Cathode Catalyst Research Articles

Machine Learning-Aided Discovery of Low-Pt High Entropy Intermetallic Compounds for Electrochemical Oxygen Reduction Reaction.

Advancing the design of cathode catalysts to significantly maximize platinum utilization and augment the longevity has emerged as a formidable challenge in the field of fuel cells. Herein, we rationally design a high entropy intermetallic compound (HEIC, Pt(FeCoNiCu)3) for catalyzing oxygen reduction reaction (ORR) by an efficient machine learning stategy, where crystal graph convolutional neural networks are employed to expedite the multicomponent design. Based on a dataset generated from first-principles calculations, the model can achieve a high prediction accuracy with mean absolute errors of 0.003 for surface strain and 0.011 eV atom-1 for formation energy. In addition, we identify two chemical features (atomic size difference and mixing enthalpy) as new descriptors to explore advanced ORR catalysts. The carbon supported Pt(FeCoNiCu)3 catalyst with small particle size is successfully synthesized by a freeze-drying-annealing technology, and exhibits ultrahigh mass activity (4.09 A mgPt-1) and specific activity (7.92 mA cm-2). Meanwhile, The catalyst also shows significantly enhanced electrochemical stability which can be ascribed to the sluggish difussion effect in the HEIC structure. Beyond offering a promising low-Pt electrocatalysts for fuel cell cathode, this work offers a new paradigm to rationally design advanced catalysts for energy storage and conversion devices.

Unveiling the degradation mechanism of cathodic MoS2/C electrocatalysts for PEMWE applications

Molybdenum dichalcogenides (MoS2) are promising non-noble alternatives to replace platinum (Pt) for Hydrogen Evolution Reaction (HER) electrocatalysis in Proton Exchange Membrane Water Electrolyzers (PEMWE). The knowledge acquired on this class of catalyst for hydrodesulfurization (HDS) reactions has enabled significant advances in designing active MoS2 for HER. However, the stability of MoS2 in the dynamic operating conditions of a PEMWE coupled to renewable energy sources is often overlooked in the literature and is the focus of the present work. Herein, using nano slabs of 2H MoS2 supported on high surface area carbon, we dynamically monitored Mo dissolution trends both under HER conditions and at more anodic potentials to mimic start-ups and shut-downs of a PEMWE device. We report minimal Mo dissolution under HER conditions but it continuously increased with higher electrode potentials. In particular, Mo dissolution peaked during the irreversible oxidation from Mo(IV) to Mo(VI) starting at E = 0.7 VRHE which in turn fully annihilates HER activity. Since no change in Mo and S surface composition was observed, the decline in HER activity was attributed to the continuous exfoliation of the 2D MoS2 stacked layers induced by oxidation/dissolution of Mo. Additionally, our findings indicate that Mo cations can redeposit onto the cathode catalytic layer, forming a Mo blue film primarily composed of Mo(VI) species. This redeposition hampers HER performance by blocking catalytic sites and diminishing the catalyst's overall efficiency. These insights demonstrate the need to avoid excursions above E = 0.6 VRHE for the safe use of MoS2 cathode catalyst in PEMWE.

Recent Achievements in Heterogeneous Bimetallic Atomically Dispersed Catalysts for Zn-Air Batteries: A Minireview.

Rechargeable Zn-air batteries (ZABs) hold promise as the next-generation energy-storage devices owing to their affordability, environmental friendliness, and safety. However, cathodic catalysts are easily inactivated in prolonged redox potential environments, resulting in inadequate energy efficiency and poor cycle stability. To address these challenges, anodic active sites require multiple-atom combinations, that is, ensembles of metals. Heterogeneous bimetallic atomically dispersed catalysts (HBADCs), consisting of heterogeneous isolated single atoms and atomic pairs, are expected to synergistically boost the cyclic oxygen reduction and evolution reactions of ZABs owing to their tuneable microenvironments. This minireview revisits recent achievements in HBADCs for ZABs. Coordination environment engineering and catalytic substrate structure optimization strategies are summarized to predict the innovation direction for HBADCs in ZAB performance enhancement. These HBADCs are divided into ferrous and nonferrous dual sites with unique microenvironments, including synergistic effects, ion modulation, electronic coupling, and catalytic activity. Finally, conclusions and perspectives relating to future challenges and potential opportunities are provided to optimise the performance of ZABs.

An impedance spectroscopy study to unravel the effect of water on proton and oxygen transport in PEM fuel cells

A recent physics-based model for liquid and gaseous water transport in the cathode catalyst layer (CCL) is incorporated into our 1d ＋ 1d model for the PEM fuel cell impedance. The model includes parametric dependencies of the CCL oxygen diffusivity and proton conductivity on the liquid saturation. Fitting of the 1d ＋ 1d model to experimental impedance spectra of a PEM fuel cell reveals two intriguing effects. Contrary to common belief, the liquid water saturation in the CCL is nearly independent of cell current density due to the growing liquid pressure gradient that drives liquid water removal from the CCL. Further, the “dry” oxygen diffusivity of the catalyst layer increases with cell current density. Apparently, at small current density, electrochemical conversion proceeds primarily in narrow pores, where the Knudsen oxygen diffusivity is low. With growing current density, larger and better connected pores with higher oxygen diffusivity dominate in the current conversion, leading to increase in effective oxygen diffusivity observed in impedance spectroscopy data.

Engineering rare earth metal Ce-N coordination as catalyst for high redox kinetics in lithium-sulfur batteries

Lithium-sulfur (Li-S) batteries are a key area of research in energy storage due to their high theoretical energy density, low cost, and environmental friendliness. However, the shuttle effect caused by lithium polysulfides (LiPSs) intermediates often results in poor cycling stability. Therefore, constructing rational cathode structures to achieve fast reaction kinetics in adsorbing and catalyzing LiPSs is the key to obtain high-performance Li-S batteries. Metallic single-atom catalysts (SACs), known for their 100 % atomic utilization rate and low cost, have demonstrated excellent catalytic activity and selectivity in the redox reactions of Li-S batteries, positioning them as one of the most promising catalysts in this field. Rare earth metallic SACs with versatile oxidation states, diverse coordination chemistry and environmentally friendly are rarely investigated in Li-S system. Herein, we fabricate a rare earth metal-based single-atom catalyst (CeSAs) supported on a three-dimensional porous N-doped carbon (3DCeSA-N-WS), and systematically study its performance in Li-S batteries. Benefitting from the atomic dispersion and versatile oxidation states (Ce3+/Ce4+), the 3DCeSA-N-WS demonstrates excellent performance in anchoring and catalyzing LiPSs, significantly enhancing the redox reaction kinetics. Consequently, the prepared sulfur cathode exhibits exceptional electrochemical performance, with a high initial specific discharge capacity of 1225 mAh g−1 at 0.2 C and a capacity retention of 76.1 % after 160 cycles. The assembled 100 mAh-level pouch cellmaintains a high specific discharge capacity of 877 mAh g−1 after 50 cycles at 0.5 C. This work provides new insights into the design of sulfur cathode catalysts, thereby contributing to the realization of high-performance Li-S batteries.

Iron, cobalt embedded nitrogen-doped carbon derived from conjugated macrocyclic polymers as electrocatalysts for oxygen reduction reaction

The synthesis of earth-abundant metal-based electrocatalysts for deploying electrochemical energy devices has become an area of considerable interest. Herein, we have illustrated a facile Friedel-Crafts reaction for designing a metalloporphyrin polymer followed by its calcination to synthesize cauliflower-like nitrogen-doped iron-cobalt bimetallic electrocatalyst (FeCoTpp-900-2) and its satisfactory performance toward reducing oxygen. The bimetallic FeCoTpp-900-2 catalyst exhibits a half-wave potential (E1/2) of 0.84 V (vs. reversible hydrogen electrode (RHE)) and an onset potential (Eonset) of 0.95 V (vs. RHE). The notable electrocatalytic activity for oxygen reduction reaction (ORR) of FeCoTpp-900-2 is attributed to the presence of ORR active nitrogen species along with the Fe-Nx/Co-Nx sites. In addition, FeCoTpp-900-2 possesses an appreciable amount of mesopores responsible for the ORR behavior. Notably, the zinc-air battery consisting of FeCoTpp-900-2 as the catalyst for the air cathode presents a maximal power density of 127.53 mW cm−2 and robust durability for 24 hours (h). Therefore, this work can contribute to the facile synthesis of bimetallic electrocatalysts with non-noble metals to explore their applications in ORR.

Li2CO3/LiF-Rich Solid Electrolyte Interface Stabilized Lithium Metal Anodes for Durable Li-CO2 Batteries

Lithium carbon dioxide (Li-CO2) batteries are considered a promising next-generation energy storage device due to their high theoretical energy density and potential carbon neutralization. Despite numerous iterative advancements in cathode catalysts for Li-CO2 batteries, the cycling stability still to be hindered by the growth of lithium dendrites during cycling, primarily due to uneven deposition and the side reaction of sufficient CO2 with the Li metal anode. In this work, bisalt electrolyte (BE) consisting of LiPF6 and LiTFSI is used as a localized anode surface stabilizer to achieve durable Li-CO2 batteries. The introduction of PF6− promotes the decomposition and reduction of TFSI−, leading to the formation of LiF-rich inorganic SEI (Li2CO3/LiF-rich) with enhanced Li+ affinity and good electronic insulating properties. This effectively inhibits lithium dendrite formation while also insulating CO2 and electrolytes from contacting the lithium anode. Consequently, the Li symmetric battery incorporating the novel BE exhibits a long cycling life of 912 hours (∼3.8 times of the cell with a single-salt electrolyte (SE)). The BE based Li-CO2 battery achieves an ultra-long cyclelife of 2720 hours (∼2.6 times of SE battery) and outstanding rate capability. In addition, the assembled belt-shaped Li-CO2 batteries could stably power a digital watch for 1267 hours.

Post mortem Study of Catalyst Degradations Occurring in High-Temperature Proton Exchange Membrane Fuel Cells Upon Start-Stop Operation

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) could replace fossil fuel-based technologies for applications which cannot involve bulky/heavy cooling systems, such as aeronautics. However, severe materials degradations upon operation prevent performance retention for acceptable lifetimes. While others have already reported degradations in HT-PEMFC, post mortem characterizations of used HT-PEMFC membrane electrode assemblies (MEAs) remain scarce. Herein, HT-PEMFC performance degradation is studied by applying a startup/shutdown protocol to a short-stack operated at 160 °C; one MEA is characterized using complementary physicochemical/electrochemical techniques to identify/understand the degradation mechanisms and their origin. This start/stop operation mode (co-flow gas reactants) leads to substantial degradation inhomogeneity. For the anode, migration, coalescence, and detachment of Pt nanoparticles are witnessed induced by high-surface-area carbon support functionalization and corrosion. The anode electrochemical surface area (ECSA) remains constant at the inlet and increases significantly at the outlet, following inhomogeneous degradation of the cathode catalyst: the Ptz+ ions formed at high potential/oxidizing conditions concentrate towards the outlet, where they redeposit locally or at the anode, after diffusion/migration across the PBI membrane. Hence, the cathode ECSA decreases significantly at the inlet. Furthermore, intense Ni-leaching from the initial PtNi alloy catalyst is reported as a result of O2 mass-transport and phosphoric acid dilution inhomogeneity.

The Influence of Membrane Thickness and Catalyst Loading on Performance of Proton Exchange Membrane Fuel Cells

This paper explores the influence of membrane thickness and catalyst loading on fuel cell performance of commercially relevant membrane electrode assemblies (MEAs). A systematic study was carried out with MEAs comprised of commercially available Pt/C electrocatalysts and reinforced PFSA membranes to better understand the practical limitations of incorporating low platinum loadings and ultra-thin membranes in commercially viable MEA designs. Three different MEA configurations were compared where membrane thickness was either 15 or 10 μm and cathode catalyst loading was either 0.4 or 0.1 mgPt cm−2. Extensive in situ electrochemical characterization was carried out to extract the relevant physical and electrochemical parameters of each MEA configuration. By changing only one variable at a time, i.e., either thickness or catalyst loading, it was possible to deconvolute the specific contributions of membrane thickness and catalyst loading on fuel cell performance. Interestingly, as membrane thickness was reduced below 15 μm, no significant changes in fuel cell performance were observed as membrane interfacial effects begin to dominate compared to bulk transport effects. Conversely, reducing catalyst layer loading from 0.4 to 0.1 mgPt cm−2 introduces significant polarization losses attributed to a combination of kinetic and mass transport effects.

Highly asymmetrically configured single atoms anchored on flame-roasting deposited carbon black as cathode catalysts for ultrahigh power density Zn-air batteries

Iron group element-based single atom (SA) catalysts are highly regarded as promising alternatives to commercial Pt/C for catalysis of oxygen reduction reaction (ORR). For applications in rechargeable zinc-air batteries (ZABs), achieving the necessary high catalytic efficiency of the SAs toward oxygen evolution reaction (OER) however remains a significant challenge. Here, highly asymmetrically configured Fe SAs created with N,S co-coordination and anchored on flame-roasting deposited carbon black (CB), Fe-N3S1/CB, are developed, achieving outstanding bifunctional oxygen catalytic efficiency, with an ultra-small potential gap of 0.661 V at 10 mA cm-2 (ΔE10), outperforming the (Pt/C+RuO2) composite catalyst (0.697 V). With a newly proposed binder-free composite air cathode design, the Fe-N3S1/CB based ZAB achieves an ultrahigh power density of 365.7 mW cm-2 at a current density of 511.3 mA cm-2, largely outperforming the (Pt/C+RuO2) based ZAB (225.9 mW cm-2 at 344.7 mA cm-2). Furthermore, the Fe-N3S1/CB based ZAB demonstrates excellent long-term stability, with only 8.2% decay in round-trip efficiency over 1000 (333.3 h) charge-discharge cycles at 10 mA cm-2. Density functional theory calculations elucidate that incorporation of sulfur into the coordination sphere of Fe facilitates the electrochemical dehydroxylation step for ORR and accelerates the electrochemical O2 desorption step for OER, thereby reducing the corresponding free energy differences on Fe SAs for largely enhanced catalytic efficiency.1. A large size hetero-atom element, sulfur, is introduced to create highly asymmetrically configured Fe single atoms for enhancements in catalytic efficiency toward both oxygen reduction reaction and oxygen evolution reaction, and a binder-free composite air cathode design is proposed to improve electrochemical performances of zinc-air batteries.2. An ultra-small potential gap of 0.661 V at 10 mA cm-2 (ΔE10) is achieved for the air cathode, and an ultrahigh discharge power density of 365.7 mW cm-2 at a current density of 511.3 mA cm-2 is acquired for the zinc-air battery.

Tetracycline hydrochloride degradation with simultaneous electricity generation by bio-electro-Fenton system configured with carbon-modified Fe, Co dual-metal cathode catalyst

Tetracycline hydrochloride (TCH), which is difficultly degradable and widely used, can induce the generation and dissemination of antibiotic resistance genes (ARGs), seriously threatening the environment and human health. Herein, X% (X = 0, 1, 3, 5) carbon-decorated CoFe2O4 catalysts were developed and were assessed by physical characterization, electrochemical performance and their electricity production capabilities in a bio-electro-Fenton (BEF) system using sodium acetate as the substrate, showing that 5 %C-CoFe2O4 exhibited excellent catalytic performance and electron transfer efficiency. Therefore, the BEF configured with 5 %C-CoFe2O4 air–cathode catalyst realized the degradation of TCH and total organic carbon (TOC) across varying concentrations of TCH (0, 10, 20, and 30 mg/L). The BEF system with 30 mg/L TCH has the maximum output voltage (0.575 V), open circuit voltage (0.692 V), power density (0.588 W/m2) and minimum internal resistance (180.293 mΩ/m2) compared to other TCH concentrations. This is attributed to the synergistic effect of microbial fuel cells (MFC) and Fenton reactions promoting continuous oxidation–reduction cycles of Fe3+/Fe2+ and Co3+/Co2+ at the cathode. Furthermore, it increased the diversity and abundance of microbial communities and inhibited the transmission of ARGs. This work develops a high-performance non-expensive cathode catalyst applied to the BEF system, which can simultaneously remove antibiotics and control ARGs propagation.

Theory-Guided Design of Unconventional Phase Metal Heteronanostructures for Higher-Rate Stable Li-CO2 and Li-Air Batteries.

Lithium-carbon dioxide (Li-CO2) and Li-air batteries hold great potential in achieving carbon neutral given their ultrahigh theoretical energy density and eco-friendly features. However, these Li-gas batteries still suffer from low discharging-charging rate and poor cycling life due to sluggish decomposition kinetics of discharge products especially Li2CO3. Here we report the theory-guided design and preparation of unconventional phase metal heteronanostructures as cathode catalysts for high-performance Li-CO2/air batteries. The assembled Li-CO2 cells with unconventional phase 4H/face-centered cubic (fcc) ruthenium-nickel heteronanostructures deliver a narrow discharge-charge gap of 0.65 V, excellent rate capability and long-term cycling stability over 200 cycles at 250 mA g-1. The constructed Li-air batteries can steadily run for above 150 cycles in ambient air. Electrochemical mechanism studies reveal that 4H/fcc Ru-Ni with high-electroactivity facets can boost redox reaction kinetics and tune discharge reactions towards Li2C2O4 path, alleviating electrolyte/catalyst failures induced by the aggressive singlet oxygen from solo decomposition of Li2CO3.

Ruthenium atoms anchored on oxygen-modified molybdenum disulfide with strong interfacial coupling as efficient and stable catalysts for lithium–oxygen batteries

Rechargeable non-aqueous lithium-oxygen batteries (LOBs) have garnered increasing attention owing to their high theoretical energy density. However, their slow cathodic kinetics hinder efficient battery reactions. Nanoscale catalysts can effectively enhance electrocatalytic activity and atomic utilization efficiency. However, the agglomeration of nanoscale catalysts (such as cluster and single atoms) during continuous discharge/charge cycles leads to decreased electrochemical performance and poor cyclic stability. Herein, the ruthenium (Ru) atomic sites anchored on an O-doped molybdenum disulfide (O-MoS2) catalyst (designated as Ru/O-MoS2) was fabricated using a facile impregnation and calcination method. Strong Ru-O coupling between Ru atoms and the O-MoS2 substrate optimizes the localized electronic structure, resulting in improved electrochemical performance and enhanced resistance to Ostwald ripening. When employed as a cathode catalyst for LOBs, Ru/O-MoS2 catalyst exhibits a high reversible specific capacity (18700.5 (±59.8) mAh g−1), good rate capability, and enhanced long-term stability (115 cycles, 1200 h). This study encourages facile and efficient strategies for the development of effective and stable electrocatalysts for use in LOBs.

Effects of Ionomer Film Thickness and Water Content on Oxygen Permeation Properties of PEFC Cathode Catalyst

In order to promote the widespread use of Polymer Electrolyte Fuel Cell (PEFC), enhancing cell performance is necessary. One significant factor affecting cell performance is the oxygen permeability in the ionomer, which depends on its nano-scale structure. In this study, to investigate the relationship between structures of catalyst layers and cell performances, we analyzed the effects of film thickness and water content on the oxygen permeation properties of ionomer in the cathode catalyst layer of PEFC using molecular dynamics simulations. We constructed a system in which oxygen molecules permeated ionomer on a platinum (Pt) surface. We found that sulfonic acid groups have a significant effect on oxygen permeation in low water content conditions.

Relationship between synthesis conditions and ORR activity of PtCo nanowire/C catalysts for PEFC cathodes

Nanowire (NW) structures have attracted attention as durable catalysts for the oxygen reduction reaction (ORR) due to their resistance to aggregation, unique morphology, and efficient electron conduction. However, NWs often suffer from limited structural stability, and there is a lack of research on their performance in membrane electrode assembly (MEA) studies. In this study, PtCo NW/C catalysts with various amounts of oleylamine (OAm) were prepared, and their oxygen reduction reaction (ORR) activity and durability were investigated by MEA and RDE testing conditions. XRD analysis and TEM observations showed that the prepared PtCo NWs were successfully alloyed,and PtCo NW alloys were observed. CV and LSV results showed that the PtCo NW/C OAm100 catalyst with 2 h of acid treatment had the best ORR activity. The I-V test results demonstrated that the PtCo NW/C OAm100 catalyst with 2 h of acid treatment had higher cell voltage, and cell performance was also excellent. It was found that the ORR activity of PtCo NW was improved by adding the appropriate amount of OAm.

In-Depth Analysis of the Impact of Ionomer Content on PEMFC Degradation By Combining Electrochemical Characterization Techniques and Transmission Line Modeling

This study analyzes the influence of the ionomer-to-carbon ratio (I/C) in cathode catalyst layers (CCL) on carbon corrosion behavior during high-potential cycling accelerated stress tests (ASTs). Membrane electrode assembly (MEA) samples with varying I/C ratios (0.5/0.85/1.2) were evaluated using polarization curve measurements and electrochemical impedance spectroscopy (EIS) under H2/air conditions. Analysis through the distribution of relaxation times (DRT) and equivalent circuit modeling revealed that the MEAs with a high I/C ratio (1.2) and a medium I/C ratio (0.85) exhibited the highest beginning of life (BoL) performance, attributed to their lower ionic resistances. Conversely, the MEA with a low I/C ratio (0.5) showed significant improvement during initial AST cycles and superior carbon degradation resistance, despite poor BoL performance. This study highlights the need for further investigation to fully understand the impact of the I/C ratio on electrode structure and carbon corrosion behavior. Furthermore, the combined results suggest that optimizing the I/C ratio could enhance the durability of PEMFC electrodes.

Main-group element-boosted oxygen electrocatalysis of Cu-N-C sites for zinc-air battery with cycling over 5000 h

Developing highly active and durable air cathode catalysts is crucial yet challenging for rechargeable zinc-air batteries. Herein, a size-adjustable, flexible, and self-standing carbon membrane catalyst encapsulating adjacent Cu/Na dual-atom sites is prepared using a solution blow spinning technique combined with a pyrolysis strategy. The intrinsic activity of the Cu-N4 site is boosted by the neighboring Na-containing functional group, which enhances O2 adsorption and optimizes the rate-determining step of O2 activation (*O2 → *OOH) during the oxygen reduction reaction process. Meanwhile, the Cu-N4 sites are encapsulated within carbon nanofibers and anchored by the carbon matrix to form a C2-Cu-N4 configuration, thereby reinforcing the stability of the Cu centers. Moreover, the introduction of Na-containing functional groups on the carbon atoms significantly reduces the positive charge on their outer shell C atoms, rendering the carbon skeletons less susceptible to corrosion by oxygen species and further preventing the dissolution of Cu centers. Under these multi-type regulations, the zinc-air battery with Cu/Na-carbon membrane catalyst as the air cathode demonstrates long-term discharge/charge cycle stability of over 5000 h. This considerable stability improvement represents a critical step towards developing Cu-N4 active sites modified with the neighboring main-group metal-containing functional groups to overcome the durability barriers of zinc-air batteries for future practical applications.

In-Depth Analysis of the Impact of Ionomer Content on PEMFC Degradation By Combining Electrochemical Characterization Techniques and Transmission Line Modeling

This study analyzes the influence of the ionomer-to-carbon ratio (I/C) in cathode catalyst layers (CCL) on carbon corrosion behavior during high-potential cycling accelerated stress tests (ASTs). Membrane electrode assembly (MEA) samples with varying I/C ratios (0.5/0.85/1.2) were evaluated using polarization curve measurements and electrochemical impedance spectroscopy (EIS) under H2/air conditions. Analysis through the distribution of relaxation times (DRT) and equivalent circuit modeling revealed that the MEAs with a high I/C ratio (1.2) and a medium I/C ratio (0.85) exhibited the highest beginning of life (BoL) performance, attributed to their lower ionic resistances. Conversely, the MEA with a low I/C ratio (0.5) showed significant improvement during initial AST cycles and superior carbon degradation resistance, despite poor BoL performance. This study highlights the need for further investigation to fully understand the impact of the I/C ratio on electrode structure and carbon corrosion behavior. Furthermore, the combined results suggest that optimizing the I/C ratio could enhance the durability of PEMFC electrodes.

Effect of Contamination in the Carbon Catalyst Support on Chemical Degradation of Polymer Electrolyte Membranes in Fuel Cells

Chemical degradation of polymer electrolyte membranes (PEMs) is an important issue related to the durability of polymer electrolyte fuel cells (PEFCs). Although various studies have been conducted on the chemical degradation of PEMs, the relationship between cathode catalyst materials and chemical degradation of the PEM has not yet been fully understood. Here, we conduct accelerated chemical degradation tests of the PEM and investigate the effect of using cathode electrocatalysts with different carbon support materials. This aims to clarify the effect of the choice of carbon support on the chemical degradation of PEMs. It is confirmed that contaminants in the carbon support material can have a significant impact on chemical degradation of the PEM.

A platinum degradation reaction model for the high-speed computation in the integrated fuel cell system simulator and its validation by the accelerated stress test data of the commercial fuel cells

A model to estimate the Pt degradation rate and the numerical methods for high-speed computation were developed for the year-long and system-scale durability simulation in an acceptable accuracy and computational time. The parameters in the model were determined to reproduce the published accelerated stress test (AST) data with the 1 cm2 MEA of 2nd-generation MIRAI (MIRAI-2), state-of-the-art commercial fuel cell electric vehicle. Accuracy of the simulation results was validated by the published data of the ASTs with the FC stack having 13 cells of MIRAI-2, which consists of the 30000 startup-shutdown cycles in 0–0.88 V and 73000 acceleration-deceleration cycles in 0.6–0.9 V. The experimental and simulation results of the residual fractions of the electrochemical surface area in the cathode catalyst layer after the ASTs were 68 and 69 %, respectively, and they agreed in an acceptable accuracy. It was confirmed from the AST simulation with the different initial particle size distributions that even the small number of the coarse particles significantly accelerated the Pt degradation. The developed model was integrated to the FC system simulator the current authors had presented and a remarkable computational speed for the year-long and system-scale durability simulation was demonstrated with a normal laptop computer.