Schottky‐Orbital Coupling Drives Ion‐Electron Transfer: Triggering Stable Fast‐Charging in MnV‐Based Phosphate Cathode
Abstract
ABSTRACT Na 4 MnV(PO 4 ) 3 , characterized by cost‐effectiveness, high voltage, and tunable chemical structure, has drawn considerable attention. However, the practical deployment is hindered by drastic local structural distortions induced by over two electron transfers, coupled with intrinsically low electronic conductivity. Herein, a Schottky and 3 d ‐orbital coupling design paradigm is performed to synergistically tailor the TM‐O coordination environment and interfacial structures, thus breaking the dual bottlenecks of poor electrode kinetics and structural fragility. Therefore, the prepared Schottky‐orbital coupling mediated Na 4 MnV(PO 4 ) 3 (SOMV) cathode exhibits continuous multistep redox with a reversible discharge capacity of 143.9 mAh g −1 at 0.1 C. Theoretical calculations and experiment demonstrate that the in‐situ generated metallic Ni 2 P particles establish intimate contact with semiconducting phosphate particles, inducing the built‐in electric field and thus facilitating the coupled ion‐electron transfer and elevating the reaction‐limited current. Eventually, the SOMV cathode achieves a remarkable rate (82.5 mAh g −1 at 30 C) and fast‐charging performance (26 s to reach 88.5 mAh g −1 ). Moreover, the multiple TM 3 d ‐orbital coupling and reinforced TM─O bonds of SOMV grant the excellent long‐term cycling stability (75.0% capacity retention after 10 000 cycles at 30 C). A universal paradigm for boosting the coupled ion‐electron transfer is established via synergistic engineering of electronic and structural properties.
Article Details
Authors (11)
Miao Du
State Key Laboratory of Integrated Optoelectronics and MOE Key Laboratory for UV Light-Emitting Materials and Technology, Department of Physics
Ze‐Lin Hao
State Key Laboratory of Integrated Optoelectronics, and MOE Key Laboratory for UV Light‐Emitting Materials and Technology, Department of Physics Northeast Normal University Changchun China
Jia‐Lin Yang
State Key Laboratory of Integrated Optoelectronics MOE Key Laboratory for UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin China
Xue‐Jiao Nie
Faculty of Chemistry Northeast Normal University Changchun China
Xiao‐Hua Zhang
State Key Laboratory of Metastable Materials Science and Technology and Key Laboratory for Microstructural Material Physics of Hebei Province, School of Science Yanshan University Qinhuangdao China
Igor V. Zatovsky
F.D. Ovcharenko Institute of Biocolloidal Chemistry Kyiv Ukraine
Xin‐Yi Zhang
Faculty of Chemistry Northeast Normal University Changchun China
Yong‐Li Heng
State Key Laboratory of Integrated Optoelectronics, and MOE Key Laboratory For UV Light‐Emitting Materials and Technology Department of Physics Northeast Normal University Changchun Jilin P. R. China
Yan Liu
Jin‐Zhi Guo
State Key Laboratory of Integrated Optoelectronics, and MOE Key Laboratory for UV Light‐Emitting Materials and Technology, Department of Physics Northeast Normal University Changchun China
Xing‐Long Wu
MOE Key Laboratory For UV Light‐Emitting Materials and Technology Northeast Normal University Changchun Jilin P. R. China