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Elucidating the Step‐Wise Solid Electrolyte Interphase Formation in Lithium‐Ion Batteries with Operando Raman Spectroscopy
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0002-0481-5544
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0001-6691-6706
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Structural Chemistry.ORCID iD: 0000-0001-5653-0383
2022 (English)In: Advanced Materials Interfaces, ISSN 2196-7350, Vol. 9, no 22, article id 2200945Article in journal (Refereed) Published
Abstract [en]

The solid electrolyte interphase (SEI) is arguably one of the most critical components of the Li-ion cell. Despite decades of studies of the SEI, its intrinsic complexity and the lack of suitable characterization tools still prevent a real consensus on the governing mechanisms to be reached. Herein, operando Raman spectroscopy supported by complimentary online electrochemical mass spectrometry is employed to study the SEI formation on Au in a model electrolyte based on LiClO4 in ethylene carbonate (EC). Both the electrolyte itself and cell contaminants, such as O2, CO2, and H2O, contribute in stepwise electro-/chemical processes to the build-up of the SEI. Effects associated with electrode/electrolyte double-layer charging, electrode adsorbate polarization (stark effect), and SEI dissolution are discerned. Lithium carbonate and lithium oxide are identified as major products formed already ≈2 V versus Li+/Li. Although Raman spectroscopy provides deeper insights into the underlying mechanisms, complementary techniques are necessary to support spectral interpretations. Classical challenges in the field of surface science, such as contaminations, have to be systematically addressed if the puzzle of the SEI ever will be completed.

Place, publisher, year, edition, pages
John Wiley & Sons, 2022. Vol. 9, no 22, article id 2200945
Keywords [en]
interphases, Li-ion batteries, operando, Raman, solid electrolyte interphase, SERS
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-480332DOI: 10.1002/admi.202200945ISI: 000823854500001OAI: oai:DiVA.org:uu-480332DiVA, id: diva2:1682402
Funder
Swedish Research Council, 2016‐04069Knut and Alice Wallenberg Foundation, 2017.0204Swedish Foundation for Strategic Research, FFL18-0269StandUpAvailable from: 2022-07-09 Created: 2022-07-09 Last updated: 2024-02-14Bibliographically approved
In thesis
1. Elucidating Chemical and Electrochemical Side-Reaction Mechanisms in Li-ion Batteries
Open this publication in new window or tab >>Elucidating Chemical and Electrochemical Side-Reaction Mechanisms in Li-ion Batteries
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Lithium-ion batteries constitute a leading technology that plays a major role in the transition towards sustainable transportation and power generation. The stability of modern batteries relies on a passivation layer formed on the negative electrode known as the solid electrolyte interphase (SEI). Despite concerted efforts to comprehend the various processes taking place during SEI formation, monitoring the reaction pathways in real-time is still very challenging. This is due to the complex interactions within the multicomponent electrochemical system, aggravated by the wide range of electrolyte compositions, electrode materials, and operating conditions.

In this thesis, operando surface enhanced Raman spectroscopy is explored to elucidate the progressive formation of the SEI on the negative electrode surface when the electrode is negatively polarised in a spectro-electrochemical cell. Complementary online-electrochemical mass spectrometry is employed to identify the associated gaseous products formed during the process. The work illustrates that the electrolyte as well as contaminants, such as O2, CO2, and H2O, contribute in electro-/chemical processes that build up the SEI. The thesis then explores reaction pathways involving a SEI-forming electrolyte additive, namely vinylene carbonate (VC), emphasizing its role as a H2O scavenging agent. In comparison to the conventional electrolyte solvent ethylene carbonate, VC exhibits a faster reaction with water impurities, particularly in presence of hydroxide ions. This results in the formation of products that are less likely to impact cell performance.

In the later part, the thesis delves into understanding the stability of electrolyte in an environment of Lewis bases (LB) typically found in the SEI. For that, individual LB (e.g., OH- and OCH3-) are mixed with typical carbonate-based solvents and the products formed as a result of the reaction are analysed. Furthermore, tris(trimethylsilyl)phosphate (TMSPa), a representative of the silyl-functionalised electrolyte additive and known for its reactivity, especially towards fluorides, is used as a means to chemically probe its reactivity towards several LB residues. This investigation aims to establish a more simplified and generally applicable reaction mechanism thereof. The products that are soluble in the electrolyte have been investigated by nuclear magnetic resonance spectroscopy and those in the gas phase is characterised by mass spectrometry. The work highlights that the residues that remain active even after the SEI formation may lead to unwanted side-reactions.

The thesis contributes to a deeper fundamental understanding of the myriad of processes that take place in batteries during SEI formation providing insights crucial for designing next-generation battery materials.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2024. p. 77
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 2365
Keywords
Lithium-ion battery, solid electrolyte interphase, electrolyte additives, reaction mechanism, ethylene carbonate, vinylene carbonate, tris(trimethylsilyl)phosphate, surface enhanced Raman spectroscopy
National Category
Materials Chemistry
Research subject
Chemistry with specialization in Materials Chemistry
Identifiers
urn:nbn:se:uu:diva-523121 (URN)978-91-513-2037-3 (ISBN)
Public defence
2024-04-05, Polhemsalen, Ångströmslaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Opponent
Supervisors
Available from: 2024-03-13 Created: 2024-02-14 Last updated: 2024-03-13

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Gogoi, NeehaMelin, TimBerg, Erik J.

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