Dopant Segregation Boosting High-Voltage Cyclability of Layered Cathode for Sodium Ion Batteries.

As a widely used approach to modify a material's bulk properties, doping can effectively improve electrochemical properties and structural stability of various cathodes for rechargeable batteries, which usually empirically favors a uniform distribution of dopants. It is reported that dopant aggregation effectively boosts the cyclability of a Mg-doped P2-type layered cathode (Na0.67Ni0.33Mn0.67O2). Experimental characterization and calculation consistently reveal that randomly distributed Mg dopants tend to segregate into the Na-layer during high-voltage cycling, leading to the formation of high-density precipitates. Intriguingly, such Mg-enriched precipitates, acting as 3D network pillars, can further enhance a material's mechanical strength, suppress cracking, and consequently benefit cyclability. This work not only deepens the understanding on dopant evolution but also offers a conceptually new approach by utilizing precipitation strengthening design to counter cracking related degradation and improve high-voltage cyclability of layered cathodes.