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At least 487 records · Page 27

Advanced PGM-free Cathode Engineering for High Power Density and Durability

Polymer electrolyte fuel cells (PEFCs) are among the most promising technologies for future electric vehicles by using clean H2 with much-improved energy conversion efficiency, longer range, and rapid refueling. However, due to a large amount of platinum group metal (PGM) catalyst used in their electrodes, their prohibitively high cost hinders broad commercialization of PEFCs for transportation. Therefore, there is a critical need to develop low-cost, high-performance PGM-free cathode catalysts that have the potential to dramatically transform the economics of PEFC commercialization by reducing catalyst costs by one to two orders of magnitude. However, before PGM-free cathodes become viable, several technical challenges associated with PGM-free cathodes must be addressed, including insufficient activity and stability of the catalysts, as well as severe water flooding and large transport losses in the electrodes. Overcoming those barriers and ultimately meeting the challenging automotive PEFC performance targets was the focus of this comprehensive research and development effort on new PGM-free cathodes. To this end, we assembled a team including leading researchers from universities and industry with different but complementary expertise and capabilities. The project combined three novel and promising approaches: Advanced metal-organic framework (MOF)-derived M-N-C catalysts with a high activity and impressive durability, Novel PGM-free specific cathode architectures and fabrication strategies capable of addressing the substantial flooding and transport resistances in thicker cathodes by introducing engineered hydrophobicity through additives and support layers, and Advanced electrode ionomers with high proton conductivity for low ohmic losses across the electrode and more uniform catalyst utilization. The implementation of these new materials and electrode designs was supported by a suite of advanced experimental and simulation tools that allows us to identify performance and durability bottlenecks, devise solutions, and establish rational material design and synthesis targets. These methods include advanced electrochemical characterization, high-resolution imaging, and multi-scale modeling. In addition, the project team leveraged a broad cross-section of the ElectroCat consortium’s national laboratory facilities and expertise in advancing these materials and design strategies. Finally, the industry partners on the project facilitated the evaluation of scaled-up synthesis and manufacturing in the United States. Over its four-year period, the project made significant year-over-year advances in PGM-free cathode performance and viability. A combination of high activity and highly durable catalysts were developed through novel catalyst synthesis strategies, which met several performance and durability targets. More specifically, a catalyst prepared from MOFs and Fe2O3 nanoparticles with ammonium chloride and chemical vapor deposition treatments yielded a significant advancement in PGM-free cathode durability. Several novel strategies for fabricating cathodes were demonstrated, including those designed to reduce flooding and thickness of the cells for significantly increased volumetric power density. An optimized cathode with high conductivity ionomer and tuned ink processing for hydrophobicity yielded high fuel cell performance with new levels power density and maximum current. The scientific studies and modeling assessment also provided an outlook for future efforts, including a focus on catalysts with an increased density of the highly stable active sites developed in this project.

08 HYDROGEN↗

ElectroCat: Platinum-Group-Metal-Free Engineered Framework Nano-Structure Catalyst (Final Technical Report)

Traditional synthesis methodologies that produce durable, highly active PGM-free electrocatalysts typically consist of a top-down approach utilizing a nitrogen-coordinating precursor, a metal precursor, and a support material. Nitrogen-coordinated transition metal complexes typically are absorbed onto a support material, which is then activated via high-temperature pyrolysis. Selection of the support and the nitrogen coordinating precursor has long been the focal point of efforts to maximize the number of accessible, catalytically active sites. In this project, GWE in collaboration with SRNL and NU will develop durable, highly active, low-cost, PGM-free electrocatalysts for polymer electrolyte membrane fuel cells designed and synthesized using a unique, bottom-up, rationally designed approach. Electrocatalysts are produced via polymerization reaction followed by a high-temperature pyrolysis step. Additionally, this project focuses on catalyst site and ORR mechanistic modeling to better understand the structure-property relationship.

08 HYDROGEN↗

Computational analysis of metal–metal bonded dimetal tetrabenzoate redox potentials in the context of ammonia oxidation electrocatalysis

Metal–metal bonded complexes are promising candidates for catalyzing redox transformations. Of particular interest is the oxidation of ammonia to dinitrogen, an important half reaction for the potential utilization of ammonia as a fuel or hydrogen carrier. This work computationally explores 30 different metal–metal bonded dimers (5 different metal centers and 6 different benzoate ligand derivatives) to explore the tunability of the redox potential when ammonia is bound to the complexes as an axial ligand, modeling the first step in ammonia oxidation electrocatalysis. We calculate the redox potentials of these compounds, making reference to experimental data when appropriate, identifying two degrees of tunability: a coarse adjustment, changing the metal center, allows for a wide range of redox potentials to be accessed (from +1.0 to –2.0 V vs. ferrocene/ferrocenium in acetonitrile solution) and a fine adjustment, the para-substituent of the benzoate derivative, which affects the redox potential in a smaller range based on the electron donating/withdrawing effects of the substituent. Ruthenium and osmium tetrabenzoate catalysts are prime candidates for next generation ammonia oxidation catalysts because their redox potentials fall within the direct ammonia fuel cell “viability zone” bracketed by the thermodynamic potentials of oxygen reduction (ORR) and nitrogen reduction (NRR). Rhodium tetrabenzoate species fall above the ORR potential, suggesting ammonia oxidation promoted by Rh 2 catalysts could instead be used to facilitate hydrogen production through coupling to hydrogen evolution at a cathode. The redox potentials of rhenium and iridium tetrabenzoate catalysts fall below the NRR potential suggesting that these compounds could be further investigated in the context of electrochemical ammonia synthesis. Each redox event studied involves electron transfer from the M–M δ* orbital regardless of choice of metal or benzoate ligand derivative; this leads us to believe that the chemical reactivity of the various studied compounds will be similar in the context of ammonia oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemistry of Materials Underpinning Photoelectrochemical Solar Fuel Production

Since its inception, photoelectrochemistry has sought to power the generation of fuels, particularly hydrogen, using energy from sunlight. Efficient and durable photoelectrodes, however, remain elusive. Here we review the current state of the art, focusing our discussion on advances in photoelectrodes made in the past decade. We open by briefly discussing fundamental photoelectrochemical concepts and implications for photoelectrode function. We next review a broad range of semiconductor photoelectrodes broken down by material class (oxides, nitrides, chalcogenides, and mature photovoltaic semiconductors), identifying intrinsic properties and discussing their influence on performance. We then identify innovative in situ and operando techniques to directly probe the photoelectrode|electrolyte interface, enabling direct assessment of structure–property relationships for catalytic surfaces in active reaction environments. We close by considering more complex photoelectrochemical fuel-forming reactions (carbon dioxide and nitrogen reduction, as well as alternative oxidation reactions), where product selectivity imposes additional criteria on electrochemical driving force and photoelectrode architecture. By contextualizing recent literature within a fundamental framework, we seek to provide direction for continued progress toward achieving efficient and stable fuel-forming photoelectrodes.

08 HYDROGEN↗

High Efficiency Reversible Solid Oxide System (Final Technical Report)

This report was generated based upon work supported by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Hydrogen and Fuel Cell Technologies Office, H2@Scale Initiative, Award Number DE-EE0008847. In this project, FuelCell Energy studied the design and performance of a system rated for 15kWe Charge/3 kWe Discharge energy storage system based on reversible solid-oxide technology.

08 HYDROGEN↗

Renewable Hydrogen to Vehicle (RH2V) – Operation Verification and Risk Mitigation Studies: Original Agreement (Modification 0) (CRADA Final Report)

Toyota has announced plans for commercial fuel cell vehicle deployment in 2015. To fully realize the benefits of fuel cell vehicles (zero emission with no performance loss in terms of vehicle range and capability), hydrogen produced efficiently from renewable sources is necessary. Most of the hydrogen fueling stations today utilize hydrogen reformed from natural gas (produced onsite or delivered). This enables more stations to be deployed cost-effectively within a network. Producing and using cost-effective renewable hydrogen in fuel cell vehicles will enable realization of the full potential. A viable option of green hydrogen that reliably delivers on the full suite of benefits for Toyota fuel cell vehicle drivers is needed. NREL is in a unique position to analyze and optimize renewable hydrogen production scenarios using the Energy Systems Integration Facility (ESIF), a facility that is specifically designed to evaluate renewable energy integration technologies. As the U.S. Department of Energy's (DOE) primary national laboratory for renewable energy and energy efficiency research and development, NREL has extensive knowledge of photovoltaic systems as well as alternative renewable technologies for efficient and reliable production of green hydrogen.

08 HYDROGEN↗

Operability of a Natural Gas–Air Rotating Detonation Engine

A combustor was developed to operate with natural gas and air as the primary propellants at elevated chamber pressures and air preheat temperatures representative of land-based power generation gas turbine engines. Detonation dynamics were studied to characterize the operability of rotating detonation-based pressure gain combustion systems for this application. Measurements of chamber wave dynamics were performed using high-frequency pressure transducers and high-speed imaging of broadband combustion chemiluminescence. The rotating detonation engine was tested with two injector configurations across a broad range of mass flux (200–500 kg/m 2 /s), equivalence ratio (0.85–1.2), and oxygen mass fraction (23.2–35%) conditions to determine the effect of operating parameters on the propagation of detonation waves in the combustor. Wave propagation speeds of up to 70% of the mixture Chapman–Jouguet detonation velocity and chamber pressure fluctuations greater than 4 times the mean chamber pressure were observed. Supplementing the air with additional oxygen, varying the equivalence ratio, and enriching the fuel with hydrogen revealed that combustor operability is sensitive to the chemical kinetics of the propellant mixture. Comparing the operational trends of the two injector configurations suggests that one design mixes the incoming propellants more effectively. Although most test conditions exhibited counter-rotating detonation waves within the chamber, the injector design with superior mixing characteristics was able to support single-wave propagation.

20 FOSSIL-FUELED POWER PLANTS↗

Development of Risk Mitigation Guidance for Hydrogen Sensor Placement Indoors and Outdoors

Guidance on Sensor Placement remains one of the top priorities for the safe deployment of hydrogen and fuel cell equipment in the commercial marketplace. Building on the success of Phase 1 work reported at ICHS2019 and published in IJHE, this paper discusses the consecutive steps to further develop and validate such guidance for mechanically ventilated enclosures. The key step included a more in-depth analysis of sensitivity to variation of physical parameters in a small enclosure, and finally, expansion of the developed approach to confined spaces in an outdoor environment.

codes and standards↗

Hydrogen production from lignocellulosic hydrolysate in an up-scaled microbial electrolysis cell with stacked bio-electrodes

Hydrogen production from renewable resources via microbial electrolysis cells (MECs) is a promising approach for sustainable energy production. Yet high hydrogen yield from real feedstocks has not been demonstrated in up-scaled MECs. In this study, a 10-L single chamber MEC with a high electrode surface area to volume ratio (66 m 2 /m 3 ) was constructed and electroactive cathodic biofilms were enriched for hydrogen evolution reaction. A high hydrogen yield of 91% was achieved using lignocellulosic hydrolysate with a hydrogen production rate of 0.71 L/L/D at an organic loading rate of 0.4 g/D. The anodic and cathodic microbial communities, with Enterococcus spp. as the known electroactive bacteria, were capable of achieving current densities of 13.7 A/m 2 and 16.5 A/m 2 , respectively. Finally, a machine learning algorithm was used to investigate the correlation between community data and electrochemical performance, and the critical genera on determining current density were identified.

54 ENVIRONMENTAL SCIENCES↗

Midwest ZEVI 2030 Charging Roadmap for I-80 Corridor

Zero-emission Medium Duty and Heavy Duty vehicles (MD-HD ZEVs) hold great promise for reducing operational costs through use of more energy eAicient propulsion technology while reducing reliance on fossil fuels. Consistent with the Department of Energy’s focus on energy innovation, ZEVs and the necessary charging and refueling infrastructure to support them represent an important area of focus for technological advancement. Widespread adoption of MD-HD ZEVs can also provide benefits by improving air quality, and lowering carbon emissions in the transportation industry. Powertrain technologies are in production today to reduce tank-to-wheel and well-to-wheel emissions of commercial vehicles to zero or near-zero emissions, but significant development remains to bring down the cost and address the operational limitations of these technologies, particularly for larger vehicles. ZEV technologies have an opportunity to be an important part of a fleet’s mix of powertrains as capital and operational costs come down. However, the greatest challenge preventing widespread adoption of ZEVs may be the lack of adequate charging and hydrogen (H₂) fueling infrastructure.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Pathways for Negative-Emissions Hydrogen: Opportunities and R&D Needs

The Carbon-Negative Hydrogen Workshop, hosted by NREL in Golden, Colorado, focused on developing a shared understanding of the importance of and opportunities for generation and use of carbon-negative H2 in industrial decarbonization. Attendees helped define research needs, spot barriers to commercialization, and identify technical challenges, opportunities, and knowledge gaps for this emerging technology area. Workshop discussion themes included energy justice in early-stage research, R&D pathways for negative-emissions H2, biomass gasification to carbon-negative H2, and policy and carbon accounting considerations.

biomass↗

Idaho national laboratory to demonstrate collaboration first versus competition to accelerate achieving a secure clean energy future by 2031

Idaho National Laboratory (INL) announced at COP27 it would reach net zero greenhouse gas (GHG) emissions by 2031. As a Nuclear, Energy and Environment, and National Homeland Security laboratory, the predominant solution to closing the clean energy gap will include nuclear as a safe, clean, reliable and affordable electricity source with the additional benefit of producing heat and hydrogen to fuel INL’s large transportation fleet. INL’s collaboration first vs. competition is essential to the program’s success. The focused actions in INL’s Nuclear Roadmap include: Infrastructure, Licensing/Regulatory, Financial, Time to Market, Fuel Cycle and Public Confidence/Communications. The roadmap also includes nuclear technology innovations and creative partnerships with utility providers, regulators, businesses, community members, and Indigenous Peoples to accelerate deployment of advanced reactors. Through development of the Net-Zero Nuclear Roadmap, INL will offer a model to provide safe and secure energy for the nation and the world by: (1) establishing the necessary infrastructure on its 890-square mile site to support demonstration, (2) showing proven pathways through the licensing and regulation process, (3) partnering with utilities to ensure commercial application, and (4) collaborating with industry to site new technologies.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Hydrogen Storage Engineering Center of Excellence Adsorbent (Final Report)

The Hydrogen Storage Engineering Center of Excellence (HSECoE) team would like to thank the U.S Department of Energy’s (DOE) Hydrogen and Fuel Cell Technologies Office for the funding to embark on such a large endeavor to develop the material and engineering science related to the use of adsorbents as the storage media for automotive applications. In addition, SRNL would like to thank the many partners of the HSECoE including U.S. automotive manufacturers, GM and Ford, potential component and materials suppliers, United Technologies Research Center, Hexagon Lincoln Composites, and BASF, Universities, Oregon State University, University of Michigan, and the University of Québec, Trois Reveres, along with the Jet Propulsion Laboratory, Pacific Northwest National Laboratory, Los Alamos National Laboratory and Savannah River National Laboratory. Individual specific contributions can be found in individual final reports submitted to DOE. No attempt is made here to attribute contributions to individual people or organizations, illustrating the cooperative arrangement of the team members.

08 HYDROGEN↗

Novel platinum group metal-free catalyst ink deposition system for combinatorial polymer electrolyte fuel cell performance evaluation

Here, a new system for rapid and precise fabrication of polymer electrolyte fuel cell (PEFC) membrane-electrode assemblies (MEAs) is introduced to facilitate rapid testing and characterization of platinum group metal-free (PGM-free) catalysts, with minimal waste of materials, using commercial combinatorial hardware and multi-channel potentiostat. The commercial combinatorial system, designed for high-throughput catalyst activity evaluation (i.e., low overpotential and current densities) using gas-diffusion electrodes (GDEs), has been further developed to enable simultaneous evaluation of the high current density performance on air of twenty-five cathodes prepared by coating catalyst-ionomer inks directly onto the membrane using a newly-developed deposition system. A nanopipette or micropipette coupled to a precise peristaltic pump is being used for precise and even catalyst ink deposition onto the membrane in each of twenty-five circular electrodes with areas of <1 cm 2 and in the precise locations required by the commercial combinatorial MEA hardware. The automated ink deposition system is coupled with a custom-designed heated vacuum table mounted on a computer-controlled XY stage to prevent deformation of the membrane and electrode layers during ink deposition onto the membrane. This system was utilized to evaluate the impact of ionomer to catalyst ratio on the hydrogen-air fuel cell performance of the PGM-free catalyst.

25 ENERGY STORAGE↗

A simple convertible electrolyzer in membraneless and membrane-based modes for understanding water splitting mechanism

State-of-the-art membrane-based electrolyzers such as proton exchange membrane electrolyzer cells, are costly, susceptible to degradation, and time-consuming for electrode evaluation and triple-phase boundary electrochemical reaction studies. Here, a simple convertible electrolyzer in membraneless and membrane-based modes is proposed. For the first time, this enables comprehensive investigations of water splitting with pure water, acidic and alkaline electrolytes in one cell. With the simple electrolyzer and high-speed visualization system, the influences of flow rate, electrolytes, concentration, and Nafion membrane on the oxygen evolution reactions (OERs), hydrogen evolution reactions (HERs) and electrolyzer performance are comprehensively investigated. Visualization results reveal that water splitting only occurred at the edge between the electrode and the Nafion membrane in pure water. However, they occurred on the whole electrode surface in alkaline and acidic electrolytes, indicating easily tunable reaction sites with the convertible electrolyzer. This demonstrates the feasibility of using the simple convertible electrolyzer for understanding the water splitting mechanism. The relation between electrolyte thickness and resistances with different electrolytes is also quantified. This research provides an insight for optimizing electrochemical devices while delivering an inexpensive and fast way for electrode evaluations and electrochemical reaction studies.

25 ENERGY STORAGE↗

Effect of Engineered Cracks in Catalyst Layers on PEMFC Catalyst Layer Durability

Proton exchange membrane fuel cells (PEMFCs) are expected to play a pivotal role in decarbonizing the transportation sector, and particularly heavy-duty vehicles (HDVs). However, improvements in durability are needed for PEMFCs to compete with state-of-the-art power sources for HDVs. Here, we examine how catalyst layer (CL) cracks that are engineered affect the CL durability by using patterned silicon templates to control the CL crack density at the micrometer scale. Electrochemical analyses show that the initial PEMFC performance is relatively unaffected by crack density, but the performance after durability testing was strongly affected. Specifically, CLs with high crack density showed higher performance relative to CLs without cracks after application of a carbon corrosion accelerated stress test. Electrochemical analyses coupled with X-ray computed tomography and scanning transmission electron microscopy with energy dispersive X-ray spectroscopy showed that the cracks provide shorter oxygen diffusion pathways to reaction sites, leading to decreased oxygen transport resistance. Additionally, we observed that the catalyst durability is unaffected by cracks. Our results provide a mechanistic explanation of the role of cracks in CL durability.

30 DIRECT ENERGY CONVERSION↗

Understanding Environmental Barrier Coating Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. Here, the goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aeroturbine applications. To provide data for the lifetime model, laboratory testing used atmospheric plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air–steam environments and reaction kinetics were assessed from 700 °C to 1350 °C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

08 HYDROGEN↗

Poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at intermediate temperatures

High temperature proton exchange membrane fuel cells are being lately investigated because of their high energy efficiency, their superior heat/water management, CO tolerance, and electrode reaction kinetics. To further advance this technology, the polymer membrane portfolio and performance should be improved for intermediate or high temperature operation (>100 °C). In this work we present new poly(diallylmethylammonium) proton conducting membranes with high ionic conductivity at 120 °C. First, new protic ionic liquids, hereafter called DAMAH + X - , were synthesized leading to diallylmethylammonium monomers with different counter-anions. By radical cyclopolymerization through thermal and photoinitiation mechanisms, self-standing protic polymeric membranes of poly(diallylmethylammonium X - ) were obtained. Membranes showed good thermal stability (>250 °C) and mechanical properties without the need of additives such as (protic) ionic liquids, solvents or inorganic charges. Great attention was paid to understand the effect of the different counter-anions on the membrane properties. As a general trend, fluorinated anions coming from strong acids confer high ionic conductivity and allow to reduce the hygroscopic properties on the protic polymeric membranes. Proton structural and dynamical stability at different temperatures and humidification conditions were investigated by Neutron Scattering (QENS and NR). The optimized poly(diallylmethylammonium X - ) shows similar ionic conductivity values than Nafion 212 under varying relative humidity conditions at 80 °C. Furthermore, it shows a high ionic conductivity value of 1.9 × 10 -3 Scm -1 at 120 °C under dry conditions.

08 HYDROGEN↗