P3/O3 Integrated Layered Oxide As High-Power And Long-Life Cathode Toward Na-Ion Batteries
SMALL(2021)
摘要
Low-cost and stable sodium-layered oxides (such as P2- and O3-phases) are suggested as highly promising cathode materials for Na-ion batteries (NIBs). Biphasic hybridization, mainly involving P2/O3 and P2/P3 biphases, is typically used to boost their electrochemical performances. Herein, a P3/O3 intergrown layered oxide (Na2/3Ni1/3Mn1/3Ti1/3O2) as high-rate and long-life cathode for NIBs via tuning the amounts of Ti substitution in Na2/3Ni1/3Mn2/3-xTixO2 (x = 0, 1/6, 1/3, 2/3) is demonstrated. The X-ray diffraction (XRD) Rietveld refinement and aberration-corrected scanning transmission electron microscopy show the co-existence of P3 and O3 phases, and density functional theory calculation corroborates the appearance of the anomalous O3 phase at the Ti substitution amount of 1/3. The P3/O3 biphasic cathode delivers an unexpected rate capability (approximate to 88.7% of the initial capacity at a high rate of 5 C) and cycling stability (approximate to 68.7% capacity retention after 2000 cycles at 1 C), superior to those of the sing phases P3-Na2/3Ni1/3Mn2/3O2, P3-Na2/3Ni1/3Mn1/2Ti1/6O2, and O3-Na2/3Ni1/3Ti2/3O2. The highly reversible structural evolution of the P3/O3 integrated cathode observed by ex situ XRD, ex situ X-ray absorption spectra, and the rapid Na+ diffusion kinetics, underpin the enhancement. These results show the important role of P3/O3 biphasic hybridization in designing and engineering layered oxide cathodes for NIBs.
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关键词
cathode, electrochemistry, layered oxides, Na‐, ion batteries, P3, O3 biphase
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