Interfacial Design Strategy for Polymeric Lithium Metal Batteries with Superfast Charge‐Transfer Kinetics

Abstract

AbstractInterfacial instability including the high charge‐transfer resistance and the uncontrolled lithium dendrite growth have severely restricted the safety, fast‐charging, and high‐power capabilities of solid‐state polymeric lithium metal batteries (PLMBs). Here, the study demonstrates the ionic nanoclusters self‐assembled between the lithium ions and a rigid‐rod sulfonated aromatic polyamide Poly 2,2′‐disulfonyl‐4,4′‐benzidine terephthalamide (PBDT) can facilitate uniform lithium deposition; meanwhile, realizing 102–103 times lower interfacial charge‐transfer resistance than PEO‐based electrolytes and excellent lithium dendrite suppression at the interfaces. The cells assembled with this solid‐state polymer electrolyte at room temperature show a record high critical current density (6 mA cm−2/3 mAh cm−2), 80% capacity retention at 10 000 cycles (5 C) with the LiFePO4 cathode. With the temperature increased to 80 °C, the cells enable almost 100% of the theoretical capacity at 3 C and high specific power density (20 kW kg−1). According to the Cryo‐TEM imaging and computational simulation results, it is concluded that these nanoscale self‐assembled ionic nanoclusters play a critical role in realizing the superfast charge‐transfer kinetics by balancing the pre‐exponential factor and activation energy at the lithium‐polymer space‐charge interfaces. This interfacial design strategy based on thermodynamically favored ion‐association and self‐assembly between the metal ions and the polyanions guarantees superior charge‐transfer kinetics in PLMBs.