Atomic to Nanoscale Origin of Vinylene Carbonate Enhanced Cycling Stability of Lithium Metal Anode Revealed by Cryo-Transmission Electron Microscopy

Batteries using lithium (Li) metal as the anode are considered promising energy storage systems because of their high specific energy densities. The crucial bottlenecks for Li metal anode are Li dendrites growth and side reactions with electrolyte inducing safety concern, low Coulombic efficiency (CE), and short cycle life. Vinylene carbonate (VC), as an effective electrolyte additive in Li-ion batteries, has been noticed to significantly enhance the CE, whereas the origin of such an additive remains unclear. Here we use cryogenic transmission electron microscopy imaging combing with energy dispersive X-ray spectroscopy elemental and electron energy loss spectroscopy electronic structure analyses to reveal the role of the VC additive. We discovered that the electrochemically deposited Li metal (EDLi) in the VC-containing electrolyte is slightly oxidized with the solid electrolyte interphase (SEI) being a nanoscale mosaic-like structure comprised of organic species, Li 2 O and Li 2 CO 3 , whereas the EDLi formed in the VC-free electrolyte is featured by a combination of fully oxidized Li with Li 2 O SEI layer and pure Li metal with multilayer nanostructured SEI. These results highlight the possible tuning of crucial structural and chemical features of EDLi and SEI through additives and consequently direct correlation with electrochemical performance, providing valuable guidelines to rational selection, design, and synthesis of additives for new battery chemistries.