%ARojaee, Ramin%ACavallo, Salvatore%AMogurampelly, Santosh%AWheatle, Bill%AYurkiv, Vitaliy%ADeivanayagam, Ramasubramonian%AForoozan, Tara%ARasul, Md%ASharifi‐Asl, Soroosh%APhakatkar, Abhijit%ACheng, Meng%ASon, Seoung‐Bum%APan, Yayue%AMashayek, Farzad%AGanesan, Venkat%AShahbazian‐Yassar, Reza%BJournal Name: Advanced Functional Materials %D2020%I %JJournal Name: Advanced Functional Materials %K %MOSTI ID: 10168753 %PMedium: X %THighly‐Cyclable Room‐Temperature Phosphorene Polymer Electrolyte Composites for Li Metal Batteries %XDespite significant interest toward solid-state electrolytes owing to their superior safety in comparison to liquid-based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high-power density batteries. Here, a novel quasi-solid Li+ ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm(-2) at room temperature. The cycling overpotential is dropped by 75% in comparison to BP-free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li+ ions around (trifluoromethanesulfonyl)imide (TFSI-) pairs and ethylene-oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li+ transport through the polymer host. Density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li+ ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid-state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long-life cycling. %0Journal Article