# Operando benchtop NMR study of ion transport through fluorine-free polymer membranes in a symmetric redox flow cell

## TL;DR

Researchers developed a fluorine-free polymer membrane for redox flow batteries and used NMR to track ion transport, showing it can work as well as traditional fluorinated membranes.

## Contribution

A fluorine-free membrane and an operando NMR method for quantifying ion transport in redox flow cells are introduced.

## Key findings

- A fluorine-free sulfonated polymer membrane achieved 92% capacity retention over 180 cycles in a symmetric redox flow cell.
- Operando benchtop NMR identified Li+ as the primary charge-balancing ion at low current densities.
- At higher current, other ionic species contributed to charge balance, revealed through relaxation correction in NMR.

## Abstract

Polymeric membranes play a key role in redox flow batteries, where they regulate ion transport and contribute to overall battery performance. Current benchmark membranes are usually perfluorinated, which increases cost and environmental impact. Here, we synthesized and tested biphenyl-isatin polymers as cation exchange membranes in a pH neutral iron-based symmetric redox flow cell. We examined the effect of sulfonation on membrane permselectivity by measuring the diffusion of common supporting electrolytes (LiCl, NaCl, KCl) and assessing crossover rejection of larger redox-active anions such as ferricyanide. The membrane with the highest performance was implemented in a ferro/ferricyanide-based symmetric redox flow cell, demonstrating 92% capacity retention over 180 cycles. These findings indicate that fluorine-free sulfonated polymers can serve as viable alternatives to perfluorinated membranes in electrochemical technologies. In parallel, we demonstrated an operando benchtop NMR method with atomic specificity for identifying and quantifying Li+ charge-balancing ions through the biphenyl-isatin-based membrane. The method involved addressing paramagnetic relaxation attenuation of 7Li NMR intensity by first quantifying ferricyanide ions with the Evans method, followed by applying relaxation correction and quantification of Li+ cations. We observed that at low current densities, Li+ ions served as the primary charge-balancing species, whereas at higher current, a deviation between charge and Li+ concentration emerged, suggesting additional contributions from other ionic species. The relaxation–correction protocol introduced here enables accurate quantification of ion transport in symmetric redox flow cells containing paramagnetic species such as ferricyanide and potentially many organic radicals. This approach provides a general framework for studying ion transport and guiding the design of next-generation membranes for diverse redox chemistries.

Operando
7Li-NMR reveals and quantifies charge-balancing ion transport through a fluorine-free biphenyl-isatin-based membrane in a symmetric iron-based redox flow cell.