Evidence for a High Temperature Whisker Growth Mechanism Active in Tungsten during In Situ Nanopillar Compression.

A series of nanopillar compression tests were performed on tungsten as a function of temperature using in situ transmission electron microscopy with localized laser heating. Surface oxidation was observed to form on the pillars and grow in thickness with increasing temperature. Deformation between 850 °C and 1120 °C is facilitated by long-range diffusional transport from the tungsten pillar onto adjacent regions of the Y2O3-stabilized ZrO2 indenter. The constraint imposed by the surface oxidation is hypothesized to underly this mechanism for localized plasticity, which is generally the so-called whisker growth mechanism. The results are discussed in context of the tungsten fuzz growth mechanism in He plasma-facing environments. The two processes exhibit similar morphological features and the conditions under which fuzz evolves appear to satisfy the conditions necessary to induce whisker growth.

Unimolecular Polypeptide Micelles via Ultrafast Polymerization of N-Carboxyanhydrides.

Polypeptide micelles are widely used as biocompatible nanoplatforms but often suffer from their poor structural stability. Unimolecular polypeptide micelles can effectively address the structure instability issue, but their synthesis with uniform structure and well-controlled and desired sizes remains challenging. Herein we report the convenient preparation of spherical unimolecular micelles through dendritic polyamine-initiated ultrafast ring-opening polymerization of N-carboxyanhydrides (NCAs). Synthetic polypeptides with exceptionally high molecular weights (up to 85 MDa) and low dispersity (D < 1.05) can be readily obtained, which are the biggest synthetic polypeptides ever reported. The degree of polymerization was controlled in a vast range (25-3200), giving access to nearly monodisperse unimolecular micelles with predictable sizes. Many NCA monomers can be polymerized using this ultrafast polymerization method, which enables the incorporation of various structural and functional moieties into the unimolecular micelles. Because of the simplicity of the synthesis and superior control over the structure, the unimolecular polypeptide micelles may find applications in nanomedicine, supermolecular chemistry, and bionanotechnology.

In Situ Transmission Electron Microscopy for Ultrahigh Temperature Mechanical Testing of ZrO2.

This work demonstrates a novel approach to ultrahigh-temperature mechanical testing using a combination of in situ nanomechanical testing and localized laser heating. The methodology is applied to characterizing and testing initially nanograined 10 mol % Sc2O3-stabilized ZrO2 up to its melting temperature. The results suggest that the low-temperature strength of nanograined, d < 50 nm, oxides is not influenced by creep. Tensile fracture of ZrO2 bicrystals produce a weak-temperature dependence suggesting that grain boundary energy dominates brittle fracture of grain boundaries even at high homologous temperatures; for example, T = 2050 °C or T ≈ 77% Tmelt. The maximum temperature for mechanical testing in this work is primarily limited by the instability of the sample, due to evaporation or melting, enabling a host of new opportunities for testing materials in the ultrahigh-temperature regime.

Nanofibrillar Si Helices for Low-Stress, High-Capacity Li+ Anodes with Large Affine Deformations.

We report on the chemical lithiation of long microscale helices composed of densely packed amorphous silicon (aSi) nanofibrils, fabricated by glancing angle deposition (GLAD) through e-beam evaporation. In situ electron microscopy and companion finite element modeling demonstrate that the nanofibrillar structure of the aSi helices allows for 2 orders of magnitude faster effective rates for Li diffusion ( D0 = 10-10 cm2/s) compared to solid aSi nanowires, while also averting fragmentation during lithiation. More importantly, it is shown that specific helical geometries can accommodate large, lithium-induced, volumetric expansions without shape distortion. A major advantage of the helical nanostructures is that the compressive force generated due to lithiation-induced expansion is an order of magnitude smaller than in straight nanocolumns that permanently buckle during lithiation. Thus, GLAD-fabricated films composed of dense periodic microscale helices with properly designed coil geometries are highly suitable for robust, high-capacity Li+ anodes.

Insights into Solid-Electrolyte Interphase Induced Li-Ion Degradation from in Situ Auger Electron Spectroscopy.

Surface reactions occurring on LiMn2O4, LiCoO2, LiNiO2, Li[Ni1/3Mn1/3Co1/3]O2, and LiFePO4 during charging and overcharging are studied by in situ and ex situ Auger electron spectroscopy. Carbon surface stability at the cathode solid-electrolyte interphase (SEI), associated with carbonate formation, decomposition, and CO/CO2 evolution, on different electrodes during cycling correlates with their cycle life. To understand how associated CO and CO2 evolution affects cycle stability, LiMn2O4 is cycled in flowing gas. Flowing Ar enhances cycle life by a factor of 2, while flowing Ar with 1% CO2 reduces cycle life by a factor of 2. CO2 is proposed to degrade cycle life by trapping Li and metal ions as carbonate in the anode SEI.

LiMn2O4 Surface Chemistry Evolution during Cycling Revealed by in Situ Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy.

This work utilizes in situ electrochemical and analytical characterization during cycling of LiMn2O4 (LMO) equilibrated at different potentials in an ultrahigh vacuum (UHV) environment. The LMO reacts with organic molecules in the vacuum to form a high surface concentration of Li2CO3 (≈50% C) during initial charging to 4.05 V. Charging to higher potentials reduces the overall Li2CO3 concentration (≈15% C). Discharging to 3.0 V increases the Li2CO3 concentration (≈30% C) and over discharging to 0.1 V again reduces its concentration (≈15% C). This behavior is reproducible over 5 cycles. The model geometry utilized suggests that oxygen from LMO can participate in redox of carbon, where LMO contributes oxygen to form the carbonate in the solid electrolyte interphase (SEI). Similar results were obtained from samples cycled ex situ, suggesting that the model in situ geometry provides reasonably representative information about surface chemistry evolution. Carbon redox at LMO and the inherent voltage instability of the Li2CO3 likely contributes significantly to its capacity fade.

The Oxygen Reduction Reaction Rate of Metallic Nanoparticles during Catalyzed Oxidation.

This work reports the oxygen reduction reaction (ORR) kinetics of metal nanoparticle catalysts between 500 and 600 °C at low oxygen partial pressures. Ex situ and in situ TEM measurements demonstrate catalyzed nanowire growth initially follows linear kinetics; characteristic of being ORR rate limited. The ORR rates of Ag, Au, Cu, Ni, Pd, Rh and Pt measured at 600 °C form a volcano plot versus relative oxidation potential. Cu nanoparticles produce the maximum ORR rate under these conditions.

Property Self-Optimization During Wear of MoS2.

Knowledge of their bulk physical properties often guides selection of appropriate tribological coating materials. However, these properties as well as the microstructure evolve dramatically under the extreme conditions imposed during mechanical wear. The dynamic response ultimately governs the material's wear performance; thus, understanding the dynamic evolution of the system is critical. This work characterizes the change in mechanical properties and microstructure as a function of wear cycles in model MoS2 films using a combination of nanowear testing, transmission electron microscopy, and site-specific nanopillar compression. Notably, mechanical wear enhances the mechanical properties of the MoS2 while simultaneously evolving a microstructure that reduces the coefficient of friction and wear rate. We hypothesize that this self-optimizing behavior underpins the exceptional lubricity and antiwear performance of MoS2.

In situ X-ray photoelectron and Auger electron spectroscopic characterization of reaction mechanisms during Li-ion cycling.

The complex nature of Li-ion battery reactions along with their sensitivity to environmental exposure necessitates in situ characterization, particularly for surface sensitive methods. In this work, we demonstrate in situ X-ray photoelectron spectroscopy and in situ Auger electron spectroscopy applied to characterize the evolution of bonding and chemistry during cycling of nanoparticle electrodes. We apply the method to study the conversion reaction associated with Li insertion and extraction from CuO nanoparticle electrodes. This approach circumvents the need for ion sputtering and mechanical erosion, previously required to remove solid electrolyte interphase during ex situ measurements. This allows the elucidation of the changes in Cu oxidation state, during initial Li insertion, without the introduction of artifacts that have caused prior disagreement in the published literature.

Large-deformation and high-strength amorphous porous carbon nanospheres.

Carbon is one of the most important materials extensively used in industry and our daily life. Crystalline carbon materials such as carbon nanotubes and graphene possess ultrahigh strength and toughness. In contrast, amorphous carbon is known to be very brittle and can sustain little compressive deformation. Inspired by biological shells and honeycomb-like cellular structures in nature, we introduce a class of hybrid structural designs and demonstrate that amorphous porous carbon nanospheres with a thin outer shell can simultaneously achieve high strength and sustain large deformation. The amorphous carbon nanospheres were synthesized via a low-cost, scalable and structure-controllable ultrasonic spray pyrolysis approach using energetic carbon precursors. In situ compression experiments on individual nanospheres show that the amorphous carbon nanospheres with an optimized structure can sustain beyond 50% compressive strain. Both experiments and finite element analyses reveal that the buckling deformation of the outer spherical shell dominates the improvement of strength while the collapse of inner nanoscale pores driven by twisting, rotation, buckling and bending of pore walls contributes to the large deformation.

Mechanical Properties of Molybdenum Disulfide and the Effect of Doping: An in Situ TEM Study.

Direct observations on nanopillars composed of molybdenum disulfide (MoS2) and chromium-doped MoS2 and their response to compressive stress have been made. Time-resolved transmission electron microscopy (TEM) during compression of the submicrometer diameter pillars of MoS2- and Cr-doped MoS2 (Cr: 0, 10, and 50 at %) allow the deformation process of the material to be observed and can be directly correlated with mechanical response to applied load. The addition of chromium to the MoS2 changed the failure mode from plastic deformation to catastrophic brittle fracture, an effect that was more pronounced as chromium content increased.

Mechanically and chemically robust sandwich-structured C@Si@C nanotube array Li-ion battery anodes.

Stability and high energy densities are essential qualities for emerging battery electrodes. Because of its high specific capacity, silicon has been considered a promising anode candidate. However, the several-fold volume changes during lithiation and delithiation leads to fractures and continuous formation of an unstable solid-electrolyte interphase (SEI) layer, resulting in rapid capacity decay. Here, we present a carbon-silicon-carbon (C@Si@C) nanotube sandwich structure that addresses the mechanical and chemical stability issues commonly associated with Si anodes. The C@Si@C nanotube array exhibits a capacity of ∼2200 mAh g(-1) (∼750 mAh cm(-3)), which significantly exceeds that of a commercial graphite anode, and a nearly constant Coulombic efficiency of ∼98% over 60 cycles. In addition, the C@Si@C nanotube array gives much better capacity and structure stability compared to the Si nanotubes without carbon coatings, the ZnO@C@Si@C nanorods, a Si thin film on Ni foam, and C@Si and Si@C nanotubes. In situ SEM during cycling shows that the tubes expand both inward and outward upon lithiation, as well as elongate, and then revert back to their initial size and shape after delithiation, suggesting stability during volume changes. The mechanical modeling indicates the overall plastic strain in a nanotube is much less than in a nanorod, which may significantly reduce low-cycle fatigue. The sandwich-structured nanotube design is quite general, and may serve as a guide for many emerging anode and cathode systems.

Catalyzed oxidation for nanowire growth.

A simple, low-cost and scalable route to substrate-supported nanowire growth is reported based on catalyzed oxidation. The process shares common features with popular catalyzed nanowire growth techniques such as vapor-liquid-solid (VLS), vapor-solid-solid (VSS), or vapor-quasi-solid (VQS) that use catalyst nanoparticles to direct the deposition of reactants from the vapor phase. Catalyzed oxidation for nanowire growth (CONG) utilizes catalyzed anion (e.g. O2) reduction from the vapor phase and metal (e.g. Fe) oxidation from the substrate to produce oxide nanowires (e.g. Fe3O4). The approach represents a new class of nanowire growth methodology that may be applied to a broad range of systems. CONG does not require expensive chemical vapor deposition or physical vapor deposition equipment and can be implemented at intermediate temperatures (400-600 °C) in a standard laboratory furnace. This work also demonstrates a passive approach to catalyst deposition that allows the process to be implemented simply with no lithography or physical vapor deposition steps. This effort validates the general approach by synthesizing MnO, Fe3O4, WO3, MgO, TiO2, ZnO, ReO3, and NiO nanowires via CONG. The process produces single crystalline nanowires that can be grown to high aspect ratio and as high-density nanowire forests. Applications of the as-grown Fe3O4 and ReO3 nanowires for lithium ion battery systems are demonstrated to display high areal energy density and power.

In situ cryogenic transmission electron microscopy for characterizing the evolution of solidifying water ice in colloidal systems.

The details of ice interface dynamics in complex systems are critical to a variety of natural and commercial processes. A platform for low temperature environmental transmission electron microscopy is developed and applied to characterization of ice crystallization in colloidal solutions. The platform is utilized for studying the phase evolution in ice during crystallization and the dynamic interactions of Au nanoparticles at the crystallization front. The results indicate that models developed to treat ice-particle interactions at the micron scale extend well to the nanoscale.

3D printing of interdigitated Li-ion microbattery architectures.

3D interdigitated microbattery architectures (3D-IMA) are fabricated by printing concentrated lithium oxide-based inks. The microbatteries are composed of interdigitated, high-aspect ratio cathode and anode structures. Our 3D-IMA, which exhibit high areal energy and power densities, may find potential application in autonomously powered microdevices.

Electron beam induced deposition of silicon nanostructures from a liquid phase precursor.

This work demonstrates electron beam induced deposition of silicon from a SiCl(4) liquid precursor in a transmission electron microscope and a scanning electron microscope. Silicon nanodots of tunable size are reproducibly grown in controlled geometries. The volume of these features increases linearly with deposition time. The results indicate that secondary electrons generated at the substrate surface serve as the primary source of silicon reduction. However, at high current densities the influence of the primary electrons is observed to retard growth. The results demonstrate a new approach to fabricating silicon nanostructures and provide fundamental insights into the mechanism for liquid phase electron beam induced deposition.

In situ transmission electron microscopy observation of silver oxidation in ionized/atomic gas.

The interaction between silver and ionized and atomic gas was observed directly by in situ transmission electron microscopy with an environmental cell for the first time. The electron beam provides dual functions as the source of both gas ionization and imaging. The concentration of ionized gas was tuned via adjusting the current density of the electron beam. Oxidation of the silver is observed in situ, indicating the presence of ionized and/or atomic oxygen. The evolution of microstructure and phase constituents was characterized. Then the oxidation rate was measured, and the relationships among grain size, mass transport rate, and electron flux were characterized. The role of the electron beam is discussed, and the results are rationalized with respect to ex situ results from the literature.