How platinum oxide affects the degradation analysis of PEM fuel cell cathodes

In this work, proton exchange membrane fuel cell cathodes are degraded with accelerated-stress-tests.These PtCo containing cathodes are analyzed at begin-of-life and end-of-test with a dedicated diagnostic procedure. For every individual load point, the oxygen transport resistance and voltage losses due to the formation of platinum oxides were obtained in addition to commonly measured electrochemical surface area, high frequency resistance, as well as cathode ionomer resistance. These data were used to break down the voltage losses into six different contributors. With this break down, performance gains and performance losses were determined at end-of-test. At low current densities, it was found that voltage losses due to degradation are dominated by the loss of specific activity and catalyst surface area - in line with the state-of-the-art knowledge. But by quantifying the losses from platinum oxide formation explicitly, we show that end-of-test an unassigned voltage loss is not only present at highest current densities, but already at low current density. More precisely, the unassigned voltage loss shows a linear increase with decreasing half cell voltage and is independent from the chosen accelerated stress test. As this unassigned loss depends on half cell voltage, it might arise from ionomer adsorption.     

High chemical stability anion exchange membrane based on poly(aryl piperidinium): Effect of monomer configuration on membrane properties

In recent years, ether-free polyaryl polymers prepared by superacid-catalyzed Friedel-Crafts polymerization have attracted great research interest in the development of anion exchange membranes(AEMs) due to their high alkali resistance and simple synthesis methods. However, the selection of monomers for high-performance polymer backbone and the relationship between polymer structure construction and properties need further investigated. Herein, a series of free-ether poly(aryl piperidinium) (PAP) with different polymer backbone steric construction were synthesized as stable anion exchange membranes. Meta-terphenyl, p-terphenyl and diphenyl-terphenyl copolymer were chosen as monomers to regulate the spatial arrangement of the polymer backbone, which tethered with stable piperidinium cation to improve the chemical stability. In addition, a multi-cation crosslinking strategy has been applied to improve ion conductivity and mechanical stability of AEMs, and further compared with the performance of uncrosslinked AEMs. The properties of the resulting AEMs were investigated and correlated with their polymer structure. In particular, m-terphenyl based AEMs exhibited better dimensional stability and the highest hydroxide conductivity of 144.2 mS/cm at 80 °C than other membranes, which can be attributed to their advantages of polymer backbone arrangement. Furthermore, the hydroxide conductivity of the prepared AEMs remains 80%–90% after treated by 2 M NaOH for 1600 h, exhibiting excellent alkaline stability. The single cell test of m-PTP-20Q4 exhibits a maximum power density of 239 mW/cm² at 80 °C. Hence, the results may guide the selection of polymer monomers to improve performance and alkaline durability for anion exchange membranes.     

Systematic study of short circuit activation on the performance of PEM fuel cell

During the operation of proton exchange membrane fuel cell (PEMFC), it always suffers from reversible performance loss caused by the oxidation of platinum catalyst on its electrode, which reduces the electrochemical active surface area. Short circuit method has been found to improve the performance of fuel cells by stripping of oxides and other adsorbed species from platinum, which needs systematical understanding the effective parameters of short circuit method on fuel cell performance. In this paper, the effects of different short circuit activation parameters (duration, interval, cycles, cut-off voltage, operating current) are carefully studied and analyzed during short circuit operations. In addition, the mechanism revealing how relevant parameters influence short circuit activations is deeply analyzed. The results show that five groups of activation parameters have obvious influence on the activation of fuel cell, indicating that the short-circuit activation effect can be optimized. Among these parameters, the short-circuit duration parameter have the greatest impact on activation, because the platinum hydroxides and oxides is gradually removed during short-circuit duration and results in a larger effective surface area of the platinum catalyst for the electrochemical reaction. However, the smallest impact is short-circuit interval. Another finding is that the five activation parameters are not independent, so the optimal activation parameter value needs to be analyzed in combination with the operating conditions. Finally, according to the activation principle, selection of appropriate short circuit activation parameters for application are proposed to further improve performance and fuel utilization by considering the safety of the stack.     

Exploring the relationship between the physical properties of activated carbon catalysts and their efficiency in catalyzing hydrogen iodide decomposition to produce hydrogen

Using simple and efficient methods to synthesize biological activated carbon catalysts (ACCs) with the decomposition of hydrogen iodide (HI) in the sulfur-iodine cycle as a typical reaction is urgently needed for the commercialization of hydrogen energy production and development. In this study, a series of ACCs with different specific surface areas (SSAs) and pore structures are prepared by comparing and controlling the changes in carbonization and activation methods of activated carbon (AC) preparation process. Hierarchical porous AC with larger SSA has higher HI decomposition efficiency. The representative samples H240H1h and H240C4h are hierarchical porous ACCs with 48.96% and 46.88% micropores, respectively, and have the highest catalytic activity in the entire series. The nitrogen adsorption and desorption curve is combined with pore size distribution data and analyzed using the capillary aggregation (Kelvin) and monolayer adsorption (Langmuir) theories. And ACC pore grading coefficient—which can improve data visualization—is introduced.     

A data-driven digital-twin prognostics method for proton exchange membrane fuel cell remaining useful life prediction

Prognostics and health management of proton exchange membrane fuel cell (PEMFC) systems have driven increasing research attention in recent years as the durability of PEMFC stack remains as a technical barrier for its large-scale commercialization. To monitor the health state during PEMFC operation, digital twin (DT), as a smart manufacturing technique, is applied in this paper to establish an ensemble remaining useful life prediction system. A data-driven DT is constructed to integrate the physical knowledge of the system and a deep transfer learning model based on stacked denoising autoencoder is used to update the DT with online measurement. A case study with experimental PEMFC degradation data is presented where the proposed data-driven DT prognostics method has applied and reached a high prediction accuracy. Furthermore, the predicted results are proved to be less affected even with limited measurement data.     

Influence of the gasket materials on the clamping pressure distribution in a PEM water electrolyzer: Bolt torques and operation mode in pre-conditioning

To keep optimally connected, all electrolysis cell elements is one of the most important design criteria. The optimal distribution of the clamping points is crucial to increasing cell performance. In this work, the compression pressure distribution inside of a 25 cm² PEM electrolysis cell was evaluated, using different materials: Teflon®, Viton®, ethylene propylene diene monomer rubber (EPDM), and nitrile rubber. Sealing material evaluation was performed taking as performance indicators: total compressed area (%) and compression pressure, for different torques applied. Pressure distribution was obtained by using pressure-sensitive films, analyzing the distribution of pressure points from three-dimensional plots (3D), and quantifying intensities of the images obtained. Results showed that pressure points distribution depends on the stiffness and thickness of the gasket materials. For a tightening torque of 3.70 N m, a pressure of 2.23 MPa is obtained with 85% of the membrane area compressed using nitrile rubber-EPDM gaskets.     

Pre-activation of SBA-15 intermediate barriers with Pd nuclei to increase thermal and mechanical resistances of pore-plated Pd-membranes

Thermal and mechanical resistances of palladium composite membranes prepared by Electroless Pore-Plating (ELP-PP) and containing SBA-15 as intermediate layer were improved by doping the silica material with Pd nuclei before its incorporation on the composite membrane. Textural properties of synthesized SBA-15 materials (both raw and doped ones) were analyzed by XRD, N₂ adsorption-desorption at 77 K and TEM, while the main properties of the composite membrane were determined by SEM and gravimetric analyses. Moreover, membrane permeation tests were also carried out with pure gases, hydrogen and nitrogen, and binary mixtures of them at temperature of 400 °C and pressure driving forces in the range of 0.5–2.5 bar. The use of bare SBA-15 intermediate layer leads to the appearance of cracks on the Pd layer during permeation experiments at high temperature. In contrast, the use of Pd-doped SBA-15 particles avoids this problem, thus improving both thermal and mechanical resistances of the composite ELP-PP Pd-membrane. Following this preparation method, an estimated Pd thickness of 7.1 μm was obtained, reaching a hydrogen permeance of 3.81·10^?4 mol s^?1 m^?2 Pa^?0.5 and ensuring an ideal H₂/N₂ separation factor higher than 2550 at 400 °C.     

Effect of anode iridium oxide content on the electrochemical performance and resistance to cell reversal potential of polymer electrolyte membrane fuel cells

An ideal polymer electrolyte membrane fuel cell (PEMFC) is one that continuously generates electricity as long as hydrogen and oxygen (or air) are supplied to its anode and cathode, respectively. However, internal and/or external conditions could bring about the degradation of its electrodes, which are composed of nanoparticle catalysts. Particularly, when the hydrogen supply to the anode is disrupted, a reverse voltage is generated. This phenomenon, which seriously degrades the anode catalyst, is referred to as cell reversal. To prevent its occurrence, iridium oxide (IrO₂) particles were added to the anode in the membrane-electrode assembly of the PEMFC single-cells. After 100 cell reversal cycles, the single-cell voltage profiles of the anode with Pt/C only and the anodes with Pt/C and various IrO₂ contents were obtained. Additionally, the cell reversal-induced degradation phenomenon was also confirmed electrochemically and physically, and the use of anodes with various IrO₂ contents was also discussed.     

Hydrogen production by silica membrane reactor during dehydrogenation of methylcyclohexane: CFD analysis

A comprehensive computational fluid dynamic model has been developed using COMSOL Multiphysics 5.4 software to predict the behavior of a membrane reactor in dehydrogenation of methylcyclohexane for hydrogen production. A reliable reaction kinetic of dehydrogenation reaction and a permeation mechanism of hydrogen through silica membrane have been used in computational fluid dynamic modeling. For performance comparison, an equivalent traditional fixed bed reactor without hydrogen removal has been also modeled. After model validation, it has been used to evaluate the operating parameters effect on the performance of both the silica membrane reactor and the equivalent traditional reactor as well. The operating temperature ranged between 473 and 553 K, pressure between 1 and 2.5 bar, sweep factor from ?6.22 to 25 and feed flow rate from 1 to 5 × 10^?6 mol/s. The membrane reactor performed better than the equivalent traditional reactor, achieving as best result complete methylcyclohexane conversion and 96% hydrogen recovery.