  Metal fluoride and oxides can store multiple lithium-ions through conversion
chemistry to enable high energy-density lithium-ion batteries. However, their
practical applications have been hindered by an unusually large voltage
hysteresis between charge and discharge voltage-profiles and the consequent low
energy efficiency (< 80%). The physical origins of such hysteresis are rarely
studied and poorly understood. Here we employ in situ X-ray absorption
spectroscopy (XAS), transmission electron microscopy (TEM),
density-functional-theory (DFT) calculations, and galvanostatic intermittent
titration technique (GITT) to first correlate the voltage profile of iron
fluoride ($FeF_3$), a representative conversion electrode material, with
evolution and spatial distribution of intermediate phases in the electrode. The
results reveal that, contrary to conventional belief, the phase evolution in
the electrode is symmetrical during discharge and charge. However, the spatial
evolution of the electrochemically active phases, which is controlled by
reaction kinetics, is different. We further propose that the voltage hysteresis
in the $FeF_3$ electrode is kinetic in nature. It is the result of Ohmic
voltage drop, reaction overpotential, and different spatial distributions of
electrochemically-active phases (i.e. compositional inhomogeneity). Therefore,
the large hysteresis can be expected to be mitigated by rational design and
optimization of material microstructure and electrode architecture to improve
the energy efficiency of lithium-ion batteries based on conversion chemistry.
