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CN-121983438-A - Three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material and preparation method thereof

CN121983438ACN 121983438 ACN121983438 ACN 121983438ACN-121983438-A

Abstract

The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material and a preparation method thereof, comprising the following steps of (1) carrying out activation treatment on carbon fiber cloth, and cleaning and drying after the reaction is finished to obtain activated carbon fiber cloth; the method comprises the steps of (1) dissolving cobalt sources, nickel sources and 2-methylimidazole ligands in different proportions in methanol, uniformly mixing to obtain a reaction solution, immersing the obtained activated carbon fiber cloth in the reaction solution, carrying out solvothermal reaction, growing three-dimensional Co/Ni-ZIF nano sheets on the surface of the carbon fiber cloth in situ, and (3) taking out, washing and drying the carbon fiber cloth after the reaction is finished to obtain the Co/Ni-ZIF nano sheet@carbon fiber cloth electrode material with the three-dimensional porous network structure.

Inventors

  • WANG CAIFENG
  • SUN JIUCHAO
  • LI XIAOYU
  • GE CHAO
  • Tong Mengyuan
  • WANG XIAO
  • Wan Xinmiao
  • BAI LANG

Assignees

  • 辽宁石油化工大学

Dates

Publication Date
20260505
Application Date
20260403

Claims (10)

  1. 1. The preparation method of the three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material is characterized by comprising the following steps of: (1) Immersing the carbon fiber cloth into concentrated nitric acid for water bath heating treatment, and cleaning and drying after the reaction is finished to obtain activated carbon fiber cloth; (2) Soaking the activated carbon fiber cloth obtained in the step (1) in the reaction solution to perform solvothermal reaction, and growing three-dimensional Co/Ni-ZIF nano sheets on the surface of the carbon fiber cloth in situ; (3) And after the reaction is finished, taking out the carbon fiber cloth, washing and drying to obtain the three-dimensional Co/Ni-ZIF nano sheet@carbon fiber cloth electrode material.
  2. 2. The method for preparing the three-dimensional Co/Ni-ZIF nanosheet @ carbon fiber cloth electrode material according to claim 1, wherein in the step (1), the carbon fiber cloth is immersed in concentrated nitric acid, and heated in a water bath at 60-120 ℃ for 4-8 hours.
  3. 3. The method for preparing the three-dimensional Co/Ni-ZIF nanosheet @ carbon fiber cloth electrode material according to claim 1, wherein in the step (2), the cobalt source is Co (NO 3 ) 2 ·6H 2 O, and the nickel source is Ni (NO 3 ) 2 ·6H 2 O).
  4. 4. The method for preparing the three-dimensional Co/Ni-ZIF nanosheets @ carbon fiber cloth electrode material according to claim 3, wherein in the step (2), the molar ratio of Co 2+ to Ni 2+ is 5:1-3, and the molar ratio of Co 2+ to 2-methylimidazole is 1:4.
  5. 5. The method for preparing the three-dimensional Co/Ni-ZIF nanosheet @ carbon fiber cloth electrode material according to claim 1, wherein in the step (2), the solvothermal reaction temperature is 120-150 ℃ and the reaction time is 6-12 h.
  6. 6. The method for preparing the three-dimensional Co/Ni-ZIF nanosheet @ carbon fiber cloth electrode material according to claim 5, wherein in the step (2), the amount of methanol is 10-30 mmol of the total molar amount of the cobalt source, the nickel source and the 2-methylimidazole corresponding to 20mL of methanol.
  7. 7. The method for preparing the three-dimensional Co/Ni-ZIF nanosheet @ carbon fiber cloth electrode material according to claim 6, wherein in the step (3), the washing liquid used in the washing step is methanol, the washing times are 3-5 times, the drying temperature is 60 ℃, and the drying time is 12 hours.
  8. 8. The method for preparing the three-dimensional Co/Ni-ZIF nanosheets @ carbon fiber cloth electrode material according to claim 7, wherein the carbon fiber cloth in the step (1) has a size of 6×6cm 2 ～10×10cm 2 , and the activated carbon fiber cloth used in the step (2) has a size of 3×3cm 2 ～5×5cm 2 .
  9. 9. The three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material is characterized by being prepared by the preparation method of any one of claims 1-7.
  10. 10. The three-dimensional Co/Ni-ZIF nanosheets @ carbon fiber cloth electrode material of claim 9, wherein the material has a structure that three-dimensional Co/Ni-ZIF nanosheets are uniformly and densely grown on the surface of carbon fibers of the carbon fiber cloth in situ to form a three-dimensional porous network structure.

Description

Three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material and preparation method thereof Technical Field The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material and a preparation method thereof. Background At present, along with the continuous improvement of the demand of electronic products, energy storage and functionalization equipment are paid attention to, and the defects of poor flexibility, poor energy storage effect and the like of traditional electrode materials (such as noble metal, silicon-based materials and rigid carbon materials) generally exist, so that the demands of emerging fields such as flexible energy storage and wearable equipment are difficult to meet. Therefore, the development of the novel flexible electrode material with excellent electrical properties is a primary innovation direction of the development of the energy storage device. The carbon fiber cloth (CC) is used as a porous textile material woven by high-strength and high-conductivity carbon fibers, not only inherits the inherent chemical stability and conductivity of the carbon material, but also has the characteristics of excellent intrinsic flexibility, high specific surface area, three-dimensional interconnected conductive network and the like due to the unique textile structure, and provides a direction for solving the problems. More importantly, the CC can be used as an ideal substrate material, and various functional materials (such as graphene, conductive polymer and metal nano particles) can be easily integrated through a surface modification and nano composite technology, so that the accurate regulation and control of electrochemical activity and sensing sensitivity are realized, and the CC has a wide application prospect in the field of flexible energy storage devices. However, the problems of limited specific surface area, poor electric conductivity and the like exist, and the problems can be effectively solved by modifying the surface of the material through proper materials. Disclosure of Invention The invention aims to overcome the defects of the prior art and provide the three-dimensional Co/Ni-ZIF nano sheet@carbon fiber cloth electrode material capable of solving the problems of poor flexibility, poor energy storage effect and poor cycling stability of the existing electrode material and the preparation method thereof. In order to solve the technical problems, the invention is realized as follows: The preparation method of the three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material comprises the following steps: (1) The activation treatment of the carbon fiber cloth, namely immersing the carbon fiber cloth into concentrated nitric acid for water bath heating treatment, and cleaning and drying after the reaction is finished to obtain the activated carbon fiber cloth; (2) The in-situ growth reaction comprises dissolving cobalt source, nickel source and 2-methylimidazole in methanol, and mixing to obtain a reaction solution, soaking the activated carbon fiber cloth obtained in the step (1) in the reaction solution, performing solvothermal reaction, and in-situ growing three-dimensional Co/Ni-ZIF nano-sheets on the surface of the carbon fiber cloth; (3) And (3) after the reaction is finished, taking out the carbon fiber cloth, washing and drying to obtain the three-dimensional Co/Ni-ZIF nano sheet@carbon fiber cloth electrode material. Further, in the step (1), the carbon fiber cloth is immersed in concentrated nitric acid, and is heated in a water bath at 60-120 ℃ for 4-8 hours. Further, in the step (2), the cobalt source is Co (NO 3)2·6H2 O) and the nickel source is Ni (NO 3)2·6H2 O). Further, the molar ratio of Co 2+ to Ni 2+ is 5:1-3, and the molar ratio of Co 2+ to 2-methylimidazole is 1:4. Further, in the step (2), the temperature of the solvothermal reaction is 120-150 ℃ and the reaction time is 6-12 hours. Further, in the step (2), the amount of methanol is 10-30 mmol of total molar amount of the cobalt source, the nickel source and the 2-methylimidazole corresponding to 20 mL methanol. In the step (3), the washing liquid used in the washing step is methanol, the washing times are 3-5 times, the drying temperature is 60 ℃, and the drying time is 12 hours. Further, the size of the carbon fiber cloth in the step (1) is 6×6 cm 2～10×10cm2, and the size of the activated carbon fiber cloth used in the step (2) is 3×3cm 2～5×5cm2. The three-dimensional Co/Ni-ZIF nanosheet@carbon fiber cloth electrode material is prepared by the preparation method, and has the structure that a three-dimensional Co/Ni-ZIF nanosheet array uniformly and compactly grows on the surface of carbon fibers of carbon fiber cloth in situ to form a three-dimensional porous network structure. The Metal Organic Frameworks (MOFs) have unique porous structures, adjustable pore st