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Zinc-air batteries are gaining attention as safe battery alternatives, with high theoretical energy densities and a high abundance of their constituent materials. However, barriers to their widespread adoption include the need to improve their cycling lifetime, as well as stability and avoiding degradation mechanisms such as zinc dendrite growth and hydrogen-producing side reactions. X-ray computed tomography (CT) is a widely used technique for the study of batteries. In-situ/operando X-ray CT has been increasingly used to study the zinc anode of zinc-air batteries to evaluate the interesting morphological changes occurring during the reaction from Zn to ZnO during discharge (vice versa during charge). However, several studies have been carried out using synchrotron X-ray sources, which have limited availability for users. In this work, we present a comprehensive study of the discharge of commercial, primary zinc-air batteries using a laboratory based X-ray source for in-situ X-ray CT measurements. Four different discharge rates are investigated (C/30, C/60, C/90 and C/150), with tomograms collected at various stages throughout each discharge. Results confirm that with decreasing C-rate (i.e., decreasing discharge current) a greater volume of zinc is reacted, with average mass utilisations of 17%, 76%, 81% and 87% for C/30, C/60, C/90 and C/150, respectively. Furthermore, quantification using X-ray CT datasets showed that there is a direct correlation between the volume of zinc remaining in the cell and the state of charge (SoC) of the cell, which deviated from linearity for the longer C-rates. Finally, a potential new mechanism for shape change is discussed, where a zinc particle is replaced with a pore of a similar volume. As well as improvements in statistical relevance gained from multiple repeats for each C-rate, the results presented here could be used in both modelling of battery performance, as well as consideration for future anode design concepts.

Lithium ion battery failure occurs across multiple length scales. In this work, the properties of thermal failure and its effects on electrode materials were investigated in a commercial battery using a combination of accelerating rate calorimetry (ARC) and multi-length scale X-ray computed tomography (CT). ARC measured the heat dissipated from the cell during thermal runaway and enabled the identification of key thermal failure characteristics such as onset temperature and the rate of heat generation during the failure. Analysis before and after failure using scanning electron microscopy (SEM) and X-ray CT were performed to reveal the effects of failure on the architecture of the whole cell and microstructure of the cathode material. Mechanical deformations to the cell architecture were revealed due to gas generation at elevated temperatures (>200 °C). The extreme conditions during thermal runaway caused the cathode particles to reduce in size by a factor of two. Electrode surface analysis revealed surface deposits on both the anode and cathode materials. The link between electrode microstructure and heat generation within a cell during failure is analysed and compared to commercially available lithium ion cells of varying cathode chemistries. The optimisation of electrode designs for safer battery materials is discussed.

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This work considers the relationship between the morphology of porous carbon materials used for supercapacitors and the electrochemical impedance spectroscopy (EIS) response. EIS is a powerful tool that can be used to study the porous 3-dimensional electrode behavior in different electrochemical systems. Porous carbons prepared by treatment of cellulose with different compositions of potassium hydroxide (KOH) were used as model systems to investigate the form vs. electrochemical function relationship. A simple equivalent circuit that represents the electrochemical impedance behavior over a wide range of frequencies was designed. The associated impedances with the bulk electrolyte, Faradaic electrode processes and different pore size ranges were investigated using a truncated version of the standard transmission line model. The analysis considers the requirements of porous materials as