LiZn/LiAlO2/Li2O‐Derived Chemical Confinement Enabling Hierarchical and Oriented Li Plating/Stripping

ABSTRACT ZnO with good lithiophilicity has widely been employed to modify the lithiophobic substrates and facilitate uniform lithium (Li) deposition. The overpotential of ZnO‐derived Li anode during cycling depends on the lithiophilicity of both LiZn and Li 2 O products upon lithiation of ZnO. However, the striking differences in the lithiophilicity between Li 2 O and LiZn would result in a high overpotential during cycling. In this research, the Al 2 O 3 / n ZnO ( n ≥ 1) hybrid layers were precisely fabricated by atomic layer deposition (ALD) to regulate the lithiophilicity of ZnO phase and Li 2 O/LiZn configuration—determining the actual Li loading amount and Li plating/stripping processes. Theoretically, the Li adsorption energy ( E a ) values of LiZn and Li 2 O in the LiZn/Li 2 O configuration are separately predicted as −2.789 and −3.447 eV. In comparison, the E a values of LiZn, LiAlO 2, and Li 2 O in the LiZn/LiAlO 2 /Li 2 O configuration upon lithiation of Al 2 O 3 /8ZnO layer are calculated as −2.899, −3.089, and −3.208 eV, respectively. Importantly, a novel introduction of LiAlO 2 into the LiZn/Li 2 O configuration could enable the hierarchical Li plating/stripping and reduce the overpotentials during cycling. Consequently, the Al 2 O 3 /8ZnO‐derived hybrid Li‐metal anode could exhibit electrochemical performances superior to these of ZnO‐derived Li anode in both symmetrical and full cells paired with a LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode.