CoSe2 / ZnSe-coated C HS hollow nanosphere material and preparation method thereof

By preparing CoSe2/ZnSe@C HS hollow nanosphere material, using hollow spherical porous carbon matrix and uniformly distributed CoSe2/ZnSe particles, the problems of sodium ion battery material's volume expansion and low conductivity in the conversion reaction are solved, and high rate performance and cycling stability are achieved.

CN120048885APending Publication Date: 2025-05-27BEIFANG UNIV OF NATITIES
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Patent Information

Application Number
CN202510248012.4
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-03-04
Publication Date
2025-05-27

AI Technical Summary

Technical Problem

The existing sodium ion battery materials have problems of volume expansion and low electronic conductivity in the conversion reaction, which affects the rate performance and cycle stability.

Method used

By preparing CoSe2/ZnSe@C HS hollow nanosphere material, which consists of a hollow spherical porous carbon matrix and uniformly distributed CoSe2/ZnSe particles, the ZIF-67/ZIF-8 hollow nanosphere material is generated by reacting metal salts with ligands, and the final material is formed by pyrolysis reduction and selenization treatment.

Benefits of technology

Through the synergistic effect of the hollow structure and porous carbon matrix, this material effectively alleviates volume expansion, improves electronic conductivity and cycling stability, and enhances the rate performance and Coulomb efficiency of sodium ion batteries.

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Abstract

The invention relates to the technical field of energy storage nanomaterials, and provides a CoSe2 / ZnSe-C HS hollow nanosphere material and a preparation method thereof.The preparation method comprises the steps that a ZIF-67 / ZIF-8 hollow nanosphere material is assembled and constructed through combination of deprotonated ligands and metal ions; the preparation method comprises the following steps: performing pyrolysis reduction on a ZIF-67 / ZIF-8 hollow nanosphere to prepare a Co / Zn-C HS hollow nanosphere material; and carrying out a derivatization reaction on the Co / Zn-coated C HS hollow nanosphere through a selenylation reaction to form the CoSe2 / ZnSe-coated C HS hollow nanosphere material composed of the hollow spherical porous carbon material matrix and CoSe2 / ZnSe particles distributed in the hollow spherical porous carbon material matrix. When the CoSe2 / ZnSe-coated C HS hollow nanosphere material is used as a negative electrode material of a sodium ion battery, volume expansion in the charging and discharging process can be effectively relieved, the capacity of the battery is improved, and the cycling stability of the battery is enhanced.
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Claims

1. A CoSe2 / ZnSe@C HS hollow nanosphere material, characterized in that: The material consists of a hollow spherical porous carbon material matrix and CoSe2 / ZnSe particles distributed in the hollow spherical porous carbon material matrix.

2. The CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 1, characterized in that: The material is prepared by reacting cobalt sulfate heptahydrate, zinc nitrate hexahydrate, methanol, 2-methylimidazole and selenium powder.

3. The CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 1, characterized in that: The material is prepared by the following method: A hollow spherical carbon material matrix coated with metal is generated by reacting a metal salt with a ligand; The hollow spherical carbon material matrix coated with metal is pyrolyzed and reduced to generate a hollow spherical porous carbon material matrix coated with intermetallic compounds and carbides; The hollow spherical porous carbon material coated with CoSe2 / ZnSe particles is generated by selenizing a hollow spherical porous carbon material matrix coated with an intermetallic compound and a carbide.

4. A method for preparing CoSe2 / ZnSe@C HS hollow nanosphere material, characterized in that: The preparation method comprises: Through the deprotonated ligands binding metal ions, ZIF-67 / ZIF-8 hollow nanosphere materials were assembled and constructed; Co / Zn@C HS hollow nanospheres were prepared by pyrolysis reduction of ZIF-67 / ZIF-8 hollow nanospheres. Co / Zn@C HS hollow nanospheres were derived into CoSe2 / ZnSe@C HS hollow nanosphere materials through selenization reaction.

5. The method for preparing the CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 4, characterized in that: The preparation method comprises the following steps: Step S1: mixing cobalt sulfate heptahydrate and zinc nitrate hexahydrate in methanol to form a metal salt dissociation solution; Step S2: mixing 2-methylimidazole into a methanol solution to generate a deprotonated 2-methylimidazole solution; Step S3: adding the metal salt dissociation solution to the deprotonated 2-methylimidazole solution to perform an assembly reaction to generate a ZIF-67 / ZIF-8 hollow nanosphere material; Step S4: preheating and pyrolysis reduction of the ZIF-67 / ZIF-8 hollow nanosphere material in sequence to obtain the Co / Zn@CHS hollow nanosphere material; Step S5: using selenium powder to perform high-temperature selenization reaction on the Co / Zn@C HS hollow nanosphere material to obtain the CoSe2 / ZnSe@CHS hollow nanosphere material.

6. The method for preparing the CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 5, characterized in that: Step S1 comprises: preparing a premix of cobalt sulfate heptahydrate and zinc nitrate hexahydrate in a molar ratio of 63:7-63:567, and adding 10 mmol of the premix into 200 mL of methanol to form a metal salt dissociation solution.

7. The method for preparing the CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 5, characterized in that: Step S2 comprises: adding 10 mmol of 2-methylimidazole solution into 200 mL of methanol to generate a deprotonated 2-methylimidazole solution.

8. The method for preparing the CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 5, characterized in that: Step S3 comprises: mixing the metal salt dissociation solution and the deprotonated 2-methylimidazole solution in a volume ratio of 1:1, stirring at room temperature for 4 hours, centrifuging, washing and drying the reaction product in sequence to obtain a ZIF-67 / ZIF-8 hollow nanosphere material.

9. The method for preparing the CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 5, characterized in that: Step S4 includes: placing the ZIF-67 / ZIF-8 hollow nanosphere material in an inert gas environment, heating the temperature to 80°C at a heating rate of 2°C / min, and then keeping the temperature for 0.5h, then heating the temperature to 700°C at a heating rate of 2°C / min, and then keeping the temperature for 2h, and naturally cooling to room temperature to obtain Co / Zn@C HS hollow nanosphere material.

10. The method for preparing CoSe2 / ZnSe@C HS hollow nanosphere material according to claim 5, characterized in that: Step S5 comprises: mixing and grinding the Co / Zn@C HS hollow nanosphere material and selenium powder in a weight ratio of 1:1 for 10 minutes, placing the ground product in an inert gas environment, heating the temperature to 80° C. at a heating rate of 2° C. / min and then keeping the temperature for 0.5 hours, then heating the temperature to 400° C. at a heating rate of 2° C. / min and then keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain CoSe2 / ZnSe@C HS hollow nanosphere material.