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Register a new userExfoliation of Few-Layer Black Phosphorus in Low-Boiling-Point Solvents and Its Application in Li-Ion Batteries
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Added by
Antonio Esau Del Rio Castillo
Publication date
2018
fields
Physics
and research's language is
English
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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 c.a. 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 mAh/g at a current density of 100 mA/g, over 100 charge/discharge cycles. Moreover, a reversible specific capacity of 345 mAh/g is achieved for the FL-BPacetone-based anode at a high current density (i.e., 1 A/g). 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.
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Phosphorus atomic chains, the utmost-narrow nanostructures of black phosphorus (BP), are highly relevant to the in-depth development of BP into one-dimensional (1D) regime. In this contribution, we report a top-down route to prepare atomic chains of BP via electron beam sculpting inside a transmission electron microscope (TEM). The growth and dynamics (i.e. rupture and edge migration) of 1D phosphorus chains are experimentally captured for the first time. Furthermore, the dynamic behaviors and associated energetics of the as-formed phosphorus chains are further corroborated by density functional theory (DFT) calculations. The 1D counterpart of BP will serve as a novel platform and inspire further exploration of the versatile properties of BP.
Black phosphorus (BP) has recently emerged as an alternative 2D semiconductor owing to its fascinating electronic properties such as tunable bandgap and high charge carrier mobility. The structural investigation of few-layer BP, such as identification of layer thickness and atomic-scale edge structure, is of great importance to fully understand its electronic and optical properties. Here we report atomic-scale analysis of few-layered BP performed by aberration corrected transmission electron microscopy (TEM). We establish the layer-number-dependent atomic resolution imaging of few-layer BP via TEM imaging and image simulations. The structural modification induced by the electron beam leads to revelation of crystalline edge and formation of BP nanoribbons. Atomic resolution imaging of BP clearly shows the reconstructed zigzag (ZZ) edge structures, which is also corroborated by van der Waals first principles calculations on the edge stability. Our study on the precise identification of BP thickness and atomic-resolution imaging of edge structures will lay the groundwork for investigation of few-layer BP, especially BP in nanostructured forms.
An outstanding challenge of theoretical electronic structure is the description of van der Waals (vdW) interactions in molecules and solids. Renewed interest in resolving this is in part motivated by the technological promise of layered systems including graphite, transition metal dichalcogenides, and more recently, black phosphorus, in which the interlayer interaction is widely believed to be dominated by these types of forces. We report a series of quantum Monte Carlo (QMC) calculations for bulk black phosphorus and related few-layer phosphorene, which elucidate the nature of the forces that bind these systems and provide benchmark data for the energetics of these systems. We find a significant charge redistribution due to the interaction between electrons on adjacent layers. Comparison to density functional theory (DFT) calculations indicate not only wide variability even among different vdW corrected functionals, but the failure of these functionals to capture the trend of reorganization predicted by QMC. The delicate interplay of steric and dispersive forces between layers indicate that few-layer phosphorene presents an unexpected challenge for the development of vdW corrected DFT.
Recent experimental measurements of light absorption in few-layer black phosphorus (BP) reveal a series of high and sharp peaks, interspersed by pairs of lower and broader features. Here, we propose a theoretical model for these excitonic states in few-layer black phosphorus (BP) within a continuum approach for the in-plane degrees of freedom and a tight-binding approximation that accounts for inter-layer couplings. This yields excitonic transitions between different combinations of the sub-bands created by the coupled BP layers, which leads to a series of high and low oscillator strength excitonic states, consistent with the experimentally observed bright and dark exciton peaks, respectively. The main characteristics of such sub-band exciton states, as well as the possibility to control their energies and oscillator strengths via applied electric and magnetic fields, are discussed, towards a full understanding of the excitonic spectrum of few-layer BP and its tunability.
Forthcoming applications in electronics and optoelectronics make phosphorene a subject of vigorous research efforts. Solvent-assisted exfoliation of phosphorene promises affordable delivery in industrial quantities for future applications. We demonstrate, using equilibrium, steered and umbrella sampling molecular dynamics, that the 1-ethyl-3- methylimidazolium tetrafluoroborate [EMIM][BF4] ionic liquid is an excellent solvent for phosphorene exfoliation. The presence of both hydrophobic and hydrophilic moieties, as well as substantial shear viscosity, allows [EMIM][BF4] simultaneously to facilitate separation of phosphorene sheets and to protect them from getting in direct contact with moisture and oxygen. The exfoliation thermodynamics is moderately unfavorable, indicating that an external stimulus is necessary. Unexpectedly, [EMIM][BF4] does not coordinates phosphorene by p-electron stacking with the imidazole ring. Instead, the solvation proceeds via hydrophobic side chains, while polar imidazole rings form an electrostatically stabilized protective layer. The simulations suggest that further efforts in solvent engineering for phosphorene exfoliation should concentrate on use of weakly coordinating ions and grafting groups that promote stronger dispersion interactions, and on elongation of nonpolar chains.
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