posted on 2017-07-19, 00:00authored byWang Hay Kan, Saravanan Kuppan, Lei Cheng, Marca Doeff, Jagjit Nanda, Ashfia Huq, Guoying Chen
For
ordered high-voltage spinel LiMn1.5Ni0.5O4 (LMNO) with the P4321 symmetry, the two consecutive two-phase transformations at
∼4.7 V (vs Li+/Li), involving three
cubic phases of LMNO, Li0.5Mn1.5Ni0.5O4 (L0.5MNO), and Mn1.5Ni0.5O4 (MNO), have been well-established. Such a mechanism
is traditionally associated with poor kinetics due to the slow movement
of the phase boundaries and the large mechanical strain resulting
from the volume changes among the phases, yet ordered LMNO has been
shown to have excellent rate capability. In this study, we show the
ability of the phases to dissolve into each other and determine their
solubility limit. We characterized the properties of the formed solid
solutions and investigated the role of non-equilibrium single-phase
redox processes during the charge and discharge of LMNO. By using
an array of advanced analytical techniques, such as soft and hard
X-ray spectroscopy, transmission X-ray microscopy, and neutron/X-ray
diffraction, as well as bond valence sum analysis, the present study
examines the metastable nature of solid-solution phases and provides
new insights in enabling cathode materials that are thermodynamically
unstable.