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FIB/SEM tomography represents an indispensable tool for the characterization of three-dimensional nanostructures in battery research and many other fields. However, contrast and 3D classification/reconstruction problems occur in many cases, which strongly limits the applicability of the technique especially on porous materials, like those used for electrode materials in batteries or fuel cells. Distinguishing the different components like active Li storage particles and carbon/binder materials is difficult and often prevents a reliable quantitative analysis of image data, or may even lead to wrong conclusions about structure-property relationships. In this contribution, we present a novel approach for data classification in three-dimensional image data obtained by FIB/SEM tomography and its applications to NMC battery electrode materials. We use two different image signals, namely the signal of the angled SE2 chamber detector and the Inlens detector signal, combine both signals and train a random forest, i.e. a particular machine learning algorithm. We demonstrate that this approach can overcome current limitations of existing techniques suitable for multi-phase measurements and that it allows for quantitative data reconstruction even where current state-of the art techniques fail, or demand for large training sets. This approach may yield as guideline for future research using FIB/SEM tomography.

Energy storage materials 38, 80 - 92 (2021). doi:10.1016/j.ensm.2021.02.029, Electrolyte filling takes place between sealing and formation in Lithium Ion Battery (LIB) manufacturing process. This step is crucial as it is directly linked to LIB quality and affects the subsequent time consuming electrolyte wetting process. Although having fast, homogeneous and complete wetting is of paramount importance, this process has not been sufficiently examined and fully understood. For instance, experimentally available data is insufficient to fully capture the complex interplay upon filling between electrolyte and air inside the porous electrode. We report here for the first time a 3D-resolved Lattice Boltzmann Method (LBM) model able to simulate electrolyte filling upon applied pressure of LIB porous electrodes obtained both from experiments (micro X-ray tomography) and computations (stochastic generation, simulation of the manufacturing process using Coarse Grained Molecular Dynamics and Discrete Element Method). The model allows obtaining advanced insights about the impact of the electrode mesostructures on the speed of electrolyte impregnation and wetting, highlighting the importance of porosity, pore size distribution and pores interconnectivity on the filling dynamics. Furthermore, we identify scenarios where volumes with trapped air (dead zones) appear and evaluate the impact of those on the electrochemical behavior of the electrodes., Published by Elsevier, Amsterdam

Nano energy 82, 105762 (1-5) (2021). doi:10.1016/j.nanoen.2021.105762, From non-destructive and cross-sectional visualization by synchrotron X-ray tomography, we suggest a novel capacity decaying mechanism of all-solid-state Na batteries built with closo-borate electrolytes caused by electrochemically generated inactive Na electrodeposits., Published by Elsevier, Amsterdam [u.a.]

Although a great variety of strategies to suppress Li dendrite have been proposed for lithium metal batteries (LMBs), a deeper understanding of the factors playing a crucial role during extended el...

ACS applied energy materials 3(12), 12565 - 12574 (2020). doi:10.1021/acsaem.0c02494, Commercially used LiNi$_{1/3}$Mn$_{1/3}$Co$_{1/3}$O$_2$ (NMC111) in lithium-ion batteries mainly consists of a large-grained nonporous active material powder prepared by coprecipitation. However, nanomaterials are known to have extreme influence on gravimetric energy density and rate performance but are not used at the industrial scale because of their reactivity, low tap density, and diminished volumetric energy density. To overcome these problems, the build-up of hierarchically structured active materials and electrodes consisting of microsized secondary particles with a primary particle scale in the nanometer range is preferable. In this paper, the preparation and detailed characterization of porous hierarchically structured active materials with two different median secondary particle sizes, namely, 9 and 37 μm, and primary particle sizes in the range 300–1200 nm are presented. Electrochemical investigations by means of rate performance tests show that hierarchically structured electrodes provide higher specific capacities than conventional NMC111, and the cell performance can be tuned by adjustment of processing parameters. In particular, electrodes of coarse granules sintered at 850 °C demonstrate more favorable transport parameters because of electrode build-up, that is, the morphology of the system of active material particles in the electrode, and demonstrate superior discharge capacity. Moreover, electrodes of fine granules show an optimal electrochemical performance using NMC powders sintered at 900 °C. For a better understanding of these results, that is, of process-structure–property relationships at both granule and electrode levels, 3D imaging is performed with a subsequent statistical image analysis. Doing so, geometrical microstructure characteristics such as constrictivity quantifying the strength of bottleneck effects and descriptors for the lengths of shortest transportation paths are computed, such as the mean number of particles, which have to be passed, when going from a particle through the active material to the aluminum foil. The latter one is at lowest for coarse-grained electrodes and seems to be a crucial quantity., Published by ACS Publications, Washington, DC

Most cathode materials for lithium-ion batteries exhibit a low electronic conductivity. Hence, a significant amount of conductive graphitic additives are introduced during electrode production. The mechanical stability and electronic connection of the electrode is enhanced by a mixed phase formed by the carbon and binder materials. However, this mixed phase, the carbon binder domain (CBD), hinders the transport of lithium ions through the electrolyte pore network. Thus, reducing the performance at higher currents. In this work we combine microstructure resolved simulations with impedance measurements on symmetrical cells to identify the influence of the CBD distribution. Microstructures of NMC622 electrodes are obtained through synchrotron X-ray tomography. Resolving the CBD using tomography techniques is challenging. Therefore, three different CBD distributions are incorporated via a structure generator. We present results of microstructure resolved impedance spectroscopy and lithiation simulations, which reproduce the experimental results of impedance spectroscopy and galvanostatic lithiation measurements, thus, providing a link between the spatial CBD distribution, electrode impedance, and half-cell performance. The results demonstrate the significance of the CBD distribution and enable predictive simulations for battery design. The accumulation of CBD at contact points between particles is identified as the most likely configuration in the electrodes under consideration., publishedVersion

Knowing the distribution of a magnetic field in bulk materials is important for understanding basic phenomena and developing functional magnetic materials. Microscopic imaging techniques employing X-rays, light, electrons, or scanning probe methods have been used to quantify magnetic fields within planar thin magnetic films in 2D or magnetic vector fields within comparable thin volumes in 3D. Some years ago, neutron imaging has been demonstrated to be a unique tool to detect magnetic fields and magnetic domain structures within bulk materials. Here, we show how arbitrary magnetic vector fields within bulk materials can be visualized and quantified in 3D using a set of nine spin-polarized neutron imaging measurements and a novel tensorial multiplicative algebraic reconstruction technique (TMART). We first verify the method by measuring the known magnetic field of an electric coil and then investigate the unknown trapped magnetic flux within the type-I superconductor lead., Mapping the distribution of magnetic fields inside bulk materials is challenging but crucial to understand and develop functional magnetic materials. Here the authors demonstrate the capability to visualize 3D vector magnetic fields inside materials using spin-polarized neutron tomography and tensorial reconstruction techniques.

Porous carbon felts (CFs) are widely used electrode materials for vanadium redox flow batteries (VRFBs). These materials differ in their precursor material, thickness, or graphitization degree and demonstrate broad differences in electrochemical performance. Prior to operation, an activation step, such as acid or heat treatment (HT), is commonly performed to improve their performance. A thermal treatment in air functionalizes the surface of the electrode and improves reaction kinetics as well as the wettability of the electrode. Herein, pristine and heat‐treated CFs are compared regarding their electrolyte wetting behavior for the use in VRFB. Contact angle (CA) measurements are conducted ex situ to investigate the effect of the HT. Furthermore, the porous CFs are examined in situ with an in‐house‐built flow cell regarding their invasion behavior with different types of electrolytes by X‐ray radiography. Additionally, the distribution of the electrolyte inside the felts is investigated by X‐ray tomography. The results demonstrate the effect of the HT and choice of electrolyte on the wetting behavior and electrolyte distribution.

Operando laboratory X-ray radiographies were carried out for imaging of two different silver-based gas diffusion electrodes containing an electroconductive Ni mesh structure, one gas diffusion electrode composed of 95 wt.% Ag and 5 wt.% polytetrafluoroethylene and one composed of 97 wt.% Ag and 3 wt.% polytetrafluoroethylene, under different operating parameters. Thereby, correlations of their electrochemical behavior and the transport of the 30 wt.% NaOH electrolyte through the gas diffusion electrodes were revealed. The work was divided into two parts. In the first step, the microstructure of the gas diffusion electrodes was analyzed ex situ by a combination of focused ion beam technology and synchrotron as well as laboratory X-ray tomography and radiography. In the second step, operando laboratory X-ray radiographies were performed during chronoamperometric measurements at different potentials. The combination of the ex situ microstructural analyses and the operando measurements reveals the impact of the microstructure on the electrolyte transport through the gas diffusion electrodes. Hence, an impact of the Ni mesh structure within the gas diffusion electrode on the droplet formation could be shown. Moreover, it could be observed that increasing overpotentials cause increasing electrolyte transport velocities and faster droplet formation due to electrowetting. In general, higher electrolyte transport velocities were found for the gas diffusion electrode with 97 wt.% Ag in contrast to that with 95 wt.% Ag.

Producción Científica, This manuscript presents the effect of the solid phase corrugation of low densityflexible cellular polymers onboth their mechanical and thermal properties. First, a detailed quantification of solid phase corrugation hasbeen carried out by means of high resolution synchrotron micro-tomography in a collection of polyethylenefoams. Subsequently, the collapse stress in compression has been analysed both from the theoretical and exper-imental points of view achieving a clear relation between the solid phase corrugation and the ratio of theoreti-cally calculated and experimentally measured collapse stress. Finally, solid phase corrugation has beencorrelated with the thermal expansion coefficient at room temperature., Ministerio de Economía, Industria y Competitividad - Fondo Europeo de Desarrollo Regional (project MAT2015-69234-R), Junta de Castilla y Leon (project VA011U16)

Turtles are one of the least explored clades regarding endocranial anatomy with few available descriptions of the brain and inner ear of extant representatives. In addition, the paleoneurology of extinct turtles is poorly known and based on only a few natural cranial endocasts. The main goal of this study is to provide for the first time a detailed description of the neuroanatomy of an extinct turtle, the Late Jurassic Plesiochelysetalloni, including internal carotid circulation, cranial endocast and inner ear, based on the first digital 3D reconstruction using micro CT scans. The general shape of the cranial endocast of P. etalloni is tubular, with poorly marked cephalic and pontine flexures. Anteriorly, the olfactory bulbs are clearly differentiated suggesting larger bulbs than in any other described extinct or extant turtle, and indicating a higher capacity of olfaction in this taxon. The morphology of the inner ear of P. etalloni is comparable to that of extant turtles and resembles those of slow-moving terrestrial vertebrates, with markedly low, short and robust semicircular canals, and a reduced lagena. In P. etalloni the arterial pattern is similar to that found in extant cryptodires, where all the internal carotid branches are protected by bone. As the knowledge of paleoneurology in turtles is scarce and the application of modern techniques such as 3D reconstructions based on CT scans is almost unexplored in this clade, we hope this paper will trigger similar investigations of this type in other turtle taxa.

Materials today 27, 21 - 32 (2018). doi:10.1016/j.mattod.2018.11.003, An intrinsic knowledge gap between current understandings obtained experimentally and the underlying working or degradation mechanisms of rechargeable lithium batteries still remains, giving direct rise to application challenges, e.g., safety issues, predicaments in identifying performance-aging factors and dilemmas in guiding further research directions. Against this background, non-destructive and three-dimensional (synchrotron) X-ray tomography that guarantees a direct visual access to inner electrodes has been employed herein to: in-situ record the evolution of internal short circuits; characterize the behaviors of widely employed separators; investigate the morphological evolution of Li electrodes under different cycling conditions; and study the degradation mechanisms of Li/carbon cells. By incorporating the currently presented results with the previously published studies on those topics, a complete picture of the degradation mechanism of rechargeable lithium batteries has been painted. This advancement of mechanistic understanding supplies the missing pieces of information to bridge fundamental R&D research activities and practical applications., Published by Elsevier Science, Amsterdam [u.a.]

Dynamic and direct visualization of interfacial evolution is helpful in gaining fundamental knowledge of all solid state lithium battery working degradation mechanisms and clarifying future research directions for constructing next generation batteries. Herein, in situ and in operando synchrotron X ray tomography and energy dispersive diffraction were simultaneously employed to record the morphological and compositional evolution of the interface of InLi anode sulfidesolid electrolyte during battery cycling. Compelling morphological evidence of interfacial degradation during all solid state lithium battery operation has been directly visualized by tomographic measurement. The accompanying energy dispersive diffraction results agree well with the observed morphological deterioration and the recorded electrochemical performance. It is concluded from the current investigation that a fundamental understanding of the phenomena occurring at the solid solid electrode electrolyte interface during all solid state lithium battery cycling is critical for future progress in cell performance improvement andmay determine its final commercial viability

We present non-destructive and non-invasive in operando X-ray tomographic investigations of the charge and discharge behavior of rechargeable alkaline-manganese (RAM) batteries (Zn-MnO2 batteries). Changes in the three-dimensional structure of the zinc anode and the MnO2 cathode material after several charge/discharge cycles were analyzed. Battery discharge leads to a decrease in the zinc particle sizes, revealing a layer-by-layer dissolving behavior. During charging, the particles grow again to almost their initial size and shape. After several cycles, the particles sizes slowly decrease until most of the particles become smaller than the spatial resolution of the tomography. Furthermore, the number of cracks in the MnO2 bulk continuously increases and the separator changes its shape. The results are compared to the behavior of a conventional primary cell that was also charged and discharged several times.

Oxygen-depolarized cathodes are a novel concept to be used in chlor-alkali electrolysis in order to generate significant energy savings. In these porous gas diffusion electrodes, hydrophilic and catalytically active microsized silver grains and a hydrophobic polytetrafluoroethylene cobweb structure are combined to obtain the optimum amount of three-phase boundaries between the highly alkaline electrolyte and the oxygen gas phase to achieve high current densities. However, the direct correlation between specific electrode structure and electrochemical performance is difficult. In this work, we report on the successful design and adaptation of an in-operando cell for X-ray (micro-computed tomography, synchrotron) and neutron imaging of an operating oxygen-depolarized cathode under realistic operation conditions, enabling the investigation of the electrolyte invasion into, and distribution inside, the porous electrode for the first time.

Carbon fiber based felt materials are widely used as gas diffusion layer (GDL) in fuel cells. Their transport properties can be adjusted by adding hydrophobic agents such as polytetrafluoroethylene (PTFE). We present a synchrotron X-ray tomographic study on the felt material Freudenberg H2315 with different PIPE finishing. In this study, we analyze changes in microstructure and shape of GDLs at increasing degree of compression which are related to their specific PTFE load. A dedicated compression device mimicking the channel-land pattern of the flowfield is used to reproduce the inhomogeneous compression found in a fuel cell. Transport relevant geometrical parameters such as porosity, pore size distribution and geometric tortuosity are calculated and consequences for media transport discussed. PTFE finishing results in a marked change of shape of compressed GDLs: surface is smoothed and the invasion of GDL fibers into the flow field channel strongly mitigated. Furthermore, the PTFE impacts the microstructure of the compressed GDL. The number of available wide transport paths is significantly increased as compared to the untreated material. These changes improve the transport capacity liquid water through the GDL and promote the discharge of liquid water droplets from the cell. (C) 2016 Elsevier B.V. All rights reserved.

The morphology of extant and extinct Squatiniformes is well conserved within this lineage, but differences are of consequence to character interpretations for phylogenetic analyses. Investigation of the extinct taxon †Pseudorhina alifera (Münster, 1842) from the Late Jurassic of Solnhofen with extant species of Squatina provide new evidence that members of Squatiniformes possess a basioccipital fovea. Presence of a basioccipital fovea is the ancestral condition in Neoselachians and hypothesized to be lost in members of Hypnosqualea. In addition, species of Squatina all posses a reduced occipital hemicentrum while the occipital hemicentrum in †Pseudorhina is unreduced, indicating the condition in Squatina is an example of postdisplacement heterochrony. Pristiophoriformes and Batoidea also are characterized by a lack of a basioccipital fovea and hemicentrum. However, extinct members of Batoidea, such as †Spathobatis, and modern taxa do possess a distinct notch in the posterior basicranium ventral to the foramen magnum. Except for the lack of an associated occipital hemicentrum, this notch is similar to the basioccipital fovea, but its homology is not yet addressed. Furthermore, within all species of Squatiniformes and Pristiophoriformes, as well as some members of Orectolobiformes and Carcharhiniformes, basiventral cartilages are laterally expanded, contributing to a broad articulation with the occipital condyle. The disparate taxa with modifications to the basiventral cartilages suggest a significant functional, rather than phylogenetic, signal for this feature. doi:10.1002/mmng.201100003

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. The investigations presented here show the results of an epigraphic analysis on ancient Roman lead ingots rescued from shipwrecks along the coast of Sicily (Italy) by means of Neutron Tomography (NT). The artefacts, including a lead horn, can be dated back to a period between the 3rd and 1st century BC. The three dimensional NT reconstructions helped the decipherment of hidden signs and partially visible details on the severely damaged objects. The findings obtained using the non-destructive procedure allowed us also to reach plausible conclusions in the context of the known commercial routes.

We report on measurements of spatial beam modulation of a polarized neutron beam induced by triangular precession regions in time-of-flight mode and the application of this novel technique spin-echo modulated small-angle neutron scattering (SEMSANS) to small-angle neutron scattering in the very small angle range. It is shown that this method can be implemented straight-forwardly in order to extend the accessible size range of structures to be investigated by SANS towards a microscopic scale by applying a divergent beam and measuring the real space correlation function. The novel approach of SEMSANS enables the application of sophisticated sample environment and measurements of magnetic samples (in contrast to the analogue method SESANS).

During the early development of turtles and other amniotes, the parabasisphenoid, or basisphenoid s.l., is formed by at least two centers of ossification: the endochondral basisphenoid s.s. and the dermal parasphenoid. This fusion is usually so dramatic that the two elements cannot be distinguished from each other in the adult stage. Here, we describe the basicranium of two species of Mesozoic turtles from Europe, Plesiochelys etalloni and Pleurosternon bullockii, partly using micro-CT (computer tomography) scans, and show that in both taxa para- and basisphenoid remain distinguishable throughout life. We also identify the extent that each of the two elements has contributed to the formation of the braincase floor. Because the structure of the parabasisphenoid determines the course of the internal carotid artery into the skull, our findings allow us to discuss the early evolution of the carotid pattern and the turtle basicranium in new detail. By surveying the main patterns of carotid circulation in extinct and extant turtles, we bring new evidence to the idea that it was largely the ossification of the parasphenoid that, along with the closure of the interpterygoid vacuity and the posterior extension of the pterygoids, shaped the internal carotid patterns as seen in modern turtles. Fil: Sterli, Juliana. Museo Paleontológico Egidio Feruglio; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Müller, Johannes. Humboldt-Universität zu Berlin; Alemania Fil: Anquetin, Jérémy. Muséum National d'Histoire Naturelle; Francia Fil: Hilger, André. Helmholtz-Zentrum für Materialien und Energie; Alemania

Liquid water exchange in two-phase flows within hydrophobic porous gas diffusion materials of polymer electrolyte membrane fuel cells was investigated spatially resolved with H-D contrast neutron radiography. A commonly used one-phase model is sufficient to describe water exchange characteristics at low water production rates. At higher rates, however, a significantly higher exchange velocity is found than predicted by a simple model. A new model for the water transport is derived based on an eruptive mechanism guided by Haines jumps, which is supported by recent experimental findings and leads to a very good agreement with the experiments. (c) 2008 American Institute of Physics.

This paper demonstrates the capabilities of the new instrument CONRAD II at Helmholtz Centre Berlin for the investigation of fuel cells. The performance gain of CONRAD II with respect to its predecessor instrument, CONRAD I, is demonstrated and different examples for in-operando measurements of polymer electrolyte membrane fuel cells are given. Furthermore, an application example for the high resolution detection system recently developed by the group is demonstrated which includes a three-dimensional measurement of the water distribution in a small fuel cell with a width of about 14 mm by means of neutron tomography.

Neutron tomography has been applied to investigate the mechanism of hydrogen assisted cracking in technical iron and supermartensitic steel. Rectangular technical iron block samples showed blistering due to intense hydrogen charging and the tomographic method revealed in situ the spatial distribution of hydrogen and cracks. Hydrogen accumulated in a small region around cracks and the cracks are filled with hydrogen gas. Cracks close to the surface contained no hydrogen. Hydrogenous tensile test samples of supermartensitic steel were pulled until rupture and showed hydrogen accumulations at the notch base and in the plastically deformed region around the fracture surface.

CONRAD-2 is an imaging instrument using low-energy (cold) neutrons. The instrument is installed at the end of a curved neutron guide which avoids the direct line of sight towards the reactor core. This ensures a very low background of high-energy neutrons and γ photons at the sample position. The cold neutron beam provides a wavelength range which is suitable for phase- and diffraction-contrast imaging such as grating interferometry and Bragg edge mapping. The instrument is well suited for high resolution imaging due to the high efficiency of the very thin scintillators that can be used for the detection of cold neutrons. An instrument upgrade was performed recently as a part of an upgrade program for the cold neutron instrumentation at HZB. The parameters of the instrument as well as some research highlights will be presented.

This paper describes non-destructive three-dimensional (3D) mapping of crystallographic phase distributions within the bulk (centimeter range) of samples with micrometer-scale resolution. The technique leverages diffraction contrast due to Bragg scattering and the large penetration power of neutrons through high-atomic-number-element-based structural materials. Our tomographic approach overcomes critical limitations of existing techniques by allowing spatially resolved phase mapping in bulk samples and offers a wide range of potential applications. The technique is demonstrated for (metastable 304L stainless) steel samples that exhibit strain-induced martensitic phase transformation after being subjected to tensile and torsional deformation. The distribution of phase fractions within the 3D reconstructed volumes was verified at select locations using neutron diffraction as well as EBSD, and results agree with transformation kinetics theory.