Integrated rocksalt–polyanion cathodes with excess lithium and stabilized cycling

Abstract

Co- and Ni-free disordered rocksalt cathodes utilize oxygen redox to increase the energy density of lithium-ion batteries, but it is challenging to achieve good cycle life at high voltages >4.5 V (versus Li/Li+). Here we report a family of Li-excess Mn-rich cathodes that integrates rocksalt- and polyanion-type structures. Following design rules for cation filling and ordering, we demonstrate the bulk incorporation of polyanion groups into the rocksalt lattice. This integration bridges the two primary families of lithium-ion battery cathodes—layered/spinel and phosphate oxides—dramatically enhancing the cycling stability of disordered rocksalt cathodes with 4.8 V upper cut-off voltage. The cathode exhibits high gravimetric energy densities above 1,100 Wh kg−1 and >70% retention over 100 cycles. This study opens up a broad compositional space for developing battery cathodes using earth-abundant elements such as Mn and Fe. Energy density and cyclability are often a trade-off for lithium-ion batteries. The authors develop cobalt- and nickel-free cathodes with both good cycling stability and high energy density through the integration of polyanion units into rocksalt structures.