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CN-122025670-A - TiO (titanium dioxide)2Composite graphite felt electrode of @ Ni @ C and preparation method thereof

CN122025670ACN 122025670 ACN122025670 ACN 122025670ACN-122025670-A

Abstract

The invention belongs to the field of electrode materials, and particularly discloses a TiO 2 @Ni@C composite graphite felt electrode and a preparation method thereof. The method comprises the following steps of S1, carrying out alkaline chemical oxidation etching surface pretreatment on a graphite felt to obtain a pretreated graphite felt, S2, electrodepositing NiTi-LDH on the pretreated graphite felt to obtain a NiTi-LDH graphite felt material, and S3, carrying out in-situ chemical reduction on the NiTi-LDH graphite felt material to obtain the Ti 2 @Ni@C composite graphite felt electrode. The method utilizes electrodeposition and in-situ chemical reduction to carry out surface modification of the graphite felt, and has the characteristics of easy realization of reaction conditions, low energy consumption and high modification and activation efficiency.

Inventors

  • XIN YANAN
  • YANG HAODI
  • ZHANG DONGBIN
  • LI JIE

Assignees

  • 成都先进金属材料产业技术研究院股份有限公司

Dates

Publication Date
20260512
Application Date
20260416

Claims (10)

  1. 1. The preparation method of the TiO 2 @Ni@C composite graphite felt electrode is characterized by comprising the following steps of: S1, performing alkaline chemical oxidation etching surface pretreatment on a graphite felt to obtain a pretreated graphite felt; S2, electrodepositing NiTi-LDH on the pretreated graphite felt to obtain a NiTi-LDH graphite felt material; And S3, carrying out in-situ chemical reduction on the NiTi-LDH graphite felt material to obtain the TiO 2 @Ni@C composite graphite felt electrode.
  2. 2. The method for preparing the TiO 2 @Ni@C composite graphite felt electrode according to claim 1, wherein the step S1 comprises the following substeps: S11, dissolving an alkaline substance in water to obtain an alkaline solution; S12, dissolving an oxidizing substance in the alkaline solution to obtain an alkaline chemical oxidation etching solution; and S13, soaking the graphite felt in the alkaline chemical oxidation etching liquid, and performing alkaline chemical oxidation etching surface pretreatment on the graphite felt to obtain the pretreated graphite felt.
  3. 3. The preparation method of the TiO 2 @Ni@C composite graphite felt electrode according to claim 2 is characterized in that the alkaline substance is one or more of sodium hydroxide, potassium hydroxide and ammonia water, the concentration of the alkaline substance in the alkaline solution is 1-10 mol/L, the oxidizing substance is one or more of sodium persulfate, potassium persulfate, ammonium persulfate, potassium bromate, potassium chlorate, potassium perchlorate, potassium permanganate and hydrogen peroxide, and the concentration of the oxidizing substance in the alkaline chemical oxidation etching solution is 1-5 mol/L.
  4. 4. The method for preparing the TiO 2 @Ni@C composite graphite felt electrode according to claim 2, wherein in the substep S13, the soaking temperature is room temperature to 100 ℃ and the soaking time is 1 to 24 hours.
  5. 5. The method for preparing the TiO 2 @Ni@C composite graphite felt electrode according to claim 1, wherein the step S2 comprises the following substeps: s21, preparing a nickel source titanium source mixed solution; And S22, taking the nickel source titanium source mixed solution as electrolyte, adopting a three-electrode system, taking the pretreated graphite felt as a working electrode, and electrodepositing NiTi-LDH on the pretreated graphite felt in a constant potential mode to obtain the NiTi-LDH graphite felt material.
  6. 6. The method for preparing the TiO 2 @Ni@C composite graphite felt electrode according to claim 5, wherein in the substep S21, the concentration of a nickel source in the nickel source titanium source mixed solution is 0.1-2 mol/L, the concentration of a titanium source is 0.1-1 mol/L, the molar ratio of nickel to titanium is 2-3:1, the nickel source is one or more of nickel nitrate, nickel sulfate and nickel chloride, and the titanium source is one or more of titanium sulfate, titanium tetrachloride and titanium sulfite.
  7. 7. The method for preparing the TiO 2 @Ni@C composite graphite felt electrode according to claim 5, wherein in the substep S22, the electrodeposition potential is-0.8V to-1.5V, and the electrodeposition time is 300-800S.
  8. 8. The method for preparing the TiO 2 @Ni@C composite graphite felt electrode according to claim 1, wherein the step S3 comprises the following substeps: S31, dissolving a reducing agent and alkali in water to obtain a chemical reducing solution; S32, placing the NiTi-LDH graphite felt material into the chemical reduction solution for chemical reduction reaction to obtain the TiO 2 @Ni@C composite graphite felt electrode.
  9. 9. The preparation method of the TiO 2 @Ni@C composite graphite felt electrode according to claim 8 is characterized in that in the substep S31, the reducing agent is sodium hypophosphite, the alkali is sodium hydroxide, and in the substep S32, the temperature of the chemical reduction reaction is 100-160 ℃ and the reaction time is 6-12 h.
  10. 10. A TiO 2 @ ni @ c composite graphite felt electrode prepared by the method of any one of claims 1 to 9.

Description

TiO 2 @Ni@C composite graphite felt electrode and preparation method thereof Technical Field The invention belongs to the field of electrode materials, and particularly relates to a TiO 2 @Ni@C composite graphite felt electrode and a preparation method thereof. Background With the development of new energy technology, the large-scale energy storage technology such as flow batteries is receiving more and more attention from people due to the advantages of intrinsic safety, long cycle life and the like. Among the many energy storage devices, carbon materials are considered to be preferred due to good electronic conductivity and thermal/mechanical stability. However, the problems of small specific surface area, poor wettability of electrolyte, low catalytic activity and the like limit the development and application of the electrolyte in water-based energy storage devices. For example, in the application of vanadium redox flow battery field, graphite felt is the electrode material currently used in mainstream, the existing graphite felt electrode material is not specially developed and designed for the vanadium redox flow battery field, and the existing specific surface area and vanadium ion catalytic activity are all required to be improved. In order to solve the above problems, the graphite felt electrode material is subjected to surface modification treatment such as activation and modification. The activation treatment mainly comprises 1) a high-temperature heat treatment method, wherein the heat treatment is mainly carried out at the temperature of 400-550 ℃ for 4-30 hours to increase the number of oxygen-containing functional groups on the surface of the carbon material, such as in Chinese patent CN 109987604A, 2) a strong oxidizing acid treatment, wherein oxygen-containing groups are introduced by using strong oxidizing acid liquid under the high-temperature conditions of hydrothermal/solvothermal and the like to improve the hydrophilic performance of the carbon material, such as in Chinese patent CN 104018340A, 3) an ion sputtering method (plasm), wherein the surface of the carbon material is bombarded by using a plasma beam under the vacuum condition to introduce defects, and 4) an electrochemical activation method, such as in China science, chemistry, 2014,44, 1280-1288. However, these methods have more or less limitations such as severe reaction conditions, severe equipment requirements, and low activation efficiency. Another solution is to load the catalyst on the surface to provide more catalytic active sites and improve the catalytic reaction capability. However, the long-term stability of the catalyst on the surface of graphite felt is an urgent problem to be solved. In view of this, the prior art is in need of improvement. Disclosure of Invention The invention aims to provide a novel Ti 2 @Ni@C composite graphite felt electrode and a preparation method thereof, wherein the electrode can be used as an electrode of an energy storage device such as an alkali metal secondary battery, a super capacitor, a flow battery and the like. In order to achieve the above purpose, the present invention adopts the following technical scheme: according to a first aspect of the present invention, there is provided a method for preparing a TiO 2 @ ni@c composite graphite felt electrode, comprising the steps of: S1, performing alkaline chemical oxidation etching surface pretreatment on a graphite felt to obtain a pretreated graphite felt; S2, electrodepositing NiTi-LDH on the pretreated graphite felt to obtain a NiTi-LDH graphite felt material; And S3, carrying out in-situ chemical reduction on the NiTi-LDH graphite felt material to obtain the TiO 2 @Ni@C composite graphite felt electrode. As a further embodiment, step S1 comprises the sub-steps of: S11, dissolving an alkaline substance in water to obtain an alkaline solution; S12, dissolving an oxidizing substance in the alkaline solution to obtain an alkaline chemical oxidation etching solution; and S13, soaking the graphite felt in the alkaline chemical oxidation etching liquid, and performing alkaline chemical oxidation etching surface pretreatment on the graphite felt to obtain the pretreated graphite felt. In a further embodiment, in the substep S11, the alkaline substance is one or more of sodium hydroxide, potassium hydroxide, and ammonia water. In a further embodiment, in the substep S11, the concentration of the alkaline substance in the alkaline solution is 1 to 10mol/L. As a further embodiment, in the substep S12, the oxidizing substance is one or more of sodium persulfate, potassium persulfate, ammonium persulfate, potassium bromate, potassium chlorate, potassium perchlorate, potassium permanganate, and hydrogen peroxide. In a further embodiment, in the substep S12, the concentration of the oxidizing substance in the alkaline chemical oxidation etching solution is 1 to 5mol/L. In a further embodiment, in the substep S13, the soaking temperature is room