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Salinity gradient power (SGP) by reverse electrodialysis is a promising method for converting SGP into electricity. Instead of the conventional approach of using seawater and freshwater, an alternative method involves using highly concentrated salt solutions (brines) alongside seawater or brackish water. Key factors influencing SGP via reverse electrodialysis (SGP-RE) include the properties of ion exchange membranes, particularly their thickness. This paper outlines a practical experimental set-up that uses both a cation membrane (CM) and an anion membrane (AM). The system is configured with three compartments: two outer compartments filled with highly concentrated brine (HIGH) and a central compartment containing a lower concentration salt solution (LOW), akin to seawater. The compartments are separated by a CM on one side and an AM on the other. The ion transport rate from the HIGH compartments to the central LOW compartment allows for determining the overall ion transport coefficient for thin membranes. Measurements of ion flux and electrochemical voltage under dynamic equilibrium conditions also enable the estimation of the SGP-RE power density (W/m2). By controlling the temperature of the HIGH and LOW solutions, this experiment further investigates the significant impact of temperature on ion transport characteristics.

In response to the growing demand for potable water, this study presents a practical methodology for designing and fabricating a hybrid desalination system that integrates reverse electrodialysis and electrodialysis using 3D-printing technology. The hybrid system combines the energy generation potential of RED with the salt removal capabilities of ED, reducing energy consumption. Customized reactors were designed to enhance flow distribution and ion exchange, with computational fluid dynamics simulations validating the hydrodynamic performance. The reactors were fabricated using 3D printing, allowing rapid, cost-effective production, with functional reactors constructed in under 24 h. The system achieved a 15% reduction in salt concentration within one hour, with a specific energy consumption of 0.1388 Wh/m3 and a water recovery rate of 50%. These results demonstrate the functionality of the RED-ED hybrid system for achieving energy savings and performing water desalination. This methodology provides a scalable and replicable solution for water treatment applications, especially in regions with abundant salinity gradients and limited freshwater resources, while offering a multidisciplinary approach that integrates physicochemical and engineering principles for effective device development.

In this study, novel pore-filled anion-exchange membranes (PFAEMs) modified with polypyrrole (PPy) and reduced graphene oxide (rGO) were developed to improve the energy harvesting performance of reverse electrodialysis (RED). The surface-modified PFAEMs were fabricated by varying the contents of PPy and rGO through simple spin coating and chemical/thermal treatments. It was confirmed that the PPy and PPy/rGO layers introduced on the membrane surface did not significantly increase the electrical resistance of the membrane and could effectively control surface characteristics, such as structural tightness, hydrophilicity, and electrostatic repulsion. The PPy/rGO-modified PFAEM showed excellent monovalent ion selectivity, more than four times higher than that of the commercial membrane (AMX, Astom Corp., Tokyo, Japan). This means that the PPy/rGO layer can effectively reduce the permeation of multivalent ions with a high charge intensity and a relatively large hydration radius compared to monovalent ions. The results of evaluating the performance of the surface-modified PFAEMs by applying them to a RED cell revealed that the decrease in potential difference occurring in the membrane was reduced by effectively suppressing the uphill transport of multivalent ions. Consequently, the PPy/rGO-modified membrane exhibited a 5.43% higher power density than the AMX membrane.

Reverse electrodialysis (RED), an emerging membrane-based technology, harnesses salinity gradient energy for sustainable power generation. Accurate characterization of electrical parameters in RED stacks is crucial to monitoring its performance and exploring possible applications. In this study, a DC electronic load module (DCELM) is implemented in a constant current condition (CC mode) for characterization of lab scale RED process, using a RED prototype in-house designed and manufactured (RU1), at different data capture setups (DCS), on which the total number of steps for data capture (NS) and the number of measurements per step (ρ) are the parameters that were modified to study their effect on obtained electrical parameters in RED. NS of 10, 50, and 100 and ρ of 10 and 20 were used with this purpose. The accuracy of resulting current and voltage steps can be enhanced by increasing NS and ρ values, and according to obtained results, the higher accuracy of resulting output current and voltage steps, with low uncertainty of the average output steps (AOS) inside the operational region of power curve, was obtained using a DCS of NS = 100 and ρ = 20. The developed DCELM is a low-cost alternative to commercial electronic load devices, and the proposed methodology in this study represents an adaptative and optimizable CC mode characterization of RED process. The results obtained in this study suggest that data capture conditions have a direct influence of RED performance, and the accuracy of electrical parameters can be improved by optimizing the DCS parameters, according to the required specifications and the scale of RED prototypes.

The power conversion of salinity gradient energy (SGE) between concentrated brine from seawater desalination and seawater by reverse electrodialysis (RED) benefits energy conservation and also dilutes the discharge concentration to relieve the damage to coastal ecosystems. However, two key performance indexes of the maximum net power density and energy conversion efficiency for a RED stack harvesting the energy usually cannot reach the optimal simultaneously. Here, an optimization study on the two indexes was implemented to improve the performance of RED in harvesting the energy. A RED model for capturing the SGE between concentrated brine and seawater was constructed, and the correlation coefficients in the model were experimentally determined. Based on the model, the effects of a single variable (concentration, flow rate, temperature, thickness of the compartment, length of the electrode) on the performance of a RED stack are analyzed. The multi-objective optimization method based on the genetic algorithm was further introduced to obtain the optimal solution set, which could achieve the larger net power density and energy conversion efficiency with coordination. The ranges of optimal feed parameters and stack size were also obtained. The optimal flow velocity of the dilute solution and the concentration of the dilute solution are approximately 7.3 mm/s and 0.4 mol/kg, respectively.

The chemical potential difference at the discharge points of coastal Wastewater Treatment Plants (WWTPs) uncovers the opportunity to harness renewable salinity gradient energy (SGE). This work performs an upscaling assessment of reverse electrodialysis (RED) for SGE harvesting of two selected WWTPs located in Europe, quantified in terms of net present value (NPV). For that purpose, a design tool based on an optimization model formulated as a Generalized Disjunctive Program previously developed by the research group has been applied. The industrial scale-up of SGE-RED has already proven to be technically and economically feasible in the Ierapetra medium-sized plant (Greece), mainly due to a greater volumetric flow and a warmer temperature. At the current price of electricity in Greece and the up-to-date market cost of membranes of 10 EUR/m2, the NPV of an optimized RED plant in Ierapetra would amount to EUR117 thousand operating with 30 RUs in winter and EUR 157 thousand for 32 RUs in summer, harnessing 10.43 kW and 11.96 kW of SGE for the winter and summer seasons, respectively. However, in the Comillas facility (Spain), this could be cost-competitive with conventional alternatives, namely coal or nuclear power, under certain conditions such as lower capital expenses due to affordable membrane commercialization (4 EUR/m2). Bringing the membrane price down to 4 EUR/m2 would place the SGE-RED’s Levelized Cost of Energy in the range of 83 EUR/MWh to 106 EUR/MWh, similar to renewable sources such as solar PV residential rooftops.

Salinity gradient energy has gained attention in recent years as a renewable energy source, especially employing reverse electrodialysis technology (RED), which is based on the role of ion exchange membranes. In this context, many efforts have been developed by researchers from all over the world to advance the knowledge of this green source of energy. However, the influence of divalent ions on the performance of the technology has not been deeply studied. Basically, divalent ions are responsible for an increased membrane resistance and, therefore, for a decrease in voltage. This work focuses on the estimation of the resistance of the RED membrane working with water flows containing divalent ions, both theoretically by combining the one-thread model with the Donnan exclusion theory for the gel phase, as well as the experimental evaluation with Fumatech membranes FAS-50, FKS-50, FAS-PET-75, and FKS-PET-75. Furthermore, simulated results have been compared to data recently reported with different membranes. Besides, the influence of membrane resistance on the overall performance of reverse electrodialysis technology is evaluated to understand the impact of divalent ions in energy generation. Results reflect a minor effect of sulfate on the gross power in comparison to the effect of calcium and magnesium ions. Thus, this work takes a step forward in the knowledge of reverse electrodialysis technology and the extraction of salinity gradient energy by advancing the influence of divalent ions on energy recovery.

In recent years, the utilization of the selective ion transport through porous membranes for osmotic power generation (blue energy) has received a lot of attention. The principal of power generation using the porous membranes is same as that of conventional reverse electrodialysis (RED), but nonporous ion exchange membranes are conventionally used for RED. The ion transport mechanisms through the porous and nonporous membranes are considerably different. Unlike the conventional nonporous membranes, the ion transport through the porous membranes is largely dictated by the principles of nanofluidics. This owes to the fact that the osmotic power generation via selective ion transport through porous membranes is often referred to as nanofluidic reverse electrodialysis (NRED) or nanopore-based power generation (NPG). While RED using nonporous membranes has already been implemented on a pilot-plant scale, the progress of NRED/NPG has so far been limited in the development of small-scale, novel, porous membrane materials. The aim of this review is to provide an overview of the membrane design concepts of nanofluidic porous membranes for NPG/NRED. A brief description of material design concepts of conventional nonporous membranes for RED is provided as well.

In this study, two different types of ion exchange membranes are used to investigate the tendency of membrane fouling with respect to surface roughness and hydrophilicity. Commercially available membranes reinforced by electrospun nanofiber have rough and hydrophilic surfaces, and lab-made pore-filling membranes exhibit a smooth and hydrophobic surface. Three different organic surfactants (i.e., cationic, anionic and non-ionic surfactants) are chosen as foulants with similar molecular weights. It is confirmed that membrane fouling by electrical attraction mainly occurs, in which anionic and cationic foulants influence anion and cation exchange membranes, respectively. Thus, less fouling is obtained on both membranes for the non-charged foulant. The membranes with a rough surface show a higher fouling tendency than those with a smooth surface in the short-term continuous fouling tests. However, during the cyclic operations of fouling and mitigation of the commercially available membranes, the irregularities of a rough membrane surface cause a rapid increase in electrical resistance from the beginning of fouling due to excessive adsorption on the surface, but the fouling is easily mitigated due to the hydrophilic surface. On the other hand, the membranes with a smooth surface show alleviated fouling from the beginning of fouling, but the irreversible fouling occurs as foulants accumulate on the hydrophobic surface which causes membrane fouling to be favorable.

This study investigates the influence of co-existing ions on the salinity gradient power generation performance of the reverse electrodialysis (RED) using three different commercial ion exchange membrane pairs. The feed solutions, including the mixture of two different salts, were prepared with 90 wt.% of NaCl and 10 wt.% of LiCl, KCl, CaCl2, MgCl2 or Na2SO4 by keeping the salt ratio between high concentrate solution and low concentrate solution constant as 1:30 (g/g) at various flow velocities (50, 125 and 200 mL/min). It was observed that the divalent ions exhibited a negative impact on the performance of the RED system due to their high valence and low ionic mobility depending on their high hydrated radius and low diffusion coefficients compared to those of the monovalent ions. On the other hand, the effect of the monovalent ions differed according to the properties of ion exchange membranes used in the RED stack. When the power generation performances of ion exchange membrane pairs employed in the RED stack were compared, it was considered that Neosepta AMX and CMX membranes provided the highest power density due to their low membrane thicknesses, low electrical resistances, and relatively high ion exchange capacities compared to other two commercial ion exchange membrane pairs.

Reverse electrodialysis (RED) power generation using seawater (SW) and river water is expected to be a promising environmentally friendly power generation system. Experiments with large RED stacks are needed for the practical application of RED power generation, but only a few experimental results exist because of the need for large facilities and a large area of ion-exchange membranes (IEMs). In this study, to predict the power output of a large RED stack, the power generation performances of a lab-scale RED stack (40 membrane pairs and 7040 cm2 total effective membrane area) with several IEMs were evaluated. The results were converted to the power output of a pilot-scale RED stack (299 membrane pairs and 179.4 m2 total effective membrane area) via the reference IEMs. The use of low-area-resistance IEMs resulted in lower internal resistance and higher power density. The power density was 2.3 times higher than that of the reference IEMs when natural SW was used. The net power output was expected to be approximately 230 W with a pilot-scale RED stack using low-area-resistance IEMs and natural SW. This value is one of the indicators of the output of a large RED stack and is a target to be exceeded with further improvements in the RED system.

Recently, there have been several studies done regarding anion exchange membranes (AEMs) based on polyepichlorohydrin (PECH), an attractive polymer enabling safe membrane fabrication due to its inherent chloromethyl groups. However, there are still undiscovered properties of these membranes emerging from different compositions of cast solutions. Thus, it is vital to explore new membrane properties for sustainable energy generation by reverse electrodialysis (RED). In this study, the cast solution composition was easily tuned by varying the ratio of active polymer (i.e., blend ratio) and quaternary agent (i.e., excess diamine ratio) in the range of 1.07–2.00, and 1.00–4.00, respectively. The membrane synthesized with excess diamine ratio of 4.00 and blend ratio of 1.07 provided the best results in terms of ion exchange capacity, 3.47 mmol/g, with satisfactory conductive properties (area resistance: 2.4 Ω·cm2, electrical conductivity: 6.44 mS/cm) and high hydrophilicity. RED tests were performed by AEMs coupled with the commercially available Neosepta CMX cation exchange membrane (CEMs).

Emerging technologies in nanotechnology and biomedical engineering have led to an increase in the use of implantable biomedical devices. These devices are currently battery powered which often means they must be surgically replaced during a patient’s lifetime. Therefore, there is an important need for a power source that could provide continuous, stable power over a prolonged time. Reverse electrodialysis (RED) based biopower cells have been previously used to generate continuous power from physiologically relevant fluids; however, the low salinity gradient that exists within the body limited the performance of the biopower cell. In this study, a miniaturized RED biopower cell design coupled with a salt cartridge was evaluated for boosting the salt concentration gradient supplied to RED in situ. For the salt cartridge, polysulfone (PSf) hollow fibers were prepared in-house and saturated with NaCl solutions to deliver salt and thereby enhance the concentration gradient. The effect of operational parameters including solution flow rate and cartridge salt concentration on salt transport performance was evaluated. The results demonstrated that the use of the salt cartridge was able to increase the salt concentration of the RED inlet stream by 74% which in turn generated a 3-fold increase in the open circuit voltage (OCV) of the biopower cell. This innovative adaptation of the membrane-based approach into portable power generation could help open new pathways in various biomedical applications.

Profiled ion-exchange membranes are promising for improving the parameters of reverse electrodialysis due to the reduction of pumping power and electrical resistance. The smooth commercial heterogeneous cation-exchange MK-40 and anion-exchange MA-41 membranes were chosen as the initial membranes. Profiled membranes with three different types of surface profiles were obtained by hot pressing the initial membranes. The bilayer membranes were made on the basis of single-layer profiled membranes by casting MF-4SK film on the profiled surfaces. The diffusion permeability of all types of single-layer and bilayer profiled membranes was higher than of the initial ones due to the appearance of large defects on their surface during pressing. The conductivity of the profiled membrane was lower in the diluted solution and higher in the concentrated solution than of the initial one for all samples except for the bilayer anion-exchange membrane. The conductivity of that sample was lower than that of the initial anion-exchange MA-41 membrane over the entire range of studied concentrations. The counter-ion transport numbers for all studied membranes were calculated based on the concentration dependences of conductivity and diffusion permeability of the membrane by the microheterogeneous model. The selectivity of single layer and bilayer profiled membranes became lower after their profiling due to the increase of the solution phases of membranes. The asymmetry of the current-voltage curves for all single-layer and bilayer profiled membranes was found. The application of the single layer and bilayer profiled membranes in reverse electrodialysis did not lead to an increase in power density.

This study covers the modification, (bio)fouling characterization, use, and cleaning of commercial heterogeneous anion exchange membranes (AEMs) to evaluate their feasibility for reverse electrodialysis (RED) applications. A surface modification with poly (acrylic) acid resulted in an improved monovalent perm-selectivity (decreased sulfate membrane transport rate). Moreover, we evaluated the (bio)fouling potential of the membrane using sodium dodecyl sulfate (SDS), sodium dodecyl benzenesulfonate (SDBS), and Aeromonas hydrophila as model organic foulants and a biofoulant, respectively. A detailed characterization of the AEMs (water contact angle, ion exchange capacity (IEC), scanning electron microscopy (SEM), cyclic voltammetry (CV), and Fourier Transform Infrared (FTIR) spectra) was carried out, verifying that the presence of such foulants reduces IEC and the maximum current obtained by CV. However, only SDS and SDBS affected the contact angle values. Cleaning of the biofouled membranes using a sodium hypochlorite aqueous solution allows for (partially) recovering their initial properties. Furthermore, this work includes a fouling characterization using real surface and sea water matrixes, confirming the presence of several types of fouling microorganisms in natural streams. A lower adhesion of microorganisms (measured in terms of total bacteria counts) was observed for the modified membranes compared to the unmodified ones. Finally, we propose a cleaning strategy to mitigate biofouling in AEMs that could be easily applied in RED systems for an enhanced long-term process performance.

Salinity gradient energy (SGE) allows the difference in salt concentration in two volumes of water to be harnessed and transformed into clean energy. The most advanced SGE technology is reverse electrodialysis (RED) cells. Recent studies have focused on ways to optimize the flow distribution in the compartments containing the water, for which it is necessary to consider the characteristics of the solutions, the cell dimensions, the operating conditions, as well as their influence on the hydrodynamics and mass transport in the system. In this study, two spacers with different gasket geometry were designed, fabricated, and compared experimentally through voltage and current measurements. The power output was computed, obtaining a maximum power density of 0.14 W/m2. Results show that the geometry of the cell components directly influences the physicochemical principles governing the RED process and is closely related to the cell output parameters. In turn, it is possible to increase the performance of a RED cell by optimizing the gasket geometry by reducing dead zones.

Ion exchange membranes (IEMs), as a part of the reverse electrodialysis (RED) system, play an important role in salinity gradient power (SGP) generation. Structure optimization of IEMs is critical to increase the power production by RED. In this work, metal organic framework (MOF)-derived nanoporous carbons (hollow zeolitic imidazolate framework (ZIF)-derived nanoporous carbons, HZCs) were incorporated in a sulfonated poly (2, 6-dimethyl-1,4-phenylene oxide) (sPPO) membrane to prepare an organic−inorganic nanocomposite cation exchange membrane (CEM). Physicochemical properties, electrochemical properties, and power generation of the synthesized nanocomposite membranes with different HZCs loading were characterized. The results show that the incorporated HZCs could tailor the microstructure of the membrane matrix, providing a superior performance of the nanocomposite membrane. With a HZCs loading of 1.0 wt.%, the nanocomposite membrane possessed the highest permselectivity of 77.61% and the lowest area resistance of 0.42 Ω·cm2, along with a super gross power density of 0.45 W/m2, which was 87.5% (about 1.87 times) higher than that of the blank sPPO membrane. Therefore, incorporating of an appropriate amount of HZCs in the ion-exchange membrane can improve the performance of the membrane, providing a promising method to increase the power generation of the RED system.

Ion-exchange membranes (IEMs) are a core component that greatly affects the performance of electrochemical energy conversion processes such as reverse electrodialysis (RED) and all-vanadium redox flow battery (VRFB). The IEMs used in electrochemical energy conversion processes require low mass transfer resistance, high permselectivity, excellent durability, and also need to be inexpensive to manufacture. Therefore, in this study, thin-reinforced anion-exchange membranes with excellent physical and chemical stabilities were developed by filling a polyethylene porous substrate with functional monomers, and through in situ polymerization and post-treatments. In particular, the thin-reinforced membranes were made to have a high ion-exchange capacity and a limited degree of swelling at the same time through a double cross-linking reaction. The prepared membranes were shown to possess both strong tensile strength (>120 MPa) and low electrical resistance (2). As a result of applying them to RED and VRFB, the performances were shown to be superior to those of the commercial membrane (AMX, Astom Corp., Japan) in the optimal composition. In addition, the prepared membranes were found to have high oxidation stability, enough for practical applications.

The development of the most effective, suitable and economic ion-exchange membranes is crucial for reverse electrodialysis (RED)—the most widely studied process to harvest salinity gradient energy from mixing seawater and river water. RED utilizes two types of membranes as core elements, namely cation exchange membranes (CEM) and anion exchange membranes (AEM). Since the preparation of AEMs is more complex compared to CEMs, the design and development of anion exchange membranes have been the focus in this study. Homogeneous AEMs based on two types of polyepichlorohydrin (PECH) with different chlorine amounts (PECH-H, 37 wt% and PECH-C, 25 wt%) were synthesized, and first-time benchmarking of the membrane properties was conducted. In addition to physicochemical membrane properties, some instrumental analyses such as SEM, FTIR and DSC were investigated to characterize these anion-exchange membranes. Based on the results, although the PECH-H-type membrane had enhanced ion-exchange properties, PECH-C-based anion-exchange membranes exhibited a higher power density of 0.316 W/m2 in a lab-scale RED system. Evidently, there is room for the development of new types of PECH-C-based AEMs with great potential for energy generation in the RED process.

The Reverse electrodialysis heat engine (REDHE) combines a reverse electrodialysis stack for power generation with a thermal regeneration unit to restore the concentration difference of the salt solutions. Current approaches for converting low-temperature waste heat to electricity with REDHE have not yielded conversion efficiencies and profits that would allow for the industrialization of the technology. This review explores the concept of Heat-to-Hydrogen with REDHEs and maps crucial developments toward industrialization. We discuss current advances in membrane development that are vital for the breakthrough of the RED Heat Engine. In addition, the choice of salt is a crucial factor that has not received enough attention in the field. Based on ion properties relevant for both the transport through IEMs and the feasibility for regeneration, we pinpoint the most promising salts for use in REDHE, which we find to be KNO3, LiNO3, LiBr and LiCl. To further validate these results and compare the system performance with different salts, there is a demand for a comprehensive thermodynamic model of the REDHE that considers all its units. Guided by such a model, experimental studies can be designed to utilize the most favorable process conditions (e.g., salt solutions).

Reverse electrodialysis is a promising membrane technology to generate energy from controlled mixing of water streams of different salinities. Electrical potentials generate on the ion exchange membranes (IEMs) when selective transport of cations and anions across the membranes driven by concentration difference. The accurate determination of the potentials developed on the IEMs is critical to fairly assess the feasibility of the technology. The Nernst–Planck–Poisson (NPP) equations for IEMs (the membranes with fixed charge) were solved numerically with the boundary updating scheme. The validity of this numerical method was verified by the identical values of Donnan potential obtained with the well-established analytical methods. The suitability and applicability of the classic Teorell–Meyer–Siever (TMS) model were assessed by comparison to the simulation results from the numerical method.

Reverse electrodialysis (RED) is a promising technology to extract sustainable salinity gradient energy. However, the RED technology has not reached its full potential due to membrane efficiency and fouling and the complex interplay between ionic flows and fluidic configurations. We investigate renewable power generation by harnessing salinity gradient energy during reverse electrodialysis using a lab-scaled fluidic cell, consisting of two reservoirs separated by a nanoporous ion exchange membrane, under various flow rates (qf) and salt-concentration difference (Δc). The current-voltage (I-V) characteristics of the single RED unit reveals a linear dependence, similar to an electrochemical cell. The experimental results show that the change of inflow velocity has an insignificant impact on the I-V data for a wide range of flow rates explored (0.01–1 mL/min), corresponding to a low-Peclet number regime. Both the maximum RED power density (Pc,m) and open-circuit voltage (ϕ0) increase with increasing Δc. On the one hand, the RED cell’s internal resistance (Rc) empirically reveals a power-law dependence of Rc∝Δc−α. On the other hand, the open-circuit voltage shows a logarithmic relationship of ϕ0=BlnΔc+β. These experimental results are consistent with those by a nonlinear numerical simulation considering a single charged nanochannel, suggesting that parallelization of charged nano-capillaries might be a good upscaling model for a nanoporous membrane for RED applications.

The saline gradient present in river mouths can be exploited using ion-exchange membranes in reverse electrodialysis (RED) for energy generation. However, significant improvements in the fabrication processes of these IEMs are necessary to increase the overall performance of the RED technology. This work proposes an innovative technique for synthesizing anion exchange membranes (AEMs) via electrospinning. The AEM synthesis was carried out by applying a high voltage while ejecting a mixture of polyepichlorohydrin (PECH), 1,4-diazabicyclo [2.2.2] octane (DABCO® 33-LV) and polyacrylonitrile (PAN) at room temperature. Different ejection parameters were used, and the effects of various thermal treatments were tested on the resulting membranes. The AEMs presented crosslinking between the polymers and significant fiber homogeneity with diameters between 1400 and 1510 nm, with and without thermal treatment. Good chemical resistance was measured, and all synthesized membranes were of hydrophobic character. The thickness, roughness, swelling degree, specific fixed-charge density and ion-exchange capacity were improved over equivalent membranes produced by casting, and also when compared with commercial membranes. Finally, the results of the study of the electrospinning parameters indicate that a better performance in electrochemical properties was produced from fibers generated at ambient humidity conditions, with low flow velocity and voltage, and high collector rotation velocity.

The reverse electrodialysis (RED) stack-harnessing salinity gradient power mainly consists of ion exchange membranes (IEMs). Among the various types of IEMs used in RED stacks, pore-filling ion exchange membranes (PIEMs) have been considered promising IEMs to improve the power density of RED stacks. The compositions of PIEMs affect the electrical resistance and permselectivity of PIEMs; however, their effect on the performance of large RED stacks have not yet been considered. In this study, PIEMs of various compositions with respect to the RED stack were adopted to evaluate the performance of the RED stack according to stack size (electrode area: 5 × 5 cm2 vs. 15 × 15 cm2). By increasing the stack size, the gross power per membrane area decreased despite the increase in gross power on a single RED stack. The electrical resistance of the PIEMs was the most important factor for enhancing the power production of the RED stack. Moreover, power production was less sensitive to permselectivities over 90%. By increasing the RED stack size, the contributions of non-ohmic resistances were significantly increased. Thus, we determined that reducing the salinity gradients across PIEMs by ion transport increased the non-ohmic resistance of large RED stacks. These results will aid in designing pilot-scale RED stacks.

The paper shows the possibility of using a microheterogeneous model to estimate the transport numbers of counterions through ion-exchange membranes. It is possible to calculate the open-circuit potential and power density of the reverse electrodialyzer using the data obtained. Eight samples of heterogeneous ion-exchange membranes were studied, two samples for each of the following types of membranes: Ralex CM, Ralex AMH, MK-40, and MA-41. Samples in each pair differed in the year of production and storage conditions. In the work, these samples were named “batch 1” and “batch 2”. According to the microheterogeneous model, to calculate the transport numbers of counterions, it is necessary to use the concentration dependence of the electrical conductivity and diffusion permeability. The electrolyte used was a sodium chloride solution with a concentration range corresponding to the conditional composition of river water and the salinity of the Black Sea. During the research, it was found that samples of Ralex membranes of different batches have similar characteristics over the entire range of investigated concentrations. The calculated values of the transfer numbers for membranes of different batches differ insignificantly: ±0.01 for Ralex AMH in 1 M NaCl. For MK-40 and MA-41 membranes, a significant scatter of characteristics was found, especially in concentrated solutions. As a result, in 1 M NaCl, the transport numbers differ by ±0.05 for MK-40 and ±0.1 for MA-41. The value of the open circuit potential for the Ralex membrane pair showed that the experimental values of the potential are slightly lower than the theoretical ones. At the same time, the maximum calculated power density is higher than the experimental values. The maximum power density achieved in the experiment on reverse electrodialysis was 0.22 W/m2, which is in good agreement with the known literature data for heterogeneous membranes. The discrepancy between the experimental and theoretical data may be the difference in the characteristics of the membranes used in the reverse electrodialysis process from the tested samples and does not consider the shadow effect of the spacer in the channels of the electrodialyzer.

Positively charged (cetylpyridinium chloride), negatively charged (sodium dodecyl sulfate), and non-charged (polyethylene glycol) surfactants are used as potential foulant in reverse electrodialysis systems supplying seawater and river freshwater. Fouling tendency of the foulants to ion-exchange membranes is investigated in terms of the adsorption by electromigration, electrostatic attraction, and macromolecule interaction in reverse electrodialysis systems. According to theoretical prediction of fouling tendency, charged foulants in seawater streams could foul ion-exchange membranes significantly. However, the worst fouling behavior is observed when the charged foulants are present in river streams. As a result of zeta potential measurement, it is found that the Debye length of the charged foulants decreases due to the higher ionic strength of seawater streams and causes to lower net electrostatic effect. It finally results in less fouling tendency in reverse electrodialysis.

In this study, novel asymmetric integral cation exchange membranes were prepared by the wet phase inversion of sulfonated polysulfone (SPSf) solutions. SPSf with different degrees of sulfonation (DS) was synthesized by variation in the amount of chlorosulfonic acid utilized as a sulfonating agent. The characterization of SPSf samples was performed using FTIR and 1H-NMR techniques. SPSf with a DS of 0.31 (0.67 meq/g corresponding ion exchange capacity) was chosen to prepare the membranes, as polymers with a higher DS resulted in poor mechanical properties and excessive swelling in water. By a systematic study, the opportunity to tune the properties of SPSf membranes by acting on the composition of the polymeric solution was demonstrated. The effect of two different phase inversion parameters, solvent type and co-solvent ratio, were investigated by morphological and electrochemical characterization. The best properties (permselectivity of 0.86 and electrical resistance of 6.3 Ω∙cm2) were obtained for the membrane prepared with 2-propanol (IPA):1-Methyl-2-pyrrolidinone (NMP) in a 20:80 ratio. This membrane was further characterized in different solution concentrations to estimate its performance in a Reverse Electrodialysis (RED) operation. Although the estimated generated power was less than that of the commercial CMX (Neosepta) membrane, used as a benchmark, the tailor-made membrane can be considered as a cost-effective alternative, as one of the main limitations to the commercialization of RED is the high membrane price.

The increasing share of renewables in electric grids nowadays causes a growing daily and seasonal mismatch between electricity generation and demand. In this regard, novel energy storage systems need to be developed, to allow large-scale storage of the excess electricity during low-demand time, and its distribution during peak demand time. Acid–base flow battery (ABFB) is a novel and environmentally friendly technology based on the reversible water dissociation by bipolar membranes, and it stores electricity in the form of chemical energy in acid and base solutions. The technology has already been demonstrated at the laboratory scale, and the experimental testing of the first 1 kW pilot plant is currently ongoing. This work aims to describe the current development and the perspectives of the ABFB technology. In particular, we discuss the main technical challenges related to the development of battery components (membranes, electrolyte solutions, and stack design), as well as simulated scenarios, to demonstrate the technology at the kW–MW scale. Finally, we present an economic analysis for a first 100 kW commercial unit and suggest future directions for further technology scale-up and commercial deployment.

Electrodialysis (ED) and reverse electrodialysis (RED) are enabling technologies which can facilitate renewable energy generation, dynamic energy storage, and hydrogen production from low-grade waste heat. This paper presents a computational fluid dynamics (CFD) study for maximizing the net produced power density of RED by coupling the Navier–Stokes and Nernst–Planck equations, using the OpenFOAM software. The relative influences of several parameters, such as flow velocities, membrane topology (i.e., flat or spacer-filled channels with different surface corrugation geometries), and temperature, on the resistivity, electrical potential, and power density are addressed by applying a factorial design and a parametric study. The results demonstrate that temperature is the most influential parameter on the net produced power density, resulting in a 43% increase in the net peak power density compared to the base case, for cylindrical corrugated channels.

Ion exchange membranes (IEMs) have consolidated applications in energy conversion and storage systems, like fuel cells and battery separators. Moreover, in the perspective to address the global need for non-carbon-based and renewable energies, salinity-gradient power (SGP) harvesting by reverse electrodialysis (RED) is attracting significant interest in recent years. In particular, brine solutions produced in desalination plants can be used as concentrated streams in a SGP-RED stack, providing a smart solution to the problem of brine disposal. Although Nafion is probably the most prominent commercial cation exchange membrane for electrochemical applications, no study has investigated yet its potential in RED. In this work, Nafion 117 and Nafion 115 membranes were tested for NaCl and NaCl + MgCl2 solutions, in order to measure the gross power density extracted under high salinity gradient and to evaluate the effect of Mg2+ (the most abundant divalent cation in natural feeds) on the efficiency in energy conversion. Moreover, performance of commercial CMX (Neosepta) and Fuji-CEM 80050 (Fujifilm) cation exchange membranes, already widely applied for RED applications, were used as a benchmark for Nafion membranes. In addition, complementary characterization (i.e., electrochemical impedance and membrane potential test) was carried out on the membranes with the aim to evaluate the predominance of electrochemical properties in different aqueous solutions. In all tests, Nafion 117 exhibited superior performance when 0.5/4.0 M NaCl fed through 500 µm-thick compartments at a linear velocity 1.5 cm·s−1. However, the gross power density of 1.38 W·m−2 detected in the case of pure NaCl solutions decreased to 1.08 W·m−2 in the presence of magnesium chloride. In particular, the presence of magnesium resulted in a drastic effect on the electrochemical properties of Fuji-CEM-80050, while the impact on other membranes investigated was less severe.

The performance of anion-exchange membranes (AEMs) in Reverse Electrodialysis is hampered by both presence of multivalent ions and fouling phenomena, thus leading to reduced net power density. Therefore, we propose a monolayer surface modification procedure to functionalize Ralex-AEMs with poly(acrylic) acid (PAA) in order to (i) render a monovalent permselectivity, and (ii) minimize organic fouling. Membrane surface modification was carried out by putting heterogeneous AEMs in contact with a PAA-based aqueous solution for 24 h. The resulting modified membranes were firstly characterized by contact angle, water uptake, ion exchange capacity, fixed charge density, and swelling degree measurements, whereas their electrochemical responses were evaluated through cyclic voltammetry. Besides, their membrane electro-resistance was also studied via electrochemical impedance spectroscopy analyses. Finally, membrane permselectivity and fouling behavior in the presence of humic acid were evaluated through mass transport experiments using model NaCl containing solutions. The use of modified PAA-AEMs resulted in a significantly enhanced monovalent permselectivity (sulfate rejection improved by >35%) and membrane hydrophilicity (contact angle decreased by >15%) in comparison with the behavior of unmodified Ralex-AEMs, without compromising the membrane electro-resistance after modification, thus demonstrating the technical feasibility of the proposed membrane modification procedure. This study may therefore provide a feasible way for achieving an improved Reverse Electrodialysis process efficiency.

Ion exchange membranes are used in different fields of energy and separation technology such as electrodialysis, reverse electrodialysis, and fuel cells. Important aspects are permselectivity, resistance, and water transport. In this paper, we focus on the effect of the bulk NaCl concentration on the membrane resistance. Data from 36 publications containing 145 datasets using 6 different methods for measuring membrane resistance were compared. This study showed that the membrane resistance is dependent on the method of measuring. Two probable causes are identified: the application of reference electrodes and the presence of direct electrode–membrane contact. In addition, three physical and three phenomenological membrane models were tested by fitting these to the datasets. First, fits in the resistance domain were compared with fits in the conductivity domain. Resistance fits are sensitive to fluctuations in low concentrations, whereas fits in the conductivity domain are subject to nonlinear responses at high concentration. Resistance fits resulted in higher coefficients of determination (R2). Then, the six models were compared. The 1-thread model with two fit parameters was in almost all cases a good start. More improvements were difficult to test due to the restricted number of data points in most of the used publications, although this study shows that the so-called Gierke model (with 4 parameters) fits better than the 3-thread model. Phenomenological models were also tested, but they did not lead to much better fits.

In this study, reverse electrodialysis power generation using an anisotropic anodic aluminum oxide membrane with nanopores of two different pore diameters is proposed and experimentally investigated for the first time. A number of experiments were carried out for various combinations of concentrations to show that the anisotropic anodic aluminum oxide membrane is superior to the conventional isotropic membrane. As a result, the highest power density that was measured from the anisotropic membrane was 15.0 mW/m2, and it was 7.2 times higher than that from the isotropic membrane. The reasons why the anisotropic membrane is superior to the isotropic membrane are explained in detail. The experiments on the anisotropic membranes with various active layer lengths and pore diameters were also conducted for exploring the effects of these engineering parameters on the power generation performance. As a result, it was shown that the length of the active layer is a more important engineering parameter than the pore diameter of the active layer. Additionally, it was also shown that a low concentration solution should be brought into contact with the active layer side of the membrane whenever an anisotropic membrane is used for reverse electrodialysis.

Reverse electrodialysis (RED) represents one of the most promising membrane-based technologies for clean and renewable energy production from mixing water solutions. However, the presence of multivalent ions in natural water drastically reduces system performance, in particular, the open-circuit voltage (OCV) and the output power. This effect is largely described by the “uphill transport” phenomenon, in which multivalent ions are transported against the concentration gradient. In this work, recent advances in the investigation of the impact of multivalent ions on power generation by RED are systematically reviewed along with possible strategies to overcome this challenge. In particular, the use of monovalent ion-selective membranes represents a promising alternative to reduce the negative impact of multivalent ions given the availability of low-cost materials and an easy route of membrane synthesis. A thorough assessment of the materials and methodologies used to prepare monovalent selective ion exchange membranes (both cation and anion exchange membranes) for applications in (reverse) electrodialysis is performed. Moreover, transport mechanisms under conditions of extreme salinity gradient are analyzed and compared for a better understanding of the design criteria. The ultimate goal of the present work is to propose a prospective research direction on the development of new membrane materials for effective implementation of RED under natural feed conditions.

Salinity gradient power is a renewable, non-intermittent, and neutral carbon energy source. Reverse electrodialysis is one of the most efficient and mature techniques that can harvest this energy from natural estuaries produced by the mixture of seawater and river water. For this, the development of cheap and suitable ion-exchange membranes is crucial for a harvest profitability energy from salinity gradients. In this work, both anion-exchange membrane and cation-exchange membrane based on poly(epichlorohydrin) and polyvinyl chloride, respectively, were synthesized at a laboratory scale (255 c m 2) by way of a solvent evaporation technique. Anion-exchange membrane was surface modified with poly(ethylenimine) and glutaraldehyde, while cellulose acetate was used for the cation exchange membrane structural modification. Modified cation-exchange membrane showed an increase in surface hydrophilicity, ion transportation and permselectivity. Structural modification on the cation-exchange membrane was evidenced by scanning electron microscopy. For the modified anion exchange membrane, a decrease in swelling degree and an increase in both the ion exchange capacity and the fixed charge density suggests an improved performance over the unmodified membrane. Finally, the results obtained in both modified membranes suggest that an enhanced performance in blue energy generation can be expected from these membranes using the reverse electrodialysis technique.

This work presents an integrated hydrogen production system using reverse electrodialysis (RED) and waste heat, termed Heat to H 2 . The driving potential in RED is a concentration difference over alternating anion and cation exchange membranes, where the electrode potential can be used directly for water splitting at the RED electrodes. Low-grade waste heat is used to restore the concentration difference in RED. In this study we investigate two approaches: one water removal process by evaporation and one salt removal process. Salt is precipitated in the thermally driven salt removal, thus introducing the need for a substantial change in solubility with temperature, which KNO 3 fulfils. Experimental data of ion conductivity of K + and NO 3 − in ion-exchange membranes is obtained. The ion conductivity of KNO 3 in the membranes was compared to NaCl and found to be equal in cation exchange membranes, but significantly lower in anion exchange membranes. The membrane resistance constitutes 98% of the total ohmic resistance using concentrations relevant for the precipitation process, while for the evaporation process, the membrane resistance constitutes over 70% of the total ohmic resistance at 40 ∘ C. The modelled hydrogen production per cross-section area from RED using concentrations relevant for the precipitation process is 0.014 ± 0.009 m 3 h − 1 (1.1 ± 0.7 g h − 1 ) at 40 ∘ C, while with concentrations relevant for evaporation, the hydrogen production per cross-section area was 0.034 ± 0.016 m 3 h − 1 (2.6 ± 1.3 g h − 1 ). The modelled energy needed per cubic meter of hydrogen produced is 55 ± 22 kWh (700 ± 300 kWh kg − 1 ) for the evaporation process and 8.22 ± 0.05 kWh (104.8 ± 0.6 kWh kg − 1 ) for the precipitation process. Using RED together with the precipitation process has similar energy consumption per volume hydrogen produced compared to proton exchange membrane water electrolysis and alkaline water electrolysis, where the energy input to the Heat to H 2 -process comes from low-grade waste heat.

In the examined heat engine, reverse electrodialysis (RED) is used to generate electricity from the salinity difference between two artificial solutions. The salinity gradient is restored through a multi-effect distillation system (MED) powered by low-temperature waste heat at 100 °C. The current work presents the first comprehensive economic and environmental analysis of this advanced concept, when varying the number of MED effects, the system sizing, the salt of the solutions, and other key parameters. The levelized cost of electricity (LCOE) has been calculated, showing that competitive solutions can be reached only when the system is at least medium to large scale. The lowest LCOE, at about 0.03 €/kWh, is achieved using potassium acetate salt and six MED effects while reheating the solutions. A similar analysis has been conducted when using the system in energy storage mode, where the two regenerated solutions are stored in reservoir tanks and the RED is operating for a few hours per day, supplying valuable peak power, resulting in a LCOE just below 0.10 €/kWh. A life-cycle assessment has been also carried out, showing that the case with the lowest environmental impact is the same as the one with the most attractive economic performance. Results indicate that the material manufacturing has the main impact; primarily the metallic parts of the MED. Overall, this study highlights the development efforts required in terms of both membrane performance and cost reduction, in order to make this technology cost effective in the future.

In electro-membrane processes, a pressure difference may arise between solutions flowing in alternate channels. This transmembrane pressure (TMP) causes a deformation of the membranes and of the fluid compartments. This, in turn, affects pressure losses and mass transfer rates with respect to undeformed conditions and may result in uneven flow rate and mass flux distributions. These phenomena were analyzed here for round pillar-type profiled membranes by integrated mechanical and fluid dynamics simulations. The analysis involved three steps: (1) A conservatively large value of TMP was imposed, and mechanical simulations were performed to identify the geometry with the minimum pillar density still able to withstand this TMP without collapsing (i.e., without exhibiting contacts between opposite membranes); (2) the geometry thus identified was subject to expansion and compression conditions in a TMP interval including the values expected in practical applications, and for each TMP, the corresponding deformed configuration was predicted; and (3) for each computed deformed configuration, flow and mass transfer were predicted by computational fluid dynamics. Membrane deformation was found to have important effects; friction and mass transfer coefficients generally increased in compressed channels and decreased in expanded channels, while a more complex behavior was obtained for mass transfer coefficients.

Reverse electrodialysis (RED) is a method to produce electricity from the reversible mixing of two salt solutions with different concentrations. RED was first employed for energy generation using sea and river water. New fields of application are energy storage and heat-to-power conversion. In energy storage applications, a stack operates in ED mode during charge and in RED mode during discharge. In a heat-to-power system, the RED stack produces electricity and the outgoing solutions are returned to their original concentrations in a heat-driven regenerator. In both new applications, the salt solutions are circulated and there is a free choice of the combination of salt and membranes for optimal performance. However, classical polymer-based membranes have some disadvantages: they are less suited for operation at higher temperatures, have reduced permselectivity at higher concentrations, and are rather permeable to water, causing an imbalance of the feed waters. We developed a new concept of pseudo-membrane (PM): a metal sheet (sometimes covered with an insoluble salt) on which opposite electrochemical reactions occur at each side of the metal surface. Because a PM is dissolving at one side and growing at the other side during operation, the current should be inverted periodically. We tested a zinc sheet as a pseudo cation exchange membrane for Zn2+ ions and a silver chloride⁻covered silver plate as a pseudo anion exchange membrane for Cl− ions in three steps. First, a stack was built with Ag/AgCl membranes in combination with normal cation exchange membranes and operated with NaCl solutions. The next stack was based on Zn membranes together with normal anion exchange membranes. This stack was fed with ZnCl2 solutions. Finally, we tested a stack with zinc and Ag/AgCl pseudo-membranes with a ZnCl2 solution. The latter RED system worked; however, after standing for one night, the stack did not function and appeared to be damaged by redox reactions. This failure was the basis for general considerations about the possibilities of ED and RED hybrid stacks, consisting of a combination of classical and pseudo ion exchange membranes. Finally, we consider the possibility of using intercalation electrodes as a pseudo-membrane.

Concentration polarization is one of the main challenges of membrane-based processes such as power generation by reverse electrodialysis. Spacers in the compartments can enhance mass transfer by reducing concentration polarization. Active spacers increase the available membrane surface area, thus avoiding the shadow effect introduced by inactive spacers. Optimizing the spacer-filled channels is crucial for improving mass transfer while maintaining reasonable pressure losses. The main objective of this work was to develop a numerical model based upon the Navier–Stokes and Nernst–Planck equations in OpenFOAM, for detailed investigation of mass transfer efficiency and pressure drop. The model is utilized in different spacer-filled geometries for varying Reynolds numbers, spacer conductivity and fluid temperature. Triangular corrugations are found to be the optimum geometry, particularly at low flow velocities. Cylindrical corrugations are better at high flow velocities due to lower pressure drop. Enhanced mass transfer and lower pressure drop by elevating temperature is demonstrated.

An energy conversion microchip consisting of two circular microchambers and a Nafion-filled microchannel is fabricated using standard micro-electro-mechanical systems (MEMS) techniques. When the chambers are filled with KCl solutions with different concentrations, the Nafion microchannel acts as a cation-selective membrane and results in the generation of electrical power through a reverse electrodialysis (RED) process. The current-potential characteristics of the Nafion membrane are investigated for devices with various microchannel lengths and electrolyte concentration ratios. It is shown that for a given voltage, the current and generated power increase with a reducing channel length due to a lower resistance. In addition, a maximum power density of 755 mW/m2 is obtained given an electrolyte concentration ratio of 2000:1 (unit is mM). The optimal device efficiency is found to be 36% given a channel length of 1 mm and a concentration ratio of 1000:1 (mM). Finally, no enhancement of the short circuit current is observed at higher concentration ratios.

In this study, we investigate power generation by reverse electrodialysis in a dense silica membrane that is between two NaCl solutions with various combinations of concentrations. Each silica membrane is fabricated by depositing a silica layer on a porous alumina substrate via chemical vapor deposition. The measured potential-current (V-I) characteristics of the silica membrane are used to obtain the transference number, diffusion potential, and electrical resistance. We develop empirical correlations for the transference number and the area-specific resistance, and present the results of power generation by reverse electrodialysis using the fabricated silica membranes. The highest measured power density is 0.98 mW/m2. In addition, we develop a contour map of the power density as a function of NaCl concentrations on the basis of the empirical correlations. The contour map shows that a power output density of 1.2 mW/m2 is achievable with the use of silica membranes and is sufficient to drive nanofluidic and microfluidic systems. The dense silica membrane has the potential for use in micro power generators in nanofluidic and microfluidic systems.