DOE OSTI2019
A new flow battery was proposed that utilizes low cost materials: iron as the only active element, cheap aqueous electrolytes, and inexpensive separators. During charging, ferrous iron (Fe 2+ ) is oxidized to ferric iron (Fe 3+ ) at the positive electrode while it (Fe 2+ ) is reduced to form iron metal (Fe 0 ) at the negative electrode. Because iron is plated at the negative electrode during charging, conventional electrode structures couple the energy storage capacity and the power rating of the battery. In order to decouple the energy and power ratings and regain the economic advantages of a flow battery, a slurry electrode design was proposed for use as the negative electrode. The slurry electrode is made by flowing electrically conductive particles in an electrolyte containing the dissolved iron species. On charging, iron is plated onto the particles. The particles can then carry the iron metal out of the cell to be stored in external reservoirs. This project looked to develop a slurry for the negative electrode of the all-iron flow battery that can operate at 200 mA/cm 2 with <100 mV overpotential, be pumped with parasitic energy costs < 10%, and promote plating on the particles. A scalable and stackable cell design of 1100 cm 2 was developed. The project was initially under contract in mid-January 2013. The project was converted from a one-year proof of concept seedling to an additional two-year program, then extended with an 18-month plus-up, and finally with an additional 6-month approved cost-overrun. During the seeding project, the concept of plating on carbon particles in a slurry was demonstrated. However, this was accomplished with high-cost multi-walled carbon nanotubes as the slurry material. The following two-year program discovered several low-cost carbon blacks that could also be used in this application. These findings were supported by an analysis that demonstrated the effectiveness of the carbon that takes into account not just the effective electronic conductivity of the slurry, but also the surface area per volume of the slurry. It was demonstrated that stable, flowable slurries could be created with these carbons, even when the carbons where fully loaded with iron during charging. During the two-year program, laboratory-scale 50 cm 2 single-cells demonstrated charge-discharge cycling at current densities of 150 mA/cm 2 and energy efficiencies of >50%. Meanwhile, cost modeling continued to show promise for this energy storage approach. Following the conversion period, the overall objective of the nominally 18-month plus up period was to close the technical gap of a 25X scale-up and reduce risk to enable commercial investment required to develop a slurry iron flow battery product. A specific objective was to demonstrate 150 cycles of performance exceeding 70% energy efficiency with a 10-cell stack of 1156 cm 2 cells operating at 100 mA/cm 2 . The 10-cell short stack was designed to have a power delivery rating of approximately 1 kW, which represents a size commensurate with the requirements of our commercialization partner at that time. A complete battery support system for the full-size cell was designed, fabricated, and tested. This includes pumps (multiple types were considered, and constant volume hose pumps were found to be acceptable for performance and cost), electrolyte rebalance reactor, and sensors and control systems. The support system proved to be well-behaved and worked well. A new low-cost membrane was developed for this system based on a microporous polymer support with a layer of hydrogel polymer. The membrane had low resistivity, and significantly reduced pressure driven fluid flow across the membrane (as compared to the un-coated microporous support). This membrane approach was scaled-up in conjunction with a commercial toll coating company, and a large amount of membrane was manufactured to support large cell and stack testing. A new concept for an electrolyte rebalance reactor to react hydrogen gas from the negative electrolyte (from plating inefficiency) with excess ferric ion in the positive electrolyte was developed. This design was very simple, low cost, and effective. The full scale 1156 cm 2 single-cell was designed, modeled, fabricated and tested. Modeling showed that uniform flow-distribution should be obtained with the designed flow distributor. The design took into consideration the need to stack the cells, and components were fabricated for a ten-cell stack. Testing of the cell for charge and discharge demonstrated current densities of 50 mA/cm 2 with efficiencies of 50%. However, optimization and long cycling could not be accomplished because the slurry electrode would plug within the cell and block the flow. This would shut down the cell after several charge-discharge cycles. Various approaches were pursued to address this problem with some progress. However, there was not adequate time to find solutions to the problem although several promising approaches were identified for future work. The final deliverable for this proposed 18-month effort was to be a 1 kW, 6 kWh slurry flow battery, with complete balance of plant, ready for testing at an ARPA-E ‘Charges’ site with an estimated capital cost less than $\$ $45/kWh for a six-hour system (excluding power electronics). The deliverable milestone was not achieved for reasons mentioned above related to the slurry plugging. At the completion of this project, it was determined that the cost targets are achievable. The cost estimate for a 1 MW system with a one-hour capacity was estimated at $\$ $140/kWh (including power electronics) and for a six-hour system was estimated at $\$ $40/kWh (including power electronics). These costs include the battery, the balance of plant, the power conditioning and a concrete pad. This program resulted in three patents including the slurry-based iron flow battery, the rebalance reactor, and the membrane separator. At the time of this report, slurry-based iron flow battery patents have been issued in the US, China, Japan, Korea, and Europe. The other patent applications were under various stages of examination. A licensee was identified and the company initiated a scale-up and development program to take this technology to the marketplace, and CWRU staff have transferred their know-how and knowledge base to the company. This technology will enhance the economic and energy security of the United States by enabling the use of intermittent renewable energy technology, such as wind and solar power, as dispatchable resources. This report summarizes the results of this research and development program.