Theoretical Prediction of Phosphorene and Nanoribbons As Fast-Charging Li Ion Battery Anode Materials

Abstract

Ideal Li-ion battery materials should have a low diffusion barrier, which can realize fast charging/discharging. Here, density function theory (DFT) computations were performed to investigate the possibility of phosphorene and its nanoribbons as anode materials for Li-ion battery. Both phosphorene and its nanoribbons are direct band gap semiconductors, and show semiconductor-to-metal transition upon lithiation with significant charge transfer. Importantly, the computed energy barrier of Li diffuses on phosphorene monolayer along zigzag direction is only 0.09 eV, which indicates the possibility of ultrafast charging/discharging. Furthermore, the fast Li ion mobility is robust and well kept in phosphorene nanoribbons. The ultrahigh Li-ion mobility well distinguishes phosphorene from other typical two-dimensional (2D) materials, such as graphene and MoS 2 , and makes phosphorene a promising anode material for Li ion batteries. ■ INTRODUCTIONBlack phosphorus (BP) is the most stable phosphorus allotrope at room temperature that was first synthesized from white phosphorus under high pressure and high temperature in 1914. 1 It is a layered material coupled together by weak van der Waals (vdW) forces, structurally well resembles graphite. However, instead of a layered planar structure in graphite, BP is a puckered structure due to the sp 3 hybridization character of tetraphosphorus. Recently, two groups reported that bulk BP can be mechanically exfoliated to atomic layers which they called phosphorene. 2,3 Phosphorene turns out to be a promising material with wide potential applications. For example, phosphorene based field effect transistors (FETs) show a high charge-carrier mobility up to 1000 cm 2 V −1 s −1 , much better than other typical two-dimensional (2D) semiconductors, such as MoS 2 (around 200 cm 2 V −1 s −1 ). 3 In contract to graphene, phosphorene is a direct band gap semiconductor whose band gap strongly depending on the number of layers. 2,4 The band gap of BP can be monotonously tunable from ∼0.3 eV in bulk to ∼1.6 eV for a monolayer. 2,4 Additionally, the band gap can also be effectively modified by strain, 5−7 stack orders, 8 electric field 8 and so on. However, the most particularly characters of phosphorene are its high anisotropic electric conductance and optical responses, 2,4,5,9,10 which distinguish it from graphene and MoS 2 .On the other hand, 2D materials attract a lot of attention in the field of lithium-ion batteries (LIBs) because of their large surface-to-volume ratio and unique electronic properties. For today's LIBs, it is highly desired with high capacity and fast charging/discharging, which naturally requires strong binding and low diffusion barriers. Graphene and MoS 2 have been considered to be novel electrode materials for advanced LIBs. 11−15 Fan et al. have reported that Li atoms can be adsorbed on the hollow position with a large binding energy of 1.3 eV. 16 The large binding energy of Li atoms ensures its high capacity. However, they also demonstrated that the energy barrier of L...

Recent advances in synthesis, properties, and applications of phosphorene

“…111 The diffusion of Li in phosphorene is ultrafast and anisotropic 112 (1.6 × 10 9 times faster along the ZZ direction than along the AM direction, and 260 times faster than in graphite). Energy barriers for the Li diffusions are very low (~0.09 eV) 112,113 suggesting excellent rate capabilities. Due to significant energy barriers difference (Fig.…”

Advanced Phosphorus‐Based Materials for Lithium/Sodium‐Ion Batteries: Recent Developments and Future Perspectives

“…[128,[240][241][242][243][244][245][246] For Figure 11. The results showed that phosphorene is highly expected to present great opportunities for both high-performance LIBs and SIBs.…”

High carrier mobility of few-layer PbX (X = S, Se, Te)

“…Typical 2D material, such as graphene or carbon based 2D materials 1-9 , boron nitride (BN) 10 , transition metal dichalcogenides (TMDs) [11][12][13][14] , and black phosphorus (BP) [15][16][17][18][19] , are investigated for applications in high-performance electronic devices in field-effect transistors (FETs) 5,14,18 , thin-film solar cell 20,21 , thermoelectric devices 22,23 and lithium-ion batteries 17,24 . Typical 2D material, such as graphene or carbon based 2D materials 1-9 , boron nitride (BN) 10 , transition metal dichalcogenides (TMDs) [11][12][13][14] , and black phosphorus (BP) [15][16][17][18][19] , are investigated for applications in high-performance electronic devices in field-effect transistors (FETs) 5,14,18 , thin-film solar cell 20,21 , thermoelectric devices 22,23 and lithium-ion batteries 17,24 .…”