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Insights into Li-ion Battery and Stainless Steel Interfaces Using Refined Photoelectron Spectroscopy Methodology
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

If sacrificing some of its material to form a passivating layer at the surface, materials may expand the range of environments where they can be used and further material degradation can decrease. This thesis aims to contribute with insights into passivating layers on especially Li-ion battery anodes (solid electrolyte interphase, SEI) but also on stainless steels, as well as the non-passivating Li-ion battery cathode/electrolyte interface layers (solid permeable interface, SPI). The studies have been performed using new possibilities offered by photoelectron spectroscopy techniques.

Depth gradients in the SEI and SPI layers were studied by combining synchrotron-based hard and soft X-ray photoelectron spectroscopy (HAXPES and SOXPES), which was further developed for Li-ion battery investigations. Stainless steel depth profiles were acquired combining HAXPES with angle resolved X-ray photoelectron spectroscopy (ARXPS).

In the Li-ion battery, organic species were more common in the outermost SEI, while some inorganic compounds were only detected in the more bulk sensitive measurements. No depth gradients were observed in the SPI. The interface between the graphite and the SEI was studied for the first time indicating lithium enrichment at the graphite surface. Furthermore, the influence of the film-forming additive propargyl methanesulphonate (PMS) on the electrode/electrolyte interfaces was studies, and cells cycled to end of life at 22°C and 55°C were compared.

For stainless steels, the thicknesses of the oxide film as well as the nickel enriched metal layer underneath the oxide were determined. A similar methodology was applied to estimate the Li-ion battery SEI thickness.

Finally, experiences from PES methodology work on the Li-ion battery systems are discussed aiming to facilitate further studies of the experimentally challenging electrochemically modified samples.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2013. , 69 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1031
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-197153ISBN: 978-91-554-8624-2 (print)OAI: oai:DiVA.org:uu-197153DiVA: diva2:611762
Public defence
2013-05-03, Häggsalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2013-04-12 Created: 2013-03-18 Last updated: 2013-08-30Bibliographically approved
List of papers
1. Comparing anode and cathode electrode/electrolyte interface composition and morphology using soft and hard X-ray photoelectron spectroscopy
Open this publication in new window or tab >>Comparing anode and cathode electrode/electrolyte interface composition and morphology using soft and hard X-ray photoelectron spectroscopy
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2013 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 97, 23-32 p.Article in journal (Refereed) Published
Abstract [en]

Electrode/electrolyte interface depth profiling was performed on lithiated graphite and delithiated lithium iron phosphate electrodes after electrochemical cycling in a balanced full cell configuration containing a carbonate based LiPF6 electrolyte. The profiling was performed by synchrotron radiation based hard X‑ray photoelectron spectroscopy, HAXPES, and soft X‑ray photoelectron spectroscopy, SOXPES. In this way, the probing depth was varied over a wide range in the order of 2-50 nm. Both more surface and more bulk sensitive investigations than possible using traditional in-house X‑ray photoelectron spectroscopy (XPS) could thus be performed. The composition and morphology of the lithiated graphite anode/electrolyte interface (solid electrolyte interphase, SEI) and the delithiated lithium iron phosphate cathode/electrolyte interface (solid permeable interface, SPI) were compared. In the vicinity of the highly reductive graphite active material in the SEI, low binding energy components like Li2O were found while no obvious composition gradients were observed in the SPI. Both in the cathode SPI and the anode SEI, significant amounts of C-O and P‑F containing compounds were found to deposit during cycling. Evidence for mixing of the porous binder and other SEI/SPI components was observed in both the anode and cathode electrode/electrolyte interfaces. The lithiated graphite SEI was estimated to be of the order of two tens of nanometers, while the cathode SPI thickness was estimated to a few nanometers only. 

National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-196469 (URN)10.1016/j.electacta.2013.03.010 (DOI)000319024500004 ()
Available from: 2013-03-08 Created: 2013-03-08 Last updated: 2017-12-06
2. Consequences of Air Exposure on the Lithiated Graphite SEI
Open this publication in new window or tab >>Consequences of Air Exposure on the Lithiated Graphite SEI
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2013 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 105, 83-91 p.Article in journal (Refereed) Published
Abstract [en]

In the present work, consequences of air exposure on the surface composition of one of the most reactive lithium-ion battery components, the lithiated graphite, was investigated using 280–835 eV soft X-ray photoelectron spectroscopy (SOXPES) as well as 1486.7 eV X-ray photoelectron spectroscopy (XPS) (∼2 and ∼10 nm probing depth, respectively). Different depth regions of the solid electrolyte interphase (SEI) of graphite cycled vs. LiFePO4 were thereby examined. Furthermore, the air sensitivity of samples subject to four different combinations of pre-treatments (washed/unwashed and exposed to air before or after vacuum treatment) was explored. The samples showed important changes after exposure to air, which were found to be largely dependent on sample pre-treatment. Changes after exposure of unwashed samples exposed before vacuum treatment were attributed to reactions involving volatile species. On washed, air exposed samples, as well as unwashed samples exposed after vacuum treatment, effects attributed to lithium hydroxide formation in the innermost SEI were observed and suggested to be associated with partial delithiation of the surface region of the lithiated graphite electrode. Moreover, effects that can be attributed to LiPF6 decomposition were observed. However, these effects were less pronounced than those attributed to reactions involving solvent species and the lithiated graphite.

Place, publisher, year, edition, pages
Elsevier, 2013
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-196470 (URN)10.1016/j.electacta.2013.04.118 (DOI)
Available from: 2013-03-08 Created: 2013-03-08 Last updated: 2017-12-06
3. Comparing Aging of MCMB Graphite/LiFePO4 cells at 22°C and 55°C. Electrochemical and Photoelectron Spectroscopy Studies.
Open this publication in new window or tab >>Comparing Aging of MCMB Graphite/LiFePO4 cells at 22°C and 55°C. Electrochemical and Photoelectron Spectroscopy Studies.
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(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-196471 (URN)
Available from: 2013-03-08 Created: 2013-03-08 Last updated: 2013-08-30
4. The buried graphite/SEI interface studied by hard X-ray photoelectron spectroscopy
Open this publication in new window or tab >>The buried graphite/SEI interface studied by hard X-ray photoelectron spectroscopy
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(English)Manuscript (preprint) (Other academic)
National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-197112 (URN)
Available from: 2013-03-18 Created: 2013-03-18 Last updated: 2016-04-20
5. The influence of PMS-additive on the electrode/electrolyte interfaces in LiFePO4/graphite Li-ion batteries
Open this publication in new window or tab >>The influence of PMS-additive on the electrode/electrolyte interfaces in LiFePO4/graphite Li-ion batteries
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2013 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 45, 23476-23486 p.Article in journal (Refereed) Published
Abstract [en]

The influence of a film-forming additive, propargyl methanesulfonate (PMS), on electrochemical performance and electrode/electrolyte interface composition of LiFePO4/graphite Li-ion batteries has been studied. Combined use of in-house X-ray photoelectron spectroscopy (XPS) and soft and hard X-ray photoelectron spectroscopy (PES) enabled nondestructive depth profiling at four different probing depths in the 2-50 nm range. Cells cycled with PMS and LiPF6 in ethylene carbonate/diethyl carbonate (EC/DEC) were compared to a reference sample cycled without PMS. In the first cycle, PMS cells showed a higher irreversible capacity, which is explained by formation of a thicker solid electrolyte interphase (SEI). After three cycles, the SET thicknesses were determined to be 19 and 25 nm for the reference and PMS samples, respectively. After the initial cycling, irreversible losses shown by the PMS cells were lower than those of the reference cell. This could be attributed to a different SET composition and lower differences in the amount of lithium between lithiated and delithiated electrodes for the PMS sample. It was suggested that PMS forms a triple-bonded radical on reduction, which further reacts with the electrolyte. The PMS additive was shown to influence the chemical composition at the positive electrode/electrolyte interface. Thicker interface layers with higher C-O and smaller LiF contributions were formed on LiFePO4 cycled with PMS.

National Category
Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-197151 (URN)10.1021/jp4045385 (DOI)000327110500005 ()
Available from: 2013-03-18 Created: 2013-03-18 Last updated: 2017-12-06
6. Quantifying the Metal Nickel Enrichment on Stainless Steel
Open this publication in new window or tab >>Quantifying the Metal Nickel Enrichment on Stainless Steel
2011 (English)In: Electrochemical and solid-state letters, ISSN 1099-0062, E-ISSN 1944-8775, Vol. 14, no 1, C1-C3 p.Article in journal (Refereed) Published
Abstract [en]

Enrichment in metallic nickel below the passive film on a stainless steel was quantified using the novel HIgh Kinetic Energy Photo-Electron Spectroscopy technique. Two surfaces were tested: one passivated in air and one polarized to the mid passive region in 0.5 M H2SO4. Primary beam energies ranging from 2 to 6 keV were used to determine the thickness of the nickel-enriched layer to 0.55 nm with a Ni content of 70%.

National Category
Engineering and Technology Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-139409 (URN)10.1149/1.3509122 (DOI)000284317600006 ()
Available from: 2010-12-23 Created: 2010-12-23 Last updated: 2017-12-11Bibliographically approved
7. Full depth profile of passive films on 316L stainless steel based on high resolution HAXPES in combination with ARXPS
Open this publication in new window or tab >>Full depth profile of passive films on 316L stainless steel based on high resolution HAXPES in combination with ARXPS
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2012 (English)In: Applied Surface Science, ISSN 0169-4332, E-ISSN 1873-5584, Vol. 258, no 15, 5790-5797 p.Article in journal (Refereed) Published
Abstract [en]

Depth profiles of the passive films on stainless steel were based on analysis with the non-destructive hard X-ray photoelectron spectroscopy (HAXPES) technique in combination with the angular resolved X-ray photoelectron spectroscopy (ARXPS). The analysis depth with ARXPS is within the passive film thickness, while the HAXPES technique uses higher excitation energies (between 2 and 12 keV) also non-destructively probing the chemical content underneath the film. Depth profiles were done within and underneath the passive film of 316L polarized in acidic solution. The passive film thickness was estimated to 2.6 nm for a sample that was polarized at 0.6 V and the main component in the passive film is, as expected, chromium. From the high resolution HAXPES spectra we suggest chromium in three different oxidation states present. Also for iron three oxides were detected. Gradients of chromium and iron concentrations and oxidation states within the film and an enrichment of nickel within a 0.5 nm layer directly underneath the passive film are some of the results discussed. 

Keyword
Stainless steel, XPS, HAXPES, Passive film
National Category
Inorganic Chemistry
Research subject
Chemistry with specialization in Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-173615 (URN)10.1016/j.apsusc.2012.02.099 (DOI)000302135700044 ()
Funder
StandUp
Available from: 2012-05-09 Created: 2012-05-02 Last updated: 2017-12-07Bibliographically approved

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