电化学电容器电极材料的研究进展

电化学电容器具有良好的脉冲充放电性能和大容量储能性能,是一种介于常规电容器和蓄电池之间的新型储能装置,应用前景非常广泛.目前用于制备电化学电容器的极化电极材料主要分为碳素材料、金属氧化物材料和导电聚合物材料.本文综述了电化学电容器的储能原理、材料的制备与电化学性质,并介绍了上述三类电化学电容器材料的最新研究进展.     

NiO-改性活性炭电极电化学电容器研究

为提高普通活性炭材料的电化学性能,用Ni(NO3)2溶液浸渍法和高温热解对活性炭进行改性处理.分别采用氮气吸附法、SEM、XPS等方法分析研究改性炭材料的比表面积、孔结构、形貌和组成;用循环伏安、恒流充放电等电化学方法研究改性活性炭电极构成的电化学电容器性能.结果表明,由Ni(NO3)2热解产生的NiO有准电容效应,与活性炭原有的双电层电容构成了复合电容,因而改性炭的电容量有明显的提高,其质量比电容达到246.1 F/g,比原样炭的130.1 F/g提高了89.2%,表观体积比电容和面积比电容分别高达169.7 F/cm3和30.1 μF/cm2,均显著优于普通炭材料.     

A methyl parathion electrochemical sensor based on Nano-TiO2, graphene composite film modified electrode

A methyl parathion electrochemical sensor based on nano-TiO₂ and graphene composite film modified glassy carbon electrode has been developed. The electrochemical behavior of MP at the sensor was investigated by cyclic voltammetry and linear sweep voltammetry. Scanning electron microscopy was used to characterize the surface morphology of nano-TiO₂ and graphene composite film. Compared with a bare glassy carbon electrode or a mono-film modified electrode, the redox peak currents of methyl parathion on the composite film modified electrode improved greatly, indicating that the sensor showed good catalytic effects. The optimal experimental condition was obtained. The results indicated that the linear sweep voltammetry responses of methyl parathion, in pH 5.2 acetate buffer solution with open-circuit accumulation for 2 min, were linear with concentrations of methyl parathion in two ranges of 0.002～5 μM and 5～100 μM. The linear equations were i_Pc(μA) = 0.0136 + 4.965c_MP(μM) (R₁² = 0.9911) and i_Pc(μA) = 21.87 + 0.8206c_MP(μM) (R₂² = 0.9914), respectively. The detection limit was 1.0 nM (S/N = 3). The sensor exhibited high sensitivity and good reproducibility as well as certain anti-interference ability. It was applied to the determination of residual MP in fresh apple sample with the recovery of 92%～102%. The result was satisfactory.     

混合超级电容器电极材料研究进展

综述了多孔碳电极材料,金属氧化物、嵌锂化合物、导电聚合物等电化学活性电极材料,以及由这些材料制备的复合电极材料的研究进展。     

Investigation of the electrochemical and electrocatalytic behavior of single-wall carbon nanotube film on a glassy carbon electrode

The electrochemical behavior of a film of single-wall carbon nanotubes (SWNTs) functionalized with carboxylic acid groups was studied extensively on a glassy carbon (GC) electrode. One stable couple corresponding to the redox of the carboxylic acid group, which was supported by XPS and IR experiments, was observed. The electrode process involved four electrons, while the rate-determining step was a one-electron reduction. The SWNT film-modified electrode showed favorable electrocatalytic behavior toward the oxidation of biomolecules such as dopamine, epinephrine, and ascorbic acid.     

Metal nanoparticle-based electrochemical stripping potentiometric detection of DNA hybridization

A new nanoparticle-based electrical detection of DNA hybridization, based on electrochemical stripping detection of the colloidal gold tag, is described. In this protocol, the hybridization of a target oligonucleotide to magnetic bead-linked oligonucleotide probes is followed by binding of the streptavidin-coated metal nanoparticles to the captured DNA, dissolution of the nanometer-sized gold tag, and potentiometric stripping measurements of the dissolved metal tag at single-use thick-film carbon electrodes. An advanced magnetic processing technique is used to isolate the DNA duplex and to provide low-volume mixing. The influence of relevant experimental variables, including the amounts of the gold nanoparticles and the magnetic beads, the duration of the hybridization and gold dissolution steps, and the parameters of the potentiometric stripping operation upon the hybridization signal, is examined and optimized. Transmission electron microscopy micrographs indicate that the hybridization event leads to the bridging of the gold nanoparticles to the magnetic beads. Further signal amplification, and lowering of the detection limits to the nanomolar and picomolar domains, are achieved by precipitating gold or silver, respectively, onto the colloidal gold label. The new electrochemical stripping metallogenomagnetic protocol couples the inherent signal amplification of stripping metal analysis with discrimination against nonhybridized DNA, the use of microliter sample volumes, and disposable transducers and, hence, offers great promise for decentralized genetic testing.     

Mechanism for the electrochemical stripping reduction of the nickel and cobalt dimethylglyoxime complexes

Reductive coulometric stripping potentiometry, a technique not hitherto described, has been used to establish that the reduction of Ni(II) and Co(II) dimethylglyoximates, adsorbed on a mercury film electrode, is a 10-electron process. Exhaustive adsorption of Ni(II) or Co(II) complexes, in the 0-4 μg L(-)(1) concentration range, was achieved by vibrationally promoted electrolysis for 3 min of ～25 μL volume samples, hanging under the working electrode in a nitrogen atmosphere. The adsorbed complexes were reduced by means of a constant current of 50 μA. The technique was successfully used for the calibration-free determination of Ni(II) in certified seawater and river water reference samples.     

Self-assembled manganese dioxide nanowires as electrode materials for electrochemical capacitors

The microstructure and morphology of sol-gel derived manganese dioxide (MnO₂) xerogels were affected by the synthesis conditions and post synthesis heat treatment. Manganese dioxide nanoparticles in sol that were dialyzed to more acidic pH (pH 5.7) value were observed to self-assemble into nanowires, whereas non-dialyzed sols remained nanoparticulate in nature. MnO₂ xerogels of disordered nanowire network exhibited comparatively higher porosity and BET surface areas. The electrochemical properties of both MnO₂ nanowire and nanoparticle thin-film electrodes were evaluated using cyclic voltammetry in a mild aqueous electrolyte (0.1 M Na₂SO₄). The charge capacities of MnO₂ nanowire-based thin-film electrodes were substantially higher (~ 800 F/g) than those of nanoparticulate thin-film electrodes (~ 700 F/g).     

Development of a method for total inorganic arsenic analysis using anodic stripping voltammetry and a Au-coated, diamond thin-film electrode

We demonstrate that a Au-coated, boron-doped, diamond thin-film electrode provides a sensitive, reproducible, and stable response for total inorganic arsenic (As(III) and As(V)) using differential pulse anodic stripping voltammetry (DPASV). As is preconcentrated with Au on the diamond surface during the deposition step and detected oxidatively during the stripping step. Au deposition was uniform over the electrode surface with a nominal particle size of 23 +/- 5 nm and a particle density of 109 cm-2. The electrode and method were used to measure the As(III) concentration in standard and river water samples. The detection figures of merit were compared with those obtained using conventional Au-coated glassy carbon and Au foil electrodes. The method was also used to determine the As(V) concentration in standard solutions after first being chemically reduced to As(III) with Na2SO3, followed by the normal DPASV determination of As(III). Sharp and symmetric stripping peaks were generally observed for the Au-coated diamond electrode. LODs were 0.005 ppb (S/N = 3) for As(III) and 0.08 ppb (S/N = 3) for As(V) in standard solutions. An As(III) concentration of 0.6 ppb was found in local river water. The relative standard deviation of the As stripping peak current for river water was 1.5% for 10 consecutive measurements and was less than 9.1% over a 10-h period. Excellent electrode response stability was observed even in the presence of up to 5 ppm of added humic acid. In summary, the Au-coated diamond electrode exhibited better performance for total inorganic As analysis than did Au-coated glassy carbon or Au foil electrodes. Clearly, the substrate on which the Au is supported influences the detection figures of merit.     

Antimony sulfide thin films in chemically deposited thin film photovoltaic cells

Antimony sulfide thin films of thickness ≈ 500 nm have been deposited on glass slides from chemical baths constituted with SbCl₃ and sodium thiosulfate. Smooth specularly reflective thin films are obtained at deposition temperatures from − 3 to 10 °C. The differences in the film thickness and improvement in the crystallinity and photoconductivity upon annealing the film in nitrogen are presented. These films can be partially converted into a solid solution of the type Sb₂S_xSe_3 − x, detected in X-ray diffraction, through heating them in contact with a chemically deposited selenium thin film. This would decrease the optical band gap of the film from ≈ 1.7 eV (Sb₂S₃) to ≈ 1.3 eV for the films heated at 300 °C. Similarly, heating at 300 °C of sequentially deposited thin film layers of Sb₂S₃-Ag₂Se, the latter also from a chemical bath at 10 °C results in the formation of AgSb(S/Se)₂ with an optical gap of ≈ 1.2 eV. All these thin films have been integrated into photovoltaic structures using a CdS window layer deposited on 3 mm glass sheets with a SnO₂:F coating (TEC-15, Pilkington). Characteristics obtained in these cells under an illumination of 850 W/m² (tungsten halogen) are as follows: SnO₂:F-CdS-Sb₂S₃-Ag(paint) with open circuit voltage (V_oc) 470 mV and short circuit current density (J_sc) 0.02 mA/cm²; SnO₂:F-CdS-Sb₂S₃-CuS-Ag(paint), V_oc ≈ 460 mV and J_sc ≈ 0.4 mA/cm²; SnO₂:F-CdS-Sb₂S_xSe_3 − x-Ag(paint), V_oc ≈ 670 mV and J_sc ≈ 0.05 mA/cm²; SnO₂:F-CdS-Sb₂S₃-AgSb(S/Se)₂-Ag(paint), V_oc ≈ 450 mV and J_sc ≈ 1.4 mA/cm². We consider that the materials and the deposition techniques reported here are promising toward developing ‘all-chemically deposited solar cell technologies.’     

Nanogap electrode fabrication for a nanoscale device by volume-expanding electrochemical synthesis

A novel nanogap fabrication method using an electrochemical nanopatterning technique is presented. Electrochemical deposition of platinum ions reduces the microgap size to the sub-50-nm range due to the self-limited volume expansion of the electrodes. Additionally, the low crystallinity of platinum reduces the line edge roughness in the electrodes, whereas the high crystallinity of gold increases it. Current compliance, a buffered resistor, and a symmetric deposition strategy are used to achieve high reliability and practicality of nanogap electrodes. As a possible application, an organic thin-film transistor using the nanogap electrodes is also demonstrated.     

Performance evaluation of galvanostatically deposited nickel oxide electrode for electrochemical supercapacitors

Nanostructured nickel oxide (NiO) electrode has been prepared using electrochemical work station operated on galvanostatic mode in supercapacitor application. Crystalline cubic structure and nanoplate-type of morphology of synthesized NiO electrode was confirmed from X-ray diffraction and scanning electron microscopy analysis respectively. The wettability study was tested by contact angle measurement, which reveals hydrophilic nature of NiO electrode with contact angle of 59°. The presence of nickel and oxygen characteristic bands in EDAX and XPS spectrum has corroborated the NiO formation. The supercapacitive properties of NiO electrode were tested by cyclic voltammogram (CV) in 1 M aqueous Na₂SO₄, KOH, NaOH electrolytes within the potential range of ??1.1 to 0.9 V, 0 to 0.4 V and ??1.2 to 0.4 respectively. The CV study demonstrates maximum specific capacitance of 481.16 Fg^??1 for 1 M Na₂SO₄. The obtained specific power, specific energy and coulombic efficiency values of NiO electrode are 19.48 kW kg^??1, 60.12 Whkg^??1, and 92.31%, respectively. In the meantime it exhibited excellent cycle life time with 92.3% specific capacitance kept after 1000 cycles. These results imply that NiO electrode is promising candidate for upcoming thin film supercapacitors and other microelectronic constructions.     

Ultrasensitive multiplexed immunoassay with electrochemical stripping analysis of silver nanoparticles catalytically deposited by gold nanoparticles and enzymatic reaction

A novel ultrasensitive multiplexed immunoassay method was developed by combining alkaline phosphatase (ALP)-labeled antibody functionalized gold nanoparticles (ALP-Ab/Au NPs) and enzyme-Au NP catalyzed deposition of silver nanoparticles at a disposable immunosensor array. The immunosensor array was prepared by covalently immobilizing capture antibodies on chitosan modified screen-printed carbon electrodes. After sandwich-type immunoreactions, the ALP-Ab/Au NPs were captured on an immunosensor surface to catalyze the hydrolysis of 3-indoxyl phosphate, which produced an indoxyl intermediate to reduce Ag(+). The silver deposition process was catalyzed by both ALP and Au NPs, which amplified the detection signal. The deposited silver was then measured by anodic stripping analysis in KCl solution. Using human and mouse IgG as model analytes, this multiplexed immunoassay method showed wide linear ranges over 4 orders of magnitude with the detection limits down to 4.8 and 6.1 pg/mL, respectively. Acceptable assay results for practical samples could be obtained. The newly designed strategy avoided cross talk and the need of deoxygenation for the electrochemical immunoassay and, thus, provided a promising potential in clinical applications.     

Ni-S-Co涂层电极的制备及其电化学性能的研究

采用电沉积的方法以泡沫镍为基体制备出非晶Ni-S-Co合金电极.用电化学测试方法分析涂层的电化学行为.结果表明,较好的制备涂层电极条件为: CoSO4·7H2O掺杂浓度为10g/L,电流密度为50mA/cm2,温度为50℃,电沉积时间为40min,pH值为4.当电解电流密度为1200A/m2时,非晶Ni-S-Co合金电极的极化电位较非晶Ni-S合金电极低95mV,较Ni金属电极低405mV;根据Tafel曲线计算出Ni、非晶Ni-S以及非晶Ni-S-Co电极的表面活化能分别为49.5、40.3和38.6kJ/mol.Ni-S-Co电极具有更高的交换电流密度和更低的析氢活化能,因此具有更高的析氢催化活性.