• Energy Research

Abstract The catalyst for the negative electrode of iron-chromium redox flow batteries (ICRFBs) is commonly prepared by adding a small amount of Bi3+ ions in the electrolyte and synchronously electrodepositing metallic particles onto the electrode surface at the beginning of charge process. Achieving a uniform catalyst distribution in the porous electrode, which is closely related to the flow field design, is critically important to improve the ICRFB performance. In this work, the effects of flow field designs on catalyst electrodeposition and battery performance are investigated. It is found that compared to the serpentine flow field (SFF) design, the interdigitated flow field (IFF) forces the electrolyte through the porous electrode between the neighboring channels and enhances species transport during the processes of both the catalyst electrodeposition and iron/chromium redox reactions, thus enabling a more uniform catalyst distribution and higher mass transport limitation. It is further demonstrated that the energy efficiency of the ICRFB with the IFF reaches 80.7% at a high current density (320 mA cm−2), which is 8.2% higher than that of the ICRFB with the SFF. With such a high performance and intrinsically low-cost active materials, the ICRFB with the IFF offers a great promise for large-scale energy storage.

Abstract The zinc bromine flow battery (ZBFB) is regarded as one of the most promising candidates for large-scale energy storage attributed to its high energy density and low cost. However, it suffers from low power density, primarily due to large internal resistances caused by the low conductivity of electrolyte and high polarization in the positive electrode. In this work, chloride based salts including KCl and NH 4 Cl are investigated as supporting electrolyte to enhance electrolyte conductivity, while graphite-felt electrodes are thermally treated to improve electrocatalytic activity. It is found that the use of 4 M NH 4 Cl as a supporting electrolyte enables the battery to be operated at a current density of 40 mA cm −2 with an energy efficiency of 74.3%, whereas without the addition of a supporting electrolyte the battery only outputs an energy efficiency of 60.4%. In combination with a thermally treated graphite-felt electrode, efficiency further reaches up to 81.8% at the same current density. More impressively, we demonstrate that even at a high current density of up to 80 mA cm −2 , the battery is capable of delivering an energy efficiency of 70%, representing one of the highest performances of ZBFBs in the open literature.

Abstract The promise of redox flow batteries (RFBs) utilizing soluble redox couples, such as all vanadium ions as well as iron and chromium ions, is becoming increasingly recognized for large-scale energy storage of renewables such as wind and solar, owing to their unique advantages including scalability, intrinsic safety, and long cycle life. An ongoing question associated with these two RFBs is determining whether the vanadium redox flow battery (VRFB) or iron-chromium redox flow battery (ICRFB) is more suitable and competitive for large-scale energy storage. To address this concern, a comparative study has been conducted for the two types of battery based on their charge–discharge performance, cycle performance, and capital cost. It is found that: i) the two batteries have similar energy efficiencies at high current densities; ii) the ICRFB exhibits a higher capacity decay rate than does the VRFB; and iii) the ICRFB is much less expensive in capital costs when operated at high power densities or at large capacities.

Abstract Conventional vanadium redox flow batteries (VRFBs) using Nafion 115 suffered from issues associated with high ohmic resistance and high capital cost. In this work, we report a commercial membrane (VANADion), consisting of a porous layer and a dense Nafion layer, as a promising alternative to Nafion 115. In the dual-layer structure, the porous layer (∼210 μm) can offer a high ionic conductivity and the dense Nafion layer (∼20 μm) can depress the convective flow of electrolyte through the membrane. By comparing with the conventional Nafion 115 in a VRFB, it is found that the change from the conventional Nafion 115 to the composite one results in an increase in the energy efficiency from 71.3% to 76.2% and an increase in the electrolyte utilization from 54.1% to 68.4% at a current density of as high as 240 mA cm−2. In addition, although two batteries show the comparable cycling performance at current densities ranging from 80 mA cm−2 to 240 mA cm−2, the composite membrane is estimated to be significantly cheaper than the conventional Nafion 115 due to the fact that the porous layer is rather cost-effective and the dense Nafion layer is rather thin. The impressive combination of desirable performance and low cost makes this composite membrane highly promising in the VRFB applications.

Abstract In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m 2 g −1 to 15.4 m 2 g −1 . The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm −2 , as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

Abstract In this work, we present a simple and cost-effective method to form a dual-scale porous electrode by KOH activation of the fibers of carbon papers. The large pores (∼10 μm), formed between carbon fibers, serve as the macroscopic pathways for high electrolyte flow rates, while the small pores (∼5 nm), formed on carbon fiber surfaces, act as active sites for rapid electrochemical reactions. It is shown that the Brunauer-Emmett-Teller specific surface area of the carbon paper is increased by a factor of 16 while maintaining the same hydraulic permeability as that of the original carbon paper electrode. We then apply the dual-scale electrode to a vanadium redox flow battery (VRFB) and demonstrate an energy efficiency ranging from 82% to 88% at current densities of 200–400 mA cm−2, which is record breaking as the highest performance of VRFB in the open literature.

Abstract The redox flow battery (RFB) is among the most promising large-scale energy storage technologies for intermittent renewables, but its cost and cycle life still remain challenging for commercialization. This work proposes and demonstrates a high-performance, low-cost and long-life tin-bromine redox flow battery (Sn/Br RFB) with the Br-mixed electrolyte. The coulombic efficiency and energy efficiency of the Sn/Br RFB reach 97.6% and 82.6% at a high operating current density of 200 mA cm−2, respectively. The peak power density at 50% state-of-charge achieves 673 and 824 mW cm−2 at 15 and 35 °C, respectively, which is among the highest performance of hybrid RFBs. To address the Sn cross-contamination issue, a Sn reverse-electrodeposition method is demonstrated, and achieves in-situ capacity recovery as well as long cycle life. Moreover, the active material cost of the Br-mixed electrolyte is merely $54 kWh−1, while capital cost of the Sn/Br RFB is estimated to be as low as $193 kWh−1 for 4-hour electricity discharge, and expected to reduce to $148 kWh−1 at the optimistic scenario in the future. With high cell performance, in-situ capacity recovery and inexpensive active materials, the Sn/Br RFB is believed to offer a promising solution for massive electricity storage.

Abstract Unlike conventional iron-chromium redox flow batteries (ICRFBs) with a flow-through cell structure, in this work a high-performance ICRFB featuring a flow-field cell structure is developed. It is found that the present flow-field structured ICRFB reaches an energy efficiency of 76.3% with a current density of 120 mA cm −2 at 25 °C. The energy efficiency can be as high as 79.6% with an elevated current density of 200 mA cm −2 at 65 °C, a record performance of the ICRFB in the existing literature. In addition, it is demonstrated that the energy efficiency of the battery is stable during the cycle test, and that the capacity decay rate of the battery is 0.6% per cycle. More excitingly, the high performance of the flow-field structured battery significantly lowers the capital cost at $137.6 kWh −1 , which is 28.2% lower than that of the conventional ICRFB for 8-h energy storage.

Abstract The redox flow battery (RFB) is one of the most promising large-scale energy storage technologies that offer a potential solution to the intermittency of renewable sources such as wind and solar. The prerequisite for widespread utilization of RFBs is low capital cost. In this work, an iron-cadmium redox flow battery (Fe/Cd RFB) with a premixed iron and cadmium solution is developed and tested. It is demonstrated that the coulombic efficiency and energy efficiency of the Fe/Cd RFB reach 98.7% and 80.2% at 120 mA cm−2, respectively. The Fe/Cd RFB exhibits stable efficiencies with capacity retention of 99.87% per cycle during the cycle test. Moreover, the Fe/Cd RFB is estimated to have a low capital cost of $108 kWh−1 for 8-h energy storage. Intrinsically low-cost active materials, high cell performance and excellent capacity retention equip the Fe/Cd RFB to be a promising solution for large-scale energy storage systems.