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Updated: Oct 28, 2025

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Published on: November 11, 2013
Structural Origins of Voltage Hysteresis in the Na-Ion Cathode P2-Na0.67[Mg0.28Mn0.72]O2: A Combined Spectroscopic
Euan N Bassey1, Philip J Reeves1, Michael A Jones1
1Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Abstract:
P2-layered sodium-ion battery (NIB) cathodes are a promising class of Na-ion electrode materials with high Na+ mobility and relatively high capacities. In this work, we report the structural changes that take place in P2-Na0.67[Mg0.28Mn0.72]O2. Using ex situ X-ray diffraction, Mn K-edge extended X-ray absorption fine structure, and 23Na NMR spectroscopy, we identify the bulk phase changes along the first electrochemical charge-discharge cycle-including the formation of a high-voltage "Z phase", an intergrowth of the OP4 and O2 phases. Our ab initio transition state searches reveal that reversible Mg2+ migration in the Z phase is both kinetically and thermodynamically favorable at high voltages. We propose that Mg2+ migration is a significant contributor to the observed voltage hysteresis in Na0.67[Mg0.28Mn0.72]O2 and identify qualitative changes in the Na+ ion mobility.
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