Lithium-ion Transport Properties in DMSO and TEGDME: Exploring the Influence of Solvation through Molecular Dynamics and Experiments.

This study explores the properties of aprotic electrolytes via the application of experimental methods, including nuclear magnetic resonance spectroscopy and electrochemical techniques, along with molecular dynamic modeling. The aim is to provide a quantitative description of the physico-chemical properties of two well-established electrolytes (case studies), each exhibiting significantly distinct dielectric properties: a LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide) solution in dimethyl sulfoxide (DMSO, dielectric constant = 46.68) and a LiTFSI solution in tetraethylene glycol dimethyl ether (TEGDME, =7.71). We obtained a comprehensive insight into the properties of the electrolytes at both the macroscopic-collective and molecular levels with particular emphasis on the interactions between the Li ions and solvent molecules. We discovered remarkable disparities in the structural arrangements, solvation behaviors, and bulk-related properties of these electrolyte systems, particularly in response to temperature changes.

Quaternized Graphene for High-Performance Moisture Swing Direct Air Capture of CO2.

Nowadays, moisture-swing adsorption technology still relies on quaternary ammonium resins with limited CO2 capacity under ambient air conditions. In this work, a groundbreaking moisture-driven sorbent is developed starting from commercial graphene flakes and using glycidyltrimethylammonium chloride for incorporation of CO2-sensitive quaternary ammonium functional groups. Boasting an outstanding CO2 capture performance under ultra-diluted conditions (namely, 3.24 mmol g-1 at CO2 400 ppm and 20% RH), the functionalized sorbent (fGO) features clear competitive advantages over current technologies for direct air capture. Notably, fGO demonstrated unprecedented moisture-swing capacity, ease of regenerability, versatility, selectivity, and longevity. These distinctive features position the fGO as an advanced and promising solution, showcasing its potential to outperform existing methods for moisture-swing direct air capture of CO2.

MWCNTs Decorated with TiO2 as Highly Performing Filler in the Preparation of Nanocomposite Membranes for Scalable Photocatalytic Degradation of Bisphenol A in Water.

Bisphenol A (BPA), an endocrine-disrupting compound with estrogenic behavior, is of great concern within the scientific community due to its high production levels and increasing concentration in various surface aquifers. While several materials exhibit excellent capacity for the photocatalytic degradation of BPA, their powdered nature and poor chemical stability render them unsuitable for practical application in large-scale water decontamination. In this study, a new class of nanocomposite membranes based on sulfonated polyethersulfone (sPES) and multiwalled carbon nanotubes decorated with TiO2 nanoparticles (MWCNTs-TiO2) were investigated as efficient and scalable photocatalysts for the photodegradation of BPA in aqueous solutions. The MWCNTs-TiO2 hybrid material was prepared through a facile and inexpensive hydrothermal method and extensively characterized by XRD, Raman, FTIR, BET, and TGA. Meanwhile, nanocomposite membranes at different filler loadings were prepared by a simple casting procedure. Swelling tests and PFG NMR analyses provided insights into the impact of filler introduction on membrane hydrophilicity and water molecular dynamics, whereas the effectiveness of the various photocatalysts in BPA removal was monitored using HPLC. Among the different MWCNTs-TiO2 content nanocomposites, the one at 10 wt% loading (sP-MT10) showed the best photoactivity. Under UV irradiation at 254 nm and 365 nm for 240 min, photocatalytic oxidation of 5 mg/L bisphenol A by sP-MT10 resulted in 91% and 82% degradation, respectively. Both the effect of BPA concentration and the membrane regenerability were evaluated, revealing that the sP-MT10 maintained its maximum BPA removal capability over more than 10 cycles. Our findings indicate that sP-MT nanocomposite membranes are versatile, scalable, efficient, and highly reusable photocatalysts for the degradation of BPA, as well as potentially for other endocrine disruptors.

NMR Investigation of Water Molecular Dynamics in Sulfonated Polysulfone/Layered Double Hydroxide Composite Membranes for Proton Exchange Membrane Fuel Cells.

The development of nanocomposite membranes based on hydrocarbon polymers is emerging as one of the most promising strategies for overcoming the performance, cost, and safety limitations of Nafion, which is the current benchmark in proton exchange membranes for fuel cell applications. Among the various nanocomposite membranes, those based on sulfonated polysulfone (sPSU) and Layered Double Hydroxides (LDHs) hold promise regarding their successful utilization in practical applications due to their interesting electrochemical performance. This study aims to elucidate the effect of LDH introduction on the internal arrangement of water molecules in the hydrophilic clusters of sPSU and on its proton transport properties. Swelling tests, NMR characterization, and Electrochemical Impedance Spectroscopy (EIS) investigation allowed us to demonstrate that LDH platelets act as physical crosslinkers between -SO3H groups of adjacent polymer chains. This increases dimensional stability while simultaneously creating continuous paths for proton conduction. This feature, combined with its impressive water retention capability, allows sPSU to yield a proton conductivity of ca. 4 mS cm-1 at 90 °C and 20% RH.

Nanocomposite Membranes for PEM-FCs: Effect of LDH Introduction on the Physic-Chemical Performance of Various Polymer Matrices.

This is a comparative study to clarify the effect of the introduction of layered double hydroxide (LDH) into various polymer matrices. One perfluorosulfonic acid polymer, i.e., Nafion, and two polyaromatic polymers such as sulfonated polyether ether ketone (sPEEK) and sulfonated polysulfone (sPSU), were used for the preparation of nanocomposite membranes at 3 wt.% of LDH loading. Thereafter, the PEMs were characterized by X-ray diffraction (XRD) and dynamic mechanical analysis (DMA) for their microstructural and thermomechanical features, whereas water dynamics and proton conductivity were investigated by nuclear magnetic resonance (PFG and T1) and EIS spectroscopies, respectively. Depending on the hosting matrix, the LDHs can simply provide additional hydrophilic sites or act as physical crosslinkers. In the latter case, an impressive enhancement of both dimensional stability and electrochemical performance was observed. While pristine sPSU exhibited the lowest proton conductivity, the sPSU/LDH nanocomposite was able to compete with Nafion, yielding a conductivity of 122 mS cm-1 at 120 °C and 90% RH with an activation energy of only 8.7 kJ mol-1. The outcome must be ascribed to the mutual and beneficial interaction of the LDH nanoplatelets with the functional groups of sPSU, therefore the choice of the appropriate filler is pivotal for the preparation of highly-performing composites.

Elucidating the Water and Methanol Dynamics in Sulfonated Polyether Ether Ketone Nanocomposite Membranes Bearing Layered Double Hydroxides.

Conventional Nafion membranes demonstrate a strong affinity for methanol, resulting in a high fuel crossover, poor mechanical stability, and thus poor performance in direct methanol fuel cells (DMFCs). This study involves the synthesis and physiochemical characterization of an alternative polymer electrolyte membrane for DMFCs based on sulfonated poly(ether ether ketone) and a layered double hydroxide (LDH) material. Nanocomposite membranes (sPL), with filler loading ranging between 1 wt% and 5 wt%, were prepared by simple solution intercalation and characterized by XRD, DMA, swelling tests, and EIS. For the first time, water and methanol mobility inside the hydrophilic channels of sPEEK-LDH membranes were characterized by NMR techniques. The introduction of LDH nanoplatelets improved the dimensional stability while having a detrimental effect on methanol mobility, with its self-diffusion coefficient almost two orders of magnitude lower than that of water. It is worth noting that anionic lamellae are directly involved in the proton transport mechanism, thus enabling the formation of highly interconnected paths for proton conduction. In this regard, sPL3 yielded a proton conductivity of 110 mS cm-1 at 120 °C and 90% RH, almost attaining the performance of the Nafion benchmark. The nanocomposite membrane also showed an excellent oxidative stability (over more than 24 h) during Fenton's test at 80 °C. These preliminary results demonstrate that an sPL3 nanocomposite can be potentially and successfully applied in DMFCs.

Exploring the Structure-Performance Relationship of Sulfonated Polysulfone Proton Exchange Membrane by a Combined Computational and Experimental Approach.

Sulfonated Polysulfone (sPSU) is emerging as a concrete alternative to Nafion ionomer for the development of proton exchange electrolytic membranes for low cost, environmentally friendly and high-performance PEM fuel cells. This ionomer has recently gained great consideration since it can effectively combine large availability on the market, excellent film-forming ability and remarkable thermo-mechanical resistance with interesting proton conductive properties. Despite the great potential, however, the morphological architecture of hydrated sPSU is still unknown. In this study, computational and experimental advanced tools are combined to preliminary describe the relationship between the microstructure of highly sulfonated sPSU (DS = 80%) and its physico-chemical, mechanical and electrochemical features. Computer simulations allowed for describing the architecture and to estimate the structural parameters of the sPSU membrane. Molecular dynamics revealed an interconnected lamellar-like structure for hydrated sPSU, with ionic clusters of about 14-18 Å in diameter corresponding to the hydrophilic sulfonic-acid-containing phase. Water dynamics were investigated by 1H Pulsed Field Gradient (PFG) NMR spectroscopy in a wide temperature range (20-120 °C) and the self-diffusion coefficients data were analyzed by a "two-sites" model. It allows to estimate the hydration number in excellent agreement with the theoretical simulation (e.g., about 8 mol H2O/mol SO3- @ 80 °C). The PEM performance was assessed in terms of dimensional, thermo-mechanical and electrochemical properties by swelling tests, DMA and EIS, respectively. The peculiar microstructure of sPSU provides a wider thermo-mechanical stability in comparison to Nafion, but lower dimensional and conductive features. Nonetheless, the single H2/O2 fuel cell assembled with sPSU exhibited better features than any earlier published hydrocarbon ionomers, thus opening interesting perspectives toward the design and preparation of high-performing sPSU-based PEMs.

New Insights into Properties of Methanol Transport in Sulfonated Polysulfone Composite Membranes for Direct Methanol Fuel Cells.

Methanol crossover through a polymer electrolyte membrane has numerous negative effects on direct methanol fuel cells (DMFCs) because it decreases the cell voltage due to a mixed potential (occurrence of both oxygen reduction and methanol oxidation reactions) at the cathode, lowers the overall fuel utilization and contributes to long-term membrane degradation. In this work, an investigation of methanol transport properties of composite membranes based on sulfonated polysulfone (sPSf) and modified silica filler is carried out using the PFG-NMR technique, mainly focusing on high methanol concentration (i.e., 5 M). The influence of methanol crossover on the performance of DMFCs equipped with low-cost sPSf-based membranes operating with 5 M methanol solution at the anode is studied, with particular emphasis on the composite membrane approach. Using a surface-modified-silica filler into composite membranes based on sPSf allows reducing methanol cross-over of 50% compared with the pristine membrane, making it a good candidate to be used as polymer electrolyte for high energy DMFCs.

How the Morphology of Nafion-Based Membranes Affects Proton Transport.

This work represents a systematic and in-depth study of how Nafion 1100 membrane preparation procedures affect both the morphology of the polymeric film and the proton transport properties of the electrolyte. The membrane preparation procedure has non-negligible consequences on the performance of the proton-exchange membrane fuel cells (PEMFC) that operate within a wide temperature range (up to 120 °C). A comparison between commercial membranes (Nafion 117 and Nafion 212) and Nafion membranes prepared by three different procedures, namely (a) Nafion-recast, (b) Nafion uncrystallized, and (c) Nafion 117-oriented, was conducted. Electrochemical Impedance Spectroscopy (EIS) and Pulsed-field gradient nuclear magnetic resonance (PFG-NMR) investigations indicated that an anisotropic morphology could be achieved when a Nafion 117 membrane was forced to expand between two fixed and nondeformable surfaces. This anisotropy increased from ~20% in the commercial membrane up to 106% in the pressed membrane, where the ionic clusters were averagely oriented (Nafion 117-oriented) parallel to the surface, leading to a strong directionality in proton transport. Among the membranes obtained by solution-cast, which generally exhibited isotropic proton transport behavior, the Nafion uncrystallized membrane showed the lowest water diffusion coefficients and conductivities, highlighting the correlation between low crystallinity and a more branched and tortuous structure of hydrophilic channels. Finally, the dynamic mechanical analysis (DMA) tests demonstrated the poor elastic modulus for both uncrystallized and oriented membranes, which should be avoided in high-temperature fuel cells.

Titanium Dioxide Grafted on Graphene Oxide: Hybrid Nanofiller for Effective and Low-Cost Proton Exchange Membranes.

A nanostructured hybrid material consisting of TiO2 nanoparticles grown and stabilized on graphene oxide (GO) platelets, was synthesized and tested as nanofiller in a polymeric matrix of sulfonated polysulfone (sPSU) for the preparation of new and low-cost nanocomposite electrolytes for proton exchange membrane fuel cell (PEMFC) applications. GO-TiO2 hybrid material combines the nanoscale structure, large interfacial area, and mechanical features of a 2D, layered material, and the hygroscopicity properties of ceramic oxides, able to maintain a suitable hydration of the membrane under harsh fuel cell operative conditions. GO-TiO2 was synthetized through a new, simple, one-pot hydrothermal procedure, while nanocomposite membranes were prepared by casting using different filler loadings. Both material and membranes were investigated by a combination of XRD, Raman, FTIR, thermo-mechanical analysis (TGA and Dynamic Mechanical Analysis) and SEM microscopy, while extensive studies on the proton transport properties were carried out by Electrochemical Impedance Spectroscopy (EIS) measurements and pulse field gradient (PFG) NMR spectroscopy. The addition of GO-TiO2 to the sPSU produced a highly stable network, with an increasing of the storage modulus three-fold higher than the filler-free sPSU membrane. Moreover, the composite membrane with 3 wt.% of filler content demonstrated very high water-retention capacity at high temperatures as well as a remarkable proton mobility, especially in very low relative humidity conditions, marking a step ahead of the state of the art in PEMs. This suggests that an architecture between polymer and filler was created with interconnected routes for an efficient proton transport.

Transport Properties and Mechanical Features of Sulfonated Polyether Ether Ketone/Organosilica Layered Materials Nanocomposite Membranes for Fuel Cell Applications.

In this work, we study the preparation of new sulfonated polyether ether ketone (sPEEK) nanocomposite membranes, containing highly ionic silica layered nanoadditives, as a low cost and efficient proton exchange membranes for fuel cell applications. To achieve the best compromise among mechanical strength, dimensional stability and proton conductivity, sPEEK polymers with different sulfonation degree (DS) were examined. Silica nanoplatelets, decorated with a plethora of sulfonic acid groups, were synthesized through the one-step process, and composite membranes at 1, 3 and 5 wt% of filler loadings were prepared by a simple casting procedure. The presence of ionic layered additives improves the mechanical strength, the water retention capacity and the transport properties remarkably. The nanocomposite membrane with 5% wt of nanoadditive exhibited an improvement of tensile strength almost 160% (68.32 MPa,) with respect to pristine sPEEK and a ten-times higher rate of proton conductivity (12.8 mS cm-1) under very harsh operative conditions (i.e., 90 °C and 30% RH), compared to a filler-free membrane. These findings represent a significant advance as a polymer electrolyte or a fuel cell application.

Understanding the Effect of UV-Induced Cross-Linking on the Physicochemical Properties of Highly Performing PEO/LiTFSI-Based Polymer Electrolytes.

We report a thorough, multitechnique investigation of the structure and transport properties of a UV-cross-linked polymer electrolyte based on poly(ethylene oxide), tetra(ethylene glycol)dimethyl ether (G4), and lithium bis(trifluoromethane)sulfonimide. The properties of the cross-linked polymer electrolyte are compared to those of a non-cross-linked sample of same composition. The effect of UV-induced cross-linking on the physico/chemical characteristics is evaluated by X-ray diffraction, differential scanning calorimetry, shear rheology, 1H and 7Li magic angle spinning nuclear magnetic resonance (NMR) spectroscopy, 19F and 7Li pulsed field gradient stimulated echo NMR analyses, electrochemical impedance spectroscopy, and Fourier transform Raman spectroscopy. Comprehensive analysis confirms that UV-induced cross-linking is an effective technique to suppress the crystallinity of the polymer matrix and reduce ion aggregation, yielding improved Li+ transport number (>0.5) and ionic conductivity (>0.1 mS cm?1) at ambient temperature, by tailoring the structural/morphological characteristics of the polymer matrix. Finally, the polymer electrolyte allows reversible operation with stable profile for hundreds of cycles upon galvanostatic test at ambient temperature of LiFePO4-based lithium-metal cells, which deliver full capacity at 0.05 or 0.1C current rate and keep high rate capabilities up to 1C. This enforces the role of UV-induced cross-linking in achieving excellent electrochemical characteristics, exploiting a practical, easy up-scalable process.

Composite Gel Polymer Electrolytes Based on Organo-Modified Nanoclays: Investigation on Lithium-Ion Transport and Mechanical Properties.

Composite gel polymer electrolytes (GPEs) based on organo-modified montmorillonite clays have been prepared and investigated. The organo-clay was prepared by intercalation of CTAB molecules in the interlamellar space of sodium smectite clay (SWy) through a cation-exchange reaction. This was used as nanoadditive in polyacrylonitrile/polyethylene-oxide blend polymer, lithium trifluoromethanesulphonate (LiTr) as salt and a mixture of ethylene carbonate/propylene carbonate as plasticizer. GPEs were widely characterized by DSC, SEM, and DMA, while the ion transport properties were investigated by AC impedance spectroscopy and multinuclear NMR spectroscopy. In particular, 7Li and 19F self-diffusion coefficients were measured by the pulse field gradient (PFG) method, and the spin-lattice relaxation times (T1) by the inversion recovery sequence. A complete description of the ions dynamics in so complex systems was achieved, as well as the ion transport number and ionicity index were estimated, proving that the smectite clay surfaces are able to "solvatate" both lithium and triflate ions and to create a preferential pathway for ion conduction.