Differentiating the dominant intrinsic kinetics for lithium dendrite growth under different circumstances by computational study.

Based on DFT calculations, we have revealed some conditions for the Li dendrite-free, dendrite-formation, and dendrite-suppression processes. [Display omitted] • Three types of competitive intrinsic kinetics processes have been identified. • The dendrite-free, -forming, and -suppressing conditions are revealed. • Adjusting the intrinsic kinetics to suppress the dendrite growth was demonstrated. Although many works have been devoted to designing the dendrite-suppression lithium anodes through modifying the growth environments or electrode configurations, studies on their related intrinsic kinetics processes are still lacking. Using DFT calculations, the intrinsic kinetics processes to control the dendrite growth in different environments are investigated herein. Under different coverage concentrations and distributions of lithium, three types of competitive kinetics processes have been identified and defined as the two-dimensional (2D) accumulation, 2D dispersion, and 3D accumulation kinetics processes based on the near-neighboring interactions in the same layer. It was found that the dendrite-free condition can be realized under the natural growth processes based on the dominant 2D accumulation processes, but the dominant kinetics processes can be replaced by the 3D accumulation processes during the nonuniform deposition processes under the condition of moderate coverage concentration, leading to the formation of dendrites. Correspondingly, the suppression condition for the dendrite growth requires that the 2D dispersion kinetics processes can triumph over the 3D accumulation kinetics processes. Therefore, we employed the lithium-affinity molecules to illustrate how to adjust the 2D dispersion kinetics processes to suppress dendrite growth. These results provide microscopic guidance suppressing dendrite growth. [ABSTRACT FROM AUTHOR]