Morphology Control of Spinel LiNi0.5Mn1.5O4 for Tuned Microstructure and Electrochemistry

HighlightsMorphology-tuned octahedral LNMO shows remarkable cycling stability at 25 °C and 55 °C.Submicron primary particles curb side reactions and greatly accelerate lithium ion diffusion.Sol–gel octahedral particles feature high crystallinity, few defects, and low inter-facial impedance.Morphology engineering alleviates intrinsic flaws of cobalt-free high-voltage spi-nel cathode materials.This tunable sol–gel route enables scalable synthesis of high-performance octahe-dral LNMO cathodes.Optimized octahedral LNMO fits long-life high-power batteries for electric vehi-cles and energy storage.High-voltage spinel LiNi0.5Mn1.5O4(LNMO) is a promising cathode for next-generation lithium-ion batteries, yet its application is limited by structural instability and poor high-temperature/high-rate performance. Here, spherical secondary polycrystalline aggregate (LNMO-PC), micron-sized primary particle (single-crystal morphology) (LNMO-SC-L), and submicron primary particle (single-crystal morphology) (LNMO-SC-S) LNMO were synthesized. Their structures, morphologies, and surface properties were characterized and electrochemical performance evaluated at room (25 °C)/high (55 °C) temperature and high rates. LNMO-SC-S exhibited the highest crystallinity, lowest Mn3+content, and minimal charge-transfer resistance. It showed superior cycling stability (93.3% retention at 1 C over 500 cycles), excellent rate capability (~20 mAh g−1at 20 C), and enhanced high-temperature performance. The submicron primary particles suppress grain-boundary degradation and Mn3+disproportionation, shortens Li+paths, and improves reaction kinetics.