Stabilizing the structure of LiMn0.5Fe0.5PO4 via the formation of concentration-gradient hollow spheres with Fe-rich surfaces

RIS ID

133883

Publication Details

Ruan, T., Wang, B., Wang, F., Song, R., Jin, F., Zhou, Y., Wang, D. & Dou, S. (2019). Stabilizing the structure of LiMn0.5Fe0.5PO4 via the formation of concentration-gradient hollow spheres with Fe-rich surfaces. Nanoscale, 11 (9), 4073-4082.

Abstract

LiMn x Fe 1-x PO 4 (LMFP) has attracted extensive interest owing to its high safety and appropriate redox potential. Nevertheless, its poor electrochemical kinetics and structural instability, depending on its manganese content, are still limiting its further application. Herein, we realize a concentration-gradient LiMn 0.5 Fe 0.5 PO 4 hollow sphere cathode material with a carbon coating (HCG-LMFP/C) by a facile and controllable two-step solvothermal approach. On the one hand, the porous hollow architecture can sustain excellent structural stabilization against the volume changes that occur during repeated Li + intercalation/deintercalation. On the other hand, the unique concentration-gradient structure with its Fe-rich surface can not only relieve interface deterioration and improve the ionic/electric conductivity due to the active nature of LiFePO 4 , but also guarantees the chemical stability of the LMFP against electrolyte attack and remarkably reduces Mn dissolution, even at elevated temperature. Therefore, the obtained concentration-gradient HCG-LMFP/C cathode shows improved high-rate performance (111 and 78 mA h g -1 at 20 and 60C rates, respectively) and excellent capacity retention (96% after 1000 cycles at the 10C rate) as well as outstanding temperature tolerance (over a temperature range from 40 °C to -10 °C). More importantly, the present gradient strategy opens up a new window for designing high-performance and stable olivine cathodes, which could also be compatible with many other energy-storage materials for various applications.

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Link to publisher version (DOI)

http://dx.doi.org/10.1039/c8nr10224d