Solvent Degradation and Polymerization in the Li-Metal Battery: Organic-Phase Formation in Solid-Electrolyte Interphases.

The products of solvent polymerization and degradation are crucial components of the Li-metal battery solid-electrolyte interphase. However, in-depth mechanistic studies of these reactions are still scarce. Here, we model the polymerization of common lithium battery electrolyte solvents─ethylene carbonate (EC) and vinylene carbonate (VC)─near the anode surface. Being consistent with the molecular calculation, ab initio molecular dynamic (AIMD) simulations reveal fast solvent decompositions upon contact with the Li anode. Additionally, we assessed the thermochemical impacts of decarboxylation reactions as well as the lithium bonding with reaction intermediates. In both EC and VC polymerization pathways, lithium bonding demonstrated profound catalytic effects while different degrees of decarboxylation were observed. The VC polymerization pathways with and without ring-opening events were evaluated systematically, and the latter one which leads to poly(VC) formation was proven to dominate the oligomerization process. Both the decomposition and polymerization reactivities of VC are found to be higher than EC, while the cross-coupling between EC and VC has an even lower-energy barrier. These findings are in good agreement with experimental evidence and explanatory toward the enhanced performance of VC-added lithium-metal batteries.