Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepare...Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.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
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
How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote ...How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote theε_(r)and E_(b)of linear poly(methyl methacrylate)(PMMA)copolymers.The PMMA-based random copolymer films(P(MMA-co-MHT)),block copolymer films(PMMA-b-PMHT),and PMMA-based blend films were prepared to investigate the effects of sequential structure,phase separation structure,and modification method on dielectric and energy storage properties of PMMA-based dielectric films.As a result,the random copolymer P(MMA-coMHT)can achieve a maximumε_(r)of 5.8 at 1 kHz owing to the enhanced orientation polarization and electron polarization.Because electron injection and charge transfer are limited by the strong electrostatic attraction ofπ-conjugated benzophenanthrene group analyzed by the density functional theory(DFT),the discharge energy density value of P(MMA-co-PMHT)containing 1 mol%MHT units with the efficiency of 80%reaches15.00 J cm^(-3)at 872 MV m^(-1),which is 165%higher than that of pure PMMA.This study provides a simple and effective way to fabricate the high performance of polymer dielectrics via copolymerization with the monomer of P-type semi-conductive polymer.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
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 batteri...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.展开更多
Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves t...Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.展开更多
Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility wit...Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.展开更多
Alkali-activated materials/geopolymer(AAMs),due to their low carbon emission content,have been the focus of recent studies on ecological concrete.In terms of performance,fly ash and slag are preferredmaterials for pre...Alkali-activated materials/geopolymer(AAMs),due to their low carbon emission content,have been the focus of recent studies on ecological concrete.In terms of performance,fly ash and slag are preferredmaterials for precursors for developing a one-part geopolymer.However,determining the optimum content of the input parameters to obtain adequate performance is quite challenging and scarcely reported.Therefore,in this study,machine learning methods such as artificial neural networks(ANN)and gene expression programming(GEP)models were developed usingMATLAB and GeneXprotools,respectively,for the prediction of compressive strength under variable input materials and content for fly ash and slag-based one-part geopolymer.The database for this study contains 171 points extracted from literature with input parameters:fly ash concentration,slag content,calcium hydroxide content,sodium oxide dose,water binder ratio,and curing temperature.The performance of the two models was evaluated under various statistical indices,namely correlation coefficient(R),mean absolute error(MAE),and rootmean square error(RMSE).In terms of the strength prediction efficacy of a one-part geopolymer,ANN outperformed GEP.Sensitivity and parametric analysis were also performed to identify the significant contributor to strength.According to a sensitivity analysis,the activator and slag contents had the most effects on the compressive strength at 28 days.The water binder ratio was shown to be directly connected to activator percentage,slag percentage,and calcium hydroxide percentage and inversely related to compressive strength at 28 days and curing temperature.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
This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiat...This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiated by the amino compounds following an anionic catalytic mechanism.LiTFSI plays both roles including the initiator and Li ion source in the polymer electrolyte.Normally,lithium bis(trifluoromethanesulfonyl)imide has difficulty in initiating the polymerization reaction of methyl methacrylate monomer,a very high concentration of lithium bis(trifluoromethanesulfonyl)imide is needed for initiating the polymerization.However,the fluoroethylene carbonate additive can work as a supporter to facilitate the degree of dissociation of lithium bis(trifluoromethanesulfonyl)imide and increase its initiator capacity due to the high dielectric constant.The as-prepared poly-methyl methacrylate-based polymer electrolyte has a high ionic conductivity(1.19×10^(−3)S cm^(−1)),a wide electrochemical stability window(5 V vs Li^(+)/Li),and a high Li ion transference number(t_(Li^(+)))of 0.74 at room temperature(RT).Moreover,this polymerization-derived polymer electrolyte can effectively work as an artificial protective layer on Li metal anode,which enabled the Li symmetric cell to achieve a long-term cycling performance at 0.2 mAh cm^(−2)for 2800 h.The LiFePO_(4)battery with polymerization-derived polymer electrolyte-modified Li metal anode shows a capacity retention of 91.17%after 800 cycles at 0.5 C.This work provides a facile and accessible approach to manufacturing poly-methyl methacrylate-based polymerization-derived polymer electrolyte and shows great potential as an interphase in Li metal batteries.展开更多
The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein...The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.展开更多
Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safet...Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.展开更多
With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy stor...With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.展开更多
Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(L...Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.展开更多
Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have bee...Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have been extensively utilized to improved high-temperature capacitive performance of dielectric polymers,the presence of thermodynamically incompatible organic and inorganic components may lead to concern about the long-term stability and also complicate film processing.Herein,zero-dimensional polymer dots with high electron affinity are introduced into photoactive allyl-containing poly(aryl ether sulfone)to form the all-organic polymer composites for hightemperature capacitive energy storage.Upon ultraviolet irradiation,the crosslinked polymer composites with polymer dots are efficient in suppressing electrical conduction at high electric fields and elevated temperatures,which significantly reduces the high-field energy loss of the composites at 200℃.Accordingly,the ultraviolet-irradiated composite film exhibits a discharged energy density of 4.2 J cm^(−3)at 200℃.Along with outstanding cyclic stability of capacitive performance at 200℃,this work provides a promising class of dielectric materials for robust high-performance all-organic dielectric nanocomposites.展开更多
Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and ...Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.展开更多
The solvent-free in situ polymerization technique has the potential to tailor-make conformal interfaces that are essential for developing durable and safe lithium metal polymer batteries(LMPBs).Hence,much attention ha...The solvent-free in situ polymerization technique has the potential to tailor-make conformal interfaces that are essential for developing durable and safe lithium metal polymer batteries(LMPBs).Hence,much attention has been given to the eco-friendly and rapid ultraviolet(UV)-induced in situ photopolymerization process to prepare solid-state polymer electrolytes.In this respect,an innovative method is proposed here to overcome the challenges of UV-induced photopolymerization(UV-curing)in the zones where UV-light cannot penetrate,especially in LMPBs where thick electrodes are used.The proposed frontal-inspired photopolymerization(FIPP)process is a diverged frontal-based technique that uses two classes(dual)of initiators to improve the slow reaction kinetics of allyl-based monomers/oligomers by at least 50%compared with the conventional UV-curing process.The possible reaction mechanism occurring in FIPP is demonstrated using density functional theory calculations and spectroscopic investigations.Indeed,the initiation mechanism identified for the FIPP relies on a photochemical pathway rather than an exothermic propagating front forms during the UV-irradiation step as the case with the classical frontal photopolymerization technique.Besides,the FIPP-based in situ cell fabrication using dual initiators is advantageous over both the sandwich cell assembly and conventional in situ photopolymerization in overcoming the limitations of mass transport and active material utilization in high energy and high power LMPBs that use thick electrodes.Furthermore,the LMPB cells fabricated using the in situ-FIPP process with high mass loading LiFePO_(4)electrodes(5.2 mg cm^(-2))demonstrate higher rate capability,and a 50%increase in specific capacity against a sandwich cell encouraging the use of this innovative process in large-scale solid-state battery production.展开更多
This study attempts to develop a reproducible thin-film formation technique called vacuum-free(VF)lamination,which transfers thin films using elastomeric polymer-based laminating mediators.Precisely,by controlling the...This study attempts to develop a reproducible thin-film formation technique called vacuum-free(VF)lamination,which transfers thin films using elastomeric polymer-based laminating mediators.Precisely,by controlling the interface characteristics of the mediator based on the work of adhesion,VF lamination is successfully performed for various thicknesses(from 20 to 240 nm)of a conjugated photoactive material composed of poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-bʹ]dithiophene))-alt-(5,5-(1ʹ,3ʹ-di-2-thienyl-5ʹ,7ʹ-bis(2-ethylhexyl)benzo[1ʹ,2ʹ-c:4ʹ,5ʹ-cʹ]dithiophene-4,8-dione)](a polymer donor)and 2,2ʹ-((2Z,2ʹZ)-((12,13-bis(2-butyloctyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2ʹʹ,3ʹʹ:4ʹ,5ʹ]thieno[2ʹ,3ʹ:4,5]pyrrolo[3,2-g]thieno[2ʹ,3ʹ:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(a nonfullerene acceptor).Interestingly,the organic photovoltaic and photodetecting applications,prepared by the VF lamination process,showed superior performance compared to those of devices prepared by conventional spin-coating.This is due to the overturned surface morphology,which led to enhanced charge transport ability and blocking of the externally injected charge.Thus,the reproducible VF lamination process,exploiting an adhesion-based elastomeric polymer mediator,is a promising thin-film formation technique for developing efficient next-generation organic optoelectronic materials consistent with the solution process.展开更多
The China Loess Plateau is subjected to severe soil erosion triggered by intense rainfall,resulting in significant harm and losses to both human society and the natural surroundings.In this study,a novel technique for...The China Loess Plateau is subjected to severe soil erosion triggered by intense rainfall,resulting in significant harm and losses to both human society and the natural surroundings.In this study,a novel technique for managing loess erosion is introduced,which involves the utilization of a combined polymer SH and ryegrass.A comprehensive series of tests were undertaken,including rainfall erosion tests,disintegration experiments,and scanning electron microscopy examinations,to assess the accumulative sediment yield(ASY),disintegration ratio,and microstructural features of both untreated and treated loess samples.The results showed a significant reduction in ASY with increased dry density of untreated loess.Furthermore,the combined technique effectively controlled erosion,limiting ASY to 266.2 g/cm^(2)in 60 minutes.This was approximately one-sixth,one-ninth,and one-fifteenth of the ASY in SH-treated loess(L-SH),ryegrass-treated loess(L-R),and untreated loess,respectively.It resisted disintegration better than ryegrass alone but slightly less than SH.This improvement was due to the combined effect of SH and ryegrass,which reduced raindrop impact,improved loess microstructure,and boosted ryegrass growth.The innovative technique holds the potential to be applied as a field-scale technique in the Loess Plateau region of China.展开更多
基金supported by Wuxi HIT New Material Research Institute and China Academy of Engineering Physics。
文摘Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.
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.
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the funding of National Key R&D Program of China(No.2020YFA0711700)Hunan National Natural Science Foundation(2021JJ30652)+3 种基金National Natural Science Foundation of China(52002404)Natural Science Foundation of Guangdong Province(2020A1515011198)Characteristic Innovation Projects of Colleges and Universities in Guangdong Province(2020KT SCX081)State Key Laboratory of Powder Metallurgy,Central South University,Changsha,China
文摘How to achieve synergistic improvement of permittivity(ε_(r))and breakdown strength(E_(b))is a huge challenge for polymer dielectrics.Here,for the first time,theπ-conjugated comonomer(MHT)can simultaneously promote theε_(r)and E_(b)of linear poly(methyl methacrylate)(PMMA)copolymers.The PMMA-based random copolymer films(P(MMA-co-MHT)),block copolymer films(PMMA-b-PMHT),and PMMA-based blend films were prepared to investigate the effects of sequential structure,phase separation structure,and modification method on dielectric and energy storage properties of PMMA-based dielectric films.As a result,the random copolymer P(MMA-coMHT)can achieve a maximumε_(r)of 5.8 at 1 kHz owing to the enhanced orientation polarization and electron polarization.Because electron injection and charge transfer are limited by the strong electrostatic attraction ofπ-conjugated benzophenanthrene group analyzed by the density functional theory(DFT),the discharge energy density value of P(MMA-co-PMHT)containing 1 mol%MHT units with the efficiency of 80%reaches15.00 J cm^(-3)at 872 MV m^(-1),which is 165%higher than that of pure PMMA.This study provides a simple and effective way to fabricate the high performance of polymer dielectrics via copolymerization with the monomer of P-type semi-conductive polymer.
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.
基金This work was supported by the Major Science and Technology Projects of Henan Province(221100230200)the National Key Research and Development Program of China(2020YFB1713500)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210).
文摘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.
基金National Natural Science Foundation of China (22078228)。
文摘Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.
基金supported by the National Natural Science Foundation of China(52003293,51927806,52272258)the Fundamental Research Funds for the Central Universities(2023ZKPYJD07)the Beijing Nova Program(20220484214).
文摘Solid polymer electrolytes(SPEs)have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility,scalability,and interface compatibility with electrodes.Herein,a novel all-solid polymer electrolyte(PPLCE)was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol)dimethacrylate(PEGDMA)acts as a structural frame,combined with poly(ethylene glycol)diglycidyl ether short chain interspersed serving as mobile ion transport entities.The preparaed PPLCEs exhibit excellent mechanical property and out-standing electrochemical performances,which is attributed to their unique three-dimensional cocontinuous structure,characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase,resulting in a distinctive nanostructure with short-range order and long-range disorder.Remarkably,the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs,which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte.When used in a lithiumion symmetrical battery configuration,the 6 wt%-PPLCE exhibites super stability,sustaining operation for over 2000 h at 30 C,with minimal and consistent overpotential of 50 mV.The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g^(-1)at current densities of 0.2 and 1 C,respectively.Even after more than 300 cycles at a current density of 0.2 C,it retaines an impressive 73.5%capacity.Moreover,it displayes stable cycling for over 180 cycles at a high current density of 0.5C.The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.
基金funded by the Deanship of Graduate Studies and Scientific Research at Jouf University under grant No.(DGSSR-2023-02-02385).
文摘Alkali-activated materials/geopolymer(AAMs),due to their low carbon emission content,have been the focus of recent studies on ecological concrete.In terms of performance,fly ash and slag are preferredmaterials for precursors for developing a one-part geopolymer.However,determining the optimum content of the input parameters to obtain adequate performance is quite challenging and scarcely reported.Therefore,in this study,machine learning methods such as artificial neural networks(ANN)and gene expression programming(GEP)models were developed usingMATLAB and GeneXprotools,respectively,for the prediction of compressive strength under variable input materials and content for fly ash and slag-based one-part geopolymer.The database for this study contains 171 points extracted from literature with input parameters:fly ash concentration,slag content,calcium hydroxide content,sodium oxide dose,water binder ratio,and curing temperature.The performance of the two models was evaluated under various statistical indices,namely correlation coefficient(R),mean absolute error(MAE),and rootmean square error(RMSE).In terms of the strength prediction efficacy of a one-part geopolymer,ANN outperformed GEP.Sensitivity and parametric analysis were also performed to identify the significant contributor to strength.According to a sensitivity analysis,the activator and slag contents had the most effects on the compressive strength at 28 days.The water binder ratio was shown to be directly connected to activator percentage,slag percentage,and calcium hydroxide percentage and inversely related to compressive strength at 28 days and curing temperature.
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funded by the National Key Research and Development Program of China(no.2020YFC1909604)Shenzhen Key Projects of Technological Research(JSGG20200925145800001)Shenzhen Basic Research Project(no.JCYJ20190808145203535).
文摘This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiated by the amino compounds following an anionic catalytic mechanism.LiTFSI plays both roles including the initiator and Li ion source in the polymer electrolyte.Normally,lithium bis(trifluoromethanesulfonyl)imide has difficulty in initiating the polymerization reaction of methyl methacrylate monomer,a very high concentration of lithium bis(trifluoromethanesulfonyl)imide is needed for initiating the polymerization.However,the fluoroethylene carbonate additive can work as a supporter to facilitate the degree of dissociation of lithium bis(trifluoromethanesulfonyl)imide and increase its initiator capacity due to the high dielectric constant.The as-prepared poly-methyl methacrylate-based polymer electrolyte has a high ionic conductivity(1.19×10^(−3)S cm^(−1)),a wide electrochemical stability window(5 V vs Li^(+)/Li),and a high Li ion transference number(t_(Li^(+)))of 0.74 at room temperature(RT).Moreover,this polymerization-derived polymer electrolyte can effectively work as an artificial protective layer on Li metal anode,which enabled the Li symmetric cell to achieve a long-term cycling performance at 0.2 mAh cm^(−2)for 2800 h.The LiFePO_(4)battery with polymerization-derived polymer electrolyte-modified Li metal anode shows a capacity retention of 91.17%after 800 cycles at 0.5 C.This work provides a facile and accessible approach to manufacturing poly-methyl methacrylate-based polymerization-derived polymer electrolyte and shows great potential as an interphase in Li metal batteries.
基金the financial support from the National Natural Science Foundation of China(Nos.22205191 and 52002346)the Science and Technology Innovation Program of Hunan Province(No.2021RC3109)+1 种基金the Natural Science Foundation of Hunan Province,China(No.2022JJ40446)Guangxi Key Laboratory of Low Carbon Energy Material(No.2020GXKLLCEM01)。
文摘The concentration difference in the near-surface region of lithium metal is the main cause of lithium dendrite growth.Resolving this issue will be key to achieving high-performance lithium metal batteries(LMBs).Herein,we construct a lithium nitrate(LiNO_(3))-implanted electroactiveβphase polyvinylidene fluoride-co-hexafluoropropylene(PVDF-HFP)crystalline polymorph layer(PHL).The electronegatively charged polymer chains attain lithium ions on the surface to form lithium-ion charged channels.These channels act as reservoirs to sustainably release Li ions to recompense the ionic flux of electrolytes,decreasing the growth of lithium dendrites.The stretched molecular channels can also accelerate the transport of Li ions.The combined effects enable a high Coulombic efficiency of 97.0%for 250 cycles in lithium(Li)||copper(Cu)cell and a stable symmetric plating/stripping behavior over 2000 h at 3 mA cm^(-2)with ultrahigh Li utilization of 50%.Furthermore,the full cell coupled with PHL-Cu@Li anode and Li Fe PO_(4) cathode exhibits long-term cycle stability with high-capacity retention of 95.9%after 900 cycles.Impressively,the full cell paired with LiNi_(0.87)Co_(0.1)Mn_(0.03)O_(2)maintains a discharge capacity of 170.0 mAh g^(-1)with a capacity retention of 84.3%after 100 cycles even under harsh condition of ultralow N/P ratio of 0.83.This facile strategy will widen the potential application of LiNO_(3)in ester-based electrolyte for practical high-voltage LMBs.
基金The work was financially supported by the National Natural Science Foundation of China(No.52173135,22207024)Jiangsu Specially Appointed Professorship,Leading Talents of Innovation and Entrepreneurship of Gusu(ZXL2022496)the Suzhou Science and Technology Program(SKY2022039).
文摘Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.
基金financially supported by the National Natural Science Foundation of China(51872090,51772097,22304055)the Hebei Natural Science Fund for Distinguished Young Scholar(E2019209433)+4 种基金the Youth Talent Program of Hebei Provincial Education Department(BJ2018020)the Natural Science Foundation of Hebei Province(E2020209151,E2022209158,B2022209026,D2023209012)the Central Guiding Local Science and Technology Development Fund Project(236Z4409G)the Science and Technology Project of Hebei Education Department(SLRC2019028)the Science and Technology Planning Project of Tangshan City(22130227H)。
文摘With the increasing demand for scalable and cost-effective electrochemical energy storage,aqueous zinc ion batteries(AZIBs)have a broad application prospect as an inexpensive,efficient,and naturally secure energy storage device.However,the limitations suffered by AZIBs,including volume expansion and active materials dissolution of the cathode,electrochemical corrosion,irreversible side reactions,zinc dendrites of the anode,have seriously decelerated the civilianization process of AZIBs.Currently,polymers have tremendous superiority for application in AZIBs attributed to their exceptional chemical stability,tunable structure,high energy density and outstanding mechanical properties.Considering the expanding applications of AZIBs and the superiority of polymers,this comprehensive paper meticulously reviews the benefits of utilizing polymeric applied to cathodes and anodes,respectively.To begin with,with adjustable structure as an entry point,the correlation between polymer structure and the function of energy storage as well as optimization is deeply investigated in respect to the mechanism.Then,depending on the diversity of properties and structures,the development of polymers in AZIBs is summarized,including conductive polymers,redox polymers as well as carbon composite polymers for cathode and polyvinylidene fluoride-,carbonyl-,amino-,nitrile-based polymers for anode,and a comprehensive evaluation of the shortcomings of these strategies is provided.Finally,an outlook highlights some of the challenges posed by the application of polymers and offers insights into the potential future direction of polymers in AZIBs.It is designed to provide a thorough reference for researchers and developers working on polymer for AZIBs.
基金supported by the National Natural Science Foundation of China(52122702,52277215)the Natural Science Foundation of Heilongjiang Province of China(JQ2021E005)。
文摘Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.
基金the National Natural Science Foundation of China(No.51973080,92066104).
文摘Polymer dielectrics capable of operating efficiently at high electric fields and elevated temperatures are urgently demanded by next-generation electronics and electrical power systems.While inorganic fillers have been extensively utilized to improved high-temperature capacitive performance of dielectric polymers,the presence of thermodynamically incompatible organic and inorganic components may lead to concern about the long-term stability and also complicate film processing.Herein,zero-dimensional polymer dots with high electron affinity are introduced into photoactive allyl-containing poly(aryl ether sulfone)to form the all-organic polymer composites for hightemperature capacitive energy storage.Upon ultraviolet irradiation,the crosslinked polymer composites with polymer dots are efficient in suppressing electrical conduction at high electric fields and elevated temperatures,which significantly reduces the high-field energy loss of the composites at 200℃.Accordingly,the ultraviolet-irradiated composite film exhibits a discharged energy density of 4.2 J cm^(−3)at 200℃.Along with outstanding cyclic stability of capacitive performance at 200℃,this work provides a promising class of dielectric materials for robust high-performance all-organic dielectric nanocomposites.
基金This work is supported by National Natural Science Founda-tion of China(U2004199)National Key Research and Devel-opment Program of China(2018YFD0200606)+1 种基金China Postdoctoral Science Foundation(2021T140615),Natural Sci-enceFoundationofHenanProvince(212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Solid polymer electrolyte(SPE) shows great potential for all-solid-state batteries because of the inherent safety and flexibility;however, the unfavourable Li+deposition and large thickness hamper its development and application. Herein, a laminar MXene functional layer-thin SPE layer-cathode integration(MXene-PEO-LFP) is designed and fabricated. The MXene functional layer formed by stacking rigid MXene nanosheets imparts higher compressive strength relative to PEO electrolyte layer. And the abundant negatively-charged groups on MXene functional layer effectively repel anions and attract cations to adjust the charge distribution behavior at electrolyte–anode interface. Furthermore,the functional layer with rich lithiophilic groups and outstanding electronic conductivity results in low Li nucleation overpotential and nucleation energy barrier. In consequence, the cell assembled with MXene-PEO-LFP, where the PEO electrolyte layer is only 12 μm, much thinner than most solid electrolytes, exhibits uniform, dendrite-free Li+deposition and excellent cycling stability. High capacity(142.8 mAh g-1), stable operation of 140 cycles(capacity decay per cycle, 0.065%), and low polarization potential(0.5 C) are obtained in this Li|MXene-PEO-LFP cell,which is superior to most PEO-based electrolytes under identical condition. This integrated design may provide a strategy for the large-scale application of thin polymer electrolytes in all-solid-state battery.
基金The support provided by the German Federal Ministry of Education and Research(BMBF)within the project“Benchbatt”(03XP0047B)is gratefully acknowledged.
文摘The solvent-free in situ polymerization technique has the potential to tailor-make conformal interfaces that are essential for developing durable and safe lithium metal polymer batteries(LMPBs).Hence,much attention has been given to the eco-friendly and rapid ultraviolet(UV)-induced in situ photopolymerization process to prepare solid-state polymer electrolytes.In this respect,an innovative method is proposed here to overcome the challenges of UV-induced photopolymerization(UV-curing)in the zones where UV-light cannot penetrate,especially in LMPBs where thick electrodes are used.The proposed frontal-inspired photopolymerization(FIPP)process is a diverged frontal-based technique that uses two classes(dual)of initiators to improve the slow reaction kinetics of allyl-based monomers/oligomers by at least 50%compared with the conventional UV-curing process.The possible reaction mechanism occurring in FIPP is demonstrated using density functional theory calculations and spectroscopic investigations.Indeed,the initiation mechanism identified for the FIPP relies on a photochemical pathway rather than an exothermic propagating front forms during the UV-irradiation step as the case with the classical frontal photopolymerization technique.Besides,the FIPP-based in situ cell fabrication using dual initiators is advantageous over both the sandwich cell assembly and conventional in situ photopolymerization in overcoming the limitations of mass transport and active material utilization in high energy and high power LMPBs that use thick electrodes.Furthermore,the LMPB cells fabricated using the in situ-FIPP process with high mass loading LiFePO_(4)electrodes(5.2 mg cm^(-2))demonstrate higher rate capability,and a 50%increase in specific capacity against a sandwich cell encouraging the use of this innovative process in large-scale solid-state battery production.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF)funded by the Ministry of Science,ICT (MSIT) (Grant Nos.2023R1A2C2008021 and RS-2023-00217270)supported by the Technology Innovation Program (Grant No.20017439,“Development of manufacturing process technique on high-speed signal transmission line for 6G device,”and Grant No.20021915,“Development on Nanocomposite Material of Optical Film[GPa]for Foldable Devices”)funded by the Ministry of Trade,Industry&Energy (MOTIE,Korea).
文摘This study attempts to develop a reproducible thin-film formation technique called vacuum-free(VF)lamination,which transfers thin films using elastomeric polymer-based laminating mediators.Precisely,by controlling the interface characteristics of the mediator based on the work of adhesion,VF lamination is successfully performed for various thicknesses(from 20 to 240 nm)of a conjugated photoactive material composed of poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-bʹ]dithiophene))-alt-(5,5-(1ʹ,3ʹ-di-2-thienyl-5ʹ,7ʹ-bis(2-ethylhexyl)benzo[1ʹ,2ʹ-c:4ʹ,5ʹ-cʹ]dithiophene-4,8-dione)](a polymer donor)and 2,2ʹ-((2Z,2ʹZ)-((12,13-bis(2-butyloctyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2ʹʹ,3ʹʹ:4ʹ,5ʹ]thieno[2ʹ,3ʹ:4,5]pyrrolo[3,2-g]thieno[2ʹ,3ʹ:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(a nonfullerene acceptor).Interestingly,the organic photovoltaic and photodetecting applications,prepared by the VF lamination process,showed superior performance compared to those of devices prepared by conventional spin-coating.This is due to the overturned surface morphology,which led to enhanced charge transport ability and blocking of the externally injected charge.Thus,the reproducible VF lamination process,exploiting an adhesion-based elastomeric polymer mediator,is a promising thin-film formation technique for developing efficient next-generation organic optoelectronic materials consistent with the solution process.
基金supported by the Natural Science Foundation of Qinghai Province(Grant No.2024-ZJ-987).
文摘The China Loess Plateau is subjected to severe soil erosion triggered by intense rainfall,resulting in significant harm and losses to both human society and the natural surroundings.In this study,a novel technique for managing loess erosion is introduced,which involves the utilization of a combined polymer SH and ryegrass.A comprehensive series of tests were undertaken,including rainfall erosion tests,disintegration experiments,and scanning electron microscopy examinations,to assess the accumulative sediment yield(ASY),disintegration ratio,and microstructural features of both untreated and treated loess samples.The results showed a significant reduction in ASY with increased dry density of untreated loess.Furthermore,the combined technique effectively controlled erosion,limiting ASY to 266.2 g/cm^(2)in 60 minutes.This was approximately one-sixth,one-ninth,and one-fifteenth of the ASY in SH-treated loess(L-SH),ryegrass-treated loess(L-R),and untreated loess,respectively.It resisted disintegration better than ryegrass alone but slightly less than SH.This improvement was due to the combined effect of SH and ryegrass,which reduced raindrop impact,improved loess microstructure,and boosted ryegrass growth.The innovative technique holds the potential to be applied as a field-scale technique in the Loess Plateau region of China.