On the origin and application of the Bruggeman correlation for analysing transport phenomena in electrochemical systems

The widely used Bruggeman equations correlate tortuosity factors of porous media with their porosity. Finding diverse application from optics to bubble formation, it received considerable attention in fuel cell and battery research, recently. The ability to estimate tortuous mass transport resistance based on porosity alone is attractive, because direct access to the tortuosity factors is notoriously difficult. The correlation, however, has limitations, which are not widely appreciated owing to the limited accessibility of the original manuscript. We retrace Bruggeman's derivation, together with its initial assumptions, and comment on validity and limitations apparent from the original work to offer some guidance on its use

Tortuosity in electrochemical devices: a review of calculation approaches

The tortuosity of a structure plays a vital role in the transport of mass and charge in electrochemical devices. Concentration polarisation losses at high current densities are caused by mass transport limitations and are thus a function of microstructural characteristics. As tortuosity is notoriously difficult to ascertain, a wide and diverse range of methods have been developed to extract the tortuosity of a structure. These methods differ significantly in terms of calculation approach and data preparation techniques. Here, a review of tortuosity calculation procedures applied in the field of electrochemical devices is presented to better understand the resulting values presented in the literature. Visible differences between calculation methods are observed, especially when using porosity–tortuosity relationships and when comparing geometric and flux-based tortuosity calculation approaches

Understanding transport phenomena in electrochemical energy devices via X-ray nano CT

Porous support layers in electrochemical devices ensure mechanical stability of membrane assemblies such as solid oxide fuel cells and oxygen transport membranes (OTMs). At the same time, porous layers affect diffusive mass transport of gaseous reactants and contribute to performance losses at high fuel utilisation and conversion ratios. Microstructural characteristics are vital to calculate mass transport phenomena, where tortuosity remains notoriously difficult to determine. Here, the tortuosity of tubular porous support layers of OTMs is evaluated via high resolution X-ray nano computed tomography. The high resolution reveals the complex microstructure of the samples to then execute a selection of image-based tortuosity calculation algorithms. Visible differences between geometric and flux-based algorithms are observed and have thus to be applied with caution

Investigating microstructural evolution during the electroreduction of UO2 to U in LiCl-KCl eutectic using focused ion beam tomography

Reprocessing of spent nuclear fuels using molten salt media is an attractive alternative to liquid-liquid extraction techniques. Pyroelectrochemical processing utilizes direct, selective, electrochemical reduction of uranium dioxide, followed by selective electroplating of a uranium metal. Thermodynamic prediction of the electrochemical reduction of UO2 to U in LiCl-KCl eutectic has shown to be a function of the oxide ion activity. The pO2− of the salt may be affected by the microstructure of the UO2 electrode. A uranium dioxide filled “micro-bucket” electrode has been partially electroreduced to uranium metal in molten lithium chloride-potassium chloride eutectic. This partial electroreduction resulted in two distinct microstructures: a dense UO2 and a porous U metal structure were characterised by energy dispersive X-ray spectroscopy. Focused ion beam tomography was performed on five regions of this electrode which revealed an overall porosity ranging from 17.36% at the outer edge to 3.91% towards the centre, commensurate with the expected extent of reaction in each location. The pore connectivity was also seen to reduce from 88.32% to 17.86% in the same regions and the tortuosity through the sample was modelled along the axis of propagation of the electroreduction, which was seen to increase from a value of 4.42 to a value of infinity (disconnected pores). These microstructural characteristics could impede the transport of O2− ions resulting in a change in the local pO2− which could result in the inability to perform the electroreduction

Tracking internal temperature and structural dynamics during nail penetration of lithium-ion cells

Mechanical abuse of lithium-ion batteries is widely used during testing to induce thermal runaway, characterize associated risks, and expose cell and module vulnerabilities. However, the repeatability of puncture or ‘nail penetration’ tests is a key issue as there is often a high degree of variability in the resulting thermal runaway process. In this work, the failure mechanisms of 18650 cells punctured at different locations and orientations are characterized with respect to their internal structural degradation, and both their internal and surface temperature, all of which are monitored in real time. The initiation and propagation of thermal runaway is visualized via high-speed synchrotron X-ray radiography at 2000 frames per second, and the surface and internal temperatures are recorded via infrared imaging and a thermocouple embedded in the tip of the penetrating nail, respectively. The influence of the nail, as well as how and where it penetrates the cell, on the initiation and propagation of thermal runaway is described and the suitability of this test method for representing in-field failures is discussed

3D characterization of diffusivities and its impact on mass flux and concentration overpotential in SOFC anodes

In recent years great effort has been taken to understand the effect of gas transport on the performance of electrochemical devices. This study aims to characterize the diffusion regimes and the possible inaccuracies of the mass transport calculation in Solid Oxide Fuel Cell (SOFC) anodes when a volume-averaged pore diameter is used. 3D pore size distribution is measured based on the extracted pore phase from an X-ray CT scan, which is further used for the calculation of a Knudsen number (Kn) map in the porous medium, followed by the voxel-based distribution of the effective diffusion coefficients for different fuel gases. Diffusion fluxes in a binary gas mixture using the lower boundary, upper boundary and average effective coefficients are compared, and the impact on overpotential is analyzed. The results show that pore diameters from tens to hundreds of nanometers result in a broad range of Knudsen number (1.1 ∼ 4.8 and 0.6 ∼ 3 for H2 and CH4 respectively), indicative of the transitional diffusion regime. The results highlight that for a porous material, such as an SOFC anode where Knudsen effects are non-negligible, using a volume-averaged pore size can overestimate the mass flux by ±200% compared to the actual value. The characteristic pore size should be chosen sensibly in order to improve the reliability of the mass transport and electrochemical performance evaluation

Investigating lithium-ion battery materials during overcharge-induced thermal runaway: an operando and multi-scale X-ray CT study

Catastrophic failure of lithium-ion batteries occurs across multiple length scales and over very short time periods. A combination of high-speed operando tomography, thermal imaging and electrochemical measurements is used to probe the degradation mechanisms leading up to overcharge-induced thermal runaway of a LiCoO2 pouch cell, through its interrelated dynamic structural, thermal and electrical responses. Failure mechanisms across multiple length scales are explored using a post-mortem multi-scale tomography approach, revealing significant morphological and phase changes in the LiCoO2 electrode microstructure and location dependent degradation. This combined operando and multi-scale X-ray computed tomography (CT) technique is demonstrated as a comprehensive approach to understanding battery degradation and failure

In-operando high-speed tomography of lithium-ion batteries during thermal runaway

Prevention and mitigation of thermal runaway presents one of the greatest challenges for the safe operation of lithium-ion batteries. Here, we demonstrate for the first time the application of high-speed synchrotron X-ray computed tomography and radiography, in conjunction with thermal imaging, to track the evolution of internal structural damage and thermal behaviour during initiation and propagation of thermal runaway in lithium-ion batteries. This diagnostic approach is applied to commercial lithium-ion batteries (LG 18650 NMC cells), yielding insights into key degradation modes including gas-induced delamination, electrode layer collapse and propagation of structural degradation. It is envisaged that the use of these techniques will lead to major improvements in the design of Li-ion batteries and their safety features

Characterising thermal runaway within lithium-ion cells by inducing and monitoring internal short circuits

Lithium-ion batteries are being used in increasingly demanding applications where safety and reliability are of utmost importance. Thermal runaway presents the greatest safety hazard, and needs to be fully understood in order to progress towards safer cell and battery designs. Here, we demonstrate the application of an internal short circuiting device for controlled, on-demand, initiation of thermal runaway. Through its use, the location and timing of thermal runaway initiation is pre-determined, allowing analysis of the nucleation and propagation of failure within 18 650 cells through the use of high-speed X-ray imaging at 2000 frames per second. The cause of unfavourable occurrences such as sidewall rupture, cell bursting, and cell-to-cell propagation within modules is elucidated, and steps towards improved safety of 18 650 cells and batteries are discussed

“It will always continue unless we can change something”: consequences of intimate partner violence for indigenous women, children, and families

Background: Violence against indigenous women and girls is endemic, yet the absence of research on the consequences of this violence from the perspectives of women presents a profound barrier to the development of knowledge, along with violence prevention and mitigation. Although family is central to many indigenous communities, existing research typically examines the consequences of intimate partner violence (IPV) on women or children in isolation, rather than examining its consequences holistically. Objective: The purpose of this article is to identify US indigenous women's perspectives about the impact of IPV on women, children, and families. Method: Data were collected with 29 indigenous women affected by violence from a Southeastern tribe in the United States. As part of a larger critical ethnography, pragmatic horizon analysis of life history interviews revealed the consequences of IPV across multiple levels. Results: Women reported profound psychological consequences resulting from IPV. The majority of women had witnessed IPV in their childhood, providing support for an intergenerational cycle of violence. Women reported psychological consequences on children, which paralleled those reported by women, leaving deep impressions on children across their life course. Consequences on children and whole families were extensive, indicating the negative ramifications of IPV transcended personal boundaries and affected children and families across multiple generations. Conclusions: Given the tight-knit nature of indigenous families and communities, the consequences across individuals and families were noteworthy. However, a dearth in research examining consequences of IPV across levels fails to capture the interconnections of consequences for women, children, and families. Given the centrality of family in many indigenous communities, examining IPV from a holistic perspective that incorporates multiple levels is recommended for IPV research and intervention development