I09-Surface and Interface Structural Analysis
I21-Resonant Inelastic X-ray Scattering (RIXS)
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A. S.
Menon
,
B. J.
Johnston
,
S. G.
Booth
,
L.
Zhang
,
K.
Kress
,
B. E.
Murdock
,
G.
Paez Fajardo
,
N. N.
Anthonisamy
,
N.
Tapia-Ruiz
,
S.
Agrestini
,
M.
Garcia-Fernandez
,
K.
Zhou
,
P. K.
Thakur
,
T. L.
Lee
,
A. J.
Nedoma
,
S. A.
Cussen
,
L. F. J.
Piper
Diamond Proposal Number(s):
[29104, 29113]
Open Access
Abstract: The desire to increase the energy density of stoichiometric layered
Li
TM
O
2
(TM = 3d transition metal) cathode materials has promoted investigation into their properties at high states of charge. Although there is increasing evidence for pronounced oxygen participation in the charge compensation mechanism, questions remain whether this is true
O
-redox, as observed in
Li
-excess cathodes. Through a high-resolution
O
K-edge resonant inelastic x-ray spectroscopy (RIXS) study of the
Mn
-free
Ni
-rich layered oxide
Li
Ni
0.98
W
0.02
O
2
, we demonstrate that the same oxidized oxygen environment exists in both
Li
-excess and non-
Li
-excess systems. The observation of identical RIXS loss features in both classes of compounds is remarkable given the differences in their crystallographic structure and delithiation pathways. This lack of a specific structural motif reveals the importance of electron correlation in the charge compensation mechanism for these systems and indicates how a better description of charge compensation in layered oxides is required to understand anionic redox for energy storage.
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Mar 2023
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B18-Core EXAFS
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Diamond Proposal Number(s):
[21847]
Open Access
Abstract: Here we report the synthesis via ceramic methods of the high-performance Mn-rich Na2.4Al0.4Mn2.6O7 oxygen-redox cathode material for Na-ion batteries which we use as a testbed material to study the effects of Al substitution and subsequent Na excess in the high-capacity, anionic redox-based cathode material Na2Mn3O7. The material shows a stable electrochemical performance, with a specific capacity of 200 mAh g-1 in the 1.5 - 4.7 voltage window at C/20 and capacity retention of 90 % after 40 cycles. Using a combination of electrochemical and structural analysis together with hybrid density functional theory calculations we explain the behaviour of this material with changes in Mn/anionic redox reactions and associated O2 release reactions occurring in the material during electrochemical cycling (Na insertion/extraction) and compare these findings to Na2Mn3O7. We expect that these results will advance understanding of the effect of dopants in Mn-rich cathode materials with oxygen redox activity to pave their way towards real applications in high-performing sodium-ion battery applications.
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Dec 2021
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B18-Core EXAFS
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Abstract: The recent report of P2–Na2/3Mg0.28Mn0.72O2 (P2-NMM) demonstrated the possibility of utilizing the oxygen redox couple in a layered oxide cathode without the need for alkali ions or vacancies in the transition metal layer. In this work, we report the synthesis of a new P2-type compound, Na2/3Mg1/4Mn7/12Co1/6O2 (P2-NMMC), which exhibits reversible specific capacities as high as 173 mAh g−1 and an improvement of the first cycle voltage hysteresis over P2-NMM. The material was characterised using a combination of ex-situ and operando techniques including X-ray diffraction (XRD), differential electrochemical mass spectrometry (DEMS) and X-ray spectroscopy (XAS) to identify potential sources for this improvement.
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Sep 2021
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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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Open Access
Abstract: Na2Ti3O7 (NTO) is considered a promising anode material for Na‐ion batteries due to its layered structure with an open framework and low and safe average operating voltage of 0.3 V vs. Na+/Na. However, its poor electronic conductivity needs to be addressed to make this material attractive for practical applications among other anode choices. Here, we report a safe, controllable and affordable method using urea that significantly improves the rate performance of NTO by producing surface defects such as oxygen vacancies and hydroxyl groups, and the secondary phase Na2Ti6O13. The enhanced electrochemical performance agrees with the higher Na+ ion diffusion coefficient, higher charge carrier density and reduced bandgap observed in these samples, without the need of nanosizing and/or complex synthetic strategies. A comprehensive study using a combination of diffraction, microscopic, spectroscopic and electrochemical techniques supported by computational studies based on DFT calculations, was carried out to understand the effects of this treatment on the surface, chemistry and electronic and charge storage properties of NTO. This study underscores the benefits of using urea as a strategy for enhancing the charge storage properties of NTO and thus, unfolding the potential of this material in practical energy storage applications.
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Feb 2021
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B18-Core EXAFS
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Abstract: We have presented a detailed investigation of the effects of Mg substitution on the structure, electrochemical performance and Na-ion diffusion in high voltage P2-type Na2/3Ni1/3-xMgxMn2/3O2 (0
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Mar 2018
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B18-Core EXAFS
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Urmimala
Maitra
,
Robert A.
House
,
James W.
Somerville
,
Nuria
Tapia-Ruiz
,
Juan G.
Lozano
,
Niccolo
Guerrini
,
Rong
Hao
,
Kun
Luo
,
Liyu
Jin
,
Miguel A.
Pérez-Osorio
,
Felix
Massel
,
David M.
Pickup
,
Silvia
Ramos
,
Xingye
Lu
,
Daniel E.
Mcnally
,
Alan V.
Chadwick
,
Feliciano
Giustino
,
Thorsten
Schmitt
,
Laurent C.
Duda
,
Matthew R.
Roberts
,
Peter G.
Bruce
Diamond Proposal Number(s):
[12559]
Abstract: The search for improved energy-storage materials has revealed Li- and Na-rich intercalation compounds to have promise as a new class of high-capacity cathodes. They exhibit capacities in excess of what would be expected from alkali-ion removal/reinsertion charge compensated by the transition-metal ions. The additional capacity is provided through charge compensation by oxygen-redox chemistry and some oxygen loss. It has been reported previously that O-redox occurs in O-2p orbitals that interact with alkali-ions in the transition-metal and alkali-ion layers (i.e. O-redox occurs in compounds containing Li+ - O2p - Li+ interactions). Na2/3[Mg0.28Mn0.72]O2 exhibits excess capacity; here we show this is also due to O-redox, despite Mg2+ residing in the transition-metal (TM) layers rather than alkali-metal ions, demonstrating that excess alkali-metal ions are not required to activate O-redox. We also show that unlike the alkali-rich compounds, Na2/3[Mg0.28Mn0.72]O2 does not lose O. Extraction of alkali ions from the alkali and TM layers in the alkali-rich compounds results in severely underbonded oxygen promoting oxygen loss, whereas Mg2+ remains in Na2/3[Mg0.28Mn0.72]O2 stabilising oxygen.
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Jan 2018
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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Previous work has shown that nanocrystalline samples of lithium tantalate and titanate prepared by high-energy milling show unusually high lithium ion conductivity. Here, we
report an X-ray absorption spectroscopy (XAS) study at the Ti K-edge and the Ta L3 edge of
samples that have been milled for various lengths of time. For both systems the results show that milling creates amorphous material whose quantity increases with the milling time. The
more extensive data for the tantalate shows that milling for only 30 minutes generates ~25%
amorphous content in the sample.
The content rises to ~60% after 16 hours. It is suggested that it is the motion of the lithium ions through the amorphous content that provides the mechanism for the high ionic conductivity.
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Feb 2017
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B18-Core EXAFS
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Kun
Luo
,
Matthew R.
Roberts
,
Niccoló
Guerrini
,
Nuria
Tapia-Ruiz
,
Rong
Hao
,
Felix
Massel
,
David M.
Pickup
,
Silvia
Ramos
,
Yi-Sheng
Liu
,
Jinghua
Guo
,
Alan V.
Chadwick
,
Laurent C.
Duda
,
Peter
Bruce
Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Conventional intercalation cathodes for lithium batteries store charge in redox reactions associated with the transition metal cations, e.g., Mn3+/4+ in LiMn2O4, and this limits the energy storage of Li-ion batteries. Compounds such as Li[Li0.2Ni0.2Mn0.6]O-2 exhibit a capacity to store charge in excess of the transition metal redox reactions. The additional capacity occurs at and above 4.5 V versus Li+/Li. The capacity at 4.5 V is dominated by oxidation of the O-2(-) anions accounting for similar to 0.43 e(-)/formula unit, with an additional 0.06 e(-)/formula unit being associated with O loss from the lattice. In contrast, the capacity above 4.5 V is mainly O loss, similar to 0.08 e(-)/formula. The O redox reaction involves the formation of localized hole states on O during charge, which are located on O coordinated by (Mn4+/Li+). The results have been obtained by combining operando electrochemical mass spec on 180 labeled Li[Li0.2Ni0.2Mn0.6]O-2 with XANES, soft X-ray spectroscopy, resonant inelastic X-ray spectroscopy, and Raman spectroscopy. Finally the general features of O redox are described with discussion about the role of comparatively ionic (less covalent) 3d metal oxygen interaction on anion redox in lithium rich cathode materials.
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Sep 2016
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B18-Core EXAFS
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Open Access
Abstract: Magnesium substituted P2-structure Na0.67Ni0.3Mn0.7O2 materials have been prepared by a facile solid-state method and investigated as cathodes in sodium-ion batteries. The Mg-doped materials described here were characterized by X-ray diffraction (XRD), 23Na solid-state nuclear magnetic resonance (SS-NMR), and scanning electron microscopy (SEM). The electrochemical performance of the samples was tested in half cells vs Na metal at room temperature. The Mg-doped materials operate at a high average voltage of ca. 3.3 V vs Na/Na+ delivering specific capacities of ∼120 mAh g–1, which remain stable up to 50 cycles. Mg doping suppresses the well-known P2–O2 phase transition observed in the undoped composition by stabilizing the reversible OP4 phase during charging (during Na removal). GITT measurements showed that the Na-ion mobility is improved by 2 orders of magnitude with respect to the parent P2–Na0.67Ni0.3Mn0.7O2 material. The fast Na-ion mobility may be the cause of the enhanced rate performance.
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Jul 2016
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