A "Biconcave-Alleviated" Strategy to Construct Aspergillus niger-Derived Carbon/MoS2 for Ultrastable Sodium Ion Storage.

Two-dimensional layered materials commonly face hindered electron transfer and poor structure stability, thus limiting their application in high-rate and long-term sodium ion batteries. In the current study, we adopt finite element simulation to guide the rational design of nanostructures. By calculating the von Mises stress distribution of a series of carbon materials, we find that the hollow biconcave structure could effectively alleviate the stress concentration resulting from expansion. Accordingly, we propose a biconcave-alleviated strategy based on the Aspergillus niger-derived carbon (ANDC) to construct ANDC/MoS2 with a hollow biconcave structure. The ANDC/MoS2 is endowed with an excellent long-term cyclability as an anode of sodium ion batteries, delivering a discharge capacity of 496 mAh g-1 after 1000 cycles at 1 A g-1. A capacity retention rate of 94.5% is achieved, an increase of almost seven times compared with the bare MoS2 nanosheets. Even at a high current density of 5 A g-1, a reversible discharge capacity around 400 mAh g-1 is maintained after 300 cycles. ANDC/MoS2 could also be used for efficient lithium storage. By using in situ TEM, we further reveal that the hollow biconcave structure of ANDC/MoS2 has enabled stable and fast sodiation/desodiation.

Shaping and Edge Engineering of Few-Layered Freestanding Graphene Sheets in a Transmission Electron Microscope.

Full exploitation of graphene's superior properties requires the ability to precisely control its morphology and edge structures. We present such a structure-tailoring approach via controlled atom removal from graphene edges. With the use of a graphitic-carbon-capped tungsten nanoelectrode as a noncontact "milling" tool in a transmission electron microscope, graphene edge atoms approached by the tool tip are locally evaporated, thus allowing a freestanding graphene sheet to be tailored with high precision and flexibility. A threshold for the tip voltage of 3.6 ± 0.4 V, independent of polarity, is found to be the determining factor that triggers the controlled etching process. The dominant mechanisms involve weakening of carbon-carbon bonds through the interband excitation induced by tunneling electrons, assisted with a resistive-heating effect enhanced by high electric field, as elaborated by first-principles calculations. In addition to the precise shape and size control, this tip-based method enables fabrication of graphene edges with specific chiralities, such as "armchair" or "zigzag" types. The as-obtained edges can be further "polished" to become entirely atomically smooth via edge evaporation/reconstruction induced by in situ TEM Joule annealing. We finally demonstrate the potential of this technique for practical uses through creating a graphene-based point electron source, whose field emission characteristics can effectively be tuned via modifying its geometry.

Mechanistic Origin of the High Performance of Yolk@Shell Bi2S3@N-Doped Carbon Nanowire Electrodes.

High-performance lithium-ion batteries are commonly built with heterogeneous composite electrodes that combine multiple active components for serving various electrochemical and structural functions. Engineering these heterogeneous composite electrodes toward drastically improved battery performance is hinged on a fundamental understanding of the mechanisms of multiple active components and their synergy or trade-off effects. Herein, we report a rational design, fabrication, and understanding of yolk@shell Bi2S3@N-doped mesoporous carbon (C) composite anode, consisting of a Bi2S3 nanowire (NW) core within a hollow space surrounded by a thin shell of N-doped mesoporous C. This composite anode exhibits desirable rate performance and long cycle stability (700 cycles, 501 mAhg-1 at 1.0 Ag-1, 85% capacity retention). By in situ transmission electron microscopy (TEM), X-ray diffraction, and NMR experiments and computational modeling, we elucidate the dominant mechanisms of the phase transformation, structural evolution, and lithiation kinetics of the Bi2S3 NWs anode. Our combined in situ TEM experiments and finite element simulations reveal that the hollow space between the Bi2S3 NWs core and carbon shell can effectively accommodate the lithiation-induced expansion of Bi2S3 NWs without cracking C shells. This work demonstrates an effective strategy of engineering the yolk@shell-architectured anodes and also sheds light onto harnessing the complex multistep reactions in metal sulfides to enable high-performance lithium-ion batteries.

Graphene Ingestion and Regrowth on "Carbon-Starved" Metal Electrodes.

The interaction between graphene and various metals plays a central role in future carbon-based device and synthesis technologies. Herein, three different types of metal nanoelectrodes (W, Ni, Au) were employed to in situ study the graphene-metal interfacial kinetic behaviors in a high-resolution transmission electron microscope. The three metals exhibit distinctly different interactions with graphene when driven by a heating current. Tungsten tips, the most carbon-starved ones, can ingest a graphene sheet continuously; nickel tips, less carbon starved, typically "eat" graphene only by taking a "bite" from its edge; gold, however, is nonactive with graphene at all, even in its molten state. The ingested graphene atoms finally precipitate as freshly formed graphitic shells encapsulating the catalytic W and Ni electrodes. Particularly, we propose a periodic extension/thickening graphene growth scenario by atomic-scale observation of this process on W electrodes, where the propagation of the underlying tungsten carbide (WC) dominates the growth dynamics. This work uncovers the complexity of carbon diffusion/segregation processes at different graphene/metal interfaces that would severely degrade the device performance and stability. Besides, it also provides a detailed and insightful understanding of the sp2 carbon catalytic growth, which is vital in developing efficient and practical graphene synthetic routes.

Reversible Tuning of Individual Carbon Nanotube Mechanical Properties via Defect Engineering.

The structural defects that inevitably exist in real-world carbon nanotubes (CNTs) are generally considered undesirable because they break the structural perfection and may result in drastically degraded CNT properties. On the other hand, the deliberate defect introduction can provide a possibility to tailor the tube mechanical properties. Herein, we present a fully controllable technique to handle defects by using in situ transmission electron microscopy (TEM). Young's modulus, quality factor of the resonation and tensile strength of CNTs can be controllably, reversibly, and repeatedly tuned. Parallel high-resolution visualizing of structural defects suggests that the property tuning cycles are primarily attributed to the reversible conversion of defects at the atomic scale: the defects are created in the form of vacancies and interstitials under electron irradiation, and they vanish through the recombination via current-induced annealing. For applications, such as reversible frequency-tuned CNT resonators, this defect-engineering technique is demonstrated to be uniquely precise; the frequency may be tuned with 0.1%/min accuracy, improved by 1 order of magnitude compared with the existing approaches. We believe that these results will be highly valuable in a variety of property-tunable CNT-based composites and devices.