Dual-doping to suppress cracking in spinel LiMn2O4: a joint theoretical and experimental study

Abstract

Electrochemical cycling stabilities were compared for undoped and Al/Co dual-doped spinel LiMn₂O₄ synthesized by solid state reactions. We observed the suppression of particle fracture in Al/Co dual-doped LiMn₂O₄ during charge/discharge cycling and its distinguishable particle morphology with respect to the undoped material. Systematic first-principles calculations were performed on undoped, Al or Co single-doped, and Al/Co dual-doped LiMn₂O₄ to investigate their structural differences at the atomistic level. We reveal that while Jahn–Teller distortion associated with the Mn³⁺O₆ octahedron is the origin of the lattice strain, the networking — i.e. the distribution of mixed valence Mn ions — is much more important to release the lattice strain, and thus to alleviating particle cracking. The calculations showed that the lattice mismatching between Li⁺ intercalation and deintercalation of LiMn₂O₄ can be significantly reduced by dual-doping, and therefore also the volumetric shrinkage during delithiation. This may account for the near disappearance of cracks on the surface of Al/Co–LiMn₂O₄ after 350 cycles, while some obvious cracks have developed in undoped LiMn₂O₄ at similar particle size even after 50 cycles. Correspondingly, Al/Co dual-doped LiMn₂O₄ showed a good cycling stability with a capacity retention of 84.1% after 350 cycles at a rate of 1C, 8% higher than the undoped phase.