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.

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.

A UV cross-linked gel polymer electrolyte enabling high-rate and high voltage window for quasi-solid-state supercapacitors

Serving as a promising alternative to liquid electrolyte in the application of portable and wearable devices,gel polymer electrolytes(GPEs)are expected to obtain more preferable properties rather than just be satisfied with the merits of high safety and deformability.Here,an easy-operated method is employed to fabricate cross-linked composite polymer membranes used for GPEs assisted by UV irradiation,in which N-doped carbon quantum dots(N-CQDs)and TiO2are introduced as photocatalysts and additives to improve the performances of GPEs.Specifically,N-CQDs participate as a cross-linker to construct the inner porous structure,and TiO2nanoparticles serve as a stabilizer to improve the electrochemical stability of GPEs under high voltage(3.5 V).The excellent thermal and mechanical stability of the membrane fabricated in this work guarantee the safety of the supercapacitors(SCs).This GPE based SC not only exhibits prominent rate performance(105%capacitance retention at the current density of 40A g^(-1))and cyclic stability(85%at 1 A g^(-1)under 3.5 V after 20,000 cycles),but also displays remarkable energy density(42.88 Wh kg^(-1))with high power density(19.3 k W kg^(-1)).Moreover,the superior rate and cycling performances of the as-prepared GPE based flexible SCs under flat and bending state confirm the feasibility of its application in flexible energy storage devices.

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.

The effect of cations on gelation of cross-linked polymers

The effects of different cation concentrations and types on rheological property and stability of Guar, Xanthan, and Partially Hydrolyzed Polyacrylamide(HPAM) cross-linked gels were analyzed through experiments. Also, a new approach was developed to reduce the negative effects of cation by application of multi-walled carbon nano-tubes(MWCNTs). The presence of cations in cross-linked gel system will reduce the viscosity of gel, the higher the cation concentration is, the lower the viscosity will be. The bivalent cation has a greater viscosity reduction effect on gel than monovalent cation. The stability of cross-linked gels is worse with cations, this situation becomes more serious under higher salinity. MWCNTs were added to HPAM gel, cross-linked by(3-Aminopropyl) triethoxysilane(APTES), they surrounded cations and removed them from polymers and reduced the reaction possibility. This method enhances the viscosity and breakdown pressure of cross-linked gels, improves the stability of HPAM cross-linked gel under different operating conditions, and can be applied to related drilling projects.

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.

Reversible Zn/polymer heterogeneous anode

Commercialization of Zn-metal anodes with low cost and high theoretical capacity is hindered by the poor reversibility caused by dendrites growth,side reactions,and the slow Zn^(2+)-transport and reaction kinetics.Herein,a reversible heterogeneous electrode of Zn-nanocrystallites/polyvinylphosphonic acrylamide(Zn/PPAm)with fast electrochemical kinetics is designed for the first time:phosphonic acid groups with strong polarity and chelation effect ensure structural reversibility and stability of the threedimensional Zn-storage-host PPAm network and the Zn/PPAm hybrid;hydrophobic carbon chains suppress side reactions such as hydrogen evolution and corrosion;weak electron-donating amide groups constitute Zn^(2+)-transport channels and promote“desolvation”and“solvation”effects of Zn^(2+)by dragging the PPAm network on the Zn-metal surface to compress/stretch during Zn plating/stripping,respectively;and the heterostructure and Zn nanocrystallites suppress dendrite growth and enhance electrochemical reactivity,respectively.Thus,the Zn/PPAm electrode shows cycle reversibility of over 6000 h with a hysteresis voltage as low as 31 mV in symmetrical cells and excellent durability and flexibility in fiber-shaped batteries.

Effect of hydroxamic acid polymers on reverse flotation of bauxite

The effect of hydroxamic acid starch (HAS) and hydroxamic acid polyacrylamide (HPAM) on the flotation of diaspore and kaolinite was investigated by flotation test. It is found that HAS depresses diaspore but activates kaolinite in acidic pulp,while HPAM activates both diaspore and kaolinite in the pH range of 2.010.5. The measurement of zeta potential shows that both HAS and HPAM can increase zeta potential of negatively charged diaspore, which indicates the existence of chemical bonding or hydrogen bonding between the reagents and diaspore. By covering the collector dodecyl amine(DDA) on diaspore surface,HAS increases the hydrophilicity of minerals and depresses the flotation of diaspore,however HPAM activates the flotation of diaspore by increasing the adsorption of DDA on diaspore surface.

Effect of electron-electron interaction on polarization process of exciton and biexciton in conjugated polymer

By using one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction,we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene.The dynamical simulation is performed by adopting the non-adiabatic evolution approach.The results show that under the effect of moderate electric field,when the strength of electron-electron interaction is weak,the singlet exciton is stable but its polarization presents obvious oscillation.With the enhancement of interaction,it is dissociated into polaron pairs,the spin-flip of which can be observed through modulating the interaction strength.For the triplet exciton,the strong electron-electron interaction restrains its normal polarization,but it is still stable.In the case of biexciton,the strong electron-electron interaction not only dissociate it,but also flip its charge distribution.The yield of the possible states formed after the dissociation of exciton and biexciton is also calculated.

Contactless Raman Spectroscopy-Based Monitoring of Physical States of Silyl-Modified Polymers during Cross-Linking

Cross-linking of silyl-modified polymers occurs at the alkoxysilane groups attached to the ends of polymer chains by hydrolysis and polycondensation mechanisms in the presence of moisture. During these reactions, three different physical states can be identified (viscous, skin effect and cross-linked state). Knowledge of the evolution of these states at each reaction time is essential to determine the open time for the adhe-sive industry and is generally obtained by a manual method. Automation of this moni-toring could avoid operator error and could be used for very long cross linking reac-tions or to screen a large number of catalysts. Thus, a contactless micro process tech-nology was developed to correlate these physical states with an optical technology, Raman spectroscopy, by monitoring the decrease in intensity of the Si-OCH3 groups during chemical reactions. This online characterization method can also be used to compare the efficiencies of several catalysts for the cross-linking of silyl-modified polymers, using a minimum amount of chemical materials.

Topological Confinement in Reversibly Interlocked Polymer Networks

Recently, we reported a series of reversibly interlocked polymer networks(RILNs), whose mechanical robustness and functionalities improvement was believed to be derived from topological interlocking of two sub-networks, although the direct evidence for the deduction is still lacking. Herein, a specially-designed RILNs system, in which the inter-component hydrogen bonds can be shielded as needed, was prepared and used to study the micro-structures of RILNs, aiming to verify the existence of mechanical interlocking in RILNs. By changing the pH of the swelling solvent, the effect exerted by the inter-component non-covalent bonds was eliminated, so detailed information of the networks structure was exposed. The small angle X-ray scattering(SAXS) and small-angle neutron scattering(SANS) results indicated that swelling-induced structural evolution of the two sub-networks mutually affected each other, even when the inter-component hydrogen bonds were absent, proving the presence of topological interlocking. The findings may help to draw a more accurate physical image and reveal the detailed structureproperty relationship of RILNs.

Evaluation of the clenbuterol imprinted monolithic column prepared by reversible addition-fragmentation chain transfer polymerization

To make more homogenous organic monolithic structure, reversible addition-fragmentation chain transfer （RAFT） process was employed in the synthesis of the clenbuterol imprinted polymer. In the synthesis, the influence of synthetic conditions on the polymer structure and separation efficiency was studied. The result demonstrated that the imprinted columns prepared with RAFT process have higher column efficiency and selectivity than the columns prepared with conventional polymerization in the present study, which may result from the higher surface area, smaller pore size and the narrower globule size distribution in their structures. The result indicated that RAFT polymerization provided better conditions for the clenbuterol imprinted monolithic polymer preparation. 2009 Xiang Chao Dong. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

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.

Molecularly Imprinted Polymers on Chloromethyl Polystyrene Resin Prepared via RAFT Polymerization

Surface molecularly imprinted polymers （SMIP） was prepared via the reversible addition-fragmentation chain transfer （RAFT） polymerization on the chloromethyl polystyrene resin （CPR） in the presence of the template D-phenylalanine. The structure of SMIP was characterized by FTIR and SEM. The adsorption behavior of D-phenylalanine of SMIP was preliminarily investigated.

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.

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℃.

TWO DIMENSIONAL PROPERTIES OF REVERSED DUCKWEED AMPHIPHILIC POLYMER

The surface pressure-Area isotherms of Reversed Duckweed amphiphili polymer were examined in view of their chemical structure and two- dimentional properties of polymer monolayer were studied.

Effect of Multi-Hydroxyl Polymer-Treated MUF Resin on the Mechanical Properties of Particleboard Manufactured with Reed Straw

The poor bonding performance between aqueous adhesives represented by melamine-urea formaldehyde(MUF)resins and reed straw hinders their applications in the field of non-wood-based panels.Multi-hydroxyl polymers are highly reactive and are often used as crosslinkers.This study fabricated a resin with a strengthened crosslinked structure by combining a multi-hydroxyl polymer and MUF resin prepolymer.The reed particleboard was prepared by using this resin as an adhesive and reed stalk as the matrix.The results show that neighboring molecules combined to form C–O–C bonds that strengthened the cross-linked structure of the resin.In addition,the viscosity of the resin was increased,and a continuous adhesive layer on the surface of reed particles was formed,which slowed the penetration of reed particles.The adhesive layer significantly improved the mechanical properties of the reed particleboard.The maximum modulus of rupture(MOR),modulus of elasticity(MOE),and internal bonding strength(IB)of the reed particleboard were 33.53,4126,and 0.79 MPa,respectively.The IB of the board was 3.3 times higher than that of the reed particleboard prepared with a conventional MUF resin.Reed straw is a non-wood biomass material that has the advantage of sustainable development and may replace woodbased materials to produce particleboard.This resin-prepared reed particleboard is expected to be used in areas such as custom furniture and engineering materials.

含硫动态高分子的研究进展

自动态共价键概念问世以来,含硫动态高分子作为动态化学中的一类重要高分子在化学、生物、材料等领域的应用取得了重大进展。硫元素作为自然界中常见元素,其来源广泛,且理化性质较为活泼,可参与多种有机化学反应,因此含硫动态高分子得到了迅速发展。本文介绍了不同类型的含硫动态共价键,简述了其动态影响因素,并探讨了多种含硫动态共价键在高分子材料设计和构建中的应用,特别是对材料化学、电子器件、生物医疗等领域的影响,最后对含硫动态高分子材料的未来发展作了展望。