Flattening of Lithium Plating in Carbonate Electrolytes Enabled by All-In-One Separator

The uncontrollable dendritic growth of metallic lithium during repeated cycling in carbonate electrolytes is a crucial obstacle hindering the practical use of Li-metal batteries (LMBs). Among numerous approaches proposed to mitigate the intrinsic constraints of Li metal, the design of a functional separator is an attractive approach to effectively suppress the growth of Li dendrites because direct contact with both the Li metal surface and the electrolyte is maintained. Here, a newly designed all-in-one separator containing bifunctional CaCO₃ nanoparticles (CPP separator) is proposed to achieve the flattening of Li deposits on the Li electrode. Strong interactions between the highly polar CaCO₃ nanoparticles and the polar solvent reduces the ionic radius of the Li⁺ -solvent complex, thus increasing the Li⁺ transference number and leading to a reduced concentration overpotential in the electrolyte-filled separator. Furthermore, the integration of CaCO₃ nanoparticles into the separator induces the spontaneous formation of mechanically-strong and lithiophilic CaLi₂ at the Li/separator interface, which effectively decreases the nucleation overpotential toward Li plating. As a result, the Li deposits exhibit dendrite-free planar morphologies, thus enabling excellent cycling performance in LMBs configured with a high-Ni cathode in a carbonate electrolyte under practical operating conditions.