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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells

Low-temperature direct ammonia fuel cells (DAFCs) use carbon-neutral ammonia as a fuel, which has attracted increasing attention recently due to ammonia's low source-to-tank energy cost, easy transport and storage, and wide availability. However, current DAFC technologies are greatly limited by the kinetically sluggish ammonia oxidation reaction (AOR) at the anode. Herein, we report an AOR catalyst, in which ternary PtIrZn nanoparticles with an average size of 2.3 ± 0.2 nm were highly dispersed on a binary composite support comprising cerium oxide (CeO 2 ) and zeolitic imidazolate framework-8 (ZIF-8)-derived carbon (PtIrZn/CeO 2 -ZIF-8) through a sonochemical-assisted synthesis method. Additionally, the PtIrZn alloy, with the aid of abundant OH ad provided by CeO 2 and uniform particle dispersibility contributed by porous ZIF-8 carbon (surface area: ~600 m 2 g -1 ), has shown highly efficient catalytic activity for the AOR in alkaline media, superior to that of commercial PtIr/C. The rotating disk electrode (RDE) results indicate a lower onset potential (0.35 vs. 0.43 V), relative to the reversible hydrogen electrode at room temperature, and a decreased activation energy (~36.7 vs. 50.8 kJ mol -1 ) relative to the PtIr/C catalyst. Notably, the PtIrZn/CeO 2 -ZIF-8 catalyst was assembled with a high-performance hydroxide anion-exchange membrane to fabricate an alkaline DAFC, reaching a peak power density of 91 mW cm -2 . Unlike in aqueous electrolytes, supports play a critical role in improving uniform ionomer distribution and mass transport in the anode. PtIrZn nanoparticles on silicon dioxide (SiO 2 ) integrated with carboxyl-functionalized carbon nanotubes (CNT–COOH) were further studied as the anode in a DAFC. A significantly enhanced peak power density of 314 mW cm -2 was achieved. Density functional theory calculations elucidated that Zn atoms in the PtIr alloy can reduce the theoretical limiting potential of *NH 2 dehydrogenation to *NH by ~0.1 V, which can be attributed to a Zn-modulated upshift of the Pt–Ir d-band that facilitates the N–H bond breakage.

25 ENERGY STORAGE↗
DOE OSTI2020

A Direct Ammonia Fuel Cell with a KOH-Free Anode Feed Generating 180 mW cm −2 at 120 °C

The motivations to operate the direct ammonia fuel cell (DAFC) with no addition of aqueous base, include facilitated fuel management and prevention of corrosion and shunt currents in the DAFC stack. We describe here a polymer electrolyte DAFC, operating at a cell temperature (T cell ) of 120 °C on ammonia and water alone as anode feed, that demonstrated peak power of 180 mW cm −2 —a record for this type of fuel cell. We offer a detailed analysis of polarization curves recorded for PE-DAFCs in the T cell range of 60 °C–120 °C, allowing to estimate the effects of KOH-free operation on the ionic and faradaic resistances, R i and R F , that determine together the value of R app , CL – an , the apparent resistance of the anode catalyst layer. The latter resistance drops ten times between 60 °C and 120 °C as result mainly of the drop in R F . Consequently, DAFC performance at T cell > 100 °C improves substantially, including the cell performance on a KOH-free anode feed. The demsontrated performance levels reported here for KOH-free DAFCs support further development of this type of ammonia/air fuel cells.

Achrai, Ben↗
DOE OSTI2021

Improving Performance and Durability of Low Temperature Direct Ammonia Fuel Cells: Effect of Backpressure and Oxygen Reduction Catalysts

Low temperature direct ammonia fuel cells (DAFCs) are attractive for transportation applications. The primary obstacle to their commercial use is their low performance and poor durability. In the present work, we focus on improving DAFCs performance and durability by examining the effect of operating backpressure and oxygen reduction reaction (ORR) catalysts such as Acta 4020, Pd/C and Pt/C. DAFCs with Acta 4020 cathode can reach a peak power density of 390 mW cm -2 which is among the best reported performance, but they can be operated for a period of 11 h at 300 mA cm -2 . DAFCs with Pd/C cathode offer a moderate performance with a peak power density of 304 mW cm -2 , but has a much improved durability - a continuous operation for up to 36 h with a slow decay rate of ~1 mV h -1 at 300 mA cm -2 . In addition, the degradation pathways for DAFCs with Pd/C cathode are probed by characterizing the initial and final electrodes by XPS, suggesting that cathodic Pd dissolution occurs during the durability test.

Electrochemistry↗
DOE OSTI2020

Effect of Ammonia on the Electrocatalysis of Oxygen Reduction Reaction in Base

We investigated the effect of ammonia on the activity of seven benchmark oxygen reduction reaction (ORR) electrocatalysts, Pt/C, Pd/C, Au/C, Ag/C, commercial Fe–N–C, zeolitic imidazolate framework (ZIF)-based Fe–N–C (Fe-ZIF), and ZIF-based Fe,Co–N–C (Fe,Co-ZIF) in alkaline media and direct ammonia fuel cell (DAFC) relevant conditions using a rotating disk electrode. We found that ammonia exposure causes considerable ORR activity loss for all studied electrocatalysts. Should we rank the electrocatalysts in terms of their ORR activity loss and their irreversible ORR activity loss as the result of exposure to ammonia (from the highest loss to the lowest loss), we get Au/C > Pt/C ≈ Pd/C > Ag/C » commercial Fe–N–C > Fe-ZIF ≈ Fe,Co-ZIF and Pd/C > Au/C > Ag/C > commercial Fe–N–C > Fe-ZIF ≈ Fe,Co-ZIF > Pt/C, respectively. The ammonia oxidation reaction activity and adsorptive properties of the Gerisher-Mauerer reaction intermediates do not govern the trend of the ORR activity loss of Pt/C, Pd/C, Au/C, and Ag/C electrocatalysts. Notably, we found that Pt/C electrocatalyst shows the lowest irreversible ORR activity loss, while Fe-ZIF and Fe,Co-ZIF electrocatalysts show the lowest overall ORR activity loss. Our comprehensive study suggests that Pt-based, Fe-ZIF, and Fe,Co-ZIF electrocatalysts are promising cathode candidates for future DAFCs.

Abbasi, Reza (ORCID:0000000249384151)↗
DOE OSTI2021

Spontaneous N 2 formation by a diruthenium complex enables electrocatalytic and aerobic oxidation of ammonia

The electrochemical conversion of ammonia to dinitrogen in a direct ammonia fuel cell (DAFC) is a necessary technology for the realization of a Nitrogen Economy. Previous efforts to catalyze this reaction with molecular complexes require the addition of exogenous oxidizing reagents or application of potentials greater than the thermodynamic potential for the oxygen reduction reaction (ORR) – the cathodic process of a DAFC. We report a stable metal–metal bonded diruthenium complex that spontaneously produces dinitrogen from ammonia under ambient conditions. The resulting reduced diruthenium material can be re-oxidized with oxygen for subsequent reactions with ammonia, demonstrating its ability to spontaneously promote both half reactions necessary for a DAFC. Here, the diruthenium complex also acts as a redox mediator for the electrocatalytic oxidation of ammonia to dinitrogen at potentials as low as –255 mV vs Fc 0/+ and operates below the ORR potential in alkaline conditions, thus achieving a thermodynamic viability relevant for the future development of DAFCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

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↗
DOE OSTI2024

Understanding Direct-Ammonia Protonic Ceramic Fuel Cells: High-Performance in the Absence of Precious Metal Catalysts

Ammonia has received considerable attention as a promising carbon-free hydrogen carrier. At temperatures above 400 °C, NH 3 is thermodynamically unstable with respect to decomposition into nitrogen and hydrogen and is, thus, suitable for direct use in solid oxide fuel cells (SOFCs) without external reforming. However, poor catalytic activity for ammonia decomposition at the moderate temperatures of protonic ceramic fuel cell (PCFC) operation has resulted in low fuel cell power output relative to operation on hydrogen and likely contributes to reported cell degradation. Here we prepared cells based on a thermodynamically robust electrolyte, a high activity cathode, and an anode with a distinctive structure to overcome challenges of poor activity and stability. Furthermore, the cells delivered peak power densities of 0.59 and 0.44 W cm –2 under H 2 and NH 3 , respectively, at 500 °C, excellent stability over a period of 200 h, and no detectable NO x in the anode exhaust gas.

25 ENERGY STORAGE↗
DOE OSTI2020

Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells

Proton-exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are promising power sources from portable electronic devices to vehicles. The high-cost issue of these low-temperature fuel cells can be primarily addressed by using platinum-group metal (PGM)-free oxygen reduction reaction (ORR) catalysts, in particular atomically dispersed metal–nitrogen–carbon (M–N–C, M = Fe, Co, Mn). Furthermore, a significant advantage of M–N–C catalysts is their superior methanol tolerance over Pt, which can mitigate the methanol cross-over effect and offer great potential of using a higher concentration of methanol in DMFCs. In this work, we investigated the ORR catalytic properties of M–N–C catalysts in methanol-containing acidic electrolytes via experiments and density functional theory (DFT) calculations. FeN 4 sites demonstrated the highest methanol tolerance ability when compared to metal-free pyridinic N, CoN 4 , and MnN 4 active sites. The methanol adsorption on MN 4 sites is even strengthened when electrode potentials are applied during the ORR. The negative influence of methanol adsorption becomes significant for methanol concentrations higher than 2.0 M. However, the methanol adsorption does not affect the 4e - ORR pathway or chemically destroy the FeN 4 sites. The understanding of the methanol-induced ORR activity loss guides the design of promising M–N–C cathode catalyst in DMFCs. Accordingly, we developed a dual-metal site Fe/Co–N–C catalyst through a combined chemical-doping and adsorption strategy. Instead of generating a possible synergistic effect, the introduced Co atoms in the first doping step act as “scissors” for Zn removal in metal–organic frameworks (MOFs), which is crucial for modifying the porosity of the catalyst and providing more defects for stabilizing the active FeN 4 sites generated in the second adsorption step. The Fe/Co–N–C catalyst significantly improved the ORR catalytic activity and delivered remarkably enhanced peak power densities (i.e., 502 and 135 mW cm -2 ) under H 2 –air and methanol–air conditions, respectively, representing the best performance for both types of fuel cells. Notably, the fundamental understanding of methanol tolerance, along with the encouraging DMFC performance, will open an avenue for the potential application of atomically dispersed M–N–C catalysts in other direct alcohol or ammonia fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2023

Benchmarking plasma and electrolysis decomposition technologies for ammonia to power generation

Ammonia is a promising energy and hydrogen carrier due to its ease of liquification, high hydrogen content, and potential to be synthesized without carbon feedstocks. Despite its widespread use in agriculture, the utilization of ammonia to deliver hydrogen or for direct power generation is still under development. Sometimes referred to as “cracking”, the standard approach for recovering hydrogen from ammonia relies on harsh reaction conditions that limit its suitability for low-carbon transitions. Here, this work investigates the technology development status and potential cost of plasma and electrolysis-based ammonia decomposition, benchmarks them with thermal-chemical decomposition, and further compares them with direct ammonia-to-power solid oxide fuel cell systems. Results suggest that in order to reach cost parity with cracking technologies, plasma-based decomposition must achieve one order of magnitude improvement in energy efficiency (to 10 kWh/kg or lower), while electrolysis decomposition must achieve enhanced durability using cheap electrolytes.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

A high-performance and durable direct NH 3 tubular protonic ceramic fuel cell integrated with an internal catalyst layer

Nickel-based cermet anode-supported protonic ceramic fuel cells (PCFCs) show great potential for direct utilization of ammonia. However, the insufficient activity of anode and the deterioration of anode activity/durability caused by the undesired interaction between nickel and ammonia greatly limit the application. Here, we report tubular PCFCs embedded with a catalytic iron layer. Such cells show peak power densities of 1.507 W cm -2 and 1.078 W cm -2 at 700 °C when using H 2 and NH 3 as fuel, respectively, which are the highest tubular PCFC performance so far ever reported. In addition, the stability of cells with the catalyst layer has been dramatically enhanced when compared with that of cells without the catalyst layer. As a result, the enhancement of activity and durability is attributed to the catalytic activity of iron for ammonia decomposition, through which the direct contact between nickel and ammonia has been minimized and the anode structure has therefore been protected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

In situ formed catalysts for active, durable, and thermally stable ammonia protonic ceramic fuel cells at 550 °C

Ammonia protonic ceramic fuel cells (NH 3 -PCFCs) are promising and attractive energy-conversion devices owing to their high energy density, zero-carbon emission, and safety. The development of NH 3 -PCFCs, however, depends largely on the insufficient activity and poor durability of typical Ni-based anodes for ammonia decomposition, especially at low temperatures such as 550 °C. Herein, we report a self-assembled heterostructured Ru 0.95 Cu 0.05 Ni x (RCN) catalyst obtained through an in situ reaction between the surface-decorated Ru 0.95 Cu 0.05 nanoparticles and the Ni grain in the anode under typical processing conditions. At 550 °C, Ni–BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 anode-supported PCFCs with RCN catalysts exhibit a high peak power density of 0.732 W cm -2 and a significantly enhanced durability of 100 h in NH 3 . Moreover, the cells demonstrate improved thermal stability compared with the bare cell during a 31-cycle thermal cycling test in NH 3 between 550 and 700 °C. In conclusion, the enhanced performance is likely attributed to the synergistic effects of Ru and Cu in RCN for NH 3 decomposition, resulting in a more vital interaction of NH 3 than that of the bare anode surfaces, as confirmed by NH 3 thermal conversion, electrochemical performance, and theoretical simulations.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Protonic Ceramic Electrochemical Cells for Synthesizing Sustainable Chemicals and Fuels

Abstract Protonic ceramic electrochemical cells (PCECs) have been intensively studied as the technology that can be employed for power generation, energy storage, and sustainable chemical synthesis. Recently, there have been substantial advances in electrolyte and electrode materials for improving the performance of protonic ceramic fuel cells and protonic ceramic electrolyzers. However, the electrocatalytic materials development for synthesizing chemicals in PCECs has gained less attention, and there is a lack of systematic and fundamental understanding of the PCEC reactor design, reaction mechanisms, and electrode materials. This review comprehensively summarizes and critically evaluates the most up‐to‐date progress in employing PCECs to synthesize a wide range of chemicals, including ammonia, carbon monoxide, methane, light olefins, and aromatics. Factors that impact the conversion, selectivity, product yield, and energy efficiencies are discussed to provide new insights into designing electrochemical cells, developing electrode materials, and achieving economically viable chemical synthesis. The primary challenges associated with producing chemicals in PCECs are highlighted. Approaches to tackle these challenges are then offered, with a particular focus on deliberately designing electrode materials, aiming to achieve practically valuable product yield and energy efficiency. Finally, perspectives on the future development of PCECs for synthesizing sustainable chemicals are provided.

03 NATURAL GAS↗
DOE OSTI2020

The Technical and Economic Potential of the H2@Scale Hydrogen Concept within the United States

The U.S. energy system is evolving as society and technologies change. Renewable electricity generation - especially from wind and solar - is growing rapidly, and alternative energy sources are being developed and implemented across the residential, commercial, transportation, and industrial sectors to take advantage of their cost, security, and health benefits. Systemic changes present numerous challenges to grid resiliency and energy affordability, creating a need for synergistic solutions that satisfy multiple applications while yielding system-wide cost and emissions benefits. One such solution is an integrated hydrogen energy system. This is the focus of H2@Scale - a U.S. Department of Energy (DOE) initiative led by the Office of Energy Efficiency and Renewable Energy’s Hydrogen and Fuel Technologies Office. H2@Scale brings together stakeholders to advance affordable hydrogen production, transport, storage, and utilization in multiple energy sectors. The H2@Scale concept involves hydrogen as an energy intermediate. Hydrogen can be produced from various conventional and renewable energy sources including as a responsive load on the electric grid. Hydrogen has many current applications and many more potential applications, such as energy for transportation - used directly in fuel cell electric vehicles (FCEVs), as a feedstock for synthetic fuels, and to upgrade oil and biomass - feedstock for industry (e.g., for ammonia production, metals refining, and other end uses), heat for industry and buildings, and electricity storage. Owing to its flexibility and fungibility, a hydrogen intermediate could link energy sources that have surplus availability to markets that require energy or chemical feedstocks, benefiting both. This document builds upon a growing body of analyses of hydrogen as an energy intermediate by reporting the results from our initial analysis of the potential impacts of the H2@Scale vision by the mid-21 st century for the 48 contiguous U.S. states. Previous estimates have been based on expert elicitation and focused on hydrogen demands. We build upon them, first, by estimating hydrogen’s serviceable consumption potential for possible hydrogen applications and the technical potential for producing hydrogen from various resources. We define the serviceable consumption potential as the quantity of hydrogen that would be consumed to serve the portion of the market that could be captured without considering economics (i.e., if the price of hydrogen were $0/kg over an extended period); thus, it can be considered an upper bound for the size of the market. We define the technical potential as the resource potential constrained by real-world geography and system performance, but not by economics. We then compare the cumulative serviceable consumption potential with the technical potential of a number of possible sources. Second, we estimate economic potential: the quantity of hydrogen at an equilibrium price at which suppliers are willing to sell and consumers are willing to buy the same quantity of hydrogen. We believe this method provides a deeper understanding than was available in the previous analyses. We develop economic potentials for multiple scenarios across various market and technology-advancement assumptions.

08 HYDROGEN↗
DOE OSTI2022

Protonic Ceramics for Energy Storage & Electricity Generation with Ammonia (Final Report)

The commercial product resulting from this R&D project will enable cost-effective synthesis of the Carbon Neutral Liquid Fuel (CNLF) ammonia, a common chemical, at a small scale for energy and industrial applications using only intermittent renewable energy, water, and air as feedstocks. These products are also capable of producing electrical energy from the CNLF in a fuel cell mode of operation. Thus, the eventual commercial product enables both single direction production of either CLNF or electricity, or alternatively functions as a fully reversible, self-contained energy storage device. The renewed interest in developing electrolysis systems is driven, in part, by the burgeoning renewable, solar, and wind industries and the need for an energy conversion and storage technology that can convert intermittent solar and wind energy into the production of hydrogen. Electrolysis systems integrated into both distributed and central renewable power plants would utilize solar and wind energy as their primary power source to produce renewably generated hydrogen for local energy storage or chemical feedstock purposes. Ammonia is an excellent surrogate for hydrogen transportation. NH3 presents an attractive alternative to hydrogen as a working fluid in reversible devices towards a sustainable green energy-oriented future. Ammonia can be easily liquefied at room temperature at about 8 bar or at -33°C at ambient pressure. In contrast, the liquefaction temperature of hydrogen is -253°C at ambient pressure. NH3 has a significantly higher volumetric energy density (12.7 MJ/L) than compressed hydrogen (4.5 MJ/L at ~70 MPa) or liquefied hydrogen (8.5 MJ/L). Additionally, ammonia is a widely used raw material for agriculture fertilizer and thus has well-established storage, transport, and handling processes (about 180 million tons of ammonia are produced annually). Techno-economic analysis suggests ammonia is the least expensive fuel among hydrogen, gasoline, natural gas, liquefied petroleum gas, and methanol.

08 HYDROGEN↗
DOE OSTI2023

Lowering the operating temperature of protonic ceramic electrochemical cells to <450 °C

Protonic ceramic electrochemical cells (PCECs) can be employed for power generation and sustainable hydrogen production. Lowering the PCEC operating temperature can facilitate its scale-up and commercialization. However, achieving high energy efficiency and long-term durability at low operating temperatures is a long-standing challenge. Here, in this work, we report a simple and scalable approach for fabricating ultrathin, chemically homogeneous, and robust proton-conducting electrolytes and demonstrate an in situ formed composite positive electrode, Ba 0.62 Sr 0.38 CoO 3–δ –Pr 1.44 Ba 0.11 Sr 0.45 Co 1.32 Fe 0.68 O 6–δ , which significantly reduces ohmic resistance, positive electrode–electrolyte contact resistance and electrode polarization resistance. The PCECs attain high power densities in fuel-cell mode (~0.75 W cm –2 at 450 °C and ~0.10 W cm –2 at 275 °C) and exceptional current densities in steam electrolysis mode (–1.28 A cm –2 at 1.4 V and 450 °C). At 600 °C, the PCECs achieve a power density of ~2 W cm –2 . Additionally, we demonstrate the direct utilization of methane and ammonia for power generation at <450 °C. Our PCECs are also stable for power generation and hydrogen production at 400 °C.

25 ENERGY STORAGE↗
DOE OSTI2021

Development of High Capacity Energy Storage Materials

Hydrogen fuel cells have the potential to offer energy and power density advantages over lithium ion batteries in automotive and portable power applications when paired with an appropriate hydrogen storage system. Development of the ideal hydrogen storage material has been immensely sought after but plagued by limitations present in each type of material. These limitations typically include nonidealistic operational temperatures, low capacities, excessive costs, lack of reversibility, or evolution of impurities which irreversibly damage fuel cell performance. Many complex metal hydrides possess suitable hydrogen capacities but unfortunately suffer from impurity release. In order to address this problem, our team has explored in-situ catalyst doping of alkali metal amides to demonstrate methodologies to reduce ammonia release. The incorporation of iridium metal in lithium amide significantly reduces the ammonia release and decomposes the ammonia to provide additional hydrogen. Furthermore, we demonstrate, for the first time, high resistance of low temperature fuel cells to ammonia in comparison with typical proton exchange membrane fuel cells. The utilization of these two approaches in tandem provides a novel pathway for the development and implementation of high capacity energy storage materials for fuel cell applications.

25 ENERGY STORAGE↗