Hybrid Organic/Inorganic Layer Interfase via Capillary Rise Infiltration for Stabilizing Li Plating from Li‑Rich to Anode‑Free Operation

Anode‑free lithium metal batteries promise high energy density but are severely limited by unstable Li nucleation and rapid failure on bare Cu current collectors. In this work, we develop a PEO@SiO₂ interphase on Cu using a capillary rise infiltration (CaRI) process, in which a polymer layer is thermally driven to infiltrate into a closely packed SiO₂ nanoparticle layer. We evaluate this interphase over a wide Li‑inventory window, from conventional Li‑rich half cells to lean‑Li and finally anode‑free configurations. The CaRI‑engineered PEO@SiO₂ layer enables more uniform Li plating/stripping with reduced nucleation overpotential and enhanced cycling stability, particularly under lean‑Li and anode‑free conditions. These results demonstrate that such a CaRI‑derived PEO@SiO₂ interphase is a practical strategy to translate Li‑rich interfacial design concepts into realistic anode‑free Li metal batteries.