three samples to the deactivation was 17.2 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 6.1 g/m 2 , i.e. the consumption rate of iridium element was 0.52 g/MAh/m 2 .
  • step 1) a rough surface with a roughness Ra of 9 ⁇ m ⁇ 11 ⁇ m was obtained by sand blasting and then soaking in boiling 37 wt%hydrochloric acid for 1 hour; in step 2) , the intermediate protective layer was coated three times; in step 3) , the metal elements contained in the first catalytic layer unit were iridium and tantalum with the molar ratio of iridium to tantalum of 80: 20, and the first catalytic layer unit was coated five times; in step 4) , the metal elements contained in the second catalytic layer unit were iridium and tantalum with the molar ratio of the iridium to tantalum elements of 90: 10; in step 5) , a third catalytic layer unit was prepared, the metal element contained in the third catalytic layer unit was iridium, and the third catalytic layer unit was coated five times. Except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Example 1, the average accumulated overcharge of the three samples to the deactivation was 16.9 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 6.2 g/m 2 , i.e. the consumption rate of iridium element was 0.52 g/MAh/m 2 .
  • step 1) after the surface of a 50 ⁇ 50 mm 2 first-grade titanium sheet was oxidized, a rough surface with a roughness Ra of 5 ⁇ m ⁇ 8 ⁇ m was obtained by sand blasting and then soaking in boiling 37 wt%hydrochloric acid for 1 hour; in step 2) , the intermediate protective layer was coated three times; in step 3) , the metal elements contained in the first catalytic layer were iridium and tantalum with the molar ratio of iridium to tantalum of 65: 35, and the first catalytic layer unit was coated seven times; in step 4) , the metal elements contained in the second catalytic layer were iridium and tantalum with the molar ratio of iridium to tantalum of 95: 5, and the second catalytic layer unit was coated eight times; except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Example 1, the average accumulated overcharge of the three samples to the deactivation was 12.1 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 4.9 g/m 2 , i.e. the consumption rate of iridium element was 0.83 g/MAh/m 2 .
  • a 50 ⁇ 50 mm 2 first-grade titanium sheet was treated by sand blasting with brown corundum until the surface roughness reaches Ra of 9 ⁇ m ⁇ 11 ⁇ m, and soaked in a 30 wt%sulfuric acid aqueous solution at 95 °C for 1.5 hours, the sheet was taken out, cleaned with deionized water, and dried to obtain a metal titanium substrate 1 suitable for coating a catalytic layer.
  • 0.035 mol tantalum ethoxide was dissolved in 200 mL n-butanol solution, then 50 ml of hydrochloric acid with a concentration of 37%was added for acidification, to prepare a precursor solution of an intermediate protective layer; the prepared precursor solution of the intermediate protective layer was coated on the surface of the substrate 1 prepared in the step 1) , wherein the loading capacity of the metal element tantalum is 1 g/m 2 , then air dried, and sintered in an air atmosphere at 500 °C; the above-mentioned procedures of coating, air drying and sintering were repeated once, and coating was carried out twice in total; the intermediate protective layer 3 was obtained by the twice coating, thereby obtaining the tantalum oxide intermediate protective layer 3.
  • the metal elements contained in the catalytic layer 2 were iridium and tantalum with the molar ratio of iridium to tantalum of 80: 20; the application method was as follows: 0.035mol of tantalum ethoxide was dissolved in 200 ml of n-butanol solution and acidified with 50 ml of hydrochloric acid with a concentration of 37%; after that, 0.065 mol of chloroiridium acid crystal was dissolved in 200 ml of n-butanol and acidified with 50 ml of hydrochloric acid with a concentration of 37%; the two salt solutions were mixed according to a volume ratio of 1: 1 to obtain a precursor solution of the catalytic layer with an element molar ratio of iridium to tantalum of 80: 20; the precursor solution of the catalytic layer was coated on the surface of the intermediate protective layer 3 prepared in step 2) , wherein the coating amount of iridium was 1 g/m 2 based on the weight of the metal element
  • the electrode prepared above was cut into three samples with a size of 25 ⁇ 25 mm 2 , and electrometallurgy was carried out in an electrolytic zinc system: the electrolyte contained 150 g/L sulfuric acid, 60 g/L zinc ion, 7 g/L divalent manganese ion, 20 mg/L industrial bovine bone glue and 0.221 g/L sodium fluoride (converted into 100 mg/L of fluoride ion concentration) , the test temperature was 43 °C, the current density was 500 A/m 2 , and the electrode deactivation was determined by setting the cell voltage to raise by 0.5V (based on the sensitivity of electrometallurgy to cell voltage) .
  • the electrolyte contained 150 g/L sulfuric acid, 60 g/L zinc ion, 7 g/L divalent manganese ion, 20 mg/L industrial bovine bone glue and 0.221 g/L sodium fluoride (converted into 100 mg/L of fluoride ion concentration)
  • the average cumulative overcharge of the three samples to deactivation was 6.4 MAh/m 2
  • step 1) a rough surface with a roughness Ra of 7 ⁇ m ⁇ 9 ⁇ m was obtained by sand blasting with brown corundum and then soaking in 7 wt%oxalic acid aqueous solution at 95 °C for 1 hour; in step 2) , a titanium tantalum oxide intermediate protective layer with a molar ratio of titanium to tantalum of 4: 1 was applied, and the intermediate protective layer was coated three times (the preparation of the precursor solution of the titanium -tantalum intermediate protective layer was the same as that of step 2) of Example 1) ; in step 3) , an iridium tantalum oxide catalytic layer with a molar ratio of iridium to tantalum of 65: 35 was applied, and the catalytic layer was coated 15 times; except for the above, the other steps were the same as the corresponding steps of Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Comparative Example 1, the average accumulated overcharge of the three samples to the deactivation was 5.1 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 9 g/m 2 , i.e. the consumption rate of iridium element was 1.17 g/MAh/m 2 .
  • step 1) after a 50 ⁇ 50 mm 2 first-grade titanium sheet was oxidized, a rough surface with a roughness Ra of 4 ⁇ m ⁇ 7 ⁇ m was obtained by soaking in 7 wt%oxalic acid aqueous solution at 95 °C for 1 hour and then soaking in the same solution at 80 °C for 15 hours; in step 2) , a titanium tantalum oxide intermediate protective layer with a molar ratio of titanium to tantalum elements of 3: 2 was applied; in step 3) , an iridium oxide catalytic layer was applied, wherein the coating amount of iridium was 1.5 g/m 2 based on the weight of the metal element iridium; except for the above, the other steps were the same as those of Comparative Example 1.
  • Performance test the same electrometallurgy test b) was conducted as in Comparative Example 1, the average accumulated overcharge of the three samples to the deactivation was 7.8 MAh/m 2 , and the residual amount of iridium element in the catalytic layer to the deactivation was 12 g/m 2 , i.e. the consumption rate of iridium element was 0.38 g/MAh/m 2 .
  • Examples 1-8 of the application adopt multiple catalytic layer units to form the catalytic layer, effectively combining the respective characteristics of the outer catalytic layer and the inner catalytic layer, thus significantly improving the service life of the coating in fluoride-containing aqueous solution.
  • Example 1-7 The service life of Examples 1-7 is longer than that of Example 8. It can be seen that the proportion of the second metal element that is not resistant to fluoride ion corrosion in the surface catalytic layer unit can be reduced as much as possible, the content of the first metal element in the outermost catalytic layer unit can be further increased, the fluoride ion corrosion resistance of the coating can be improved, and the service life of the electrode can be further improved.
  • Examples 4-7 The service life of Examples 4-7 is significantly longer than that of Examples 1-3 and 8. It can be seen that further increasing the content of the first metal element in the inner catalytic layer unit is beneficial to improve the service life of the electrode.

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  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne une électrode et son procédé de fabrication et une utilisation associée. L'électrode comprend un substrat et une couche catalytique; la couche catalytique est positionnée sur la surface supérieure et/ou la surface inférieure du substrat, et la couche catalytique comprend une pluralité d'unités de couche catalytique ayant différentes compositions chimiques; une unité de couche catalytique située le plus à l'extérieur dans la couche catalytique qui se trouve à distance de la direction du substrat est une couche d'oxyde contenant un premier élément métallique; d'autres unités de couche catalytique, à l'exception de l'unité de couche catalytique la plus à l'extérieur, sont des couches composites d'oxyde contenant un premier élément métallique et un second élément métallique; le pourcentage molaire du premier élément métallique dans chaque couche des unités de couche catalytique représentant un total d'éléments métalliques dans chaque couche des unités de couche catalytique augmente couche par couche le long de la direction à distance du substrat. L'électrode peut être utilisée comme anode insoluble en électrométallurgie, peut réduire la tension de cellule pour jouer un rôle d'économie d'énergie tout en possédant une longue durée de vie dans le processus d'électrométallurgie dans lequel l'électrolyte contient une concentration élevée en ions fluorure, et les problèmes de pollution de l'environnement, comme l'anode en plomb et l'influence sur la pureté du produit, n'auront pas lieu.
EP20864249.6A 2019-09-10 2020-11-10 Électrode et son procédé de fabrication et utilisation associée Pending EP4028580A4 (fr)

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CN201910850530.8A CN112553657B (zh) 2019-09-10 2019-09-10 一种电极及其制备方法和用途
PCT/CN2020/127682 WO2021047687A2 (fr) 2019-09-10 2020-11-10 Électrode et son procédé de fabrication et utilisation associée

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JP7168729B1 (ja) * 2021-07-12 2022-11-09 デノラ・ペルメレック株式会社 工業用電解プロセス用電極
CN113948724B (zh) * 2021-10-15 2023-11-24 上海冉昇新材料科技有限公司 一种再生式燃料电池用导电扩散层材料及其制备方法
WO2024073867A1 (fr) * 2022-10-02 2024-04-11 Magneto Special Anodes (suzhou) Co., Ltd. Électrode et son utilisation
EP4677138A1 (fr) * 2023-03-09 2026-01-14 Magneto Special Anodes B.V. Revêtements d'oxydes métalliques mélangés appliqués à l'aide d'un dépôt spatial de couches atomiques et leurs utilisations
CN119433451B (zh) * 2024-09-28 2025-05-30 安徽络特斯科技有限公司 一种用于金属电解阳极板的铱钽涂层及制备方法

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JPS63235493A (ja) * 1987-03-24 1988-09-30 Tdk Corp 酸素発生用電極及びその製造方法
JP2713788B2 (ja) * 1989-12-22 1998-02-16 ティーディーケイ株式会社 酸素発生用電極及びその製造方法
JPH0633287A (ja) * 1992-07-17 1994-02-08 Permelec Electrode Ltd 電解用電極及びその製造方法
JP3124848B2 (ja) 1992-11-11 2001-01-15 ペルメレック電極株式会社 金属箔の電解による製造方法
JP2925938B2 (ja) * 1994-04-04 1999-07-28 古河電気工業株式会社 酸素発生用電極とその製造方法
JP3653296B2 (ja) * 1995-01-23 2005-05-25 石福金属興業株式会社 電解用電極及びその製造方法
JP2002146215A (ja) 2000-11-09 2002-05-22 Nippon Seitai Kk 燃焼性を改善したプラスチック成形品
JP3832645B2 (ja) * 2002-04-01 2006-10-11 石福金属興業株式会社 電解用電極及びその製造方法
JP4284387B2 (ja) * 2003-09-12 2009-06-24 株式会社和功産業 電解用電極及びその製造方法
JP4771130B2 (ja) * 2005-11-25 2011-09-14 ダイソー株式会社 酸素発生用電極
JP5281779B2 (ja) * 2007-09-20 2013-09-04 Ｄｏｗａメタルマイン株式会社 亜鉛電解液の製造方法
ITMI20110089A1 (it) * 2011-01-26 2012-07-27 Industrie De Nora Spa Elettrodo per evoluzione di ossigeno in processi elettrochimici industriali
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WO2021047687A2 (fr) 2021-03-18
KR20230088625A (ko) 2023-06-20
EP4028580A4 (fr) 2023-08-16
WO2021047687A3 (fr) 2021-04-29
CA3149248A1 (fr) 2021-03-18
CN112553657B (zh) 2023-06-02
CN112553657A (zh) 2021-03-26

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