首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 46 毫秒
1.
The electrochemical properties of carbon films, of thickness between 200 and 500 nm, sputter-coated on gold- and platinum-coated 6 MHz piezoelectric quartz crystal oscillators, as new electrode materials have been investigated. Comparative studies under the same experimental conditions were performed on bulk electrodes. Cyclic voltammetry was carried out in 0.1 M KCl electrolyte solution, and kinetic parameters of the model redox systems Fe(CN)63−/4− and [Ru(NH3)6]3+/2+ as well as the electroactive area of the electrodes were obtained. Atomic force microscopy was used in order to examine the surface morphology of the films, and the properties of the carbon films and the electrode-solution interface were studied by electrochemical impedance spectroscopy. The results obtained demonstrate the feasibility of the preparation and development of nanometer thick carbon film modified quartz crystals. Such modified crystals should open up new opportunities for the investigation of electrode processes at carbon electrodes and for the application of electrochemical sensing associated with the EQCM.  相似文献   

2.
The charging processes and methanol oxidation that occur during the oxidation-reduction cycles in a ruthenium oxide thin film electrode (deposited by the sol-gel method on Pt covered quartz crystals) were investigated by using cyclic voltammetry, chronoamperometry and electrochemical quartz crystal nanobalance techniques. The ruthenium oxide rutile phase structure was determined by X-ray diffraction analysis. The results obtained during the charging of rutile ruthenium oxide films indicate that in the anodic sweep the transition from Ru(II) to Ru(VI) occurs followed by proton de-intercalation. In the cathodic sweep, electron injection occurs followed by proton intercalation, leading to Ru(II). The proton intercalation/de-intercalation processes can be inferred from the mass/charge relationship which gives a slope close to 1 g mol−1 (multiplied by the Faraday constant) corresponding to the molar mass of hydrogen. From the chronoamperometric measurements, charge and mass saturation of the RuO2 thin films was observed (440 ng cm−2) during the charging processes, which is related to the total number of active sites in these films. Using the electrochemical quartz crystal nanobalance technique to study the methanol oxidation reaction at these films was possible to demonstrate that bulk oxidation occurs without the formation of strongly adsorbed intermediates such as COads, demonstrating that Pt electrodes modified by ruthenium oxide particles can be promising catalysts for the methanol oxidation as already shown in the literature.  相似文献   

3.
Vanadium nitride (VN) powder was synthesized by calcining V2O5 xerogel in a furnace under an anhydrous NH3 atmosphere at 400 °C. The structure and surface morphology of the obtained VN powder were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The supercapacitive behavior of VN in 1 M KOH electrolyte was studied by means of cyclic voltammetry (CV), constant current charge-discharge cycling (CD) and electrochemical impedance spectroscopy (EIS). The XRD result indicates that the obtained VN belongs to the cubic crystal system (Fm3m [2 2 5]) with unit-cell parameter 4.15 Å. SEM images show the homogeneous surface of the obtained VN. The CV diagrams illustrate the existence of fast and reversible redox reactions on the surface of VN electrode. The specific capacitance of VN is 161 F g−1 at 30 mV s−1. Furthermore, the specific capacitance remains 70% of the original value when the scan rate increases from 30 to 300 mV s−1. CD experiments show that VN is suitable for CD at high current density, and the slow and irreversible faradic reactions exist during the charge-discharge process of the VN electrode. The experimental results indicate that VN is a promising electrode material for electrochemical supercapacitors.  相似文献   

4.
The electrochemical impedance spectroscopy (EIS) was used to study the characteristics of CO2 corrosion of N80 and 4Cr steels with corrosion scales. The results indicated that CO2 corrosion scale on tube steel could prevent the rate of mass transfer remarkably, corrosion rate was controlled by ions diffusion in corrosion scale, which led to finite length diffusion impedance occurred in electrochemical impedance spectra. Additionally, pitting of N80 steel could lead to additional capacitive reactance in impedance spectrum. The ion diffusion coefficient in corrosion scale and porosity of corrosion scale could be calculated by Warburg impedance coefficient, the results shown that the value of H+ diffusion coefficient in N80 and 4Cr corrosion scale is (3.46 and 1.76) × 10−10 m2 s−1, respectively. The protective ability of 4Cr corrosion scale was better than that of N80 corrosion scale.  相似文献   

5.
A Li hexagonal boron nitride (hBN) intercalation compound (Li-hBNIC) was successfully synthesized by the annealing of powder or bulk hBN and Li at 1523 K. By an XRD analysis, a strong peak indicating the expansion of BN interlayer distance due to Li-intercalation was observed at an angle lower than that of hBN (0 0 2). In the sample, the interlayer distance and its expansion ratio were 3.76 Å and 12.6%, respectively, and these values were similar to those of a first stage Li-graphite intercalation compound (Li-GIC), LiC6. The electrical conductivity of the sample was increased by several orders of magnitude, from 10−15 to 10−7 Ω−1 cm−1 at room temperature. Li de-intercalation was confirmed by the dispersion of the sample in purified water.  相似文献   

6.
Poly(3-methylthiophene) (P3MT)-based porous silicon (PS) substrates were fabricated and characterized by cyclic voltammetry, scanning electron microscopy, and auger electron spectroscopy. After doping urease (Urs) into the polymeric matrix, sensitivity and physicochemical properties of the P3MT-based PS substrate was investigated compared to planar silicon (PLS) and bulk Pt substrates. PS substrate was formed by electrochemical anodization in an etching solution composed of HF, H2O, and ethanol. Subsequently, Ti and Pt thin-films were sputtered on the PS substrate. Effective working electrode area (Aeff) of the Pt-deposited PS substrate was determined from a redox reaction of Fe(CN)63−/Fe(CN)64− redox couple in which nearly reversible cyclic voltammograms were obtained. The ip versus v1/2 plots showed that Aeff of the PS-based Pt thin-film electrode was 1.62 times larger than that of the PLS-based electrode.Electropolymerization of P3MT on both types of electrodes were carried out by the anodic potential scanning under the given potential range. And then, urease molecules were doped to the P3MT film by the chronoamperometry. Direct electrochemistry of a Urs/P3MT/Pt/Ti/PS electrode in an acetonitrile solution containing 0.1 mol/L NaClO4 was introduced compared to a P3MT/Pt/Ti/PS electrode at scan rates of 10 mV s−1, 50 mV s−1, and 100 mV s−1.Amperometric sensitivity of the Urs/P3MT/Pt/Ti/PS electrode was ca. 1.67 μA mM−1 per projected unit square centimeter, and that of the Urs/P3MT/Pt/Ti/PLS electrode was ca. 1.02 μA mM−1 per projected unit square centimeter in a linear range of 1-100 mM urea concentrations. 1.6 times of sensitivity increase was coincident with the results from cyclic voltammetrc analysis.Surface morphology from scanning electron microscopy (SEM) images of Pt-deposited PS electrodes before and after the coating of Urs-doped P3MT films showed that pore diameter and depth were 2 μm and 10 μm, respectively. Multilayered-film structures composed of metals and organics for both electrodes were also confirmed by auger electron spectroscopy (AES) depth profiles.  相似文献   

7.
Simultaneous dilatometric and electrochemical measurements are employed for studying the kinetic parameters and mechanism for hydrogen transport through metal oxides. As a model, CeO2 layer on a palladium wire substrate is investigated. Hydrogen is dissolved in aqueous solutions where their acidity and the oxide layer thickness are the studied parameters. Based on both open circuit potential and length changes, it is deduced that molecular diffusion through pores and imperfections in the ceria lattice is the rate determining step and no chemical reactions are involved in the oxide bulk. The following diffusion coefficients are calculated by using a diffusional transport model: D(1 N KOH)=1.69×10−11 cm2 s−1D(1 N H2SO4)=1.72×10−11 cm2 s−1.  相似文献   

8.
The electrodeposition of metallic Copper in binary mixture ionic liquid/organic solvent (tri-n-octylmethylammonium chloride (TOMAC))/chloroform (CHCl3) was investigated. The electrochemical behavior of Cu(II) in TOMAC/CHCl3 at glassy carbon working electrode at room temperature was studied by cyclic voltammetry and spectroscopy impedance. The results from the cyclic voltammetry showed that the electrodeposition of metallic Cu in the binary mixture ionic liquid/organic solvent was an irreversible process and was controlled by the diffusion of Cu(II) on a glassy carbon working electrode. The average value of αnα was found to be 0.23 at 25 °C and the diffusion coefficient (D0) of Cu(II) was calculated to be 7.12 10− 9 cm2/s at room temperature. The performance of TOMAC ionic liquid such as internal resistance has been investigated with electrochemical impedance spectroscopy (EIS). The scanning electron microscopy (SEM) micrographs was used to observe that the copper plating was moderately dense and contains fine crystallites with average sizes of about 1 μm at room temperature. Energy dispersive X-ray analysis (EDAX) profile showed that the obtained film was copper.  相似文献   

9.
In this study, a symmetric electrochemical capacitor was fabricated by adopting a lithium iron phosphate (LiFePO4)-activated carbon (AC) composite as the core electrode material in 1.0 M Na2SO3 and 1.0 M Li2SO4 aqueous electrolyte solutions. The composite electrodes were prepared via a facile mechanical mixing process. The structural properties of the nanocomposite electrodes were characterised by scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) analysis. The electrochemical performances of the prepared composite electrode were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that a maximum specific capacitance of 112.41 F/g was obtained a 40 wt% LiFePO4 loading on an AC electrode compared with that of a pure AC electrode (76.24 F/g) in 1 M Na2SO3. The improvement in the capacitive performance of the 40 wt% LiFePO4–AC composite electrode is believed to be attributed to the contribution of the synergistic effect of the electric double layer capacitance (EDLC) of the AC electrode and pseudocapacitance via the intercalation/extraction of H+, OH, Na+ and SO32− and Li+ ions in LiFePO4 lattices. In contrast, it appears that the incorporation of LiFePO4 into AC electrodes does not increase the charge storage capability when Li2SO4 is used as the electrolyte. This behaviour can be explained by the fact that the electrolyte system containing SO42− only exhibits EDLC in the Fe-based electrodes. Additionally, Li+ ions that have lower conductivity and mobility may lead to poorer charge storage capability compared to Na+ ions. Overall, the results reveal that the AC composite electrodes with 40 wt% LiFePO4 loading on a Na2SO3 neutral electrolyte exhibit high cycling stability and reversibility and thus display great potential for electrochemical capacitor applications.  相似文献   

10.
Spherical LiFePO4/C powders were synthesized by the conventional solid-state reaction method via Ni doping. Low-cost asphalt was used as both the reduction agent and the carbon source. An Ni-doped spherical LiFePO4/C composite exhibited better electrochemical performances compared to an un-doped one. It presented an initial discharge capacity of 161 mAhg−1 at 0.1 C rate (the theoretical capacity of LiFePO4 with 5 wt% carbon is about 161 mAhg−1). After 50 cycles at 0.5 C rate, its capacity remained 137 mAhg−1 (100% of the initial capacity) compared to 115 mAhg−1 (92% of the initial capacity) for an un-doped one. The electrochemical impedance spectroscopy analysis and cyclic voltammograms results revealed that Ni doping could decrease the resistance of LiFePO4/C composite electrode drastically and improve its reversibility.  相似文献   

11.
To further improve the electrochemical performance of LiFePO4/C, Nd doping has been adopted for cathode material of the lithium ion batteries. The Nd-doped LiFePO4/C cathode was synthesized by a novel solid-state reaction method at 750 °C without using inert gas. The Li0.99Nd0.01FePO4/C composite has been systematically characterized by X-ray diffraction, EDS, SEM, TEM, charge/discharge test, electrochemical impedance spectroscopy and cyclic stability. The results indicate that the prepared sample has olivine structure and the Nd3+ and carbon modification do not affect the structure of the sample but improve its kinetics in terms of discharge capacity and rate capability. The Li0.99Nd0.01FePO4/C powder exhibited a specific initial discharge capacity of about 161 mAh g− 1 at 0.1 C rate, as compared to 143 mAh g− 1 of LiFePO4/C. At a high rate of 2 C, the discharge capacity of Li0.99Nd0.01FePO4/C still attained to 115 mAh g− 1 at the end of 20 cycles. EIS results indicate that the charge transfer resistance of LiFePO4/C decreases greatly after Nd doping.  相似文献   

12.
In this work a new membrane electrode based on Pt-coated Nafion membrane was fabricated. Chemical deposition process was used to coat platinum on Nafion 117 membrane and then Pt-coated Nafion membrane was hot pressed on gas diffusion layer (GDL) to make new membrane electrode. The electrochemical and chemical studies of the Pt-coated Nafions were investigated by electrochemical techniques, X-ray diffraction and scanning electron microscopy. The electrochemical results indicated that as the concentration of H2PtCl6 increased, the oxygen reduction reaction rate increased until the concentration was reached where the reduction reaction was limited by the problem of mass transport. The electrochemical results for oxygen reduction reaction showed that the new electrode which prepared by plating Nafion membrane with 0.06 M H2PtCl6 in electroless plating solution, has a higher performance than other electrodes. The XRD results showed that the average platinum particle size of the best sample was about 3 nm. The loading of platinum for this electrode was 0.153 mg cm−2.  相似文献   

13.
Jinyi Han 《Surface science》2006,600(13):2752-2761
The interaction of O2 with Pd(1 1 1), Pd(1 1 0) and Pd(1 0 0) was studied in the pressure range 1-150 Torr by the techniques of temperature programmed decomposition (TPD), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The oxidation of Pd was rate-determined by oxygen diffusion into Pd metal followed by the diffusion into PdO once the bulk oxide layer was formed. The dissolution of oxygen atoms into Pd metal followed the Mott-Cabrera model with diffusion coefficient 10−16 cm2 s−1 at 600 K and activation energy of 60-85 kJ mol−1. The bulk oxide phase was formed when a critical oxygen concentration was reached in the near-surface region. The formation of PdO was characterized by a decrease in the oxygen uptake rate, the complete fading of the metallic Pd LEED pattern and an atomic ratio O/Pd of 0.15-0.7 as measured by AES. The diffusion of oxygen through the bulk oxide layer again conformed to the Mott-Cabrera parabolic diffusion law with diffusion coefficient 10−18 cm2 s−1 at 600 K and activation energy of 111-116 kJ mol−1. The values for the diffusion coefficient and apparent activation energy increased as the surface atom density of the single crystals increased.  相似文献   

14.
Lithium ion conducting solid-state composites consisting of lithium ion conducting ionic liquid, lithium bis(trifluoromethanesulfonyl)amide (Li-TFSA) dissolved 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide (EMI-TFSA), denoted by [yMLi+][EMI+][TFSA] in this study, and various oxide particles such as SiO2, Al2O3, TiO2 (anatase and rutile) and 3YSZ are synthesized via a liquid route for the molar concentration of lithium, y, to be 1. The composite consists of SiO2 and the ionic liquid with y = 0.2 was also prepared. The ionic liquid are quasi-solidified at the above oxide particle surfaces when x is below 40 for y = 1 and x is below 30 for y = 0.2, corresponding to the confinable thickness of the ionic liquid at the oxides' surfaces to be approximately 5-10 nm regardless of the oxide compositions. The electrical conductivities of x vol.%[yMLi+][EMI+][TFSA-]-SiO2, Al2O3, TiO2s or 3YSZ composites are evaluated by ac impedance measurements. The quasi-solid-state composites exhibited liquid-like high apparent conductivity, e.g. 10− 3.3-10− 2.0 S cm− 1 in the temperature range of 323-538 K for SiO2-ionic liquid composites with y = 1. The self-diffusion coefficients of the constituent species of x vol.% [yMLi+][EMI+][TFSA] (x is below 40, y = 0.2 and 1) − SiO2 are evaluated by the Pulse Gradient Spin Echo (PGSE)-NMR technique in the temperature range of 298-348 K. By the quasi-solidification of the ionic liquid at SiO2 particle surfaces, the absolute values of the diffusion coefficients of all constituent species decreased. The SiO2 surfaces work to promote ionization of ion pair, [EMI+][TFSA], while significant influence on the solvation coordination, [Li(TFSA)n + 1]n, was not observed. The apparent transport numbers of Li-containing species both in the bulk and the quasi-solidified ionic liquid showed similar values with each other, which was evaluated to be in the range of 0.010-0.017 for y = 0.2 and 0.051-0.093 for y = 1 in the abovementioned temperature range.  相似文献   

15.
The electrochemical and microstructural properties of carbon film electrodes made from carbon film electrical resistors of 1.5, 15, 140 Ω and 2.0 kΩ nominal resistance have been investigated before and after electrochemical pre-treatment at +0.9 V vs SCE, in order to assess the potential use of these carbon film electrodes as electrochemical sensors and as substrates for sensors and biosensors. The results obtained are compared with those at electrodes made from previously investigated 2 Ω carbon film resistors. Cyclic voltammetry was performed in acetate buffer and phosphate buffer saline electrolytes and the kinetic parameters of the model redox system Fe(CN)63−/4− obtained. The 1.5 Ω resistor electrodes show the best properties for sensor development with wide potential windows, similar electrochemical behaviour to those of 2 Ω and close-to-reversible kinetic parameters after electrochemical pre-treatment. The 15 and 140 Ω resistor electrodes show wide potential windows although with slower kinetics, whereas the 2.0 kΩ resistor electrodes show poor cyclic voltammetric profiles even after pre-treatment. Electrochemical impedance spectroscopy related these findings to the interfacial properties of the electrodes. Microstructural and morphological studies were carried out using contact mode Atomic Force Microscopy (AFM), Confocal Raman spectroscopy and X-ray diffraction. AFM showed more homogeneity of the films with lower nominal resistances, related to better electrochemical characteristics. X-ray diffraction and Confocal Raman spectroscopy indicate the existence of a graphitic structure in the carbon films.  相似文献   

16.
The silver nanoparticles were prepared on the glassy carbon (GC) electrode, modified with p-iso propyl calix[6]arene, by preconcentration of silver ions in open circuit potential and followed by electrochemical reduction of silver ions. The stepwise fabrication process of Ag nanoparticles was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. The prepared Ag nanoparticles were deposited with an average size of 70 nm and a homogeneous distribution on the surface of electrode. The observed results indicated that the presence of calixarene layer on the electrode surface can control the particle size and prevent the agglomeratione and electrochemical deposition is a promising technique for preparation of nanoparticles due to its easy-to-use procedure and low cost of implementation. Cyclic voltammetry experiments showed that Ag nanoparticles had a good catalytic ability for the reduction of hydrogen peroxide (H2O2). The effects of p-isopropyl calix[6]arene concentration, applied potential for reduction of Ag+, number of calixarene layers and pH value on the electrocatalytic ability of Ag nanoparticles were investigated. The present modified electrode exhibited a linear range from 5.0 × 10−5 to 6.5 × 10−3 M and a detection limit 2.7 × 10−5 M of H2O2 (S/N = 3) using amperometric method.  相似文献   

17.
Porous LiNi0.75Co0.25O2 microspheres are successfully prepared by a simple hydrothermal process by using H[Ni0.75Co0.25OOH]3 and LiOH as starting materials in the presence of urea for the first time. The synthesized samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (SBET), and electrochemical performance. The synthesized LiNi0.75Co0.25O2 has a good electrochemical performance with an initial discharge capacity of 169.3 mA g−1 and good capacity retention of 96.7% after 50 cycles at 0.2 C (25 mA g−1). The electrochemical lithium ion insertion/extraction process is quite reversible even at 5 C. Furthermore, the structure in the charge-discharge process is stable and the impedance increased slowly during cycling.  相似文献   

18.
The transport of Na through the polycrystalline ceramic arc tube of high intensity discharge lamps has been investigated. This complex process consists of several steps: solution in the ceramics, diffusion through the ceramics, leaving the bulk phase, evaporation from the surface. Among the listed processes the kinetics of the diffusion was examined in the temperature range 400-1200 °C, separately from other disturbing effects. X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS) were used to determine the concentration depth profiles. The obtained results confirmed that the grain boundary diffusion plays an important role in the transport process of sodium through the ceramic wall. The bulk and the grain boundary diffusion coefficients and the temperature dependencies of these transport processes have been determined. The activation energy of Na bulk diffusion is 56.5 ± 6.7 kJ/mol at 900-1200 °C, respectively the activation energies of Na grain boundary diffusion amount to 97.5 ± 21.6 kJ/mol in the temperature range 700-1100 °C and 7.7 ± 4.0 × 10−2 kJ/mol at 400-700 °C. The preexponential factor of the bulk diffusion was found to be Do = 5.1 × 10−15 ± 9.5 × 10−17 cm2/s in the temperature range 900-1200°C, whereas the preexponential factors of grain boundary diffusion are Do = 1.1 × 10−10 ± 1.1 × 10−11 cm2/s at 700-1100 °C and Do = 7.5 × 10-15 ± 1.5 × 10−17 cm2/s at 400-700 °C.  相似文献   

19.
This study examines the initial performance and durability of a solid oxide cell applied for co-electrolysis of CO2 and H2O. Such a cell, when powered by renewable/nuclear energy, could be used to recycle CO2 into sustainable hydrocarbon fuels. Polarization curves and electrochemical impedance spectroscopy were employed to characterize the initial performance and to break down the cell resistance into the resistance for the specific processes occurring during operation. Transformation of the impedance data to the distribution of relaxation times (DRT) and comparison of measurements taken under systematically varied test conditions enabled clear visual identification of five electrode processes that contribute to the cell resistance. The processes could be assigned to each electrode and to gas concentration effects by examining their dependence on gas composition changes and temperature.This study also introduces the use of the DRT to study cell degradation without relying on a model. The durability was tested at consecutively higher current densities (and corresponding overpotentials). By analyzing the impedance spectra before and after each segment, it was found that at low current density operation (− 0.25 A/cm2 segment) degradation at the Ni/YSZ electrode was dominant, whereas at higher current densities (− 0.5 A/cm2 and − 1.0 A/cm2), the Ni/YSZ electrode continued to degrade but the serial resistance and degradation at the LSM/YSZ electrode began to also play a major role in the total loss in cell performance. This suggests different degradation mechanisms for high and low current density operation.  相似文献   

20.
LiFePO4-positive electrode material was successfully synthesized by a solid-state method, and the effect of storage temperatures on kinetics of lithium-ion insertion for LiFePO4-positive electrode material was investigated by electrochemical impedance spectroscopy. The charge-transfer resistance of LiFePO4 electrode decreases with increasing the storage temperatures. This suggests that it has a high electrochemical activity at high temperature. The diffusion coefficient of lithium ion is greatly increased with increasing the storage temperatures, indicating that the kinetics of Li+ and electron transfer into the electrodes were much fast at high storage temperature.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号