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 “Sn$_{4}$P$_{3}$”/NHC electrode (with nominal composition “Sn$_{4}$P$_{3}$”: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 g$_{electrode}$$^{−1}$ at 50 mA g$^{−1}$ and 440 mAh g$_{electrode}$$^{−1}$ over 500 cycles (83% capacity retention). Morphology and solid electrolyte interphase formation of cycled “Sn$_{4}$P$_{3}$”/NHC electrodes is studied via electron microscopy and X-ray photoelectron spectroscopy. The expansion of the electrode upon sodiation (300 mAh g$_{electrode}$$^{−1}$) is only about 12–14% as determined by in situ electrochemical dilatometry, giving a reasonable explanation for the excellent cycle life despite the conversion-type storage mechanism. In situ X-ray diffraction shows that the discharge product is Na$_{15}$Sn$_{4}$. The formation of mostly amorphous Na$_{3}$P is derived from the overall (electro)chemical reactions. Upon charge the formation of Sn is observed while amorphous P is derived, which are reversibly alloying with Na in the subsequent cycles. However, the formation of Sn$_{4}$P$_{3}$ can be certainly excluded.
