Crystal habits of LiMn2O4 and their influence on the electrochemical performance

Crystal habits of LiMn2O4 prepared through a sol–gel method using different starting materials (metal acetates and metal nitrates) are studied using a crystal shape algorithm. Density functional theory (DFT) as implemented in VASP is employed to study the thermodynamic stabilities and the electronic structure of the different hkl planes of LiMn2O4, as identified by the crystal shape algorithm. The crystal habit of lithium manganate prepared through the metal acetate route, LiMn2O4 (A), seems to possess a higher thermodynamic stability compared to the metal nitrate route viz. LiMn2O4 (N). Electrochemical cycling measurements show that the capacity retention in LiMn2O4 (A) is better than LiMn2O4 (N) at low (C/10) as well as at higher (5C) rates.

► Two different crystal habits of LiMn2O4 are studied using a crystal shape algorithm. ► The thermodynamic stabilities and the electronic structure of the different hkl planes of LiMn2O4, as identified by the crystal shape algorithm, are studied using Density Functional Theory as implemented in VASP. ► The well defined crystal habit of LiMn2O4 prepared through the metal acetate route seems to possess a higher thermodynamic stability and better electrochemical properties compared to the irregular crystal habit of LiMn2O4 prepared through the metal nitrate route.