I20-EDE-Energy Dispersive EXAFS (EDE)
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Andrew S.
Leach
,
Jennifer
Hack
,
Monica
Amboage
,
Sofia
Diaz-Moreno
,
Haoliang
Huang
,
Patrick L.
Cullen
,
Martin
Wilding
,
Emanuele
Magliocca
,
Thomas
Miller
,
Christopher
Howard
,
Daniel
Brett
,
Paul
Shearing
,
Paul F.
Mcmillan
,
Andrea E.
Russell
,
Rhodri
Jervis
Diamond Proposal Number(s):
[22008, 15650]
Open Access
Abstract: A polymer electrolyte fuel cell (PEFC) has been designed to allow operando X-ray absorption spectroscopy (XAS) measurements of catalysts. The cell has been developed to operate under standard fuel cell conditions, with elevated temperatures and humidification of the gas-phase reactants, both of which greatly impact the catalyst utilisation. X-ray windows in the endplates of the cell facilitate collection of XAS spectra during fuel cell operation while maintaining good compression in the area of measurement. Results of polarisation curves and cyclic voltammograms (CVs) showed that the operando cell performs well as a fuel cell, while also providing XAS data of suitable quality for robust XANES analysis. The cell has produced comparable XAS results when performing a cyclic voltammogram to an established in situ cell when measuring the Pt LIII edge. Similar trends of Pt oxidation, and reduction of the formed Pt oxide, have been presented with a time resolution of 5 seconds for each spectrum, paving the way for time-resolved spectral measurements of fuel cell catalysts in a fully-operating fuel cell.
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May 2021
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I13-2-Diamond Manchester Imaging
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Diamond Proposal Number(s):
[21587]
Open Access
Abstract: Accurate modelling of particle shrinkage during biomass pyrolysis is key to the production of biochars with specific morphologies. Such biochars represent sustainable solutions to a variety of adsorption-dependent environmental remediation challenges. Modelling of particle shrinkage during biomass pyrolysis has heretofore been based solely on theory and ex-situ experimental data. Here we present the first in-situ phase-contrast X-ray imaging study of biomass pyrolysis. A novel reactor was developed to enable operando synchrotron radiography of fixed beds of pyrolysing biomass. Almond shell particles experienced more bulk shrinkage and less change in porosity than did walnut shell particles during pyrolysis, despite their similar composition. Alkaline pretreatment was found to reduce this difference in feedstock behaviour. Ex-situ synchrotron X-ray microtomography was performed to study the effects of pyrolysis on pore morphology. Pyrolysis led to a redistribution of pores away from particle surfaces, meaning newly formed surface area may be less accessible to adsorbates.
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Jan 2021
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I13-1-Coherence
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Ana Katrina C.
Estandarte
,
Jiecheng
Diao
,
Alice
Llewellyn
,
Anmol
Jnawali
,
Thomas M. M.
Heenan
,
Sohrab R.
Daemi
,
Josh J.
Bailey
,
Silvia
Cipiccia
,
Darren
Batey
,
Xiaowen
Shi
,
Christoph
Rau
,
Dan J. L.
Brett
,
Rhodri
Jervis
,
Ian K.
Robinson
,
Paul
Shearing
Diamond Proposal Number(s):
[25852, 25440, 24129, 22373, 22309, 21652]
Abstract: Due to complex degradation mechanisms, disparities between the theoretical and practical capacities of lithium-ion battery cathode materials persist. Specifically, Ni-rich chemistries such as LiNi0.8Mn0.1Co0.1O2 (or NMC811) are one of the most promising choices for automotive applications; however, they continue to suffer severe degradation during operation that is poorly understood, thus challenging to mitigate. Here we use operando Bragg coherent diffraction imaging for 4D analysis of these mechanisms by inspecting the individual crystals within primary particles at various states of charge (SoC). Although some crystals were relatively homogeneous, we consistently observed non-uniform distributions of inter- and intracrystal strain at all measured SoC. Pristine structures may already possess heterogeneities capable of triggering crystal splitting and subsequently particle cracking. During low-voltage charging (2.7–3.5 V), crystal splitting may still occur even during minimal bulk deintercalation activity; and during discharging, rotational effects within parallel domains appear to be the precursor for the nucleation of screw dislocations at the crystal core. Ultimately, this discovery of the central role of crystal grain splitting in the charge/discharge dynamics may have ramifications across length scales that affect macroscopic performance loss during real-world battery operation.
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Dec 2020
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I11-High Resolution Powder Diffraction
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Open Access
Abstract: Renewable technologies, and in particular the electric vehicle revolution, have generated tremendous pressure for the improvement of lithium ion battery performance. To meet the increasingly high market demand, challenges include improving the energy density, extending cycle life and enhancing safety. In order to address these issues, a deep understanding of both the physical and chemical changes of battery materials under working conditions is crucial for linking degradation processes to their origins in material properties and their electrochemical signatures. In situ and operando synchrotron-based X-ray techniques provide powerful tools for battery materials research, allowing a deep understanding of structural evolution, redox processes and transport properties during cycling. In this review, in situ synchrotron-based X-ray diffraction methods are discussed in detail with an emphasis on recent advancements in improving the spatial and temporal resolution. The experimental approaches reviewed here include cell designs and materials, as well as beamline experimental setup details. Finally, future challenges and opportunities for battery technologies are discussed.
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Nov 2020
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I14-Hard X-ray Nanoprobe
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Thomas M. M.
Heenan
,
Aaron
Wade
,
Chun
Tan
,
Julia E.
Parker
,
Dorota
Matras
,
Andrew S.
Leach
,
James B.
Robinson
,
Alice
Llewellyn
,
Alexander
Dimitrijevic
,
Rhodri
Jervis
,
Paul D.
Quinn
,
Dan J. L.
Brett
,
Paul R.
Shearing
Diamond Proposal Number(s):
[20841, 23858]
Open Access
Abstract: The next generation of automotive lithium‐ion batteries may employ NMC811 materials; however, defective particles are of significant interest due to their links to performance loss. Here, it is demonstrated that even before operation, on average, one‐third of NMC811 particles experience some form of defect, increasing in severity near the separator interface. It is determined that defective particles can be detected and quantified using low resolution imaging, presenting a significant improvement for material statistics. Fluorescence and diffraction data reveal that the variation of Mn content within the NMC particles may correlate to crystallographic disordering, indicating that the mobility and dissolution of Mn may be a key aspect of degradation during initial cycling. This, however, does not appear to correlate with the severity of particle cracking, which when analyzed at high spatial resolutions, reveals cracking structures similar to lower Ni content NMC, suggesting that the disconnection and separation of neighboring primary particles may be due to electrochemical expansion/contraction, exacerbated by other factors such as grain orientation that are inherent in such polycrystalline materials. These findings can guide research directions toward mitigating degradation at each respective length‐scale: electrode sheets, secondary and primary particles, and individual crystals, ultimately leading to improved automotive ranges and lifetimes.
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Nov 2020
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I12-JEEP: Joint Engineering, Environmental and Processing
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Donal P.
Finegan
,
Eric
Darcy
,
Matthew
Keyser
,
Bernhard
Tjaden
,
Thomas M. M.
Heenan
,
Rhodri
Jervis
,
Josh J.
Bailey
,
Nghia T.
Vo
,
Oxana V.
Magdysyuk
,
Michael
Drakopoulos
,
Marco Di
Michiel
,
Alexander
Rack
,
Gareth
Hinds
,
Dan J. L.
Brett
,
Paul
Shearing
Diamond Proposal Number(s):
[13884]
Open Access
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.
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Oct 2017
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I12-JEEP: Joint Engineering, Environmental and Processing
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Leon
Brown
,
Rema
Abdulaziz
,
Rhodri
Jervis
,
Vidal
Bharath
,
Thomas J.
Mason
,
Robert C.
Atwood
,
Christina
Reinhard
,
Leigh
Connor
,
Douglas
Inman
,
Daniel J. L.
Brett
,
Paul R.
Shearing
Diamond Proposal Number(s):
[9690]
Abstract: A novel electrochemical cell has been designed and built to allow for in situ energy-dispersive X-ray diffraction measurements to be made during reduction of UO2 to U metal in LiCl–KCl at 500°C. The electrochemical cell contains a recessed well at the bottom of the cell into which the working electrode sits, reducing the beam path for the X-rays through the molten-salt and maximizing the signal-to-noise ratio from the sample. Lithium metal was electrodeposited onto the UO2 working electrode by exposing the working electrode to more negative potentials than the Li deposition potential of the LiCl–KCl eutectic electrolyte. The Li metal acts as a reducing agent for the chemical reduction of UO2 to U, which appears to proceed to completion. All phases were fitted using Le Bail refinement. The cell is expected to be widely applicable to many studies involving molten-salt systems.
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Mar 2017
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I12-JEEP: Joint Engineering, Environmental and Processing
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Donal P.
Finegan
,
Eric
Darcy
,
Matthew
Keyser
,
Bernhard
Tjaden
,
Thomas M. M.
Heenan
,
Rhodri
Jervis
,
Josh J.
Bailey
,
Romeo
Malik
,
Nghia T.
Vo
,
Oxana V.
Magdysyuk
,
Robert
Atwood
,
Michael
Drakopoulos
,
Marco
Dimichiel
,
Alexander
Rack
,
Gareth
Hinds
,
Dan J. L.
Brett
,
Paul R.
Shearing
Diamond Proposal Number(s):
[13884]
Abstract: 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[thin space (1/6-em)]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[thin space (1/6-em)]650 cells and batteries are discussed.
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Mar 2017
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I12-JEEP: Joint Engineering, Environmental and Processing
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L D
Brown
,
Rema
Abdulaziz
,
Rhodri
Jervis
,
Vidal
Bharath
,
R C
Attwood
,
Christina
Reinhard
,
Leigh
Connor
,
S J R
Simons
,
D.
Inman
,
D J L
Brett
,
Paul
Shearing
Diamond Proposal Number(s):
[9690]
Open Access
Abstract: The electrochemical reduction of uranium dioxide to metallic uranium has been investigated in lithium chloridepotassium chloride eutectic molten salt. Laboratory based electrochemical studies have been coupled with in situ energy dispersive X-ray diffraction, for the first time, to deduce the reduction pathway. No intermediate phases were identified using the X-ray diffraction before, during or after electroreduction to form α-uranium. This suggests that the electrochemical reduction occurs via a single, 4-electron-step, process. The rate of formation of α-uranium is seen to decrease during electrolysis and could be a result of a build-up of oxygen anions in the molten salt. Slow transport of O2− ions away from the UO2 working electrode could impede the electrochemical reduction.
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Sep 2015
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I12-JEEP: Joint Engineering, Environmental and Processing
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James
Robinson
,
Leon D.
Brown
,
Rhodri
Jervis
,
Oluwadamilola
Taiwo
,
Thomas M.m.
Heenan
,
Jason
Millichamp
,
Thomas J.
Mason
,
Tobias P.
Neville
,
Ralph
Clague
,
David
Eastwood
,
Christina
Reinhard
,
P.d
Lee
,
Daniel J.l.
Brett
,
Paul R.
Shearing
Diamond Proposal Number(s):
[8612]
Open Access
Abstract: Thermal gradients can arise within solid oxide fuel cells (SOFCs) due to start-up and shut-down, non-uniform gas distribution, fast cycling and operation under internal reforming conditions. Here, the effects of operationally relevant thermal gradients on Ni/YSZ SOFC anode half cells are investigated using combined synchrotron X-ray diffraction and thermal imaging. The combination of these techniques has identified significant deviation from linear thermal expansion behaviour in a sample exposed to a one dimensional thermal gradient. Stress gradients are identified along isothermal regions due to the presence of a proximate thermal gradient, with tensile stress deviations of up to 75 MPa being observed across the sample at a constant temperature. Significant strain is also observed due to the presence of thermal gradients when compared to work carried out at isothermal conditions.
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Aug 2015
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