Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes

Robert A. House, Urmimala Maitra, Miguel A. Pérez-Osorio, Juan G. Lozano, Liyu Jin, James W. Somerville, Laurent C. Duda, Abhishek Nag, Andrew Walters, Ke-Jin Zhou, Matthew R. Roberts and Peter G. Bruce ()
Additional contact information
Robert A. House: University of Oxford
Urmimala Maitra: University of Oxford
Miguel A. Pérez-Osorio: University of Oxford
Juan G. Lozano: University of Oxford
Liyu Jin: University of Oxford
James W. Somerville: University of Oxford
Laurent C. Duda: Uppsala University
Abhishek Nag: Diamond Light Source
Andrew Walters: Diamond Light Source
Ke-Jin Zhou: Diamond Light Source
Matthew R. Roberts: University of Oxford
Peter G. Bruce: University of Oxford

Nature, 2020, vol. 577, issue 7791, 502-508

Abstract: Abstract In conventional intercalation cathodes, alkali metal ions can move in and out of a layered material with the charge being compensated for by reversible reduction and oxidation of the transition metal ions. If the cathode material used in a lithium-ion or sodium-ion battery is alkali-rich, this can increase the battery’s energy density by storing charge on the oxide and the transition metal ions, rather than on the transition metal alone1–10. There is a high voltage associated with oxidation of O2− during the first charge, but this is not recovered on discharge, resulting in reduced energy density11. Displacement of transition metal ions into the alkali metal layers has been proposed to explain the first-cycle voltage loss (hysteresis)9,12–16. By comparing two closely related intercalation cathodes, Na0.75[Li0.25Mn0.75]O2 and Na0.6[Li0.2Mn0.8]O2, here we show that the first-cycle voltage hysteresis is determined by the superstructure in the cathode, specifically the local ordering of lithium and transition metal ions in the transition metal layers. The honeycomb superstructure of Na0.75[Li0.25Mn0.75]O2, present in almost all oxygen-redox compounds, is lost on charging, driven in part by formation of molecular O2 inside the solid. The O2 molecules are cleaved on discharge, reforming O2−, but the manganese ions have migrated within the plane, changing the coordination around O2− and lowering the voltage on discharge. The ribbon superstructure in Na0.6[Li0.2Mn0.8]O2 inhibits manganese disorder and hence O2 formation, suppressing hysteresis and promoting stable electron holes on O2− that are revealed by X-ray absorption spectroscopy. The results show that voltage hysteresis can be avoided in oxygen-redox cathodes by forming materials with a ribbon superstructure in the transition metal layers that suppresses migration of the transition metal.

Date: 2020
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DOI: 10.1038/s41586-019-1854-3

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