CN-119315006-B - Carbon nano tube multi-metal sulfide negative electrode material and preparation method and application thereof

Abstract

The invention discloses a carbon nano tube multi-metal sulfide anode material and a preparation method and application thereof. The preparation method comprises the steps of dissolving dicyandiamide in water, adding transition metal chloride salt, stirring to uniformly disperse the transition metal chloride salt, drying and grinding the solution to obtain powder, calcining the powder at high temperature under an inert atmosphere, cooling, grinding, adding a sulfur source, vulcanizing at high temperature, and cooling to obtain the carbon nano tube multi-metal sulfide anode material. According to the invention, dicyandiamide is used as the sole carbon source, and the prepared carbon nano tube multi-metal sulfide negative electrode material has higher specific capacity as a sodium ion battery negative electrode material, and the rate capability of the sodium ion battery negative electrode material is greatly improved, and the cycle stability under high rate is also greatly improved.

Inventors

• HUANG YIGUO
• YE JIANSHAN

Assignees

• 华南理工大学

Dates

Publication Date

20260508

Application Date

20241009

Claims (6)

1. 1. The preparation method of the carbon nano tube multi-metal sulfide anode material is characterized by comprising the following steps of: (1) Dissolving dicyandiamide in water, and fully stirring to obtain dicyandiamide solution with the concentration of 0.25-0.35M; (2) Adding transition metal chloride salt into the dicyandiamide solution obtained in the step (1), and stirring for 1-2 h, wherein the transition metal chloride salt comprises more than two of ferric chloride, cobalt chloride and nickel chloride, and the molar ratio of the total amount of the transition metal chloride salt to the dicyandiamide is 1:10-30; (3) Drying the solution obtained in the step (2) at 80-95 ℃ for 3-5 h, and grinding the obtained solid to obtain powder; (4) Heating the powder obtained in the step (3) to 700-900 ℃ under Ar atmosphere at a heating rate of 2-10 ℃ per minute, calcining for 1-3 hours at high temperature, and cooling to obtain a precursor; (5) Grinding the precursor obtained in the step (4), adding sulfur powder, uniformly mixing, heating the mixture to 400-500 ℃ at a heating rate of 2-5 ℃ per minute under Ar atmosphere for vulcanization for 1.5-3 hours, and cooling to obtain the carbon nano tube multi-metal sulfide anode material.
2. 2. The carbon nanotube multi-metal sulfide negative electrode material prepared by the preparation method of claim 1.
3. 3. A negative electrode sheet comprising the carbon nanotube multi-metal sulfide negative electrode material of claim 2.
4. 4. The preparation method of the negative electrode plate is characterized by comprising the following steps of uniformly mixing the carbon nano tube multi-metal sulfide negative electrode material, the conductive agent and the binder according to a certain proportion, adding N-methyl pyrrolidone as a solvent, stirring to obtain uniform slurry, coating the slurry on a copper foil with a certain thickness, and then drying and cutting to obtain the negative electrode plate.
5. 5. Use of the carbon nanotube-multimetal sulfide negative electrode material according to claim 2 or the negative electrode sheet according to claim 3 for manufacturing a secondary battery.
6. 6. The use according to claim 5, wherein the secondary battery is a sodium ion battery.

Description

Carbon nano tube multi-metal sulfide negative electrode material and preparation method and application thereof Technical Field The invention belongs to the technical field of battery cathode materials, and particularly relates to a carbon nano tube multi-metal sulfide cathode material, and a preparation method and application thereof. Background With the continuous development of civilization, the demand of human beings for energy is increasing, however, fossil fuels as main energy sources of society are nonrenewable and pollute the environment, and for sustainable development of human society, clean renewable energy sources such as solar energy, wind energy, water energy and the like are required to be developed greatly. However, these renewable energy sources have regional and time-efficiency problems, and the secondary battery can store the renewable energy sources as important energy storage devices, so that stable output of the energy sources is realized. Sodium Ion Batteries (SIBs) have low cost, abundant sodium resources, and similar principles of operation as Lithium Ion Batteries (LIBs) as important secondary batteries, and are considered as one of the most promising candidates for the next-generation sustainable energy storage systems. The current common sodium ion battery cathode material is mainly hard carbon, the material has low cost and good cycle stability, but has relatively low specific capacity (about 300 mAh/g), the rate capability is poor, and the mechanism of storing sodium by the hard carbon is controversial so far, which greatly limits the further development of the hard carbon. Therefore, there is an urgent need to find and develop anode materials suitable for sodium ion batteries to meet the practical requirements thereof in energy storage. Transition Metal Sulfides (TMSs) are considered to be very promising anode materials for sodium-ion batteries due to their high theoretical specific capacity. However, transition metal sulfides are semiconductor materials with low conductivity, and at the same time, have large volume changes during sodium modification, are easily aggregated or crushed, and these factors seriously hinder the practical application thereof. Therefore, the development of the transition metal sulfide with high specific capacity and high rate performance as the negative electrode material of the sodium ion battery has very important significance. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a high-rate performance carbon nano tube multi-metal sulfide anode material, and a preparation method and application thereof; the preparation method is simple and low in cost, and the material is applied to the negative electrode material of the sodium ion battery for assembling the sodium ion battery, so that the specific capacity and the rate capability of the electrode are improved, and the long-cycle stability of the battery is also improved. The present invention achieves the above object by the following means. The preparation method of the carbon nano tube multi-metal sulfide anode material comprises the following steps: (1) Dissolving dicyandiamide in water, and fully stirring to obtain dicyandiamide solution (colorless transparent solution); (2) Adding transition metal chloride salt into the dicyandiamide solution obtained in the step (1), and stirring (obtaining transparent solution), wherein the transition metal chloride salt comprises more than two of ferric chloride, cobalt chloride and nickel chloride; (3) Drying the solution obtained in the step (2), and grinding the obtained solid to obtain powder; (4) Heating the powder obtained in the step (3) to 700-900 ℃ under an inert atmosphere, calcining at high temperature, and cooling to obtain a precursor (a metal simple substance encapsulated by black massive solid carbon nano tubes); (5) Grinding the precursor obtained in the step (4), adding a sulfur source, uniformly mixing, heating to 400-500 ℃ in an inert atmosphere, vulcanizing, and cooling to obtain the carbon nano tube multi-metal sulfide negative electrode material (black powder). Preferably, the dicyandiamide solution in step (1) has a concentration of 0.25-0.35M; Preferably, the stirring time in the step (1) is 10-20min. Preferably, step (1) is performed at room temperature. Preferably, the water of step (1) is deionized water. Preferably, the molar ratio of the total amount of the transition metal chloride salt to dicyandiamide in the step (2) is 1:10-30; Preferably, the stirring time in the step (2) is 1-2h. Preferably, step (2) is performed at room temperature. Preferably, the temperature of the drying in step (3) is 80-95 ℃; Preferably, the drying time in the step (3) is 3-5h; Preferably, the powder obtained by grinding in the step (3) is 100-300 mesh material. Preferably, the heating of step (3) is oil bath heating. Preferably, the inert atmosphere of step (4) is Ar; Preferably, the high temperature calcin