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.

In-situ polymerized PEO-based solid electrolytes contribute better Li metal batteries:Challenges,strategies,and perspectives

Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.

Necessity and feasibility of improving the residual resistance factor of polymer flooding in heavy oil reservoirs

The efficiency of water flooding in heavy oil reservoirs would be improved by increasing the viscosity of the displacing phase, but the sweep efficiency is not of significance due to the low mobility of the vicious oil. On the basis of mobility control theory, increasing the residual resistance factor not only reduces the water-oil mobility ratio but also decreases the requirement for viscosity enhancement of the polymer solution. The residual resistance factor caused by hydrophobic associating polymer solution is higher than that caused by polyacrylamide solution in brine containing high concentrations of calcium and magnesium ions. The results of numerical simulations show that the polymer flooding efficiency improved by increasing the residual resistance factor is far better than that by only increasing solution viscosity. The recovery factor of heavy oil reservoirs （70 mPa·s） can be enhanced by hydrophobic associating polymer solution of high residual resistance factor （more than 3） and high effective viscosity （24 mPa·s）. Therefore, increasing the residual resistance factor of the polymer solution not only decreases the requirement for the viscosity of polymer solution injected into heavy oil reservoirs but also is favorable to enhanced oil recovery during polymer flooding.

Displacement of polymer solution on residual oil trapped in dead ends

For waterflooding reservoir,oil trapped in pore's dead ends is hardly flushed out,and usually becomes one typical type of residual oil.The microscopic displacement characteristics of polymer solution with varied viscoelastic property were studied by numerical and experimental method.According to main pore structure characteristics and rheological property of polymer solution through porous media,displacement models for residual oil trapped in dead ends were proposed,and upper-convected Maxwell rheological model was used as polymer solution's constitutive equation.The flow and stress field was given and displacement characteristic was quantified by introducing a parameter of micro swept coefficient.The calculated and experimental results show that micro swept coefficient rises with the increase of viscoelasticity;for greater viscoelasticity of polymer solution,vortices in the dead end have greater swept volume and displacing force on oil,and consequently entraining the swept oil in time.In addition,micro swept coefficient in dead end is function of the inclination angle(θ) between pore and dead end.The smaller of θ and 180-θ,the flow field of viscoelastic fluid is developed in dead ends more deeply,resulting in more contact with oil and larger swept coefficient.

Factors influencing the aggregation behavior of residual associative polymer in produced oily fluids

The influence of emulsified oil, suspended solids, Fe3＋, Fe2＋, cationic water clarifier and sulfate-reducing （SR） bacteria on the aggregation behavior of residual hydrophobic modified polyacrylamide in treated oily wastewater from polymer flooding was studied by fluorescence spectroscopy and dynamic light scattering. The result of I1/I3 showed that the polarity of hydrophobic microdomains increased, whereas the size of the hydrophobic microdomains may be decreased, where the value of I1/I3 represents the ratio of the intensity of peak 11 （374.0 nm） to that of peak/3 （385.0 nm） of the vibration fine structure of pyrene monomer emission in residual polymer solution. The results of the ratio of I1 at 48 h to I1 at 0 h （I1,48h/I1,0h） indicated that oil and cationic water clarifier could inhibit the aggregation to some extent, while Fe2＋ and suspended solids were helpful for aggregation, and Fe3＋ and SR bacteria had no significant influence on the aggregation of polymer.

Visualization of adaptive polymer flow and displacement in medium-permeable 3D core-on-a-chip

Polymer flooding has been witnessed an effective technology for enhancing oil recovery from medium-to low-permeability reservoirs;however, direct visualization of polymer solution flow in such reservoir condition is still lacking. In this work, a three-dimensional (3D) core-on-a-chip device with a permeability of around 200 mD was prepared and employed to visualize the pore-scale flow and displacement of a self-adaptive polymer (SAP, 8.7 × 106 g·mol−1)−whose microscopic association structure and macroscopic viscosity can reversibly change in response to shear action−versus partially hydrolyzed polyacrylamide (HPAM), by recording their flow curves, monitoring dynamic transportation process via particle imaging velocimetry, and building 3D structure of remaining oil. The results show that, in single-phase flow, all polymer solutions exhibit flow thinning and then thickening regions as flow rate increases, but the transition between two regimes occurs at a small Weissenberg number (10−3−10−1) in this medium-permeable condition. In contrast to HPAM-1 with close weight-average molecular weight (Mw), the adaptive character not only extends SAP's shear-govern region, allowing SAP to propagate piece by piece and achieve higher accessible pore volume, but it also enhances the elastic resistibility of polymer in the extension-dominated regime, increasing the microscopic displacement efficiency. These two effects result in 1.5–3 times more oil recovery factor for SAP than for HPAM-1. Regarding ultra-high-Mw HPAM-2 (25 × 106 g·mol−1), plugging and chain degradation do occur, thus producing lower oil recovery than SAP. This work provides a direct approach for in-situ assessment of polymer-based displacing system under a more authentic condition of practical reservoirs.

Morphology and conductivity of in-situ PEO-LiClO_4-TiO_2 composite polymer electrolyte

PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.

Application of Molecularly Imprinted Polymers for the Analysis of Pesticide Residues in Food—A Highly Selective and Innovative Approach

The increasing application of pesticides for agricultural purposes involves serious risk to the environment and human health due to either exposure or through residues in food and drinking water. Since food safety is of mandatory importance there is a growing interest on the development of selective, simple, rapid, cost-effective and reliable analytical methodologies in order to ensure that pesticides residues should not be found at levels above the established maximum pesticide residue limits (MRLs). In recent years, a new methodology based on the development of molecularly imprinting polymers (MIPs) allows not only pre-concentration and cleaning of the sample but also selective extraction of the target analyte, which is crucial, particularly when the sample is complex and impurities can interfere with quantification. The scope of this review is to provide a general overview on MIPs field, with emphasis on MIP preparation and its use as sorbents for solid-phase extraction. This paper will be focused on the review of the current state of the art in the use of MIPs as selective materials in molecularly imprinted solid-phase extraction (MISPE) for the analysis of pesticide residues from food matrices. A review of preparation and application of MIPs in food matrices, will also be discussed.

A NOVEL EOR POLYMER (Ⅱ)——INVESTIGATION ON IN-SITU GELATION OF SMRF SYSTEM IN BEREA CORE

In-situ gelation of aqueous sulfomethylated resorcinol formaldehyde (SMRF) system inBerea core has been investigated. Two sets of displacement experiments were conducted with thissystem (containing 5% NaCl, 0. 036% CaCl_2. 2H_2O). The brine permeabilities of the coreswere reduced significantly from about 600 to 0.1 md. The in-situ gelation in Berea core occurreda little bit earlier than gelation anticipated from bulk test in the experiments. The gel time waseasier to control at initial pH between 6 and 8. During injection of SMRF system, the apparentviscosity was less than 1 mPa·s at 41℃.

In-Situ Composition and Luminescence of Europium and Terbium Coordination Polymers/PEMA Hybrid Thick Films

Europium and terbium coordination polymers of pyridine-3-carboxylic acid were in-situ composed with ethyt methacrylate （ EMA ）. With the polymerization of EMA monomer and the formation of europium and terbium coordination polymers of pyridiae- 3-carboxylic acid, the transparent hybrid thick fihns composed of [ Eu（ NIC ）3 ]n （ [ Tb（ NIC）3 ]n ） and poly ethyl mettuwrylate （ PEMA ） have been prepared. The luminescence properties and energy transfer of these polymeric composites were studied with absorption spectra, fluorescent excitation trod emission spectra in detail. All the hybrid thick films composed of terbium coordination polymer show the characteristic strong green emission of terbium ions, which implies the same energy transfer mechanism as the pure complex and the hybrid composite film is a suitable sabstrate for the luminescence of terbium ions. In the range of camposing concentration of luminescent species （0.01,0.025,0.05,0.1 mmol /15 mL EMA ）, emission intensities increase with the increasing of corresponding composing concentration and the concentration quenching effect does not take place.

Three dimensional phase field study on the thickness effect of ferroelectric polymer thin film

The electromechanical behavior of poly(vinylidene fluoride-trifluoroethylene)[P(VDF -TrFE)]ferroelectric thin film was investigated using the three dimensional(3D) phase-field method. Various energetic contributions,including elastic,electrostatic,and domain wall energy were taken into account in the variational functional of the phase field model.Evolution of the microscopic domain structures of P(VDF-TrFE) polymer film was simulated.Effects of the in-plane residual stress,the film thickness and externally applied electric bias field on the electromechanical properties of the film were explored.The obtained numerical results showed that the macroscopic responses of the electric hysteresis loops are sensitive to the residual stress and electric bias field.It was also found that thickness has a great effect on the electric hysteresis loops and remanent polarization.

Theoretical analysis of microscopic oil displacement mechanism by viscoelastic polymer solution

The microscopic oil displacement mechanism in viscoelastic polymer flooding is theoretically analyzed with mechanical method.The effects of viscoelasticity of polymer solution on such three kinds of residual oil as in pore throat,in sudden expansion pore path,and in dead end are analyzed.Results show that the critical radius of mobile residual oil for viscoelastic polymer solution is larger than that for viscous polymer solution,which makes the oil that is immobile in viscous polymer flooding displaced under the condition of viscoelastic polymer solution.The viscous polymer solution hardly displaces the oil in dead ends.However,when the effect of viscoelasticity is considered,the residual oil in sudden expansion pore paths and dead ends can be partly displaced. A dimensionless parameter is suggested to denote the relative dominance of gravity and capillary pressure.The larger the dimensionless parameter,the more accurate the increment expressions.

Experimental Study on Influencing Factors of Resistance Coefficient and Residual Resistance Coefficient in Oilfield Z

In order to clarify the major influence factors of resistance coefficient and residual resistance coefficient, so as to provide the basis for optimizing the polymer flooding schemes in oilfield Z of Bohai Sea, artificial cores were made by simulated the characteristic parameters of real reservoir and the spacing of production-injection wells. The main parameters considered include reservoir permeability, polymer solution concentration and polymer injection rate. Core experiment of polymer flooding was taken by considering all the main parameters. The result showed that resistance coefficient and residual resistance coefficient decrease with the increase of core permeability. Resistance coefficient and residual resistance coefficient increase with the increase of concentration of polymer solution. The increment of displacement pressure in low permeability core is higher than in medium and high permeability core. The resistance coefficient increase with higher displacing velocity, and the increment in high permeability core is higher than in low permeability?core. The displacement velocity has little effect on the residual resistance coefficient. The experimental results can effectively guide the formulation of polymer flooding scheme in offshore oilfields, and optimize the appropriate injection rate and concentration of polymer solution for different properties of reservoirs, thus ensuring the effectiveness of polymer flooding in offshore oilfields.

Tuning desolvation kinetics of in-situ weakly solvating polyacetal electrolytes for dendrite-free lithium metal batteries

The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.

Eutectic Solution Enables Powerful Click Reaction for In-Situ Construction of Advanced Gel Electrolytes

Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.

井地过渡带对聚合物驱油剂性能影响研究

利用井地过渡带剪切模拟实验装置,以疏水缔合聚合物AP-P4为研究对象,研究不同吸水强度条件下,剪切后聚合物溶液的表观黏度、流变性、阻力和残余阻力系数、微观结构以及水动力学半径的变化情况。结果表明,经井地过渡带剪切后,随着吸水强度的增大,聚合物AP-P4溶液的黏度损失率高达61.4%,建立阻力系数和残余阻力系数的能力降低40.0%以上,但其建立残余阻力系数能力的降低幅度要比建立阻力系数能力的降低幅度小。聚合物溶液的储能模量和损耗模量降低,微观结构被破坏的越严重,水动力学半径越小。

双向振动下高聚物胶凝戈壁土的动力特性试验研究

地震灾害是我国岩土工程中经常遇到的问题之一,为研究戈壁土受地震作用时的动力特性变化规律,采用大型动静三轴试验系模拟土体在受到地震纵横波共同作用时的激振应力,研究掺入一定量的高聚物胶凝材料后的高聚物戈壁土受双向振动作用下各因素对戈壁土动剪切模量、阻尼比及残余变形的影响。研究结果表明:双向振动下,动剪切模量随动剪切应变的增长逐渐减小,随径向动应力比增加,动剪切模量呈现出先增后减的趋势;围压和固结比与动剪切模量呈现出正相关;相位在0°~180°内增长时,双向振动作用下的试样动剪应力增大,动剪切模量随之增加,而阻尼比受各因素的影响较小。高聚物胶凝戈壁土的残余变形随高聚物质量比的增大而迅速减小;在相位差为180°时的动残余体应变和残余剪应变均增大。研究结果初步探明了高聚物胶凝戈壁土在双向振动下的动力变形特性,可为高聚物胶凝戈壁土的应用及工程抗震设计提供参考。

高聚物胶凝戈壁土的动残余变形特性试验研究

高聚物胶凝戈壁土是将高聚物与戈壁土按一定比例拌合而成的,可有效提高戈壁土的力学性能。为研究高聚物胶凝戈壁土的动残余变形特性,采用中型动三轴试验研究了高聚物质量比、围压、固结比和动应力比等对高聚物胶凝戈壁土残余剪应变和残余体应变的影响。结果表明:高聚物胶凝材料能有效降低戈壁土的动残余变形,高聚物胶凝戈壁土在经受30次循环荷载后产生的残余剪应变为天然戈壁土的15.0%~18.8%,残余体应变为天然戈壁土的12.1%~22.2%;掺入高聚物质量比为3%和12%时,残余剪应变的减小幅度为85.0%、95.2%,残余体应变的减小幅度为87.9%、95.5%,且高聚物质量比越大,减小幅度越大。采用投影寻踪回归(projection pursuit regression,PPR)分析了各影响因数对残余变形的影响权重,得出高聚物胶凝戈壁土动残余剪应变和残余体应变的影响权重依次为高聚物质量比、围压、动应力比和固结比。采用指数函数对高聚物胶凝戈壁土的残余变形与振次的关系进行拟合,建立了能反映高聚物质量比影响的高聚物胶凝戈壁土的修正残余变形模型。

Recent advances in magnetic molecularly imprinted polymers and their application in the food safety analysis

Food safety is a worldwide concern and is directly related to human health.Therefore,convenient,effective,and economical methods and technologies for food safety analysis have been developed continuously.Magnetic molecularly imprinted polymers(MMIPs)have gained extensive attention in recent years,as they have high selectivity,high adsorption capacity,and are easy to isolate from food samples.Recently,advanced strategies for the synthesis of MMIPs have been proposed to solve problems of template leakage and non-specific adsorption,and to increase the biocompatibility,adsorption rate,as well as adsorption capacity of the imprinted materials.In this review,we focus on new attempts at modification of magnetic core and MMIPs’surfaces,and the selection of template,functional monomer,cross-linker as well as porogen.Studies are summarized that used advanced MMIPs for the recognition and adsorption of pesticide residues,veterinary drug residues,mycotoxins,contaminants,and adulterations in foodstuffs over the last 5 years.Finally,some still existing challenges and future prospects to further promote MMIPs properties are also discussed.

新型超交联聚合物在蜂蜜中抗生素残留的检测研究

为了实现蜂蜜中多种抗生素的残留量同时测定,优化前处理流程,合成了一种新型的多孔聚合物材料(POP),应用于检测蜂蜜中的11种抗生素残留。前处理采用多孔聚合物材料分散吸附方式,液相色谱串联质谱以0.1%(v/v)甲酸水溶液和乙腈为流动相进行洗脱,AtiantisR T3色谱柱(2.1 mm×50 mm,1.7μm)分离,11种抗生素可在4 min内达到良好分离效果。四环素类、磺胺类、喹诺酮类药物分别在10~500、2~100和1~50μg/L范围内线性关系良好,检出限分别为3.0、0.6和0.3μg/kg,定量限分别为10.0、2.0和1.0μg/kg。11种抗生素在低、中、高三水平加标下的平均回收率为90.9%~108.7%,相对标准偏差为2.1%~9.4%。相较于传统固相萃取净化方式,使用POP的检测方法具有操作便捷、节能高效的特点;且重复性好,回收率高,可用于蜂蜜中多种抗生素残留的检测。