Revealing and Elucidating ALD‐Derived Control of Lithium Plating Microstructure

The practical implementation of Li metal batteries is hindered by difficulties in controlling the Li metal plating microstructure. While previous atomic layer deposition (ALD) studies have focused on directly coating Li metal with thin films for the passivation of the electrode–electrolyte interface, a different approach is adopted, situating the ALD film beneath Li metal and directly on the copper current collector. A mechanistic explanation for this simple strategy of controlling the Li metal plating microstructure using TiO2 grown on copper foil by ALD is presented. In contrast to previous studies where ALD‐grown layers act as artificial interphases, this TiO2 layer resides at the copper–Li metal interface, acting as a nucleation layer to improve the Li metal plating morphology. Upon lithiation of TiO2, a LixTiO2 complex forms; this alloy provides a lithiophilic surface layer that enables uniform and reversible Li plating. The reversibility of lithium deposition is evident from the champion cell (5 nm TiO2), which displays an average Coulombic efficiency (CE) of 96% after 150 cycles at a moderate current density of 1 mA cm−2. This simple approach provides the first account of the mechanism of ALD‐derived Li nucleation control and suggests new possibilities for future ALD‐synthesized nucleation layers. A thin film of atomic layer deposition (ALD)‐grown TiO2 deposited on a copper current collector enables uniform and stable nucleation of lithium metal by forming a lithiophilic layer of LixTiO2 and reducing the overpotential for lithium deposition. Growing atomically precise thin films on copper current collectors is a promising strategy for lithium nucleation control.