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[ES] Un aumento de la generación de energía a partir de fuentes renovables (solar, eólica) requiere una alta flexibilidad de las redes eléctricas. En este sentido, las baterías de flujo redox de vanadio (BFRV) han demostrado una excelente capacidad para proporcionar dicha flexibilidad, mediante el almacenamiento eficiente de energía eléctrica en el rango de los kWh a los MWh. Sin embargo, sus elevados costes son en la actualidad unos de los mayores inconvenientes que dificultan una amplia penetración en el mercado. En la presente Tesis Doctoral se presenta el desarrollo y evaluación de una celda tubular especialmente diseñada con una membrana de 5.0mm. Las células tubulares así diseñadas deberían alcanzar una mayor densidad de potencia (kWm^(-3)). Del mismo modo, la sustitución de uno de los electrodos por un electrodo bifuncional de aire debería de incrementar la energía específica de dicha celda (Whkg^(-1)) y reducir, por tanto, los costes energéticos asociados (€/kWh). El diseño de la celda desarrollado en la presente Tesis Doctoral facilita la fabricación de los colectores y membranas actuales con el empleo de procesos de extrusión y marca un paso importante hacia la fabricación rentable de semiceldas y celdas completas en el futuro. Para evaluar el comportamiento de la nueva celda diseñada se han llevado a cabo estudios de polarización, de espectroscopia de impedancia, y medidas de ciclos de carga/descarga. Las celdas desarrolladas presentan una corriente de descarga máxima de 89.7mAcm^(-2) y una densidad de potencia de 179.2kW/m^3. Además, los bajos sobrepotenciales residuales obtenidos en los electrodos de la celda resultan prometedores. No obstante, la resistencia del área específica de celda de 3.2 ohm*cm² impone limitaciones significativas en la densidad de corriente. Eficiencias Coulomb del 95 % han sido obtenidas, comparables a los valores alcanzados en celdas planas de referencia. Sin embargo, las pérdidas óhmicas resultan elevadas, reduciendo la eficiencia energética del sistema al 56 %. Las celdas tubulares fabricadas con un electrodo de difusión de gas de una sola capa con Pt/IrO2 como catalizador permiten alcanzar densidades de corriente máximas de 32mAcm^(-2) (Ecell =2.1 V/0.56V Ch/Dch). Los elevados sobrepotenciales de activación y el reducido voltaje en circuito abierto (debido a potenciales mixtos) conducen a una densidad de potencia comparativamente baja de 15.4mW/ cm². El paso de iones de vanadio a través de la membrana se considera uno de los grandes inconvenientes en este tipo de celdas tubulares, lo que lleva a que la densidad de energía real de 23.2Wh l^(-1) caiga por debajo del valor nominal de 63.9Wh l^(-1). / [CAT] Un augment de la generació d'energia a partir de fonts renovables (solar, eòlica) requereix una alta flexibilitat de les xarxes elèctriques. En aquest sentit, les bateries de flux redox de vanadi (VRFB) han demostrat una excel·lent capacitat per a proporcionar aquesta flexibilitat, mitjançant l'emmagatzematge eficient d'energia elèctrica en el rang dels kWh als MWh. En la present Tesi Doctoral es presenta el desenvolupament i avaluació d'una cel·la tubular especialment dissenyada amb una membrana de 5.0mm. Les cèl·lules tubulars així dissenyades haurien assolir una major densitat de potència (kWm^(-3)). De la mateixa manera, la substitució d'un dels elèctrodes per un elèctrode bifuncional d'aire hauria d'incrementar l'energia específica d'aquesta cel·la (Whkg^(-1)) i reduir, per tant, els costos energètics associats (€/kWh). El disseny de la cel·la desenvolupat en la present tesi doctoral facilita la fabricació dels col·lectors i membranes actuals amb l'ocupació de processos d'extrusió i marca un pas important cap a la fabricació rendible de semiceldas i cel·les completes en el futur. Per avaluar el comportament de la nova cel·la dissenyada s'han dut a terme estudis de polarització, d'espectroscòpia d'impedància, i mesures de cicles de càrrega/ descàrrega. Les cel·les desenvolupades presenten un corrent de descàrrega màxima de 89.7mAcm^(-2) i una densitat de potència de 179.2kW/m^3. A més, els baixos sobrepotencials residuals obtinguts en els elèctrodes de la cel·la resulten prometedors. No obstant això, la resistència de l'àrea específica de cel·la de 3.2 ohm*cm² imposa limitacions significatives en la densitat de corrent. Eficiències Coulomb del 95 % han estat obtingudes, comparables als valors assolits en cel·les planes de referència. No obstant això, les pèrdues òhmiques resulten elevades, reduint l'eficiència energètica del sistema al 56 %. Les cel·les tubulars fabricades amb un elèctrode de difusió de gas d'una sola capa amb Pt/IrO2 com a catalitzador permeten assolir densitats de corrent màximes de 32mAcm^(-2) (Ecell =2.1 V/0.56V Ch/Dch). Els elevats sobrepotencials d'activació i el reduït voltatge en circuit obert (a causa de potencials mixtes) condueixen a una densitat de potència comparativament baixa de 15.4mW/ cm². El pas de ions de vanadi a través de la membrana es considera un dels grans inconvenients en aquest tipus de cel·les tubulars, el que porta al fet que la densitat d'energia real de23.2Wh l^(-1) caigui per sota del valor nominal de 63.9Wh l^(-1). / [EN] An increase of the power generation from volatile renewable sources (solar, wind) requires a high flexibility in power grids. All Vanadium Redox Flow Batteries (VRFBs) have demonstrated their ability to provide flexibility by storing electrical energy on a kWh to MWh scale. High power and energy specific costs do, however prevent a wide market penetration. In this dissertation a tubular cell design with a membrane diameter of 5.0mm is developed and evaluated. Tubular VRFB cells shall lead to an enhanced power den- sity (kWm^(-3)). Replacement of an electrode with a bifunctional air electrode (Vanadium/ Air Redox Flow Battery) shall allow to increase the specific energy (Whkg^(-1)) and reduce energy specific costs (€/kWh). The developed design facilitates a fabrication of the current collectors and membrane by an extrusion process and marks an important step towards the cost-efficient ex- trusion of entire half cells and cells in the future. To evaluate the cell performance and investigate loss mechanisms, polarization curve, electrochemical impedance spectroscopy and charge/discharge cycling measurements are conducted. Tubular VRFB cells with flow-by electrodes reveal a maximum dis- charge current and power density of 89.7mAcm^(-2) and 179.2kW/m^3, respectively. Low residual overpotentials at the cell's electrodes are encouraging, but the area spe- cific cell resistance of 3.2 ohm*cm² imposes limitations on the current density. Coulomb efficiencies of 95% are comparable to values of planar reference cells, but high ohmic losses reduce the system energy efficiency to 56 %. Tubular VARFB cells with a mono-layered gas diffusion electrode and a Pt/IrO2 catalyst allow for a maximum current density of 32mAcm^(-2) (Ecell =2.1 V/0.56V Ch/Dch). High activation overpotentials and a reduced open-circuit voltage (due to mixed potentials) lead to a comparably low power density of 15.4mW/ cm². Cross- over of vanadium ions through the membrane are considered as a major drawback for tubular VARFB cells and the actual energy density of 23.2Wh l^(-1) falls below the nominal value of Wh l^(-1). / Financial support of my research activities was provided by the BMBF through the common research project tubulAir±. / Ressel, SP. (2019). Tubular All Vanadium and Vanadium/Air Redox Flow Cells [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/131203 / TESIS

The GB power system will see huge growth in transmission connected wind farms over the next decade, driven by European clean energy targets. The majority of the UK’s wind development is likely to be offshore and many of these wind farms will be interfaced to the grid through power converters. This will lead to a loss of intrinsic inertia and an increasing challenge for the system operator to keep grid frequency stable. Given this challenge, there is increasing interest in understanding the capabilities of converter control systems to provide a synthesised response to grid transients. It is interesting to consider whether this response should be demanded of wind turbines, with a consequential reduction in their output, or if advanced energy storage can provide a viable solution. In order to investigate how large offshore wind farms could contribute to securing the power system, wind turbine and wind farm models have been developed. These have been used to design a patented method of protecting permanent magnet generator’s converters under grid faults. Furthermore, these models have enabled investigation of methods by which a wind turbine can provide inertial and frequency response. Conventionally inertial response relies on the derivative of a filtered measurement of system frequency; this introduces either noise, delay or both. This research proposes alternative methods, without these shortcomings, which are shown to have fast response. Overall, wind farms are shown to be technically capable of providing both high and low frequency response; however, holding reserves for low frequency response inevitably requires spilling wind. Wind’s intermittency and full output operation are in tension with the need of the power system for reliable frequency response reserves. This means that whilst wind farms can meet the technical requirements to hold reserves, they bid uncompetitive prices in the market. This research shows that frequency response market prices are likely to rise in future suggesting that the Vanadium Redox Flow Battery is one technology which could enter this market and also complement wind power. Novel control incorporating fuzzy logic to manage the battery is developed to allow a hybrid wind and storage system to aggregate the benefits of frequency response and daily price arbitrage. However, the research finds that the costs of smoothing wind power output are a burden on the store’s revenue, leading to a method of optimising the combined response from an energy store and generator that is the subject of a patent application. Furthermore, whilst positive present value may be derived from this application, the long payback periods do not represent attractive investments without a small storage subsidy.

Large-scale electrochemical energy storage is a technology that is uniquely suited to integrate intermittent renewable energy sources with the electric grid on a large scale. Grid-based energy storage also has the potential to reduce costs associated with periods of peak electric demand. For these reasons, this work describes the potential applications for grid-based energy storage, and then reviews large-scale energy storage technology innovations since the development of the lead-acid battery. The potential value of grid-based battery energy storage is discussed in the context of restructured electricity markets; then, a dynamic model-based economic optimization routine is developed to gauge the potential value of a vanadium redox flow battery (VRFB) operating for wholesale energy arbitrage and frequency regulation in Texas. Based on this analysis, the relative value of a VRFB in various regions of Texas for energy arbitrage and frequency regulation is examined. It is shown that frequency regulation is an appealing application for a grid-based VRFB, with a VRFB utilized for frequency regulation service in Texas potentially worth approximately $1500/kW. Finally, the effect of a VRFB’s characteristics on its value for frequency regulation and energy arbitrage are compared, and the operational insight developed in this work is used to glean how policies to integrate a large-scale energy storage with the electricity market might be crafted. / text

This work presents the first alkaline redox flow battery (a-RFB) based on the coordination chemistry of cobalt(III/II) and iron(III/II) with amino-alcohol ligands in concentrated NaOH([subscript aq]). The a-RFB was developed by carrying out systematic structural and electrochemical characterizations of various redox-active coordination compounds to find the most suitable candidates for electrochemical energy storage. In the characterization studies, particular attention was given to the redox couple Fe(III/II)- TEA, where TEA = triethanolamine, because of its importance in the fields of supramolecular chemistry, magnetic memory films, and electrochemical energy storage. The structures of Fe(III)-TEA in the solid state and in alkaline solution are reported for the first time. Moreover, experimental evidence is presented for the existence of an EC reaction in the heterogeneous reduction of Fe(III/II)-TEA in concentrated base. Furthermore, experiments were carried out to study the reactivity of Fe(II)-TEA with O2. This is important because O2 reacts spontaneously with Fe(II)-TEA to produce hydrogen peroxide, decreasing the charging-discharging capacity of the a-RFB. The reduction of oxygen by Fe(II)-TEA in concentrated base was studied by UV-Vis spectroscopy and coulometric titrations. Additionally, a new method for the quick identification of redox couples with slow EC reactions, k[subscript f] < 0.1 s-1, is presented. The new method is based on scanning electrochemical microscopy (SECM) and consists of creating a thin-layer cell between the tip and substrate electrode. During analysis of a redox couple, the tip reports a current transient proportional to the decaying concentration of the product of the E reaction, from which an apparent forward rate constant for the C reaction can be determined. This method was designed for the field of RFB research, where the identification of redox couples with no EC reactions is necessary to ensure that a battery can run for thousands of cycles. Lastly, surface oxidation of polycrystalline Ir ultramicroelectrodes was studied by the surface interrogation mode of SECM (SI-SECM), using Fe(II)-TEA as the titrant. This was done to demonstrate the existence of hydrous oxides of Ir(IV) and Ir(V) prior to the onset of oxygen evolution in concentrated base. Numerical simulations were carried out using commercial software and were used to validate the experimental results reported in this work. / text

Symmetric nonaqueous redox flow batteries (RFBs) use negative and positive battery solutions of the same solution composition to operate at high cell voltages. This research effort targets these systems since they offer performance improvements derived from using nonaqueous systems and symmetric active species. Nonaqueous solutions permit significantly higher cell voltages than state-of-the-art aqueous RFBs and symmetric active species chemistries reduce the required complexity of cell reactors. Both performance advantages correspond to significant cost improvements beyond already commercially competitive aqueous RFB chemistries. This document focuses on two classes of symmetric nonaqueous RFB chemistries: coordination complexes such as vanadium acetylacetonate [V(acac)₃] or chromium acetylacetonate [Cr(acac)₃], and organic active species such as 9,10-diphenylanthracene (DPA). V(acac)₃ delivers reversible electrochemistry that supports a 2.2 V equilibrium cell potential, but there are some gaps in the understanding of its degradation mechanisms. Cr(acac)₃ supports redox reactions that suggest cell potentials above 4 V, but shows signs of irreversibility in voltammetry experiments and is not yet well understood. Finally, the DPA system could be interesting because it does not use metal active species, and its voltammetry promises cell potentials above 3 V. Yet DPA suffers from low solubility in nonaqueous solvents that limit its practicality. These three systems show promise for symmetric nonaqueous RFBs and offer avenues for further improvement. Voltammetry and spectroelectrochemical electrolysis experiments on the metal coordination complexes clarify the mechanisms behind the voltammetry on these symmetric chemistries. Ligand dissociation causes the irreversible behavior observed in voltammetry on Cr(acac)₃. The same experiments reaffirm the expected cyclability of V(acac)₃. Chemical functionalization of the DPA center is performed to investigate the solubility and reactivity of various derivatives. Functionalizing DPA with ethylene glycol chains to form 'DdPA' significantly increases solubility limits from 0.6 mM and 44 mM for DPA in acetonitrile and 1,2-dimethoxyethane, respectively, to 12 mM and 0.21 M for DdPA in the same solvents. At the same time, DdPA retains redox activity that promises 3 V cell potentials. Ultimately, a custom, nonaqueous-compatible redox flow reactor was designed and used to test the performance of V(acac)₃, DPA, and DdPA under various operating conditions. Contradicting previous reports, V(acac)₃ delivers stable cycling over the 21- cycle experimental protocol. Exploration over a range of flow rates and current densities give energy and power densities up to 1.09 WhL^-1 and 0.16 Wcm^-2, respectively, for the battery solution compositions examined. These experiments further predict values up to 28 WhL^-1 and at least 0.22 Wcm^-2 for optimized V(acac)₃ battery solutions. DPA and DdPA deliver the highest operating potential observed from organic nonaqueous RFBs, discharging at 3 V and 2.9 V, but require further work to understand degradation in the systems.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22842号 / 工博第4782号 / 新制||工||1748(附属図書館) / 京都大学大学院工学研究科電気工学専攻 / (主査)教授 引原 隆士, 教授 土居 伸二, 教授 木本 恒暢 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Waste-heat-to-power (WHP) recovers electrical power from exhaust heat emitted by industrial and commercial facilities. Waste heat is available in enormous quantities. The U.S. Department of Energy estimates 5-13 quadrillion BTUs/yr with a technical potential of 14.6 GW are available and could be utilized to generate power by converting the heat into electricity. The research proposed here will define a system that can economically recover energy from waste heat through a thermal regenerative electrochemical system. The primary motivation came from a patent and the research sponsored by the National Renewable Energy Laboratory (NREL). The proposed system improves on this patent in four major ways: by using air/oxygen, rather than hydrogen; by eliminating the cross diffusion of counter ions and using a dual membrane cell design; and by using high concentrations of electrolytes that have boiling points below water. Therefore, this system also works at difficult-to-recover low temperatures. Electrochemical power is estimated at 0.2W/cm2, and for a 4.2 M solution at 1 L/s, the power of a 100 kW system is 425 kW. Distillation energy costs are simulated and found to be 504 kJ/s for a 1 kg/s feed stream. The conversion efficiency is then calculated at 84%. The Carnot efficiency for a conservative 50% conversion efficiency is compared to the ideal Carnot efficiency. Preliminary work suggests an LCOE of 0.6¢/kWh. Industrial energy efficiency could be boosted by up to 10%. Potential markets include power stations, industrial plants, facilities at institutions like universities, geothermal conversion plants, and even thermal energy storage.

Renewable energy applications (i.e. fuel cells, flow batteries, electrolyzers) have been at the forefront of green energy and environmental research over the past couple of decades and the research associated with them has skyrocketed due to changes in funding and incentives. The extensive research over the years have resulted in higher efficiency and longer lasting devices for renewable energy applications, but there is still a major bottleneck that all these devices share; the ion-exchange membrane (IEM). The development of polymer ion-exchange membranes has been very beneficial for these devices as they allow for higher working temperatures and increase the longevity and efficiency of said devices. IEM research can be summed up into two major types of membranes; proton- and anion-exchanging. Of these materials, proton-exchanging membrane (PEM) are well established and studied due to how long they have been manufactured and the ease of manufacturing. There has been a variety of different PEMs developed and tested, but none have been commercialized as heavily or used as universally as Nafion® (developed by DuPont in the 1960s) although it still suffers from setbacks like its high cost, low working temperatures and its low tolerance for fuel impurities. On the other hand, anion-exchange membranes (AEM) have become popular in this field of study as they boast a non-acidic substitute as well as more efficient oxygen reduction reactions allowing for operation without the use of expensive catalysts. AEMs are first in line to replace commercial PEMs like Nafion®, the major bottleneck being their ionic conductivities. Pairing the structural characteristics of PEMs with the efficient and more cost effective AEMs we sought out to design and synthesize new IEMs to compete with current commercial membranes. By using ring opening metatheses polymerization (ROMP) we have designed and developed numerous hydrocarbon polynorbornene derivative membranes with the intention of incorporating amino-phosphine ion exchange groups (IEG) to compete with current IEMs in both efficiency and cost with the major application of fuel cells and flow batteries in mind. We also performed different modifications to the initial membranes such as crosslinking and alkyl chain addition to increase the mechanical strength and mitigate the degradation of the membranes. Using results gathered from developing polynorbornene IEMs, we pivoted to another multitude of membranes, this time focusing on the PEM capabilities of fluorinated polymers instead of their hydrocarbon alternatives for use in redox flow batteries with the main goal of decreasing electrolyte crossover, therefore increasing the longevity of the devices. Several new IEMs were designed as composite membranes of Nafion® and aromatic organic IEGs and synthesized to compete with the current commercial IEMs while testing the effect of different aromatic IEGs on the salt permeability and mechanical strength of the membrane. Synthesis of a stable IEM with good electrolyte crossover and conductivity properties was achieved by combining a grafted Nafion® backbone with 2-phenylbenzimidazole side chains containing a long hydrocarbon chain to facilitate hydrophobicity and increase mechanical strength. These composite membranes take advantage of the imidazole’s highly stable chemical backbone and proton exchanging properties allowing it to withstand highly acidic and oxidative environments as well as relying on benzimidazoles tight packing to reduce electrolyte permeability throughout the membrane.