<p>  </p> <p>Nowadays, clean and renewable energy sources like wind and solar power have been rapidly growing for the goal of phasing out traditional fossil fuels, achieving carbon neutrality, and realizing sustainable development. Long-duration and large-scale energy storage is needed to address the intermittent nature of these sources. Especially, redox flow battery (RFB) is an attractive energy storage device for large scale applications because of its high scalability, design flexibility, and intrinsic safety. The all vanadium redox flow battery stands for the state-of-the-art system, but the high vanadium cost and limited energy density are among the limiting factors for wide commercialization. Therefore, it is necessary to develop new RFB materials that are cost-effective and highly soluble. Organic redox-active molecules (redoxmers) hold great potential to satisfy these requirements due to structural diversity, tunable chemical and electrochemical properties, and earth-abundant sources. With rational structural design, organic redoxmers can show favorable properties such as high solubility, suitable redox potential, and good chemical stability. However, current efforts are mainly on the development of anolyte redoxmers, e.g. phenazine, anthraquinone and viologen. Only limited types of catholyte candidates have been reported such as ferrocene and TEMPO. The major reason for such slow-paced progress is the limited chemical stability of these catholyte redoxmers. To bridge this critical gap, my efforts are focused mainly on the design and development of promising catholyte redoxmers for both aqueous organic (AORFBs) and non-aqueous organic redox flow batteries (NRFBs).</p> <p>Phenoxazine functionalized with a hydrophilic tetraalkylammonium group demonstrates good water solubility and suitable redox potential. Cyclic voltammograms (CV) and flow cell testing were used to evaluate the electrochemical properties and battery performance, respectively. Besides, the battery fading mechanism was systematically investigated by CV, liquid chromatography mass spectra (LC-MS) and electron paramagnetic resonance (EPR) spectroscopy. The redoxmer decomposition mechanism analysis will benefit future redoxmer development by guiding the molecular design of more stable structure candidates. </p> <p>A structural design strategy for the development of novel TMPD-based (tetramethyl-<em>p</em>-phenylenediamine) catholyte redoxmers for NORFBs is presented. Two categories of functional groups, including oligo(ethylene glycol) (EG) either chains and phenyl rings, were incorporated into the TMPD core to improve solubility and stability in non-aqueous electrolytes, respectively. EPR characterization and bulk electrolyte (BE) analysis were carried out to evaluate the redoxmers stability. In addition, DFT studies were conducted to understand the impacts of functional groups on redox potential and chemical stability. The present work demonstrates the feasibility of constructing promising redoxmers from TMPD and provides insights into molecular designing of catholytes to achieve high solubility and excellent stability for non-aqueous redox flow batteries.</p>

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Ce travail de thèse porte sur la réalisation d’une batterie redox-flow fonctionnant grâce à la circulation de suspensions de matériaux d’insertion du lithium afin d’accroitre leur densité d’énergie. Le recours à des cellules microfluidiques permet de s’affranchir des limitations causées par les membranes échangeuses d’ions. Il s’articule dans un premier temps sur la synthèse contrôlée par voie hydrothermale de nanoparticules de LiCoO2 et leur caractérisation en suspension aqueuses. Cette étape permet de déterminer à la fois les propriétés électrochimiques des suspensions, leur état d’agrégation ainsi que leur comportement rhéologique en vue d’une utilisation redox-flow. Le transfert électronique entre une particule en suspension et les électrodes de la cellule est un aspect fondamental de ce type de batteries. Ce transfert est étudié grâce la technique de collision électrochimique dans laquelle la réponse de chaque agrégat est détecté individuellement par une ultramicroélectrode ce qui permet d’établir de nombreuses propriétés physique-chimiques de ces suspensions. Ce travail propose ensuite de s’affranchir de l’utilisation des membranes et de leurs limitations par le recours aux techniques de la microfluidique. La formation d’un écoulement co-laminaire en microcanal permet d’obtenir une cellule redox-flow opérationnelle. La conception et le fonctionnement de ces cellules est étudié en vue de la mise en circulation de suspensions de nanoparticules dans ce type de systèmes. / The aim of this work is to make a redox-flow battery that runs on lithium insertion material suspensions in order to increase the energy density of such systems. The use of microfluidic technics allows to solve the issues and limitations of ion exchange membrane by removing them. In the first part controlled size LiCoO2 nanoparticles are synthesized by hydrothermal route and dispersed into suspensions. The aggregation state of these suspensions are investigated using diffusion light scattering and transmission electronic cryoscopy. Rheological properties were also characterized for redox-flow use. The electronic transfer between a particle in suspension and the flow cell electrodes is crucial for their performances. This transfer is studied in the second part using the single event collision technic which consist of isolating individual aggregate electrochemical response at the surface of an ultramicroelectrode. This approach allows an extensive investigation of suspensions aggregates size, mobility and insertion reaction kinetic. Finally this works propose to replace the conventional ion exchange membrane by the mean of microfluidic technics. In co-laminar condition the fluid interface acts as a separation membrane to create a membrane-less redox-flow battery. The last part focuses on the fabrication of microfluidic cells and the behavior of suspensions in micro-channels.

With its long cycle life and scalable design, the vanadium redox flow battery (VRB) is a promising technology for grid energy storage. However, high materials costs have impeded its commercialization. An essential but costly component of the VRB is the ion-exchange membrane. The ideal VRB membrane provides a highly conductive path for protons, prevents crossover of reactive species, and is tolerant of the acidic and oxidizing chemical environment of the cell. In order to study membrane performance and optimize cell design, mathematical models of the separator membrane have been developed. Where previous VRB membrane models considered minimal details of membrane transport, generally focusing on conductivity or self-discharge at zero current, the model presented here considers coupled interactions between each of the major species by way of rigorous material balances and concentrated solution theory. The model describes uptake and transport of sulfuric acid, water, and vanadium ions in Nafion membranes, focusing on operation at high current density. Governing equations for membrane transport are solved in finite difference form using the Newton-Raphson method. Model capabilities were explored, leading to predictions of Ohmic losses, vanadium crossover, and electro-osmotic drag. Experimental methods were presented for validating the model and for further improving estimates of uptake parameters and transport coefficients. / text

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Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / Electrochemical behaviour of Ce, Fe, Cr,V and Mn in the presence of DTPA, EDTA, EDDS, NTA ligands were investigated by using cyclic voltammetry, a rotating disc electrode and electrochemical impedance spectroscopy for use in redox flow battery (RFB) systems. RFB is currently used for energy storage, the vanadium, which is used in most of the RFB’s, however suffers from species crossover and sluggish reactions, which limit the lifetime of the battery. These various ligands and metal complexes mentioned above where all examined to identify the suitable and favoured electrolyte that can be used for a RFB system. Kinetic parameters such as potential, limiting current, transfer coefficient, diffusion coefficients, and rate constants were studied. RDE experiments confirmed that the parameters measured by CV are similar under hydrodynamic conditions and can be used to determine the kinetic parameters of the redox couples. The use of DTPA as a ligand for complexation of Ce(IV) gave more favourable results compared to other ligand with various metal complexes used in this study [1-3]. The results of kinetic studies of Ce(IV)–DTPA complex shows promise as an electrolyte for a redox flow battery. The separation of V(IV)/(V), Fe (III)/(IV),Cr(III)/(IV),Mn (III)/(IV) and Ce(III)/(IV) with various ligands (EDTA, EDDS, NTA and DTPA) were also investigated using capillary electrophoresis. To understand the speciation of these metal complexes as used in this study and particularly the vanadium, for the reason that it has a complicated (V) oxidation state. The charge/discharge performance of all electrolytes used in this work was determined and a high voltage achieved when Ce-DTPA was used, and it is compared to that of the vanadium electrolyte currently in use. This was evaluated with systems studied previously. Therefore, Ce-DTPA will be a suitable electrolyte for redox flow battery systems.

Thesis advisor: Udayan Mohanty / Rechargeable batteries, especially lithium ion batteries, have greatly transformed mobile electronic devices nowadays. Due to the ever-depletion of fossil fuel and the need to reduce CO2 emissions, the development of batteries needs to extend the success in small electronic devices to other fields such as electric vehicles and large-scale renewable energy storage. Li-ion batteries, however, even when fully developed, may not meet the requirements for future electric vehicles and grid-scale energy storage due to the inherent limitations related with intercalation chemistry. As such, alternative battery systems should be developed in order to meet these important future applications. This dissertation presents our successes in improving Li-O2 battery performance for electric vehicle application and integrating a redox flow battery into a photoelectrochemical cell for direct solar energy storage application. Li-O2 batteries have attracted much attention in recent years for electric vehicle application since it offers much higher gravimetric energy density than Li-ion ones. However, the development of this technology has been greatly hindered by the poor cycling performance. The key reason is the instability of carbon cathode under operation conditions. Our strategy is to protect the carbon cathode from reactive intermediates by a thin uniform layer grown by atomic layer depostion. The protected electrode significantly minimized parasitic reactions and enhanced cycling performance. Furthermore, the well-defined pore structures in our carbon electrode also enabled the fundamental studies of cathode reactions. Redox flow batteries (RFB), on the other hand, are well-suited for large-scale stationary energy storage in general, and for intermittent, renewable energy storage in particular. The efficient capture, storage and dispatch of renewable solar energy are major challenges to expand solar energy utilization. Solar rechargeable redox flow batteries (SRFBs) offer a highly promising solution by directly converting and storing solar energy in a RFB with the integration of a photoelectrochemical cell. One major challenge in this field is the low cell open-circuit potential, mainly due to the insufficient photovoltages of the photoelectrode systems. By combining two highly efficient photoelectrodes, Ta3N5 and Si (coated with GaN), we show that a high-voltage SRFB could be unassistedly photocharged and discharged with a high solar-to-chemical efficiency. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

In an effort to reduce global emissions by electrifying vehicles and machines with internal combustion engines has led to the development of batteries that are more powerful and efficient than the common lead acid battery.  One of the most popular batteries being used for such an installation is lithium ion, but due to its short effective usable lifetime, charging time, and costs has driven researcher to other technologies to replace it.  Vanadium redox flow batteries have come into the spotlight recently as a means of replacing rechargeable batteries in electric vehicles and has previously be used mainly to store energy for load leveling.  It possesses many qualities that would be beneficial to electrify vehicles.  The battery has the ability for power and energy to be sized independently which is not dissimilar to internal combustion vehicles.  It also has the potential for a tolerance to low discharges, fast response time, and can quickly be refueled by replacing the electrolyte; just like is done when a car refuels at the gas station.  The purpose of the study is to determine the possibility of using vanadium redox flow batteries to power heavy construction equipment, a wheel loader, with a finite amount of space available for implementation.  A model has been designed in MATLAB to determine how long the battery could last under typically applications for the wheel loader which needs a peak power of 200 kW.  From the volume available it has been determined that the battery can be installed with an energy capacity of 148 kWh.  The results of the model show that vanadium redox flow batteries can be used to power a wheel loader but due to the limiting energy density and cell components it remains to be impractical.

As society strives to transition for sustainable energy generation is it a major challenge to optimize and develop the renewable energy generation that currently exists, both in terms of individual components and their interactions in the entire energy system. The generation from renewable sources is often irregular and not always when the demand arises. By being able to store the excess energy generated and then deliver it when the demand occur results in a more sustainable energy system. Flow batteries are a possible technology for energy storage. An important component of flow batteries are vanadium and to find methods for extracting vanadium in an economical way is an important step in the development of this technology. The idea behind the thesis was therefore to investigate different extraction methods for vanadium where the most promising methods, from an economic and energy perspective, are examined in more detail. The vanadium should then be used to electrolyte in flow batteries. It has also been examined how the cost is affected by moving a planned facility for extraction from the ashes to a developing country with lower personnel costs. In the thesis was also included to explore similar projects on a larger scale conducted in Sweden, how the view of vanadium is from an EU perspective and how flow batteries can be a part of an energy system. The methods considered most promising is extraction from mineral mining and extraction from ashes. A planned production plant has been dimensioned for both processes of production and energy demand is calculated. The study showed that both processes are expected to produce vanadium below current purchase price, which would then contribute to a cheaper production cost of flow batteries. It turned out that the production of vanadium from ash extraction would be significantly reduced by moving the business to a developing country. The operation stage in the mining operation which accounts for the highest energy demand is the size reduction of the ore. In the extraction process of vanadium from ash, it is primarily the fusion furnace and the fly ash filter required which has the highest energy demand. The similar extraction projects investigated was, from ashes, the so-called SOTEX process in Stenungsund and the mineral mining process had the Ranstad project as reference. The EU approach to vanadium is currently that the metal is not classified as a critical raw material but if economic instability would occur in any of the major manufacturing countries it would be considered as a more critical raw material. Flow batteries functioning as energy storage in a PV hybrid system was investigated and it was concluded that flow batteries are technically well suited for energy storage in this type of system. / Då samhället strävar efter att övergå till en hållbar energiproduktion är det en stor utmaning att effektivisera och utveckla den förnyelsebara energiproduktion som idag finns, både när det gäller enskilda komponenter och deras samspel i hela energisystem. Produktion från förnyelsebara energikällor sker ofta ojämnt och inte alltid när behovet uppstår. Genom att kunna lagra den överskottsenergi som produceras och sedan leverera den då behovet uppstår medför det till ett mer hållbart energisystem. Flödesbatterier är en möjlig teknik för lagring av energi. En viktig komponent i flödesbatterierna är vanadin och att hitta metoder för att utvinna vanadin på ett ekonomiskt sätt är ett viktigt steg i utvecklingen av denna teknik. Idén bakom examensarbetet var därför att kartlägga olika utvinningsmetoder för vanadin där de mest lovande metoderna, från ett ekonomiskt och energi perspektiv, undersöks mer utförligt. Vanadinet i sin tur ska sedan användas till elektrolyt i flödesbatterier. Det har även undersökts hur kostnaden påverkas av att flytta en tänkt anläggning för utvinning ur aska till ett utvecklingsland med lägre personalkostnader. I examensarbetet ingick även att undersöka liknande projekt i större skala som bedrivits i Sverige, hur synen på vanadin är ur ett EU perspektiv samt hur flödesbatterier kan vara en del av ett energisystem. De metoder som ansetts mest lovande är utvinning från mineralbrytning samt utvinning ur aska. En tänkt produktionsanläggning har dimensionerats för båda processer där produktionskostnad och energiförbrukning beräknats. Studien visade att båda processerna förväntas kunna producera vanadin under dagens inköpspris vilket då skulle bidra till en billigare produktionskostnad för flödesbatterier. Det visade sig att produktionen av vanadin ur askutvinning skulle minskas avsevärt genom att flytta verksamheten till ett utvecklingsland. Det moment i gruvdriften som står för största energiförbrukningen är storleksreduceringen av den malm som bryts. Vid processen för utvinning av vanadin ur aska är det främst den smältningsugn samt det filter för flygaska som krävs. De liknande projekt som verkat inom utvinning ur aska var den s.k. SOTEX processen i Stenungsund och för mineralbrytning har Ranstad projektet undersökts. EU:s syn på vanadin är i nuläget att metallen inte klassas som en kritisk råvara men om ekonomisk instabilitet skulle uppstå i något av de större tillverkande länderna skulle råvaran klassas som mer kritisk. Flödesbatteri fungerande som energilagring i ett förnyelsebart energisystem undersöktes där slutsatsen var att flödesbatterier tekniskt sett är mycket väl lämpade som energilagring i denna typ av system.

Les batteries redox à circulation d'électrolyte constituent une solution prometteuse pour le stockage de masse de l'électricité. Parmi elles, la technologie au plomb soluble dans l'acide méthanesulfonique est intéressante pour son architecture de cellule simplifiée et son faible coût potentiel. Ses performances sont toutefois limitées par l'électrode positive de PbO2 qui implique un faible rendement énergétique et une courte durée de vie des cellules. Le premier objectif de cette thèse est de mieux comprendre les mécanismes électrochimiques en jeu à l'électrode positive. La cinétique de la réaction parasite de production d'oxygène est étudiée. Des mécanismes de dissolution du PbO2 sont proposés et des additifs sont testés pour améliorer sa cyclabilité. Les réponses complexes du potentiel de l'électrode en cyclage galvanostatique sont également interprétées. Le second objectif est de proposer un réacteur innovant comprenant une électrode positive de grande surface spécifique. La structure « nid d'abeilles » est en particulier étudiée. Un réacteur utilisant cette structure est proposé, ses caractéristiques principales sont simulées avec un modèle électrochimique ad hoc, et des prototypes sont fabriquées et testés en cyclage. / Redox-flow batteries are considered as a promising solution for massive electrical storage. In particular, the soluble lead-methanesulfonic acid technology is interesting due to the simple design of the cells and the potentially low associated costs. However some hurdles remain for its development, namely a low energy efficiency as well as a very limited lifetime, both of which being associated with the positive PbO2-electrode. The first goal of this Ph.D. thesis is to provide a better understanding of the electrochemical mechanisms taking place at the positive electrode. The kinetic behaviour of the parasitic oxygen evolution during charging is assessed. Some mechanisms involved in the dissolution of PbO2 are proposed and additives are tested for improving its cyclability. The complex potential responses of the electrode during galvanostatic cycling are also interpreted. The second purpose is to suggest a new reactor comprising a high specific surface area positive electrode. The honeycomb structure is especially studied. A reactor that includes a honeycomb-shaped positive electrode is proposed: its main characteristics are simulated using an electrochemical model and prototypes are fabricated and experimentally tested in cycling.