Molecularly aligned electron channels for ultrafast-charging practical lithium-metal batteries

Charge transfer across interfaces constitutes the rate-determining step in electrochemical systems. Sluggish kinetics triggers side reactions and hazardous surface morphologies, as represented by dendritic/dead lithium (Li 0 ) in Li-metal batteries (LMBs), especially under ultrafast charging (UFC). Here we report an approach to accelerate interfacial charge transfer by redesigning the solvent molecular structure into a distinctive planar coordination of lone-pair electrons (LPEs) with alkaline cations (Li + or Na + ). This planar-aligned electron channel (PAEC) greatly strengthens the coupling between LPEs and Li + , promoting Li + /Li 0 redox reaction kinetics and reversibility. The designed electrolyte dramatically enables stable cycling of industrial 2 Ah Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 pouch cells at an ultrahigh rate of 4 C, achieving 100% full charge within 15 min at a charging power density of 1,747.6 W kg −1 . We establish a link between the solvation electronic structure and charge-transfer dynamics, highlighting a potential strategy for electrolyte design under extreme electrochemical conditions.