Size-Dependent Electrochemical Performance Mediated by Stress-Induced Cracking in Zn2SnO4 Electrodes.

Correlating the microscopic structural characteristics with the macroscopic electrochemical performance in electrode materials is critical for developing excellent-performance lithium-ion batteries, which however remains largely unexplored. Here, we show that the Zn2SnO4 (ZTO) nanowires (NWs) with smaller diameters (d < 5 nm) exhibit slower capacity fade rate and better cycling stability, as compared with the NWs with larger diameters ranging from tens to hundreds of nanometers. By applying in situ transmission electron microscopy (TEM), we discover a strong correlation of cracking behavior with the NW diameter. Upon the first lithiation, there exists a critical diameter of ∼80 nm, below which the NWs neither crack nor fracture, and above which the cracks could easily nucleate and propagate along the specific planes, resulting in the deteriorated cycling stability in larger sized electrodes. Further theoretical calculations based on the finite element model and the climbing image nudged elastic band method faithfully predict the size-dependent cracking behaviors, which may result from the synergistic effect of axial stress evolution as well as preferential Li-ion migration directions during the first lithiation. This work provides a real-time tracking of the tempo-spatial structural evolution of a single ZTO NW, which facilitates a fundamental understanding of how the sample size affects the electrochemical behavior and thus offers a reference for future battery design and application strategy.

Novel Ultra-Stable 2D SbBi Alloy Structure with Precise Regulation Ratio Enables Long-Stable Potassium/Lithium-Ion Storage.

The inferior cycling stabilities or low capacities of 2D Sb or Bi limit their applications in high-capacity and long-stability potassium/lithium-ion batteries (PIBs/LIBs). Therefore, integrating the synergy of high-capacity Sb and high-stability Bi to fabricate 2D binary alloys is an intriguing and challenging endeavor. Herein, a series of novel 2D binary SbBi alloys with different atomic ratios are fabricated using a simple one-step co-replacement method. Among these fabricated alloys, the 2D-Sb0.6 Bi0.4 anode exhibits high-capacity and ultra-stable potassium and lithium storage performance. Particularly, the 2D-Sb0.6 Bi0.4 anode has a high-stability capacity of 381.1 mAh g-1 after 500 cycles at 0.2 A g-1 (≈87.8% retention) and an ultra-long-cycling stability of 1000 cycles (0.037% decay per cycle) at 1.0 A g-1 in PIBs. Besides, the superior lithium and potassium storage mechanism is revealed by kinetic analysis, in-situ/ex-situ characterization techniques, and theoretical calculations. This mainly originates from the ultra-stable structure and synergistic interaction within the 2D-binary alloy, which significantly alleviates the volume expansion, enhances K+ adsorption energy, and decreases the K+ diffusion energy barrier compared to individual 2D-Bi or 2D-Sb. This study verifies a new scalable design strategy for creating 2D binary (even ternary) alloys, offering valuable insights into their fundamental mechanisms in rechargeable batteries.

Unexpected Two-Dimensional Polarons Induced by Oxygen Vacancies in Layered Structure MoO3-x.

Unveiling the effects of oxygen vacancies on the structural stability of layered α-MoO3 is critical for optimizing its physical and chemical properties. Herein, we present experimental evidence regarding the phase stability of α-MoO3 with ∼2% oxygen vacancy concentrations. Interestingly, we report a previously ignored oxygen-deficient orthorhombic MoO3-x phase in space group Cmcm. Further density functional theory calculations reveal a detailed phase transition mechanism from α-MoO3 to MoO3-x. More importantly, we demonstrate that two-dimensional (2D) large polarons must exist to stabilize the MoO3-x crystal structure. 2D large polarons are suspected to exist in numerous quasi-2D systems but have never been found in layered α-MoO3 or other molybdenum oxides. Our work contributes to a basic understanding of the polaronic behavior in MoO3-x and may broaden the application realm of molybdenum oxides.

Size-Dependent Phase Transition in Ultrathin Ga2O3 Nanowires.

Gallium oxide (Ga2O3) has attracted extensive attention as a potential candidate for low-dimensional metal-oxide-semiconductor field-effect transistors (MOSFETs) due to its wide bandgap, controllable doping, and low cost. The structural stability of nanoscale Ga2O3 is the key parameter for designing and constructing a MOSFET, which however remains unexplored. Using in situ transmission electron microscopy, we reveal the size-dependent phase transition of sub-2 nm Ga2O3 nanowires. Based on theoretical calculations, the transformation pathways from the initial monoclinic ß-phase to an intermediate cubic γ-phase and then back to the ß-phase have been mapped and identified as a sequence of Ga cation migrations. Our results provide fundamental insights into the Ga2O3 phase stability within the nanoscale, which is crucial for advancing the miniaturization, light weight, and integration of wide-bandgap semiconductor devices.

Na+ Migration Mediated Phase Transitions Induced by Electric Field in the Framework Structured Tungsten Bronze.

Framework structured tungsten bronzes serve as promising candidates for electrode materials in sodium-ion batteries (SIBs). However, the tungsten bronze framework structure changes drastically as mediated by the sodium ion concentration at high temperatures. While the three-dimensional ion channels facilitate fast ion storage and transport capabilities, the structural instability induced by Na+ migration is a big concern regarding the battery performance and safety, which unfortunately remains elusive. Here, we show the real-time experimental evidence of the phase transitions in framework structured Na0.36WO3.14 (triclinic phase) by applying different external voltages. The Na+-rich (Na0.48WO3, tetragonal phase) or -deficient (NaxWO3, x < 0.36, hexagonal phase) phase nucleates under the positive or negative bias, respectively. Combined with the theoretical calculations, the atomistic phase transition mechanisms associated with the Na+ migration are directly uncovered. Our work sheds light on the phase instability in sodium tungsten bronzes and paves the way for designing advanced SIBs with high-stability.

Pseudo-Elasticity and Variable Electro-Conductivity Mediated by Size-Dependent Deformation Twinning in Molybdenum Nanocrystals.

Deformation twinning merits attention because of its intrinsic importance as a mode of energy dissipation in solids. Herein, through the atomistic electron microscopy observations, the size-dependent twinning mechanisms in refractory body-centered cubic molybdenum nanocrystals (NCs) under tensile loading are shown. Two distinct twinning mechanisms involving the nucleation of coherent and inclined twin boundaries (TBs) are uncovered in NCs with smaller (diameter < ≈5 nm) and larger (diameter > ≈5 nm) diameters, respectively. Interestingly, the ultrahigh pseudo-elastic strain of ≈41% in sub-5 nm-sized crystals is achieved through the reversible twinning mechanism. A typical TB cross-transition mechanism is found to accommodate the NC re-orientation during the pseudo-elastic deformation. More importantly, the effects of different types of TBs on the electrical conductivity based on the repeatable experimental measurements and first-principles calculations are quantified. These size-dependent mechanical and electrical properties may prove essential in advancing the design of next-generation flexible nanoelectronics.

Integrating Dually Encapsulated Si Architecture and Dense Structural Engineering for Ultrahigh Volumetric and Areal Capacity of Lithium Storage.

High-theoretical-capacity silicon anodes hold promise in lithium-ion batteries (LIBs). Nevertheless, their huge volume expansion (∼300%) and poor conductivity show the need for the simultaneous introduction of low-density conductive carbon and nanosized Si to conquer the above issues, yet they result in low volumetric performance. Herein, we develop an integration strategy of a dually encapsulated Si structure and dense structural engineering to fabricate a three-dimensional (3D) highly dense Ti3C2Tx MXene and graphene dual-encapsulated Si monolith architecture (HD-Si@Ti3C2Tx@G). Because of its high density (1.6 g cm-3), high conductivity (151 S m-1), and 3D dense dual-encapsulated Si architecture, the resultant HD-Si@Ti3C2Tx@G monolith anode displays an ultrahigh volumetric capacity of 5206 mAh cm-3 (gravimetric capacity: 2892 mAh g-1) at 0.1 A g-1 and a superior long lifespan of 800 cycles at 1.0 A g-1. Notably, the thick and dense monolithic anode presents a large areal capacity of 17.9 mAh cm-2. In-situ TEM and ex-situ SEM techniques, and systematic kinetics and structural stability analysis during cycling demonstrate that such superior volumetric and areal performances stem from its dual-encapsulated Si architecture by the 3D conductive and elastic networks of MXene and graphene, which can provide fast electron and ion transfer, effective volume buffer, and good electrolyte permeability even with a thick electrode, whereas the dense structure results in a large volumetric performance. This work offers a simple and feasible strategy to greatly improve the volumetric and areal capacity of alloy-based anodes for large-scale applications via integrating a dual-encapsulated strategy and dense-structure engineering.

An Efficient Strategy toward Multichambered Carbon Nanoboxes with Multiple Spatial Confinement for Advanced Sodium-Sulfur Batteries.

Intricate hollow carbon structures possess vital function for anchoring polysulfides and enhancing the utilization of sulfur in room-temperature sodium-sulfur batteries. However, their synthesis is extremely challenging due to the complex structure. Here, a facile and efficient strategy is developed for the controllable synthesis of N/O-doped multichambered carbon nanoboxes (MCCBs) by selective etching and stepwise carbonization of ZIF-8 nanocubes. The MCCBs consist of porous carbon shells on the outside and connected carbon grids with a hollow structure on the inside, bringing about a MCCBs structure. As a sulfur host, the multichambered structure has better spatial encapsulation and integrated conductivity via the inner interconnected carbon grids, which combines the characteristics of short charge transfer path and superb physicochemical adsorption along with mechanical strength. As expected, the S@MCCBs cathode realizes decent cycle stability (0.045% capacity decay per cycle over 800 cycles at 5 A g-1) and enhanced rate performance (328 mA h g-1 at 10 A g-1). Furthermore, in situ transmission electron microscopy (TEM) observation confirms the good structural stability of the S@MCCBs during the (de)sodiation process. Our work demonstrates an effective strategy for the rational design and accurate construction of intricate hollow materials for high-performance energy storage systems.

Cation Defect Mediated Phase Transition in Potassium Tungsten Bronze.

Applying in situ transmission electron microscopy, the phase instability in potassium tungsten bronze (KxWO3, 0.18 < x < 0.57) induced by heating was investigated. The atomistic phase transition pathway of monoclinic K0.20WO3 → hexagonal KmWO3 (0.18 < m < 0.20) → cubic WO3 induced by cationic defects (K and W vacancies) was directly revealed. Unexpectedly, a K+-rich tetragonal KnWO3 (0.40 < n < 0.57) phase would nucleate as well, which may result from the blockage of K+ diffusion at the grain boundaries. Our results point out the critical role of the cationic defects in mediating the crystal structures in KxWO3, which provide reference to rational structural design for extensive high-temperature applications.

Room-temperature oxygen vacancy migration induced reversible phase transformation during the anelastic deformation in CuO.

From the mechanical perspectives, the influence of point defects is generally considered at high temperature, especially when the creep deformation dominates. Here, we show the stress-induced reversible oxygen vacancy migration in CuO nanowires at room temperature, causing the unanticipated anelastic deformation. The anelastic strain is associated with the nucleation of oxygen-deficient CuOx phase, which gradually transforms back to CuO after stress releasing, leading to the gradual recovery of the nanowire shape. Detailed analysis reveals an oxygen deficient metastable CuOx phase that has been overlooked in the literatures. Both theoretical and experimental investigations faithfully predict the oxygen vacancy diffusion pathways in CuO. Our finding facilitates a better understanding of the complicated mechanical behaviors in materials, which could also be relevant across multiple scientific disciplines, such as high-temperature superconductivity and solid-state chemistry in Cu-O compounds, etc.

Green, Template-Less Synthesis of Honeycomb-like Porous Micron-Sized Red Phosphorus for High-Performance Lithium Storage.

Large-volume-expansion-induced material pulverization severely limits the electrochemical performance of high-capacity red phosphorus (RP) in alkali-ion batteries. Honeycomb-like porous materials can effectively solve the issues due to their abundant interconnected pore structures. Nevertheless, it is difficult and greatly challenging to fabricate a honeycomb-like porous RP that has not yet been fabricated via chemical synthesis. Herein, we successfully fabricate a honeycomb-like porous micron-sized red phosphorus (HPRP) with a controlled pore structure via a large-scale green and template-less hydrothermal strategy. It is demonstrated that dissolved oxygen in the solution can accelerate the destruction of P9 cages of RP, thus forming abundant active defects with a faster reaction rate, so the fast corrosion forms the honeycomb-like porous structure. Owing to the free volume, interconnected porous structure, and strong robustness, the optimized HPRP-36 can mitigate drastic volume variation and prevent pulverization during cycling resulting in tiny particle-level outward expansion, demonstrated by in situ TEM and ex situ SEM analysis. Thus, the HPRP-36 anode delivers a large reversible capacity (2587.4 mAh g-1 at 0.05 A g-1) and long-cycling stability with over 500 cycles (∼81.9% capacity retention at 0.5 A g-1) in lithium-ion batteries. This generally scalable, green strategy and deep insights provide a good entry point in designing honeycomb-like porous micron-sized materials for high-performance electrochemical energy storage and conversion.

Atomistic and dynamic structural characterizations in low-dimensional materials: recent applications of in situ transmission electron microscopy.

In situ transmission electron microscopy has achieved remarkable advances for atomic-scale dynamic analysis in low-dimensional materials and become an indispensable tool in view of linking a material's microstructure to its properties and performance. Here, accompanied with some cutting-edge researches worldwide, we briefly review our recent progress in dynamic atomistic characterization of low-dimensional materials under external mechanical stress, thermal excitations and electrical field. The electron beam irradiation effects in metals and metal oxides are also discussed. We conclude by discussing the likely future developments in this area.

Isolated π-Interaction Sites in Mesoporous MOF Backbone for Repetitive and Reversible Dynamics in Water.

We report the introduction of π-interaction sites into a series of chemically robust metal-organic frameworks (MOFs), MOF-526, -527, and -528, with progressively increased pore size, 1.9-3.7 nm, and the inclusion and release of large organic molecules in water. The mesopores in these MOFs lead to fast adsorption kinetics, whereas the π-interaction between isolated porphyrin units in the MOF backbone and polycyclic structure of the organic guests provides excellent reversibility. Specifically, seven large organic dyes were quantitatively captured by the porphyrin units of these MOFs in a 2:1 molar ratio, exhibiting unprecedented kinetics for MOFs [e.g., 4.54 × 105 L/mol for rhodamine B] at an extremely low concentration (10 ppm) in water. Rotational-echo double-resonance NMR experiments revealed that the distance between the guest molecules and porphyrin units in MOFs was in the range from 3.24 to 3.37 Å, confirming the specific π-interaction. Repetitive and reversible dynamics was achieved in these MOFs for 10 complete inclusion-release cycles without any decay in performance, which is ideally suited for the removal and recycle of large polycyclic organic molecules from water. The performance of MOF-526 rivals that of state-of-the-art carbon and polymers.

Fabrication of CuO-Pt core-shell nanohooks by in situ reconstructing the Pt-shells.

The design of various nanostructures with specific compositions and shapes is highly demanded due to the widespread use of micro/nano electro-mechanical systems. In this work, one-dimensional CuO-Pt core-shell nanowires (NWs) are acquired by depositing Pt nanoparticles onto CuO NWs and then mechanically-shaped into nanohooks. Subsequently, the hook-like shape is maintained by the Pt-shell which is reconstructed via Joule heat and re-solidified after cooling down, during which the elastic strain energy is stored in the CuO-core. The results provide a simple strategy to design nanostructures with various compositions and shapes, implying the potential applications in mechanical energy storage and shape memory nanodevices.