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Whole-Voltage-Range Solid-Solution Reaction in Layered Oxide Cathode of Sodium-Ion Batteries.

Meng RenZhuo ZhuZhaohui LiangYaohui HuangTong ZhangMachuan HouKai ZhangZonghai ChenYushi HeZifeng MaJun ChenFujun Li
Published in: Small (Weinheim an der Bergstrasse, Germany) (2023)
Layered manganese-based oxides (LMOs) are promising cathode materials for sodium-ion batteries (SIBs) due to their versatile structures. However, the Jahn-Teller effect of Mn 3+ induces severe distortion of MnO 6 octahedra, and the resultant low symmetry is responsible for the gliding of MnO 2 layers and then inferior multiple-phase transitions upon Na + extraction/insertion. Here, hexagonal P2-Na 0.643 Li 0.078 Mn 0.827 Ti 0.095 O 2 is synthesized through the incorporation of Li and Ti into the distorted orthorhombic P'2-Na 0.67 MnO 2 to function as a phase-transition-free oxide cathode. It is revealed that Li in both the transition-metal and Na layers enhances the covalency of Mn-O bonds and allows degeneracy of Mn 3d e g orbitals to favor the formation of hexagonal phase, and the high strength of Ti-O bonds reduces the electrostatic interaction between Na and O for suppressed Na + /vacancy rearrangements. These collectively lead to a whole-voltage-range solid-solution reaction between 1.8 and 4.3 V with a small volume variation of 1.49%. This rewards its excellent cycling stability (capacity retention of 90% after 500 cycles) and rate capability (89 mAh g -1 at 2000 mA g -1 ).
Keyphrases
  • ion batteries
  • transition metal
  • room temperature
  • high resolution
  • mass spectrometry
  • single cell
  • density functional theory
  • early onset
  • ionic liquid
  • reduced graphene oxide
  • solid state