Mixture of Anthraquinone Sulfo-Derivatives as an Inexpensive Organic Flow Battery Negolyte: Optimization of Battery Cell.

Anthraquinone-2,7-disulfonic acid (2,7-AQDS) is a promising organic compound, which is considered as a negolyte for redox flow batteries as well as for other applications. In this work we carried out a well-known reaction of anthraquinone sulfonation to synthesize 2,7-AQDS in mixture with other sulfo-derivatives, namely 2,6-AQDS and 2-AQS. Redox behavior of this mixture was evaluated with cyclic voltammetry and was almost identical to 2,7-AQDS. Mixture was then assessed as a potential negolyte of anthraquinone-bromine redox flow battery. After adjusting membrane-electrode assembly composition (membrane material and flow field)), the cell demonstrated peak power density of 335 mW cm-2 (at SOC 90%) and capacity utilization, capacity retention and energy efficiency of 87.9, 99.6 and 64.2%, respectively. These values are almost identical or even higher than similar values for flow battery with 2,7-AQDS as a negolyte, while the price of mixture is significantly lower. Therefore, this work unveils the promising possibility of using a mixture of crude sulfonated anthraquinone derivatives mixture as an inexpensive negolyte of RFB.

Analysis of the Composition of Bromide Anion Oxidation Products in Aqueous Solutions with Different pH via Rotating Ring-Disk Electrode Method.

We measured the ring collection coefficient of bromide anion oxidation products in a neutral and slightly alkaline medium on a rotating ring-disk electrode (glassy carbon disk, platinum ring) varying the following parameters: disk electrode rotation velocity, sodium bromide concentration, pH of the medium (in the range of 6−12), anode current on the disk, and the electroreduction potential of the bromide anion oxidation products on the ring. The data obtained are presented via dependences of the cathode ring current on the disk current ratio vs. the ring electrode potential. The analysis of the results was carried out by comparing the experimental polarization curves of the ring electrode with the data of cyclic voltammetry in model solutions to determine the electrical activities of various bromine compounds in positive oxidation states. We claim that the RRDE method could be used to obtain quantitative and qualitative data on the electrooxidation of bromide ions in neutral and alkaline solutions. For the most effective regeneration of the spent oxidizer, the values of pH > 10 and moderate concentrations of NaBr should be used.

Bromine Crossover in Operando Analysis of Proton Exchange Membranes in Hydrogen-Bromate Flow Batteries.

The manuscript deals with the fundamental problem of platinum hydrogen oxidation catalyst poisoning of the hybrid chemical power source based on bromate electroreduction and hydrogen electro-oxidation reactions. The poisoning is caused by the crossover of bromine-containing species through the proton exchange membrane separating compartments of the flow cell. Poisoning results in a drastic decrease in the flow cell performance. This paper describes the results of the direct measurement of bromine-containing species' crossover through perfluorosulfonic acid membranes of popular vendors in a hydrogen-bromate flow cell and proposes corresponding scenarios for the flow battery charge-discharge operation based on the electrolyte's control of the pH value. The rate of the crossover of the bromine-containing species through the membrane is found to be inversely proportional to the membrane thickness.

A Composite Membrane Based on Sulfonated Polystyrene Implanted in a Stretched PTFE Film for Vanadium Flow Batteries.

The quality of ion-selective membranes determines the efficiency of Vanadium Flow Batteries (VFBs), and alternatives to expensive Nafion™ materials are actively being searched for. One of the membrane architecture approaches is to imitate the Nafion™ structure with two separate phases: a conductive sulfonated polymer and an inner matrix. We introduce a new composite material based on sulfonated styrene polymerized inside the pores of a stretched PTFE matrix. Variation of polystyrene content and a sulfonation degree allowed to obtain membranes with IEC from to 0.96 to 1.84 mmol/g. Balanced vanadium permeability (ca. 5.5 ⋅ 10-6  cm2 /min) and proton conductivity (ca. 50 mS/cm) were achieved for the material with 21-23 % polystyrene content and a sulfonation degree up to 94 %. Membranes showed stable cycling with 81 % energy efficiency in a single-cell VFB. This work contributes to the existing knowledge of Nafion alternatives by providing a cheap and scalable method of membrane production.

Electrolyte Flow Field Variation: A Cell for Testing and Optimization of Membrane Electrode Assembly for Vanadium Redox Flow Batteries.

A great deal of research has been dedicated to improving the performance of vanadium redox flow battery (VRFB). In this work, we propose the design of a cell for testing membrane electrode assembly of VRFB, which enables the optimization of the flow field, conditions of charge-discharge tests, and the nature of components (electrodes, membrane) with minimal time and material expenses. The essence of the proposed cell is that the system of channels distributing the electrolyte is made by cutting shaped holes in the sheets of graphite foil (GF). This manner allows easy modification of the flow field configurations. Polarization curves for serpentine, interdigitated, and flow-through systems were measured according to procedures used in such studies. Cell with GF plates being tested with vanadium-sulfuric acid electrolyte, outperforms the cell with conventional graphite plates with the same parameters of the flow field. It demonstrates 734 mW cm-2 of peak power density at SOC 50 and 84.3 % of energy efficiency at 84.5 % of electrolyte utilization under galvanostatic charge/discharge cycling with 75 mA cm-2 .