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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 163 records · Page 9

Scalable and Highly-Efficient Microbial Electrochemical Reactor for Hydrogen Generation from Wastes

The overall goal of this project was to develop a scalable and highly efficient hybrid microbial electrochemical reactor for hydrogen recovery from waste streams at a cost of less than $\$$2/kg H₂. The specific objectives were: (1) to design and fabricate a scalable and highly efficient microbial electrochemical cell (MEC) reactor, and (2) to determine the techno-economic feasibility of the system for H₂ generation from organic-rich waste streams. We achieved the first objective by (a) developing low-cost electrode materials, (b) synthesizing a highly efficient cathode catalyst in a scalable manner, (c) evaluating and validating the developed electrode material and catalyst in MEC reactors, and (d) designing and fabricating a larger reactor that incorporates (a) to (c). We met the second objective by (a) identifying the impacts of wastewater composition and operational conditions on H₂ production, and (b) developing a cost-performance model that identified critical parameters affecting the system's performance and cost, providing a pathway for further improvement.

08 HYDROGEN↗

From Oxygen Generation to Metals Production: In Situ Resource Utilization by Molten Oxide Electrolysis

For the exploration of other bodies in the solar system, electrochemical processing is arguably the most versatile technology for conversion of local resources into usable commodities: by electrolysis one can, in principle, produce (1) breathable oxygen, (2) silicon for the fabrication of solar cells, (3) various reactive metals for use as electrodes in advanced storage batteries, and (4) structural metals such as steel and aluminum. Even so, to date there has been no sustained effort to develop such processes, in part due to the inadequacy of the database. The objective here is to identify chemistries capable of sustaining molten oxide electrolysis in the cited applications and to examine the behavior of laboratory-scale cells designed to generate oxygen and to produce metal. The basic research includes the study of the underlying high-temperature physical chemistry of oxide melts representative of lunar regolith and of Martian soil. To move beyond empirical approaches to process development, the thermodynamic and transport properties of oxide melts are being studied to help set the limits of composition and temperature for the processing trials conducted in laboratory-scale electrolysis cells. The goal of this investigation is to deliver a working prototype cell that can use lunar regolith and Martian soil to produce breathable oxygen along with metal by-product. Additionally, the process can be generalized to permit adaptation to accommodate different feedstock chemistries, such as those that will be encountered on other bodies in the solar system. The expected results of this research include: (1) the identification of appropriate electrolyte chemistries; (2) the selection of candidate anode and cathode materials compatible with electrolytes named above; and (3) performance data from a laboratory-scale cell producing oxygen and metal. On the strength of these results it should be possible to assess the technical viability of molten oxide electrolysis for in situ resource utilization on the Moon and Mars. In parallel, there may be commercial applications here on earth, such as new green technologies for metals extraction and for treatment of hazardous waste, e.g., fixing heavy metals.

Khetpal, Deepak↗

Template Assisted Lithium Superoxide Growth for Lithium-Oxygen Batteries

Developing batteries with energy densities comparable to internal combustion technology is essential for a worldwide transition to electrified transportation. Li-O2 batteries are seen as the ‘holy grail’ of battery technologies since they have the highest theoretical energy density of all battery technologies. Current lithium-oxygen (Li-O2) batteries suffer from large charge overpotentials related to electronic resistivity of the insulating lithium peroxide (Li2O2) discharge product. One potential solution is the formation and stabilization of a lithium superoxide (LiO2) discharge intermediate that exhibits good electronic conductivity. However, LiO2 is reported to be unstable at ambient temperature despite its favorable formation energy at -1.0 eV/atom. In this paper, based on our recent work on the development of cathode materials for aprotic lithium oxygen batteries including two intermetallic compounds, LiIr3 and LiIr, that are found to form good template interfaces with LiO2, a simple goodness of fit R factor to gauge how well a template surface structure can support LiO2 growth is developed. The R factor is a quantitative measurement to calculate the geometric difference in the unit cells of specific Miller Index 2D planes of the template surface and LiO2. Using this as a guide, the R factors for LiIr3, LiIr, and La2NiO4+, are found to be good. This guide is attested by simple extension to other noble metal intermetallics with electrochemical cycling data including LiRh3, LiRh, and Li2Pd. Finally, the template concept is extended to main group elements and the R factors for LiO2 (111) and Li2Ca suggest that Li2Ca is a possible candidate for the template assisted LiO2 growth strategy.

Intermetallics↗

Advanced spacecraft fuel cell systems.

The specific goals of the system selected for development are 10,000 hours of operation with refurbishment, 20 lb/kW at a sustained power of 7 kW, and 21 kW peaking capability for durations of two hours. The system is designed to operate on low pressure, propulsion grade hydrogen and oxygen. Product water is removed by a passive water removal method that employs a porous hydrophobic membrane as a part of the water transport plate. Aspects of system component testing are discussed together with advanced materials to be used. It was found that the initial performance of a cell with a gold catalyzed cathode is superior to a cell with platinum catalyst. The problem of a certain inability to maintain the desired gas-electrolyte-catalyst interface is the main source of difficulty with the gold-based catalysts.

Thaller, L. H.↗

Highly Tunable Syngas Product Ratios Enabled by Novel Nanoscale Hybrid Electrolytes Designed for Combined CO 2 Capture and Electrochemical Conversion

Coupling renewable energy with the electrochemical conversion of CO 2 to chemicals and fuels has been proposed as a strategy to achieve a new circular carbon economy and help mitigate the effects of anthropogenic CO 2 emissions. Liquid-like Nanoparticle Organic Hybrid Materials (NOHMs) are composed of polymers tethered to nanoparticles and are previously explored as CO 2 capture materials and electrolyte additives. Here, in this study, two types of aqueous NOHM-based electrolytes are prepared to explore the effect of CO 2 binding energy (i.e., chemisorption versus physisorption) on CO 2 electroreduction over a silver nanoparticle catalyst for syngas production. Poly(ethylenimine) (PEI) and Jeffamine M2070 (HPE) are ionically tethered to SiO 2 nanoparticles to form the amine-containing NOHM-I-PEI and ether-containing NOHM-I-HPE, respectively. At less negative cathode potentials, PEI and NOHM-I-PEI-based electrolytes produce CO at higher rates than 0.1 molal. KHCO 3 due to favorable catalyst-electrolyte interactions. Whereas at more negative potentials, H 2 production is favored because of the carbamate electrochemical inactivity. Conversely, HPE and NOHM-I-HPE-based electrolytes display poor CO 2 reduction performance at less negative potentials. At more negative potentials, their performance approached that of 0.1 molal. KHCO 3 , highlighting how the polymer functional groups of NOHMs can be strategically selected to produce value-added products from CO 2 with highly tunable compositions.

36 MATERIALS SCIENCE↗

Enhancing the Faradaic efficiency of solid oxide electrolysis cells: progress and perspective

Abstract To reduce global warming, many countries are shifting to sustainable energy production systems. Solid oxide electrolysis cells (SOECs) are being considered due to their high hydrogen generation efficiency. However, low faradaic efficiency in scaling SOEC technology affects costs and limits large-scale adoption of hydrogen as fuel. This review covers SOECs’ critical aspects: current state-of-the-art anode, cathode, and electrolyte materials, operational and materials parameters affecting faradaic efficiency, and computational modeling techniques to resolve bottlenecks affecting SOEC faradaic efficiency.

Gaikwad, Prashik S. (ORCID:0000000179510115)↗

Z-Pinch Magneto-Inertial Fusion Propulsion Engine Design Concept

Fusion-based nuclear propulsion has the potential to enable fast interplanetary transportation. Due to the great distances between the planets of our solar system and the harmful radiation environment of interplanetary space, high specific impulse (Isp) propulsion in vehicles with high payload mass fractions must be developed to provide practical and safe vehicles for human spaceflight missions. Magneto-Inertial Fusion (MIF) is an approach which has been shown to potentially lead to a low cost, small fusion reactor/engine assembly (1). The Z-Pinch dense plasma focus method is an MIF concept in which a column of gas is compressed to thermonuclear conditions by an estimated axial current of approximately 100 MA. Recent advancements in experiments and the theoretical understanding of this concept suggest favorable scaling of fusion power output yield as I(sup 4) (2). The magnetic field resulting from the large current compresses the plasma to fusion conditions, and this is repeated over short timescales (10(exp -6) sec). This plasma formation is widely used in the field of Nuclear Weapons Effects (NWE) testing in the defense industry, as well as in fusion energy research. There is a wealth of literature characterizing Z-Pinch physics and existing models (3-5). In order to be useful in engineering analysis, a simplified Z-Pinch fusion thermodynamic model was developed to determine the quantity of plasma, plasma temperature, rate of expansion, energy production, etc. to calculate the parameters that characterize a propulsion system. The amount of nuclear fuel per pulse, mixture ratio of the D-T and nozzle liner propellant, and assumptions about the efficiency of the engine, enabled the sizing of the propulsion system and resulted in an estimate of the thrust and Isp of a Z-Pinch fusion propulsion system for the concept vehicle. MIF requires a magnetic nozzle to contain and direct the nuclear pulses, as well as a robust structure and radiation shielding. The structure, configuration, and materials of the nozzle must meet many severe requirements. The configuration would focus, in a conical manner, the Deuterium-Tritium (D-T) fuel and Lithium-6/7 liner fluid to meet at a specific point that acts as a cathode so the Li-6 can serve as a current return path to complete the circuit. In addition to serving as a current return path, the Li liner also serves as a radiation shield. The advantage to this configuration is the reaction between neutrons and Li-6 results in the production of additional Tritium, thus adding further fuel to the fusion reaction and boosting the energy output. To understand the applicability of Z-Pinch propulsion to interplanetary travel, it is necessary to design a concept vehicle that uses it. The propulsion system significantly impacts the design of the electrical, thermal control, avionics, radiation shielding, and structural subsystems of a vehicle. The design reference mission is the transport of crew and cargo to Mars and back, with the intention that the vehicle be reused for other missions. Several aspects of this vehicle are based on a previous crewed fusion vehicle study called Human Outer Planet Exploration (HOPE), which employed a Magnetized Target Fusion (MTF) propulsion concept. Analysis of this propulsion system concludes that a 40-fold increase of Isp over chemical propulsion is predicted. This along with a greater than 30% predicted payload mass fraction certainly warrants further development of enabling technologies. The vehicle is designed for multiple interplanetary missions and conceivably may be suited for an automated one-way interstellar voyage.

Miernik, Janie H.↗

Can Cobalt Be Eliminated from Lithium-Ion Batteries?

Following the discovery of LiCoO 2 (LCO) as a cathode in the 1980s, layered oxides have enabled lithium-ion batteries (LIBs) to power portable electronic devices that sparked the digital revolution of the 21st century. Since then, LiNi x Mn y Co z O 2 (NMC) and LiNi x Co y Al z O 2 (NCA) have emerged as the leading cathodes for LIBs in electric vehicle (EV) application and have become crucial components in the fight against global warming. However, the surging demand for LIBs has led to an extremely tight supply. The EV sector has already dominated the LIB market, even though EV sales were only 2–3% of total passenger vehicle sales in 2020. EV sales are expected to grow 10-fold by the end of this decade, and close to 90% of the total LIB demand will come from the EV sector. As a result, LIB manufacturers must aggressively ramp up cell production to keep pace with the immense growth of the EV market, a quest that brings scrutiny to the cost and sustainability of current LIB manufacturing practices. Here, cathodes are a critical component that largely determines the energy density and 40–50% of the total cell cost in LIBs. Rigorous consideration of the cathode performance and material cost is crucial in sustaining EV adoption. In this Viewpoint, we discuss why using cobalt in cathodes is unsustainable in the long run and highlight the features of cobalt-free cathodes.

25 ENERGY STORAGE↗

Two Artificial Leaf Architectures for Solar Formate Production From CO 2 and H 2 O

Sunlight-powered artificial leaves for the production of formate from CO 2 are an attractive route to solar fuels, yet existing solar formate devices remain low in performance, and their architecture and material choices are underexplored. Herein, we report the fabrication of two distinct fully integrated, self-standing solar formate device architectures and elucidate the underlying design principles and material selection strategies. The first architecture integrates a Si photocathode with a BiVO 4 photoanode and utilizes a highly active Pd catalyst for CO 2 reduction. It represents the first artificial leaf device comprising two photoelectrodes (excluding photovoltaic [PV]-biased electrodes) for effective formate production under single-beam illumination. The second architecture employs a dark cathode and a dark anode driven by a 4-junction perovskite solar cell and uses a highly stable Bi catalyst for CO 2 reduction. This device delivers a record-high formate production rate of 174 µmol h −1 with a remarkable solar-to-formate energy efficiency of 2% among all artificial leaf devices reported to date. Finally, these results demonstrate the feasibility and outline the design principles of both PV-free and PV-assisted device architectures in solar fuel production.

electrocatalysis↗

Electrochemical incineration of wastes

A low temperature electrolysis process has been developed for the treatment of solid waste material and urine. Experiments are described in which organic materials are oxidized directly at the surface of an electrode. Also, hypochlorite is generated electrochemically from chloride component of urine. Hypochlorite can act as a strong oxidizing agent in solution. The oxidation takes place at 30-60 C and the gaseous products from the anodic reaction are carbon dioxide, nitrogen, oxygen. Hydrogen is formed at the cathode. Carbon monoxide, and nitrogen oxides and methane were not detected in the off gases. Chlorine was evolved at the anode in relatively low amounts.

Kaba, L.↗

Solid State Multinuclear Magnetic Resonance Investigation of Electrolyte Decomposition Products on Lithium Ion Electrodes

Solid electrolyte interphase (SEI) formation in lithium ion cells prepared with advanced electrolytes is investigated by solid state multinuclear (7Li, 19F, 31P) magnetic resonance (NMR) measurements of electrode materials harvested from cycled cells subjected to an accelerated aging protocol. The electrolyte composition is varied to include the addition of fluorinated carbonates and triphenyl phosphate (TPP, a flame retardant). In addition to species associated with LiPF6 decomposition, cathode NMR spectra are characterized by the presence of compounds originating from the TPP additive. Substantial amounts of LiF are observed in the anodes as well as compounds originating from the fluorinated carbonates.

Li-ion battery electrolytes↗

Roundtable on Foundational Science for Carbon-Neutral Hydrogen Technologies (Technology Status Document)

This document summarizes the status of carbon-neutral hydrogen production, storage and transport, and utilization. The state of the art in the implementation, limitations, and challenges of these technologies are summarized. Sources of hydrogen are broadly categorized as hydrcoarbons or water and the processes used to convert these sources to hydrogen as catalytic, thermochemical, or electrochemical. Catalytic steam methane reforming of methane is the dominant process today. Other processes have smaller production volumes and the technology is less mature, but are being deployed at increasing rates, most notably water electrolyzers for hydrogen fueling stations. Efficient transport and storage of hydrogen is one of the major challenges facing a hydrogen-based energy economy. This arises in part from its low volumetric energy density necessitating very high pressures or cryogenic temperatures to store sufficient amounts for practical applications. High-pressure compressed hydrogen cylinders are the incumbent hydrogen storage technology for applications such as light-duty fuel cell electric vehicles, for example. The storage of hydrogen in materials or in chemicals is being pursued to address the issues associated with compression, such as parasitic energy loss and weight, size, and cost of storage containers. The complex nature of the chemical and physical processes involved in the uptake, storage, and release of hydrogen has slowed the discovery of suitable hydrogen storage materials. Both small and large-scale storage face the challenge of embrittlement of the storage media by hydrogen. There is a myriad of uses of hydrogen offering the promises of improving the efficiency of various applications and reducing or eliminating CO 2 emissions. These range from direct electrochemical conversion to electricity to power vehicles and grid-level stationary applications to combustion to production of chemicals and commodities. One of the most impactful applications in terms of reduction of CO 2 emissions is fuel cell passenger vehicles and heavy-duty vehicles such as class 8 trucks. The challenges facing widespread deployment of fuel cells, beyond the major hurdle of the lack of a hydrogen distribution infrastructure, are cost and durability, primarily related to the precious metal cathode catalyst and its durability. The other uses of hydrogen from conversion to hydrocarbons, polymer upcycling, and upgrading of bio-oils are at varying stages of maturity and also face fundamental challenges associated with catalytic processes and materials.

08 HYDROGEN↗

Two‐Membrane Dual Non‐Aqueous/Aqueous Electrolyte Flow Cell Operation for Electrochemical Conversion of CO 2 to Methyl Formate

Recently, tandem cathodic reactions have been demonstrated in non-aqueous solvents to couple CO 2 reduction to a secondary reaction to create novel species that are not produced in aqueous CO 2 electrolysis. One reaction that can be performed with high selectivity and durability is the electrochemical conversion of CO 2 to formic acid and in-situ esterification with methanol to produce methyl formate. However, the translation to a high-performance flow electrolyzer is far from trivial, as the non-aqueous catholyte leads to reactor challenges including flooding the gas diffusion electrode. Here, in this study, a two-membrane flow electrolyzer with both anion and cation exchange membranes was used with flowing methanol catholyte and aqueous anolyte. This design prevented methanol from flooding the cathode, which was a pervasive limiting issue for electrolyzers with a single membrane. Methyl formate production at 42.9 % faradaic efficiency was achieved with pure methanol in a flow electrolyzer with stable performance beyond 80 min. However, low-water-content catholyte compositions also led to increased cell resistance and lower operating current densities. Thus, with the present ionomer materials there is a tradeoff between methyl formate selectivity and current density depending on water concentration, highlighting a need for new ionomers tailored for desirable non-aqueous solvents such as methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of advanced fuel cell system

Weight, life and performance characteristics optimization of hydrogen-oxygen fuel cell power systems were considered. A promising gold alloy cathode catalyst was identified and tested in a cell for 5,000 hours. The compatibility characteristics of candidate polymer structural materials were measured after exposure to electrolyte and water vapor for 8,000 hours. Lightweight cell designs were prepared and fabrication techniques to produce them were developed. Testing demonstrated that predicted performance was achieved. Lightweight components for passive product water removal and evaporative cooling of cells were demonstrated. Systems studies identified fuel cell powerplant concepts for meeting the requirements of advanced spacecraft.

Grevstad, P. E.↗

Low-Pressure Electrolytic Ammonia (LPEA) Production

The project goal was to advance and demonstrate the techno-economic viability of a low-pressure electrolytic ammonia (LPEA) process for producing ammonia from electricity, hydrogen, and nitrogen. The critical enabling technology of the LPEA process is a proton-conducting electrolyte (PCE) developed by EERC and North Dakota State University (NDSU) capable of high proton conductivity (at least 1×10 -2 [0.01] siemens/centimeter [S/cm]) at 200°–300°C. An affordable PCE that works at 200°–300°C has been a major goal of the global electrochemistry industry for over 25 years, because it would enable operation at temperatures high enough to prevent catalyst poisoning and simplify water management and low enough to avoid temperature-driven degradation of fuel cell components comprising materials with differing coefficients of thermal expansion. Also critical to LPEA performance is a cathode catalyst capable of ammonia synthesis at a rate of ≥1×10 -10 moles/second-cm 2 catalyst surface area (mol-s -1 cm -2 ) in screening tests conducted at room temperature, and 1×10 -7 mol-s -1 cm -2 at 200°–300°C for commercial viability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V

Nickel-rich layered cathode materials promise high energy density for next-generation batteries when coupled with lithium metal anodes. However, the practical capacities accessible are far less than the theoretical values due to their structural instability during cycling, especially when charged at high voltages. Here we demonstrate that stable cycling with an ultra-high cut-off voltage of 4.8 V can be realized by using an appropriate amount of lithium difluorophosphate in a common commercial electrolyte. The Li||LiNi 0.76 Mn 0.14 Co 0.10 O 2 cell retains 97% of the initial capacity (235 mAh g -1 ) after 200 cycles. The cycling stability is ascribed to the robust interphase on the cathode. It is formed by lithium difluorophosphate decomposition, which is facilitated by the catalytic effect of transition metals. The decomposition products (Li 3 PO 4 and LiF) form a protective interphase. This suppresses transition metal dissolution and cathode surface reconstruction. It also facilitates uniform Li distribution within the cathode, effectively mitigating the strain and crack formation.

25 ENERGY STORAGE↗

Co-Extrusion (CoEx) for Cost Reduction of Advanced High-Energy-and-Power Battery Electrode Manufacturing

Co-Extrusion (CoEx) is a deposition technology developed at PARC that uses engineered fluidic channels to cause multiple streams of dissimilar fluids to impart shape to one another. Here, we describe the use of CoEx to produce structured cathode electrode films to improve electrochemical performance of thick electrode films. CoEx enables us to create structured electrode films that have periodic regions of enhanced ionic conductivity, enabling higher utilization of thicker cathode films at high discharge rates. While increasing electrode thickness is a known method for increasing energy density of battery electrodes, this increase in energy density typically also results in reduced power density. This project, a collaboration between the Palo Alto Research Center, Oak Ridge National Laboratories, and Ford Motor Company, seeks to first validate the benefits of CoEx at the coin cell level, before performing the necessary R&D effort to scale production up to large (10+ Ah) pouch cells that will show increased energy density without a reduction in power density. We used conventional battery materials (commercially available NMC, PVDF, carbon black, and graphite) to produce structured electrodes via CoEx and compared them to thick and thin conventionally produced (unstructured) battery electrodes. CoEx electrodes show improved high rate performance compared to unstructured electrodes, resulting in higher energy density pouch cells compared to the baseline electrode of 7 and 11% in volumetric and gravimetric energy density, respectively. These electrodes also showed substantially improved electrochemical performance at high discharge rates compared to thick conventional electrodes.

25 ENERGY STORAGE↗

Steady state composition with low Fe(2+) concentrations for efficient O2 production by 'magma' electrolysis of lunar soils

Parameters are estimated for a hypothetical, well stirred, continuous-feed electrolytic cell that converts 20 percent of a lunar soil feedstock to O2 gas, 26 percent to Fe-Si metal, 13 percent to spinel, and 41 percent to slag. Advantages of a molten Fe-Si cathode for trapping metal on reduction, a relatively conductive steady-state composition in equilibrium with spinel (a proposed container material), and close electrodes (less than 1 cm cathode-anode distance) are discussed. To produce 1 ton of O2, about 6 MHW of energy are required for the electrolysis and IR heating within the melt, and another about 6 MHW may be introduced as waste heat through internal resistance of the electrodes. Thus, to produce 1 ton of O2 per 24 hours, about 0.5 MW of power delivered to the cell would be required.

Haskin, Larry A.↗