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At least 253 records · Page 14

Ion-Exchange Membrane-Centric Durability Testing and Degradation Characterization for Industry-Relevant CO 2 Reduction

Electrochemical CO 2 reduction is a promising conversion process for producing value-added fuels and chemicals from electricity and CO 2 as a sustainable carbon feedstock to domestically produce fuels and chemicals from industrial waste. Having reached industrially viable performance metrics with small-scale CO 2 electrolysis cells, the field must now increasingly focus on extending the device durability of large stacks to achieve equivalent metrics for 35,000+ hours to decrease maintenance and capital costs. Reported device lifetimes have increased in recent years, with the longest stability studies for CO, ethylene, and formic acid production being published in 2024–2025 with operation times of 4500, 1000, and 5200 h, respectively. Unfortunately, significant extension of the device durability is still required. Here, we provide an overview of ion-exchange membranes (IEMs) and provide insight into the variety of degradation mechanisms that must be overcome to enable the community to meet durability targets. In an effort to accelerate the extension of device lifetimes, we propose a general approach for characterizing CO 2 electrolysis cell degradation before and after durability testing to better elucidate the mechanisms and failure modes of IEMs in zero-gap cells. Furthermore, we encourage the adoption of operando characterizations in tandem with accelerated stress and durability tests, postulating that their combined applications will be increasingly valuable. We hope that this perspective motivates future durability studies to evaluate degradation across the entire electrolysis cell.

09 BIOMASS FUELS↗

Alkaline Stability of Quaternized Diels–Alder Polyphenylenes

Alkaline stability of anion exchange membranes is an essential requirement for the practical application of alkaline membrane fuel cells. In this study, we investigate the alkaline stability of Diels-Alder polyphenylenes (DAPPs) under various stability testing conditions. Structural analysis and membrane properties of the DAPPs indicated that different chemical structural changes of quaternized DAPPs occur depending on test conditions. Benzyltrimethylammonium functionalized DAPPs degraded rapidly via nucleophilic benzyl substitution under a relatively mild condition ca. 80 °C, 4 M NaOH whereas DAPPs with hexyltrimethylammonium (HTMA DAPP) exhibited much better alkaline stability. While only crosslinking of unreacted alkyl bromides of HTMA DAPP occurred at 80 °C, we observed the degradation of the cations via β- elimination after long term testing. At higher temperature or reduced relative humidity (RH) conditions, e.g., 160 °C or RH 10%, the rapid degradation of the cation in HTMA DAPP occurred via nucleophilic methyl substitution. These results suggest that accelerated stress tests may not be a quick and straightforward alternative to prolonged alkaline stability tests of AEMs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ordered Pt 3 Co Intermetallic Nanoparticles Derived from Metal–Organic Frameworks for Oxygen Reduction

Highly ordered Pt alloy structures are proved effective to improve their catalytic activity and stability for the oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, we report a new approach to preparing ordered Pt 3 Co intermetallic nanoparticles through a facile thermal treatment of Pt nanoparticles supported on Co-doped metal-organic framework (MOF)-derived carbon. In particular, the atomically dispersed Co sites, which are originally embedded into MOF-derived carbon, diffuse into Pt nanocrystals and form ordered Pt 3 Co structures. It is very crucial for the formation of the ordered Pt 3 Co to carefully control the doping content of Co into the MOFs and the heating temperatures for Co diffusion. The optimal Pt 3 Co nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential up to 0.92 V vs. RHE and only losing 12 mV after 30,000 potential cycling between 0.6 and 1.0 V. The highly ordered intermetallic structure was retained after the accelerated stress tests evidenced by atomic-scale elemental mapping. Fuel cell tests further verified the high intrinsic activity of the ordered Pt 3 Co catalysts. Unlike the direct use of MOF-derived carbon supports for depositing Pt, we utilized MOF-derived carbon containing atomically dispersed Co sites as Co sources to prepare ordered Pt 3 Co intermetallic catalysts. Finally, the new synthesis approach provides an effective strategy to develop active and stable Pt alloy catalysts by leveraging the unique properties of MOFs such as 3D structures, high surface areas, and controlled nitrogen doping.

25 ENERGY STORAGE↗

Electrochemical Evolution of Fuel Cell Platinum Nanocatalysts on Carbon Nanotubes at the Atomic Scale

The evolution of Pt nanoparticles supported on carbon nanotubes is analyzed before and after electrochemical potential cycling, using identical location aberration-corrected transmission electron microscopy, for applications in proton exchange membrane fuel cells. The work is focused on the half-cell accelerated stress test protocol of potential cycles ranging between 1.0 and 1.5 V RHE to represent the start-up/shutdown settings of a fuel cell vehicle. The research work reveals that particle migration and coalescence are key mechanisms for a reduction in the Pt nanoparticle surface area at the early stages of potential cycling. Further, the mechanism for particle movement and coalescence is attributed to carbon corrosion, catalyzed either by Pt or by bulk corrosion of the carbon nanotubes. Carbon corrosion results in the appearance of carbon vacancies at the carbon nanotube/Pt nanoparticle interface during cycling, as well as the formation of edge and surface defects. During cycling, the concentration of the dissoluble Pt increases. As soon as a significant amount is reached, subnanometer/atomic clusters emerge on the carbon nanotube support, which can move and coalesce, or redeposit on the surface of larger particles through Ostwald ripening.

25 ENERGY STORAGE↗

Recreating Fuel Cell Catalyst Degradation in Aqueous Environments for Identical-Location Scanning Transmission Electron Microscopy Studies

The recent surge in interest of proton exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles increases the demand on the durability of oxygen reduction reaction electrocatalysts used in the fuel cell cathode. This prioritizes efforts aimed at understanding and subsequently controlling catalyst degradation. Identical-location scanning transmission electron microscopy (IL-STEM) is a powerful method that enables precise characterization of degradation processes in individual catalyst nanoparticles across various stages of cycling. Recreating the degradation processes that occur in PEMFC membrane electrode assemblies (MEAs) within the aqueous cell used for IL-STEM experiments is vital for generating an accurate understanding of these processes. In this work, we investigate the type and degree of catalyst degradation achieved by cycling in an aqueous cell compared to a PEMFC MEA. While significant degradation is observed in IL-STEM experiments performed on a traditional Pt catalyst using the standard accelerated stress test potential window (0.6-0.95 VRHE), degradation of a PtCo catalyst designed for heavy-duty vehicle use is very limited compared to that observed in MEAs. We therefore explore various experimental parameters such as temperature, acid type, acid concentration, ionomer content, and potential window to identify conditions that reproduce the degradation observed in MEAs. We find that by extending the cycling potential window to 0.4-1.0 V RHE in an electrolyte containing Pt ions, the degraded particle size distribution and alloy composition better match that observed in MEAs. In particular, these conditions increase the relative contribution of Ostwald ripening, which appears to play a more significant role in the degradation of larger alloy particles supported on high-surface-area carbons than coalescence. Results from this work highlight the potential for discrepancies between ex situ aqueous experiments and MEA tests. While different catalysts may require a unique modification to the AST protocol, strategies provided in this work enable future in situ and identical-location experiments that will play an important role in the development of robust catalysts for heavy-duty vehicle applications.

30 DIRECT ENERGY CONVERSION↗

Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies

Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN 4 )-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm –2 at 0.7 V under HDV conditions (0.25 mgPt cm –2 and 250 kPa abs pressure) and retaining 1.20 A cm –2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. Importantly, the first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN 4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substrate with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Temperature Polymer Electrolyte Membrane Fuel Cells with High Phosphoric Acid Retention

Phosphoric acid loss poses immense hurdles for the durability of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Here we report quaternary ammonium-biphosphate ion-pair HT-PEMFCs that do not lose phosphoric acids under normal and accelerated stress conditions. Additionally, our energetics study explains the acid loss behavior of the conventional phosphoric acid-polybenzimidazole (PA-PBI) system by two mechanisms. If PA loss occurs via acid evaporation, the acid loss is constant over time. On the other hand, when water activity in the PA-PBI system is high, exponential decay of PA loss occurs via the water replacement mechanism. Combined 31 P NMR and computational studies show that the proposed ion-pair system has six times higher interaction energy, which allows for containing all PAs in the membrane electrode assemblies under a broad range of operating conditions. In addition, polar interactions between the phosphonic acid ionomer and phosphoric acid explain acid retention in the electrodes of the ion-pair HT-PEMFCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Stability of Manganese Chromium Antimonate Electrocatalysts through Multimodal In Situ and Operando Measurements

Herein, we utilize an on-line electrochemical flow cell coupled with an inductively coupled plasma-mass spectrometer (ICP-MS) to characterize the impact of composition and reactant gas on the multielement dissolution of Mn(-Cr)-Sb-O electrocatalysts. Compared to Mn 2 O 3 and Cr 2 O 3 oxides, we find that the antimonate framework stabilizes Mn at OER potentials and Cr at both ORR and OER potentials. Furthermore, dissolution of Mn and Cr from Mn(-Cr)-Sb-O is found to be driven by ORR reaction rate, with minimal dissolution under N 2 . We observe preferential dissolution of Cr totaling 13% over 10 minutes at 0.3, 0.6, and 0.9 V vs RHE, with only 1.5% loss of Mn, indicating an enrichment of Mn at the surface of the particles. Despite this asymmetric dissolution, in situ X-ray absorption spectroscopy (XAS) showed no measurable changes in the Mn K-edge at comparable potentials. This lack of change could suggest that modification to the Mn oxidation state in the surface layer is too small or that layer is too thin to be measured with the bulk XAS measurement. Lastly, on-line ICP-MS was used to assess the effects of applied potential, scan rate, and current of Mn-Cr-Sb-O during cyclic voltammetry and accelerated stress tests. With this deeper understanding of the interplay between oxygen reduction and dissolution, testing procedures were identified to maximize both activity and stability. This work highlights the use of multi-modal in situ characterization techniques in tandem to build a more complete model of stability and develop protocols for optimizing catalyst performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regulating Catalytic Properties and Thermal Stability of Pt and PtCo Intermetallic Fuel-Cell Catalysts via Strong Coupling Effects between Single-Metal Site-Rich Carbon and Pt

Developing low platinum-group-metal (PGM) catalysts for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles (HDVs) remains a great challenge due to the highly demanded power density and long-term durability. Here, this work explores the possible synergistic effect between single Mn site-rich carbon (Mn SA -NC) and Pt nanoparticles, aiming to improve intrinsic activity and stability of PGM catalysts. Density functional theory (DFT) calculations predicted a strong coupling effect between Pt and MnN 4 sites in the carbon support, strengthening their interactions to immobilize Pt nanoparticles during the ORR. The adjacent MnN 4 sites weaken oxygen adsorption at Pt to enhance intrinsic activity. Well-dispersed Pt (2.1 nm) and ordered L1 2 -Pt 3 Co nanoparticles (3.3 nm) were retained on the Mn SA -NC support after indispensable high-temperature annealing up to 800 °C, suggesting enhanced thermal stability. Both PGM catalysts were thoroughly studied in membrane electrode assemblies (MEAs), showing compelling performance and durability. The Pt@Mn SA -NC catalyst achieved a mass activity (MA) of 0.63 A mg Pt –1 at 0.9 V iR-free and maintained 78% of its initial performance after a 30,000-cycle accelerated stress test (AST). The L1 2 -Pt 3 Co@Mn SA -NC catalyst accomplished a much higher MA of 0.91 A mg Pt –1 and a current density of 1.63 A cm –2 at 0.7 V under traditional light-duty vehicle (LDV) H 2 –air conditions (150 kPa abs and 0.10 mg Pt cm –2 ). Furthermore, the same catalyst in an HDV MEA (250 kPa abs and 0.20 mg Pt cm –2 ) delivered 1.75 A cm –2 at 0.7 V, only losing 18% performance after 90,000 cycles of the AST, demonstrating great potential to meet the DOE targets.

25 ENERGY STORAGE↗

Sparsely Dispersed CeO x ‑Stabilized Pt Nanoparticles Overcome Pt Loading–Durability Trade-Off for Highly Durable Heavy-Duty Fuel Cells

Proton-exchange-membrane fuel cells (PEMFCs) are clean and sustainable mobile power sources for transportation. Recently, their deployment in heavy-duty vehicles (HDVs) has attracted growing interest owing to their high energy scalability and lower infrastructure requirements. However, to meet the stringent requirements for efficiency and long-term durability for HDV applications, PEMFCs typically employ a relatively high platinum group metal (PGM) loading (>0.2 mg PGM /cm 2 ). This elevated PGM loading significantly increases the stack and system costs, surpassing the U.S. Department of Energy (DOE) target of $\$ 60$/kW for commercial viability. Reducing PGM loading while maintaining performance and durability remains a central challenge for HDV fuel cells. Here we exploit metal oxide–Pt interactions and utilize the strong CeO x –Pt interaction to design a CeO x @Pt catalyst structure with exceptional durability. At a low total PGM loading (0.1 mg PGM /cm 2 ), the CeO x @Pt/C catalyst demonstrates high fuel cell performance (8.8 kW/g PGM ) and stability (power retention >90%) after the challenging HDV durability testing (90,000 accelerated-stress-test cycles). With the CeO x @Pt/C catalyst, we showcase over 70% reduction in Pt cost from the M2FCT target (to $\$ 9$/kW), highlighting its promising potential for enabling stable and cost-effective fuel cell systems for heavy-duty applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrospun Ti–Zr Oxide Heterostructures Enable Strongly Anchored Ultralow-Ir Anodes for Durable Acidic Oxygen Evolution

Proton-exchange-membrane water electrolysis (PEMWE) requires acidic oxygen-evolution-reaction (OER) anodes that combine high activity, high durability, and low Ir loading. Here, we report a Ti-Zr composite electrospun oxide (ESO) nanorod support that enables ultralow-Ir anodes for high-performance PEMWE. Zr-containing Ti oxide heterostructures stabilize anatase-rich TiO2, tune the local oxygen-coordination environment, and strengthen interfacial anchoring of IrOx under acidic anodic conditions. The electrospun nanorod network further creates an open, mechanically coherent catalyst layer that improves Ir utilization, ionomer penetration, and mass transport. At an anode loading of 0.2 mgIr cm-2, the optimized Ir/TiZr20-ESO anode delivers a PEMWE mass activity of 0.99 A mgIr-1 at 1.45 V, 28.3 and 43.0 times higher than commercial Ir black and commercial IrO2/TiO2, respectively. The same anode reaches 3.0 and 4.0 A cm-2 at 1.75 and 1.83 V, respectively, and sustains 2000 h operation at 2.0 A cm-2. Also, accelerated stress tests up to 525 hours over 31,500 cycles confirm promising long-term durability, with an insignificant performance decay of 0.4 μV per cycle. Density functional theory indicates that the Ti-Zr oxide heterostructure suppresses Ti demetallation and strengthens IrO2 interfacial binding, rationalizing the improved high-current-density stability.

25 ENERGY STORAGE↗

Ionomer-free and recyclable porous-transport electrode for high-performing proton-exchange-membrane water electrolysis

Abstract Clean hydrogen production requires large-scale deployment of water-electrolysis technologies, particularly proton-exchange-membrane water electrolyzers (PEMWEs). However, as iridium-based electrocatalysts remain the only practical option for PEMWEs, their low abundance will become a bottleneck for a sustainable hydrogen economy. Herein, we propose high-performing and durable ionomer-free porous transport electrodes (PTEs) with facile recycling features enabling Ir thrifting and reclamation. The ionomer-free porous transport electrodes offer a practical pathway to investigate the role of ionomer in the catalyst layer and, from microelectrode measurements, point to an ionomer poisoning effect for the oxygen evolution reaction. The ionomer-free porous transport electrodes demonstrate a voltage reduction of > 600 mV compared to conventional ionomer-coated porous transport electrodes at 1.8 A cm −2 and <0.1 mg Ir cm −2 , and a voltage degradation of 29 mV at average rate of 0.58 mV per 1000-cycles after 50k cycles of accelerated-stress tests at 4 A cm −2 . Moreover, the ionomer-free feature enables facile recycling of multiple components of PEMWEs, which is critical to a circular clean hydrogen economy.

08 HYDROGEN↗

Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells

Nitrogen-coordinated single atom iron sites (FeN 4 ) embedded in carbon (Fe–N–C) are the most active platinum group metal-free oxygen reduction catalysts for proton-exchange membrane fuel cells. Still, current Fe–N–C catalysts lack sufficient long-term durability and are not yet viable for practical applications. Here we report a highly durable and active Fe–N–C catalyst synthesized using heat treatment with ammonia chloride followed by high-temperature deposition of a thin layer of nitrogen-doped carbon on the catalyst surface. We propose that catalyst stability is improved by converting defect-rich pyrrolic N-coordinated FeN 4 sites into highly stable pyridinic N-coordinated FeN 4 sites. The stability enhancement is demonstrated in membrane electrode assemblies using accelerated stress testing and a long-term steady-state test (>300 h at 0.67 V), approaching a typical Pt/C cathode (0.1 mg Pt cm -2 ). The encouraging stability improvement represents a critical step in developing viable Fe–N–C catalysts to overcome the cost barriers of hydrogen fuel cells for numerous applications.

08 HYDROGEN↗

Regulating in situ gaseous deposition to construct highly durable Fe–N–C oxygen-reduction fuel cell catalysts

The activity–stability trade-off challenges the design of high-performance atomically dispersed iron–nitrogen–carbon (Fe–N–C) catalysts for the acidic oxygen reduction reaction in polymer electrolyte fuel cells. Here we develop an in situ chemical vapour deposition approach during catalyst synthesis to break the trade-off, producing highly stable Fe–N–C catalysts while maintaining adequate oxygen reduction reaction activity. The optimal catalyst exhibits a half-wave potential of 0.867 V, remaining unchanged after an accelerated stress test (AST) of 100,000 potential cycles in rotating disk electrode tests. In membrane electrode assemblies under H 2 –air conditions, it delivers 93 mA cm −2 at 0.8 V after a standard AST of 30,000 voltage cycles, and shows minimal current density losses (2.9% at 0.6 V; 14.2% at 0.7 V) after an extended AST up to 120,000 cycles. Furthermore, the catalyst’s durability improvement is primarily due to the in situ chemical vapour deposition, which strengthens Fe–N bonds, increases active-site density, mitigates iron aggregates and reduces surface porosity.

Chemical engineering↗

Zr-doped ceria additives for enhanced PEM fuel cell durability and radical scavenger stability

Doped ceria compounds demonstrate excellent radical scavenging abilities and are promising additives to improve the chemical durability of polymer electrolyte membrane (PEM) fuel cells. Here in this paper, Ce 0.85 Zr 0.15 O 2 (CZO) nanoparticles were incorporated into the cathode catalyst layers (CLs) of PEM fuel cells (based on Nafion XL membranes containing 6.0 μg cm -2 ion-exchanged Ce) at loadings of 10 and 55 μg cm -2 . When compared to a CZO-free baseline, CZO-containing membrane electrode assemblies (MEAs) demonstrated extended lifetimes during PEM chemical stability accelerated stress tests (ASTs), exhibiting reduced electrochemical gas crossover, open circuit voltage decay, and fluoride emission rates. The MEA with high CZO loading (55 μg cm -2 ) demonstrated performance losses, which are attributed to Ce poisoning of the PEM and CL ionomer regions, which is supported by X-ray fluorescence (XRF) analysis. In the MEA with the low CZO loading (10 μg cm -2 ), both the beginning of life (BOL) performance and the performance after 500 hours of ASTs were nearly identical to the BOL performance of the CZO-free baseline MEA. XRF analysis of the MEA with low CZO loading reveals that the BOL PEM Ce concentrations are preserved after 1408 hours of ASTs and that Ce contents in the cathode CL are not significant enough to reduce performance. Therefore, employing a highly effective radical scavenger such as CZO, at a loading of 10 μg cm -2 in the cathode CL, dramatically mitigates degradation effects, which improves MEA chemical durability and minimizes performance losses.

36 MATERIALS SCIENCE↗

Heteropoly acid functionalized fluoroelastomer with outstanding chemical durability and performance for vehicular fuel cells

To further facilitate commercialization of automotive fuel cells, durability concerns need to be addressed. Currently the addition of a mechanical support in the membrane is able to adequately solve issues of mechanical degradation, but chemical degradation via oxygenated radical attack remains an unsolved challenge. Typical mitigation strategies use cerium or manganese species to serve as radical scavengers, but these ions are able to migrate in the membrane and even leach out of the system. The approach used in this paper is to covalently link and immobilize a heteropoly acid (HPA), more specifically 11-silicotungstic acid (HSiW11), a lacunary HPA of the Keggin structure to a fluoroelastomer, serving as both a radical decomposition catalyst and the proton conducting acid. This dual functionality allows for both high content of radical scavenging species and high ion-exchange capacity. An efficient three step, high yield (77%), commercially viable synthesis for this polymer is reported. The synthesis route for making this new heteropoly acid functionalized polymer is confirmed using infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis (TGA). The material exhibits clustering of the HSiW11 moieties, resulting in a poorly connected proton conducting phase when dry, but excellent conductivity is achieved at elevated humidities (0.298 S cm -1 at 80 °C and 95% RH). The proton conductivity shows an enhancement above 60 °C due to a softening of the polymer, as shown by DSC. Under an aggressive chemical accelerated stress test (AST), 90 °C, 30% RH, zero current, and pure O 2 , the PolyHPA losses only 0.05 V of open circuit voltage (OCV) after 500 h, greatly out performing any other material reported in the literature. For comparison, the Nafion® N211 fuel cell drops below 0.8 V after only 76 h under the same conditions. Finally, in fuel cell testing the PolyHPAs have outstanding chemical stability and also possess very low in situ high frequency resistance (HFR) leading to high performance (1.14 W cm -2 at 2 A cm -2 ), compared to 1.11 W cm -2 for the Nafion® N211 fuel cell at the same current. At 75 wt% HSiW11 loading, the fuel cell HFR showed a 22% decrease over N211.

30 DIRECT ENERGY CONVERSION↗