Although studies of transition metal sulfides (TMS) as anode materials for sodium-ion batteries are extensively reported, the short cycle life is still a thorny problem that impedes their practical application. In this work, a new capacity fading mechanism of the TMS electrodes is demonstrated; that is, the parasitic reaction between electrolyte anions (i.e., ClO4 - ) and metal sulfides yields non-conductive and unstable solid-electrolyte interphase (SEI) and meanwhile, corrosively turns metal sulfides into less-active oxides. This knowledge guides the development of an electrochemical strategy to manipulate the anion decomposition and construct a stable interface that prevents extensive parasitic reactions. It is shown that introducing sodium nitrate to the electrolyte radically changes the Na+ solvation structure by populating nitrate ions in the first solvation sheath, generating a stable and conductive SEI layer containing both Na3 N and NaF. The optimized interface enables an iron sulfide anode to stably cycle for over 2000 cycles with negligible capacity loss, and a similar enhancement in cycle performance is demonstrated on a number of other metal sulfides. This work discloses metal sulfides' cycling failure mechanism from a unique perspective and highlights the critical importance of manipulating the interface chemistry in sodium-ion batteries.
Keywords: anion decomposition; capacity decay mechanism; interface modulation; metal sulfides; sodium ion storage.
© 2023 Wiley-VCH GmbH.