Unlocking Charge Transfer Limitations for Extreme Fast Charging of Li‐Ion Batteries

Abstract Extreme fast charging (XFC) of high‐energy Li‐ion batteries is a key enabler of electrified transportation. While previous studies mainly focused on improving Li ion mass transport in electrodes and electrolytes, the limitations of charge transfer across electrode–electrolyte interfaces remain underexplored. Herein we unravel how charge transfer kinetics dictates the fast rechargeability of Li‐ion cells. Li ion transfer across the cathode–electrolyte interface is found to be rate‐limiting during XFC, but the charge transfer energy barrier at both the cathode and anode have to be reduced simultaneously to prevent Li plating, which is achieved through electrolyte engineering. By unlocking charge transfer limitations, 184 Wh kg −1 pouch cells demonstrate stable XFC (10‐min charge to 80 %) which is otherwise unachievable, and the lifetime of 245 Wh kg −1 21700 cells is quintupled during fast charging (25‐min charge to 80 %).