Thermal transport in monocrystalline and polycrystalline lithium cobalt oxide

Efficient heat dissipation in batteries is important for thermal management against thermal runaway and chemical instability at elevated temperatures. Nevertheless, thermal transport processes in battery materials have not been well understood especially considering their complicated microstructures. In this study, lattice thermal transport in lithium cobalt oxide (LiCoO2), a popular cathode material for lithium ion batteries, is investigated via molecular dynamics-based approaches and thermal resistance models. A LiCoO2 single-crystal is shown to have thermal conductivities in the order of 100 W m−1 K−1 with strong anisotropy, temperature dependence, and size effects. By comparison, polycrystalline LiCoO2 is more isotropic with much lower thermal conductivities. This difference is caused by random grain orientations, the thermal resistance of grain boundaries, and size-dependent intra-grain thermal conductivities that are unique to polycrystals. The grain boundary thermal conductance is calculated to be in the range of 7.16–25.21 GW m−2 K−1. The size effects of the intra-grain thermal conductivities are described by two empirical equations. Considering all of these effects, two thermal resistance models are developed to predict the thermal conductivity of polycrystalline LiCoO2. The two models predict a consistent thermal conductivity–grain size relationship that agrees well with molecular dynamics simulation results. The insights revealed by this study may facilitate future efforts on battery materials design for improved thermal management.