LiNi0.5Mn1.5O4 (LNMO) is a promising positive electrode material for lithium ion batteries because it shows a high potential of 4.7 V vs. Li/Li+. Its charge–discharge reaction includes two consecutive phase transitions between LiNi0.5Mn1.5O4 (Li1) 2 Li0.5Ni0.5Mn1.5O4 (Li0.5) and Li0.5 2 Ni0.5Mn1.5O4 (Li0) and the complex transition kinetics that governs the rate capability of LNMO can hardly be analyzed by simple electrochemical techniques. Herein, we apply temperature-controlled operando X-ray absorp- tion spectroscopy to directly capture the reacting phases from 20 1C to 40 1C under potential step (chronoamperometric) conditions and evaluate the phase transition kinetics using the apparent first-order rate constants at various temperatures. The constant for the Li1 2 Li0.5 transition (process 1) is larger than that for the Li0.5 2 Li0 transition (process 2) at all the measured temperatures, and the corresponding activation energies are 29 and 46 kJ mol 1 for processes 1 and 2, respectively. The results obtained are discussed to elucidate the limiting factor in this system as well as in other electrode systems.
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