Federica Marone

Visualization and Quantification of Electrochemical and Mechanical Degradation in Li Ion Batteries

Battery Breakdown Although a range of materials can be used for chemically storing electrical charge, many cannot be made into batteries that retain their capacity over many cycles. Failure may be because of secondary reactions, poisoning through the formation of surface coatings, or volumetric changes leading to fracture. Ebner et al. (p. 716, published online 17 October) studied this last scenario in an operating battery using synchrotron x-ray tomographic microscopy, tracking both the chemical changes in the battery and the resulting mechanical changes in a tin oxide model system, which is known to undergo large volume changes. Synchrotron x-ray tomography can be used to study failure modes in an operating battery. High–energy-density materials that undergo conversion and/or alloying reactions hold promise for next-generation lithium (Li) ion batteries. However, these materials experience substantial volume change during electrochemical operation, which causes mechanical fracture of the material and structural disintegration of the electrode, leading to capacity loss. In this work, we use x-ray tomography during battery operation to visualize and quantify the origins and evolution of electrochemical and mechanical degradation. Tomography provides the time-resolved, three-dimensional chemical composition and morphology within individual particles and throughout the electrode. In the model material tin(II) oxide, we witness distributions in onset and rate of core-shell lithiation, crack initiation and growth along preexisting defects, and irreversible distortion of the electrode, highlighting tomography as a tool to guide the development of durable materials and strain-tolerant electrodes.

Stripe and ring artifact removal with combined wavelet — Fourier filtering

A fast, powerful and stable filter based on combined wavelet and Fourier analysis for the elimination of horizontal or vertical stripes in images is presented and compared with other types of destriping filters. Strict separation between artifacts and original features allowing both, suppression of the unwanted structures and high degree of preservation of the original image information is endeavoured. The results are validated by visual assessments, as well as by quantitative estimation of the image energy loss. The capabilities and the performance of the filter are tested on a number of case studies related to applications in tomographic imaging. The case studies include (i) suppression of waterfall artifacts in electron microscopy images based on focussed ion beam nanotomography, (ii) removal of different types of ring artifacts in synchrotron based X-ray microtomography and (iii) suppression of horizontal stripe artifacts from phase projections in grating interferometry.

The depth distribution of azimuthal anisotropy in the continental upper mantle

The most likely cause of seismic anisotropy in the Earth’s upper mantle is the lattice preferred orientation of anisotropic minerals such as olivine. Its presence reflects dynamic processes related to formation of the lithosphere as well as to present-day tectonic motions. A powerful tool for detecting and characterizing upper-mantle anisotropy is the analysis of shear-wave splitting measurements. Because of the poor vertical resolution afforded by this type of data, however, it has remained controversial whether the splitting has a lithospheric origin that is ‘frozen-in’ at the time of formation of the craton, or whether the anisotropy originates primarily in the asthenosphere, and is induced by shear owing to present-day absolute plate motions. In addition, predictions from surface-wave-derived models are largely incompatible with shear-wave splitting observations. Here we show that this disagreement can be resolved by simultaneously inverting surface waveforms and shear-wave splitting data. We present evidence for the presence of two layers of anisotropy with different fast-axis orientations in the cratonic part of the North American upper mantle. At asthenospheric depths (200–400 km) the fast axis is sub-parallel to the absolute plate motion, confirming the presence of shear related to current tectonic processes, whereas in the lithosphere (80–200 km), the orientation is significantly more northerly. In the western, tectonically active, part of North America, the fast-axis direction is consistent with the absolute plate motion throughout the depth range considered, in agreement with a much thinner lithosphere.

Low-dose, simple, and fast grating-based X-ray phase-contrast imaging

Phase sensitive X-ray imaging methods can provide substantially increased contrast over conventional absorption-based imaging and therefore new and otherwise inaccessible information. The use of gratings as optical elements in hard X-ray phase imaging overcomes some of the problems that have impaired the wider use of phase contrast in X-ray radiography and tomography. So far, to separate the phase information from other contributions detected with a grating interferometer, a phase-stepping approach has been considered, which implies the acquisition of multiple radiographic projections. Here we present an innovative, highly sensitive X-ray tomographic phase-contrast imaging approach based on grating interferometry, which extracts the phase-contrast signal without the need of phase stepping. Compared to the existing phase-stepping approach, the main advantages of this new method dubbed “reverse projection” are not only the significantly reduced delivered dose, without the degradation of the image quality, but also the much higher efficiency. The new technique sets the prerequisites for future fast and low-dose phase-contrast imaging methods, fundamental for imaging biological specimens and in vivo studies.

Determination of Material Properties of Gas Diffusion Layers: Experiments and Simulations Using Phase Contrast Tomographic Microscopy

Understanding the transport properties of porous materials plays an important role in the development and optimization of polymer electrolyte fuel cells (PEFCs). In this study numerical simulations of different transport properties are compared and validated with data obtained using recently developed experimental techniques. The study is based on a Toray TGP-H-060 carbon paper, a common gas diffusion layer (GDL) material in PEFC. Diffusivity, permeability, and electric conductivity of the anisotropic, porous material are measured experimentally under various levels of compression. A sample of the GDL is imaged with synchrotron-based X-ray tomography under three different compression levels. Based on these three-dimensional images, diffusivity, permeability, and conductivity are calculated numerically. Experimental and numerical results agree in general. Deviations are observed for the through-plane conductivity. An explanation for the discrepancy is presented and affirmed by numerical simulations on a virtually created structure model. This proves that numerical simulation based on tomography data is a versatile tool for the investigation and development of porous structures used in PEFCs.

Fossilized nuclei and germination structures identify Ediacaran "animal embryos" as encysting protists

High-resolution imaging of 570-million-year-old fossils suggests that they were not remnants of early animals. Globular fossils showing palintomic cell cleavage in the Ediacaran Doushantuo Formation, China, are widely regarded as embryos of early metazoans, although metazoan synapomorphies, tissue differentiation, and associated juveniles or adults are lacking. We demonstrate using synchrotron-based x-ray tomographic microscopy that the fossils have features incompatible with multicellular metazoan embryos. The developmental pattern is comparable with nonmetazoan holozoans, including germination stages that preclude postcleavage embryology characteristic of metazoans. We conclude that these fossils are neither animals nor embryos. They belong outside crown-group Metazoa, within total-group Holozoa (the sister clade to Fungi that includes Metazoa, Choanoflagellata, and Mesomycetozoea) or perhaps on even more distant branches in the eukaryote tree. They represent an evolutionary grade in which palintomic cleavage served the function of producing propagules for dispersion.

Emerging Approaches in Synchrotron Studies of Materials from Cultural and Natural History Collections

Synchrotrons have provided significant methods and instruments to study ancient materials from cultural and natural heritages. New ways to visualise (surfacic or volumic) morphologies are developed on the basis of elemental, density and refraction contrasts. They now apply to a wide range of materials, from historic artefacts to paleontological specimens. The tunability of synchrotron beams owing to the high flux and high spectral resolution of photon sources is at the origin of the main chemical speciation capabilities of synchrotron-based techniques. Although, until recently, photon-based speciation was mainly applicable to inorganic materials, novel developments based, for instance, on STXM and deep UV photoluminescence bring new opportunities to study speciation in organic and hybrid materials, such as soaps and organometallics, at a submicrometric spatial resolution over large fields of view. Structural methods are also continuously improved and increasingly applied to hierarchically structured materials for which organisation results either from biological or manufacturing processes. High-definition (spectral) imaging appears as the main driving force of the current trend for new synchrotron techniques for research on cultural and natural heritage materials.

Progress in In Situ X-Ray Tomographic Microscopy of Liquid Water in Gas Diffusion Layers of PEFC

Water management is an important factor for optimizing polymer electrolyte fuel cells (PEFC) under high current density conditions as required for the automotive application. The characteristics of the local liquid saturation of the gas diffusion layer (GDL) is of particular interest. Here we report on the development of in-situ X-ray tomographic microscopy (XTM) with a pixel sizes in the order of 2 μm and sensitivity for carbon and liquid water for the quantitative analysis of liquid water in GDLs. In-situ XTM of PEFC is a major experimental challenge. A complete cell needs to be operated under realistic conditions in the constraint space of the small field of view on the beamline sample stage. Further phase segmentation of the images is required to successfully analyze the quantitative properties of the different phases. For this a workflow, applying differential images between dry and wet structures has been developed. Cells with Toray TGP-H-060 GDLs were analyzed in-situ. Droplets that appear on the GDL surface are connected to a significant water structure inside the GDL. Further the water cluster size distribution in the GDL shows that while small droplets (<100 pl) are numerous, most of the water is contained in few larger clusters.

Fast reconstruction algorithm dealing with tomography artifacts

Highly brilliant X-rays delivered by third generation synchrotron facilities coupled with modern detector technology permit routinely acquisition of high resolution tomograms in few minutes, making high throughput experiments a reality and bringing real-time tomography closer. New solutions for fast post-processing of such large amount of data are mandatory to fully exploit advantages provided by the high acquisition speed enabling new experiments until recently even unimaginable. The TOMCAT beamline1 is well equipped for fast and high throughput experiments2, 3. Here, we will focus on our solutions regarding the reconstruction process and discuss a fast reconstruction algorithm4, based on the Fourier Transform method as opposed to slower standard Filtered Back-Projection routines. We perform the critical step of such method, the polar-to-Cartesian mapping in the Fourier space, by convolution with the Fourier transform of functions with particular characteristics. This convolution approach combines speed with accuracy, making real-time data postprocessing closer to reality. This fast reconstruction algorithm implemented at TOMCAT also features several plug-ins, aimed at taming reconstruction artifacts. Here, we will discuss a new approach for removing rings from reconstructed datasets arising from defective detector pixels and/or damaged scintillator screens. This new method is based on a combined wavelet- FFT decomposition5. Another important feature of the presented reconstruction algorithm deals with local tomographic datasets, characterized by incomplete data. We show here that ad-hoc padding of the sinograms prior to reconstruction significantly reduces typical artifacts related to data incompleteness, making local tomography a valuable acquisition mode when small volumes in relatively large samples are of interest.

Determination of Liquid Water Distribution in Porous Transport Layers

Porous transport layers (PTL), also termed gas diffusion layers (GDL) play an important role for the mass transport on the milliscopic scale and its related losses, especially at high current densities and under condensing conditions. Understanding the mass transport properties of the PTL is therefore essential to understand and improve the water management as well as power density in the high current domain. PTL’s are structured to fulfill a multitude of requirements, such as to allow access of reactants to the catalyst layer and removal of gaseous and liquid product water. Therefore it is highly porous and hydrophobized with polytetrafluorethylene (PTFE). Furthermore electrons need be to collected or distributed at the CLs. PTL’s need therefore to be based on a conducting substrate which is chemically inert (e.g. carbon fibers). Furthermore the structure of the GDL needs to mechanically withstand the clamping pressure of the cell/stack which is necessary to reduce contact resistance and avoid leakages. Assuming no transport bottleneck in the CL, the strongest limitation comes from the flooding of PTL pores with liquid water and a subsequent shortage of oxygen in the cathode CL. Liquid water and transport thereof in the PTL has therefore been widely investigated [1-3]. However to date no systematic data of the structure of water in the PTL with the required micrometer resolution has been available. In this work, x-ray micro tomography at the Tomcat Beamline of the Swiss Light Source has been employed.