KR-102961103-B1 - ANODE FOR ALUMINIUM SECONDARY BATTERY AND METHOD OF MANUFACTURING THE SAME

Abstract

The present invention relates to a negative electrode for an aluminum secondary battery and a method for manufacturing the same, comprising: a porous MXene current collector; and an aluminum metal formed within the pores of the porous MXene current collector. Since the negative electrode for an aluminum secondary battery according to the present invention includes a porous MXene current collector, it can suppress corrosion of the negative electrode in an ionic liquid-based electrolyte, and since it has a high surface area, it can improve the redox movement performance of aluminum ions. Furthermore, a secondary battery comprising the negative electrode for an aluminum secondary battery according to the present invention can achieve improved charge-discharge cycling stability.

Inventors

• 윤영수
• 김선준
• 허영훈
• 이주연

Assignees

• 고려대학교 산학협력단
• 한국과학기술연구원

Dates

Publication Date

20260507

Application Date

20230821

Claims (10)

1. porous MXene current collector; and Aluminum metal formed within the pores of the above-mentioned porous MXene current collector; comprising, A negative electrode for an aluminum secondary battery, wherein the pore volume of the porous MXene current collector is 0.005 to 0.03 cm³ /g.
2. In Article 1, The above porous MXene current collector comprises one or more materials selected from the group consisting of M 2 X, M 3 X 2 , and M 4 X 3 , for a negative electrode for an aluminum secondary battery. (M is a transition metal, and X is C or N.)
3. In Article 1, The above porous MXene current collector is any one selected from the group consisting of Ti₂C , (Ti 0.5 , Nb 0.5 ) ₂C , V₂C , Nb₂C , Mo₂C , Mo₂N , (Ti 0.5 , Nb 0.5 ) ₂C , Ti₂N , W 1.33C , Nb 1.33C , Mo 1.33C , Mo 1.33Y 0.67C , Ti₃C₂ , TiCN , Zr₃C₂ , Hf₃C₂ , Ti₄N₃ , Nb₄C₃ , Ta₄C₃ , V₄C₃ , ( Mo , V ) ₄C₃ , Mo₄VC₄ , Mo₂TiC₂ , Cr₂TiC₂ , Mo₂ScC₂ , and Mo₂Ti₂C₃ . A negative electrode for an aluminum secondary battery comprising the above material.
4. delete
5. A step of manufacturing a porous MXene current collector having a pore volume of 0.005 to 0.03 cm³ /g; and A method for manufacturing a negative electrode for an aluminum secondary battery, comprising the step of forming aluminum metal in the pores of the porous MXene current collector manufactured above.
6. In Article 5, The step of manufacturing the above porous MXene current collector is, Step of manufacturing MXene; A step of preparing a mixture by mixing the above-mentioned MXene, polymer beads, and solvent; A step of manufacturing a film by vacuum filtering the above-mentioned mixture; and A method for manufacturing a negative electrode for an aluminum secondary battery, comprising the step of heat-treating the above-manufactured film.
7. In Article 6, A method for manufacturing a negative electrode for an aluminum secondary battery, wherein the polymer beads are one or more polymer beads selected from the group consisting of polystyrene beads, polypropylene beads, polycarbonate beads, and polyalomer beads.
8. In Article 6, A method for manufacturing a negative electrode for an aluminum secondary battery, wherein, with respect to 100 volume% of the above mixture, the polymer beads are included in an amount of 1 to 80 volume%.
9. In Article 6, A method for manufacturing a negative electrode for an aluminum secondary battery, wherein the heat treatment temperature is 300 to 700 ℃.
10. Negative electrode for aluminum secondary battery; Electrolyte; and Includes a positive electrode; The negative electrode for the aluminum secondary battery comprises a porous MXene current collector and aluminum metal formed within the pores of the porous MXene current collector, and An aluminum secondary battery having a pore volume of 0.005 to 0.03 cm³ /g of the porous MXene current collector.

Description

Anode for Aluminum Secondary Battery and Method of Manufacturing the Same The present invention relates to a negative electrode for an aluminum secondary battery and a method for manufacturing the same, and more specifically, to a negative electrode for an aluminum secondary battery capable of suppressing electrode corrosion in an electrolyte and a method for manufacturing the same. Aluminum secondary batteries based on multivalent aluminum metal cathodes are promising next-generation energy storage devices that can surpass current lithium-ion secondary batteries in terms of electrochemical performance and mass scalability due to their high specific capacity and volumetric capacity (2,980 mAh/g and 8,046 mAh/ cm³ , respectively) and abundant aluminum resources. However, slow ion transport on the surface of aluminum metal anodes caused by oxide passivation layers significantly hinders the commercialization of aluminum secondary batteries. Therefore, chloroaluminate ionic liquid-based electrolytes with high electrochemical stability are attracting attention as an alternative to conventional oxygen-containing organic electrolyte systems. In ionic liquid-based electrolyte systems , the aluminum oxidation / reduction reaction follows a unique reaction mechanism based on anionic redox chemistry, in which 4Al₂Cl₆₇₀ However, the insufficient reaction kinetics of aluminum metal cathodes delay the charge storage kinetics of aluminum-based dual-ion batteries, limiting their wide range of applications. The reaction kinetics of aluminum metal cathodes are significantly influenced by the migration rate ofAl₂Cl₇⁻ from the electrode surface , as the local anion concentration increases rapidly due to the Al³⁺ reduction reaction. Therefore, three-dimensional electrode design targeting a larger electrochemically active surface area and enhanced anion transport rates is key to the development of high-performance aluminum metal cathodes. However, there was a problem where the electrochemical performance of aluminum-based dual-ion batteries was significantly degraded, as the use of aluminum metal cathodes continued to be difficult due to large volume changes, unexpected dendritic metal growth, and severe morphological changes caused by Lewis acid ionic liquid-based electrolytes. In particular, Lewis acid ionic liquid-based electrolytes are highly corrosive, severely deforming the surface of the aluminum metal cathode and resulting in non-uniform morphology. MXene is a two-dimensional (2D) transition metal carbide and/or nitride with the chemical formula M n+1 X n Tx, where M represents the initial transition metal, X represents carbon and/or nitrogen, n is an integer between 1 and 4, and Tx represents a surface functional group. Due to high electrical conductivity coexisting with high-density surface functional groups, primarily composed of -OH, -O, and -F, MXene can be an unrivaled candidate as a catalytic electrode material that promotes the reversible phase transition reaction of Al ions. The high-density functional groups and negatively charged surfaces have a high affinity for Al ions, which can promote uniform Al metal nucleation and growth. However, two-dimensional MXene sheets tend to form a densely stacked structure during assembly, leading to problems such as poor active surfaces, slow ion transport kinetics, and insufficient electrolyte absorption capacity. Figure 1 is a cross-sectional SEM image of the porous MXene current collector and the negative electrode for an aluminum secondary battery according to the present invention. Figure 2 is an XPS spectrum of a porous MXene current collector manufactured according to one embodiment of the present invention. FIG. 3 is a flowchart illustrating the manufacturing process of the negative electrode for an aluminum secondary battery according to the present invention. Figure 4 is a schematic diagram illustrating the manufacturing process of the porous MXene current collector of the present invention. Figure 5 is a graph of the N2 adsorption-desorption curve of a porous MXene current collector manufactured according to one embodiment of the present invention. Figure 6 is an SEM image of a negative electrode for an aluminum secondary battery manufactured according to one embodiment of the present invention. Figure 7 is an XPS spectrum of Al for a negative electrode for an aluminum secondary battery manufactured according to one embodiment of the present invention. FIG. 8 is a graph showing the EIS profile of a negative electrode for an aluminum secondary battery manufactured according to one embodiment of the present invention. FIG. 9 is a graph showing the electrochemical cathode performance of an aluminum secondary battery negative electrode manufactured according to one embodiment of the present invention. FIG. 10 is a graph showing the aluminum deposition/dissolution profile according to the area current density of a negative electrode for an aluminum secondary battery man