Nanostructured electrocatalytic materials and porous electrodes for direct methanol fuel cells

Direct methanol fuel cells （DMFCs） are promising for use in portable devices because of advantages such as high fuel energy density, low working temperature and low emission of pollutants. Nanotechnology has been used to improve the performance of DMFCs. Catalytic materials composed of small, metallic particles with unique nanostructure supparted on carbons or metal oxides have been widely investigated for use in DMFCs. Despite our increased understanding of this type of fuel cell, many challenges still remain. This paper reviews the current developments of nanostructured elec- trocatalytic materials and porous electrodes for use in DMFCs. In particular, this review focuses on the synthesis and characterization of nanostructured catalysts and supporting materials. Both computational and experimental approaches to optimize mass transportation in porous electrodes of DMFCs, such as theoretical modeling of internal transfer processes and preparation of functional structures in membrane electrode assemblies, are introduced.

The effect of transition metal ions (M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I^-/I_3^-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn^(2+),Ni^(2+),Co^(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu^(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu^(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni^(2+), PANI-Co^(2+),PANI-Mn^(2+) and PANI-Cu^(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.

Electrochemical Properties of Electrodes with Different Shapes and Diffusion Kinetic Analysis of Microbial Fuel Cells on Ocean Floor

Microbial fuel cell(MFC) on the ocean floor is a kind of novel energy-harvesting device that can be developed to drive small instruments to work continuously.The shape of electrode has a great effect on the performance of the MFC.In this paper,several shapes of electrode and cell structure were designed,and their performance in MFC were compared in pairs:Mesh(cell-1) vs.flat plate(cell-2),branch(cell-3) vs.cylinder(cell-4),and forest(cell-5) vs.disk(cell-6) FC.Our results showed that the maximum power densities were 16.50,14.20,19.30,15.00,14.64,and 9.95 mWm-2 for cell-1,2,3,4,5 and 6 respectively.And the corre-sponding diffusion-limited currents were 7.16,2.80,18.86,10.50,18.00,and 6.900 mA.The mesh and branch anodes showed higher power densities and much higher diffusion-limited currents than the flat plate and the cylinder anodes respectively due to the low diffusion hindrance with the former anodes.The forest cathode improved by 47% of the power density and by 161% of diffusion-limited current than the disk cathode due to the former's extended solid/liquid/gas three-phase boundary.These results indicated that the shape of electrode is a major parameter that determining the diffusion-limited current of an MFC,and the differences in the elec-trode shape lead to the differences in cell performance.These results would be useful for MFC structure design in practical applica-tions.

Highly conductive and transparent carbon nanotube-based electrodes for ultrathin and stretchable organic solar cells

In this work, we have presented a freestanding and flexible CNT-based film with sheet resistance of 60 ？/ and transmittance of 82% treated by nitric acid and chloroauric acid in sequence. Based on modified CNT film as a transparent electrode, we have demonstrated an ultrathin, flexible organic solar cell（OSC） fabricated on 2.5-μm PET substrate. The efficiency of OSC, combined with a composite film of poly（3-hexylthiophene）（P3HT） and phenyl-C61 butyric acid methyl ester（PCBM） as an active layer and with a thin layer of methanol soluble biuret inserted between the photoactive layer and the cathode, can be up to 2.74% which is approximate to that of the reference solar cell fabricated with ITO-coated glass（2.93%）. Incorporating the as-fabricated ITO-free OSC with pre-stretched elastomer, 50% compressive deformation can apply to the solar cells. The results show that the as-prepared CNT-based hybrid film with outstanding electrical and optical properties could serve as a promising transparent electrode for low cost, flexible and stretchable OSCs, which will broaden the applications of OSC and generate more solar power than it now does.

In-situ design and construction of lithium-ion battery electrodes on metal substrates with enhanced performances：A brief review

For the ever-growing demand of advanced lithium-ion batteries, it is highly desirable to grow self-supported micro-/nanostructured arrays on metal substrates as electrodes directly. The in-situ growth of electrode materials on the conducting substrates greatly simplifies the electrode fabrication process without using any binders or conductive additives. Moreover, the well-ordered arrays closely connected to the current collectors can provide direct electron transport pathways and enhanced accommodation of strains arisen from lithium ion lithiation/delithiation. This article summarizes our recent work on design and construction of lithium-ion battery electrodes on metal substrates. An aqueous solution-based process and a microemulsion-mediated process have been respectively presented to control the kinetic and thermodynamic processes for the micro-/nanostructured array growth on metal substrates, with particular attention to CuO nanorod arrays and microcog arrays successfully prepared on Cu foil substrates. They can be directly used as binder-free electrodes to build advanced lithium-ion batteries with high energy, high safety and high stability.

APPLICATIONS AND MANUFACTURE OF THE MICROSCALE LONG-OPTICAL-PATH ELECTROCHEMICAL CELL WITH A PLUG-IN THIN-LAYER ELECTRODE

The construction and characteristics of a microscale long-optical-path electrochemi- cal cell with a plug-in thin-layer electrode are described.Using ferricyanide as the test species,the thermodynamic parameters of electron transfer processes are determined at car- bon,plantinum,and gold electrodes.

Efficient Thickness of Solid Oxide Fuel Cell Composite Electrode

The efficient thickness of a composite electrode for solid oxide fuel cells was directly calculated by developing a physical model taking into account of the charge transfer process, the oxygen ion and electron transportation, and the microstructure characteristics of the electrode. The efficient thickness, which is defined as the electrode thickness corresponding to the minimum electrode polarization resistance, is formulated as a function of charge transfer resistivity, effective resistivity to ion and electron transport, and three-phase boundary length per unit volume. The model prediction is compared with the experimental reports to check the validity. Simulation is performed to show the effect of microstructure, intrinsic material properties, and electrode reaction mechanism on the efficient thickness. The results suggest that when an electrode is fabricated, its thickness should be controlled regarding its composition, particle size of its components, the intrinsic ionic and electronic conductivities,and its reaction mechanisms as well as the expected operation temperatures. The sensitivity of electrode polarization resistance to its thickness is also discussed.

Review on transition metal compounds based counter electrode for dye-sensitized solar cells

Commercial application of the dye-sensitized solar cells（DSCs） depends on great improvement of the power conversion efficiency and reduction of the fabrication cost. Generally, developing low cost counter electrode catalysts to replace the expensive Pt counter electrode is a feasible path to reduce the production cost of DSCs. In this review article, we summarize the recent progress on the transition metal compound based counter electrode catalysts containing carbides, nitrides, oxides, sulfides, phosphide, selenides, borides, silicide, and telluride toward the regeneration of the traditional iodide redox couple.Moreover, the benefits and drawbacks of each kind of CE catalyst are discussed and the research directions to design new counter electrode catalysts in future research are also proposed.

A novel scrape-applied method for the manufacture of the membrane-electrode assembly of the fuel-cell system

This study investigates the transfer of the scrape-applied method from the electrodes of a lithium battery to the membrane-electrode assembly of fuel cells, including Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cell. Three methods are commonly used to manufacture lithium battery electrodes： the roller-applied method, the spraying-applied method, and the scrape-applied method. This study develops novel scrape-applied equip- ment for lithium battery electrodes. This method is novel and suitable for producing fuel cell, better than other tradi- tional methods. In this study, the stability of coating process was tested by measuring the weight and thickness of a dry electrode. The stability and reproducibility of electrode fab- rication were examined by systematic data analysis. Finally, the study used a specially designed single cell composed of 16 conductive segments, which are insulated locally. The current passing through each segment was measured using Hall Effect sensors connected to the segment compartments. Based on the measured distribution of the local current in a segmented single cell, the influence of flooding and stoi- chiometry variation of feed gas was discussed in terms of electrochemical reaction rate. The experimental results serve as an important basis for future research in this field, which hold potential benefits to the academia and the industry.

Effects of the Specific Area and the Thermal Stability of a Polymer on the Catalytic Activities of Polymer Immobilized Co-Pd Catalysts by SAMI

Co-Pd bimetallic catalysts immobilized with four kinds of resins with different specific areas were prepared by means of the solvated metal atom impregnation (SMAI) method. The results of the XRD and the magnetic measurement showed that as the specific area of the resin increased, the particle sizes of Co and Pd on the catalysts with the same metal content decreased, so the catalytic activity of the catalysts for the hydrogenation of diacetone alcohol as well as the reduction of oxygen on the fuel cell electrode increased. Below 140 , the conversion of diacetone alcohol increased as the reaction temperature increased, and above 140 , the conversion decreased because of the rupture of the resin.

Interfacial engineering of printable bottom back metal electrodes for full-solution processed flexible organic solar cells

Printing of metal bottom back electrodes of flexible organic solar cells（FOSCs） at low temperature is of great significance to realize the full-solution fabrication technology. However, this has been difficult to achieve because often the interfacial properties of those printed electrodes, including conductivity, roughness, work function,optical and mechanical flexibility, cannot meet the device requirement at the same time. In this work, we fabricate printed Ag and Cu bottom back cathodes by a low-temperature solution technique named polymer-assisted metal deposition（PAMD） on flexible PET substrates. Branched polyethylenimine（PEI） and ZnO thin films are used as the interface modification layers（IMLs） of these cathodes. Detailed experimental studies on the electrical, mechanical, and morphological properties, and simulation study on the optical properties of these IMLs are carried out to understand and optimize the interface of printed cathodes. We demonstrate that the highest power conversion efficiency over 3.0% can be achieved from a full-solution processed OFSC with the device structure being PAMDAg/PEI/P3 HT：PC61BM/PH1000. This device also acquires remarkable stability upon repeating bending tests.

Supported Cu/Ni Bimetallic Cluster Electrocatalysts Boost CO_(2) Reduction

Supported metal clusters with the integrated advantages of single-atom catalysts and conventional nanoparticles held great promise in the electrocatalytic carbon dioxide reduction(ECO_(2)R)operated at low overpotential and high current density.However,its precise synthesis and the understanding of synergisti-cally catalytic effects remain challenging.Herein,we report a facile method to synthesize the bimetallic Cu and Ni clusters anchored on porous carbon(Cu/Ni-NC)and achieve an enhanced ECO_(2)R.The aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy were employed to verify the metal dispersion and the coordination of Cu/Ni clusters on NC.As a result of this route,the target Cu/Ni-NC exhibits excellent electrocatalytic performance including a stable 30 h electrolysis at 200 mA cm^(-2) with carbon monoxide Faradaic efficiency of∼95.1%using a membrane electrode assembly electrolysis cell.Combined with the in situ analysis of the surface-enhanced Fourier transform infrared spectroelectrochemistry,we propose that the synergistic effects between Ni and Cu can effectively promote the H_(2)O dissociation,thereby accelerate the hydrogenation of CO_(2)to*COOH and the overall reaction process.

Photoelectrochemical properties of MWCNT-TiO_2 hybrid materials as a counter electrode for dye-sensitized solar cells

The MWCNT-Ti02 hybrid materials were prepared by a simply mixing method and used as a counter electrode （CE） for dye-sensitized solar cells. Compared with the platinum CE, MWCNT-TiO2 CE has the similar redox voltage and current response in the cyclic voltammetry. The electrochemical catalytic activity was characterized by the electrochemical impedance spectroscopy and Tafel curve, including the equivalent circuit, the exchange current density, the limiting diffusion current density, and the diffusion coefficient of triiodide/iodide redox species. The results indicate that the reduction process from triiodide to iodide is determined by the kinetic-controlled and diffusion-limited processes. The device performance is optimal based on the MWCNT-TiO2 （mass ratio of 2：1） CE, such as the open-circuit voltage of 0.72 V, the short-circuit photocurrent density of 15.71 mA/cm2, the fill factor of 0.68, and the photon-to-electron conversion efficiency of 7.69%.

Synthesis of α-Mo_2C by Carburization of α-MoO_3 Nanowires and Its Electrocatalytic Activity towards Tri-iodide Reduction for Dye-Sensitized Solar Cells

Nanowire-shaped α-Mo O3 was synthesized on a large scale by hydrothermal route.Nanocrystalline α-Mo2 C phase was obtained by the carburization of α-Mo O3 nanowires with urea as a carbon source precursor.The phase purity and crystalline size of the synthesized materials were ascertained by using powder X-ray diffraction.The shape and morphology of synthesized materials were characterized by field-emission scanning electron microscopy（FE-SEM） and high resolution transmission electron microscopy（HR-TEM）.The electrocatalytic activity of α-Mo2 C for I-/I3^-redox couple was investigated by the cyclic voltammetry.The synthesized α-Mo2 C was subsequently applied as counter electrode in dye-sensitized solar cells to replace the expensive platinum.

Fabrication and optimization of La_(0.4)Sr_(0.6)Co_(0.2)Fe_(0.7)Nb_(0.1)O_(3-δ) electrode for symmetric solid oxide fuel cell with zirconia based electrolyte

La（0.4）Sr（0.6）Co（0.2）Fe（0.7）Nb（0.1）O（3-δ）（LSCFN）was applied as both anode and cathode for symmetrical solid oxide fuel cells（SSOFCs）with zirconia based electrolyte.The cell with LSCFN electrode was fabricated by tape-casting and screen printing.Fabrication process was optimized firstly by comparing co-sintering and separate-sintering of electrode and electrolyte.To further improve the LSCFN electrode properties,oxygen ionic conductor of Gd（0.1）Ce（0.9）O（2-δ）（GDC）was added into the LSCFN electrode.The preferred composition of LSCFN-GDC composite electrode was found to be 1：1 in weight ratio with polarization resistance of 0.16Ωcm^2at 800~℃.The maximum power densities of LSCFN-GDC｜｜GDC/YSZ/GDC｜｜LSCFN-GDC tested in H2and CH4with 3%H2O were 395 m W cm^（-2）and 124 m W cm^（-2）at 850~？C,respectively,which were much higher than that of LSCFN｜｜GDC/YSZ/GDC｜｜LSCFN cells at same condition,possibly due to the extension of the triple phase boundary induced by the addition of GDC.The cell showed reasonable stability using H2and CH4with 3%H2O as fuels and no significant power output degradation was observed after total 200 h operation.

Improving photoelectrochemical activity of dye sensitized solar cell by a bilayered electrode with an overlayer of mesoporous anatase TiO_2

For better performance of dye sensitized solar cells （DSSCs）, a bilayer structured electrode was constructed by employing a mesoporous anatase TiO2 overlayer above a commercial P25 TiO2 nanoparticles underlayer. The mesoporous anatase TiO2, prepared through a facile surfactant-assisted sol-gel process, possessed large pore size and well inter-connected network structure, both beneficial for dye adsorption and electron transfer. The dye adsorption capability of the mesoporous TiO2 was nearly twice that of the P25 counterpart. In the electrode, the mesoporous TiO2 film enhanced both dye adsorption and lightharvest, to increase photocurrent （Jsc） from 12.32 to 14.78 mA/cm^2. Compared to the single P25 TiO2 film, the synergy of the mesoporous TiO2 and the P25 TiO2 nanoparticle films in the electrode resulted in a 24% improvement in light-to-electricity conversion efficiency （η）. This bilayered electrode provides an alternative approach for further developing a photovoltaic device with better cell performance.

Optical haze of transparent and conductive silver nanowire films

Contemporary nanostructured transparent electrodes for use in solar cells require high transmittance and high conductivity, dictating nanostructures with high aspect ratios. Optical haze is an equally important yet unstudied parameter in transparent electrodes for solar cells that is also determined by the geometry of the nanostructures that compose the electrode. In this work, the effect of the silver nanowire diameter on the optical haze values in the visible spectrum was investigated using films composed of wires with either small diameters （N60 nm） or large diameters （~150 nm）. Finite difference time domain （FDTD） simulations and experimental transmittance data confirm that smaller diameter nanowires form higher performing transparent conducting electrode （TCE） films according to the current figure of merit. While maintaining near constant transmittance and conductivity for each film, however, it was observed experimentally that films composed of silver nanowires with larger diameters have a higher haze factor than films with smaller diameters. This confirms the FDTD simulations of the haze factor for single nanowires with similarly large and small diameters. This is the first record of haze properties for Ag NWs that have been simulated or experimentally measured, and also the first evidence that the current figure of merit for TCEs is insufficient to evaluate their performance in solar cell devices.

Resistive switching characteristics of Ni/HfO_2/Pt ReRAM

This study investigated the resistive switching characteristics of the Ni/HfCVPt structure for nonvolatile memory application.The Ni/HfO_2/Pt device showed bipolar resistive switching（RS） without a forming process, and the formation and rupture of conducting filaments are responsible for the resistive switching phenomenon.In addition,the device showed some excellent memory performances,including a large on/off ratio（〉 3×10~5）,very good data retention（〉 10~3 s @ 200℃） and uniformity of switching parameters.Considering these results,the Ni/HfO_2/Pt device has the potential for nonvolatile memory applications.