I12-JEEP: Joint Engineering, Environmental and Processing
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Emily C.
Giles
,
Abbey
Jarvis
,
Pierrot S.
Attidekou
,
Kieran
O'Regan
,
Rosie
Madge
,
Alexander T.
Sargent
,
Beatrice
Browning
,
Anton
Zorin
,
Roberto
Sommerville
,
Alex J.
Green
,
Stefan
Michalik
,
Philip A.
Chater
,
Daniel
Reed
,
Emma
Kendrick
,
Laura L.
Driscoll
,
Peter
Slater
,
Phoebe K.
Allan
,
Paul
Anderson
,
Luke
Sweeney
Open Access
Abstract: Understanding the degradation of large format lithium-ion pouch cells – critical for electric vehicle applications – is vital to extend their lifetime and allow potential second-life application. Here, the impact on capacity fade and material degradation in two end-of-life cells, which were additionally subjected to accelerated aging to mimic extended use in second-life applications, were examined using powder synchrotron X-ray diffraction, Raman spectroscopy and electrochemical impedance spectroscopy, complemented by detailed post mortem analyses. The dominant mechanism of capacity loss under these conditions was found to be lithium inventory depletion, driven by processes such as electrolyte decomposition, lithium plating and solid electrolyte interphase growth. Structural changes in the graphite anode, including amorphization and reduced active material, were more pronounced under severe overcharging conditions. The blended cathode showed lithium inventory loss in both phases, but 92–94% capacity recovery was observed on subsequent cycling in half cells vs Li, illustrating its robustness, with little structural degradation observed. The finding that electrolyte degradation/loss in these cells was a more critical contributor to cell degradation toward the knee-point than electrode active material degradation/loss indicates that increasing – or replenishing – the electrolyte content could be a strategy to extend the usable life of such cells.
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Nov 2025
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I21-Resonant Inelastic X-ray Scattering (RIXS)
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Yanfang
Wang
,
Cheng
Li
,
Yingzhi
Li
,
Raquel
De Benito
,
Jacob
Williams
,
Joshua M.
Stratford
,
Zhiqiang
Li
,
Chun
Zeng
,
Ning
Qin
,
Hongzhi
Wang
,
Yulin
Cao
,
Dominic
Gardner
,
Wilgner
Lima Da Silva
,
Sahil
Tippireddy
,
Qingmeng
Gan
,
Fangchang
Zhang
,
Wen
Luo
,
Joshua W.
Makepeace
,
Ke-Jin
Zhou
,
Kaili
Zhang
,
Fucai
Zhang
,
Phoebe K.
Allan
,
Zhouguang
Lu
Diamond Proposal Number(s):
[35147]
Abstract: Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy-density lithium-ion batteries. However, achieving long-term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt-free layered oxide, Li0.693[Li0.153Ni0.190Mn0.657]O2 (LLNMO). After 50 cycles at 50 mA/g (~0.2 C), the cathode retains 97.4% of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable rhombohedral symmetry (R-3m) with unique local structures. The face-sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration-induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de-/lithiation (< 2.3% along the c-axis) and excellent structural reversibility. These findings highlight that layered oxides with a metastable framework are promising cathode candidates for next-generation ultra-high-energy lithium-ion batteries.
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Feb 2025
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DIAD-Dual Imaging and Diffraction Beamline
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Diamond Proposal Number(s):
[30971]
Open Access
Abstract: Controllable sorption selectivity in zeolites is crucial for their application in catalysis, gas separation and ion-exchange. Whilst existing approaches to achieving sorption selectivity with natural zeolites typically rely on screening for specific geological deposits, here we develop partial interzeolite transformation as a straightforward and highly tuneable method to achieve sorption selectivity via forming dual-phase composites with simultaneous control of both phase-ratio and morphology. The dual-cation (strontium and caesium) exchange properties of a series of granular mordenite/zeolite P composites formed from a parent natural mordenite material are demonstrated in complex, industrially relevant multi-ion environments pertinent to nuclear waste management. The relative uptake of caesium and strontium is controlled via the extent of transformation: composites exhibit significantly increased ion-exchange affinity for strontium compared to both the parent mordenite and physical mixtures of mordenite/zeolite P phases with similar phase ratios. The composite with a 40[thin space (1/6-em)]:[thin space (1/6-em)]60 mordenite[thin space (1/6-em)]:[thin space (1/6-em)]zeolite P ratio composite achieves higher uptake rates than the natural clinoptilolite material currently used to decontaminate nuclear waste streams at the Sellafield site, UK. In situ X-ray image-guided diffraction experiments during caesium exchange demonstrate that the mordenite core retains rapid caesium uptake likely responsible for the unique ion-exchange chemistry achievable through the partial inter-zeolite transformation. These results offer a straightforward and controllable route to optimised zeolite functionality and a strategy to engineer composites from low-grade natural sources at low cost and with formulation advantages for industrial deployment.
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Aug 2024
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B18-Core EXAFS
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Bo
Dong
,
Andrey
Poletayev
,
Jonathon
Cottom
,
Javier
Castells-Gil
,
Ben
Spencer
,
Cheng
Li
,
Pengcheng
Zhu
,
Yongxiu
Chen
,
Jaime-Marie
Price
,
Laura L.
Driscoll
,
Phoebe K.
Allan
,
Emma
Kendrick
,
Saiful
Islam
,
Peter R.
Slater
Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Lithium nickel oxide, LiNiO2, has attracted considerable interest as a high energy cathode for next generation lithium ion batteries. Nevertheless, shortcomings such as significant cycling capacity decay and low stability in ambient atmosphere have hindered its practical application, and consequently most work has focused on the more stable Mn and Co doped analogues Li(Ni,Mn,Co)O2. Here, we report an investigation of an alternative strategy, sulfate modification, in the LiNiO2 (LNO) system. We show that improved performance can be achieved, attributed to the dual effect of a low level of bulk doping and the presence of a self-passivation Li2SO4 layer formed beyond the solid solution limit. Ab initio simulations suggest that the behavior is similar to that of other high valent dopants such as W and Mo. These dual effects contribute to the improved air stability and enhanced electrochemical performance for the sulfate modified lithium-rich LNO, leading to high initial capacities (~245 mAhg-1 at 25 mA/g, and ~205 mAhg-1 at 100 mA/g) and better capacity retention. Overall, the results show that polyanion modification represents an excellent alternative low cost strategy to improve the performance of lithium nickel oxide cathode materials.
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Apr 2024
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I12-JEEP: Joint Engineering, Environmental and Processing
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Arthur
Fordham
,
Zoran
Milojevic
,
Emily
Giles
,
Wenjia
Du
,
Rhodri E.
Owen
,
Stefan
Michalik
,
Philip A.
Chater
,
Prodip K.
Das
,
Pierrot S.
Attidekou
,
Simon M.
Lambert
,
Phoebe K.
Allan
,
Peter R.
Slater
,
Paul A.
Anderson
,
Rhodri
Jervis
,
Paul R.
Shearing
,
Dan J. I.
Brett
Diamond Proposal Number(s):
[27719]
Open Access
Abstract: The growing demand for electric vehicles (EVs) continues to raise concern for the disposal of lithium-ion batteries reaching their end of life (EoL). The cells inside EVs age differently depending on multiple factors. Yet, following extraction, there are significant challenges with characterizing degradation in cells that have been aged from real-world EV usage. We employed four non-destructive techniques—infrared thermography, ultrasonic mapping, X-ray tomography, and synchrotron X-ray diffraction—to analyze the aging of Nissan Leaf large-format pouch cells that were arranged in different orientations and locations within the pack. The combination of these methods provided complementary insights into cell degradation, with rotated/vertically aligned cells exhibiting distinct aging patterns compared with flat/horizontally aligned cells. These findings offer valuable information for pack design and demonstrate how cost-effective non-destructive techniques can provide practical assessment capabilities comparable to synchrotron studies. This approach enables decision support during EoL, enhancing battery production efficiency and minimizing material waste.
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Nov 2023
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Open Access
Abstract: Sb- and Nb-doped Zr and Sn-umbites have been prepared using hydrothermal synthesis with both high purity and yield. All four materials display excellent removal of Cs+ cations from acidic, neutral, and basic solutions, abating at least 80% of the Cs present. This performance is retained in the presence of competing Na+ cations as well as across the pH range. The most sustained selectivity is observed in acidic media, with evidence of a minor reduction in selectivity under basic conditions. The umbites have successfully been shaped into pellets, introducing macroporosity and retaining the selective uptake of Cs in the presence of excess Na. Through thermal treatment, samples of partially Cs-exchanged umbite can be converted into dense silicate phases where radioactive Cs can be immobilized in a potential wasteform for long term storage. These findings present doped umbites as prospective materials for industrial use with selective abatement properties and capabilities for deployment followed by end of life geological disposal.
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Jan 2023
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I19-Small Molecule Single Crystal Diffraction
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Open Access
Abstract: Lithium-rich oxides are attracting intense interest as the next generation cathode materials for lithium-ion batteries due to their high theoretical capacity. Nevertheless, these materials suffer from a number of shortcomings, such as oxygen loss at high voltage, large hysteresis and poor rate capability. In this work, we show that through a dual cation doping strategy replacing Ti with Mo and Mg, the disordered rocksalt (DRS) Li1.2Ni0.4Ti0.4O2 is transformed into a new cation ordered layered phase Li1.2Ni0.4Mo0.2Mg0.2O2, with the high valence dopant Mo6+ on the (0,0,0) site. Li1.2Ni0.4Mo0.2Mg0.2O2 showed improved performance compared to that of the similarly prepared DRS Li1.2Ni0.4Ti0.4O2 material (~190 mAhg-1 vs ~105 mAhg-1 after 10 cycles, respectively). The characteristics of the electrochemical process were studied using ex situ XRD and XAS, which indicated the involvement of both Ni and Mo redox during the cycling as well as the electrochemical instability of the layered phase which changes to a disordered rocksalt phase on cycling.
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Jan 2023
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[22115]
Open Access
Abstract: Binary metal oxides have received sustained interest as anode materials due to their desirable capacities, exceeding theoretical values particularly in the first discharge. Although they have received increasing attention in recent years, topical debates persist regarding not only their lithiation mechanisms but also the origin of additional capacity. Aiming to resolve these disagreements, we perform a systematic study of a series of iron and manganese oxides to investigate their phase behavior during first discharge. Using a combination of in operando pair distribution function measurements and our recently developed Metropolis non-negative matrix factorization approach to address the analytical challenges concerning materials’ nanoscopic nature and phase heterogeneity, here we report unexpected observation of non-equilibrium FeOx solid-solution phases and pulverization of MnO. These processes are correlated with the extra capacities observed at different depths of discharge, pointing to a metal-dependent nature of this additional capacity and demonstrating the advantage of our approach with promising prospects for diverse applications.
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Aug 2021
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I15-1-X-ray Pair Distribution Function (XPDF)
I15-Extreme Conditions
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Diamond Proposal Number(s):
[17785, 13681]
Open Access
Abstract: Hard carbons are the leading candidate anode materials for sodium-ion batteries. However, the sodium-insertion mechanisms remain under debate. Here, employing a novel analysis of operando and ex situ pair distribution function (PDF) analysis of total scattering data, supplemented by information on the local electronic structure provided by operando 23Na solid-state NMR, we identify the local atomic environments of sodium stored within hard carbon and provide a revised mechanism for sodium storage. The local structure of carbons is well-described by bilayers of curved graphene fragments, with fragment size increasing, and curvature decreasing with increasing pyrolysis temperature. A correlation is observed between the higher-voltage (slope) capacity and the defect concentration inferred from the size and curvature of the fragments. Meanwhile, a larger lower-voltage (plateau) capacity is observed in samples modeled by larger fragment sizes. Operando PDF data on two commercially relevant hard carbons reveal changes at higher-voltages consistent with sodium ions stored close to defective areas of the carbon, with electrons localized in the antibonding π*-orbitals of the carbon. Metallic sodium clusters approximately 13–15 Å in diameter are formed in both carbons at lower voltages, implying that, for these carbons, the lower-voltage capacity is determined by the number of regions suitable for sodium cluster formation, rather than by having microstructures that allow larger clusters to form. Our results reveal that local atomic structure has a definitive role in determining storage capacity, and therefore the effect of synthetic conditions on both the local atomic structure and the microstructure should be considered when engineering hard carbons.
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Aug 2021
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[22115]
Open Access
Abstract: Binary metal oxides are attractive anode materials for lithium-ion batteries. Despite sustained effort into nanomaterials synthesis and understanding the initial discharge mechanism, the fundamental chemistry underpinning the charge and subsequent cycles—thus the reversible capacity—remains poorly understood. Here, we use in operando X-ray pair distribution function analysis combining with our recently developed analytical approach employing Metropolis Monte Carlo simulations and non-negative matrix factorisation to study the charge reaction thermodynamics of a series of Fe- and Mn-oxides. As opposed to the commonly believed conversion chemistry forming rocksalt FeO and MnO, we reveal the two oxide series topotactically transform into non-native body-centred cubic FeO and zincblende MnO via displacement-like reactions whose kinetics are governed by the mobility differences between displaced species. These renewed mechanistic insights suggest avenues for the future design of metal oxide materials as well as new material synthesis routes using electrochemically-assisted methods.
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Jan 2021
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