Direct Observation of a Metastable Crystal Phase of LixFePO4 under Electrochemical Phase Transition
Journal of the American Chemical Society2013Vol. 135(15), pp. 5497–5500
Citations Over TimeTop 1% of 2013 papers
Yuki Orikasa, Takehiro Maeda, Yukinori Koyama, Haruno Murayama, Katsutoshi Fukuda, Hajime Tanida, Hajime Arai, Eiichiro Matsubara, Yoshiharu Uchimoto, Zempachi Ogumi
Abstract
The phase transition between LiFePO4 and FePO4 during nonequilibrium battery operation was tracked in real time using time-resolved X-ray diffraction. In conjunction with increasing current density, a metastable crystal phase appears in addition to the thermodynamically stable LiFePO4 and FePO4 phases. The metastable phase gradually diminishes under open-circuit conditions following electrochemical cycling. We propose a phase transition path that passes through the metastable phase and posit the new phase's role in decreasing the nucleation energy, accounting for the excellent rate capability of LiFePO4. This study is the first to report the measurement of a metastable crystal phase during the electrochemical phase transition of LixFePO4.
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