Residual alkali-evoked cross-linked polymer layer for anti-air-sensitivity LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)cathode

High-energy density lithium-ion batteries(LIBs)with layered high-nickel oxide cathodes(LiNi_(x)Co_(y)Mn_(1-x-y)O_(2),x≥0.8)show great promise in consumer electronics and vehicular applications.However,LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)faces challenges related to capacity decay caused by residual alkalis owing to high sensitivity to air.To address this issue,we propose a hazardous substances upcycling method that fundamentally mitigates alkali content and concurrently induces the emergence of an anti-air-sensitive layer on the cathode surface.Through the neutralization of polyacrylic acid(PAA)with residual alkalis and then coupling it with 3-aminopropyl triethoxysilane(KH550),a stable and ion-conductive cross-linked polymer layer is in situ integrated into the LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)(NCM)cathode.Our characterization and measurements demonstrate its effectiveness.The NCM material exhibits impressive cycling performance,retaining 88.4%of its capacity after 200 cycles at 5 C and achieving an extraordinary specific capacity of 170.0 mA h g^(-1) at 10 C.Importantly,this layer on the NCM efficiently suppresses unfavorable phase transitions,severe electrolyte degradation,and CO_(2)gas evolution,while maintaining commendable resistance to air exposure.This surface modification strategy shows widespread potential for creating air-stable LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)cathodes,thereby advancing high-performance LIBs.

Mechanism of high Li-ion conductivity in poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network based electrolyte revealed by solid-state NMR

Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.

Tuning the cross-linked structure of basic poly(ionic liquid)to develop an efficient catalyst for the conversion of vinyl carbonate to dimethyl carbonate

Dimethyl carbonate(DMC)is a crucial chemical raw material widely used in organic synthesis,lithiumion battery electrolytes,and various other fields.The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol.However,the utilization of this catalyst presents several challenges during the process,including equipment corrosion,the generation of solid waste,susceptibility to deactivation,and complexities in separation and recovery.To address these limitations,a series of alkaline poly(ionic liquid)s,i.e.[DVBPIL][PHO],[DVCPIL][PHO],and[TBVPIL][PHO],with different crosslinking degrees and structures,were synthesized through the construction of cross-linked polymeric monomers and functionalization.These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics.Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC.It was discovered that the appropriate cross-linking degree and structure of the[DVCPIL][PHO]catalyst resulted in a DMC yield of up to 80.6%.Furthermore,this catalyst material exhibited good stability,maintaining its catalytic activity after repeated use five times without significant changes.The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.

Adsorptive Removal of Copper Ions from Aqueous Solution Using Cross-linked Magnetic Chitosan Beads

The performance of cross-linked magnetic chitosan, coated with magnetic fluids and cross-linked with ePichlorohydrin, was investigated for the adsorption of Copper （Ⅱ） from aqueous solutions. Infrared spectra of chitosan before and after modification showed that the coating and cross-linking are effective. Experiments were performed at different pH of solution and contact time, and appropriate conditions for the adsorption of Cu（Ⅱ） were determined. Experimental equilibrium data were correlated with Langmuir and Freundlich isotherms for determination of the adsorption potential. The results showed that the Langmuir isotherm was better compared with the Freundlich isotherm, and the uptake of Cu（Ⅱ） was 78.13 mg·g^- 1. The kinetics of adsorption corresponded with the first-order Langergren rate equation, and Langergren rate constants were determined.

Study of action mechanisms and properties of Cr^(3+) cross-linked polymer solution with high salinity

Performance characteristics of partially hydrolyzed polyacrylamide （HPAM） and cross- linked polymer （CLP, Cr^3＋ as the cross linker） solutions have been investigated. A Brookfield viscometer, rheometer, dynamic light scattering system, and core flow device have been used to measure the viscosity, viscoelasticity, polymer coil dimensions, molecular configuration, flow characteristics, and profile modification. The results show that, under conditions of high salinity and low HPAM and Cr^3＋ concentrations, cross-linking mainly occurred between different chains of the same HPAM molecule in the presence of Cr^3＋, and a cross-linked polymer （CLP） system with a local network structure was formed. Compared with an HPAM solution of the same concentration, the apparent viscosity of the CLP solution increased slightly or remained almost unchanged, but its viscoelasticity （namely storage modulus, loss modulus, and first normal stress difference） increased, and the resistance coefficient and residual resistance coefficient increased significantly. This indicates that the CLP solution exhibits a strong capability to divert the sequentially injected polymer flood from high-permeability zones to low- permeability zones in a reservoir. Under the same HPAM concentration conditions, the dimensions of polymer coils in the CLP solution increased slightly compared with the dimensions of polymer coils in HPAM solution, which were smaller than the rock pores, indicating that the cross-linked polymer solution was well adapted to reservoir rocks. Core flood experiments show that at the same cost of reagent, the oil recovery by CLP injection （HPAM-1, Cr^3＋ as the cross linker） is 3.1% to 5.2% higher than that by HPAM- 2 injection.

Applications of Crown Ether Cross-Linked Chitosan for the Analysis of Lead and Cadmium in Environmental Water Samples

A new type of crown ether cross-linked chitosan was synthesized by the reaction of chitosan with 4,4′-dibromodibenzo-18-crown-6 (Br-DBC). Its token structure was analyzed with FT-IR and NMR and the adsorption behaviors for lead and cadmium in environmental water samples by FAAS were studied. In addition the best analysis conditions were discussed and the adsorption mechanism was explained. As the enrichment factor is above 100, both recoveries are 94%–106%, the detection limits of lead and cadmium are 0.5μg·L?1 and 0.04 μg·L?1 and the relatively standard deviations of lead and cadmium are 3.1% and 2.8% respectively, this new method was successfully applied to the determination of environmental water samples. This method is fast and simple and it greatly enhances the determination ability of FAAS for lead and cadmium.

Cross-Linked Hollow Graphitic Carbon as Low-Cost and High-Performance Anode for Potassium Ion Batteries

Large-scale and low-cost preparation of carbon-based potassium anode with long life and high capacity is one of the footstones for the development of potassium ion batteries(PIBs).Herein,a low-cost carbon-based material,cross-linked hollow graphitic carbon(HGC),is large scale synthesized to apply for PIBs anode.Its hollow structure can afford sufficient space to overcome the damage caused by the volume expansion of graphitic carbon(GC).While the cross-linked structure forms a compact interconnection network that allows electrons to rapid transfer between different GC frameworks.Electrochemical measurements demonstrated that the HGC anode exhibited low charge/discharge plateau(about 0.25 V and 0.1 V)and excellent specific capacity as high as 298 m A h g^(-1)at the current density of 50 m A g^(-1).And more important,after 200 cycles the capacity of HGC anode still shows 269 m A h g^(-1)(the decay rate of per cycle is only 0.048%).Meanwhile,the use of commercial traditional electrolyte(KPF_(6))and cheap raw materials that provide new hope for trying and realizing the large-scale production of PIBs based on carbon anode materials.

Free-radical evolution and decay in cross-linked polytetrafluoroethylene irradiated by gamma-rays

Electron spin resonance techniques were employed to investigate the effects of the absorbed dose and post-irradiation conditions on the evolution and decay of free-radicals in cross-linked polytetrafluoroethylene(XPTFE),induced byγ-ray radiation.Chain-end free-radicals,chain alkyl free-radicals,and tertiary alkyl free-radicals were detected when XPTFE was irradiated under Ar atmosphere.The corresponding peroxy free-radicals were formed upon exposure of irradiated XPTFE to air;the freeradicals concentration first increased linearly with increasing absorbed dose and then gradually saturated.The free-radicals yield under air atmosphere was greater than that under Ar,and the peroxy free-radicals were preserved for a relatively long time when irradiated XPTFE was stored under air atmosphere.The chain alkyl free-radicals may be converted to chain end free-radicals byβ-scission,while chain end free-radicals are more sensitive to oxygen than chain alkyl free-radicals.When the annealing temperature was raised above the a-transition temperature of XPTFE,the decay of the free-radicals was greatly affected and accelerated by the motion of the molecules over the long range.

Study on the Structure of Peroxide Cross-Linked Polyethylene Pipes with Several Stabilizers

Cross-linked polyethylene (PEX) pipes used in hot water supply are required for high mechanical strength and high creep resistance at high temperature. Especially PEX-a pipes which are made by peroxide cross-linking have better performance, such as creep resistance and thermal shock resistance than the pipes made by the other cross-linking method. Because the PEX-a pipes indicate the higher cross-link degree as compared with the other PEX pipes. In this study, the PEX-a pipes which were mixed with several stabilizers were tested to evaluate the effects on cross-link degree and the oxygen induction time. And also they are evaluated with the chlorine aqueous solution by the performance of the long-term hydrostatic pressure test and the long-term hydro dynamic pressure test. As a result, it was found that the combination of antioxidants for PEX-a pipes plays an important role to prolong the oxygen induction time without inhibiting the cross-linking. From the results of the 1H pulsed NMR measurement over the melting point of polyethylene, it was found that each peroxide PEX pipe with different antioxidant combinations indicated the different proportion and crosslink density of cross-linked region, in addition, that these pipes had the effective structure of cross-linking for the hydrostatic and hydrodynamic pressure test with the chlorine aqueous solution. Therefore, it was considered to be useful results for studies of the stricture of cross-linking of polyethylene.

In situ formed cross-linked polymer networks as dual-functional layers for high-stable lithium metal batteries

Lithium-metal anodes(LMAs)have been recognized as the ultimate anodes for next-generation batteries with high energy density,but stringent assembly-environment conditions derived from the poor moisture stability dramatically hinder the transformation of LMAs from laboratory to industry.Herein,an in situ formed cross-linked polymer layer on LMAs is designed and constructed by a facile thiol-acrylate click chemistry reaction between poly(ethylene glycol)diacrylate(PEGDA)and the crosslinker containing multi thiol groups under UV irradiation.Owing to the hydrophobic nature of the layer,the treated LMAs demonstrate remarkable humid stability for more than 3 h in ambient air(70%relative humidity).The coating humid-resistant protective layer also possesses a dual-functional characterization as solid polymer electrolytes by introducing lithium bis(trifluoromethanesulfonyl)imide in the system in advance.The intimate contact between the polymer layer and LMAs reduces interfacial resistance in the assembled Li/LiFePO_(4)or Li/LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cell effectively,and endows the cell with an outstanding cycle performance.

Dynamic Mechanical and Thermal Properties of Cross-linked Polystyrene/Glass Fiber Composites

Cross-linked polystyrene/glass fiber composites were fabricated using cross-linked polystyrene （CLPS） as matrix and E-glass fiber as the reinforcement. Surfaces of E-glass fibers were modified by vinyl triethoxysilane （VTES）, vinyl trimethoxysilane （VTMS） and γ-methacryloylpropyl trimethoxysilane （MPS）. The treated glass fibers were analyzed by fourier transform infrared spectroscopy （FTIR）. Dynamic mechanical thermal analysis （DMTA） and thermo-gravimetric analysis （TGA） were employed to investigate the effect of glass fibers surface modification on viscoelastic behavior and thermal properties. The morphology of fracture surfaces of various composites was observed by scanning electron microscopy （SEM）. The results revealed that these coupling agents were connected to the surfaces of the fibers by chemical bonding. Dynamic mechanical properties as well as thermal stability of the composites were improved considerablely, but to varying degrees depending on the fiber modification. The diversities of improvement of properties were attributed to the different interfacial adhesion between CLPS matrix and the glass fibers.

Study on Biocompatibility of Cross-linked Hyaluronic Acid Derivatives

Objective:The cross-linked production,which was prepared by HA and cross-linking agent STMP,EDC,GP through cross-linking reaction,might be used in drug delivery system(DDS).To ensure the security of clinical application,the excellent properties such as none cell toxicity,nonirritant,none general toxicity,none immunological rejection are necessary.Methods:In accordance with the request of GB/T 16886.1 on security evaluation of medical biomaterials,cell toxicity test,hemolysis test,intracutaneous stimulation test,acute toxicity test,and hypersensitive test were required.Results:Cell toxicity of HA-STMP,HA-EDC,HA-GP were all less than 1.All hypersensitive tests were eligible.But HA-EDC,HA-GP produced different degrees of slight thrill,slight toxicity,hemolysis rate,which were larger than the standard value.Conclusion:HA-STMP possesses favourable biocompatibility,which is a kind of ideal biomaterials and drug carriers.

Synthesis and characterization of a series of cross-linked polyamines for removal of Erichrome Black T from aqueous solution

A new series of polymers comprising four terpolymers was synthesized via Mannich polycondensation of benzene1,4diamine,formaldehyde and piperazine by varying the benzene1,4diamine and piperazine ratio.The new polyamines(labeled Dipip)were characterized using 13C solidstate NMR,FTIR,TGA,DSC,XRD,SEM and EDX.The adsorptive performances of the synthesized polymers for Erichrome Black T(EBT)uptake from aqueous solution were investigated under batch process.Equilibrium,kinetic,and thermodynamic studies were conducted to determine the influence of different operational parameters of the adsorption process.The two most promising polymers among the series show an excellent EBT removal efficiency of~100%and~95%with high adsorption capacities of 775 mgg 1 and 917 mgg 1,respectively at a meager dosage of 5 mg.The sorption of EBT on the polymers was well described by RedlichPeterson&Langmuir model while the kinetic studies indicate that pseudosecond order model was followed.For the thermodynamic studies,the negative AG and positive AH values obtained suggest a spontaneity of the sorption process which was endothermic in nature.The results of reusability test of the resins were promising even at the fourth cycle,showcasing the potentials of the new polymers in dyes contaminated water treatment.

Synthesis and Properties of Lactic Acid-based Cross-linked Poly(ester-amide)

A novel lactic acid-based cross-linked poly（ester-amide） （LCPEA） was synthesized. The gel fraction of the LCPEA could be modulated by the reaction conditions and it affected the mechanical and thermal properties of the LCPEA. The tensile strength, elastic modulus and bend strength of the LCPEA of 65% gel fraction were 4.65, 136.55 and 39.63 MPa, respectively. The thermal decomposition temperature （50 wt%） of the LCPEA was around 410℃.

Dehydration Mechanism of Secondary Cross-linked Gels

In this paper, microscopic characteristics of preformed gels （PGs） and secondary cross-linked gels （SCG） with the same concentration were analyzed by atomic force microscopy （AFM）. Experimental results indicate that the microstructure of secondary cross-linked gels is a thick 3-D network, in which micro-holes and irregular macro-holes are embedded. The maximum width of the irregular macro-holes is 200 nm. In the SCG two different chemical bonds were formed, which leads to the structural inhomogeneity and the asymmetry of the crosslinking density. The structural inhomogeneity of SCG results in the formation of irregular macro-holes. The excessive cross-linking density is the primary reason for dehydration of SCG and the presence of irregular macro-holes in SCG can facilitate dehydration.

Characterization of Ionic Conducting Cross-linked Polyether Electrolytes

An appropriate amount of toluene 2,4-diisocyanate（TDI） was added into polyether（[（CH2CH2O）13 CH2O]n/Li salt electrolyte to form a cross-linked network,with improving the film proces sability and thermal stability.The relation between the structure and ioinc conductive properties of the cross-lined polyether electrolytes was investigated by means of Fourier transform infra-red spectroscopy（FTIR）,differential scanning calorimetry（DSC）,mechanical property and AC impedance spectroscopy.The electrolytes system is found to have two glass transitions,and it is found that the two Tgs increase with increasing salt concentration.At the some Li salt concentration,the conductivity of cross-liked polyether/LiN（CF3SO2）2 complex system is higher than that of LiClo4,At EO/Li=25：1（mol ratio）,the former conductivity changes with temperature,while the later coincids with Arrhenius formula（σ=Ae^-Ea/RT）.The cross-linked polyether/LiN（CF3 SO2）2 electrolyte exhibits the maximum σ=10^-4.75S/cm at 30℃.

Effect on rabbits’intraocular structure by cross-linked hyaluronic formations as vitreous substitute

AIM:To develop a new material for retina filling and to investigate its effect on intraocular structure and histocompatibility in rabbit eyes.METHODS:The polymer-derived hyaluronic acid(HA)was formed by UV light cross-linked with N-vinyl-pyrrolidone.Vitrectomy was performed in the rabbits,and then crosslinked HA hydrogels at different concentrations were injected.Intraocular pressure measurements,cornea check-up,and B-ultrasound examination were performed during the follow-up period.After six weeks’follow-up,the rabbits were sacrificed,and both eyes were removed for hematoxylin-eosin(HE)staining,and the polymer materials were observed under electron microscopy.RESULTS:The particle size of the cross-linked HA hydrogels was mainly around at 100 nm.After vitrectomy and injection into vitreous cavity optical coherence tomography showed that the polymeric material HA had no significant effect on the overall thickness of the retina.The intraocular pressure returned to the normal level gradually at week 4.B-ultrasound results revealed that there is no significant change in the eye tissue given to HA material.The pathological and transmission electron microscopy results showed no obvious pathological change in the primary cells and rod cells under the retina tissue.CONCLUSION:HA-based cross-linked biopolymers has good biocompatibility in rabbit eyes,showing a promising potential as vitreous substitutes.

A Self-Healing and Nonflammable Cross-Linked Network Polymer Electrolyte with the Combination of Hydrogen Bonds and Dynamic Disulfide Bonds for Lithium Metal Batteries

The self-healing solid polymer electrolytes(SHSPEs)can spontaneously eliminate mechanical damages or micro-cracks generated during the assembly or operation of lithium-ion batteries(LIBs),significantly improving cycling performance and extending service life of LIBs.Here,we report a novel cross-linked network SHSPE(PDDP)containing hydrogen bonds and dynamic disulfide bonds with excellent self-healing properties and nonflammability.The combination of hydrogen bonding between urea groups and the metathesis reaction of dynamic disulfide bonds endows PDDP with rapid self-healing capacity at 28°C without external stimulation.Furthermore,the addition of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(EMIMTFSI)improves the ionic conductivity(1.13×10^(−4)S cm^(−1)at 28°C)and non-flammability of PDDP.The assembled Li/PDDP/LiFePO_(4)cell exhibits excellent cycling performance with a discharge capacity of 137 mA h g^(−1)after 300 cycles at 0.2 C.More importantly,the self-healed PDDP can recover almost the same ionic conductivity and cycling performance as the original PDDP.

Self-Cross-Linked Tannin-Aminated Tannin Surface Coatings for Particleboard

Aminated tannins were prepared by reacting mimosa condensed tannin extract with ammonia yielding the substitution of many,if not all of the tannin hydroxyl groups with–NH_(2)groups.A tannin-aminated tannin(ATT)particleboard coating was then prepared by reacting raw tannin extract with aminated tannin extract and thus cross-linking the two by substituting tannin’s hydroxyl groups with the–NH_(2)groups on the aminated tannin to form–NH-bridges between the two.The resulting particleboard coating gave encouraging results when pressed at 180℃for 3 min.Conversely,the system in which tannin was reacted/cross-liked with urea(ATU)by a similar amination reaction did not perform as well as the ATT system,and this even when a higher curing temperature and longer hot press time were used.In particular its water repellence was worse probably due to the presence of urea and such a system with lower reactivity.Nonetheless,substituting the tannin–OHs with the urea–NH_(2)groups appeared to also take place.ATT gave better results than ATU as regards water repellence and mechanical resistance as shown by the cross cut test.The ATT system was shown to be between 95%and 98%biosourced.The difference appeared to be due,by TMA analysis,to the much faster formation of the ATT hardened network leading to a better cross-linked polymer coating.The chemical species formed for both the ATT and ATU system were studied by MALDI ToF and CP MAS^(13)C NMR.

Study on Removal of Cr(VI)from Aqueous Solution by Cross-Linked Chitosan

In this paper,the adsorbent for the removal of hexavalent Cr(Chromium)from aqueous solutions has been prepared by modifying chitosan composite with EP(Epichlorohydrin)or GA(Glutaraldehyde).The modified cross-linked chitosan was characterized by SEM(Scanning Electron Microscopy)and FT-IR(Fourier Transform Infrared Spectroscopy).Batch adsorption experiments were carried out to evaluate the adsorption of Cr(VI)by the cross-linked chitosan under different conditions.Furthermore,the sorption mechanism of Cr(VI)by the cross-linked chitosan was investigated by applying Langmuir and Freundlich isotherm equations to the data obtained.The concentration of Cr in solution was determined by ICP-MS(Inductively Coupled Plasma Mass Spectrometry).The cross-linked chitosan can be an efficient sorbent for Cr(VI).