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CN-122025565-A - P/CNT self-supporting electrode material and preparation method and application thereof

CN122025565ACN 122025565 ACN122025565 ACN 122025565ACN-122025565-A

Abstract

The invention belongs to the field of battery energy storage, and relates to a P/CNT self-supporting electrode material, a preparation method and application thereof. The P/CNT self-supporting electrode material comprises red phosphorus and carbon nanotubes. In the P/CNT electrode material provided by the invention, the red P and the CNT material exist in a P-C chemical bond mode, so that the binding force of the P/CNT electrode material is greatly improved, the stability of the electrode material is improved, and the conductivity of the red P is improved. The method has the advantages of mild reaction conditions, simple and convenient operation, simple equipment and process, and eliminates the dangers and the use of toxic solutions and solvents related to the production of the traditional lithium ion battery.

Inventors

  • WEI YANBIN
  • ZHU ZHENXING
  • ZHANG QI
  • WEI FEI
  • ZHANG SHIJUN

Assignees

  • 中国石油化工股份有限公司
  • 中石化(北京)化工研究院有限公司
  • 清华大学

Dates

Publication Date
20260512
Application Date
20241108

Claims (12)

  1. 1. A P/CNT self-supporting electrode material, comprising red phosphorus and carbon nanotubes.
  2. 2. The P/CNT self-supporting electrode material according to claim 1, wherein the red phosphorus content is 20-70 wt%, preferably 30-60 wt%, and the carbon nanotubes content is 30-80 wt%, preferably 40-70 wt%, based on the weight of the P/CNT self-supporting electrode material.
  3. 3. The P/CNT self-supporting electrode material of claim 1, wherein a phosphorus-carbon chemical bond is formed between the red phosphorus and the carbon nanotubes.
  4. 4. The P/CNT self-supporting electrode material according to claim 1, wherein the thickness of the P/CNT self-supporting electrode material is 10-500 μm, preferably 50-200 μm.
  5. 5. The P/CNT self-supporting electrode material according to claim 1, wherein the P/CNT self-supporting electrode material is free of conductive agents and binders.
  6. 6. The P/CNT self-supporting electrode material according to any one of claims 1-5, wherein the P/CNT self-supporting electrode material is made from red phosphorus and carbon nanotubes by blending, milling and filtration.
  7. 7. The method for preparing the P/CNT self-supporting electrode material according to any one of claims 1 to 6, comprising the steps of: (1) Mixing red phosphorus and a carbon nano tube solution, and grinding to obtain a P/CNT electrode material precursor solution; (2) And filtering the P/CNT electrode material precursor solution to obtain the P/CNT self-supporting electrode material.
  8. 8. The method of claim 7, wherein step (1) comprises: adding red phosphorus into a carbon nano tube aqueous solution, stirring to form a uniform P/CNT solution, and sanding the P/CNT solution to obtain a P/CNT electrode material precursor solution.
  9. 9. The method according to claim 7 or 8, wherein the red phosphorus is a powder having a particle size of 0.1 to 2 μm.
  10. 10. The method for preparing the polishing pad according to claim 8, wherein the time for polishing is 5-10 hours.
  11. 11. The method of claim 7, wherein step (2) further comprises drying the filtered product.
  12. 12. Use of the P/CNT self-supporting electrode material according to any one of claims 1-6 for the preparation of a negative electrode material for a sodium ion battery.

Description

P/CNT self-supporting electrode material and preparation method and application thereof Technical Field The invention belongs to the field of battery energy storage, and particularly relates to a P/CNT self-supporting electrode material and a preparation method thereof, and application of the P/CNT self-supporting electrode material in preparation of a sodium ion battery negative electrode material. Background Lithium ion batteries are widely used in the energy storage field, but lithium resources adopted by the lithium ion batteries are limited in reserve on the earth, so that other battery systems need to be developed to partially replace the lithium ion batteries. Sodium resources are more abundant than lithium in the earth and have lower cost and electrochemical properties similar to those of lithium, so that sodium ion batteries are the best choice for partial application in place of lithium ion batteries. Up to now, various sodium ion battery anode materials such as carbon materials, alloy materials, organic compounds, transition metal oxides, and the like have been reported. The carbon material is cheap and has better cycle life, and the development prospect of industrial application is better. However, the reversible specific capacity of the carbon negative electrode material represented by hard carbon is relatively low, so that the research and development of the sodium storage negative electrode material with high specific capacity and long service life has important application significance. The sodium ion battery phosphorus anode material has the highest theoretical capacity (2596 mAh g -1) and proper sodium storage potential, and is widely focused. Phosphorus (P) mainly exists in 3 allotropes, namely white phosphorus, red phosphorus and black phosphorus. Among them, white phosphorus is toxic and unstable in air, and is unsuitable for use as an electrode material. Red phosphorus and black phosphorus are relatively stable and can be used as sodium storage electrode materials. However, P occurs with serious volume changes (about 400%) during sodium deintercalation, resulting in poor structural stability, fast battery capacity decay, poor initial coulombic efficiency and long-term cycling stability. Therefore, most researchers improve the sodium storage performance of P as a sodium ion battery material by reducing the P size, compounding with a carbon material, alloying with other metal materials, overcladding with a conductive polymer film, and the like. Carbon nanotubes have good flexibility, mechanical properties and electrical conductivity and are often used as materials to improve the volume expansion and electrical conductivity of electrode materials. Disclosure of Invention The invention aims to provide a P-based self-supporting electrode material and a preparation method thereof, wherein the material has better electrochemical performance, has great application potential in the field of battery energy storage, and the preparation method has the characteristics of simple process, environment friendliness, energy conservation, high efficiency and the like. To achieve the above object, a first aspect of the present invention provides a P/CNT self-supporting electrode material including red phosphorus (red P) and carbon nanotubes. Optionally, the content of red phosphorus is 20-70 wt%, preferably 30-60 wt%, and the content of carbon nanotubes is 30-80 wt%, preferably 40-70 wt%, based on the weight of the P/CNT self-supporting electrode material. In the invention, a phosphorus-carbon chemical bond is formed between the red phosphorus and the carbon nano tube. Optionally, the thickness of the P/CNT self-supporting electrode material is 10-500 μm, preferably 50-200 μm. Optionally, the P/CNT self-supporting electrode material of the present invention is free of conductive agents and binders. Optionally, the P/CNT self-supporting electrode material is prepared by blending, grinding and filtering red phosphorus and carbon nanotubes. The second aspect of the present invention provides a method for preparing the above P/CNT self-supporting electrode material, comprising the steps of: (1) Mixing red phosphorus and a carbon nano tube solution, and grinding to obtain a P/CNT electrode material precursor solution; (2) And filtering the P/CNT electrode material precursor solution to obtain the P/CNT self-supporting electrode material. Optionally, step (1) includes: adding red phosphorus into a carbon nano tube aqueous solution, stirring to form a uniform P/CNT solution, and sanding the P/CNT solution to obtain a P/CNT electrode material precursor solution. Optionally, the red phosphorus is powder, and the particle size of the red phosphorus is 0.1-2 mu m. Optionally, the sanding time is 5-10 h. Optionally, step (2) further comprises drying the filtered product. The third aspect of the invention provides an application of the P/CNT self-supporting electrode material in preparing a negative electrode material