Glycol Methyl Ether Acrylate Research Articles

Curcumin-Loaded PnBA-b-POEGA Nanoformulations: A Study of Drug-Polymer Interactions and Release Behavior.

The current study focuses on the development of innovative and highly-stable curcumin (CUR)-based therapeutics by encapsulating CUR in biocompatible poly(n-butyl acrylate)-block-poly(oligo(ethylene glycol) methyl ether acrylate) (PnBA-b-POEGA) micelles. State-of-the-art methods were used to investigate the encapsulation of CUR in PnBA-b-POEGA micelles and the potential of ultrasound to enhance the release of encapsulated CUR. Dynamic light scattering (DLS), attenuated total reflection Fourier transform infrared (ATR-FTIR), and ultraviolet-visible (UV-Vis) spectroscopies confirmed the successful encapsulation of CUR within the hydrophobic domains of the copolymers, resulting in the formation of distinct and robust drug/polymer nanostructures. The exceptional stability of the CUR-loaded PnBA-b-POEGA nanocarriers over a period of 210 days was also demonstrated by proton nuclear magnetic resonance (1H-NMR) spectroscopy studies. A comprehensive 2D NMR characterization of the CUR-loaded nanocarriers authenticated the presence of CUR within the micelles, and unveiled the intricate nature of the drug-polymer intermolecular interactions. The UV-Vis results also indicated high encapsulation efficiency values for the CUR-loaded nanocarriers and revealed a significant influence of ultrasound on the release profile of CUR. The present research provides new understanding of the encapsulation and release mechanisms of CUR within biocompatible diblock copolymers and has significant implications for the advancement of safe and effective CUR-based therapeutics.

3D Printed Solid Polymer Electrolytes with Bicontinuous Nanoscopic Domains for Ionic Liquid Conduction and Energy Storage.

Solid polymer electrolytes (SPEs) offer several advantages compared to their liquid counterparts, and much research has focused on developing SPEs with enhanced mechanical properties while maintaining high ionic conductivities. The recently developed polymerization-induced microphase separation (PIMS) technique offers a straightforward pathway to fabricate bicontinuous nanostructured materials in which the mechanical properties and conductivity can be independently tuned. In this work SPEs with tunable mechanical properties and conductivities are prepared via digital light processing 3D printing, exploiting the PIMS process to achieve nanostructured ion-conducting materials for energy storage applications. A rigid crosslinked poly(isobornyl acrylate-stat-trimethylpropane triacrylate) scaffold provided materials with room temperature shear modulus above 400MPa, while soft poly(oligoethylene glycol methyl ether acrylate) domains containing the ionic liquid 1-butyl-3-methylimidazolium bis-(trifluoromethyl sulfonyl)imide endowed the material with ionic conductivity up to 1.2 mS cm-1 at 30°C. These features make the 3D-printed SPE very competitive for applications in all solid energy storage devices, including supercapacitors.

External Measurement of Swallowed Volume During Exercise Enabled by Stretchable Derivatives of PEDOT:PSS, Graphene, Metallic Nanoparticles, and Machine Learning

AbstractEpidermal sensors for remote healthcare and performance monitoring require the ability to operate under the effects of bodily motion, heat, and perspiration. Here, the use of purpose‐synthesized polymer‐based dry electrodes and graphene‐based strain gauges to obtain measurements of swallowed volume under typical conditions of exercise is evaluated. The electrodes, composed of the common conductive polymer poly(3,4 ethylenedioxythiophene) (PEDOT) electrostatically bound to poly(styrenesulfonate)‐b‐poly(poly(ethylene glycol) methyl ether acrylate) (PSS‐b‐PPEGMEA), collect surface electromyography (sEMG) signals on the submental muscle group, under the chin. Simultaneously, the deformation of the surface of the skin is measured using strain gauges comprising single‐layer graphene supporting subcontinuous coverage of gold and a highly plasticized composite containing PEDOT:PSS. Together, these materials permit high stretchability, high resolution, and resistance to sweat. A custom printed circuit board (PCB) allows this multicomponent system to acquire strain and sEMG data wirelessly. This sensor platform is tested on the swallowing activity of a cohort of 10 subjects while walking or cycling on a stationary bike. Using a machine learning (ML) model, it is possible to predict swallowed volume with absolute errors of 36% for walking and 43% for cycling.

Synthesis and Characterization of Temperature‐/pH‐Responsive Hydrogels for Drug Delivery

AbstractA temperature‐/pH‐responsive hydrogel was successfully prepared by in situ free radical polymerization of N‐isopropyl acrylamide (NIPAm), itaconic acid (IA), and poly (ethylene glycol) methyl ether acrylate (OEGA). The pore size, mechanical strength, and swelling ratio of the P(NIPAm‐IA‐OEGA) were strongly affected by the contents of IA. 5‐Fluorouracil (5‐Fu) was chosen as a model drug, and the maximum drug loading was 68 mg/g. P(NIPAm‐IA‐OEGA) had a much greater release rate in a simulated intestinal fluid environment (47.73 %, 16 h) than in gastric juice (33.11 %, 16 h). The hemolysis test and cytotoxicity test proved that prepared hydrogel had good biocompatibility. In summary, P(NIPAm‐IA‐OEGA) can be used for oral drug delivery systems in cancer therapy.

Surface hydrolysis-anchored eugenol self-polishing marine antifouling coating

Traditional self-polishing antifouling coatings kill surface organisms by releasing toxic substances, which are damaging to the ecosystem. As a natural antimicrobial substance, eugenol is environmentally friendly and has been proven by different research teams to be effective in enhancing the anti-fouling effect of coatings in the real sea. While in these previous research works, the eugenol was released directly into the seawater thus cannot further serve as surface antifouling effect, leading to a limited antifouling effect of the coating. In this work, the quaternary ammonium component was introduced into the butyl ester-based resin - poly (eugenol methacrylate - acryloyloxyethyltrimethyl ammonium chloride - hexafluorobutyl methacrylate - methyl methacrylate - butyl methacrylate - ethylene glycol methyl ether acrylate) (EMQFP) coating for the first time by simple one-step free radical polymerization method. On the one hand, the eugenol produced by hydrolysis is anchored to the quaternary ammonium on the coating surface for a period of time due to the cationic-π interaction, instead of being released into seawater immediately after hydrolysis, thus increasing the utilization rate of eugenol; on the other hand, the negatively charged carboxylate groups generated after hydrolysis in the coating are mutually attracted to quaternary ammonium through electrostatic effect, so the resin chain segment conformation on the coating surface adjusted to produce zwitterionic-like structure, and the hydration of zwitterionic inhibits primary fouling adhesion.

A Quasi‐Solid Electrolyte by In Situ Polymerization of Selective Solvent for Lithium‐Metal Batteries

AbstractLithium (Li) metal is a competitive anode material for rechargeable high energy density batteries due to its high specific capacity and low reduction potential. However, great challenges remain in addressing uncontrollable Li dendrite growth and unstable interface. Herein, we report a quasi‐solid electrolyte enabled by in situ polymerization of polyethylene glycol methyl ether acrylate. Meanwhile, a LiF‐enriched solid electrolyte interphase (SEI) is built on Li‐metal surface by function of the fluoroethylene carbonate additive. The SEI with a good mechanical stability prompts the dense and uniform Li deposition behavior. The in situ polymerized gel polymer electrolyte exhibits an ionic conductivity of 1.71×10−4 S cm−1 at 30 °C, and a considerable oxidative stability up to 4.5 V (vs. Li/Li+). The Li||Li symmetric cells delivers a long‐term cycle life over 1400 h and a low voltage hysteresis at 0.5 mA cm−2, 1 mAh cm−2. To be paired with a LiFePO4 positive electrode, the cell shows a high discharge capacity of 135.6 mAh g−1 and capacity retention of 92.7 % after 300 cycles. This work provides a reference for the practical development of quasi‐solid electrolyte for lithium‐metal battery.

Modification of silica particles with poly(phenylboronic acid) brushes for fabricating hollow mesoporous carbon nanospheres

AbstractPorous carbon nanospheres have attracted extensive attention due to their excellent advantages in specific surface area, pore distribution, and electronic conductivity. Herein, boron‐doped hollow carbon nanospheres with mesoporous walls have been successfully synthesized via a combination of hard/soft templating and boronic acid/sugar ligation. Surface‐initiated Cu(0) mediated reversible deactivation radical polymerization was used to initiate the polymerization of 2‐hydroxyethyl acrylate and poly(ethylene glycol) methyl ether acrylate from the surface of silica. 4‐carboxy‐3‐fluorophenylboronic acid was introduced as a boron precursor by N‐(3‐dimethylaminopropyl)‐N′‐ethylcarbodiimide hydrochloride coupling and fructose was introduced as a carbon precursor by boronic esters. After carbonization and template etching, boron‐doped porous carbon spheres could be obtained. We believe such in‐situ heteroatom‐doped method has great potential in preparing hollow mesoporous carbon nanospheres with excellent properties.

Cell-Derived Vesicles with Increased Stability and On-Demand Functionality by Equipping Their Membrane with a Cross-Linkable Copolymer.

Cell-derived vesicles retain the cytoplasm and much of the native cell membrane composition. Therefore, they are attractive for investigations of membrane biophysics, drug delivery systems, and complex molecular factories. However, their fragility and aggregation limit their applications. Here, the mechanical properties and stability of giant plasma membrane vesicles (GPMVs) are enhanced by decorating them with a specifically designed diblock copolymer, cholesteryl-poly[2-aminoethyl methacrylate-b-poly(ethylene glycol) methyl ether acrylate]. When cross-linked, this polymer brush enhances the stability of the GPMVs. Furthermore, the pH-responsiveness of the copolymer layer allows for a controlled cargo loading/release, which may enable various bioapplications. Importantly, the cross-linked-copolymer GPMVs are not cytotoxic and preserve in vitro membrane integrity and functionality. This effective strategy to equip the cell-derived vesicles with stimuli-responsive cross-linkable copolymers is expected to open a new route to the stabilization of natural membrane systems and overcome barriers to biomedical applications.

Enhanced Electrochemical Performance of NCM811 Cathodes with Functionalized PVDF Graft Copolymer Binders

Nickel-rich Li(Ni x Co y Mn1–x–y O2) (x ≥ 0.6) (NCM) cathodes are regarded as the predominant cathode materials for next-generation Li-ion batteries due to their high specific energy density. However, undesired structural disruption and thermal instability were observed with the increase of Ni content e.g. Ni0.8Co0.1Mn0.1(NCM811), which are often attributed to the transition metal (TM) ion dissolution, phase change, oxygen release and microcracks formed on the secondary particles during cycling. Therefore, the rapid capacity loss and poor capacity retention have hindered the successful practical applications for NCM811 cathodes. To solve these abovementioned problems, many strategies have been proposed. One of most effective way is to design and explore functional and novel polymer binder materials. Although poly(vinylidene fluoride) (PVDF), as the benchmark binder in battery community, has been widely used for decades, lacking of functional groups and poor chemical interactions with the active particles makes it no longer the optimal choice for more challenging cathodes.Herein, to explore the possibilities and broaden the range of functional polymers for boosting the performance of NCM811 cathodes, we propose grafting from poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) to obtain PVDF-based polymers with a comb-like architecture, where the PVDF-CTFE was chosen as a substrate backbone to provide the initiating sites for further modification. Atom transfer radical polymerization (ATRP), the controlled radical polymerization technique was used to obtain well-controlled grafted chains with low dispersity and desired length and architecture. A random copolymer of poly(ethylene glycol) methyl ether acrylate and poly(tert-butyl acrylate) (PEGMEA-co-PtBA) was first grafted from the PVDF-CTFE backbone, then after hydrolysis of PtBA to poly(acrylic acid) (PAA), the PVDF-CTFE-g-PEGMEA-co-PAA graft copolymers were obtained. Benefiting from the ethylene oxide conductive segments in PEGMEA, the Li ion diffusion and transport was significantly improved. The chelation of TM ions to -COOH groups from PAA would effectively mitigate the TM dissolution and prevent phase transition of NCM811. To test the electrochemical performances of NCM811 cathodes prepared with the designed polymer binder, PVDF and PVDF-CTFE were compared as the control groups in this study. The rate performance of the Li|NCM811 cells showed that PVDF-CTFE-g-PEGMEA-co-PAA binder gave comparable discharge capacities to PVDF and PVDF-CTFE at 0.1C-2C (Figure 1a), however, under 4C with faster charging/discharging, the discharge capacities of PVDF-CTFE-g-PEGMEA-co-PAA were much higher than the two control groups. When increasing the NCM811 weight ratio from 85 wt% to 93 wt%, where the contribution from the conductive carbon is less, the differences were even more significant (Figure 1b). PVDF-CTFE-g-PEGMEA-co-PAA delivered higher capacity at all rates, especially at 2C and 4C, suggesting faster Li ion transport and enhanced electronic properties in the cathodes. Figure 1. Rate performance of Li|NCM811 cells with binder PVDF (grey), PVDF-CTFE (orange) and PVDF-CTFE-g-PEGMEA-co-PAA (green) in the voltage range of 2.9–4.3 V using NCM811/carbon black/binder weight ratio of a) 85/10/5 and b) 93/4/3. Figure 1

Constructing self-healing high-strength elastomer with condensed state microphase separation by solubilization and copolymerization

Self-healing is a fascinating property for materials, but it is still a challenge to simply, effectively and greenly prepare self-healing material. Here, a self-healing elastomer was fabricated by solubilization copolymerization of ethylene glycol methyl ether acrylate (MEA) and N-isopropylacrylamide (NIPAM). When NIPAM content was 40%, “strong condensed state” emerged and led to obvious microphase separation, which greatly improved stress to 3.5 MPa at break (≈650%). Meantime, because the condensed state was still weak in the copolymer, the dissociation and re-association could occur to improve self-healing performance. The copolymer had about 60% self-healing efficiency after 8h at 100 °C, and the actual stress was 2 MPa at break (≈500%). The copolymer with good solubility can be easily recycled and reprocessed. A wrinkled skin-core conductive filament also was prepared by wet spinning and stretching coating, which was conductive and stretchable. And the self-healing core can drive conductive PEDOT: PSS shell to re-touch after break. • The solubilization copolymerization preparation is more simple, effective and green. • Microphase separation structure are formed by polymerizing monomer with micellar distribution. • NIPAM condensed state can achieve dissociation and re-association to improved self-healing performance. • Copolymers have good mechanical properties, self-healing properties, recyclability and secondary processability.

Elucidating the Impact of Hydrophilic Segments on 19F MRI Sensitivity of Fluorinated Block Copolymers.

A major challenge in the preparation of polymeric 19F magnetic resonance imaging (MRI) contrast agents (CAs) is signal attenuation caused by reduced segmental mobility of partly fluorinated polymers possessing large numbers of fluorine atoms. Previous studies have thus mainly focused on the development of fluorinated segments for improved 19F MRI; however, detailed investigations of the role of hydrophilic segments on imaging performance remain scarce. In this study, three hydrophilic and biocompatible monomers, i.e., 2-(methylsulfinyl)ethyl acrylate (MSEA), oligo(ethylene glycol) methyl ether acrylate (OEGA), and oligo(2-methyl-2-oxazoline) acrylate (OMOXA), were used to prepare perfluoropolyether (PFPE)-containing amphiphilic block polymers through reversible addition-fragmentation chain-transfer (RAFT) polymerization. The effect of the different hydrophilic segments on 19F imaging performance was explored. The three polymers could be readily dissolved in aqueous solutions, forming assemblies with the hydrophobic PFPE as the core and the hydrophilic chains as the shell. Molecular dynamics simulations demonstrate that the POMOXA chains adopt a rigid, extended conformation, leading to a relatively short 19F NMR spin-spin relaxation time (T2), lower NMR detectable 19F spins (i.e., visibility), and the least intense 19F MRI signal. In contrast, although PMSEA-PFPE has a shorter 19F NMR T2 than POEGA-PFPE, the much higher 19F spin visibility enhances its MRI signal intensity. The result confirms the importance of maintaining both high fluorine visibility and long T2 relaxation time to prepare effective CAs and highlight the key role of the nonfluorinated hydrophilic segments in determining these parameters.

Degradable Linear and Bottlebrush Thioester-Functional Copolymers through Atom-Transfer Radical Ring-Opening Copolymerization of a Thionolactone

Polymers with tailored architectures and degradability were prepared through thiocarbonyl addition ring-opening (TARO) atom-transfer radical polymerization (ATRP) using dibenzo[c,e]oxepin-5(7H)-thione (DOT), Cu(I)Br, and tris[2-(dimethylamino)ethyl]amine (Me6TREN) as the thionolactone, catalyst, and ligand, respectively, in combination with a selection of acrylic comonomers. Although copolymers with selectively degradable backbone thioesters and low dispersities (1.10 ≤ D̵ ≤ 1.26) were achieved using DMSO, acetonitrile, or toluene as the solvent, the Cu(I)-catalyzed dethionation of DOT to its (oxo)lactone analogue limited the achievable copolymer DOT content. Using anhydrous polymerization conditions minimized the side reaction and provided degradable copolymers with a higher (≤32 mol %) thioester content. Water-soluble molecular brushes were prepared by grafting poly(ethylene glycol) methyl ether acrylate–DOT copolymers from a pre-made multi-ATRP initiator. Due to copolymerization kinetics, the thioesters were installed close to the junctions and enabled the fast (<1 min) cleavage of the arms from the core to give water-soluble products using 10 mM oxone.

Topographical Design and Thermal-Induced Organization of Interfacial Water Structure to Regulate the Wetting State of Surfaces.

Smart surfaces with superhydrophobic/superhydrophilic characteristics can be controlled by external stimuli, such as temperature. These transitions are attributed to the molecular-level conformation of the grafted polymer chains due to the varied interactions at the interface. Here, tunable surfaces were prepared by grafting two well-known thermo-responsive polymers, poly(N-isopropylacrylamide) (PNIPAM) and poly(oligoethylene glycol)methyl ether acrylate (POEGMA188) onto micro-pollen particles of uniform morphology and roughness. Direct Raman spectra and thermodynamic analyses revealed that above the lower critical solution temperature, the bonded and free water at the interface partially transformed to intermediate water that disrupted the “water cage” surrounding the hydrophobic groups. The increased amounts of intermediate water produced hydrogen bonding networks that were less ordered around the polymer grafted microparticles, inducing a weaker binding interaction at the interface and a lower tendency to wet the surface. Combining the roughness factor, the bulk surface assembled by distinct polymer-grafted-pollen microparticles (PNIPAM or POEGMA188) could undergo a different wettability transition for liquid under air, water, and oil. This work identifies new perspectives on the interfacial water structure variation at a multiple length scale, which contributed to the temperature-dependent surface wettability transition. It offers inspiration for the application of thermo-responsive surface to liquid-gated multiphase separation, water purification and harvesting, biomedical devices, and printing.

Poly(poly(ethylene glycol) methyl ether acrylate) micelles for highly CO2 permeable membranes

Herein, we report highly CO2-permeable membranes obtained by blending in situ self-assembled micellar-structured poly(poly(ethylene glycol) methyl ether acrylate) (PPEGMEA) with poly(ether-block-amide) (Pebax). PPEGMEA with different molecular weights were prepared by varying the concentration of benzoyl peroxide (BPO) in a Pebax/PEGMEA/BPO mixture during radical polymerization. Significantly, the Pebax/PPEGMEA (30/70 w/w) blend membrane comprised highly CO2-philic PPEGMEA micelles, which appreciably increased the d-spacing of the Pebax matrix. Consequently, the blend membrane containing a high molecular weight of PPEGMEA exhibited an unprecedented CO2 permeability enhancement of 1054% compared to the pristine Pebax membrane while maintaining good CO2 selectivity relative to H2, O2, N2, CO, and CH4 because of the enriched polyethylene glycol moieties. This excellent separation performance was maintained for 100 h, validating the good long-term separation performance of the membrane. Furthermore, the membrane exhibited good mechanical strength and plasticization tolerance, resulting in excellent CO2 separation performance under equimolar CO2/N2 or CO2/CH4 mixed gas conditions (CO2 permeability of 1250 Barrer and CO2/N2 and CO2/CH4 selectivity of 31.5 and 12.7, respectively), up to a CO2 partial pressure of 10 atm. Our simple but effective in situ micelle-induced blending approach is a significant step toward realizing high-performance CO2 separation membranes.

Chitosan Grafted Poly (Ethylene Glycol) Methyl Ether Acrylate Particulate Hydrogels for Drug Delivery Applications.

Chitosan (CS) crosslinking has been thoroughly investigated, but the chemical reactions leading to submicronic hydrogel formulations pose problems due to various physical/chemical interactions that limit chitosan processability. The current study employs the chemical modification of chitosan by Michael addition of poly (ethylene glycol) methyl ether acrylate (PEGA) to the amine groups to further prepare chitosan particulate hydrogels (CPH). Thus, modified CS is subjected to a double crosslinking, ionic and covalent, in water/oil emulsion. The studied process parameters are polymer concentration, stirring speed, and quantity of ionic crosslinker. The CPH were structurally and morphologically characterized through infrared spectroscopy, scanning electron microscopy, light scattering granulometry, and zeta potential, showing that modified CS allows better control of dimensional properties and morphology as compared with neat CS. Swelling properties were studied in acidic and neutral pH conditions, showing that pH-dependent behavior was maintained after grafting and double crosslinking. The applicability of the prepared materials was further tested for drug loading and in vitro delivery of levofloxacin (LEV), showing excellent capacity. CPH were found to be cyto- and hemocompatible demonstrating their potential for effective use as a controlled release system for different biomedical applications.

GeFSIX‐1‐Cu based semi‐interpenetrating network mixed matrix membranes for efficient CO2 separation

AbstractIn order to increase CO2 separation efficiency, semi‐interpenetrating network mixed matrix membranes (SIPN‐MMMs) were loaded with GeFSIX‐1‐Cu (Cu(4,4′‐bipyridine)2(GeF6)) and poly ethylene glycol dimethyl ether (PEGDME). Two long‐chain polymers poly ethylene glycol diacrylate (PEGDA) and poly ethylene glycol methyl ether acrylate (PEGMEA) jointly constituted a crosslinked PEO backbone, and CO2‐philic short‐chain polymer PEGDME and anion‐pillared hybrid porous materials GeFSIX‐1‐Cu were embedded into the backbone to introduce strong CO2 adsorption sites and provide extra pore channels. Increasing GeFSIX‐1‐Cu loading in SIPN‐MMMs initially improved CO2 permeability and CO2/N2, CO2/CH4, and CO2/H2 selectivity, because the porous structure of GeFSIX‐1‐Cu provides additional pore channels for gas transport. In addition, the strong binding affinity between GeF62− and CO2 leads to improved membrane selectivity. When GeFSIX‐1‐Cu loading increased above 3 wt%, both CO2 permeability and CO2/N2, CO2/CH4, and CO2/H2 selectivity decreased, due to agglomeration of excess GeFSIX‐1‐Cu loading in SIPN‐MMMs. The highest CO2 permeability of 786 Barrer and CO2/N2 ideal selectivity of 43 (at GeFSIX‐1‐Cu loading of 3 wt%) were 36% and 38% higher than those of pure SIPN membrane, respectively, resolving the trade‐off between permeability and selectivity, and surpassing the Robeson upper bound (2008).

Disulfide Metathesis-Assisted Lithium-Ion Conduction for PEO-Based Polymer Electrolytes.

The disulfide metathesis is a promising candidate in the dynamically exchanged strategy for improving the self-healing ability of polymer electrolytes (PEs). However, the enhancement effects on the ionic conductivities of PEs are generally ignored while introducing a dynamic covalent bond to PEs. Herein, the oligo(ethylene oxide)-based additive containing a disulfide bond (S-S additive) was synthesized via Michael addition reaction of cystamine and poly(ethylene glycol) methyl ether acrylate (PEGA). Short PEG chains complexed with Li+ in a S-S additive migrated rapidly in PEs because of the dynamically exchanged strategy of the disulfide bond. Moreover, disulfide bonds in a S-S additive possessed the ability to exchange with the cross-linked network containing disulfide bonds (S-S net). The as-prepared PEs exhibited a high room temperature ionic conductivity of 1.24 × 10-4 S cm-1, demonstrating that the disulfide metathesis-assisted Li+ conduction was feasible for enhancing ionic conductivities of PEs. Relative to other PEO-based PEs, these disulfide-containing PEs possessed a high Li+ transference number (0.54). Furthermore, the lithium-metal batteries (LMBs) assembled with PEs in the presence of a S-S additive presented stable cycle performance, indicating the promising potential of these PEs as candidates for next-generation LMBs.

An acrylate-based quasi-solid polymer electrolyte incorporating a novel dinitrile poly(ethylene glycol) plasticizer for lithium-ion batteries

The performance of solid polymer electrolytes is characterized by lower ionic conductivity than conventional liquid electrolytes but provides advantages in terms of operational safety. A quasi-solid polymer electrolyte (QSPE) based on a new plasticizer 4,7,10,13-tetraoxahexadecane-1,16-dinitrile (bCN-PEG4) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) incorporated into a polyacrylates matrix was successfully prepared via UV-induced copolymerization. The matrix consists of units of trimethylolpropane ethoxylate triacrylate (ETPTA), poly(ethylene glycol) diacrylate (PEGDA), and the monoacrylate poly(ethylene glycol) methyl ether acrylate (mPEGa). The QSPE containing 55 wt% bCN-PEG4 exhibits highly uniform morphology, thermal stability > 200 °C, ionic conductivity of 1.8 × 10−4 S cm−1 at 30 °C, and 1.3 × 10−3 S cm−1 at 80 °C, coupled with very high electrochemical stability (> 5 V vs. Li/Li+) and a low glass transition temperature (− 55.7 °C). A cycling experiment in a Li/QPSE/Li cell setup demonstrated the compatibility toward lithium metal additionally. The bCN-PEG4 offers an overall satisfying performance as a plasticizer in a poly(ethylene oxide)-based solid polymer electrolyte. The new QSPE is an alternative to dinitrile-based (e.g., succinonitrile) or glycol ether-based (e.g., tetraglyme) plasticizers with application potential in high-voltage lithium-ion batteries.Graphical abstract

Synthesis of a dual UCST-type thermosensitive and acid-degradable nanogel based on poly(N-acryloyl glycinamide) and a ketal-containing crosslinker

In the present study, we designed a dual upper critical solution temperature (UCST) type thermosensitive and acid-degradable nanogel via UV-light initiated RAFT-mediated polymerization-induced thermal self-assembly (PITSA). The dual stimuli-triggered nanogel was prepared with N-acryloyl glycinamide as the precursor monomer of a hydrogen-bonding UCST-type thermosensitive polymer, a new pH-sensitive ketal-containing crosslinker, and poly(poly(ethylene glycol) methyl ether acrylate) acting as both a macromolecular chain transfer agent and a surfactant, called macro-transurf. The resulting spherical nanogel exhibits dual thermo- and pH-sensitive properties, as determined by UV–Vis spectrophotometry and/or dynamic light scatterring measurements at different values of pH (4, 6 and 9) and temperature (5 and 55 °C). The nanogel displays a UCST phase transition at 41 °C in buffer solution (pH = 9) and is degraded rapidly (25 and 45 min) in acidic environments (pH 4 and pH 6).

Self‐Healing Polymer Electrolyte for Dendrite‐Free Li Metal Batteries with Ultra‐High‐Voltage Ni‐Rich Layered Cathodes

Practical applications of polymer electrolytes in lithium (Li) metal batteries with high-voltage Ni-rich cathodes have been hindered by the dendrite growth and poor oxidative stability of electrolytes. Herein, a self-healing polymer electrolyte is developed by in situ copolymerization of 2-(3-(6-methyl4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate (UPyMA) and ethylene glycol methyl ether acrylate (EGMEA) monomers. With the electrolyte, the dendrite growth is inhibited by spontaneously repairing dendrite-induced defects, cracks, and voids at the Li/electrolyte interface; the suppressed dendrite growth and associated electro-chemo behaviors are visualized by the kinetic Mont-Carlo simulation. Benefitting from the high ionic conductivity, wide electrochemical window and good interfacial stability, the self-healing polymer electrolyte enables stable cycling of the LiNi0.8 Mn0.1 Co0.1 O2 (NMC811) cathode under 4.7V, achieving a high specific capacity of ≈228.8mAh g-1 and capacity retention of 80.4% over 500 cycles. The new electrolyte is very promising for developing highly safe and dendrite-free Li metal batteries with high energy density.