Strong Covalent Metal-Ligand Interaction Enables a Fast Kinetic and Structurally Stable Na-Ion Layered Cathode.

Autor: Li JC; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Xu S; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Tian J; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Peng B; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China., Sun Y; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Tang J; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China., Liu Z; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Liu Y; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China., Zuo D; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Xu C; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Rao Y; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China., Deng Y; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China., Zhou H; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China., Guo S; College of Engineering and Applied Sciences, Jiangsu Key Laboratory of Artificial Functional Materials, National Laboratory of Solid State Microstructures, Collaborative Innovation Centre of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, 210093, P. R. China.; Lab of Power and Energy Storage Batteries, Shenzhen Research Institute of Nanjing University, Shenzhen, 518057, P. R. China.
Jazyk: angličtina
Zdroj: ChemSusChem [ChemSusChem] 2024 Aug 27, pp. e202401538. Date of Electronic Publication: 2024 Aug 27.
DOI: 10.1002/cssc.202401538
Abstrakt: Anionic redox chemistry has attracted increasing attention for the improvement in the reversible capacity and energy density of cathode materials in Li/Na-ion batteries. However, adverse electrochemical behaviors, such as voltage hysteresis and sluggish kinetics resulting from weak metal-ligand interactions, commonly occur with anionic redox reactions. Currently, the mechanistic investigation driving these issues still remains foggy. Here, we chemically designed Na 0.8 Fe 0.4 Ti 0.6 S 2 and Na 0.8 Fe 0.4 Ti 0.6 O 2 as model cathodes to explore the covalency effects on metal-ligand interactions during anionic redox process. Na 0.8 Fe 0.4 Ti 0.6 S 2 with strengthened covalent interaction of metal-ligand bonds exhibits smaller voltage hysteresis and faster kinetics than Na 0.8 Fe 0.4 Ti 0.6 O 2 during (de)sodiation process. Theoretical calculations suggest that Fe is the dominant redox-active center in Na 0.8 Fe 0.4 Ti 0.6 S 2 , whereas the redox-active center moves from Fe to O with the removal of Na + in Na 0.8 Fe 0.4 Ti 0.6 O 2 . We attribute the above different redox behaviors between Na 0.8 Fe 0.4 Ti 0.6 S 2 and Na 0.8 Fe 0.4 Ti 0.6 O 2 to the charge transfer kinetics from ligand to metal. Moreover, the structural stability of Na 0.8 Fe 0.4 Ti 0.6 S 2 is enhanced by increasing the cation migration barriers through strong metal-ligand bonds during desodiation. These insights into the originality of metal-ligand interactions provide guidance for the design of high-capacity and structurally stable cathode materials for Li/Na-ion batteries.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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