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1.
孙维林 《高分子科学》2012,30(5):759-769
A novel conjugated hyperbranched polymer containing bithiazole rings(PBTADB) was synthesized by polycondensation of 1,3,5-benzenetricarboxaldehyde and 2,2’-diamino-4,4’-bithiazole(DABT).The structure of the hyperbranched polymer was confirmed by FT-IR and 1H-NMR.PBTADB dissolved in organic polar solvents such as DMSO and NMP.Bithiazole rings were introduced to provide bidentate N-donor sites for binding metal ions.The metal complexes were prepared by chelation of the polymer with Co2+ and Sm3+.The magnetic behavior of coordination compounds was measured as a function of magnetic field strength(0-4.8×106 A/m) at 5 K and as a function of temperature(5-300 K) at magnetic field strength of 2.4×106 A/m.The magnetic hysteresis loops of PBTADB-Sm3+and PBTADB-Co2+showed the typical ’S’ shape at 5 K with the Curie-Weiss temperature Tθ=96 K and 41 K respectively.The results show that they exhibit properties of soft ferromagnetic materials.  相似文献   

2.
In this work we have studied the effect of 1,2-dimethoxyethane(1,2-DME) addition(from 0 to 90 vol%)on the electrochemical behaviour of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide(EMIm TFSI) as an electrolyte for supercapacitors,using cyclic voltammetry,electrochemical impedance spectroscopy and constant power methods.Also,the ionic conductivity and viscosity of EMIm TFSI and1,2-DME have been measured and discussed.The conductivity of the EMIm TFSI could be increased from 5.67 m S/cm up to 24.21 m S/cm by mixing EMIm TFSI with 1,2-DME.The stored power values for supercapacitors increased from 13 k W/kg to 20.5 k W/kg(correspond to 2 s application line),when the concentration of 1,2-DME increased up to 40 vol%.The supercapacitors based on the 40 vol% of 1,2-DME deliver the higher power density at the constant energy density,showing an excellent characteristics applicable in high rate supercapacitor devices.Nearly ideal capacitive behaviour has been established at potential scan rates v ≤ 10 m V/s and cell potential E ≤ 2.7 V.  相似文献   

3.
An ethanol biosensor was fabricated based on a Methylobacterium organophilium-immobilized eggshell membrane and an oxygen(O2) electrode.A linear response for ethanol was obtained in the range of 0.050-7.5 mmol/L with a detection limit of 0.025 mmol/L(S/N= 3) and a R.S.D.of 2.1%.The response time was less than 100 s at room temperature and ambient pressure. The optimal loading of bacterial cells on the biosensor membrane is 40 mg(wet weight).The optimal working conditions for the microbial biosensor are pH 7.0 phosphate buffer(50 mmol/L) at 20-25℃.The interference test,operational and storage stability of the biosensor are studied in detail.Finally,the biosensor is applied to determine the ethanol contents in various alcohol samples and the results are comparable to that obtained by gas chromatographic method and the results are satisfactory.Our proposed biosensor provides a convenient,simple and reliable method to determine ethanol content in alcoholic drinks.  相似文献   

4.
Replacement of phosphoric acid electrolyte by phosphosilicate gel based electrolytes is proposed for performance enhancement of phosphoric acid fuel cell(PAFC).Phosphosilicate gel in paste form and in powder form is synthesized from tetraethoxysilane and orthophosphoric acid using sol-gel method for two different P/Si ratio of 5 and 1.5 respectively.Replacement of phosphoric acid electrolyte by phosphosilicate gel paste enhances the peak power generation of the fuel cell by 133% at 120 ℃ cell temperature;increases the voltage generation in the ohmic regime and extends the maximum possible load current.Polyinyl alcohol(PVA) is used to bind the phosphosilicate gel powder and to form the hybrid crosslinked gel polymer electrolyte membrane.Soaking the membrane with phosphoric acid solution,instead of that with water improves the proton conductivity of the membrane,enhances the voltage and power generation by the fuel cell and extends the maximum possible operating temperature.At lower operating temperature of 70 ℃,peak power produced by phosphosilicate gel polymer electrolyte membrane fuel cell(PGMFC) is increased by 40% compared to that generated by phosphoric acid fuel cell(PAFC).However,the performance of composite membrane diminishes as the cell temperature increases.Thus phosphosilicate gel in paste form is found to be a good alternative of phosphoric acid electrolyte at medium operating temperature range while phosphosilicate gel-PVA composite offers performance enhancement at low operating temperatures.  相似文献   

5.
陈枫  傅强 《高分子科学》2014,32(12):1724-1736
Inspired by the photoprotection, radical scavenging of melanin together with versatile adhesive ability of mussel proteins, polydopamine(PDA) nanoparticles were successfully prepared and incorporated into environmentally friendly polymer, poly(propylene carbonate)(PPC) via solvent blending. The prepared composites exhibited excellent thermal stability in air and nitrogen atmosphere and extraordinary mechanical properties. The composites displayed eminent increase of temperature at 5% weight loss(T5%) by 30-100 K with 0.3 wt%-2.0 wt% loadings, meanwhile, the tensile strength and Young's modulus were significantly improved from 11.5 MPa and 553.7 MPa to 40.5 MPa and 2411.2 MPa, respectively. The kinetic calculation indicated that improvement of T5% is presumably derived from suppressing chain-end unzipping. The glass transition temperature(Tg) of the PPC/PDA composites increased by 8-10 K. This is probably due to hydrogen bonding interaction since the abundant proton donors along PDA chains would interact with proton acceptors like C = O and C―O―C in PPC which would cause restriction of segmental motion of PPC chains.  相似文献   

6.
The effects of temperature and pressure on the steam reforming of methane 3H2+CO) were investigated in a membrane reactor (MR) with a hydrogen permeable membrane. The studies used a novel silica-based membrane prepared by using the chemical vapor deposition (CVD) technique with a permeance for H2 of 6.0×l0-8 mol·m-2·s-1·Pa-1 at 923 K. The results in a packed-bed reactor (PBR) were compared to those of the membrane reactor at various temperatures (773-923 K) and pressures (1-20 atm, 101.3-2026.5 kPa) using a commercial Ni/MgAl2O4 catalyst. The conversion of methane was improved significantly in the MR by the countercurrent removal of hydrogen at all temperatures and allowed product yields higher than the equilibrium to be obtained. Pressure had a positive effect on the hydrogen yield because of the increase in driving force for the permeance of hydrogen. The yield of hydrogen increased with pressure and reached a value of 73×10-6 mol·g-1·s-1 at 2026.5 kPa and 923 K which was higher by 108% than the value of 35×10-6 mol·g-1·s-1 obtained for the equilibrium yield. The results obtained with the silica-based membrane were similar to those obtained with various other membranes as reported in the literature.  相似文献   

7.
New siloxane and sulfone containing poly(benzimidazole/sulfone/siloxane/amide)(PBSSA) has been prepared for the formation of hybrid membranes(PBSSA/PS-S/SiNPs) with sulfonated polystyrene(PS-S) and 0.1 wt%-2 wt% silica nanoparticles(SiNPs). Field emission scanning electron micrographs showed good dispersion of filler, formation of dense nanoporous honeycomb like structure and uniform ionic pathway in these hybrids. The porous membrane structure was responsible for the fine water retention capability and higher proton conductivity of the new hybrids. Increasing the amount of nanoparticles from 0.1 wt% to 2 wt% increased the tensile stress of acid doped PBSSA/PS-S/SiNPs nanocomposites from 65.7 MPa to 68.5 MPa. A relationship between nanofiller loading and thermal stability of the membranes was also experientially studied, as the glass transition temperature of phosphoric acid doped PBSSA/PS-S/SiNPs nanocomposites increased from 207 °C to 215 °C. The membranes also had higher ion exchange capacity(IEC) around 2.01 mmol/g to 3.01 mmol/g. The novel membranes with high IEC value achieved high proton conductivity of 1.10-2.34 S/cm in a wide range of humidity values at 80 °C which was higher than that of perfluorinated Nafion 117 membrane(1.1 × 10-1 S/cm) at 80 °C(94% RH). A H2/O2 fuel cell using the PBSSA/PS-S/SiNP 2(IEC 3.01 mmol/g) showed better performance than that of Nafion 117 at 40 °C and 30% RH.  相似文献   

8.
The aim of this paper is to report the effect of the addition of cellulose nanocrystals(CNCs) on the mechanical, thermal and barrier properties of poly(vinyl alcohol)/chitosan(PVA/Cs) bio-nanocomposites films prepared through the solvent casting process. The characterizations of PVA/Cs/CNCs films were carried out in terms of X-ray diffraction(XRD), transmission electron microscopy(TEM), scanning electron microscopy(SEM), thermogravimetric analysis(TGA and DTG), oxygen transmission rate(OTR), and tensile tests. TEM and SEM results showed that at low loading levels, CNCs were dispersed homogenously in the PVA/Cs matrix. The tensile strength and modulus in films increased from 55.1 MPa to 98.4 MPa and from 395 MPa to 690 MPa respectively, when CNCs content went from 0 wt% to 1.0 wt%. The thermal stability and oxygen barrier properties of PVA/Cs matrix were best enhanced at 1.0 wt% of CNCs loading. The enhanced properties attained by incorporating CNCs can be beneficial in various applications.  相似文献   

9.
其鲁 《高分子科学》2006,(2):213-220
A copolymer of poly(acrylonitrile-co-styrene) (SAN) was synthesized via an emulsion polymerization method. Novel polymer electrolyte membranes cast from the blends of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), SAN and fumed silica (SiO2) are microporous and can be used in polymer lithium-ion batteries. The membrane shows excellent characteristics such as high ionic conductivity and good mechanical strength when the mass ratio between SAN and PVDF-HFP and SiO2 is 3.5/31.5/5. The ionic conductivity of the membrane soaked in a liquid electrolyte of 1 mol/L LiPF6/EC/DMC/DEC is 4.9×10-3 S cm-1 at 25℃. The membrane is electrochemical stable up to 5.5 V versus Li /Li in the liquid electrolyte. The influences of SiO2 content on the porosity and mechanical strength of the membranes were studied. Polymer lithium-ion batteries based on the membranes were assembled and their performances were also studied.  相似文献   

10.
Platinum nanowire (PtNW) can be grown by electrodeposition in polycarbonate membrane, with the average diameter of the nanowires about 250 nm. The PtNW and multiwalled carbon nanotubes (CNT) are then dispersed into chitosan (CHIT) solution. The resulting PtNW-CNT-CHIT material brings new capabilities for electrochemical devices by using the synergistic action of the electrocatalytic activity of PtNW and CNT. By dropping the PtNW-CNT-CHIT film onto the glassy carbon (GO) electrode surface, and after evaporation an amperometric sensor for the determination of indole-3-acetic acid (IAA) was developed. The oxidation current of IAA increased significantly at the PtNW-CNT-CHIT film coated GC electrode, in contrast to that at the CNT-CHIT modified GC. The linear response of the sensor is from 50 ng/ml to 50 μg/ml with a detection limit of 25 ng/mL.  相似文献   

11.
A method to quantify crazing deformations by tensile tests for polystyrene (PS) and polyolefin elastomer (POE) blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume (△V) against longitudinal variation (△I) showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.  相似文献   

12.
用水热法在氧化铝陶瓷膜管上原位合成丝光沸石膜   总被引:2,自引:0,他引:2  
The mordenite membrane was prepared on a α-Al 2O 3 tube by in situ hydrothermal synthesis. The crystallization was carried out at 443 K for 2~4 days. Silica sol and sodium aluminate were used as the sources of silica and alumina, respectively, and tetraethylammonium bromide (TEABr) as the template. The molar composition of the parent solution was 11 4Na 2O∶1 0Al 2O 3∶40SiO 2∶2500H 2O∶1 5TEABr. SEM and XRD were used to characterize the powder product and the composite membrane. The synthesized mordenite membrane proved to be in a full coverage and an excellent intergrowth. The mordenite crystals were about 20~30 μm and the thickness of the mordenite membrane was 30~40 μm. Based on the SEM pictures of the membrane in the early stage of hydrothermal synthesis, a growth model for the mordenite membrane was assumed. At first a gel layer was formed on the surface of the alumina tube. Nucleation took place in the gel layer but not at the interface of the gel layer and bulk solution. The gel layer provided the nutrients for the growth of zeolite crystals. After the gel layer was consumed completely, the zeolite crystals or membrane were exposed to the bulk solution. The membrane separation test on the mordenite membrane showed that the permeances of pure H 2 and N 2 at 298 K were 6 92×10 -7 and 1 81×10 -7 mol/(m 2·s·Pa), respectively. The ideal selectivity of H 2/N 2 was 3 82, which is higher than that of Knudsen mechanism. It suggested that the mordenite membrane had the ability of molecular sieving.  相似文献   

13.
Lithium–sulfur(Li–S)battery as a high-energy density electrochemical energy storage system has attracted many researchers’attention.However,the shuttle effect of Li–S batteries and the challenges associated with lithium metal anode caused poor cycle performance.In this work,the organosulfide poly(sulfur-1,3-diisopropenylbenzene)(PSD)was prepared as cathode material and additive of P(VDFHFP)polymer electrolyte(P(VDF-HFP)).It was verified that P(VDF-HFP)polymer electrolyte with 10%PSD(P(VDF-HFP)-10%PSD)showed a higher ionic conductivities than that of liquid electrolyte up to2.27×10-3 S cm-1 at room temperature.The quasi-solid-state Li-S batteries fabricated with organosulfide cathode material PSD and P(VDF-HFP)based functional polymer electrolyte delivered good cycling stability(780 m Ah g-1 after 200 th cycle at 0.1 C)and rate performance(613 m Ah g-1 at 1 C).The good cycling performance could be attributed to the synergistic effect of components,including the interaction between polysulfides and polymer main chain in the organosulfide cathode,the sustained organic/inorganic hybrid stable SEI layer formed by polymer electrolyte additive PSD,the improved cathode/electrolyte interface and the good affinity between P(VDF-HFP)based functional polymer electrolyte and Li metal surface.This strategy herein may provide a new route to fabricate high-performance Li–S batteries through the organosulfide cathode and functional polymer electrolyte.  相似文献   

14.
Lithium-ion batteries (LIBs)have attracted wide attention because of their broad prospects in electric vehicles. However,the safety problems and low multiplier performance of the commercial polyolefin separator limit their further development,due to the poor dimensional thermal stability and low electrolyte absorption rate. Poly(ether ether ketone)(PEEK)and carbon nanotube(CNT)are compounded to coat on polypropylene (PP) to prepare Janus composite separator (PP@C) through the phase inversion method. PP@C composite separator does not deform at 180 ℃ for 0. 5 h(only slight deformation),illustrating excellent thermal stability. The electrolyte absorption rate of PP@C2 is 193. 8%. The electrolyte uptake rate of the PP@C2 composite membrane was 193. 8%,which was 64. 5% higher than the PP membrane,showing a superduper electrolyte permeability. As a result,the specific discharge capacity of LIBs assembled with PP@C2 composite separator is 157. 6 mA·h/g at 0. 2 C and 129. 8 mA·h/g at 2 C,showing good rate performance with the capacity recovery rate of more than 99%. This might be attributed to the ultra-high thermal stability of PEEK,the good affinity of the electrolyte,the high conductivity of CNT,as well as the uniform dispersion of Li+ ,so that the separator can have excellent electrochemical performance while improving safety. © 2022, Science Press (China). All rights reserved.  相似文献   

15.
Ultraviolet(UV)-induced graft copolymerization of allyl acetate(AA) monomer onto polyethylene terephthalate) (PET) films and the subsequent sulfonation on the monomer units in the grafting chain using chlorosulfonic acid(ClSO3H) were carried out to prepare proton exchange membranes(PEMs) for fuel cells.A maximum grafting value of 12.8%was found for 35 vol%allyl acetate after 3 h radiation time.Optimum concentration of C1SO3H was selected for the sulfonation reaction to be 0.05 mol/L based on the degree of sulfonation and the tensile strength studies of the membrane.The degree of sulfonation increased as the sulfonation reaction temperature and sulfonation time were increasing.The radiation grafting and the sulfonation have been confirmed by titrimetric and gravimetric analyses as well as FTIR spectroscopy.The maximum ion exchange capacity(IEC) of 0.04125 mmol g-1 was found at 12.1%degree of sulfonation and the maximum proton conductivity was found to be 0.035 S cm-1 at 30℃and a relative humidity of 60%.The various physical and chemical properties of the PEMs such as water uptake,mechanical strength,thermal durability and oxidative stability were also studied.To investigate the suitability of the prepared membrane for fuel cell applications,its properties were compared with those of Nafion 117.  相似文献   

16.
Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.  相似文献   

17.
The vapor-phase synthesis of 3-methylindole from glycerol and aniline over Cu/NaY modified by K2O was investigated. The catalysts were characterized by X-ray diffraction (XRD) and the temperature- programmed desorption of ammonia (NH3-TPD). The effect of the reaction temperature on the activity and selectivity of Cu]NaY-K2O catalyst was also investigated. The results indicated that the addition of K2O to Cu/NaY increased the selectivity of the catalyst remarkably because the amount of middle-strong acid sites decreased clearly. The decrease of the reaction temperature was beneficial for the increase of 3- methylindole selectivity. Over Cu/NaY-K2O, the selectivity of 3-methylindole reached 75% and the yield of the target product was up to 47% at 220 ℃. A probable catalytic mechanism for the synthesis of 3- methylindole from glycerol and aniline was proposed.  相似文献   

18.
The change color effect of gold nanoparticle solutions was studied by means of resonance scattering and absorption spectrometry and scan electron microscopy. The red Au nanoparticles with a size of 10 nm exhibit a resonance absorption peak and a resonance scattering peak all at 525 nm. After some inorganic electrolyte was added to a red Au nanoparticles solution, the color of the solution became blue and the absorbance at 600-700 nm was significantly increased. The ratio of the concentration of rnonovalent cations, at which the resonance scattering of the system at 525 nm is maximal to that of divalent cations, is in the range of 100 : 1--100 ; 1. 8. It is in good agreement with the Schulze-Hardy rule of the coagulation value of electrolyte. After adding some cationic surfactants to the above solution, the color of the solution is in deep blue, with two resonance absorption peaks at 550 and 680 nm, and a greatly enhanced resonance scattering peak at 525 nm. The experiments demonstrate that the stronger the hydrophobicity of the cationic surfactant is, the stronger the change color effect of the Au nanoparticle solution promoted by cationic surfactant is. The change color effect of Au nanoparticle solution is resulted from the increased diameter of Au nanoparticles, and the changes of resonance absorotion DeaR and resonance scattering.  相似文献   

19.
In this paper, 1,2,4-triazolium methanesulfonate(C2H4N+3CH3SO-3, [Tri][MS]), an ionic conductor, was successfully synthesized. It exhibited high ionic conductivity of 18.60 m S cm-1at 140CdSC and reached up to 36.51 m S cm-1at 190CdSC. [Tri][MS] was first applied to modify Nafion membrane to fabricate [Tri][MS]/Nafion membrane by impregnation method at 150CdSC. The prepared composite membrane showed high thermal stability with decomposed temperature above 200CdSC in air atmosphere. In addition, the membrane indicated good ionic conductivity with 3.67 m S cm-1at 140CdSC and reached up to 13.23 m S cm-1at 180CdSC. The structure of the [Tri][MS] and the composite membrane were characterized by FTIR and the compatibility of [Tri][MS] and Pt/C catalyst was studied by a cyclic voltammetry(CV) method. Besides, the[Tri][MS]/Nafion membrane(thickness of 65 μm) was evaluated with single fuel cell at high temperature and without humidification. The highest power density of [Tri][MS]/Nafion membrane was 3.20 m W cm-2at 140CdSC and 4.90 m W cm-2at 150CdSC, which was much higher than that of Nafion membrane.  相似文献   

20.
A novel sulfonated diamine monomer, 4,6-bis(4-arninophenoxy)-naphthalene-2-sulfonic acid(BAPNS), was synthesized. A series of sulfonated polyimide copolymers was prepared from BAPNS, 1,4,5,8-naphthalenetetracarboxylic dianhydride(NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether(ODA). Flexible, transparent, and mechanically strong membranes were obtained. The novel sulfonated polyimide(SPI) membranes show higher conductivity, for example, SPI-100 shows a conductivity of 0.0698 S/cm at 80℃(SPI-X: Xrefers to molar fraction of BAPNS). The membranes exhibit the permeability of methanol from 2.18×10^-7 cm2/s to 2.57×10^-7 cm2/s, which is much lower than that of Nafion(2.00×10 6 cm^2/s). The copolymers were thermally stable up to 330℃. The sulfonated polyimide copolymers also show reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 100%(molar fraction) BAPNS is 1.35 GPa under high moisture condi- tions. The optimum concentration of BAPNS was found to be 100%(molar fraction) from the view point of proton conductivity, methanol permeability, and membrane stability.  相似文献   

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