Donal P. Finegan

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.

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.

Quantifying Bulk Electrode Strain and Material Displacement within Lithium Batteries via High-Speed Operando Tomography and Digital Volume Correlation

Tracking the dynamic morphology of active materials during operation of lithium batteries is essential for identifying causes of performance loss. Digital volume correlation (DVC) is applied to high‐speed operando synchrotron X‐ray computed tomography of a commercial Li/MnO2 primary battery during discharge. Real‐time electrode material displacement is captured in 3D allowing degradation mechanisms such as delamination of the electrode from the current collector and electrode crack formation to be identified. Continuum DVC of consecutive images during discharge is used to quantify local displacements and strains in 3D throughout discharge, facilitating tracking of the progression of swelling due to lithiation within the electrode material in a commercial, spiral‐wound battery during normal operation. Displacement of the rigid current collector and cell materials contribute to severe electrode detachment and crack formation during discharge, which is monitored by a separate DVC approach. Use of time‐lapse X‐ray computed tomography coupled with DVC is thus demonstrated as an effective diagnostic technique to identify causes of performance loss within commercial lithium batteries; this novel approach is expected to guide the development of more effective commercial cell designs.

Comparison of three‐dimensional analysis and stereological techniques for quantifying lithium‐ion battery electrode microstructures

Lithium‐ion battery performance is intrinsically linked to electrode microstructure. Quantitative measurement of key structural parameters of lithium‐ion battery electrode microstructures will enable optimization as well as motivate systematic numerical studies for the improvement of battery performance. With the rapid development of 3‐D imaging techniques, quantitative assessment of 3‐D microstructures from 2‐D image sections by stereological methods appears outmoded; however, in spite of the proliferation of tomographic imaging techniques, it remains significantly easier to obtain two‐dimensional (2‐D) data sets. In this study, stereological prediction and three‐dimensional (3‐D) analysis techniques for quantitative assessment of key geometric parameters for characterizing battery electrode microstructures are examined and compared. Lithium‐ion battery electrodes were imaged using synchrotron‐based X‐ray tomographic microscopy. For each electrode sample investigated, stereological analysis was performed on reconstructed 2‐D image sections generated from tomographic imaging, whereas direct 3‐D analysis was performed on reconstructed image volumes. The analysis showed that geometric parameter estimation using 2‐D image sections is bound to be associated with ambiguity and that volume‐based 3‐D characterization of nonconvex, irregular and interconnected particles can be used to more accurately quantify spatially‐dependent parameters, such as tortuosity and pore‐phase connectivity.

Design of a miniature flow cell for in situ x-ray imaging of redox flow batteries

Flow batteries represent a possible grid-scale energy storage solution, having many advantages such as scalability, separation of power and energy capabilities, and simple operation. However, they can suffer from degradation during operation and the characteristics of the felt electrodes are little understood in terms of wetting, compression and pressure drops. Presented here is the design of a miniature flow cell that allows the use of x-ray computed tomography (CT) to study carbon felt materials in situ and operando, in both lab-based and synchrotron CT. Through application of the bespoke cell it is possible to observe felt fibres, electrolyte and pore phases and therefore enables non-destructive characterisation of an array of microstructural parameters during the operation of flow batteries. Furthermore, we expect this design can be readily adapted to the study of other electrochemical systems.

Laser-preparation of geometrically optimised samples for X-ray nano-CT

A robust and versatile sample preparation technique for the fabrication of cylindrical pillars for imaging by X‐ray nano‐computed tomography (nano‐CT) is presented. The procedure employs simple, cost‐effective laser micro‐machining coupled with focused‐ion beam (FIB) milling, when required, to yield mechanically robust samples at the micrometre length‐scale to match the field‐of‐view (FOV) for nano‐CT imaging. A variety of energy and geological materials are exhibited as case studies, demonstrating the procedure can be applied to a variety of materials to provide geometrically optimised samples whose size and shape are tailored to the attenuation coefficients of the constituent phases. The procedure can be implemented for the bespoke preparation of pillars for both lab‐ and synchrotron‐based X‐ray nano‐CT investigations of a wide range of samples.

Identifying the Cause of Rupture of Li‐Ion Batteries during Thermal Runaway

Abstract As the energy density of lithium‐ion cells and batteries increases, controlling the outcomes of thermal runaway becomes more challenging. If the high rate of gas generation during thermal runaway is not adequately vented, commercial cell designs can rupture and explode, presenting serious safety concerns. Here, ultra‐high‐speed synchrotron X‐ray imaging is used at >20 000 frames per second to characterize the venting processes of six different 18650 cell designs undergoing thermal runaway. For the first time, the mechanisms that lead to the most catastrophic type of cell failure, rupture, and explosion are identified and elucidated in detail. The practical application of the technique is highlighted by evaluating a novel 18650 cell design with a second vent at the base, which is shown to avoid the critical stages that lead to rupture. The insights yielded in this study shed new light on battery failure and are expected to guide the development of safer commercial cell designs.

Algorithmic structural segmentation of defective particle systems: a lithium-ion battery study: ALGORITHMIC STRUCTURAL SEGMENTATION OF DEFECTIVE PARTICLE SYSTEMS

We describe a segmentation algorithm that is able to identify defects (cracks, holes and breakages) in particle systems. This information is used to segment image data into individual particles, where each particle and its defects are identified accordingly. We apply the method to particle systems that appear in Li‐ion battery electrodes. First, the algorithm is validated using simulated data from a stochastic 3D microstructure model, where we have full information about defects. This allows us to quantify the accuracy of the segmentation result. Then we show that the algorithm can successfully be applied to tomographic image data from real battery anodes and cathodes, which are composed of particle systems with very different morpohological properties. Finally, we show how the results of the segmentation algorithm can be used for structural analysis.

Microstructural Analysis of the Effects of Thermal Runaway on Li-Ion and Na-Ion Battery Electrodes

Thermal runaway is a phenomenon that occurs due to self-sustaining reactions within batteries at elevated temperatures resulting in catastrophic failure. Here, the thermal runaway process is studied for a Li-ion and Na-ion pouch cells of similar energy density (10.5 Wh, 12 Wh, respectively) using accelerating rate calorimetry (ARC). Both cells were constructed with a z-fold configuration, with a standard shutdown separator in the Li-ion and a low-cost polypropylene (PP) separator in the Na-ion. Even with the shutdown separator, it is shown that the self-heating rate and rate of thermal runaway in Na-ion cells is significantly slower than that observed in Li-ion systems. The thermal runaway event initiates at a higher temperature in Na-ion cells. The effect of thermal runaway on the architecture of the cells is examined using X-ray microcomputed tomography, and scanning electron microscopy (SEM) is used to examine the failed electrodes of both cells. Finally, from examination of the respective electrodes, likely due to the carbonate solvent containing electrolyte, it is suggested that thermal runaway in Na-ion batteries (NIBs) occurs via a similar mechanism to that reported for Li-ion cells.

Revealing Microstructural Defects in Commercial Li-Ion Batteries under Electrochemical Fatigue Cycling

Li-ion batteries serve a range of applications within daily life. From portable electronics to the automotive industry, the global reliance on Li-ion battery technologies is projected to grow at an exponential rate over the next decade. With increasing market demands and widespread application, however, comes the unique responsibility of scientists and engineers to characterize and understand the aging and failure properties of batteries. The aim of this research is to simultaneously satisfy the following consumer demands: a) the materials should be long lasting, particularly important in the automotive industry, and b) devices made with battery materials should be safe to operate. To better address these technological challenges, researchers worldwide are beginning to turn to microscopy to understand how the materials perform in their service conditions and to identify the root cause for failures to mitigate the risk of consumer dissatisfaction and, ultimately, to preserve consumer safety.