Phase Dynamics on Conversion-Reaction-Based Tin-Doped Ferrite Anode for Next-Generation Lithium Batteries

The conventional view of conversion reaction is based on the reversibility, returning to an initial material structure through reverse reaction at each cycle in cycle life, which impedes the complete understanding on a working mechanism upon a progression of cycles in conversion-reaction-based battery electrodes. Herein, a series of tin-doped ferrites (Fe_{3- x}Sn _xO₄, x = 0-0.36) are prepared and applied to a lithium-ion battery anode. By achieving the ideal reoxidation into SnO₂, the Fe_2.76Sn_0.24O₄ composite anchored on reduced graphene oxide shows a high reversible capacity of 1428 mAh g^-1 at 200 mA g^-1 after 100 cycles, which is the best performance of Sn-based anode materials so far. Significantly, a newly formed γ-FeOOH phase after 100 cycles is identified from topological features through synchrotron X-ray absorption spectroscopy with electronic and atomic structural information, suggesting the phase transformation from magnetite to lepidocrocite upon cycling. Contrary to the conventional view, our work suggests a variable working mechanism in an iron-based composite with the dynamic phases from iron oxide to iron oxyhydroxide in the battery cycle life, based on the reactivity of metal nanoparticles formed during reaction toward the solid electrolyte interface layer.