CN-121990551-A - Sodium ion battery carbon negative electrode material based on high-sulfur petroleum coke, and preparation method and application thereof

CN121990551ACN 121990551 ACN121990551 ACN 121990551ACN-121990551-A

Abstract

The invention relates to a sodium ion battery carbon cathode material based on high sulfur petroleum coke, a preparation method and application thereof, wherein the high sulfur petroleum coke raw material is crushed into a target particle size, and then under the air atmosphere, adding a sulfur-fixing agent, an inhibitor and a surface modifier, carrying out fusion granulation, carrying out gradient heating treatment, depolymerizing and demagnetizing to obtain the carbon anode material. Compared with the prior art, the method can realize the chemical transformation process of sulfur in the high-sulfur petroleum coke, and the method is accompanied with structural reforming of the petroleum coke, and endows the material with rich pores so as to solve the problem of damage of sulfur escape to the material structure. Research shows that the material prepared by the method has excellent gram capacity and long cycle life.

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. A preparation method of a sodium ion battery carbon negative electrode material based on high-sulfur petroleum coke is characterized by comprising the following steps of crushing a high-sulfur petroleum coke raw material to a target particle size, adding a sulfur-fixing agent, an inhibitor and a surface modifier in an air atmosphere, carrying out fusion granulation, carrying out gradient heating treatment, depolymerizing and demagnetizing, and obtaining the carbon negative electrode material.
2. The method for preparing the sodium ion battery carbon cathode material based on the high-sulfur petroleum coke, which is characterized in that the high-sulfur petroleum coke is a byproduct obtained by treating residual oil through a delayed coking process in the crude oil refining process; the target particle size of crushed high sulfur petroleum coke raw material is D50=3-10 μm; the sulfur content in the high sulfur petroleum coke particles is greater than or equal to 2.4wt%.
3. The method for preparing a sodium ion battery carbon negative electrode material based on high sulfur petroleum coke according to claim 1, wherein the sulfur-fixing agent comprises a component A and a component B, the chemical formula is A m+x B n-y , m is the absolute value of the valence of A, n is the absolute value of the valence of B, and xxm=yxn; The component A is at least one of zinc, iron and manganese, and the component B is at least one of NO 3 - 、CH 3 COO - 、OH - 、HCO 3 - 、O 2 - .
4. The method for preparing the sodium ion battery carbon negative electrode material based on the high-sulfur petroleum coke, which is disclosed in claim 1, is characterized in that the inhibitor is one or more of Na 3 PO 4 ,Mg 2 (PO 4 ) 3 ,Ca 2 (PO 4 ) 3 .
5. The method for preparing the sodium ion battery carbon negative electrode material based on the high-sulfur petroleum coke, which is disclosed in claim 1, is characterized in that the surface modifier is asphalt, phenolic resin, glucose or sucrose.
6. The preparation method of the sodium ion battery carbon cathode material based on the high-sulfur petroleum coke, which is disclosed in claim 1, is characterized in that the mass ratio of the high-sulfur petroleum coke, the inhibitor and the surface modifier is 100:0.5-2:10-20; the addition amount of the sulfur-fixing agent needs to satisfy the equation 1, wherein the addition amount of the sulfur-fixing agent is = [ (mass of high sulfur petroleum coke is the sulfur content)/molecular molar mass of sulfur ].
7. The method for preparing the sodium ion battery carbon cathode material based on the high-sulfur petroleum coke, which is characterized in that the gradient heating treatment comprises first-stage calcination and second-stage calcination; The first-stage calcination is carried out in an inert atmosphere, wherein the temperature T1 of the first-stage calcination is 200-350 ℃, the temperature rising rate is 1-5 ℃ per minute, and the calcination time is 2-4 hours; The temperature T2 of the second stage calcination is 900-1300 ℃, the temperature rising rate is 5-10 ℃ per minute, and the calcination time is 4-20h.
8. The preparation method of the sodium ion battery carbon cathode material based on the high-sulfur petroleum coke, which is disclosed in claim 7, is characterized in that the inert atmosphere is one or a mixture of a plurality of gases including nitrogen, argon and hydrogen, and the inert gas pressure in the calcination process is 10 Pa-100 Pa.
9. A sodium ion battery carbon negative electrode material based on high sulfur petroleum coke prepared by the method of any one of claims 1-8.
10. Use of the carbon negative electrode material for sodium ion battery based on high sulfur petroleum coke according to claim 9, wherein the carbon negative electrode material is used as a negative electrode material for sodium ion secondary battery.

Description

Sodium ion battery carbon negative electrode material based on high-sulfur petroleum coke, and preparation method and application thereof Technical Field The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery carbon negative electrode material based on high-sulfur petroleum coke, and a preparation method and application thereof. Background Based on the 'double carbon' target, new energy power generation modes such as wind energy, solar energy and the like are rapidly developed, but the instability of intermittent power generation brings great challenges to a power grid. Energy storage can greatly alleviate the problem, and sodium ion batteries are receiving great attention as an important technical means for energy storage. The sodium ion battery mainly comprises a positive electrode material, a negative electrode material, an electrolyte, a separator and a current collector, wherein the carbon-based negative electrode material is considered as the optimal negative electrode material of the sodium ion battery. Low cost, high performance carbon negative electrode materials are one of the factors restricting commercial application of sodium ion batteries. The carbon negative electrode material can be divided into hard carbon and soft carbon, wherein the hard carbon material represented by biomass and resin has faster development, but the large-scale application of the sodium ion battery is greatly influenced by the higher price. As a representative of soft carbon, petroleum coke is a petrochemical byproduct, has the characteristics of large supply quantity, stable yield, high consistency and the like, and is regarded as a carbon source of a sodium ion battery carbon cathode material with commercial potential. Depending on the sulfur content, petroleum cokes can be classified into low sulfur petroleum cokes, medium sulfur petroleum cokes, and high sulfur petroleum cokes, wherein low sulfur petroleum cokes benefit from a wide range of application scenarios and are on demand. The high sulfur petroleum coke suffers from the disadvantages of higher sulfur content, more impurities and the like, and cannot be applied to the scene of low sulfur petroleum coke, so that a solution is needed. At present, the application of the low-cost high-sulfur petroleum coke in the carbon cathode material of the sodium ion battery is rarely reported. The method is characterized in that (1) the petroleum coke is easy to generate graphitization transformation at high temperature, so that the capability of storing sodium ions is poor, and therefore, the carbonization treatment temperature needs to be strictly controlled, (2) sulfur in the high-sulfur petroleum coke is mainly organic sulfur, the ratio of the sulfur is usually more than 90%, the removal difficulty is high, especially at lower carbonization temperature, (3) the structure of a carbon material is seriously influenced by an improper desulfurization process such as a chemical method, so that the electrochemical performance of the carbon material is deteriorated, and (4) the sulfur in the carbon material can have adverse effects on a sodium ion battery, such as the reduction of the cycle life of the battery, the energy density of the battery, and the like. Therefore, how to obtain sulfur-containing carbon anode materials prepared based on medium-high sulfur petroleum coke without desulfurization is a great technical challenge. Currently, there is no corresponding solution within the industry. Chinese patent CN 202211181805.1 discloses a method for preparing a graphite anode material based on high-sulfur petroleum coke, which comprises the steps of mixing the high-sulfur petroleum coke, a sulfur regulator and a surface modifier, granulating to prepare pellets, carrying out first-stage roasting on the pellets, carrying out second-stage roasting under negative pressure, and finally graphitizing and roasting to prepare the graphite anode material, wherein the sulfur content of the high-sulfur petroleum coke is more than or equal to 3%, the sulfur regulator comprises a component A and a component B, the component A is (NH 4+)n X, wherein X is an anion, n is the absolute value of the valence of the anion, the component B is MCl m, wherein M is a cation, and M is the valence of the cation. Disclosure of Invention The invention aims to overcome the defects in the prior art and provide a sodium ion battery carbon negative electrode material based on high-sulfur petroleum coke, a preparation method and application thereof, and the low-cost and high-performance carbon negative electrode material is prepared by using low-cost medium-high-sulfur petroleum coke. The invention solves the problem that the sulfur element has an influence on the battery performance deterioration on the premise of keeping the sulfur element in the high-sulfur petroleum coke, thereby avoiding the problems of carbon material structure transformation, material el