KR-20260062451-A - MANUFACTURING METHOD OF CARBON-COPPER TIN SULFIDE COMPOSITE FOR SODIUM SECONDARY BATTERY ANODE MATERIAL

Abstract

The present invention relates to a method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, comprising the steps of: mixing an amine-based surfactant and a thiol-based surfactant to form a surfactant mixture solution; adding carbon powder, tin precursor powder, and copper precursor powder to the surfactant mixture solution to form a reaction preparation solution; and heat-treating the reaction preparation solution to cause a reaction.

Inventors

• 최재원
• 진영호
• 유혜린

Assignees

• 경상국립대학교산학협력단

Dates

Publication Date

20260507

Application Date

20241029

Claims (12)

1. A step of forming a surfactant mixture solution by mixing an amine-based surfactant and a thiol-based surfactant; A step of forming a reaction preparation solution by adding carbon powder, tin precursor powder, and copper precursor powder to the above surfactant mixture solution; and A step comprising the reaction preparation solution heat-treating to react the above-mentioned reaction preparation solution; Method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode.
2. In paragraph 1, A method for preparing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, wherein the above amine-based surfactant comprises one or more selected from the group consisting of oleyl amine, dodecyl amine, lauryl amine, octyl amine, trioctyl amine, dioctyl amine, and hexadecyl amine.
3. In paragraph 1, A method for preparing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, wherein the above-mentioned thiol-based surfactant is an alkane thiol (CnSH, where n is 4≤n≤30).
4. In paragraph 1, A method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, wherein the above-mentioned thiol-based surfactant comprises one or more selected from the group consisting of hexadecane thiol, dodecane thiol, heptadecane thiol, and octadecane thiol.
5. In paragraph 1, A method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, wherein the above amine-based surfactant and the above thiol-based surfactant are mixed in a volume ratio of 1:10 to 1:30.
6. In paragraph 1, A method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, wherein the carbon powder is included in an amount of 3.0 to 4.5 mg per unit volume of 1 mL of the above surfactant mixed solution.
7. In paragraph 1, A method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, wherein the tin precursor powder is included in an amount of 0.005 to 0.015 mg per unit volume of 1 mL of the surfactant mixed solution.
8. In paragraph 1, A method for preparing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode, wherein the copper precursor powder is included in an amount of 0.1 to 0.2 mg per unit volume of 1 mL of the above surfactant mixed solution.
9. In paragraph 1, A method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, wherein the heat treatment is performed for 3 to 5 hours within a range of 200 to 240 ℃.
10. A carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, manufactured by a manufacturing method according to any one of claims 1 to 9.
11. In Paragraph 10, A carbon-copper-tin-sulfide composite for a sodium secondary battery negative electrode material, wherein the carbon body is included in an amount of 50 to 70 parts by weight per 100 parts by weight of the composite.
12. A sodium secondary battery comprising a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material manufactured according to any one of claims 1 to 9.

Description

Manufacturing Method of Carbon-Copper Tin Sulfide Composite for Sodium Secondary Battery Anode Material The present invention relates to a method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material, and more specifically, to a method for manufacturing a carbon-copper-tin sulfide composite for a sodium secondary battery negative electrode material by growing copper-tin sulfide on the surface of a carbon body through a one-pot process using a surfactant. This result is the outcome of the Phase 3 Leading University-Industry Cooperation Project (LINC 3.0), funded by the Ministry of Education and the National Research Foundation of Korea. With the rise of environmental concerns, energy storage technology is having a significant impact on various fields, such as portable electronic devices and electric vehicles, and its importance is increasing. Sodium-ion batteries (SIBs) are being discussed as a next-generation energy storage technology and an alternative to lithium-ion batteries (LIBs). While sodium-ion batteries can offer advantages in terms of an appropriate voltage range and cost, a problem arises where cycle performance degrades during the charge-discharge process because the sodium ion size (1.02 Å) is inherently larger than the lithium ion size (0.76 Å). Accordingly, the selection of the cathode material, which influences the movement of sodium ions between the negative and positive electrodes, is a critical factor. Previous studies have shown that while commercially available graphite is unsuitable for sodium-ion batteries, metal sulfides have been identified as suitable cathode materials. Metal sulfides can generally provide high theoretical capacity by storing sodium ions through intercalation and conversion reactions. Specifically, copper-tin sulfide ( Cu₃SnS₄ ) , a bimetallic sulfide, has been used in semiconductor, photocatalytic, and electrocatalytic applications due to its abundant and non-toxic properties. Copper-tin sulfide can be used as a suitable negative electrode material in sodium-ion batteries because it provides a high theoretical capacity (719.7 mAhg⁻¹ ) through conversion and alloying reactions with sodium ions. However, copper-tin sulfide has limitations in terms of cycle stability due to the low conductivity of metal sulfides and volume expansion that occurs during the sodiumation process. Accordingly, there is a need for research on methods to manufacture materials for sodium secondary battery anodes that offer high theoretical capacity and improved cycle stability using a simple and economical approach. FIG. 1 is a flowchart illustrating a method for manufacturing a carbon-copper-tin sulfide composite according to one embodiment of the present invention. FIG. 2 illustrates an image of copper tin sulfide according to one embodiment of the present invention. Figure 3 is an image illustrating the synthesis process of copper tin sulfide according to temperature in one embodiment of the present invention. Figure 4 is a graph showing the synthesis results of copper-dodecanethiol and copper sulfide according to one embodiment of the present invention. FIG. 5 shows an image of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. FIG. 6 is an elemental mapping image showing the EDS analysis results of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. Figure 7 is a graph showing the XRD analysis results of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. FIG. 8 is a graph showing the results of Raman spectrum analysis of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. Figure 9 is a graph showing the XPS analysis results of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. FIG. 10 is a graph showing the XRD analysis results after thermogravimetric analysis (TGA) of a carbon-copper tin sulfide composite according to one embodiment of the present invention. FIG. 11 is a graph showing the results of the electrochemical performance evaluation of copper tin sulfide according to one embodiment of the present invention. FIG. 12 is a graph showing the results of the electrochemical performance evaluation of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. FIG. 13 is a graph showing the Nyquist plot of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. FIG. 14 is a graph showing the results of the cycle performance evaluation of a carbon-copper-tin sulfide composite according to one embodiment of the present invention. FIG. 15 is a graph showing the results of the cycle performance evaluation of copper sulfide according to one embodiment of the present invention. FIG. 16 is a graph showing the results of the analysis of the overpotential characterist