A Kinetic Performance-Informed Technoeconomic Assessment-Life Cycle Assessment Model of Ce and V Redox Flow Batteries
Authors: Buchanan Cailin , Singh Nirala 
Published: July 2022

The EIA projects that 60% of cumulative capacity additions in the U.S. by 2050 will be renewable electric generating technologies.1 The use of intermittent renewable energy in the U.S. electricity grid requires energy storage. NREL predicts that for a scenario in which 80% of electricity in the U.S. comes from renewable energy by 2050, 120 GW of energy storage would be needed,2 yet as of 2020, the U.S. has only 24 GW of storage capacity.3 Redox flow batteries (RFBs) are a useful technology for ensuring the smooth integration of renewable energy into the U.S. electricity grid because of their long lifecycles and discharge times. RFBs are currently too expensive for market deployment, however, with the all vanadium RFB (VRFB) costing double the DOE target.4,5 One way to improve the cost effectiveness of RFBs is to explore chemistries that increase the voltage window. The replacement of the VO2+/ VO2
+ chemistry at the positive electrode of a VRFB with the Ce3+/Ce4+ chemistry would result in an increased theoretical voltage, but it is unclear how the kinetic, ohmic, and mass transport overvoltages would change. Additionally, studies of the environmental burdens of life cycle phases of Ce RFBs are limited. To advance the most cost effective and least environmentally harmful RFB, in this study, we develop a combined Technoeconomic Assessment-Life Cycle Assessment (TEA-LCA) model that is informed by our performance measurements to compare the levelized cost of electricity (LCOE) and levelized greenhouse gas (LGHG) emissions of VRFBs and Ce-V RFBs.

The TEA-LCA model allows the user to select from a list of positive and negative electrode redox chemistries, solvents, electrode materials, and electricity grid generation profiles to calculate the LCOE and LGHG emissions of the battery for the delivery of 1 kWh of energy. A solver function optimizes the current density that minimizes either LCOE or LGHGs. The TEA-LCA model uses a bottom-up approach, in which energy- and power-dependent capital costs and environmental burdens are calculated by converting the amount of material to a kWh basis. Cost estimates are sourced from vendors and GHG emissions are pulled from the GREET database and literature. The amount of active species required to deliver 1 kWh of electricity at a specified discharge time is calculated using the redox couple properties, including redox potential, exchange current density, and limiting currents. These performance parameters are based on measurements collected in lab. The use phase burdens are calculated using the roundtrip efficiency of the battery and the price and GHGs associated with the electricity grid generation mix. End-of-life costs consist of the economic and environmental burdens of recycling and disposing of the battery material and are collected from vendors and GREET.

The TEA-LCA model answers important questions related to the optimal operating conditions of an RFB. In addition to comparing the economic and environmental performances of the VRFB and Ce-V RFB, it demonstrates how different electricity grid mixes influence total cost and emissions and highlights the difference in optimal operating current density if cost or GHG emissions are prioritized, e.g., lower current density results in fewer emissions but higher cost in carbon-intensive electricity grid profiles. Preliminary results using literature values show that the Ce-V RFB has an LCOE that is 45% lower than the VRFB LCOE, with capital costs dominating. We will present the finalized LCOE for the VRFB and Ce-V RFB, as well as LGHGs, as a function of discharge time and electricity grid mix. Sensitivity analyses of the input parameters found that for both RFBs, the discount rate, discharge faradaic efficiency, and lifetime of battery had the most influence on LCOE, with a 20% decrease in discharge faradaic efficiency resulting in a 16% increase in LCOE for the VRFB. The results of this TEA-LCA model show that the use of cerium is a viable option for reducing the cost of RFBs to advance their use in renewable energy storage grid applications. Additionally, this model is generalizable to other batteries and electrochemical systems, such as CO2 conversion. Thus, the development of this TEA-LCA model represents not only an advancement to the field of redox flow batteries but also the wider field of electrochemistry.

U.S. EIA. Annual Energy Outlook. (2021).

Mai, T. et al.
Renewable Electricity Futures Study. NREL. (2012).

CSS University of Michigan. U. S. Grid Energy Storage Factsheet. (2021).

Mongird, K. et al.
2020 Grid Energy Storage Technology Cost and Performance Assessment. (2020).

Weber, A. Z. et al.
J. Appl. Electrochem.
41, 1137–1164 (2011).

Smith, G. F. & Getz, C. A. Ind. Eng. Chem. Res.
10, 191–195 (1938).