Influence of the Cation on the Reaction Mechanism of Sodium Uptake and Release in Bivalent Transition Metal Thiophosphate Anodes: A Case Study of Fe$_2$P$_2$S$_6$

Abstract

The layered active material Fe$_2$P$_2$S$_6$ was examined as anode material in sodium-ion batteries (SIBs) and compared to previously investigated Ni$_2$P$_2$S$_6$. A reversible specific capacity of 540 mAh g$^{−1}$ was achieved after 250 cycles, depicting similar electrochemical performance as observed for Ni$_2$P$_2$S$_6$. The rate capability and long-term behavior of these two materials are also very similar. Another objective was to elucidate the reaction mechanism during discharging and charging by applying several techniques such as X-ray diffraction, pair distribution function analysis as well as X-ray absorption and solid state NMR spectroscopy. The results clearly demonstrate that the majority of Fe$^{2+}$ is reduced to elemental Fe during the uptake of 5 Na/f.u., while an amorphous intermediate is generated, which was identified as Na$_4$P$_2$S$_6$ by solid state NMR spectroscopy. Completely discharging against a Na metal counter electrode leads to the formation of nanocrystalline Na$_2$S and indications of the formation of polymeric phosphorus were found. In sum, the Na uptake reaction process observed for Fe$_2$P$_2$S$_6$ coincides with the previously unraveled reaction pathway of Ni$_2$P$_2$S$_6$. We therefore conclude that a universal reaction takes places for bivalent transition metal thiophosphate (M$_2$P$_2$S$_6$) electrodes in SIBs