Novel polyimide binder for achieving high-rate capability and long-term cycling stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cathode via constructing polar and micro-branched crosslinking network structure

LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)material,as the promising cathode candidate for next-generation highenergy lithium-ion batteries,has gained considerable attention for extremely high theoretical capacity and low cost.Nevertheless,the intrinsic drawbacks of NCM811 such as unstable structure and inevitable interface side reaction result in severe capacity decay and thermal runaway.Herein,a novel polyimide(denoted as PI-Om DT)constructed with the highly polar and micro-branched crosslinking network is reported as a binder material for NCM811 cathode.The micro-branched crosslinking network is achieved by using 1,3,5-Tris(4-aminophenoxy)benzene(TAPOB)as a crosslinker via condensation reaction,which endows excellent mechanical properties and large free volume.Meanwhile,the massive polar carboxyl(-COOH)groups provide strong adhesion sites to active NCM811 particles.These functions of PIOm DT binder collaboratively benefit to forming the mechanically robust and homogeneous coating layer with rapid Li+diffusion on the surface of NCM811,significantly stabilizing the cathode structure,suppressing the detrimental interface side reaction and guaranteeing the shorter ion-diffusion and electron-transfer paths,consequently enhancing electrochemical performance.As compared to the NCM811 with PVDF binder,the NCM811 using PI-Om DT binder delivers a superior high-rate capacity(121.07 vs.145.38 m Ah g^(-1))at 5 C rate and maintains a higher capacity retention(80.38%vs.91.6%)after100 cycles at 2.5–4.3 V.Particularly,at the high-voltage conditions up to 4.5 and 4.7 V,the NCM811 with PI-Om DT binder still maintains the remarkable capacity retention of 88.86%and 72.5%after 100 cycles,respectively,paving the way for addressing the high-voltage operating stability of the NCM811 cathode.Moreover,the full-charged NCM811 cathode with PI-Om DT binder exhibits a significantly enhanced thermal stability,improving the safety performance of batteries.This work opens a new avenue for developing high-energy NCM811 based lithium-ion batteries with long cycle-life and superior safety performance using a novel and effective binder.

A crosslinking hydrogel binder for high-sulfur content S@pPAN cathode in rechargeable lithium batteries

High-energy density lithium-sulfur(Li-S) batteries have received intensive attention as promising energy storage system.Among diverse sulfur-based cathodes,sulfurized pyrolyzed poly(acrylonitrile)(S@pPAN)cathode delivered superior electrochemical performance.However,the sulfur content of S@pPAN is relatively low(<50 wt%),which significantly limits the energy density.Herein,a hydrogel SA-Cu binder was proposed with a crosslinking network constructed by Cu^(2+) ions.The introduction of Cu^(2+) ions enabled excellent electrochemical behaviors of S@pPAN cathode even with high sulfur content of 52.6 wt% via chemical interaction with sulfur and polysulfide.Moreover,a favorable cathode interphase was formed containing electrochemically active and conductive CuSx.S@pPAN/SA-Cu exhibited a high sulfur utilization of 85.3%,long cycling stability over 1000 cycles and remarkable capacity of 1200 mAh g_(s)^(-1) even at10 C.Furthermore,ascribed to the improved electrode structure,high-loading electrode(sulfur loading:4 mg cm^(-2)) displayed stable cycling with areal capacity of 5.26 mAh cm^(-2)(1315 mAh g_(s)^(-1)) after 40 cycles.This study provides new directions to prepare high-sulfur content and high-loading S@pPAN cathode for higher energy density.

Upcycling of Poly(butylene adipate-co-terephthalate)into Dual Covalent Adaptable Networks through Chain Breaking-Crosslinking Strategy

Poly(butylene adipate-co-terephthalate)(PBAT),a widely studied biodegradable material,has not effectively addressed the problem of plastic waste.Taking into consideration the cost-effectiveness,upcycling PBAT should take precedence over direct composting degradation.The present work adopts a chain breaking-crosslinking strategy,upcycling PBAT into dual covalent adaptable networks(CANs).During the chainbreaking stage,the ammonolysis between PBAT and polyethyleneimine(PEI)established the primary crosslinked network.Subsequently,styrene maleic anhydride copolymer(SMA)reacted with the hydroxyl group,culminating in the formation of dual covalent adaptable networks.In contrast to PBAT,the PBAT-dual-CANs exhibited a notable Young's modulus of 239 MPa,alongside an inherent resistance to creep and solvents.Owing to catalysis from neighboring carboxyl group and excess hydroxyl groups,the PBAT-dual-CANs exhibited fast stress relaxation.Additionally,they could be recycled through extrusion and hot-press reprocessing,while retaining their biodegradability.This straightforward strategy offers a solution for dealing with plastic waste.

COORDINATION CROSSLINKING OF NITRILE RUBBER FILLED WITH COPPER SULFATE PARTICLES

By incorporating copper sulfate （CuSO4） particles into acrylonitrile butadiene rubber （NBR） followed by heat pressing, a novel vulcanization method is developed in rubber through the formation of coordination crosslinking. This method totally differs from traditional covalent or non-covalent vulcanization approaches of rubber. No other vulcanizing agent or additional additive is involved in this process. By analyzing the results of DMA, XPS and FT-IR, it is found that the crosslinking of CuSO4 particles filled NBR was induced by in situ coordination between nitrogen atoms of nitrile groups （-CN） and copper ions （Cu^2＋） from CuSO4. SEM and EDX results revealed the generation of a core （CuSO4 solid particle）- shell （adherent NBR） structure, which leads to a result that the crosslinked rubber has excellent mechanical properties. Moreover, poly（vinyl chloride） （PVC） and liquid acrylonitrile-butadiene rubber （LNBR） were used as mobilizer to improve the coordination crosslinking of CuSO4/NBR. The addition of PVC or LNBR could lead to higher crosslink density and better mechanical properties of coordination vulcanization. In addition, crystal water in CuSO4 played a positive role to coordination crosslinking of rubber because it decreased the metal point of CuSO4 and promoted the metal ionization.

Interplay between entanglement and crosslinking in determining mechanical behaviors of polymer networks

In polymer physics,the concept of entanglement refers to the topological constraints between long polymer chains that are closely packed together.Both theory and experimentation suggest that entanglement has a significant influence on the mechanical properties of polymers.This indicates its promise for materials design across various applications.However,understanding the relationship between entanglement and mechanical properties is complex,especially due to challenges related to length scale constraints and the diffculties of direct experimental observation.This research delves into how the polymer network structure changes when deformed.We specifically examine the relationship between entanglement,crosslinked networks,and their roles in stretching both entangled and unentangled polymer systems.For unentangled polymers,our findings underscore the pivotal role of crosslinking bond strength in determining the system's overall strength and resistance to deformation.As for entangled polymers,entanglement plays a pivotal role in load bearing during the initial stretching stage,preserving the integrity of the polymer network.As the stretching continues and entanglement diminishes,the responsibility for bearing the load increasingly shifts to the crosslinking network,signifying a critical change in the system's behavior.We noted a linear correlation between the increase in entanglement and the rise in tensile stress during the initial stretching stage.Conversely,the destruction of the network correlates with a decrease in tensile stress in the later stage.The findings provide vital insights into the complex dynamics between entanglement and crosslinking in the stretching processes of polymer networks,offering valuable guidance for future manipulation and design of polymer materials to achieve desired'mechanical properties.

ULTRASONIC BEHAVIOR OF EPOXY RESINS/POLY (ETHYLENE OXIDE) BLENDS CURED WITH PHTHALIC ANHYDRIDE

By means of ultrasonic attenuation apparatus, the ultrasonic velocity and attenuation ofanhydride-cured epoxy resins (EP)/poly (ethylene oxide) (PEO) blends were measured on thebasis of pulse-echo method. It was found that the sonic velocity of the blends decreased as thetemperature increased, but attenuation coefficient increased and possessed a peak value. Largervelocity and smaller attenuation coefficient(α)can be obtained from perfect crosslinking networkstructures of pure DGEBA cured with phthalic anhydride(PA). As for cured DGEBA/PEO blendsystems,sonic velocity decreased as a function of PEO concentration,but attenuation coefficient(α) increased.

Molecular design, synthesis strategies and recent advances of hydrogels for wound dressing applications

With the changes in the modern disease spectrum,pressure ulcers,diabetic feet,and vascular-derived diseases caused refractory wounds is increasing rapidly.The development of wound dressings has partly improved the effect of wound management.However,traditional wound dressings can only cover the wound and block bacteria,but are generally powerless to recurrent wound infection and tissue healing.There is an urgent need to develop a new type of wound dressing with comprehensive performance to achieve multiple effects such as protecting the wound site from the external environment,absorbing wound exudate,anti-inflammatory,antibacterial,and accelerating wound healing process.Hydrogel wound dressings have the aforementioned characteristics,and can keep the wound in a moist environment because of the high water content,which is an ideal choice for wound treatment.This review introduces the wound healing process and the development and performance advantages of hydrogel wound dressings.The choice of different preparation materials gives the particularities of different hydrogel wound dressings.It also systematically explains the main physical and chemical crosslinking methods for hydrogel synthesis.Besides,in-depth discussion of four typical hydrogel wound dressings including double network hydrogels,nanocomposite hydrogels,drug-loaded hydrogels and smart hydrogels fully demonstrates the feasibility of developing hydrogels as wound dressing products and their future development trends.

Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is im- portant for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 ℃ for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.

Toughening Mechanism of Nanocomposite Physical Hydrogels Fabricated by a Single Gel Network with Dual Crosslinking-- The Roles of the Dual Crosslinking Points

A facile method to fabricate tough and highly stretchable polyacrylamide （PAM） nanocomposite physical hydrogel （NCP gel） was proposed. The hydrogels are dually crosslinked single network with the PAM grafted vinyl hybrid silica nanoparticles （VSNPs） as the analogous covalent crosslinking points and the reversible hydrogen bonds among the PAM chains as the physical crosslinking points. In order to further elucidate the toughening mechanism of the PAM NCP gel, especially to understand the role of the dual crosslinking points, the PAM hybrid hydrogels （H gels） and a series of poly（acrylamide-co-dimethylacrylamide） （P（AM-co-DMAA）） NCP gels were designed and fabricated. Their mechanical properties were compared with those of the PAM NCP gels. The PAM H gels are prepared by simply mixing the PAM chains with bare silica nanoparticles （SNPs）. Relative to the poor mechanical properties of the PAM H gel, the PAM NCP gel is remarkably tough and stretchable and also generates large number of micro-cracks to stop notch propagation, indicating the important role of PAM grafted VSNPs in toughening the NCP gel. In the P（AM-co-DMAA） NCP gels, the P（AM-co- DMAA） chains are grafted on VSNPs and the polydimethylacrylamide （PDMAA） only forms very weak hydrogen bonds between themselves. It is found that mechanical properties of the PAM NCP gel, such as the tensile strength and the elongation at break, are enhanced significantly, but those of the P（AM-co-DMAA） NCP gels decreased rapidly with decreasing AM content. This result reveals the role of the hydrogen bonds among the grafted polymer chains as the physical crosslinking points in toughening the NCP gel.

Controllable growth and flexible optoelectronic devices of regularly-assembled Bi2S3 semiconductor nanowire bifurcated junctions and crosslinked networks

Regularly assembled structures of nanowires, such as aligned arrays, junctions and interconnected networks, have great potential for the applications in logical circuits, address decoders, photoelectronic devices and transparent electrodes. However, for now it is still lack of effective approaches for constructing nanowire bifurcated junctions and crosslinked networks with ordered orientations and high quality. Herein, we report the controlled growth of Bi2S3 semiconductor nanowire bifurcated junctions and crosslinked networks with well-aligned directions and high crystalline degree by utilizing the proportional lattice match between nanowires and substrates. Taking advantages of the “tip-to-stem splice” assembly of individual nanowires, the precise orientation alignments of Bi2S3 semiconductor nanowire bifurcated junctions and crosslinked networks were successfully realized. The controlled growth mechanism and structural evolution process have been elucidated by detailed atomic structure characterizations and modeling. The highly crystal quality and direct energy bandgap of as-assembled photodetectors based on individual bismuth sulfide nanowires enabled high photoresponsivity and fast switch time under light illumination. The three-terminal devices based on nanowire bifurcated junctions present rapid carrier transport across the junction. The flexible photodetectors based on nanowire crosslinked networks show very minimal decay of photocurrent after long-term bending test. This work may provide new insights for the guided construction and regular assembly of low-dimensional ordered functional nanostructures towards advanced nanotechnologies.

Thiol-ene crosslinked cellulose-based gel polymer electrolyte with good structural integrity for high cycling performance lithium-metal battery

Gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechanical properties of GPEs usually deteriorate dramatically when polymer matrices are plasticized by a liquid electrolyte, which leads to significant loss of battery performance. Therefore, the long-term structural integrity and good mechanical strength are critical characteristics of GPEs designed for highperformance batteries. Here, an ecologically compatible cellulose-based GPE with a crosslinked structure is synthesized via a facile and effective thiol-ene click chemistry method. The prepared thiol-ene crosslinked GPE possesses enhanced mechanical strength(10.95 MPa) and rigid structure, which enabled us to fabricate Li Fe PO_(4)|Li batteries with ultra-long cycling performance. The capacity retention of the crosslinked cellulose-based GPE can be up to 84% at 0.5 C, even after 350 cycles, which is considerably higher than that of non-crosslinked GPE for which rapid decline in capacity occurs after 200 cycles. In addition, a GPE preparation method described in this work compares favorably well with existing commercial electrolytes for lithium metal batteries.

Synthesis of an Azobenzene-containing Main-chain Crystalline Polymer and Photodeformation Behaviors of Its Supramolecular Hydrogen-bonded Fibers

The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are described. This main-chain azo polymer(namely Azo-MP6) was prepared via first the synthesis of a diacrylate-type azo monomer and its subsequent Michael addition copolymerization with trans-1,4-cyclohexanediamine under a mild reaction condition. Azo-MP6 was found to have a linear main-chain chemical structure instead of a branched one, as verified by comparing its ~1H-NMR spectrum with that of the azo polymer prepared via the polymer analogous reaction of AzoMP6 with acetic anhydride. The thermal stability, phase transition behavior, and photoresponsivity of Azo-MP6 were characterized with TGA,DSC, POM, XRD, and UV-Vis spectroscopy. The experimental results revealed that it had good thermal stability, low glass transition temperature,broad crystalline phase temperature range, and highly reversible photoresponsivity. Physically crosslinked supramolecular hydrogen-bonded fibers with good mechanical properties and a high alignment order of azo mesogens were readily fabricated from Azo-MP6 by using the simple melt spinning method, and they could show "reversible" photoinduced bending under the same UV light irradiation and good anti-fatigue properties.