Recherche

Lithium-rich layered oxides, containing cobalt, despite being promising high-capacity cathode materials, need alternatives to eliminate toxic and geopolitically restricted cobalt. An ongoing search for low-cost, Co-free Li-rich cathode materials with a better structural stability lead to investigation of Li_1.16Ni_0.19Fe_0.18Mn_0.46O₂ (LNFM), where cobalt is replaced by abundant iron. Our LNFM not only delivered a high capacity of 229 mAh/g but also has a stable average discharge voltage when cycled to upper cutoff potential of 4.8 V in additive-free electrolyte.

We report an in-depth investigation of the local atomic geometry, electronic and crystallographic structure evolution of nano-sized LiMn₂O₄ using operando XAS and XRD to shed light on (de-)lithiation mechanism when cycled in wide voltage range of 2.0 to 4.3 V vs Li⁺/Li. Leveraging on these findings, a novel electrochemical cycling protocol, with periodic deep discharge, yields superior electrochemical performance cycled in the range of 3.3 to 4.3 V exhibiting an excellent structure cyclability and an unprecedented increase in the specific capacity upon long cycling.