Like phosphorene, phosphorene nanoribbon (PNR) promises exotic properties but unzipping phosphorene into edge-defined PNR is non-trivial because of uncontrolled cutting of phosphorene along random directions. Here a facile electrochemical strategy to fabricate zigzag-edged PNRs in high yield (>80%) is reported. The presence of chemically active zigzag edges in PNR allows it to spontaneously react with Li to form a Li ion conducting Li P phase, which can be used as a protective layer on Li metal anode in lithium metal batteries (LMBs). PNR protective layer prevents the parasitic reaction between lithium metal and electrolyte and promotes Li ion diffusion kinetics, enabling homogenous Li ion flux and long-time cycling stability up to 1100 h at a current density of 1 mA cm . LiFePO |PNR-Li full-cell batteries with an areal capacity of 2 mAh cm , a lean electrolyte (20 µl mAh ) and a negative/positive (N/P) electrodes ratio of 3.5 can be stably cycled over 100 cycles.
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