Atomistic Observation of Desodiation-Induced Phase Transition in Sodium Tungsten Bronze.

The phase instability in layered-structure Na0.5WO3.25 induced by the extraction of Na ions was investigated by applying transmission electron microscopy. Real-time atomic-scale observation reveals the phase transition pathway: Na0.5WO3.25 (triclinic) → NaxWO3 (cubic) → WO3 (monoclinic) with specific orientation relationships. The dynamic evolution of Na0.5WO3.25/NaxWO3 phase boundaries shows that Na0.5WO3.25 will cleave along the (100)T and (010)T and recrystallize as (101)C and (010)C of NaxWO3, respectively. The phase transition pathway can be well-explained according to the structural characteristics in the three phases. By better understanding of the phase instability induced by the extraction of Na ions in possible layered-structure cathode materials, this work provides a reference for the design of sophisticated strategies toward high-performance Na-ion batteries.