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1.
Composite polymer electrolyte based on a new class of filler added to a PEGDME/LiClO4 model system has been investigated. “Ceramic super acids” used consist of grafted SO42− groups on Al2O3 particles surface obtained by calcinations route. Conductivity, DSC and FT-IR measurements performed on such composite electrolytes, when compared to the model PEGDME/LiClO4 electrolyte, showed only slight improvement of their inner characteristics. In contrary, Li/Li symmetric cells study, by means of impedance spectroscopy, has presented a spectacular decrease of the interfacial resistance compare to the model electrolyte. This result opens a new pathway of investigation to master the lithium metal/polymer electrolyte interface.  相似文献   

2.
Zhiying Li  Yang Liu  Jun Li  Jinghong Li 《Polymer》2005,46(18):7578-7584
Composite electrolyte comprising methylsisesquioxane (MSQ) filler and 1-butyl-3-methyl-imidazolium-tetrafluoroborate (BMImBF4) ionic liquid (IL) in poly(2-hydroxyethyl methacrylate) (PHEMA) matrix had been prepared. The polymer matrix was formed by free radical polymerization of HEMA macromer, and MSQ was produced in situ from methyl-trimethoxysilane by the sol-gel method. Infrared spectroscopy and dynamic mechanical analysis were employed to give insight into the interactions among the methylsisesquioxane filler, BMImBF4 and the PHEMA polymer matrix. The PHEMA-IL-MSQ hybrids and the PHEMA-IL electrolyte without MSQ were investigated regarding their ionic conductivity and thermal and electrochemical properties. BMImBF4 increased the thermal stability of the polymer and provided the ion conductivity; MSQ filler as the additive increased the mechanical strength of the polymer and provided the ion conductive pathway. The electrolyte with MSQ at the 10 wt% showed the highest ionic conductivity of 5×10−4 S cm−1 which was five times higher than that of the electrolyte without MSQ, and the electrochemical window was up to 3.6 V.  相似文献   

3.
The particle composites Al2O3/(2 and 3Y)TZP and MgAl2O4/3Y-TZP were tested in bending at temperature of 1280 °C over strain rates from 3.4 × 10−7 to 1 × 10−4 s−1 and over stresses from 23 to 85 MPa. Strain rate of the composites decreased as a volume fraction of Al2O3 or MgAl2O4 increased. MgAl2O4/3Y-TZP composites deformed easier under the comparable conditions than alumina/zirconia composites. Four models of composite creep behaviour were compared to the experimental data. All the models were unsuitable for MgAl2O4/3Y-TZP, in turn an isostress, an isostrain and a constrained isostrain models provide the good predictions for creep rates for alumina/zirconia ceramics, but the rheological model appeared not good. The threshold stresses approach seems to be useful for describing superplastic flow of MgAl2O4/3Y-TZP composites.  相似文献   

4.
Alumina (Al2O3) nanoparticles have been used as fillers in the preparation of poly(vinylidenefluoride-co-hexafluorpropylene) (P(VDF-HFP))-based porous polymer electrolyte. The degree of crystallization of polymer film filled with Al2O3 nanoparticles decreases with increase of the mass fraction of Al2O3 nanoparticles and the amorphous phases of polymer film expand accordingly. The Al2O3 nanoparticles play the role of solid plasticizer for polymer matrix. Nevertheless that excessive Al2O3 nanoparticles existing in polymer matrix leads to micro-phase separation between polymer matrix and fillers. As a result, both ionic conductivity and lithium ions transference number reduces whereas the activation energy for ions transport increases. When the polymer film is filled with 10% of the mass fraction of Al2O3 nanoparticles, polymer electrolyte possesses the ionic conductivity up to 1.95 × 10−3 S cm−1 and the lithium ions transference number to 0.73 while the activation energy for ions transport of them falls to 5.6 kJ mol−1. Effect of Al2O3 on the electrochemical properties of polymer electrolyte has been investigated in this paper. Analysis of FTIR spectra shows that there is the interaction between Al2O3 nanoparticles and polymer chains.  相似文献   

5.
Fe3O4-graphene nanocomposite was prepared by a gas/liquid interface reaction. The structure and morphology of the Fe3O4-graphene nanocomposite were characterized by X-ray diffraction, scanning electron microscopy and high-resolution transmission electron microscopy. The electrochemical performances were evaluated in coin-type cells. Electrochemical tests show that the Fe3O4-22.7 wt.% graphene nanocomposite exhibits much higher capacity retention with a large reversible specific capacity of 1048 mAh g−1 (99% of the initial reversible specific capacity) at the 90th cycle in comparison with that of the bare Fe3O4 nanoparticles (only 226 mAh g−1 at the 34th cycle). The enhanced cycling performance can be attributed to the facts that the graphene sheets distributed between the Fe3O4 nanoparticles can prevent the aggregation of the Fe3O4 nanoparticles, and the Fe3O4-graphene nanocomposite can provide buffering spaces against the volume changes of Fe3O4 nanoparticles during electrochemical cycling.  相似文献   

6.
In view of the safety concerns and the requirements of high energy density lithium batteries, the room temperature ionic liquids (RTILs) are being investigated as suitable candidates to substitute organic electrolytes in polymer electrolytes. In this article, we report synthesis, characterization, and electrochemical properties of nanocomposite polymer electrolytes (NCPEs) comprising of a RTIL [n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI)] and nano-sized ceramic fillers (SiO2, Al2O3 or BaTiO3) hosted in electrospun poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HFP)] membranes. The addition of BMITFSI and ceramic fillers in polymer electrolytes results in high ionic conductivity at room temperature. The cells prepared with BMITFSI and different NCPEs show good interfacial stability and oxidation stability at >5.5 V with the highest value of 6.0 V for the NCPE incorporating BaTiO3. The cell with the NCPE containing BaTiO3 delivers high initial discharge capacity of 165.8 mA h g−1, which corresponds to 97.5% utilization of active material under the test conditions, and showed the least % capacity fade after prolonged cycling.  相似文献   

7.
A series of nanocomposite polymer electrolytes (NCPEs) comprising nanoparticles of BaTiO3, Al2O3 or SiO2 were prepared by electrospinning technique. The nano-sized ceramic fillers were incorporated into poly(vinylidene fluoride-co-hexafluoropropylene) [P(VdF-HEP)] membranes during the electrospinning process. The resultant porous membranes are good absorbent of the liquid electrolyte and exhibit high electrolyte retention capacity. The presence of the ceramic nanoparticles has positive effect on the mechanical properties of the membranes. The ionic conductivity and the electrochemical stability window of the electrospun P(VdF-HFP)-based polymer are enhanced by the presence of the fillers. The cell Li/LiFePO4 based on the NCPE containing BaTiO3 delivers a discharge capacity of 164 mAh/g, which corresponds to 96.5% utilization of the active material. In comparison, the performance of Li/LiFePO4 cells with NCPEs containing Al2O3 and SiO2 was observed to be lower with respective discharge capacities of 153 and 156 mAh/g. The enhanced performance of the BaTiO3-based-NCPE is attributed mainly to its better interaction with the host polymer and compatibility with lithium metal.  相似文献   

8.
The present work deals with the findings on optical and ion transport behavior in a ferrite-doped polymer nanocomposite electrolyte system, namely, [(100 ? x) PVA + xLiC2H3O2]: yLiFe5O8. This polymer electrolyte system has been characterized by SEM, DSC, IR and C-V measurements. The addition of filler seems to disturb the crystalline nature of the host matrix while the doping of salt shows a similar structure, but with a separate entity in SEM images. DSC studies reflect the interaction of the salt/filler with polymer with a change in morphology of the composite system. These results are well-corroborated by IR data. The effect of salt or filler in the enhancement of the a.c. conductivity of nanocomposite polymer electrolyte (NCPE) as well as dielectric relaxation behavior has been investigated with the help of impedance spectroscopy data. The a.c. conductivity of nanocomposite polymer electrolytes is seen to be best described by the universal power law.  相似文献   

9.
Dry reforming of methane was studied over Ni catalysts supported on γAl2O3, CeO2, ZrO2 and MgAl2O4 (670 °C, 1.5 bar, 16–20 l CH4 mlcatalyst−1 h−1). It is shown that MgAl2O4 supported Ni catalysts promoted with both CeO2 and ZrO2 are promising catalysts for dry reforming of methane with carbon dioxide. Within a certain composition range, the simultaneous promotion with CeO2 and ZrO2 has great influence on the amount of coke and the catalyst service time. XRD analyses indicate that formation of crystalline CexZr1−xO2 mixed oxide phases occurs on double promotion. In particular, incorporation of low amounts of Zr in the CeO2 fluorite structure provides stable dry reforming catalysis. As shown with TPR, promotion leads to a higher reduced state of Ni. SEM, XRD and TPR analyses demonstrate that highly dispersed, doubly promoted Ni catalysts with a strong metal-support interaction are essential for stable dry reforming and suppression of the formation of carbon filaments.  相似文献   

10.
The nanocomposite of hematite@carbon nanosprings (α-Fe2O3@CNSs) was synthesized by simple precipitation and following heat treatment, in which the amount of α-Fe2O3 can be easily controlled by changing the synthesis conditions. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electronic microscopy (SEM), Brunau–Emmertt–Teller (BET), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the as-synthesized nanocomposite. When applied as anode in Li-ion batteries (LIBs), the effect of α-Fe2O3/CNSs weight ratio on electrochemical performance of α-Fe2O3@CNSs nanocomposite has been researched. Enhancing the amount of α-Fe2O3 in nanocomposite would make the increase of specific capacity, but led to the degradation of cyclic stability and rate capability. The electrode of S-FeC (with weight ratio of CNSs/α-Fe2O3 about 4:1) could deliver a charge capacity of 527.6 mAh g−1at 0.2 C with excellent cyclability (96.9% capacity retention after 50 cycles), and retained 343.3 mAh g−1even at the rate of 5.0 C. In comparison with pure CNSs and α-Fe2O3, the improved cycling performance, specific capacity and rate capability of S-FeC should be mainly attributed to the combined effects of uniformly dispersed nanosized α-Fe2O3 particles and the highly strong network of CNSs.  相似文献   

11.
Au nanoparticles (AuNPs) are good quenchers once they closely contact with luminophore. Here we reported a simple approach to obtain enhanced electrogenerated chemiluminescence (ECL) behavior based on Au/CdS nanocomposite films by adjusting the amount of AuNPs in the nanocomposite. The maximum enhancement factor of about 4 was obtained at an indium tin oxide (ITO) electrode in the presence of co-reactant H2O2. The mechanism of this enhancement was discussed in detail. The strong ECL emission from Au/CdS nanocomposites film was exploited to determine H2O2. The resulting ECL biosensors showed a linear response to the concentration of H2O2 ranging from 1.0 × 10−8 to 6.6 × 10−4 mol L−1 with a detection limit of 5 nmol L−1 (S/N = 3) and good stability and reproducibility.  相似文献   

12.
Different types of dense 5–97% ZrO2–MgAl2O4 composites have been prepared using a MgAl2O4 spinel obtained by calcining a stoichiometric mixture of aluminium tri-hydroxide and caustic MgO at 1300 °C for 1 h, and a commercial yttria partially stabilized zirconia (YPSZ) powder as starting raw materials by sintering at various temperatures ranging from 1500 to 1650 °C for 2 h. The characteristics of the MgAl2O4 spinel, the YPSZ powder and the various sintered products were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area, particle size analysis, Archimedes principle, and Vickers indentation method. Characterization results revealed that the YPSZ addition increases the sintering ability, fracture toughness and hardness of MgAl2O4 spinel, whereas, the MgAl2O4 spinel hampered the sintering ability of YPSZ when sintered at elevated temperatures. A 20-wt.% YPSZ was found to be sufficient to increase the hardness and fracture toughness of MgAl2O4 spinel from 406 to 1314 Hv and 2.5 to 3.45 MPa m1/2, respectively, when sintered at 1600 °C for 2 h.  相似文献   

13.
An alkaline polymer gel electrolyte (PGE) film was prepared by solution polymerization of acrylate-KOH-H2O at room temperature, and the preparation conditions were optimized in view of the mechanical properties and ionic conductivity of the film. The PGE film with the optimized composition of 0.02% K2S2O8, 16.75% acrylic acid and 83.23 wt.% 4 mol l−1 KOH solution is transparent, rubber-like and dimensionally stable with improved mechanical properties as compared with gelled electrolyte. The specific conductivity of the film is 0.288 s cm−1 at room temperature and the conductivity values follow the Arrhenius equation with the activation energy of ∼10 kJ mol−1. These data suggest that the ionic conduction proceeds in the same mechanism as in aqueous alkaline solution. Experimental results from the laboratory Zn/Air, Zn/MnO2 and Ni/Cd cells using the PGE film as electrolyte demonstrate that the PGE film has almost the same chemical and electrochemical stability as aqueous alkaline solution, and shows good performance characteristics for application of alkaline primary and secondary battery systems.  相似文献   

14.
The effect of TiO2 on the formation and microstructure of magnesium aluminate spinel (MgAl2O4) at 1600 °C in air and reducing conditions were investigated. Under reducing conditions, stoichiometric MgAl2O4 spinel shifted toward alumina-rich types owing to volatilization of MgO, resulting in an increase in the porosity of fired samples. Addition of graphite to mixtures of MgO and Al2O3 intensified the reducing conditions and accelerated the formation of non-stoichiometric MgAl2O4. For TiO2-containing samples on addition of MgAl2O4, magnesium aluminum titanium oxide (MgxAl2(1−x)Ti(1+x)O5, x = 0.2 or 0.3) was detected as a minor phase. Under reducing conditions, XRD peak shifts were smaller for TiO2-containing samples than for samples without TiO2 owing to the formation of a solid solution of TiO2 in MgAl2O4 and establishment of alumina-rich spinel, which have opposite effects on increasing the lattice parameter. In bauxite-containing samples, MgAl2O4 spinel, corundum, magnesium orthotitanate spinel (Mg2TiO4) and amorphous phases were identified. Mg2TiO4 spinel formed a complete solid solution with MgAl2O4 spinel but Mg2TiO4 remained as a distinct phase owing to the heterogeneous microstructure of bauxite-containing samples. Also dense microstructure established in air fired TiO2 containing samples. The results are discussed with emphasis on the application and design of alumina-magnesia-carbon refractory materials, which are used in the steel industry.  相似文献   

15.
The performance of different Cu/CeO2/Al2O3 catalysts of varying compositions is investigated for the oxidative steam reforming of methanol (OSRM) in order to produce the hydrogen selectively for polymer electrolyte membrane (PEM) fuel cell applications. All the catalysts were prepared by co-precipitation method and characterized for their surface area, pore volume and oxidation–reduction behavior. The effect of various operating parameters studied are as follows: reaction temperature (200–300 °C), contact-time (W/F = 3–15 kgcat s mol− 1) and oxygen to methanol (O/M) molar ratio (0–0.5). The steam to methanol (S/M) molar ratio = 1.5 and pressure = 1 atm were kept constant. Among all the catalysts studied, catalyst Cu–Ce–Al:30–20–50 exhibited 100% methanol conversion and 179 mmol s− 1 kgcat− 1 hydrogen production rate at 280 °C with carbon monoxide formation as low as 0.19%. The high catalytic activity and hydrogen selectivity shown by ceria promoted Cu/Al2O3 catalysts is attributed to the improved specific surface area, dispersion and reducibility of copper which were confirmed by characterizing the catalysts through temperature programmed reduction (TPR), CO chemisorption, X-ray diffraction (XRD) and N2 adsorption–desorption studies. Reaction parameters were optimized in order to produce hydrogen with carbon monoxide formation as low as possible. The time-on-stream stability test showed that the Cu/CeO2/Al2O3 catalysts were quite stable.  相似文献   

16.
Wen-Jing Li 《Electrochimica acta》2010,55(28):8680-8685
The electrochemical properties of nanocomposite Fe2O3-Se thin film prepared by pulsed laser deposition (PLD) method have been investigated by cyclic voltammetry and charge/discharge measurements. A large reversible capacity of nanocomposite Fe2O3-Se thin film was found to be around 650 mAh g−1. A new couple of reduction and oxidation peaks at 1.4 and 1.8 V were observed from cyclic voltammogram for the first time. Our data demonstrated that nanocomposite Fe2O3-Se exhibit larger capacity and better cycle performance than pure Fe2O3. The electrochemical reaction mechanisms of Fe2O3-Se with lithium were examined by X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM) and selected-area electron diffraction (SAED). The reversible conversions reaction of nanosized metal Fe with Li2Se and Li2O formed after initial discharge process into FeSe and Fe2O3 respectively were revealed.  相似文献   

17.
We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 × 10−3 S cm−1, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H2O2) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H2O2 and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H2O2 concentrations (86 μM–10 mM). This sensor exhibited good sensitivity (194.9 μA mM−1 cm−2), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of −0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H2O2 with high performance and excellent stability.  相似文献   

18.
The effect of quaternary ammonium on discharge characteristic of Li/O2 cells was studied by using Super-P carbon as air cathode, a 0.2 mol kg−1 LiSO3CF3 1:3 (wt.) PC/DME solution as baseline electrolyte, and tetrabutylammonium triflate (NBu4SO3CF3) as an electrolyte additive or a co-salt. Results show that Li/O2 cells can run normally in an electrolyte with NBu4SO3CF3 as the sole conductive salt. However, such cells suffer lower voltage and capacity as compared with those using the lithium ionic baseline electrolyte. This is due to the larger molar volume of quaternary ammonium cation, which results in less deposition of oxygen reduction products on the surface of carbon. When used as an electrolyte additive or a co-salt, the ammonium is shown to increase capacity of Li/O2 cells. The plot of differential capacity versus cell voltage shows that the Li/O2 cell with ammonium added has broad and scatted differential capacity peaks between the voltages of two reactions of “2Li + O2 → Li2O2” and “2Li + Li2O2 → 2Li2O”. This phenomenon can be attributed to the phase transfer catalysis (PTC) property of quaternary ammonium on the second reaction. Due to inverse effects of the cation geometric volume and the PTC property of ammonium ions on the discharge capacity, there is an optimum range for the concentration of ammonium. It is shown that the addition of NBu4SO3CF3 increases discharge capacity of Li/O2 cell only when its concentration is in a range from 5 mol% to 50 mol% vs. the total of Li/ammonium mixed salt, and that the optimum concentration is about 5 mol%. In this work we show that the addition of 5 mol% NBu4SO3CF3 into the baseline electrolyte can increase discharge capacity of a Li/O2 cell from 732 mAh g−1 to 1068 mAh g−1 (in reference to the weight of Super-P carbon) when the cell is discharged at 0.2 mA cm−2.  相似文献   

19.
MnO2 embedded PPy nanocomposite (MnO2/PPy) thin film electrodes were electrochemically synthesized over polished graphite susbtrates. Growing PPy polymer chains provides large surface area template that enables MnO2 to form as nanoparticles embeded within polymer matrix. Co-deposition of MnO2 and PPy has a complimentary action in which porous PPy matrix provides high active surface area for the MnO2 nanoparticles and, on the other hand, MnO2 nanoparticles nucleated over polymer chains contribute to enhanced conductivity and stability of the nanocomposite material by interlinking the PPy polymer chains. The MnO2/PPy nanocomposite thin film electrodes show significant improvement in the redox performance as cyclic voltammetric studies have shown. Specific capacitance of the nanocomposite is remarkably high (∼620 F g−1) in comparision to its constituents MnO2 (∼225 F g−1) and PPy (∼250 F g−1). Photoelectron spectroscopy studies show that hydrated manganese oxide in the nanocomposite exists in the mixed Mn(II) to Mn(IV) oxidation states. Accordingly, chemical structures of MnO2 and PPy constituents in the nanocomposite are not influenced by the co-deposition process. The MnO2/PPy nanocomposite electrode material however shows significantly improved high specific capacitity, charge-discharge stability and the redox performance properties suitable for application in the high energy density supercapcitors.  相似文献   

20.
LiNi1/3Co1/3Mn1/3O2 was applied as a promising material to the all-solid-state lithium cells using the 80Li2S·19P2S5·1P2O5 (mol%) solid electrolyte. The cell showed the first discharge capacity of 115 mAh g−1 at the current density of 0.064 mA cm−2 and retained the reversible capacity of 110 mAh g−1 after 10 cycles. The interfacial resistance was observed in the impedance spectrum of the all-solid-state cell charged to 4.4 V (vs. Li) and the transition metal elements were detected on the solid electrolyte in the vicinity of LiNi1/3Co1/3Mn1/3O2 by the TEM observations with EDX analyses. The electrochemical performance was improved by the coating of LiNi1/3Co1/3Mn1/3O2 particles with Li4Ti5O12 film. The interfacial resistance was decreased and the discharge capacity was increased from 63 to 83 mAh g−1 at 1.3 mA cm−2 by the coating. The electrochemical performance of LiNi1/3Co1/3Mn1/3O2 was compared with that of LiCoO2, LiMn2O4 and LiNiO2 in the all-solid-state cells. The rate capability of LiNi1/3Co1/3Mn1/3O2 was lower than that of LiCoO2. However, the reversible capacity of LiNi1/3Co1/3Mn1/3O2 at 0.064 mA cm−2 was larger than that of LiCoO2, LiMn2O4 and LiNiO2.  相似文献   

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