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CN-121990550-A - High-sulfur petroleum coke-based carbon negative electrode material and preparation method and application thereof

CN121990550ACN 121990550 ACN121990550 ACN 121990550ACN-121990550-A

Abstract

The invention relates to a high sulfur petroleum coke-based carbon negative electrode material, a preparation method and application thereof, which are characterized in that a non-stoichiometric titanium dioxide coated carbon negative electrode material is obtained through one-step reaction, a titanium source is dissolved in an organic solvent under the condition of liquid phase, adding particles obtained by crushing the high-sulfur petroleum coke, uniformly dispersing a titanium source on the surfaces of the particles obtained by crushing the high-sulfur petroleum coke, and drying to obtain a precursor material with titanium dioxide dispersed on the surfaces of the particles obtained by crushing the high-sulfur petroleum coke. The precursor material is subjected to first calcination and second calcination to prepare the carbon anode material with electrochemical catalytic activity. Compared with the prior art, the invention effectively improves the conductivity of the coating layer and the whole carbon anode material, and on the other hand, the defect center has stronger catalytic property, can improve the reactivity of sulfur element in the carbon anode material and reduce the influence of the sulfur element on the battery performance.

Inventors

  • LI BING
  • HUANG HONGLIANG
  • LU QI
  • XIE TINGTING
  • DUAN YU
  • DONG YUJIA
  • WANG ZHICHENG

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司

Dates

Publication Date
20260508
Application Date
20241107

Claims (10)

  1. 1. The preparation method of the high-sulfur petroleum coke-based carbon anode material is characterized by comprising the following steps of: s1, preprocessing a high-sulfur petroleum coke raw material, namely crushing the high-sulfur petroleum coke raw material to a target particle size, and then drying the crushed high-sulfur petroleum coke raw material at 50-200 ℃ in an air atmosphere, and reducing the water content of the crushed high-sulfur petroleum coke raw material to below 100ppm to obtain preprocessed high-sulfur petroleum coke particles; s2, preparing a titanium-containing solution, namely mixing a titanium source and an organic solvent in a mass ratio of 1:10-50, and then adding anhydrous citric acid into the obtained titanium-containing organic solution, wherein the mass ratio of the titanium-containing organic solution to the anhydrous citric acid is 50-150:1, so as to obtain the titanium-containing solution; S3, coating titanium dioxide, namely uniformly mixing the high-sulfur petroleum coke particles pretreated in the step S1 with the titanium-containing solution obtained in the step S2, and drying; s4, calcining for the first time, namely placing the powder dried in the step S3 into a graphite sagger, and keeping the temperature of 200-400 ℃ for 0.5-2h; s5, fusion granulation, namely mixing the particles prepared in the step S4 with high-softening-point asphalt according to the mass ratio of 100:5-15, and shaping the particles to D50=20-30 mu m by using a fusion coating machine; S6, performing secondary calcination, namely placing the shaped particles in a graphite sagger, heating to 500-700 ℃ at 1-3 ℃ per min under nitrogen atmosphere, heating to 900-1200 ℃ at 5-15 ℃ per min, keeping the temperature for 4-12 hours, and crushing and demagnetizing the particles to obtain the final carbon material.
  2. 2. The method for preparing the high-sulfur petroleum coke-based carbon negative electrode material according to claim 1, wherein the target particle size of crushed high-sulfur petroleum coke raw material in the step S1 is d50=3-6 μm; the sulfur content of the pretreated high-sulfur petroleum coke particles is 3-10 wt%.
  3. 3. The preparation method of the high-sulfur petroleum coke-based carbon cathode material according to claim 1, wherein the titanium source in the step S2 is one or two of n-butyl titanate and isopropyl titanate, The organic solvent is one or more of absolute ethyl alcohol, absolute methyl alcohol and absolute ethylene glycol, The mass ratio of the titanium source to the organic solvent is 1:10-25; the mass ratio of the titanium-containing organic solution to the anhydrous citric acid is 100:1.
  4. 4. The preparation method of the high-sulfur petroleum coke-based carbon cathode material according to claim 1, wherein in the step S3, the mass ratio of the titanium-containing organic solution to the pretreated high-sulfur petroleum coke particles is 0.5-3:100, the drying temperature is 50-200 ℃, and the drying atmosphere is air.
  5. 5. The preparation method of the high-sulfur petroleum coke-based carbon cathode material according to claim 4, wherein the mass ratio of the titanium source to the pretreated high-sulfur petroleum coke particles is 0.5-2:100, and the drying temperature is 80-150 ℃.
  6. 6. The method for preparing a high sulfur petroleum coke-based carbon negative electrode material according to claim 1, wherein the first calcination in step S4 is to raise the temperature to the calcination temperature at 2 ℃ per min under oxygen of 0.01MPa, and naturally cool to room temperature after calcination.
  7. 7. The preparation method of the high-sulfur petroleum coke-based carbon negative electrode material according to claim 1, wherein the mass ratio of the particles obtained by the first calcination in the step S5 to the high-softening-point asphalt is 100:5-10, and the softening point temperature of the asphalt is more than or equal to 250 ℃.
  8. 8. The method for producing a high sulfur petroleum coke-based carbon negative electrode material according to claim 1, wherein the particle breakage classification d50=5 to 8 μm in step S6.
  9. 9. A high sulfur petroleum coke-based carbon negative electrode material produced by the method of any one of claims 1-8.
  10. 10. Use of the high sulfur petroleum coke based carbon negative electrode material according to claim 9, wherein the carbon negative electrode material is used as a negative electrode material of a sodium ion secondary battery.

Description

High-sulfur petroleum coke-based carbon negative electrode material and preparation method and application thereof Technical Field The invention relates to the technical field of sodium ion batteries, in particular to a high-sulfur petroleum coke-based carbon anode material and a preparation method and application thereof. Background The transformation of the social energy structure makes electrochemical energy storage technologies represented by lithium ion secondary batteries widely applied to various commercialized energy storage scenes. However, the lithium resources on the earth are limited, and all the energy storage demands on the world cannot be met, so that searching for the complementary energy storage technology of the lithium ion battery becomes the competitive focus in the new energy field in all countries of the world. The sodium ion secondary battery with similar principle and structure to the lithium ion battery has the advantages of low cost, excellent high-low temperature performance, rate capability and the like, and is considered to have great commercial value in the energy storage field. However, the lack of negative electrode materials, which are subject to both performance and cost, has led to slow development of commercial scale applications of sodium ion batteries. Therefore, it is needed to find a negative electrode material of a sodium ion battery similar to a graphite negative electrode material of a lithium ion battery, which has the characteristics of stable performance, low cost, easy mass production of a preparation process and the like, so that the development bottleneck of large-scale commercial application of the sodium ion secondary battery can be broken through. The carbon material has the characteristics of high conductivity, rich structure, good chemical and physical properties and the like, and is the optimal negative electrode material of the sodium ion battery. The carbon materials can be divided into hard carbon and soft carbon, wherein the hard carbon anode material prepared based on raw materials such as biomass, resin and the like has the advantages of high specific capacity and the like, but the carbon yield is low, the treatment process is complex, the cost is high, and the soft carbon material prepared based on raw materials such as asphalt and the like has low specific capacity. Therefore, the development of the carbon anode material for the sodium ion battery with low cost, high specific capacity and simple process has extremely high value. The high sulfur petroleum coke is used as a crude oil processing byproduct, annual production in China can exceed 1000 ten thousand tons, the price is extremely low, the prepared carbon material has high specific capacity due to the electrochemical activity of sulfur element, the problems of low first week coulomb efficiency, poor cycle life and the like are caused by the accompanying side reaction, and the practical application is limited. Chinese patent CN202211148480.7 discloses a desulfurization and modification method of medium-high sulfur petroleum coke, which comprises the steps of mixing and calcining the medium-high sulfur petroleum coke and a compound treating agent to obtain a treated material, wherein the treating agent comprises a carrier, an active ingredient compounded in the carrier, the active ingredient comprises an ingredient A, an ingredient B and an ingredient C, wherein the ingredient A is at least one nano metal particle of iron and nickel, the ingredient B is at least one nano metal particle of cobalt, molybdenum, potassium and barium, the ingredient C is boron, the molar ratio of the ingredient A to the ingredient B to the ingredient C is 1 (0.01-0.5), the atmosphere in the calcining stage is an ammonia-containing atmosphere and/or a water vapor-containing atmosphere, and the temperature in the calcining stage is 400-800 ℃. A method for preparing graphite by using medium-high sulfur petroleum coke and application of the prepared graphite material in lithium secondary batteries. The technical scheme is a conventional sulfur removal process, and the purpose of removing sulfur elements in the high-sulfur petroleum coke is achieved by utilizing the combined action of ammonia gas and a composite treating agent. According to the technical scheme, the composite treating agent and the semi-calcined desulfurization petroleum coke are separated by screening, and the particle sizes of the composite treating agent and the semi-calcined desulfurization petroleum coke are close, so that a separation effect of 100% cannot be achieved. Meanwhile, the technical scheme can not realize 100% sulfur removal effect, so that the problem of batch stability of the sulfur content of the final material is caused, and the large-scale production is not facilitated. Based on the above, if the electrochemical performance of the carbon material can be ensured without removing sulfur, the method is a better technical scheme. Dis