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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Cerium migration during PEM fuel cell accelerated stress testing

Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humidity cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.

30 DIRECT ENERGY CONVERSION↗

Accelerated test protocols to predict service life and durability of solid oxide fuel cells

Reliable accelerated test protocols are needed for solid oxide fuel cell research to facilitate rapid learning on key durability issues, identify potential modes of failure expeditiously, and eventually predict the calendar lifetime of an electrochemical cell. In this work, solid oxide fuel cells operated at a constant current density were compared to cells undergoing accelerated measurements, which are composed of intermittent current injection to the cell. A general accelerated test profile was developed by cycling a solid oxide fuel cell from open circuit to a predetermined operating current density that is the same as the current density during a steady-state operation, to accelerate the local redox environment. The following parameters were studied: current density, operation temperature, moist level, sintering temperature, cycling current, cycling frequency, and operation time. Up to 1,320,000 cycles were generated in this work. The cell degradation was accelerated by nearly 10 times, suggesting the feasibility of using this protocol for acceleration test to predict life performance and durability of solid oxide fuel cells.

08 HYDROGEN↗

PtCo Cathode Catalyst Morphological and Compositional Changes after PEM Fuel Cell Accelerated Stress Testing

Development of Pt catalysts alloyed with transition metals has led to a new class of state-of-the-art electrocatalysts for oxygen reduction at the cathode of proton exchange membrane fuel cells; however, the durability of Pt-based alloy catalysts is challenged by poor structural and chemical stability. There is a need for better understanding of the morphological and compositional changes that occur to the catalyst under fuel cell operation. In this work, we report in-depth characterization results of a Pt-Co electrocatalyst incorporated in the cathode of membrane electrode assemblies, which were evaluated before and after accelerated stress tests designed specifically to enhance catalyst degradation. Electron microscopy, spectroscopy, and 3D electron tomography analyses of the Pt-Co nanoparticle structures suggest that the small- and intermediate-sized Pt-Co particles, which are typically Pt-rich in the fresh condition, undergo minimal morphological changes, whereas intermediate- and larger-sized Pt-Co nanoparticles that exhibit a porous “spongy” morphology and initially have a higher Co content, transform into hollowed-out shells, which is driven by continuous leaching of Co from the Pt-Co catalysts. We further show how these primary Pt-Co nanoparticle morphologies group toward a lower Co, larger size portion of the size vs. composition distribution, and provide details of their nanoscale morphological features.

30 DIRECT ENERGY CONVERSION↗

DEGRADATION IN PERFORMANCE OF LANTHANUM STRONTIUM MANGANITE BASED SOLID OXIDE FUEL CELL CATHODES UNDER ACCELERATED TESTING

The performance of solid oxide fuel cells (SOFCs) with three different lanthanum strontium manganite (LSM) based cathode compositions were evaluated. All cells were yttria-stabilized zirconia (Zr0.92Y0.08O2-δ, 8YSZ) electrolyte-supported button cells, consisting of a nickel oxide – yttria-stabilized zirconia (NiO-8YSZ) anode and a cathode of 8YSZ and LSM. The three LSM compositions differed in the amount of excess Mn: Composition A was (La0.85Sr0.15)0.90MnO3±δ (10% excess Mn); Composition B was (La0.80Sr0.20)0.95MnO3±δ (5% excess Mn); and Composition C was (La0.80Sr0.20)0.98MnO3±δ (2% excess Mn). The cells were tested under conventional and accelerated conditions, where the accelerated conditions were meant to simulate the results of months of long-term testing in just 500 hours (approximately three weeks) of testing by using high operating temperature and current density. Accelerated tests showed lower degradation rates, lower continuous area specific resistance (ASR), and higher power output than conventional tests for all cathode compositions. Continuous measurements of the cells' output voltage versus time, together with periodic electrochemical impedance spectroscopy (EIS) measurements, were used to evaluate the performance of the cells in terms of ASR degradation rates (% ASR rise per kh) and power outputs. The EIS measurements also permitted a partial deconvolution of the cathode ASR from the anode ASR. Cathodes with 10% excess Mn tested under accelerated conditions had the lowest degradation rates, but the highest continuous ASR and lowest power outputs. Cathodes with 2% excess Mn tested under accelerated conditions had the lowest continuous ASR and highest power outputs; thus it was concluded that cells with the lowest amount of excess Mn cathodes performed the best.

08 HYDROGEN↗

Accelerated Stress Testing of Fuel Cell Membranes Subjected to Combined Mechanical/Chemical Stressors and Cerium Migration

A highly accelerated stress test (HAST) has been developed to generate local stressful conditions that are representative of those in automotive fuel cell stacks. Using a 50-cm 2 cell cycled between 0.05 and 1.2 A/cm 2 with a low inlet RH in the co-flow configuration, the HAST creates a distribution of combined mechanical/chemical stressors in the membrane with the maximum chemical stress occurring near the gas inlets and the maximum mechanical stress near the outlets. Conducting HASTs using a current distribution measurement tool and a shorting/crossover diagnostic method to track the state of health of a robust membrane containing both a mechanical support and a chemical stabilizing additive, the result shows that the membrane location with the most severe thinning coincides with that of the deepest membrane hydration cycling. Upon examination of the cerium redistribution patterns after the test, it was found that the severe humidity cycling generated by the HAST condition near the outlet region not only generated the highest membrane mechanical stress but also resulted in the strongest water flux, which may cause local depletion of the cerium added as chemical stabilizer. Further study is required to decouple the cerium migration effect from the possible mechanical/chemical synergistic degradation effect.

25 ENERGY STORAGE↗

Improved Accelerated Stress Tests Based on Fuel Cell Vehicle Data

UTC will led a top-tier team of industry and national laboratory participants to update and improve DOE’s Accelerated Stress Tests (AST’s) for hydrogen fuel cells. This in-depth investigation will focused on critical fuel cell components (e.g. membrane electrode assemblies - MEA) whose durability represented barriers for widespread commercialization of hydrogen fuel cell technology. UTC had access to MEA materials that had accrued significant load time under real-world conditions in PureMotion® 120 power plant used in transit buses. These materials are referred to as end-of-life (EOL) components in the rest of this document. Advanced characterization techniques were used to evaluate degradation mode progress using these critical cell components extracted from both bus power plants and corresponding materials tested using the DOE AST’s. These techniques were applied to samples at beginning-of-life (BOL) to serve as a baseline. These comparisons advised the progress of the various failure modes that these critical components were subjected to, such as membrane degradation, catalyst support corrosion, platinum group metal dissolution, and others. Gaps in the existing ASTs predicted the degradation observed in the field in terms of these modes were outlined. Using the gaps, new AST’s were recommended and tested to better reflect the degradation modes seen in field operation. Also, BOL components were degraded in a test vehicle at UTC designed to accelerate the bus field operation.

08 HYDROGEN↗

Accelerated Testing Validation

The DOE Fuel Cell technical team recommended ASTs were performed on 2 different MEAs (designated P5 and HD6) from Ballard Power Systems. These MEAs were also incorporated into stacks and operated in fuel cell bus modules that were either operated in the field (three P5 buses) in Hamburg, or on an Orange county transit authority drive cycle in the laboratory (HD6 bus module). Qualitative agreement was found in the degradation mechanisms and rates observed in the AST and in the field. The HD6 based MEAs exhibited lower voltage degradation rates (due to catalyst corrosion) and slower membrane degradation rates in the field as reflected by their superior performance in the high potential hold and open-circuit potential AST tests. The quantitative correlation of the degradation rates will have to take into account the various stressors in the field including temperature, relative humidity, start/stops and voltage cycles.

08 HYDROGEN↗

Membrane Accelerated Stress Test Development for Polymer Electrolyte Fuel Cell Durability Validated Using Field and Drive Cycle Testing

A combined chemical/mechanical accelerated stress test (AST) was developed for proton exchange membrane (PEM) fuel cells based on relative humidity cycling (RHC) between dry and saturated gases at open circuit voltage (OCV). Membrane degradation and failure were investigated using scanning electron microscopy and small- and wide-angle X-ray scattering. Changes to membrane thickness, hydrophilic domain spacing, and crystallinity were observed to be most similar between field-operated cells and OCV RHC ASTs, where local thinning and divot-type defects are the primary failure modes. While RHC in air also reproduces these failure modes, it is not aggressive enough to differentiate between different membrane types in >1,333 hours (55 days) of testing. Conversely, steady-state OCV tests result in significant ionomer morphology changes and global thinning, which do not replicate field degradation and failure modes. It is inferred that during the OCV RHC AST, the decay of the membrane's mechanical properties is accelerated such that materials can be evaluated in hundreds, instead of thousands, of hours, while replicating the degradation and failure modes of field operation; associated AST protocols are recommended as OCV RHC at 90°C for 500 hours with wet/dry cycle durations of 30s/45s and 2m/2m for automotive and bus operation, respectively.

25 ENERGY STORAGE↗

Durability evaluation of a Fe–N–C catalyst in polymer electrolyte fuel cell environment via accelerated stress tests

In this work, an “atomically-dispersed” iron-nitrogen-carbon (Fe–N–C) catalyst was used to provide a systematic comparison of platinum group metal (PGM)-free electrocatalyst degradation as a function of accelerated stress tests (ASTs) in an acidic polymer electrolyte fuel cell (PEFC). It was determined that the majority of catalyst degradation was caused by cell operation in presence of O 2 . In contrast, potential cycling of the Fe–N–C-containing cathode under inert atmosphere over typical PEFC cathode operation from 0.95 to 0.6 V had little to no effect. The increase in kinetic overpotential is shown to be the major source of the PEFC performance decrease during the ASTs. These results continue to showcase the need for development of robust PGM-free electrocatalysts in concert with improved electrochemical performance.

25 ENERGY STORAGE↗

Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2 -Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s ) due to higher initial Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology

25 ENERGY STORAGE↗

Impacts of electrode coating irregularities on polymer electrolyte membrane fuel cell lifetime using quasi in-situ infrared thermography and accelerated stress testing

In-line quality control diagnostics for roll-to-roll (R2R) manufacturing techniques will play a key role in the future commercialization of the polymer electrolyte membrane fuel cell (PEMFC) used in automotive applications. These diagnostics monitor the fabrication of the membrane electrode assembly (MEA), which detect and flag any non-uniformity that may potentially harm PEMFC performance and/or lifetime. This will require quantitative thresholds and a clear distinction between harmful defects and harmless coating irregularities. Thus, novel fuel cell hardware with quasi in-situ infrared (IR) thermography capabilities is utilized to understand how bare spots in the cathode electrode impact MEA lifetime. An accelerated stress test (AST) simulates chemical and mechanical degradation modes seen in vehicular operation. The actual open circuit voltage and rate of change of this voltage are used as in-situ indicators for MEA failure, enabling capture of the progression of failure point development. Bare spot coating irregularities located at the center of the electrode were found to have no impact on MEA lifetime when compared to a pristine MEA. However, MEA lifetime was found to be considerably shortened when these same irregularities are located at the cathode inlet and, especially, the anode inlet regions of the fuel cell.

36 MATERIALS SCIENCE↗

Non-Kinetic Losses Caused by Electrochemical Carbon Corrosion in PEM Fuel Cells

This paper presented non-kinetic losses in PEM fuel cells under an accelerated stress test of catalyst support. The cathode with carbon-supported Pt catalyst was prepared and characterized with potential hold at 1.2 V vs. SHE in PEM fuel cells. Irreversible losses caused by carbon corrosion were evaluated using a variety of electrochemical characterizations including cyclic voltammetry, linear sweep voltammetry, electrochemical impedance spectroscopy, and polarization technique. Ohmic losses at the cathode with potential hold were determined using its capacitive responses. Concentration losses in PEM fuel cells were analyzed in terms of Tafel behavior and thin film/flooded-agglomerate dynamics.

30 DIRECT ENERGY CONVERSION↗

Long Term Degradation of LSM Based SOFC Cathodes: Use of a Proven Accelerated Test Regimen

The overall goals of the program were: • To understand the microstructural basis of long-term performance loss in solid oxide fuel cells (SOFCs) with cathodes based on lanthanum strontium manganite (LSM, (La 1–x Sr x ) 1–yM nO 3±z ); • To develop strategies for optimizing LSM–based cathodes that achieve improved long-term performance, while exhibiting microstructural and chemical stability, for commercial fuel cell systems. The research project carried out accelerated testing of SOFCs with LSM-based cathodes of selected compositions. After intervals of accelerated testing (and control tests using non-accelerated conditions), the cells underwent extensive microstructural characterization to determine the physical and chemical changes in the cells. By analysis of a) the results of the testing, b) the observed microstructural changes, and c) the differences in these correlations between different cathode compositions and test durations, the research: • Identified a correlation between microstructural change and performance loss: specifically, between decrease of three-phase boundary (TPB) density and increase of area specific re-sistance (ASR) during operation; • Identified a cathode composition parameter — Mn excess, defined as 1/(1–y) in (La 1–x Sr x ) 1–y MnO 3±z ) — and how it affects TPB density, ASR and change of cell performance over time.

08 HYDROGEN↗