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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

Stable-Cycling Sustainable Na-Ion Batteries with Olivine Iron Phosphate Cathode in an Ether Electrolyte

Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO 4 fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO 4 recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO 4 to NaFePO 4 to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (~2.4 V) at the end of the discharge process of the FePO 4 ||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF 6 diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO 4 to form single-phase Na 0.9 FePO 4 . Na 0.9 FePO 4 ||hard carbon full cells demonstrated a remarkable capacity retention of ~84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO 4 .

36 MATERIALS SCIENCE↗

Lithium inventory tracking as a non-destructive battery evaluation and monitoring method

Tracking the active lithium (Li) inventory in an electrode shows the true state of a Li battery, akin to a fuel gauge for an engine. However, non-destructive Li inventory tracking is currently unavailable. Here, in this work, we used the theoretical capacity of a transition metal oxide to convert capacity into a Li inventory analysis. The Li inventory in electrodes was tracked reliably to show how battery formulations and test methods affect performance. Contrary to capacity, Li inventory tracking reveals stoichiometric variations near the electrode–electrolyte interface. Verifiable results rationalized differences in measurements, clarifying and reducing interferences from cell formulations and experimental manipulations. By tracing four variables from formation to end-of-life, we characterize electrode and cell performance with a thermodynamic framework. Accurate rationalization of subtle differences in Li inventory utilization promises precise battery engineering, evaluation, failure analysis and risk mitigation. The method could be applicable from cell design optimization and fabrication to battery management, improving battery performance and reliability.

25 ENERGY STORAGE↗

Understanding intercalation chemistry for sustainable aqueous zinc–manganese dioxide batteries

Rechargeable aqueous Zn-MnO 2 technology combines one of the oldest battery chemistries with favourable sustainability characteristics, including safety, cost and environmental compatibility. However, the ambiguous charge storage mechanism presents a challenge to fulfil the great potential of this energy technology. In this work, we leverage on advanced electron microscopy, electrochemical analysis and theoretical calculations to look into the intercalation chemistry within the cathode material, or α-MnO 2 more specifically. We show that Zn 2+ insertion into the cathode is unlikely in the aqueous system; rather, the charge storage process is dominated by proton intercalation to form α-H x MnO 2 . We further reveal anisotropic lattice change as a result of entering protons proceeding from the surface into the bulk of α-MnO 2 , which accounts for the structural failure and capacity decay of the electrode upon cycling. Our work not only advances the fundamental understanding of rechargeable zinc batteries but also suggests the possibility to optimize proton intercalation kinetics for better-performing cell designs. A rechargeable aqueous Zn-MnO 2 battery features a combination of favourable sustainability characteristics from safety to cost. The authors deploy advanced characterizations and theoretical calculations to provide fresh insight into the charge storage mechanism, which not only closes an ongoing debate but suggests ways forward.

25 ENERGY STORAGE↗

Understanding resistances in capacitive deionization devices

The desalination characteristics of capacitive deionization (CDI) are significantly impacted by the cell resistance. Here we apply electrochemical impedance spectroscopy (EIS) to analyze the resistive properties of a CDI device, which include EIS measurements on a complete assembled cell (in two wire mode) and EIS measurements with additional contacts to decouple electrode/electrolyte and contact impedances (four wire mode). These measurements shed light on the interface between current collector and electrode as well as the internal capacitive and resistive elements of the cell. With two-wire and four-wire EIS measurements, we find that the often observed high-frequency arc(s) in the impedance spectra can be due to contact effects and/or an internal ionic-transfer resistance that is locally in parallel with macropore wall capacitance. In some cases, the two associated arcs in the Nyquist plot are overlapping and present simultaneously, making their identification in the EIS spectra difficult unless both two-wire and four-wire measurements are made. Despite causing a large high-frequency arc in the Nyquist plot, we find that the apparent internal ionic-transfer resistance is negligible compared to the resistances of the electrode, separator, and external electronic components. Here, an investigation of the contact impedance between the electrode and current collector reveals a parallel RC arc that can grow over time if an improper material is used (e.g., titanium). In our system, the electrode ionic resistance dominates the total Ohmic power dissipation, which has implications for scale-up of CDI systems and future improvements of cell design.

36 MATERIALS SCIENCE↗

Hybrid nanocapsules for in situ TEM imaging of gas evolution reactions in confined liquids

Liquid cell transmission electron microscopy (TEM) enables the direct observation of dynamic physical and chemical processes in liquids at the nanoscale. Quantitative investigations into reactions with fast kinetics and/or multiple reagents will benefit from further advances in liquid cell design that facilitate rapid in situ mixing and precise control over reagent volumes and concentrations. This work reports the development of inorganic–organic nanocapsules for high-resolution TEM imaging of nanoscale reactions in liquids with well-defined zeptoliter volumes. These hybrid nanocapsules, with 48 nm average diameter, consist of a thin layer of gold coating a lipid vesicle. As a model reaction, the nucleation, growth, and diffusion of nanobubbles generated by the radiolysis of water is investigated inside the nanocapsules. When the nanobubbles are sufficiently small (10–25 nm diameter), they are mobile in the nanocapsules, but their movement deviates from Brownian motion, which may result from geometric confinement by the nanocapsules. Gases and fluids can be transported between two nanocapsules when they fuse, demonstrating in situ mixing without using complex microfluidic schemes. The ability to synthesize nanocapsules with controlled sizes and to monitor dynamics simultaneously inside multiple nanocapsules provides opportunities to investigate nanoscale processes such as single nanoparticle synthesis in confined volumes and biological processes such as biomineralization and membrane dynamics.

36 MATERIALS SCIENCE↗

Self-Healing, Improved Efficiency Solid State Rechargeable Li/I 2 Based Battery

Solid state electrolytes are receiving significant interest due to the prospect of improved safety, however, addressing the incidence and consequence of internal short circuits remains an important issue. In this study, a battery based on a LiI-LiI(HPN) 2 solid state electrolyte demonstrated self-healing after internal shorting where the cells recovered and continued to cycle effectively. The functional rechargeable electrochemistry of the self-forming Li/I 2 -based battery was investigated through interfacial modification by inclusion of Li metal (at the negative interface), and/or fabricated carbon nanotube substrates at the positive interface. A cell design with lithium metal at the negative and a carbon substrate at the positive interface produced Coulombic efficiencies > 90% over 60 cycles. Finally, the beneficial effects of moderately elevated temperature were established where a 10 °C temperature increase led to ~5× lower resistance.

25 ENERGY STORAGE↗

Operando Topography and Mechanical Property Mapping of CO 2 Reduction Gas-Diffusion Electrodes Operating at High Current Densities

Electrochemical atomic force microscopy (EC-AFM) enables measurement of electrode topography and mechanical properties during electrochemical reactions. However, for aqueous-based reactions that make gas products, such as CO 2 reduction and water splitting into CO/H 2 , current densities below 1 mA cm −2 have been necessary to prevent formation of bubbles at the electrode; such bubbles can stick to the AFM probe and prevent further AFM imaging. Here, we demonstrate a novel cell design with a gas-diffusion electrode (GDE) to exhaust the gas products, thereby enabling high current density EC-AFM measurements at 1, 10, and 100 mA cm −2 that are not disturbed by bubble formation at the electrode surface. These experiments revealed a stable morphological structure of Cu catalysts deposited on GDEs during high current density operation. Systematic spatially resolved maps of deformation and adhesion showed no signs of a gas-liquid interface between catalyst particles of the GDE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stress Corrosion Cracking of NaSICON Membranes in Aqueous Electrolytes for Redox-Flow Batteries

The sodium super-ionic conductor (NaSICON) has versatile applications as a ceramic electrolyte for energy storage, where it can serve as an impermeable separator in solid-state batteries and redox flow systems. In particular, NaSICON systems have been proposed to be relatively stable in contact with water, making them compatible with aqueous battery chemistries. However, owing to their brittle nature and metal oxide constituents, stress-corrosion cracking (SCC) is an important failure mechanism that has not been previously explored. In this study, we assess the fracture toughness of NaSICON membranes in contact with aqueous solutions that are relevant to redox flow systems. Microindentation was performed to generate visible surface cracks and residual stress, which were observed to grow in length after exposure to aqueous solutions. This allows for a quantitative measurement of fracture toughness, which decreases after exposure to water. To contextualize these results, we develop a simplified model of the fracture behavior in aqueous redox-flow batteries that incorporate NaSICON membranes, illustrating the importance of SCC in cell design. This work provides quantitative insights into SCC as a failure mode in NaSICON, enhancing our understanding of the chemo-mechanical behavior of ceramic electrolytes in contact with aqueous solutions.

Zhang, Mengyao↗

Isospin dependence of Nucleon-Nucleon Short-range Correlations in Inclusive Scattering with Tritium and Helium-3

The nucleon-nucleon (NN) potential has a strong repulsive core. When a two-nucleon (sub)system falls into this range, they will interact strongly at short distance, and move away from each other with momenta above the Fermi level. This is called the NN Short range Correlations (SRCs). Previous experiments reported a neutron-proton pair (isos inglet) dominance in high-momentum nucleons. In inclusive electron scattering, this np dominance will cause a scaling behavior of cross sections at 1.4 < xbj = Q2/2m? < 2 where the high-momentum nucleons dominate. At Je?erson Lab Hall A we checked this hypothesis with electron Quasi-elastic (QE) scattering on A=3 nuclei systems. Our unique gas cell design made electron-tritium scattering possible for the ?rst time in a decade. The 2H, 3H, and 3He inclusive cross sections at 1 < xbj < 3 were measured in two experiments (E12-11-112 and E12-14-011) with a wide Q2 range (0.4 < Q2 < 3 GeV2). This thesis dis cusses the physics goals, experiment setup, and data analysis of the E12-11-112 experiment. Ratios of 3H/2H, 3He/2H and 3H/3He as well as absolute cross sections are presented at 0.4 < Q2 < 1.8 GeV2. NN SRC plateaus are observed in the cross section ratios at high Q2. The 3H/3He ratio of 0.84±0.01 at NN SRC dominant kinematics indicates a np to pp SRC pair ratio of 2.2±0.2 in A=3 nuclei. That implies a preference in T = 0 isospin singlet con?guration. No plateaus are observed at xbj > 2.

Li, Shujie↗

Development and Implementation of Digital Image Correlation for Out-of-Cell Burst Testing

This report details the progress made towards utilizing in-situ methods to observe and quantify unirradiated Zircaloy-4 (Zr4) fuel cladding deformation during out-of-cell design basis accident conditions, specifically during loss-of-coolant accident (LOCA) burst testing in the Severe Accident Test Station at Oak Ridge National Laboratory. Digital image correlation (DIC) was implemented to calculate cladding strain during burst and infrared (IR) thermography was used to attempt a correlation of strain with temperature and to investigate thermal gradients. For both techniques, early experimentation revealed experimental modifications were necessary for implementation. For DIC, this manifested as shortened cladding lengths which could be centered in front of the viewing chamber bored through the IR furnace side, and for IR thermography this meant conducting burst tests in air without a reaction tube and the incorporation of a SiC shell to eliminate direct IR reflections from the tungsten lamps. In the following, the technical issues and subsequent origin of these modifications are discussed, laying the framework for a proof-of-concept DIC/IR characterization of a burst test in the final section.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

CO 2 and Renewable Electricity into Chemicals: Formic Acid Production from Coal Flue Gas

Formic acid (FA) is an industrial chemical. It is used as a preservative for silage, as a digestive aid for animals, as a fluid for fracking, as a pharmaceutical intermediate and in leather tanning. The global formic acid market is valued at 777.4 million USD in 2020 and is expected to reach 851.8 million USD by the end of 2026. A new major formic acid application is the use of formic acid as a key feedstock for the bioprocessing industry. It has the potential to grow tremendously if we can lower the cost of formic acid production compared with the current fossil-fuel one. Recently, Dioxide Materials has developed a technology that can directly convert CO 2 to pure formic acid with a three-compartment CO 2 electrolyzer. However, the electrolyzer performance needs further improvement for the technology to be commercially viable. The major objective of this project is to develop the electrolyzer technology to enable formic acid as a feedstock for the bioprocessing industry to be economically manufactured from flue gas from a coal fired pilot plant. In particular, the project is to understand how to run the electrolyzer for the conversion of CO 2 into formic acid using flue gas from a coal fired power plant as a source of CO 2 . The work will include characterizing how the performance of the electrolyzer changes with low CO 2 concentration and impurities, developing new cell designs that can still operate with feedstocks with low CO 2 concentrations, testing simulated flue gas in the electrolyzer system and developing filters to remove any impurities that arise.

01 COAL, LIGNITE, AND PEAT↗

Aerosol Manufacturing Technology to Produce Low-Cobalt Li-ion Battery Cathodes

Although considerable progress has been made with battery materials over the last 10 years, the cathode remains a major performance-limiting material in Li-ion battery (LIB) technology. New materials and battery chemistries will overcome some of the remaining challenges, but cathode materials must also be manufactured at a lower cost and with a smaller environmental footprint using new processes that can also enable improved control over stoichiometry, morphology, and compositional homogeneity. Cabot, Argonne National Laboratory and SAFT research teams are combining their extensive expertise in particle synthesis, battery materials and cell design to develop a low-cost, flexible aerosol manufacturing technology for production of high-performance cathode active materials (CAM). This project will develop low-Co CAMs via Reactive Spray Technology (RST) and Flame Spray Pyrolysis (FSP) to reach performance targets of < 50 mg Cobalt/Wh.

25 ENERGY STORAGE↗

Development of an L-Edge X-ray Absorbance Spectrometer for Monitoring Dissolver Solutions in H-Canyon

Savannah River National Laboratory has developed a monitor to measure plutonium and uranium concentrations in solutions of dissolved nuclear fuel. The monitor will be installed in the sample aisle location for the 6.3D Dissolver in the Savannah River Site’s H-Canyon and used in support of the electrolytic dissolution such as Fast Critical Assembly fuel. The monitor is based on the atomic absorbance of x-rays. Elements are differentiated by the appearance of absorbance features at specific energies of the x-ray spectrum that correspond to L-edge transitions of inner core electrons. Hence, the technique is called L-Edge X-Ray Absorbance Spectroscopy (L-XRAS). The technique is suitable for nuclear fuel processing due to its relative insensitivity to other components of the dissolver solution, such as nitric acid, transition metals (Fe, Cr, Ni, Mn) such as those from stainless steel, particulates, and catalysts and additives. The instrumentation consists of a commercially available x-ray source and detector, a sample cell designed to interface with the airlift sampler associated with H-Canyon Tank 6.3D, and a stainless steel enclosure. SRNL wrote instrument control software and developed chemometric models to interpret x-ray intensity spectra and estimate analyte concentrations and uncertainties in real time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Chloride-Based Volatility for Waste Reduction and/or Reuse of Metallic-, Oxide- and Salt-Based Reactor Fuels

The objective of the chloride based volatility project (CBV) was to demonstrate the ability to separate uranium from used fuel to enable process improvements resulting in 10x reduction of waste volume, while maintaining safeguards standards and global backend costs at $\$$1/MW-hr. Current industrial practices perform separations of used fuel using solvent media in the form of aqueous and molten salt processes, resulting in contaminated process waste. The CBV approach utilized solid state chemistry with no solvent media and was successful in chlorinating uranium and fission product oxides that sublimed into the gas phase and were collected in targeted condensation zones based on temperature gradients of chlorinated products. Recovery of better than 95% of initial uranium in the form of UCl4 was demonstrated when simulated used nuclear fuel was used. Laser induced breakdown spectroscopy, LIBS, and ultraviolet-visible spectroscopy, UV-Vis, were combined into a high temperature flow cell design and utilized as process monitoring techniques to observed chlorinated products leave the reaction vessel in real time.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High Throughput Solvent-free Manufacturing of Battery Electrodes

The project goal is to develop and demonstrate an advanced solvent-free lithium-ion battery electrode process through proposed Advanced Dry Electrode Process (ADEP) equipment, which is expected to exhibit a better binder fibrillization and high throughput and suitable for high performance electrode manufacturing, and commonize the anode and cathode dry processing equipment, supply chain and operation for lithium-ion battery OEMs for replacing the solvent-based slurry casting. Our proposed approach will facilitate low-cost battery production by addressing the following gaps in present dry electrode processing: • Extend the dry electrode fabrication process to lithium-ion battery anode manufacturing • Increase the active material content for anodes and cathodes • Intensify the process through improved mixing, powder rheology and surface modifications • Enable processing of next-generation electrode materials that are not stable to solvent or ambient air exposure. The project objectives include the development of anode-compatible binder and binder fibrillization promoter for low irreversible capacity loss, low electrode binder content yet higher film mechanical strength, and the optimization of solvent-free anode and cathode process for low cost (>60% electrode cost reduction), high performance (10% increase in energy density without sacrificing cycle life) and high throughput to enable next generation lithium-ion battery electrode production. Solvent-free electrode manufacturing will also enable next-generation cell designs based on prelithiated anodes or solid-state electrolytes.

25 ENERGY STORAGE↗

Laser process and corresponding structures for forming contact holes of solar cells

Contact holes of solar cells are formed by laser ablation to accommodate various solar cell designs. Use of a laser to form the contact holes is facilitated by replacing films formed on the diffusion regions with a film that has substantially uniform thickness. Contact holes may be formed to deep diffusion regions to increase the laser ablation process margins. The laser configuration may be tailored to form contact holes through dielectric films of varying thicknesses.

14 SOLAR ENERGY↗

The Role of Innovation in the Circularity of EV Lithium-Ion Batteries

This case study analysis highlights the role of innovations in EV battery design (cells, modules, and packs), reverse supply chain, and recycling processes in yielding value for the economics of recycling (and have the largest impact on the circularity of LIBs). Part of the assessment of value will be a semi-quantitative evaluation of the value of resilience in the rapidly evolving LIB market – i.e., there are a variety of risks that recyclers would face in making a financial commitment to a recycling facility including; the possibility that batteries would not be collected in sufficient quantities, the market for key constituents (e.g., cobalt) might decrease because of changes in battery chemistry, battery manufacturers may not be willing to pay as much for recycled material, etc. The analysis would be semi-quantitative in that two simple models would be used to assess 1. material flows using a previously developed excel-based reverse supply chain flows model, and 2. A LIB recycling process material and energy balance cost model that will be used to qualitatively assess the cost impacts of process innovations and changes in feed streams. Both sets of models are highly speculative in that they rely on a multitude of assumptions and input values (e.g., EV adoption rates) that vary widely in the literature. Additionally, the initial process flow diagrams and equipment lists for the recycling cost model are based on the Argonne EverBatt model, which is still under development. However, in combination with a critical review of the literature, economic modeling can yield valuable insights into the role of innovation in the circularity of LIBs and high-technology (“energy relevant”) products in general.

28 EE - Advanced Manufacturing Office (EE-5A)↗