Gel polymer electrolytes based on sulfonamide functional polymer nanoparticles for sodium metal batteries.

In this work, we investigate the development of polymer electrolytes for sodium batteries based on sulfonamide functional polymer nanoparticles (NaNPs). The synthesis of the polymer NaNPs is carried out by emulsion copolymerization of methyl methacrylate and sodium sulfonamide methacrylate in the presence of a crosslinker, resulting in particle sizes of 50 nm, as shown by electron microscopy. Then, gel polymer electrolytes are prepared by mixing polymer NPs and different organic plasticizers including carbonates, glymes, sulfolanes and ionic liquids.

Maintaining hexagonal structures through interfacial positioning of crosslinkers for nanofiltration.

Hypothesis: Optimizing interfacial positioning of crosslinkers within a reactive self-assembled hexagonal lyotropic liquid crystals (HLLC) system could assist in retaining the hexagonal structure during polymerization and thereby improving water filtration performances of the as-synthesized nanofiltration membranes.

Experiments: The positioning of the hydrophilic crosslinker, poly (ethylene glycol) diacrylate (PEGDA), within the reactive HLLC system was systematically investigated using H and C solid nuclear magnetic resonance (NMR) and small angle X-ray scattering (SAXS) techniques. The structural variation and water filtration performances of these HLLC systems with/without crosslinkers after polymerization were further studied using grazing incidence SAXS (GISAXS) and crossflow filtration tests, respectively.

Poly(Ionic Liquid) Electrolytes at an Extreme Salt Concentration for Solid-State Batteries.

Polymer-in-salt electrolytes were introduced three decades ago as an innovative solution to the challenge of low Li-ion conductivity in solvent-free solid polymer electrolytes. Despite significant progress, the approach still faces considerable challenges, ranging from a fundamental understanding to the development of suitable polymers and salts. A critical issue is maintaining both the stability and high conductivity of molten salts within a polymer matrix, which has constrained their further exploration.

Structure and Dynamics in Solid Electrolyte Composites of the Organic Ionic Plastic Crystal HMGFSI and Lithium Sulphonamide Functional Acrylate Polymer Nanoparticles.

Solid electrolyte composites between organic ionic plastic crystals (OIPCs) and polymers can potentially show enhanced mechanical properties and ion conduction. These properties can be determined by the formation of interfacial regions which affect the structure, thermal properties, and ion transport of the composite material. Here we studied the properties of composites between the OIPC hexamethylguanidinium bis(fluorosulfonyl)imide (HMGFSI) and acrylate polymer nanoparticles functionalised with lithium, using various techniques including solid-state NMR spectroscopy.

Advanced High-Voltage Electrolyte Design Using Poly(ethylene Oxide) and High-Concentration Ionic Liquids for All-Solid-State Lithium-Metal Batteries.

Poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) are among the most promising materials for solid-state lithium metal batteries (LMBs) due to their inherent safety advantages; however, they suffer from insufficient room-temperature ionic conductivity (up to 10 S cm) and limited oxidation stability (<4 V). In this study, a novel "polymer-in-high-concentrated ionic liquid (IL)" (PiHCIL) electrolyte composed of PEO, -propyl--methylpyrrolidinium bis(fluorosulfonyl) imide (CmpyrFSI) IL, and LiFSI is designed. The EO/[Li/IL] ratio has been widely varied, and physical and electrochemical properties have been explored.

Enhancing Cycle Life of Rechargeable Zinc Hybrid Batteries in a Low-Cost, Nonfluorinated Dual-Cation Electrolyte.

Rechargeable zinc batteries (RZBs) are highly attractive as energy storage solutions due to their low cost and sustainability. Nevertheless, the use of fluorine-free zinc electrolyte systems to create affordable, ecofriendly, and safe RZBs has been largely overlooked in the battery community. Previously, we showcased the utilization of a fluorine-free, nonaqueous electrolyte comprising zinc dicyanamide (Zn(dca)) in dimethyl sulfoxide (DMSO) to enable the electrochemical cycling of zinc.

A case study using spectroscopy and computational modelling for Co speciation in a deep eutectic solvent.

Cobalt has a vital role in the manufacturing of reliable and sustainable clean energy technologies. However, the forecasted supply deficit for cobalt is likely to reach values of 150 kT by 2030. Therefore, it is paramount to consider end-of-life devices as secondary resources for cobalt.

Impact of optimised quasi-block structures on the properties of polymer electrolytes.

A set of ionic quasi-block copolymers were investigated to determine the effects of their composition and structure on their performance in their application as solid-state battery electrolytes. Diffusion and electrochemical tests have shown that these new quasi-block electrolytes have comparable performance to traditional block copolymers reaching ionic conductivities of 3.8 × 10 S cm and lithium-ion diffusion of 4.

Understanding Polymerized Ionic Liquids as Solid Polymer Electrolytes for Sodium Batteries.

Solid polymer electrolytes (SPEs) have emerged as promising candidates for sodium-based batteries due to their cost-effectiveness and excellent flexibility. However, achieving high ionic conductivity and desirable mechanical properties in SPEs remains a challenge. In this study, we investigated an AB diblock copolymer, PS-PEA(BuImTFSI), as a potential SPE for sodium batteries.

Insights into the Carbon Dioxide Separation Performance of Bis(trifluoromethylsulfonyl)imide-based Plastic Crystal Composite Membranes with Fluorinated Polar Polymers.

Membrane-based gas separation technologies are one solution towards mitigating global emissions of CO. New membrane materials with improved separation performance are still highly sought after. Composite membranes based on organic ionic plastic crystals (OIPCs) have shown preferential interaction for CO over N, leading in some cases to competitive CO/N selectivities.

Atomic Layer Deposition of the Geometry Separated Lewis and Brønsted Acid Sites for Cascade Glucose Conversion.

Solid acid catalysts with bi-acidity are promising as workhouse catalysts in biorefining to produce high-quality chemicals and fuels. Herein, we report a new strategy to develop bi-acidic cascade catalysts by separating both acid sites in geometry via the atomic layer deposition (ALD) of Lewis acidic alumina on Brønsted acidic supports. Visualized by transmission electron microscopy and electron energy loss spectroscopy mapping, the ALD-deposited alumina forms a conformal alumina domain with a thickness of around 3 nm on the outermost surface of mesoporous silica-alumina.

Lyotropic Liquid Crystal (LLC)-Templated Nanofiltration Membranes by Precisely Administering LLC/Substrate Interfacial Structure.

Mesoporous materials based on lyotropic liquid crystal templates with precisely defined and flexible nanostructures offer an alluring solution to the age-old challenge of water scarcity. In contrast, polyamide (PA)-based thin-film composite (TFC) membranes have long been hailed as the state of the art in desalination. They grapple with a common trade-off between permeability and selectivity.

New organic ionic plastic crystals utilizing the morpholinium cation.

Organic ionic plastic crystals (OIPCs) are emerging candidates as safer, quasi solid-state ion conductors for various applications, especially for next-generation batteries. However, a fundamental understanding of these OIPC materials is required, particularly concerning how the choice of cation and anion can affect the electrolyte properties. Here, we report the synthesis and characterisation of a range of new morpholinium-based OIPCs and demonstrate the benefit of the ether functional group in the cation ring.

Development of New Plastic-Crystal Based Electrolytes using Pyrrolidinium- Bis(fluorosulfonyl)imide Dicationic Salts.

Dicationic organic salts are an interesting class of solid-state electrolyte materials due to their unique structure. Here we present, for the first time, the synthesis and characterization of three dicationic-FSI salts, 1,2-bis(N-methylpyrrolidinium)ethane bi(bis(fluorosulfonyl)imide) ([C -Pyrr1][FSI] ), 1,2-bis(N-ethylpyrrolidinium)ethane bi(bis(fluorosulfonyl)imide) ([C -Pyrr2][FSI] ) and 1,2-bis(N-n-propylpyrrolidinium)ethane bi(bis(fluorosulfonyl)imide) ([C -Pyrr3][FSI] ). The structure and dynamics of the organic salts were probed using variable temperature solid-state NMR and were compared with the thermal and transport properties.

Hybrid Artificial Solid Electrolyte Interphase with Dendrite-Free Lithium Deposition and High Ion Transport Kinetics.

Interfacial issues and dendritic Li deposition in lithium metal batteries (LMBs) hamper the practical application of liquid or solid-state cells. Here, a hybrid solid electrolyte interphase (SEI), based on hydroxyl-functionalized boron nitride (BN) nanosheets and poly(vinyl alcohol), is designed to solve the unstable nature of the Li anode-electrolyte interface. Rather than acquiring a rich Li halide environment through intense electrolyte decomposition, the hybrid SEI effectively regulates electrolyte decomposition and guarantees uniform Li plating via boosting interfacial Li ion transport at the interface.

Probing the molecular interactions and physicochemical properties of a cobalt-based redox electrolyte system for thermo-electrochemical cells.

Redox-active materials play a primary role in the high-performance electrochemical device research field. Their bulk ion dynamics and performances can be studied using different electrochemical analysis methods, but their molecular level interactions and dynamics on which these depend are often not well understood. Here, nuclear magnetic resonance (NMR) relaxation and double-stimulated echo pulsed field gradient (PFG) techniques have been used to gain insights into the molecular level interactions, exchange dynamics and self-diffusivity of the various species present in a cobalt-based redox active electrolyte system used for thermo-electrochemical applications, including how these factors depend on the oxidation state and concentration of the redox species.

Exploration of phase diagram, structural and dynamic behavior of [HMG][FSI] mixtures with NaFSI across an extended composition range.

Hexamethylguanidinium bis(fluorosulfonyl)imide ([HMG][FSI]) has recently been shown to be a promising solid state organic ionic plastic crystal with potential application in advanced alkali metal batteries. This study provides a detailed exploration of the structural and dynamic behavior of [HMG][FSI] mixtures with the sodium salt NaFSI across the whole composition range from 0 to 100 mol%. All mixtures are solids at room temperature.

Atomically-thin Schottky-like photo-electrocatalytic cross-flow membrane reactors for ultrafast remediation of persistent organic pollutants.

The remediation of persistent organic pollutants in surface and ground water represents a major environmental challenge worldwide. Conventional physico-chemical techniques do not efficiently remove such persistent organic pollutants and new remediation techniques are therefore required. Photo-electro catalytic membranes represent an emerging solution that can combine photocatalytic and electrocatalytic degradation of contaminants along with molecular sieving.

High-Performance Cycling of Na Metal Anodes in Phosphonium and Pyrrolidinium Fluoro(sulfonyl)imide Based Ionic Liquid Electrolytes.

We have investigated the sodium electrochemistry and the evolution and chemistry of the solid-electrolyte interphase (SEI) upon cycling Na metal electrodes in two ionic liquid (IL) electrolytes. The effect of the IL cation chemistry was determined by examining the behavior of a phosphonium IL (PFSI) in comparison to its pyrrolidinium-based counterpart (CmpyrFSI) at near-saturated NaFSI salt concentrations (superconcentrated ILs) in their dry state and with water additive. The differences in their physical properties are reported, with the PFSI system having a lower viscosity, higher conductivity, and higher ionicity in comparison to the CmpyrFSI-based electrolyte, although the addition of 1000 ppm (0.

Plastic crystal-based electrolytes using novel dicationic salts.

The unique structures of dications increase the number of possible combinations of cations and anions that can be used to obtain new materials with a wide range of physicochemical properties. However, structure-property relationships related to dicationic organic salts are seldom explored. Here, we report the synthesis and characterization of two new dicationic salts, 1,2-bis(-ethylpyrrolidinium)ethane bis(trifluoromethanesulfonyl)imide ([C-Pyrr2][TFSI]) and 1,2-bis(-propylpyrrolidinium)ethane bis(trifluoromethanesulfonyl)imide ([C-Pyrr3][TFSI]).

Insights into the Interaction between Immobilized Biocatalysts and Metal-Organic Frameworks: A Case Study of PCN-333.

The immobilization of enzymes in metal-organic frameworks (MOFs) with preserved biofunctionality paves a promising way to solve problems regarding the stability and reusability of enzymes. However, the rational design of MOF-based biocomposites remains a considerable challenge as very little is known about the state of the enzyme, the MOF support, and their host-guest interactions upon immobilization. In this study, we elucidate the detailed host-guest interaction for MOF immobilized enzymes in the biointerface.

Towards a High-Flux Separation Layer from Hexagonal Lyotropic Liquid Crystals for Thin-Film Composite Membranes.

Hexagonal lyotropic liquid crystals (HLLC) with uniform pore size in the range of 1~5 nm are highly sought after as promising active separation layers of thin-film composite (TFC) membranes, which have been confirmed to be efficient for water purification. The potential interaction between an amphiphile-based HLLC layer and the substrate surface, however, has not been fully explored. In this research, hydrophilic and hydrophobic microporous polyvinylidene fluoride (PVDF) substrates were chosen, respectively, to prepare TFC membranes with the active layers templated from HLLC, consisting of dodecyl trimethylammonium bromide, water, and a mixture of poly (ethylene glycol) diacrylate and 2-hydroxyethyl methacrylate.

Zwitterionic materials with disorder and plasticity and their application as non-volatile solid or liquid electrolytes.

Zwitterionic materials can exhibit unique characteristics and are highly tunable by variation to the covalently bound cationic and anionic moieties. Despite the breadth of properties and potential uses reported to date, for electrolyte applications they have thus far primarily been used as additives or for making polymer gels. However, zwitterions offer intriguing promise as electrolyte matrix materials that are non-volatile and charged but non-migrating.

Operando magnetic resonance imaging for mapping of temperature and redox species in thermo-electrochemical cells.

Low-grade waste heat is an abundant and underutilised energy source. In this context, thermo-electrochemical cells (i.e.

New Insights into Decoupled Cation and Anion Transport and Dynamic Heterogeneity in a Diethyl(methyl)(isobutyl)phosphonium Hexafluorophosphate Organic Ionic Plastic Crystal.

Organic ionic plastic crystals (OIPCs) are an emerging family of materials with demonstrated applications in electrochemical devices such as lithium/sodium ion batteries, dye-sensitized solar cells, and hydrogen fuel cells. Herein, we present direct evidence of anion diffusion through a relatively static background of a cation lattice in an ionic plastic crystal compound, [P][PF], in an elevated temperature solid phase. We found all anions are diffusive, whereas only a small population of cations is diffusive.