Mitigation of the effects of multivalent ion transport in reverse electrodialysis

Reverse electrodialysis (RED) is a sustainable method to harvest energy using the salinity gradient between fresh and seawater. RED technology is developing but efficiencies are still limited when using natural feed water sources. One significant constraint is induced by the presence of multivalent ions in sea and river water (i.e. Mg2+, Ca2+, SO42-). Uphill transport and an increase in membrane resistance in the presence of magnesium ions significantly reduce the power density output obtainable. The choice of cation exchange membrane determines the magnesium transport and as such the power density. Here we investigate four cation exchange membrane types and relate their properties to the stack performance using three different magnesium concentrations on either river and/or seawater side: 1) a highly cross-linked styrene-divinyl benzene monovalent selective cation exchange membrane (Neosepta CMS); 2) a monovalent selective cation exchange membrane that contains a thin polyethyleneimine (PEI) anion exchange layer (Selemion CSO); 3) a multivalent ion (e.g. magnesium) permeable cation exchange membrane with an engineered molecularly open structure facilitating the transport of multivalent ions as recently developed (T1 Fujifilm); 4) a standard cation exchange membrane (Type I Fujifilm (reference)). The first two membranes both retain magnesium ions, while the other two membranes are considered permeable for magnesium ions. The results show that power density strongly depends on the composition of both river and seawater. Power density decreases in the presence of magnesium, an effect being strongest with magnesium at both river and seawater side, followed by the river water side and the seawater side. The negative effect of multivalent ion transport against the concentration gradient, so called uphill transport, in RED can be significantly minimized when monovalent selective membranes such as the highly cross-linked Neosepta CMS membrane or the AEM coated Selemion CSO membrane are used. However, the use of such membranes directly results in a strong increase in membrane resistance due to the lower ion mobility of magnesium ions inside these membranes. As a consequence, power densities in RED are not improved. Especially at high magnesium concentrations, this effect is very strong at higher concentrations, the membranes are no longer able to retain magnesium ions effectively. More beneficial is the application of multivalent permeable membranes with a more 'open' structure that allow the free movement of both sodium and magnesium ions through the membrane. Maybe somewhat counter intuitively, such membranes (especially the Fujifilm multivalent permeable T1 membrane) have low resistance values combined with reasonable OCV values leading to high power densities under almost all magnesium concentrations, especially at long term applications. Highest power densities well exceeding 0.3 W/m2 are still obtained when only sodium is present. However, when magnesium ions are present power densities in the order of 0.2–0.25 W/m2 can still be obtained for these membranes.