title: Phase transition kinetics of LiNi0.5Mn1.5O4 analyzed by temperature-controlled operando X-ray absorption spectroscopy.
abstract: 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) ↔ Li0.5Ni0.5Mn1.5O4 (Li0.5) and Li0.5 ↔ 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 absorption spectroscopy to directly capture the reacting phases from -20 °C to 40 °C 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 ↔ Li0.5 transition (process 1) is larger than that for the Li0.5 ↔ 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.
authors.affiliation: Office of Society-Academia Collaboration for Innovation, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan. ikuma-takahashi@mail.nissan.co.jp.
authors.forename: Ikuma
authors.initials: I
authors.lastname: Takahashi
authors.forename: Hajime
authors.initials: H
authors.lastname: Arai
authors.forename: Haruno
authors.initials: H
authors.lastname: Murayama
authors.forename: Kenji
authors.initials: K
authors.lastname: Sato
authors.forename: Hideyuki
authors.initials: H
authors.lastname: Komatsu
authors.forename: Hajime
authors.initials: H
authors.lastname: Tanida
authors.forename: Yukinori
authors.initials: Y
authors.lastname: Koyama
authors.forename: Yoshiharu
authors.initials: Y
authors.lastname: Uchimoto
authors.forename: Zempachi
authors.initials: Z
authors.lastname: Ogumi