A robust all-organic protective layer towards ultrahigh-rate and large-capacity Li metal anodes

The low cycling efficiency and uncontrolled dendrite growth resulting from an unstable and heterogeneous lithium–electrolyte interface have largely hindered the practical application of lithium metal batteries. In this study, a robust all-organic interfacial protective layer has been developed to achieve a highly efficient and dendrite-free lithium metal anode by the rational integration of porous polymer-based molecular brushes (poly(oligo(ethylene glycol) methyl ether methacrylate)-grafted, hypercrosslinked poly(4‐chloromethylstyrene) nanospheres, denoted as x PCMS- g -PEGMA) with single-ion-conductive lithiated Nafion. The porous x PCMS inner cores with rigid hypercrosslinked skeletons substantially increase mechanical robustness and provide adequate channels for rapid ionic conduction, while the flexible PEGMA and lithiated Nafion polymers enable the formation of a structurally stable artificial protective layer with uniform Li + diffusion and high Li + transference number. With such artificial solid electrolyte interphases, ultralong-term stable cycling at an ultrahigh current density of 10 mA cm −2 for over 9,100 h (>1 year) and unprecedented reversible lithium plating/stripping (over 2,800 h) at a large areal capacity (10 mAh cm −2 ) have been achieved for lithium metal anodes. Moreover, the protected anodes also show excellent cell stability when paired with high-loading cathodes (~4 mAh cm −2 ), demonstrating great prospects for the practical application of lithium metal batteries.