Silicon is widely recognized as the most promising upgrade for graphite anodes due to its much higher capacity, natural abundance, and ability to be directly applied in the slurry-based, roll-to-roll production lines. However, in addition to the fast capacity decay, silicon anodes also suffer from inferior calendar life in practical applications due to the unstable solid-electrode interface (SEI). Until now, strategies to effectively improve the calendar life by tailored SEIs remain largely unclear, especially in high-Si content, zero-graphite anodes. Here, silicon anodes with superior calendar life are developed by adding small concentrations of multivalent salts into the baseline electrolyte. The Ca additive reacts with the F ions in the electrolyte, forming a layer of nanocrystalline CaF2 that is closely coated around the silicon particles. The CaF2-enabled new SEI is strong and dense, which effectively protects the silicon core from side reactions, leading to lower capacity decay after calendar aging at high voltage. More importantly, the Ca additive is effective universally for all available commercial silicon or SiO sources. This study provides a feasible and low-cost solution for developing silicon anodes with long calendar life, paving the way towards commercially viable silicon anodes.

Mg batteries utilizing oxide cathodes can theoretically surpass the energy density of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg2+ migration within oxides, which severely handicaps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks is surprisingly deficient. Here, we present a combined experimental and theoretical study of Mg migration within three spinel oxides, which reveal critical features that influence it. Experimental activation energies for a Mg2+ hop to an adjacent vacancy, as low as ∼0.6 eV, are reported. These barriers are low enough to support functional electrodes based on the intercalation of Mg2+. Subsequent electrochemical experiments demonstrate that significant demagnesiation is indeed possible, but the challenges instead lie with the chemical stability of the oxidized states. Our findings enhance the understanding of cation transport in solid structures and renew the prospects of finding materials capable of high density of energy storage.