Feasibility investigations on a novel micro-manufacturing process for fabrication of fuel cell bipolar plates: Internal pressure-assisted embossing of micro-channels with in-die mechanical bonding

In this paper, we present the results of our studies on conceptual design and feasibility experiments towards development of a novel hybrid manufacturing process to fabricate fuel cell bipolar plates that consists of multi-array micro-channels on a large surface area. The premises of this hybrid micro-manufacturing process stem from the use of an internal pressure-assisted embossing process (cold or warm) combined with mechanical bonding of double bipolar plates in a single-die and single-step operation. Such combined use of hydraulic and mechanical forming forces and in-process bonding will (a) enable integrated forming of micro-channels on both surfaces (as anode and cathode flow fields) and at the middle (as cooling channels), (b) reduce the process steps, (c) reduce variation in dimensional tolerances and surface finish, (d) increase the product quality, (e) increase the performance of fuel cell by optimizing flow-field designs and ensuring consistent contact resistance, and (f) reduce the overall stack cost. This paper explains two experimental investigations that were performed to characterize and evaluate the feasibility of the conceptualized manufacturing process. The first investigation involved hydroforming of micro-channels using thin sheet metals of SS304 with a thickness of 51 μm. The width of the channels ranged from 0.46 to 1.33 mm and the height range was between 0.15 and 0.98 mm. Our feasibility experiments resulted in that different aspect ratios of micro-channels could be fabricated using internal pressure in a controllable manner although there is a limit to very sharp channel shapes (i.e., high aspect ratios with narrow channels). The second investigation was on the feasibility of mechanical bonding of thin sheet metal blanks. The effects of different process and material variables on the bond quality were studied. Successful bonding of various metal blanks (Ni201, Al3003, and SS304) was obtained. The experimental results from both investigations demonstrated the feasibility of the proposed manufacturing technique for making of the fuel cell bipolar plates.     

汽轮机转子枞树型轮槽铣刀的制造研究

文了深入探讨．章在对枞树型轮槽精铣刀进行分析的基础上,结合实际生产经验,对其制造工艺流程、加工难点等问题进行并进一步对轮槽铣刀的关键加工技术进行了分析研究,制定出了合理有效的加工制造策略．为轮槽铣刀的加工制造提供了全面系统的技术参考．     

A well-dispersed catalyst on porous silicon micro-reformer for enhancing adhesion in the catalyst-coating process

A Cu/Mn/ZnO catalyst slurry was modified with polyvinyl alcohol (PVA) as a dispersant and organic binder. The slurry, which forms a crack-free coating, was injected directly into an open microchannel before anodic bonding with Pyrex glass. To improve adherence, porous silicon (pore size <1 μm) was fabricated in the microchannel. Ultrasonic vibration test (180 W, 20 min) showed good adhesion with only 6 wt.% loss. The thicker catalyst layer, with lower thermal diffusivity (0.98 mm²/s), reduced heat loss during reaction on cratered design and performed better than two other geometric designs (blank, straight). The microchannel with cratered design can be deposited with a catalyst up to 24.4 mg, and has a hydrogen production rate of 0.85 mmol h⁻¹ and 86% methanol conversion at 200 °C under a feed rate of 2SCCM.     

The sol-gel route: A versatile process for up-scaling the fabrication of gas-tight thin electrolyte layers

Sol-gel routes are often investigated and adapted to prepare, by suitable chemical modifications, submicronic powders and derived materials with controlled morphology, which cannot be obtained by conventional solid state chemistry paths. Wet chemistry methods provide attractive alternative routes because mixing of species occurs at the atomic scale. In this paper, ultrafine powders were prepared by a novel synthesis method based on the sol-gel process and were dispersed into suspensions before processing. This paper presents new developments for the preparation of functional materials like yttria-stabilized-zirconia (YSZ, 8% Y₂O₃) used as electrolyte for solid oxide fuel cells. YSZ thick films were coated onto porous Ni-YSZ substrates using a suspension with an optimized formulation deposited by either a dip-coating or a spin-coating process. The suspension composition is based on YSZ particles encapsulated by a zirconium alkoxide which was added with an alkoxide derived colloidal sol. The in situ growth of these colloids increases significantly the layer density after an appropriated heat treatment. The derived films were continuous, homogeneous and around 20 μm thick. The possible up-scaling of this process has been also considered and the suitable processing parameters were defined in order to obtain, at an industrial scale, homogeneous, crack-free, thick and adherent films after heat treatment at 1400 °C.     

A novel method for producing hydrogen based on the Ca–Br cycle

The Ca–Br cycle is a promising method for efficiently producing hydrogen from water; however, it suffers from limitations inherent to gas–solid reactions. The cycle depends on the repeatable transformation of calcium bromide to calcium oxide and back to calcium bromide. The use of pure solids for these reactions would lead to rapid particle degradation and slow reaction kinetics. To circumvent these problems, a new reactor concept based on molten calcium bromide with dissolved calcium oxide has been proposed and developed. Preliminary experimental results indicate that the solubility of calcium oxide in calcium bromide at 800 °C is at least 1.2 wt%, a level that is expected to be high enough to make the proposed process work as designed. Early attempts to hydrolyze molten calcium bromide indicated that solid calcium oxide formation may inhibit reactivity, and thus injection of the moisture into the salt must be optimized.     

A novel beam-down,gravity-fed,solar thermochemical receiver/reactor for direct solid particle decomposition: Design,modeling, and experimentation

A novel solar-thermochemical reactor for the reduction of ZnO powder using concentrated sunlight has been designed, constructed and tested. The purpose of the reactor is to accomplish the first step in a two-step water-splitting process to generate hydrogen renewably from sunlight using the ZnO redox cycle. Abbreviated as GRAFSTRR (Gravity-Fed Solar-Thermochemical Receiver/Reactor), the reactor is closed to the atmosphere, and features an inverted conical-shaped reaction surface along which reactant powder descends continuously as a moving bed, undergoing a thermochemical reaction at high temperature upon exposure to highly concentrated sunlight within the reaction cavity. Heat transfer and Zn production within the cavity have been modeled, as well as the influence of effective reactant particle size on reactive surface area. Initial experiments using a high-flux solar simulator successfully demonstrated the mechanical stability of the reactor and primary systems, namely particle entrainment in the vortex flow, moving bed adhesion to the reaction surface, and the solid particle delivery and exit mechanism. This paper presents the GRAFSTRR concept, select design choices, and a summary of pertinent findings from experimental and numerical investigations.     

Bio-hydrogen production based on catalytic reforming of volatiles generated by cellulose pyrolysis: An integrated process for ZnO reduction and zinc nanostructures fabrication

The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor-solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H₂ when compared to pure cellulose. The process was also carried out in a tubular furnace with N₂ atmosphere, at temperatures up to 900 °C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.     

A novel approach to improve the mathematical modelling of the internal reforming process for solid oxide fuel cells using the orthogonal least squares method

This paper presents a novel approach to experimental and numerical investigations of the methane/steam reforming reaction process over a nickel/yttria-stabilized zirconia fine powder catalyst. Methane/steam reforming is primarily considered as a hydrogen production process for Solid Oxide Fuel Cells, and therefore its reaction kinetic was investigated experimentally and numerically. The present paper describes the innovative implementation of an orthogonal least squares (generalized least squares: GLS) algorithm for the calculation of the reaction kinetics involving precise information and the uncertainties of the obtained results. The GLS method was applied to evaluate the reaction rate and therefore fractional conversion of methane. An analysis of the mathematical model points out that the experimental inaccuracy could be reduced and allowed for the calculation of the most probable values of kinetic parameters and their uncertainties. The GLS method secures a higher accuracy of measured data and estimates the most probable value of all model parameters.     

A novel co-precipitation method for preparation of Pt-CeO2 composites on multi-walled carbon nanotubes for direct methanol fuel cells

Ceria (CeO₂) as co-catalytic material with Pt on multi-walled carbon nanotubes (Pt-CeO₂/MWCNT) is synthesized by a co-precipitation method. The physicochemical characterizations of the catalysts are carried out by using transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) techniques. Electrocatalytic activities of the catalysts for methanol oxidation is examined by cyclic voltammetry and chronoamperometry techniques and it is found that Pt-CeO₂/MWCNT catalysts exhibited a better activity and stability than did the unmodified Pt/MWCNT catalyst. CO-stripping results indicate the facile removal of intermediate poisoning species CO in the presence of CeO₂, which is helpful for CO and methanol electro-oxidation.     

A novel Swiss-roll micro-combustor with double combustion chambers: A numerical investigation on effect of solid material on premixed CH4/air flame blow-off limit

A novel Swiss-roll micro-combustor with double combustion chambers is proposed to improve flame stability and extend blow-off limits. This study is aimed to numerically investigate the effect of solid material (i.e., SiC, stainless steel and copper) on premixed CH₄/air flame blow-off limit and reveal the flame stability mechanism. The simulated results show that this developed novel Swiss-roll micro-combustor not only can significantly anchor the flame owing to the flow recirculation behind the flame holders and the backward-facing steps, but also can further extend CH₄ blow-off limits owing to heat recirculation in the long Swiss-roll preheating channels. The three solid material micro-combustors present the relatively slight difference in the recirculation-zone size but the remarkably difference in heat recirculation and heat loss. Good heat recirculation and low heat loss rate are the dominant reason that is responsible for the differences of the blow-off limits in this micro-combustor. The stainless steel micro-combustor achieves the highest blow-off limits while the copper micro-combustor achieves the lowest blow-off limit. These deep insights can give some useful information to design a similar Swiss-roll micro-combustor.     

Thermodynamic study on the integrated supercritical water gasification with reforming process for hydrogen production: Effects of operating parameters

In this paper, a conceptual process design of the integrated supercritical water gasification (SCWG) and reforming process for enhancing H₂ production has been developed. The influence of several operating parameters including SCWG temperature, SCWG pressure, reforming temperature, reforming pressure and feed concentration on the syngas composition and process efficiency was investigated. In addition, the thermodynamic equilibrium calculations have been carried out based on Gibbs free energy minimization by using Aspen Plus. The results showed that the higher H₂ production could be obtained at higher SCWG temperature, the H₂ concentration increased from 5.40% at 400 °C to 38.95% at 600 °C. The lower feed concentration was found to be favorable for achieving hydrogen-rich gas. However, pressure of SCWG had insignificant effect on the syngas composition. The addition of reformer to the SCWG system enhanced H₂ yield by converting high methane content in the syngas into H₂. The modified SCWG enhanced the productivity of syngas to 151.12 kg/100kg_feed compared to 120.61 kg/100kg_feed of the conventional SCWG system. Furthermore, H₂ yield and system efficiency increased significantly from 1.81 kg/100kg_feed and 9.18% to 8.91 kg/100kg_feed, and 45.09%, respectively, after the modification.     

Toward low-cost Pd/ceramic composite membranes for hydrogen separation: A case study on reuse of the recycled porous Al2O3 substrates in membrane fabrication

The development of hydrogen energy systems has placed a high demand on hydrogen-permeable membranes as compact hydrogen separators and purifiers. Although Pd/Ceramic composite membranes are particularly effective in this role, the high cost of these membranes has greatly limited their applications; this high cost stems largely from the use of expensive substrate material. This problem may be solved by substrate recycling and the use of lower cost substrates. As a case study, we employed expensive asymmetric microporous Al₂O₃ and low-cost macroporous symmetric Al₂O₃ as membrane substrates (average pore sizes are 0.2 and 3.3 μm, respectively). The palladium membranes were fabricated by electroless plating, and substrate recycling was carried out by palladium dissolution with a hot HNO₃ solution. The functional surface layer of the microporous Al₂O₃ was damaged during substrate recycling, and the reuse of the substrate led to poor membrane selectivity. With the assistance of pencil coating as a facile and environmentally benign surface treatment, the macroporous Al₂O₃ can be successfully utilized. Furthermore, the macroporous Al₂O₃ can be also recycled and reused as membrane substrate, yielding highly permeable, selective and stable palladium membranes. Consequently, the substrate cost can be further decreased, and the applications of this kind of membranes would expand.     

A novel integration of a green power-to-ammonia to power system: Reversible solid oxide fuel cell for hydrogen and power production coupled with an ammonia synthesis unit

Renewable energy is a key solution in maintaining global warming below 2 °C. However, its intermittency necessitates the need for energy conversion technologies to meet demand when there are insufficient renewable energy resources. This study aims to tackle these challenges by thermo-electrochemical modelling and simulation of a reversible solid oxide fuel cell (RSOFC) and integration with the Haber Bosch process. The novelty of the proposed system is usage of nitrogen-rich fuel electrode exhaust gas for ammonia synthesis during fuel cell mode, which is usually combusted to prevent release of highly flammable hydrogen into the environment. RSOFC round-trip efficiencies of 41–53% have been attained when producing excess ammonia (144 kg NH₃/hr) for the market and in-house consumption respectively. The designed system has the lowest reported ammonia electricity consumption of 6.4–8.21 kWh/kg NH₃, power-to-hydrogen, power-to-ammonia, and power-generation efficiencies of 80%, 55–71% and, 64–66%.     

A novel flow battery: A lead acid battery based on an electrolyte with soluble lead(II) Part VIII. The cycling of a 10 cm × 10 cm flow cell

The design of a 10 cm × 10 cm flow cell for the soluble lead acid flow battery is described. A number of extended charge/discharge cycling experiments are presented to demonstrate the capability of the battery to cycle over lengthy periods and to identify the problems that limit the number of cycles that can be achieved. A charge efficiency below 100%, leading to a build up of deposits on both electrodes and a consequent drop in the concentration of Pb²⁺ in the electrolyte are found to limit cycle life.