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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

Effects of Lithium-ion Battery Recycling Wastes on Ammonia-Oxidizing Bacteria

Increased demand for lithium-ion batteries (LIB) necessitates development of effective recycling methods for critical battery materials. Oak Ridge National Laboratory (ORNL) is exploring membrane solvent extraction (MSX) for the hydrometallurgical recycling of LIB materials. In this study, waste from MSX was investigated for its impact on the ammonia-oxidizing organism, Nitrosomonas europaea—a model organism for nitrogen removal during wastewater treatment. It was found that Raffinate 4 from ORNL was inhibitory to the growth and nitrite production of N. europaea, likely due to its nickel content. Further investigation is currently underway.

99 GENERAL AND MISCELLANEOUS↗

Separation of cobalt, nickel, and manganese in leach solutions of waste lithium-ion batteries using Dowex M4195 ion exchange resin

Current methods to separate and recover critical metals from waste lithium-ion battery (LIB) scrap require multiple unit operations that involve selective leaching and a combination of separation methods. These methods include impurity removal, solvent extraction, ion exchange, and precipitation, to achieve high purity Co and Ni products. In this paper an efficient extraction strategy was developed to individually separate Ni and Co from a LIB leachate that was generated from an electrochemical leaching process. By using Dowex M4195 resin, as the only method of separation, additional impurity removal operations were not needed. After loading and eluting, three different fractions were obtained: 99.0% Ni concentrate, 98.5% Co concentrate, and a Li/Mn rich concentrate allowing the separation of Ni, Co and Mn. Here, the developed process is then presented as an alternative for metal recovery from leachates from scrap LIBs with minimum chemical addition and pH adjustment.

36 MATERIALS SCIENCE↗

Ultraselective sequestration of Li + and Mg 2+ from brines via a reusable polyoxoniobate-based ion sponge

Lithium (Li) and magnesium (Mg) are designated as critical mineral materials (CMM) due to their essential roles in clean energy technologies. However, extracting high-purity Li + from brine remains a formidable challenge owing to the presence of Mg 2+ , a physicochemical similar ion that often exists in excess. Here, we introduce a polyoxoniobate-based “Mg-PONb sponge” that enables ultraselective and rapid Li + /Mg 2+ separation across an exceptionally broad range of Mg/Li ratios (0.02 to 200.63). This framework achieves >99.9% Mg 2+ removal with negligible Li + loss in under 1 min, yielding Li + /Mg 2+ selectivity values exceeding 5000. The sponge demonstrates excellent recyclability, maintaining >99% Mg 2+ rejection and Li + permeability across five regeneration cycles without structural degradation. Mechanistic investigations reveal that selective Mg 2+ capture originates from strong coordination with terminal oxygens on the PONb cluster, driving rapid formation of porous Mg-PONb frameworks. This work presents a generalizable, scalable strategy for Li + /Mg 2+ separation and offers a sustainable path toward enhanced Li and Mg recovery from complex brine sources.

Chen, Linfeng [Lawrence Berkeley National Laborato↗

Challenges and Development of Tin-Based Anode with High Volumetric Capacity for Li-Ion Batteries

Abstract The ever-increasing energy density needs for the mass deployment of electric vehicles bring challenges to batteries. Graphitic carbon must be replaced with a higher-capacity material for any significant advancement in the energy storage capability. Sn-based materials are strong candidates as the anode for the next-generation lithium-ion batteries due to their higher volumetric capacity and relatively low working potential. However, the volume change of Sn upon the Li insertion and extraction process results in a rapid deterioration in the capacity on cycling. Substantial effort has been made in the development of Sn-based materials. A SnCo alloy has been used, but is not economically viable. To minimize the use of Co, a series of Sn–Fe–C, Sn y Fe, Sn–C composites with excellent capacity retention and rate capability has been investigated. They show the proof of principle that alloys can achieve Coulombic efficiency of over 99.95% after the first few cycles. However, the initial Coulombic efficiency needs improvement. The development and application of tin-based materials in LIBs also provide useful guidelines for sodium-ion batteries, potassium-ion batteries, magnesium-ion batteries and calcium-ion batteries. Graphic Abstract

25 ENERGY STORAGE↗

The indirect electrochemical refining of lunar ores

Recent work performed on an electrolytic cell is reported which addresses the implicit limitations in various approaches to refining lunar ores. The cell uses an oxygen vacancy conducting stabilized zirconia solid electrolyte to effect separation between a molten salt catholyte compartment where alkali metals are deposited, and an oxygen-evolving anode of composition La(0.89)Sr(0.1)MnO3. The cell configuration is shown and discussed along with a polarization curve and a steady-state current-voltage curve. In a practical cell, cathodically deposited liquid lithium would be continuously removed from the electrolytic cell and used as a valuable reducing agent for ore refining under lunar conditions. Oxygen would be indirectly electrochemically extracted from lunar ores for breathing purposes.

Semkow, Krystyna W.↗

Nested Pebble Bed Blanket (NesPeB)

Recent advances in magnetic confinement fusion technology have attracted billions of dollars of investments in startups from venture capitals and corporations, resulting in the development of devices aiming to demonstrate net energy gain in a self-heated burning plasma, such as SPARC (under construction) and others. However, future fusion power plants must operate in regimes that will require technologies far beyond current experience. According to a National Academies of Science, Engineering, and Medicine report, to have nuclear fusion power plants contributing in a timely manner to the planned reduction of atmospheric carbon dioxide, a pilot plant should be built by 2035, and it should demonstrate fusion power production and the performance of the tritium fuel system (requiring a high enough tritium breeding) by 2040. A recognized key technology gap by [26] is the fusion first wall and blanket since no current blanket concept is considered satisfactory or has been built and proven. The first wall and blanket in magnetic fusion reactors form a vital and complex system, as it must satisfy different functions such as power extraction, tritium breeding, plasma containment, radiation shielding, and safety. The list of design requirements is even longer: high enough tritium production for fusion self-sufficiency, low material activation, decay heat and shutdown dose rates, high thermal efficiency, high-capacity factor, high magnets-divertor-vacuum vessel-first wall life, low corrosion, low cost, and intrinsically safe (requiring minimal licensing). Despite fifty-plus years of research, the first wall and blanket concepts proposed suffer from fundamental technical problems and immaturity (TRL=2-3) that jeopardize the timely delivery of a commercial fusion power plant. A fusion first-wall blanket has never been built nor tested, and a "winning", practical functioning design requires enough engineering margins (high enough tritium breeding considering the uncertainty, etc.), manufacturing simplicity, ease of continuous operation, maintenance, and low cost. A new, groundbreaking blanket concept called "Nested Pebble Bed Blanket" (NesPeB) was developed at ORNL under the successful ARPA-E GAMOW FERMI project (patent application allowed by the USPTO). The NesPeB blanket concept addresses current blanket concepts' shortcomings and technical immaturity, paving the way for accelerated delivery of fusion power plants. NesPeB is based on nested pebbles, which are binary-sized lithium-ceramic pebbles enclosed in "Beryllide" perforated and coated spherical shells, which are also binary-sized, stacked on top of each other, forming a "bed" and cooled by Nitrogen gas also "sweeping" the Helium and Tritium generated by the neutron irradiation of Lithium; the vacuum vessel plasma facing material is Molybdenum-96 and -97 with the first wall cooled by Helium while the divertor armor is made of Tungsten. The simulations of the NesPeB blanket using Fusion Reactors Models Integrator (FERMI) are encouraging as they estimate a tritium breeding ratio (TBR) greater than 1.2 using natural Lithium, acceptable pressure drop, and excellent heat transfer properties. Furthermore, the NesPeB blanket is not limited by magneto-hydro-dynamics (MHD) effects, is designed for online refueling, relies on existing tritium extraction technologies, has a simple construction, and limits the corrosion and chemical reactivity problems. NesPeB has the potential to be transformational and disruptive since it can solve all the main, challenging technical problems of fusion device blankets and accelerate a pilot plant delivery for 10 or more years.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A future, intense source of negative hydrogen ions

By directly heating lithium hydride in a vacuum, up to 18 micro-A/sq cm of negative hydrogen has been obtained from the crystal lattice. The amount of ion current extracted and analyzed is closely related to the temperature of the sample and to the rate at which the temperature is changed. The ion current appears to be emission limited and saturates with extraction voltage. For a fixed extraction voltage, the ion current could be maximized by placing a grid between the sample surface and the extraction electrode. Electrons accompanying the negative ions were removed by a magnetic trap. A Wein velocity filter was designed and built to provide definitive mass analysis of the extracted ion species. This technique when applied to other alkali hydrides may produce even higher intensity beams possessing low values of emittance.

Siefken, Hugh↗

A laboratory-scale process for producing dilithium beryllium tetrafluoride (FLiBe) with dissolved uranium tetrafluoride

Flibe Energy, Incorporated (FEI)'s conceptual Lithium Fluoride Thorium Reactor (LFTR) incorporates a chemical processing facility aimed at recovering uranium and other valuable volatile radionuclides while managing harmful radionuclides from the used fuel. The fuel utilized in this reactor is a combination of dilithium beryllium tetrafluoride (Li 2 BeF 4 or FLiBe) and uranium tetrafluoride (UF 4 ), (FLiBe/U). FEI's plan involves extracting the uranium and other valuable volatile fluoride-forming radionuclides using nitrogen trifluoride (NF 3 ). To facilitate laboratory-scale testing of uranium extraction using NF 3 and address the toxicity and physical hazards associated with beryllium and beryllium fluoride (BeF 2 ), we used a two-step process to prepare the simulated fuel salt. The first step entailed thermally decomposing ammonium beryllium tetrafluoride [(NH 4 ) 2 BeF 4 ] (ABeF) through a nominal 3-step process, combined with appropriate amounts of lithium fluoride (LiF) and UF 4 , resulting in the formation of beryllium fluoride (BeF 2 ). In the second step, the mixture was repeatedly melted and frozen at the melting point of FLiBe to prepare the eutectic FLiBe with dissolved UF 4 . Although the concept appears straightforward, the production of FLiBe/U involved various challenges. These challenges included transporting the gaseous decomposition products of ABeF, hydrogen fluoride (HF) and ammonia (NH 3 ), while preventing the formation of ammonium fluoride (NH 4 F). Additionally, it was necessary to control the reaction between the higher-than-anticipated water content in the commercial ABeF with NH 3 , HF, and the condensed NH 4 F, protect UF 4 from forming an unknown black compound, select suitable structural materials to mitigate fluoride corrosion, address the risks associated with beryllium toxicity through equipment design and operational protocols, and monitor process conditions. This article provides an account of the thermal decomposition chemistry observed in the commercial ABeF, describes the FLiBe/U production apparatus, describes the experiences and process refinements developed to prepare FLiBe/U, and presents our characterizations of prepared FLiBe/U.

Ammonium beryllium fluoride thermal decomposition↗

Targeted Rare Earth Element Extraction from Mine Drainage Treatment Solids Informed by Advanced Characterization

In support of a clean energy transition in the U.S., National Energy Technology Laboratory (NETL) has collaborated with staff at Hedin Environmental and students at the University of Pittsburgh to characterize critical mineral content and recovery potential from acid mine drainage treatment solids (AMD solids). AMD solids in Appalachia are an unconventional feedstock of rare earth elements (REEs), with potential of suppling 1,102 tons REE/year. To inform recovery efforts, select AMD solids were examined using synchrotron microprobe analysis in conjunction with USGS-developed geochemical modeling to indicate likely phases hosting critical minerals (REE, Co, Ni, etc.) and associated metals . More than 100 AMD solids were collected from 94 passive AMD treatment systems in Pennsylvania, where limestone aggregates are used for acidity neutralization. As pH increases, dissolved metals and critical minerals in AMD are attenuated as surface coatings on limestone. The collected AMD solids contained up to 2000 mg/kg REE, up to 13,000 mg/kg transition metals (Co, Ni, Zn) and up to 440 mg/kg Li. Regardless of the diverse chemical compositions from AMD solids (Al-rich, Mn-rich, or Al,Fe,Mn-rich), REEs were mostly associated with Al and Mn (hydr)oxides, while select heavy REEs (e.g., Gd, Dy) were co-localized with Fe (hydr)oxides. Co and Ni have different distribution zones, while both co-localized with Mn (hydr)oxides. Based on this characterization, NETL developed a patent-pending innovative step-leaching protocol, “Targeted Rare Earth Extraction (TREE)” to effectively recover up to 90% REE and 60% Co in separate steps. In addition, select post-TREE solid residuals (purified Al oxides, or Mn oxides) can be further developed into functional materials (e.g., lithium and CO2 sorbents) needed for green energy transition and carbon management. This characterization-informed approach as well as TREE processing from AMD solids can be used for other legacy wastes (e.g., coal ash, oil and gas drill cutting, mine tailings), and offers an opportunity to transform waste streams into environmental and economic assets that meet U.S. Department of Energy and U.S. Environmental Protection Agency goals.

characterization and extraction of rare earth elem↗

Life‐Cycle Assessment Considerations for Batteries and Battery Materials

Abstract Rechargeable batteries are necessary for the decarbonization of the energy systems, but life‐cycle environmental impact assessments have not achieved consensus on the environmental impacts of producing these batteries. Nonetheless, life cycle assessment (LCA) is a powerful tool to inform the development of better‐performing batteries with reduced environmental burden. This review explores common practices in lithium‐ion battery LCAs and makes recommendations for how future studies can be more interpretable, representative, and impactful. First, LCAs should focus analyses of resource depletion on long‐term trends toward more energy and resource‐intensive material extraction and processing rather than treating known reserves as a fixed quantity being depleted. Second, future studies should account for extraction and processing operations that deviate from industry best‐practices and may be responsible for an outsized share of sector‐wide impacts, such as artisanal cobalt mining. Third, LCAs should explore at least 2–3 battery manufacturing facility scales to capture size‐ and throughput‐dependent impacts such as dry room conditioning and solvent recovery. Finally, future LCAs must transition away from kg of battery mass as a functional unit and instead make use of kWh of storage capacity and kWh of lifetime energy throughput.

25 ENERGY STORAGE↗

Computer Modeling of Non-Isothermal Crystallization

A realistic computer model for simulating isothermal and non-isothermal phase transformations proceeding by homogeneous and heterogeneous nucleation and interface-limited growth is presented. A new treatment for particle size effects on the crystallization kinetics is developed and is incorporated into the numerical model. Time-dependent nucleation rates, size-dependent growth rates, and surface crystallization are also included. Model predictions are compared with experimental measurements of DSC/DTA peak parameters for the crystallization of lithium disilicate glass as a function of particle size, Pt doping levels, and water content. The quantitative agreement that is demonstrated indicates that the numerical model can be used to extract key kinetic data from easily obtained calorimetric data. The model can also be used to probe nucleation and growth behavior in regimes that are otherwise inaccessible. Based on a fit to data, an earlier prediction that the time-dependent nucleation rate in a DSC/DTA scan can rise above the steady-state value at a temperature higher than the peak in the steady-state rate is demonstrated.

Kelton, K. F.↗

A review study of rare Earth, Cobalt, Lithium, and Manganese in Coal-based sources and process development for their recovery

The world’s majority predominantly relies on foreign sources for supplying critical minerals. This renders the countries susceptible to supply chain disruption and urges them to develop alternative sources to compete in technological advancements. Among many proven newly identified sources, coal and coal-based materials present their opportunities. Due to the complex structure of coal, many mineral forms can be found in coal-related sources, including critical element-containing minerals. Among the fifty critical elements and minerals defined by the USGS, the rare earth elements, cobalt, lithium, and manganese, are particularly significant as they have enormous importance in high-technology product development. These critical metals can be found in high concentrations in coal-derived sources, such as coal refuse, coal combustion products, and coal acid mine drainage, and be recovered through various separation techniques. Further, this study aims to advance the understanding of these elements' extraction and commercial potential from coal and coal-related sources and help address the world's challenges in the critical mineral supply chain. The concentrations and occurrences of these four commodities in coal-related sources were first reviewed. Later, their recovery processes were discussed, and a conceptual process flowsheet was proposed to selectively recover the rare earth elements, lithium, cobalt, and manganese from coal-based sources.

58 GEOSCIENCES↗

Learning heterogeneous reaction kinetics from X-ray videos pixel by pixel

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries and electrocatalysts. Experimental characterizations of such materials by operando microscopy produce rich image datasets, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Learning heterogeneous reaction kinetics from X-ray movies pixel-by-pixel

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries 1 and electrocatalysts 2. Experimental characterizations of such materials by operando microscopy produce rich image datasets 3–6, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation 7. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.

Chueh, William↗

Learning Molecular Mixture Property Using Chemistry-Aware Graph Neural Network

Recent advances in machine learning (ML) are expediting materials discovery and design. One significant challenge facing ML for materials is the expansive combinatorial space of potential materials formed by diverse constituents and their flexible configurations. This complexity is particularly evident in molecular mixtures, a frequently explored space for materials, such as battery electrolytes. Owing to the complex structures of molecules and the sequence-independent nature of mixtures, conventional ML methods have difficulties in modeling such systems. Here, we present MolSets, a specialized ML model for molecular mixtures, to overcome the difficulties. Representing individual molecules as graphs and their mixture as a set, MolSets leverages a graph neural network and the deep sets architecture to extract information at the molecular level and aggregate it at the mixture level, thus addressing local complexity while retaining global flexibility. We demonstrate the efficacy of MolSets in predicting the conductivity of lithium battery electrolytes and highlight its benefits in the virtual screening of the combinatorial chemical space. Published by the American Physical Society 2024

Zhang, Hengrui (ORCID:0000000231831654)↗

Synthesizing Lithium Sorbents Using Acid Mine Drainage Solids

In this study, we prepared HMO from coal mine drainage (CMD) solids and examined the practicability of recovering Li from oil and gas produced waters and geothermal brines. We aim to innovate high-value added products from the existing extract REEs and CMs processing chain of legacy byproducts associated with coal production. CMD solids, which are precipitates collected from exhausted limestone gravels of passive CMD treatment beds, are enriched in rare earth elements (REEs) and other critical minerals (CMs), and therefore, considered as a viable alternative source for REEs/CMs to supply the Nation’s demands. A patented extraction process developed by NETL (TREE) has been demonstrated as a cost-effective and efficient approach to recover REEs/CMs from CMD solids. Here, we selected residuals of CMD solids from the TREE process that are enriched in manganese (Mn) (&gt;20% w/w) and successfully prepared LMO using a solid-state method modified from Yoshizuka et al. (2002).

Cheng, Chin-Min↗