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Resonant inelastic X-ray scattering and X-ray absorption spectroscopy on the negative electrode material Li0.5Ni0.25TiOPO4 in a Li-ion battery
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Soft X-Ray Physics. (Mjukröntgenfysik, Soft X-Ray Physics)
ECME, FST Marrakech, University Cadi Ayyad, BP549, Av. A. Khattabi, Marrakech, Morocco.
ECME, FST Marrakech, University Cadi Ayyad, BP549, Av. A. Khattabi, Marrakech, Morocco.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry.
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2011 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 13, no 14, 6544-6551 p.Article in journal (Refereed) Published
Abstract [en]

We have studied the first lithiation/delithiation cycle of the Li-ion battery electrode material LixNi0.25TiOPO4 applying X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). A set of ten identical LixNi0.25TiOPO4 battery electrodes have been cycled and left in different states of charge in the range of x = 0.5 … 2.5, before disassembly in an Ar filled glove box. We find that Ni-, Ti-, and O-ions are affected simultaneously, rather than sequentially, upon lithiation of the material. In particular, Ni is reduced from Ni2+ to Ni0 but only partially re-oxidized to Ni1+, again, by delithiation. Overall, there is considerable “crosstalk” between the different atomic species and non-linearity in the response of the electronic structure during the lithiation/delithiation process. Fortuitously, the background variation in Ni L-XAS shows to contain valuable information about solid–electrolyte interface (SEI) creation, showing that the SEI is a function of the degree of lithiation.

Place, publisher, year, edition, pages
2011. Vol. 13, no 14, 6544-6551 p.
Keyword [en]
Valence number, Soft X-ray spectroscopy, Li-ion battery, RIXS
National Category
Atom and Molecular Physics and Optics Inorganic Chemistry
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics; Chemistry with specialization in Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-149316DOI: 10.1039/C0CP02668AISI: 000288678900017OAI: oai:DiVA.org:uu-149316DiVA: diva2:404517
Available from: 2011-03-17 Created: 2011-03-17 Last updated: 2017-12-11Bibliographically approved
In thesis
1. Redox Reactions in Li-ion Battery Cycling and in Cu Corrosion Studied by Soft X-ray Spectroscopy
Open this publication in new window or tab >>Redox Reactions in Li-ion Battery Cycling and in Cu Corrosion Studied by Soft X-ray Spectroscopy
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The topic of this thesis is redox reactions in two technologically important contexts: firstly, in Li-ion battery electrodes during cycling, and secondly, in copper corrosion in oxygen-free ground water containing sulfide. In an attempt to expand the understanding of the charge uptake process in battery electrodes and the chemical reactions on copper surfaces upon sulfide exposure, soft X-ray spectroscopy has been used to study the electronic structure of these systems.

To ascertain the changes in electron density at different atomic sites in a battery electrode material, both X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) have been applied to different electrode materials. This thesis explains in detail the assembling procedure, cycling, and situ sample preparation of the battery materials. Furthermore, two different designs used in in situ experiments for study of batteries during cycling are also discussed.

The main result from the Li-ion battery materials is the justification to abandon the view of valences as integers. This is true for all battery electrodes examined in this thesis. Generally, oxygen plays a more important role in the charge uptake than commonly assumed, but also the transition metals and other species apart from expected behavior. In LiMnPO4, even the notion of Li as strictly Li+ must be questioned.

Copper is intended to act as a corrosion barrier in a nuclear waste repository. In the corrosion experiments presented in this thesis, different copper oxides were exposed to the conditions present at the planned repository site, with exception for the concentration of sulfide, which was greatly increased.

The conclusion from these experiments is that sulfide effectively reduces Cu(II) oxide to Cu(I) compounds and possibly forms a compound containing both oxygen and sulfur. Also, the thickness and inhomogeneity of the copper oxide surface layers are of great importance for the corrosion mechanisms, including passivation.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2011. 69 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 812
National Category
Physical Sciences
Identifiers
urn:nbn:se:uu:diva-148396 (URN)978-91-554-8036-3 (ISBN)
Public defence
2011-05-06, room 2001, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
Opponent
Supervisors
Available from: 2011-04-14 Created: 2011-03-05 Last updated: 2011-05-05Bibliographically approved

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Hollmark, HåkanGustafsson, TorbjörnEdström, Kristina

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