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The Elestor solution
The choice of hydrogen and bromine
From all the different chemistries that theoretically could be used to design a flow battery, Elestor has selected hydrogen and bromine as active materials. This leads to several advantages. The choice of hydrogen and bromine was purely driven by Elestor’s mission to build a storage system with the lowest possible storage costs per MWh. While taking full advantage of the typical flow battery features, this mission cannot be accomplished without inexpensive chemistries.
Hydrogen and bromine are abundantly available on a global scale. The supply is not restricted to geographical availability, and cannot be dominated by a small group of suppliers, unlike, say, lithium, cobalt and vanadium.
The above factors add up to very low-priced active materials. Not only presently, but for decades to come, indeed, even when large volumes will be required for high volume production of hydrogen bromine flow batteries.
Another advantage of selecting hydrogen and bromine is that these enable a high power density [W/m2] as well as a high energy density [kWh/m3], both contributing to the reduction of storage costs per MWh.
The heart of all Elestor’s storage systems is the cell stack. This stack consists of a number of individual electrochemical cells, as shown above, connected in series.
Each membrane in this stack in contact with the electrolyte circuit, an aqueous solution of hydrogen bromide (HBr) and diatomic bromine (Br2), on one side. On the other side, each membrane is in contact with a hydrogen (H2) gas circuit. Both active materials circulate in a closed loop along their own respective side of the cell. The electrolyte (HBr/Br2 solution) and hydrogen (H2) circuits are separated by a proton-conductive membrane.
Long-term performance of hydrogen-bromine flow batteries using single-layered and multi-layered wire-electrospun SPEEK/PFSA/PVDF membranes
Sanaz Abbasiab, Yohanes Antonius Hugob, Zandrie Bornemanac, Wiebrand Koutb and Kitty Nijmeijer*ac
aMembrane Materials and Processes, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands. E-mail: D.C.Nijmijer@tue.nl
bElestor BV P.O. Box 882, 6800 AW Arnhem, The Netherlands
cDutch Institute for Fundamental Energy Research (DIFFER), P.O. Box 6336, 5600 HH Eindhoven, The Netherlands
Abstract
Sulfonated poly (ether ketone) (SPEEK), perfluorosulfonic acid (PFSA), and polyvinylidene fluoride (PVDF) were wire-electrospun. Subsequently, multiple electrospun layers in different arrangements were hot-pressed into sustainable membranes for use in hydrogen-bromine flow batteries (HBFBs). The relationship between the electrospun layer composition and arrangement, membrane properties, and battery performance was explored. Wire-electrospinning and hot-pressing improved SPEEK and PFSA/PVDF compatibility, yielding dense membranes. Higher SPEEK contents lead to rougher morphologies, while the insulating nature of PVDF decreases the ion exchange capacity (IEC) and HBr uptake compared to commercial PFSA. The multi-layer assembly negatively impacted the membrane transport properties compared to the single-layer arrangement. Although wire-electrospinning improves the polymer dispersion and fixed charge density, SPEEK-rich regions of the blend membranes lack the high selectivity of PFSA, thus reducing the ionic conductivity. This is especially clear in the multi-layer membranes with accumulated SPEEK in the intermediate layer in the through-plane direction. Following initial property comparisons, thinner wire-electrospun SPEEK membranes were prepared with area resistance in the PFSA-comparable range. Among the wire-electrospun SPEEK/PFSA/PVDF membranes, the single-layered membrane with 8 wt% SPEEK (SPF1-8; 62 μm) displayed stable HBFB performance at 200 mA cm−2 over 100 cycles (64 cm2 active area). Based on the ex-situ measurements and cell performance results, a total of ∼10.5 wt% SPEEK is suggested as the limit for both single and multi-layered wire-electrospun membranes, combined with a maximum membrane thickness of ∼50 μm. This ensures robust HBFB performance, positioning wire-electrospun SPEEK/PFSA/PVDF membranes as a PFSA alternative in energy storage.
Wire based electrospun composite short side chain perfluorosulfonic acid/ polyvinylidene fluoride membranes for hydrogen-bromine flow batteries
Yohanes Antonius Hugo a, b, Wiebrand Kout b, Antoni Forner-Cuenca a, Zandrie Borneman a, c, Kitty Nijmeijer a, c, *
a Membrane Materials and Processes, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, PO Box 513, 5600MB Eindhoven, the Netherlands
b Elestor B.V., 6827 AV Arnhem, the Netherlands
c Dutch Institute for Fundamental Energy Research (DIFFER), P.O. Box 6336, 5600 HH Eindhoven, the Netherlands
⁎ Corresponding author. E-mail address: d.c.nijmeijer@tue.nl (K. Nijmeijer).
Abstract
A main component of a hydrogen-bromine flow battery (HBFB) is the ion exchange membrane. Available membranes have a trade-off between the major requirements: high proton conductivity, low bromine species crossover, and high mechanical and chemical stability. To overcome this, electrospinning of a highly proton conductive polymer (short side chain perfluorosulfonic acid (SSC PFSA)) and a hydrophobic inert polymer (polyvinylidene fluoride (PVDF)) was used to electrospin composite polymer fiber mats. Piles of multiple mats were hot pressed resulting in dense ion exchange membranes. Membranes with three different SSC PFSA/PVDF ratios were prepared, characterized, and subjected to short and long term (1500 h) HBFB testing. The electrospun membranes have performances very comparable to those of commercial membranes. For the SSC PFSA/PVDF electrospun membrane, a higher SSC PFSA loading gives a higher membrane proton conductivity compared to a lower loading, but at the expense of a higher bromine species crossover. The SSC PFSA/PVDF (50/50 wt%) membrane shows a coulombic efficiency of 98%, a voltaic efficiency of 80% and an initial available capacity of 105 Ah L− 1 at a current density of 150 mA cm− 2, which equals that of the current benchmark long side chain PFSA membrane. This performance is constant over 200 cycles during 2 months of continuous HBFB operation.
High selectivity-conductivity reinforced perfluorosulfonic acid membranes for hydrogen-bromine flow batteries.
Yohanes Hugo1, 2, Wiebrand Kout1, Friso Sikkema1, Zandrie Borneman2, Kitty Nijmeijer2
1Elestor B.V., 6812 AR Arnhem, the Netherlands
2Membrane Materials and Processes, Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, PO box 513, 5600 MB Eindhoven, The Netherlands
Abstract
Reinforced proton exchange membrane (PEM) were developed to increase the mechanical strength of thin membranes (≤30 µm) for PEM fuel cell applications. In hydrogen-bromine flow batteries (HBFBs), Br2 and Br– crossover through the membrane may affect the lifetime of HBFBs as a result of dissolution or passivation of the platinum catalyst. One study suggested that the reinforcement reduces the bulk Br2 and Br– transport and x-y (in-plane) swelling [1].