Atomistic mechanisms of hard carbon formation from polyvinylidene chloride

Hard carbons are a class of disordered materials with widespread application in energy storage. Despite decades of research, their atomistic formation mechanisms have remained elusive, due to the difficulty of both in situ experimental characterization and first-principles simulations. Here, we describe the formation mechanism of hard carbon from the thermal decomposition of polyvinylidene chloride (PVDC), using first-principles-quality simulations with a bespoke machine-learned interatomic potential model. Our results indicate a two-stage process, consisting of (i) radical-mediated dehydrochlorination, which generates reactive unsaturated carbon sites, and (ii) progressive carbon-carbon cross-linking followed by thermally activated rearrangement into an extended sp²-bonded network. We provide an atomistic account of non-hexagonal ring motifs emerging during pyrolysis, supporting the established theory that these motifs induce the intrinsic curvature that frustrates graphitic ordering in hard carbons.