Species transport mechanisms governing crossover and capacity loss in vanadium redox flow batteries

Vanadium redox flow batteries (VRFBs) are an emerging energy storage technology that offers unique advantages for grid-scale energy storage due to their flexible design and decoupled power/energy feature. Despite their popularity, a series of technical challenges hinder their widespread implementation. Among these, capacity loss (i.e., loss of energy storage capability) due to the undesired species crossover across the membrane has been identified as the key issue limiting the longevity of these systems. This issue is primarily governed by the properties of the membrane and can be mitigated by using proper membrane architectures with desired features. Presently, identifying proper membrane architectures for VRFB systems is hampered by the lack of a fundamental understanding of the nature of species transport mechanisms and how they are related to the membrane properties and key operating conditions. This Ph.D. study seeks to address this critical challenge by exploring the fundamental mechanisms responsible for species transport within the membrane. The overall objective of this dissertation study is to establish a fundamental understanding of the multi-ionic transport in VRFB membranes by investigating the ionic transport mechanisms responsible for crossover, and utilize this understanding to reveal the role of membrane properties and operating conditions on the capacity loss. To achieve these goals, a combined experimental and computational study was designed. An experimentally validated, 2-D, transient VRFB model that can track the vanadium crossover and capture the related capacity loss was developed. In addition to the model, several electrochemical techniques were used to characterize different types of membrane and study the effects of various operating conditions on the species crossover. Using these computational and experimental tools, an in-depth understanding of the species transport mechanisms within the membrane and how they are related to membrane properties and operating conditions of VRFBs has been obtained. Finally, this understanding was utilized to identify effective mitigation strategies to minimize the capacity fade and improve the long-term performance of these systems.Ph.D., Mechanical engineering -- Drexel University, 201

Modeling the Effect of Channel Tapering on the Pressure Drop and Flow Distribution Characteristics of Interdigitated Flow Fields in Redox Flow Batteries

This article belongs to the Special Issue CFD Applications in Energy Engineering Research and Simulation.Optimization of flow fields in redox flow batteries can increase performance and efficiency, while reducing cost. Therefore, there is a need to establish a fundamental understanding on the connection between flow fields, electrolyte flow management and electrode properties. In this work, the flow distribution and pressure drop characteristics of interdigitated flow fields with constant and tapered cross-sections are examined numerically and experimentally. Two simplified 2D along-the-channel models are used: (1) a CFD model, which includes the channels and the porous electrode, with Darcy’s viscous resistance as a momentum sink term in the latter; and (2) a semi-analytical model, which uses Darcy’s law to describe the 2D flow in the electrode and lubrication theory to describe the 1D Poiseuille flow in the channels, with the 2D and 1D sub-models coupled at the channel/electrode interfaces. The predictions of the models are compared between them and with experimental data. The results show that the most influential parameter is γ , defined as the ratio between the pressure drop along the channel due to viscous stresses and the pressure drop across the electrode due to Darcy’s viscous resistance. The effect of Re in the channel depends on the order of magnitude of γ , being negligible in conventional cells with slender channels that use electrodes with permeabilities in the order of 10−12m2 and that are operated with moderate flow rates. Under these conditions, tapered channels can enhance mass transport and facilitate the removal of bubbles (from secondary reactions) because of the higher velocities achieved in the channel, while being pumping losses similar to those of constant cross-section flow fields. This agrees with experimental data measured in a single cell operated with aqueous vanadium-based electrolytes.This work was supported by the research project PID2019-106740RB-I00 of the Spanish Ministry of Science, Innovation and Universities, the project PEM4ENERGY-CM-UC3M funded by the call "Programa de apoyo a la realización de proyectos interdisciplinares de I+D para jóvenes investigadores de la Universidad Carlos III de Madrid 2019-2020" under the frame of the "Convenio Plurianual Comunidad de Madrid-Universidad Carlos III de Madrid", and the Energy and Environment Research Grant of the Spanish Iberdrola Foundation

Modeling of Ion Crossover in Vanadium Redox Flow Batteries: A Computationally-Efficient Lumped Parameter Approach for Extended Cycling

In this work, we have developed a zero-dimensional vanadium redox flow battery (VRFB) model which accounts for all modes of vanadium crossover and enables prediction of long-term performance of the system in a computationally-efficient manner. Using this model, the effects of membrane thickness on a 1000-cycle operation of a VRFB system have been investigated. It was observed that utilizing a thicker membrane significantly reduces the rate of capacity fade over time (up to similar to 15%) at the expense of reducing the energy efficiency (up to similar to 2%) due to increased ohmic losses. During extended cycling, the capacity of each simulated case was observed to approach an asymptote of similar to 60% relative capacity, as the concentrations in each half-cell reach a quasi-equilibrium state. Simulations also indicated that peak power density and limiting current density exhibit a similar asymptotic trend during extended cycling (i.e., an similar to 10-15% decrease in the peak power density and an similar to 20-25% decrease in the limiting current density is observed as quasi-equilibrium state is reached). (C) 2015 The Electrochemical Society. All rights reserved

Melatonin: Role in Increasing Plant Tolerance in Abiotic Stress Conditions

Nowadays, due to the environmental stress factors that limit the production of crops, it has become very difficult to find suitable areas to enable the plant to reach its optimum product potential. Abiotic stress is very effective in decreasing agricultural production. Factors such as drought, salinity, high and low temperature, flood, radiation, heavy metals, oxidative stress, and nutrient deficiency can be considered as abiotic stress factors, and these sources of stress negatively affect plant growth, quality and productivity. Melatonin (MEL) was first identified in plants in 1995 and is increasingly becoming important for its role and effects in the plant system. MEL has been shown to have a substantial role in plant response to growth, reproduction, development, and different stress factors. In addition to its regulatory role, MEL also plays a protective role against different abiotic stresses such as metal toxicity, temperature, drought, and salinity. In plants, an important role of MEL is to alleviate the effects of abiotic stresses. In this review, the effects of MEL on plant growth, photosynthetic activity, metabolism, physiology, and biochemistry under abiotic stress conditions as a plant growth regulator will be examined

Enhancing Mass Transport in Redox Flow Batteries by Tailoring Flow Field and Electrode Design

In this study, we investigate the mass transport effects of various flow field designs paired with raw and laser perforated carbon paper electrodes in redox flow batteries (RFBs). Previously, we observed significant increases in peak power density and limiting current density when perforated electrodes were used in conjunction with the serpentine flow field. In this work, we expand on our earlier findings by investigating various flow field designs (e.g., serpentine, parallel, interdigitated, and spiral), and continuously measuring pressure drop in each configuration. In all cases, these perforated electrodes are found to be associated with a reduction in pressure drop from 4% to 18%. Flow field designs with a continuous path from inlet to outlet (i.e., serpentine, parallel, spiral) are observed to exhibit improved performance (up to 31%) when paired with perforated electrodes, as a result of more facile reactant delivery and resulting greater utilization of the available surface area. Conversely, flow fields with discontinuous paths which force electrolyte to travel through the electrode (e.g. interdigitated), are adversely affected by the creation of perforations due to the high permeability 'channels' in the electrode. These results demonstrate that mass transport can significantly limit the performance of RFBs with carbon paper electrodes. (C) 2015 The Electrochemical Society. All rights reserved

International Summer Engineering Program on fuel cells for undergraduate engineering students

In this paper the experiences and lessons learned from an International Summer Engineering Program (ISEP 2009) Centred around a fuel cell course are presented. ISEP was run at Middle East Technical University (METU) in Turkey with participation from The University of Texas-Austin (Texas) and The Pennsylvania State University (Penn State). The program contained 21 METU, 7 Texas and 2 Penn State students from a range of engineering majors. The fuel cell class was designed to strengthen fuel cell, core engineering, and global competency skills through a series of increasingly complex computer projects and global competency assignments. Results from an extensive evaluation completed by the students at the end of the summer are presented. Relative to most other international engineering programs or a typical engineering class, the biggest value-added educational component of the program is seen as the intensive formal and informal interaction achieved between the METU and US students. Copyright (C) 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved

Towards Selective Removal of Bromide from Drinking Water Resources using Electrochemical Desalination

Disinfection of drinking water is crucial in water treatment as it suppresses waterborne pathogenic diseases. However, as an unintended consequence, disinfection generates disinfection byproducts (DBP). DBPs are cytotoxic, carcinogenic, and nephrotoxic especially when they are brominated. Brominated DBP formation is governed by the interaction of reactive precursors such as natural organic matter (NOM), and Brˉ with oxidants that are added as disinfectants (e.g., chlorine, chloramines, ozone). Historically, the main strategy to control the formation of DBP was to remove NOM from water by coagulation, adsorption, bio-filtration, pre-oxidation, or membrane separation; however, processes that remove NOM do not necessarily remove Brˉ. Herein, we investigated the utilization of combined capacitive and faradaic ion removal in a flow cell to remove Brˉ as well as Clˉ concurrently with more selectivity towards the former. The effectiveness of the proposed technique was evaluated by determining the maximum salt adsorption capacity and measuring the specific ion concentration with ion chromatography. In a binary equimolar mixture of Brˉ and Clˉ, Brˉ was more selectively adsorbed over Clˉ at 1.2 V applied potential due to the contribution of bromine gas evolution to the capacitive deionization

MODELING OF BIPOLAR PLATES FOR PROTON EXCHANGE MEMBRANE FUEL CELLS

Fuel cell technology is one of the most economic and efficient ways to utilize hydrogen energy. Various types of fuel cells are present regarding the fuel type and amount of power produced. Among these, proton exchange membrane fuel cells (PEMFCs) are very promising. In this work, a 2D proton exchange membrane fuel cell unit cell was modeled using Comsol Multiphysics software. Cell section was taken parallel to flow direction. Obstacles with various geometries were placed in the flow channel in order to force more reactant species to react. The goal is to have current and power densities that approach ideal performance and to minimize losses. As boundary conditions, several inlet velocities were applied. Also, the effect of setting different pressure values at the outlet was investigated. Consequently, it was observed that increasing inlet velocity and outlet pressure, feeding more reactant at the cathode compared to the anode, and increasing the depth of the obstacles placed through the channel enhanced the fuel cell performance

Optimized Anion Exchange Membranes for Vanadium Redox Flow Batteries

In order to understand the properties of low vanadium permeability anion exchange membranes for vanadium redox flow batteries (VRFBs), quaternary ammonium functionalized Radel (QA-Radel) membranes with three ion exchange capacities (IECs) from 1.7 to 2.4 mequiv g^–1 were synthesized and 55–60 μm thick membrane samples were evaluated for their transport properties and in-cell battery performance. The ionic conductivity and vanadium permeability of the membranes were investigated and correlated to the battery performance through measurements of Coulombic efficiency, voltage efficiency and energy efficiency in single cell tests, and capacity fade during cycling. Increasing the IEC of the QA-Radel membranes increased both the ionic conductivity and VO²⁺ permeability. The 1.7 mequiv g^–1 IEC QA-Radel had the highest Coulombic efficiency and best cycling capacity maintenance in the VRFB, while the cell’s voltage efficiency was limited by the membrane’s low ionic conductivity. Increasing the IEC resulted in higher voltage efficiency for the 2.0 and 2.4 mequiv g^–1 samples, but the cells with these membranes displayed reduced Coulombic efficiency and faster capacity fade. The QA-Radel with an IEC of 2.0 mequiv g^–1 had the best balance of ionic conductivity and VO²⁺ permeability, achieving a maximum power density of 218 mW cm^–2 which was higher than the maximum power density of a VRFB assembled with a Nafion N212 membrane in our system. While anion exchange membranes are under study for a variety of VRFB applications, this work demonstrates that the material parameters must be optimized to obtain the maximum cell performance