Aliovalent Substitutions in Olivine Lithium Iron Phosphate and Impact on Structure and Properties

Abstract Lithium transition metal phosphate olivines are enabling a new generation of high power, thermally stable, long‐life rechargeable lithium batteries that may prove instrumental in the worldwide effort to develop cleaner and more sustainable energy. Nanoscale (<100 nm) derivatives of the olivine family LiMPO 4 (M = Fe, Mn, Co, Ni) are being adopted in applications ranging in size scale from hybrid and plug‐in hybrid electric vehicles to utilities‐scale power regulation. Following the previous paradigm set with intercalation oxides, most studies have focused on the pure ordered compounds and isovalent substitutions. In contrast, even the possibility for, and role of, aliovalent doping has been widely debated. Here, critical tests of plausible defect compensation mechanisms using compositions designed to accommodate Mg 2+ , Al 3+ , Zr 4+ , Nb 5+ ions on the M1 and/or M2 sites of LiFePO 4 with appropriate charge‐compensating defects are carried out, and conclusive crystallographic evidence for lattice doping, e.g., up to at least 12 atomic percent added Zr, is obtained. Structural and electrochemical analyses show that doping can reduce the lithium miscibility gap, increase phase transformation kinetics during cycling, and expand Li diffusion channels in the structure. Aliovalent modifications may be effective for introducing controlled atomic disorder into the ordered olivine structure to improve battery performance.