B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Prussian White (PW, Na2Fe[Fe(CN)6]·xH2O) is a leading low-cost cathode material for sodium-ion batteries. Yet, recycling remains largely unaddressed due to the incompatibility of conventional pyrometallurgical and hydrometallurgical routes with its cyanometallate framework. Here, a closed-loop direct recycling process for PW cathodes is reported, for both manufacturing scrap and end-of-life (EOL) sodium-ion cells. Electrodes were delaminated using a low-energy ice-stripping technique, and the recovered powder was regenerated via mild, 80°C aqueous resodiation without calcination or corrosive solvents. The resodiation process simultaneously reinserts Na+ ions, reduces Fe3+ to Fe2+, and promotes surface regeneration through temperature and anion-activated ‘surface healing’, a mechanism supported by control experiments and confirmed by XRD, Fe K-edge XAS, XPS, Raman spectroscopy, and electron microscopy. Resodiated PW recovers 96%–97% of pristine half-cell capacity and, in full-cell configurations paired with hard carbon, retains ∼80% of initial capacity after 300 cycles, outperforming the pristine benchmark of ∼60%. The total energy input for resodiation at 80°C is ∼0.50 kWh, lower than that estimated for fresh PW synthesis (∼3.98 kWh). This work provides an experimentally validated pathway for closed-loop recovery of Prussian White cathodes, with direct relevance to sustainable scale-up of sodium-ion battery technology.
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Jun 2026
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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Ni-rich layered oxides such as (LiNixMnyCo1−x−yO2 (x ≥ 0.6)) exhibit structural degradation, surface instability, and poor lithium ion transport, particularly under extreme temperature conditions, limiting their viability for next generation high energy batteries. This work demonstrates that low-level boron (B25) and tin–boron codoping (SB25) enhance the structural resilience and electrochemical performance of LiNi0.9Mn0.05Co0.05O2 (NMC955) cathodes across a range of temperatures: −5 °C, 25 °C, and 45 °C. Both dopants integrate into the layered α-NaFeO2 structure, expanding lattice parameters and reducing cation mixing, while preserving particle morphology. At sub-ambient temperatures (−5 °C) where slow Li-ion transport is the primary limitation, Sn–B codoping delivers a 25% improvement in specific capacity at 500 mA g−1 relative to pristine NMC955, suppresses the emergence of a second high resistance charge transfer (RCT reduces from 717 Ω to 71.4 Ω), and maintains the highest exchange current densities, 0.3 A m−2. At 25 °C RCT is reduced, from 10.34 Ω in pristine NMC955 to 8.79 Ω, and the effective diffusion coefficient increases, from 1.5 to 1.6 × 10−12 cm−2 s−1, demonstrating enhanced low temperature transport kinetics. Long-term cycling at approximately 1C shows improved capacity retentions of 92.7% (B25) and 88.7% (SB25) after 100 cycles versus 78% for undoped NMC. Postmortem XPS/XAS confirm that codoping suppresses electrolyte-induced transition metal fluorination and CEI thickening, with Sn–B showing the smallest change in Ni oxidation state and local coordination after 200 cycles. Together, these results establish Sn–B co-doping as a scalable and effective strategy to simultaneously enhance the structural stability, interfacial chemistry, and low-temperature transport kinetics of Ni-rich NMC cathodes for demanding lithium-ion battery applications.
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Apr 2026
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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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I11-High Resolution Powder Diffraction
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Jeremy P.
Lowen
,
Tharigopala V.
Beatriceveena
,
Joshua W.
Makepeace
,
Teresa
Insinna
,
Mark P.
Stockham
,
Bo
Dong
,
Sarah J,
Day
,
Clare P.
Grey
,
Emma
Kendrick
,
Peter R.
Slater
,
Paul A.
Anderson
Diamond Proposal Number(s):
[35016]
Open Access
Abstract: All-solid-state batteries utilising a Li-metal anode have long promised to be the next-generation of high-performance energy storage device, with a step-change in energy density, cycling stability and cell safety touted as potential advantages compared to conventional Li-ion battery cells. A key to enabling this technology is the development of solid-state electrolytes with the elusive combination of high ionic conductivity, wide electrochemical stability and the ability to form a conductive and stable interface with Li metal. Presently, oxide and sulfide-based materials, particularly garnet and argyrodite-type structures, have proved most promising for this application. However, these still suffer from a number of challenges, including resistive lithium metal interfaces, poor lithium dendrite suppression (at high current density) and low voltage stability. Here we report the first application of lithium imide, an antifluorite-structured material, as a solid electrolyte in a Li-metal battery. Low-temperature synthesis of lithium imide produces promising Li-ion conductivity, reaching > 1 mS cm-1 at 30 ˚C using a modest post-synthetic mechanochemical treatment, as well as displaying at least 5 V stability vs Li+/Li. In situ electrochemical operation of lithium imide with Li-metal electrodes reveals an apparent 1000-fold increase in its measured conductivity, whilst appearing to remain an electronic insulator. It is postulated that stoichiometry variation at the grain boundary may contribute to this conductivity improvement. Furthermore, the material is shown to possess impressive resistance to hard shorting under high current density conditions (70 mA cm-2) as well as the ability to operate in Li-metal battery cells. These results not only highlight the promising performance of lithium imide, but also its potential to be the basis for a new family of antifluorite based solid electrolytes.
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Apr 2025
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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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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Ternary niobium-based oxides have shown great potential as negative electrodes for Li-ion batteries due to their structural stability and high-rate capabilities. A hydrothermal reaction at 240 °C is used to synthesise MnNb2O6 (MNO) from different alkaline MOH solutions with M = Li, Na, K, yielding MNO-Li, MNO-Na, and MNO-K and a new phase, Ca0.25Mn0.75Nb2O6 (CMNO). Powder X-ray diffraction (PXRD) reveals that the as-made MNO materials have disordered columbite structures, with Mn and Nb randomly distributed over octahedral sites, and these become ordered upon annealing at 1000 °C. In contrast, CMNO has an ordered arrangement of Ca/Mn and Nb, which may be due to the larger ionic radius of Ca2+. The crystalline morphology of the samples is dependent on the synthesis medium, with intricately shaped particles of 10s of nm observed using scanning electron microscopy. Spectroscopic studies (X-ray photoelectron spectroscopy and X-ray absorption fine structure) confirm the Mn2+ oxidation state in all materials. MNO-Na has the highest cyclability towards Li uptake, up to 200 cycles with capacity retention of 64 % and specific capacity of 182 mA·h·g-1, while CMNO showed the highest capacity after 50 cycles, 142 mA·h·g-1, which indicates that structure expansion controls the quantity of Li inserted. Ex-situ PXRD studies revealed that all materials undergo a conversion reaction during first lithiation although MNO-Na and CMNO show better structural stability, regaining their crystallinity.
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Oct 2023
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B18-Core EXAFS
I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[25166, 14239]
Open Access
Abstract: A Mn2+-Li-Nb disordered rock-salt oxide cathode is prepared by a solid-state reaction under 5% H2/N2, and its electrochemical property shows a high voltage plateau at 4.8 V, with irreversible structural changes in the first cycle due to O redox processes; this is supported by powder X-ray diffraction and ex-situ laboratory Mn K-edge XANES data.
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Oct 2023
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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Open Access
Abstract: A primary target of energy storage is the all solid state battery, however finding a suitable solid state electrolyte has proven troublesome. Lithium garnet materials are promising solid state electrolytes with high room temperature conductivity, a wide electrochemical window, high chemical stability with Li metal and have minimal hazards. However, lithium garnets suffer from slow, energy demanding synthesis, rapid proton exchange (leading to high interfacial resistance between the garnet and electrodes), mechanical instabilities with Li metal and require specific handling methods to achieve the highest performing materials (such as full processing under Ar). Here we report a Ti/Ce co-doped high entropy lithium garnet material with four B site dopants, with the formula Li6.5La3Zr1Nb0.5Ce0.25Ti0.25O12. This material benefits from rapid simultaneous sintering and densification directly from the starting materials, allowing formation of dense pellets in <1hr at 1100°C using only a standard, cheap, muffle furnace. Li6.5La3Zr1Nb0.5Ce0.25Ti0.25O12 also has high conductivity (0.5 mS cm-1 at 25°C), scalability and insensitivity to both rapid furnace ramp rates and long dwell times. There is also an indication of unusual behaviour towards limiting lithium dendrite propagation, which is also discussed.
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Aug 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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Nuria
Tapia-Ruiz
,
A. Robert
Armstrong
,
Hande
Alptekin
,
Marco A.
Amores
,
Heather
Au
,
Jerry
Barker
,
Rebecca
Boston
,
William R
Brant
,
Jake M.
Brittain
,
Yue
Chen
,
Manish
Chhowalla
,
Yong-Seok
Choi
,
Sara I. R.
Costa
,
Maria
Crespo Ribadeneyra
,
Serena A
Cussen
,
Edmund J.
Cussen
,
William I. F.
David
,
Aamod V
Desai
,
Stewart A. M.
Dickson
,
Emmanuel I.
Eweka
,
Juan D.
Forero-Saboya
,
Clare
Grey
,
John M.
Griffin
,
Peter
Gross
,
Xiao
Hua
,
John T. S.
Irvine
,
Patrik
Johansson
,
Martin O.
Jones
,
Martin
Karlsmo
,
Emma
Kendrick
,
Eunjeong
Kim
,
Oleg V
Kolosov
,
Zhuangnan
Li
,
Stijn F L
Mertens
,
Ronnie
Mogensen
,
Laure
Monconduit
,
Russell E
Morris
,
Andrew J.
Naylor
,
Shahin
Nikman
,
Christopher A
O’keefe
,
Darren M. C.
Ould
,
Robert G.
Palgrave
,
Philippe
Poizot
,
Alexandre
Ponrouch
,
Stéven
Renault
,
Emily M.
Reynolds
,
Ashish
Rudola
,
Ruth
Sayers
,
David O.
Scanlon
,
S.
Sen
,
Valerie R.
Seymour
,
Begoña
Silván
,
Moulay Tahar
Sougrati
,
Lorenzo
Stievano
,
Grant S.
Stone
,
Chris I.
Thomas
,
Maria-Magdalena
Titirici
,
Jincheng
Tong
,
Thomas J.
Wood
,
Dominic S
Wright
,
Reza
Younesi
Open Access
Abstract: Increasing concerns regarding the sustainability of lithium sources, due to their limited availability and consequent expected price increase, have raised awareness of the importance of developing alternative energy-storage candidates that can sustain the ever-growing energy demand. Furthermore, limitations on the availability of the transition metals used in the manufacturing of cathode materials, together with questionable mining practices, are driving development towards more sustainable elements. Given the uniformly high abundance and cost-effectiveness of sodium, as well as its very suitable redox potential (close to that of lithium), sodium-ion battery technology offers tremendous potential to be a counterpart to lithium-ion batteries (LIBs) in different application scenarios, such as stationary energy storage and low-cost vehicles. This potential is reflected by the major investments that are being made by industry in a wide variety of markets and in diverse material combinations. Despite the associated advantages of being a drop-in replacement for LIBs, there are remarkable differences in the physicochemical properties between sodium and lithium that give rise to different behaviours, for example, different coordination preferences in compounds, desolvation energies, or solubility of the solid–electrolyte interphase inorganic salt components. This demands a more detailed study of the underlying physical and chemical processes occurring in sodium-ion batteries and allows great scope for groundbreaking advances in the field, from lab-scale to scale-up. This roadmap provides an extensive review by experts in academia and industry of the current state of the art in 2021 and the different research directions and strategies currently underway to improve the performance of sodium-ion batteries. The aim is to provide an opinion with respect to the current challenges and opportunities, from the fundamental properties to the practical applications of this technology.
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Jul 2021
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