Cette thèse a pour but de développer des matériaux de cathode pour le Mg-Ion. Après avoir sélectionné l’électrolyte et les conditions de caractérisations électrochimiques, deux familles de matériau d’insertion ont été étudiées : les phases de Chevrel et les dioxydes de manganèse.Les phases de Chevrel Mo6S8 et Mo6Se8 ont été l’objet d’une étude de compréhension couplant électrochimie et analyse XPS ex situ. Les deux phases ont ainsi été caractérisées par voltampérométrie, GITT et PITT donnant des coefficients de diffusion de l’ordre de 10-11 à 10-14 cm2.s-1. Des mécanismes d’oxydoréduction non conventionnels ont été observés par analyse XPS indiquant un transfert de charge au niveau de l’anion en plus de la réduction des métaux de transition. La comparaison des deux matériaux Mo6S8 et Mo6Se8 indique que le soufre participe d’avantage au transfert de charge que le sélénium.Dans le second volet une étude comparative est menée sur deux structures prometteuses du MnO2, la hollandite et la birnessite. Il a été mis en évidence qu’une hydratation de l’électrolyte est nécessaire pour permettre l’insertion des ions Mg2+ dans les différentes structures de MnO2. Des analyses par RMN 1H et XPS ont ainsi révélé un phénomène de co-insertion des cations Mg2+ et des molécules d’eau. Cependant la cyclabilité de ces composés reste limitée et des capacités irréversibles de 50 à 80% sont mesurées. Ces travaux de compréhension sont cependant un premier pas pour la conception de nouveaux matériaux d’insertion réversibles pour les accumulateurs Mg-Ion. / This PhD thesis aims to develop Mg-Ion cathode materials. Once the electrolyte selected and the electrochemical characterization system established, two insertion materials families were studied: Chevrel phases and manganese dioxides.The Chevrel phases Mo6S8 and Mo6Se8 have been the subject of a coupled electrochemistry / XPS ex situ understanding study. The two phases were characterized by voltammetry, GITT and PITT showing diffusion coefficients ranging from 10-11 to 10-14 cm2.s-1. Unconventional redox mechanisms were observed by XPS studies indicating a charge transfer inside the anions in addition to the reduction of the transition metals. The comparison of the two materials Mo6S8 and Mo6Se8 indicates the sulfur is more involved in the charge transfer than the selenium.In the second part, two MnO2 promising structures have been selected and studied: hollandite and birnessite. We evidenced that electrolyte hydratation is needed to allow the insertion inside the different MnO2 structures. RMN 1H and XPS analyses revealed a co-insertion phenomenon involving Mg2+ cations and H2O molecules. However, these compounds exhibit a poor cyclability and irreversible capacities of 50% to 80%. This understanding work is a first step towards the design of new reversible insertion materials for Mg-Ion batteries.

abstract: Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates. / Dissertation/Thesis / M.S. Materials Science and Engineering 2013

<p>  The interfacial reactions of the electrolytes at the electrode-electrolyte interface determine critical properties of the battery chemistries including the reaction reversibility, kinetic, and thermal stability etc. Rationally designing the solvation structure of the liquid electrolytes is paramount in altering their interfacial behaviors and achieving desirable battery performance. This thesis aims to provide fundamental understandings to the electrolyte solvation structure design in its correlations to the battery interphase stability and formation mechanism, interfacial desolvation kinetic, and thermal stability, providing strategies to build next-generation secondary batteries with improved energy density, wide-temperature capability, and thermal safety. </p> <p>Developing high-voltage lithium metal battery (LMB) with metallic Li anode and nickel-rich metal oxide cathode is a feasible approach to enhance the battery energy density. However, inferior interfacial stabilities of conventional electrolytes towards highly reductive anode and oxidative cathode cause severe parasitic reactions. This thesis investigates the solvation structures of ether-based electrolytes and their interfacial decomposition pathways to selectively control the solid electrolyte interphase (SEI) composition. Combined theoretical and experimental studies demonstrate that lessening the coordination strength of the solvent molecules can improve the ion aggregating degrees in the solvation shell and preferentially promote the anion decomposition. Detailed surficial characterizations identify that weakly-solvating electrolytes generate robust SEIs with enriched inorganic components on anode and cathode surface, which kinetically prohibits parasitic reactions. The strategy successfully facilitates the long-term cycling of high energy LMBs. Weakening the solvent coordination ability is also identified effective to promote the desolvation kinetic and realize high battery energy retention at low temperatures.</p> <p>The approach of tailoring ion-pairing behavior to achieve stabilized electrode-electrolyte interface is further validated in multivalent battery systems such as Magnesium-ion batteries (MIBs). Multivalent cations like Mg2+ and Zn2+ possess high electron density which results in strong coordination to solvent molecules and hindered desolvation process. They usually induce large reaction overpotential and low efficiency. The methoxy-amine-based electrolytes for MIBs are selected in terms of elucidating their interfacial failure mechanism and the solvation structure-dependent reaction stabilities with Mg metal anode. The study reveals an unknown amine solvent dehydrogenation mechanism that compromises the Mg anode stability. The tight coordination between solvent amine group (-NH2) and cation causes its direct reduction with H2 release. The dehydrogenation products tend to diffuse into the liquid electrolyte phase, which promotes the interfacial electrolyte decay. This work also demonstrates the approach to strengthen the solvent molecule stabilities via restructuring the Mg2+ solvation shell. Introducing anion coordination to Mg2+ can effectively relief the amine-cation interaction and suppress its reduction. As the result, hundreds of stable cycling from Mg metal anode with more than 99.6 % efficiency is achieved.</p> <p>Finally, the thermal stability of electrolytes featuring various solvation structures are studied in LMBs via quantitative thermal analysis and surficial characterization techniques. The thermal runaway of batteries which is known to be initiated via SEI decomposition and propagated by exothermic electrode-electrolyte reactions exhibit great dependence on the solvation structures of the liquid electrolytes. The results suggest that strong solvent-coordinating electrolytes with solvent-separated ion pair structures are prone to exothermic reduction decompositions. While the organic-rich SEI tends to decompose at low temperatures and initiate thermal runaway easily. Therefore, designing electrolytes with anion involved solvation shells that generate inorganic SEI can effectively mitigate the thermal runaway behavior. Supplementary research focusing on the thermal safety of Potassium-ion battery also indicates the critical role of SEI stability on the overall battery safety aspect, which is governed by the electrolyte composition.</p>

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第18607号 / エネ博第303号 / 新制||エネ||62(附属図書館) / 31507 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 佐川 尚, 教授 平藤 哲司 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

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