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Öğe Full-Scale Regulation Enabled High-Performance Sodium O3-Type Layered Cathodes(Wiley-V C H Verlag Gmbh, 2025) Hong, Ningyun; Zhang, Shuncheng; Li, Jianwei; Wang, Haoji; Huang, Jiangnan; Hu, Xinyu; Zhang, BaichaoO3-type cathodes hold considerable promise in achieving rapid commercialization due to high energy density. However, severe structural/interfacial deterioration, along with kinetic hindrance, typically resulting in rapid capacity fading and serious safety risk at elevated cut-off voltages. Herein, inspired from solubility limitation of hetero-elements, synchronous surface-to-bulk multifunctionally full-scale modified O3-NaNi1/3Fe1/3Mn1/3O2 is proposed to maintain its state of health (SOH). The perovskite-type CaZrO3 protective layer in situ formed on the surface of primary particles, helps to construct a stable cathode-electrolyte-interphase architecture, mitigate the unexpected interfacial side reactions and prevent transition metal dissolution. Simultaneously, Ca2+ pillars, robust Zr-O bonds and the highly electronegative F- are adequately anchored into ternary lattice sites of Na-TM-O, respectively, thereby reinforcing the TMO6 octahedra and facilitating Na+ diffusion. Notably, the intrinsic lattice strain is effectively alleviated due to an additional intergrowth phase transition of P3-OP2. More impressively, migration of Jahn-Teller distorted Fe4+O6 is further restrained, originating from the strengthened coordination environment under deep-desodiation state. Consequently, as-designed NFM-CZF achieves an impressive rate capability and a remarkable capacity retention of 83.8 % after 300 cycles at 2 C. This elaborate work shed valuable insight into mechanism of regulating internal full Wyckoff-site and external surface structure for sodium-ion batteries with enhanced durability.Öğe An in situ dual-modification strategy for O3-NaNi1/3Fe1/3Mn1/3O2 towards high-performance sodium-ion batteries(Royal Soc Chemistry, 2023) Hong, Ningyun; Li, Jianwei; Guo, Shihong; Han, Huawei; Wang, Haoji; Hu, Xinyu; Huang, JiangnanO3-type NaNi1/3Fe1/3Mn1/3O2 (NFM) is one of the most representative cathode materials with low cost and high capacity advantages. However, the sluggish diffusion kinetics and severe cathode-electrolyte interfacial reaction are serious roadblocks to commercialization. Hereby, a novel method of in situ V-modification is well-designed to play dual roles in reconstructing the crystal lattice and interface structure. Notably, the broadened layer spacing of O-Na-O and shortened TM-O bond are attributed to successful doping of V5+ into the bulk, accelerating the transmission of sodium ions and improving the structure stability. Concomitantly, the construction of a thin surface coating layer is beneficial for mitigating volume expansion and inhibiting structural degradation, which is validated by in situ X-ray diffraction coupled with the synchrotron X-ray absorption spectroscopy. Consequently, the rationally designed V-modified NFM cathode exhibits excellent cycling performances, exhibiting great capacity retention of 75.8% after 500 cycles at 2C in a half cell, and 85.6% capacity retention is observed after 150 cycles at 1C in the full cell. This work provides new insights into the development of O3-type layered oxide cathodes toward long-cycle life applications for large-scale energy storage systems.











