Non-aqueous metal-air (Li-O2 and Na-O2) batteries have been emerging as one of the most promising high-energy storage systems to meet the requirements for demanding applications due to their high theoretical specific energy. In the present thesis work, advanced characterization techniques are demonstrated for the exploration of metal-O2 batteries. Prominently, the electrochemical reactions occurring within the Li-O2 and Na-O2 batteries upon cycling are studied by in operando powder X-ray diffraction (XRD). In the first part, a new in operando cell with a combined form of coin cell and pouch cell is designed. In operando synchrotron radiation powder X-ray diffraction (SR-PXD) is applied to investigate the evolution of Li2O2 inside the Li-O2 cells with carbon and Ru-TiC cathodes. By quantitatively tracking the Li2O2 evolution, a two-step process during growth and oxidation is observed. This newly developed analysis technique is further applied to the Na-O2 battery system. The formation of NaO2 and the influence of the electrolyte salt are followed quantitatively by in operando SR-PXD. The results indicate that the discharge capacity of Na-O2 cells containing a weak solvating ether solvent depends heavily on the choice of the conducting salt anion, which also has impact on the growth of NaO2 particles. In addition, the stability of the discharge product in Na-O2 cells is studied. Using both ex situ and in operando XRD, the influence of sodium anode, solvent, salt and oxygen on the stability of NaO2 are quantitatively identified. These findings bring new insights into the understanding of conflicting observations of different discharge products in previous studies. In the last part, a binder-free graphene based cathode concept is developed for Li-O2 cells. The formation of discharge products and their decomposition upon charge, as well as different morphologies of the discharge products on the electrode, are demonstrated. Moreover, considering the instability of carbon based cathode materials, a new type of titanium carbide on carbon cloth cathode is designed and fabricated. With a surface modification by loading Ru nanoparticles, the titanium carbide shows enhanced oxygen reduction/evolution activity and stability. Compared with the carbon based cathode materials, titanium carbide demonstrated a higher discharge and charge efficiency.

Le besoin accru de stockage d'énergie via Li- et batteries Na-ion nécessite une recherche continue de nouveaux matériaux de cathode ayant une densité énergétique plus élevée et étant sûr et durable. Ainsi, nous avons exploré des composés à base de borate capables de réagir avec Li/ Na-ions de manière réversible, soit par le biais de réactions topotactic- ou de conversion. Nous nous sommes concentrés sur les candidats avec des anions polyborate, qui devraient montrer des potentiels redox élevés par rapport aux matériaux à base BO3. Li6CuB4O10 utilisant comme composé modèle, nous avons montré la possibilité d'obtenir des potentiels d'oxydo-réduction de 4.2 et 3.9 V par rapport à Li pour l'α- et ß polymorphes. L'activité redox a été rationalisée par spectroscopie EPR et calculs DFT. Nous révélons en outre la relation structurelle / synthétique entre les deux polymorphes et montrons une conductivité ionique élevée de 1.4 mS / cm à 500 °C pour une forme de HT d'-Li6CuB4O10. De plus, nous avons pu préparer deux pentaborates 3d-métal nouveau sodium Na3MB5O10 (M = Fe, Co). M = Fe, nous avons observé une intercalation Na réversible à un potentiel moyen de 2.5 V par rapport à Na, alors Na3CoB5O10 avéré être inactif électrochimique. Dévier à partir de composés d'insertion / désinsertion classiques, nous avons étudié la électrochimique entraîné la réaction d'un oxyborate bismuth Bi4B2O9 contre Li par des mesures électrochimiques combinées avec XRD et TEM. Nous avons constaté qu'il est possible de faire défiler ce matériau réversible entre 1.7 et 3.5 V avec un potentiel redox d'environ 2.3 V par rapport à Li avec seulement 5% en poids de carbone et une faible polarisation ~ 300 mV. / The increased need of energy storage via Li- and Na-ion batteries requires a continuous search for new cathode materials having higher energy density and being safe and sustainable. Thus, we explored borate based compounds capable of reacting with Li/ Na-ions in a reversible way either through topotactic- or conversion reactions. We focused on candidates with polyborate anions, that are expected to show elevated redox potentials compared to BO3 based materials. Using Li6CuB4O10 as a model compound we showed the possibility to achieve redox potentials of 4.2 and 3.9 V vs Li for the α- and β-polymorphs. The redox activity was rationalized through EPR spectroscopy and DFT calculations. We further reveal the structural/ synthetic relation between the two polymorphs and show a high ionic conductivity of 1.4 mS/cm at 500°C for a HT form of α-Li6CuB4O10. Moreover we were able to prepare two new sodium 3d-metal pentaborates Na3MB5O10 (M = Fe, Co). For M = Fe we observed a reversible Na intercalation at an average potential of 2.5 V vs Na, whereas Na3CoB5O10 turned out to be electrochemical inactive. Deviating from classical insertion/ deinsertion compounds, we studied the electrochemical driven reaction of a bismuth oxyborate Bi4B2O9 versus Li through electrochemical measurements combined with XRD and TEM. We found that it is possible to reversible cycle this material between 1.7 and 3.5 V with an redox potential of ~2.3 V vs Li with only 5wt% carbon and a small polarization ~300 mV. Owing to the complexity of 3d-metal borate chemistry encountered through this PhD, the chances of having a borate based positive electrode for next generation Li-ion batteries is rather slim.

Les batteries au lithium tout solide présentent un grand intérêt pour le développement de systèmes de stockage de grande densité (volumique) d'énergie et sûrs notamment en raison de leur excellente stabilité thermique par rapport aux technologies lithium-ions à électrolyte liquide. Cependant, avec l'épaisseur de la batterie, de fortes limitations cinétiques sont observées, en raison i/ de la relativement faible mobilité des ions dans les matériaux inorganiques et ii/ de la présence de joints de grains généralement bloquants aux interfaces solide/solide. De plus au cours de la charge/décharge de la batterie, les matériaux actifs (réservoir de l'énergie) changent de volume ce qui induit des contraintes mécaniques interfaciales qui provoquent la formation de micro-fractures très dommageables à la cyclabilité de ces systèmes. Cette thèse concerne la réalisation et la caractérisation de batteries inorganiques monolithiques (avec les électrodes composites) en utilisant une méthode de frittage: Spark Plasma Sintering (SPS). La formulation des électrodes composites est fondamentale car ce sont de multi-matériaux qui doivent présenter de nombreuses fonctionnalités: 1) une grande densité d'énergie 2) une bonne percolation électronique (resp. ionique) enfin 3) une bonne tenue mécanique avec des interfaces électrodes/electrolyte stables afin d'assurer la durée de vie des cellules.Le principal objectif est de trouver des relations, pour des matériaux donnés, entre la texture des poudres initiales, la microstructure des céramiques obtenues par frittage SPS et les propriétés électriques (électronique et ionique) ainsi que les performances électrochimiques. / All-solid batteries with inorganic solid electrolytes are attractive candidates in electrochemical energy storage since they offer high safety, reliability and energy density. Aiming to increase the surface capacity strong efforts have been made to increase the thickness of the electrode. However, the thicker electrode, the more stress is generated at the solid/solid interfaces because of the volume change of the active material during lithium insertion/desinsertion upon cycling, which leads to formation of micro-cracks between the components and finally a bad cycling life. The possible answer to this issue is to build in place of a dense phase pure electrode, a composite electrode which is a multifunctional material. This composite electrode should contain a lot of electrochemically active material, the reservoir of energy; together with electronic and ionic conductor additives, to ensure efficient and homogeneous transfer of electrons and ions in the electrode volume.The main scope of this thesis was to develop all-solid-state batteries prepared by SPS method for applications at elevated temperatures. These batteries consist of a two composite electrodes separated by the NASICON-type solid electrolyte Li1.5Al0.5Ge1.5(PO4)3. The main objective was to find relationships, for given materials, between the initial powder granulometry (grain size, size distribution, agglomeration), the microstructure of ceramics obtained by SPS sintering, and the electrochemical performances of the final batteries. By creating electrodes with novel materials and better composition, the trade-off of power density and energy density can be minimized.

The aim of this work is to describe final properties of the electrodes based on the amount of pressure used during its production. In the theoretical part of this work, secondary electrochemical accumulators are described, with the focus on Li-ion accumulators. In the main part of this work, the production of Li-ion accumulators, with usage of different pressures during its production is described. In the final part of this work, the examination of these created cells for the classification of the optimal production pressure is described.

Lead-acid batteries are the oldest and most common type of secondary cells. Their biggest use is as a power source for a car starter. Bipolar lead-acid batteries could also be used for new applications such as power sources for hybrid electrical vehicles (HEV) for their high power. But there are still many technical problems limiting its use in these applications, which have to be overcome. This could cover parasite reactions as is gas creation, heat removal from the battery and another big problem is substrate corrosion. This diploma thesis concerns the actual state of bipolar lead batteries in the world with detail orientation to substrate corrosion. This thesis describes the conductometric method of lotion conductivity measurement and its modification for measurement of lead grid conductivity. From that we can find out, that when material loses more conductivity, the greater the corrosion. This thesis describes needed preparative experiments for assurance, that the conductometric method can be used for corrosion speed measurement and there are other experiments testing different lead alloys for corrosion speed.

Dans les années à venir, la production d’Energie devra passer par l’utilisation de moyens plus respectueux de l’environnement tels que les énergies renouvelables. Leur caractère intermittent nécessite cependant la mise en place d’un stockage à grande échelle. Parmi les différentes technologies à disposition, les batteries Na-ion apparaissent comme une solution de choix grâce aux ressources de sodium illimitées. Dans ce contexte, nous nous sommes donc intéressés à la synthèse et la caractérisation de nouveaux matériaux d’électrodes positives pour batteries Na-ion. Les oxydes de métaux de transition et plus particulièrement le système Na-Mn-O a attiré notre attention pour les avantages que procure le manganèse en termes de non toxicité, de faible coût et d’abondance. Les phases Na4Mn2O5, lacunaire en oxygène, et Na2Mn3O7, lacunaire en cation manganèse, montrent des capacités spécifiques intéressantes par l’action de différents phénomènes redox. Na2Mn3O7 peut notamment être réduite, pour former la phase Na4Mn3O7 et oxydée, par l’action de l’activité redox de l’oxygène, donnant des capacités de 160 et 120 mAh/g, respectivement. Dans le but d’élargir l’étude à un métal de transition pouvant être oxydé à un état de valence +V, la phase isoformulaire Na2V3O7 a également été étudiée et un Na+ peut être réversiblement extrait de cette dernière. / N the coming years, the production of Energy will have to go through the use of more environmentally friendly means such as renewable energies. However, their intermittent nature requires the establishment of a large-scale storage. Among the various technologies available, Na-ion batteries appear as a solution of choice thanks to unlimited sodium resources. In this context, we are interested in the synthesis and characterization of new positive electrode materials for Na-ion batteries. The transition metal oxides, and more particularly the Na-Mn-O system, have drawn our attention to the benefits of manganese in terms of non-toxicity, low cost and abundance. The phase Na4Mn2O5 (with oxygen vacancies) and Na2Mn3O7 (with manganese vacancies) show interesting specific capacities by the action of various redox phenomena. Na2Mn3O7 may be reduced, to form the phase Na4Mn3O7 and oxidized, by the action of the oxygen redox activity, giving capacities of 160 and 120 mAh/g, respectively. In order to extend the study to a transition metal that can be oxidized to a +V valence state, Na2V3O7 has also been studied and one Na+ can be reversibly extracted from it.

Au cours des dernières années, de nombreuses recherches se sont concentrées sur les batteries afin de satisfaire leur demande croissante pour de nombreuses applications. Les matériaux hybrides métal/carbone ont fait l'objet d'une grande attention en tant qu'anodes pour les batteries ioniques Li et Na en raison de leur capacité plus élevée par rapport aux anodes graphite/carbone dur. Cependant, l'expansion de la taille des NPs métalliques et la forte capacité irréversible pendant le 1ercycle sont les principaux inconvénients à surmonter et représentent l'objectif principal de cette thèse. Trois types d'hybrides ont été étudiés (C@Sn et C@SiO2pour les LIBs, et C@Sb pour les NIBs) et des voies de synthèse originales ont été développées qui ont permis d'obtenir des matériaux avec des NPs petites et homogènes distribuées dans le réseau de carbone. Plusieurs paramètres expérimentaux ont été optimisés, conduisant à une vaste palette de matériaux avec des porosités, des structures et des granulométries différentes. La température et la charge de particules se sont avérées être les principaux paramètres affectant la porosité et la taille des particules ainsi que les performances électrochimiques. L'augmentation de la température et de la charge de NPs ont conduit à une porosité plus faible qui a permis de diminuer la capacité irréversible et d'améliorer la capacité réversible. En même temps, le cycle à long terme a été affecté négativement en raison de la formation de particules non confinées et agglomérées. Un compromis entre la charge de carbone/porosité/structure a été déterminé pour chaque système et les mécanismes électrochimiques traités sur la base d'analyses post-mortem. / During the last years a lot of research has been focused on batteries to satisfy their increasing demand for a broad application. Metal-based/carbon hybrid materials received great attention as anodes for Li and Na ion batteries due to their higher capacity compared to graphite/hard carbons anodes. However, the metal particle size expansion and the high irreversible capacity during cycling are the main inconvenients to be overcome and represent the main goal of this thesis. Three type of hybrids were studied(C@Sn and C@SiO2for LIBs, and C@Sb for NIBs) and original synthesis pathways were developed which allowed to obtain materials with small and homogeneous distributed particles in the carbon network. Several experimental parameters were tuned leading to a large pallet of materials exhibiting different porosities, structures and particle size/distribution. The temperature and the particle loading were found to be the main parameters affecting the porosity and the particle size and further the electrochemical performances. The increase of both temperature and particle loading lead to smaller porosity which successfully allowed to diminish the irreversible capacity and to improve the reversible capacity. In the same time, the long-term cycling was negatively affected due to the formation of un-confined and agglomerated particles. The extent of particle agglomeration and consequently of capacity fading was found to depend on the type of metal and synthesis route. A compromise between the carbon loading/porosity/structure was determined for each system and the electrochemical mechanisms addressed based on post-mortem analyses.

The increasing number of vehicles in Colombian cities have resulted in alarmingly low quality of air, further resulting in increasing health issues. One potential solution to this issue could be a shift from ICEVs (internal combustion engine vehicles) to EVs (electric vehicles). However, EVs in Colombia are still very expensive, an issue that needs to be addressed in order for the EV market to increase enough to be able address the issue of low air quality in cities. One way of overcoming these cost barriers could be through implementation of a market for SLB (second life batteries), meaning that a battery retired from usage in EVs would be remanufactured, resold and reused in another application. Through SLB, the owner cost of EVs could potentially be decreased. SLB could also help improve the case for nondispatchable renewable energy sources by providing low cost BESS (battery energy storage solutions). Thus, SLB has the potential to facilitate sustainable transition within both the transport and the energy sector. This thesis aims to assess the potential of SLB in Colombia. This is done through a literature review where the current state of SLB is investigated, several interviews with potential stakeholders for a SLB market in Colombia, and a techno-economic assessment of four potential BESS applications in Colombia. The literature review provides with current knowledge and state of SLB in general. The interviews provide important insight to potential stakeholders’ view on SLB for the specific case of Colombia. The techno-economic assessment includes a sensitivity analysis aiming to provide insights in which factors, such as e.g. battery purchasing price or charging cost, that that gives rise to the largest impact on feasibility of SLB. Findings from the interviews shows a strong collective commitment from the interviewees to working towards cleaner air, resulting in high engagement and collaborative efforts between stakeholders for the SLB case. The main issue highlighted by stakeholders regards technoeconomic uncertainties of SLB. Findings from the techno-economic assessment indicates that SLB is viable for larger applications such as BESS at solar farms, but not for smaller applications such as backup power in residential buildings. However, SLB is not deemed to be a game changer for either application, and there are still many uncertainties regarding both technological and economic aspects that needs to be further investigated. The sensitivity analysis shows that the factors resulting in the highest impact on feasibility of SLB is battery SOH (state of health) at the beginning of SLB usage, and battery and repurposing cost. It will be hard to address both of these factors simultaneously due to a higher SOH would render higher battery prices, and vice versa. The findings from the thesis shows that SLB can facilitate sustainable transition within both the transport and energy sectors but is not to be considered a game changer for these sectors. However, even though SLB’s contribution to sustainable transition is not revolutionary, it is still necessary from a sustainability perspective. Given the environmental footprint of EV batteries and the amount of hazardous waste retired EV batteries will give rise to, circular economy must be pursued. / Det ökande antalet fordon i colombianska städer har resulterat i oroväckande låg luftkvalitet, vilket ytterligare resulterat i ökande hälsoproblem. En potentiell lösning på det problemet kan vara en övergång från ICEVs (förbränningsmotorfordon) till EV (elfordon). EVs i Colombia är fortfarande väldigt dyra, en fråga som måste adresseras för att EV-marknaden ska kunna öka tillräckligt för att kunna ge en inverkan på problemet med låg luftkvalitet i städer. Ett sätt att övervinna dessa kostnadshinder skulle kunna vara genom att implementera en marknad för SLB (second life-batterier), vilket innebär att ett batteri som bedömts inte längre uppfylla kraven för användning i EVs, och därmed byts ut, skulle kunna byggas om, säljas vidare och återanvändas i andra applikationer. Genom SLB kan ägarkostnaderna för EVs potentiellt sänkas. SLB skulle också kunna användas för att tillhandahålla billigare BESS (batterilagringslösningar) hos icke-reglerbara förnyelsebara kraftverk, såsom solkraftverk. Således har SLB potentialen att underlätta för hållbara förändringar inom både transportsektorn och energisektorn. Den här uppsatsen ämnar att utvärdera SLBs potential i Colombia. Detta görs genom en litteraturöversikt där det nuvarande tillståndet av SLBs undersöks, flera intervjuer med potentiella intressenter för en SLB-marknad i Colombia, och en tekno-ekonomisk bedömning av fyra potentiella BESS-applikationer i Colombia. Litteraturöversikten samlar aktuell kunskap och status inom SLB i allmänhet. Intervjuerna ger viktig insikt om potentiella intressenters syn på SLB för det specifika fallet i Colombia. Den tekno-ekonomiska bedömningen inkluderar en känslighetsanalys som syftar till att ge insikter i vilka faktorer, som t.ex. batteriets inköpspris eller laddningskostnad, som ger upphov till den största effekten på SLBs genomförbarhet. Resultat från intervjuerna visar ett starkt kollektivt engagemang från de intervjuade att arbeta mot renare luft, vilket resulterar i högt engagemang och samarbete mellan intressenterna. Det största problemet med SLB från intressenternas synpunkt berör tekno-ekonomiska osäkerheter. Resultat från den tekno-ekonomiska bedömningen indikerar att SLB är ekonomiskt försvarbart för större applikationer som BESS vid solkraftverk, men inte för mindre applikationer som t.ex. för reservenergi i bostadshus. SLB anses dock inte vara ett genombrott för användning vid någon av applikationerna, och det finns fortfarande många osäkerheter när det gäller både tekniska och ekonomiska aspekter som måste undersökas ytterligare. Känslighetsanalysen visar att de faktorer som resulterar i den högsta påverkan på genomförbarheten av SLB är batteriets SOH (hälsotillstånd) i början av SLB-användning och kostnaden för batteri och ombyggnad av batterier. Det kommer dock att vara svårt att hantera båda dessa faktorer samtidigt på grund av att högre SOH skulle ge högre batteripriser, och vice versa. Resultaten från uppsatsen visar att SLB kan underlätta för hållbara förändringar inom både transport- och energisektorerna, men att det inte ska betraktas som något fantastiskt genombrott för dessa sektorer. Även fast SLBs bidrag till hållbara förändringar är inte revolutionerande, är det fortfarande en nödvändig faktor ur ett hållbarhetsperspektiv. Med tanke på miljöavtrycket för EV-batterier och mängden av farligt avfall som EV-batterier kommer att ge upphov till då de inte längre är önskvärda, måste cirkulär ekonomi bedrivas i största möjliga mån.

Batteries play a pivotal role in the modern world, powering everything from portable electronics to electric vehicles, and are critical in the shift towards renewable energy sources by enabling efficient energy storage. This thesis presents new computational strategies to understand and predict surface degradation and stacking faults in battery cathodes, phenomena that have crucial impact on the battery lifetime. The starting point is a detailed first-principles analysis of LiNiO₂ surface degradation, assessing the thermodynamics of oxygen release and its impact on the surface integrity of this prospective cathode material. This research led to the development of a method for the automated enumeration of surface reconstructions and the development of a Python software package implementing the methodology, thereby greatly accelerating the computational surface characterization of electrode materials. The methodology made it feasible to extend the investigation to LiCoO₂ surfaces, comparing their oxygen retention and surface stability with LiNiO₂ and identifying the unique properties of the two transition metals that control their behavior during battery operation. In addition to surface phase changes, stacking faults are another important class of two-dimensional defects that can affect the properties of cathode materials. Combining information from first principles calculations with 17O nuclear magnetic resonance (NMR) spectroscopy provided by collaborators, we uncovered how stacking faults affect the capacity and cyclability of Li₂MnO₃ cathodes, a prototypical lithium-rich material with oxygen redox activity. Although automated first-principles calculations are, in principle, an ideal tool for understanding atomic-scale degradation phenomena in batteries, they are computationally demanding and, therefore, limited to materials with simple compositions. In the final chapter, we explore the application of machine learning for further accelerating computational battery degradation simulations by leveraging existing data first-principles calculations for predicting the stability of new surface reconstructions. This chapter points toward a new direction that should be further explored in the future. The research presented in this thesis not only advances the understanding of lithium-ion battery cathode materials but also introduces more-widely applicable computational methodologies that lay a foundation for the development of advanced materials for energy storage applications. This work demonstrates the benefits of integrating traditional computational methods with machine learning, contributing to ongoing progress in materials science and opening up new possibilities for advancements in energy technology and material engineering.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23515号 / 工博第4927号 / 新制||工||1769(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 陰山 洋, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM