Alternate Synthesis Method for High‐Performance Manganese Rich Cation Disordered Rocksalt Cathodes

Abstract Cation‐disordered rocksalt (DRX) cathodes have recently emerged as a promising class of cobalt‐free, high‐capacity cathodes for lithium‐ion batteries. To facilitate their commercialization, the development of scalable synthesis techniques providing control over composition and morphology is critical. To this end, a sol‐gel synthesis route to prepare Mn‐rich DRX cathodes with high capacities is presented here. Several compositions with varied Mn content and nominal F doping are successfully prepared using this technique. In‐situ X‐ray diffraction measurements demonstrate that DRX formation proceeds at moderate temperature (800 °C) through the sol‐gel route, which enables intimate mixing among reactive intermediate phases that form at lower temperatures. All synthesized compositions possess cation short‐range order, as evidenced by neutron pair distribution function and electron diffraction analysis. These DRX materials demonstrate promising electrochemical performance with reversible capacities up to 275 mAh g. Compared to the baseline oxide (Li_1.2Mn_0.4Ti_0.4O₂), the Mn‐rich compositions exhibit improved cycling stability, with some showing an increase in capacity upon cycling. Overall, this study demonstrates the feasibility of preparing high‐capacity DRX cathodes through a sol‐gel based synthesis route, which may be further optimized to provide better control over the product morphology compared to traditional synthesis methods.