• Energy Research

Polybromides formation in aqueous bromine electrolytes and influence on H2/Br2redox flow battery performance is investigated the first time.

A transition from fossil to renewable energy requires the development of sustainable electric energy storage systems capable to accommodate an increasing amount of energy, at larger power and for a longer time. Flow batteries are seen as one promising technology to face this challenge. As different innovations in this field of technology are still under development, reproducible, comparable and verifiable life cycle assessment studies are crucial to providing clear evidence on the sustainability of different flow battery systems. Based on a review of 20 relevant life cycle assessment studies for different flow battery systems, published between 1999 and 2021, this contribution explored relevant methodological choices regarding the sequence of phases defined in the ISO 14,040 series: goal and scope definition, inventory analysis, impact assessment and interpretation. Inspired by good practice examples, common gaps and weaknesses were identified and recommendations for comparative life cycle assessment studies were derived. This includes suggestions for an expanded functional unit definition, a provision of more detailed and transparent reporting of LCI data while using input/output tables. Outcomes of this study are also of relevance for the amendment of the Batteries Directive 2006/66/EC, where first drafts are under revision in the European Council, including the introduction of a battery passport, which should encourage battery producers to reduce their carbon footprint and avoid problematic materials.

In this study, 1.6 M vanadium electrolytes in the oxidation forms V(III) and V(V) were prepared from V(IV) in sulfuric (4.7 M total sulphate), V(IV) in hydrochloric (6.1 M total chloride) acids, as well as from 1:1 mol mixture of V(III) and V(IV) (denoted as V3.5+) in hydrochloric (7.6 M total chloride) acid. These electrolyte solutions were investigated in terms of performance in vanadium redox flow battery (VRFB). The half-wave potentials of the V(III)/V(II) and V(V)/V(IV) couples, determined by cyclic voltammetry, and the electronic spectra of V(III) and V(IV) electrolyte samples, are discussed to reveal the effect of electrolyte matrix on charge-discharge behavior of a 40 cm2 cell operated with 1.6 M V3.5+ electrolytes in sulfuric and hydrochloric acids. Provided that the total vanadium concentration and the conductivity of electrolytes are comparable for both acids, respective energy efficiencies of 77% and 72–75% were attained at a current density of 50 mA∙cm−2. All electrolytes in the oxidation state V(V) were examined for chemical stability at room temperature and +45 °C by titrimetric determination of the molar ratio V(V):V(IV) and total vanadium concentration.

One of the most important parameters for the design of redox flow batteries is a uniform distribution of the electrolyte solution over the complete electrode area. The performance of redox flow batteries is usually investigated by general measurements of the cell in systematic experimental studies such as galvanostatic charge-discharge cycling. Local inhomogeneity within the electrode cannot be locally-resolved. In this study a printed circuit board (PCB) with a segmented current collector was integrated into a 40 cm2 all-vanadium redox flow battery to analyze the locally-resolved current density distribution of the graphite felt electrode. Current density distribution during charging and discharging of the redox flow battery indicated different limiting influences. The local current density in redox flow batteries mainly depends on the transport of the electrolyte solution. Due to this correlation, the electrolyte flow in the porous electrode can be visualized. A PCB electrode can easily be integrated into the flow battery and can be scaled to nearly any size of the electrode area. The carbon coating of the PCB enables direct contact to the corrosive electrolyte, whereby the sensitivity of the measurement method is increased compared to state-of-the-art methods.

The performance of redox flow batteries is notably influenced by the electrolyte, especially in slurry-based flow batteries, as it serves as both an ionic conductive electrolyte and a flowing electrode. In this study, carbon additives were introduced to achieve a rechargeable zinc slurry flow battery by minimizing the zinc plating on the bipolar plate that occurs during charging. When no carbon additive was present in the zinc slurry, the discharge current density was 24 mA∙cm−2 at 0.6 V, while the use of carbon additives increased it to up to 38 mA∙cm−2. The maximum power density was also increased from 16 mW∙cm−2 to 23 mW∙cm−2. Moreover, the amount of zinc plated on the bipolar plate during charging decreased with increasing carbon content in the slurry. Rheological investigation revealed that the elastic modulus and yield stress are directly proportional to the carbon content in the slurry, which is beneficial for redox flow battery applications, but comes at the expense of an increase in viscosity (two-fold increase at 100 s−1). These results show how the use of conductive additives can enhance the energy density of slurry-based flow batteries.

A series of vanadium redox‐flow battery (VRFB) electrolytes at 1.55 m vanadium and 4.5 m total sulfate concentration are prepared from vanadyl sulfate solution and tested under conditions of appearance of “power drop” effect (discharge at high current density from high state‐of‐charge). A correlation between the initial electrolyte composition, the thermal stability of catholyte, and the susceptibility of VRFB to exhibit a “power drop” effect is derived. The increase in total acidity to 3 m, expressed as concentration of sulfuric acid in precursor vanadyl sulfate solution, enables “power drop”‐free operation of VRFB at least at 75 mA cm−2. Thermally‐induced degradation of electrolyte is evaluated based on decrease in vanadium concentration in the electrolyte series after exposure to the temperature of 45 °C and based on characterization of catholytes series using 51V, 17O, and 1H nuclear magnetic resonance spectroscopy.