The main aim of this thesis is to reveal the chemical structures of the solid-liquid interphase in lithium ion batteries by NMR spectroscopy in order to understand the working mechanism of electrolyte additives for achieving stable cycling performance. In the first part, a combination of solution and solid-state NMR techniques, including dynamic nuclear polarization (DNP) are employed to monitor the formation of the solid electrolyte interphase (SEI) on next-generation, high-capacity Si anodes in conventional carbonate electrolytes with and without fluoroethylene carbonate (FEC) additives. A model system of silicon nanowire (SiNW) electrode is used to avoid interference from the polymeric binder. To facilitate characterization via one- and two-dimensional NMR, ^13C-enriched FEC was synthesized and used, ultimately allowing a detailed structural assignment of the organic SEI. FEC is found to first defluorinated to form soluble vinylene carbonate (VC) and vinoxyl species, which react to form both soluble and insoluble branched ethylene-oxide-based polymers. In the second part, the same methodology is applied to study the decomposition products of pure FEC or VC electrolytes containing 1 M LiPF_6. The pure FEC/VC system simplifies the electrolyte solvent formulation and avoids the interaction between different solvent molecules. Polymeric SEIs formed in pure FEC or VC electrolytes consist mainly of cross-linked PEO and aliphatic chain functionalities along with additional carbonate and carboxylate species. The presence of cross-linked PEO-type polymers in FEC and VC correlates with good capacity retention and high Coulombic efficiencies of the SiNWs anode. Using ^29Si DNP NMR, the interfacial region between SEI and the Si surface was probed for the first time with NMR spectroscopy. Organosiloxanes form upon cycling, confirming that some of the organic SEI is covalently bonded to the Si surface. It is suggested that both the polymeric structure of the SEI and the nature of its adhesion to the redox-active materials are important for electrochemical performance. Finally, the soluble decomposition products of EC formed during electrochemical cycling have been thoroughly analyzed by solution NMR and mass spectrometry, in order to explain the capacity-fading of Si anodes in a conventional EC-based electrolyte and address questions that arose when studying the additive-containing electrolytes. The detailed structures for the EC-degradation products are determined: a linear oligomer consist of ethylene oxide and carbonate units is observed as the major degradation product of EC.

Die Röntgenabsorptionsspektroskopie (XAS) ist eine element-spezifische Charakterisierungs-methode, welche es erlaubt die elektronische und chemische Struktur der SEI zu untersuchen. In dieser Arbeit stelle ich ein neues Verfahren vor, das die Transmissions-XAS von Flüssigkeiten und Dünnschicht-Batterieelektroden unter in-situ Bedingungen mit weicher Röntgenstrahlung ermöglicht. Thematisch ist die Arbeit in zwei Teile gegliedert. Das neuartige Verfahren wird zunächst umfangreich vorgestellt und dann zur Untersuchung der Solid Electrolyte Interphase (SEI) auf Silizium angewendet. Das Verfahren basiert auf einer elektrochemischen Halbzelle, die mit einem Stapel aus zwei Siliziumnitrid-Membranfenster ausgestattet ist, um den Elektrolyten einzuschließen. Eines der Membranfenster ist gleichzeitig der Träger für die Dünnschicht-Siliziumanode, die Ladezyklen mit einer Kathode aus metallischem Lithium durchläuft. Nachdem sich die SEI gebildet hat, wird mittels eines Röntgenstrahls von hoher Intensität vorsätzlich eine Blase erzeugt, um überschüssigen Elektrolyten abzudrängen und einen dünnen Elektrolytfilm über der SEI zu stabilisieren. Durch den Elektrolytfilm bleibt die SEI in-situ. Das erzeugte System aus Blase, Elektrolytfilm, SEI und Siliziumanode wird dann mittels Transmissions-XAS untersucht. Im zweiten Teil meiner Arbeit werden dann Silizium Dünnschicht-Anoden mit dem vorgestellten Verfahren am Elektronenspeicherring BESSY II in Berlin untersucht. Bei der elektrochemischen Charakterisierung zeigen die Dünnschicht-anoden alle für die De-/Lithiierung von Silizium üblichen Merkmale. Als Hauptbestandteile der SEI wurden Lithiumacetat, Li Ethylendicarbonat oder -monocarbonat, Li Acetylacetonat, LiOH und LiF ermittelt. Darüber hinaus deuten Anzeichen von Aldehyden auf flüssige Einschlüsse in einer möglich-erweise porösen SEI Struktur hin. / X-ray Absorption Spectroscopy (XAS) is an element-specific technique, which allows to probe the electronic and chemical structure of the SEI. In this work, I introduce a novel approach for transmission XAS on liquids and thin-film battery electrode materials under in-situ conditions in the soft X-ray regime. Thematically, this work is divided into two parts: 1) the introduction of this novel method and 2) its application to investigate the Solid Electrolyte Interphase (SEI) on silicon thin film anodes. The presented technique is based on an electrochemical half-cell equipped with a sandwich of two silicon nitride membrane windows to encapsulate the electrolyte. One of the membranes acts as substrate for the silicon thin-film anode, which is cycled with a metallic lithium counter-electrode. After the SEI has formed, a gas bubble is intentionally introduced through radiolysis by a high intensity X-ray to push out excessive electrolyte and stabilize a thin electrolyte layer on top of the SEI, keeping it in-situ. The obtained stack comprised of bubble, electrolyte thin-layer, SEI and anode, is then probed with transmission XAS. The second part of this work utilizes the presented method to investigate the SEI on amorphous silicon anodes at the BESSY II synchrotron facility in Berlin. The anodes’ electrochemical characterization shows all significant features of silicon’s de-/lithiation. The SEI’s main components are determined as Li acetate, Li ethylene di-carbonate or Li ethylene mono-carbonate, Li acetylacetonate, LiOH, and LiF. Additionally, the evidence for aldehyde species indicates possible liquid inclusions within a presumably porous SEI morphology.

abstract: This work investigates in-situ stress evolution of interfacial and bulk processes in electrochemical systems, and is divided into two projects. The first project examines the electrocapillarity of clean and CO-covered electrodes. It also investigates surface stress evolution during electro-oxidation of CO at Pt{111}, Ru/Pt{111} and Ru{0001} electrodes. The second project explores the evolution of bulk stress that occurs during intercalation (extraction) of lithium (Li) and formation of a solid electrolyte interphase during electrochemical reduction (oxidation) of Li at graphitic electrodes. Electrocapillarity measurements have shown that hydrogen and hydroxide adsorption are compressive on Pt{111}, Ru/Pt{111}, and Ru{0001}. The adsorption-induced surface stresses correlate strongly with adsorption charge. Electrocatalytic oxidation of CO on Pt{111} and Ru/Pt{111} gives a tensile surface stress. A numerical method was developed to separate both current and stress into background and active components. Applying this model to the CO oxidation signal on Ru{0001} gives a tensile surface stress and elucidates the rate limiting steps on all three electrodes. The enhanced catalysis of Ru/Pt{111} is confirmed to be bi-functional in nature: Ru provides adsorbed hydroxide to Pt allowing for rapid CO oxidation. The majority of Li-ion batteries have anodes consisting of graphite particles with polyvinylidene fluoride (PVDF) as binder. Intercalation of Li into graphite occurs in stages and produces anisotropic strains. As batteries have a fixed size and shape these strains are converted into mechanical stresses. Conventionally staging phenomena has been observed with X-ray diffraction and collaborated electrochemically with the potential. Work herein shows that staging is also clearly observed in stress. The Li staging potentials as measured by differential chronopotentiometry and stress are nearly identical. Relative peak heights of Li staging, as measured by these two techniques, are similar during reduction, but differ during oxidation due to non-linear stress relaxation phenomena. This stress relaxation appears to be due to homogenization of Li within graphite particles rather than viscous flow of the binder. The first Li reduction wave occurs simultaneously with formation of a passivating layer known as the solid electrolyte interphase (SEI). Preliminary experiments have shown the stress of SEI formation to be tensile (~+1.5 MPa). / Dissertation/Thesis / Deconvolution programm - see Appendix C / ECdata4 program - see Appendix C / Ph.D. Materials Science and Engineering 2011

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22456号 / 工博第4717号 / 新制||工||1737(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20000号 / 工博第4244号 / 新制||工||1657(附属図書館) / 33096 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The development and commercialization of alkali ion secondary batteries has played a critical role in the development of personal electronics and electric vehicles. The recent increase in demand for electric vehicles has pushed for lighter batteries with a higher energy density to reduce the weight of the vehicle while with an emphasis on improving the mile range. A resurgence has occurred in lithium, and sodium, metal anode research due to their high theoretical capacities, low densities, and low redox potentials. However, Li and Na metal anodes suffer from major safety issues and long-term cycling stability. This dissertation focuses on the investigation of the interfacial chemistries between alkali metal-carbon host interactions and the electrode-electrolyte interactions of the cathode and anode with boron-based electrolytes to establish design rules for "lean" alkali metal composite anodes and improve long-term stability to enable alkali metal batteries for practical electrochemical applications. Chapter 2 of this thesis focuses on the design and preliminary investigation of "lean" lithium-carbon nanofiber (<5 mAh cm-2) composite anodes in full cell testing using a LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode. We used the electrodeposition method to synthesize the Li-CNF composite anodes with a range of electrodeposition capacities and current densities and electrolyte formulations. Increasing the electrodeposition capacity improved the cycle life with 3 mAh cm-2 areal capacity and 2% vinylene carbonate (VC) electrolyte additive gave the best cycle life before reaching a state of "rapid cell failure". Increasing the electrodeposition rate reduced cycling stability and had a faster fade in capacity. The electrodeposition of lithium metal into a 2D graphite anode significantly improved cycle life, implying the increased crystallinity of the carbon substrate promotes improved anode stability and cycling capabilities. As the increased crystallinity of the carbon anode was shown to improve the "lean" composite anode's performance, Chapter 3 focuses on utilizing a CNF electrode designed with a higher degree of graphitization and probing the interacting mechanism of Li and Na with the CNF host. Characterization of the CNF properties found the material to be more reminiscent of hard carbon materials. Electrochemical analysis showed better long-term performance for Na-CNF symmetric cells. Kinetic analysis, using cyclic voltammetry (CV), revealed that Na ions successfully (de)intercalated within the CNF crystalline interlayers, while Li ions were limited to surface adsorption. A change in mechanism was quickly observed in the Na-CNF symmetric cycling from metal stripping/plating to ion intercalation/deintercalation, enabling the superior cycling stability of the composite anode. Improving the Na metal stability is necessary for enabling Na-CNF improved long-term performance. Sodium batteries have begun to garner more attention for grid storage applications due to their overall lower cost and less volumetric constraint required. However, sodium cathodes have poor electrode-electrolyte stability, leading to nanocracks in the cathode particles and transition metal dissolution. Chapter 4 focuses on electrolyte engineering with the boron salts sodium difluoro(oxolato)borate (NaDFOB) and sodium tetrafluoroborate (NaBF4) mixed together with sodium hexafluorophosphate (NaPF6) to improve the electrode-electrolyte compatibility and cathode particle stability. The electrolytes containing NaDFOB showed improved electrochemical stability at various temperatures, the formation of a more robust electrode-electrolyte interphase, and suppression in transition metal (TM) reduction and dissolution of the cathode particles measured after cycling. In Chapter 5, we focus on the electrochemical properties and the anode-electrolyte interfacial chemistry properties of the sodium borate salt electrolytes. Similar to Chapter 4, the NaDFOB containing electrolytes have improved electrochemical performance and stability. Following the same electrodeposition parameters as Chapter 2, we find the NaDFOB electrolytes improves the stability of electrodeposited Na metal and the "lean" composite anode's cyclability. This study suggests the great potential for the NaDFOB electrolytes for Na ion battery applications. / Doctor of Philosophy / The ever-increasing demand for high energy storage in personal electronics, electric vehicles, and grid energy storage has driven for research to safely enable alkali metal (Li and Na) anodes for practical energy storage applications. Key research efforts have focused on developing alkali metal composite anodes, as well as improving the electrode-electrolyte interfacial chemistries. A fundamental understanding of the electrode interactions with the electrolyte or host materials is necessary to progress towards safer batteries and better battery material design for long-term applications. Improving the interfacial interactions between the host-guest or electrode-electrolyte interfaces allows for more efficient charge transfer processes to occur, reduces interfacial resistance, and improves overall stability within the battery. As a result, there is great potential in understanding the host-guest and electrode-electrolyte interactions for the design of longer-lasting and safer batteries. This dissertation focuses on probing the interfacial chemistries of the battery materials to enable "lean" alkali metal composite anodes and improve electrode stability through electrolyte interactions. The anode-host interactions are first explored through preliminary design development for "lean" alkali composite anodes using carbon nanofiber (CNF) electrodes. The effect on increasing the crystallinity of the CNF host on the Li- and Na-CNF interactions for enhanced electrochemical performance and stability is then investigated. In an effort to improve the capabilities of Na batteries, the electrode-electrolyte interactions of the cathode- and anode-electrolyte interfacial chemistries using sodium borate salts are probed using electrochemical and X-ray analysis. Overall, this dissertation explores how the interfacial interactions affect, and improve, battery performance and stability. This work provides insights for understanding alkali metal-host and electrode-electrolyte properties and guidance for potential future research of the stabilization for Li- and Na-metal batteries.

Thesis advisor: Dunwei Wang / Thesis advisor: Matthias Waegele / Lithium metal anode (LMA) holds great promise as alternative anode material for next-generation high energy density batteries. Efficiency and safety are two most critical concerns that impede practical application of LMA due to unstable interface between the electrode and the electrolyte. Solid electrolyte interphase (SEI), a passivation layer formed from electrolyte decompositions on the LMA surface, dictates the chemical and mechanical evolution of the electrode/electrolyte interface, and therefore directly affect the cycle life of lithium metal batteries. Although significant progress has been achieved to improve battery performance, a thorough understanding of SEI functions and properties is still inadequate. Both compositional and structural complexity severely hinder the efforts to uncover the SEI formation and evolution mechanism. To achieve stable lithium plating and stripping over cycling, it is necessary to lay a foundation of composition-structure-property relationships that can guide rational design of ideal SEI.First, to solve the safety and efficiency issues simultaneously, a facile and effective way to enable LMA in nonflammable electrolyte was identified by simply introducing oxygen into the battery. Reversible lithium plating and stripping was realized in a flame retardant triethyl phosphate solvent otherwise incompatible to LMA. A unique electrochemically induced electrolyte decomposition pathway was proposed and studied computationally and experimentally. The SEI formation mechanism enriches the knowledge of on the complex reactions toward an ideal SEI. The operation of Li-O2 batteries and Li-ion batteries were also demonstrated in a nonflammable phosphate electrolyte system. To understand the unique role of different SEI compositions, in the second part of this thesis, we designed and synthesized two-component artificial SEI model structures for comparison study. Our central hypothesis is that tailoring LiF and Li3PO4 compositions in the SEI layer can achieve a balanced and improved electrode/electrolyte stability. A magnetron sputtering method was developed to prepare LiF and Li3PO4 mixture films on Cu substrate. Preliminary results from battery cycling tests shows that mixture SEI structure is correlated to improved Coulumbic efficiency. Next, to understand detailed Li+ ion transport properties of the SEI. We presented an outline the current understanding of Li+ ion transport mechanisms and their dependence on the SEI. We also built on this fundamental knowledge to discuss practical effects in experimental systems. Lastly, we shared our perspectives on critical remaining questions in this field. In parallel to study on electrochemical energy system, developing electrochemical methods for integrated catalysis constitutes another part of thesis. We demonstrated that reactivity of an immobilized iron catalyst could be altered by application of an electrochemical potential to a surface to enable polymerization of different classes of monomers. A method was developed to pattern functional surfaces by using electrochemical potential to activate and deactivate polymerization reactions. The orthogonal reactivity of switchable polymerization catalysts was utilized to create patterned surfaces functionalized with two different polymers initiated from mixtures of monomers. / Thesis (PhD) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

La miniaturisation des appareils électroniques et la multiplication de leurs fonctionnalités conduisent à développer des microsources d’énergie adaptées, parmi lesquelles figurent les microbatteries au lithium. Malgré leurs excellentes performances, ces systèmes de stockage électrochimique tout solide restent toutefois limités en termes de capacité surfacique. Cette caractéristique étant intrinsèquement liée aux matériaux d’électrodes, nous avons choisi de nous intéresser à des couches minces de CuO, dont la capacité volumique théorique (426 µAh .cm-2.µm-1) est sensiblement plus élevée que celle des matériaux d’intercalation utilisés jusqu’à présent. Ce matériau réagit avec le lithium selon un mécanisme particulier, dit de conversion, qui induit la formation d’un système multiphasé et nanostructuré d’une grande complexité. Dans le cadre de ce travail, la compréhension des mécanismes électrochimiques et chimiques mis en jeu au cours du cyclage de couches minces d’oxyde de cuivre (CuO) a été l’objectif majeur. Celui-ci a nécessité une caractérisation fine du matériau actif d’électrode et des interfaces générées (interfaces solide/solide et interface solide/électrolyte). Ces études ont été principalement menées à partir de la Spectroscopie Photoélectronique à Rayonnement X (XPS), de la Microscopie à Force Atomique (AFM) et d’une modélisation théorique exploitant les méthodes de la chimie quantique. Les propriétés chimiques et morphologiques des couches minces de CuO cyclées ont été corrélées à leur comportement électrochimique. Une forte influence de leur structure et de leur morphologie initiales a pu être ainsi mise en évidence / The miniaturization of electronic components and the increasing number of their functionalities lead to the development of suitable energy microsources, among which lithium microbatteries appear. Despite the excellent performances of these all-solid-state electrochemical power sources, one main limitation that remains is their surface capacity. Its value being intrinsically connected to the nature of electrode materials, we chose to focus on CuO thin films which are characterized by a theoretical volumetric capacity (426 µAh .cm-2.µm-1) in far larger than the one of conventional intercalation materials used today. Indeed, this material reacts with lithium according to a particular mechanism, referred as conversion reaction, inducing the formation of a multiphase nanostructured system with a high complexity. In the framework of this study, understanding of electrochemical and chemical mechanisms which take place during the cycling of copper oxide thin films (CuO) was the main objective. This one has required a fine characterization of the electrode active material and the generated interfaces (solid/solid interfaces and solid/electrolyte interface). These studies have been mainly carried out with X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and theoretical approaches based on quantum chemistry methods. The chemical and morphological properties of the cycled CuO thin films have been linked to their electrochemical behavior. An important influence of their initial structure and morphology was then evidenced.

The stability of electrode/electrolyte interfaces in Li-ion batteries is crucial to the performance, lifetime and safety of the entire battery system. In this work, interface processes have been studied in LiFePO4/graphite Li-ion battery cells.  The first part has focused on improving photoelectron spectroscopy (PES) methodology for making post-mortem battery analyses. Exposure of cycled electrodes to air was shown to influence the surface chemistry of the graphite. A combination of synchrotron and in-house PES has facilitated non-destructive interface depth profiling from the outermost surfaces into the electrode bulk. A better understanding of the chemistry taking place at the anode and cathode interfaces has been achieved. The solid electrolyte interphase (SEI) on a graphite anode was found to be thicker and more inhomogeneous than films formed on cathodes. Dynamic changes in the SEI on cycling and accumulation of lithium close to the carbon surface have been observed.    Two electrolyte additives have also been studied: a film-forming additive propargyl methanesulfonate (PMS) and a flame retardant triphenyl phosphate (TPP). A detailed study was made at ambient and elevated temperature (21 and 60 °C) of interface aging for anodes and cathodes cycled with and without the PMS additive. PMS improved cell capacity retention at both temperatures. Higher SEI stability, relatively constant thickness and lower loss of cyclable lithium are suggested as the main reasons for better cell performance. PMS was also shown to influence the chemical composition on the cathode surface. The TPP flame retardant was shown to be unsuitable for high power applications. Low TPP concentrations had only a minor impact on electrolyte flammability, while larger amounts led to a significant increase in cell polarization. TPP was also shown to influence the interface chemistry at both electrodes. Although the additives studied here may not be the final solution for improved lifetime and safety of commercial batteries, increased understanding has been achieved of the degradation mechanisms in Li-ion cells. A better understanding of interface processes is of vital importance for the future development of safer and more reliable Li-ion batteries.

Lithium Ion Batteries (LIBs) are important in today's society, powering cars and mobile devices. LIBs consist of a negative anode commonly made of graphite, and a positive cathode commonly made from transition metal oxides. Between these electrodes are separators and organic solvent based electrolyte. Due to the high potential of LIBs the electrolyte is reduced at the anode. The electrolyte reduction results in the formation of a layer called the Solid Electrolyte Interphase (SEI), which prohibits the further breakdown of the electrolyte. Despite being researched for over50 years, the composition formation of the SEI is still poorly understood. The aim of this project is to develop strategies for efficient identification and classification of various active and intermediate components in the SEI, to, in turn, gain an understanding of the reactions taking place, which will help find routes to stabilize and tailor the composition of the SEI layer for long-term stability and optimal battery performance. For a model gold/li-ion battery electrolyte system, Raman spectra will be obtained using Surface Enhanced Raman Spectroscopy (SERS) in a spectroelectrochemical application where the voltage of the working gold electrode is swept from high to low potentials. Spectra of common components of the SEI as well as similar compounds will be simulated using Density Functional Theory (DFT). The DFT data is also used to calculate the spontaneity of reactions speculated to form the SEI. The simulated data will be validated by comparing it to experimental spectra from pure substances. The spectroelectrochemical SERS results show a clear formation of Li-carbonate at the SERS substrate, as well as the decomposition of the electrolyte into other species, according to the simulated data. It is however shown that there are several issues when modelling spectra, that makes it harder to correlate the simulated spectra with the spectroelectrochemical spectra. These issues include limited knowledge of the structure of the compounds thought to form on the anode surface, and incorrect choices in simulational parameters. To solve these issues, more work is needed in these areas, and the spectroelectrochemical methods used in this thesis needs to be combined with other experimental methods to narrow down the amount of compounds to be modelled. More work is also needed to avoid impurities in the electrolyte. Impurities leads to a thick inorganic layer which prohibits the observation of species in the organic layer.