In situ p-block protective layer plating in carbonate-based electrolytes enables stable cell cycling in anode-free lithium batteries

‘Anode-free’ Li metal batteries offer the highest possible energy density but face low Li coulombic efficiency when operated in carbonate electrolytes. Here we report a performance improvement of anode-free Li metal batteries using p -block tin octoate additive in the carbonate electrolyte. We show that the preferential adsorption of the octoate moiety on the Cu substrate induces the construction of a carbonate-less protective layer, which inhibits the side reactions and contributes to the uniform Li plating. In the mean time, the reduction of Sn 2+ at the initial charging process builds a stable lithophilic layer of Cu 6 Sn 5 alloy and Sn, improving the affinity between the Li and the Cu substrate. Notably, anode-free Li metal pouch cells with tin octoate additive demonstrate good cycling stability with a high coulombic efficiency of ~99.1%. Furthermore, this in situ p -block layer plating strategy is also demonstrated with other types of p -block metal octoate, as well as a Na metal battery system, demonstrating the high level of universality. A p -block metal octoate additive in carbonate electrolytes enables the reversible plating/stripping of alkali metal in anode-free batteries by forming a protective layer with a preferentially adsorbed octoate moiety and uniformly plated p -block metal.