I13-2-Diamond Manchester Imaging
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Matthew P.
Jones
,
Huw C. W.
Parks
,
Alice V.
Llewellyn
,
Hamish T.
Reid
,
Chun
Tan
,
Aaron
Wade
,
Thomas M. M.
Heenan
,
Francesco
Iacoviello
,
Shashidhara
Marathe
,
Paul R.
Shearing
,
Rhodri
Jervis
Diamond Proposal Number(s):
[28650]
Open Access
Abstract: During battery operation, cracking occurs in Nickel Manganese Cobalt (NMC) oxide secondary particles. Cracked particles appear darker in micro-computed tomography (micro-CT) images due to the partial volume effect, where voxels containing both void and solid yield intermediate grey-levels. This work presents an automated method for tracking grey-level changes caused by this effect in large, statistically meaningful micro-CT datasets containing over 10 000 individual particles. It extends earlier work using the GREAT algorithm to analyze NMC particles in tomography images. The new GREAT2 algorithm increases processing speed, from around 1,400 particles per day with GREAT to over 10 000 particles in under a minute. Furthermore, this work introduces methods for automated tracking of grey-level intensity changes in individual particles through different states of charge in an operando experiment. This capability enables temporal analysis of particle degradation mechanisms. Additional data processing methods are presented that extract useful insights. Through this work we show that the large sample sizes, enabled by this method and GREAT2, allow for statistically robust analysis of particle populations. These advances significantly accelerate the tomographic study of cracking in battery electrodes. The GREAT2 algorithm and associated workflows have been made available as the GRAPES Python toolkit.
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Jun 2025
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I13-2-Diamond Manchester Imaging
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Diamond Proposal Number(s):
[22198]
Open Access
Abstract: Solid-state lithium batteries are developing rapidly as a promising next-generation battery, while challenges still persist in understanding their degradation processes during cycling due to the difficulties in characterization. In this study, the 3D morphological evolution of the Li3PS4 solid electrolyte was tracked during electrochemical cycles (plating and stripping) until short circuit by utilizing in situ synchrotron X-ray computed tomography with sufficient spatial and temporal resolution. During the degradation process, cracks in the electrolyte alternately generated from the two electrode/electrolyte interfaces and propagated until shorting. The lithium dendrites filled in the electrolyte cracks but had a greatly reduced filling ratio after the first plating stage; therefore, the cell could continue working for some time after the solid electrolyte was fully fractured by cracks. The compression of the two lithium electrodes mainly occurred in initial cycles where a ca. 4–7 μm reduction in thickness was observed. The mechanical force and electric potential fields were modeled to visualize their redistributions in different stages of cycling. The release of strain energy after the first penetration and thereafter the subsequent driving forces are discussed. These results reveal a fast degradation of solid electrolyte in the initial cycles, providing insights for further modifications and improvements in solid-state batteries.
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May 2025
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I13-2-Diamond Manchester Imaging
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Huw C. W.
Parks
,
Matthew
Jones
,
Aaron
Wade
,
Alice
Llewellyn
,
Chun
Tan
,
Hamish
Reid
,
Ralf
Ziesche
,
Thomas M. M.
Heenan
,
Shashidhara
Marathe
,
Christoph
Rau
,
Paul R.
Shearing
,
Rhodri
Jervis
Diamond Proposal Number(s):
[28650]
Open Access
Abstract: To understand fracture behaviour in battery materials, X-ray computed tomography (X-ray CT) has become the primary technique for non-destructive particle and crack analysis. Cracking causes performance decline in polycrystalline NMC811 by exposing new surfaces for parasitic electrolyte reactions and disconnecting active material from the electrode matrix. First cycle crack formation has been documented, but definitive electrochemically induced particle fracture is challenging to assess due to complex sample preparation and high-resolution X-ray imaging requirements. Presented here is an operando X-ray CT technique that enables accurate observation of fracture behaviour during de-/lithiation. A non-linear relationship between fracture behaviour and cell voltage was uncovered, and evidence of particle reformation during re-lithiation. Using a grey level analysis algorithm for fracture detection, we expedite damage evaluation in several thousands of particles throughout the electrochemical process, understanding crack initiation, propagation, and closure on a large, statistical scale and give the ability to track any one of the thousands of particles through its individual electrochemical history. Additionally, we explore the effects of continued volumetric hysteresis on particle damage. For the first time, we demonstrate the complex plurality of fracture behaviour in commercial lithium-ion battery materials, aiding in designing mitigation strategies against particle fracture.
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Mar 2025
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I12-JEEP: Joint Engineering, Environmental and Processing
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Donal P.
Finegan
,
Julia
Billman
,
Jacob
Darst
,
Peter
Hughes
,
Jesus
Trillo
,
Matt
Sharp
,
Alex
Benson
,
Martin
Pham
,
Inez
Kesuma
,
Mark
Buckwell
,
Hamish T.
Reid
,
Charlie
Kirchner-Burles
,
Matilda
Fransson
,
David
Petrushenko
,
Thomas M. M.
Heenan
,
Rhodri
Jervis
,
Rhodri
Owen
,
Drasti
Patel
,
Ludovic
Broche
,
Alexander
Rack
,
Oxana
Magdysyuk
,
Matt
Keyser
,
William
Walker
,
Paul
Shearing
,
Eric
Darcy
Diamond Proposal Number(s):
[24112, 20903, 17641]
Open Access
Abstract: The thermal response of Li-ion cells can greatly vary for identical cell designs tested under identical conditions, the distribution of which is costly to fully characterize experimentally. The open-source Battery Failure Databank presented here contains robust, high-quality data from hundreds of abuse tests spanning numerous commercial cell designs and testing conditions. Data was gathered using a fractional thermal runaway calorimeter and contains the fractional breakdown of heat and mass that was ejected, as well as high-speed synchrotron radiography of the internal dynamic response of cells during thermal runaway. The distribution of thermal output, mass ejection, and internal response of commercial cells are compared for different abuse-test conditions, which when normalized on a per amp-hour basis show a strong positive correlation between heat output from cells, the fraction of mass ejected from the cells, their energy- and power-density. Ejected mass was shown to contain 10 × more heat per gram than non-ejected mass. The causes of ‘outlier’ thermal and ejection responses i.e., extreme cases, are elucidated by high-speed radiography which showed how occurrences such as vent clogging can create more hazardous conditions. High-speed radiography also demonstrated how the time-resolved interplay of thermal runaway propagation and mass ejection influences the total heat generated.
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Mar 2024
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Ralf F.
Ziesche
,
Thomas M. M.
Heenan
,
Pooja
Kumari
,
Jarrod
Williams
,
Weiqun
Li
,
Matthew E.
Curd
,
Timothy L.
Burnett
,
Ian
Robinson
,
Dan J. L.
Brett
,
Matthias J.
Ehrhardt
,
Paul D.
Quinn
,
Layla B.
Mehdi
,
Philip J.
Withers
,
Melanie
Britton
,
Nigel D.
Browning
,
Paul R.
Shearing
Open Access
Abstract: Demand for low carbon energy storage has highlighted the importance of imaging techniques for the characterization of electrode microstructures to determine key parameters associated with battery manufacture, operation, degradation, and failure both for next generation lithium and other novel battery systems. Here, recent progress and literature highlights from magnetic resonance, neutron, X-ray, focused ion beam, scanning and transmission electron microscopy are summarized. Two major trends are identified: First, the use of multi-modal microscopy in a correlative fashion, providing contrast modes spanning length- and time-scales, and second, the application of machine learning to guide data collection and analysis, recognizing the role of these tools in evaluating large data streams from increasingly sophisticated imaging experiments.
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May 2023
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I12-JEEP: Joint Engineering, Environmental and Processing
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William Q.
Walker
,
Kylie
Cooper
,
Peter
Hughes
,
Ian
Doemling
,
Mina
Akhnoukh
,
Sydney
Taylor
,
Jacob
Darst
,
Julia
Billman
,
Matthew
Sharp
,
David
Petrushenko
,
Rhodri
Owen
,
Martin
Pham
,
Thomas
Heenan
,
Alexander
Rack
,
Oxana
Magdysyuk
,
Thomas
Connolley
,
Dan
Brett
,
Paul
Shearing
,
Donal
Finegan
,
Eric
Darcy
Diamond Proposal Number(s):
[24112, 20903, 17641]
Abstract: Consideration of thermal runaway heat output variability is paramount for the development of safe lithium-ion battery assemblies. This study utilizes data gathered from fractional thermal runaway calorimetry (FTRC) experiments to conduct a comparative analysis of thermal runaway heat output for three cell formats (18650, 21700, and 33600) as a function of trigger method (heaters, internal short-circuiting device, and nail penetration). The analysis is based on comparisons for the calculated total energy yield, fractional energy yield, heat rate, and heat flux. This study reveals that nail penetration tends to result in higher thermal runaway heat output for larger cells (21700 & 33600); these experiments also tended to result in higher fractions of the total energy being released through the cell body. The smaller cells (18650) did not appear to have significant variation in heat output as a function of trigger method. This finding suggests that, for this cell type, worst-case scenario heat output could be achievable in assembly level testing regardless of the utilized trigger method. This study also demonstrates successful translation of FTRC results, as recorded in the Battery Failure Databank, into meaningful analysis that breaks down the influence of specific conditions on thermal runaway heat output.
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Mar 2022
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Ralf F.
Ziesche
,
Jennifer
Hack
,
Lara
Rasha
,
Maximilian
Maier
,
Chun
Tan
,
Thomas M. M.
Heenan
,
Henning
Markötter
,
Nikolay
Kardjilov
,
Ingo
Manke
,
Winfred
Kockelmann
,
Dan J. L.
Brett
,
Paul R.
Shearing
Open Access
Abstract: In recent years, low-temperature polymer electrolyte fuel cells have become an increasingly important pillar in a zero-carbon strategy for curbing climate change, with their potential to power multiscale stationary and mobile applications. The performance improvement is a particular focus of research and engineering roadmaps, with water management being one of the major areas of interest for development. Appropriate characterisation tools for mapping the evolution, motion and removal of water are of high importance to tackle shortcomings. This article demonstrates the development of a 4D high-speed neutron imaging technique, which enables a quantitative analysis of the local water evolution. 4D visualisation allows the time-resolved studies of droplet formation in the flow fields and water quantification in various cell parts. Performance parameters for water management are identified that offer a method of cell classification, which will, in turn, support computer modelling and the engineering of next-generation flow field designs.
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Mar 2022
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I11-High Resolution Powder Diffraction
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Andrew Stephen
Leach
,
Alice
Llewellyn
,
Chao
Xu
,
Chun
Tan
,
Thomas M. M.
Heenan
,
Alex
Dimitrijevic
,
Karin
Kleiner
,
Clare P.
Grey
,
Dan J. L.
Brett
,
Chiu C.
Tang
,
Paul R.
Shearing
,
Rhodri
Jervis
Diamond Proposal Number(s):
[22498, 24122]
Open Access
Abstract: Understanding the performance of commercially relevant cathode materials for lithium-ion (Li-ion) batteries is vital to realize the potential of high-capacity materials for automotive applications. Of particular interest is the spatial variation of crystallographic behavior across (what can be) highly inhomogeneous electrodes. In this work, a high-resolution X-ray diffraction technique was used to obtain operando transmission measurements of Li-ion pouch cells to measure the spatial variances in the cell during electrochemical cycling. Through spatially resolved investigations of the crystallographic structures, the distribution of states of charge has been elucidated. A larger portion of the charging is accounted for by the central parts, with the edges and corners delithiating to a lesser extent for a given average electrode voltage. The cells were cycled to different upper cutoff voltages (4.2 and 4.3 V vs. graphite) and C-rates (0.5, 1, and 3C) to study the effect on the structure of the NMC811 cathode. By combining this rapid data collection method with a detailed Rietveld refinement of degraded NMC811, the spatial dependence of the degradation caused by long-term cycling (900 cycles) has also been shown. The variance shown in the pristine measurements is exaggerated in the aged cells with the edges and corners offering an even lower percentage of the charge. Measurements collected at the very edge of the cell have also highlighted the importance of electrode alignment, with a misalignment of less than 0.5 mm leading to significantly reduced electrochemical activity in that area.
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Jan 2022
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I12-JEEP: Joint Engineering, Environmental and Processing
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Matt
Sharp
,
John
Darst
,
Peter
Hughes
,
Julia
Billman
,
Martin
Pham
,
David
Petrushenko
,
Thomas
Heenan
,
Rhodri
Jervis
,
Rhodri Ellis
Owen
,
Drasti
Patel
,
Wenjia
Du
,
Harry
Michael
,
Alexander
Rack
,
Oxana
Magdysyuk
,
Thomas
Connolley
,
Dan
Brett
,
Gareth
Hinds
,
Matthew
Keyser
,
Eric
Darcy
,
Paul
Shearing
,
William Q.
Walker
,
Donal
Finegan
Diamond Proposal Number(s):
[24112, 20903, 17641]
Open Access
Abstract: Thermal runaway of lithium-ion batteries can involve various types of failure mechanisms each with their own unique characteristics. Using fractional thermal runaway calorimetry and high-speed radiography, the response of three different geometries of cylindrical cell (18650, 21700, and D-cell) to different abuse mechanisms (thermal, internal short circuiting, and nail penetration) are quantified and statistically examined. Correlations between the geometry of cells and their thermal behavior are identified, such as increasing heat output per amp-hour (kJ Ah-1) of cells with increasing cell diameter during nail penetration. High-speed radiography reveals that the rate of thermal runaway propagation within cells is generally highest for nail penetration where there is a relative increase in rate of propagation with increasing diameter, compared to thermal or internal short-circuiting abuse. For a given cell model tested under the same conditions, a distribution of heat output is observed with a trend of increasing heat output with increased mass ejection. Finally, internal temperature measurements using thermocouples embedded in the penetrating nail are shown to be unreliable thus demonstrating the need for care when using thermocouples where the temperature is rapidly changing. All data used in this manuscript are open access through the NREL and NASA Battery Failure Databank.
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Jan 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[24178]
Open Access
Abstract: Nickel-rich cathodes (LiNixMnyCo1-x-yO2, x > 0.6) permit higher energy in lithium-ion rechargeable batteries but suffer from accelerated degradation at potentials above 4.1 V versus Li/Li+. Here, we present a proof-of-concept in situ pouch cell and methodology for correlative 2D synchrotron transmission X-ray microscopy with 3D lab-based micro-CT. XANES analysis of the TXM data enables tracking of Ni edge energy within and between the polycrystalline NMC811 particles embedded in the operating electrode through its initial delithiation. By using edge energy as a proxy, state-of-charge heterogeneities can be tracked at the nanoscale, revealing the role of cracked particles as potential nucleation points for failure and highlighting the challenges in achieving uniform (de-)lithiation. We propose, in future work, to leverage the pouch cell design presented here for longitudinal TXM-XANES studies of nickel-rich cathodes across multiple cycles and operating variables and investigate the effect of dopants and microstructural optimization in mitigating degradation.
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Nov 2021
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