Comparative analysis between a PEM fuel cell and an internal combustion engine driving an electricity generator: Technical, economical and ecological aspects

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Creazione e sviluppo di un sistema di controllo in tempo reale per un sistema fuel cell

The control of a proton exchange membrane fuel cell system (PEM FC) for domestic heat and power supply requires extensive control measures to handle the complicated process. Highly dynamic and non linear behavior, increase drastically the difficulties to find the optimal design and control strategies. The objective is to design, implement and commission a controller for the entire fuel cell system. The fuel cell process and the control system are engineered simultaneously; therefore there is no access to the process hardware during the control system development. Therefore the method of choice was a model based design approach, following the rapid control prototyping (RCP) methodology. The fuel cell system is simulated using a fuel cell library which allowed thermodynamic calculations. In the course of the development the process model is continuously adapted to the real system. The controller application is designed and developed in parallel and thereby tested and verified against the process model. Furthermore, after the commissioning of the real system, the process model can be also better identified and parameterized utilizing measurement data to perform optimization procedures. The process model and the controller application are implemented in Simulink using Mathworks` Real Time Workshop (RTW) and the xPC development suite for MiL (model-in-theloop) and HiL (hardware-in-the-loop) testing. It is possible to completely develop, verify and validate the controller application without depending on the real fuel cell system, which is not available for testing during the development process. The fuel cell system can be immediately taken into operation after connecting the controller to the process.

The colloidal tool-box approach for fuel cell catalysts: Systematic study of perfluorosulfonate-ionomer impregnation and Pt loading

In this study, the correlation between the impregnation of proton exchange membrane fuel cell catalysts with perfluorosulfonate-ionomer (PFSI) and its electrochemical and electrocatalytic properties is investigated for different Pt loadings and carbon supports using a rotating-disk electrode (RDE) setup. We concentrate on its influence on the electrochemical surface area (ECSA) and the oxygen reduction reaction (ORR) activity. For this purpose, platinum (Pt) nanoparticles are prepared via a colloidal based preparation route and supported on three different carbon supports. Based on RDE experiments, we show that the ionomer has an influence both on the Pt utilization and the apparent kinetic current density of ORR. The experimental data reveal a strong interaction in the microstructure between the electrochemical properties and the surface properties of the carbon supports, metal loading and ionomer content. This study demonstrates that the colloidal synthesis approach offers interesting potential for systematic studies for the optimization of fuel cell catalysts.

Computational modeling of intermediate temperature proton exchange membrane (PEM) fuel cells

A two-phase three-dimensional computational model of an intermediate temperature (120--190°C) proton exchange membrane (PEM) fuel cell is presented. This represents the first attempt to model PEM fuel cells employing intermediate temperature membranes, in this case, phosphoric acid doped polybenzimidazole (PBI). To date, mathematical modeling of PEM fuel cells has been restricted to low temperature operation, especially to those employing Nafion ® membranes; while research on PBI as an intermediate temperature membrane has been solely at the experimental level. This work is an advancement in the state of the art of both these fields of research. With a growing trend toward higher temperature operation of PEM fuel cells, mathematical modeling of such systems is necessary to help hasten the development of the technology and highlight areas where research should be focused.^ This mathematical model accounted for all the major transport and polarization processes occurring inside the fuel cell, including the two phase phenomenon of gas dissolution in the polymer electrolyte. Results were presented for polarization performance, flux distributions, concentration variations in both the gaseous and aqueous phases, and temperature variations for various heat management strategies. The model predictions matched well with published experimental data, and were self-consistent.^ The major finding of this research was that, due to the transport limitations imposed by the use of phosphoric acid as a doping agent, namely low solubility and diffusivity of dissolved gases and anion adsorption onto catalyst sites, the catalyst utilization is very low (∼1--2%). Significant cost savings were predicted with the use of advanced catalyst deposition techniques that would greatly reduce the eventual thickness of the catalyst layer, and subsequently improve catalyst utilization. The model also predicted that an increase in power output in the order of 50% is expected if alternative doping agents to phosphoric acid can be found, which afford better transport properties of dissolved gases, reduced anion adsorption onto catalyst sites, and which maintain stability and conductive properties at elevated temperatures.^

Sulfonated poly(arylene-co-imide)s as water stable proton exchange membrane materials for fuel cells

A novel sulfonated poly(arylene-co-imide)s were synthesized by Ni(0) catalytic copolymerization of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and naphthalimide dichloride monomer. The synthesized copolymers with the - SO3H group on the side-chain of polymers possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. Because of the introduction of electron donating phenoxy groups into naphthalimide moieties, the hydrolysis of the imide rings was depressed. The resulting copolymers exhibited excellent water stability. The copolymer membranes display no apparently change in appearance, flexibility, and toughness after a soaking treatment in pressurized water at 140 degrees C for 250 h.

Blends based on sulfonated poly[bis(benzimidazobenzisoquinolinones)] and poly(vinylidene fluoride) for polymer electrolyte membrane fuel cell

A new blend system consisting of an amorphous sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI) and the semi-crystalline poly(vinylidene fluoride) (PVDF) was prepared for proton exchange membranes. The miscibility behavior of a series of blends of SPBIBI with PVDF at various weight ratios was studied by WXRD, DSC and FTIR. The properties of the blend membranes were investigated, and it was found that the introduction of PVDF in the SPBIBI matrix altered the morphological structure of the blend membranes, which led to the formation of improved connectivity channels. For instance, the conductivity of the blend membrane containing 10 wt% PVDF displayed the highest proton conductivity (i.e., 0.086 S cm(-1)) at room temperature, a value almost twofold that of the pristine SPBIBI membranes (i.e., 0.054S cm(-1)) under identical conditions.

Synthesis and properties of water stable poly[bis(benzimidazobenzisoquinolinone)] ionomers for proton exchange membranes fuel cells

A novel sulfonated tetraamine, di(triethylammonium)-4,4'-bis(3,4-diaminophenoxy)biphenyl-3,3'-disulfonate (BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4'-dihydroxybiphenyl with 5-chloro-2-nitroaniline, followed by sulfonation and reduction. A high-temperature polycondensation of sulfonated tetraamine, non-sulfonated tetraamine (4,4 -bis(3,4-aminophenoxy)biphenyl) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (a) or 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianydride (b) gave the poly[bis(benzimidazobenzisoquinolinones)] ionomers SPBIBI-a(x) or SPBIBI-b(x), where x refers to the molar percentage of the sulfonated tetraamine monomer. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The ionomer membranes displayed excellent dimensional and hydrolytic stabilities.

RuxNb1-xO2 catalyst for the oxygen evolution reaction in proton exchange membrane water electrolysers

Bimetallic catalyst system of ruthenium oxide (RuO) and niobium oxide (NbO) was prepared using the Adams method and the hydrolysis method. Physical and electrochemical characterizations of the catalysts were studied using X-ray diffraction (XRD), Scanning electron microscopy (SEM), cyclic voltammogram (CV) and polarization measurements. NbO addition to RuO was found to increase the stability of RuO. In Adams method the sodium nitrate was found to be forming complex with NbO at high temperature reaction. This makes Adams method unsuitable for the synthesis of RuO -NbO bimetallic system. Hydrolysis method on other hand does not have this problem. But a proper mixture of two oxides was not obtained in hydrolysis method. A lower crystallite size for bimetallic system was obtained with Adams method compared to hydrolysis method. RuO prepared by Adams method had higher activity compared to the hydrolysis counterpart in electrolyzer operation with nafion membrane. A cell voltage of 1.62 V was obtained with RuO (A) at 1 A/cm. A higher stability for RuNbO(A) compared to RuO(A) was observed in continuous cyclic voltammogram and electrolyzer cell test. Copyright © 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

A microblock ionomer in proton exchange membrane electrolysis for the production of high purity hydrogen

Proton exchange membranes (PEM’s) are currently under investigation for membrane water electrolysis (PEMWE) to deliver efficient production of the high purity hydrogen needed to supply emerging clean-energy technologies such as hydrogen fuel cells. The microblock aromatic ionomer described in this work achieves high mechanical strength in an aqueous environment as a result of its designed, biphasic morphology and displays many of the qualities required in a PEM. The new ionomer membrane thus shows good proton conductivity (63 mS cm−1 at 80 °C and 100% RH), while retaining mechanical integrity under high temperature, hydrated conditions. Testing in electrolysis has shown good energy efficiency (1.67 V at 1 A cm−2 and 80 °C, corresponding to 4 kWh/Nm3 of H2), making this ionomer a potential candidate for commercial application in PEMWE.

Lowering grain boundary resistance of BaZr0.8Y0.2O3−δ with LiNO3 sintering-aid improves proton conductivity for fuel cell operation

A novel sintering additive based on LiNO3 was used to overcome the drawbacks of poor sinterability and low grain boundary conductivity in BaZr0.8Y0.2O3-δ (BZY20) protonic conductors. The Li-additive totally evaporated during the sintering process at 1600°C for 6 h, which led to highly dense BZY20 pellets (96.5% of the theoretical value). The proton conductivity values of BZY20 with Li sintering-aid were significantly larger than the values reported for BZY sintered with other metal oxides, due to the fast proton transport in the "clean" grain boundaries and grain interior. The total conductivity of BZY20-Li in wet Ar was 4.45 × 10-3 S cm-1 at 600°C. Based on the improved sinterability, anode-supported fuel cells with 25 μm-thick BZY20-Li electrolyte membranes were fabricated by a co-firing technique. The peak power density obtained at 700°C for a BZY-Ni/BZY20-Li/La0.6Sr0.4Co0.2Fe 0.8O3-δ (LSCF)-BZY cell was 53 mW cm-2, which is significantly larger than the values reported for fuel cells using electrolytes made of BZY sintered with the addition of ZnO and CuO, confirming the advantage of using Li as a sintering aid.

Effect of properties of active carbon supports on performance of Pt/C catalysts in polymer electrolyte membrane fuel cell

The Pt/C catalysts were prepared with pine active carbon and Vulcan XC-72 active carbon as the supports. The performances of the Pt/C catalysts in polymer electrolyte membrane fuel cell were compared. The result indicates that the performance of Pt/Vulcan XC-72 is better than that of Pt/pine. The physical and chemical properties of the two active carbons were measured using several analysis techniques. It was found that the pore size, specific conductivity and the surface function group significantly influence the performance of the electrocatalyst.

Physical and electrochemical evaluation of ATO supported IrO2 catalyst for proton exchange membrane water electrolyser

Antimony doped tin oxide (ATO) was studied as a support material for IrO₂ in proton exchange membrane water electrolyser (PEMWE). Adams fusion method was used to prepare the IrO₂-ATO catalysts. The physical and electrochemical characterisation of the catalysts were carried out using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder conductivity, cyclic voltammetry (CV) and membrane electrode assembly (MEA) polarisation. The BET surface area and electronic conductivity of the supported catalysts were found to be predominantly arisen from the IrO₂. Supported catalyst showed higher active surface area than the pristine IrO₂ in CV analysis with 85% H₃PO₄ as electrolyte. The MEA performance using Nafion®−115 membrane at 80 °C and atmospheric pressure showed a better performance for IrO₂ loading ≥60 wt.% than the pristine IrO₂ with a normalised current density of 1625 mA cm⁻² @1.8 V for the 60% IrO₂-ATO compared to 1341 mA cm⁻² for the pristine IrO₂ under the same condition. The higher performance of the supported catalysts was mainly attributed to better dispersion of active IrO₂ on electrochemically inactive ATO support material, forming smaller IrO₂ crystallites. A 40 wt.% reduction in the IrO₂ was achieved by utilising the support material.

Investigation of supported IrO2 as electrocatalyst for the oxygen evolution reaction in proton exchange membrane water electrolyser

Indium tin oxide (ITO) was used as a support for IrO2 catalyst in the oxygen evolution reaction. IrO2 nanoparticles were deposited in various loading on commercially available ITO nanoparticle, 17–28 nm in size using the Adam's fusion method. The prepared catalysts were characterised using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The BET surface area of the support (35 m2/g) was 3 times lower than the unsupported IrO2 (112.7 m2/g). The surface area and electronic conductivity of the catalysts were predominantly contributed by the IrO2. The supported catalysts were tested in a membrane electrode assembly (MEA) for electrolyser operation. The 90% IrO2-ITO gave similar performance (1.74 V@1 A/cm2) to that of the unsupported IrO2 (1.73 V@1 A/cm2) in the MEA polarisation test at 80 °C with Nafion 115 membrane which was attributed to a better dispersion of the active IrO2 on the electrochemically inactive ITO support, giving rise to smaller catalyst particle and thereby higher surface area. Large IrO2 particles on the support significantly reduced the electrode performance. A comparison of TiO2 and ITO as support material showed that, 60% IrO2 loading was able to cover the support surface and giving sufficient conductivity to the catalyst.