Preparation method and application for metal sulfide hollow microspheres with enriched sulfur vacancies

Patent metadata

Field	Value
Publication number	US-11967716-B2
Application number	US-202217584732-A
Country	US
Kind code	B2
Filing date	Jan 26, 2022
Priority date	Feb 4, 2021
Publication date	Apr 23, 2024
Grant date	Apr 23, 2024

Abstract

Disclosed is a hollow sulfide microsphere with enriched sulfur vacancies, which is prepared by a method comprising the steps of: dissolving cobalt nitrate and nickel nitrate in a mixed solution of N, N-dimethylformamide and acetone with an equal volume; then adding a chelating agent thereto, subjecting a resulting mixture to a solvothermal reaction to obtain a coordination polymer microsphere; dissolving the coordination polymer microsphere and a sulfurization agent in an organic solvent, and reacting to obtain a hollow sulfide microsphere; and subjecting the hollow sulfide microsphere to reduction treatment with sodium borohydride, centrifuging, washing and drying to obtain the hollow sulfide microsphere with enriched sulfur vacancies having a particle size of 1-2.5 μm, a shell thickness of 15-30 nm and a specific capacity of the material of 763.4 C g −1 (current density is 1 A g −1 ).

First claim

What is claimed is:

1. A sulfide hollow microsphere with enriched sulfur vacancies prepared through the following steps:
1) Dissolving cobalt nitrate and nickel nitrate in a mixed solution of N, N-dimethylformamide and acetone to obtain a solution A;
2) Dissolving a chelating agent with a carboxylate group in the solution A to obtain a solution B;
3) Transferring the solution B into a stainless-steel autoclave lined Teflon and reacting at 140-160° C. for 1-5 h, cooling, centrifuging, washing and drying to obtain a coordination polymer microsphere;
4) Dissolving the coordination polymer microsphere and a sulfurization agent in an organic solvent, reacting at 120-160° C. for 0.5-6 h, cooling, centrifuging, washing and drying to obtain a sulfide hollow microsphere;
5) Dispersing the hollow sulfide microsphere in a sodium borohydride solution, stirring for 0.5-2 h, centrifuging, washing and drying to obtain sulfide hollow microspheres with enriched sulfur vacancies;
wherein a particle size and a shell thickness of the sulfide hollow microsphere are 1-2.5 μm and 15-30 nm, respectively; and
the sulfur vacancies accounts for 45.64% to 65.34% in the sulfide hollow microsphere.

2. The sulfide hollow microspheres with enriched sulfur vacancies according to claim 1 , wherein in step 1), a volume ratio of N, N-dimethylformamide and acetone is 1:1, and a molar ratio of cobalt nitrate and nickel nitrate is 2-4:1-2.

3. The sulfide hollow microspheres with enriched sulfur vacancies according to claim 1 , wherein in step 2), the chelating agent is selected from the group consisting of isophthalic acid, trimesic acid, terephthalic acid, and 3,5-pyridinedicarboxylic acid; the chelating agent is dissolved in the solution A and stirred for 6 h, and a molar ratio of the chelating agent to a total amount of cobalt nitrate and nickel nitrate is 1-2:2-4.

4. The sulfide hollow microspheres with enriched sulfur vacancies according to claim 1 , wherein in step 3), the washing treatment is conducted with absolute ethanol, and the drying is under vacuum.

5. The sulfide hollow microspheres with enriched sulfur vacancies according to claim 1 , wherein in step 4), the sulfurization agent is selected from the group consisting of thioacetamide, thiourea, L-cysteine, and sodium sulfide, a mass ratio of the coordination polymer microsphere to the sulfurization agent is 2-4:1-8, the organic solvent is absolute ethanol, and the dispersion is performed with ultrasonic treatment for 15 min.

6. The sulfide hollow microspheres with enriched sulfur vacancies according to claim 1 , wherein in step 4), the washing treatment is conducted with absolute ethanol, and the drying is under vacuum.

7. The sulfide hollow microspheres with enriched sulfur vacancies according to claim 1 , wherein in step 5), a concentration of the sodium borohydride aqueous solution is 0.5-2 mol/L, preferably 1 mol/L, the washing is conducted by deionized water, and the drying is under vacuum.

8. An application of the sulfide hollow microspheres with enriched sulfur vacancies according to claim 1 for preparing electrode materials.

9. The application according to claim 8 , wherein in step 1), a volume ratio of N, N-dimethylformamide and acetone is 1:1, and a molar ratio of cobalt nitrate and nickel nitrate is 2-4:1-2.

10. The application according to claim 8 , wherein in step 2), the chelating agent is selected from the group consisting of isophthalic acid, trimesic acid, terephthalic acid, and 3,5-pyridinedicarboxylic acid, the chelating agent is dissolved in the solution A and stirred for 6 h, and a molar ratio of the chelating agent to a total amount of cobalt nitrate and nickel nitrate is 1-2:2-4.

11. The application according to claim 8 , wherein in step 3), the washing is conducted with absolute ethanol, and the drying is vacuum drying.

12. The application according to claim 8 , wherein in step 4), the sulfurization agent is selected from the group consisting of thioacetamide, thiourea, L-cysteine, and sodium sulfide, a mass ratio of the coordination polymer microsphere to the sulfurization agent is 2-4:1-8, the organic solvent is absolute ethanol, and the dispersion is ultrasonic dispersion for 15 min.

13. The application according to claim 8 , wherein in step 4), the washing is conducted by washing with absolute ethanol, and the drying is under vacuum.

14. The application according to claim 8 , wherein in step 5), a concentration of the aqueous sodium borohydride solution is 0.5-2 mol/L, preferably 1 mol/L, the washing is conducted with deionized water, and the drying is under vacuum.

15. The application according to claim 8 , wherein the electrode material is a battery-type electrode material.

16. The application according to claim 9 , wherein the electrode material is a battery-type electrode material.

17. The application according to claim 10 , wherein the electrode material is a battery-type electrode material.

18. The application according to claim 11 , wherein the electrode material is a battery-type electrode material.

Assignees

• Beijing Institute Tech

Inventors

• Shao Ziqiang
• Jia Shuai
• Wei Jie
• Huang Zhen
• Gong Baixue

Classifications

• C01G53/82 Primary

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M4/5815 Primary

  Sulfides · CPC title

• C01G53/11

  Sulfides; Oxysulfides · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01P2002/85

  by XPS, EDX or EDAX data · CPC title