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)M...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.展开更多
Thermosensitive hydrogel can integrate vapor molecular capture,in-situ liquefaction,and thermal-induced water release for freshwater capture.This study aimed to examine the dynamic behavior of poly(N-isopropylacrylami...Thermosensitive hydrogel can integrate vapor molecular capture,in-situ liquefaction,and thermal-induced water release for freshwater capture.This study aimed to examine the dynamic behavior of poly(N-isopropylacrylamide)(PNIPAM)single chain and cross-linking thermosensitive hydrogel through molecular dynamics simulation.Specifically,the impact of lower critical solution temperature(LCST)on the conformation of polymer chain and the interaction between water and polymer chain were also investigated.The polymer chain conformation underwent a transition from coil to globule when the temperature exceeded the LCST,indicating the temperature responsiveness of PNIPAM.Additionally,thermosensitive hydrogel samples with different cross-linking degrees(DOC)were studied,and relevant parameters such as the number of free water,the diffusion coefficient of water,and the pore size distribution were counted to evaluate the temperature responsiveness and water release characteristics of thermosensitive hydrogel.展开更多
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 l...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.展开更多
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 drama...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.展开更多
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,...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.展开更多
Noncovalentlycross-linkedpolymermaterials through healing,recycling,and reprocessing can reduce materials consumption and alleviate environmental pollution.However,it remains a huge challenge to fabricate super-strong...Noncovalentlycross-linkedpolymermaterials through healing,recycling,and reprocessing can reduce materials consumption and alleviate environmental pollution.However,it remains a huge challenge to fabricate super-strong noncovalently cross-linked polymer materials with mechanical strength comparable to high-performance engineering polymers.Herein,healable and reprocessable noncovalently cross-linked polymer compositeswith an unprecedented mechanical strength are fabricated by complexation of polyacrylic acid(PAA),polyvinylpyrrolidone(PVPON),and carbonized polymer dots(CPDs)(denoted as PAA-PVPON-CPDs).The incorporation of 15 wt%CPDs generates PAA-PVPON-CPDs compositeswith a tensile strength of∼158 MPa and Young’s modulus of∼8.2GPa.Servingas nanofillers,theCPDs can establish strong interactions with polymers in PAA-PVPON composites.The CPDs and the in situ-formed PAAPVPON nanoparticles work in concert to significantly strengthen the PAA-PVPON-CPDs composites to an unprecedented strength.The PAA-PVPON-CPDs composites exhibit excellent impact resistance and damage tolerance because of the high mechanical strength of the composites and the energy dissipation mechanism of the CPDs and PAA-PVPON nanoparticles.Moreover,the fractured PAA-PVPON-CPDs composites can be healed to restore their original mechanical strength.展开更多
The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious int...The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.展开更多
Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors c...Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.展开更多
Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other f...Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other features,a detailed description of the crosslink density in these mixtures.In the case of vulcanized immiscible blends,the distribution of the cross-link density within each of the NR-and BR-rich domains is key information,but difficult to determine using the conventional approaches used for one-component crosslinked elastomers.In this study,the vulcanization within NR/BR blends is investigated using a robust^(1)H double-quantum(DQ)MAS recoupling experiment,BaBa-xy16.Two kinds of cross-linked NR/BR blends were considered with two different microstructures for the BR component.The bulk organization of the resulting blends was first probed by analyzing the^(1)H spin-lattice relaxation behavior.In a second step,BaBa-xy16 was used to investigate,in a selective way,the cross-link heterogeneities within NR/BR blends.In particular,for immiscible NR/BR mixtures,the distribution of the cross-link density between both phases was compared and the observed differences were discussed.展开更多
Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolyte...Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolytes,composite solid electrolytes(CSEs)exhibit both high ionic conductivity and excellent interfacial contact with the electrodes.Incorporating active nanofib-ers into the polymer matrix demonstrates an effective method to fabricate CSEs.However,current CSEs based on traditional poly(ethylene oxide)(PEO)polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations,which limit further improvements in Li+conductivity and electrochemical stability.Herein,we synthesize a novel PEO based cross-linked polymer(CLP)as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40×10^(−4)S cm^(−1).Li_(0.3)La_(0.557)TiO_(3)(LLTO)nanofibers are incorporated into the CLP matrix to form composite solid electrolytes,achieving enhanced ionic conductivity without showing filler agglomeration.The high content of Li-conductive nanofibers improves the mechanical strength,ensures the conductive network,and increases the total Li+conductivity to 3.31×10^(−4)S cm^(−1).The all-solid-state Li|LiFePO_(4)batteries with LLTO nanofiber-incorporated CSEs are able to deliver attractive specific capacity of 147 mAh g^(−1)at room temperature,and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.展开更多
Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium...Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium dendrite growth lead to the limited serving life and hinder the practical application of lithium metal batteries.Here,a tri-monomer copolymerized gel polymer electrolyte(TGPE)with a cross-linked reticulation structure was prepared by introducing a cross-linker(polyurethane group)into the acrylate-based in situ polymerization system.The soft segment of polyurethane in TGPE enables the far migration of lithium ions,and the-NH forms hydrogen bonds in the hard segment to build a stable cross-linked framework.This system hinders anion migration and leads to a high Li^(+)migration number(t_(Li^(+))=0.65),which achieves uniform lithium deposition and effectively inhibits lithium dendrite growth.As a result,the assembled symmetric cell shows robust reversibility over 5500 h at a current density of 1 mA cm^(-2).The LFP∷TGPE∷Li cell has a capacity retention of 89.8%after cycling 800 times at a rate of 1C.In summary,in situ polymerization of TGPE electrolytes is expected to be a candidate material for high-energy-density lithium metal batteries.展开更多
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 satisfie...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.展开更多
In this study, we modified microcrystalline cellulose by cross-linking it with epichlorohydrin to obtain a rapid and efficient adsorbent for the removal of Reactive Blue 4 dye from aqueous solution. Evidences of the c...In this study, we modified microcrystalline cellulose by cross-linking it with epichlorohydrin to obtain a rapid and efficient adsorbent for the removal of Reactive Blue 4 dye from aqueous solution. Evidences of the cross-linking of the microcrystalline cellulose were obtained by Fourier transform infrared spectroscopy, X-ray diff raction, Brunauer–Emmett–Teller analysis, thermogravimetric analysis, and scanning electron microscopy. We investigated the eff ects of adsorbent dosage, p H, initial dye concentration, temperature, and contact time on the dye adsorption capacity. The results showed that the adsorption equilibrium time was just 20 min and the maximum adsorption capacity was 69.79 mg/g. The adsorption isotherm data fitted the Langmuir isotherm model well, and the adsorption kinetics data followed the pseudo-second-order kinetic model. The results of the thermodynamic analysis suggest that the adsorption process was spontaneous and exothermic. Recyclability experiments demonstrated the good reusability of this adsorbent. Electrostatic interaction was found to dominate the adsorption process.展开更多
The urgent need for immediate personal protection against chemical warfare agents(CWAs)spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices.Her...The urgent need for immediate personal protection against chemical warfare agents(CWAs)spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices.Herein,as a new concept for CWA decontamination catalyst design,sub-nanoscale,catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures.The obtained membrane catalysts exhibit high swelling ratio with aqueous content as 84 wt%and therefore,demonstrate quasi-homogeneous catalytic activity toward the rapid hydrolysis of both CWA,soman(GD)(t_(1/2)=5.0 min)and CWA simulant,methyl paraoxon(DMNP)(t_(1/2)=8.9 min).Meanwhile,due to the covalent nature of cross-linkages and the high flexibility of polymer strands,the membranes possess promising mechanical strength and toughness that can stand the impact of high gas pressures and show high permeation for both CO_(2)and O_(2),enabling their extended applications in the field of collective/personal protective materials with body comfort.展开更多
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 cycli...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.展开更多
The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate) -block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block(PLDMA) in ethanol was investigated....The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate) -block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block(PLDMA) in ethanol was investigated. The results show that the size and morphology of the resulting micelle or micellar aggregates are ascribed to the content of ethanol and the nature of the solvent mixture. PbS nanoparticles were formed in the micelle by in situ reaction with H2S gas. The morphology and size of the self-assembly objects were investigated using scanning electron microscopy (SEM) and transmission electron microscopy(TEM).展开更多
In the exploration of next-generation high-energy–density batteries,lithium metal is regarded as an ideal candidate for anode materials.However,lithium metal batteries (LMBs) face challenges in practical applications...In the exploration of next-generation high-energy–density batteries,lithium metal is regarded as an ideal candidate for anode materials.However,lithium metal batteries (LMBs) face challenges in practical applications due to the risks associated with organic liquid electrolytes,among which their low flash points are one of the major safety concerns.The adoption of high flash point quasi-solid polymer electrolytes(QSPE) that is compatible with the lithium metal anode and high-voltage cathode is therefore a promising strategy for exploring high-performance and high-safety LMBs.Herein,we employed the in-situ polymerization of poly (epoxidized soya fatty acid Bu esters-isooctyl acrylate-ditrimethylolpropane tetraacrylate)(PEID) to gel the liquid electrolyte that formed a PEID-based QSPE (PEID-QSPE).The flash point of PEID-QSPE rises from 25 to 82℃ after gelation,contributing to enhanced safety of the battery at elevated temperatures,whereas the electrochemical window increases to 4.9 V.Moreover,the three-dimensional polymer framework of PEID-QSPE is validated to facilitate the uniform growth of the solid electrolyte interphase on the anode,thereby improving the cycling stability of the battery.By employing PEID-QSPE,the Li|LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cell achieved long-term cycling stability (Coulombic efficiency,99.8%;>200 cycles at 0.1 C) even with a high cathode loading (~5 mg cm^(-2)) and an ultrathin Li(~50μm).This electrolyte is expected to afford inspiring insights for the development of safe and long-term cyclability LMBs.展开更多
Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing we...Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.展开更多
This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped...This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.展开更多
With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complicatio...With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complications.Currently,reagents based on modified natural polymers(which are naturally occurring compounds)and synthetic polymers(SPs)which are polymeric compounds created industrially,are widely used to prevent emerging complications in the drilling process.However,compared to modified natural polymers,SPs form a family of high-molecular-weight compounds that are fully synthesized by undergoing chemical polymerization reactions.SPs provide substantial flexibility in their design.Moreover,their size and chemical composition can be adjusted to provide properties for nearly all the functional objectives of drilling fluids.They can be classified based on chemical ingredients,type of reaction,and their responses to heating.However,some of SPs,due to their structural characteristics,have a high cost,a poor temperature and salt resistance in drilling fluids,and degradation begins when the temperature reaches 130℃.These drawbacks prevent SP use in some medium and deep wells.Thus,this review addresses the historical development,the characteristics,manufacturing methods,classification,and the applications of SPs in drilling fluids.The contributions of SPs as additives to drilling fluids to enhance rheology,filtrate generation,carrying of cuttings,fluid lubricity,and clay/shale stability are explained in detail.The mechanisms,impacts,and advances achieved when SPs are added to drilling fluids are also described.The typical challenges encountered by SPs when deployed in drilling fluids and their advantages and drawbacks are also discussed.Economic issues also impact the applications of SPs in drilling fluids.Consequently,the cost of the most relevant SPs,and the monomers used in their synthesis,are assessed.Environmental impacts of SPs when deployed in drilling fluids,and their manufacturing processes are identified,together with advances in SP-treatment methods aimed at reducing those impacts.Recommendations for required future research addressing SP property and performance gaps are provided.展开更多
基金supported by the National Natural Science Foundation of China(52162030)the Yunnan Major Scientific and Technological Projects(202202AG050003)+4 种基金the Key Research and Development Program of Yunnan Province(202103AA080019)the Scientific Research Foundation of Kunming University of Science and Technology(20220122)the Graduate Student Top Innovative Talent Program of Kunming University of Science and Technology(CA23107M139A)the Analysis and Testing Foundation of Kunming University of Science and Technology(2023T20220122)the Shenzhen Science and Technology Program(KCXST20221021111201003)。
文摘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.
基金supported by National Natural Science Foundation of China(No.52206073)Fundamental Research Funds for the Central Universities(No.3132023119)Guangdong Basic and Applied Basic Research Foundation(Nos.2024A1515011379 and 2023A1515110613).
文摘Thermosensitive hydrogel can integrate vapor molecular capture,in-situ liquefaction,and thermal-induced water release for freshwater capture.This study aimed to examine the dynamic behavior of poly(N-isopropylacrylamide)(PNIPAM)single chain and cross-linking thermosensitive hydrogel through molecular dynamics simulation.Specifically,the impact of lower critical solution temperature(LCST)on the conformation of polymer chain and the interaction between water and polymer chain were also investigated.The polymer chain conformation underwent a transition from coil to globule when the temperature exceeded the LCST,indicating the temperature responsiveness of PNIPAM.Additionally,thermosensitive hydrogel samples with different cross-linking degrees(DOC)were studied,and relevant parameters such as the number of free water,the diffusion coefficient of water,and the pore size distribution were counted to evaluate the temperature responsiveness and water release characteristics of thermosensitive hydrogel.
基金financial support from the National Key Technology R&D Program in the 12th Five Year Plan of PetroChina (No: 2011ZX05010-003-02)the National Key Technology R&D Program in the 12th Five Year Plan of CNOOC (No: 2011ZX05024-04-05-03)
文摘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.
基金the Science and Technology Department of Henan Province of China(Grant No.222102240060 and 222300420541)the Education Department of Henan Province of China(Grant No.22B430023)supported by the Program for Innovative Research Team(in Science and Technology)in University of Henan Province(Grant No.23IRTSTHN009)。
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China(NSFC grant no.21935004).
文摘Noncovalentlycross-linkedpolymermaterials through healing,recycling,and reprocessing can reduce materials consumption and alleviate environmental pollution.However,it remains a huge challenge to fabricate super-strong noncovalently cross-linked polymer materials with mechanical strength comparable to high-performance engineering polymers.Herein,healable and reprocessable noncovalently cross-linked polymer compositeswith an unprecedented mechanical strength are fabricated by complexation of polyacrylic acid(PAA),polyvinylpyrrolidone(PVPON),and carbonized polymer dots(CPDs)(denoted as PAA-PVPON-CPDs).The incorporation of 15 wt%CPDs generates PAA-PVPON-CPDs compositeswith a tensile strength of∼158 MPa and Young’s modulus of∼8.2GPa.Servingas nanofillers,theCPDs can establish strong interactions with polymers in PAA-PVPON composites.The CPDs and the in situ-formed PAAPVPON nanoparticles work in concert to significantly strengthen the PAA-PVPON-CPDs composites to an unprecedented strength.The PAA-PVPON-CPDs composites exhibit excellent impact resistance and damage tolerance because of the high mechanical strength of the composites and the energy dissipation mechanism of the CPDs and PAA-PVPON nanoparticles.Moreover,the fractured PAA-PVPON-CPDs composites can be healed to restore their original mechanical strength.
基金supported by the National Natural Science Foundation of China(Nos.52172214,52272221,52171182)the Postdoctoral Innovation Project of Shandong Province(No.202102003)+2 种基金The Key Research and Development Program of Shandong Province(2021ZLGX01)the Qilu Young Scholar ProgramHPC Cloud Platform of Shandong University are also thanked.
文摘The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.
基金financially supported by the Sichuan Science and Technology Program(2022YFS0025 and 2024YFFK0133)supported by the“Fundamental Research Funds for the Central Universities of China.”。
文摘Tactile perception plays a vital role for the human body and is also highly desired for smart prosthesis and advanced robots.Compared to active sensing devices,passive piezoelectric and triboelectric tactile sensors consume less power,but lack the capability to resolve static stimuli.Here,we address this issue by utilizing the unique polarization chemistry of conjugated polymers for the first time and propose a new type of bioinspired,passive,and bio-friendly tactile sensors for resolving both static and dynamic stimuli.Specifically,to emulate the polarization process of natural sensory cells,conjugated polymers(including poly(3,4-ethylenedioxythiophen e):poly(styrenesulfonate),polyaniline,or polypyrrole)are controllably polarized into two opposite states to create artificial potential differences.The controllable and reversible polarization process of the conjugated polymers is fully in situ characterized.Then,a micro-structured ionic electrolyte is employed to imitate the natural ion channels and to encode external touch stimulations into the variation in potential difference outputs.Compared with the currently existing tactile sensing devices,the developed tactile sensors feature distinct characteristics including fully organic composition,high sensitivity(up to 773 mV N^(−1)),ultralow power consumption(nW),as well as superior bio-friendliness.As demonstrations,both single point tactile perception(surface texture perception and material property perception)and two-dimensional tactile recognitions(shape or profile perception)with high accuracy are successfully realized using self-defined machine learning algorithms.This tactile sensing concept innovation based on the polarization chemistry of conjugated polymers opens up a new path to create robotic tactile sensors and prosthetic electronic skins.
基金financial support from the French National Research Agency(ANR)[grant number ANR-22-CE06-0031]。
文摘Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other features,a detailed description of the crosslink density in these mixtures.In the case of vulcanized immiscible blends,the distribution of the cross-link density within each of the NR-and BR-rich domains is key information,but difficult to determine using the conventional approaches used for one-component crosslinked elastomers.In this study,the vulcanization within NR/BR blends is investigated using a robust^(1)H double-quantum(DQ)MAS recoupling experiment,BaBa-xy16.Two kinds of cross-linked NR/BR blends were considered with two different microstructures for the BR component.The bulk organization of the resulting blends was first probed by analyzing the^(1)H spin-lattice relaxation behavior.In a second step,BaBa-xy16 was used to investigate,in a selective way,the cross-link heterogeneities within NR/BR blends.In particular,for immiscible NR/BR mixtures,the distribution of the cross-link density between both phases was compared and the observed differences were discussed.
基金the Department of Energy,Office of Energy Efficiency and Renewable Energy(EERE),under Award Number DE-EE0007806.
文摘Solid electrolytes have gained attention recently for the development of next-generation Li-ion batteries since they can fun-damentally improve the battery stability and safety.Among various types of solid electrolytes,composite solid electrolytes(CSEs)exhibit both high ionic conductivity and excellent interfacial contact with the electrodes.Incorporating active nanofib-ers into the polymer matrix demonstrates an effective method to fabricate CSEs.However,current CSEs based on traditional poly(ethylene oxide)(PEO)polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations,which limit further improvements in Li+conductivity and electrochemical stability.Herein,we synthesize a novel PEO based cross-linked polymer(CLP)as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40×10^(−4)S cm^(−1).Li_(0.3)La_(0.557)TiO_(3)(LLTO)nanofibers are incorporated into the CLP matrix to form composite solid electrolytes,achieving enhanced ionic conductivity without showing filler agglomeration.The high content of Li-conductive nanofibers improves the mechanical strength,ensures the conductive network,and increases the total Li+conductivity to 3.31×10^(−4)S cm^(−1).The all-solid-state Li|LiFePO_(4)batteries with LLTO nanofiber-incorporated CSEs are able to deliver attractive specific capacity of 147 mAh g^(−1)at room temperature,and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.
基金support from the National Natural Science Foundation of China(52077096)
文摘Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium dendrite growth lead to the limited serving life and hinder the practical application of lithium metal batteries.Here,a tri-monomer copolymerized gel polymer electrolyte(TGPE)with a cross-linked reticulation structure was prepared by introducing a cross-linker(polyurethane group)into the acrylate-based in situ polymerization system.The soft segment of polyurethane in TGPE enables the far migration of lithium ions,and the-NH forms hydrogen bonds in the hard segment to build a stable cross-linked framework.This system hinders anion migration and leads to a high Li^(+)migration number(t_(Li^(+))=0.65),which achieves uniform lithium deposition and effectively inhibits lithium dendrite growth.As a result,the assembled symmetric cell shows robust reversibility over 5500 h at a current density of 1 mA cm^(-2).The LFP∷TGPE∷Li cell has a capacity retention of 89.8%after cycling 800 times at a rate of 1C.In summary,in situ polymerization of TGPE electrolytes is expected to be a candidate material for high-energy-density lithium metal batteries.
基金funding supports from the Natural Science Basis Research Plan in Shaanxi Province of China(2019JLZ-10)the Independent Research Project of National Key Laboratory of Electrical Insulation and Power Equipment(EIPE19111)。
文摘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.
文摘In this study, we modified microcrystalline cellulose by cross-linking it with epichlorohydrin to obtain a rapid and efficient adsorbent for the removal of Reactive Blue 4 dye from aqueous solution. Evidences of the cross-linking of the microcrystalline cellulose were obtained by Fourier transform infrared spectroscopy, X-ray diff raction, Brunauer–Emmett–Teller analysis, thermogravimetric analysis, and scanning electron microscopy. We investigated the eff ects of adsorbent dosage, p H, initial dye concentration, temperature, and contact time on the dye adsorption capacity. The results showed that the adsorption equilibrium time was just 20 min and the maximum adsorption capacity was 69.79 mg/g. The adsorption isotherm data fitted the Langmuir isotherm model well, and the adsorption kinetics data followed the pseudo-second-order kinetic model. The results of the thermodynamic analysis suggest that the adsorption process was spontaneous and exothermic. Recyclability experiments demonstrated the good reusability of this adsorbent. Electrostatic interaction was found to dominate the adsorption process.
基金the National Key Research and Development Program of China(No.2018YFB0704200)the Project of State Key Laboratory of NBC Protection for Civilian(No.ZKGSG-ZB-20194334)+1 种基金the National Natural Science Foundation of China(Nos.21961142018 and 51873067)Natural Science Foundation of Guangdong Province(Nos.2021A1515012024 and 2021A1515010271)。
文摘The urgent need for immediate personal protection against chemical warfare agents(CWAs)spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices.Herein,as a new concept for CWA decontamination catalyst design,sub-nanoscale,catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures.The obtained membrane catalysts exhibit high swelling ratio with aqueous content as 84 wt%and therefore,demonstrate quasi-homogeneous catalytic activity toward the rapid hydrolysis of both CWA,soman(GD)(t_(1/2)=5.0 min)and CWA simulant,methyl paraoxon(DMNP)(t_(1/2)=8.9 min).Meanwhile,due to the covalent nature of cross-linkages and the high flexibility of polymer strands,the membranes possess promising mechanical strength and toughness that can stand the impact of high gas pressures and show high permeation for both CO_(2)and O_(2),enabling their extended applications in the field of collective/personal protective materials with body comfort.
基金supported by R&D Program of Power Batteries with Low Temperature and High Energy,Science and Technology Bureau of Changchun(19SS013)Key Subject Construction of Physical Chemistry of Northeast Normal University+1 种基金the Fundamental Research Funds for the Central Universities(2412020FZ007,2412020FZ008)National Natural Science Foundation of China(22102020)
文摘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.
基金Suppored by the National Natural Science Foundation of China ( Nos 20374024 and 20534040) and the Program forChangjiang Scholars and Innovative Research Team in Universities(No IRT0422)
文摘The self-assembly behavior of the amphiphilic block copolymer poly( methyl methacrylate) -block-poly( lead dimethacrylate) (PMMA-b-PLDMA) with cross-linked hydrophilic block(PLDMA) in ethanol was investigated. The results show that the size and morphology of the resulting micelle or micellar aggregates are ascribed to the content of ethanol and the nature of the solvent mixture. PbS nanoparticles were formed in the micelle by in situ reaction with H2S gas. The morphology and size of the self-assembly objects were investigated using scanning electron microscopy (SEM) and transmission electron microscopy(TEM).
基金the S&T Program of Hebei (Grant Nos. 22344402D,22373709D)the National Natural Science Foundation of China(Grant Nos. 22108151, 22108202, 22109084, 22209010,22379014, and 22309101)+3 种基金the Beijing Natural Science Foundation(Grant Nos. Z200011, L233004)the Young Elite Scientists Sponsorship Program by CAST (Grant No. 2021QNRC001)the Seed Fund of Shanxi Research Institute for Clean Energythe support from the Department of Science and Technology of Jilin Province (Grant No. 20210301021GX)。
文摘In the exploration of next-generation high-energy–density batteries,lithium metal is regarded as an ideal candidate for anode materials.However,lithium metal batteries (LMBs) face challenges in practical applications due to the risks associated with organic liquid electrolytes,among which their low flash points are one of the major safety concerns.The adoption of high flash point quasi-solid polymer electrolytes(QSPE) that is compatible with the lithium metal anode and high-voltage cathode is therefore a promising strategy for exploring high-performance and high-safety LMBs.Herein,we employed the in-situ polymerization of poly (epoxidized soya fatty acid Bu esters-isooctyl acrylate-ditrimethylolpropane tetraacrylate)(PEID) to gel the liquid electrolyte that formed a PEID-based QSPE (PEID-QSPE).The flash point of PEID-QSPE rises from 25 to 82℃ after gelation,contributing to enhanced safety of the battery at elevated temperatures,whereas the electrochemical window increases to 4.9 V.Moreover,the three-dimensional polymer framework of PEID-QSPE is validated to facilitate the uniform growth of the solid electrolyte interphase on the anode,thereby improving the cycling stability of the battery.By employing PEID-QSPE,the Li|LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cell achieved long-term cycling stability (Coulombic efficiency,99.8%;>200 cycles at 0.1 C) even with a high cathode loading (~5 mg cm^(-2)) and an ultrathin Li(~50μm).This electrolyte is expected to afford inspiring insights for the development of safe and long-term cyclability LMBs.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea Government(MSIT)(No.NRF-2021R1A2C2004109)the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(No.P0020612,2022 The Competency Development Program for Industry Specialist).
文摘Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.
基金Natural Science Foundation of China (51603031)Liaoning Provincial Natural Science Foundation of China (2020-MS-087)China Scholarship Council(202306080157)。
文摘This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.
文摘With the growth of deep drilling and the complexity of the well profile,the requirements for a more complete and efficient exploitation of productive formations increase,which increases the risk of various complications.Currently,reagents based on modified natural polymers(which are naturally occurring compounds)and synthetic polymers(SPs)which are polymeric compounds created industrially,are widely used to prevent emerging complications in the drilling process.However,compared to modified natural polymers,SPs form a family of high-molecular-weight compounds that are fully synthesized by undergoing chemical polymerization reactions.SPs provide substantial flexibility in their design.Moreover,their size and chemical composition can be adjusted to provide properties for nearly all the functional objectives of drilling fluids.They can be classified based on chemical ingredients,type of reaction,and their responses to heating.However,some of SPs,due to their structural characteristics,have a high cost,a poor temperature and salt resistance in drilling fluids,and degradation begins when the temperature reaches 130℃.These drawbacks prevent SP use in some medium and deep wells.Thus,this review addresses the historical development,the characteristics,manufacturing methods,classification,and the applications of SPs in drilling fluids.The contributions of SPs as additives to drilling fluids to enhance rheology,filtrate generation,carrying of cuttings,fluid lubricity,and clay/shale stability are explained in detail.The mechanisms,impacts,and advances achieved when SPs are added to drilling fluids are also described.The typical challenges encountered by SPs when deployed in drilling fluids and their advantages and drawbacks are also discussed.Economic issues also impact the applications of SPs in drilling fluids.Consequently,the cost of the most relevant SPs,and the monomers used in their synthesis,are assessed.Environmental impacts of SPs when deployed in drilling fluids,and their manufacturing processes are identified,together with advances in SP-treatment methods aimed at reducing those impacts.Recommendations for required future research addressing SP property and performance gaps are provided.