A hybrid fuel cell system integrated with methanol steam reformer and methanation reactor

In this paper, a hybrid fuel cell system integrated with methanol steam reformer and methanation reactor is demonstrated. Methanol steam reformer employed in this system is to produce hydrogen-rich reformate in connection with a methanation reactor to reduce the carbon monoxide content effectively, and the reformate gas is sent into a low-temperature polymer electrolyte fuel cell for direct electric power generation. The optimum conditions (temperature, water to methanol ratio, and space velocity) for methanol steam reforming (MSR) reaction and methanation (MET) reaction are verified by experiments. A comparison between pure hydrogen, reformate surrogate, and actual reformate is performed. The results show that the power density of this hybrid system achieves 245.2 mW/cm² while it achieves 268.8 mW/cm² when employing pure hydrogen as the fuel. An alternative novel method to solve the problem of hydrogen storage and transportation is provided and the in-situ hydrogen production and utilizing through low-temperature fuel cell system is realized, which is helpful to accelerate the commercialization process of the fuel cell.     

Study of the impact of reactants utilization on the performance of PEMFC commercial stacks by impedance spectroscopy

Reactants utilization is a key stake for a PEMFC system: a too low utilization leads to a waste of reactant but a too high utilization may result in a detrimental starvation. To study these impacts, two commercial stacks were characterised by impedance spectroscopy under different hydrogen and oxygen utilizations (from nominal conditions to quasi-starvation). One was fresh while the other was operated on-field during 10,000 h. This study shows that the two capacitive loops in the lowest frequency range (1 Hz and below) correspond respectively to oxygen and hydrogen mass transfer limitations: the limiting reactant can be clearly identified from the impacted frequencies. The size of these loops was increased by up to 30% when the cell operated at high reactant utilizations. These results could therefore pave the way to the development of algorithms able to estimate the degree of starvation of some cells.     

An innovating application of PEM fuel cell: Current source controlled by hydrogen supply

Fuel cells are complex systems which can be considered as low voltage electrical source. Preliminary investigations led with a single proton exchange membrane fuel cell, either short-circuited or hybridized by discharged supercapacitors, could evidence the behavior as a current source, in which the current is directly controlled by the hydrogen flow rate. This operation mode imposes the fuel cell voltage to be far below the threshold recommended by the fuel cell manufacturer. The paper deals with this unusual application of fuel cell and its benefits such as the high quality current, free of oscillations that might be upgraded for superconducting coil supply. To investigate this operation mode an appropriate single fuel cell model is established and then validated by means of a test bench equipped with a proton exchange membrane single fuel cell.     

Influence of doping level in Yttria-Stabilised-Zirconia (YSZ) based-fillers as degradation inhibitors for proton exchange membranes fuel cells (PEMFCs) in drastic conditions

Yttria-Stabilized-Zirconia fillers with different Y₂O₃ loadings are used to prepare composite Nafion membranes for PEMFCs. XRD and BET demonstrate the formation of a c-ZrO₂ mesoporous structure. SEM reveals a size reduction of the agglomerates increasing the ZrO₂ doping level. A good mechanical resistance, no variation into the water retention, swelling restraint and an increased Ion Exchange Capacity (IEC) of the membranes are found respect to reference membrane, above all for highly doped membranes, indicating an acidic properties enhancement. Proton conductivity (PC) at 100%RH (80–100 °C) is unchanged for composite membranes compared to reference. At 75%RH, PC is positively affected by the highest YSZ loadings. Fenton's test on membranes evidences a higher oxidative chemical stability for composite membranes. This improved stability is confirmed by accelerated stress test in drastic conditions: composite highly doped membranes work for more than 110 cycles with a good performance and lower H₂-crossover against 95 cycles and higher H₂-crossover than reference membrane.     

On the state and stability of fuel cell catalyst inks

Catalyst layers (CL), as an active component of the catalyst coated membrane (CCM), form the heart of the polymer electrolyte membrane fuel cell (PEMFC). For optimum performance of the fuel cell, obtaining suitable structural and functional characteristics for the CL is crucial. Direct tuning of the microstructure and morphology of the CL is non-trivial; hence catalyst inks as CL precursors need to be modulated, which are then applied onto a membrane to form the CCM. Obtaining favorable dispersion characteristics forms an important prerequisite in engineering catalyst inks for large scale manufacturing. In order to facilitate a knowledge-based approach for developing fuel cell inks, this work introduces new tools and methods to study both the dispersion state and stability characteristics, simultaneously. Catalyst inks were prepared using different processing methods, which include stirring and ultrasonication. The proposed tools are used to characterize and elucidate the effects of the processing method. Structural characterization of the dispersed particles and their assemblages was carried out by means of transmission electron microscopy. Analytical centrifugation (AC) was used to study the state and stability of the inks. Herein, we introduce new concepts, S score, and stability trajectory, for a time-resolved assessment of inks in their native state using AC. The findings were validated and rationalized using transmittograms as a direct visualization technique. The flowability of inks was investigated by rheological measurements. It was found that probe sonication only up to an optimum amplitude leads to a highly stable colloidal ink.     

Optimal topology and distribution of catalyst in PEMFC

The equations that govern the various transport phenomena occurring in a polymer electrolyte membrane fuel cell (PEMFC) were formulated and implemented in a commercial finite element software, in order to predict the fuel cell current density with respect to the operating conditions. The numerical model showed polarization curves in accordance with literature. The catalyst utilization was then improved by optimizing the platinum distribution (design variable) in the fuel cell, so as to maximize current density (objective function) for a fixed total amount of platinum (constraint). The first analysis showed that, for equal anode and cathode catalyst layer thicknesses, maximal current density was achieved by placing more catalyst in the cathode than in the anode. The second analysis showed that, for equal anode and cathode catalyst layer density, maximal current density was achieved by using a catalyst layer that is thicker on the cathode side than that on the anode side. Finally, a topological optimization of the platinum density within the cathode catalyst layer was performed with a gradient based algorithm, and the results showed that at a high stoichiometric ratio, the best design has most of its platinum placed where the reaction rate is the highest, i.e., close to the membrane layer.     

Multi-skeletal PtPdNi nanodendrites as efficient electrocatalyst with high activity and durability towards oxygen reduction reaction

Engineering alloy nanostructures with a combination of highly active noble metals (Pt and Pd) and less electronegative non-noble metal (Ni) is found to be crucial for improving surface reactivity by enriching with active Pt sites. Herein, a multi-skeletal PtPdNi nanodendrites (NDs) was successfully formed by a simple one-pot method with structure directing agent. The modification of Pt electronic structure and their interaction due to compressive strain were explored using benchmark characterization techniques, which showed that the PtPdNi NDs possess Pt-enriched surface, corroborating to more active catalyst sites for oxygen reduction reaction (ORR) in acidic medium. The PtPdNi NDs have a higher electrochemical surface area (63 m² g^?1) and an earlier onset potential (1.01 V) than PtPd NDs, PtNi NDs, and commercial Pt/C catalysts, indicating the outstanding ORR performance. The high mass and specific activities, as well as superior durability after accelerated degradation test (ADT), highlight the remarkable electrocatalytic performance of PtPdNi NDs over others. As a result, enhancing Pt utilization through the formation of PtPdNi NDs could be a reliable strategy to improve ORR electrocatalysis for polymer electrolyte membrane fuel cell (PEMFC) applications.     

Experimental investigation on the voltage uniformity for a PEMFC stack with different dynamic loading strategies

The operating life of the proton exchange membrane fuel cell stack is mainly decided by performances of its weakest single cell because of the “Buckets effect”, thus high voltage uniformity during a dynamic loading process is key to the stack durability. In this work, a 3-kW stack is examined experimentally on its voltage uniformity (voltage coefficient variation (Cv)) under conditions of loading from open-circuit state (0 A) to nominal current (165 A) and stack temperatures of 30 °C, 45 °C and 65 °C. Different dynamic loading strategies, namely constant loading rate strategy, decreasing loading rate strategy, and increasing loading rate (square/cube increasing loading rate) strategy, are examined and compared. Results display that during the loading process, (a) the voltage uniformity rises abruptly and goes down quickly when the loading current is small (e.g. from 0 A to 22 A), (b) the voltage uniformity under a small loading current is better than that under the open-circuit state, and (c) voltage uniformity decreases as the loading current increases from a small value to the nominal current. Comparisons of different current loading strategies show that as the stack temperature rises from 30 °C to 65 °C, the stack Cv value under the open-circuit state increases from 1.12 to 1.84 and decreases from 3.85 to 2.45 in the nominal current state. The maximum Cv for the decreasing loading rate strategy decreases from 16.25 to 9.49 and that of the constant loading rate strategy also decreases from 5.85 to 4.96. Cv values of the square current increasing loading rate strategy keep below 3.85 under conditions of the three stack temperatures and display a slight fluctuation during the whole current loading process, which indicates that the strategy can effectively make the stack being of an excellent voltage uniformity during the instantaneous response process.     

Fault-tolerant control through dynamic surface triple-step approach for proton exchange membrane fuel cell air supply systems

Due to complex electrochemical and thermal phenomena, varying operations towards automotive applications, and vulnerable ancillaries in proton exchange membrane fuel cells (PEMFCs), fault diagnosis and fault-tolerant control (FTC) design have become important aspects to improve the reliability, safety and performance of PEMFC systems. This paper presents a novel FTC scheme for automotive PEMFC air supply systems via coordinated control of the air flow rate and the pressure in cathodes. A dynamic surface triple-step approach is first proposed considering nonlinear dynamics and the multi-input multi-output (MIMO) property, which combines the advantage of dynamic surface control in avoiding an “explosion of complexity” and the advantage of triple-step control in guaranteeing a simple structure and high performance. The normal case, the faulty case at the supply manifold and the faulty case in the back pressure valve are considered in the FTC design, with the stability of the overall system proved using Lyapunov methods. MATLAB/Simulink simulations with a high-fidelity PEMFC model verify the effectiveness of the proposed FTC scheme in regulating the air flow rate and oxygen excess ratio and maintaining the pressure of the cathode at a desired level even under faulty conditions.     

Passive fuel cell/lithium-ion capacitor hybridization for vehicular applications

Electric recreational vehicles represent a new challenge in terms of power supply systems compared to the current light-duty electric vehicles, which achieve high performance and long-range. The recreational vehicles need to heed the limited dimension requirements while assuring the high requested power. This paper proposes an integration of Lithium-Ion Capacitor (LIC) with Fuel Cell (FC) without any power electronic device for a three-wheel electric motorcycle. Unlike other hybrid power supply systems, the proposed FC-LIC passive configuration is lighter, compact, more efficient, and simpler to implement. Due to the different impedance of the components the system is self-management, in which FC supplies the average power component and LIC operates as a low-pass filter. In this respect, a simulator is built based on experimental tests to study the system performance in terms of hydrogen consumption and FC degradation. Subsequently, the system is tested under three standard motorcycle driving cycles at three different FC system lifespan stages. The obtained results demonstrate that a passive topology can supply the requested power along different FC stages of life and reported just an increment of 12% of hydrogen consumption at the oldest condition compared to the new condition.