Probing Operando Electrochemical Strain Generation in α-NaFeO₂ Composite Cathodes during Cycling of Na-Ion Batteries

The transition metal oxide (TMO) cathodes in Na-ion batteries suffer from low-capacity retention. Chemo-mechanical instabilities lead to the deterioration of the electrochemical performance of TMO cathodes in Li-ion batteries. However, there is not much known about the chemo-mechanical instabilities in the TMO cathodes for Na-ion batteries. Understanding the governing forces behind the interplay between the electrochemical performance and mechanical stability in TMO cathodes is critical for the development of Na-ion batteries. Here, we synchronize the digital image correlation (DIC) technique with electrochemical analysis to capture the real-time deformation behavior of the α-NaFeO₂ cathodes during cycling. When the charge cutoff voltage is 3.6 V, the cathode experiences reversible deformations (except for the first cycle). There is negative strain (shrinkage) generation during Na extraction and positive strain (expansion) generation during the subsequent Na insertion. A detailed analysis of the potential-dependent strain rate evolution points out complicated phase transformations and nonequilibrium conditions in the α-NaFeO₂ cathodes during cycling. When the charge cutoff voltage was increased to 4.2 V, there was a rapid capacity loss and large plastic deformations in the α-NaFeO₂ cathodes. We provide an in-depth discussion about the possible mechanisms behind the chemo-mechanical instabilities in the α-NaFeO₂. The correlation is critical to develop material-based strategies to mitigate instability mechanisms in TMO cathodes for Na-ion batteries.