Rational Design of Vinylene Carbonate-Inspired 1,3-Dimethyl-1H-imidazol-2(3H)-one Additives to Stabilize High-Voltage Lithium Metal Batteries.

Lithium metal batteries (LMBs) employing high-voltage nickel-rich cathodes represent a promising strategy to enable higher energy density storage systems. However, instability at the electrolyte-electrode interfaces (EEIs) currently impedes the translation of these advanced systems into practical applications. Herein, 1,3-dimethyl-1H-imidazol-2(3H)-one (DMIO), integrating structural features of vinylene carbonate (VC) while substituting oxygen with electron-donating nitrogen, has been synthesized and validated as a multifunctional electrolyte additive for high-voltage LMBs. Theoretical calculations and experimental results demonstrate that the potent electron-donating nitrogen in DMIO enables preferential DMIO oxidation at the cathode while preserving its carbon-carbon double bond for a concomitant reduction on the anode. Thereby, robust DMIO-derived EEIs are generated, reinforcing cycling in the full cells. Additionally, DMIO leverages Lewis acid-based interactions to coordinate and sequester protons from acidic LiPF6 decomposition byproducts, concurrently retarding LiPF6 hydrolysis while attenuating parasitic consumption of EEIs by acidic species. Consequently, incorporating DMIO into conventional carbonate electrolytes enables an improved capacity retention of Li||NCM622 cells to 81% versus 26% in the baseline electrolyte after 600 cycles. Similarly, DMIO improves Li anode cycling performance, displaying extended life spans over 200 h in Li||Li symmetric cells and enhancing Coulombic efficiency from 76% to 88% in Li||Cu cells. The synergistic effects of DMIO on both the cathode and anode lead to substantially improved cell lifetime. This rationally designed, multifunctional electrolyte additive paradigm provides vital insights that can be translatable to further electrolyte molecular engineering strategies.

A Green Asymmetric Bicyclic Co-Solvent Molecule for High-Voltage Aqueous Lithium-Ion Batteries.

Hybridizing aqueous electrolytes with organic co-solvents can effectively expand the voltage window of aqueous electrolytes while reducing salt usage, but most reported co-solvents are usually flammable and toxic, hardly achieving compatibility between safety and electrochemical performance. Here, a new non-flammable and non-toxic low-salt-concentration (1.85 m) aqueous electrolyte is reported using the green co-solvent isosorbide dimethyl ether (IDE). Owing to its unique 3D molecular structure, IDE can form a five-membered ring structure by binding the Li ion. The steric hindrance effect from IDE weakens its solvation ability, generating anion-participated solvation structures that produce a robust and uniform LiF-rich solid electrolyte interphase layer while containing elastic IDE-derived organics. Moreover, the multiple O atoms in IDE can effectively regulate the intermolecular hydrogen bonding networks, reducing H2O molecule activity and expanding the electrochemical window. Such unique solvation structures and optimized hydrogen bonding networks enabled by IDE effectively suppress electrode/electrolyte interfacial side reactions, achieving a 4.3 V voltage window. The as-developed Li4Ti5O12(LTO)||LiMn2O4(LMO) full cell delivers outstanding cycling performance over 450 cycles at 2 C. The proposed green hybrid aqueous electrolyte provides a new pathway for developing high-voltage aqueous lithium batteries.

Acetalized starch-based nanoparticles stabilized acid-sensitive Pickering emulsion as a potential antitumor drug carrier.

Pickering emulsions are attracting increased attention owing to their therapeutic applications. However, the slow-release property of Pickering emulsions and the in vivo solid particle accumulation caused by the solid particle stabilizer film limit their applications in therapeutic delivery. In this study, drug-loaded, acid-sensitive Pickering emulsions were prepared using acetal-modified starch-based nanoparticles as stabilizers. The acetalized starch-based nanoparticles (Ace-SNPs) not only act as a solid-particle emulsifier to stabilize Pickering emulsions but also exhibit acid sensitivity and degradability, conducive to the destabilization of Pickering emulsions to release the drug and reduce the effect of particle accumulation in an acidic therapeutic environment. In vitro drug release profiles show that 50 % of curcumin was released in 12 h in an acidic medium (pH 5.4), whereas only 14 % of curcumin was released in 12 h at higher pH (7.4), indicating that the Ace-SNP stabilized Pickering emulsion possess good acid-responsive release characteristics in acidic environments. Moreover, acetalized starch-based nanoparticles and their degradation products showed good biocompatibility, and the resulting curcumin-loaded Pickering emulsions exhibited significant anticancer activity. These features suggest that the acetalized starch-based nanoparticle-stabilized Pickering emulsion has the potential for application as an antitumor drug carrier to enhance therapeutic effects.

Facile Fabrication of Starch-Based Microrods by Shear-Assisted Antisolvent-Induced Nanoprecipitation and Solidification.

Rod-like particles have attracted increasing attention because of their unique shape-dependent properties, which enable their superior performance compared to their isotropic counterparts. Thus, rod-like particles have potential applications in many fields, especially in biomedicine. However, the fabrication of uniform rod-like particles is challenging because of the principle of interfacial energy minimization. Herein, we present a facile, rapid, and cost-effective strategy for preparing starch-based microrods with tunable aspect ratios via shear-assisted antisolvent-induced nanoprecipitation and solidification. The preformed spherical particles swollen by the mixed solvent were elongated by the shear force and solidified in rod-like shape by antisolvent induction. The resulting starch-based microrods can encapsulate hydrophobic active substances and be modified with functional groups, indicating their potential applications as drug carriers and biologically active materials. The formation mechanism of the starch-based microrods discovered in this study provides a new perspective on the fabrication of rod-like polymer particles.

Li-N Interaction Induced Deep Eutectic Gel Polymer Electrolyte for High Performance Lithium-Metal Batteries.

As emerging eutectic mixtures, deep eutectic electrolytes (DEEs) show unique properties for Li-metal batteries (LMBs). However, the limited choice and inferior electrode compatibility hinder their further development in LMBs. Herein, we report a new 1,2-dimethylimidazole (DMIm)-based deep eutectic gel polymer electrolyte induced by Li-N interaction. We demonstrate that incorporating electron-withdrawing polyvinylidene difluoride (PVDF) polymer into the DMIm-based DEE changes the coordination environment of Li+ ions, leading to a high transference number of Li+ ions (0.65) and superior interface stability between the electrolyte and Li anode. The deep eutectic gel polymer electrolyte exhibits excellent non-flammability, high ionic conductivity (1.67 mS cm-1 at 30 °C), and high oxidation voltage (up to 4.35 V vs. Li/Li+ ). The Li||LFP cell based on the newly developed deep eutectic gel polymer electrolyte can achieve superior long-term cycling stability at a wide range of rates.

Robust cellulose-based composite adsorption membrane for heavy metal removal.

Adsorptive membranes offer an effective mode to remove heavy metal ions from contaminated water, due to the synergies made possible by low-cost, high-affinity adsorbents and highly scalable filtration in one system. However, the development of adsorptive membranes is hampered by their instability in the aqueous phase and low binding affinity with a broad spectrum of heavy metals in a reasonable flux. Herein, a regenerated cellulose support membrane is strongly grafted with stable and covalent-bonded polyelectrolyte active layers synthesized by a reactive layer-by-layer (LBL) assembly method. The LBL assembled layers have been successfully tested by scanning electron microscopy, Fourier-transform infrared spectroscopy and X-ray photo-electron spectroscopy. The covalent bonding provides the membrane with long-term stability and a tunable water flux compared to a membrane assembled by electrostatic bonding. The maximum adsorption capacity of the membrane active layers can reach up to 194 mg/g, showing more efficient adsorption at lower heavy metal concentration and higher pH value of feed solution. The membrane can remove multiple ions, such as Cu, Pb, and Cd, by adsorption and is easy to be regenerated and recovered. The strong covalent bonding can extend the membrane lifetime in water purification to remove multiple heavy metals at high efficiency.

Starch-based nanospheres modified filter paper for o/w emulsions separation and contaminants removal.

There is a pressing need around the world to develop novel functional biodegradable materials to separate oil/water mixtures and emulsions completely. Recently, superhydrophilicity and underwater superoleophobicity materials have been attracted attention due to their high efficiency in oil/water separation. However, it is still a challenge to prepare materials that combine oil/water separation and water purification in an environment-friendly way. In this work, biodegradable starch-based nanospheres (SNPs) coated filter paper was prepared in a low-cost, simple, and environmentally friendly manner. The SNPs coating could not only help to change the wettability of the substrate material but also build the hierarchical micro and nano structures which are conducive to separation and purification process. After modification by coating SNPs, the filter paper exhibited excellent performance in a wide range of oil/water mixtures or emulsions separation and the wettability of the filter paper could be regulated by adjusting the pH value. The modified filter paper presented good recyclability after several separation process. Furthermore, the as-prepared filter paper could also remove water-soluble contaminants during the oil/water separation process, thus realizing to combine separation and purification process in one single step. This biodegradable starch-based separating material with good separation performance, stability and recyclability has significant application potential in practical separation and purification process.

Thermoresponsive starch-based particle-stabilized Pickering high internal phase emulsions as nutraceutical containers for controlled release.

Pickering high internal phase emulsions (HIPEs) stabilized solely by bioderived starch-based particles hold potential for application in the food and pharmaceutical fields. This paper reports the use of a thermoresponsive 2-hydroxy-3-butoxypropyl starch (HBPS) particle as a representative natural biocompatible material for use as an effective stabilizer for HIPE formation. HBPS is synthesized by using butyl glycidyl ether as a hydrophobic reagent to change the hydrophobic-hydrophilic balance of starch, and then starch-based particles are fabricated by a simple nanoprecipitation procedure. The size of particles increased with an increase in temperature, and the particles are essentially monodisperse with a PDI of about 0.1 when the temperature was above 15 °C. These HBPS particles were subsequently used as an effective stabilizer to fabricate stable oil-in-water (o/w) Pickering HIPEs with an internal phase volume of 80% at different stabilizer concentrations. The results demonstrated that increasing the particle concentration is conducive to the formation of stable Pickering HIPEs with greater stiffnesses. In addition, the nutraceutical material (ß-carotene) was encapsulated into HIPEs and in vitro release experiments revealed that the release in this system can be controlled by adjusting the temperature.

Polymer Brush Graft-Modified Starch-Based Nanoparticles as Pickering Emulsifiers.

We study biosourced core-shell particles with a starch-based core and thermo-responsive polymer brush shell using surface-initiated single-electron transfer living radical polymerization (SI-SET-LRP) as a Pickering stabilizer. The shell endows the Pickering stabilizer with reversible emulsification/demulsification of oil and water properties. The initiator attached to the starch-based nanosphere (Br-SNP) core particle was first fabricated using the precipitation method. Subsequently, dense poly( N-isopropylacrylamide) (PNIPAM) brush graft-modified starch-based nanoparticles (SNP- g-PNIPAM) were obtained via the SI-SET-LRP process. Interfacial properties of the resultant particles were analyzed by interfacial tensiometer measurements, as were the effects of the grafted polymer chain length and temperature on the interfacial activity. Pickering emulsion was obtained using SNP- g-PNIPAM particles as the stabilizer. The effect of the concentration of the Pickering stabilizer on the size of emulsion droplets was analyzed. The emulsification/demulsification process of the Pickering emulsion can be reversed and easily repeated by changing the temperature.

Water-in-oil Pickering emulsion polymerization of N-isopropyl acrylamide using starch-based nanoparticles as emulsifier.

Inverse Pickering emulsions stabilized by naturally derived particles are of interesting during the past decade. In this study, starch-based nanoparticles were used as a particulate emulsifier to stabilize a w/o Pickering emulsion. The effects of particle concentration and oil volume fraction on the emulsion type and stability were investigated in detail. Catastrophic phase inversion from o/w to w/o emulsions occurred at a volume fraction of oil of 0.3-0.4, without altering the particle wettability. Further, a linear relation existed between the average droplet diameter and total amounts of starch-based nanoparticles. The obtained starch-based nanoparticles also served as a Pickering stabilizer to conduct a w/o Pickering polymerization. Raspberry-like thermoresponsive starch-poly(N-isopropyl acrylamide) nanocomposites with a well-defined structure were synthesized.

Fabrication of shape-tunable macroparticles by seeded polymerization of styrene using non-cross-linked starch-based seed.

Nonspherical colloidal particles with various geometries and different compositions have attracted tremendous attention and been widely researched. The preparation of polymer colloidal particles with controlled shapes by seeded polymerization is recognized as the most promising technique owing to the precise control of various morphologies and using non-cross-linked seed particles are of particular interest. Seeds particles derived from natural biopolymers are seldom applied. Hence, non-cross-linked starch-based seed could be used to fabricate the anisotropic particles by soap-free seed polymerization. Non-cross-linked starch-based seed particles were prepared by a nanoprecipitation method. Starch/polystyrene composite colloidal particles with shape-tunable were fabricated by soap-free seeded polymerization using starch-based seed. The effect of the polymerization time, monomer feed ratio and seed type were investigated. The seed particles with a single- or multi-hole structure were obtained after swelling with styrene. The resulting particles including golf-like, raspberry-like, octahedron-like and snowman-like structures, was fabricated on the polymerization process. This study firstly reports that the morphology of composite particles from golf-like to snowman-like at high monomer feed ratio using starch-based seed. At low monomer feed ratio, raspberry-like particles were obtained by surface nucleation increasing process. In addition, seed type also effect the morphology of composite particles.

Polycaprolactone nanocomposite reinforced by bioresource starch-based nanoparticles.

Biodegradable polymer nanocomposites with bioresource starch-based nanoparticles (SNPs) as reinforcing fillers for polycaprolactone (PCL) were prepared by melt blending. Scanning electron microscopy observation revealed that SNPs as spherical particles were evenly dispersed in the PCL matrix without any aggregation even with the content of SNPs increasing to 10wt% in the nanocomposite. Consequently, the rheological performances of PCL have been improved efficaciously after incorporation with SNPs as well as mechanical properties, especially with a percolation network structure of SNPs in the PCL matrix formed. In addition, the enzymatic hydrolysis experiments showed a more interesting behavior that the hydrolysis rates had been accelerated apparently in the nanocomposites than that in the neat PCL as observed. Such high performance nanocomposites may have great potential in expanding the utilization of starch from sustainable resources and the practical application of PCL-based biodegradable materials.

Interfacial Activity of Starch-Based Nanoparticles at the Oil-Water Interface.

Understanding the interfacial activity of polysaccharide nanoparticles adsorbed at oil-water interfaces is essential and important for the application of these nanoparticles as Pickering stabilizers. The interfacial properties of starch-based nanospheres (SNPs) at the interface of an n-hexane-water system were investigated by monitoring the interfacial tension at different bulk concentrations. The three-phase contact angle (θ) and the adsorption energy (ΔE) increased with increasing size and degree of substitution with octenyl succinic groups (OSA) in the particles. Compared with the OSA-modified starch (OSA-S) macromolecule, the SNPs effectively reduced the interfacial tension of the n-hexane-water system at a relatively higher concentration. These results and the method reported herein are useful for selecting and preparing polysaccharide nanoparticles as Pickering stabilizers for oil-water emulsions.

Tough, rapid-recovery composite hydrogels fabricated via synergistic core-shell microgel covalent bonding and Fe3+ coordination cross-linking.

We developed tough, rapid-recovery composite hydrogels that are fabricated via core-shell microgel covalent bonding and Fe3+ dynamic metal coordination cross-linking. First, core-shell microgels are used as cross-linking agents and initiators to prepare homogeneous hydrogel networks with rapid recovery in the absence of an organic cross-linking agent. The toughness and recoverability of the composite hydrogels can be improved by adding the dynamic reversibility of ionic cross-linking. Owing to the synergistic effect of microgel covalent bonding, Fe3+ coordination cross-linking, and H-bond cross-linking, the multi-cross-linked composite hydrogels exhibit excellent toughness and a fast recovery rate. These characteristics demonstrate that the dynamic reversibility of the ionic cross-linking can significantly improve the toughness and recoverability of the hydrogels. In addition, the core-shell microgels play a key role in toughening the hydrogels and accelerating their recovery by transferring stress to grafted polymer chains and homogenizing the hydrogel network.