This work presents a comprehensive investigation into optimizing cathode formulations for lithium-ion batteries (LIBs), focusing on advancing energy density, C-rate capability, and cost efficiency. A special focus was on the measurement and assessment of the electronic conductivity of cathodes. Electrode slurries with varying formulations were prepared and coated, examining the effects of cathode active materials (CAMs), binders, and conductive additives (CAs). Variations in electrode loading and density were done to provide a holistic perspective on electrode production parameters. Electrochemical performance was evaluated through half-coin cells (HCC), electronic resistance meas-urement (ERM), and electrochemical impedance spectroscopy (EIS) using three-electrode cells. Experimental data were used to develop semi-empirical models and behavioral schemes, offering new insights into cathode design. The first key outcome highlights a holistic understanding of cathode development. Comparisons of CAMs such as Lithium-Nickel-Cobalt-Manganese oxide (NCM) and Lith-ium-Manganese-Iron phosphate (LMFP) emphasized the impact of crystal density, press density and specific capacity on the reachable volumetric energy density. Electrode de-sign parameters like electrode loading, press density and porosity were assessed for their impact on C-rate capability, cost and volumetric energy density. Temperature and state-of-charge (SoC) effects on resistance types were characterized, revealing essential impacts on electrode kinetics. Secondly, the thesis focuses on characterizing electronic resistance at the electrode compound and electrode/current collector interface and its correlation with typically used performance indicators such as half coin cells. Using a newly commercially availa-ble electronic resistance measurement device (HIOKI RM2610), electronic resistances were measured, and important impact factors were identified. A total electronic re-sistance (TER) threshold of 0.25 Ω∙cm² was established, below which further perfor-mance gains were not measurable in half coin cells. These findings can enable predic-tions of cathode performance based on electronic resistance measurement (ERM) re-sults, a major contribution to the field of cathode development. Lastly, the gained insights were applied to develop a more efficient cathode optimiza-tion strategy. The integration of electronic resistance measurement (ERM) can signifi-cantly reduce the need for extensive electrochemical testing and can therefore help to make electrode development more time and cost efficient.:1 TABLE OF CONTENTS Danksagung I Abstract II 1 Table of contents 3 2 Symbols and Abbreviations 6 2.1 Formula Symbols and Constants 6 2.2 Abbreviations 7 3 Introduction 9 3.1 Motivation and Aims of the Thesis 9 3.2 Structure of This Thesis 11 4 Fundamentals and State of the Art 13 4.1 Function Principle and Components of a LIB 13 4.1.1 Cathode 15 4.1.2 Anode 15 4.1.3 Electrolyte 15 4.1.4 Separator and Current Collector 16 4.2 Thermodynamics 17 4.2.1 Energy Storage Principle of a LIB 17 4.2.2 Electrical Potential of a LIB 20 4.2.3 Li-Capacity 23 4.3 LIB Cell Kinetics 25 4.3.1 Electronic Resistances in the Cell 29 4.3.2 Electrolyte Resistance 30 4.3.3 Charge-Transfer Resistance 36 4.3.4 Solid State Diffusion Resistance 38 4.4 Cathode Development in LIB 39 4.4.1 Cathode Active Materials (CAM) 39 4.4.2 Conductive Additives (CA) and Binder 41 4.4.3 Cathode Electrode Development 43 4.5 LIB in Automotive Use 44 4.6 Definitions and Relevant Quantities 47 4.6.1 C-rate 47 4.6.2 SoC 47 4.6.3 Cycle Life and State of Health (SoH) 47 4.6.4 Area Types 47 4.6.5 Resistance Normalization 48 4.6.6 Calculation Boundaries 48 5 Materials and Methods 50 5.1 Materials and Electrode Production 50 5.1.1 Active Materials 50 5.1.2 Inactive Materials 50 5.1.3 Electrode Preparation 51 5.2 Cells and Test Methods 52 5.2.1 Thickness Measurement, Press Density and Porosity Calculation 52 5.2.2 Electrode Peel Test 53 5.2.3 Electronic Resistance Measurement (ERM) 53 5.2.4 HCC – C-rate (and OCV) Testing 55 5.2.5 Sandwich Pouch (SWP) – and Testing 55 5.2.6 3-Electrode Cells and EIS Measurements 56 6 Cathode Design Influence Factors 58 6.1 Qualitative Understanding of Cathode Design Influence Factors 58 6.2 Quantifying Influence of Loading, Porosity and C-rate 67 6.3 Quantifying Temperature and SoC Dependencies of Resistance Types 73 6.4 Cathode Design Schematics 85 7 Electronic Resistances in Cathodes 89 7.1 ERM Methods and Their Advantages and Disadvantages 89 7.2 Utilizing and Understanding Dry Multi-point Measurements 97 7.3 Correlation of ERM With HCC Performance 104 7.4 CAs Specific Strengths and Weaknesses 109 7.5 Synergy Effects of CA-mixtures and its Predictability 111 8 Tailored Cathode Designs with Help of ERM 117 8.1 On the Relevance and Need for Binder in a Cathode 117 8.2 Impact of Binder and CA Reduction on Cycle Life 121 8.3 Cathode Optimization Calculations 124 9 Summary and Outlook 131 10 References 135 11 Table of Figures 141 12 Table of Tables 148 13 List of scientific Contributions 149 Appendix 150 Appendix A: Capacities Influenced by CAM Cracking and Diffusion at High Degree of Lithiation 150 Appendix B: Different Operating Windows of LMFP 152 Appendix C: Additional Results for Electronic Resistance in Cathode Measurements 153 Appendix D: Price Assumptions and Calculations 155 Appendix E: Use of Writing Tools for this Work 156 Appendix F: Curriculum vitae 157

La cathode creuse est un élément clef des propulseurs à plasma. Dans un propulseur à plasma, un gaz propulsif est ionisé dans un canal de décharge puis accéléré hors de celui-ci afin de créer la poussée. Dans le propulseur de Hall en particulier, l'ionisation du gaz est provoquée par l'injection dans le canal de décharge d'un intense courant électronique (de quelques ampères à plus d'une centaine d'ampères). L'élément chargé de fournir le courant électronique de la décharge, la cathode creuse, est crucial dans le fonctionnement du propulseur. Or, celle-ci est souvent idéalisée dans les modèles de propulseur et n'est que rarement étudiée pour sa physique propre. Pourtant, le développement de propulseurs de Hall de haute puissance, destinés à terme à équiper l'ensemble des missions spatiales, requiert la mise au point de cathodes capable de délivrer un fort courant (jusqu'à plus de 100 A) sur des durées de l'ordre de la dizaine de milliers d'heures. Or, la mise au point de nouvelles cathodes s'est révélée difficile en raison de l'absence de modèle susceptible de prédire a priori les performances d'une cathode en fonction de sa conception. On se propose ici de mettre en place un modèle prédictif de cathode creuse capable de retranscrire la physique du fonctionnement de la cathode. L'objectif in fine est bien sûr d'utiliser ce modèle afin de faire le lien entre la conception de la cathode et son fonctionnement dans le but de guider le développement de futures cathodes. On présentera tout d'abord brièvement le contexte d'application des cathodes creuses, et on donnera un rapide aperçu du principe de fonctionnement global de la cathode. Ensuite, après avoir effectué un tour d'horizon des différents modèles numériques de cathode creuse préexistants dans la littérature, on détaillera le modèle de la cathode développé ici, qui incorpore une description fluide du plasma, ainsi que des transferts thermiques aux parois, qui conditionnent en grande partie le bon fonctionnement de la cathode. Un soin particulier sera apporté à la validation des résultats de simulation vis-à-vis des mesures expérimentales disponibles dans la littérature, ce qui nous permettra de perfectionner certains points du modèle afin de mieux traduire la réalité physique. En particulier, une modélisation spécifique de la région de transition entre la décharge interne de la cathode et la plume du propulseur sera réalisée. Ce modèle permettra de mettre en évidence certains phénomènes d'instabilité du plasma spécifiques de cette décharge, qui ont été jusqu'ici observés expérimentalement mais jamais pleinement intégrés aux modèles de cathode creuse. A l'aide du modèle validé, on procèdera à l'analyse physique de l'ensemble des phénomènes qui gouvernent le fonctionnement d'une cathode particulière, la cathode NSTAR développée par la NASA au Jet Propulsion Laboratory. Ensuite, on s'appuiera sur le modèle numérique pour comprendre l'impact sur le fonctionnement de la cathode des choix de conception au travers d'une étude paramétrique autour de la cathode NSTAR. Les tendances dégagées nous permettront de formuler des recommandations quant au développement de cathodes de haute puissance. Enfin, dans le but d'illustrer la versatilité du modèle développé, le comportement d'une cathode creuse employant une géométrie alternative à la cathode NSTAR sera également présenté. / A hollow cathode is a critical component of plasma thrusters. In a plasma thruster, a propellant gas is ionized in a discharge chamber and accelerated out of it so as to generate thrust. In Hall thrusters in particular, the ionization of the gas is caused by an intense electron current (from a few to hundred amps) which flows through the discharge chamber. The hollow cathode is the device which is responsible for providing the discharge current. This key element is often idealized in thruster numerical models and its physical behavior is rarely studied for its own sake. Yet, developing high power Hall thrusters, designed to propel in the long run every type of space mission, requires new hollow cathodes able to supply an intense electron current (over 100 A) over a duration on the order of ten thousand hours. So far, designing new cathodes proved difficult because of the lack of model capable of predicting the performance of a cathode based on its design. In this work, we build up a predictive model of a hollow cathode capable of simulating the physics relevant to the operation of the cathode. In the end, we aim at using this model to associate design characteristics of the cathode to key aspects of the cathode performance during operation. Our goal with this model is to guide the development of future high power hollow cathodes. We will first briefly describe the range of application of hollow cathodes related to space propulsion. Then we will give a brief account of the working principles of the cathode and we will set the numerical models available in the literature prior to this one out. The numerical model developed in this work will then be described. It includes a fluid treatment of the plasma as well as an account of the heat fluxes to the walls which largely control the performance of the cathode. Simulation results will be thoroughly compared to experimental measurements available in the literature and specific aspects of the model will be refined to match up simulation results with the physical reality. For instance, a model that specifically represents the transition region between the internal plasma of the cathode and the plume of the cathode will be described. This model will enable us to highlight plasma instability phenomena which were so far observed experimentally, yet never properly included in hollow cathode models. Using the model just developed, we will analyze the physics of a particular hollow cathode which has been developed by NASA at the Jet Propulsion Laboratory, the NSTAR hollow cathode. Then, thanks to the numerical model, we will be able to carry out a parametric study revolving around the design of the NSTAR cathode. This will allow us to bring out the influence of the design on the cathode performance and we will eventually express recommendations regarding the design of future high power cathodes. To conclude, the versatility of the numerical model built up here will also be displayed through simulations of the behavior of a hollow cathode based on an alternate geometry.

Le Canada est un joueur majeur dans l’industrie de l’aluminium. Pour demeurer compétitif mondialement, le coût de production de l’aluminium doit constamment être réduit. Les cellules d’électrolyse requièrent une grande quantité d’énergie (~13 kWh/kg) pour produire l’aluminium. De plus, l’efficacité du procédé Hall-Héroult est diminuée par la présence de dépôts à l’interface entre l’aluminium et le bloc cathodique. Ces dépôts causent une restriction pour le passage du courant engendrant une augmentation de la perte de potentiel. Les dépôts à la surface du bloc cathodique se divisent en différentes catégories. Il y a le pied de talus qui est situé sous le talus et sur le bloc cathodique. La partie du pied de talus près de la paroi de la cellule d’électrolyse possède une composition chimique similaire au talus. La partie à l’extrémité du pied de talus possède un ratio de cryolite plus élevé que le talus et elle est davantage sursaturée en alumine. L’extrémité du pied de talus peut atteindre jusqu’à 85 % d’Al[indice inférieur 2]O[indice inférieur 3]. Le pied de talus se forme par les pertes de chaleur situées au niveau de la paroi et au fond de la cellule. Il prend de l’expansion lorsque la température locale est inférieure à la température de solidification de la phase Na[indice inférieur 3]AlF[indice inférieur 6] (944 °C à un ratio de cryolite de 2,5). Le ratio de cryolite de l’extrémité du pied de talus augmente puisqu’il y a migration des cations Na[indice supérieur +] vers la cathode. La boue est composée d’un mélange d’Al[indice inférieur 2]O[indice inférieur 3] solide en suspension dans le bain électrolytique liquide. Elle est située, en général, au centre de la cellule d’électrolyse et sur le bloc cathodique. De plus, un film de bain sursaturé en alumine peut se retrouver entre le pied de talus et la boue au centre. Le ratio de cryolite de la boue se situe entre 2,2 et 2,5 et la concentration d’Al[indice inférieur 2]O[indice inférieur 3] varie entre 20 % et 50 %. La température de solidification de la phase Na[indice inférieur 3]AlF[indice inférieur 6] est fortement influencée par l’excès d’AlF[indice inférieur 3] et par la concentration en CaF[indice inférieur 2]. De plus, il y a présence d’une fraction liquide dans les dépôts dès 730 °C compte tenu de la présence de Na[indice inférieur 5]Al[indice inférieur 3]F[indice inférieur 14], Na[indice inférieur 2]Ca[indice inférieur 3]Al[indice inférieur 2]F[indice inférieur 14] et NaCaAlF[indice inférieur 6]. La fraction liquide augmente lorsque le ratio de cryolite diminue. Il y a évaporation de bain acide à partir d’environ 730 °C. Les dépôts dans la cellule d’électrolyse sont donc à l’état solide-liquide dès que la température atteint environ 730 °C.

Today’s most pressing problems would greatly benefit from an integrated production method for food, water, and energy. Biological fuel cells can offer such a production method, but current designs cannot be scaled to meet global demand. The ability of five different fungal strains to secrete laccase was evaluated under optimized culture conditions using three inducers. A specialized electrode was developed to increase the loading of laccase on the cathode. Trametes versicolor was then immobilized at the modified cathode and shown to secrete electrochemically active laccase. This hybrid design combines the power density of an enzymatic catalyst with the robustness of a microbial catalyst by facilitating biological renewal of the enzymatic catalyst laccase.

No description available.

>Magister Scientiae - MSc / Oxygen reduction reaction (ORR) is carried out in the cathode of the proton exchange membrane fuel cell (PEMFC) and it is known for its sluggish kinetics and the existence of two-pathway mechanism, related with the production of water and hydrogen peroxide. Nowadays, the design of novel cathode catalysts that are able to generate both high oxygen reduction currents and water as main product is a challenge since it causes an enhancement in the performance of PEMFC. Generally, these catalysts are composed of platinum nanoparticles, bearing in mind its high activity towards the ORR. However, the use of platinum means an increase in the total cost of PEMFCs due to its scarcity and high cost. This topic has been the motivation for a wide research in the field of PEMFCs during the last several years, being the main goal to design efficient and low cost catalysts for the cathode of PEMFCs. In this Master thesis project, platinum-palladium (Pt-Pd) catalysts supported on carbon black (CB), carbon nanofibers (CNF) and carbon xerogels (CX) were synthesised using methanol (MeOH), formaldehyde (FMY), n-propanol (nPrOH), ethanol (EtOH) and ascorbic acid (AA). The as-prepared materials were physically characterised by energy dispersive X-ray (EDS), X-ray diffraction (XRD) and transmission electronic microscopy (TEM), in order to determine its composition and morphological characteristics. The catalytic activity towards ORR was assessed by means of electrochemical techniques as rotating disc electrode (RDE) and cyclic voltammetry (CV).

Thesis advisor: Dunwei Wang / Non-aqueous Li-O2 batteries promise the highest theoretical specific energy among all rechargeable batteries. It is the only candidate that can be comparable with the internal combustion engine in terms of gravimetric energy density. This makes Li-O2 batteries preferable in the application of electric vehicles or drones. However, the materialization of this technology has been hindered by the poor cycling performance. The major reason for the degradation of the battery at the current research stage has been identified as the decomposition of the electrolyte and the cathode. These parasitic reactions will lower the yield of the desired product and induce huge overpotential during the recharge process. By carefully examining the degradation mechanism, we have identified the reactive oxygen species as the culprit that will corrode the cathode and attack the organic solvents. While parallel efforts have been devoted to reduce the reactivity of these species toward electrolyte, the main focus of this thesis is to identify suitable material platforms that can provide optimum performance and stability as cathodes. A bio-inspired wood-derived N-doped carbon is first introduced to demonstrate the benefit of hierarchical pore structures for Li-O2 cathodes. But the instability of the carbon cathode itself limits the lifetime of the battery. To improve the stability of carbon, we further introduce a catalytic active surface coating of FeOx on a three dimensionally ordered mesoporous carbon. The isolation of carbon from the reactive intermediates greatly improves the stability of the cathode. Yet the imperfections of the protection layer on carbon calls for a stable substrate that can replace carbon. TiSi2 is explored as the candidate. With the decoration of Pd catalysts, the Pd/TiSi2 cathode can provide extraordinary stability toward reactive oxygen species. But this composite cathode suffers from the detachment of the Pd catalyst. A Co3O4 surface layer is further introduced to enhance the adhesion of the catalyst, which doubles the lifetime of the cathode. To achieve a fully stable cathode, Ru catalyst with stronger adhesion on TiSi2 directly is explored and identified to be robust in the operating conditions of Li-O2 batteries. The expedition for stable cathodes in Li-O2 batteries is expected to provide a clean material platform. This platform can simplify the study in evaluating the effectiveness of catalysts, the reaction mechanism at the cathode and the stability of the electrolyte. Toward the end of this thesis, an exploration is made to enable rechargeable Mg metal battery with a conversion Br2 cathode. This new system can avoid the dendritic growth of Li metal by the adoption of Mg as the anode and can promise better cathode kinetics by forming a soluble discharge product. / Thesis (PhD) — Boston College, 2017. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Um detector de catodo quente é construído. As características de operação foram medidas e estabelecido o ponto ótimo de operação na detecção de átomos de sódio. Uma aplicação do detector desenvolvido foi feita com experimentos de deflexão de feixe atômico por luz. Os casos para deflexão por onda caminhante e onda estacionária foram investigados. A dependência com a dessintonia entre a freqüência do laser &#969&#8747 e a freqüência da transição 3S1/2 (F=2, m=2) &#8594 3P3/2 (F=3, m=3) do átomo de sódio foi analisada para todos os casos. / A hot wire detector has been constructed. The operational characteristics were measured and the optimum operational point was established in sodium atoms detection experiment. An application of the developed detector was made with atomic beams deflections by light. The cases for running wave and standing wave were also investigated. The detuning dependence between the laser frequency &#969&#8747 and the transition frequency 3S1/2 (F=2, m=2) &#8594 3P3/2 (F=3, m=3) of the sodium atom was analyzed for all cases.

Electric propulsion for spacecraft has become increasingly commonplace in recent decades as designers take advantage of the significant propellant savings it can provide over traditional chemical propulsion. As electric propulsion systems are designed for very low thrust, the operational time required over the course of an entire mission is often quite long. The two most common types of electric thrusters both use hollow cathodes as electron emitters in the process of ionizing the propellant gas. These cathodes are one of the main life-limiting components of both ion and Hall thrusters designed to operate for tens of thousands of hours. Failure often occurs as a result of erosion by sputtering from high-energy ions generated in the plasma. The mechanism that is responsible for creating these high-energy ions is not well understood, and significant efforts have gone into characterizing the plasma produced by hollow cathodes. This work uses both a Langmuir probe and an emissive probe to characterize the variation of the plasma potential and density, the electron temperature, and the electron energy distribution function in the near plume region of a hollow cathode. The cathode used in this experiment is typical of one used in a 200-W class Hall thruster. Measurements were made to determine the variation of these parameters with radial position from the cathode orifice. Changes associated with varying the propellant and flow rate were also investigated. Results obtained from the cathode while running on both argon and xenon are shown. Two different methods for calculating the plasma density and electron temperature were used and are compared. The density and temperature were not strongly affected by reductions in the propellant flow rate. The electron energy distribution functions showed distinct shifts toward higher energies when the cathode was operated at lower flow rates. The plasma potential also displayed an abrupt change in magnitude near the cathode centerline. Significant increases in the magnitude of plasma potential oscillations at lower propellant flow rates were observed. Ions formed at the highest instantaneous plasma potentials may be responsible for the life-limiting erosion that is observed during long-duration operation of hollow cathodes.

The need for cleaner and more efficient alternative energy sources is becoming urgent as concerns mount about climate change wrought by greenhouse gas emissions. Solid oxide fuel cells (SOFCs) are one of the most efficient options if the goal is to reduce emissions while still operating on fossil energy resources. One of the foremost problems in SOFCs that causes efficiency loss is the polarization resistance associated with the oxygen reduction reaction(ORR) at the cathodes. Hence, improving the cathode design will greatly enhance the overall performance of SOFCs. Lanthanum nickelate, La2NiO4+δ (LNO), is a mixed ionic and electronic conductor that has competitive surface oxygen exchange and transport properties and excellent electrical conductivity compared to perovskite-type oxides. This makes it an excellent candidate for solid oxide fuel cell (SOFC) applications. It has been previously shown that composites of LNO with Sm0.2Ce0.8O2-δ (SDC20) as cathode materials lead to higher performance than standalone LNO. However, in contact with lanthanide-doped ceria, LNO decomposes resulting in free NiO and ceria with higher lanthanide dopant concentration. In this study, the aforementioned instability of LNO has been addressed by compositional tailoring of LNO: lanthanide doped ceria (LnxCe1-xO2,LnDC)composite. By increasing the lanthanide dopant concentration in the ceria phase close to its solubility limit, the LNO phase has been stabilized in the LNO:LnDC composites. Electrical conductivity of the composites as a function of LNO volume fraction and temperature has been measured, and analyzed using a resistive network model which allows the identification of a percolation threshold for the LNO phase. The thermomechanical compatibility of these composites has been investigated with SOFC systems through measurement of the coefficients of thermal expansion. LNO:LDC40 composites containing LNO lower than 50 vol%and higher than 40 vol% were identified as being suitable to incorporate into full button cell configuration from the standpoint of thermomechanical stability and adequate electrical conductivity. Proof-of-concept performance comparison for SOFC button cells manufactured using LNO: La0.4Ce0.6O2-δ composite to the conventional composite cathode materials has also been provided. This thermodynamics-based phase stabilization strategy can be applied to a wider range of materials in the same crystallographic family, thus providing the SOFC community with alternate material options for high performance devices.