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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Self-regulating surface chemistry for more robust highly durable solid oxide fuel cell cathodes

Solid oxide fuel cells (SOFCs) offer direct conversion of hydrogen or hydrocarbon fuels to electricity with high energy conversion efficiency (>50%). Impurities that block active reaction sites on the electrode surface can markedly degrade the oxygen exchange rate, and lead to a reduction in long term durability of such devices. In this work, we propose to develop electrodes that are tolerant to Si which is one of the most prevalent cathode impurities. This work draws on our recent method to fully recover oxygen exchange kinetics following Si induced aging of ceria containing cathodes. We take advantage of elements, which over time during SOFC operation, are released by exsolution to actively trap (i.e. getter) Si impurities in a self-regulating chemical fashion. The objective is to evaluate impurity scavenging by added reactive elements that are intentionally exsolved from the SOFC cathode electrode during operation. In this study, we chose to focus our effort on one cathode material: Pr doped ceria (PCO). This material has the advantage of not containing strontium, an element known to segregate to the surface of the well-known perovkite based cathodes materials, thereby degrading their performance. As for the Si getter, we choose to focus on lanthanum, which is added in PCO in solid solution.

03 NATURAL GAS↗
DOE OSTI2019

Joint charge storage for high-rate aqueous zinc-manganese dioxide batteries

Aqueous rechargeable zinc-manganese dioxide batteries have great promise for large-scale energy storage due to the use of environmental friendly, abundant, and rechargeable Zn metal anode and MnO2 cathode. In the literature various intercalation and conversion reaction mechanisms have been reported depending on the origin of the starting materials, but it is not clear how these mechanisms can be simultaneously manipulated to improve the charge storage and transport properties. Here, we report a systematical study to understand the electrolyte controlled charge-storage mechanisms in layered d-MnO2. A joint Zn2+ intercalation pseudocapacitance in bulky d-MnO2 and H+ conversion reaction pathway in a wide C-rate charge-discharge range facilitates the high rate performance of high capacity d-MnO2 cathodes. The Zn-d-MnO2 system delivers discharge capacity of 136.9 mAh g-1 at 20 C and capacity retention of 92% over 4,000 cycles with joint charge storage mechanisms.

Jin, Yan↗
DOE OSTI2019

Lithium Insertion Mechanism in Iron Fluoride Nanoparticles Prepared by Catalytic Decomposition of Fluoropolymer

Metal fluorides with high redox potential and capacity from strong metal-fluoride bonds and conversion reaction, makes them promising cathodic materials but detailed lithium insertion and extraction mechanisms have not been clearly understood and explained to date. Here we report low temperature synthesis of electrochemically active FeF3/FeF2 nanoparticles by catalytic decomposition of fluoropolymer [perfluoropolyether (PFPE)] using hydrated iron oxalate precursor in air and inert atmosphere. Freshly synthesized FeF3 nanoparticle delivered specific capacity over 210 mAh/g with decent cycling performance as a Li-ion battery cathode. Both in situ and ex situ characterization techniques were used to investigate the detailed PFPE decomposition and fluorination mechanism leading to FeF3/FeF2 formation as well as initial lithium insertion mechanism in FeF3 cathode. Specifically, a detailed understanding was investigated using thermogravimetric - mass spectroscopy (TGA-MS), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), transmission electron microscopy (TEM), scanning electron microscopy (SEM) - energy dispersive spectroscopy (EDS), and X-ray absorption near edge structure (XANES). The novel synthesis route developed not only offers an access to electrochemically active metal fluorides but also offers a catalytic approach for decomposing highly inert fluoropolymers for environmental protection.

Li-ion Battery, cathode, FeF3, FeF2, Fluoropolumer↗
DOE OSTI2026

Comparing Tandem Cell Designs for Electrochemical CO 2 Reduction to Ethylene

Electrochemical carbon dioxide reduction (CO 2 R) is a promising approach for the decentralized production of fuels such as ethylene (C 2 H 4 ). However, the use of Cu, the most efficient metal CO 2 R catalyst for the generation of C 2 H 4 known to date, generally yields a product stream with poor selectivity. In an effort to increase selectivity, the reaction from CO 2 to C 2 H 4 can be broken down into two steps using tandem CO 2 R electrolyzers: formation of CO from CO 2 and subsequent reduction of CO to C 2 H 4 . Here, in this study, we present two novel tandem electrolyzer architectures that closely integrate two cathodes, one for CO generation and one for conversion to C 2 H 4 , while still enabling independent electrical control of the cathodic surfaces. Cathode segmentation in each of these designs also permits the controlled sequencing of mass flow of chemical intermediates in the order of Au to Cu cathode catalysts, in contrast to earlier work relying on uncontrolled, passive diffusion to facilitate the flow of chemical intermediates between catalysts. When comparing the performance of the newly developed electrolyzer cell designs with a dual electrolyzer system, we found that the dual electrolyzer system yields the highest C 2 H 4 faradaic efficiencies (FEs) of 31% and C 2 H 4 concentrations (∼8 mol %). However, a single Cu-containing electrolyzer outperformed all three tandem systems in terms of C 2 H 4 FE (34%). Our findings, enabled by independent control of the two tandem cathode surfaces, indicate that tandem CO 2 R systems need to be evaluated carefully by testing them at various relevant current densities.

C2H4↗
DOE OSTI2020

Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries

Metal fluorides present a high redox potential among the conversion-type compounds, which make them specially work as cathode materials of lithium ion batteries. To mitigate the notorious cycling instability of conversion-type materials, substitutions of anion and cation have been proposed but the role of foreign elements in reaction pathway is not fully evaluated. In this work, we explored the lithiation pathway of a rutile-Fe 0.9 Co 0.1 OF cathode with multimodal analysis, including ex situ and in situ transmission electron microscopy and synchrotron X-ray techniques. Our work revealed a prolonged intercalation–extrusion–cation disordering process during phase transformations from the rutile phase to rocksalt phase, which microscopically corresponds to topotactic rearrangement of Fe/Co–O/F octahedra. During this process, the diffusion channels of lithium transformed from 3D to 2D while the corner-sharing octahedron changed to edge-sharing octahedron. DFT calculations indicate that the Co and O cosubstitution of the Fe 0.9 Co 0.1 OF cathode can improve its structural stability by stabilizing the thermodynamic semistable phases and reducing the thermodynamic potentials. We anticipate that our study will inspire further explorations on untraditional intercalation systems for secondary battery applications.

25 ENERGY STORAGE↗
DOE OSTI2025

Computational Analysis of Anode and Cathode Structuring Effects on Charge and Discharge in Graphite|LiNi 0.6 Mn 0.2 Co 0.2 O 2 Batteries

Structured electrodes (SEs) improve the rate capability of Lithium-ion batteries by engineering micrometer-scale electrolyte regions into the electrode, promoting rapid ionic transport. Prior research has focused on structuring one electrode (anode or cathode) with an analysis on either the charge or discharge performance. We present a holistic study using three-dimensional models to investigate the isolated effects of structuring either electrode and the combined effects of structuring both electrodes on the charge and discharge capacity of single-layer cells at 4 C and 6 C. Volumetric and gravimetric discharge energy density (Wh/L stack and Wh/kg stack ) and charge capacity (Ah/kg stack and Ah/L stack ) are evaluated for multi-layer pouch cell stacks. Pairing SE anodes with SE cathodes demonstrated improvements up to 15% in discharge Wh/kg stack and up to 33% in charge Ah/kg stack over a conventional cell; Energy required to charge per Ah/kg stack was improved by 13%–14%. SE cathodes paired with a conventional anode exhibited improvements of 0.3%–22% across all performance metrics evaluated. Conversely, pairing a SE anode with a conventional cathode demonstrated improved charge capacity up to 13% but showed a 2%–23% lower discharge energy density. The importance of aligning SEs in a cell from a performance and manufacturing perspective is also analyzed.

25 ENERGY STORAGE↗
DOE OSTI2018

Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries

The need/desire to lower the consumption of fossil fuels and its environmental consequences has reached unprecedented levels in recent years. A global effort has been undertaken to develop advanced renewable energy generation and especially energy storage technologies, as they would enable a dramatic increase in the effective and efficient use of renewable (and often intermittent) energy sources. The development of electrical energy storage (EES) technologies with high energy and power densities, long life, low cost, and safe use represents a challenge from both the fundamental science and technological application points of view. While the advent and broad deployment of lithium-ion batteries (LIBs) has dramatically changed the EES landscape, their performance metrics need to be greatly enhanced to keep pace with the ever-increasing demands imposed by modern consumer electronics and especially the emerging automotive markets. Current battery technologies are mostly based on the use of a transition metal oxide cathode (e.g., LiCoO 2 , LiFePO 4 , or LiNiMnCoO 2 ) and a graphite anode, both of which depend on intercalation/insertion of lithium ions for operation. While the cathode material currently limits the battery capacity and overall energy density, there is a great deal of interest in the development of high-capacity cathode materials as well as anode materials. Conversion reaction materials have been identified/proposed as potentially high-energy-density alternatives to intercalation-based materials. Yet, conversion reaction materials react during lithiation to form entirely new products, often with dramatically changed structure and chemistry, by reaction mechanisms that are still not completely understood. This makes it difficult to clearly distinguish the limitations imposed by the mechanism and practical losses from initial particle morphology, synthetic approaches, and electrode preparations. Transition metal compounds such as transition metal oxides, sulfides, fluorides, phosphides, and nitrides can undergo conversion reactions yielding materials with high theoretical capacity (generally from 500 to 1500 mA h g –1 ). Specifically, a number of transition metal oxides and sulfides have shown excellent electrochemical properties as high-capacity anode materials. In addition, some transition metal fluorides have shown great potential as cathode materials for Li rechargeable batteries. In this Account we present mechanistic studies, with emphasis on the use of operando methods, of selected examples of conversion-type materials as both potentially high-energy-density anodes and cathodes in EES applications. We also include examples of the conceptually similar conversion-type reactions involving chalcogens and halogens, with emphasis on the Li–S system. In this case we focus on the problems arising from the low electrical conductivities of elemental sulfur and Li 2 S and the “redox shuttle” phenomena of polysulfides. In addition to mechanistic insights from the use of operando methods, we further cover several key strategies in electrode materials design such as controlling the size, morphology, composition, and architecture.

25 ENERGY STORAGE↗
DOE OSTI2023

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↗
DOE OSTI2025

Ferromagnetic Atomic d ‐ p Orbital Hybridization for Promoting Al‐S Batteries

Rechargeable aluminum‐sulfur batteries (Al‐S) are emerging as a promising alternative energy storage system beyond lithium‐ion batteries due to their high energy density, abundant material resources, and economic efficiency. However, their practical application remains challenged by sluggish conversion kinetics, polysulfide shuttling, and low sulfur cathode utilization. While extensive studies have focused on enhancing polysulfide adsorption through catalytic strategies, the roles of electronic structure in dictating catalytic performance remain underexplored. Here, this work unveils the critical effect of unpaired electronic structure on the catalytic performance of single atom ferromagnetic transition metals through a systematic evaluation of three typical atomically dispersed ferromagnetic single atoms—Fe, Co, and Ni—supported on porous carbon (denoted as PC‐SAFAs). Comprehensive characterizations and density functional theory (DFT) calculations reveal that the PC‐SAFe catalysts, exhibiting the highest spin polarization arising from unpaired electrons, demonstrate the strongest interactions with polysulfide, thereby facilitating rapid and reversible polysulfide conversion reactions. Consequently, Al‐S batteries incorporating the optimized PC‐SAFe cathode achieve an impressive specific capacity of 508.8 mAh g −1 at 1.0 A g −1 after 500 cycles, along with much improved rate capability. In conclusion, this work provides a deeper understanding of the role of electronic structure in catalytic chemistry, and offers new insights for developing high‐performance Al‐S batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Electrochemical nanofluid or particle suspension energy conversion and storage device

An electro-chemical energy conversion and storage device includes an enclosure, a first electrode operatively connected to the enclosure, a second electrode operatively connected to the enclosure, a nanofluid or particle suspension in the enclosure, a heat transfer unit, and a circulation system for circulating the nanofluid or particle suspension to the heat transfer unit. The nanofluid includes nanoparticles plus a dielectric or ionic fluid. The particle suspension includes particles plus a dielectric or ionic fluid. A wide range of nanoparticles or particles can be used. For example the following nanoparticles or particles can be used: metal and metal alloy particles for anodic dissolution and thermal transport; hydrides as source of hydrogen ions; lithium and lithium alloys; intercalated graphite and carbon aerogel as Li source (anodic material); intercalated transition metal oxide as Li sink (cathodic material); and semiconductors for photovoltaic conversion in photo-electrochemical or hybrid electrochemical cell.

25 ENERGY STORAGE↗
DOE OSTI2018

Fluidized Bed Production of Surface Functionalized Powders for Solid Oxide Fuel Cell Cathodes

Fuel cells offer tremendous potential for highly efficient conversion of fossil fuels to useable electrical power. Solid oxide fuel cells (SOFC) are particularly attractive, due to their high efficiency and capability to utilize either hydrogen or hydrocarbon fuels. Presently, there is considerable incentive to develop medium temperature (600 C to 800 C) SOFC's, in order to reduce the material compatibility issues and the engineering challenges associated with higher operating temperatures. Developing cathode materials with viable performance at intermediate temperatures is presently one of the key challenges in commercialization of solid oxide fuel cells. Recent works have shown the advantages of using surface functionalized cathode materials to improve SOFC performance at intermediate temperatures. However, present techniques for surface functionalization are expensive and difficult to implement in commercial SOFC production. In this SBIR Program, Structured Materials Industries, Inc. (SMI), along with partners FuelCell Energy, Inc. (FCE) and the University of Connecticut (UConn), demonstrated a simple and economical process to produce surface functionalized cathode materials, based on fluidized bed technology. SMI has developed a variation on this technology, known as Fluidized Bed Chemical Vapor Deposition (FBCVD), and is presently implementing and commercializing FBCVD as an economical and scalable process to deposit coatings on powder materials. In Phase I of this Project, the SBIR team demonstrated technical feasibility of this approach for producing high performance SOFC cathode materials. In this Phase II Project, the SBIR team refined and optimized the FBCVD process and the surface functionalized cathode materials. Surface functionalized powders of various composition and morphology were produced at SMI using the FBCVD process. Electrochemical characterization of the powders was done at FCE under actual SOFC operating conditions. The results demonstrated the potential for significant improvement in SOFC performance. Long term testing at FCE showed the performance enhancement to be stable with time. Advanced materials characterization at UConn identified the composition and morphology of the materials. SMI's FBCVD processed materials represent a "drop in" replacement for present cathode materials, and should have minimal impact on SOFC production costs. SMI has designed a scaled up FBCVD system for high volume production of SOFC cathode materials, and is well positioned for future implementation and commercialization of the technology developed in this SBIR.

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

A highly oxygen reduction reaction active and CO 2 durable high-entropy cathode for solid oxide fuel cells

One big obstacle for the oxygen reduction reaction (ORR) electrode in solid oxide fuel cells (SOFCs) is the poor reaction activity and fast degradations caused by CO 2 poisoning. Here, in this study, we report our design of an active A-site Ca-rich high-entropy Pr 0.1875 Ba 0.1875 Sr 0.1875 La 0.1875 Ca 0.25 CoO 3-δ (PBSLC 25 C) electrode, guided by the O p-band theory. Here, when applied as a cathode in solid oxide fuel cells (SOFCs), it demonstrates high ORR activity and excellent CO 2 tolerance under realistic operating conditions. Ni-YSZ-based anode-supported cells with PBSLC 25 C cathodes demonstrate excellent peak power densities of 1.14 W cm -2 , 1.04 W cm -2 , and 0.77 W cm -2 in the air with 1%, 5%, and 10% CO 2 , respectively, at 750 °C. The engineered high-entropy PBSLC 25 C effectively diminishes the CO 2 poisoning effect and maintains active surfaces for fast oxygen exchange, as confirmed by the cell durability test in air containing CO 2 (5 and 10 vol%), Raman spectroscopy, and density functional theory calculations.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS2006

Alpha-Voltaic Sources Using Liquid Ga as Conversion Medium

A family of proposed miniature sources of power would exploit the direct conversion of the kinetic energy of alpha particles into electricity. In addition to having long operational lives, these sources are expected to operate with energy-conversion efficiencies from 70 to 90 percent. A power source as proposed (see figure) would be an electrolytic cell in which liquid gallium would serve as both an electrolyte and an energy-conversion medium. The cell would contain an iridium cathode and a zirconium anode. The alpha particles, each with a kinetic energy approx.5.8 MeV, would be emitted by radioactive decay of Cm-244, which has a half-life of 18 years. The Cm-244 source would be positioned so that the a particles would enter the liquid gallium, where their kinetic energy would be dissipated mostly through ionization of Ga atoms, creating Ga(+) ions and free electrons. The electrons would be collected by iridium cathode, and the Ga(+) ions would be neutralized at the zirconium cathode by electrons returning after flowing through an external circuit. Gallium is a candidate for use as the electrolyte and the energy-conversion medium because in the liquid state it is a semimetal: its electrical conductivity is greater than that of a typical semiconductor but small in comparison with the conductivities of metals. Consequently, in liquid gallium, electrons and Ga(+) can exist without immediate recombination and can be moved by electric fields. It is expected that electric fields, resulting at least partly from the difference between the work functions of the electrode metals, would move the electrons and ions to their respective electrodes. The open-circuit potential of the cell is expected to be 1.62 V - equal to the difference between the work functions of iridium and zirconium. Unlike in a solid-state energy conversion medium, the impingement of energetic a particles would not give rise to displacement damage in the liquid gallium. Hence, the cell should have a long life, limited only by the half-life of Cm-244. A cell having a volume less than 25 cu mm, containing 1 curie of Cm-244 (the curie is a unit of radioactivity equal to 3.7 10(exp 10) disintegrations per second) is expected to deliver a current between 7 and 12 mA, which, at the expected open-circuit potential, would provide a power in the approximate range of 11 to 20 mW.

Patel, Jagdish U.↗
DOE OSTI2024

Unveiling Morphology and Crystallinity Dynamics in Ni x Mn 1– x CO 3 Cathode Precursors through Batch-Mode Coprecipitation

This study delves into the synthesis and control of Ni x Mn 1–x CO 3 , a critical class of Mn-rich, Co-free precursors vital for cathode-oxide materials in energy storage and conversion technologies. Employing batch-mode coprecipitation, we systematically generated samples with varying Ni concentrations (x = 0, 0.1, 0.3, 0.5, 0.7, and 0.9) and conducted a comprehensive analysis of their compositions, crystallinities, transition-metal distributions, and particle morphologies through both experimental and computational methods. A significant variation in particle size and crystallinity was observed, contingent on the Ni content. Further, a pivotal transition emerged at Ni concentrations above x = ~0.5, transforming uniform morphologies, such as spherical, monodisperse, pseudo-single-crystalline particles, into bimodal, polycrystalline structures. Furthermore, the study highlights the role of Ni–ammonia complexes leading to Ni-deficient precipitates and underscores the importance of ammonia concentration in achieving precise Ni content control. This study unveils critical reaction conditions governing Mn-rich precursor properties that are vital for cathode-oxides, emphasizing the need for meticulous synthetic control and offering the potential for practical applications in advanced energy storage and conversion systems.

25 ENERGY STORAGE↗
DOE OSTI2019

Current Status and Future Prospects of Metal–Sulfur Batteries

Lithium–sulfur batteries are a major focus of academic and industrial energy-storage research due to their high theoretical energy density and the use of low-cost materials. The high energy density results from the conversion mechanism that lithium–sulfur cells utilize. The sulfur cathode, being naturally abundant and environmentally friendly, makes lithium–sulfur batteries a potential next-generation energy-storage technology. The current state of the research indicates that lithium–sulfur cells are now at the point of transitioning from laboratory-scale devices to a more practical energy-storage application. Based on similar electrochemical conversion reactions, the low-cost sulfur cathode can be coupled with a wide range of metallic anodes, such as sodium, potassium, magnesium, calcium, and aluminum. These new “metal–sulfur” systems exhibit great potential in either lowering the production cost or producing high energy density. Inspired by the rapid development of lithium–sulfur batteries and the prospect of metal–sulfur cells, here, over 450 research articles are summarized to analyze the research progress and explore the electrochemical characteristics, cell-assembly parameters, cell-testing conditions, and materials design. In addition to highlighting the current research progress, the possible future areas of research which are needed to bring conversion-type lithium–sulfur and other metal–sulfur batteries into the market are also discussed.

25 ENERGY STORAGE↗
DOE OSTI2021

Revisiting metal fluorides as lithium-ion battery cathodes

Metal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF 3 using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF 2 and CuF 2 . Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F- sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle's surface, along with a cation-ordered and stacking-disordered phase, A-Li x Fe y F 3 , which is structurally related to alpha-/beta-LiMn 2+ Fe 3+ F 6 and which topotactically transforms to B- and then C-Li x Fe y F 3 , before forming LiF and Fe. Lithiation of FeF 2 and CuF 2 results in a buffer phase between FeF 2 /CuF 2 and LiF. Overall, the resulting principles will aid future developments of a wider range of isomorphic metal fluorides.

25 ENERGY STORAGE↗