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Electrochemical technologies for water treatment, resource recovery, energy generation, and energy storage rely on charged polymer membranes to selectively transport ions. With the rise of applications involving hypersaline brines, such as management of desalination brine or the recovery of ions from brines, there is an urgent need for membranes that can sustain high conductivity and selectivity under such challenging conditions. Current membranes are constrained by an inherent trade-off between conductivity and selectivity, alongside concerns regarding their high costs. Moreover, a gap in the fundamental understanding of ion transport within charged membranes at high salinities prevents the development of membranes that could meet these stringent requirements efficiently. Here, we present the synthesis of scalable, highly charged membranes that demonstrate high conductivity and selectivity while contacting 1 and 5 molal NaCl solutions. A detailed analysis of the membrane transport properties reveals that the high proportion of bound water in the membranes, enabled by the high charge content and hydrophilic structure of the polymers, enhances both the ion partitioning and diffusion selectivities of the membranes. These structure/property relationships derived from this study offer valuable guidance for designing next-generation membranes that simultaneously achieve exceptional conductivity and selectivity in high-salinity conditions.

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Exploring high-performance anion exchange membranes (AEM) for water electrolyzers (AEMWEs) is significant for green hydrogen production. However, the current AEMWEs are restricted by the poor mechanical strength and low OH- conductivity of AEMs, leading to the low working stability and low current density. Here, we develop a robust AEM with polybiphenylpiperidium network by combining the crosslinking with triazine and the capping with pyridine for advanced AEMWEs. The AEM exhibits an excellent mechanical strength (79.4 MPa), low swelling ratio (19.2 %), persistent alkali stability (¼ 5,000 hours) and high OH- conductivity (247.2 mS cm-1) which achieves the state-of-the-art AEMs. Importantly, when applied in AEMWEs, the corresponding electrolyzer equipped with commercial nickel iron and nickel molybdenum catalysts obtained a current density of up to 3.0 A cm-2 at 2 V and could be stably operated ~430 h at a high current density of 1.6 A cm-2, which exceeds the most of AEMWEs. Our results suggest that triazine crosslinking and pyridine capping can effectively improve the overall performance of the AEMWEs.

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Redox flow batteries (RFB) often operate at extreme pH conditions and may require cooling to prevent high temperatures. The stability of the battery membranes at these extreme pH-values at high temperatures is still largely unknown. In this paper, a systematic screening of the performance and stability of nine commercial membranes at pH 14 and pH ≤ 0 with temperatures up to 80 °C is conducted in an organic aqueous RFB. Swelling, area resistance, diffusion crossover, battery performance and membrane stability after 40-80 °C temperature treatment are shown, after which a recommendation is made for different user scenarios. The Aquivion E98-05 membrane performed best for both the Tiron/2,7-AQDS battery and the DHPS/Fe(CN)6 battery at 40 mA/cm2, with stable results after 1 week of storage at 80 °C. At 80 mA/cm2, E-620-PE performed best in the DHPS/Fe(CN)6 battery, while Sx-050DK performed best in the Tiron/2,7-AQDS battery.

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Ion exchange membranes (IEMs) play a critical role in aqueous organic redox flow batteries (AORFBs). Traditional IEMs that feature microphase-separated microstructures are well-developed and easily available but suffer from the conductivity/selectivity tradeoff. The emerging charged microporous polymer membranes show the potential to overcome this tradeoff, yet their commercialization is still hindered by tedious syntheses and demanding conditions. We herein combine the advantages of these two types of membrane materials via simple in situ hypercrosslinking of conventional IEMs into microporous ones. Such a concept is exemplified by the very cheap commercial quaternized polyphenylene oxide membrane. The hypercrosslinking treatment turns poor-performance membranes into high-performance ones, as demonstrated by the above 10-fold selectivity enhancement and much-improved conductivities that more than doubled. This turn is also confirmed by the effective and stable pH-neutral AORFB with decreased membrane resistance and at least an order of magnitude lower capacity loss rate. This battery shows advantages over other reported AORFBs in terms of a low capacity loss rate (0.0017 % per cycle) at high current density. This work provides an economically feasible method for designing AORFB-oriented membranes with microporosity.

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Addressing the characterization of Natural Organic Matter (NOM) removal by functionalized membranes in water treatment, this study evaluates the effectiveness of two commercial ion-exchange membrane adsorbers: Sartobind® Q (with quaternary amines) and D (with tertiary amines). Using Suwannee River NOM (SRNOM) as a surrogate, Langmuir adsorption isotherms revealed maximum capacities (Qmax) of 2966 ± 153 mg C/m2 and 2888 ± 112 mg C/m2, respectively. Variations in flux from 50 to 500 LMH had a minimal impact on breakthrough times, proving low diffusion limitations. The macroporous (3-5 µm) functionalized cellulose-based membranes exhibited high permeabilities of 10,800 L/(h m2 bar). Q maintained positive zeta potential vs. pH, while D's zeta potential decreased above pH 7 due to amine deprotonation and turning negative above an isoelectric point of 9.1. Regeneration with 0.01 M NaOH achieved over 95% DOC regeneration for Sartobind® D, characterizing reversibility through a pH-swing. Cyclic adsorption showed that Q maintained its capacity with over 99% DOC regeneration, while D required acidic conditioning after the first regeneration cycle to mitigate capacity reduction and re-deprotonate the adsorber. These results have demonstrated the potential suitability of adsorber membranes, designed originally for biotechnological purposes, for the possible removal of disinfection byproduct precursors in drinking water treatment.

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To fulfill the industrial requirements of salt fractionation and recovery from saline wastewater, a two-chamber selective electrodialysis (SED) stack incorporating commercial monovalent selective anion exchange membranes was employed and investigated in this study. Three different initial concentration ratios of NaCl/Na2SO4, namely 1:1 (10 g/L:10 g/L), 3:1 (30 g/L:10 g/L), and 5:1 (50 g/L:10 g/L) were examined to simulate various scenarios of saline wastewater. The influence of applied current density on membrane selectivity and overall system efficiency was further evaluated. The results indicated that an increase in the NaCl fraction within the feed solution directly correlates with enhanced concentration and purity of Na2SO4 in the product, achieving purities exceeding 92 %. A lower current density contributed to improved concentration and purity of Na2SO4, whereas higher current densities were conducive to augmenting the concentration and purity of NaCl. Additionally, a linear correlation was observed between the volumetric water transport and NaCl migration. Through numerical simulations, the concentrations of Na2SO4 and NaCl in the effluent were predicted, facilitating a comparative analysis with the salt fractionation efficiency of commercial nanofiltration membranes. Subsequent assessments of energy consumption and current efficiency revealed that the SED system ensured high product concentration and purity at reasonably low energy consumption (0.22-0.28 kWh per kg NaCl) alongside a high current efficiency (83-89 %). These findings offer critical insights into the optimization of salt fractionation process and highlight its economic and technical feasibility for the sustainable management of industrial saline wastewater.

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Here, we examine electromembrane systems for low-concentration desalination applicable to ultrapure water production. In addition to electrodialysis and ion concentration polarization (ICP) desalination, we propose a recovery-reduced ICP strategy for reducing the width of the desalted outlet for a higher salt removal ratio (SRR). The correlation between conductivity changes and thickness of the ion depletion zone is identified for electrodialysis, ICPH (1:1), and ICPQ (3:1) with a low-concentration feed solution (10 mM, 1 mM, 0.1 mM NaCl). Based on the experimental results, the scaling law and SRR for the electroconvection zone are summarized, and current efficiency (CE) and energy per ion removal (EPIR) depending on SRR are also discussed. As a result, the SRR of electrodialysis is mostly around 50%, but that of recovery-reduced ICP desalination is observed up to 99% under similar operating conditions. Moreover, at the same SRR, the CE of recovery-reduced ICP is similar to that of electrodialysis, but the EPIR is calculated to be lower than that of electrodialysis. Considering that forming an ion depletion zone up to half the channel width in the electromembrane system typically requires much power consumption, an ICP strategy that can adjust the width of the desalted outlet for high SRR can be preferable.

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Redox flow batteries (RFBs) are increasingly being considered for a wide range of energy storage applications, and such devices rely on proton exchange membranes (PEMs) to function. PEMs are high-cost, petroleum-derived polymers that often possess limited durability, variable electrochemical performance, and are linked to discharge of perfluorinated compounds. Alternative PEMs that utilize biobased materials, including lignin and sulfonated lignin (SL), low-cost byproducts of the wood pulping process, have struggled to balance electrochemical performance with dimensional stability. Herein, SL nanoparticles are demonstrated for use as a nature-derived, ion-conducting PEM material. SL nanoparticles (NanoSLs) can be synthesized for increased surface area, uniformity, and miscibility compared with macrosized lignin, improving proton conductivity. After addition of polyvinyl alcohol (PVOH) as a structural backbone, membranes with the highest NanoSL concentration demonstrated an ion exchange capacity of 1.26 meq g-1, above that of the commercial PEM Nafion 112 (0.98 meq g-1), along with a conductivity of 80.4 mS cm-1 in situ, above that of many biocomposite PEMs, and a coulombic efficiency (CE), energy efficiency (EE) and voltage efficiency (VE) of 91%, 68% and 78%, respectively at 20 mA cm-2. These nanocomposite PEMs demonstrate the potential for valorization of forest biomass waste streams for high value clean energy applications.

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Ion exchange membranes allowing the passage of charge-carrying ions have established their critical role in water, environmental, and energy-relevant applications. The design strategies for high-performance ion exchange membranes have evolved beyond creating microphase-separated membrane morphologies, which include advanced ion exchange membranes to ion-selective membranes. The properties and functions of ion-selective membranes have been repeatedly updated by the emergence of materials with subnanometer-sized pores and the understanding of ion movement under confined micropore ion channels. These research progresses have motivated researchers to consider even greater aims in the field, i.e., replicating the functions of ion channels in living cells with exotic materials or at least targeting fast and ion-specific transmembrane conduction. To help realize such goals, we briefly outline and comment on the fundamentals of rationally designing membrane pore channels for ultrafast and specific ion conduction, pore architecture/chemistry, and membrane materials. Challenges are discussed, and perspectives and outlooks are given.

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Osmotic energy, as a renewable clean energy with huge energy density and stable yield, has received widespread attention over the past decades. Reverse electrodialysis (RED) based on ion-exchange membranes is an important method of obtaining osmotic energy from salinity gradients. The preparation of ion-exchange membranes with both high ion selectivity and ion permeability is in constant exploration. In this work, metal hydroxide-organic framework (MHOF) membranes are successfully prepared onto porous anodic aluminum oxide (AAO) membranes by a facile hydrothermal method to form Ni2(OH)2@AAO composite membranes, used for osmotic energy conversion. The surface is negatively charged with cation selectivity, and the asymmetric structure and extreme hydrophilicity enhance the ionic flux for effective capture of osmotic energy. The maximum output power density of 5.65 W m-2 at a 50-fold KCl concentration gradient is achieved, which exceeds the commercial benchmark of 5 W m-2. Meanwhile, the composite membrane can also show good performance in different electrolyte solutions and acid-base environments. This work provides a new avenue for the construction and application of MHOF membranes in efficient osmotic energy conversion.

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Capacitive deionization (CDI), an emerging method to eliminate ions from water at a low cost, has garnered significant interest in recent years. This study evaluates the implication of cation exchange resin loading on the membrane via the nonsolvent-induced phase inversion method. After determining the quantity of resins efficiently loaded on the membrane, it was subsequently utilized as a cation exchange membrane in the membrane capacitive deionization (MCDI) unit to examine the performance removal of Ni2+. The results show that the amount of resins influenced the membrane structure and significantly improved the efficiency of Ni2+ removal. The sulfonic acid group show a strong intensity directly proportional to the quantity of resins based on the FTIR measurement. In conjunction with the enhanced resin amount, ion exchange capacity and water content were increased. Simultaneously, there was an observed elevation in the water contact angle and the roughness of the membrane surface with increased resin amount. In the MCDI unit, membrane M20 (20% by weight resin) was employed to elucidate its roles in the CDI unit, encompassing an examination of various concentrations and flow rates, with Ni2+ utilized as a test contaminant. The results demonstrated that using membrane M20 in the MCDI (MCDI-M20) unit consistently exhibited higher adsorption levels than the CDI unit, reaching 19.80 mg g-1 ACC in the MCDI-M20 unit, while CDI unit achieved 10.27 mg g-1 ACC at 200 mg L-1 Ni2+ concentration and a flow rate of 10 mL min-1 at 1.2 V. Additionally, Ni2+ concentrations and flow rates in CDI system had an evident impact on the duration of adsorption due to the mechanisms of ions transport on the membrane. This study suggests that employing the prepared membrane in the MCDI unit enhanced the removal of Ni2+ from the solution, contributing to sustainable development goals.

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While electrodialysis (ED) demonstrates lower energy consumption than reverse osmosis (RO) in the desalination of low salinity waters, RO continues to be the predominant technology for brackish water desalination. In this study, we probe this skewed market share and project the potential for future disruption by ED through systematic assessment of the levelized cost of water (LCOW). Using rigorous process- and economic-models, we minimize the LCOW of RO and ED systems, highlighting important tradeoffs between capital and operating expenditure for each technology. With optimized current state-of-the-art systems, we find that ED is more economical than RO for feed salinities ≤ 3 g L-1, albeit to a minor extent. Considering that RO is a highly mature technology, we focus on predicting the future potential of ED by evaluating plausible avenues for capital and operating cost reduction. Specifically, we find that reduction in the price of ion-exchange membranes (i.e., < 60 USD m-2) can ensure competitiveness with RO for feed salinities up to 5 g L-1. For higher feed salinities (≥ 5 g L-1) we reveal that the LCOW of ED may effectively be reduced by decreasing ion-exchange membrane resistance, while preserving high current efficiency. Through extensive assessment of structure-property-performance relationships, we precisely identify target membrane charge densities and diffusion coefficients which optimize the LCOW of ED, thus providing novel guidance for future membrane material development. Overall, we emphasize that with a unified approach - whereby ion-exchange membrane price is reduced and performance is enhanced - ED can become the economically preferable technology compared to RO across the entire brackish water salinity range.

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Membrane transport properties are crucial for electrochemical devices, and these properties are influenced by the composition and concentration of the electrolyte in contact with the membrane. We apply this general membrane-electrolyte system approach to alkaline flow batteries, studying the conductivity and ferricyanide crossover of Nafion and E-620. We report undetectable crossover for as-received Nafion and E-620 after both sodium and potassium exchange but high ferricyanide permeability of 10-7 to 10-8 cm2 s-1 for Nafion subjected to pretreatment prevalent in the flow battery literature. We show how the electrolyte mass fraction in hydrated membranes regulates the influence of ion concentration on membrane conductivity, identifying that increasing electrolyte concentration may not increase membrane conductivity even when it increases electrolyte conductivity. To illustrate this behavior, we introduce a new metric, the membrane penalty, as the ratio of the conductivity of the electrolyte to that of the membrane equilibrated with the electrolyte. We discuss the trade-off between flow battery volumetric capacity and areal power density that arises from these findings. Finally, we apply insights from this approach to provide recommendations for use of membranes in alkaline flow cells and electrochemical reactors in general.

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In this study, electrodeionization (EDI) in bath mode was tested regarding its capability to remove phosphate (PO4 3- ) ions from aqueous solutions. Various parameters affecting the phosphate removal rate via EDI were determined. The results showed that the phosphate removal rate depends on the applied voltage and that the optimum potential was 15 V, corresponding to a phosphate removal rate of 97%. Changing the stream rate of the phosphate-containing solution also affected the phosphate removal rate. Changing the pH of the phosphate-containing solution from 2 to 6 enhanced the phosphate removal rate from 80% to 97%. The presence of Cl- , NO3 - , and SO4 2- ions did not affect the phosphate removal rate. The highest mass transfer coefficient (k) of phosphate was calculated to be 7.85 × 10-4  m/s, and the flux was calculated to be 3.72 × 10-4  mol/m2  s1 at a flow velocity of 3 L/h. Thus, the study results showed the feasibility of EDI as an alternative membrane process for removing phosphate from aqueous solutions. PRACTITIONER POINTS: Electrodeionization was employed for the removal of phosphate. The removal of phosphate exhibited dependence on applied potential. EDI demonstrated a remarkable 97% efficiency in phosphate removal. The pH of the solution was found to influence the removal rate.

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Bromate (BrO3-) is a disinfection byproduct formed during the chemical oxidation of water containing bromide. Due to the carcinogenic effect of bromate, its maximum permissible concentration in drinking water has been set to 10 µg/L by the World Health Organization. In this study, the removal of BrO3- ions from aqueous solutions via electrodeionization (EDI) was investigated. The removal rate of BrO3- varied with the applied potential, and at 10 V, a removal rate of 99% was achieved. However, further increasing the applied potential to 30 V had a negative effect on the removal rate. Additionally, a low bromate concentration in the product water was achieved by reducing Na2SO4 conductivity in the electrode compartment. The removal of BrO3- is pH dependent, and at pH 1, only 17.5% was removed. However, increasing the pH of the solution to 5 increased the removal rate to 99.6%. Increasing the operating time and number of cells in the EDI stack improved the removal rate of BrO3-, and its concentration decreased from 5 mg/L to 1.4 µg/L. The calculated flux for BrO3- was 2.17 × 10-5 mol/m2s, specific power consumption was 89.98-W/hg KBrO3, and mass-transfer coefficient was 5.4 × 10-4 m/s at 10 V.

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Evaporative technology for lithium mining from salt-lakes exacerbates freshwater scarcity and wetland destruction, and suffers from protracted production cycles. Electrodialysis (ED) offers an environmentally benign alternative for continuous lithium extraction and is amenable to renewable energy usage. Salt-lake brines, however, are hypersaline multicomponent mixtures, and the impact of the complex brine-membrane interactions remains poorly understood. Here, we quantify the influence of the solution composition, salinity, and acidity on the counterion selectivity and thermodynamic efficiency of electrodialysis, leveraging 1250 original measurements with salt-lake brines that span four feed salinities, three pH levels, and five current densities. Our experiments reveal that commonly used binary cation solutions, which neglect Na+ and K+ transport, may overestimate the Li+/Mg2+ selectivity by 250% and underpredict the specific energy consumption (SEC) by a factor of 54.8. As a result of the hypersaline conditions, exposure to salt-lake brine weakens the efficacy of Donnan exclusion, amplifying Mg2+ leakage. Higher current densities enhance the Donnan potential across the solution-membrane interface and ameliorate the selectivity degradation with hypersaline brines. However, a steep trade-off between counterion selectivity and thermodynamic efficiency governs ED's performance: a 6.25 times enhancement in Li+/Mg2+ selectivity is accompanied by a 71.6% increase in the SEC. Lastly, our analysis suggests that an industrial-scale ED module can meet existing salt-lake production capacities, while being powered by a photovoltaic farm that utilizes <1% of the salt-flat area.

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Polymer ion-exchange membranes are featured in a variety of modern technologies including separation, concentration and purification of gases and liquids, chemical and electrochemical synthesis, and hydrogen power generation. In addition to transport properties, the strength, elasticity, and chemical stability of such materials are important characteristics for practical applications. Perfluorosulfonic acid (PFSA) membranes are characterized by an optimal combination of these properties. Today, one of the most well-known practical applications of PFSA membranes is the development of fuel cells. Some disadvantages of PFSA membranes, such as low conductivity at low humidity and high temperature limit their application. The approaches to optimization of properties are modification of commercial PFSA membranes and polymers by incorporation of different additive or pretreatment. This review summarizes the approaches to their modification, which will allow the creation of materials with a different set of functional properties, differing in ion transport (first of all proton conductivity) and selectivity, based on commercially available samples. These approaches include the use of different treatment techniques as well as the creation of hybrid materials containing dopant nanoparticles. Modification of the intrapore space of the membrane was shown to be a way of targeting the key functional properties of the membranes.

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Fermentation effluents from organic wastes contain simple organic acids and ethanol, which are good electron sources for exoelectrogenic bacteria, and hence are considered a promising substrate for hydrogen production in microbial electrolysis cells (MECs). These fermentation products have different mechanisms and thermodynamics for their anaerobic oxidation, and therefore the composition of fermentation effluent significantly influences MEC performance. This study examined the microbial electrolysis of a synthetic fermentation effluent (containing acetate, propionate, butyrate, lactate, and ethanol) in two-chamber MECs fitted with either a proton exchange membrane (PEM) or an anion exchange membrane (AEM), with a focus on the utilization preference between the electron sources present in the effluent. Throughout the eight cycles of repeated batch operation with an applied voltage of 0.8 V, the AEM-MECs consistently outperformed the PEM-MECs in terms of organic removal, current generation, and hydrogen production. The highest hydrogen yield achieved for AEM-MECs was 1.26 L/g chemical oxygen demand (COD) fed (approximately 90% of the theoretical maximum), which was nearly double the yield for PEM-MECs (0.68 L/g COD fed). The superior performance of AEM-MECs was attributed to the greater pH imbalance and more acidic anodic pH in PEM-MECs (5.5-6.0), disrupting anodic respiration. Although butyrate is more thermodynamically favorable than propionate for anaerobic oxidation, butyrate was the least favored electron source, followed by propionate, in both AEM- and PEM-MECs, while ethanol and lactate were completely consumed. Further research is needed to better comprehend the preferences for different electron sources in fermentation effluents and enhance their microbial electrolysis.

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Electrodialysis desalination uses ion exchange membranes, membrane spacers, and conductors to remove salt from water. Membrane spacers, made of polymeric strands, reduce concentration polarization. These spacers have properties such as porosity and filament shape that affect their performance. One important property is the spacer-bulk attack angle. This study systematically reviews the characteristics of a 45° attack angle of spacers and its effects on concentration polarization and fluid dynamics. Membrane spacers in a channel create distinct flow fields and concentration profiles. When set at a 45° attack angle, spacers provide greater turbulence and mass-heat transfer than traditional spacers. This is because both the transverse and longitudinal filaments become diagonal in relation to the bulk flow direction. A lower attack angle (<45°) results in a lower pressure drop coupled with a decline in wakes and stream disruption because when the filaments are more parallel to the primary fluid direction, the poorer their affect. This research concludes that membrane spacers with a 45° spacer-bulk attack angle function optimally compared to other angles.

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Ion exchange membranes, especially cation exchange membranes (CEMs), are an important component in membrane-based energy generation and storage because of their ability to transport cations via the electrochemical potential gradient while preventing electron transport. However, developing a CEM with low areal resistance, high permselectivity, and stability remains difficult. In this study, electrospun graphene oxide/polyethersulfone (GO/PES) composite nanofibers were prepared with varying concentrations of GO. To fabricate a CEM, the pores of the electrospun GO/PES nanofiber substrates were filled with a Nafion ionomer. The pore-filled PES nanofiber loaded with 1% GO revealed a noticeable improvement in hydrophilicity, structural morphology, and mechanical properties. The 1% GO/PES pore-filled CEM was compared to a Nafion membrane of a varying thickness and without a nanofiber substrate. The CEM with a nanofiber substrate showed permselectivity of 85.75%, toughness of 111 J/m3, and areal resistance of 3.7 Ω cm2, which were 12.8%, 4.3 times, and 4.0 times better, respectively, than those of the Nafion membrane at the same thickness. The development of a reinforced concrete-like GO/PES nanofiber structure containing stretchable ionomer-enhanced membrane surfaces exhibited suitable areal resistance and reduced the thickness of the composite membrane without compromising the mechanical strength, suggesting its potential application as a cation exchange membrane in electrochemical membrane-based systems.