In Canada, more than 1.11 TWh of energy per year is generated by diesel generators in off-grid remote areas. Delivering energy to these territories always has a high cost for the local and federal governments both financially and environmentally. Substituting fossil fuels with clean energies is the solution. However, the unreliability and intermittency of renewable energies (RE) are always challenging issues that need to be solved. Zinc air flow battery (ZAFB) with decoupled power and energy capacity can bring sustainability and reliability for microgrids. In this study, an efficient model was developed for ZAFB, which is applicable for large-scale modeling, and incorporated in microgrid modeling. A bilevel optimization approach was implemented in the microgrid model to find the optimal size and control of the microgrid simultaneously over the project lifetime. Using model predictive control (MPC) and based on user-defined foresight horizon and known information like energy demand and RE resources, the control model decides the future changes in microgrid components. This tool is used to propose the best microgrid design for these communities to reduce or eliminate their dependency on fossil fuels. The functionality of this tool was evaluated by three case studies in British Columbia: Blind Channel, Hot Springs Cove and Moresby Island. Zero CO2 emission and zero fuel consumption were achieved by a 100% RE microgrid consisting of wind and tidal turbines and large ZAFB. The net present cost (NPC) of this system and cost of energy are 39 – 46 % and 55 – 60 % less than the base case costs in which diesel is the main energy source. ZAFB with a longer storage duration (50 – 60 hours) satisfies 17 – 23% of annual energy demand in these case studies. / Graduate

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In the past decade, rechargeable batteries attracted the attention from the researchers in search for renewable and sustainable energy sources. Up to date, lithium-ion battery is the most commercialized and has been supplying power to electronic devices and hybrid and electric vehicles. Lithium-ion battery, however, does not satisfy the expectations of ever-increasing energy and power density, which of their limits owes to its intercalation chemistry and the safety.1-2 Therefore, metal-air battery drew much attention as an alternative for its high energy density and a simple cell configuration.1 There are several different types of metal-air batteries that convey different viable reaction mechanisms depending on the anode metals; such as Li, Al, Ca, Cd, and Zn. Redox reactions take place in a metal-air cell regardless of the anode metal; oxidation reaction at the anode and reduction reaction at the air electrode. Between the two reaction, the oxygen reduction reaction (ORR) at the air electrode is the relatively the limiting factor within the overall cell reactions. The sluggish ORR kinetics greatly affects the performance of the battery system in terms of power output, efficiency, and durability. Therefore, researchers have put tremendous efforts in developing highly efficient metal air batteries and fuel cells, especially for high capacity applications such as electric vehicles. Currently, the catalyst with platinum nanoparticles supported on carbon material (Pt-C) is considered to exhibit the best ORR activities. Despite of the admirable electrocatalytic performance, Pt-C suffers from its lack of practicality in commercialization due to their prohibitively high cost and scarcity as of being a precious metal. Thus, there is increasing demand for replacing Pt with more abundant metals due economic feasibility and sustainability of this noble metal.3-5 Two different attitudes are taken for solution. The first approach is by optimizing the platinum loading in the formulation, or the alternatively the platinum can be replaced with non-precious materials. The purpose of this work is to discover and synthesize alternative catalysts for metal-air battery applications through optimized method without addition of precious metals. Different non-precious metals are investigated as the replacement of the precious metal including transition metal alloys, transition metal or mixed metal oxides, and chalcogenides. These types of metals, alone, still exhibits unsatisfying, yet worse, kinetics in comparison to the precious metals. Nitrogen-doped carbon material is a recently well studied carbon based material that exhibits great potential towards the cathodic reaction.6 Nitrogen-doped carbon materials are found to exhibit higher catalytic activity compared to the mentioned types of metals for its improved conductivity. Benefits of the carbon based materials are in its abundance and minimal environmental footprints. However, the degradation of these materials has demonstrated loss of catalytic activity through destruction of active sites containing the transition metal centre, ultimately causing infeasible stability. To compensate for these drawbacks and other limits of the nitrogen-doped carbon based catalysts, nitrogen-doped carbon nanotubes (NCNT) are also investigated in the series of study. The first investigation focuses on a development of a simple method to thermally synthesize a non-precious metal based nitrogen-doped graphene (NG) electrocatalyst using exfoliated graphene (Ex-G) and urea with varying amounts of iron (Fe) precursor. The morphology and structural features of the synthesized electrocatalyst (Fe-NG) were characterized by SEM and TEM, revealing the existence of graphitic nanoshells that potentially contribute to the ORR activity by providing a higher degree of edge plane exposure. The surface elemental composition of the catalyst was analyzed through XPS, which showed high content of a total N species (~8 at.%) indicative of the effective N-doping, present mostly in the form of pyridinic nitrogen groups. The oxygen reduction reaction (ORR) performance of the catalyst was evaluated by rotating disk electrode voltammetry in alkaline electrolyte and in a zinc-air battery cell. Fe-NG demonstrated high onset and half-wave potentials of -0.023 V (vs. SCE) and -0.110 V (vs. SCE), respectively. This excellent ORR activity is translated into practical zinc-air battery performance capabilities approaching that of commercial platinum based catalyst. Another approach was made in the carbon materials to further improve the cost of the electrode. Popular carbon allotropes, CNT and graphene, are combined as a composite (GC) and heteroatoms, nitrogen and sulfur, are introduced in order to improve the charge distribution of the graphitic network. Dopants were doped through two step processes; nitrogen dopant was introduced into the graphitic framework followed by the sulfur dopant. The coexistence of the two heteroatoms as dopants demonstrated outstanding ORR performance to those of reported as metal free catalysts. Furthermore, effects of temperature were investigated through comparing ORR performances of the catalysts synthesized in two different temperatures (500 ??? and 900 ???) during the N-doping process (consistent temperature was used for S-doping). Through XPS analysis of the surface chemistry of catalysts produced with high temperature during the N-doping step showed absence of N-species after the subsequent S-doping process (GC-NHS). Thus, the synergetic effects of the two heteroatoms were not revealed during the half-cell testing. Meanwhile, the two heteroatoms were verified in the catalyst synthesized though using low temperature during the N-doping process followed by the S-doping step (GC-NLS). Consequently, ORR activity of the resulting material demonstrated promising onset and half-wave potentials of -0.117 V (vs. SCE) and -0.193 V (vs. SCE). In combination of these investigations, this document introduces thorough study of novel materials and their performance in its application as ORR catalyst in metal air batteries. Moreover, this report provides detailed fundamental insights of carbon allotropes, and their properties as potential elecrocatalysts and essential concepts in electrochemistry that lies behind zinc-air batteries. The outstanding performances of carbon based electrocatalyst are reviewed and used as the guides for further direction in the development of metal-air batteries as a promising sustainable energy resource in the future.

Global warming and depletion in fossil fuels have forced the society to search for alternate, clean sustainable energy sources. An obvious solution to the aforesaid problem lies in electrochemical energy storage systems like fuel cells and batteries. The desirable properties attributed to these devices like quick response, long life cycle, high round trip efficiency, clean source, low maintenance etc. have made them very attractive as energy storage devices. Compared to many advanced battery chemistries like nickel-metal hydride and lithium - ion batteries, metal-air batteries show several advantages like high energy density, ease of operation etc. The notable characteristics of metal - air batteries are the open structure with oxygen gas accessed from ambient air in the cathode compartment. These batteries rely on oxygen reduction and oxygen evolution reactions during discharging and charging processes. The efficiency of these systems is determined by the kinetics of oxygen reduction reaction. Platinum is the most preferred catalyst for many electrochemical reactions. However, high cost and stability issues restrict the use of Pt and hence there is quest for the development of stable, durable and active electrocatalysts for various redox reactions. The present thesis is directed towards exploring the electrocatalytic aspects of titanium carbonitride. TiCN, a fascinating material, possesses many favorable properties such as extreme hardness, high melting point, good thermal and electrical conductivity. Its metal-like conductivity and extreme corrosion resistance prompted us to use this material for various electrochemical studies. The work function as well as the bonding in the material can be tuned by varying the composition of carbon and nitrogen in the crystal lattice. The current study explores the versatility of TiCN as electrocatalyst in aqueous and non-aqueous media. One dimensional TiC0.7N0.3 nanowires are prepared by simple one step solvothermal method without use of any template and are characterized using various physicochemical techniques. The 1D nanostructures are of several µm size length and 40 ± 15 nm diameter (figure 1). Orientation followed by attachment of the primary particles results in the growth along a particular plane (figure 2). (a) (b) (c) Figure 1. (a) SEM images of TiC0.7N0.3 nanowires (b) TEM image and (c) High resolution TEM image showing the lattice fringes. (a) (b) (d) Figure 2. Bright field TEM images obtained at different time scales of reaction. (a) 0 h; (b) 12 h; (c) 72 h and (d) 144 h. The next aspect of the thesis discusses the electrochemical performance of TiC0.7N0.3 especially for oxygen reduction. Electrochemical oxygen reduction reaction (ORR) reveals that the nanowires possess high activity for ORR and involves four electron process leading to water as the product. The catalyst effectively converts oxygen to water with an efficiency of 85%. A comparison of the activity of different (C/N) compositions of TiCN is shown in figure 3. The composition TiC0.7N0.3 shows the maximum activity for the reaction. The catalyst is also very selective for ORR in presence of methanol and thus cross-over issue in fuel cells can be effectively addressed. Density functional theory (DFT) calculations also lead to the same composition as the best for electrocatalysis, supporting the experimental observations. Figure 3. Linear sweep voltammetric curves observed for different compositions of titanium carbonitride towards ORR. The next chapter deals with the use of TiC0.7N0.3 as air cathode for aqueous metal - air batteries. The batteries show remarkable performance in the gel- and in liquid- based electrolytes for zinc - air and magnesium - air batteries. A partial potassium salt of polyacrylic acid (PAAK) is used as the polymer to form a gel electrolyte. The cell is found to perform very well even at very high current densities in the gel electrolyte (figures 4 and 5). Figure 4 Photographs of different components of the gel - based zinc - air battery. (a) (b) Figure 5. a) Discharge curves at different current densities of 5, 20, 50 and 100 mA/cm2 for zinc-air system with TiC0.7N0.3 cathode b) Charge – discharge cycles at 50 mA/cm2 for the three electrode configuration with TiC0.7N0.3 nanowire for ORR and IrO2 for OER and Zn electrode (2h. cycle period). Similarly, the catalytic activity of TiC0.7N0.3 has also been explored in non-aqueous electrolyte. The material acts as a bifunctional catalyst for oxygen in non- aqueous medium as well. It shows a stable performance for more than 100 cycles with high reversibility for ORR and OER (figure 6). Li-O2 battery fabricated with a non-aqueous gel- based electrolyte yields very good output. (a) (b) (c) Figure 6. Galvanostatic charge –discharge cycles. (a) at 1 mA/cm2 (b) specific capacity as a function of no. of cycles (c) photographs of PAN-based gel polymer electrolyte. Another reaction of interest in non –aqueous medium is I-/I3-. redox couple. TiC0.7N0.3 nanowires show small peak to peak separation, low charge transfer resistance and hence high activity. The catalyst is used as a counter electrode in dye sensitized a solar cell that shows efficiencies similar to that of Pt, state of the art catalyst (figure 7). (a) (b) (c) Figure 7 (a) Cyclic voltammograms for I-/I3 - redox species on TiC0.7N0.3 nanowires (red), TiC0.7N0.3 particle (black) and Pt (blue). (b) Photocurrent density - voltage characteristics for DSSCs with different counter electrodes. TiC0.7N0.3 nanowire (black), TiC0.7N0.3 particle (blue), Pt (red). (c) Photograph of a sample cell. (a) (b) (c) (d) Figure 8 a) Comparison ORR activity for (i) NiTiO3(black), (ii) N-rGO (red), (iii) NiTiO3 – N-rGO (green) and (iv) Pt/C (blue) (b) Linear sweep voltammograms for OER observed on NiTiO3 – N-rGO composite (black), NiTiO3 (brown), N-rGO (blue), glassy carbon (red) in 0.5 M KOH. (c) Galvanostatic discharge curves of NiTiO3 – N-rGO as air electrode (d) Charge – discharge cycle at 5 mA/cm2 for the rechargeable battery with 10 min. cycle period. The last part of the thesis discusses about a ceramic oxide, nickel titanate. The electrocatalytic studies of the material towards ORR and OER reveal that the catalyst shows remarkable performance as a bifunctional electrode. A gel - based zinc - air battery fabricated with nickel titanate – reduced graphene oxide composite shows exceptional performance of 1000 charge-discharge cycles in the rechargeable mode (figure 8). Of course, the primary battery configuration works very well too The thesis contains seven chapters on the aspects mentioned above with summary and future perspectives given as the last chapter. An appendix based on TiN nanotubes and supercapacitor studies is given at the end.

Der zunehmende Einsatz regenerativer Energiequellen erfordert die Nutzung von Energiezwischenspeichern, die umweltfreundlich, günstig und skalierbar sein sollten. Die Zink-Luft-Flussbatterie (ZLFB) kann perspektivisch diese Anforderungen erfüllen, wobei zur Bereitstellung der gespeicherten Energie eine Suspension aus Zinkpartikeln in einem gelierten Elektrolyt durch eine elektrochemische Zelle gepumpt wird. Um die Strömungsstruktur der ZLFB auszulegen und Fehlfunktionen zu vermeiden, ist ein grundlegendes Verständnis der Rheologie der Zinksuspension notwendig. Außerdem kann über die Einstellung einer geeigneten Strömung die bei der Entladung erreichte elektrische Leistungsdichte gesteigert werden. Bereits die Flüssigphase der Zinksuspension weist eine komplexe nicht-Newtonsche Rheologie auf, welche durch die Zugabe der Partikel komplexer wird. Für das grundlegende Verständnis der Rheologie werden daher Modellexperimente durchgeführt, wobei in dieser Arbeit ein L-förmiger Kanal mit Strömungsaufweitung untersucht wurde, um die komplexen strömungsmechanischen Eigenschaften der Zinksuspension abzubilden. Zur Erfassung des Strömungsfeldes ist eine Ortsauflösung von 1 … 2 mm in einem Messbereich von 20 × 15 mm2 erforderlich. Ultraschall ist prinzipiell geeignet, um das Strömungsfeld in der opaken Suspension zu erfassen, wobei die wesentliche Herausforderung in den starken Wellenfrontverzerrungen besteht, welche durch die Zinkpartikel eingebracht werden. Es konnte gezeigt werden, dass die Ultrasound Imaging Velocimetry (UIV) robuster gegenüber diesen Störungen ist, als die Ultraschall-Doppler-Velozimetrie (UDV). Die UIV wurde daher mittels Geschwindigkeitsnormal an die messtechnischen Randbedingungen der Zinksuspension angepasst und charakterisiert. Bei einer Ortsauflösung von 1,6 mm wurde eine Gesamtmessunsicherheit von 2,5 % axial und 4,1 % lateral zur Schallausbreitungsrichtung erreicht. Das im Modellexperiment gemessene Strömungsfeld weist eine Totzone an der Strömungsumlenkung auf, deren Auftreten durch eine von der Scherhistorie abhängige Viskosität erklärt werden kann. Dieser Effekt wird als Thixotropie bezeichnet. Durch die In-situ-Messung der Strömung in einer aktiven ZLFB kann eine Korrelation von Strömung und elektrischer Leistung erfolgen und die erzielte Leistungsdichte perspektivisch durch eine Anpassung der Strömung gesteigert werden. Bei der Messung im 2,6 mm hohen Anodenspalt muss aufgrund der komplexen Rheologie der Suspension und der daraus resultierenden hohen Geschwindigkeitsgradienten eine Ortsauflösung von unter 100 µm bei gleichzeitig kleiner Ultraschallfrequenz realisiert werden, da der Ultraschall für hohe Frequenzen nicht in die Zinksuspension eindringt. Um dieses Ziel zu erreichen, wurde die Super Resolution Ultrasound Particle Tracking Velocimetry (SRPTV) genutzt, welche Ortsauflösungen unterhalb des Beugungslimits ermöglicht. Einzelne nichtlineare Streupartikel werden mittels Harmonic Imaging isoliert abgebildet und verfolgt, wobei die durch die Zinkpartikel eingebrachten Wellenfrontstörungen durch einen kohärenzgewichteten Strahlformer kompensiert werden. Es wurde eine Ortsauflösung von 67 µm axial und 30 µm lateral zur Schallausbreitungsrichtung bei einer Anregungswellenlänge von 330 µm erreicht. Trotz der stark streuenden Zinksuspension, konnte so eine Messung in der aktiven ZLFB mit einer maximalen Messunsicherheit von 12,5 % durchgeführt werden. Dabei wurde eine Wandgleitgeschwindigkeit von 3 mm s−1 bei einer maximalen Geschwindigkeit von etwa 8 mm s−1 festgestellt. Die SRPTV kann darüber hinaus in anderen technischen Prozessen eingesetzt werden, in denen Suspensionsströmungen in kleinen Geometrien auftreten.:Symbolverzeichnis xiii Abkürzungsverzeichnis xv 1 Einleitung 1 1.1 Motivation und Zielstellung 1 1.2 Stand der Technik 4 1.3 Lösungsansatz und Struktur der Arbeit 8 2 Theoretische Grundlagen 11 2.1 Grundlagen der Schallausbreitung 11 2.1.1 Schallausbreitung in homogenen Medien 11 2.1.2 Schallausbreitung in inhomogenen Medien 13 2.2 Ultraschall Bildgebung 14 2.2.1 Phased-Array-Prinzip 15 2.2.2 Plane wave imaging 16 2.2.3 Grenzen der Schallfeldfokussierung 16 2.3 Messung von Strömungsfeldern 17 2.3.1 Ultraschall-Doppler-Velozimetrie 18 2.3.2 Ultrasound Imaging Velocimetry 19 2.3.3 Ultrasound Particle Tracking Velocimetry 19 2.4 Nichtlineare akustische Effekte 20 2.4.1 Beschreibung von Linearität 20 2.4.2 Interaktion von nichtlinearen Streupartikeln und Schallwelle 20 2.4.3 Harmonic Imaging 21 3 Experimentelle Grundlagen 25 3.1 Charakterisierung der Zinksuspension 25 3.1.1 Zusammensetzung der Zinksuspension 25 3.1.2 Bestimmung von Dämpfung und Schallgeschwindigkeit 26 3.1.3 Bestimmung der spezifischen akustischen Impedanz 29 3.2 Messtechnik 30 3.2.1 Ultraschallforschungsplattform: Phased Array Ultrasound Dopp- ler Velocimeter 30 3.2.2 Ultraschallwandler 32 4 Verfahren zur Strömungsmessung im Modellexperiment 37 4.1 Experimenteller Aufbau 37 4.2 Untersuchung geeigneter Verfahren zur Messung von Strömungsfel- dern in der Zinksuspension 38 4.3 Optimierung der Signalverarbeitung und Charakterisierung der Messei- genschaften 44 4.3.1 Geschwindigkeitsnormal 44 4.3.2 Optimierung der Messsystemparameter 45 4.3.3 Charakterisierung der Messeigenschaften 48 4.3.4 Validierung 49 4.4 Messung der Suspensionsströmung im Modellexperiment 55 4.4.1 Messergebnisse 55 4.4.2 Vergleich von Simulation und Messung 58 4.5 Fazit 61 5 Verfahren zur In-situ-Strömungsmessung in einer Zink-Luft-Flussbatterie 63 5.1 Experimenteller Aufbau 63 5.2 Strömungsmessung unterhalb des Beugungslimits - Super Resolution Ultrasound Particle Tracking Velocimetry (SRPTV) 65 5.2.1 Nutzung nichtlinearer Streupartikel 68 5.2.2 Trennung von linearem und nichtlinearem Signalanteil 72 5.2.3 Strahlformung mit Kompensation der Streuung 76 5.2.4 Particle Tracking 80 5.3 Charakterisierung der Messeigenschaften 81 5.3.1 Vorgehen zur Charakterisierung der Messeigenschaften 82 5.3.2 Untersuchung der Positionsunsicherheit 83 5.3.3 Untersuchung der Geschwindigkeitsunsicherheit 92 5.4 Messung an einer aktiven Zink-Luft-Flussbatterie 95 5.4.1 Aufbau und Durchführung 95 5.4.2 Messergebnisse 97 5.4.3 Vergleich von Simulation und Messung 97 5.5 Fazit 102 6 Zusammenfassung und Ausblick 103 6.1 Erkenntnisse und Fortschritt 103 6.1.1 Ultrasound Imaging Velocimetry 103 6.1.2 Super Resolution Ultrasound Particle Tracking Velocimetry 104 6.1.3 Fazit 106 6.2 Ausblick und weiterführende Arbeiten 106 6.2.1 Messtechnik 106 6.2.2 Anwendung 107 Literaturverzeichnis 109 Publikationsverzeichnis 117 Artikel in Zeitschriften mit peer-review 117 Tagungsbeiträge 117 Patente 119 / For the efficient use of renewable energies, energy storage systems are required that are environmentally friendly, low priced and scalable. The zinc-air flow battery (ZAB), which is operated by pumping an opaque suspension of zinc particles in an gelled electrolyte through an electrochemical cell, is a promising candidate as energy storage system for these requirements. To design the fluidic structures and avoid malfunction, a fundamental understanding of the rheology of the zinc suspension is required. Additionally, the electrical performance of the cell can be imporved by optimizing the flow in the electrochemical cell. The liquid phase of the suspension itself has complex non-Newtonian properties, which are even more complex when the particles are considered. For the fundamental understanding of the suspension rheology, model experiments are conducted. In this work an L-shaped channel with a widening is used to represent relevant effects from the complex rheology of the suspension. To measure the flow field, a spatial resolution of 1 … 2 mm and a measurement area of 20 × 15 mm2 are required. Ultrasound can be used to measure the flow in opaque liquids, but wavefront distortions are introduced by the zinc particles. Established measurement methods for homogeneous opaque fluids, the Ultrasound Imaging Velocimetry (UIV) and the Ultrasound Doppler Velocimetry (UDV), were compared for the application at the suspension. The UIV has a 50 % lower random deviation, which makes it more suitable for the flow measurement in the suspension and it was adapted to the measurement conditions in the suspension. At a spatial resolution of 1.66 mm, a velocity uncertainty of 2.5 % axial and 4.1 % lateral to the ultrasound propagation were achieved. The application of the UIV to the suspension flow in the model experiment revealed a thixotropic behavior of the fluid, which resulted in a dead flow zone opposite to the inlet of the channel. The in situ measurement of the flow in an active ZAB, allows to correlate electrical performance and flow and thereby an improvement of the cell performance by adapting the flow. For the measurement in the anodic channel with a width of 2.6 mm, a spatial resolution of 100 µm is required because of the high velocity gradients due to the non-Newtonian rheology of the suspension. The high spatial resolution has to be achieved at low ultrasound frequencies, since the ultrasound does not penetrate into the suspension for high frequencies. To achieve this, the Super Resolution Ultrasound Particle Tracking Velocimetry (SRPTV) was used, which allows a spatial resolution beyond the diffraction limit. Harmonic Imaging is used to image isolated non-linear tracer particles, which are tracked for velocity estimation. The speckle and image distortion due to the induced wavefront distortions are compensated with a coherence weighting beamformer. A spatial resolution of 67 µm axial and 30 µm lateral to the ultrasound propagation were achieved. Despite the strong scattering of the ultrasound at the zinc particles, a maximum velocity uncertainty of 12.5 % referred to the maximum velocity was achieved for the measurement in the active ZAB. A slip velocity of 3 mm at a maximum velocity of 8 mm was observed. The SRPTV can be applied to other technical processes, where suspension flows in small geometries play an important role.:Symbolverzeichnis xiii Abkürzungsverzeichnis xv 1 Einleitung 1 1.1 Motivation und Zielstellung 1 1.2 Stand der Technik 4 1.3 Lösungsansatz und Struktur der Arbeit 8 2 Theoretische Grundlagen 11 2.1 Grundlagen der Schallausbreitung 11 2.1.1 Schallausbreitung in homogenen Medien 11 2.1.2 Schallausbreitung in inhomogenen Medien 13 2.2 Ultraschall Bildgebung 14 2.2.1 Phased-Array-Prinzip 15 2.2.2 Plane wave imaging 16 2.2.3 Grenzen der Schallfeldfokussierung 16 2.3 Messung von Strömungsfeldern 17 2.3.1 Ultraschall-Doppler-Velozimetrie 18 2.3.2 Ultrasound Imaging Velocimetry 19 2.3.3 Ultrasound Particle Tracking Velocimetry 19 2.4 Nichtlineare akustische Effekte 20 2.4.1 Beschreibung von Linearität 20 2.4.2 Interaktion von nichtlinearen Streupartikeln und Schallwelle 20 2.4.3 Harmonic Imaging 21 3 Experimentelle Grundlagen 25 3.1 Charakterisierung der Zinksuspension 25 3.1.1 Zusammensetzung der Zinksuspension 25 3.1.2 Bestimmung von Dämpfung und Schallgeschwindigkeit 26 3.1.3 Bestimmung der spezifischen akustischen Impedanz 29 3.2 Messtechnik 30 3.2.1 Ultraschallforschungsplattform: Phased Array Ultrasound Dopp- ler Velocimeter 30 3.2.2 Ultraschallwandler 32 4 Verfahren zur Strömungsmessung im Modellexperiment 37 4.1 Experimenteller Aufbau 37 4.2 Untersuchung geeigneter Verfahren zur Messung von Strömungsfel- dern in der Zinksuspension 38 4.3 Optimierung der Signalverarbeitung und Charakterisierung der Messei- genschaften 44 4.3.1 Geschwindigkeitsnormal 44 4.3.2 Optimierung der Messsystemparameter 45 4.3.3 Charakterisierung der Messeigenschaften 48 4.3.4 Validierung 49 4.4 Messung der Suspensionsströmung im Modellexperiment 55 4.4.1 Messergebnisse 55 4.4.2 Vergleich von Simulation und Messung 58 4.5 Fazit 61 5 Verfahren zur In-situ-Strömungsmessung in einer Zink-Luft-Flussbatterie 63 5.1 Experimenteller Aufbau 63 5.2 Strömungsmessung unterhalb des Beugungslimits - Super Resolution Ultrasound Particle Tracking Velocimetry (SRPTV) 65 5.2.1 Nutzung nichtlinearer Streupartikel 68 5.2.2 Trennung von linearem und nichtlinearem Signalanteil 72 5.2.3 Strahlformung mit Kompensation der Streuung 76 5.2.4 Particle Tracking 80 5.3 Charakterisierung der Messeigenschaften 81 5.3.1 Vorgehen zur Charakterisierung der Messeigenschaften 82 5.3.2 Untersuchung der Positionsunsicherheit 83 5.3.3 Untersuchung der Geschwindigkeitsunsicherheit 92 5.4 Messung an einer aktiven Zink-Luft-Flussbatterie 95 5.4.1 Aufbau und Durchführung 95 5.4.2 Messergebnisse 97 5.4.3 Vergleich von Simulation und Messung 97 5.5 Fazit 102 6 Zusammenfassung und Ausblick 103 6.1 Erkenntnisse und Fortschritt 103 6.1.1 Ultrasound Imaging Velocimetry 103 6.1.2 Super Resolution Ultrasound Particle Tracking Velocimetry 104 6.1.3 Fazit 106 6.2 Ausblick und weiterführende Arbeiten 106 6.2.1 Messtechnik 106 6.2.2 Anwendung 107 Literaturverzeichnis 109 Publikationsverzeichnis 117 Artikel in Zeitschriften mit peer-review 117 Tagungsbeiträge 117 Patente 119

Single-atom catalysts (SACs), as promising alternatives to Pt-based catalysts, suffer from the limited choice of center metals and low single-atom loading. Here, we report a pentacoordinated Zr-based SAC with nontrivial axial O ligands (denoted O−Zr−N−C) for oxygen reduction reaction (ORR). The O ligand downshifts the d-band center of Zr and confers Zr sites with stable local structure and proper adsorption capability for intermediates. Consequently, the ORR performance of O−Zr−N−C prominently surpasses that of commercial Pt/C, achieving a half-wave potential of 0.91 V vs. reversible hydrogen electrode and outstanding durability (92 % current retention after 130-hour operation). Moreover, the Zr site shows good resistance towards aggregation, enabling the synthesis of Zr-based SAC with high loading (9.1 wt%). With the high-loading catalyst, the zinc-air battery (ZAB) delivers a record-high power density of 324 mW cm−2 among those of SAC-based ZABs.