Thermodynamic analysis of ethanol processors – PEM fuel cell systems

This work presents a simulative energy efficiency analysis performed on fuel processor – PEM fuel cell systems, considering ethanol as fuel and steam reforming or autothermal reforming as processes to produce hydrogen.     

Managing fuel variability in LPG-based PEM fuel cell systems – I: Thermodynamic simulations

Hydrocarbon-based polymer electrolyte membrane fuel cell systems are promising solutions for auxiliary power units and remote systems. The sequence of steam reforming, water–gas shift and preferential oxidation reactors is a common fuel processing methodology. The heat released by burning the hydrogen-depleted anode waste gas is utilized to drive the endothermic reforming reaction and to generate steam, while the other two sub-processes are exothermic. Balancing these heat fluxes, while maintaining the narrow temperature windows required for each of these reactions, is a key system control challenge. Strategies based on a priori knowledge of fuel composition result in instability, reduction in system efficiency or transgression of safe limits in critical parameters when fuel composition varies. To address this, we have developed and implemented a control strategy that uses more readily measurable quantities to perform control actions, and is independent of knowledge about exact fuel composition or flow rate. In this paper, we analyze the effectiveness of the new control strategy by quantifying its effects on liquefied petroleum gas based polymer electrolyte membrane fuel cell systems. Results indicate that even in extreme cases of fuel composition variation, this control strategy enables the determination of set points such that the system efficiency and other critical parameters are held in a narrow range around optimal values.     

Influence of catalyst structure on PEM fuel cell performance – A numerical investigation

The effect of the catalyst microstructure on a 5 cm² PEM fuel cell performance is numerically investigated. The catalyst layer composition and properties (i.e. ionomer volume fraction, platinum loading, particle radius, electrochemical active area and carbon support type), and the mass transport resistance due to the ionomer and liquid water surrounding the catalyst particles, are incorporated into the model. The effects of the above parameters are discussed in terms of the polarization curves and the local distributions of the key parameters. An optimum range of the ionomer volume fraction was found and a gain of 39% in the performance was achieved. As regards the platinum loading and catalyst particle radius, the results showed that a higher loading and a smaller radius leads to an increase in the PEMFC performance. Further, the influence of the electrochemical active area produces an overall increase of 22% in current density and this was due to the use of a new material developed as support for Pt particles, an iodine doped graphene, which has better electrical contacts and additional pathways for water removal. Using this parameter, the numerical model has been validated and good agreement with experimental data was achieved, thus giving confidence in the model as a design tool for future improvements of the catalyst structure.     

Analytical modeling of PEM fuel cell i–V curve

The performance of a fuel cell is characterized by its i–V curve. In this study, the performance of a bench scale fuel cell stack, run on hydrogen/air, is measured experimentally for different air flow rates and temperatures. The experimental data, obtained from the 40-W proton exchange membrane fuel cell (PEMFC), are used in estimating the parameters of a completely analytical model that describes the i–V curve. The analytical model consists of the three fundamental losses experienced by a fuel cell, namely: activation, ohmic, and concentration losses. The current loss is also considered in the model. While the Tafel constants, ohmic resistance, and the concentration loss constant are estimated through regression, the limiting current density and the current loss are obtained through measurements. The effect of temperature on the fuel cell performance, exchange current density, and current loss is also investigated. Both the exchange current density and the current loss are plotted against temperature on an Arrhenius-like plot and the related parameters are estimated. The theoretical equations derived in the literature, which model fuel cell performance, are found to reasonably fit the obtained experimental data.     

Biomass-integrated gasification fuel cell systems – Part 2: Economic analysis

For the seven technically feasible Biomass-Integrated Gasification Fuel Cell (B-IGFC) systems investigated in this two-part system analysis, the interactions between the used biomass gasification processes, gas processing technologies and SOFC concepts are investigated primarily employing ASPEN PLUS™ flowsheeting models. Based on the results of the system simulations, the power production costs are estimated for the various B-IGFC systems. The impact of the most important assumptions made for the presented thermo-economic system analysis is assessed through a sensitivity analysis.     

Non-stoichiometric tungsten-carbide-oxide-supported Pt–Ru anode catalysts for PEM fuel cells – From basic electrochemistry to fuel cell performance

Durability and cost of Proton Exchange Membrane fuel cells (PEMFCs) are two major factors delaying their commercialization. Cost is associated with the price of the catalysts, while durability is associated with degradation and poisoning of the catalysts, primarily by CO. This motivated us to develop tungsten-carbide-oxide (W_xC_yO_z) as a new non-carbon based catalyst support for Pt–Ru–based anode PEMFC catalyst. The aim was to improve performance and obtain higher CO tolerance compared to commercial catalysts. The performance of obtained PtRu/W_xC_yO_z catalysts was investigated using cyclic voltammetry, linear scan voltammetry and rotating disk electrode voltammetry. Particular attention was given to the analysis of CO poisoning, to better understand how W_xC_yO_z species can contribute to the CO tolerance of PtRu/W_xC_yO_z. Improved oxidation of CO_ads at low potentials (E < 0.5 V vs. RHE) was ascribed to OH provided by the oxide phase at the interfacial region between the support and the PtRu particles. On the other hand, at high potentials (E > 0.5 V vs. RHE) CO removal proceeds dominantly via OH provided from the oxidized metal sites. The obtained catalyst with the best performance (30% PtRu/W_xC_yO_z) was tested as an anode catalyst in PEM fuel cell. When using synthetic reformate as a fuel in PEMFC, there is a significant power drop of 35.3 % for the commercial 30% PtRu/C catalyst, while for the PtRu/W_xC_yO_z anode catalyst this drop is around 16 %.     

Quasi-stationary UI-characteristic model of a PEM fuel cell–Evaluating the option of self-humidifying operation

This work presents a zero-dimensional PEM fuel cell UI-characteristic model created in MATLAB Simulink® for operation with dry or humidified air supply. It is parameterised and validated based on the results of stack operation by varying stack temperature (50–80 °C), gas pressure (1.0–2.4 bar) and air humidification (0.0–1.0). The model is based on physical and electrochemical correlations and expanded by empirically assumptions concerning the influence of the humidification and limiting current density on the performance. The UI-model is intended to be integrated into a comprehensive zero-emission powertrain model. Since non-humidified operation of PEM fuel cell systems provides benefits for mobile applications by reducing space demand and system complexity, the objective of the model is to relate performance to the operating conditions and underlying physical parameters. Results confirm the feasibility of a self-humidifying stack operation at high performance by optimal parameter setting.     

Conceptual design of an integrated thermally self-sustained methanol steam reformer – High-temperature PEM fuel cell stack manportable power generator

We have investigated the concept of an integrated system for small, manportable power units. The focus of this study is the direct thermal coupling of a methanol steam reformer (MSR) and a high-temperature proton exchange membrane fuel cell (HT PEMFC) stack. A recently developed low-temperature (LT) MSR catalyst (CuZnGaO_x) was synthesized and tested in a designed reforming reactor. The experimental data show that at 200 °C the complete conversion of methanol is achievable with a hydrogen yield of 45 cm³ min^?1 g_CAT^?1. An experimental setup for measuring the characteristics of the integrated system was designed and used to measure the characteristics of the two-cell HT PEMFC stack. The obtained kinetic parameters and the HT PEMFC stack characteristics were used in the modeling of the integrated system. The simulations confirmed that the integrated LT MSR/HT PEMFC stack system, which also includes a vaporizer, can achieve a thermally self-sustained working point. The base-case scenario, established on experimental data, predicts a power output of 8.5 W, a methanol conversion of 98.5%, and a gross electrical efficiency (based on the HHV) of the system equal to 21.7%. However, by implementing certain measures, the power output and the electrical efficiency can readily be raised to 11.1 W and 35.5%, respectively.     

On the tungsten carbide synthesis for PEM fuel cell application – Problems,challenges and advantages

Fuel cell application of tungsten carbide is revisited starting with four different tungsten carbide precursors used for high temperature synthesis. It was shown that the final products greatly depend on the nature of the precursor. Using tungsten peroxide/2-propanol derived precursor almost pure WC was obtained which was subjected to further electrochemical investigation. It was shown that it is necessary to decorate WC with Pt nanoparticles in order to obtain satisfactory fuel cell performance, but catalytic activity of Pt/WC anode catalyst is not expected to overcome the activity of Pt/C. It is argued that new synthetic routes for the preparation of WC should be directed towards obtaining highly dispersed WC, that is, WC with high external surface area available for Pt deposition, rather than high specific surface area WC with large contribution of micropores having no importance when it comes to the use of WC as a catalyst support. The true benefit of the use of WC as catalyst support is found in increased CO tolerance/CO oxidation activity of WC-supported Pt catalysts. Qualitative mechanistic view on increased CO oxidation activity of Pt/WC is offered.     

Direct methanol fuel cell systems for backup power – Influence of the standby procedure on the lifetime

This paper compares different backup power systems for uninterruptible emergency power supply (UPS) in the kW-power range. The cost structure of direct methanol fuel cell systems (DMFCs) is deduced from a DMFC system developed for the replacement of batteries in small fork-lift trucks. The setup for new DMFC backup power systems will be further simplified and those systems will be operated without expensive sensors necessary for laboratory testing. A detailed cost structure of such systems is shown, and in a cost comparison the competitiveness to other existing UPS technologies is indicated.In spite of reduced sensor systems the efficient and secure operation of the system must be guaranteed. The demanded durability in case of UPS is ten years in discontinuous operation. To achieve the long term stability the right treatment of the stack during standby was identified by tests on single cells as well as on short stacks. A number of different standby procedures have been tested in order to identify how the MEAs must be treated in order to avoid premature degradation during standby.     

Raising efficiency of hydrogen generation from alkaline water electrolysis – Energy saving

This paper presents an attempt to make the alkaline electrolytic production of hydrogen more efficient by adding in situ activating compounds in ionic and complex form. Cobalt and tungsten based ionic activators (i.a.), added directly into the electrolyte during the electrolytic process, reduce energy requirements per mass unit of hydrogen produced for about 15%, compared to non-activated system, for a number of current densities in a wide temperature range. Energy saving is higher at higher temperatures and on higher current densities. Structural and morphological characteristic of deposit formed on the cathode during the electrolytic process reveal very interesting and unique pattern with highly developed surface area and uniform distribution of the pores. Obtained deposit also exhibit a long term stability.     

How fuzzy logic can improve PEM fuel cell MPPT performances?

This paper addresses the development of new variable step size fuzzy based MPPT controller. In this study, the fuzzy logic approach is firstly used to auto-scale the variable step size of the Incremental Conductance (IC) MPPT controller. Secondly, the proposed variable step size fuzzy based MPPT controller is used to track the output power of the PEM fuel cell system composed of 7 kW fuel cell supplying a 50Ω resistive load via a DC-DC boost converter controlled using the proposed MPPT. The proposed variable step size fuzzy-based MPPT controller is compared to the conventional fixed step size IC, the variable step size IC and the fuzzy scaled variable step size IC MPPTs using the implemented Matlab/Simulink PEM Fuel Cell power system model. Comparative simulation results between the four studied MPPTs show better performances for the proposed fuzzy based variable step size MPPT in term of: response time reduction between 3.6% and 82.35%; overshoot reduction between 34.55% and 100%; and ripple reduction between 70.93% and 100%, improving as consequence the fuel cell lifetime affected by high current ripple.     

An energetic–exergetic analysis of a residential CHP system based on PEM fuel cell

The use of fuel cell systems for distributed residential power generation represents an interesting alternative to traditional thermoelectric plants due to their high efficiency and the potential recovering of the heat generated by the internal electrochemical reactions. In this paper the study of a micro cogenerative (CHP) energy system based on a Proton Exchange Membrane fuel cell (PEMFC) is reported.     

Experimental investigation of water droplet–air flow interaction in a non-reacting PEM fuel cell channel

It has been well documented that water production in PEM fuel cells occurs in discrete locations, resulting in the formation and growth of discrete droplets on the gas diffusion layer (GDL) surface within the gas flow channels (GFCs). This research uses a simulated fuel cell GFC with three transparent walls in conjunction with a high speed fluorescence photometry system to capture videos of dynamically deforming droplets. Such videos clearly show that the droplets undergo oscillatory deformation patterns. Although many authors have previously investigated the air flow induced droplet detachment, none of them have studied these oscillatory modes. The novelty of this work is to process and analyze the recorded videos to gather information on the droplets induced oscillation. Plots are formulated to indicate the dominant horizontal and vertical deformation frequency components over the range of sizes of droplets from formation to detachment. The system is also used to characterize droplet detachment size at a variety of channel air velocities. A simplified model to explain the droplet oscillation mechanism is provided as well.     

Maximum conversion efficiency of hydrogen fuel cells

Çengel and Boles discuss in their Thermodynamics textbook that the Carnot efficiency bound is not applicable to fuel cells, whereas some researchers have raised objection that maximum conversion efficiency of fuel cells is limited to the Carnot efficiency. We apply the conservation of energy and entropy balance equations to derive expressions for the maximum work of hydrogen-oxygen, hydrogen-air and methane-air fuel cells. We show that the theoretical efficiency of a fuel cell may exceed that of a Carnot engine operating between the same low and high temperatures. Contrary to past studies in that the efficiency of an ideal hydrogen fuel cell is shown to decline with temperature, the maximum efficiency is observed to first decrease with reactants temperature, then remains unaltered and finally rises. The lowest value of the maximum efficiency is found to be 79.3%, 75.7%, and 82.1% for hydrogen-oxygen, hydrogen-air and methane-air fuel cells, respectively. By increasing the stoichiometric coefficient of air, the efficiencies of both hydrogen-air and methane-air fuel cells monotonically increase and they approach the 100% limit at a stoichiometric coefficient of 7.2 and 9.8, respectively. It is shown that a Carnot engine whose heat is supplied by an isothermal combustor proposed in some past studies is not a correct means for comparison of the ideal performance of fuel cells and heat engines.     

The design of stationary and mobile solid oxide fuel cell–gas turbine systems

A general thermodynamic model has shown that combined fuel cell cycles may reach an electric-efficiency of more than 80%. This value is one of the targets of the Department of Energy (DOE) solid oxide fuel cell–gas turbine (SOFC–GT) program. The combination of a SOFC and GT connects the air flow of the heat engine and the cell cooling. The principle strategy in order to reach high electrical-efficiencies is to avoid a high excess air for the cell cooling and heat losses. Simple combined SOFC–GT cycles show an efficiency between 60 and 72%. The combination of the SOFC and the GT can be done by using an external cooling or by dividing the stack into multiple sub-stacks with a GT behind each sub-stack as the necessary heat sink. The heat exchangers (HEXs) of a system with an external cooling have the benefit of a pressurization on both sides and therefore, have a high heat exchange coefficient. The pressurization on both sides delivers a low stress to the HEX material. The combination of both principles leads to a reheat (RH)-SOFC–GT cycle that can be improved by a steam turbine (ST) cycle. The first results of a study of such a RH-SOFC–GT–ST cycle indicate that a cycle design with an efficiency of more than 80% is possible and confirm the predictions by the theoretical thermodynamic model mentioned above. The extremely short heat-up time of a thin tubular SOFC and the market entrance of the micro-turbines give the option of using these SOFC–GT designs for mobile applications. The possible use of hydrocarbons such as diesel oil is an important benefit of the SOFC. The micro-turbine and the SOFC stack will be matched depending on the start-up requirements of the mobile system. The minimization of the volume needed is a key issue. The efficiency of small GTs is lower than the efficiency of large GTs due to the influence of the leakage within the stages of GTs increasing with a decreasing size of the GT. Thus, the SOFC module pressure must be lower than in larger stationary SOFC–GT systems. This leads to an electrical-efficiency of 45% of a cycle used as a basis for a design study. The result of the design study is that the space available in a mid-class car allows the placement of such a system, including space reserves. A further improvement of the system might allow an electrical-efficiency of about 55%.     

Reforming of natural gas—hydrogen generation for small scale stationary fuel cell systems

The reforming of natural gas to produce hydrogen for fuel cells is described, including the basic concepts (steam reforming or autothermal reforming) and the mechanisms of the chemical reactions. Experimental work has been done with a compact steam reformer, and a prototype of an experimental reactor for autothermal reforming was tested, both containing a Pt-catalyst on metallic substrate. Experimental results on the steam reforming system and a comparison of the steam reforming process with the autothermal process are given.     

Microbial fuel cell – A novel self-powered wastewater electrolyser for electrocoagulation of heavy metals

This paper describes the suitability of the Microbial Fuel Cell (MFC) for generation of electrical power with a simultaneous synthesis of active catholyte in the form of caustic solution. The active solution formed inside a terracotta based MFC reactor was a product of self-powered wastewater electrolysis utilizing i) wastewater with added sodium acetate as a carbon source and ii) neat urine. The catholyte solution that has been actively synthesized was harvested and used for precipitation of heavy metals such as: iron, copper and zinc showing its suitability for use in electro-coagulation (electro-flocculation). This proposed alternative approach to self-powered electrocoagulation is based on electrochemically formed caustic catholyte within the inner cathode chamber of the MFC and then used ex situ to form metal hydroxides that precipitate out from heavy metal solutions.     

Nonlinear control of fuel cell hybrid power sources: Part I – Voltage control

In this paper is proposed a nonlinear control for fuel cell/battery/ultracapacitor hybrid power sources (HPS) that improves the performance and durability of fuel cell. The nonlinear voltage control is analyzed and designed using a systematic approach. The design goal is to stabilize the HPS output voltage at a low voltage ripple that is also spread in a large frequencies band. All the results have been validated in several simulations. The simulation results successfully show that nonlinear voltage control performs good performances in the frequency-domain (a high spreading level of power spectrum) and in the time domain (a low level of output voltage ripple factor), too.     

Nonlinear control of fuel cell hybrid power sources: Part II – Current control

In this paper is proposed a nonlinear current-mode control for the fuel cell/battery/ultracapacitor hybrid power sources (HPS) that improves the ripple factor of the fuel cell current. The nonlinear current control is analyzed and designed using a systematic approach. The design goal is to generate an anti-ripple via buck current controlled source in order to mitigate the inverter current ripple. All the results have been validated in several simulations. The simulation results successfully show that nonlinear current-mode control determines in the low frequency-domain better performances than other current-mode control techniques, such as the hysteretic current-mode controller or the peak current-mode controller. The current ripple factor is one of the used performance indicators.