Membrane Capacitive Deionization Research Articles

Advancing the Electrosorption Selectivity of Nitrate Through Fine-Tuning Hydrophobic Ammonium Functional Groups in Anion Exchange Membranes for Membrane Capacitive Deionization

Advancing the Electrosorption Selectivity of Nitrate Through Fine-Tuning Hydrophobic Ammonium Functional Groups in Anion Exchange Membranes for Membrane Capacitive Deionization

Fluoride removal using membrane capacitive deionization: The role of pH-dependent dissolved inorganic carbon

Defluorination technology is crucial for ensuring safe and accessible water. The application of capacitive deionization (CDI) technology faces challenges due to competitive adsorption of fluoride ions within complex natural fluoride-rich brackish water matrices, which often contain high levels of dissolved inorganic carbon (DIC) species (mainly HCO3– and CO32–). These DIC species are pH-dependent, playing a significant role in the selective removal of fluoride by the CDI process. Thus, there is a knowledge gap in understanding the effects of membranes in membrane capacitive deionization (MCDI) on fluoride removal. In this study, we examined the key operating parameters in CDI and MCDI, including applied constant voltages and different types of anion-exchange membranes (AEMs), on the desalination performance in F- and dissolved inorganic carbon water matrices. The application of AEMs significantly improved the salt adsorption capacity (SAC) for both F- and DIC species, and reduced energy consumption. However, it simultaneously resulted in a notable decrease in F- selectivity as membranes control mass transfer. Higher applied voltages enhance the SAC performance for F- and DIC species, but also induce more severe Faradaic reactions, leading to increased energy consumption and lower energy efficiency. Additionally, ion species and pH changes during CDI and MCDI processes are interrelated, indicating that stability tests of CDI electrodes in batch mode are not reliable when using the same testing solution repeatedly. The diverse valence states of ions in the solution impact pH variations under different voltages in the CDI/MCDI process. These findings provide valuable insights into the development of water purification and desalination technology, particularly for the application and further advancement of selective fluoride removal by the CDI process.

Bipolar Membrane Capacitive Deionization for the Selective Capture of Lithium Ions from Brines and Conversion to Lithium Hydroxide

Meeting the increasing demand for lithium in vehicle electrification and renewable energy storage requires innovations in lithium-ion (Li+) separations. Traditional solar evaporation methods for lithium recovery are slow and consume tremendous volumes of water and secondary chemicals (acids and bases). This study introduces a bipolar membrane capacitive deionization (BPM-CDI) unit for direct lithium extraction and LiOH production without the external addition of acids and bases. Utilizing de-lithiated lithium-iron-phosphate (LFP) coated carbon cloth electrodes, the BPM-CDI unit demonstrates selective Li+ capture over competing ions. Molecular dynamics simulations and H-cell experiments elucidate pH inversion mechanisms during Li+ release, yielding LiOH. The BPM-CDI platform efficiently removes Li+ from synthetic brines featuring 8x higher Mg2+ concentrations (200 ppm Mg2+) and 26x higher Na+ concentrations (682 ppm Na+), achieving a LiOH concentration of 124 ppm (36 ppm Li+) after 8 cycles of recirculation. Post-mortem analysis confirms electrode integrity and stability. BPM-CDI integrated with selective electrodes is a promising electrochemical separation-reactor platform for lithium recovery while producing LiOH.

GIS-based multi-criteria approach for ranking suitable areas for the implementation of PV-Powered MCDI desalination plants in the Rheris Watershed, Southeast Morocco

In Morocco's oases, which rely heavily on surface water from mountain sources, the threat of decreasing rainfall presents a significant challenge, leading to a decline in surface water availability. This study focuses on the Rheris Watershed in Southeast Morocco, where brackish water desalination emerges as a viable alternative to ensure sustainable water supply for agriculture. Prior to the deployment of a pilot plant integrating a desalination unit, selecting an optimal site for PV-powered MCDI desalination plants was critical. This selection was based on a range of criteria, including Groundwater Quantity, Global Horizontal Irradiation, Temperature, Evaporation, Water Salinity, Water Quantity, Well Density and Slope. These criteria were evaluated using a combination of the Analytical Hierarchy Process (AHP), and geospatial data obtained from Remote Sensing (RS) and Geographic Information System (GIS) techniques.This case study in the Rheris watershed identified potential sites for future Membrane Capacitive Deionization (MCDI) desalination projects, High suitability areas encompass 280.45 km² (30.91 %), located west of Tinejdad, Khettarat Moulay Hachem, north of Goulmima, and south of Tinghir. Low suitability areas cover 63.75 km² (7.02 % of the study area), including regions south of Tadighoust and Tinejdad. Moderate suitability areas span 562.86 km² (62.05 %), involving central regions of Goulmima, Tadighoust, Tinejdad, and Tinghir. Based on the results of the study, the recommendations include focusing on areas identified as highly suitable for MCDI technology for sustainable agriculture, refining selection criteria based on local data, exploring brine management strategies, and adopting integrated water management approaches to ensure sustainable resource use.

Investigation of the Deionization Rate of Asymmetric Capacitive Deionization Technology for the Treatment of Short-Chain Perfluoroalkyl Substances (PFAS)

Objectives : This study aims to introduce and evaluate the effectiveness of asymmetric membrane capacitive deionization (ACDI) in removing short-chain perfluoroalkyl substances (PFAS), specifically perfluorobutane sulfonic acid (PFBS), from aqueous solutions. This study offers important insights for the advancement of CDI technology in the sustainable treatment of industrial wastewater containing PFAS.Methods : ACDI was employed by removing the anion exchange membrane from conventional membrane capacitive deionization system. The effect of key operational parameters such as voltage (0.5~1.2 V), initial concentration (50~500 mg/L), and flow rate (1~5 ml/min) on PFBS removal efficiency was systematically investigated. Additionally, PFBS removal performance in the presence of chloride ions was also investigated to determine competing ion effects.Results and Discussion : The ACDI system significantly outperformed both CDI and MCDI, achieving a maximum deionization rate of 0.032 mg/g/s, compared to 0.012 mg/g/s for CDI and 0.01 mg/g/s for MCDI. Increasing the applied voltage from 0.5 V to 1.2 V enhanced the deionization rate, with the highest rate observed at 1.2 V. Higher initial PFBS concentrations also improved the deionization rate, increasing from 0.0009 mg/g/s at 50 mg/L to 0.032 mg/g/s at 500 mg/L. The optimal flow rate was found to be 2 ml/min, balancing ion contact time and throughput, resulting in the highest deionization rate. The presence of competing ions, such as chloride, reduced PFBS removal efficiency, as shown by the decrease in deionization rate when NaCl was added to the feed solution.Conclusion : Overall, the ACDI system demonstrated superior deionization capacity and energy efficiency for PFBS removal, highlighting its potential as a sustainable and efficient technology for treating water contaminated with short-chain PFAS. Future research should address the challenges posed by competing ions in real-world wastewater to further optimize the ACDI system’s performance.

Ameliorating Ion-Transport Resistances in Membrane Capacitive Deionization Using Patterned Ion-Exchange Membranes and Ionomer Infiltrated Electrodes

Currently, 2 billion people live in water scarce regions and 4 billion people experience water scarcity for at least 1 month per year [1]. Besides implications to the broad masses, the U.S. Marine Corps also face enormous challenges of generating potable water during squad level field missions. Reverse osmosis is the most reliable and economical process for desalinating water, but it requires piping that can tolerate large pressures and is not conducive for portable missions. Membrane capacitive deionization (MCDI) is a modular and electrified water desalination platform that does not generate significant acoustic, thermal, or electromagnetic signatures nor does it require high pressure piping. Flow-by MCDI, which is commercialized, uses electrical energy to remove ions from water. The system architecture feature two porous electrodes covered by ion-exchange membranes – the latter material is used to prevent co-ion adsorption and greater Coulombic efficiency than the variant that does not utilize ion-exchange membranes.Our previous research improved the energy efficiency of MCDI by using IEMs with lower area-specific resistance (ASR) values and porous ionic conductors in the spacer channel that augmented solution conductivity and curtailed ohmic losses. Reducing these resistances enabled the MCDI to operate at 700 mV lower cell voltage at 2 mA cm-2 current density. This is important for shrinking the size of the MCDI unit and lowering the overall capital costs.This talk presents our recent work examining ionic charge transport resistance at patterned and non-patterned ion-exchange membrane interfaces in MCDI. Membrane surface patterning increased the interfacial area between the membrane and aqueous stream promoting greater salt removal fluxes. Soft-lithography methods were used to micropattern poly(phenylene alkylene) cation exchange membranes and anion exchange membranes with systematically varied topographies (e.g., cylindrical well and line structures that vary from 9 to 20 mm). We can reduce the MCDI cell voltage by 1 V when utilizing micropatterned ion-exchange membranes and ionomer infiltrated electrodes (operating at 2 mA cm-2 with a 2000 ppm NaCl feed). This translated to a 2.4x greater energy normalized adsorbed salt (ENAS) value - a metric used to assess the energy consumption for MCDI. Our future work examines electrode materials deposited at pattern membrane interfaces to reduce interfacial transport resistances from the membrane to the electrode. This strategy has been shown to be effective in reducing charge-transfer resistances in both proton exchange membrane (PEM) and AEM fuel cells and reducing the water dissociation kinetics resistance in bipolar membranes [2-5]. References Somini Sengupta, Weiyi Cai, A Quarter of Humanity Faces Looming Water Crises, in The New York Times. 2019: United States of America.Kole, S., et al., Bipolar membrane polarization behavior with systematically varied interfacial areas in the junction region. Journal of Materials Chemistry A, 2021. 9(4): p. 2223-2238.Breitwieser, M., et al., Tailoring the Membrane-Electrode Interface in PEM Fuel Cells: A Review and Perspective on Novel Engineering Approaches. Advanced Energy Materials, 2018. 8(4).Hee-Tak Kim, T.V.R., Ho-Jin Kweon, Microstructured Membrane Electrode Assembly for direct methanol fuel cell. Journal of The Electrochemical Society, 2007. 154(10).Tomizawa, M., et al., Heterogeneous pore-scale model analysis of micro-patterned PEMFC cathodes. Journal of Power Sources, 2023. 556. Figure 1

Nitrogen-doped activated carbon composite electrode for deionization of phosphate removal and DFT model adsorption of phosphates

Phosphate discharge in sewage can result in water eutrophication, posing a threat to aquatic ecosystems. Membrane capacitive deionization (MCDI) has demonstrated outstanding performance and significant potential for salt removal and nutrient recovery. In this study, a nitrogen-doped activated carbon electrode material (NAC) was synthesized through one-step pyrolysis to selectively remove phosphate from MCDI. At a voltage of 1.2V, a flow rate of 20 mL/min, and a pH of 6.51, the phosphate adsorption capacity of the NAC electrode was determined to be 1.60 mg/g. The study revealed that NAC pHpzc increased from 4.14 to 6.44, effectively broadening the pH range for phosphate removal. In the presence of competing ions (NO3−, Cl−, and SO42−) at a concentration of 0.5 M, the electroadsorption capacity of phosphate decreased to 1.21 mg/g, 1.14 mg/g, and 1.02 mg/g, respectively. The kinetic parameters of adsorption indicated that NAC electroadsorbed phosphate through physical adsorption, with the maximum adsorption capacity achieved at 303K. Data from the Freundlich isothermal model suggested that phosphate adsorption by the NAC electrode involves a multilayer adsorption process. A carbon structure model of density functional theory (DFT), incorporating doped nitrogen, was constructed based on XPS analysis. Following nitrogen doping, the electrostatic potential (ESP) of unsaturated carbon atoms became more positive, enhancing the ability of nitrogen-doped activated carbon to adsorb phosphate. This study provides compelling evidence that nitrogen doping facilitates the adsorption of phosphate by carbon materials.

Autonomous real-time control for membrane capacitive deionization

Artificial intelligence has been employed to simulate and optimize the performance of membrane capacitive deionization (MCDI), an emerging ion separation process. However, a real-time control for optimal MCDI operation has not been investigated yet. In this study, we aimed to develop a reinforcement learning (RL)-based control model and investigate the model to find an energy-efficient MCDI operation strategy. To fulfill the objectives, we established three long-short term memory models to predict applied voltage, outflow pH, and outflow electrical conductivity. Also, four RL agents were trained to minimize outflow concentration and energy consumption simultaneously. Consequently, actor-critic (A2C) and proximal policy optimization (PPO2) achieved the ion separation goal (<0.8 mS/cm) as they determined the electrical current and pump speed to be low. Particularly, A2C kept the parameters consistent in charging MCDI, which caused lower energy consumption (0.0128 kWh/m3) than PPO2 (0.0363 kWh/m3). To understand the decision-making process of A2C, the Shapley additive explanation based on the decision tree model estimated the influence of input parameters on the control parameters. The results of this study demonstrate the feasibility of RL-based controls in MCDI operations. Thus, we expect that the RL-based control model can improve further and enhance the efficiency of water treatment technologies.

Commercialization Efforts of Capacitive Deionization Technology in Water Treatment Processes

AbstractAlthough capacitive deionization (CDI) technology has been studied intensively for more than 20 years, its commercialization remains in the initial stage, which is partly caused by the insufficient knowledge exchange between academia and industry. This concept reviews multiple scaling‐up efforts in the CDI technology for treating real water streams, following a case‐by‐case fashion. While the cell architecture in pilot scales is limited to the membrane CDI, highlighting the necessary role of ion‐exchange components during scaling‐ups, different ways of electrode stacking, i. e., monopolar and bipolar, are available. The performance indicators of these CDI systems when treating real water streams are summarized to gain insights into industrial practices. Importantly, key discrepancies in cell components and performances between pilot‐scale and lab‐scale studies are emphasized. The main challenges in large‐scale CDI systems for industrial purposes are discussed, providing hints for a better integration of research and applications.

N-doped carbon achieved by pyrolyzing urea and active carbon for the capacitive deionization coupled PMS oxidation system

Tetracyclines are among the most widely used antibiotics, and the saline organic wastewater generated during their production has caused serious environmental problems. Thus, it is imperative to develop effective methods for treating this antibiotic wastewater. In this study, we examined the structural characteristics and electrochemical performance of nitrogen-doped carbon materials and assessed the effects of nitrogen doping on the performance of a peroxymonosulfate (PMS)-coupled membrane capacitive deionization (MCDI) system for removing tetracycline (TC) and salt. Having optimized the carbonization temperature and system operating parameters, we observed that in response to an increase in carbonization temperature, there was an increase in the abundance of surface functional groups in the material, which promoted the ion migration capacity of the electrode and PMS activation sites. In addition, we observed that nitrogen doping can alter the electrical properties of carbon materials, provide a larger number of adsorption sites, and enhance the interactions between carbon structures and salt ions, thereby improving material properties. Under optimal operating conditions, the salt adsorption and tetracycline removal rates reached 30.2 % and 61.8 %, respectively. Our findings in this study provide a feasible method for the treatment of saline tetracycline wastewater.

Synergizing MBR and MCDI systems as a sustainable solution for decentralized wastewater reclamation and reuse

Decentralized wastewater reclamation and reuse systems have drawn much attention due to their capability for reducing the energy demand for water conveyance and reclaiming wastewater for local re-use. While membrane bioreactor (MBR) stands as a mature technology offering comprehensive solid and liquid separation, membrane capacitive deionization (MCDI) presents a promising avenue for ion separation. Unfortunately, MCDI has seldom been incorporated into decentralized wastewater reclamation and reuse systems. This study aims to exemplify the design and the operation of the synergistic integration of MBR and MCDI system with a practical capacity of 1 m3 d− 1, showcasing its efficacy in reclaiming and reusing water at regional level. The integrated system demonstrated significant high removal of total organic carbon (from 97 to 2 mg L− 1) and chemical oxygen demand (COD, from 218 to < 3 mg L− 1). Meantime, nearly complete transformation (approximately 91%) of NH3 to NO3− within the MBR effluent was observed with a hydraulic retention time of 4.3–4.8 h and a food-to-microorganism of 0.15–0.20 kg COD kg− 1 MLSS d− 1 which can be further removed through the MCDI system (> 92% TN removal). A significant milestone of MCDI unit was reached with the remarkable removal efficiency of total ions (93%) and water recovery (80%) using a stop-flow regeneration approach coupled with an optimized voltage of 2.0 V. The MCDI unit not only proved its high stability but also featured low energy consumption (0.44 kWh m− 3). Overall, synergizing MBR and MCDI systems emerges as a sustainable and effective solution for decentralized wastewater reclamation and reuse, contributing to a more environmentally friendly and resource-efficient water management paradigm.

Multi-chamber membrane capacitive deionization coupled with peroxymonosulfate to achieve simultaneous removal of tetracycline and peroxymonosulfate reaction byproducts

Advanced oxidation technologies based on peroxymonosulfate (PMS) have been extensively applied for the degradation of antibiotics. However, the degradation process inevitably introduces SO42- and other sulfur-containing anions, these pollutants pose a huge threat to the water and soil environment. Addressing these concerns, this study introduced PMS oxidation into a multi-chamber membrane capacitive deionization (MC-MCDI) device to achieve simultaneous tetracycline (TC) degradation and removal of PMS reaction byproduct ions. The experimental results demonstrated that when the TC solution (40 mg L−1) was pre-adsorbed for 10 min, the voltage was 1.2 V and the concentration of PMS solution added was 4 mg mL−1, the removal efficiency of TC and ion can reach 77.4 % and 46.5 % respectively. Furthermore, the activation process of PMS in MC-MCDI/PMS system and the reactive oxygen (ROS) that mainly produce degradation were deeply investigated. Finally, liquid chromatography-mass spectrometry (LC-MS) was employed to identify intermediates of TC degradation, propose potential degradation pathways, and analyze the toxicities of the intermediates. In addition, in five cycles, the MC-MCDI/PMS system demonstrated excellent stability. This study provides an effective strategy for treating TC wastewater and a novel approach for simultaneous TC degradation and desalination.

Selective phosphate removal with manganese oxide composite anion exchange membranes in membrane capacitive deionization

The discharge of excessive phosphorous into water bodies can lead to serious eutrophication threatening aquatic ecosystem. Membrane capacitive deionization (MCDI) is an effective platform for deionizing aqueous streams; however, conventional MCDI is unable to selectively remove targeted ions from a liquid mixture. In this work, we fabricated manganese oxide composite anion exchange membranes (AEMs) for MCDI to enhance phosphate removal selectivity from sodium chloride-sodium dihydrogen phosphate (10:1 M ratio) aqueous mixtures. We systematically investigated several critical factors, such as constant current or voltage operation, applied voltage amount, process stream pH, and manganese oxide (Mn2O3) content in the AEM, on phosphate removal efficiency and phosphate selectivity. A trade-off was observed between phosphate removal and selectivity when increasing the cell voltage. Under the best conditions, a MCDI unit with a 20 wt% Mn2O3 composite AEM and a bipolar membrane facilitated high phosphate removal efficiency of ≥ 31.8 % and a phosphate over chloride selectivity of 1.1 while showing stability for at least 30 cycles. To help understand how Mn2O3 composite AEM boosts phosphate selectivity, static electronic structure calculations were performed, and they revelated that hydrogen phosphate absorption on Mn2O3 composite AEM was 314 kcal/mol more exothermic than that on pristine AEM while chloride adsorption on Mn2O3 composite AEM was 2.2 kcal/mol less exothermic than that on a pristine AEM. Overall, this work presents an effective strategy for selectively removing phosphate from model wastewater solutions and the mechanistic understanding that governs ion selectivity in composite ion-exchange membranes used in MCDI.

Reducing Ohmic Resistances in Membrane Capacitive Deionization Using Micropatterned Ion‐Exchange Membranes, Ionomer Infiltrated Electrodes, and Ionomer‐Coated Nylon Meshes

Membrane capacitive deionization (MCDI) is an emerging water desalination platform that is compact, electrified, and does not require high‐pressure piping. Herein, highly conductive poly(phenylene alkylene) ion‐exchange membranes (IEMs) are micropatterned with different surface geometries for MCDI. The micropatterned membranes increase the interfacial area with the liquid stream leading to a 700 mV reduction in cell voltage when operating at constant current (2 mA cm−2; 2000 ppm NaCl feed) while improving the energy normalized adsorbed salt (ENAS) value by 1.4 times. Combining the micropatterned poly(phenylene alkylene) IEMs with poly(phenylene alkylene) ionomer‐filled electrodes reduces the cell voltage by 1000 mV and improves the ENAS values by 2.3 times relative to the base case. This reduction in cell voltage allows for higher current density operation (i.e., 3–4 mA cm−2) . The reduction in cell voltage is ascribed to the ameliorating ohmic resistances related to ion transport at the membrane‐process stream interface and in the carbon cloth electrode. Finally, porous ionic conductors are implemented into the spacer channel with flat and micropatterned IEM configurations and ionomer infiltrated electrodes. For the configuration with flat IEMs, the porous ionic conductor improves ENAS values across the current density regime (2–4 mA cm−2), while for micropatterned IEMs it gets improved only at 4 mA cm−2.

Membrane capacitive deionization (MCDI): A flexible and tunable technology for customized water softening

There is a growing demand for water treatment systems for which the quality of feedwater in and product water out are not necessarily fixed with “tunable” technologies essential in many instances to satisfy the unique requirements of particular end-users. For example, in household applications, the optimal water hardness differs for particular end uses of the supplied product (such as water for potable purposes, water for hydration, or water for coffee or tea brewing) with the inclusion of specific minerals enhancing the suitability of the product in each case. However, conventional softening technologies are not dynamically flexible or tunable and, typically, simply remove all hardness ions from the feedwater. Membrane capacitive deionization (MCDI) can potentially fill this gap with its process flexibility and tunability achieved by fine tuning different operational parameters. In this article, we demonstrate that constant-current MCDI can be operated flexibly by increasing or decreasing the current and flow rate simultaneously to achieve the same desalination performance but different productivity whilst maintaining high water recovery. This characteristic can be used to operate MCDI in an energy-efficient manner to produce treated water more slowly at times of normal demand but more rapidly at times of peak demand. We also highlight the “tunability” of MCDI enabling the control of effluent hardness over different desired ranges by correlating the rates of hardness and conductivity removal using a power function model. Using this model, it is possible to either i) soften water to the same hardness level regardless of the fluctuation in hardness of feed waters, or ii) precisely control the effluent hardness at different levels to avoid excessive or insufficient hardness removal.

Metadata and feature importance analyses of membrane capacitive deionization models: Is a water treatment artificial intelligence panacea possible?

Membrane capacitive deionization (MCDI) is an emerging technology for water purification and desalination. Artificial intelligence (AI) techniques using machine learning (ML) and deep learning (DL) have been widely applied to overcome the drawbacks of conventional numerical models in predicting effluent concentrations, an important parameter to estimate the energy consumption and degree of desalination of the MCDI process. However, despite the remarkable progress of these ML/DL models, relevant studies have only been conducted with limited datasets, leading to a substantial controversy regarding model accuracy. Therefore, in this study, we comprehensively evaluated the performances and applicability of multiple ML/DL models for MCDI using metadata (i.e., performance indices) and feature importance analyses. One MCDI dataset containing both constant-current and constant-voltage operations was reconfigured uniformly or unevenly depending on operation modes. Subsequently, six ML models and one DL model were used to execute the analyses using performance indices. Collectively, this study suggests that a perfect ML/DL model for the water treatment process may not exist, and understanding data types is as important as selecting appropriate models to build a data-driven AI model when process performance is greatly affected by specific input variables (i.e., current and voltage).

ENHANCING COPPER REMOVAL THROUGH INTEGRATED CAPACITIVE DEIONIZATION WITH HETEROGENEOUS CATION EXCHANGE MEMBRANE

Capacitive deionization (CDI) is a novel technique to eliminate ions present in the solution. This study was designed to evaluate the impact of cation exchange resin loading on the membrane using the nonsolvent-induced phase inversion method. After optimizing the resin loading on the membrane, the prepared membrane was employed for the membrane capacitive deionization (MCDI). A concentration of 500 mg.L-1 Cu2+ was used as a test contaminant in the CDI system to study Cu2+ removal and recovery at different voltages. Results showed that resin loading substantially influenced the membrane structure and enhanced the Cu2+ removal by the CDI technique. The presence of cation exchange resin on the membrane was found by the appearance of a peak at 1,007 cm-1, 1,035 cm-1, and 1,128 cm-1 in the FTIR spectra of the –SO3 group, which became more significant as the amount of resin increased. The prepared membrane’s water uptake and ion exchange capacity increased as the quantity of resins loaded onto the membrane increased. When monitoring a current-time graph during CDI tests, an adsorption amount of 6.9 mg.g-1 of Cu2+ and recovery efficiency of 51.7 % at the 10th cycle in the MCDI cell was observed for M20 (20% by wt resin). Using the prepared membrane in the CDI system has the potential to remove Cu2+ from the solution selectively.

Integrated sulfonated poly ether ketone membrane capacitive deionization for lithium recovery from diluted binary solutions

To harness the abundant lithium (Li)-containing aqueous resources and meet the growing demand for Li, membrane-based processes for selective Li recovery have garnered extensive attention. The incorporation of sulfonate groups into membranes is a crucial strategy for fine-tuning ion selectivity, which has been widely used in nanofiltration and electrodialysis for Li separation; however, its potential in the membrane capacitive deionization (MCDI) process for Li recovery remains largely unexplored. This study bridges this research gap by integrating activated carbon (AC) electrodes of capacitive deionization (CDI) with sulfonate poly ether ketone (SPEK) membranes, featuring varying degrees of sulfonation (SPEK-20, SPEK-40, and SPEK-60), and evaluating their Li recovery performance using Li/M (M representing competing cations such as Na, K, Mg, Ca) binary solutions. The synthesized membrane electrodes underwent thorough characterization, confirming the successful formation of sulfonate groups in the SPEK membrane, revealing the SPEK layer with a cross-section thickness below 10 µm, and identifying the hydrophilicity of the AC/SPEK electrode surface. The MCDI results unveiled the significant impact of incorporating SPEK membranes on Li recovery performance in monovalent-cation competing feeds compared to bare AC electrodes, boosting the Li removal rate and Li selectivity in Li/K feed by over 210 % and 120 %, respectively. Meanwhile, SPEK membranes demonstrate a preferable affinity for capturing and releasing divalent ions, with the variations in sulfonation degree exerting a greater influence on cases involving divalent cations.

Evaluating boron removal from aqueous solutions using membrane capacitive deionization (MCDI): Efficacy and limitations

In the present study, the feasibility of employing activated carbon-based membrane capacitive deionization (MCDI) for boron removal was systematically evaluated under various conditions, including different applied voltages, pH levels, initial boron concentrations, and boron-to-chloride molar ratios. When the pH of the solution exceeds 9, borate ions with a negative charge become the predominant species, facilitating easier removal during the charging period of both capacitive deionization (CDI) and MCDI. As demonstrated, MCDI can achieve a relatively higher mean deionization capacity of 2.84±0.19 mg/g at 1.2 V and pH 11, associated with a corresponding high charge efficiency of 99% and low energy consumption of 0.04 kWh/m3. More specifically, the results revealed a significant improvement in boron removal performance with the incorporation of ion exchange membranes into CDI. Additionally, MCDI exhibited considerably higher selectivity of boron over chloride ions compared to CDI, attributed to the charge promotion effect. However, the selectivity coefficient of boron over chloride was still need to be improved, identified as the primary constraint of MCDI. With the same ionic charge, chloride with smaller hydrated radius compared to boron was preferentially electrosorbed, thereby suppressing the electrosorption of borate ions. These findings suggest potential future directions for the treatment of boron in practical applications such as seawater desalination and wastewater reclamation in the semiconductor industry.

Assessing the suitability of desalination techniques for hydraulic barriers

Seawater intrusion is a worldwide increasing challenge, which lowers the freshwater availability by salination of fresh groundwater resources in coastal areas. The abstraction-desalination-recharge (ADR) methodology can combat seawater intrusion, whereby desalination is hereby the key factor for the overall efficiency of aquifer remediation. Which desalination technique is suitable within ADR depends on several factors and was not discussed before. We use a multi-criteria decision analysis and cost analysis to compare nanofiltration, reverse osmosis, electrodialysis, and (membrane) capacitive deionization and show for three case scenarios which desalination technique is most suitable within ADR. Overall, electrodialysis, nanofiltration, and reverse osmosis have shown the best utility value for saline groundwater salinity of 1–10 g L−1, whereby electrodialysis is more suitable for lower salinities. The lowest desalination costs are calculated for nanofiltration and reverse osmosis with 0.3–0.6 € m−3 depending on specific energy costs. Even capacitive deionisation can be a suitable alternative for low, slightly saline groundwater (1 g L−1) if the technology readiness level and a lifetime of electrodes increase and material costs decrease. These new insights provide a data analysis, costs, and decision support for desalination which are needed for the holistic approach to counteract seawater intrusion.