Development of an All-Aqueous Thermally Regenerative Redox Flow Battery to Support Fossil Fuel Assets
Low-temperature thermal energy, a largely untapped resource, holds significant promise for large-scale electrical power generation globally. Various stationary sources, including industrial entities and thermal power plants, emit considerable low-temperature heat that currently remains unutilized. This energy is often overlooked because its low temperature renders it unsuitable for efficient power generation using conventional methods. However, current research is exploring diverse technologies capable of converting low-temperature heat into grid-scale power, aiming to enhance grid efficiency, further decarbonization initiatives, and facilitate a shift toward more decentralized power systems. One such innovative technology is the thermally regenerative battery (TRB), noted for its high power and energy densities compared to similar technologies, positioning it as a potential game-changer in power generation. TRBs integrate two scalable and well-established unit operations: a redox flow battery and a distillation column. This integration suggests that once an effective TRB chemistry is established, the pathway to commercialization could be expedited. The copper-based thermally regenerative ammonia battery (Cu aq -TRAB) stands out as the first TRB that circumvents electrodeposition/dissolution reactions, stabilizing Cu(I) and Cu(II) within the electrolyte and maintaining stability of all electroactive species in an aqueous phase. This stabilization has led to improvements in coulombic efficiency, open circuit potential, and copper solubility, thereby enhancing power density, energy density, and overall energy efficiency. Preliminary tests were conducted to determine the effects of various electrolyte species on the performance metrics of the battery, both theoretically and experimentally. These tests revealed that the solubility of copper in the Cu aq -TRAB electrolyte was constrained by the Cu(I)-NH 3 complex. Adjusting the background electrolyte to 5 M NH4Br and the ligand concentration to 4 M NH 3 enabled the copper concentration to reach a maximum of 0.6 M. This modification led to an estimated theoretical maximum energy density of 9.5 Wh L -1 for the Cu aq -TRAB. Additionally, full cell testing indicated a tradeoff between peak power and energy density with varying copper and ammonia concentrations. Increasing the applied current density during discharge linearly raised the average power output, with a minimal reduction in energy density due to a balance between higher ohmic overpotential and reduced time for undesirable ammonia crossover. Furthermore, a comprehensive numerical sensitivity analysis of the complete Cu aq -TRAB system was performed. This analysis aimed to assess how the battery and the distillation column responded to changes in system input parameters, providing insights into optimal research directions for enhancing system performance. The analysis revealed that at room temperature, battery power was significantly more sensitive to ohmic losses than to mass transfer, with reaction rates having minimal impact. This trend continued even at higher temperatures. Also, the thermal energy required for ammonia separation was studied, showing that increased temperatures generally reduced energy requirements, except in low-pressure scenarios above 65 °C. An investigation into membrane performance in the Cu aq -TRAB was undertaken, given the significant impact of ammonia transport control and ohmic losses on system performance. Various membranes were evaluated to identify key performance metrics. Among the tested membranes, Selemion CMVN exhibited the highest performance, with a peak power density of 84 mW cm -2 and average values of 26 ± 6.8 mW cm -2 for power density and 2.9 Wh L -1 for energy density at an applied current density of 50 mA cm -2 . An economic assessment indicated a levelized cost of storage at $410 per MWh under optimal conditions, highlighting the commercial potential of the Cu aq -TRAB when utilizing cost-effective, readily available materials.