Imperial College London

Dr Samuel J Cooper

Faculty of EngineeringDyson School of Design Engineering




samuel.cooper Website




ObservatorySouth Kensington Campus





Publication Type

31 results found

Nguyen T-T, Demortière A, Fleutot B, Delobel B, Delacourt C, Cooper Set al., The electrode tortuosity factor: Why the conventional tortuosity factor is not well suited for quantifying transport in porous Li-ion battery electrodes and what to use instead, npj Computational Materials, ISSN: 2057-3960

The tortuosity factor of porous battery electrodes is an important parameter used to correlate electrode microstructure with performance through numerical modeling. Therefore, having an appropriate method for the accurate determination of tortuosity factors is critical. This paper presents a numerical approach, based on simulations performed on microstructural image data, which enables a comparison between two common experimental methods. Several key issues with the conventional “flow through” type tortuosity factor are highlighted, when used to characterise electrodes. As a result, a new concept called the “electrode tortuosity factor” is introduced, which captures the transport processes relevant to porous electrodes better than the “flow through” type tortuosity factor. The simulation results from this work demonstrate the importance of non-percolating (“dead-end”) pores in the performance of real electrodes. This is an important result for optimizing electrode design that should be considered by electrochemical modelers. This simulation tool is provided as an open-source MATLAB application and is freely available online as part of the TauFactor platform.

Journal article

Gayon-Lombardo A, Lukas M, Brandon N, Cooper Set al., 2020, Pores for thought: Generative adversarial networks for stochastic reconstruction of 3D multi-phase electrode microstructures with periodic boundaries, npj Computational Materials, Vol: 6, Pages: 1-11, ISSN: 2057-3960

The generation of multiphase porous electrode microstructures is a critical step in the optimisation of electrochemical energy storage devices. This work implements a deep convolutional generative adversarial network (DC-GAN) for generating realistic n-phase microstructural data. The same network architecture is successfully applied to two very different three-phase microstructures: A lithium-ion battery cathode and a solid oxide fuel cell anode. A comparison between the real and synthetic data is performed in terms of the morphological properties (volume fraction, specific surface area, triple-phase boundary) and transport properties (relative diffusivity), as well as the two-point correlation function. The results show excellent agreement between datasets and they are also visually indistinguishable. By modifying the input to the generator, we show that it is possible to generate microstructure with periodic boundaries in all three directions. This has the potential to significantly reduce the simulated volume required to be considered “representative” and therefore massively reduce the computational cost of the electrochemical simulations necessary to predict the performance of a particular microstructure during optimisation.

Journal article

Nguyen T-T, Demortiere A, Fleutot B, Delobel B, Cooper SJ, Delacourt Cet al., 2020, Resolving the Discrepancy in Tortuosity Determination for Battery Porous Electrodes Via a Numerical Approach, ECS Meeting Abstracts, Vol: MA2020-01, Pages: 2724-2724

Journal article

Finegan DP, Cooper SJ, 2019, Battery safety: data-driven prediction of failure, Joule, Vol: 3, Pages: 2599-2601, ISSN: 2542-4351

Accurate prediction of battery failure, both online and offline, facilitates design of safer battery systems through informed-engineering and on-line adaption to unfavorable scenarios. With the wide range of batteries available and frequently evolving pack designs, accurate prediction of cell behavior under different conditions is very challenging and extremely time consuming. In this issue of Joule, Li et al.1 used data from a previously reported finite-element model to train machine learning algorithms to predict whether a cell will undergo an internal short circuit when exposed to a selection of mechanical abuse conditions. The presented approach aims to alleviate, and yet is still limited by, a common challenge facing data-driven prediction methods: access to robust, plentiful, high-quality, and relevant experimental data.

Journal article

Smith CTG, Mills CA, Pani S, Rhodes R, Bailey JJ, Cooper SJ, Pathan TS, Stolojan V, Brett DJL, Shearing PR, Silva SRPet al., 2019, X-ray micro-computed tomography as a non-destructive tool for imaging the uptake of metal nanoparticles by graphene-based 3D carbon structures., Nanoscale, Vol: 11, Pages: 14734-14741

Graphene-based carbon sponges can be used in different applications in a large number of fields including microelectronics, energy harvesting and storage, antimicrobial activity and environmental remediation. The functionality and scope of their applications can be broadened considerably by the introduction of metallic nanoparticles into the carbon matrix during preparation or post-synthesis. Here, we report on the use of X-ray micro-computed tomography (CT) as a method of imaging graphene sponges after the uptake of metal (silver and iron) nanoparticles. The technique can be used to visualize the inner structure of the graphene sponge in 3D in a non-destructive fashion by providing information on the nanoparticles deposited on the sponge surfaces, both internal and external. Other deposited materials can be imaged in a similar manner providing they return a high enough contrast to the carbon microstructure, which is facilitated by the low atomic mass of carbon.

Journal article

Song B, Bertei A, Wang X, Cooper S, Ruiz-Trejo E, Chowdhury R, Podor R, Brandon Net al., 2019, Unveiling the mechanisms of solid-state dewetting in Solid Oxide Cells with novel 2D electrodes, Journal of Power Sources, Vol: 420, Pages: 124-133, ISSN: 0378-7753

During the operation of Solid Oxide Cell (SOC) fuel electrodes, the mobility of nickel can lead to significant changes in electrode morphology, with accompanying degradation in electrochemical performance. In this work, the dewetting of nickel films supported on yttriastabilized zirconia (YSZ), hereafter called 2D cells, is studied by coupling in-situ environmentalscanning electron microscopy (E-SEM), image analysis, cellular automata simulation and electrochemical impedance spectroscopy (EIS). Analysis of experimental E-SEM images shows that Ni dewetting causes an increase in active triple phase boundary (aTPB) length up to a maximum, after which a sharp decrease in aTPB occurs due to Ni de-percolation. Thismicrostructural evolution is consistent with the EIS response, which shows a minimum in polarization resistance followed by a rapid electrochemical degradation. These results reveal that neither evaporation-condensation nor surface diffusion of Ni are the main mechanisms of dewetting at 560-800 °C. Rather, the energy barrier for pore nucleation within the dense Ni film appears to be the most important factor. This sheds light on the relevant mechanisms and interfaces that must be controlled to reduce the electrochemical degradation of SOC electrodes induced by Ni dewetting.

Journal article

Yin C, Liu X, Wei J, Tan R, Zhou J, Ouyang M, Wang H, Cooper SJ, Wu B, George C, Wang Qet al., 2019, “All-in-Gel” design for supercapacitors towards solid-state energy devices with thermal and mechanical compliance, Journal of Materials Chemistry A, Vol: 7, Pages: 8826-8831, ISSN: 2050-7488

“All-in-gel” supercapacitor is designed <italic>via</italic> ionogel composite electrolyte and Bucky gel electrodes. These flexible, conductive and shape-conformable gels represent a step change in the design of safe energy storage devices for wearable electronics, in particular those facing the increased demands of hazardous operational environments.

Journal article

Liu X, Taiwo O, Yin C, Ouyang M, Chowdhury R, Wang B, Wang H, Wu B, Brandon N, Wang Q, Cooper Set al., 2019, Aligned lonogel electrolytes for high‐temperature supercapacitors, Advanced Science, Vol: 6, Pages: 1-7, ISSN: 2198-3844

Ionogels are a new class of promising materials for use in all‐solid‐state energy storage devices in which they can function as an integrated separator and electrolyte. However, their performance is limited by the presence of a crosslinking polymer, which is needed to improve the mechanical properties, but compromises their ionic conductivity. Here, directional freezing is used followed by a solvent replacement method to prepare aligned nanocomposite ionogels which exhibit enhanced ionic conductivity, good mechanical strength, and thermal stability simultaneously. The aligned ionogel based supercapacitor achieves a 29% higher specific capacitance (176 F g−1 at 25 °C and 1 A g−1) than an equivalent nonaligned form. Notably, this thermally stable aligned ionogel has a high ionic conductivity of 22.1 mS cm−1 and achieves a high specific capacitance of 167 F g−1 at 10 A g−1 and 200 °C. Furthermore, the diffusion simulations conducted on 3D reconstructed tomography images are employed to explain the improved conductivity in the relevant direction of the aligned structure compared to the nonaligned. This work demonstrates the synthesis, analysis, and use of aligned ionogels as supercapacitor separators and electrolytes, representing a promising direction for the development of wearable electronics coupled with image based process and simulations.

Journal article

Ouyang M, Bertei A, Cooper SJ, Wu Y, Liu X, Boldrin P, Kishimoto M, Wu B, Brandon NPet al., 2019, Design of fibre Ni/CGO anode and model interpretation, ECS Transactions, Vol: 91, Pages: 1721-1739, ISSN: 1938-6737

© The Electrochemical Society. A new structure of Ni/gadolinium-doped ceria (CGO) is prepared by a highly tuneable and facile combination of electrospinning and tape-casting method. The structure consists of a network made by continuous Ni fibres and filled in with CGO matrices. When used as the anode of solid oxide fuel cell (SOFC), though it has a lower triple phase boundary (TPB) density, it exhibits better performance compared with impregnated and cermet Ni/CGO with higher nickel loading. An algorithm is developed to determine the ceria-pore double phase boundary (DPB) density with different distance from nickel phase. Using the results, the relative electrochemical reaction rate on DPB and TPB of three different electrodes are calculated and proves that fibre-matrices structure has the morphology advantage of efficiently making use of all ceria-pore DPB. The relative contribution of DPB and TPB in anode reaction of SOFC is quantified in the first time and the importance of DPB is further stressed. This work provides new inspirations in material design of SOFC/SOEC and develops a novel strategy to evaluate the performance of electrodes quantitatively.

Journal article

Usseglio-Viretta FLE, Colclasure A, Mistry AN, Claver KPY, Pouraghajan F, Finegan DP, Heenan TMM, Abraham D, Mukherjee PP, Wheeler D, Shearing P, Cooper SJ, Smith Ket al., 2018, Resolving the discrepancy in tortuosity factor estimation for Li-Ion battery electrodes through micro-macro modeling and experiment, Journal of The Electrochemical Society, Vol: 165, Pages: A3403-A3426, ISSN: 1945-7111

Battery performance is strongly correlated with electrode microstructural properties. Of the relevant properties, the tortuosity factor of the electrolyte transport paths through microstructure pores is important as it limits battery maximum charge/discharge rate, particularly for energy-dense thick electrodes. Tortuosity factor however, is difficult to precisely measure, and thus its estimation has been debated frequently in the literature. Herein, three independent approaches have been applied to quantify the tortuosity factor of lithium-ion battery electrodes. The first approach is a microstructure model based on three-dimensional geometries from X-ray computed tomography (CT) and stochastic reconstructions enhanced with computationally generated carbon/binder domain (CBD), as CT is often unable to resolve the CBD. The second approach uses a macro-homogeneous model to fit electrochemical data at several rates, providing a separate estimation of the tortuosity factor. The third approach experimentally measures tortuosity factor via symmetric cells employing a blocking electrolyte. Comparisons have been made across the three approaches for 14 graphite and nickel-manganese-cobalt oxide electrodes. Analysis suggests that if the tortuosity factor were characterized based on the active material skeleton only, the actual tortuosities would be 1.35–1.81 times higher for calendered electrodes. Correlations are provided for varying porosity, CBD phase interfacial arrangement and solid particle morphology.

Journal article

Daemi SR, Tan C, Volkenandt T, Cooper SJ, Palacios-Padros A, Cookson J, Brett DJL, Shearing PRet al., 2018, Visualizing the carbon binder phase of battery electrodes in three dimensions, ACS Applied Energy Materials, Vol: 1, Pages: 3702-3710, ISSN: 2574-0962

This study presents a technique to directly characterize the carbon and binder domain (CBD) in lithium-ion (Li-ion) battery electrodes in three dimensions and use it to determine the effective transport properties of a LiNi0.33Mn0.33Co0.33O2 (NMC) electrode. X-ray nanocomputed tomography (nano-CT) is used to image an electrode composed solely of carbon and binder, whereas focused ion beam–scanning electron microscopy is used to analyze cross-sections of a NMC electrode to gain morphological information regarding the electrode and CBD porosity. Combining the information gathered from these techniques reduces the uncertainty inherent in segmenting the nano-CT CBD data set and enables effective diffusivity of its porous network to be determined. X-ray microcomputed tomography (micro-CT) is then used to collect a NMC data set that is subsequently segmented into three phases, comprised of active material, pore, and CBD. The effective diffusivity calculated for the nano-CT data set is incorporated for the CBD present in the micro-CT data set to estimate the ensemble tortuosity factor for the NMC electrode. The tortuosity factor greatly increases when compared to the same data set segmented without considering the CBD. The porous network of the NMC electrode is studied with a continuous pore size distribution approach that highlights median radii of 180 nm and 1 μm for the CBD and NMC pores, respectively, and with a pore throat size distribution calculation that highlights median equivalent radii of 350 and 700 nm.

Journal article

Niania M, Podor R, Britton TB, Li C, Cooper SJ, Svetkov N, Skinner S, Kilner Jet al., 2018, In situ study of strontium segregation in La<inf>0.6</inf>Sr<inf>0.4</inf>Co<inf>0.2</inf>Fe<inf>0.8</inf>O<inf>3- δ</inf>in ambient atmospheres using high-temperature environmental scanning electron microscopy, Journal of Materials Chemistry A, Vol: 6, Pages: 14120-14135, ISSN: 2050-7496

Samples of the solid oxide fuel cell cathode material La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF) were annealed using High-Temperature Environmental Scanning Electron Microscopy (HT-ESEM) from room temperature to 1000 °C in atmospheres of pure oxygen, pure water and ambient lab air. Image series of each heat treatment were taken where microstructural changes were observed and compared between samples. Strontium segregation rate was found to be significantly increased in the presence of pure water as compared to pure O2and ambient air. Electron backscattered diffraction (EBSD) was performed in order to assess the effect of crystal orientation on particle formation and surface sensitive chemical analysis techniques were used to determine the chemical changes at the grain surface as a result of the different heat treatments. It was shown that crystal orientation affected the nature and growth rate of strontium-based particles, however, due to the pseudo-symmetry of La0.6Sr0.4Co0.2Fe0.8O3-δ, precise crystal orientation relationships could not be determined. The chemical composition of the grain surface was found to be approximately equal under each atmosphere.

Journal article

Niania M, Podor R, Britton TB, Li C, Cooper SJ, Svetkov N, Skinner S, Kilner Jet al., 2018, Correction: In situ study of strontium segregation in La<inf>0.6</inf>Sr<inf>0.4</inf>Co<inf>0.2</inf>Fe<inf>0.8</inf>O<inf>3- δ</inf>in ambient atmospheres using high-temperature environmental scanning electron microscopy (J. Mater. Chem. A (2018) DOI: 10.1039/c8ta01341a), Journal of Materials Chemistry A, Vol: 6, Pages: 14464-14464, ISSN: 2050-7488

© 2018 The Royal Society of Chemistry. Correction for 'In situ study of strontium segregation in La0.6Sr0.4Co0.2Fe0.8O3-δin ambient atmospheres using high-temperature environmental scanning electron microscopy' by Mathew Niania et al., J. Mater. Chem. A, 2018, DOI: 10.1039/c8ta01341a. The authors regret that the name of the first author of ref. 37 was displayed as "F. Pisigkin". The correct name should be "F. Piskin". The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.

Journal article

Liu X, Naylor Marlow M, Cooper S, Song B, Chen X, Brandon N, Wu Bet al., 2018, Flexible all-fiber electrospun supercapacitor, Journal of Power Sources, Vol: 384, Pages: 264-269, ISSN: 0378-7753

We present an all-fiber flexible supercapacitor with composite nanofiber electrodes made via electrospinning and an electrospun separator. With the addition of manganese acetylacetonate (MnACAC) to polyacrylonitrile (PAN) as a precursor for the electrospinning process and subsequent heat treatment, the performance of pure PAN supercapacitors was improved from 90 F.g-1 to 200 F.g-1 (2.5 mV.s-1) with possible mass loadings of MnACAC demonstrated as high as 40 wt%. X-ray diffraction measurements showed that after thermal treatment, the MnACAC was converted to MnO, meanwile, the thermal decomposition of MnACAC increased the graphitic degree of the carbonised PAN. Scanning electron microscopy and image processing showed that static electrospinning of pure PAN and PAN-Mn resulted in fiber diameters of 460 nm and 480 nm respectively after carbonisation. Further analysis showed that the fiber orientation exhibited a slight bias which was amplified with the addition of MnACAC. Use of focused ion beam scanning electron microscopy tomography also showed that MnO particles were evenly distributed through the fiber at low MnACAC concentrations, while at a 40 wt% loading the MnO particles were also visible on the surface. Comparison of the electrospun separators showed improved performance relative to a commercial Celgard separator (200 F.g-1 vs 141 F.g-1).

Journal article

Téllez Lozano H, Druce J, Cooper SJ, Kilner JAet al., 2017, Double perovskite cathodes for proton-conducting ceramic fuel cells: are they triple mixed ionic electronic conductors?, Science and Technology of Advanced Materials, Vol: 18, Pages: 977-986, ISSN: 1468-6996

Published by National Institute for Materials Science in partnership with Taylor & Francis. 18 O and 2 H diffusion has been investigated at a temperature of 300 °C in the double perovskite material PrBaCo 2 O 5+δ (PBCO) in flowing air containing 200 mbar of 2 H 2 16 O. Secondary ion mass spectrometry (SIMS) depth profiling of exchanged ceramics has shown PBCO still retains significant oxygen diffusivity (~1.3 × 10 −11 cm 2 s −1 ) at this temperature and that the presence of water ( 2 H 2 16 O), gives rise to an enhancement of the surface exchange rate over that in pure oxygen by a factor of ~3. The 2 H distribution, as inferred from the 2 H 2 16 O − SIMS signal, shows an apparent depth profile which could be interpreted as 2 H diffusion. However, examination of the 3-D distribution of the signal shows it to be nonhomogeneous and probably related to the presence of hydrated layers in the interior walls of pores and is not due to proton diffusion. This suggests that PBCO acts mainly as an oxygen ion mixed conductor when used in PCFC devices, although the presence of a small amount of protonic conductivity cannot be discounted in these materials.

Journal article

Cooper SJ, Bertei A, Finegan DP, Brandon NPet al., 2017, Simulated impedance of diffusion in porous media, Electrochimica Acta, Vol: 251, Pages: 681-689, ISSN: 0013-4686

This paper describes the use of a frequency domain, finite-difference scheme to simulate the impedance spectra of diffusion in porous microstructures. Both open and closed systems are investigated for a range of ideal geometries, as well as some randomly generated synthetic volumes and tomographically derived microstructural data. In many cases, the spectra deviate significantly from the conventional Warburg-type elements typically used to represent diffusion in equivalent circuit analysis. A key finding is that certain microstructures show multiple peaks in the complex plane, which may be misinterpreted as separate electrochemical processes in real impedance data. This is relevant to battery electrode design as the techniques for nano-scale fabrication become more widespread. This simulation tool is provided as an open-source MatLab application and is freely available online as part of the TauFactor platform.

Journal article

Cooper SJ, brandon NP, 2017, Solid Oxide Fuel Cell Lifetime and Reliability, Solid Oxide Fuel Cell Lifetime and Reliability Critical Challenges in Fuel Cells, Editors: Ruiz-Trejo, BOLDRIN, Publisher: Academic Press, Pages: 1-15, ISBN: 9780128097243

For its holistic approach, this book can be used both as an introduction to these issues and a reference resource for all involved in research and application of solid oxide fuel cells, especially those developing understanding in ...

Book chapter

Cooper SJ, Niania M, Hoffmann, Kilner Jet al., 2017, Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres, Physical Chemistry Chemical Physics, Vol: 19, Pages: 12199-12205, ISSN: 1463-9084

A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H₂O and CO₂) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La₀.₆Sr₀.₄Co₀.₂Fe₀.₈O₃-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO₂. The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

Journal article

Cooper SJ, Brandon NP, 2017, An Introduction to Solid Oxide Fuel Cell Materials, Technology and Applications, ISBN: 9780081011027

© 2017 Elsevier Ltd. All rights reserved. This chapter begins with a brief history of fuel cell development and introduces solid oxide fuel cells (SOFCs) as high efficiency energy conversion devices. Following this the fundamentals of SOFC performance and cell design are explored, with special focus given to the significance of operating temperature and microstructure. Next the current commercial status of SOFCs is outlined in brief. Finally, SOFC degradation, the major theme of this book, is introduced; the various mechanisms are split into the two broad categories of physical and chemical degradation.


Cooper SJ, Bertei A, Shearing PR, Kilner JA, Brandon NPet al., 2016, TauFactor: An open-source application for calculating tortuosity factors from tomographic data, SoftwareX, Vol: 5, Pages: 203-210, ISSN: 2352-7110

TauFactor is a MatLab application for efficiently calculating the tortuosity factor, as well as volume fractions, surface areas and triple phase boundary densities, from image based microstructural data. The tortuosity factor quantifies the apparent decrease in diffusive transport resulting from convolutions of the flow paths through porous media. TauFactor was originally developed to improve the understanding of electrode microstructures for batteries and fuel cells; however, the tortuosity factor has been of interest to a wide range of disciplines for over a century, including geoscience, biology and optics. It is still common practice to use correlations, such as that developed by Bruggeman, to approximate the tortuosity factor, but in recent years the increasing availability of 3D imaging techniques has spurred interest in calculating this quantity more directly. This tool provides a fast and accurate computational platform applicable to the big datasets (>10^8 voxels) typical of modern tomography, without requiring high computational power.

Journal article

Finegan DP, Cooper SJ, Tjaden B, Taiwo OO, Gelb J, Hinds G, Brett DJL, Shearing PRet al., 2016, Characterising the structural properties of polymer separators for lithium-ion batteries in 3D using phase contrast X-ray microscopy, Journal of Power Sources, Vol: 333, Pages: 184-192, ISSN: 1873-2755

Separators are an integral component for optimising performance and safety of lithium-ion batteries; therefore, a clear understanding of how their microstructure affects cell performance and safety is crucial. Phase contrast X-ray microscopy is used here to capture the microstructures of commercial monolayer, tri-layer, and ceramic-coated lithium-ion battery polymer separators. Spatial variations in key structural parameters, including porosity, tortuosity factor and pore size distribution, are determined through the application of 3D quantification techniques and stereology. The architectures of individual layers in multi-layer membranes are characterised, revealing anisotropy in porosity, tortuosity factor and mean pore size of the three types of separator. Detailed structural properties of the individual layers of multi-layered membranes are then related with their expected effect on safety and rate capability of cells.

Journal article

Ni N, Cooper SJ, Williams R, Kemen N, McComb DW, Skinner Set al., 2016, Degradation of (La0.6Sr0.4)0.95(Co0.2Fe0.8)O3-δ Solid Oxide Fuel Cell Cathodes at the Nanometre Scale and Below, ACS Applied Materials & Interfaces, Vol: 8, Pages: 17360-17370, ISSN: 1944-8244

The degradation of intermediate temperature solid oxide fuel cell (ITSOFC) cathodes has been identified as a major issue limiting the development of ITSOFCs as high efficiency energy conversion devices. In this work, the effect of Cr poisoning on (La0.6Sr0.4)0.95(Co0.2Fe0.8)O3-δ (LSCF6428), a particularly promising ITSOFC cathode material, was investigated on symmetrical cells using electrochemical impedance spectroscopy and multi-scale structural/chemical analysis by advanced electron and ion microscopy. The systematic combination of bulk and high-resolution analysis on the same cells allows, for the first time, to directly correlate Cr induced performance degradation with subtle and localized structural/chemical changes of the cathode down to the atomic scale. Up to two orders of magnitude reduction in conductivity, oxygen surface exchange rate and diffusivity were observed in Cr poisoned LSCF6428 samples. These effects are associated with the formation of nanometer size SrCrO4; grain boundary segregation of Cr; enhanced B-site element exsolution (both Fe and Co); and reduction in the Fe valence, the latter two being related to Cr substitution in LSCF. The finding that significant degradation of the cathode happens before obvious microscale change points to new critical SOFC degradation mechanisms effective at the nanometer scale and below.

Journal article

Tjaden B, Cooper SJ, Brett DJL, Kramer D, Shearing PRet al., 2016, On the origin and application of the Bruggeman correlation for analysing transport phenomena in electrochemical systems, Current Opinion in Chemical Engineering, Vol: 12, Pages: 44-51, ISSN: 2211-3398

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.

Journal article

Cooper SJ, Li T, Bradley RS, Li K, Brandon NP, Kilner JAet al., 2015, Multi length-scale quantification of hierarchical microstructure in designed microtubular SOFC electrodes, Pages: 1857-1864, ISSN: 1938-5862

© The Electrochemical Society. The transport properties of a micro-tubular solid oxide fuel cell (MT-SOFC) anode have been analysed by imaging and simulation at multiple length-scales. The anode support investigated was manufactured using a phase inversion-assisted co-extrusion process, which generated a hierarchical and highly anisotropic microstructure. The resulting pore network was observed to contain two distinct, but interacting transport systems. The features in these systems spanned several orders of magnitude and as such it was not possible to image or model them simultaneously. The simulations indicated that the design of the microstructure was beneficial for the radial transport required by these cells; however this conclusion was only obtained by considering diffusive systems at many length-scales.

Conference paper

Tariq F, Kishimoto M, Cui G, Yufit V, Lomberg M, Ruiz-Trejo E, Chen Z, Brandon NPet al., 2015, Advanced 3D imaging and analysis of SOFC electrodes, Pages: 2067-2074, ISSN: 1938-5862

© The Electrochemical Society. An ability to meet our increasing energy demands will be facilitated though improving the next generation of electrochemical devices. The ability to directly image in 3D and analyse solid oxide fuel cell (SOFC) electrodes at high resolutions provides key insights in understanding structure-property relationships; as electrochemical reactions and transport phenomena are strongly affected by complex microstructure. Here we use tomographic techniques to probe 3D electrode structures at nanometer to micrometer length scales. In doing so the first characterisation of specific necks and interfaces alongside their particle sizes within SOFC electrodes is derived. Micro/nano structural changes are followed to facilitate understanding the differences which occur with shape, structures and morphology at high resolution. These are correlated with both measured experimental values and simulations to provide insight into microstructure-property relationships. We also demonstrate approaches to intelligently design electrodes through scaffolds, and potentially 3D printed structures, all towards optimising the structure for performance.

Conference paper

Eastwood DS, Bradley RS, Tariq F, Cooper SJ, Taiwo OO, Gelb J, Merkle A, Brett DJL, Brandon NP, Withers PJ, Lee PD, Shearing PRet al., 2014, The application of phase contrast X-ray techniques for imaging Li-ion battery electrodes, NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS, Vol: 324, Pages: 118-123, ISSN: 0168-583X

Journal article

Cooper SJ, Kishimoto M, Tariq F, Bradley RS, Marquis AJ, Brandon NP, Kilner JA, Shearing PRet al., 2013, Microstructural Analysis of an LSCF Cathode Using In Situ Tomography and Simulation, ECS Transactions, Vol: 57, Pages: 2671-2678, ISSN: 1938-6737

Electrode tortuosity factor is a key input parameter in many fuel cell simulations. Three-dimensional microstructural data obtained from in-situ synchrotron X-ray nano-computed tomography is used as the basis for comparing five approaches to quantify the tortuosity factor. Three of these techniques are based on diffusivity simulations and showed strong correlation, but had consistently different absolute values. A random walk method showed a good degree of correlation to the diffusive approaches, but had the largest values overall. Lastly, a calculation that used a mean pore centroid approach showed little correlation to any of the other three methods, but compared well with the conventional Bruggeman correlation. Due to the diffusive nature of the ionic transport in electrodes, the authors would recommend calculating tortuosity factors using a diffusive approach based on the voxels rather than a remeshed volume.

Journal article

Tariq F, Kishimoto M, Cooper SJ, Shearing PR, Brandon NPet al., 2013, Advanced 3D Imaging and Analysis of SOFC Electrodes, ECS Transactions, Vol: 57, Pages: 2553-2562, ISSN: 1938-6737

Solid Oxide Fuel Cells (SOFC) are electrochemical devices where performance is dependent on reactions inside porous electrode microstructures; their complexity is inadequately described using 2D imaging. Here we use X-ray Nano-CT tomographic techniques to probe 3D electrode structures (anodes and cathodes) at micro-nanometer length scales produced using a focused ion beam. Subsequently, micro/nano structural changes in SOFC electrodes are followed and quantified to facilitate understanding changes that occur in shape, structures and morphology at high sub-100nm resolution. Time-resolved (4D) imaging revealed Ni-YSZ oxidation markedly increased above 500 ºC and LSCF densification at 700 ºC may close pores. Utilising 3D electrode data as geometric inputs for numerical models, revealed that increased strains were located at Ni-YSZ interfaces and at microstructure constrictions for both anodes and cathodes when heated. The results show nano/micro structural changes can affect the performance of SOFC electrodes. This combined experimental and modelling approach can help in establishing structure/performance relationships providing key insights important for transport, electrochemistry and strains in both SOFC anodes and cathodes and understanding sources of performance degradation.

Journal article

Cooper SJ, Eastwood DS, Gelb J, Damblanc G, Brett DJL, Bradley RS, Withers PJ, Lee PD, Marquis AJ, Brandon NP, Shearing PRet al., 2013, Image Based Modelling of of Microstructural Heterogeneity in LiFePO4 Electrodes for Li-ion Batteries, Journal of Power Sources, Vol: 247, Pages: 1033-1039, ISSN: 0378-7753

Battery and fuel cell simulations commonly assume that electrodes are macro-homogeneous and isotropic. These simulations have been used to successfully model performance, but give little insight into predicting failure. In Li-ion battery electrodes, it is understood that local tortuosity impacts charging rates, which may cause increased degradation. This report describes a novel approach to quantifying tortuosity based on a heat transfer analogy applied to X-ray microscopy data of a commercially available LiFePO4 electrode. This combination of X-ray imaging and image-based simulation reveals the microscopic performance of the electrode; notably, the tortuosity was observed to vary significantly depending on the direction considered, which suggests that tortuosity might best be quantified using vectors rather than scalars.

Journal article

Shearing PR, Eastwood DS, Bradley RS, Gelb J, Cooper SJ, Tariq F, Brett DJ, Brandon NP, Withers PJ, Lee PDet al., 2013, Exploring electrochemical devices using X-ray microscopy: 3D microstructure of batteries and fuel cells, Microscopy and Analysis, Vol: 27

Journal article

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