Effects of HF on the Lithiation Behavior of the Silicon Anode in LiPF6 Organic Electrolyte Solution

As one of the major impurities in the organic electrolyte, HF can react with the alkali components in the solid electrolyte interphase (SEI), such as lithium alkoxide and lithium carbonate, to form more LiF-rich SEI. Here, the effects of HF on the lithiation behavior of the single crystal Si(111) anode were studied using scanning electron microscopy, soft X-ray emission spectroscopy, and windowless energy-dispersive X-ray spectroscopy. When the Li-Si alloy is formed in 1.0 M LiPF 6 in the propylene carbonate solvent, it has a layered structure that contained the first layer of crystalline Li 15 Si 4 (c-Li 15 Si 4 ) alloy pyramids, the second layer of amorphous Li 13 Si 4 (a-Li 13 Si 4 ) alloy, and a third layer of Li-diffused Li x Si alloy. When the more concentrated HF is in the electrolyte solution, less amount of the c-Li 15 Si 4 alloy is formed in the first layer. It suggests that the Si lithiation can form only amorphous Li x Si alloy relative to the components in the electrolytes. The study also explains why only amorphous Li x Si alloy formation was observed in some previous studies.