Polyelectrolyte Research Articles

Self-Templating Copolymerization to Produce Robust Conductive Nanocoatings Based on Conjugated Polymer Brushes with Implementable Memristive Characteristics.

An effective synthesis of conductive polymer brushes, i.e., self-templating surface-initiated copolymerization (ST-SICP), is developed. It proceeds through copolymerization of pendant thiophene groups in the precursor multimonomer poly(3-methylthienyl methacrylate) (PMTM) brushes with free 3-methylthiophene (3MT) monomers leading to PMTM-co-P3MT brushes. This approach leads to improved conformational freedom of generated conjugated poly(thiophene)-based chains and their higher share in the brushes with respect to conjugation of pendant thiophene groups only. As a result, best performing conjugated PMTM-co-P3MT brushes demonstrate high ohmic conductivity in both out-of-plane and in-plane direction. Furthermore, thanks to the covalent anchoring as well as intra- and intermolecular connections, highly stable and mechanically robust nanocoatings are produced which can survive mechanical cleaning and long-term storage under ambient conditions. Grafting of ionic poly(sodium 4-styrenesulfonate) (PSSNa) in between PMTM-co-P3MT chains brings new properties to such binary mixed brushes that can operate as thin-film memristive coating with switchable conductance. It is worth mentioning that the crucial synthetic steps, i.e., grafting of precursor PMTM brushes by surface-initiated organocatalyzed atom transfer radical polymerization (SI-O-ATRP) and PSSNa chains by surface-initiated photoiniferter-mediated polymerization (SI-PIMP) are conducted under ambient conditions using only microliter volumes of reagents providing methodology that can be considered for use beyond the laboratory scale.

Ferroelectric BaTiO3 Regulating the Local Electric Field for Interfacial Stability in Solid-State Lithium Metal Batteries.

Solid-state Li metal batteries (SSLMBs) are widely investigated since they possess promising energy density and high safety. However, the poor interfacial compatibility between the electrolyte and electrodes limits their promising development. Herein, a robust composite electrolyte (poly(vinyl ethylene carbonate) electrolyte with 3 wt % of BaTiO3, PVEC-3BTO) with excellent interfacial performance is rationally designed by incorporating ferroelectric BaTiO3 (BTO) nanoparticles into the poly(vinyl ethylene carbonate) (PVEC) electrolyte matrix. Benefiting from the high dielectric constant and ferroelectric properties of BTO, the interfacial compatibility between electrolytes and electrodes was significantly improved. The enhanced Li+ transference number (0.64) of solid electrolyte and in situ generated BaF2 inorganic interphase contribute to the enhanced cycling stability of PVEC-3BTO based Li//Li symmetrical batteries. Furthermore, the antioxidation ability of PVEC-3BTO has also been enhanced by modulating the local electric field for good pairing with high-voltage LiCoO2 material. Therefore, in this work, the mechanism of BTO for improving interfacial compatibility is revealed, and also useful methods for addressing the interface issues of SSLMBs have been provided.

Investigation of Ionic Polymers' Stabilizing and Flocculating Properties in Dispersed Activated Carbons Systems.

Activated carbons obtained via the thermochemical treatment of lemon balm and mint herbs were applied for ionic polymers adsorption, which directly affects the stability of these types of aqueous suspensions. The examined carbonaceous materials were characterized by well-developed specific surface area (approximately 1000 m2/g) and mesoporous structure. The adsorbed amounts of anionic poly(acrylic acid) and cationic polyethyleneimine from one-component solutions reached significant levels, but the efficiency of adsorption of these compounds from binary solutions slightly decreased. Moreover, the ionic polymers showed stabilizing properties towards the activated carbons suspensions. For both adsorbents, the most stable suspensions were systems containing both types of polymeric macromolecules with different ionic characters. This was due to the occurrence of electrosteric and depletion stabilization mechanisms. Furthermore, the zeta potential and size of particle aggregates were also influenced by the presence of polymers in the aqueous suspensions of activated carbons.

Ethylene glycol derivative-pendanted quaternary ammonium antibacterial polymers with low cytotoxicity

Cationic poly(quaternary ammonium) (pQA) polymers exhibit excellent antibacterial efficacy but high cytotoxicity (thus low selectivity), hampering their widespread use as antibacterial agents. Herein, we systematically synthesized a series of pQA polymers (pQA−EG) containing biocompatible ethylene glycol (EG) derivative pendant groups with different chain lengths and connectivities (acyclic/cyclic). The antibacterial efficacy of pQA−EG was optimized by a moderate EG chain length, which endowed the polymer with balanced hydrophobicity/charge density. The high chain flexibility of the EG derivative combined with its good hydrophilicity was critical for significantly lowering the cytotoxicity of pQA−EG. Hence, compared with pQA polymers containing alkyl pendant groups, the pQA−EG polymer containing a long flexible EG derivative pendant group exhibited significantly lower cytotoxicity and higher selectivity as well as satisfactory antibacterial activity and kinetics. Our study offers a rational platform for synthesizing low-toxicity antibacterial polymers and provides fundamental insights into their structure−biological activity relationships.

Polymerizable Deep Eutectic Solvent-Based Polymer Electrolyte for Advanced Dendrite-Free, High-Rate, and Long-Life Li Metal Batteries.

The recently developed advanced electrolytes possess many crucial qualities, including robust stability, Li dendrite-free, and comparable interface compatibility, for the manufacturing of Li metal batteries with a high energy density. In this study, lithium bis(trifluoromethane)sulfonimide, acrylamide, and succinonitrile were first used to design a polymerizable monomer. Then, it went through in situ thermal polymerization to attain a new solid polymer electrolyte [named poly(PDES)]. The synthesized poly(PDES) electrolyte achieved higher ionic conductivity (∼1.89 × 10-3 S cm-1), oxidation potential (∼5.10 V versus Li+/Li), and a larger lithium-ion transfer number (∼0.63). Moreover, poly(PDES) was nonflammable and could effectively inhibit the formation of Li dendrites. As a result, the assembled batteries using the poly(PDES) electrolyte for both Li||LiFePO4 and Li||LiNi0.8Co0.1Mn0.1O2 exhibited excellent interface compatibility and electrochemical performances. This poly(PDES) electrolyte has promising potential for broad application in lithium-metal batteries with elevated energy density and safety performance in the near future.

Anionic magnetic nanosorbents immobilized with peptide aptamer for selective adsorption with bisphenol A

This study focused on synthesis of anionic magnetite nanoparticles (MNPs) immobilized with a bisphenol A (BPA)-specific peptide aptamer for selective BPA adsorption. The MNP surface was coated with anionic poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) to provide water dispersibility and stability. These nanosorbents, with a saturation magnetization value of 47 emu/g, responded well to the change in zeta potential and hydrodynamic size with varying dispersion pH. The aptamer loading capacity of particles was 0.12 mg/mg MNPs, and the nanosorbents exhibited a 47% BPA adsorption capacity. Importantly, they shown high selectivity in capturing BPA over structurally similar molecules.

Removal of algae from ballast water by cationic flocculant-composite titanium xerogel coagulant: Differences in freshwater and seawater

The treatment of ballast water has been garnering increasing attention, with planktonic algae removal being a crucial part. Coagulation has been demonstrated as an effective method for algae removal, albeit few coagulants exhibit excellent coagulation performance in both freshwater and seawater. To address this issue, the cationic flocculant poly dimethyl diallyl ammonium chloride (PDADMAC) was composited with titanium xerogel coagulant (TXC), abbreviated as PT. Using the algae Cyclotella meneghiniana as the research object, the algal removal performance and mechanisms of PT in freshwater and seawater were investigated. Cell integrity, superoxide dismutase (SOD) activity, and malondialdehyde (MDA) content of C. meneghiniana during floc storage were also evaluated. The PT composite coagulant exhibited excellent coagulation performance in both freshwater and seawater. Its algal removal ability was superior to TXC and the commercial coagulants polyaluminum chloride (PAC) and polymerized ferrous sulfate (PFS), with removal rates for C. meneghiniana reaching 98.3 % in freshwater and 98.4 % in seawater at a 80 mg/L dosage. PT also exhibited excellent removal performance over wide dosage and pH ranges. PT acted via distinct coagulation mechanisms in freshwater and seawater, with charge neutralization and bridging played major roles in freshwater and sweeping being important in seawater. The floc storage experiment indicated that the coagulation process did not directly lead to algal cell fragmentation, but PT accelerated and exacerbated oxidative stress and oxidative damage to algal cells during floc storage. Furthermore, PT also showed excellent removal performance for the marine diatom Skeletonema costatum and the freshwater cyanobacteria Cylindrospermopsis raciborskii. This work not only provides a novel approach for algae removal in ballast water, but also enhances our understanding of the coagulation behavior of titanium-based coagulants in different water environments.

All-atom molecular dynamics simulations of polymer and polyelectrolyte brushes.

Densely grafted polymer and polyelectrolyte (PE) brushes, owing to their significant abilities to functionalize surfaces for a plethora of applications in sensing, diagnostics, current rectification, surface wettability modification, drug delivery, and oil recovery, have attracted significant attention over the past several decades. Unfortunately, most of the attention has primarily focused on understanding the properties of the grafted polymer and the PE chains with little attention devoted to studying the behavior of the brush-supported ions (counterions needed to screen the PE chains) and water molecules. Over the past few years, our group has been at the forefront of addressing this gap: we have employed all-atom molecular dynamics (MD) simulations for studying a wide variety of polymer and PE brush systems with specific attention to unraveling the properties and behavior of the brush-supported water molecules and ions. Our findings have revealed some of the most fascinating properties of such brush-supported ions and water molecules, including the most remarkable control of nanofluidic transport afforded by the specific ion and water responses induced by the PE brushes grafted on the inner walls of the nanochannel. This feature article aims to summarize some of our key contributions associated with such atomistic simulations of polymer and PE brushes and brush-supported water molecules and counterions.

Lipid/polyelectrolyte complexes - effects of the polyelectrolyte architecture on the self-assembled structures.

Self-assembly is a key process in forming biological materials. Especially the interaction between amphiphiles and polyelectrolytes has been widely investigated in recent years due to their potential application in industry and medicine, with a special focus on gene therapy. Accordingly, we investigated the formation of lipoplexes by mixing the cationic lipid DOTAP (1,2-dioleoyl-3-trimethylammonium-propane (chloride salt)) with different anionic polyelectrolytes (PE), such as NaPA (sodium polyacrylate), CMC (sodium carboxymethyl cellulose) with different degrees of substitution (DS, namely, different charge density), PSS (sodium polystyrenesulfonate) and DNA (deoxyribonucleic acid sodium salt). The goal of this project was to explore the influence of different system parameters, such as the charge ratio, CR = [+]/[-] = [DOTAP]/[PE], the charge density of the PE, or the type of PE on the morphology of the formed complexes. The investigation of these systems was performed by cryo-transmission electron microscopy (cryo-TEM), and with small-angle X-ray scattering (SAXS), to support our findings. In our experiments, we obtained a comprehensive picture of the formed lipoplexes, and how their structure depends on the different properties of the employed polyelectrolyte. Although the basic nanostructure of all complexes is lamellar, their detailed morphology depends strongly on parameters of the PE, e.g., the persistence length, charge density, or the polymer backbone. Understanding these specific interactions will allow the formation of more stable and optimized complexes as they are needed for drug or genetic material delivery.

Self-degrading functional unit introduction for anti-oxidation ability enhancement of a poly(vinyl ethylene carbonate) electrolyte

A novel poly(vinyl ethylene carbonate-3-sulfolene) electrolyte has been developed by copolymerizing monomer precursors, which has a wide electrochemical stability window of 5 V (vs. Li+/Li) attributed to the pre-degradation of sulfolene-based functional units.

Lowest gelation concentration in a complex-coacervate-driven self-assembly system, achieved by redox-RAFT synthesis of high molecular weight block polyelectrolytes.

The objective of this work was to synthesize high molecular weight polyelectrolyte complex (PEC) micelles that are effective in controlling the rheology of aqueous solutions at low concentrations, paving the way for industrial applications of thickeners based on the principle of electrostatic self-assembly. Redox-initiated RAFT (reversible addition-fragmentation chain-transfer) polymerization was used to obtain anionic block polyelectrolytes based on poly(sodium 2-acrylamido-2-methylpropane sulfonate) and poly(acrylamide)-poly(AMPS)-block-poly(AM) (di-block) and poly(AMPS)-block-poly(AM)-block-poly(AMPS) (tri-block), with molecular weights of 237 kDa and 289 kDa and polydispersities of 1.29 and 1.34, respectively. A random poly(AMPS)-co-poly(AM) copolymer was also synthesized for comparison. PEC micelles were obtained upon mixing with cationic poly(N-[3-(dimethylamino)propyl]methacrylamide hydrochloride) - poly(DMAPMA), forming viscoelastic gels at unprecedented low concentrations of <3 wt% for the di-block and <1 wt% for the tri-block, which to date is the lowest demonstrated gelation concentration for a synthetic PEC micelle system. Differences between tri-block and di-block architectures are discussed, with the former being more affected by the addition of salt, which is attributed to percolated network breakdown. The random co-polymer was shown not to be an effective thickener but displayed a surprising lack of phase separation upon coacervation. The assemblies were characterized using dynamic light scattering (DLS) and cryo transmission electron microscopy (cryoTEM), revealing spherical micelles with a diameter of approximately 200 nm for the diblock and a mixture of spherical micelles and network particles for the tri-block PEC micelles. The micelles were not affected by dilution down to a polymer concentration of 7.8 × 10-4% (approx. 0.03 μM). Responsiveness to salinity, pH, and temperature was studied using DLS, revealing a critical NaCl concentration of 1.1 M for the block copolymer micelles.

Development of a label-free, sensitive gold nanoparticles-poly(adenine) aptasensing platform for colorimetric determination of aflatoxin B1 in corn.

In this work, a sensitive colorimetric bioassay method based on a poly(adenine) aptamer (polyA apt) and gold nanoparticles (AuNPs) was developed for the determination of aflatoxin B1 (AFB1). The polyA apt, adsorbed on the AuNPs, especially can bind to the analyte while deterring non-specific interactions. This nano aptasensor uses cationic polymer poly(diallyl dimethyl ammonium chloride) (PDDA), as an aggregating agent, to aggregate gold nanoparticles. PolyA apt-decorated gold nanoparticles (AuNPs/polyA apt) show resistance to PDDA-induced aggregation and maintains their dispersed state (red color) with the optical absorbance signal at λ = 520 nm. However, in the presence of AFB1 in the assay solution, the specific aptamer reacts with high affinity and folds into its three-dimensional form. Aggregation of AuNPs induced by PDDA caused their optical signal shift to λ = 620 nm (blue color). AFB1 concentration in the bioassay solution determines the amount of optical signal shift. Therefore, optical density ratio in two wavelengths (A620/520) can be used as a sturdy colorimetric signal to detect the concentration of aflatoxin B1. AFB1 was linearly detected between 0.5 and 20 ng mL-1, with a detection limit of 0.09 ng mL-1 (S/N = 3). The fabricated aptasensor was applied to the detection of AFB1 in real corn samples.

Alternatives to fluorinated binders: recyclable copolyester/carbonate electrolytes for high-capacity solid composite cathodes.

Optimising the composite cathode for next-generation, safe solid-state batteries with inorganic solid electrolytes remains a key challenge towards commercialisation and cell performance. Tackling this issue requires the design of suitable polymer binders for electrode processability and long-term solid-solid interfacial stability. Here, block-polyester/carbonates are systematically designed as Li-ion conducting, high-voltage stable binders for cathode composites comprising of single-crystal LiNi0.8Mn0.1Co0.1O2 cathodes, Li6PS5Cl solid electrolyte and carbon nanofibres. Compared to traditional fluorinated polymer binders, improved discharge capacities (186 mA h g-1) and capacity retention (96.7% over 200 cycles) are achieved. The nature of the new binder electrolytes also enables its separation and complete recycling after use. ABA- and AB-polymeric architectures are compared where the A-blocks are mechanical modifiers, and the B-block facilitates Li-ion transport. This reveals that the conductivity and mechanical properties of the ABA-type are more suited for binder application. Further, catalysed switching between CO2/epoxide A-polycarbonate (PC) synthesis and B-poly(carbonate-r-ester) formation employing caprolactone (CL) and trimethylene carbonate (TMC) identifies an optimal molar mass (50 kg mol-1) and composition (wPC 0.35). This polymer electrolyte binder shows impressive oxidative stability (5.2 V), suitable ionic conductivity (2.2 × 10-4 S cm-1 at 60 °C), and compliant viscoelastic properties for fabrication into high-performance solid composite cathodes. This work presents an attractive route to optimising polymer binder properties using controlled polymerisation strategies combining cyclic monomer (CL, TMC) ring-opening polymerisation and epoxide/CO2 ring-opening copolymerisation. It should also prompt further examination of polycarbonate/ester-based materials with today's most relevant yet demanding high-voltage cathodes and sensitive sulfide-based solid electrolytes.

Hydrophilic and Apolar Hydration in Densely Grafted Cationic Brushes and Counterions with Large Mobilities.

We employ an all-atom molecular dynamics (MD) simulation framework to unravel water microstructure and ion properties for cationic [poly(2-(methacryloyloxy)ethyl) trimethylammonium chloride] (PMETAC) brushes with chloride ions as counterions. First, we identify locally separate water domains (or first hydration shells) each around {N(CH3)3}+ and the C═O functional groups of the PMETAC chain and one around the Cl- ion. These first hydration shells around the respective moieties overlap, and the extent of the overlap depends on the nature of the species triggering it. Second, despite the overlap, the water molecules in these domains demonstrate disparate properties dictated by the properties of the atoms and groups around which they are located. For example, the presence of the methyl groups makes the {N(CH3)3}+ group trigger apolar hydration as evidenced by the corresponding orientation of the dipole of the water molecules around the {N(CH3)3}+ moiety. These water molecules around the {N(CH3)3}+ group also have enhanced tetrahedrality compared to the water molecules constituting the hydration layer around the C═O group and the Cl- counterion. Our simulations also identify that there is an intervening water layer between the Cl- ion and {N(CH3)3}+ group: this layer prevents the Cl- ion from coming very close to the {N(CH3)3}+ group. As a consequence, there is a significantly large mobility of the Cl- ions inside the PMETAC brush layer. Furthermore, the C═O group of the polyelectrolyte (PE) chain, due to the partial negative charge on the oxygen atom and the specific structure of the PMETAC brush system, demonstrates strongly hydrophilic behavior and enforces a specific dipole response of water molecules analogous to that experienced by water around anionic species of high charge density. In summary, our findings confirm that PMETAC brushes undergo hydrophilic hydration at one site and apolar hydration at another site and ensure large mobility of the supported Cl- counterions.

Development of composite polyelectrolyte complex membranes as cathodes for aqueous zinc-ion batteries

Zinc-ion batteries (ZIBs) are an interesting alternative to lithium batteries due to their high specific capacity, eco-friendly properties, and ease of processing. Cathodes are an essential component of ZIBs that provide electron storage capacity. In this study, composite polyelectrolyte complexes (C-PECs) made from cationic poly(diallyldimethylammonium chloride) (PDADMAC) and anionic poly(sodium-4-styrenesulfonate) (PSS), along with carbon blacks N550 and layer-structured δ-MnO2 were used to create ZIB cathodes. Interestingly, various salt ions content (0, 1, 2 M NaCl), used as plasticizer to induce softening of the C-PEC at the processing stage were found to strongly affects the cathode’s performance. Results show that the composite exhibited an optimum battery specific capacity of approximately 7.78 mA cm−2.

Knockdown of BACE1 by a multistage brain-targeting polyion complex improved memory and learning behaviors in APP/PS1 transgenic mouse model

Cleavage of Amyloid precursor protein (APP) by the β-site amyloid precursor protein cleaving enzyme 1 (BACE1) is the rate-limiting step in the production of amyloid-β (Aβ) synaptotoxins. The siRNA-mediated silencing to attenuate the expression of BACE1 to ameliorate cognitive dysfunction in mice had been investigated. To improve therapeutic gene delivery to the central nervous system, cationic copolymer poly(ethylene glycol)-b-poly[N-(N′-{N′′-[N′′′-(2-aminoethyl)-2-aminoethyl]-2-aminoethyl}-2-aminoethyl)aspartamide]-cholesterol was synthesized, then RVG29 and Tet1 peptides were exploited as ligands to construct a dual-targeting brain gene delivery polyion complex (Tet1/RVG29-PIC). The cell uptake of a coculture cell model showed that the Tet1/RVG29-PIC exhibited notable transport characteristics and possessed affinity towards nerve cells. In vivo transfection, Tet1/RVG29-PIC possessed the highest expression of luciferase in brain compared with that of RVG29-PIC or Tet1-PIC, which were 1.25 and 1.22 times respectively. Silence BACE1 expression using siRNA-expressing plasmid loaded Tet1/RVG29-PIC that improved behavioral deficits in the APP/PS1 mouse model, demonstrating the favorable brain delivery properties of Tet1/RVG29-PIC by synergistical engagement of GT1B and nicotinic acetylcholine receptors. Our results suggested that the nanoformulation has the potential to be exploited as a multistage-targeting gene vector for the CNS disease therapy.

Nanofiltration membrane performance of layer-by-layer membranes with different polyelectrolyte concentrations

Nanofiltration membranes produced with polyelectrolytes via the layer-by-layer technique are frequently researched, but misunderstood parameter is the polyelectrolyte concentration. Higher polyelectrolyte (PE) concentrations are known to produce thicker PE layers, but its effect on the membrane performance has only been studied in a limited fashion, leading to premature conclusions. In this work, two well-known strong polyelectrolytes, PDADMAC and PSS were used to prepare membranes using coating solutions with polyelectrolyte concentrations of 0.01, 0.1, 1.0, 2.5 and 5.0 wt% and two different salt concentrations in the coating solution of 0.05 and 1 M, as higher salt concentrations lead to thicker PE layers. The membrane performance of the prepared membranes is researched in terms of pure water permeability (PWP), molecular weight cut-off (MWCO) and the retention of different salts. In the first bilayer, membranes coated with a 0.05 M salt solution showed lower PWPs and MWCOs and higher salt retentions by increasing the PE concentration. After a certain number of coated bilayers, the MWCO and salt retentions reach a plateau for all PE concentrations; but the plateau value was obtained earlier by coating with a higher PE concentration. The membranes coated with the 1 M salt concentration had lower or comparable retention rates, except for MgCl2, than those coated with 0.05 M salt. The higher salt concentration resulted in more abundant PDADMAC in the membrane, which promotes the MgCl2 retentions for all bilayers. In conclusion, we found that the polyelectrolyte concentration significantly alters the membrane performance, but after coating 7 bilayers, the same size exclusion plateaus are reached.

Hexagonal Boron Nitride as Filler for Silica-Based Elastomer Nanocomposites.

Two-dimensional hexagonal boron nitride (hBN) has attracted tremendous attention over the last few years, thanks to its stable structure and its outstanding properties, such as mechanical strength, thermal conductivity, electrical insulation, and lubricant behavior. This work demonstrates that hBN can also improve the rheological and mechanical properties of elastomer composites when used to partially replace silica. In this work, commercially available pristine hBN (hBN-p) was exfoliated and ball-mill treated in air for different durations (2.5, 5, and 10 h milling). Functionalization occurred with the -NH and -OH groups (hBN-OH). The functional groups were detected using Fourier-Transform Infrared pectroscopy (FT-IR) and were estimated to be up to about 7% through thermogravimetric analysis. The presence of an increased amount of oxygen in hBN-OH was confirmed using Scanning Electron Microscopy coupled with Energy-Dispersive X-ray Spectroscopy. (SEM-EDS). The number of stacked layers, estimated using WAXD analysis, decreased to 8-9 in hBN-OH (10 h milling) from about 130 in hBN-p. High-resolution transmission electron microscopy (HR-TEM) and SEM-EDS revealed the increase in disorder in hBN-OH. hBN-p and hBN-OH were used to partially replace silica by 15% and 30%, respectively, by volume, in elastomer composites based on poly(styrene-co-butadiene) from solution anionic polymerization (S-SBR) and poly(1,4-cis-isoprene) from Hevea Brasiliensis (natural rubber, NR) as the elastomers (volume (mm3) of composites released by the instrument). The use of both hBNs in substitution of 30% of silica led to a lower Payne effect, a higher dynamic rigidity, and an increase in E' of up to about 15% at 70 °C, with similar/lower hysteresis. Indeed, the composites with hBN-OH revealed a better balance of tan delta (higher at low temperatures and lower at high temperatures) and better ultimate properties. The functional groups reasonably promote the interaction of hBN with silica and with the silica's coupling agent, sulfur-based silane, and thus promoted the interaction with the elastomer chains. The volume of the composite, measured using a high-pressure capillary viscometer, increased by about 500% and 400% after one week of storage in the presence of hBN-p and hBN-OH. Hence, both hBNs improved the processability and the shelf life of the composites. Composites obtained using hBN-OH had even filler dispersion without the detachments of the filler from the elastomer matrix, as shown through TEM micrographs. These results pave the way for substantial improvements in the important properties of silica-based composites for tire compounds, used to reduce rolling resistance and thus the improve environmental impacts.

Fluorinated and safety-reinforced copolymer solid electrolytes for high-voltage all-solid-state sodium metal batteries

Poly (ethylene oxide)-based all-solid-state electrolytes are extensively regarded as highly promising contenders for the upcoming era of sodium metal batteries. Nevertheless, the intrinsic elevated highest occupied molecular orbital (HOMO) and the strong sodium-ion adsorption energy lead to a narrow electrochemical stability window (ESW) and a sluggish ion transport kinetics, thus retarding its widespread application in high-voltage batteries. About these shortcomings, we propose a strategy of fluorine substitution through a ready UV-initiated free-radical copolymerization to regulate the orbital level sodium-ion adsorption energy of poly (ethylene oxide) electrolytes. The characterization confirmed the success in the introduction of fluorine into the polymer (referred to as P-co-F). DFT calculations demonstrated a lower HOMO (-7.061 eV) in fluorine-substituted polymer electrolyte, which enabled to expand the ESW up to 5.55 V. Besides, the sodium-ion adsorption energy on P-co-F was decreased from −2.78 eV to −3.43 eV, facilitating the rapid transport of sodium ion. In addition, Polyethylene terephthalate (PET) was adopted as a support frame, which would reinforce the mechanical properties of polymer electrolytes. The electrochemical tests suggested P-co-F exhibited a profound interfacial stability in the Na//Na symmetrical system throughout an operational duration of 4690 h at 0.1 mA cm−2. The assembled all-solid-state battery manifested remarkable stability during continuous cycling at room temperature for 200 cycles, retaining an impressive 96.59 % of its initial capacity at 0.1C. The intriguing fluorine-induced effect, coupled with a cost-effective safety substrate, will provide valuable insights for the rational molecular design of innovative electrolytes and easy production scalability for all-solid-state Na metal batteries.

Triptycene Branched Poly(aryl-co-aryl piperidinium) Electrolytes for Alkaline Anion Exchange Membrane Fuel Cells and Water Electrolyzers.

Alkaline polymer electrolytes (APEs) are essential materials for alkaline energy conversion devices such as anion exchange membrane fuel cells (AEMFCs) and water electrolyzers (AEMWEs). Here, we report a series of branched poly(aryl-co-aryl piperidinium) with different branching agents (triptycene: highly-rigid, three-dimensional structure; triphenylbenzene: planar, two-dimensional structure) for high-performance APEs. Among them, triptycene branched APEs showed excellent hydroxide conductivity (193.5 mS cm-1 @80 °C), alkaline stability, mechanical properties, and dimensional stability due to the formation of branched network structures, and increased free volume. AEMFCs based on triptycene-branched APEs reached promising peak power densities of 2.503 and 1.705 W cm-2 at 75/100 % and 30/30 % (anode/cathode) relative humidity, respectively. In addition, the fuel cells can run stably at a current density of 0.6 A cm-2 for 500 h with a low voltage decay rate of 46 μV h-1 . Importantly, the related AEMWE achieved unprecedented current densities of 16 A cm-2 and 14.17 A cm-2 (@2 V, 80 °C, 1 M NaOH) using precious and non-precious metal catalysts, respectively. Moreover, the AEMWE can be stably operated under 1.5 A cm-2 at 60 °C for 2000 h. The excellent results suggest that the triptycene-branched APEs are promising candidates for future AEMFC and AEMWE applications.