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CN-121976258-A - Titanium-manganese surface composite modified corrugated anode plate for EMD and preparation method thereof

CN121976258ACN 121976258 ACN121976258 ACN 121976258ACN-121976258-A

Abstract

The invention discloses a titanium-manganese surface composite modified corrugated anode plate for EMD and a preparation method thereof, and belongs to the technical field of anode plate materials for electrolysis. The anode plate comprises a corrugated titanium substrate and a titanium-manganese modified layer on the surface of the corrugated titanium substrate, wherein the corrugated titanium substrate and the titanium-manganese modified layer form metallurgical bonding through high-temperature diffusion, and the titanium-manganese modified layer comprises, by weight, 93.0% -94.5% of titanium and 5.5% -7.0% of manganese, and the thickness is 20-50 mu m. The preparation method comprises the steps of preprocessing a corrugated titanium substrate, coating slurry containing titanium-manganese compound powder and metal manganese powder on the surface of the substrate, and performing heat treatment in protective atmosphere or vacuum to diffuse manganese element into the titanium substrate to form the titanium-manganese modified layer. The invention solves the problems of high oxygen evolution overpotential, high cost of noble metal coating and easy spalling of pure titanium anode, has the advantages of strong binding force, high electrocatalytic activity, low energy consumption and controllable cost, and is suitable for the industries of electrolytic manganese dioxide and chlor-alkali.

Inventors

  • LI QING

Assignees

  • 湖南擎诚新材料科技有限公司

Dates

Publication Date
20260505
Application Date
20260326

Claims (10)

  1. 1. The titanium-manganese surface composite modified corrugated anode plate for EMD is characterized by comprising the following components: The corrugated titanium substrate is formed by pressing a titanium plate with the titanium content of 99.9-99.999 wt%; And a titanium-manganese modified layer compounded on the surface of the corrugated titanium substrate, wherein a metallurgical bonding layer formed by high-temperature diffusion is arranged between the titanium-manganese modified layer and the corrugated titanium substrate, and the titanium-manganese modified layer contains titanium element and manganese element.
  2. 2. The corrugated anode plate of claim 1 wherein the titanium manganese modified layer contains 93.0% -94.5% by weight of titanium and 5.5% -7.0% by weight of manganese.
  3. 3. The corrugated anode plate of claim 1 or 2 wherein the titanium manganese modified layer has a thickness of 20-50 μm and the elements of the titanium manganese modified layer diffuse into the substrate to a depth of 100-300 μm.
  4. 4. The corrugated anode plate according to claim 1 or 2, wherein the titanium-manganese modified layer is formed by a high-temperature diffusion manganese permeation process after being coated with a slurry containing titanium-manganese compound powder and manganese metal powder, wherein the titanium-manganese compound powder is obtained by high-temperature synthesis of titanium hydride and manganese metal powder.
  5. 5. A method for preparing the titanium manganese surface composite modified corrugated anode plate for EMD according to any one of claims 1-4, comprising the steps of: S1, preprocessing a substrate, namely providing a titanium plate with the titanium content of 99.9-99.999wt%, pressing to form a corrugated titanium substrate, and cleaning and activating the surface of the titanium substrate; s2, slurry coating, namely uniformly coating slurry containing titanium-manganese compound powder and metal-manganese powder on the surface of the pretreated corrugated titanium substrate to form a coating; s3, heat treatment, namely heat treating the coated titanium substrate in a protective atmosphere or vacuum environment to diffuse manganese element in the coating to the titanium substrate so as to form a titanium-manganese modified layer.
  6. 6. The method according to claim 5, wherein in step S1, the cleaning activation treatment includes blasting and pickling the titanium substrate.
  7. 7. The preparation method according to claim 5, wherein in the step S2, the titanium manganese compound powder is obtained by mixing titanium hydride and manganese metal powder in a mass ratio of 1:1 to 2:1, synthesizing at a high temperature of 1200 ℃ to 1500 ℃, and grinding.
  8. 8. The method according to claim 5, wherein in step S2, the slurry further comprises a water-soluble binder, and the step of degumming and dehydrogenation treatment is performed at 100 ℃ for 1 to 2 hours after the coating.
  9. 9. The method according to claim 5, wherein in step S3, the heat treatment is performed at a temperature ranging from 850 ℃ to 950 ℃, and the heat treatment process comprises a plurality of temperature gradient stages, and the core diffusion manganese stage is kept at 900 ℃ for at least 360 minutes.
  10. 10. Use of the corrugated anode plate of any one of claims 1-4 as an anode in electrolytic manganese dioxide production or chlor-alkali industry.

Description

Titanium-manganese surface composite modified corrugated anode plate for EMD and preparation method thereof Technical Field The invention relates to the technical field of anode plate materials for electrolysis, in particular to a titanium-manganese surface composite modified corrugated anode plate for EMD (electrolytic manganese dioxide) and a preparation method thereof. Background Electrolytic manganese dioxide is a key raw material for the battery industry, and the production efficiency and energy consumption of the electrolytic manganese dioxide are closely related to the performance of anode materials. Pure titanium plates are commonly used as electrolytic anodes because of their excellent corrosion resistance and electrical conductivity. However, the pure titanium anode has the problems of high oxygen evolution overpotential, large cell voltage, low electrolysis efficiency and the like in the long-term electrolysis process, so that the energy consumption is increased. To improve the performance of titanium anodes, surface coatings or modification techniques, such as coating with noble metal oxide (e.g., ruthenium iridium) are commonly used in the art. Although the coating can promote the electrocatalytic activity, the problems of high cost, insufficient binding force between the coating and a substrate, easy peeling and failure under strong acid and high current density and the like exist, and the large-scale application and long-term stability of the coating are limited. Therefore, it is of great importance to develop an anode material with moderate cost, strong binding force, excellent electrochemical performance and long service life. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides a titanium-manganese surface composite modified corrugated anode plate for EMD and a preparation method thereof. The anode plate is formed with a metallurgically bonded titanium-manganese modified layer on the surface of the titanium substrate, so that the electrocatalytic activity and bonding strength of the anode are obviously improved, and the purposes of reducing cell voltage, improving electrolysis efficiency and saving energy consumption are achieved. The invention provides a titanium-manganese surface composite modified corrugated anode plate for EMD, which comprises a corrugated titanium substrate and a titanium-manganese modified layer, wherein the corrugated titanium substrate is formed by pressing a titanium plate with the titanium content of 99.9-99.999wt%, and the titanium-manganese modified layer is composited on the surface of the corrugated titanium substrate, and a metallurgical bonding layer formed by high-temperature diffusion is arranged between the titanium-manganese modified layer and the corrugated titanium substrate, wherein the titanium-manganese modified layer contains titanium element and manganese element. Preferably, the titanium element content in the titanium-manganese modified layer is 93.0% -94.5% and the manganese element content is 5.5% -7.0% by weight. Preferably, the thickness of the titanium-manganese modified layer is 20-50 μm, and the diffusion depth of the elements of the titanium-manganese modified layer into the titanium substrate is 100-300 μm. Preferably, the titanium-manganese modified layer is formed by high-temperature diffusion manganese permeation process after being coated by slurry containing titanium-manganese compound powder and metal manganese powder, wherein the titanium-manganese compound powder is obtained by high-temperature synthesis of titanium hydride and metal manganese powder. In a second aspect, the invention provides a preparation method of the titanium-manganese surface composite modified corrugated anode plate for EMD, which comprises the following steps: S1, preprocessing a substrate, namely providing a titanium plate with the titanium content of 99.9-99.999wt%, pressing to form a corrugated titanium substrate, and cleaning and activating the surface of the titanium substrate; s2, slurry coating, namely uniformly coating slurry containing titanium-manganese compound powder and metal-manganese powder on the surface of the pretreated corrugated titanium substrate to form a coating; s3, heat treatment, namely heat treating the coated titanium substrate in a protective atmosphere or vacuum environment to diffuse manganese element in the coating to the titanium substrate so as to form a titanium-manganese modified layer. Preferably, in the step S1, the cleaning and activating treatment comprises sand blasting treatment and acid washing treatment on the titanium substrate, and the acid washing is preferably performed by adopting an HF/HNO 3 mixed solution so as to better remove surface oxide films and greasy dirt. Preferably, in step S2, the titanium manganese compound powder is obtained by mixing titanium hydride and manganese metal powder according to a mass ratio of 1:1 to 2:1, synthesizing at a high tempera