Emerging Frontiers in Multichannel Membrane Capacitive Deionization: Recent Advances and Future Prospects.

Capacitive deionization (CDI) has emerged as a promising desalination technology and recently promoted the development of multichannel membrane capacitive deionization (MC-MCDI). In MC-MCDI, the independent control of multiflow channels, including the feed and electrolyte channels, enables the optimization of electrode operation in various modes, such as concentration gradients and reverse voltage discharge, facilitating semicontinuous operation. Moreover, the integration of redox couples into MC-MCDI has led to advancements in redox-mediated desalination. Specifically, the introduction of redox-active species helps enhance the ion removal efficiency and reduce energy consumption during desalination. This systematic approach, combining principles from CDI and electrodialysis, results in more sustainable and efficient desalination. These advancements have contributed to improved desalination performance and practical feasibility, rendering MC-MCDI an increasingly attractive option for addressing water scarcity challenges. Despite the considerable interest in and potential of this process, there is currently no comprehensive review available that covers the operational features and applications of MC-MCDI. Therefore, this Review provides an overview of recent research progress, focusing on the unique cell configuration, vital operation principles, and potential advantages over conventional CDI. Additionally, innovative applications of MC-MCDI are discussed. The Review concludes with insights into future research directions, potential opportunities in industrial desalination technology, and the fundamental and practical challenges for successful implementation.

A New Family of Layered Metal-Organic Semiconductors: Cu/V-Organophosphonates.

Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2 O)2 V(µ-O)(PPA)2 ] (where PPA is phenylphosphonate). The crystal structure of [Cu(H2 O)2 V(µ-O)(PPA)2 ] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H2 O)2 V(µ-O)(PPA)2 ] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H2 O)2 V(µ-O)(PPA)2 ] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m-1 . Temperature-dependent magnetization measurements show that [Cu(H2 O)2 V(µ-O)(PPA)2 ] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H2 O)2 V(µ-O)(PPA)2 ] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H2 O)2 V(µ-O)(PPA)2 ] shows high electrochemical, and thermal stability.

Dual-Use of Seawater Batteries for Energy Storage and Water Desalination.

Seawater batteries are unique energy storage systems for sustainable renewable energy storage by directly utilizing seawater as a source for converting electrical energy and chemical energy. This technology is a sustainable and cost-effective alternative to lithium-ion batteries, benefitting from seawater-abundant sodium as the charge-transfer ions. Research has significantly improved and revised the performance of this type of battery over the last few years. However, fundamental limitations of the technology remain to be overcome in future studies to make this method even more viable. Disadvantages include degradation of the anode materials or limited membrane stability in aqueous saltwater resulting in low electrochemical performance and low Coulombic efficiency. The use of seawater batteries exceeds the application for energy storage. The electrochemical immobilization of ions intrinsic to the operation of seawater batteries is also an effective mechanism for direct seawater desalination. The high charge/discharge efficiency and energy recovery make seawater batteries an attractive water remediation technology. Here, the seawater battery components and the parameters used to evaluate their energy storage and water desalination performances are reviewed. Approaches to overcoming stability issues and low voltage efficiency are also introduced. Finally, an overview of potential applications, particularly in desalination technology, is provided.

Pseudocapacitance: From Fundamental Understanding to High Power Energy Storage Materials.

There is an urgent global need for electrochemical energy storage that includes materials that can provide simultaneous high power and high energy density. One strategy to achieve this goal is with pseudocapacitive materials that take advantage of reversible surface or near-surface Faradaic reactions to store charge. This allows them to surpass the capacity limitations of electrical double-layer capacitors and the mass transfer limitations of batteries. The past decade has seen tremendous growth in the understanding of pseudocapacitance as well as materials that exhibit this phenomenon. The purpose of this Review is to examine the fundamental development of the concept of pseudocapacitance and how it came to prominence in electrochemical energy storage as well as to describe new classes of materials whose electrochemical energy storage behavior can be described as pseudocapacitive.

Nanoporous Block Copolymer Membranes with Enhanced Solvent Resistance Via UV-Mediated Cross-Linking Strategies.

In this work, a block copolymer (BCP) consisting of poly((butyl methacrylate-co-benzophenone methacrylate-co-methyl methacrylate)-block-(2-hydroxyethyl methacrylate)) (P(BMA-co-BPMA-co-MMA)-b-P(HEMA)) is prepared by a two-step atom-transfer radical polymerization (ATRP) procedure. BCP membranes are fabricated applying the self-assembly and nonsolvent induced phase separation (SNIPS) process from a ternary solvent mixture of tetrahydrofuran (THF), 1,4-dioxane, and dimethylformamide (DMF). The presence of a porous top layer of the integral asymmetric membrane featuring pores of about 30 nm is confirmed via scanning electron microscopy (SEM). UV-mediated cross-linking protocols for the nanoporous membrane are adjusted to maintain the open and isoporous top layer. The swelling capability of the noncross-linked and cross-linked BCP membranes is investigated in water, water/ethanol mixture (1:1), and pure ethanol using atomic force microscopy, proving a stabilizing effect of the UV cross-linking on the porous structures. Finally, the influence of the herein described cross-linking protocols on water-flux measurements for the obtained membranes is explored. As a result, an increased swelling resistance for all tested solvents is found, leading to an increased water flux compared to the pristine membrane. The herein established UV-mediated cross-linking protocol is expected to pave the way to a new generation of porous and stabilized membranes within the fields of separation technologies.

Dye-Loaded Mechanochromic and pH-Responsive Elastomeric Opal Films.

In this work, the preparation and fabrication of elastomeric opal films revealing reversible mechanochromic and pH-responsive features are reported. The core-interlayer-shell (CIS) particles are synthesized via stepwise emulsion polymerization leading to hard core (polystyrene), crosslinked interlayer (poly(methyl methacrylate-co-allyl methacrylate), and soft poly(ethyl acrylate-co-butyl acrylate-co-(2-hydroxyethyl) methacrylate) shell particles featuring a size of 294.9 ± 14.8 nm. This particle architecture enables the application of the melt-shear organization technique leading to elastomeric opal films with orange, respectively, green brilliant reflection colors dependent on the angle of view. Moreover, the hydroxyl moieties as part of the particle shell are advantageously used for subsequent thermally induced crosslinking reactions enabling the preparation of reversibly tunable mechanochromic structural colors based on Bragg's law of diffraction. Additionally, the CIS particles can be loaded upon extrusion or chemically by a postfunctionalization strategy with organic dyes implying pH-responsive features. This convenient protocol for preparing multi-responsive, reversibly stretch-tunable opal films is expected to enable a new material family for anti-counterfeiting applications based on external triggers.

Rings and Chains: Synthesis and Characterization of Polyferrocenylmethylene.

The synthesis and characterization of polyferrocenylmethylene (PFM) starting from dilithium 2,2-bis(cyclopentadienide)propane and a Me2 C[1]magnesocenophane is reported. Molecular weights of up to Mw  = 11 700 g mol-1 featuring a dispersity, Ð, of 1.40 can be achieved. The material is studied by different methods comprising nuclear magnetic resonance (NMR) spectroscopy, matrix-assisted laser desorption/ionization time of flight (MALDI-ToF) mass spectrometry, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) measurements elucidating the molecular structure and thermal properties of these novel polymers. Moreover, cyclic voltammetry (CV) reveals quasi-reversible oxidation and reduction behavior and communication between the iron centers. Also, the crystal structure of a related cyclic hexamer is presented.

Design of Carbon/Metal Oxide Hybrids for Electrochemical Energy Storage.

Next generation electrochemical energy storage materials that enable a combination of high specific energy, specific power, and cycling stability can be obtained by a hybridization approach. This involves electrode materials that contain carbon and metal oxide phases linked on a nanoscopic level and combine characteristics of supercapacitors and batteries. The combination of the components requires careful design to create synergistic effects for an increased electrochemical performance. Improved understanding of the role of carbon as a substrate has advanced the power handling and cycling stability of hybrid materials significantly in recent years. This Concept outlines different design strategies for the design of hybrid electrode materials: (1) the deposition of metal oxides on readily existing carbon substrates and (2) co-synthesizing both carbon and metal oxide phase during the synthesis procedure. The implications of carbon properties on the hybrid material's structure and performance will be assessed and the impact of the hybrid electrode architecture will be analyzed. The advantages and disadvantages of all approaches are highlighted and strategies to overcome the latter will be proposed.

Ordered Mesoporous Titania/Carbon Hybrid Monoliths for Lithium-ion Battery Anodes with High Areal and Volumetric Capacity.

Free-standing, binder-free, and conductive additive-free mesoporous titanium dioxide/carbon hybrid electrodes were prepared from co-assembly of a poly(isoprene)-block-poly(styrene)-block-poly(ethylene oxide) block copolymer and a titanium alkoxide. By tailoring an optimized morphology, we prepared macroscopic mechanically stable 300 µm thick monoliths that were directly employed as lithium-ion battery electrodes. High areal mass loading of up to 26.4 mg cm-2 and a high bulk density of 0.88 g cm-3 were obtained. This resulted in a highly increased volumetric capacity of 155 mAh cm-3 , compared to cast thin film electrodes. Further, the areal capacity of 4.5 mAh cm-2 represented a 9-fold increase compared to conventionally cast electrodes. These attractive performance metrics are related to the superior electrolyte transport and shortened diffusion lengths provided by the interconnected mesoporous nature of the monolith material, assuring superior rate handling, even at high cycling rates.

In Situ Tracking of Partial Sodium Desolvation of Materials with Capacitive, Pseudocapacitive, and Battery-like Charge/Discharge Behavior in Aqueous Electrolytes.

Aqueous electrolytes can be used for electrical double-layer capacitors, pseudocapacitors, and intercalation-type batteries. These technologies may employ different electrode materials, most importantly high-surface-area nanoporous carbon, two-dimensional materials, and metal oxides. All of these materials also find more and more applications in electrochemical desalination devices. During the electrochemical operation of such electrode materials, charge storage and ion immobilization are accomplished by non-Faradaic ion electrosorption, Faradaic ion intercalation at specific crystallographic sites, or ion insertion between layers of two-dimensional materials. These processes may or may not be associated with a (partial) loss of the aqueous solvation shell around the ions. Our work showcases the electrochemical quartz crystal microbalance as an excellent tool for quantifying the change in effective solvation. We chose sodium as an important cation for energy storage materials (sodium-based aqueous electrolytes) and electrochemical desalination (saline media). Our data show that a major amount of water uptake occurs during ion electrosorption in nanoporous carbon, while battery-like ion insertion between layers of titanium disulfide is associated with an 80% loss of the initially present solvation molecules. Sodiation of MXene is accomplished by a loss of 90% of the number of solvent molecules, but nanoconfined water in-between the MXene layers may compensate for this large degree of desolvation. In the case of sodium manganese oxide, we were able to demonstrate the full loss of the solvation shell.

In situ hydrodynamic spectroscopy for structure characterization of porous energy storage electrodes.

A primary atomic-scale effect accompanying Li-ion insertion into rechargeable battery electrodes is a significant intercalation-induced change of the unit cell volume of the crystalline material. This generates a variety of secondary multiscale dimensional changes and causes a deterioration in the energy storage performance stability. Although traditional in situ height-sensing techniques (atomic force microscopy or electrochemical dilatometry) are able to sense electrode thickness changes at a nanometre scale, they are much less informative concerning intercalation-induced changes of the porous electrode structure at a mesoscopic scale. Based on a electrochemical quartz-crystal microbalance with dissipation monitoring on multiple overtone orders, herein we introduce an in situ hydrodynamic spectroscopic method for porous electrode structure characterization. This new method will enable future developments and applications in the fields of battery and supercapacitor research, especially for diagnostics of viscoelastic properties of binders for composite electrodes and probing the micromechanical stability of their internal electrode porous structure and interfaces.

Mechanochemistry-assisted synthesis of hierarchical porous carbons applied as supercapacitors.

A solvent-free synthesis of hierarchical porous carbons is conducted by a facile and fast mechanochemical reaction in a ball mill. By means of a mechanochemical ball-milling approach, we obtained titanium(IV) citrate-based polymers, which have been processed via high temperature chlorine treatment to hierarchical porous carbons with a high specific surface area of up to 1814 m2 g-1 and well-defined pore structures. The carbons are applied as electrode materials in electric double-layer capacitors showing high specific capacitances with 98 F g-1 in organic and 138 F g-1 in an ionic liquid electrolyte as well as good rate capabilities, maintaining 87% of the initial capacitance with 1 M TEA-BF4 in acetonitrile (ACN) and 81% at 10 A g-1 in EMIM-BF4.

Non-invasive in†situ dynamic monitoring of elastic properties of composite battery electrodes by EQCM-D.

Reversible Li-ion intercalation into composite Li-ion battery (LIB) electrodes is often accompanied by significant dimensional electrode changes (deformation) resulting in significant deterioration of the cycling performance. Viscoelastic properties of polymeric binders affected by intercalation-induced deformation of composite LIB electrodes have never been probed in situ on operating electrochemical cells. Here, we introduce a newly developed noninvasive method, namely electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D), for in situ monitoring of elastic properties of polymeric binders during charging of LIB electrodes. As such, we find EQCM-D as a uniquely suitable tool to track the binder's structural rigidity/softness in composite Li insertion electrodes in real-time by the characteristic increase/decrease of the dissipation factor during the charging-discharging process. The binders partially swollen in aprotic solutions demonstrate intermediate viscoelastic charge-rate-dependent behavior, revealing rigid/soft behavior at high/low charging rates, respectively. The method can be adjusted for continuous monitoring of elastic properties of the polymeric binders over the entire LIB electrodes cycling life.

An electrochemical in situ study of freezing and thawing of ionic liquids in carbon nanopores.

Room temperature ionic liquids (RTILs) are an emerging class of electrolytes enabling high cell voltages and, in return, high energy density of advanced supercapacitors. Yet, the low temperature behavior, including freezing and thawing, is little understood when ions are confined in the narrow space of nanopores. This study shows that RTILs may show a tremendously different thermal behavior when comparing bulk with nanoconfined properties as a result of the increased surface energy of carbon pore walls. In particular, a continuous increase in viscosity is accompanied by slowed-down charge-discharge kinetics as seen with in situ electrochemical characterization. Freezing reversibly collapses the energy storage ability and thawing fully restores the initial energy density of the material. For the first time, a different thermal behavior in positively and negatively polarized electrodes is demonstrated. This leads to different freezing and melting points in the two electrodes. Compared to bulk, RTILs in the confinement of electrically charged nanopores show a high affinity for supercooling; that is, the electrode may freeze during heating.

High-Performance Lithium-Ion Batteries with High Stability Derived from Titanium-Oxide- and Sulfur-Loaded Carbon Spherogels.

This study presents a novel approach to developing high-performance lithium-ion battery electrodes by loading titania-carbon hybrid spherogels with sulfur. The resulting hybrid materials combine high charge storage capacity, electrical conductivity, and core-shell morphology, enabling the development of next-generation battery electrodes. We obtained homogeneous carbon spheres caging crystalline titania particles and sulfur using a template-assisted sol-gel route and carefully treated the titania-loaded carbon spherogels with hydrogen sulfide. The carbon shells maintain their microporous hollow sphere morphology, allowing for efficient sulfur deposition while protecting the titania crystals. By adjusting the sulfur impregnation of the carbon sphere and varying the titania loading, we achieved excellent lithium storage properties by successfully cycling encapsulated sulfur in the sphere while benefiting from the lithiation of titania particles. Without adding a conductive component, the optimized material provided after 150 cycles at a specific current of 250 mA g-1 a specific capacity of 825 mAh g-1 with a Coulombic efficiency of 98%.

Black goes green: single-step solvent exchange for sol-gel synthesis of carbon spherogels as high-performance supercapacitor electrodes.

Nanoporous carbon materials with customized structural features enable sustainable and electrochemical applications through improved performance and efficiency. Carbon spherogels (highly porous carbon aerogel materials consisting of an assembly of hollow carbon nanosphere units with uniform diameters) are desirable candidates as they combine exceptional electrical conductivity, bespoke shell porosity, tunability of the shell thickness, and a high surface area. Herein, we introduce a novel and more environmentally friendly sol-gel synthesis of resorcinol-formaldehyde (RF) templated by polystyrene spheres, forming carbon spherogels in an organic solvent. By tailoring the molar ratio of resorcinol to isopropyl alcohol (R/IPA) and the concentration of polystyrene, the appropriate synthesis conditions were identified to produce carbon spherogels with adjustable wall thicknesses. A single-step solvent exchange process from deionized water to isopropyl alcohol reduces surface tension within the porous gel network, making this approach significantly time and cost-effective. The lower surface tension of IPA enables solvent extraction under ambient conditions, allowing for direct carbonization of RF gels while maintaining a specific surface area loss of less than 20% compared to supercritically dried counterparts. The specific surface areas obtained after physical activation with carbon dioxide are 2300-3600 m2 g-1. Transmission and scanning electron microscopy verify the uniform, hollow carbon sphere network morphology. Specifically, those carbon spherogels are high-performing electrodes for energy storage in a supercapacitor setup featuring a specific capacitance of up to 204 F g-1 at 200 mA g-1 using 1 M potassium hydroxide (KOH) solution as the electrolyte.

Removal of Mo(VI), Pb(II), and Cu(II) from wastewater using electrospun cellulose acetate/chitosan biopolymer fibers.

Environmentally friendly polymers such as cellulose acetate (CA) and chitosan (CS) were used to obtain electrospun fibers for Cu2+, Pb2+, and Mo6+ capture. The solvents dichloromethane (DCM) and dimethylformamide (DMF) allowed the development of a surface area of 148 m2 g-1 for CA fibers and 113 m2 g-1 for cellulose acetate/chitosan (CA/CS) fibers. The fibers were characterized by IR-DRIFT, SEM, TEM, CO2 sorption isotherms at 273 K, Hg porosimetry, TGA, stress-strain tests, and XPS. The CA/CS fibers had a higher adsorption capacity than CA fibers without affecting their physicochemical properties. The capture capacity reached 102 mg g-1 for Cu2+, 49.3 mg g-1 for Pb2+, and 13.1 mg g-1 for Mo6+. Furthermore, optimal pH, adsorption times qt, and C0 were studied for the evaluation of kinetic models and adsorption isotherms. Finally, a proposal for adsorbate-adsorbent interactions is presented as a possible capture mechanism where, in the case of Mo6+, a computational study is presented. The results demonstrate the potential to evaluate the fibers in tailings wastewater from copper mining.

Nitrogen-Doped Graphene-Like Carbon Intercalated MXene Heterostructure Electrodes for Enhanced Sodium- and Lithium-Ion Storage.

MXene is investigated as an electrode material for different energy storage systems due to layered structures and metal-like electrical conductivity. Experimental results show MXenes possess excellent cycling performance as anode materials, especially at large current densities. However, the reversible capacity is relatively low, which is a significant barrier to meeting the demands of industrial applications. This work synthesizes N-doped graphene-like carbon (NGC) intercalated Ti3C2Tx (NGC-Ti3C2Tx) van der Waals heterostructure by an in situ method. The as-prepared NGC-Ti3C2Tx van der Waals heterostructure is employed as sodium-ion and lithium-ion battery electrodes. For sodium-ion batteries, a reversible specific capacity of 305 mAh g-1 is achieved at a specific current of 20 mA g-1, 2.3 times higher than that of Ti3C2Tx. For lithium-ion batteries, a reversible capacity of 400 mAh g-1 at a specific current of 20 mA g-1 is 1.5 times higher than that of Ti3C2Tx. Both sodium-ion and lithium-ion batteries made from NGC-Ti3C2Tx shows high cycling stability. The theoretical calculations also verify the remarkable improvement in battery capacity within the NGC-Ti3C2O2 system, attributed to the additional adsorption of working ions at the edge states of NGC. This work offers an innovative way to synthesize a new van der Waals heterostructure and provides a new route to improve the electrochemical performance significantly.

Nuclear magnetic resonance study of ion adsorption on microporous carbide-derived carbon.

A detailed understanding of ion adsorption within porous carbon is key to the design and improvement of electric double-layer capacitors, more commonly known as supercapacitors. In this work nuclear magnetic resonance (NMR) spectroscopy is used to study ion adsorption in porous carbide-derived carbons. These predominantly microporous materials have a tuneable pore size which enables a systematic study of the effect of pore size on ion adsorption. Multinuclear NMR experiments performed on the electrolyte anions and cations reveal two main environments inside the carbon. In-pore ions (observed at low frequencies) are adsorbed inside the pores, whilst ex-pore ions (observed at higher frequencies) are not adsorbed and are in large reservoirs of electrolyte between carbon particles. All our experiments were carried out in the absence of an applied electrical potential in order to assess the mechanisms related to ion adsorption without the contribution of electrosorption. Our results indicate similar adsorption behaviour for anions and cations. Furthermore, we probe the effect of sample orientation, which is shown to have a marked effect on the NMR spectra. Finally, we show that a (13)C →(1)H cross polarisation experiment enables magnetisation transfer from the carbon architecture to the adsorbed species, allowing selective observation of the adsorbed ions and confirming our spectral assignments.

Horn-like Pore Entrance Boosts Charging Dynamics and Charge Storage of Nanoporous Supercapacitors.

Optimizing the synergy between nanoporous carbons and ionic liquids can significantly enhance the energy density of supercapacitors. The highest energy density has been obtained as the size of porous carbon matches the size of ionic liquids, while it may result in slower charging dynamics and thus reduce the power density. Enhancing energy storage without retarding charging dynamics remains challenging. Herein, we designed porous electrodes by introducing an optimized horn-like entrance to the nanopore, which can concurrently improve supercapacitors' charging dynamics and energy storage. Our results revealed the mechanism of improved charging lies in the gradual desolvation process and optimized ion motion paths: the former expedites the adsorption of the counterion by reducing the transitional energy barrier for ions entering the pores, and the latter accelerates the co-ion desorption and eliminates ion overfilling. Meanwhile, the enhancement of energy density could be attributed to the multi-ion coordinated migration.