Dual-ion Regulation of Coordination Chemistry for High-voltage Stabilized P2-Type Cathode
Nano Energy(2024)
Abstract
P2-Na2/3Ni1/3Mn2/3O2 has shown great potential as cathode material for sodium-ion batteries with its high theoretical capacity and energy density. However, severe structural changes are induced by charging P2-Na2/3Ni1/3Mn2/3O2 above 4.2V, resulting in rapid capacity decay and poor kinetic capability. In this study, we propose a Zn/Ti synergistic modification strategy to stabilize the P2-type cathode under high voltage. It is found that the P2-O2 phase transition with large volume change is replaced by a milder P2-Z phase transition with the noteworthy improvement in structural stability and Na+ diffusion kinetics, due to the disordered Na+/vacancy and the suppressed of the sliding of transition metal layers, as disclosed by density functional theory calculations and in-situ X-ray diffraction. Concurrently, The phenomenon of Ni and O reductive coupling is inhibited by regulating local O coordination owing to the incorporation of a strong Ti−O covalence bond, leading to the more reversible charge compensation mechanism and the inhibited lattice O evolution, as clearly revealed by ex-situ X-ray absorption spectroscopy and Differential Electrochemical Mass Spectrometry. Consequently, we obtained a stable P2-Na0.67Zn0.05Ni0.28Mn0.52Ti0.15O2 cathode, achieving an average discharge voltage of 3.62V at 0.1C and a capacity retention of 80% after 500 cycles at 2C. This research provides valuable insights into the enhancement of sodium-ion battery cathode materials by utilizing different functional ions in synergy.
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Key words
The disordered Na+/vacancy,P2-Z phase transition,Na+ kinetics
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