Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct in...Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct ink writing(DIW)is one of the most popular 3D printing techniques owing to its ability to print multiple materials simultaneously and its high compatibility with printing inks.However,DIW presents significant challenges,particularly in the printing of high-performance polymers.The main challenges are as follows:1.The rigid structures and reaction kinetics of high-performance polymers make developing new inks difficult.2.The limited types of available high-performance polymers underscore the need for new DIW-suitable materials.3.Layer-by-layer stacking weakens interlayer bonding,affecting the mechanical properties of the printed product.4.The accuracy and speed of DIW printing are insufficient for large-scale manufacturing.After introducing the topic,the requirements for DIW printing inks are first reviewed,emphasizing the importance of thixotropic agents.Then,research progress regarding DIW printing of high-performance polymers is comprehensively reviewed according to the requirements of different polymer inks.Additionally,the applications of these materials across various fields are summarized.Finally,the challenges in DIW printing of high-performance polymers,along with corresponding solutions and future development prospects,are discussed in detail.展开更多
Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation...Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...展开更多
Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challe...Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challenge owing to the intrinsic trade-off relationship.Herein,we utilized the in situ controllable reduction of graphene oxide(GO)within a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene)(P(VDF-Tr FE-CFE))matrix to regulate the dielectric properties.The as-obtained composite exhibited a high relative dielectric constant of 1415coupled with a low loss tangent of 0.380 at 100 Hz.Experimental and theoretical studies indicate that the increased degree of electron conjugation and conductivity of the reduced GO(RGO)are responsible for the high-k.The constrained reduction degree of GO,combined with its homogeneous dispersion in the polymer matrix,effectively suppresses long-range charge carrier migration,thereby minimizing dielectric loss.This novel strategy could be successfully applied to both organic and aqueous systems.Furthermore,a high-performance flexible capacitive proximity sensor was exemplified by the optimization of both the dielectric layer and electrode pattern,exhibiting excellent sensitivity and stability.The fundamental mechanisms elucidated in this study provide crucial design principles for developing dielectric PMCs with tailored properties,thereby opening new avenues for advanced flexible electronic applications.展开更多
CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is...CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is commonly burned for heat or disposed of as waste.The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds.These considerations are derived from two fundamental aspects of lignin:its recalcitrant/heterogeneous nature and aromatic methoxy substituents.展开更多
Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O...Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the...Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.展开更多
Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need fo...Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.展开更多
Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2...Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid an...Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.展开更多
Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cat...Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.展开更多
Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we dev...Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.展开更多
The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by th...The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.展开更多
Current thermochromic materials for smart windows suffer from poor environmental stability,lack of self-healing and recyclability,and susceptibility to contamination.In this study,thermochromic supramolecular ionogels...Current thermochromic materials for smart windows suffer from poor environmental stability,lack of self-healing and recyclability,and susceptibility to contamination.In this study,thermochromic supramolecular ionogels with excellent environmental stability,efficient room-temperature self-healing and recyclability properties,as well as amphiphobic slippery surfaces,are fabricated by incorporating binary ionic liquids into a rationally designed self-healing polyurethane with perfluoroalkyl side chains.The outstanding and stable thermochromic performance of the resulting ionogels stems from the hydrogen bond-mediated,confined,and reversible phase separation of ionic liquids within the polyurethane network,enabling the ionogels to effectively reduce indoor temperatures and enhance the comfort of occupants.The surface-enriched perfluoroalkyl side chains enable various liquids,including water,alkanes,and edible oils,to easily slide off the ionogel surface without leaving any residue,preventing the transmittance decrease and thermochromic performance degradation caused by contaminations.The dynamic hydrogen bonds within the polyurethane network enable the ionogels to repeatedly heal physical and chemical damages,as well as to be recycled multiple times without performance loss,thereby reducing maintenance costs and minimizing material waste.This study provides a novel approach to developing advanced thermochromic materials for smart windows,potentially improving the building energy efficiency and sustainability.展开更多
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmenta...Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmentally friendly catalytic systems,especially in constructing efficient and recyclable catalysts under water or solvent-free conditions.Here,we designed two novel coordination polymers Cd-CPs and Fe-CPs to investigate their catalytic performance in water.Gratifyingly,it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions,while it was effective for the synthesis of1,3,5-triazines through acceptorless dehydrogenative coupling strategies.The features of broad substrate,high atom efficiency,and good catalyst reusability highlight the feasibility of this transformation.In additional,we demonstrated the spindle-like structures Fe-P,derived from the Fe-CPs via phosphorylation,which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability.This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction,and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.展开更多
A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal st...A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.展开更多
The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity...The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity and poor oxidative stability.To address these issues,we introduce a novel in-situ ionization strategy using radical polymer poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl acrylate)(PTPA)to enhance ionic conductivity and achieve a high electrochemical stability window in PEO-based electrolyte.Density functional theory(DFT)calculations and molecular dynamics(MD)simulations reveal that the in-situ generation of PTPA+from PTPA within the battery,not only exceptionally decreases the low Highest Occupied Molecular Orbital(HOMO)energy level,but also exhibits a robust anchoring effect on TFSI-anions in the electrolyte,which boosts Li^(+) migration and enables dense Li deposition behavior.As a result,the PEO/10 wt%PTPA/LiTFSI electrolyte demonstrates remarkable oxidative stability up to 5 V and a high Li^(+)transference number(0.57).Li-Li symmetric cells maintain stability over 1000 h at 0.2 mA cm^(-2),and LiFePO_(4)(LFP)//Li battery also presents an enduring cyclic performance over 500 cycles with a remarkable high-capacity retention of 91.8% at 0.5C.Impressively,by coupling with a high-voltage LiCoO_(2)(LCO)cathode(cut-off voltage 4.6 V),the assembled ASSLBs reach a capacity retention of 87.1% after 500 cycles at 1C.Our study explores the mechanism of radical polymer in PEO-based electrolyte and provides a fire-new strategy for construction of high-performance and multifunctional ASSLBs.展开更多
Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials...Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.展开更多
基金supported by National Key Research and Development Program of China(Grant No.2022YFB3809000)Major Science and Technology Project of Gansu Province(Grant No.23ZDGA011)+1 种基金National Natural Science Foundation of China(Grant No.22275199,52105224)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB04701022021).
文摘Compared to subtractive manufacturing and casting,3D printing(additive manufacturing)offers advantages,such as the rapid production of complex structures,reduced material waste,and environmental friendliness.Direct ink writing(DIW)is one of the most popular 3D printing techniques owing to its ability to print multiple materials simultaneously and its high compatibility with printing inks.However,DIW presents significant challenges,particularly in the printing of high-performance polymers.The main challenges are as follows:1.The rigid structures and reaction kinetics of high-performance polymers make developing new inks difficult.2.The limited types of available high-performance polymers underscore the need for new DIW-suitable materials.3.Layer-by-layer stacking weakens interlayer bonding,affecting the mechanical properties of the printed product.4.The accuracy and speed of DIW printing are insufficient for large-scale manufacturing.After introducing the topic,the requirements for DIW printing inks are first reviewed,emphasizing the importance of thixotropic agents.Then,research progress regarding DIW printing of high-performance polymers is comprehensively reviewed according to the requirements of different polymer inks.Additionally,the applications of these materials across various fields are summarized.Finally,the challenges in DIW printing of high-performance polymers,along with corresponding solutions and future development prospects,are discussed in detail.
基金This work was financially supported by the National Natural Science Foundation of China(No.15076017).
文摘Di(4-bromophenyl)ketone and various aromatic diamines as the monomers,a series of novel poly(imino ketone)s (PIKs)have been synthesized via palladium-catalyzed aryl amination,which is Hartwig-Buchwald polycondensation reaction.The structures of PIKs are characterized by means of elemental analysis,FT-IR,~1H-NMR and UV-Vis spectroscopy. The results show a good agreement with the proposed structure.The general properties of PIKs are studied by DSC,TG and wide-angle X-ray diffraction,the solubility behavior is...
基金financially supported by the Innovation and Technology Commission of the Hong Kong SAR Government(No.MRP/020/21)Hong Kong Polytechnic University(No.847A)+1 种基金RI-Wear Seed Fund of Poly U(1-CD8J)Start-up Fund of Poly U(1-BD49)。
文摘Polymer matrix composites with high dielectric constants and low dielectric losses are in high demand for flexible electronics.However,simultaneously satisfying these requirements poses a significant scientific challenge owing to the intrinsic trade-off relationship.Herein,we utilized the in situ controllable reduction of graphene oxide(GO)within a poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene)(P(VDF-Tr FE-CFE))matrix to regulate the dielectric properties.The as-obtained composite exhibited a high relative dielectric constant of 1415coupled with a low loss tangent of 0.380 at 100 Hz.Experimental and theoretical studies indicate that the increased degree of electron conjugation and conductivity of the reduced GO(RGO)are responsible for the high-k.The constrained reduction degree of GO,combined with its homogeneous dispersion in the polymer matrix,effectively suppresses long-range charge carrier migration,thereby minimizing dielectric loss.This novel strategy could be successfully applied to both organic and aqueous systems.Furthermore,a high-performance flexible capacitive proximity sensor was exemplified by the optimization of both the dielectric layer and electrode pattern,exhibiting excellent sensitivity and stability.The fundamental mechanisms elucidated in this study provide crucial design principles for developing dielectric PMCs with tailored properties,thereby opening new avenues for advanced flexible electronic applications.
基金the Army Research Office under Cooperative Agreement Number W911NF-22-2-0257the National Science Foundation(NSF)Growing Convergence Research program(NSF GCR CMMI 1934887)in Materials Life Cycle Management for financial support during the writing of this manuscript.
文摘CONSPECTUS:Lignocellulosic biomass is an ideal feedstock for the next generation of sustainable,high-performance,polymeric materials.Although lignin is a highly available and low-cost source of natural aromatics,it is commonly burned for heat or disposed of as waste.The use of lignin for new materials introduces both challenges and opportunities with respect to incumbent petrochemical-based compounds.These considerations are derived from two fundamental aspects of lignin:its recalcitrant/heterogeneous nature and aromatic methoxy substituents.
文摘Under solvothermal conditions,1,4‑naphthalenedicarboxylic acid(H_(2)ndc)and 9,9′‑dihexyl‑2,7‑di(pyridin‑4‑yl)fluorene(hfdp)reacted with Co^(2+)ions and Cd^(2+)ions to form two coordination polymers,[Co(hfdp)(ndc)(H2O)]·DMA}n(1)and{[Cd(hfdp)(ndc)(H_(2)O)]·DMA}_(n)(2),respectively(DMA=N,N‑dimethylacetamide).Single‑crystal X‑ray diffraction analyses showed that both complexes 1 and 2 contain similar structures.Topological analysis indicates that complexes 1 and 2 have a{44·62}planar structure.In addition,both complexes reveal good thermal stability and fluorescence sensing performance.They exhibited good sensitivity and selectivity towards 2,4,6‑trinitrophenol(TNP)by fluorescent quenching.The limits of detection of 1 and 2 for TNP were 0.107 and 0.327μmol·L^(-1),respectively.CCDC:2475515,1;2475516,2.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金financially supported by the International Cooperation Program of the Ministry of Science and Technology of Hubei Province(No.2023EHA069)Shenzhen Science and Technology Program(No.JCYJ20230807143702005)the National Foreign Experts Program(No.G2022027015L)。
文摘Liver is a vital organ in the human body and plays a central role in the metabolism and detoxification of endotoxins and exotoxins.Bilirubin is an endotoxin derived from hemoglobin(Hb).Removing excess bilirubin in the blood is crucial for the treatment of liver diseases.Hemoperfusion,which relies on adsorbents to efficiently adsorb toxins,is a widely applied procedure for the removal of blood toxins.To broaden and improve the range and performance of hemoperfusion adsorbents,we synthesized cationic hyper crosslinked polymers(HCPs)with strong affinity for bilirubin.This material exhibited outstanding adsorption performance,with a maximum adsorption capacity of 934 mg/g and a removal efficiency of 96%.Further investigation confirmed their excellent selectivity,reusability,and biocompatibility.These findings expand the potential applications of HCPs and provide insight into strategies for constructing promising hemoperfusion adsorbent materials.
基金supported by the National Natural Science Foundation of China(Nos.22322107,22101169 and 22071144)by Shanghai Scientific and Technological Committee(No.22010500300).
文摘Organic pollutants,a pivotal factor in water pollution,have persistently menaced the aquatic ecosystem,as well as the sustainable development of human health,economy,and society.Consequently,there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water.Here,we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions.These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants,characterized by high apparent adsorption rate constants(kobs)and maximum adsorption capacities(qmax,e).Notably,Compound NCCP-1 demonstrated a remarkable qmax,e of 459 mg/g for bisphenol A(BPA),ranking among the highest values reported for organic polymer adsorbents.In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them,primarily mediated by the hydrophobic effect.Furthermore,NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles,highlighting its potential for practical applications in water treatment.
文摘Four distinct coordination polymers(CPs)were successfully synthesized by altering solvent types and adjusting ligand concentrations,and their crystal structures were investigated.[Co(L)(FDCA)(H_(2)O)_(2)]·0.5H_(2)O(1)was synthesized as a 2D structure using Coas the metal source,methanol‑water(4∶6,V/V)as the solvent,and specific concentrations of 2,5‑furandicarboxylic acid(H_(2)FDCA)and 1,3,5‑triimidazole benzene(L).Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of[Co(HL)2(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(2).Using Cu(Ⅱ)as the metal source,methanol/water(9∶1,V/V)as the solvent,and specific concentrations of L and H2FDCA,the 1D chain structure of[Cu(L)(FDCA)(H_(2)O)]·2H_(2)O(3)was synthesized.Upon increasing the concentrations of L and H2FDCA,and switching the solvent to pure water,the 1D chain structure of[Cu(HL)_(2)(H_(2)O)_(2)](FDCA)_(2)·6H_(2)O(4)was obtained.This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs.In addition,the solid‑state photoluminescence of CPs 1‑4 at room temperature was studied,and their morphological changes were observed via scanning electron microscopy.Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand,facilitating ligand‑metal ion coordination.CCDC:2403934,1;2403935,2;2403936,3;2403938,4.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金the financial support provided by the National Natural Science Foundation of China(22478267,22438009,U24A20535)Basic Research Program of Jiangsu province(BK20243002)+1 种基金Prospective Application Research Project of Suzhou(SYC2022042)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Antibiotics,as an emerging pollutant due to their extensive use and difficulty in biodegradation,can cause harm to health through bioaccumulation.To address this,various photocatalysts have been developed for rapid antibiotic removal.However,their low concentrations limit mass transfer efficiency,resulting in suboptimal performance.Adsorption is crucial for enhancing photocatalytic efficiency.In this study,a series of binary heterojunction catalysts(x%BWO@STHP)were synthesized,consisting of Bi_(2)WO_(6)(BWO)grafted with sulfonated triptycene-based hypercrosslinked polymer(STHP).The high specific surface area of STHP,combined withπ-πconjugation and ionic interactions with antibiotics,significantly enhances adsorption capacity.This facilitates effective contact between low-concentration pollutants in aqueous solutions and the active sites of the catalyst.The formation of a Z-scheme heterojunction between BWO and STHP facilitates photogenerated charge separation,and further significantly improves photocatalytic degradation performance.Specifically,the 20%BWO@STHP catalyst achieved rapid adsorption equilibrium for oxytetracycline(OTC),doxycycline(DOX),and tetracycline(TC)within 2 min and completely degraded them after 15 min of irradiation.Compared to pristine BWO,the photocatalytic reaction rate constants are significantly increased,being 9.69 times higher for OTC and 13.45 times higher for DOX.The catalyst exhibits excellent reusability and holds promising potential for practical applications.
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金financially supported by the Russian Science Foundation(No.23-13-00205)。
文摘Star-shaped six-arm polymers with hexaaza[2_(6)]orthoparacyclophane core and arms of block copolymers of poly-2-ethyl-5,6-dihydrooxazine with poly-2-isopropyl-5,6-dihydrooxazine were synthesized successfully using cationic ring-opening polymerization.The ratio of blocks,the order of their attachment to the core,and arm length were varied.Conformation of synthesized stars was determined by methods of molecular hydrodynamics and optics.It has been shown that star-shaped molecules were characterized by high intramolecular density,and the arm folding increased with their lengthening.The influence of the structure of block copolymers and their molar mass on the critical micelle concentration has been established.Complexes of synthesized star-shaped block copolymers with curcumin were obtained and the efficient binding of curcumin to polymer molecules was demonstrated.The behavior of the aqueous solutions of the prepared polymer stars and their complexes with curcumin was investigated by light scattering and turbidimetry methods.The influence of the structure and molar mass of star polymers on their thermoresponsiveness and the phase separation temperatures in aqueous solutions was analyzed.A slight increase in the phase separation temperature was found on passage from polymer solutions to solutions of polymer complexes with hydrophobic curcumin.
基金the funding support from the Smart Medicine and Engineering Interdisciplinary Innovation Project of Ningbo University(No.ZHYG003)。
文摘Glassy polymers are widely used in biomedical applications in a solvent environment,yet their long-term performance is governed by the competing effects of physical aging and solvent-induced plasticization.Here,we develop a constitutive model that explicitly couples the solvent concentration,structural relaxation,and mechanical response.This framework is built on a multiplicative decomposition of deformation and an Eyring-type flow rule,with structural evolution described by an effective temperature.A generalized shift factor is introduced to quantify how the solvent concentration and effective temperature jointly affect the relaxation time,thereby integrating physical aging and plasticization.The model is subsequently applied to methacrylate(MA)-based copolymer networks immersed in phosphate-buffered saline for up to nine months.Simulations accurately capture key experimental features,including the strong softening of highly swellable networks,the partial recovery due to aging,and the mitigating role of hydrophobic crosslinking in reducing solvent uptake.While the current single-mode description cannot reproduce the full relaxation spectrum,it establishes an efficient framework for predicting the long-term mechanical performance under coupled environmental and mechanical loading.This study provides a constitutive description of solvent-swollen glassy polymers,offering mechanistic insight into the interplay between plasticization and aging.Beyond biomedical MA networks,this framework establishes a foundation for predicting the long-term performance of polymer glasses under coupled aqueous environmental and mechanical loading.
基金supported by National Natural Science Foundation of China(Grant No.22378066,22108040)Collaboration&Innovation Platform Project of National Independent Innovation Demonstration Zone(Fuzhou,Xiamen&Quanzhou)(Project No:3502ZCQXT2023004).
文摘The extraction of uranium from seawater via membrane adsorption is a promising strategy for ensuring a long-term supply of uranium and the sustainability of nuclear energy.However,this approach has been hindered by the longstanding challenge of identifying sustainable membrane materials.In response,we propose a prototypal hybridization strategy to design a novel series of aminated conjugated microporous polymer(CMPN)@collagen fiber membrane(COLM).These sustainable and low-cost membrane materials allow a rapid and high-affinity kinetic to capture 90%of the uranium in just 30 min from 50 ppm with a high selectivity of Kd>105 mL·g^(−1).They also afford a robustly reusable adsorption capacity as high as 345 mg·g^(−1)that could harvest 1.61 mg·g^(−1)of uranium in a short 7-day real marine engineering in Fujian Province,even though suffered from very low uranium concentration of 3.29μg·L^(−1)and tough influence of salts such as 10.77 g·L^(−1)of Na^(+),1.75μg·L^(−1)of VO_(3)^(−)etc.in the rough seas.The structural evidence from both experimental and theoretical studies confirmed the formation of favorable chelating motifs from the amino group on CMPN-COLM,and the intensification by the synergistic effect from the size-sieving action of CMPN and the capillary inflow effect of COLM.
基金supported by the National Natural Science Foundation of China(22475082,21971083)。
文摘Current thermochromic materials for smart windows suffer from poor environmental stability,lack of self-healing and recyclability,and susceptibility to contamination.In this study,thermochromic supramolecular ionogels with excellent environmental stability,efficient room-temperature self-healing and recyclability properties,as well as amphiphobic slippery surfaces,are fabricated by incorporating binary ionic liquids into a rationally designed self-healing polyurethane with perfluoroalkyl side chains.The outstanding and stable thermochromic performance of the resulting ionogels stems from the hydrogen bond-mediated,confined,and reversible phase separation of ionic liquids within the polyurethane network,enabling the ionogels to effectively reduce indoor temperatures and enhance the comfort of occupants.The surface-enriched perfluoroalkyl side chains enable various liquids,including water,alkanes,and edible oils,to easily slide off the ionogel surface without leaving any residue,preventing the transmittance decrease and thermochromic performance degradation caused by contaminations.The dynamic hydrogen bonds within the polyurethane network enable the ionogels to repeatedly heal physical and chemical damages,as well as to be recycled multiple times without performance loss,thereby reducing maintenance costs and minimizing material waste.This study provides a novel approach to developing advanced thermochromic materials for smart windows,potentially improving the building energy efficiency and sustainability.
基金financial support of this work by the National Natural Science Foundation of China(No.21861039)Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX24_2530)the Fundamental Research Funds for the Central Universities。
文摘Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives.However,it is challenging to develop environmentally friendly catalytic systems,especially in constructing efficient and recyclable catalysts under water or solvent-free conditions.Here,we designed two novel coordination polymers Cd-CPs and Fe-CPs to investigate their catalytic performance in water.Gratifyingly,it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions,while it was effective for the synthesis of1,3,5-triazines through acceptorless dehydrogenative coupling strategies.The features of broad substrate,high atom efficiency,and good catalyst reusability highlight the feasibility of this transformation.In additional,we demonstrated the spindle-like structures Fe-P,derived from the Fe-CPs via phosphorylation,which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability.This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction,and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
文摘A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.
基金supported by the National Natural Science Foundation of China(51973236,51573213)Zhuhai Industry University-Research Cooperation Program(2320004002721)。
文摘The practical application of poly(ethylene oxide)(PEO)-based solid polymer electrolytes in all-solid-state lithium-metal batteries(ASSLBs)still suffers from persistent challenges associated with low ionic conductivity and poor oxidative stability.To address these issues,we introduce a novel in-situ ionization strategy using radical polymer poly(2,2,6,6-tetramethyl-1-piperidinyloxy-4-yl acrylate)(PTPA)to enhance ionic conductivity and achieve a high electrochemical stability window in PEO-based electrolyte.Density functional theory(DFT)calculations and molecular dynamics(MD)simulations reveal that the in-situ generation of PTPA+from PTPA within the battery,not only exceptionally decreases the low Highest Occupied Molecular Orbital(HOMO)energy level,but also exhibits a robust anchoring effect on TFSI-anions in the electrolyte,which boosts Li^(+) migration and enables dense Li deposition behavior.As a result,the PEO/10 wt%PTPA/LiTFSI electrolyte demonstrates remarkable oxidative stability up to 5 V and a high Li^(+)transference number(0.57).Li-Li symmetric cells maintain stability over 1000 h at 0.2 mA cm^(-2),and LiFePO_(4)(LFP)//Li battery also presents an enduring cyclic performance over 500 cycles with a remarkable high-capacity retention of 91.8% at 0.5C.Impressively,by coupling with a high-voltage LiCoO_(2)(LCO)cathode(cut-off voltage 4.6 V),the assembled ASSLBs reach a capacity retention of 87.1% after 500 cycles at 1C.Our study explores the mechanism of radical polymer in PEO-based electrolyte and provides a fire-new strategy for construction of high-performance and multifunctional ASSLBs.
基金Financial support from National Natural Science Foundation of China(Nos.51702056 and 51772135)the Ministry of Education of China(6141A02022516)China Postdoctoral Science Foundation(2017M622902 and 2019T120790).
文摘Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.
