Sequenced Interfacial Chemistry for Stabilizing Reactive Lithium Metal Anodes

The significant power held by lithium metal (Li⁰) anodes has remained promising on paper for nearly a century owing to its extreme reactivity and the consequent severe interfacial instability. Here we report the effect of sequential interfacial electrochemistry in regulating the Li⁰-reactivity that convolutes Li⁺ transport, Li⁰ deposition, and solid-electrolyte interphase (SEI) formation. Combining experimental observations and theoretical calculations, we reveal that crystalline oxides coordinate interfacial cation-anion interactions and enforce structural and chemical orders at the Li⁰-electrolyte interface. The ordered microenvironment reorganizes the otherwise chaotic, multistep reactions into a temporally and spatially coherent sequence that orchestrates solvation regulation, Li⁰ nucleation and growth, and SEI assembly, thereby markedly enhancing the stability of the Li⁰ electrodes. The dual-regulation principle thus established exerts energetic and spatial control through sequenced interfacial chemistry that could offer a universal strategy for stabilizing reactive metal anodes across diverse battery chemistries.