Perborate as novel fuel for enhanced performance of membraneless fuel cells

This paper presents the development of membraneless sodium perborate fuel cell using acid/alkaline electrolyte. In the acid/alkaline electrolyte, perborate works both as an oxidant as well as reductant. Sodium perborate affords hydrogen peroxide in aqueous medium. The cell converts the energy released by H₂O₂ decomposition with H⁺ and OH^? ions into electricity and produces water and oxygen. Such a novel design eliminates the need of a membrane, in which acid and alkaline electrolytes contact with each other. At room temperature, the laminar flow-based microfluidic membraneless fuel cell can reach a maximum power density of 34 mW/cm² with the molar ratio of [Perborate]/[NaOH]?=?1 as fuel and [Perborate]/[H₂SO₄]?=?2 as oxidant. The paper reports for the first time the use of sodium perborate as the oxidant and reductant. The developed fuel cell emits no CO₂, features no proton exchange membrane, inexpensive catalysts, and simple planar structure, which enables high design flexibility and easy integration of the microscale fuel cell into actual microfluidic systems and portable power applications.     

Oxide anode materials for solid oxide fuel cells

A major advantage of solid oxide fuel cells (SOFCs) over polymer electrolyte membrane (PEM) fuel cells is their tolerance for the type and purity of fuel. This fuel flexibility is due in large part to the high operating temperature of SOFCs, but also relies on the selection and development of appropriate materials — particularly for the anode where the fuel reaction occurs. This paper reviews the oxide materials being investigated as alternatives to the most commonly used nickel–YSZ cermet anodes for SOFCs. The majority of these oxides form the perovskite structure, which provides good flexibility in doping for control of the transport properties. However, oxides that form other crystal structures, such as the cubic fluorite structure, have also shown promise for use as SOFC anodes. In this paper, oxides are compared primarily in terms of their transport properties, but other properties relative to SOFC anode performance are also discussed.     

Preparation and characterization of carbon-related materials supports for catalysts of direct methanol fuel cells

In this work, two types of carbon materials such as CBs and GNFs were treated by a fluorination in order to study the effect of surface modification. The carbon-supported platinum (Pt) and ruthenium (Ru) catalysts were prepared using two types of carbon materials to check the influence of the fluorinated carbon supports on the activity of catalysts. The crystalline characteristics of the carbon-supported catalysts were determined by XRD method. Electrochemical properties of the electrocatalysts were analyzed by cyclic voltammetry (CV) experiments. When fluorinated GNFs were used as catalyst supports, the current density obtained in fuel cell was greater than that of CBs-supported catalyst; meaning GNFs-supported catalysts had a higher performance relative to CBs-supported catalysts. These results were supported with the CV results that showed the greater activity for PtRu at higher potentials.     

Influence of fuel and media on membraneless sodium percarbonate fuel cell

This paper reports the media flexibility of membraneless sodium percarbonate fuel cell (MLSPCFC) using acid/alkaline bipolar electrolyte in which the anode is in acidic media while the cathode is in alkaline media, or vice versa. Investigation of the cell operation is conducted by using formic acid as a fuel and sodium percarbonate as an oxidant for the first time under ‘acid–alkaline media’ configurations. The MLSPCFC architecture enables interchangeable operation with different media combinations. The experimental results indicate that operating under acid–alkaline media conditions significantly improves the fuel cell performance compared with all-acidic and all-alkaline conditions. The effects of flow rates and the concentrations of various species at both the anode and cathode on the cell performance are also investigated. It has been demonstrated that the laminar flow-based microfluidic membraneless fuel cell can reach a maximum power density of 25.62 mW cm^?2 with a fuel mixture flow rate of 0.3 mL min^?1 at room temperature.     

Lanthanum chromite as an anode material for solid oxide fuel cells

The electrochemical behavior of pure lanthanum chromite and strontium dopedlanthanum chromite was studied by impedance spectroscopy under H₂/H₂O, CO/CO₂ and CH₄/H₂O. Results show that the electrochemical oxidation of H₂ is faster than that of CO or CH₄. Strontium doping enhances the anodic activity of the material. The impedance diagrams are composed of two semi-circles. The high frequency one does not appear to be related to a chemical or electrochemical reaction. The low frequency one is linked to the nature and concentration of the electroactive species. Paper presented at the 4th Euroconference on Solid State Ionics in Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Complexed sol-gel synthesis of improved Pt-Ru-Os-based anode electro-catalysts for direct methanol fuel cells

A high specific surface area (SSA) Pt-Ru-Os-based anode catalyst synthesized by a novel complexed sol-gel (CSG) process shows better catalytic activity in comparison to pure equi-atomic compositions of Pt-Ru anode catalysts synthesized by similar sol-gel processes. A homogeneous amorphous gel was successfully synthesized by complexing platinum(II) acetylacetonate, ruthenium(III) acetylacetonate and osmium(III) chloride with tetramethylammonium hydroxide (TMAH) used as a complexing agent. Phase-pure Pt(Ru,Os) and Pt(Ru) solid solutions possessing high specific surface area (∼110-120 m²/g) were successfully synthesized by controlled removal of carbonaceous species present in the as-prepared precursor generated from the CSG process. This has been successfully achieved by precise thermal treatments of the precursor using controlled oxidizing atmospheres. Results indicate that the nano-crystalline Pt(Ru,Os) solid solution of nominal composition 50 at%-Pt-40 at% Ru-10 at% Os possesses good chemical homogeneity, and reveals excellent catalytic activity, thus demonstrating the potential of the novel CSG process for synthesizing high-performance Pt-Ru-Os-based catalysts for direct methanol fuel cells.     

Microstructure and performance of novel Ni anode for hollow fibre solid oxide fuel cells

Nickel anodes were deposited on hollow fibre yttria-stabilised zirconia (YSZ) electrolyte substrates for use in solid oxide fuel cells (SOFCs). The hollow fibres are characterised by porous external and internal surfaces supported by a central gas-tight layer (300 μm total wall thickness and 1.6 mm external diameter). The YSZ hollow fibres were prepared by a phase inversion technique followed by high temperature sintering in the range 1200 to 1400 °C. Ni anodes were deposited on the internal surface by electroless plating involving an initial catalyst deposition step with PdCl₂ followed by Ni plating (with a NiSO₄, NaH₂PO₂ and sodium succinate based solution at 70 °C). Fabrication and nickel deposition parameters (nature of solvents, air gap, temperature, electroless bath composition) and heat treatments in oxidising/reducing environments were investigated in order to improve anode and electrolyte microstructure and fuel cell performance. A parallel study of the effect of YSZ sintering temperature, which influences electrolyte porosity, on electrolyte/anode microstructure was performed on mainly dense discs (2.3 mm thick and 15 mm diameter). Complete cells were tested with both disc and hollow fibre design after a La_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (LSCF) cathode was deposited by slurry coating and co-fired at 1200 °C. Anodes prepared by Ni electroless plating on YSZ electrolytes (discs and hollow fibres) sintered at lower temperature (1000–1200 °C) benefited from a greater Ni penetration compared to electrolytes sintered at 1400 °C. Further increases in anode porosity and performance were achieved by anode oxidation in air at 1200–1400 °C, followed by reduction in H₂ at 800 °C.     

Successive electrodeposition of polydopamine and PtPd metal on a graphene oxide support for use as anode fuel cell catalysts

Successive electropolymerization of dopamine and electrodeposition of Pd and/or Pt on a graphene oxide (GO) support were used to prepare anode catalysts for low-temperature fuel cells. Transmission electron microscopy images were used to investigate the morphologies and distribution of the prepared catalysts, which showed the metal formed as nanoparticles on the catalysts. The GO surface was favorable for the modification with electropolymerized polydopamine (PDA) and the electrodeposition of metal catalyst nanoparticles using a simple preparation process. The PDA-loaded GO composite was used as a matrix for the dispersion of Pt and Pd nanoparticles. GO could be simultaneously modified by PDA and reduced without using reducing agents. The electrocatalytic performance of the catalysts for the oxidation of selected small molecule fuels (e.g., methanol, ethanol and formic acid) was examined. An outstanding catalytic activity and stability was found for the prepared Pt/Pd/PDA/GO composite, which was attributed to the high active surface area.     

Hydrogenase-based nanomaterials as anode electrode catalyst in polymer electrolyte fuel cells

We consider hydrogenase-based nanomaterials for possible use as anode electrode catalysts in polymer electrolyte fuel cells (PEFCs). We choose Fe-only hydrogenase component of Desulfovibrio desulfuricans (DdHase) as a hydrogenase complex, and investigate its catalytic activity for H₂ dissociation using ab initio calculations based on density functional theory (DFT). We found two possible H-H bond cleavage pathways, which are heterolytic and possess low activation barriers. Moreover, the H₂ dissociation can be promoted by inducing spin polarization of the H₂ adduct. We report that hydrogenase or hydrogenase-based nanomaterials can manipulate to exhibit the catalytic activity equivalent to the well-known platinum catalyst.     

Electrochemical performance of ceria-gadolinia electrolyte based direct carbon fuel cells

A direct carbon fuel cell offers a high efficiency alternative to traditional coal fired electrical power plants. In this paper, the electrochemical performance of electrolyte supported button cells with Gd₂O₃-doped CeO₂ (CGO) electrolyte is reported over the temperature range 600 to 800 °C with solid carbon as a fuel and He/CO₂ as the purge gases in the fuel chamber. The electrochemical characterisation of the cells was carried out by the Galvanostatic Current Interruption (GCI) technique and measuring V-I and P-I curves. Power densities over 50 mWcm^-2 have been demonstrated using carbon black as the fuel. Results indicate that at low temperatures around 600 °C, the direct electrochemical oxidation of carbon takes place. However, at higher temperatures (800 °C) both direct electrochemical oxidation and the reverse Boudouard reaction take place leading to some loss in fuel cell thermodynamic efficiency and reduced fuel utilisation due to the in-situ production of CO. In order to avoid reverse Boudouard reaction whilst maximising performance, an operating temperature of around 700 °C appears optimal. Further, the electrochemical performance of fuel cells has been compared for graphite and carbon black fuels. It was found that graphitic carbon fuel is electrochemically less reactive than relatively amorphous carbon black fuel in the DCFC when tested under similar conditions.     

The modification of anode material for direct borohydride fuel cell

The direct borohydride fuel cell (DBFC) is a promising device that converts chemical energy into electricity by electrochemical reactions. This type of power source is technically more simple than traditional fuel cells, because it does not require any hydrogen container and noble metals. Hydrogen evolution during hydrolysis can be inhibited by modification of anode materials. Extensive studies are focused on various specific electrocatalysts and their impact on oxidation and hydrolysis of borohydride. The aim of the study is to determine the effect of anode material composition using borohydride as a fuel. In order to enhance the utilization of borohydride fuel, AB₅-type alloy (LaMnNi_3.55Al_0.30Mn_0.40Co_0.75) was modified by adding Si or two kinds of carbon materials using the ball milling method. The most proper electrolyte was selected. The physical and electrochemical properties of anode materials were evaluated by scanning electron microscopy (SEM), cyclic voltammetry, chronopotentiometric measurements and electrochemical impedance spectroscopy. Studies showed that graphite was the best additive to anode material due to its density, compact structure and improvement of conductivity.

     

Interaction of samaria-doped ceria anode with highly dispersed Ni catalysts in a medium-temperature solid oxide fuel cell during long-term operation

Mixed conducting samaria-doped ceria (SDC) anode with highly dispersed Ni catalysts exhibited a stable high performance over 1100 h in solid oxide fuel cell (SOFC) operated at constant current density of 0.6 A cm^− 2 at 800 °C. While the apparent average size of Ni particles was found to be increased, both the IR-free polarization performance (reflecting an effective reaction area) and the ohmic resistance (reflecting an electronic network) were not changed noticeably during the long-term operation. It was found by scanning electron microscope (SEM) and scanning transmission electron microscope (STEM) that Ni particles were rather stabilized by changing the morphology at the portion contacting with SDC surface presumably due to a strong interaction.     

Synthesis and characterization of nanoparticulate films for intermediate temperature solid oxide fuel cells

Nanocrystalline strontium-doped lanthanum manganite (LSM) with a high specific surface area of 70 m²/g was synthesized via spray pyrolysis. The as prepared powder was characterized by ex-situ X-ray diffraction (XRD), in-situ high temperature X-ray diffraction (HTXRD), ex-situ nitrogen adsorption and high resolution scanning electron microscopy (HRSEM). LSM nanopowders with a mean particle size of 40 nm were dispersed in water-based media using ultrasonication. Nanocomposite LSM-GDC (gadolinium doped ceria) thin films were prepared by single step spin coating of co-stabilized LSM and GDC dispersions. The thickness of these thin films (≤ 1 μm) is more than 10 times lower than conventional cathode layers prepared by screen printing. The interfacial polarization resistances were 68, 118 and 220 mΩ cm² at 850, 800 and 750 °C, respectively. The high performance is attributed to small grain size, high porosity and large specific surface area. This method offers a very cost effective approach for the preparation of electrochemically highly active porous thin films, particularly applicable for micro solid oxide fuel cells.     

Electrochemical properties of metal oxides as anode materials for lithium ion batteries

Some oxides have been investigated as alternative materials for Li-ion batteries. In particular, the In₂O₃ anodic compound, synthesized in our laboratory, and some commercial powders (PbO, PbO₂ and Fe₂O₃) were studied. The morphology of the oxides was analyzed by SEM investigation. The electrochemical characteristics obtained on composite thin-film electrodes based on these materials are here reported, in term of specific capacity and cyclability. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Ceramic materials as supports for low-temperature fuel cell catalysts

The performance and durability of low-temperature fuel cells seriously depend on catalyst support materials. Catalysts supported on high surface area carbons are widely used in low temperature fuel cells. However, the corrosion of carbonaceous catalyst-support materials such as carbon black has been recognized as one of the causes of performance degradation of low-temperature fuel cells, in particular under repeated start-stop cycles or high-potential conditions. To improve the stability of the carbon support, materials with a higher graphitic character such as carbon nanotubes and carbon nanofibers have been tested in fuel cell conditions. These nanostructured carbons show a several-fold lower intrinsic corrosion rate, however, do not prevent carbon oxidation, but rather simply decrease the rate. Due their high stability in fuel cell environment, ceramic materials (oxides and carbides) have been investigated as carbon-substitute supports for fuel cell catalysts. Moreover, the higher specific electrocatalytic activity of some ceramic supported metals than unsupported and carbon supported ones, suggests the possibility of a synergistic effect by supporting metal catalyst on ceramic supports. This paper presents an overview of ceramic materials tested as a support for fuel cell catalysts, with particular attention addressed to the electrochemical activity and stability of the supported catalysts.     

Electrical properties of yttrium doped strontium titanate with A-site deficiency as potential anode materials for solid oxide fuel cells

Yttrium doped strontium titanate with A-site deficiency ((Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ) was synthesized by conventional solid state reaction. The deficiency limit of A-site in (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ is below 6 mol% in Ar/H₂ (5%) at 1500 °C. The sinterability of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples decreases slightly with increasing A-site deficiency level (x). The ionic conductivity of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples increases while the electronic conductivity decreases with increasing A-site deficient amount. The defect chemistry analysis indicates that the introduction of A-site deficiency results in not only the increase of oxygen vacancy concentration but also the decrease of Ti³⁺-ion concentration. The latter plays the main role in the electrical conduction. (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ shows good thermal-cyclic performance in electrical conductivity and has an excellent chemical compatibility with YSZ electrolyte below 1500 °C.     

Electrochemical properties of rutile TiO2 nanorods as anode material for lithium-ion batteries

In this paper, we synthesized rutile TiO₂ nanorods by hydrolysis of TiCl₄ ethanolic solution in water at 50?°C. Scanning electron microscopy and transmission electron microscopy images show that the as-prepared sample was consisted of nanoflowers of about 500?nm in sizes, and each petal of nanoflowers was assembled by several nanorods. We tested the electrochemical properties of the rutile TiO₂ nanorods as an anode material for lithium-ion batteries. The rutile TiO₂ nanorods exhibited a large initial discharge capacity of 223?mA?h?g^?1, and the stabilized capacity was as high as 170?mA?h?g^?1 after 100 cycles. These improved electrochemical performances may be attributed to the shorter diffusion length for both the electron and Li⁺, and the large electrode?Celectrolyte contact area offered by the nanorods with a large specific surface area, which facilitated the lithium ions insertion and extraction.     

Electrochemical performance of modified artificial graphite as anode material for lithium ion batteries

Artificial graphite anode material was modified by coating an amorphous carbon layer on the particle surface via a sol-gel and pyrolysis route. The electrochemical measurements demonstrate that appropriate carbon coating can increase the specific capacity and the initial coulombic efficiency of the graphite material, while excessive carbon coating leads to the decrease in specific capacity. Thick coating layer is obviously unfavorable for the lithium ion diffusion due to the increased diffusion distance, but the decreased specific surface area caused by carbon coating is beneficial to the decrease of initial irreversible capacity loss. The sample coated with 5 wt.% glucose exhibits a stable specific capacity of 340 mAhg^?1. Carbon coating can remarkably enhance the rate capability of the graphite anode material, which is mainly attributed to the increased diffusion coefficient of lithium ion.     

Fabrication and characterization of hermetic solid oxide fuel cells without sealant

A simplified solid oxide fuel cell (SOFC) design has been developed that would eliminate the need for external sealants yet maintains the hermetic requirements necessary for separation of fuel from oxidant. This hermetic seal is based on the formation of a solid-state interface, between the electrolyte and the interconnect. The novel SOFC design eliminates unnecessary interface formation and material addition, thus greatly simplifying fuel cell stacks. Overcasting and co-casting techniques were used to fabricate symmetric cell and lateral geometries in order to examine the interfacial characteristics of the hermetic structure and particularly the solid-state seal. Leakage rates determined from mass spectrometry were about 4.57 * 10^− 7 L/s at 750 °C.