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CN-116947016-B - Power type sodium ion negative electrode material for energy storage, battery, preparation method and application

CN116947016BCN 116947016 BCN116947016 BCN 116947016BCN-116947016-B

Abstract

The invention belongs to the technical field of sodium ion batteries, and particularly relates to a power type sodium ion negative electrode material for energy storage, a battery, a preparation method and application. The preparation raw materials of the negative electrode material of the power type sodium ion battery for energy storage provided by the invention are an organic carbon source, black phosphorus and a titanium source, wherein the organic carbon source comprises biochemical sludge, tar residues and plant tissues subjected to acidification treatment. After twice heat treatment, the obtained negative electrode material has high specific capacity and good rate capability and cycle stability, and can be used for preparing a power type sodium ion battery for energy storage.

Inventors

  • WANG LISHI
  • MA ZHENDE
  • DING ZHE

Assignees

  • 安徽纳微聚能新能源科技有限公司

Dates

Publication Date
20260505
Application Date
20230731

Claims (10)

  1. 1. The preparation method of the power type sodium ion battery cathode material for energy storage is characterized by comprising the following steps of: Ball milling an organic carbon source, black phosphorus and a titanium source in an inert atmosphere, and then sequentially performing heat treatment twice in the inert atmosphere, wherein the first heat treatment is to heat up to 400-550 ℃ at a heating rate of 2-6 ℃ per minute and keep for 60-80 min, and the second heat treatment is to heat up to 700-900 ℃ at a heating rate of 10-18 ℃ per minute and keep for 1.5-2 h; the organic carbon source comprises biochemical sludge, tar residues and plant tissues subjected to acidification treatment, wherein the acidification treatment comprises the steps of soaking the plant tissues in 3% -6% wt of phosphoric acid aqueous solution for 1-2 hours, washing the plant tissues with water until the water is neutral, and drying the plant tissues until the water content is less than or equal to 2.0%.
  2. 2. The preparation method of claim 1, wherein the mass ratio of the biochemical sludge, the tar residue and the acidified plant tissue is 2-4:1-3:5-7, and the water content of the biochemical sludge is 35% -45%.
  3. 3. The method according to claim 2, wherein the molar ratio of phosphorus element in the black phosphorus to carbon element in the organic carbon source is 2 to 5:10, and/or The molar ratio of the titanium element in the titanium source to the carbon element in the organic carbon source is 1.5-3:10, and/or The titanium source is selected from at least one of titanium oxide and sodium titanate.
  4. 4. The method according to claim 1, further comprising washing the product obtained by the first heat treatment with water and an aqueous ethanol solution before the second heat treatment, and drying.
  5. 5. A negative electrode material of a power type sodium ion battery for energy storage, characterized by being prepared by the preparation method according to any one of claims 1 to 4.
  6. 6. The use of the negative electrode material of claim 5 for preparing a power type sodium ion battery for energy storage.
  7. 7. A power type sodium ion battery for energy storage, which is characterized by comprising a positive electrode material, a negative electrode material, electrolyte and a diaphragm, wherein the negative electrode material is the negative electrode material of claim 5.
  8. 8. The power type sodium ion battery for energy storage according to claim 7, wherein the positive electrode material comprises at least one of sodium vanadium fluorophosphate, sodium vanadium phosphate, sodium iron phosphate, sodium vanadium monofluorophosphate and sodium iron pyrophosphate, and/or The electrolyte comprises a carbonate solvent, an additive and sodium salt, wherein the additive comprises at least one of fluoroethylene carbonate, pentafluoro-3 ',5' -bistrifluoromethyl-1, 1' -biphenyl, bisfluoroethylene carbonate and tris (2, 2-trifluoroethyl) phosphate.
  9. 9. The power type sodium ion battery for energy storage according to claim 8, wherein the carbonate solvent comprises at least one of methyl ethyl carbonate and diethyl carbonate, and ethylene carbonate, and/or In the electrolyte, the sodium salt is at least one of sodium tetrafluoroborate, sodium difluorosulfimide, sodium difluorooxalato borate, sodium hexafluorophosphate and sodium perchlorate.
  10. 10. The method for preparing the power type sodium ion battery for energy storage according to any one of claims 8 or 9, which is characterized by comprising the following steps of adding the sodium salt into the carbonate solvent, uniformly mixing, adding the additive, uniformly mixing, and removing water and oxygen to obtain the electrolyte; Mixing the anode material, the conductive agent and the binder, and preparing anode slurry by taking N-methyl pyrrolidone as a mixed medium; uniformly coating the positive electrode slurry on two surfaces of a positive electrode current collector aluminum foil, drying, and then rolling and cutting to obtain a positive electrode plate; Mixing the negative electrode material, the conductive agent, the thickening agent and the adhesive according to claim 5, and preparing negative electrode slurry by taking deionized water as a mixed medium; and manufacturing the positive pole piece, the isolating film and the negative pole piece into the power type sodium ion battery for energy storage according to the conventional process of the rechargeable battery.

Description

Power type sodium ion negative electrode material for energy storage, battery, preparation method and application Technical Field The invention belongs to the technical field of sodium ion batteries, and particularly relates to a power type sodium ion negative electrode material for energy storage, a battery, a preparation method and application. Background Large-scale energy storage is key to realizing the practical use of renewable energy sources. Lithium ion batteries are one of the most successful secondary ion batteries in the energy storage field, and have been widely used in the fields of electronic products, electric automobiles and the like. However, lithium cannot meet the huge demand of energy storage on battery raw materials due to resource restriction. Sodium Ion Batteries (SIBs) are similar to the working principle of lithium ion batteries, but sodium resources have the unique advantages of abundant reserves, convenient exploitation, no alloying reaction between sodium and aluminum, lower use cost compared with copper foils required by lithium ion batteries because aluminum foils can be used for selecting anode and cathode materials of the batteries, low charge density of sodium, high diffusion rate in aqueous or non-aqueous electrolyte, good stability and high safety because of use at high temperature of 30-80 ℃. These advantages make sodium ion batteries one of the ideal choices for large-scale energy storage technology, which has attracted considerable attention in recent years. However, the radius of sodium ions is larger, so that the electrode material can undergo serious phase change and slow reaction kinetics in the charge and discharge process, and the application of the electrode material as the electrode material is restricted. The sodium ion battery mainly comprises a positive electrode material, a negative electrode material, electrolyte, a diaphragm and other parts, wherein the negative electrode material plays roles of loading and releasing Na ions, and has an important influence on the overall dynamic performance of the battery. Therefore, the improvement of the negative electrode material of the sodium ion battery is of great significance for improving the electrical performance of the sodium ion battery. Disclosure of Invention Aiming at the technical problems, the invention provides a power type sodium ion negative electrode material for energy storage, a battery, a preparation method and application. The negative electrode material of the power type sodium ion battery for energy storage, provided by the invention, has high specific capacity, good rate capability and good cycling stability, and can be used for preparing the power type sodium ion battery for energy storage. In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme: The invention provides a preparation method of a power type sodium ion battery anode material for energy storage, which specifically comprises the following operations: Ball milling an organic carbon source, black phosphorus and a titanium source in an inert atmosphere, and then sequentially performing heat treatment twice in the inert atmosphere, wherein the first heat treatment is to heat up to 400-550 ℃ at a heating rate of 2-6 ℃ per minute and keep for 60-80 min, and the second heat treatment is to heat up to 700-900 ℃ at a heating rate of 10-18 ℃ per minute and keep for 1.5-2 h; the organic carbon source comprises biochemical sludge, tar residues and plant tissues subjected to acidification treatment, wherein the acidification treatment comprises the steps of soaking the plant tissues in 3% -6% wt of phosphoric acid aqueous solution for 1-2 hours, washing the plant tissues with water until the water is neutral, and drying the plant tissues until the water content is less than or equal to 2.0%. According to the preparation method provided by the invention, through a specific precursor composition and a heat treatment process, the prepared anode material is a hard carbon material doped with phosphorus and titanium. The raw materials of the preparation method comprise natural pores in plant tissues subjected to acidification treatment, a rudiment skeleton is provided for the formation of the anode material, biochemical sludge and tar residues belong to carbon-containing solid wastes, and the carbon content is high. The black phosphorus has stable structure, high carrier mobility, high theoretical capacity, good thermal stability and high anisotropism, is favorable for improving the cycle stability of the anode material, but has the problem of volume expansion after sodium storage, titanium doping is favorable for shortening the migration path of Na +, increasing the conductivity of the anode material, providing rich sites for Na + deintercalation, but lower initial cycle coulomb efficiency, biochemical sludge and tar residues have certain viscosity, and the anode material is favorable for doping p