Exfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries

The liquid-phase exfoliation (LPE) of black phosphorus (BP) is a strategic route for the large-scale production of phosphorene and few-layer BP (FL-BP) flakes. The exploitation of this exfoliated material in cutting-edge technologies, e.g., in flexible electronics and energy storage, is however limited by the fact that the LPE of BP is usually carried out at a high boiling point and in toxic solvents. In fact, the solvent residual is detrimental to device performance in real applications; thus, complete solvent removal is critical. Here, we tackle these issues by exfoliating BP in different low-boiling-point solvents. Among these solvents, we find that acetone also provides a high concentration of exfoliated BP, leading to the production of FL-BP flakes with an average lateral size and thickness of ∼30 and ∼7 nm, respectively. The use of acetone to produce less defective few-layer BP flakes (FL-BPacetone) from bulk crystals is a straightforward process which enables the rapid preparation of homogeneous thin films thanks to the fast solvent evaporation. The ratio of edge to bulk atoms for the BP flakes here produced, combined with the use of low-boiling-point solvents for the exfoliation process, suggests that these thin films are promising anodes for lithium-ion batteries. To this end, we tested Li-ion half cells with FL-BPacetone anodes achieving a reversible specific capacity of 480 mA h g–1 at a current density of 100 mA g–1, over 100 charge/discharge cycles. Moreover, a reversible specific capacity of 345 mA h g–1 is achieved for the FL-BPacetone-based anode at high current density (i.e., 1 A g–1). These findings indicate that the FL-BPacetone-based battery is promising with regards to the design of fast charge/discharge devices. Overall, the presented process is a step forward toward the fabrication of phosphorene-based devices.