Efficient experimental method for purifying allergens from aqueous extracts.

Studying the molecular and immunological basis of allergic diseases often requires purified native allergens. The methodologies for protein purification are usually difficult and may not be completely successful. The objective of this work was to describe a methodology to purify allergens from their natural source, while maintaining their native form. The purification strategy consists of a three-step protocol and was used for purifying five specific allergens, Ole e 1, Amb a 1, Alt a 1, Bet v 1 and Cup a 1. Total proteins were extracted in PBS (pH 7.2). Then, the target allergens were pre-purified and enriched by salting-out using increasing concentrations of ammonium sulfate. The allergens were further purified by anion exchange chromatography. Purification of Amb a 1 required an extra step of cation exchange chromatography. The detection of the allergens in the fractions obtained were screened by SDS-PAGE, and Western blot when needed. Further characterization of purified Amb a 1 was performed by mass spectrometry. Ole e 1, Alt a 1, Bet v 1 and Cup a 1 were obtained at > 90 % purity. Amb a 1 was obtained at > 85 % purity. Overall, we propose an easy-to-perform purification approach that allows obtaining highly pure allergens. Since it does not involve neither chaotropic nor organic reagents, we anticipate that the structural and biological functions of the purified molecule remain intact. This method provides a basis for native allergen purification that can be tailored according to specific needs.

Online Mixed-Bed Ion Exchange Chromatography for Native Top-Down Proteomics of Complex Mixtures.

Native top-down mass spectrometry (nTDMS) allows characterization of protein structure and noncovalent interactions with simultaneous sequence mapping and proteoform characterization. The majority of nTDMS studies utilize purified recombinant proteins, with significant challenges hindering application to endogenous systems. To perform native top-down proteomics (nTDP), where endogenous proteins from complex biological systems are analyzed by nTDMS, it is essential to separate proteins under nondenaturing conditions. However, it remains difficult to achieve high resolution with MS-compatible online chromatography while preserving protein tertiary structure and noncovalent interactions. Herein, we report the use of online mixed-bed ion exchange chromatography (IEC) to enable separation of endogenous proteins from complex mixtures under nondenaturing conditions, preserving noncovalent interactions for nTDP analysis. We have successfully detected large proteins (>146 kDa) and identified endogenous metal-binding and oligomeric protein complexes in human heart tissue lysate. The use of a mixed-bed stationary phase allowed retention and elution of proteins over a wide range of isoelectric points without altering the sample or mobile phase pH. Overall, our method provides a simple online IEC-MS platform that can effectively separate proteins from complex mixtures under nondenaturing conditions and preserve higher-order structure for nTDP applications.

Profiling Protein-Protein Interactions in the Human Brain by Refined Cofractionation Mass Spectrometry.

Proteins usually execute their biological functions through interactions with other proteins and by forming macromolecular complexes, but global profiling of protein complexes directly from human tissue samples has been limited. In this study, we utilized cofractionation mass spectrometry (CF-MS) to map protein complexes within the postmortem human brain with experimental replicates. First, we used concatenated anion and cation Ion Exchange Chromatography (IEX) to separate native protein complexes in 192 fractions and then proceeded with Data-Independent Acquisition (DIA) mass spectrometry to analyze the proteins in each fraction, quantifying a total of 4,804 proteins with 3,260 overlapping in both replicates. We improved the DIA's quantitative accuracy by implementing a constant amount of bovine serum albumin (BSA) in each fraction as an internal standard. Next, advanced computational pipelines, which integrate both a database-based complex analysis and an unbiased protein-protein interaction (PPI) search, were applied to identify protein complexes and construct protein-protein interaction networks in the human brain. Our study led to the identification of 486 protein complexes and 10054 binary protein-protein interactions, which represents the first global profiling of human brain PPIs using CF-MS. Overall, this study offers a resource and tool for a wide range of human brain research, including the identification of disease-specific protein complexes in the future.

Empirical Confirmation of Theoretical Predictions for Amorphous H/VO4 Cathodes: Advancing Durability and Efficiency in Zinc-Ion Batteries.

Advancing cathode materials is crucial for the broader application of aqueous zinc-ion batteries (ZIBs) in energy storage systems. This study presents amorphous H/VO4 (HVO), a novel cathode material engineered by substituting H+ for Mg2+ in Mg2VO4 (MgVO), designed to enhance performance of ZIBs. Initial exploration of MgVO through ab initio molecular dynamics (AIMD) simulations and density functional theory (DFT) calculations revealed a favorable Mg2+ and Zn2+ exchange mechanism. This mechanism notably reduces electrostatic interactions and facilitates ion diffusion within the host lattice. Building upon these findings, in this work, theoretical calculations analysis indicated that amorphous HVO offers a higher diffusion coefficient for Zn2+ ions and fewer electrostatic interactions compared to its crystalline MgVO precursor. Subsequent empirical validation is achieved by synthesizing amorphous HVO using a rapid ion-exchange process, effectively replacing Mg2+ with H+ ions. The synthesized amorphous HVO demonstrated 100% capacity retention after 18000 cycles at a current density of 2 A g-1 and exhibited exceptional rate performance. These findings underscore the significant potential of HVO cathodes to enhance the durability and efficiency of aqueous ZIBs, positioning them as promising candidates for future energy storage technologies.

Spontaneous Compositional-Interfacial Co-Modification Engineering via Ion Exchange Reaction Between Perovskite and Electron-Transporting Layer for Exceptionally Long-Term Stability of Photovoltaics.

The long-term stability of perovskite solar cells (PSCs) is still challenging for commercialization and mainly linked to the life span of perovskite films. Herein, a spontaneous compositional-interfacial co-modification strategy is developed based on the ion exchange reaction by introducing ammonium hexafluorophosphate (NH4PF6) into antisolvent to form gradient structures through a simple one-step solvent engineering. With the assistance of the ion exchange reaction, NH4PF6 forms a multifunctional structure to protect perovskite films from both internal and external factors for the exceptionally long-term stability of photovoltaics. The reason for this is linked to the high hydrophobicity of NH4PF6 for preventing H2O invasion, suppressing ion migration by forming hydrogen bonding, and reducing perovskite defects. The resulting unencapsulated devices show exceptionally long-term stability under standardized the International Summit on Organic Photovoltaic Stability (ISOS) protocols, with over 94%, 81%, and 83% retained power conversion efficiencies after aging tests under N2 (ISOS-D-1I), ambient air (ISOS-D-1), and 85 °C (ISOS-D-2I) for 14016, 2500, and 1248 h, respectively. These performances compare well with the state-of-the-art stability of inverted PSCs. Further investigations are conducted to study the evolution of macroscopic morphology and microscopic crystal structure in aged perovskite films, aiming to provide evidence supporting the aforementioned improvements in stability.

Amorphous K-Co-Mo-Sx Chalcogel: A Synergy of Surface Sorption and Ion-Exchange.

Chalcogel represents a unique class of meso- to macroporous nanomaterials that offer applications in energy and environmental pursuits. Here, the synthesis of an ion-exchangeable amorphous chalcogel using a nominal composition of K2CoMo2S10 (KCMS) at room temperature is reported. Synchrotron X-ray pair distribution function (PDF), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) reveal a plausible local structure of KCMS gel consisting of Mo5+ 2 and Mo4+ 3 clusters in the vicinity of di/polysulfides which are covalently linked by Co2+ ions. The ionically bound K+ ions remain in the percolating pores of the Co-Mo-S covalent network. XANES of Co K-edge shows multiple electronic transitions, including quadrupole (1s→3d), shakedown (1s→4p + MLCT), and dipole allowed 1s→4p transitions. Remarkably, despite a lack of regular channels as in some crystalline solids, the amorphous KCMS gel shows ion-exchange properties with UO2 2+ ions. Additionally, it also presents surface sorption via [S∙∙∙∙UO2 2+] covalent interactions. Overall, this study underscores the synthesis of quaternary chalcogels incorporating alkali metals and their potential to advance separation science for cations and oxo-cationic species by integrating a synergy of surface sorption and ion-exchange.

Artificial Multi-Stimulus-Responsive E-Skin Based on an Ionic Film with a Counter-Ion Exchange Reagent.

Sensing pressure and temperature are two important functions of human skin that integrate different types of tactile receptors. In this paper, a deformable artificial flexible multi-stimulus-responsive sensor is demonstrated that can distinguish mechanical pressure from temperature by measuring the impedance and the electrical phase at the same frequency without signal interference. The electrical phase, which is used for measuring the temperature, is totally independent of the pressure by controlling the surface micro-shapes and the ion content of the ionic film. By doping the counter-ion exchange reagent into the ionic liquid before pouring, the upper temperature measuring limit increases from 35 to 50 °C, which is higher than the human body temperature and the ambient temperature on Earth. The sensor shows high sensitivity to pressure (up to 0.495 kPa-1) and a wide temperature sensing range (-10 to 50 °C). A multimodal ion-electronic skin (IEM-skin) with an 8 × 8 multi-stimulus-responsive sensor array is fabricated and can successfully sense the distribution of temperature and pressure at the same time. Finally, the sensors are used for monitoring the touching motions of a robot-arm finger controlled by a remote interactive glove and successfully detect the touching states and the temperature changes of different objects.

Colloidal CsBr Nanocrystals Triggered Inorganic Cation and Anion Exchange Enables High-Performance Perovskite Solar Cells.

Achieving longitudinal doping of specific ions by surface treatment remains a challenge for perovskite solar cells, which are often limited by dopant and solvent compatibility. Here, with the flowing environment created by CsBr colloidal nanocrystals, ion exchange is induced on the surface of the perovskite film to enable the homogeneous distribution of Cs+ and gradient distribution of Br- simultaneously at whole depth of the film. Meanwhile, assisted by long-chain organic ligands, the excess PbI2 on the surface of perovskite film is converted to a more stable quasi-2D perovskite, which realizes effective passivation of defects on the surface. As a result, the unfavorable n-type doping on the top surface is suppressed, so that the energy level alignment between perovskite and hole transport layer is optimized. On the basis of co-modification of the surface and the bulk, the PCE of champion device reaches 23.22% with enhanced VOC of 1.12 V. Device maintains 97.12% of the initial PCE in dark ambient air at 1% RH after 1056 h without encapsulation, and 91.56% of the initial PCE under light illumination of 1 sun in N2 atmosphere for more than 200 h. The approach demonstrated here provides an effective strategy for the nondestructive introduction of inorganic ions in perovskite film.

Unleashing the Power of Osmotic Energy: Metal Hydroxide-Organic Framework Membranes for Efficient Conversion.

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.

Proton Exchange Membranes from Sulfonated Lignin Nanocomposites for Redox Flow Battery Applications.

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.

Influence of the isolation method on characteristics and functional activity of mesenchymal stromal cell-derived extracellular vesicles.

BACKGROUND AIMS: Extracellular vesicle (EV) isolation methods are based on different physicochemical properties and may result in the purification of distinct EV populations. We compared two different isolation methods suitable for producing clinical-grade mesenchymal stromal cell-derived EVs (MSC-EVs)-ion exchange chromatography (IEX) and ultrafiltration (UF)-and evaluated their impact on the composition and functional properties of EVs. METHODS: EVs were purified from conditioned culture medium using an anion exchange resin (IEX) or Amicon filters with a 100-kDa cutoff (UF) (MilliporeSigma, Burlington, MA, USA). We assessed nanoparticle size and distribution by nanoparticle tracking analysis (NTA) and tunable resistive pulse sensing (TRPS) and morphology by transmission electron microscopy. We also measured protein, lipid and total RNA concentration and immunophenotyped both EV populations by flow cytometry (MACSPlex assay; Miltenyi Biotec, Bergisch Gladbach, Germany). Moreover, immunomodulatory activity was tested using a standardized macrophage polarization assay and T-cell stimulation assay. Finally, proteomic analysis and cytokine quantification were carried out to better characterize both EV populations. RESULTS: We found by both TRPS and NTA that IEX and UF yielded a comparable amount of total particles with similar size and distribution. In addition, a similar quantity of lipids was obtained with the two procedures. However, IEX yielded 10-fold higher RNA quantity and a larger amount of proteins than UF. MSC-EVs isolated from IEX and UF were positive for the exosome markers CD9, CD63 and CD81 and showed a comparable surface marker expression pattern. Both populations demonstrated immunomodulatory activity in vitro, as they prevented acquisition of the M1 phenotype in lipopolysaccharide-stimulated macrophages and inhibited acquisition of the activation markers CD69 and CD25 on T cells, but the IEX-EVs exerted a significantly greater immunomodulatory effect on both macrophages and T cells compared with UF-EVs. Proteomic analysis and gene ontology enrichment analysis revealed no major differences between the preparations. Finally, cytokine quantification revealed that IEX-EVs were more enriched in some crucial anti-inflammatory and immunomodulatory cytokines (e.g., IL-2, IL-10, transforming growth factor beta and vascular endothelial growth factor) compared with UF-EVs. CONCLUSIONS: MSC-EVs isolated by IEX and UF displayed similar physicochemical, phenotypic and functional characteristics. In our conditions, both EV populations demonstrated important anti-inflammatory activity in macrophages and T cells. However, IEX-EVs were more potent than UF-EVs, which may indicate the superiority of this method for the production of clinical-grade EVs.

ZnH2P4N8: Case Study on Topochemical Imidonitridophosphate High-Pressure Synthesis.

Nitridophosphates are subject of current research, as they have a broad spectrum of properties and potential applications, such as ion conductors or luminescent materials. Yet, the subclass of imidonitridophosphates has been studied less extensively. The primary reason is that the controlled N-H functionalization of nitridophosphates is not straight forward, making targeted synthesis more challenging. Inspired by the high-pressure (HP) post-synthetic modification of nitridophosphates, we present the topochemical HP deprotonation of phosphorus nitride imides using the high-pressure polymorph ß-PN(NH) as an example. Additional incorporation of Zn2+ results in the first quaternary transition metal imidonitridophosphate ZnH2P4N8. The crystal structure was elucidated by single-crystal X-ray diffraction (SCXRD), energy-dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (PXRD) and solid-state magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). In addition, the presence of H as part of an imide group was confirmed by IR spectroscopy. The potential of this defunctionalization approach for controlling the N-H content is demonstrated by the preparation of partially deprotonated intermediates ZnxH4-2xP4N8 (x≈0.5, 0.85). This topochemical high-pressure reaction represents a promising way to prepare, control and manipulate new imide-based materials without altering their overall anionic framework.

Orthogonal Phase Transfer of Oppositely Charged FeII4L6 Cages.

Coordination cages and their encapsulated cargo can be manoeuvred between immiscible liquid layers in a process referred to as phase transfer. Among the stimuli reported to drive phase transfer, counterion exchange is the most widespread. This method exploits the principle that counterions contribute strongly to the solubility preferences of coordination cages, and involves exchanging hydrophilic and hydrophobic counterions. Nevertheless, phase transfer of anionic cages remains relatively unexplored, as does selective phase transfer of individual cages from mixtures. Here we compare the phase transfer behaviour of two FeII4L6 cages with the same size and geometry, but with opposite charges. As such, this study presents a rare example wherein an anionic cage undergoes phase transfer upon countercation exchange. We then combine these two cages, and demonstrate that their quantitative separation can be achieved by inducing selective phase transfer of either cage. These results represent unprecedented control over the movement of coordination cages between different physical compartments, and are anticipated to inform the development of next-generation supramolecular systems.

Zeolite/Polymer Composites Prepared by Photopolymerization: Effect of Compensation Cations on Opacity and Gas Adsorption Applications.

The fabrication of structured zeolite adsorbents through photopolymerization-based 3D printing which offers a solution to the limitations of conventional shaping techniques has been demonstrated but many parameters still need to be optimized. In this study, we studied the influence of zeolite compensation cations on the photopolymerization and the composite's properties. Modified zeolites (LTA 4 A and FAU 13X exchanged with K+ , Li+ , Sr2+ , Ca2+ or Mg2+ ) were incorporated in PEGDA with BDMK as photoinitiator, and the formulation was cured under mild conditions (LED@405 nm, room temperature, under air). Our results indicate that the nature of zeolite compensation cations affects the colorimetric properties of polymer/zeolite composites: a better translucency parameter results in higher depth of cure. After calcination at 650 °C and complete removal of PEGDA, pure zeolitic monoliths were tested for adsorption of gas molecules of interest (carbon dioxide, dichlorobenzene and water). Structured 4 A and 13X monoliths obtained by 3D printing exhibit comparable adsorption capacity to commercial beads prepared from the same zeolites. This study enhances our understanding of the photopolymerization process involved in the production of polymer/zeolite composites. These composites are used in the fabrication of zeolitic objects through 3D printing, offering potential solutions to various environmental and dental challenges.

Realization of digital twin for dynamic control toward sample variation of ion exchange chromatography in antibody separation.

Digital twin (DT) is a virtual and digital representation of physical objects or processes. In this paper, this concept is applied to dynamic control of the collection window in the ion exchange chromatography (IEC) toward sample variations. A possible structure of a feedforward model-based control DT system was proposed. Initially, a precise IEC mechanistic model was established through experiments, model fitting, and validation. The average root mean square error (RMSE) of fitting and validation was 8.1% and 7.4%, respectively. Then a model-based gradient optimization was performed, resulting in a 70.0% yield with a remarkable 11.2% increase. Subsequently, the DT was established by systematically integrating the model, chromatography system, online high-performance liquid chromatography, and a server computer. The DT was validated under varying load conditions. The results demonstrated that the DT could offer an accurate control with acidic variants proportion and yield difference of less than 2% compared to the offline analysis. The embedding mechanistic model also showed a positive predictive performance with an average RMSE of 11.7% during the DT test under >10% sample variation. Practical scenario tests indicated that tightening the control target could further enhance the DT robustness, achieving over 98% success rate with an average yield of 72.7%. The results demonstrated that the constructed DT could accurately mimic real-world situations and perform an automated and flexible pooling in IEC. Additionally, a detailed methodology for applying DT was summarized.

A new method for the robust expression and single-step purification of dCas9 for CRISPR interference/activation (CRISPRi/a) applications.

CRISPR-Cas9 (Clustered Regularly Interspaced Short Palindromic Repeats-CRISPR associated enzyme 9) is known for its simplicity, versatility, and scalability in genome editing applications. In vitro Cas9, when complexed with sgRNA, binds and cleaves the complementary target sequences with almost perfect precision. The enzyme is exploited for various applications in understanding and changing gene function. dCas9 (deactivated or dead Cas9) is a double mutated version of Cas9 that bears mutations in the nuclease domains of the enzyme and thus cannot cleave the target DNA. dCas9 is equally advantageous since it can alter gene expression using various transcriptional activators CRISPRa and repressors CRISPRi. Additionally, dCas9 can bind to the desired target gene without cleaving it, making it a unique reagent to study the kinetics and stability of RNA-protein-DNA interactions required to design more efficient and specific gene-editing nucleases. An appreciable quantity of pure and homogeneous protein is needed to characterise dCas9 for its structural and functional understanding. This study used an N-terminal acidic tag to express the dCas9 in an E. coli-bacterial host. A simple single-step protocol for robust and efficient production of dCas9 has been described. The study and methods are distinctive as the purification is performed in a single step using inexpensive multi-modal hydroxyapatite chromatography. The purified protein can be used in different in vitro and in vivo studies.

Development of Membranes and Separators to Inhibit Cross-Shuttling of Sulfur in Polysulfide-Based Redox Flow Batteries: A Review.

The global rapid transition from fossil fuels to renewable energy resources necessitates the implementation of long-duration energy storage technologies owing to the intermittent nature of renewable energy sources. Therefore, the deployment of grid-scale energy storage systems is inevitable. Sulfur-based batteries can be exploited as excellent energy storage devices owing to their intrinsic safety, low cost of raw materials, low risk of environmental hazards, and highest theoretical capacities (gravimetric: 2600 Wh/kg and volumetric: 2800 Wh/L). However, sulfur-based batteries exhibit certain scientific limitations, such as polysulfide crossover, which causes rapid capacity decay and low Coulombic efficiency, thereby hindering their implementation at a commercial scale. In this review article, we focus on the latest research developments between 2012-2023 to improve the separators/membranes and overcome the shuttle effect associated with them. Various categories of ion exchange membranes (IEMs) used in redox batteries, particularly polysulfide redox flow batteries and lithium-sulfur batteries, are discussed in detail. Furthermore, advances in IEM constituents are summarized to gain insights into different fundamental strategies for attaining targeted characteristics, and a critical analysis is proposed to highlight their efficiency in mitigating sulfur cross-shuttling issues. Finally, future prospects and recommendations are suggested for future research toward the fabrication of more effective membranes with desired properties.

Open-Framework Vanadate as Efficient Ion Exchanger for Uranyl Removal.

The elimination of uranium from radioactive wastewater is crucial for the safe management and operation of environmental remediation. Here, we present a layered vanadate with high acid/base stability, [Me2NH2]V3O7, as an excellent ion exchanger capturing uranyl from highly complex aqueous solutions. The material possesses an indirect band gap, ferromagnetic characteristic and a flower-like morphology comprising parallel nanosheets. The layered structure of [Me2NH2]V3O7 is predominantly upheld by the H-bond interaction between anionic framework [V3O7]nn- and intercalated [Me2NH2]+. The [Me2NH2]+ within [Me2NH2]V3O7 can be readily exchanged with UO22+. [Me2NH2]V3O7 exhibits high exchange capacity (qm = 176.19 mg/g), fast kinetics (within 15 min), high removal efficiencies (>99%), and good selectivity against an excess of interfering ions. It also displays activity for UO22+ ion exchange over a wide pH range (2.00-7.12). More importantly, [Me2NH2]V3O7 has the capability to effectively remove low-concentration uranium, yielding a residual U concentration of 13 ppb, which falls below the EPA-defined acceptable limit of 30 ppb in typical drinking water. [Me2NH2]V3O7 can also efficiently separate UO22+ from Cs+ or Sr2+ achieving the highest separation factors (SFU/Cs of 589 and SFU/Sr of 227) to date. The BOMD and DFT calculations reveal that the driving force of ion exchange is dominated by the interaction between UO22+ and [V3O7]nn-, whereas the ion exchange rate is influenced by the mobility of UO22+ and [Me2NH2]+. Our experimental findings indicate that [Me2NH2]V3O7 can be considered as a promising uranium scavenger for environmental remediation. Additionally, the simulation results provide valuable mechanistic interpretations for ion exchange and serve as a reference for designing novel ion exchangers.

Toward a Circular Lithium Economy with Electrodialysis: Upcycling Spent Battery Leachates with Selective and Bipolar Ion-Exchange Membranes.

Recycling spent lithium-ion batteries offers a sustainable solution to reduce ecological degradation from mining and mitigate raw material shortages and price volatility. This study investigates using electrodialysis with selective and bipolar ion-exchange membranes to establish a circular economy for lithium-ion batteries. An experimental data set of over 1700 ion concentration measurements across five current densities, two solution compositions, and three pH levels supports the techno-economic analysis. Selective electrodialysis (SED) isolates lithium ions from battery leachates, yielding a 99% Li-pure retentate with 68.8% lithium retention, achieving relative ionic fluxes up to 2.41 for Li+ over transition metal cations and a selectivity of 5.64 over monovalent cations. Bipolar membrane electrodialysis (BMED) converts LiCl into high-purity LiOH and HCl, essential for battery remanufacturing and reducing acid consumption via acid recycling. High current densities reduce ion leakage, achieving lithium leakage as low as 0.03%, though hydronium and hydroxide leakage in BMED remains high at 11-20%. Our analysis projects LiOH production costs between USD 1.1 and 3.6 per kilogram, significantly lower than current prices. Optimal SED and BMED conditions are identified, emphasizing the need to control proton transport in BMED and improve cobalt-lithium separation in SED to enhance cost efficiency.

Membrane Design Principles for Ion-Selective Electrodialysis: An Analysis for Li/Mg Separation.

Selective electrodialysis (ED) is a promising membrane-based process to separate Li+ from Mg2+, which is the most critical step for Li extraction from brine lakes. This study theoretically compares the ED-based Li/Mg separation performance of different monovalent selective cation exchange membranes (CEMs) and nanofiltration (NF) membranes at the coupon scale using a unified mass transport model, i.e., a solution-friction model. We demonstrated that monovalent selective CEMs with a dense surface thin film like a polyamide film are more effective in enhancing the Li/Mg separation performance than those with a loose but highly charged thin film. Polyamide film-coated CEMs when used in ED have a performance similar to that of polyamide-based NF membranes when used in NF. NF membranes, when expected to replace monovalent selective CEMs in ED for Li/Mg separation, will require a thin support layer with low tortuosity and high porosity to reduce the internal concentration polarization. The coupon-scale performance analysis and comparison provide new insights into the design of composite membranes used for ED-based selective ion-ion separation.