Bingchao Yang

Flexible All-Solid-State Supercapacitors based on Liquid-Exfoliated Black-Phosphorus Nanoflakes.

Flexible all-solid-state supercapacitors are fabricated with liquid-exfoliated black-phosphorus (BP) nanoflakes as an electrode material. These devices deliver high specific volumetric capacitance, power density, and energy density, up to 13.75 F cm(-3) , 8.83 W cm(-3) , and 2.47 mW h cm(-3) , respectively, and an outstanding long life span of over 30 000 cycles, demonstrating the excellent performance of the BP nanoflakes as a flexible electrode material in electrochemical energy-storage devices.

Te‐Doped Black Phosphorus Field‐Effect Transistors

Element doping allows manipulation of the electronic properties of 2D materials. Enhanced transport performances and ambient stability of black-phosphorus devices by Te doping are presented. This provides a facile route for achieving airstable black-phosphorus devices.

Enhanced stability of black phosphorus field-effect transistors with SiO2 passivation

Few-layer black phosphorus (BP) has attracted much attention due to its high mobility and suitable band gap for potential applic5ations in optoelectronics and flexible devices. However, its instability under ambient conditions limits its practical applications. Our investigations indicate that by passivation of the mechanically exfoliated BP flakes with a SiO2 layer, the fabricated BP field-effect transistors (FETs) exhibit greatly enhanced environmental stability. Compared to the unpassivated BP devices, which show a fast drop of on/off current ratio by a factor of 10 after one week of ambient exposure, the SiO2-passivated BP devices display a high retained on/off current ratio of over 600 after one week of exposure, just a little lower than the initial value of 810. Our investigations provide an effective route to passivate the few-layer BPs for enhancement of their environmental stability.

Large anisotropic thermal transport properties observed in bulk single crystal black phosphorus

The anisotropy of thermal transport properties for bulk black phosphorus (BP) single crystal, which might be of particular interest in the fabrication of thermoelectric/optoelectronic devices, was investigated by using angular dependent thermal conductivity and Seebeck coefficient measurements at various temperatures. We found that the maximum thermal conductivities in x (zigzag), y (armchair), and z (perpendicular to the puckered layers) directions are 34, 17, and 5 W m−1 K−1, respectively, exhibiting large anisotropy. At temperature around 200 K, a large Seebeck coefficient up to +487 ± 10 μV/K has been obtained in x direction, which is 1.5 times higher than that in z direction. The large anisotropy of thermal transport properties can be understood from the crystal structure and bonding characters of BP. In addition, the energy gap has been obtained from nuclear spin lattice relaxation measurements, which is consistent with the value derived from temperature-dependent Seebeck coefficient measurements.

Degradation of black phosphorus: a real-time 31P NMR study

In this work, degradation behaviors and mechanisms of black phosphorus (BP) crystals in air under ambient conditions were investigated by nuclear magnetic resonance spectroscopy. It has been found that the 31P NMR line intensity for BP decreases exponentially during aging even at the very first several hours, suggesting the origin of the degradation of transport properties. In addition to phosphoric acid, new phosphorous acid was also well resolved in the final aging products. Moreover, BP has been found to be stable in water without the presence of oxygen molecules. These findings are relevant for better understanding of degradation behaviors of BP upon aging and should be helpful for overcoming a barrier that might hamper progress toward applications of BP as a 2D material.

Large and Anisotropic Linear Magnetoresistance in Single Crystals of Black Phosphorus Arising From Mobility Fluctuations

Black Phosphorus (BP) is presently attracting immense research interest on the global level due to its high mobility and suitable band gap for potential application in optoelectronics and flexible devices. It was theoretically predicted that BP has a large direction-dependent electrical and magnetotransport anisotropy. Investigations on magnetotransport of BP may therefore provide a new platform for studying the nature of electron transport in layered materials. However, to the best of our knowledge, magnetotransport studies, especially the anisotropic magnetoresistance (MR) effect in layered BP, are rarely reported. Here, we report a large linear MR up to 510% at a magnetic field of 7 Tesla in single crystals of BP. Analysis of the temperature and angle dependence of MR revealed that the large linear MR in our sample originates from mobility fluctuations. Furthermore, we reveal that the large linear MR of layered BP in fact follows a three-dimensional behavior rather than a two-dimensional one. Our results have implications to both the fundamental understanding and magnetoresistive device applications of BP.

Flexible Black-Phosphorus Nanoflake/Carbon Nanotube Composite Paper for High-Performance All-Solid-State Supercapacitors

We proposed a simple route for fabrication of the flexible BP nanoflake/carbon nanotube (CNT) composite paper as flexible electrodes in all-solid-state supercapacitors. The highly conductive CNTs not only play a role as active materials but also increase conductivity of the hybrid electrode, enhance electrolyte shuttling and prevent the restacking between BP nanoflakes. The fabricated flexible all-solid-state supercapacitor (ASSP) device at the mass proportion of BP/CNTs 1:4 was found to deliver the highest volumetric capacitance of up to 41.1 F/cm3 at 0.005 V/s, superior to the ASSP based on the bare graphene or BP. The BP/CNTs (1:4) device delivers a rapid charging/discharging up to 500 V/s, which exhibits the characteristic of a high power density of 821.62 W/cm3, while having outstanding mechanical flexibility and high cycling stability over 10 000 cycles (91.5% capacitance retained). Moreover the BP/CNTs (1:4) ASSP device still retains large volumetric capacitance (35.7 F/cm3 at the scan rate of 0.005 V/s) even after 11 months. In addition, the ASSP of BP/CNTs (1:4) exhibits high energy density of 5.71 mWh/cm3 and high power density of 821.62 W/cm3. As indicated in our work, the strategy of assembling stacked-layer composites films will open up novel possibility for realizing BP and CNTs in new-concept thin-film energy storage devices.

Sulfur-Doped Black Phosphorus Field-Effect Transistors with Enhanced Stability

Black phosphorus (BP) has drawn great attention owing to its tunable band gap depending on thickness, high mobility, and large Ion/ Ioff ratio, which makes BP attractive for using in future two-dimensional electronic and optoelectronic devices. However, its instability under ambient conditions poses challenge to the research and limits its practical applications. In this work, we present a feasible approach to suppress the degradation of BP by sulfur (S) doping. The fabricated S-doped BP few-layer field-effect transistors (FETs) show more stable transistor performance under ambient conditions. After exposing to air for 21 days, the charge-carrier mobility of a representative S-doped BP FETs device decreases from 607 to 470 cm2 V-1 s-1 (remained as high as 77.4%) under ambient conditions and a large Ion/ Ioff ratio of ∼103 is still retained. The atomic force microscopy analysis, including surface morphology, thickness, and roughness, also indicates the lower degradation rate of S-doped BP compared to BP. First-principles calculations show that the dopant S atom energetically prefers to chemisorb on the BP surface in a dangling form and the enhanced stability of S-doped BP can be ascribed to the downshift of the conduction band minimum of BP below the redox potential of O2/O2-. Our work suggests that S doping is an effective way to enhance the stability of black phosphorus.

Liquid-Exfoliation of S-doped Black Phosphorus Nanosheets for Enhanced Oxygen Evolution Catalysis

Black phosphorus (BP) has recently drawn great attention in the field of electrocatalysis due to its distinct electrocatalytic activity for the oxygen evolution reaction (OER). However, the slow OER kinetics and the poor environmental stability of BP seriously limits its overall OER performance and prevents its electrocatalysis application. Here, sulfur (S)-doped BP nanosheets, which are prepared using high-pressure synthesis followed by liquid exfoliation, have been demonstrated to have much better OER electrocatalytic activity and environmental stability compared to their undoped counterparts. The S-doped BP nanosheets display a Tafel slope of 75 mV dec-1, which is a favorable value refered to the kinetics of OER in electrochemical tests. Notably, there is no degradation of S-doped BP nanosheets after six days exposure to ambient, indicating an excellent environmental stability of the S-doped BP. The density functional theory calculations show that the OER activity of BP originate from its crystal defects and heteroatom S doping can effectively enhance its OER activity and stability. These results highlight the doping effect on electrocatalytic activities and stability of BP and provide a simple and effective method to design highly efficient OER catalysts based on the modification of BP.

Metallic Layered Germanium Phosphide GeP5 for High Rate Flexible All-Solid-State Supercapacitors

In this study, high quality GeP5 crystals with two-dimensional (2D) layered structures and novel electrical conductivity of 2.4 × 106 S m−1 have been prepared under high-temperature high-pressure oriented growth technique (HTHP-OGT). The as-synthesized GeP5 nanoflakes, after liquid phase exfoliation, show promising potential for application as electrode materials in all-solid-state supercapacitors (ASSPs). The as-prepared GeP5-ASSP exhibits excellent electrochemical performances, including an ultrahigh scan rate of 1000 V s−1, a high specific capacitance of up to 35.86 F cm−3 at 5 mV s−1, a great power density of 397.24 W cm−3 and an energy density of 4.98 mW h cm−3. Moreover, the device can retain 83.7% and 88% of the initial capacitance retention at 180° bending and after 10 000 cycles, respectively, showing outstanding flexibility and superior cycling stability. These properties indicate the promising application of the metallic layered GeP5 for flexible energy storage devices.