Single‐Atom Reversible Lithiophilic Sites toward Stable Lithium Anodes

Abstract Lithiophilic sites with high binding energy to Li have shown the capability to guide uniform Li deposition, however, the irreversible reaction between Li and lithiophilic sites causes a loss of lithiophilicity. Herein, the concept of using reversible lithiophilic sites, such as single‐atoms (SAs) doped graphene, as a host, is systematically inspected in the context of Li metal battery (LMB) performance. Here, it is proposed that the binding energy to Li atoms should be within a certain threshold range, i.e., strong enough to inhibit Li dendrite growth and weak enough to avoid host structure collapse. Six kinds of SAs are utilized; doped 3D graphene, nitrogen‐doped 3D graphene, and pure 3D graphene, whose performance in LMBs are compared with each other. It is discovered that the SA‐Mn doped 3D graphene (SAMn@NG) has the most reversible lithiophilic site, in which adsorption strength with Li is suitable to guide uniform deposition and keep the structure stable. During Li plating/stripping, the changes of the atomic structures in SAMn@NG, such as change of bond length and bond angle around Mn atoms are much smaller than those on SAZr@NG, although its binding energy is higher, enabling a much‐improved battery performance in SAMn@NG. This work provides a new insight to design lithiophilic sites in LMBs.