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Continued emission of green house gases has energized research activity worldwide to develop efficient ways to harness renewal energy. The availability of large scale energy storage technologies is essential to make renewal energy a reliable source of energy. Redox flow batteries show potential in this direction. These batteries typically need expensive membranes which need replacement be-cause of fouling. The recently proposed soluble lead redox flow battery (SLRFB), in which lead ions deposit on electrodes in charge cycle and dissolve back in discharge cycle, can potentially cut down the cost of energy storage by eliminating membrane. A number of challenges need to be overcome though. Low cycleability, residue formation, and low efficiencies are foremost among these, all of which require an understanding of the underlying mechanisms. A model of laminar flow-through SLRFB is first developed to understand buildup of residue on electrodes with continued cycling. The model accounts for spatially and temporally growing concentration boundary layers on electrodes in a self consistent manner by permitting local deposition/dissolution rates to be controlled by local ion transport and reaction conditions. The model suggests controlling role for charge transfer reaction on electrodes (anode in particular) and movement of ions in the bulk and concentration boundary layers. The non-uniform current density on electrodes emerges as key to formation of bare patches, steep decrease in voltage marking the end of discharge cycle, and residue buildup with continuing cycles. The model captures the experimental observations very well, and points to improved operational efficiency and decreased residue build up with cylindrical electrodes and alternating flow direction of recirculation. The underlying mechanism for more than an order of magnitude increase in cycle life of a beaker cell battery with increase in stirrer speed is unraveled next. Our experiments show that charging with and without stirring occurs identically, which brings up the hitherto unknown but quite strong role of natural convection in SLRFB. The role of stirring is determined to be dislodgement/disintegration of residue building up on electrodes. The depletion of active material from electrolyte due to residue formation is offset by “internal regeneration mechanism”, unraveled in the present work. When the rate of residue formation, rate of dislodging/disintegration from electrode, and rate of regeneration of active material in bulk of the electrolyte becomes equal, perpetual operation of SLRFB is expected. The identification of strong role of free convection in battery is put to use to demonstrate a battery that requires stirring/mixing only intermittently, during open circuit stages between charge and discharge cycles when no current is drawn. Inspired by our experimental finding that the measured currents for apparently diffusion limited situations (no external flow) are far larger than the maxi-mum possible theoretical value, the earlier model is modified to account for natural convection driven by concentration gradient of lead ions in electrolyte. The model reveals the presence of strong natural convection in battery. The induced flow in the vicinity of the electrodes enhances mass transport rates substantially, to the extent that even in the absence of external flow, normal charge/discharge of battery is predicted. The model predicted electrochemical characteristics are verified quantitatively through voltage-time measurements. The formation of flow circulation loops driven by electrode processes is validated qualitatively through PIV measurements. Natural convection is predicted to play a significant role in the presence of external flow as well. The hitherto unexplained finding in the literature on insensitivity of charge-discharge characteristics to electrolyte flow rate is captured by the model when mixed mode of convection is invoked. Flow reversal and wavy flow are predicted when natural convection and forced convection act in opposite directions in the battery. The effect of the presence of non-conducting material (PbO on anode) on the performance of SLRFB is studied using a simplified approach in the model. The study reveals the presence of charge coup de fouet phenomenon in charge cycle. The phenomenon as well as the predicted effect of depth of discharge on the magnitude of charge coup de fouet are confirmed experimentally.

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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.

Results have shown that flow batteries may be a solution in the future as an effective and environmental friendly method to an energy storage system (ESS). The technology is reliable and has a high efficiency that comes with low energy losses and a long lifetime. The range of possible fields is suitable for cutting energy peaks in the power grid, by always have a ready and available energy storage that balances the production. By comparing the advantages of flow batteries with conventional batteries it is mainly the fact that they can conserve energy for a long time without being self-discharged thanks to that the storage capacity is in principle endless and limited by the size of the electrolytes tanks that makes them a great energy storage system. The batteries won’t take any damage or decrease in performance when charging or discharging it or if you exhausts it to 100 % and leave it discharged for a long time. The only disadvantages with flow batteries are that they are built upon an advanced design and are built of components made of expensive materials. The main objective of this thesis is to develop an experimental basis for assessing a small pilot module of a flow battery with respect to how different concentrations of salts, flow rates and different currents/voltages affect the performance of the battery. We start by performing the experiment with a polymeric ion exchange membrane and see what values and the advantages and disadvantages it entails.

In this work I describe various approaches to electrochemical energy storage at the grid-scale. Chapter 1 provides an introduction to energy storage and an overview of the history and development of flow batteries. Chapter 2 describes work on the hydrogen-chlorine regenerative fuel cell, detailing its development and the record-breaking performance of the device. Chapter 3 dives into catalyst materials for such a fuel cell, focusing on ruthenium oxide based alloys to be used as chlorine redox catalysts. Chapter 4 introduces and details the development of a performance model for a hydrogen-bromine cell. Chapter 5 delves into the more recent work I have done, switching to applications of quinone chemistries in flow batteries. It focuses on the pairing of one particular quinone (2,7-anthraquinone disulfonic acid) with bromine, and highlights the promising performance characteristics of a device based on this type of chemistry. / Engineering and Applied Sciences

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.