Thermally Regenerative Flow Batteries with pH Neutral Electrolytes for Harvesting Low-Grade Heat

TL;DR

This paper introduces a pH-neutral thermally regenerative flow battery that harvests low-grade heat efficiently, demonstrating a stable operation with notable temperature coefficient and power density, and provides a detailed model for optimization.

Contribution

The work develops a novel pH-neutral TRFB with specific electrolytes, achieving high temperature coefficient and power density, along with a comprehensive model for flow and reaction analysis.

Findings

Cell temperature coefficient of 1.9 mV/K

Power density of 9 μW/cm²

Efficiency reaching 11% of Carnot at 37 K difference

Abstract

Harvesting waste heat with temperatures lower than 100 oC can improve system efficiency and reduce greenhouse gas emissions, yet it has been a longstanding and challenging task. Electrochemical methods for harvesting low-grade heat have attracted research interest in recent years due to the relatively high effective temperature coefficient of the electrolytes (> 1 mV/K) compared with the thermopower of traditional thermoelectric devices. Comparing with other electrochemical devices such as temperature-variation based thermally regenerative electrochemical cycle and temperature-difference based thermogalvanic cells, the thermally regenerative flow battery (TRFB) has the advantages of providing a continuous power output, decoupling the heat source and heat sink and recuperating heat, and compatible with stacking for scaling up. However, TRFB suffers from the issue of stable operation due to the challenge of pH matching between catholyte and anolyte solutions with desirable temperature coefficients. In this work, we demonstrate a PH-neutral TRFB based on KI/KI3 and K3Fe(CN)6/K4Fe(CN)6 as the catholyte and anolyte, respectively, with a cell temperature coefficient of 1.9 mV/K and a power density of 9 uW/cm2. This work also presents a comprehensive model with a coupled analysis of mass transfer and reaction kinetics in a porous electrode that can accurately capture the flow rate dependence of power density and energy conversion efficiency. We estimate that the efficiency of the pH-neutral TRFB can reach 11% of the Carnot efficiency at the maximum power output with a temperature difference of 37 K. Via analysis, we identify that the mass transfer overpotential inside the porous electrode and the resistance of the ion exchange membrane are the two major factors limiting the efficiency and power density, pointing to directions for future improvements.