First‐Principles Study on Polymer Electrolyte Interface Engineering for Lithium Metal Anodes

Abstract Modifying the interface between the lithium metal anode (LMA) and the electrolyte is crucial for achieving high‐performance lithium metal batteries (LMBs). Recent research indicates that altering Li‐metal interfaces with polymer coatings is an effective approach to extend LMBs′ cycling lifespan. However, the physical properties of these polymer‐Li interfaces have not yet been fully investigated. Therefore, the structural stability, electronic conductivity, and ionic conductivity of polymer‐Li interfaces were examined based on first‐principles calculations in this study. Several representative polymer compounds utilized in LMBs were assessed, including polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyethylene oxide (PEO). Our research revealed that lithium fluoride is formed upon fluoropolymer degradation, explaining previously observed experimental results. Polymers containing nitrile groups exhibit strong adhesion to lithium metal, facilitating the formation of the stable interface layer. Regarding electronic conductivity, the fluoropolymers preserve a good insulating property, which diminished marginally in the presence of lithium, but that of PAN and PEO significantly reduces. Additionally, lithium diffusion on PTFE and PEO demonstrates low diffusion barriers and high coefficients, enabling easy transportation. Overall, our investigation reveals that the interfaces formed between various polymers and LMA have distinct characteristics, providing new fundamental insights for designing composites with tailored interface properties.