In Situ Constructing Robust and Highly Conductive Solid Electrolyte with Tailored Interfacial Chemistry for Durable Li Metal Batteries.

Employing nanofiber framework for in situ polymerized solid-state lithium metal batteries (SSLMBs) is impeded by the insufficient Li+ transport properties and severe dendritic Li growth. Both critical issues originate from the shortage of Li+ conduction highways and nonuniform Li+ flux, as randomly-scattered nanofiber backbone is highly prone to slippage during battery assembly. Herein, a robust fabric of Li0.33 La0.56 Ce0.06 Ti0.94 O3-δ /polyacrylonitrile framework (p-LLCTO/PAN) with inbuilt Li+ transport channels and high interfacial Li+ flux is reported to manipulate the critical current density of SSLMBs. Upon the merits of defective LLCTO fillers, TFSI- confinement and linear alignment of Li+ conduction pathways are realized inside 1D p-LLCTO/PAN tunnels, enabling remarkable ionic conductivity of 1.21 mS cm-1 (26 °C) and tLi+ of 0.93 for in situ polymerized polyvinylene carbonate (PVC) electrolyte. Specifically, molecular reinforcement protocol on PAN framework further rearranges the Li+ highway distribution on Li metal and alters Li dendrite nucleation pattern, boosting a homogeneous Li deposition behavior with favorable SEI interface chemistry. Accordingly, excellent capacity retention of 76.7% over 1000 cycles at 2 C for Li||LiFePO4 battery and 76.2% over 500 cycles at 1 C for Li||LiNi0.5 Co0.2 Mn0.3 O2 battery are delivered by p-LLCTO/PAN/PVC electrolyte, presenting feasible route in overcoming the bottleneck of dendrite penetration in in situ polymerized SSLMBs.