Synthetically Produced Isocubanite as an Anode Material for Sodium-Ion Batteries: Understanding the Reaction Mechanism During Sodium Uptake and Release

Bulk isocubanite (CuFe2S3) was synthesized via a multistep high-temperature synthesis and was investigated as an anode material for sodium-ion batteries. CuFe2S3 exhibits an excellent electrochemical performance with a capacity retention of 422 mA h g–1 for more than 1000 cycles at a current rate of 0.5 A g–1 (0.85 C). The complex reaction mechanism of the first cycle was investigated via PXRD and X-ray absorption spectroscopy. At the early stages of Na uptake, CuFe2S3 is converted to form crystalline CuFeS2 and nanocrystalline NaFe1.5S2 simultaneously. By increasing the Na content, Cu+ is reduced to nanocrystalline Cu, followed by the reduction of Fe2+ to amorphous Fe0 while reflections of nanocrystalline Na2S appear. During charging up to −5 Na/f.u., the intermediate NaFe1.5S2 appears again, which transforms in the last step of charging to a new unknown phase. This unknown phase together with NaFe1.5S2 plays a key role in the mechanism for the following cycles, evidenced by the PXRD investigation of the second cycle. Even after 400 cycles, the occurrence of nanocrystalline phases made it possible to gain insights into the alteration of the mechanism, which shows that CuxS phases play an important role in the region of constant specific capacity.