Vanadium Redox Flow Batteries VRFBs are promising energy storage systems with highly recyclable electrolytes. The recycling of these systems usually involves ammonium-based salt precipitation steps, which produce toxicgases and contaminated water as waste. In this study, a novel method has been developed to recycle vanadiumdirectly from VRFB electrolyte solutions. The purity and characteristics of the final product have been analyzedusing X-ray Diffraction and Cyclic Voltammetry analysis. The method developed in this study has a precipitationrecovery of 98%. However, further investigation is needed to improve product purity and method optimization. / Sammanfattning på svenska: Vanadium Redox Flödes Batterier VRFB är lovande energilagringssystem medmycket återvinningsbara elektrolyter. Återvinningen av dessa system innefattar vanligtvis ammoniumbaseradesaltutfällningssteg som producerar giftiga gaser och förorenat vatten som avfall. I denna studie har en ny metodutvecklats för återvinning av vanadium direkt från VRFB elektrolytlösningar. Renheten och egenskaperna hosslutprodukten har analyserats med X-ray diffraktion och cyclic voltammetry analys. Metoden som utvecklats idenna studie har återvinnings kapacitet på 98 %. Ytterligare utredning behövs inom förbättring av produktensrenhet samt metods optimering.

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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.

This work is in the introduction focused on the introduction of technologies for electrical energy storage, their description and capturing the main advantages and disadvantages. After this capture follows comparison of the various technologies in terms of efficiency , discharge time and the price for1 kWh . Following section focuses on electrochemical model VRB batteries , which describes the equations describing the behavior of a battery depending on the chemical an electrical properties . In the penultimate chapter, I introduced the language of object- oriented modeling language Modelica and the most common programs based on it, including a short introduction for modeling in MathModelica. The last part deals with the modeling of specific VRB battery, which we have at the faculty.

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As the world transitions to intermittent renewable energy sources like solar and wind, the need for long-duration energy storage technologies is becoming more and more prominent. In this regard, flow batteries are seen as a promising solution, owing to their inherent advantages like decoupling of power and energy, extremely high cycle life and negligible self-discharge. However, there are multiple engineering challenges to overcome before the widespread application of flow batteries.   This study, carried out at a leading manufacturer of vanadium-based flow batteries, VoltStorage GmbH, addresses one of those challenges related to the hydraulic sealing of the endplate assembly of the battery. The endplate assembly is prone to losing its structural integrity over the continuous operation, thus failing to achieve its intended purpose of hydraulic sealing. Additionally, it is susceptible to enhanced contact resistance during operation, thus harming the battery performance. Therefore, the primary objective of this study was to develop a modular test rig that could evaluate the endplate assembly's performance in an accelerated manner but without using electrolytes to eliminate the complications of dealing with the sulfuric acid solution (i.e. electrolyte). So, air was chosen as the working fluid to offer clean and highly repeatable testing.   The study began with a literature review of the flow batteries. It was found that the literature concerning the engineering aspects of a flow battery was limited. Therefore, it was followed by an in-depth analysis of the stack design of VoltStorage and the engineering challenges linked to the endplate assembly. Importantly, the root cause of the problem of hydraulic sealing was identified, which was the pressure cycling of the monopole. After that, the test rig was designed and developed based on the understanding of the engineering challenge and to realize the objective of a modular design. The design modularity was desirable to test multiple assemblies simultaneously without increasing the floor footprint. Three parameters were chosen to characterize the assembly: monopole deflection, internal resistance and air leak rate. Due to the system's complexity, experiments to monitor these parameters were divided into two phases, i.e., rig qualification and full-scale testing. The first phase aimed to characterize their baseline behaviour and evaluate the rig's robustness; the next phase aimed at monitoring their behaviour evolution with continuous operation.   The monopole deflection measurements during the first phase indicated a maximum deflection of 0.3 mm. The air-electrolyte equivalence was also established by making the deflection behaviour similar during air and electrolyte operation. Much higher pressure had to be applied with air (~1.6 bar gauge) than water (~0.8 bar gauge) to achieve this equivalence. Moreover, the internal resistance and air leak rate measurements conducted during the first phase provided baseline values (6.341 ± 0.731 mΩ and 1.241 ± 0.091 Pa∙l/s, respectively, with a 95% confidence level) against which any change during continuous operation could be differentiated. However, the full-scale testing could not be performed due to the global supply chain disruptions and the limited time frame of the project. Nevertheless, a vital objective of the design, to modularize the rig so that it could be scaled up quickly and test multiple assemblies simultaneously to facilitate the rapid prototyping of different designs, was realized in the project.   Flow batteries are a promising technology for long-duration energy storage, although there are some challenges to overcome. In addition, to be defined as a truly sustainable solution, the problems linked with vanadium mining and the high capital costs of the system have to be eliminated. With the rapidly expanding development and deployment of these systems, it is expected that they will be an essential part of our future grids.   To conclude, in this project, a testing system was developed which could perform a dry mechanical and electrical integrity check of the endplate assembly of a flow battery in an accelerated manner. The system could prove to be vital in enhancing the reliability of stack-based systems and hence foster their widespread applicability. The future work that can benefit this system is assembling the set of 5 short stacks and performing a continuous operation to monitor the behaviour evolution of the stacks. This step would help assess the testing system's shortcomings and subsequently make the required modifications. / I takt med att världen övergår till intermittenta förnybara energikällor som sol- och vindkraft blir behovet av teknik för energilagring med lång varaktighet alltmer framträdande. Flödesbatterier ses i detta avseende som en lovande lösning på grund av deras inneboende fördelar, t.ex. frikoppling av kraft och energi, extremt lång livslängd och försumbar självurladdning. Det finns dock flera tekniska utmaningar som måste övervinnas innan flödesbatterier kan användas på bred front.  Den här studien, som utfördes hos VoltStorage GmbH, en ledande tillverkare av vanadiumbaserade flödesbatterier, tar upp en av dessa utmaningar som rör den hydrauliska tätningen av batteriets ändplatta. Ändtplattan är benägen att förlora sin strukturella integritet under kontinuerlig drift, vilket innebär att den inte uppnår sitt avsedda syfte, nämligen hydraulisk tätning. Dessutom är den känslig för ökat kontaktmotstånd under drift, vilket skadar batteriets prestanda. Det primära målet med denna studie var därför att utveckla en modulär testrigg som kan utvärdera ändplattans prestanda på ett påskyndat sätt, men utan att använda elektrolyter för att eliminera komplikationerna med att hantera svavelsyralösningen (dvs. elektrolyten). Därför valdes luft som arbetsvätska för att erbjuda rena och mycket repeterbara tester.   Studien inleddes med en litteraturgenomgång av flödesbatterier. Det konstaterades att litteraturen om de tekniska aspekterna av ett flödesbatteri var begränsad. Därför följdes den av en djupgående analys av VoltStorages stapelkonstruktion och de tekniska utmaningarna i samband med ändplattans montering. Det var viktigt att identifiera grundorsaken till problemet med hydraulisk tätning, vilket var tryckcykling av monopolen. Därefter utformades och utvecklades testriggen utifrån förståelsen av den tekniska utmaningen och för att förverkliga målet med en modulär konstruktion. Modulariteten i konstruktionen var önskvärd för att testa flera enheter samtidigt utan att öka golvytan. Tre parametrar valdes ut för att karakterisera enheten: monopolens avböjning, inre motstånd och luftläckagehastighet. På grund av systemets komplexitet delades experimenten för att övervaka dessa parametrar upp i två faser, dvs. kvalificering av riggen och provning i full skala. Den första fasen syftade till att karakterisera deras grundbeteende och utvärdera riggens robusthet, medan nästa fas syftade till att övervaka deras funktionella respons utveckling vid kontinuerlig drift.   Mätningarna av monopolens nedböjning under den första fasen visade på en maximal nedböjning på 0,3 mm. Likvärdigheten mellan luft och elektrolyt fastställdes också genom att utböjningsbeteendet var likartat under drift med luft och elektrolyt. Ett mycket högre tryck måste tillämpas med luft (~1,6 bar gauge) än med vatten (~0,8 bar gauge) för att uppnå denna likvärdighet. Dessutom gav de mätningar av det inre motståndet och luftläckaget som utfördes under den första fasen basvärden (6,341 ± 0,731 mΩ respektive 1,241 ± 0,091 Pa∙l/s, med en konfidensnivå på 95 %) mot vilka eventuella förändringar under kontinuerlig drift kunde särskiljas. Den fullskaliga testningen kunde dock inte genomföras på grund av störningar i den globala leveranskedjan och projektets begränsade tidsram. Ett viktigt mål med konstruktionen, att modularisera riggen så att den snabbt kan skalas upp och testa flera enheter samtidigt för att underlätta snabb prototypframställning av olika konstruktioner, förverkligades dock i projektet.  Flödesbatterier är en lovande teknik för energilagring under lång tid, även om det finns vissa utmaningar att övervinna. För att kunna definieras som en verkligt hållbar lösning måste dessutom de problem som är kopplade till vanadinbrytning och systemets höga kapitalkostnader undanröjas. Med den snabbt ökande utvecklingen och spridningen av dessa system förväntas de bli en viktig del av våra framtida nät.   Sammanfattningsvis utvecklades i detta projekt ett testsystem som kan utföra en torr mekanisk och elektrisk integritetskontroll av ändplattan i ett flödesbatteri på ett påskyndat sätt. Systemet kan visa sig vara avgörande för att öka tillförlitligheten hos stapelbaserade system och därmed främja deras utbredda användbarhet. Det framtida arbete som kan gynna detta system är att montera en uppsättning av fem korta staplar och utföra en kontinuerlig operation för att övervaka staplarnas funktionella responsutveckling. Detta steg skulle hjälpa till att bedöma testsystemets brister och därefter göra de ändringar som krävs.