Recent developments in X-ray diffraction/scattering computed tomography for materials science.

X-ray diffraction/scattering computed tomography (XDS-CT) methods are a non-destructive class of chemical imaging techniques that have the capacity to provide reconstructions of sample cross-sections with spatially resolved chemical information. While X-ray diffraction CT (XRD-CT) is the most well-established method, recent advances in instrumentation and data reconstruction have seen greater use of related techniques like small angle X-ray scattering CT and pair distribution function CT. Additionally, the adoption of machine learning techniques for tomographic reconstruction and data analysis are fundamentally disrupting how XDS-CT data is processed. The following narrative review highlights recent developments and applications of XDS-CT with a focus on studies in the last five years. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Cycling Rate-Induced Spatially-Resolved Heterogeneities in Commercial Cylindrical Li-Ion Batteries.

Synchrotron high-energy X-ray diffraction computed tomography has been employed to investigate, for the first time, commercial cylindrical Li-ion batteries electrochemically cycled over the two cycling rates of C/2 and C/20. This technique yields maps of the crystalline components and chemical species as a cross-section of the cell with high spatiotemporal resolution (550 × 550 images with 20 × 20 × 3 µm3 voxel size in ca. 1 h). The recently developed Direct Least-Squares Reconstruction algorithm is used to overcome the well-known parallax problem and led to accurate lattice parameter maps for the device cathode. Chemical heterogeneities are revealed at both electrodes and are attributed to uneven Li and current distributions in the cells. It is shown that this technique has the potential to become an invaluable diagnostic tool for real-world commercial batteries and for their characterization under operating conditions, leading to unique insights into "real" battery degradation mechanisms as they occur.

In situ X-ray diffraction computed tomography studies examining the thermal and chemical stabilities of working Ba0.5Sr0.5Co0.8Fe0.2O3-δ membranes during oxidative coupling of methane.

In this study we present the results from two in situ X-ray diffraction computed tomography experiments of catalytic membrane reactors (CMRs) using Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) hollow fibre membranes and Na-Mn-W/SiO2 catalyst during the oxidative coupling of methane (OCM) reaction. The negative impact of CO2, when added to the inlet gas stream, is seen to be mainly related to the C2+ yield, while no evidence of carbonate phase(s) formation is found during the OCM experiments. The main degradation mechanism of the CMR is suggested to be primarily associated with the solid-state evolution of the BSCF phase rather than the presence of CO2. Specifically, in situ XRD-CT and post-mortem SEM/EDX measurements revealed a collapse of the cubic BSCF phase and subsequent formation of secondary phases, which include needle-like structures and hexagonal Ba6Co4O12 and formation of a BaWO4 layer, the latter being a result of chemical interaction between the membrane and catalyst materials at high temperatures.

Exploring cycling induced crystallographic change in NMC with X-ray diffraction computed tomography.

This study presents the application of X-ray diffraction computed tomography for the first time to analyze the crystal dimensions of LiNi0.33Mn0.33Co0.33O2 electrodes cycled to 4.2 and 4.7 V in full cells with graphite as negative electrodes at 1 µm spatial resolution to determine the change in unit cell dimensions as a result of electrochemical cycling. The nature of the technique permits the spatial localization of the diffraction information in 3D and mapping of heterogeneities from the electrode to the particle level. An overall decrease of 0.4% and 0.6% was observed for the unit cell volume after 100 cycles for the electrodes cycled to 4.2 and 4.7 V. Additionally, focused ion beam-scanning electron microscope cross-sections indicate extensive particle cracking as a function of upper cut-off voltage, further confirming that severe cycling stresses exacerbate degradation. Finally, the technique facilitates the detection of parts of the electrode that have inhomogeneous lattice parameters that deviate from the bulk of the sample, further highlighting the effectiveness of the technique as a diagnostic tool, bridging the gap between crystal structure and electrochemical performance.

Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes.

The performance of lithium ion electrodes is hindered by unfavorable chemical heterogeneities that pre-exist or develop during operation. Time-resolved spatial descriptions are needed to understand the link between such heterogeneities and a cell's performance. Here, operando high-resolution X-ray diffraction-computed tomography is used to spatially and temporally quantify crystallographic heterogeneities within and between particles throughout both fresh and degraded LixMn2O4 electrodes. This imaging technique facilitates identification of stoichiometric differences between particles and stoichiometric gradients and phase heterogeneities within particles. Through radial quantification of phase fractions, the response of distinct particles to lithiation is found to vary; most particles contain localized regions that transition to rock salt LiMnO2 within the first cycle. Other particles contain monoclinic Li2MnO3 near the surface and almost pure spinel LixMn2O4 near the core. Following 150 cycles, concentrations of LiMnO2 and Li2MnO3 significantly increase and widely vary between particles.

Spatially Resolving Lithiation in Silicon-Graphite Composite Electrodes via in Situ High-Energy X-ray Diffraction Computed Tomography.

Optimizing the chemical and morphological parameters of lithium-ion (Li-ion) electrodes is extremely challenging, due in part to the absence of techniques to construct spatial and temporal descriptions of chemical and morphological heterogeneities. We present the first demonstration of combined high-speed X-ray diffraction (XRD) and XRD computed tomography (XRD-CT) to probe, in 3D, crystallographic heterogeneities within Li-ion electrodes with a spatial resolution of 1 µm. The local charge-transfer mechanism within and between individual particles was investigated in a silicon(Si)-graphite composite electrode. High-speed XRD revealed charge balancing kinetics between the graphite and Si during the minutes following the transition from operation to open circuit. Subparticle lithiation heterogeneities in both Si and graphite were observed using XRD-CT, where the core and shell structures were segmented, and their respective diffraction patterns were characterized.

Design of next-generation ceramic fuel cells and real-time characterization with synchrotron X-ray diffraction computed tomography.

Ceramic fuel cells offer a clean and efficient means of producing electricity through a variety of fuels. However, miniaturization of cell dimensions for portable device application remains a challenge, as volumetric power densities generated by readily-available planar/tubular ceramic cells are limited. Here, we demonstrate a concept of 'micro-monolithic' ceramic cell design. The mechanical robustness and structural integrity of this design is thoroughly investigated with real-time, synchrotron X-ray diffraction computed tomography, suggesting excellent thermal cycling stability. The successful miniaturization results in an exceptional power density of 1.27 W cm-2 at 800 °C, which is among the highest reported. This holistic design incorporates both mechanical integrity and electrochemical performance, leading to mechanical property enhancement and representing an important step toward commercial development of portable ceramic devices with high volumetric power (>10 W cm-3), fast thermal cycling and marked mechanical reliability.