Nucleation mechanism and substrate modification of lithium metal anode

Abstract

Li is highly attractive anode material for next-generation high-energy-density batteries, such as Li-air, Li-sulfur, and solid-state Li-based systems because of its exceedingly low electrode potential (−3.04 V vs the standard hydrogen electrode) and ultra-high theoretical capacity (3860 mAh·g−1). However, Li metal anodes and Li-based batteries are plagued by issues, including unstable solid electrolyte interface (SEI), dead Li formation, and uncontrollable dendritic growth. These limitations result in low cycling stability and could induce short circuits, thermal runaway, and safety hazards. In recent years, a variety of efficient strategies have been proposed to alleviate the challenges faced by Li anodes. For example, the design of Li-free anodes (with Li supplied from the lithiated cathode) or Li-composite anodes has attracted significant attention. Their population can be ascribed to the use of non-excessive Li metal that could be potentially safer and easier to produce. In Li-free and Li-composite anodes, the initial nucleation sites play a crucial role in influencing the subsequent Li electroplating behavior. Stable, homogenous Li electrodeposition is crucial for improving Coulomb efficiency and inhibiting dendrite formation. Moreover, it is also desirable to explore the nucleation and growth mechanism of Li metal on substrates or current collectors. Therefore, in this article, we aim to provide an overview of the mechanism of Li nucleation and strategies to enhance Li metal batteries via substrate modification. The mechanisms of Li nucleation are discussed in terms of nucleation-driven forces and the relation between nuclei size/distribution and overpotential/current density. Heterogeneous nucleation and Chazalviel space charge models are introduced to describe the deposition behaviors of Li in the initial nucleation stage. In the heterogeneous nucleation process, the formation of Li nuclei and its kinetics depend on the nucleation barrier, which correlates with the properties of substrates, such as their crystal structure, lattice matching, facets, and defects. The space charge model can be applied to low-concentration electrolytes or rapid Li deposition, where the decrease in ion concentration on the electrode surface induces a localized space charge and polarized electric field. This subsequently affects the microstructure and morphology of the deposited Li. After discussing the nucleation mechanism and substrate effect, strategies to stabilize nucleation and suppress dendrite are highlighted, such as three-dimensional frameworks, heterogeneous crystal nuclei, Li storage buffer layers, electric field effects, and lattice matching engineering. Information gained from the perspective of Li nucleation and the substrate effect might enlighten the development of strategies to upgrade metallic Li anodes for application in Li-based batteries.