Advancements in Li-ion batteries are needed especially for the development of electric vehicles and stationary energy storage. Prior research has shown mesoscale variations in electrode electronic conductive properties, which can cause capacity loss and uneven electrochemical behavior of Li-ion batteries. A micro-four-line probe (μ4LP) was used to measure electronic conductivity and contact resistance over mm-length scales in that prior work. This work describes improvements to overcome the challenge of unreliable surface contact between theμ4LP and the sample. Ultimately a second generation flexible probe called the micro-radial-surface probe (μ4LP) was designed and produced. The test fixture was also optimized to obtain consistent contact with the new measurement probe and to perform measurements at a lower force. The μ4LP was then used to study the effect of heterogeneity on calendering, which is the compression of electrode films to obtain a uniform thickness and desired porosity. The thickness, electronic conductivity and contact resistance of two cathodes and one anode were measured before and after calendering. The the spatial standard deviation divided by the mean was used as a measure of heterogeneity. The results show variability in conductive properties increased for two of the three samples after calendering, despite the increased uniformity in thickness of the electrodes. This suggests that additional quality control metrics are needed besides thickness to be able to identify uneven degradation and produce longer lasting batteries.

Advancements in Li-ion batteries are needed especially for the development of electric vehicles and stationary energy storage. Prior research has shown mesoscale variations in electrode electronic conductive properties, which can cause capacity loss and uneven electrochemical behavior of Li-ion batteries. A micro-four-line probe (μ4LP) was used to measure electronic conductivity and contact resistance over mm-length scales in that prior work. This work describes improvements to overcome the challenge of unreliable surface contact between theμ4LP and the sample. Ultimately a second generation flexible probe called the micro-radial-surface probe (μ4LP) was designed and produced. The test fixture was also optimized to obtain consistent contact with the new measurement probe and to perform measurements at a lower force. The μ4LP was then used to study the effect of heterogeneity on calendering, which is the compression of electrode films to obtain a uniform thickness and desired porosity. The thickness, electronic conductivity and contact resistance of two cathodes and one anode were measured before and after calendering. The the spatial standard deviation divided by the mean was used as a measure of heterogeneity. The results show variability in conductive properties increased for two of the three samples after calendering, despite the increased uniformity in thickness of the electrodes. This suggests that additional quality control metrics are needed besides thickness to be able to identify uneven degradation and produce longer lasting batteries.

This thesis describes research to understand the relationships between materials, microstructure, transport processes, and battery performance for primary alkaline battery cathodes. Specifically, the effect of various carbon additives, with different physical properties, on electronic transport or conductivity within battery cathodes was investigated. Generally, the electronic conductivity increases with carbon additives that have higher aspect ratios, smaller particle diameters, higher surface areas, and lower bulk densities. Other favorable carbon aspects include more aggregated and elongated carbon domains which permit good particleto-particle contacts. Of the various carbon additives investigated, graphene nanopowder was the best performer. This graphene nanopowder had the smallest particle diameter, highest surface area, and one of the lowest Scott densities of the carbon additives investigated as well as well-connected, interspersed carbon pathways. Notably, a typical effective ionic conductivity is more than 50 times less than the electronic conductivity (5.7 S/m to 300 S/m, respectively) for a high-performance cathode. Thus, alkaline battery cathodes could be redesigned to improve ionic conductivity for optimal performance. This work expanded on previously published work by relating additional carbon-additive material properties--specifically, particle morphology, surface area and Scott density--and their corresponding cathode microstructure to the fundamental transport processes in alkaline battery cathodes.

Next-generation batteries with improved microstructure and performance are on their way to meet the market demands for high-energy and power storage systems. Among different types of batteries, Li-ion batteries remain the best choice for their high energy density and long lifetime. There is a constant but slow improvement in Li-ion batteries by developing new materials and fabrication techniques. However, further improvements are still needed to meet government and industry goals for cost, cycling performance, and cell lifetime. A fundamental understanding of particle-level interactions can shed light on designing new porous electrodes for high-performance batteries. This is a complex problem because electrodes have a multi-component, multi-phase microstructure made through multiple fabrication processes (i.e., mixing, coating, drying, and calendering). Each of these processes can affect the final microstructure (particle and pore locations) differently. This work seeks to understand the porous microstructure evolution of Li-ion electrodes during the drying and calendering fabrication processes by a combination of modeling and experimental approaches. The goal is to understand the mechanisms by which the electrode components and fabrication processes determine the battery microstructure and subsequent cell performance. A multi-phase smoothed particle (MPSP) model has been developed on a publically available simulation platform known as LAMMPS. This model was used to simulate particle-level interactions and predict the mechanical and transport properties of four fabricated electrodes (i.e. a graphite anode and three traditional metal oxide cathodes). One challenge was to include different electrode components and their interactions and relate them to physical properties like density and viscosity that can be measured experimentally. Another challenge was to generate required electrode property data for model validation, which in general was not found in the literature. Therefore, a series of experiments were conducted to provide that information, namely slurry viscosity, electronic conductivity, porosity, tortuosity, elastic modulus, and electrode crosssections. Understanding these properties has value to the battery community independent of their use in this study. The MPSP model helps us explain observed transport heterogeneity after calendering but brings up new questions about the drying process that have not been addressed in previous works. Therefore, the drying fabrication step was studied experimentally in more detail to fill this knowledge gap and explain our simulation results. The MPSP model can also be used as a predictive tool to explore the design space of Li-ion electrodes where conducting the actual experiments is very challenging. For example, the distinct effect of particle size, shape, orientation, and stiffness on electrode transport and mechanical properties are difficult to determine independently, and therefore this model is an ideal tool to understand the effect of these properties. The final model, which is publically available, could be used with adjustments by future workers to test new materials, fabrication processes, or electrode design (e.g., a multi-layered structure).

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24587号 / 工博第5093号 / 新制||工||1975(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 古川 修平, 教授 生越 友樹, 准教授 堀毛 悟史, 教授 松田 建児 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The goal of this work is to further understand the relationships between porous electrode microstructure and mass transport properties. This understanding allows us to predict and improve cell performance from fundamental principles. The investigated battery systems are the widely used rechargeable Li-ion battery and the non-rechargeable alkaline battery. This work includes three main contributions in the battery field listed below. Direct Measurement of Effective Electronic Transport in Porous Li-ion Electrodes. An accurate assessment of the electronic conductivity of electrodes is necessary for understanding and optimizing battery performance. The bulk electronic conductivity of porous LiCoO2-based cathodes was measured as a function of porosity, pressure, carbon fraction, and the presence of an electrolyte. The measurements were performed by delamination of thin-film electrodes from their aluminum current collectors and by use of a four-line probe. Imaging and Correlating Microstructure To Conductivity. Transport properties of porous electrodes are strongly related to microstructure. An experimental 3D microstructure is needed not only for computation of direct transport properties, but also for a detailed electrode microstructure characterization. This work utilized X-ray tomography and focused ion beam (FIB)/scanning electron microscopy (SEM) to obtain the 3D structures of alkaline battery cathodes. FIB/SEM has the advantage of detecting carbon additives; thus, it was the main tomography tool employed. Additionally, protocols and techniques for acquiring, processing and segmenting series of FIB/SEM images were developed as part of this work. FIB/SEM images were also used to correlate electrodes' microstructure to their respective conductivities for both Li-ion and alkaline batteries. Electrode Microstructure Metrics and the 3D Stochastic Grid Model. A detailed characterization of microstructure was conducted in this work, including characterization of the volume fraction, nearest neighbor probability, domain size distribution, shape factor, and Fourier transform coefficient. These metrics are compared between 2D FIB/SEM, 3D FIB/SEM and X-ray structures. Among those metrics, the first three metrics are used as a basis for SG model parameterization. The 3D stochastic grid (SG) model is based on Monte Carlo techniques, in which a small set of fundamental inter-domain parameters are used to generate structures. This allows us to predict electrode microstructure and its effects on both electronic and ionic properties.

No description available.

[ES] Esta tesis está centrada en la combinación de diferentes tecnologías para mejorar las tecnologías emergentes de captura y almacenamiento de carbono (CSS) y la revalorización del CO2 capturado. La principal tecnología estudiada en esta tesis fueron las membranas de transporte de oxigeno (OTMs), las cuales pueden producir oxigeno puro de forma más flexible que las actuales tecnologías de producción de oxigeno, como la destilación criogénica de aire. La producción de oxigeno puro es crucial para desarrollar reactores de oxicombustión que podrían ser mas eficientes para la captura de CO2 que los reactores actuales de combustión con aire. Los estudios sobre OTMs se dividieron en dos temas principales: membranas de bifásicas estables en CO2 y membranas basadas en BSCF (Ba1-xSrxCo1-yFeyO3-¿). Por otro lado, para la revalorización del CO2 capturado, se estudio' la tecnología de looping químico basada en catalizador de oxido de cerio, que aprovecha las propiedades redox del catalizador a diferentes pO2 y altas temperaturas (entre 700- 1400 ¿C). En general, las principales etapas limitantes en OTMs son la transferencia de oxigeno a trave's de la membrana y las reacciones superficiales. Por eso, una mejora en las propiedades de la capa catalítica podri'a mejorar la permeacio'n total de oxigeno. El primer estudio sobre membranas bifásicas se centro' el estudio de capas catali'ticas con distintas proporciones de ambas fases. Para este estudio, se selecciono' el NFO-CTO (NiFe2O4/Ce0.8Tb0.2O2-¿) como composite. Este material ya ha sido estudiado en nuestro laboratorio, y mostró una gran estabilidad en atmósferas de CO2, pero con baja permeación de O2 en comparación con otros composites. Este estudio mostró resultados interesantes, y se combino' con medidas de espectroscopia de impedancia electroqui'mica (EIS), utilizadas habitualmente para estudiar electrodos para pilas de combustible de o'xido so'lido (SOFC) y pilas de electro'lisis de o'xido so'lido (SOEC). El segundo estudio sobre composites para OTMs se centro' en el aumento de la permeacio'n de oxi'geno con composites basados en espinela-fluorita. En este caso, el transporte de oxigeno esta' controlado, adema's de por la temperatura y el gradiente de pO2, por la conductividad ambipolar, en la que intervienen las conductividades eléctrica e io'nica. Asi', se cambio' la fase de NFO por la fase de CMO (Co2MnO4) que tiene mayor conductividad total que el NFO. El composite resultante (CMO-CTO) ha mostrado un mayor rendimiento que el material predecesor NFO-CTO. Como se ha mencionado anteriormente, el otro estudio sobre OTM se realizo' con membranas basadas en BSCF. En este estudio, la membrana capilar BSCF fue electrificada para aumentar la temperatura de la membrana por efecto Joule y como consecuencia un aumento en la permeación de oxigeno. Además, se estudió este efecto bajo deshidrogenacio'n oxidativa de etano, obteniéndose una mejora importante para las membranas BSCF electrificadas en comparación con las membranas BSCF no electrificadas. Estos estudios abren las puertas al uso de ellas con reactores a más baja temperatura. El último estudio se centra en la revalorización del CO2 mediante el reformado de metano por ciclos químicos. Los ciclos químicos están basados en las propiedades redox del catalizador y las dos etapas de reducción y oxidación del catalizador. La reducción del catalizador es realizada mediante temperatura y en condiciones inertes o con corrientes reductoras como por ejemplo en metano. Los estudios se centran en la reducción a través de metano que trabaja a temperaturas más bajas que para corrientes inertes y, ademas, proporciona corrientes de syngas (mezcla de CO y H2) en la etapa de reducción del catalizador, que mejora la eficiencia global del proceso. La revalorización del CO2 se realizaba en la etapa de oxidación del catalizador. La oxidación de estos catalizadores podría formarse con flujos de H2O y/o / [CA] Aquesta tesi està centrada en la combinació de diferents tecnologies per millorar les tecnologies emergents de captura i emmagatzematge de carboni (CSS) i la revalorització del CO2 capturat. La principal tecnologia estudiada en aquesta tesi van ser les membranes de transport d'oxigen (OTMs), les quals poden produir oxigen pur de manera més flexible que les actuals tecnologies de producció d'oxigen, com la destil·lació criogènica de l'aire. La producció d'oxigen pur és crucial per al desenvolupament de reactors d'oxicombustió que podrien ser més eficients per a la captura de CO2 que els reactors actuals de combustió amb aire. Els estudis sobre OTMs es van dividir en dos temes principals: membranes composites de dos fases estables en CO2 i membranes basades en BSCF (Ba1- xSrxCo1-yFeyO3-). D'altra banda, per a la revalorització del CO2 capturat, es va estudiar la tecnologia de looping químic basada en catalitzador d'òxid de ceri, que aprofita les propietats redox del catalitzador a diferents pO2 i altes temperatures (entre 700-1400 ºC). En general, les principals etapes limitants en OTMs són la transferència d'oxigen a través de la membrana i les reaccions superficials. Per això, una millora en les propietats de la capa catalítica podria millorar la permeació total d'oxigen. El primer estudi sobre membranes bifàsiques es va centrar en l'estudi de capes catalítiques amb diferents proporcions de ambdues fases. Per a aquest estudi, es va seleccionar el NFO-CTO (NiFe2O4/Ce0.8Tb0.2O2-δ) com a composite. Aquest material ja ha sigut estudiat en el nostre laboratori, i va mostrar una gran estabilitat en atmosferes de CO2, però amb baixa permeació d'O2 en comparació amb altres composites. Aquest estudi va mostrar resultats interessants, i es va combinar amb mesures d'espectroscòpia d'impedància electroquímica (EIS), utilitzades habitualment per estudiar elèctrodes per a piles de combustible d'òxid sòlid (SOFC) i piles d'electròlisi d'òxid sòlid (SOEC). El segon estudi sobre composites per a OTMs es va centrar en l'augment de la permeació d'oxigen amb composites basats en espinela-fluorita. En aquest cas, el transport d'oxigen està controlat, a més de per la temperatura i el gradient de pO2, per la conductivitat ambipolar, en la qual intervenen les conductivitats elèctrica i iònica. Així, es va canviar la fase de NFO per la fase de CMO (Co2MnO4) que té una major conductivitat total que el NFO. El composite resultant (CMO-CTO) ha mostrat un major rendiment que el material predecessor NFO-CTO. L'últim estudi es centra en la revalorització del CO2 mitjançant el reformat de metà per cicles químics. Els cicles químics estan basats en les propietats redox del catalitzador i les dues etapes de reducció i oxidació del catalitzador. La reducció del catalitzador és realitzada mitjançant temperatura i en condicions inertes o amb corrents reductores com per exemple en metà. Els estudis se centren en la reducció a través de metà que treballa a temperatures més baixes que per a corrents inertes i, a més, proporciona corrents de syngas (barreja de CO i H2) en l'etapa de reducció del catalitzador, que millora l'eficiència global del procés. La revalorització del CO2 es realitzava en l'etapa d'oxidació del catalitzador. L'oxidació d'aquests catalitzadors podria formar-se amb fluxos de H2O i/o CO2 a altes temperatures 700- 1000 ºC. El nostre estudi es centra en òxids de ceri dopats al 10% amb elements 19Chapter 0: Preamble trivalent, generalment lantànids. En aquest estudi es va correlacionar la velocitat de splitting del CO2 en l'etapa d'oxidació amb el volum de cel·la de l'estructura cristal·lina i la conductivitat total d'aquests materials. / [EN] This thesis is focused on the combination of different technologies to improve emerging technologies for carbon capture and storage (CSS) and the revalorization of the CO2 captured. The leading technology studied in this thesis was oxygen transport membranes (OTMs) that could produce pure oxygen more flexibly than the current oxygen production technologies like cryogenic air distillation. The production of pure oxygen is crucial for developing oxycombustion reactors that could be more efficient for carbon capture than traditional combustion reactors. The OTMs studies were divided into two main topics: dual-phase membranes with stable operation in CO2 and BSCF-based membranes (Ba1-xSrxCo1-yFeyO3-¿). For the revalorization of the captured CO2, the chemical looping technology based on a cerium oxide catalyst was studied, which takes advantage of the redox properties of the catalyst at different pO2 and high temperatures (between 700-1400 ¿C). In general, the principal limiting steps for OTMs were the bulk oxygen transfer and the surface exchange reactions. In this matter, the improvement in the behaviour of the catalytic layer could achieve better oxygen permeation. The first study for dual- phase membranes was focused on the role of the different dual-phase ratios in the behaviour as a catalytic layer in OTMs. For this study, NFO-CTO (NiFe2O4/Ce0.8Tb0.2O2-¿) was selected as dual-phase material. This material was previously studied and showed high stability under CO2 environments but with poor oxygen flux compared with other dual-phase materials. The study considered for the present Thesis showed interesting results, and it was combined with electrochemical impedance spectroscopy (EIS) measurements, commonly used to study electrodes for solid oxide fuel cells (SOFC) and solid oxide electrolysis cells (SOEC). The second study in dual-phase materials for OTMs focused on the increase in oxygen permeation for spinel-fluorite-based materials. In this matter, the bulk oxygen transports are controlled, apart from the temperature and the pO2 gradient, by the ambipolar conductivity, where the electrical and the ionic conductivities are involved. So, the NFO phase was changed for the CMO phase (Co2MnO4), which has higher total conductivity than the NFO. The resultant dual- phase material (CMO-CTO) performed better than the predecessor NFO-CTO material. As mentioned previously, the other study on OTMs focused on BSCF-based membranes. In this study, the BSCF capillary membrane was electrified in order to increase the membrane temperature via the Joule effect and, as a consequence, an increase in the oxygen permeation. In addition, this effect under oxidative dehydrogenation of ethane was studied, obtaining an essential improvement for electrified BSCF membranes compared with non-electrified BSCF membranes. These studies have opened new gates to operate these membranes at lower reactor temperatures. Finally, the last study was focused on CO2 upcycling via chemical looping methane reforming. Chemical looping is based on the redox properties of the catalyst in two principal steps, reduction and oxidation of the catalyst. The catalyst reduction is performed with temperature in inert conditions or with reducing streams like methane. We were focused on the reduction via methane that works at lower temperatures than inert streams and could provide syngas streams (a mixture of CO and H2) that improve global efficiency. The revalorization of the CO2 was performed in the other step, the oxidation part of the cycle. The oxidation of those catalysts could be formed with H2O and/or CO2 streams at high temperatures of 700-1000 ¿C. Our study was focused on 10% doped cerium oxide with trivalent elements. In this study, the CO2 splitting on the oxidation step was correlated with the crystal structure parameters and the total conductivity of these materials. / Laqdiem Marín, M. (2024). Development of high temperature MIEC catalytic reactors for energy conversion and storage aplications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/204871

To date, most two-dimensional conjugated metal–organic frameworks (2D c-MOFs) are based on planar polycyclic aromatic hydrocarbons (PAHs), which limits the ability to introduce additional substituents to control their properties. This thesis introduces a novel monomer ligand derived from highly substituted, core-twisted hexahydroxy-hexa-cata-benzocoronenes (6X-6OH-cHBCs), resulting in a new class of wavy 2D c-MOFs. The structural rigidity and self-complementary nature of the c-HBC ligand makes it a valuable monomer for constructing these novel 2D c-MOFs. Despite the wavy structure, effective conjugation between layers was achieved. This led to the formation of electronically conductive materials, as demonstrated by 6F-cHBC-Cu, which exhibited a conductivity of 1.82∙10-2 S/cm. Furthermore, the wavy motif of the c-HBC ligand promoted extended crystal growth in the z-direction. This was demonstrated by the formation of several micrometer-long single crystals of 6F-cHBC-Cu. The monomers were synthesized through a flexible three-step process, allowing for the incorporation of various substituents or functional groups, thus enabling control over ligand symmetry. This process enabled the synthesis of monomers with diverse symmetries: C6 symmetry (12OH-cHBC), C3 symmetry (6X-6OH-cHBC), and asymmetric monomers (e.g., 3F-6OH-cHBC). This structural variety allowed for systematic investigations into structure-property relationships, offering valuable insights into how monomer design influences the resulting MOF properties. The homologous 6X-cHBC-Cu MOF series (X = H, F, Cl, Br) illustrated that both the electron-withdrawing effect and the size of the substituent significantly impact crystallinity. This in turn enhances fundamental properties such as electronic conductivity, charge carrier mobility, accessible pore size, thermal stability, and morphology. Reactivity trends for the synthesized monomers were also established, showing that strong electron-withdrawing groups like fluorine or hydroxyl directly correlate with enhanced monomer reactivity, optimizing synthetic conditions. Incorporating fluorine into the monomer structure significantly improved the resulting MOF properties, providing a valuable design strategy for future monomers. Finally, this research demonstrated that wavy 2D c-MOFs can rival traditional flat ligands in terms of crystallinity and electronic properties, such as conductivity and charge carrier mobility, thereby expanding the potential for novel 2D c-MOF members.

Le domaine émergeant de l’électronique imprimée nécessite de nouveaux matériaux peu coûteux et non toxiques pour réaliser de nombreux systèmes tels que des circuits logiques, des capteurs, des affichages, des thermoélectriques ou même du photovoltaïque sur substrat souple. Il s’agit aussi d’optimiser le fonctionnement de couches granulaires de semiconducteurs de type n et p.BiCuOS a été identifié comme un semiconducteur de type p possédant des propriétés intéressantes. Cependant, sa forte sous stoechiométrie en cuivre induit un dopage de type p trop élevé qui nuit à ses propriétés semiconductrices. De plus, comme la plupart des composés à base de chalcogénures, BiCuOS se décompose lors d’un frittage, et ne peut être densifié thermiquement. Dans le but d’optimiser des couches minces de BiCuOS, des solutions doivent ainsi être trouvées pour i) réduire le taux de dopage ; ii) obtenir de bonnes mobilités dans des couche peu denses. De nombreuses substitutions chimiques ont été essayées telles que celle du soufre par l’iode et celle du cuivre par l’argent. Ces substitutions ont permis de réduire fortement le taux de porteurs de charge. D’autre part, nous avons étudié l’effet du greffage de molécules à la surface des grains de semiconducteurs sur la conduction électronique. Des molécules conjuguées (acides téréphtaliques substitués) et des polymères dérivés des polythiophènes ont été adsorbés à la surface d’un semiconducteur modèle de type n, ZnO. L’amélioration du transfert électronique intergranulaire a été expliquée par le saut des électrons au travers de la LUMO de ces molécules.L’élaboration d’encres de particules semiconductrices stabilisées par de telles molécules a permis la fabrication par voie liquide de jonctions diodes p-n ZnO/BiCuOS avec de bonnes performances malgré l’absence de propriétés photovoltaïques. Plus largement, ce travail est une contribution à la mise en forme de nouveaux systèmes d’électronique hybride par voie de chimie douce, dont le développement permettrait la commercialisation de technologies plus respectueuses de l’environnement. / The emerging domain of printed electronics requires new cheap and non-toxic materials for applications such as logic devices, sensors, displays, thermoelectric and photovoltaic devices. It also requires optimizing the conduction in granular semiconductors. BiCuOS has been identified as a promising p-type semiconductor for such applications. However, its high copper under-stoichiometry, induces an important p-type doping, which is detrimental for its use as a photovoltaic absorber. Moreover, like all chalcogenide based materials, it shows a poor chemical stability during sintering, thermal treatment necessary to enhance transport properties. In order to optimize its properties, solutions must be found i) to control the doping content, ii) to obtain good charge carrier mobilities in thin films. On the one hand, we have explored different kinds of substitutions such as iodine for sulfur or silver for copper, which successfully enabled to strongly reduce the charge carrier density. On the other hand, we have studied the effect of grafting conjugated molecules (terephthalic acid and polythiophene derivatives) onto the surface of a model n-type semiconductor (ZnO) to study their effect on the intergranular transport. Electronic transfer improvement occurs by transfer though a lowered energy barrier formed by the LUMO of the molecules. The formulation of optimized inks using these molecules as additives allowed the thin film deposition of p-n diodes formed with ZnO/BiCuOS. Although no photovoltaic effect has been detected yet, the p-n junctions showed high nonlinear properties and are strongly photosensitive. With this work, we have participated to the elaboration of new sulfides and hybrid interfaces systems for the improvement of semiconductor devices. The development of such hybrid electronic devices through soft chemistry method is a valuable step towards the commercialization of sustainable technologies.