posted on 2023-12-28, 13:04authored byDaniel
D. Robertson, Helen Cumberbatch, David J. Pe, Yiyi Yao, Sarah H. Tolbert
Fast-charging Li-ion batteries are
technologically important for
the electrification of transportation and the implementation of grid-scale
storage, and additional fundamental understanding of high-rate insertion
reactions is necessary to overcome current rate limitations. In particular,
phase transformations during ion insertion have been hypothesized
to slow charging. Nanoscale materials with modified transformation
behavior often show much faster kinetics, but the mechanism for these
changes and their specific contribution to fast-charging remain poorly
understood. In this work, we combine operando synchrotron
X-ray diffraction with electrochemical kinetics analyses to illustrate
how nanoscale crystal size leads to suppression of first-order insertion-induced
phase transitions and their negative kinetic effects in MoO2, a tunnel structure host material. In electrodes made with micrometer-scale
particles, large first-order phase transitions during cycling lower
capacity, slow charge storage, and decrease cycle life. In medium-sized
nanoporous MoO2, the phase transitions remain first-order,
but show a considerably smaller miscibility gap and shorter two-phase
coexistence region. Finally, in small MoO2 nanocrystals,
the structural evolution during lithiation becomes entirely single-phase/solid-solution.
For all nanostructured materials, the changes to the phase transition
dynamics lead to dramatic improvements in capacity, rate capability,
and cycle life. This work highlights the continuous evolution from
a kinetically hindered battery material in bulk form to a fast-charging,
pseudocapacitive material through nanoscale size effects. As such,
it provides key insight into how phase transitions can be effectively
controlled using nanoscale size and emphasizes the importance of these
structural dynamics to the fast rate capability observed in nanostructured
electrode materials.