Pushing Stoichiometries of Lithium-Rich Layered Oxides Beyond Their Limits

[Image: see text] Lithium-rich layered oxides (LRLOs) are opening unexplored frontiers for high-capacity/high-voltage positive electrodes in Li-ion batteries (LIBs) to meet the challenges of green and safe transportation as well as cheap and sustainable stationary energy storage from renewable sources. LRLOs exploit the extra lithiation provided by the Li(1.2)TM(0.8)O(2) stoichiometries (TM = a blend of transition metals with a moderate cobalt content) achievable by a layered structure to disclose specific capacities beyond 200–250 mA h g(–1) and working potentials in the 3.4–3.8 V range versus Li. Here, we demonstrate an innovative paradigm to extend the LRLO concept. We have balanced the substitution of cobalt in the transition-metal layer of the lattice with aluminum and lithium, pushing the composition of LRLO to unexplored stoichiometries, that is, Li(1.2+x)(Mn,Ni,Co,Al)(0.8–x)O(2−δ). The fine tuning of the composition of the metal blend results in an optimized layered material, that is, Li(1.28)Mn(0.54)Ni(0.13)Co(0.02)Al(0.03)O(2−δ), with outstanding electrochemical performance in full LIBs, improved environmental benignity, and reduced manufacturing costs compared to the state-of-the-art.