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CN-122025566-A - Phenolic resin-based tin-carbon negative electrode material and preparation method thereof

CN122025566ACN 122025566 ACN122025566 ACN 122025566ACN-122025566-A

Abstract

The invention relates to the technical field of sodium battery cathodes, and particularly discloses a phenolic resin-based tin-carbon cathode material and a preparation method thereof: mixing phenolic substances with aldehyde substances, adding a solid tin source which is tin powder or/and tin dioxide powder, stirring uniformly, adding catalyst ammonia water, heating for reaction, monitoring viscosity in the reaction process, discharging when the viscosity is more than or equal to 800 mPa.s, drying, crushing, grinding, and carbonizing in an inert atmosphere. According to the invention, the phenolic resin-based tin-carbon anode material with good charge and discharge performance is prepared by taking the tin powder or/and the tin dioxide powder as the tin source, so that the cost is reduced, the risks of waste water generation and human body injury caused by using the liquid tin source are avoided, and the preparation method does not have obvious adverse effect on a kiln, thereby having great popularization prospect.

Inventors

  • WANG YU
  • WANG JUAN
  • MENG QINGSHI
  • QI XINGGUO
  • LI SHUJUN

Assignees

  • 溧阳中科海钠科技有限责任公司

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. A preparation method of a phenolic resin-based tin-carbon anode material is characterized by specifically mixing phenolic substances and aldehyde substances, adding a solid tin source, wherein the solid tin source is tin powder or/and tin dioxide powder, stirring uniformly, adding catalyst ammonia water, heating for reaction, monitoring viscosity in the reaction process, discharging when the viscosity is more than or equal to 800 mPa.s, drying, crushing, grinding, and carbonizing in an inert atmosphere.
  2. 2. The method for preparing a phenolic resin-based tin-carbon negative electrode material according to claim 1, wherein the particle size of the solid tin source is not more than 50 μm.
  3. 3. The method for preparing a phenolic resin-based tin-carbon negative electrode material according to claim 1, wherein the reaction temperature is 40-90 ℃.
  4. 4. The method for preparing the phenolic resin-based tin-carbon anode material according to claim 1, wherein the carbonization temperature is 1200-1600 ℃ and the carbonization time is 1-10h.
  5. 5. The method for preparing a phenolic resin-based tin-carbon negative electrode material according to claim 4, wherein the carbonization temperature is 1300 ℃ and the carbonization time is 3 hours.
  6. 6. The method for preparing the phenolic resin-based tin-carbon anode material according to claim 1, wherein the ammonia water is 25-28% of ammonia water by mass percent.
  7. 7. The method for preparing the phenolic resin-based tin-carbon anode material according to claim 1, wherein the phenolic substance is one of phenol, resorcinol, phloroglucinol and m-aminophenol, and the aldehyde substance is one of formaldehyde and paraformaldehyde.
  8. 8. The method for preparing the phenolic resin-based tin-carbon anode material according to claim 7, wherein the aldehyde substance is an analytically pure formaldehyde aqueous solution or an analytically pure paraformaldehyde powder with the mass percentage of 35-40%.
  9. 9. The preparation method of the phenolic resin-based tin-carbon anode material according to claim 8, wherein when the solid tin source is tin powder or/and tin dioxide powder and the aldehyde substance is an analytically pure formaldehyde aqueous solution, the mass of the solid tin source is calculated in g, the volumes of the analytically pure formaldehyde aqueous solution and ammonia water are calculated in ml, the addition amount ratio of the analytically pure formaldehyde aqueous solution to the solid tin source is 1.56-17.8ml/g, and the addition amount ratio of ammonia water to the solid tin source is 0.078-3.55ml/g.
  10. 10. A phenolic resin-based tin-carbon negative electrode material prepared according to the preparation method of any one of claims 1-9.

Description

Phenolic resin-based tin-carbon negative electrode material and preparation method thereof Technical Field The invention relates to the technical field of sodium-electricity negative electrode materials, in particular to a phenolic resin-based tin-carbon negative electrode material and a preparation method thereof. Background The hard carbon material is a cathode material commonly used for sodium electricity, and has the advantages of long cycle life, high safety, specific capacity, good conductivity and the like compared with a graphite cathode material, so that the hard carbon material becomes the cathode material which is the fastest commercialized in sodium batteries and is widely applied to the fields of new energy automobiles, energy storage and the like. However, the reversible specific capacity of the hard carbon anode material which is commercially applied at present is only about 300mAh/g, and the application range of the sodium battery is limited. If the transition metal element with high specific capacity such as tin is introduced into the hard carbon anode material, the electrochemical performance, especially the specific capacity, of the material can be effectively improved, and the processing performance of the material is not excessively affected when the main component of the material is still the hard carbon material. The phenolic resin has good pyrolysis and carbonization performances, hard carbon with high binding force can be formed in the pyrolysis process at the temperature of more than 1000 ℃, the yield can reach 50%, the phenolic resin is very stable in air, the conductivity can be flexibly controlled along with the heat treatment temperature, the specific surface area is high, and the capacity after being manufactured into a carbon negative electrode can reach more than 330mAh/g, so the phenolic resin becomes one of hot materials for developing a high-capacity electrode. For this reason, in the prior art, a multi-directional attempt is made to prepare a phenolic resin-based tin-carbon negative electrode material, so as to obtain a tin-carbon negative electrode material with higher specific capacity and energy density. For example, chinese patent application No. 201010132581.6 discloses a method for preparing a tin oxide/carbon composite electrode material for a lithium ion battery (application publication No. CN 101800306A), which adopts a solvent blending method to prepare a tin salt and phenolic resin blend, then adds a compound to convert the tin salt into tin oxide, and finally carbonizes to prepare the tin oxide/carbon composite electrode material, wherein the tin salt contains chlorine and other elements, but the introduced tin salt causes serious corrosion to a kiln during carbonization. In order to overcome the technical defects, chinese patent application No. 201110129495.4 discloses a tin-carbon composite material for a lithium ion battery cathode, a preparation method thereof and a lithium ion battery (application publication No. CN 102255079A), wherein a porous high-molecular phenolic resin with high pore volume and high specific surface is prepared by adopting a phenol monomer and an aldehyde monomer, then the porous high-molecular phenolic resin is placed in a tin-containing chloride aqueous solution, tin hydroxide precipitation is formed in holes of the phenolic resin by adding an aqueous ammonia solution, and after high-temperature roasting, the porous high-molecular phenolic resin is cracked and carbonized to obtain a tin-carbon composite material with the tin content of 35-70 w%, the specific capacity of the tin-carbon composite material can reach 605mAh/g at most, the cycling stability is good, and the capacity of the tin-carbon composite material after 20 times of cycling is about 453mAh/g. For example, china patent application No. 201810129376.0 discloses a tin-carbon composite hollow sphere material of a negative electrode of a sodium ion battery and application thereof (application publication No. CN 108376774A), which is prepared by weighing trisaminophenol and tin chloride according to a ratio of 1:3-1:6, dissolving in deionized water, adding formaldehyde and ammonia water, placing the solution on a magnetic stirrer for stirring reaction for 30 minutes to obtain solution A, adding acetone into the solution A for standing, centrifugally separating the solution obtained in the previous step, placing the solution in an oven for drying at a preset temperature to obtain a spherical product B with a hollow structure, placing the powdery product B in a quartz boat, and carbonizing the quartz boat in a high-temperature tubular furnace for a preset time at the preset temperature to obtain the tin-carbon composite hollow sphere material. The battery is assembled into a button cell for testing, the charge-discharge cutoff voltage of the button cell is 0.01-2.6V, and the charge-discharge current is 500mA/g. However, in these technical routes, in order to ensure the uni