determines water and salt permeation in commercial ion exchange membranes. ChemRxiv. Preprint.Ion exchange membrane (IEM) performance in electrochemical processes such as fuel cells, redox flow batteries, or reverse electrodialysis (RED) is typically quantified through membrane selectivity and conductivity, which together determine the energy efficiency. However, water and co-ion transport (i.e., osmosis and salt diffusion / fuel crossover) also impact energy efficiency by allowing uncontrolled mixing of the electrolyte solutions to occur. For example, in RED with hypersaline water sources, uncontrolled mixing consumes 20-50% of the available mixing energy. Thus, in addition to high selectivity and high conductivity, it is desirable for IEMs to have low permeability to water and salt in order to minimize energy losses.Unfortunately, there is very little quantitative water and salt permeability information available for commercial IEMs, making it difficult to select the best membrane for a particular application. Accordingly, we measured the water and salt transport properties of 20 commercial IEMs and analyzed the relationships between permeability, diffusion and partitioning according to the solution-diffusion model. We found that water and salt permeance vary over several orders of magnitude among commercial IEMs, making some membranes better-suited than others to electrochemical processes that involve high salt concentrations and/or concentration gradients. Water and salt diffusion coefficients were found to be the principal factors contributing to the differences in permeance among commercial IEMs. We also observed that water and salt permeability were highly correlated to one another for all IEMs studied, regardless of polymer type or reinforcement. This finding suggests that transport of mobile salt in IEMs is governed by the microstructure of the membrane, and provides clear evidence that mobile salt does not interact strongly with polymer chains in highly-swollen IEMs. File list (2)download file view on ChemRxiv RK-P3A-Manuscript-v5.1 clean ChemRxiv.pdf (700.14 KiB) download file view on ChemRxiv RK-P3A-SI-v5 clean.pdf (365.46 KiB)

Ion exchange membranes (IEMs) are versatile materials relevant to a variety of water and waste treatment, energy production, and industrial separation processes. The defining characteristic of IEMs is their ability to selectively allow positive or negative ions to permeate, which is referred to as permselectivity. Measured values of permselectivity that equal unity (corresponding to a perfectly selective membrane) or exceed unity (theoretically impossible) have been reported for cation exchange membranes (CEMs). Such nonphysical results call into question our ability to correctly measure this crucial membrane property. Because weighing errors, temperature, and measurement uncertainty have been shown to not explain these anomalous permselectivity results, we hypothesized that a possible explanation are junction potentials that occur at the tips of reference electrodes. In this work, we tested this hypothesis by comparing permselectivity values obtained from bare Ag/AgCl wire electrodes (which have no junction) to values obtained from single-junction reference electrodes containing two different electrolytes. We show that permselectivity values obtained using reference electrodes with junctions were greater than unity for CEMs. In contrast, electrodes without junctions always produced permselectivities lower than unity. Electrodes with junctions also resulted in artificially low permselectivity values for AEMs compared to electrodes without junctions. Thus, we conclude that junctions in reference electrodes introduce two biases into results in the IEM literature: (i) permselectivity values larger than unity for CEMs and (ii) lower permselectivity values for AEMs compared to those for CEMs. These biases can be avoided by using electrodes without a junction.

In electrochemical processes such as electrodialysis or redox flow batteries, where ion exchange membranes (IEMs) play a critical role in process performance, energy losses can be reduced by minimizing the permeability of IEMs to water and salt. In pure, homogeneous polymer membranes, water permeability is known to be controlled by the size of the free volume elements. However, there is very limited evidence concerning the extent to which this theory applies to practical, commercial IEMs, which frequently have more complex structures. We recently reported water and salt transport characteristics (i.e., permeability, partition, and diffusion coefficients) of 20 commercial IEMs, and demonstrated that water and salt transport were governed primarily by the microstructure of the membrane rather than the polymer chemistry. To further investigate the factors that determine water and salt transport in commercial IEMs, in this study we adopted a statistical approach informed by free volume theory and other literature to examine relationships between transport characteristics and water uptake (i.e., swelling) in addition to fixed charge concentration, ion exchange capacity (IEC), Manning parameter, and contact angle. Our analysis shows that water uptake had the strongest correlation with water and salt transport in commercial IEMs, which is consistent with the predictions of free volume theory for homogeneous polymers; however, the relationship observed between water uptake and permeability in commercial membranes was not as straightforward as that reported in the literature for homogeneous polymers. Membrane charge (IEC) was also correlated with permeability and diffusion coefficients, but to a more limited extent than water uptake, while the Manning parameter and contact angle did not appear to be correlated to any transport properties. Furthermore, there are indications that microstructural differences among membranes may significantly affect permeability. Therefore, further study of IEM microstructure, e.g., phase separation, is an important strategy for advancing the development of commercial IEMs.

Ion exchange membrane (IEM) performance in electrochemical processes such as fuel cells, redox flow batteries, or reverse electrodialysis (RED) is typically quantified through membrane selectivity and conductivity, which together determine the energy efficiency. However, water and co-ion transport (i.e., osmosis and salt diffusion / fuel crossover) also impact energy efficiency by allowing uncontrolled mixing of the electrolyte solutions to occur. For example, in RED with hypersaline water sources, uncontrolled mixing consumes 20-50% of the available mixing energy. Thus, in addition to high selectivity and high conductivity, it is desirable for IEMs to have low permeability to water and salt in order to minimize energy losses. Unfortunately, there is very little quantitative water and salt permeability information available for commercial IEMs, making it difficult to select the best membrane for a particular application. Accordingly, we measured the water and salt transport properties of 20 commercial IEMs and analyzed the relationships between permeability, diffusion and partitioning according to the solution-diffusion model. We found that water and salt permeance vary over several orders of magnitude among commercial IEMs, making some membranes better-suited than others to electrochemical processes that involve high salt concentrations and/or concentration gradients. Water and salt diffusion coefficients were found to be the principal factors contributing to the differences in permeance among commercial IEMs. We also observed that water and salt permeability were highly correlated to one another for all IEMs studied, regardless of polymer type or reinforcement. This finding suggests that transport of mobile salt in IEMs is governed by the microstructure of the membrane, and provides clear evidence that mobile salt does not interact strongly with polymer chains in highly-swollen IEMs. <br>

Ion exchange membrane (IEM) performance in electrochemical processes such as fuel cells, redox flow batteries, or reverse electrodialysis (RED) is typically quantified through membrane selectivity and conductivity, which together determine the energy efficiency. However, water and co-ion transport (i.e., osmosis and salt diffusion / fuel crossover) also impact energy efficiency by allowing uncontrolled mixing of the electrolyte solutions to occur. For example, in RED with hypersaline water sources, uncontrolled mixing consumes 20-50% of the available mixing energy. Thus, in addition to high selectivity and high conductivity, it is desirable for IEMs to have low permeability to water and salt in order to minimize energy losses. Unfortunately, there is very little quantitative water and salt permeability information available for commercial IEMs, making it difficult to select the best membrane for a particular application. Accordingly, we measured the water and salt transport properties of 20 commercial IEMs and analyzed the relationships between permeability, diffusion and partitioning according to the solution-diffusion model. We found that water and salt permeance vary over several orders of magnitude among commercial IEMs, making some membranes better-suited than others to electrochemical processes that involve high salt concentrations and/or concentration gradients. Water and salt diffusion coefficients were found to be the principal factors contributing to the differences in permeance among commercial IEMs. We also observed that water and salt permeability were highly correlated to one another for all IEMs studied, regardless of polymer type or reinforcement. This finding suggests that transport of mobile salt in IEMs is governed by the microstructure of the membrane, and provides clear evidence that mobile salt does not interact strongly with polymer chains in highly-swollen IEMs. <br>