Dynamic Structure Evolution of Extensively Delithiated High Voltage Spinel Li1+xNi0.5Mn1.5O4 x < 1.5.

High voltage spinel is one of the most promising next-generation cobalt-free cathode materials for lithium ion battery applications. Besides the typically utilized compositional range of LixNi0.5Mn1.5O4 0 < x < 1 in the voltage window of 4.90-3.00 V, additional 1.5 mol of Li per formula unit can be introduced into the structure, in an extended voltage range to 1.50 V. Theoretically, this leads to significant increase of the specific energy from 690 to 1190 Wh/kg. However, utilization of the extended potential window leads to rapid capacity fading and voltage polarization that lack a comprehensive explanation. In this work, we conducted potentiostatic entropymetry, operando XRD and neutron diffraction on the ordered stoichiometric spinel LixNi0.5Mn1.5O4 within 0 < x < 2.5 in order to understand the dynamic structure evolution and correlate it with the voltage profile. During the two-phase reaction from cubic (x < 1) to tetragonal (x > 1) phase at ∼2.8 V, we identified the evolution of a second tetragonal phase with x > 2. The structural evaluation during the delithiation indicates the formation of an intermediate phase with cubic symmetry at a lithium content of x = 1.5. Evaluation of neutron diffraction data, with maximum entropy method, of the highly lithiated phase LixNi0.5Mn1.5O4 with 2 < x < 2.5 strongly suggests that lithium ions are located on octahedral 8a and tetrahedral 4a positions of the distorted tetragonal phase I41amd. Consequently, we were able to provide a conclusive explanation for the additional voltage step at 2.10 V, the sloping voltage profile below 1.80 V, and the additional voltage step at ∼3.80 V.

Real-time observation of nucleation and growth of Au on CdSe quantum dot templates.

Semiconductor quantum dot (QD) arrays can be useful for optical devices such as lasers, solar cells and light-emitting diodes. As the size distribution influences the band-gap, it is worthwhile to investigate QDs prepared using different solvents because each of them could influence the overall morphology differently, depending on the ligand network around individual QDs. Here, we follow the nucleation and growth of gold (Au) on CdSe QD arrays to investigate the influence of surface ligands and thereby realized interparticle distance between QDs on Au growth behaviour. We particularly emphasize on the monolayer stage as the Au decoration on individual QDs is expected at this stage. Therefore, we sputter-deposit Au on each QD array to investigate the morphological evolution in real-time using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). The growth kinetics - independent of the template - signifies that the observed template-mediated nucleation is limited only to the very first few monolayers. Delicate changes in the Au growth morphology are seen in the immediate steps following the initial replicated decoration of the QD arrays. This is followed by a subsequent clustering and finally a complete Au coverage of the QD arrays.

Surface distortion of Fe dot-decorated TiO2 nanotubular templates using time-of-flight grazing incidence small angle scattering.

Physical properties of nanoclusters, nanostructures and self-assembled nanodots, which in turn are concomitantly dependent upon the morphological properties, can be modulated for functional purposes. Here, in this article, magnetic nanodots of Fe on semiconductor TiO2 nanotubes (TNTs) are investigated with time-of-flight grazing incidence small-angle neutron scattering (TOF-GISANS) as a function of wavelength, chosen from a set of three TNT templates with different correlation lengths. The results are found corroborating with the localized scanning electron microscopy (SEM) images. As we probe the inside and the near-surface region of the Fe-dotted TNTs with respect to their homogeneity, surface distortion and long-range order using TOF-GISANS, gradual aberrations at the top of the near-surface region are identified. Magnetization measurements as a function of temperature and field do not show a typical ferromagnetic behavior but rather a supermagnetic one that is expected from a nonhomogeneous distribution of Fe-dots in the intertubular crevasses.

Low-Temperature Charging and Aging Mechanisms of Si/C Composite Anodes in Li-Ion Batteries: An Operando Neutron Scattering Study.

The addition of Si compounds to graphite anodes has become an attractive way of increasing the practical specific energies in Li-ion cells. Previous studies involving Si/C anodes lacked direct insight into the processes occurring in full cells during low-temperature operation. In this study, a powerful combination of operando neutron diffraction, electrochemical tests, and post-mortem analysis is used for the investigation of Li-ion cells. 18650-type cylindrical cells in two different aging states are investigated by operando neutron diffraction. The experiments reveal deep insights and important trends in low-temperature charging mechanisms involving intercalation, alloying, Li metal deposition, and relaxation processes as a function of charging C-rates and temperatures. Additionally, the main aging mechanism caused by long-term cycling and interesting synergistic effects of Si and graphite are elucidated.

Structural and magnetic properties of cobalt iron disulfide (CoxFe1-xS2) nanocrystals.

We report on synthesis and investigation of nanocrystalline cobalt-iron-pyrites with an emphasis on nanocrystal structure, morphology and magnetic behavior. The nanocrystals (NCs) were 5-25 nm in diameter as characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). With an increase in Fe fraction, X-ray diffraction and small-angle-X-ray scattering (SAXS) showed a systematic decrease in lattice constant, primary grain/NC size (15 to 7 nm), and nanoparticle (NP) size (70 to 20 nm), respectively. The temperature dependence of the DC magnetization and AC susceptibility versus frequency revealed a number of magnetic phases in Co x Fe1-xS2. Samples with x = 1 and x = 0.875-0.625 showed evidence of superspin glass (SSG) behavior with embedded ferromagnetic (FM) clusters of NPs. For x = 0.5, samples retained their mixed phases, but showed superparamagnetic (SPM) behavior with antiferromagnetic clusters suppressing magnetic dipolar interactions. Below x = 0.5, the pyrites show increasing paramagnetic character. We construct a phase diagram, which can be understood in terms of competition between the various dipolar, exchange, inter- and intracluster interactions. Our results suggest that NC size and shape can be tuned to engineer spin-polarized ferromagnetism of n-doped iron pyrite.

Realizing topological stability of magnetic helices in exchange-coupled multilayers for all-spin-based system.

Topologically stabilized spin configurations like helices in the form of planar domain walls (DWs) or vortex-like structures with magnetic functionalities are more often a theoretical prediction rather than experimental realization. In this paper we report on the exchange coupling and helical phase characteristics within Dy-Fe multilayers. The magnetic hysteresis loops with temperature show an exchange bias field of around 1.0 kOe at 10 K. Polarized neutron reflectivity reveal (i) ferrimagnetic alignment of the layers at low fields forming twisted magnetic helices and a more complicated but stable continuous helical arrangement at higher fields (ii) direct evidence of helices in the form of planar 2π-DWs within both layers of Fe and Dy. The helices within the Fe layers are topologically stabilized by the reasonably strong induced in-plane magnetocrystalline anisotropy of Dy and the exchange coupling at the Fe-Dy interfaces. The helices in Dy are plausibly reminiscent of the helical ordering at higher temperatures induced by the field history and interfacial strain. Stability of the helical order even at large fields have resulted in an effective modulation of the periodicity of the spin-density like waves and subsequent increase in storage energy. This opens broad perspectives for future scientific and technological applications in increasing the energy density for systems in the field of all-spin-based engineering which has the potential for energy-storing elements on nanometer length scales.

Templating growth of gold nanostructures with a CdSe quantum dot array.

In optoelectronic devices based on quantum dot arrays, thin nanolayers of gold are preferred as stable metal contacts and for connecting recombination centers. The optimal morphology requirements are uniform arrays with precisely controlled positions and sizes over a large area with long range ordering since this strongly affects device performance. To understand the development of gold layer nanomorphology, the detailed mechanism of structure formation are probed with time-resolved grazing incidence small-angle X-ray scattering (GISAXS) during gold sputter deposition. Gold is sputtered on a CdSe quantum dot array with a characteristic quantum dot spacing of ≈7 nm. In the initial stages of gold nanostructure growth, a preferential deposition of gold on top of quantum dots occurs. Thus, the quantum dots act as nucleation sites for gold growth. In later stages, the gold nanoparticles surrounding the quantum dots undergo a coarsening to form a complete layer comprised of gold-dot clusters. Next, growth proceeds dominantly via vertical growth of gold on these gold-dot clusters to form an gold capping layer. In this capping layer, a shift of the cluster boundaries due to ripening is found. Thus, a templating of gold on a CdSe quantum dot array is feasible at low gold coverage.

Identification of Ge/Si intermixing processes at the Bi/Ge/Si(111) surface.

The chemical contrast between Si and Ge obtained by scanning tunneling microscopy on Bi-covered Si(111) surfaces is used as a tool to identify two vertical Ge/Si intermixing processes. During annealing of an initially pure Ge monolayer on Si, the intermixing is confined to the first two layers approaching a 50% Ge concentration in each layer. During epitaxial growth, a growth front induced intermixing process acting at step edges is observed. Because of the open atomic structure at the step edges, relative to the terraces, a lower activation barrier for intermixing at the step edge, compared to the terrace, is observed.

Nanowires and nanorings at the atomic level.

The step-flow growth mode is used to fabricate Si and Ge nanowires with a width of 3.5 nm and a thickness of one atomic layer (0.3 nm) by self-assembly. Alternating deposition of Ge and Si results in the formation of a nanowire superlattice covering the whole surface. One atomic layer of Bi terminating the surface is used to distinguish between the elements Si and Ge. A difference in apparent height is measured in scanning tunneling microscopy images for Si and Ge. Also, different kinds of two-dimensional Si/Ge nanostructures like alternating Si and Ge nanorings having a width of 5-10 nm were grown.