The historical development of lithium metal batteries is briefly introduced.• General strategies for protection of Li metal anodes are reviewed. • Specific challenges of ASSBs, Li-S and Li-air batteries are extensively discussed.• Current development status is reviewed and compared to the EU SET Plan targets.

In this study, the artificial solid electrolyte interphase (SEI) formed on lithium metal when treated in ZnCl2 solutions is thoroughly investigated. The artificial SEI on lithium metal electrodes substantially decreases the interfacial resistance by ca. 80% and improves cycling stability in comparison to untreated lithium. The presence of a native SEI negatively affects the morphology and interfacial resistance of the artificial SEI. Increasing the ZnCl2 concentration in tetrahydrofuran (THF) (precursor solution) results in higher homogeneity of the surface morphology. Independent of the ZnCl2 concentrations, the artificial SEI is composed of C x , CO, LiCl, Li2CO3, ZnCl2, and Li x Zn y alloys. ZnCl2 (1 M) produces the most homogenous surface and additional surface species with carbonyl side groups. Nonetheless, the ZnCl2 concentration only has a small effect on the interfacial resistance or cycling stability. Using ethyl methyl carbonate (EMC) as the solvent significantly reduces the interfacial resistance to 7 Ω cm2, in comparison to 25 Ω cm2 for THF. The composition of the artificial SEIs varies depending on the solvent. Either way, the SEI consists of C x Li x C, LiCl, Li2CO3, ZnCl2, and LiZn alloys. The THF-based SEI additionally features ether and carbonyl groups, LiZnO, and Zn metal. For the artificial SEI formed with both solvents, the atomic percentage of the LiZn alloy increases close to the Li surface.