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CN-117401779-B - Electrode composite material and preparation method and application thereof

CN117401779BCN 117401779 BCN117401779 BCN 117401779BCN-117401779-B

Abstract

The invention belongs to the technical field of electrocatalysis, and particularly relates to an electrode composite material, and a preparation method and application thereof. The invention provides an electrode composite material which comprises a carbon matrix, and modified tin dioxide and tricobalt tetraoxide loaded on the carbon matrix, wherein the modified tin dioxide comprises tin dioxide, rare earth elements doped in the tin dioxide and zirconium. According to the invention, the rare earth element and zirconium are doped in the tin dioxide, so that a solid solution oxide can be formed with the tin dioxide, and tin dioxide crystal grains are thinned by doping the rare earth element and zirconium, so that the solid solution film becomes more compact, uniform and continuous, and the activity and stability of the catalyst are greatly improved. According to the invention, the carbon matrix is modified by the modified tin dioxide and the cobaltosic oxide, the modified material loaded on the carbon matrix has fine crystal grains, is uniform and compact and has no crack, and meanwhile, the carbon matrix material has good conductivity, and the electrocatalytic degradation performance and the catalyst stability of the composite material are improved by the synergistic effect of the modified material and the carbon matrix.

Inventors

  • YUAN QINBO
  • Niu Zehui

Assignees

  • 清创人和生态工程技术有限公司

Dates

Publication Date
20260505
Application Date
20231106

Claims (10)

  1. 1. The electrode composite material is characterized by comprising a carbon matrix, and modified tin dioxide and tricobalt tetraoxide which are loaded on the carbon matrix, wherein the carbon matrix is any one of conductive polyacrylonitrile carbon felt, conductive activated carbon felt, conductive viscose graphite felt and conductive carbon fiber cloth; the modified tin dioxide comprises tin dioxide and rare earth elements and zirconium doped in the tin dioxide, wherein the rare earth elements and the zirconium are doped in a crystal lattice of the tin dioxide; the preparation method of the electrode composite material comprises the following steps: mixing tin salt, rare earth element-containing metal salt, zirconium salt, cobalt salt, binder and water to obtain a precursor solution; Carrying out first impregnation on the carbon matrix in the precursor solution, taking out, and sequentially carrying out first drying and first calcination to obtain a loaded carbon matrix; carrying out second impregnation on the carbon-loaded matrix in the precursor solution, taking out, and sequentially carrying out second drying and second calcination to obtain the electrode composite material; the electrode composite material is directly applied to neutral electrolyzed water degradation organic matters as a metal oxide anode.
  2. 2. The electrode composite of claim 1, wherein the rare earth element comprises one or more of cerium, lanthanum, gadolinium, neodymium, europium, and erbium.
  3. 3. The electrode composite material according to claim 1, wherein the doping mass percentage of the rare earth element in the modified tin dioxide is 1-10%; The doping mass percentage of the zirconium in the modified tin dioxide is 1-10%.
  4. 4. The electrode composite material according to claim 1, wherein the modified tin dioxide is loaded on the electrode composite material in a mass percentage of 10-20%; the loading mass percentage of the cobaltosic oxide on the electrode composite material is 1-5%.
  5. 5. The method for preparing the electrode composite material according to any one of claims 1 to 4, comprising the steps of: mixing tin salt, rare earth element-containing metal salt, zirconium salt, cobalt salt, binder and water to obtain a precursor solution; Carrying out first impregnation on the carbon matrix in the precursor solution, taking out, and sequentially carrying out first drying and first calcination to obtain a loaded carbon matrix; and (3) carrying out second impregnation on the carbon-loaded matrix in the precursor solution, taking out, and sequentially carrying out second drying and second calcination to obtain the electrode composite material.
  6. 6. The preparation method according to claim 5, wherein the tin salt comprises tin dichloride and/or tin tetrachloride; The rare earth element-containing metal salt comprises one or more of rare earth element-containing nitrate, rare earth element-containing sulfate and rare earth element-containing chloride; the zirconium salt comprises one or more of zirconium oxychloride, zirconium nitrate and zirconium sulfate; The cobalt salt comprises one or more of cobalt sulfate, cobalt nitrate, cobalt chloride and cobalt acetate; The binder comprises polyvinylpyrrolidone and aluminum silica sol.
  7. 7. The method according to claim 6, wherein the molar concentration of tin salt in the precursor solution is 0.1 to 0.2mol/L; the molar concentration of the rare earth element-containing metal salt in the precursor solution is 0.002-0.02 mol/L; the molar concentration of the zirconium salt in the precursor solution is 0.002-0.02 mol/L; The molar concentration of cobalt salt in the precursor solution is 0.002-0.01 mol/L; The dosage ratio of water, polyvinylpyrrolidone and aluminum silica sol in the precursor solution is 100mL:0.2g:250 muL.
  8. 8. The method according to claim 5, wherein the first calcination is performed at a temperature of 400-550 ℃ for 10min; The repetition times of the first impregnation, the first drying and the first calcination are 5-7 times.
  9. 9. The method according to claim 5, wherein the second calcination is performed at a temperature of 450-550 ℃ for 30-180 min.
  10. 10. Use of an electrode composite material according to any one of claims 1 to 4 or an electrode composite material prepared by a preparation method according to any one of claims 5 to 9 as a metal oxide anode.

Description

Electrode composite material and preparation method and application thereof Technical Field The invention belongs to the technical field of electrocatalysis, and particularly relates to an electrode composite material, and a preparation method and application thereof. Background The metal oxide anode has high catalytic performance, high current efficiency and good stability, but has the problems of short service life and reduced electrocatalytic activity with the extension of electrolysis time. Therefore, it is important to develop an anode with a long service life and high stability by further improving the performance of the metal oxide anode. The failure mechanism of the oxide anode is researched, a matrix modification approach of the anode is obtained, and an intermediate layer can be added between the matrix and the active coating. The addition of the intermediate layer can increase the binding force between the substrate and the coating, protect the substrate from passivation, and improve the performance of the anode, thereby prolonging the service life of the anode. As the material of the intermediate layer, the intermediate electrode material has good conductivity and oxidation resistance, and researches on the intermediate electrode material show that a compact SnO 2 -based solid solution film can be formed by doping SnO 2 with metal. The corrosion resistance at high potential has achieved excellent performance in earlier work, and conventional doping metals include Mn, cr or Sb. However, the stability of the product needs to be further enhanced when the industrialization is realized. Disclosure of Invention The invention aims to provide an electrode composite material, a preparation method and application thereof. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides an electrode composite material, which comprises a carbon matrix, and modified tin dioxide and tricobalt tetraoxide loaded on the carbon matrix; The modified tin dioxide comprises tin dioxide and rare earth elements and zirconium doped in the tin dioxide. Preferably, the rare earth element comprises one or more of cerium, lanthanum, gadolinium, neodymium, europium and baits. Preferably, the doping mass percentage of the rare earth element in the modified tin dioxide is 1-10%; The doping mass percentage of the zirconium in the modified tin dioxide is 1-10%. Preferably, the load mass percentage of the modified tin dioxide on the electrode composite material is 10-20%; the loading mass percentage of the cobaltosic oxide on the electrode composite material is 1-5%. The invention also provides a preparation method of the electrode composite material, which comprises the following steps: mixing tin salt, rare earth element-containing metal salt, zirconium salt, cobalt salt, binder and water to obtain a precursor solution; Carrying out first impregnation on the carbon matrix in the precursor solution, taking out, and sequentially carrying out first drying and first calcination to obtain a loaded carbon matrix; and (3) carrying out second impregnation on the carbon-loaded matrix in the precursor solution, taking out, and sequentially carrying out second drying and second calcination to obtain the electrode composite material. Preferably, the tin salt comprises tin dichloride and/or tin tetrachloride; The rare earth element-containing metal salt comprises one or more of rare earth element-containing nitrate, rare earth element-containing sulfate and rare earth element-containing chloride; the zirconium salt comprises one or more of zirconium oxychloride, zirconium nitrate and zirconium sulfate; The cobalt salt comprises one or more of cobalt sulfate, cobalt nitrate, cobalt chloride and cobalt acetate; The binder comprises polyvinylpyrrolidone and aluminum silica sol. Preferably, the molar concentration of tin salt in the precursor solution is 0.1-0.2 mol/L; the molar concentration of the rare earth element-containing metal salt in the precursor solution is 0.002-0.02 mol/L; the molar concentration of the zirconium salt in the precursor solution is 0.002-0.02 mol/L; The molar concentration of cobalt salt in the precursor solution is 0.002-0.01 mol/L; The dosage ratio of water, polyvinylpyrrolidone and aluminum silica sol in the precursor solution is 100mL:0.2g:250 muL. Preferably, the temperature of the first calcination is 400-550 ℃ and the time is 10min; The repetition times of the first impregnation, the first drying and the first calcination are 5-7 times. Preferably, the temperature of the second calcination is 450-550 ℃ and the time is 30-180 min. The invention also provides an application of the electrode composite material prepared by the technical scheme or the preparation method of the technical scheme as a metal oxide anode. The invention provides an electrode composite material which comprises a carbon matrix, and modified tin dioxide and tricobalt tetraoxide l