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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E02-JEM ARM 300CF
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Jichao
Zhang
,
Jiexin
Zhu
,
Liqun
Kang
,
Qing
Zhang
,
Longxiang
Liu
,
Fei
Guo
,
Kaiqi
Li
,
Jianrui
Feng
,
Lixue
Xia
,
Lei
Lv
,
Wei
Zong
,
Paul R.
Shearing
,
Dan J. L.
Brett
,
Ivan P.
Parkin
,
Xuedan
Song
,
Liqiang
Mai
,
Guanjie
He
Diamond Proposal Number(s):
[32058, 33118]
Open Access
Abstract: Electrochemical urea splitting provides a sustainable and environmentally benign route for facilitating energy conversion. Nonetheless, the sustained efficiency of urea splitting is impeded by a scarcity of active sites during extended operational periods. Herein, an atomic heterostructure engineering strategy is proposed to promote the generation of active species via synthesizing unique Ru–O4 coordinated single atom catalysts anchored on Ni hydroxide (Ru1–Ni(OH)2), with ultralow Ru loading mass of 40.6 μg cm−2 on the nickel foam for commercial feasibility. Leveraging in situ spectroscopic characterizations, the structure-performance relationship in low and high urea concentrations was investigated and exhibited extensive universality. The boosted generation of dynamic Ni3+ active sites ensures outstanding activity and prominent long-term durability tests in various practical scenarios, including 100 h Zn–urea–air battery operation, 100 h alkaline urine electrolysis, and over 400 h stable hydrogen production in membrane electrode assembly (MEA) system under industrial-level current density.
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Nov 2023
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B18-Core EXAFS
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Renier Arabolla
Rodríguez
,
Manuel Avila
Santos
,
Abil E.
Aliev
,
Richard I.
Walton
,
Luis A. Tavera
Carrasco
,
Eduardo L. Perez
Cappe
,
Marlene González
Montiel
,
Edgar O. Pérez
Reyex
,
Nelcy Della Santina
Mohallem
,
Reza J.
Kashtiban
,
Yodalgis Mosqueda
Laffita
,
Carolina Leyva
Insunza
,
Paul R.
Shearing
,
Dan J. L.
Brett
Diamond Proposal Number(s):
[14239]
Abstract: The current work reports an unprecedented multifunctional material with optical activity and a modified magnetic response by a unique combination of doping with P and Fe into the spinel LiMn2O4. Through inductively coupled plasma – optical emission spectroscopy, X-ray absorption near-edge spectroscopy, X-ray diffraction and scanning transmission electron microscopy, the chemical composition, oxidation state and the crystalline structure are determined. Solid-state UV-Vis spectroscopy, magnetic susceptibility and electronic conductivity reveal the critical importance of the interaction between iron and phosphorus when simultaneously doping the crystalline structure of LiMn2O4. The presence of Fe and P considerably increases charge carrier concentration as a mechanism for enhancing electronic conductivity. Fe and P doping also creates Fe-Fe spin interactions that allow double electron optical excitations. This opens a pathway to create multifunctional materials for light-assisted charging lithium-ion batteries. P doping also induces the formation of magnetic clusters arising from the Fe-O-Fe, Fe-O-Mn and Mn-O-Mn spin exchange interactions. The magnetic response of the materials is strongly influenced by the relative amount of Fe in octahedral or tetrahedral sites of the spinel structure. Such ferrimagnetic behaviour has not been reported before LiMn2O4 doped with Fe or P separately. The potential applicability of this newly identified magnetic feature was demonstrated by a significant capacity gain when a lithium-ion cell is exposed to a static external magnetic field.
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Nov 2023
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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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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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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
E02-JEM ARM 300CF
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Longxiang
Liu
,
Liqun
Kang
,
Arunabhiram
Chutia
,
Jianrui
Feng
,
Martyna
Michalska
,
Pilar
Ferrer
,
David
Grinter
,
Georg
Held
,
Yeshu
Tan
,
Fangjia
Zhao
,
Fei
Guo
,
David
Hopkinson
,
Christopher
Allen
,
Yanbei
Hou
,
Junwen
Gu
,
Ioannis
Papakonstantinou
,
Paul
Shearing
,
Dan
Brett
,
Ivan P.
Parkin
,
Guanjie
He
Diamond Proposal Number(s):
[29340, 32501, 30614, 29809, 32058]
Open Access
Abstract: The electrochemical synthesis of hydrogen peroxide (H2O2) via a two-electron (2e-) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. However, the development of efficient electrocatalysts is still facing lots of challenges like insufficient understanding of active sites. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst (PCC) for H2O2 electrochemical production. The optimized PCC900 exhibits unprecedented activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.
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Mar 2023
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E01-JEM ARM 200CF
E02-JEM ARM 300CF
I20-Scanning-X-ray spectroscopy (XAS/XES)
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Runjia
Lin
,
Liqun
Kang
,
Karolina
Lisowska
,
Weiying
He
,
Siyu
Zhao
,
Shusaku
Hayama
,
Dan
Brett
,
Graham
Hutchings
,
Furio
Corà
,
Ivan
Parkin
,
Guanjie
He
Diamond Proposal Number(s):
[29254, 29207]
Open Access
Abstract: Electrocatalytic oxygen reduction reaction (ORR) has been intensively studied for efficient and environmentally benign energy conversion processes. However, insufficient understanding of ORR 2e--pathway mechanism at the atomic level inhibits rational design of electrocatalysts with both high activity and selectivity, causing concerns including catalyst degradation due to Fenton reaction or poor efficiency of H2O2 electrosynthesis. Herein we show that the generally accepted ORR electrocatalyst design based on a Sabatier volcano plot argument optimises activity but is unable to account for the 2e--pathway selectivity; an extended “dynamic active site saturation” model that examines in addition the hydrogenation kinetics linked to the OOH* adsorption energy enables us to resolve the activity-selectivity compromise. Through electrochemical and operando spectroscopic studies on the ORR process governed by a series of Co-N x /carbon nanotube hybrids, a construction-driven approach that aims to create the maximum number of 2e- ORR sites by directing the secondary ORR electron transfer step towards the 2e- intermediate is proven to be attainable by manipulating O2 hydrogenation kinetics. Control experiments reveal the O2 hydrogenation chemistry is related to a catalyst reconstruction with lower symmetry around the Co active centre induced by the application of a cathodic potential. The optimised catalyst exhibits a ~100% H2O2 selectivity and an outstanding activity with an ORR potential of 0.82 V versus the reversible hydrogen electrode to reach the ring current density of 1 mA cm-2 by using rotating ring-disk electrode measurement, which is the best-performing 2e- ORR electrocatalyst reported to date, and approaches the thermodynamic limit.
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Mar 2023
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E02-JEM ARM 300CF
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Haobo
Dong
,
Ruirui
Liu
,
Xueying
Hu
,
Fangjia
Zhao
,
Liqun
Kang
,
Longxiang
Liu
,
Jianwei
Li
,
Yeshu
Tan
,
Yongquan
Zhou
,
Dan J. L.
Brett
,
Guanjie
He
,
Ivan
Parkin
Diamond Proposal Number(s):
[30614, 29809]
Open Access
Abstract: A stable cathode–electrolyte interface (CEI) is crucial for aqueous zinc-ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode-electrolyte interface (CEI) in AZIBs. A water-soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion-dominated to capacitance-controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO− from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn2+; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn2+ at the CEI, where the Zn-Birnessite MnO2 battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology.
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Dec 2022
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B18-Core EXAFS
E01-JEM ARM 200CF
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Ruoyu
Xu
,
Liqun
Kang
,
Konstantinos G.
Papanikolaou
,
Bolun
Wang
,
Sushila
Marlow
,
Qian
He
,
Peng
Zhang
,
Jianfang
Wang
,
Dan J. I.
Brett
,
Michail
Stamatakis
,
Feng Ryan
Wang
Diamond Proposal Number(s):
[20643, 19318, 19246, 19072, 20629]
Open Access
Abstract: Proton exchange membrane fuel cells require oxygen reduction catalysts with high activity and stability. Pt based alloy materials are most widely applied ORR catalyst due to its high intrinsic activity, but usually suffer from rapid deactivation as a result of particle agglomeration, detachment, Ostwald ripening and/or Pt dissolution. Here we investigate the degradation of the PdPt alloys via in situ X-ray absorption fine structure, Δμ analysis, identical location-electron microscopy and DFT calculations. We conclude that the origin of high activity and stability of the PdPt catalyst stems from the oxidation resistance of metallic Pt, forming mainly surface adsorbed O species at high potentials. Two stage degradation process are observed, showing an evolution of dynamic surface dependent ORR performance along with the deactivation process. The careful design of Pt alloy structure leads to controlled surface oxygen behaviours. This opens a new way to increase the lifespan of fuel cells and improve the Pt utilization efficiency.
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Nov 2022
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E01-JEM ARM 200CF
E02-JEM ARM 300CF
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Jianwei
Li
,
Ningjing
Luo
,
Liqun
Kang
,
Fangjia
Zhao
,
Yiding
Jiao
,
Thomas J.
Macdonald
,
Min
Wang
,
Ivan P.
Parkin
,
Paul R.
Shearing
,
Dan J. L.
Brett
,
Guoliang
Chai
,
Guanjie
He
Diamond Proposal Number(s):
[22553, 22604, 30614]
Open Access
Abstract: Layered manganese oxides adopting pre-accommodated cations have drawn tremendous interest for the application as cathodes in aqueous zinc-ion batteries (AZIBs) owing to their open 2D channels for fast ion-diffusion and mild phase transition upon topochemical (de)intercalation processes. However, it is inevitable to see these “pillar” cations leaching from the hosts owing to the loose interaction with negatively charged Helmholtz planes within the hosts and shearing/bulking effects in 2D structures upon guest species (de)intercalation, which implies a limited modulation to prevent them from rapid performance decay. Herein, a new class of layered manganese oxides, Mg0.9Mn3O7·2.7H2O, is proposed for the first time, aims to achieve a robust cathode for high-performance AZIBs. The cathode can deliver a high capacity of 312 mAh g−1 at 0.2 A g−1 and exceptional cycling stability with 92% capacity retention after 5 000 cycles at 5 A g−1. The comprehensive characterizations elucidate its peculiar motif of pined Mg-□Mn-Mg dumbbell configuration along with interstratified hydrogen bond responsible for less Mn migration/dissolution and quasi-zero-strain characters. The revealed new structure-function insights can open up an avenue toward the rational design of superstructural cathodes for reversible AZIBs.
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Nov 2022
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