Identifying the effect of fluorination on cation and anion redox activity in Mn based cation-disordered cathode
Li-rich disordered rock-salt cathode (DRX) materials with advantage of low cost, long cycle life, nature abundant resource and high power and energy density attracted a great deal of scholarly attention. However, the poor cycle stability and the unclear realization of cation and anion redox activity in low-cost element system have severely hindered the construction of high-performance DRX. Herein, a promising class of Ti-Mn based cathode materials Li 1.25 Mn 0.25 Nb 0.25 Ti 0.25 O 2 and Li 1.25 Mn 0.25 Ti 0.5 O 1.75 F 0.25 were designed and successfully synthesized to construct high energy density DRX and investigate the effect of fluorination on cation and anion redox activity. The results show that both fluoridized and unfluoridized DRX possess a similar structure ( Fm -3 m), but distinctly different charge/discharge profiles. The fluoridized cathode shows high initial charge/discharge capacity of 317.3/283.9 mAh g −1 , specific energy density of 1370.4/735.5 Wh kg −1 and stable capacity retention with a discharge capacity of 202.6 mAh g −1 after 20 cycles at 20 mA g −1 . Combining relevant spectroscopic results and HRTEM images, we revealed that the excellent cyclability of Li 1.25 Mn 0.25 Ti 0.5 O 1.75 F 0.25 is rooted in the weakened adverse effects of moderated oxygen redox and the reduced Jahn–Teller distortion effect resulting from Mn 3+ , endowing the fluoridized DRX with better structural stability and larger Mn 2+ /Mn 4+ reservoir. The strategy of constructing low cost oxyfluoride and the understanding of the mechanism of fluorination induced cation and anion redox activity would provide reference for the development of high-performance DRX materials.
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