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Sn4P3 is introduced for the first time as an anode material for Na‐ion batteries. Sn4P3 delivers a high reversible capacity of 718 mA h g−1, and shows very stable cycle performance with negligible capacity fading over 100 cycles, which is attributed to the confinement effect of Sn nanocrystallites in the amorphous phosphorus matrix during cycling.
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