In Situ X-Ray Diffraction Studies on Structural Changes of a P2 Layered Material during Electrochemical Desodiation/Sodiation

Abstract

Sodium layered oxides with mixed transition metals have received significant attention as positive electrode candidates for sodium-ion batteries because of their high reversible capacity. The phase transformations of layered compounds during electrochemical reactions are a pivotal feature for understanding the relationship between layered structures and electrochemical properties. A combination of in situ diffraction and ex situ X-ray absorption spectroscopy reveals the phase transition mechanism for the ternary transition metal system (Fe-Mn-Co) with P2 stacking. In situ synchrotron X-ray diffraction using a capillary-based microbattery cell shows a structural change from P2 to O2 in P2-Na0.7Fe0.4Mn0.4Co0.2O2 at the voltage plateau above 4.1 V on desodiation. The P2 structure is restored upon subsequent sodiation. The lattice parameter c in the O2 structure decreases significantly, resulting in a volumetric contraction of the lattice toward a fully charged state. Observations on the redox behavior of each transition metal in P2-Na0.7Fe0.4Mn0.4Co0.2O2 using X-ray absorption spectroscopy indicate that all transition metals are involved in the reduction/oxidation process.