Archetypical layered oxide with oxygen redox capability bears additional lithium ion in transition metal layer, and its local coordination with oxygen is crucial in triggering the oxygen redox activity. These...
Sodium metal (Na) anodes are considered the most promising anode for high‐energy‐density sodium batteries because of their high capacity and low electrochemical potential. However, Na metal anode undergoes uncontrolled Na dendrite growth, and unstable solid electrolyte interphase layer (SEI) formation during cycling, leading to poor coulombic efficiency, and shorter lifespan. Herein, a series of Na‐ion conductive alloy‐type protective interface (Na‐In, Na‐Bi, Na‐Zn, Na‐Sn) is studied as an artificial SEI layer to address the issues. The hybrid Na‐ion conducting SEI components over the Na‐alloy can facilitate uniform Na deposition by regulating Na‐ion flux with low overpotential. Furthermore, density functional study reveals that the lower surface energy of protective alloys relative to bare Na is the key factor for facilitating facile ion diffusion across the interface. Na metal with interface layer facilitates a highly reversible Na plating/stripping for ≈790 h, higher than pristine Na metal (100 h). The hybrid self‐regulating protective layers exhibit a high mechanical flexibility to promote dendrite free Na plating even at high current density (5 mA cm−2), high capacity (10 mAh cm−2), and good performance with Na3V2(PO4)3 cathode. The current study opens a new insight for designing dendrite Na metal anode for next generation energy storage devices.
Lithium-rich layered oxides, despite their potential as high-energy-density cathode materials, are impeded by electrochemical performance deterioration upon anionic redox. Although this deterioration is believed to primarily result from structural disordering, our understanding of how it is triggered and/or occurs remains incomplete. Herein, we propose a theoretical picture that clarifies the irreversible transformation and redox asymmetry of lithium-rich layered oxides by introducing a series of global and local dynamic structural evolution processes involving slab gliding and transition-metal migration. We show that slab gliding plays a key role in trigger/initiating the structural disordering and consequent degradation of the anionic redox reaction. We further reveal that the ‘concerted disordering mechanism’ of slab gliding and transition-metal migration produces spontaneously irreversible/asymmetric lithiation and de-lithiation pathways, causing irreversible structural deterioration and the asymmetry of the anionic redox reaction. Our findings suggest slab gliding as a crucial, yet underexplored, method for achieving a reversible anionic redox reaction.
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