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Over the last century, X-ray imaging instruments and their accompanying tomographic reconstruction algorithms have developed considerably. With improved tomogram quality and resolution, voxel sizes down to tens of nanometers can now be achieved. Moreover, recent advancements in readily accessible lab-based X-ray computed tomography (X-ray CT) instruments have produced spatial resolutions comparable to specialist synchrotron facilities. Electrochemical energy conversion devices, such as fuel cells and batteries, have inherently complex electrode microstructures to achieve competitive power delivery for consideration as replacements for conventional sources. With resolution capabilities spanning tens of microns to tens of nanometers, X-ray CT has become widely employed in the three-dimensional (3D) characterization of electrochemical materials. The ability to perform multiscale imaging has enabled characterization from system-down to particle-level, with the ability to resolve critical features within device microstructures. X-ray characterization presents a favorable alternative to other 3D methods, such as focused ion beam scanning electron microscopy, due to its non-destructive nature, which allows four-dimensional (4D) studies, three spatial dimensions plus time, linking structural dynamics to device performance and lifetime. X-ray CT has accelerated research from fundamental understanding of the links between cell structure and performance, to the improvement in manufacturing and scale-up of full electrochemical cells. Furthermore, this has aided in the mitigation of degradation and cell-level failures, such as thermal runaway. This review presents recent developments in the use of X-ray CT as a characterization method and its role in the advancement of electrochemical materials engineering. [ABSTRACT FROM AUTHOR]

Abstract In recent years, the ability to examine the processes that cause the catastrophic failure of batteries as a result of thermal runaway has improved substantially. In this work, the effect of thermal runaway on the microstructure of the electrodes of a Na-ion battery is examined using X-ray computed tomography for the first time. The thermal failure induced via accelerating rate calorimetry enabled the examination of failed electrodes, which were subsequently compared with fresh samples. Pre- and post-mortem microstructural analysis shows changes in both electrodes as a result of the thermal runaway process at the micrometre length-scale. It is seen that the cathode shows the largest changes in structure, with the anode remaining morphologically similar post-failure at the sub-micron length-scale. The formation of a highly X-ray attenuating layer, which is proposed to be a metallic product of the thermal runaway reaction, is observed, indicating that the thermal runaway mechanisms which occur in Na-ion batteries may be similar to those reported for Li-ion systems. Graphical abstract Image 1 Highlights • Na-ion electrodes examined after undergoing thermal runaway at two length scales. • Bulk changes in both electrodes observed at micro-scale. • Nano-scale analysis highlights similar anode morphology post failure. • Cathode observed to be fundamentally degraded due to the runaway reaction. • Reduction of cathode and crossover of anode material detailed after thermal failure. [ABSTRACT FROM AUTHOR]

This study aims to correlate the active triple phase boundaries (TPBs) to the variation of as-prepared anode microstructures and Ni densifications based on the reconstructed 3D volume of an SOFC anode, providing a point of comparison with theoretical studies that reveal the relationship of TPBs and the material microstructure using randomly packed spheres models. The TPB degradation mechanisms are explained using a particle network model. The results indicate that in low porosity regime, the TPBs sharply increase with the porosity until the percolation threshold (10%); at intermediate porosity (10%–25%), a balance of surface area between three phases is more critical than that of volume fraction to reach the optimal TPB density; in the high porosity regime (>25%), the TPBs start to drop due to the shrinkage and detachment of Ni/YSZ interfaces. The TPB density is inversely proportional to the degree of Ni densification as long as the Ni content is above the percolation threshold (35%) and can be improved by 70% within 7% change of porosity provided that the over-densification is mitigated. This has implications for the design of SOFC microstructures as well for electrode durability, where Ni agglomeration is known to deleteriously impact long-term operation. [ABSTRACT FROM AUTHOR]

Solid state batteries have attracted extensive attention, but the lithium penetration through the solid electrolyte remains a critical barrier to commercialisation and is not yet fully understood. In this study, the 3D morphological evolution of cracks with deposited lithium were tracked as they penetrated through the solid electrolyte during repetitive plating. This is achieved by utilising in-situ synchrotron X-ray computed tomography with high spatial and temporal resolutions. Thin-sheet cracks were observed to penetrate the solid electrolyte without immediate short-circuiting of the cell. Changes in their width and volume were quantified. By calculating the volume of deposited lithium, it was found that the lithium was only partially filled in cracks, and its filling ratio quickly dropped from 94.95% after the 1st plating to ca. 20% after the 4th plating. The filling process was revealed through tracking the line profile of grayscale along cracks. It was found that lithium grew much more slowly than cracks, so that the cracks near the cathode side were largely hollow and the cell could continue to operate. The deposited lithium after short circuit was segmented and its distribution was visualised. DVC analysis was applied to map local high stress and strain, which aggregated along cracks and significantly increased at areas where new cracks formed. [Display omitted] • The 3D morphological evolution of cracks and deposited Li was tracked by in-situ X-ray CT during plating until short circuit. • Lithium only partially filled the cracks, and propagated more slowly than the cracks resulting in a lag of short circuit. • The lithium filling ratio dropped from 94% to ca. 20% during plating, primarily due to the high speed of crack growth. • Stress and strain in the LPS aggregated along the cracks and their branches, forcing cracks to propagate in these areas. [ABSTRACT FROM AUTHOR]

The thermal response of Li-ion cells can greatly vary for identical cell designs tested under identical conditions, the distribution of which is costly to fully characterize experimentally. The open-source Battery Failure Databank presented here contains robust, high-quality data from hundreds of abuse tests spanning numerous commercial cell designs and testing conditions. Data was gathered using a fractional thermal runaway calorimeter and contains the fractional breakdown of heat and mass that was ejected, as well as high-speed synchrotron radiography of the internal dynamic response of cells during thermal runaway. The distribution of thermal output, mass ejection, and internal response of commercial cells are compared for different abuse-test conditions, which when normalized on a per amp-hour basis show a strong positive correlation between heat output from cells, the fraction of mass ejected from the cells, their energy- and power-density. Ejected mass was shown to contain 10 × more heat per gram than non-ejected mass. The causes of 'outlier' thermal and ejection responses i.e., extreme cases, are elucidated by high-speed radiography which showed how occurrences such as vent clogging can create more hazardous conditions. High-speed radiography also demonstrated how the time-resolved interplay of thermal runaway propagation and mass ejection influences the total heat generated. [ABSTRACT FROM AUTHOR]

In this study, we aim to parametrically reveal the dependence of electrochemical performance on a variety of microstructural characteristics at multi-length scale in a micro-tubular solid oxide fuel cell to shed light on the advanced electrode design. Numerical Direct Simulation Monte Carlo method is used on the tomographically-reconstructed 3D microstructure of the anode to characterise the tortuosity factors as a function of the porosity and pore diameter accounting for the Knudsen flow. These are subsequently incorporated in the mass transport in 2D electrochemical simulations. Results show that the Knudsen tortuosity factor is two times larger than that estimated by the continuum physics. High substrate porosity and pore size show unnoticeable effect in facilitating the mass transport provided that the micro-channels span over 60% of the radial thickness. The width and radial distribution of the micro-channels have little influence on the mass transport, but the compactness greatly affects the global performance. Optimal designs are identified as i) 80% micro-channel length and 27% substrate porosity to reach maximum power density (1.18 W cm−2) with lowered mechanical strength, or ii) 60% micro-channels length and 27% porosity to obtain a more balanced performance (0.96 W cm−2) with better long-term structural integrity. Image 1 • Knudsen tortuosity factor is two times larger than that obtained by continuum flow. • Channels length should be 60% of the anode thickness to eliminate the H 2 depletion. • 10% longer micro-channels yield similar mass flux as 5% less anode porosity does. • The width of the micro-channels is insignificant in enhancing the mass transport. • Hierarchical electrode optimisation scheme is proposed for different applications. [ABSTRACT FROM AUTHOR]

Abstract Intentionally inducing worst-case thermal runaway scenarios in Li-ion cells on-demand is a definitive way to test the efficacy of battery systems in safely mitigating the consequences of catastrophic failure. An internal short-circuiting (ISC) device is implanted into three 18650 cell designs: one standard, one with a bottom vent, and one with a thicker casing. Through an extensive study of 228 cells, the position at which thermal runaway initiates is shown to greatly affect the tendency of cells to rupture and incur side-wall breaches at specific locations. The risks associated with each failure mechanism and position of the ISC device are quantified using a custom calorimeter that can decouple the heat from ejected and non-ejected contents. Causes of high-risk failure mechanisms, such as bursting and side-wall breaches, are elucidated using high-speed synchrotron X-ray imaging at 2000 frames per second and image-based 3D thermal runaway computational models, which together are used to construct a comprehensive description of external risks based on internal structural and thermal phenomena. [ABSTRACT FROM AUTHOR]

Due to their high theoretical capacity compared to that of state-of-the-art graphite-based electrodes, silicon electrodes have gained much research focus for use in the development of next generation lithium-ion batteries. However, a major drawback of silicon as an electrode material is that it suffers from particle fracturing due to huge volume expansion during electrochemical cycling, thus limiting commercialization of such electrodes. Understanding the role of material microstructure in electrode degradation will be instrumental in the design of stable silicon electrodes. Here, we demonstrate the application of synchrotron-based X-ray tomographic microscopy to capture and track microstructural evolution, phase transformation and fracturing within a silicon-based electrode during electrochemical lithiation. [ABSTRACT FROM AUTHOR]

Thermal gradients can arise within solid oxide fuel cells (SOFCs) due to start-up and shut-down, non-uniform gas distribution, fast cycling and operation under internal reforming conditions. Here, the effects of operationally relevant thermal gradients on Ni/YSZ SOFC anode half cells are investigated using combined synchrotron X-ray diffraction and thermal imaging. The combination of these techniques has identified significant deviation from linear thermal expansion behaviour in a sample exposed to a one dimensional thermal gradient. Stress gradients are identified along isothermal regions due to the presence of a proximate thermal gradient, with tensile stress deviations of up to 75 MPa being observed across the sample at a constant temperature. Significant strain is also observed due to the presence of thermal gradients when compared to work carried out at isothermal conditions. [ABSTRACT FROM AUTHOR]

Fracture of lithium-ion battery electrodes is found to contribute to capacity fade and reduce the lifespan of a battery. Traditional fracture models for batteries are restricted to consideration of a single, idealised particle; here, advanced X-ray computed tomography (CT) imaging, an electro-chemo-mechanical model and a phase field fracture framework are combined to predict the void-driven fracture in the electrode particles of a realistic battery electrode microstructure. The electrode is shown to exhibit a highly heterogeneous electrochemical and fracture response that depends on the particle size and distance from the separator/current collector. The model enables prediction of increased cracking due to enlarged cycling voltage windows, cracking susceptibility as a function of electrode thickness, and damage sensitivity to discharge rate. This framework provides a platform that facilitates a deeper understanding of electrode fracture and enables the design of next-generation electrodes with higher capacities and improved degradation characteristics. [Display omitted] • Realistic fracture predictions in an entire electrode microstructure. • Highly heterogeneous electrochemical and fracture response is predicted. • Prediction of elevated cracking due to enlarged cycling voltage windows. • Cracking shown to occur as a function of electrode thickness. • Increasing damage as the rate of discharge is increased. [ABSTRACT FROM AUTHOR]

It remains difficult to detect internal mechanical deformation and gas-induced degradation in lithium-ion batteries, especially outside specialized diagnostics laboratories. In this work, we demonstrate that electrochemical acoustic time-of-flight (EA-ToF) spectroscopy can be used as an insightful and field-deployable diagnostic/prognostic technique to sense the onset of failure. A 210 mAh commercial lithium-ion cell undergoing thermal abuse testing is probed with in situ and operando EA-ToF spectroscopy, together with simultaneous fractional thermal runaway calorimetry (FTRC) and synchrotron X-ray imaging. The combination of X-ray imaging and EA-ToF analysis provides new understanding into the through-plane mechanical deformation in lithium-ion batteries through direct visualisation and the acoustic ToF response. Internal structural changes, such as gas-induced delamination, are identified using EA-ToF spectroscopy due to variations in the attenuation and signal peak shifts. This is corroborated using X-ray imaging, demonstrating EA-ToF spectroscopy as a promising technique for detecting onset of battery failure. • Cell defects and failure investigated with X-ray imaging and acoustic spectroscopy. • Acoustic spectrograms provide indicators of gas-induced delamination. • Correlative X-ray imaging complements high-speed pulse-echo ultrasonic probing. • Cell defects are identifiable, including electrode non-uniformity and gas phases. [ABSTRACT FROM AUTHOR]

Diagnostic systems for Li-ion batteries have become increasingly important due to the larger size, and cost of the batteries being deployed in increasingly demanding applications, including electric vehicles. Here, ultrasound acoustic time-of-flight (ToF) analysis is conducted under a range of operating conditions. Measurements are performed on a commercial pouch cell during varying discharge rates to identify a range of effects that influence the acoustic ToF measurements. The cell was examined using X-ray computed tomography to ensure no significant defects were present and to confirm the layered structure in the region being investigated, validating the signal pattern observed. Analyses of the acoustic signals obtained suggest that stresses are generated in the electrodes during both the charge and discharge of the cell with the magnitude of Young's modulus for the component materials being both a function of the state-of-charge and applied current. Characteristic responses for both electrodes during the charge/discharge cycle highlight the potential application of the technique as a real-time diagnostic tool. • Ultrasound measurement demonstrated as a potential operando diagnostic for Li-ion batteries. • Response of batteries shown to be highly rate dependent at large C-rates. • Time-of-flight measurement shown to identify electrochemical stiffness in cells. [ABSTRACT FROM AUTHOR]