In Situ Lattice-Resolution Revelation of the Origins of Unexplored Anisotropic Sodiation Kinetics and Phase Transition in the Niobium Sulfide Anode.

Layered transition metal dichalcogenides (TMDs) have exhibited huge potential as anode materials for sodium-ion batteries. Most of them usually store sodium via an intercalation-conversion mechanism, but niobium sulfide (NbS2) may be an exception. Herein, through in situ transmission electron microscopy, we carefully investigated the insertion behaviors of Na ions in NbS2 and directly visualized anisotropic sodiation kinetics. Lattice-resolution imaging coupled with density functional theory calculations reveals the preferential diffusion of Na ions within layers of NbS2, accompanied by observable interlayer lattice expansion. Impressively, the Na-inserted layers can still withstand in situ mechanical testing. Further in situ observation vertical to the a/b plane of NbS2 tracked the illusive conversion reaction, which could result from interlayer gliding or wrinkling associated with stress accumulation. In situ electron diffraction measurements ruled out the possibility of such a conversion mechanism and identified a phase transition from pristine 3R-NbS2 to 2H-NaNbS2. Therefore, the NbS2 anode stores Na ions via only the intercalation mechanism, which conceptually differs from the well-known intercalation-conversion mechanism of typical TMDs. These findings not only decipher the whole sodiation process of the NbS2 anode but also provide valuable reference for unraveling the precise sodium storage mechanism in other TMDs.

A 2D-0D-2D Sandwich Heterostructure toward High-Performance Room-Temperature Gas Sensing.

The construction of two-dimensional (2D) van der Waals (vdW) heterostructures over black phosphorus (BP) has been attracting significant attention to better utilize its inherent properties. The sandwich of zero-dimensional (0D) noble metals within BP-based vdW heterostructures can provide efficient catalytic channels, modulating their surface redox potentials and therefore inducing versatile functionalities. Herein, we realize a 2D WS2-Au-BP heterostructure, in which Au nanoparticles are connected between BP and WS2 via ionic bonds. The ultralow conduction band minimum position, the reduced adsorption energies of O2, and the increased dissociation barrier energy of O2- into 2O contribute greatly to improving the long-term stability of BP in the air. The formation of heterostructures can reduce the potential barrier energy in target gas molecules, thus enhancing the absorption energy and charge transfer. Taking the paramagnetic NO2 gas molecules as a representative, a stable response magnitude of 2.11 to 100 ppb NO2 is achieved for 80 days, which is far larger than the initial responses of most BP-based materials. A practical gas sensing system is also developed to demonstrate its real-world implementation. This work provides a promising demonstration of 0D noble metal within 2D BP-based vdW heterostructure for simultaneously improving the long-term stability and room-temperature reversible gas sensing.

In Situ Atomic-Scale Deciphering of Multiple Dynamic Phase Transformations and Reversible Sodium Storage in Ternary Metal Sulfide Anode.

Ternary metal sulfides (TMSs), endowed with the synergistic effect of their respective binary counterparts, hold great promise as anode candidates for boosting sodium storage performance. Their fundamental sodium storage mechanisms associated with dynamic structural evolution and reaction kinetics, however, have not been fully comprehended. To enhance the electrochemical performance of TMS anodes in sodium-ion batteries (SIBs), it is of critical importance to gain a better mechanistic understanding of their dynamic electrochemical processes during live (de)sodiation cycling. Herein, taking BiSbS3 anode as a representative paradigm, its real-time sodium storage mechanisms down to the atomic scale during the (de)sodiation cycling are systematically elucidated through in situ transmission electron microscopy. Previously unexplored multiple phase transformations involving intercalation, two-step conversion, and two-step alloying reactions are explicitly revealed during sodiation, in which newly formed Na2BiSbS4 and Na2BiSb are respectively identified as intermediate phases of the conversion and alloying reactions. Impressively, the final sodiation products of Na6BiSb and Na2S can recover to the original BiSbS3 phase upon desodiation, and afterward, a reversible phase transformation can be established between BiSbS3 and Na6BiSb, where the BiSb as an individual phase (rather than respective Bi and Sb phases) participates in reactions. These findings are further verified by operando X-ray diffraction, density functional theory calculations, and electrochemical tests. Our work provides valuable insights into the mechanistic understanding of sodium storage mechanisms in TMS anodes and important implications for their performance optimization toward high-performance SIBs.

Enhancing the ambient stability of few-layer black phosphorus by surface modification.

Based on high-throughput density functional theory calculations, we investigated the adsorption characteristics of various elements across the Periodic Table on few-layer black phosphorus (BP). Using the criterion that the ratio of adsorption energy (E ads) to bulk cohesive energy (E coh) is greater than one (E ads/E coh > 1), we selected fifteen elements. The adsorption of these elements on few-layer BPs could significantly shift their conduction-band minimum (CBM) downward, suggesting the possibility of preventing the few-layer BPs from oxidation if the CBM can be shifted below the O2/O2 - redox potential. Our study offers an efficient approach to overcoming the technical barrier in the practical application of few-layer BPs by enhancing its ambient stability via surface modification.

CO Adsorption on Metal-Decorated Phosphorene.

Using first principle calculations, we have investigated the adsorption of CO gas on various metal-decorated phosphorene. Almost all of the metals were considered to decorate phosphorene. By comparing binding energy (E b) and cohesive energy (E c), only 10 metals (Li, Na, K, Rb, Cs, Ca, Sr, Ba, Pd, and La) can stably decorate phosphorene and avoid clustering. CO adsorptions on these metal-decorated systems were calculated, and the mechanism of interaction between CO and metal atoms was analyzed in detail. E a shows a significant improvement after metal decoration, excerpt for Rb and Cs. The results imply that Li-, Na-, K-, Ca-, Sr-, Ba-, and La-decorated phosphorene could be used as CO elimination or reversible CO storage.

Orientation Effects in Ballistic High-Strained P-type Si Nanowire FETs.

In order to design and optimize high-sensitivity silicon nanowire-field-effect transistor (SiNW FET) pressure sensors, this paper investigates the effects of channel orientations and the uniaxial stress on the ballistic hole transport properties of a strongly quantized SiNW FET placed near the high stress regions of the pressure sensors. A discrete stress-dependent six-band k.p method is used for subband structure calculation, coupled to a two-dimensional Poisson solver for electrostatics. A semi-classical ballistic FET model is then used to evaluate the ballistic current-voltage characteristics of SiNW FETs with and without strain. Our results presented here indicate that [110] is the optimum orientation for the p-type SiNW FETs and sensors. For the ultra-scaled 2.2 nm square SiNW, due to the limit of strong quantum confinement, the effect of the uniaxial stress on the magnitude of ballistic drive current is too small to be considered, except for the [100] orientation. However, for larger 5 nm square SiNW transistors with various transport orientations, the uniaxial tensile stress obviously alters the ballistic performance, while the uniaxial compressive stress slightly changes the ballistic hole current. Furthermore, the competition of injection velocity and carrier density related to the effective hole masses is found to play a critical role in determining the performance of the nanotransistors.

Negative index of refraction in metallic metamaterial comprising split-ring resonators.

We numerically investigate the negative index of refraction in a metamaterial composed of metallic split-ring resonators, which exhibits simultaneously negative permittivity and permeability without resorting to additional metallic wires. It is confirmed that, in the left-handed band, negative permittivity is generated in analogy to the cut-wire metamaterial and negative permeability comes from the antisymmetric resonant mode, which occurs at a frequency band about 3 times higher than the fundamental magnetic resonance proposed by Pendry [IEEE Trans. Microwave Theory Tech. 47, 2075 (1999)].