Free-Standing Black Phosphorus Thin Films for Flexible Quasi-Solid-State Micro-Supercapacitors with High Volumetric Power and Energy Density.

Micro-supercapacitors (micro-SCs) are significant micro-scale power sources and energy storage components for miniaturized electronic and flexible devices, where electrodes play a key role in determining their electrochemical performances. The efficient intercalation of ions between the stacking layers of two-dimensional layered materials (2DLM) makes them great candidates as thin-film electrodes in micro-SCs, where one can achieve much enhanced volumetric capacitance. However, a great challenge is to develop a high-yield production method for high-quality 2DLM thin-film electrodes. In this work, we have successfully reported a scalable fabrication process for free-standing black phosphorous (BP) thin films, derived from high-quality few-layer BP nanoflakes via a modified electrochemical exfoliation route, for flexible quasi-solid-state micro-SCs (QMSCs). The as-fabricated QMSCs exhibit an excellent stable electrochemical performance at a high scan rate of up to 100 V s-1. More importantly, our QMSC device can not only achieve an outstanding energy density of 3.63 mW h cm-3, a remarkable power density of 10.1 W cm-3, and a superior cycle span (94.3% capacity retention even after 50 000 cycles), but also deliver excellent mechanical flexibility demonstrated by 91.3% capacity retention after 500 mechanical bending cycles. More interestingly, to meet the energy density and power density needs for various practical applications, multiple QMSCs can be successfully integrated in parallel or in series, which is demonstrated by lighting up of the red-light-emitting diode. The BP-based QMSCs can be patterned on a single substrate with flexible photodetectors based on same BP thin film to form a self-powered optoelectronic system.