News - Finden

Our paper on the first region-of-interest high resolution X-ray diffraction computed tomography experiment of a Si-graphite electrode used for Li-ion battery applications has been published in Nano Letters

Our scientists’ new work on Si-graphite electrodes used for Li-ion battery applications with high resolution in situ X-ray chemical imaging has been published in a new paper, “Spatially Resolving Lithiation in Silicon–Graphite Composite Electrodes via in Situ High-Energy X-ray Diffraction Computed Tomography” in Nano Letters. The work was performed with Donal Finegan from the National Renewable Energy Laboratory and in collaboration with a team from the Electrochemical Innovation Lab (EIL) from UCL Chemical Engineering using ESRF’s ID15A beamline.

Optimizing the chemical and morphological parameters of lithium-ion (Li-ion) electrodes is extremely challenging, due in part to the absence of techniques to construct spatial and temporal descriptions of chemical and morphological heterogeneities. In this work, we present the first demonstration of combined high-speed X-ray diffraction (XRD) and XRD computed tomography (XRD-CT) to probe, in 3D, crystallographic heterogeneities within Li-ion electrodes with a spatial resolution of 1 μm. The local charge-transfer mechanism within and between individual particles was investigated in a silicon(Si)−graphite composite electrode. High-speed XRD revealed charge balancing kinetics between the graphite and Si during the minutes following the transition from operation to open circuit. Subparticle lithiation heterogeneities in both Si and graphite were observed using XRD-CT, where the core and shell structures were segmented, and their respective diffraction patterns were characterized.

Figure: (a) XRD-CT slice taken at the beginning of the charge step showing a phase-distribution map of LiC₁₂ (red), crystalline Si (green), and lithium silicides Li_xSi (blue). According to additive colour mixing, the colour teal represents a mixture of green (Si) and blue (lithiated Si). (b) Magnified regions of interest showing large particles of Li_xSi phase with crystalline Si cores (1-3) and smaller Li_xSi particles (4) interspersed in the graphite matrix. The yellow arrow highlights what looks to be evidence of delamination from a crystalline Si core.

Read the article at https://pubs.acs.org/doi/full/10.1021/acs.nanolett.9b00955

A new cell for industrially relevant studies of operating PEM fuel cells using hard X-rays

Finden scientists’ new work on the design and application of a new cell for proton-exchange membrane fuel cells has been published in a new paper, “X-ray transparent proton-exchange membrane fuel cell design for in situ wide and small angle scattering tomography” in the Journal of Power Sources. The cell design and experimental work was performed by Isaac Martens and Jakub Drnec using ESRF’s ID31 beamline.

We have constructed a 5 cm² proton exchange membrane hydrogen fuel cell optimized for transparency of high energy X-rays. This cell allows for in situ elastic scattering measurements (WAXS, SAXS) during electrochemical operation with minimal trade-offs in cell performance vs benchtop designs, and is capable of reaching automotive current densities. A key feature is that the beam enters the cell at grazing incidence to the electrodes, massively increasing the effective pathlength and therefore the signal-to-background ratio. The transparency in the plane of the sample permits imaging coupled with advanced techniques, such as X-ray diffraction computed tomography.

The work was done at the The European Synchrotron (ESRF) and research partners included; University of British Columbia, Université Grenoble Alpes, University of Helsinki, Aalto University, Baltic Fuel Cells and University College London.

Read the article at https://www.sciencedirect.com/science/article/abs/pii/S0378775319308997

First chemical imaging study on 3D printed catalysts used for CO2 methanation

Finden scientists new work on the characterisation on 3D printed catalysts has been published in a new paper, “3D printed Ni/Al2O3 based catalysts for CO2 methanation – a comparative and operando XRD-CT study” in the Journal of CO2 Utilization. The X-ray chemical imaging work was performed with Vesna Middelkoop from the Flemish Institute for Technological Research (VITO) using ESRF’s ID15A beamline.

Ni-alumina-based catalysts were directly 3D printed into highly adaptable monolithic/multi-channel systems and evaluated for CO₂ methanation. By employing emerging 3D printing technologies for catalytic reactor design such as 3D fibre deposition (also referred to as direct write or microextrusion), we developed optimised techniques for tailoring both the support’s macro- and microstructure, as well as its active particle precursor distribution. A comparison was made between 3D printed commercial catalysts, Ni-alumina based catalysts and their conventional counterpart, packed beds of beads and pellet. Excellent CO₂ conversions and selectivity to methane were achieved for the 3D printed commercial catalyst (95.75% and 95.63% respectively) with stability of over 100 h. The structure-activity relationship of both the commercial and in-house 3D printed catalysts was explored under typical conditions for CO₂ hydrogenation to CH₄, using operando ‘chemical imaging’, namely X-Ray Diffraction Computed Tomography (XRD-CT). The 3D printed commercial catalyst showed a more homogenous distribution of the active Ni species compared to the in-house prepared catalyst. For the first time, the results from these comparative characterisation studies gave detailed insight into the fidelity of the direct printing method, revealing the spatial variation in physico-chemical properties (such as phase and size) under operating conditions.

Institute for Technological Research (VITO), Ghent University, University Colleges Leuven-Limburg, Grenoble Alpes University and University College London.

Read the article at https://www.sciencedirect.com/science/article/pii/S2212982019303063

New work on sustainable iron-based oxygen carriers for hydrogen production published

Graphical abstract

Finden Ltd collaborated with Yoran De Vos (Ghent University) to look at the evolution of an Fe-based oxygen carrier under operando conditions. The project has resulted in a paper published in the International Journal of Greenhouse Gas Control titled, “Sustainable iron-based oxygen carriers for hydrogen production – Real-time operando investigation.“

In this work, a spray-dried Fe-based oxygen carrier with an in situ generated Mg_1-xAl_2-yFe_x+yO₄-support was investigated during packed-bed chemical looping operation with methane at 900 °C. The evolution of the solid-state chemistry taking place in the oxygen carrier material was investigated in real-time with synchrotron X-ray diffraction while the spatial distribution of the phases was investigated using X-ray diffraction computed tomography (XRD-CT). These measurements revealed that some Fe-cations were systematically taken up and released from the spinel support. This take-up and release was shown to be strongly related with the oxidation state of the active phase. Although this take-up and release of Fe-cations decreased the amount of Fe-oxides active in the chemical looping process, the oxygen transfer capacity was still sufficiently high. The microstructure of the oxygen carriers along the length of the packed reactor bed was also investigated with scanning electron microscopy (SEM). The experiments indicate that the MgFeAlO_x support with an extra Fe-based active phase is a promising material for oxygen carriers, as it forms a sustainable non-toxic, stable and green alternative to the typical Ni-based oxygen carriers, for hydrogen generation by chemical looping.

The work was done at the The European Synchrotron (ESRF) and research partners included; Flemish Institute for Technological Research (VITO), Ghent University and University College London.

Read the paper at https://www.sciencedirect.com/science/article/abs/pii/S175058361930146X.

Our paper on the first X-ray diffraction tomography experiment of real-life size micro-tubular SOFC has been published in Nature Communications

Figure various micro-monolithic anode supports after sintering

Various micro-monolithic anode supports after sintering at 1450 °C. SEM images of central-axis-view of: a 3, b 4, and c 7 channels; Cross-sectional images of d sponge between the shell and two channels in the 7-channel anode, e sponge between the central channel and surrounding two channels in the 7-channel anode; f close-up image of anode/electrolyte interface

Our new work on a state-of-the-art SOFC has been published in a paper “Design of next-generation ceramic fuel cells and real-time characterization with synchrotron X-ray diffraction computed tomography“ in Nature Communications.

Solid oxide fuel cells offer a clean and efficient means of producing electricity through a variety of fuels. However, miniaturization of cell dimensions for portable device applications remains a challenge, as volumetric power densities generated by readily-available planar/tubular ceramic cells are limited. In our work, we demonstrate a concept of ‘micro-monolithic’ ceramic cell design and evaluate the mechanical robustness and structural integrity of this design, for the first time, with synchrotron X-ray diffraction computed tomography. The successful miniaturization results in an exceptional power density of 1.27 W cm⁻² at 800 °C, which is among the highest reported. This holistic design incorporates both mechanical integrity and electrochemical performance, leading to mechanical property enhancement and representing an important step toward commercial development of portable ceramic devices with high volumetric power (>10 W cm⁻³), fast thermal cycling and marked mechanical reliability. This is also the first time a real-life size solid oxide fuel cell has been investigated in situ demonstrating that such experiments are now possible, adding a very powerful characterisation tool for the SOFC community in general.

The synchrotron experiments were conceived, designed and performed by Dr Antony Vamvakeros and Dorota Matras in collaboration with a team from the Electrochemical Innovation Lab (EIL) from UCL Chemical Engineering using ESRF’s ID15A beamline using a state-of-the-art SOFC designed by Imperial College.

Read the full article at https://www.nature.com/articles/s41467-019-09427-z

Operando and Postreaction Diffraction Imaging of the La–Sr/CaO Catalyst in the Oxidative Coupling of Methane Reaction

$Operando and Postreaction Diffraction Imaging figure$ Our paper on Operando and Postreaction Diffraction Imaging of the La–Sr/CaO Catalyst in the Oxidative Coupling of Methane Reaction has been published online by The Journal of Physical Chemistry.

A La–Sr/CaO catalyst was studied operando during the oxidative coupling of methane (OCM) reaction using the X-ray diffraction computed tomography technique. Full-pattern Rietveld analysis was performed in order to track the evolving solid-state chemistry during the temperature ramp, OCM reaction, as well as after cooling to room temperature. We observed a uniform distribution of the catalyst main components: La₂O₃, CaO–SrO mixed oxide, and the high-temperature rhombohedral polymorph of SrCO₃. These were stable initially in the reaction; however, doubling the gas hourly space velocity resulted in the decomposition of SrCO₃ to SrO, which subsequently led to the formation of a second CaO–SrO mixed oxide. These two mixed CaO–SrO oxides differed in terms of the extent of Sr incorporation into their unit cell. By applying Vegard’s law during the Rietveld refinement, it was possible to create maps showing the spatial variation of Sr occupancy in the mixed CaO–SrO oxides. The formation of the Sr-doped CaO species is expected to have an important role in this system through the enhancement of the lattice oxygen diffusion as well as increased catalyst basicity.

Read the full article at https://pubs.acs.org/doi/10.1021/acs.jpcc.8b09018

Tomographic software nDTomo released!

The nDTomo software is now publicly available for download. Developed by our research scientist Dr. Antony Vamvakeros and primarily designed for processing XRD-CT data, it can be used for other tomographic techniques as well. The software suite contains GUIs for the acquisition, pre-processing and analysis of X-ray chemical tomography data. Download it at https://github.com/antonyvam/ndtomo

A masterpiece on a on a pin head

Finden Ltd’s work with microfocus X-ray beams at Diamond Light Source recently appeared in an article in The Telegraph, “Old Master paintings shown to be ‘crusting over’ by microscope 10 billion times brighter than the Sun.” Dr. Stephen Price explains in the article,

“We were able to plot the different chemistry from the surface down to the base layer where the canvas would be.

“Knowing some of the more eventful history of the painting, such as fire damage, led us to work out what had caused the chemistry change.”

Excerpt from article. Read the full article at https://www.telegraph.co.uk/news/2019/01/26/old-master-paintings-shown-crusting-microscope-10-billion-times/

His work has also appeared on the Physics World website, “Diamond Light Source – when a tool becomes a gem”.

“Stephen Price, a researcher at Finden and formerly a Diamond Light Source scientist, is currently working with the Rijksmuseum in Amsterdam on a sample of Rembrandt’s painting “Homer”, which dates back to 1663. As he explains, the sample is of a white bloom or crust that forms on the painting despite the best efforts of conservationists. His aim has been to identify the chemistry of the crust and hopefully determine how to prevent such crusts forming.

Using the microfocus X-ray beam at Diamond to scan the sample at different angles, they were able to show how the lead paint had reacted with atmospheric pollutants including sulphur dioxide, which was forming the white crust disfiguring the painting. “Using this information the conservation team at the Rijks can investigate further how to prevent and reverse this degradation process,” says Price.”

Excerpt from article. Read the full article at Physics World.

We have just published an article relating to the Homer painting – Unravelling the spatial dependency of the complex solid-state chemistry of Pb in a paint micro-sample from Rembrandt’s Homer using XRD-CT – Chemical Communications (RSC Publishing). Read more about this exciting work at https://pubs.rsc.org/en/content/articlehtml/2019/cc/c8cc09705d

Prof. Andrew Beale discusses our recently published paper on 5D diffraction imaging in his Behind the Paper article – Chemistry in multiple dimensions

Solid catalysts are used in almost every field of the chemical industry, ranging from pharmaceuticals to petrochemicals as well as the automotive industry, to produce the desired products. These catalytic solids usually comprise complex 3D structures which can be inhomogeneous. In recent years, it has been realised that it is crucial to investigate these materials using characterisation techniques that provide spatially-resolved information as these heterogeneities can play a crucial role in the catalyst performance.

In our recent paper in Nature Communications we show that synchrotron X-ray diffraction computed tomography (XRD-CT) can be used to study the evolution in solid-state composition in complex materials in 3D under real process conditions and as a function of time; specifically a complex multi-component Ni-Pd/CeO₂-ZrO₂/Al₂O₃ solid catalyst under operating conditions.

Read the full article at https://chemistrycommunity.nature.com/channels/1465-behind-the-paper/posts/40955-5d-chemical-imaging

5D operando tomographic diffraction imaging of a catalyst bed

Our paper on 5D operando tomographic diffraction imaging of a catalyst bed has been published online by Nature Communications, volume 9, Article number: 4751 (2018)

We report the results from the first 5D tomographic diffraction imaging experiment of a complex Ni–Pd/CeO₂–ZrO₂/Al₂O₃ catalyst used for methane reforming. This five-dimensional (three spatial, one scattering and one dimension to denote time/imposed state) approach enabled us to track the chemical evolution of many particles across the catalyst bed and relate these changes to the gas environment that the particles experience. Rietveld analysis of some 2 × 10⁶ diffraction patterns allowed us to extract heterogeneities in the catalyst from the Å to the nm and to the μm scale (3D maps corresponding to unit cell lattice parameters, crystallite sizes and phase distribution maps respectively) under different chemical environments. We are able to capture the evolution of the Ni-containing species and gain a more complete insight into the multiple roles of the CeO₂-ZrO₂ promoters and the reasons behind the partial deactivation of the catalyst during partial oxidation of methane.

Read the full article at https://doi.org/10.1038/s41467-018-07046-8

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