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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 361 records · Page 20

Impact of Proton Activity on Fuel-Cell Performance (CRADA Final Report)

The key attribute that is being investigated is the dependence of the oxygen-reduction and hydrogen-oxidation reaction kinetics on proton activity. The influence of proton activity on the kinetics is also important in the determination of limiting factors that impact overall fuel-cell performance. At lower humidities, which are required to simplify fuel-cell water and thermal management (especially for higher-temperature operation) and enable next generation fuel cells, the ionomer water content will be different than that in today’s fuel cells. Such changes in water content directly impact the activity and concentration of protons. Thus, it is necessary to quantify this impact of proton activity on the reaction kinetics, and to determine means to mitigate any detrimental impacts to enable high performance. To realize the above goals of understanding the intrinsic interactions of proton activity on hydrogen-oxidation and oxygen-reduction kinetics, systematic investigations were carried out and a novel technique, a rapid microelectrode with environmental control, was realized. The experimental campaign at LBNL worked alongside that of TokyoTech and both were complemented by mathematical modeling of the key phenomena. The results demonstrated a robust method to analyze the kinetic behavior and an impact of proton activity, although greater delineation in terms of ion concentration versus activity was not obtained fully due in part to limited lab access during the COVID pandemic.

30 DIRECT ENERGY CONVERSION↗

Durable Mn-Based PGM-Free Catalysts for Polymer Electrolyte Membrane Fuel Cells

This proposed project aims to develop and evaluate novel manganese based, nitrogen-derived, PGM-free electrocatalysts (denoted as Mn-N-C) to fully address the membrane electrolyte assemblies (MEA)’s ionomer degradation issue resulting from iron. Four thrusts will be pursed in this proposed project. First, advanced first-principles computation methods will be employed to accelerate the rational catalyst design and synthesis. Second, an effective hydro-gel method will be used to maximize atomic Mn active sites embedded in carbon matrix. Next, state-of-the art methods in fuel cell companies will be used to fabricate MEAs containing the Mn-N-C catalysts. Finally, industry standards will be rigorously followed to evaluate fuel cell performance and durability of the Mn-N-C catalysts. With successful completion of the project, it is expected that the following outcomes will be achieved. (1) A set of MEAs containing the Mn-N-C catalysts and with active area large than 50 cm 2 for independent testing, (2) testing results demonstrating that the MEAs of Mn-N-C catalysts have mass activity of 0.044 A/cm 2 at 0.9 VIR-free and H 2 /air performance of 0.50 V at 1.0 A/cm 2 ; (3) fundamental understanding of the composition-structure-property relation of the PGM-free Mn- N-C catalysts, and (4) computational data, measurement data, and publications deposited into the database of ElectroCat Consortium.

08 HYDROGEN↗

Towards Automated Design of Polymer Precursors for Rational Design of Porous Carbon-Materials [Slides]

Overview: Developed capability enables easy building of realistic polymer structures and a straightforward evaluation of polymer properties using different computational approaches. Topics of relevance to LANL mission: fundamental understanding of gas, vapor, ion, and liquid transport in polymer materials with applications in carbon capture, clean energy, hydrogen production (e.g., fuel cells and electrolyzes); Toxic element removal; Design of polymer binders in explosives. Workforce Development: Project provided a valuable opportunity to for a PI to manage a LANL research effort, expand collaborations (e.g., MPA division), and establish research topic that aligns with the LANL mission; The capability built was highlighted in the proposal "Versatile Polyolefins-Based Ionomer Platform for Next Generation Polymer Electrolyte Membrane and Hydrogen Production" lead by InnoSense LLC in collaboration with MPA-1 and T-1 as a response to DOE's call DE-FOA-0003003: Science Foundations for Energy Earthshots.

36 MATERIALS SCIENCE↗

Computational project t23_h2_pump [Slide]

Calculations using density functional theory (DFT) were used to understand the electrochemical phenyl oxidation of ionomers on the anode catalyst of the water eletrolyzers, which significantly impacts the performance and durability of these devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fuel Cell Membrane Electrode Assemblies with Ultra-Low Pt Nanofiber Electrodes (Final Report)

H 2 /air fuel cell membrane-electrode-assemblies (MEAs) were fabricated with electrospun particle/polymer nanofiber mat cathodes (0.1 mg Pt /cm 2 or 0.2 mg Pt /cm 2 Pt/C, PtCo/C or PtNi/C) and anodes (0.1 mg/cm 2 Pt/C), where the binder was a mixture of acid-form perfluorosulfonic acid ionomer (e.g., Nafion™) and poly(acrylic acid) (PAA) carrier polymer or sodium-form PFSA with a carrier polymer of either PAA or polyethylene oxide (PEO). For the latter two cases, the water-soluble carrier was removed from the fibers after electrospinning. MEAs with Pt/C anode/cathode catalyst loadings of 0.1 mg Pt /cm2 each, an 1100 EW PFSA binder (Nafion™ dispersion), and a Nafion 211 membrane produced high power at both high and low relative humidity (RH) conditions, e.g., a maximum power density of 919 mW/cm 2 at 100% RH and 832 mW/cm 2 at 40% RH for a test at 80 °C and 200 kPa abs . The high power at low RH was attributed to nm-size pores within the fibers that trap water via capillary condensation thus maintaining a high proton conductivity of the PFSA binder in the cathode and especially the anode while minimizing/eliminating ionic isolation of catalyst particles in low water content, poorly conductive binder. At the same time, micro-porosity between fibers in the cathode allows for fast removal of electrogenerated water, thus minimizing cathode flooding. Nanofiber MEAs with Pt alloy catalyst cathodes also performed well, where a fibrous PtCo/C catalyst cathode at a loading of 0.1 mg/cm 2 produced 20% more power than a conventional powder cathode MEA, e.g., a maximum power density of 1,045 mW/cm 2 vs. 869 mW/cm 2 at 80 °C, 100% RH, and 200 kPa abs , and a PtNi/C fiber cathode MEAs prepared with Na+-form Nafion + PEO generated a maximum power of 820 mW/cm 2 at 40% RH. Fiber electrode MEAs with a neat Nafion binder (prepared from Na+-form Nafion + PEO or PAA) where the cathode Pt loading was ~0.1 mg/cm 2 exhibited a 25% loss in maximum power at 30,000 metal dissolution cycles, as compared to a 12% loss when the cathode binder was H+-form Nafion + PAA. The performance of a fiber mat electrode MEA with Pt/C catalyst (0.2 mg/cm 2 cathode loading and 0.1 mg/cm 2 anode loading) was excellent. At 80 oC and 200 kPa abs , the maximum power density was 1104 mW/cm 2 . The maximum power was independent of feed gas humidity for 40 < RH < 100%. The power loss after a metal dissolution AST (30,000 voltage cycles) was only 13%.

08 HYDROGEN↗

Active and Durable PGM-free Cathodic Electrocatalysts for Fuel Cell Application

Platinum Group Metal-free (PGM-free) Oxygen Reduction Reaction (ORR) electrocatalysts possess high intrinsic activity measured by a Rotating Disk Electrode (RDE) method. However, under fuel cell operating conditions, PGM-free ORR electrocatalysts have underperformed compared to platinum catalysts. PGM-free ORR electrocatalyst’s fuel cell performance can be improved by designing and optimizing the cathodic catalyst layer (CL) and Membrane Electrode Assembly (MEA) construction such that: 1) it efficiently provides oxygen access to ORR active sites (through catalyst morphology control); 2) it removes water from the CL (by tuning the hydrophobicity of the PGM-free catalysts and the catalyst layer structure); and 3) it increases proton conductivity (by homogeneous mixing of catalysts and ionomer). Studying the CL is complex due to the absence of well-established protocols of MEA activation, especially compared to platinum-containing catalysts. PGM-free fuel cell testing protocols would need to optimize potentiostatic vs galvanostatic measurements, scan rates, parameters of Electrochemical Impedance Spectroscopy (EIS) and Beginning of Experiment (BOE) criteria. To make the PGM-free catalyst’s fuel cell performance comparable to platinum, the synergistic effort of materials design, fine tuning of the catalyst layer and comprehensive electrochemical analysis is required.

08 HYDROGEN↗

Durable High Power Density Fuel Cell Cathodes for Heavy-Duty Vehicles

The aim of this project was to advance the performance and durability of proton exchange membrane fuel cells (PEMFCs) for their use in the electrification of heavy-duty vehicles (HDVs). With an emphasis on total cost of ownership for HDVs, the development of the fuel cells focuses more heavily on the efficiency and lifetime (i.e., durability) than past focus on platinum group metal (PGM) costs and power density. This project takes a unique approach to achieving these goals – using next-generation polymer electrolytes in the electrodes that yield significant improvements in performance and dramatic reductions in degradation rates. A key outcome of the project was an ionomer/catalyst combination of a Pt catalyst on a low surface area carbon support (Pt/LSC) with a high oxygen permeability ionomer (HOPI) that met both the project’s performance target (current at 0.8 V, >0.3 A/cm 2 ) and durability target (voltage loss at 0.8 A/cm 2 , <30 mV) with the goal of projected a >4X increase in life-time.

08 HYDROGEN↗

Machine learning for optimizing the manufacture and operation of intermediate temperature fuel cells

The project developed machine learning and artificial intelligence (ML/AI) methodologies for guiding and accelerating the materials design and processing of new high temperature proton conducing electrode ionomer binders and reinforced membranes for high-temperature proton exchange membrane fuel cell (HT-PEMFC; aka intermediate-temperature polymer electrolyte membrane fuel cells).

08 HYDROGEN↗

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Review of the Use of Immobilized Ionic Liquids in the Electrochemical Conversion of CO2

This paper is a review on the application of imidazolium-based ionic liquids tethered to polymer backbones in the electrochemical conversion of CO2 to carbon monoxide and formic acid. These tethered ionic liquids have been incorporated into novel anion ion exchange membranes for CO2 electrolysis, as well as for ionomers that have been incorporated into the cathode catalyst layer, providing a co-catalyst for the reduction reaction. In using these tethered ionic liquids in the cathode catalyst composition, the cell operating current increased by a factor of two or more. The Faradaic efficiencies also increased by 20–30%. This paper provides a review of the literature, in addition to providing some new experimental results from Dioxide Materials, in the electrochemical conversion of CO2 to CO and formic acid.

09 BIOMASS FUELS↗

Transformative Impacts of Laser-Induced Breakdown Spectroscopy on Environmental and Biological Research at Oak Ridge National Laboratory

This manuscript will present an advancement of transformative research that has been conducted at Oak Ridge National Laboratory (ORNL) over a 25-year period (2000–2025) on a variety of environmental and biological matrices. These investigations derived a fundamental understanding of how elemental detection and analysis of these matrices led to the knowledge and discovery of natural processes in plants and the environment. Each project led to the initiation of a new research area which unearthed awesome and novel breakthroughs. Highlights are listed below: 1. The preliminary research at ORNL centered on the detection of aerosols utilizing Laser-induced Breakdown Spectroscopy (LIBS) technology. The Clean Air Act Amendment (CAAA) of 1990 highlighted the importance of identifying hazardous air pollutants (HAPs) due to their impact on environmental and human health, thereby underscoring the need to detect various toxic elements. Research in aerosol chemistry aimed to identify these harmful elements released by factories during periods of increased emissions in their manufacturing processes. LIBS emerged as the most effective method for real-time, in situ measurements of metal species in both gaseous and aerosol phases. 2. An understanding of the presence of total carbon in soils gives perspective on how to develop carbon sequestration strategies. The recognition that carbon sinks can evolve back to carbon sources to emit back to the atmosphere was an important consideration. Also, the concentration of carbon in soil indicates the health of land areas for growing crops successfully. 3. The direct detection of most of the elements in a wood sample in a single emission spectrum, without sample preparation, encouraged the research to use the LIBS technique for preservative treated wood coupled with use of multivariate statistical methodology. Additionally, it encouraged the researchers to try to differentiate natural woods from different parts of the country, and it was successfully demonstrated that LIBS coupled with MVA analysis could differentiate wood of different species from each other and of similar species grown in different environments based on their elemental spectra. This was a breakthrough since it revealed a systematic approach to connect elemental scarcity and abundance to either drought or typical rainfall conditions for the hardwood trees grown in specific areas. 4. Furthermore, the research progressed to reveal physiological and developmental processes contributing to biomass production such that the variation in leaf elemental composition increases our understanding of terrestrial nutrient cycles, as well as tracking the transfer of toxic elements from soils to living organisms. 5. Recently another breakthrough viz., ionomics initiated the correlation of elements to specific genes, uncovering the function that the element performed in the plant. More recently, this has been extended from plants to fungi as well as fungi growing in symbiotic relations with plants.

09 BIOMASS FUELS↗

Near-ambient solid polymer fuel cell

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as replacement for batteries.

Holleck, G. L.↗

Development of Electrochemical Supercapacitors for EMA Applications

A limitation of the typical electrochemical capacitor is the maximum available power and energy density, and an improvement in capacitance per unit weight and volume is needed. A solid-ionomer electrochemical capacitor having a unit cell capacitance greater than 2 F/sq cm and a repeating element thickness of 6 mils has been developed. This capacitor could provide high-current pulses for electromechanical actuation (EMA). Primary project objectives were to develop high-capacitance particulates, to increase capacitor gravimetric and volumetric energy densities above baseline and to fabricate a 10-V capacitor with a repeating element thickness of 6 mils or less. Specific EMA applications were identified and capacitor weight and volume projections made.

Kosek, John A.↗

Thin Film Catalyst Layers for Direct Methanol Fuel Cells

One of the primary obstacles to the widespread use of the direct methanol fuel cell (DMFC) is the high cost of the catalyst. Therefore, reducing the catalyst loading well below the current level of 8-12 mg/cm 2 would be important to commercialization. The current methods for preparation of catalyst layers consisting of catalyst, ionomer and sometimes a hydrophobic additive are applied by either painting, spraying, decal transfer or screen printing processes. Sputter deposition is a coating technique widely used in manufacturing and therefore particularly attractive. In this study we have begun to explore sputtering as a method for catalyst deposition. Present experiments focus on Pt-Ru catalyst layers for the anode.

Witham, C. K.↗

Electrical Impedance of Ionic Polymeric Metal Composites

In recent years the use of ionic polymer metal composites such as Nafion-based platinum ionomers have emerged as electroactive polymer materials with great potential for robotics and other applications. An effective activation of these materials requires understanding of their mechanism of operation. Generally, the material needs to be maintained hydrated to assure its electromechanical activity. To allow the control of the response of the material, a study is underway to investigate the electrical response. Particular emphasis is placed on possible electrochemical reactions and deviations from linear dielectric behavior. Currently, efforts are made to determine the necessary drive characteristics of the source to allow low power operation (< or = 1.0 W) of the material as an actuator.

Leary, S.↗

Multi-Functional Sandwich Composites for Spacecraft Applications: An Initial Assessment

Current spacecraft implement relatively uncoupled material and structural systems to address a variety of design requirements, including structural integrity, damage tolerance, radiation protection, debris shielding and thermal insulation. This investigation provided an initial assessment of multi-functional sandwich composites to integrate these diverse requirements. The need for radiation shielding was addressed through the selection of polymeric constituents with high hydrogen content. To provide increased damage tolerance and debris shielding, manufacturing techniques were developed to incorporate transverse stitching reinforcement, internal layers, and a self-healing ionomer membrane. To assess the effects of a space environment, thermal expansion behavior of the candidate foam materials was investigated under a vacuum and increasing temperature. Finally, a thermal expansion model was developed for foam under vacuum conditions and its predictive capability assessed.

Adams, Daniel O.↗

Direct methanol feed fuel cell with reduced catalyst loading

Improvements to direct feed methanol fuel cells include new protocols for component formation. Catalyst-water repellent material is applied in formation of electrodes and sintered before application of ionomer. A membrane used in formation of an electrode assembly is specially pre-treated to improve bonding between catalyst and membrane. The improved electrode and the pre-treated membrane are assembled into a membrane electrode assembly.

Kindler, Andrew↗

Norbornene-Based Polymer Electrolytes for Lithium Cells

Norbornene-based polymers have shown promise as solid electrolytes for lithium-based rechargeable electrochemical cells. These polymers are characterized as single-ion conductors. Single-ion-conducting polymers that can be used in lithium cells have long been sought. Single-ion conductors are preferred to multiple-ion conductors as solid electrolytes because concentration gradients associated with multiple-ion conduction lead to concentration polarization. By minimizing concentration polarization, one can enhance charge and discharge rates. Norbornene sulfonic acid esters have been synthesized by a ring-opening metathesis polymerization technique, using ruthenium-based catalysts. The resulting polymer structures (see figure) include sulfonate ionomers attached to the backbones of the polymer molecules. These molecules are single-ion conductors in that they conduct mobile Li+ ions only; the SO3 anions in these polymers, being tethered to the backbones, do not contribute to ionic conduction. This molecular system is especially attractive in that it is highly amenable to modification through functionalization of the backbone or copolymerization with various monomers. Polymers of this type have been blended with poly(ethylene oxide) to lend mechanical integrity to free-standing films, and the films have been fabricated into solid polymer electrolytes. These electrolytes have been demonstrated to exhibit conductivity of 2 10(exp -5)S/cm (which is high, relative to the conductivities of other solid electrolytes) at ambient temperature, plus acceptably high stability. This type of norbornene-based polymeric solid electrolyte is in the early stages of development. Inasmuch as the method of synthesis of these polymers is inherently flexible and techniques for the fabrication of the polymers into solid electrolytes are amenable to optimization, there is reason to anticipate further improvements.

Cheung, Iris↗