Special Issue "Vanadium Redox Flow Battery and Its Applications"

A special issue of Batteries (ISSN 2313-0105).

Deadline for manuscript submissions: closed (31 December 2018)

Special Issue Editor

Guest Editor
Prof. emer Maria Skyllas-Kazacos

School of Chemical Engineering, The University of New South Wales, UNSW, Sydney, NSW 2052, Australia
Website | E-Mail
Interests: vanadium redox flow battery; flow batteries; electrode materials; membranes; cell design; sensors; control; modelling; simulation

Special Issue Information

Dear Colleagues,

It has now been more than 30 years since the first patent on the Vanadium Redox Flow Battery (VFB) was granted to our group at University of New South Wales (UNSW Sydney) and we are thrilled to see the increasing interest that has led to the extensive research, development, field trials and now commercial production of the VFB around the world. VFB can now be regarded as a mature energy storage technology, but, as with all mature technologies, ongoing research is helping to improve performance and reduce cost for broader implementation in a range of energy storage applications. In this first Special Issue dedicated to the Vanadium Redox Flow Battery, we hope to collect contributions from all the research groups and companies currently engaged in VFB research, development and manufacture in order to describe the current state-of-the-art across the full range of flow battery topics to serve as an important reference to the energy storage industry and to flow battery researchers engaged in this rapidly growing field.

Prof. Dr. Maria Skyllas-Kazacos
Guest Editor

Manuscript Submission Information

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Keywords

  • vanadium electrolytes
  • electrolyte production methods
  • electrode materials
  • membranes
  • sensors
  • stack design and modelling
  • cell materials
  • simulation
  • advanced control
  • cost analysis
  • manufacturing
  • quality control
  • field studies
  • system design
  • performance evaluation

Published Papers (15 papers)

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Research

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Open AccessArticle
A One-Dimensional Stack Model for Redox Flow Battery Analysis and Operation
Received: 1 January 2019 / Revised: 6 February 2019 / Accepted: 12 February 2019 / Published: 22 February 2019
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Abstract
Current redox flow battery (RFB) stack models are not particularly conducive to accurate yet high-throughput studies of stack operation and design. To facilitate system-level analysis, we have developed a one-dimensional RFB stack model through the combination of a one-dimensional Newman-type cell model and [...] Read more.
Current redox flow battery (RFB) stack models are not particularly conducive to accurate yet high-throughput studies of stack operation and design. To facilitate system-level analysis, we have developed a one-dimensional RFB stack model through the combination of a one-dimensional Newman-type cell model and a resistor-network to evaluate contributions from shunt currents within the stack. Inclusion of hydraulic losses and membrane crossover enables constrained optimization of system performance and allows users to make recommendations for operating flow rate, current densities, and cell design given a subset of electrolyte and electrode properties. Over the range of experimental conditions explored, shunt current losses remain small, but mass-transfer losses quickly become prohibitive at high current densities. Attempting to offset mass-transfer losses with high flow rates reduces system efficiency due to the increase in pressure drop through the porous electrode. The development of this stack model application, along with the availability of the source MATLAB code, allows for facile approximation of the upper limits of performance with limited empiricism. This work primarily presents a readily adaptable tool to enable researchers to perform either front-end performance estimates based on fundamental material properties or to benchmark their experimental results. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Vanadium Oxygen Fuel Cell Utilising High Concentration Electrolyte
Received: 20 December 2018 / Revised: 8 February 2019 / Accepted: 12 February 2019 / Published: 19 February 2019
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Abstract
A vanadium oxygen fuel cell is a modified form of a conventional vanadium redox flow battery (VRFB) where the positive electrolyte (VO2+/VO2+ couple) is replaced by the oxygen reduction (ORR) process. This potentially allows for a significant improvement in [...] Read more.
A vanadium oxygen fuel cell is a modified form of a conventional vanadium redox flow battery (VRFB) where the positive electrolyte (VO2+/VO2+ couple) is replaced by the oxygen reduction (ORR) process. This potentially allows for a significant improvement in energy density and has the added benefit of overcoming the solubility limits of V (V) at elevated temperatures, while also allowing the vanadium negative electrolyte concentration to increase above 3 M. In this paper, a vanadium oxygen fuel cell with vanadium electrolytes with a concentration of up to 3.6 M is reported with preliminary results presented for different electrodes over a range of current densities. Using precipitation inhibitors, the concentration of vanadium can be increased considerably above the commonly used 2 M limit, leading to improved energy density. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Optimal Charging of Vanadium Redox Flow Battery with Time-Varying Input Power
Received: 14 November 2018 / Revised: 19 January 2019 / Accepted: 31 January 2019 / Published: 10 February 2019
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Abstract
The battery energy storage system has become an indispensable part of the current electricity network due to the vast integration of renewable energy sources (RESs). This paper proposes an optimal charging method of a vanadium redox flow battery (VRB)-based energy storage system, which [...] Read more.
The battery energy storage system has become an indispensable part of the current electricity network due to the vast integration of renewable energy sources (RESs). This paper proposes an optimal charging method of a vanadium redox flow battery (VRB)-based energy storage system, which ensures the maximum harvesting of the free energy from RESs by maintaining safe operations of the battery. The VRB has a deep discharging capability, long cycle life, and high energy efficiency with no issues of cell-balancing, which make it suitable for large-scale energy storage systems. The proposed approach determines the appropriate charging current and the optimal electrolyte flow rate based on the available time-varying input power. Moreover, the charging current is bounded by the limiting current, which prevents the gassing side-reactions and protects the VRB from overcharging. The proposed optimal charging method is investigated by simulation studies using MATLAB/Simulink. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Degradation Phenomena of Bismuth-Modified Felt Electrodes in VRFB Studied by Electrochemical Impedance Spectroscopy
Received: 13 November 2018 / Revised: 9 December 2018 / Accepted: 17 January 2019 / Published: 23 January 2019
Cited by 1 | PDF Full-text (5664 KB) | HTML Full-text | XML Full-text
Abstract
The performance of all-V redox flow batteries (VRFB) will decrease when they are exposed to dynamic electrochemical cycling, but also when they are in prolonged contact with the acidic electrolyte. These phenomena are especially severe at the negative side, where the parasitic hydrogen [...] Read more.
The performance of all-V redox flow batteries (VRFB) will decrease when they are exposed to dynamic electrochemical cycling, but also when they are in prolonged contact with the acidic electrolyte. These phenomena are especially severe at the negative side, where the parasitic hydrogen evolution reaction (HER) will be increasingly favored over the reduction of V(III) with ongoing degradation of the carbon felt electrode. Bismuth, either added to the electrolyte or deposited onto the felt, has been reported to suppress the HER and therefore to enhance the kinetics of the V(II)/V(III) redox reaction. This study is the first to investigate degradation effects on bismuth-modified electrodes in the negative half-cell of a VRFB. By means of a simple impregnation method, a commercially available carbon felt was decorated with Bi 2 O 3 , which is supposedly present as Bi(0) under the working conditions at the negative side. Modified and unmodified felts were characterized electrochemically using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a three-electrode setup. Surface morphology of the electrodes and composition of the negative half-cell electrolyte were probed using scanning electron microscopy (SEM) and X-ray fluorescence spectroscopy (TXRF), respectively. This was done before and after the electrodes were subjected to 50 charge-discharge cycles in a battery test bench. Our results suggest that not only the bismuth catalyst is dissolved from the electrode during battery operation, but also that the presence of bismuth in the system has a strong accelerating effect on electrode degradation. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Investigations on a Mesoporous Glass Membrane as Ion Separator for a Redox Flow Battery
Received: 17 August 2018 / Revised: 12 November 2018 / Accepted: 17 December 2018 / Published: 5 January 2019
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Abstract
This article reports extensive studies of a Vycor® porous glass (VPG) membrane as an ion separator for an all-vanadium redox flow battery (VRFB). The VPG membrane had an average pore size of 4 nm and porosity of ~28%. The VPG ion separator [...] Read more.
This article reports extensive studies of a Vycor® porous glass (VPG) membrane as an ion separator for an all-vanadium redox flow battery (VRFB). The VPG membrane had an average pore size of 4 nm and porosity of ~28%. The VPG ion separator exhibited higher proton diffusivity but lower conductivity than the Nafion® 117 membrane because the former is intrinsically nonionic. The VRFB equipped with the VPG ion separator (VPG-VRFB) exhibited much better stability during long-term cyclic operation than the VRFB equipped with the Nafion-117 membrane (Nafion-VRFB) because the ionic Nafion membrane could be contaminated by vanadium ions exchanged into the water channels. This increases its area specific resistance, while the VPG does not have ion exchange capacity and hence has less vanadium ion contamination. The VPG-VRFB was found to outperform the Nafion-VRFB in energy efficiency (EE) during long-term cyclic operation although the former underperformed the latter in the initial period of continued operation. The VPG ion separator also showed markedly better thermal stability and temperature tolerance than the Nafion membrane as indicated by the significantly smaller losses of EE and discharge capacity for the VPG-VRFB than for the Nafion-VRFB after operating at 45 °C. The outstanding temperature tolerance of the VPG ion separator is due primarily to its rigid and non-swelling pore structure and nonionic nature, which are highly resistant to thermal distortion and vanadium ion contamination. The excellent temperature tolerance of the VPG may be useful for applications where temperature control is difficult. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Monitoring the State of Charge of the Positive Electrolyte in a Vanadium Redox-Flow Battery with a Novel Amperometric Sensor
Received: 27 September 2018 / Revised: 13 November 2018 / Accepted: 19 December 2018 / Published: 5 January 2019
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Abstract
Vanadium redox-flow batteries are a promising energy storage technology due to their safety, long-term stability, and independent adjustability of power and capacity. However, the vanadium crossover through the membrane causes a self-discharge, which results in a capacity shift towards one half cell. This [...] Read more.
Vanadium redox-flow batteries are a promising energy storage technology due to their safety, long-term stability, and independent adjustability of power and capacity. However, the vanadium crossover through the membrane causes a self-discharge, which results in a capacity shift towards one half cell. This leads to a gradual decrease in its efficiency over time. Capacity balancing methods for compensation of this effect require a reliable online state of charge (SoC) monitoring. Most common methods cannot provide exact values of the individual concentration of each species in both electrolytes. In particular, the state of the positive electrolyte cannot yet be precisely determined. In this work, an amperometric SoC monitoring is proposed as a new approach. First, the suitability of the principle is investigated with a rotating disc electrode (RDE). Then, a sensor based on a gas diffusion layer (GDL) is developed and tested in the positive electrolyte. The dependencies between oxidative current and V(IV)-concentration are examined as well as those between reduction current and V(V)-concentration. Using both relationships, a reliable measurement of all relevant concentrations is possible. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessCommunication
Towards Production of a Highly Catalytic and Stable Graphene-Wrapped Graphite Felt Electrode for Vanadium Redox Flow Batteries
Received: 13 October 2018 / Revised: 2 November 2018 / Accepted: 5 November 2018 / Published: 3 December 2018
Cited by 1 | PDF Full-text (1770 KB) | HTML Full-text | XML Full-text
Abstract
Despite the appealing features of vanadium redox flow batteries as a promising energy storage solution, the polarization losses, among other factors, prevent widespread applications. The dominant contribution to these polarization losses is the sluggish (even irreversible) electron-transfer towards reactions, leading to large over-potentials [...] Read more.
Despite the appealing features of vanadium redox flow batteries as a promising energy storage solution, the polarization losses, among other factors, prevent widespread applications. The dominant contribution to these polarization losses is the sluggish (even irreversible) electron-transfer towards reactions, leading to large over-potentials (poor rate capability). In particular, the positive half-cell reaction suffers from a complex mechanism since electron- and oxygen-transfer processes are key steps towards efficient kinetics. Thus, the positive reaction calls for electrodes with a large number of active sites, faster electron transfer, and excellent electrical properties. To face this issue, a graphene-wrapped graphite felt (GO-GF) electrode was synthesized by an electrospray process as a cost-effective and straightforward way, leading to a firm control of the GO-deposited layer-by-layer. The voltage value was optimized to produce a homogeneous deposition over a GF electrode after achieving a stable Taylor cone-jet. The GO-GF electrode was investigated by cyclic voltammetry and electrochemical impedance spectroscopy in order to elucidate the electrocatalytic properties. Both analyses reflect this excellent improvement by reducing the over-potentials, improving reversibility, and enhancing collected current density. These findings confirm that the GO-GF is a promising electrode for high-performance VRFB, overcoming the performance-limiting issues in a positive half-reaction. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Verification of Redox Flow Batteries’ Functionality by Electrochemical Impedance Spectroscopy Tests
Received: 28 September 2018 / Revised: 24 October 2018 / Accepted: 30 October 2018 / Published: 6 November 2018
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Abstract
The state-of-the-art functionality test of classic redox-flow-stacks measures the current–voltage characteristic with the technical electrolyte. This research paper aims to simplify the validation of redox flow batteries’ functionality by conducting electrochemical impedance spectroscopy (EIS) on redox flow stacks. Since the electrolyte used in [...] Read more.
The state-of-the-art functionality test of classic redox-flow-stacks measures the current–voltage characteristic with the technical electrolyte. This research paper aims to simplify the validation of redox flow batteries’ functionality by conducting electrochemical impedance spectroscopy (EIS) on redox flow stacks. Since the electrolyte used in the batteries is usually toxic and aggressive, it would be a significant simplification to verify the functionality with an alternative, non-toxic fluid. EIS measurements on batteries with larger sized electrodes, multiple cells, and different fluids were performed. It was demonstrated that all impedances are repeatable, thereby validating this procedure as a qualification method for full-size and complex batteries with an alternative fluid. EIS measurements were able to detect deliberately manipulated cells. This research uses three different analysis methods for the acquired data to identify errors. The respective approaches are, firstly, (1) a comparison of the Nyquist plots; secondly, (2) a comparison of the Bode plots; and thirdly, (3) a comparison of the calculated characteristic values of the equivalent circuits. The analysis found that all methods are suitable to detect errors in the batteries. Nevertheless, the bode-plot comparison method proves to be especially advantageous, because it enables a quantitative statement. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Conversion of Spent Coffee Beans to Electrode Material for Vanadium Redox Flow Batteries
Received: 6 September 2018 / Revised: 12 October 2018 / Accepted: 22 October 2018 / Published: 1 November 2018
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Abstract
This study presents the application of pyrolyzed spent coffee beans as a potential electrode material to replace commercial bipolar graphite plate in vanadium redox flow batteries (VRB). The results indicate that the biochar obtained from spent coffee beans shows relatively good electrochemical charge [...] Read more.
This study presents the application of pyrolyzed spent coffee beans as a potential electrode material to replace commercial bipolar graphite plate in vanadium redox flow batteries (VRB). The results indicate that the biochar obtained from spent coffee beans shows relatively good electrochemical charge transfer kinetics of vanadium redox reactions as well as generates higher energy and voltage efficiency in a static cell test when compared to TF6 bipolar graphite plate. Additionally, the biochar was activated via steam at various activation times to increase its surface area, and their effect on the kinetics of the electrochemical reactions was investigated. The activated carbon did not exhibit any improvement neither in electron transfer kinetics nor in the battery efficiency, despite their increased surface area. The performed studies demonstrate that the biochar obtained from spent coffee beans can be a low-cost electrode material for VRB with improved performance characteristics. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessCommunication
Effect of Operating Temperature on Individual Half-Cell Reactions in All-Vanadium Redox Flow Batteries
Received: 26 September 2018 / Revised: 29 October 2018 / Accepted: 30 October 2018 / Published: 1 November 2018
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Abstract
Systematic steady-state measurements were performed in order to investigate the effect of operating temperature on the individual half-cell reactions in all vanadium redox flow cells. Results confirm that the kinetic losses are dominated by the negative half-cell reaction. Steady-state polarization and AC impedance [...] Read more.
Systematic steady-state measurements were performed in order to investigate the effect of operating temperature on the individual half-cell reactions in all vanadium redox flow cells. Results confirm that the kinetic losses are dominated by the negative half-cell reaction. Steady-state polarization and AC impedance measurements allowed for extraction of kinetic parameters (exchange current densities, activation energy) of the corresponding half-cell reaction. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Characterisation of a 200 kW/400 kWh Vanadium Redox Flow Battery
Received: 30 September 2018 / Revised: 20 October 2018 / Accepted: 22 October 2018 / Published: 1 November 2018
Cited by 3 | PDF Full-text (3768 KB) | HTML Full-text | XML Full-text
Abstract
The incessant growth in energy demand has resulted in the deployment of renewable energy generators to reduce the impact of fossil fuel dependence. However, these generators often suffer from intermittency and require energy storage when there is over-generation and the subsequent release of [...] Read more.
The incessant growth in energy demand has resulted in the deployment of renewable energy generators to reduce the impact of fossil fuel dependence. However, these generators often suffer from intermittency and require energy storage when there is over-generation and the subsequent release of this stored energy at high demand. One such energy storage technology that could provide a solution to improving energy management, as well as offering spinning reserve and grid stability, is the redox flow battery (RFB). One such system is the 200 kW/400 kWh vanadium RFB installed in the energy station at Martigny, Switzerland. This RFB utilises the excess energy from renewable generation to support the energy security of the local community, charge electric vehicle batteries, or to provide the power required to an alkaline electrolyser to produce hydrogen as a fuel for use in fuel cell vehicles. In this article, this vanadium RFB is fully characterised in terms of the system and electrochemical energy efficiency, with the focus being placed on areas of internal energy consumption from the regulatory systems and energy losses from self-discharge/side reactions. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
Variable Porous Electrode Compression for Redox Flow Battery Systems
Received: 28 September 2018 / Revised: 16 October 2018 / Accepted: 19 October 2018 / Published: 22 October 2018
Cited by 1 | PDF Full-text (2254 KB) | HTML Full-text | XML Full-text
Abstract
Vanadium redox flow batteries (VRFBs) offer great promise as a safe, cost effective means of storing electrical energy on a large scale and will certainly have a part to play in the global transition to renewable energy. To unlock the full potential of [...] Read more.
Vanadium redox flow batteries (VRFBs) offer great promise as a safe, cost effective means of storing electrical energy on a large scale and will certainly have a part to play in the global transition to renewable energy. To unlock the full potential of VRFB systems, however, it is necessary to improve their power density. Unconventional stack design shows encouraging possibilities as a means to that end. Presented here is the novel concept of variable porous electrode compression, which simulations have shown to deliver a one third increase in minimum limiting current density together with a lower pressure drop when compared to standard uniform compression cell designs. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessCommunication
Novel Approaches for Solving the Capacity Fade Problem during Operation of a Vanadium Redox Flow Battery
Received: 10 August 2018 / Revised: 11 September 2018 / Accepted: 12 September 2018 / Published: 1 October 2018
Cited by 2 | PDF Full-text (2695 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The vanadium redox flow battery (VRFB) is one of the most mature and commercially available electrochemical technologies for large-scale energy storage applications. The VRFB has unique advantages, such as separation of power and energy capacity, long lifetime (>20 years), stable performance under deep [...] Read more.
The vanadium redox flow battery (VRFB) is one of the most mature and commercially available electrochemical technologies for large-scale energy storage applications. The VRFB has unique advantages, such as separation of power and energy capacity, long lifetime (>20 years), stable performance under deep discharge cycling, few safety issues and easy recyclability. Despite these benefits, practical VRFB operation suffers from electrolyte imbalance, which is primarily due to the transfer of water and vanadium ions through the ion-exchange membranes. This can cause a cumulative capacity loss if the electrolytes are not rebalanced. In commercial systems, periodic complete or partial remixing of electrolyte is performed using a by-pass line. However, frequent mixing impacts the usable energy and requires extra hardware. To address this problem, research has focused on developing new membranes with higher selectivity and minimal crossover. In contrast, this study presents two alternative concepts to minimize capacity fade that would be of great practical benefit and are easy to implement: (1) introducing a hydraulic shunt between the electrolyte tanks and (2) having stacks containing both anion and cation exchange membranes. It will be shown that the hydraulic shunt is effective in passively resolving the continuous capacity loss without detrimentally influencing the energy efficiency. Similarly, the combination of anion and cation exchange membranes reduced the net electrolyte flux, reducing capacity loss. Both approaches work efficiently and passively to reduce capacity fade during operation of a flow battery system. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Open AccessArticle
The Effect of Sulfuric Acid Concentration on the Physical and Electrochemical Properties of Vanadyl Solutions
Received: 30 May 2018 / Revised: 19 July 2018 / Accepted: 23 July 2018 / Published: 1 September 2018
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Abstract
The effects of sulfuric acid concentration in VO2+ solutions were investigated via electrochemical methods and electron paramagnetic resonance. The viscosity of solutions containing 0.01 M VOSO4 in 0.1–7.0 M H2SO4 was measured. Diffusion coefficients were independently measured via [...] Read more.
The effects of sulfuric acid concentration in VO2+ solutions were investigated via electrochemical methods and electron paramagnetic resonance. The viscosity of solutions containing 0.01 M VOSO4 in 0.1–7.0 M H2SO4 was measured. Diffusion coefficients were independently measured via electrochemical methods and electron paramagnetic resonance (EPR), with excellent agreement between the techniques employed and literature values. Analysis of cyclic voltammograms suggest the oxidation of VO2+ to VO2+ is quasi-reversible at high H2SO4 concentrations (>5 mol/L), and approaching irreversible at lower H2SO4 concentrations. Further analysis reveals a likely electrochemical/chemical (EC) mechanism where the H2SO4 facilitates the electrochemical step but hinders the chemical step. Fundamental insights of VO2+/H2SO4 solutions can lead to a more comprehensive understanding of the concentration effects in electrolyte solutions. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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Review

Jump to: Research

Open AccessReview
Electrocatalysis at Electrodes for Vanadium Redox Flow Batteries
Received: 30 July 2018 / Revised: 20 August 2018 / Accepted: 23 August 2018 / Published: 13 September 2018
Cited by 2 | PDF Full-text (2099 KB) | HTML Full-text | XML Full-text
Abstract
Flow batteries (also: redox batteries or redox flow batteries RFB) are briefly introduced as systems for conversion and storage of electrical energy into chemical energy and back. Their place in the wide range of systems and processes for energy conversion and storage is [...] Read more.
Flow batteries (also: redox batteries or redox flow batteries RFB) are briefly introduced as systems for conversion and storage of electrical energy into chemical energy and back. Their place in the wide range of systems and processes for energy conversion and storage is outlined. Acceleration of electrochemical charge transfer for vanadium-based redox systems desired for improved performance efficiency of these systems is reviewed in detail; relevant data pertaining to other redox systems are added when possibly meriting attention. An attempt is made to separate effects simply caused by enlarged electrochemically active surface area and true (specific) electrocatalytic activity. Because this requires proper definition of the experimental setup and careful examination of experimental results, electrochemical methods employed in the reviewed studies are described first. Full article
(This article belongs to the Special Issue Vanadium Redox Flow Battery and Its Applications)
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