Polymer-Based Artificial Solid Electrolyte Interphase Layers for Li- and Zn-Metal Anodes: From Molecular Engineering to Operando Visualization

Metal anodes promise improvements in energy density and cost; however, their performance is determined within the first several nanometers at the interface. This review reports on how polymer-based artificial solid electrolyte interphases (SEIs) are engineered to stabilize Li and aqueous-Zn anodes, and how these designs are now evaluated against operando readouts rather than post-mortem snapshots. We group the related molecular strategies into three classes: (i) side-chain/ionomer chemistry (salt-philic, fluorinated, zwitterionic) to increase cation selectivity and manage local solvation; (ii) dynamic or covalently cross-linked networks to absorb microcracks and maintain coverage during plating/stripping; and (iii) polymer–ceramic hybrids that balance modulus, wetting, and ionic transport characteristics. We then benchmark these choices against metal-specific constraints—high reductive potential and inactive Li accumulation for Li, and pH, water activity, corrosion, and hydrogen evolution reaction (HER) for Zn—showing why a universal preparation method is unlikely. A central element is a system of design parameters and operando metrics that links material parameters to readouts collected under bias, including the nucleation overpotential (ηnuc), interfacial impedance (charge transfer resistance (Rct)/SEI resistance (RSEI)), morphology/roughness statistics from liquid-cell or cryogenic electron microscopy (Cryo-EM), stack swelling, and (for Li) inactive-Li inventory. By contrast, planar plating/stripping and HER suppression are primary success metrics for Zn. Finally, we outline parameters affecting these systems, including the use of lean electrolytes, the N/P ratio, high areal capacity/current density, and pouch-cell pressure uniformity, and discuss closed-loop workflows that couple molecular design with multimodal operando diagnostics. In this view, polymer artificial SEIs evolve from curated “recipes” into predictive, transferable interfaces, paving a path from coin-cell to prototype-level Li- and Zn-metal batteries.