Room‐temperature Na‐ion batteries (NIBs) have recently attracted attention as potential alternatives to current Li‐ion batteries (LIBs). The natural abundance of sodium and the similarity between the electrochemical properties of NIBs and LIBs make NIBs well suited for applications requiring low cost and long‐term reliability. Here, the first successful synthesis of a series of Na3(VO1−x PO4)2F1+2x (0 ≤ x ≤ 1) compounds as a new family of high‐performance cathode materials for NIBs is reported. The Na3(VO1−x PO4)2F1+2x series can function as high‐performance cathodes for NIBs with high energy density and good cycle life, although the redox mechanism varies depending on the composition. The combined first‐principles calculations and experimental analysis reveal the detailed structural and electrochemical mechanisms of the various compositions in solid solutions of Na3(VOPO4)2F and Na3V2(PO4)2F3. The comparative data for the Na y (VO1−x PO4)2F1+2x electrodes show a clear relationship among V3+/V4+/V5+ redox reactions, Na+−Na+ interactions, and Na+ intercalation mechanisms in NIBs. The new family of high‐energy cathode materials reported here is expected to spur the development of low‐cost, high‐performance NIBs.
Large-scale electric energy storage is a key enabler for the use of renewable energy. Recently, the room-temperature Na-ion battery has been rehighlighted as an alternative low-cost technology for this application. However, significant challenges such as energy density and long-term stability must be addressed. Herein, we introduce a novel cathode material, Na1.5VPO4.8F0.7, for Na-ion batteries. This new material provides an energy density of ~600 Wh kg(-1), the highest value among cathodes, originating from both the multielectron redox reaction (1.2 e(-) per formula unit) and the high potential (~3.8 V vs Na(+)/Na) of the tailored vanadium redox couple (V(3.8+)/V(5+)). Furthermore, an outstanding cycle life (~95% capacity retention for 100 cycles and ~84% for extended 500 cycles) could be achieved, which we attribute to the small volume change (2.9%) upon cycling, the smallest volume change among known Na intercalation cathodes. The open crystal framework with two-dimensional Na diffusional pathways leads to low activation barriers for Na diffusion, enabling excellent rate capability. We believe that this new material can bring the low-cost room-temperature Na-ion battery a step closer to a sustainable large-scale energy storage system.
Battery chemistry based on earth-abundant elements has great potential for the development of cost-effective, large-scale energy storage systems. Herein, we report, for the first time, that maricite NaFePO 4 can function as an excellent cathode material for Na ion batteries, an unexpected result since it has been regarded as an electrochemically inactive electrode for rechargeable batteries. Our investigation of the Na re-(de)intercalation mechanism reveals that all Na ions can be deintercalated from the nano-sized maricite NaFePO 4 with simultaneous transformation into amorphous FePO 4 . Our quantum mechanics calculations show that the underlying reason for the remarkable electrochemical activity of NaFePO 4 is the significantly enhanced Na mobility in the transformed phase, which is $one fourth of the hopping activation barrier. Maricite NaFePO 4 , fully sodiated amorphous FePO 4 , delivered a capacity of 142 mA h g À1 (92% of the theoretical value) at the first cycle, and showed outstanding cyclability with a negligible capacity fade after 200 cycles (95% retention of the initial cycle).The demand for large-scale energy storage systems (EESs) has prompted considerable effort in the development of new types of batteries with cost-effective and sustainable properties. While the high cost of current Li ion batteries (LIBs) remains one of the major hurdles towards large-scale energy storage applications, 1-12 battery chemistry based on earth-abundant elements offers a feasible solution. Recently, Na ion batteries (NIBs) have been considered as a promising alternative to LIBs since the underlying electrochemical reaction is similar to that of LIBs, but is based on the unlimited resources of Na from seawater. [13][14][15][16][17][18][19][20] The use of redox chemistry using earth abundant transition metals would provide the optimal combination with Na electrochemistry further highlighting the advantage of NIBs.In recent years, considerable research has been carried out on Fe-based electrode materials for use in NIBs. Broader contextWe report, for the rst time, that maricite NaFePO 4 can function as an excellent cathode material for Na ion batteries, an unexpected result since it has been regarded as an electrochemically inactive electrode for rechargeable batteries. Our investigation of the Na re-(de)intercalation mechanism reveals that all Na ions can be deintercalated from the nanosized maricite NaFePO 4 with simultaneous transformation into amorphous FePO 4 . Our quantum mechanics calculations show that the underlying reason for the remarkable electrochemical activity of NaFePO 4 is the signicantly enhanced Na mobility in the transformed phase, which is $one fourth of the hopping activation barrier. Maricite NaFePO 4 , fully sodiated amorphous FePO 4 , delivered a capacity of 142 mA h g À1 (92% of the theoretical value) at the rst cycle, and showed outstanding cyclability with a negligible capacity fade aer 200 cycles (95% retention of the initial cycle).540 | Energy Environ. Sci., 2015, 8, 540-545This jour...
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