Assessment on the Use of High Capacity “Sn4P3”/NHC Composite Electrodes for Sodium‐Ion Batteries with Ether and Carbonate Electrolytes

This work reports the facile synthesis of a Sn–P composite combined with nitrogen doped hard carbon (NHC) obtained by ball‐milling and its use as electrode material for sodium ion batteries (SIBs). The “Sn4P3”/NHC electrode (with nominal composition “Sn4P3”:NHC = 75:25 wt%) when coupled with a diglyme‐based electrolyte rather than the most commonly employed carbonate‐based systems, exhibits a reversible capacity of 550 mAh gelectrode−1 at 50 mA g−1 and 440 mAh gelectrode−1 over 500 cycles (83% capacity retention). Morphology and solid electrolyte interphase formation of cycled “Sn4P3”/NHC electrodes is studied via electron microscopy and X‐ray photoelectron spectroscopy. The expansion of the electrode upon sodiation (300 mAh gelectrode−1) is only about 12–14% as determined by in situ electrochemical dilatometry, giving a reasonable explanation for the excellent cycle life despite the conversion‐type storage mechanism. In situ X‐ray diffraction shows that the discharge product is Na15Sn4. The formation of mostly amorphous Na3P is derived from the overall (electro)chemical reactions. Upon charge the formation of Sn is observed while amorphous P is derived, which are reversibly alloying with Na in the subsequent cycles. However, the formation of Sn4P3 can be certainly excluded.