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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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Li Morphology Evolution during Initial Cycles in a Gel Composite Polymer Electrolyte

Understanding and controlling lithium morphology evolution and lithium dendrite formation and growth during cycling is one of the key challenges for high-energy lithium metal batteries. This challenge applies to liquid electrolyte batteries as well as solid-state and semi-solid-state batteries. Our current knowledge about the evolution of the Li morphology is mostly obtained from liquid electrolyte-based studies in a Li–Li symmetrical cell configuration. The knowledge obtained in such conditions may not readily transfer into solid-state or semi-solid-state batteries. In this work, Li morphology evolution during initial cycling in a full cell configuration with the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NMC 622) cathode and a semi-solid-state gel composite electrolyte is monitored via post-mortem photographs and scanning electron microscopy at multiple length scales. The gel composite electrolyte contains a cross-linked poly(ethylene oxide)-based polymer electrolyte, ceramic fillers, and a liquid plasticizer. The results show that severe surface pitting occurs as early as the second stripping cycle. Pit formation and continuous dissolution during the stripping process are the main cause of the Li surface roughening and dendrite growth mechanism in the model gel composite electrolyte. Comparing Li dendrite growth mechanisms in liquid, polymer, and ceramic solid electrolytes, the dendrite growth mechanism observed in this model electrolyte resembles that of the liquid electrolyte the most. This study suggests that strategies to control Li morphology and prevent dendrite growth in a gel composite electrolyte should be similar to strategies applicable to liquid electrolytes.

25 ENERGY STORAGE↗

Degradation science: Integrating modeling and experiments to predict localized corrosion processes (Annual Progress Report)

Additively manufactured (AM) eutectic high-entropy alloys (EHEAs), such as nano-lamellar AlCoCrFeNi 2.1 , have excellent strength, ductility, and wear resistance even at elevated temperatures, but their corrosion behavior in aggressive acids at different length scales remain poorly understood. This work investigates the corrosion behavior of laser powder bed–fused (L-PBF) AlCoCrFeNi 2.1 as a function of annealing temperatures, probing degradation mechanisms from nanoscopic to macroscopic length scales. The alloy is dual phase consisting of a ductile FCC L1 2 phase and a high-strength BCC B2 phase. Rapid solidification during L-PBF produces a far-from-equilibrium nano-lamellar structure with nearly homogeneous elemental distribution, which tends to evolve upon annealing toward Cr/Co/Fe-enriched FCC and Al/Ni-enriched B2. Three conditions were studied: as-printed, 600 °C/5 h, and 1000 °C/1 h, over which B2 lamellae coarsen, lamellar spacing increases, and elemental segregation becomes more prominent. Microstructure and chemistry were characterized by scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), while in-situ electrochemical atomic force microscopy (EC-AFM) was used to link early (<5 h) local dissolution to microstructure after exposure in sulfuric acid. EC-AFM highlights preferential dissolution of the BCC/B2 phase where the surrounding matrix is Cr-depleted and directly quantifies the dissolution rates within individual phases, tracks the transition from early nano-scale attack to partial repassivation, to correlate height differences with current and impedance responses. To monitor longer-term behavior (up to 96 h), ex-situ AFM, SEM, and confocal imaging were combined with conventional bulk electrochemical tests, bridging nanoscale observations to micro/meso-scale damage morphologies. At the meso-scale, the deepest dissolution channels align with the build-direction lamellae and melt-pool boundaries, indicating that printing directionality guides the propagation of these localized corrosion sites. Annealing modifies corrosion by restructuring BCC/FCC phase fractions, lamellar spacing, and Cr/Al segregation, thereby changing the cathode/anode ratio and passive film stability. The results clarify how as-printed and annealed nano-lamellar architectures differ in their susceptibility to selective dissolution; how elemental segregation competes with residual stresses along the build direction. With these insights, future work will use CALPHAD-guided alloy modification to stabilize higher Cr contents in the B2 phase while retaining a dominant FCC+B2/BCC microstructure, with the goal of designing mechanically robust, corrosion-resistant EHEAs for safety-critical applications to leverage the LLNL’s broader national and global security mission.

36 MATERIALS SCIENCE↗

Experimental Investigation of the Distribution of Shock Effects in Regolith Impact Ejecta Using an Ejecta Recovery Chamber

Because the mass-flux of solar system meteoroids is concentrated in the approx. 200 microns size range, small-scale impacts play a key role in driving the space weathering of regoliths on airless bodies. Quantifying this role requires improved data linking the mass, density and velocity of the incoming impactors to the nature of the shock effects produced, with particular emphasis on effects, such as production of impact melt and vapor, that drive the optical changes seen in space weathered regoliths. Of particular importance with regard to space weathering is understanding not only the composition of the shock melt created in small-scale impacts, but also how it is partitioned volumetrically between the local impact site and more widely distributed ejecta. To improve the ability of hypervelocity impact experiments to obtain this type of information, we have developed an enclosed sample target chamber with multiple-geometry interior capture cells for in-situ retention of ejecta from granular targets. A key design objective was to select and test capture cell materials that could meet three requirements: 1) Capture ejecta fragments traveling at various trajectories and velocities away from the impact point, while inducing minimal additional damage relative to the primary shock effects; 2) facilitate follow-up characterization of the ejecta either on or in the cell material by analytical SEM, or ex-situ by microprobe, TEM and other methods; and 3) enable the trajectories of the captured and characterized ejecta to be reconstructed relative to the target.

Christoffersen, R.↗

Improved cycle stability and high-rate capability of LiNbO 3 -coated Li 3 VO 4 as anode material for lithium-ion battery

Lithium vanadate (Li 3 VO 4 ) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li 3 VO 4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, in this study, we report the synthesis of lithium niobate LiNbO 3 -coated Li 3 VO 4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li 3 VO 4 . To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO 3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.

25 ENERGY STORAGE↗

Low Temperature Formation of Carbonaceous Grains from Hydrocarbons and PAHs with the COSmIC Facility

Complex carbon molecules and ions are ubiquitous in space and form the building blocks of the carbonaceous components of cosmic dust grains, ultimately contributing to the formation of planets. We report experimental investigations of the low temperature chemical pathways leading to the formation of cosmic grain analogs from gas phase molecular precursors to better understand the evolution of cosmic carbon. The study of the formation of dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. Although dust plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of carbonaceous dust. The experiments were performed using the Cosmic Simulation Chamber (COSmIC) to generate and characterize solid grains formed from gas phase precursors under controlled conditions representative of astrophysical environments [1]. Using COSmIC, it is possible to investigate the evolution of cosmic carbon from the formation of neutral and ionized hydrocarbons and PAHs in the gas phase [2], to solid carbon grains [3, 4, 5]. This is achieved by using a pulsed slit discharge nozzle to produce an adiabatic jet expansion and cool down Ar-hydrocarbon and PAH gas mixtures to astrophysically relevant temperature before inducing chemistry by generating a plasma discharge in the stream of the expansion. This plasma induced chemistry results in the formation of complex molecules and solid particles, analogs of cosmic grains in situ in the plasma expansion (i.e., without wall effects) that are carried by the accelerated gas in the expansion, and collected on substrates placed a few centimeters downstream of the electrodes. The results of a preliminary solid phase ex-situ analysis of cosmic grain analogs produced from a series of gas mixtures including hydrocarbons such as CH4 and C2H2 [3] and PAHs [4, 5] found in circumstellar ejecta of late C stars will be discussed. SEM imaging was used to provide insight on the impact of the precursors on the morphology and growth structure of the grains produced [3]. Laser desorption mass spectrometry was used to identify the molecules making up the main structures within the condensed grains [4] while X-ray irradiation and X-ray photoemission spectroscopy were used to investigate the impact the impact of stellar X-rays on cosmic dust.

Carbonaceous Grains↗

Enhanced grindability of bastnaesite ore by ex-situ CO 2 treatment under the partial pressure of 0-100 psi

High grinding energy consumption has long constrained the sustainable development of mineral processing. This study introduces an innovative technology that employs ex-situ CO 2 treatment to enhance the grindability of bastnaesite ore. The grinding aid effect was evaluated under CO 2 partial pressures ranging from 0 psi to 100 psi using particle size distribution and the Bond work index (BWI), while the underlying mechanism was elucidated with various characterization techniques including inductively coupled plasma (ICP), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Brunauer-Emmett-Teller (BET). The optimal grinding aid effect was achieved at 100 psi partial pressure, 50% slurry concentration, and 3 h reaction duration. Correspondingly, the P80 of the grinding product decreased from 81.76 μm to 72.73 μm and the BWI of bastnaesite ore decreased from 6.96 kW·h/t to 6.30 kW·h/t, a reduction of 9.48%. The grinding aid effect primarily resulted from the transformation of sparingly soluble carbonates like calcite and dolomite into more soluble bicarbonates, which created substantial cracks and pores, thereby reducing the ore's hardness and improving its grindability. By significantly saving grinding energy consumption while delivering environmental benefits, this technology exhibits great promise for further optimization and widespread adoption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bridging the length scales on mechanical property evaluation (Final Report)

The development of small-scale mechanical testing in combination with microstructural investigation is of great interest to the nuclear materials community for both materials development and monitoring applications. Dramatically reducing the sample sizes to reduce radioactivity and obtaining mechanical properties of irradiated samples is truly intriguing. Moreover, such studies promise a range of benefits including cost reduction, fundamental insight in structure-property relationships, increased statistics on less sample material, and reinvestigation of prior irradiated and tested reactor samples while simultaneously enabling the generation of mechanical test data on ion beam irradiated materials with limited penetration depths. Small scale materials testing on sub-sized samples has been studied for several decades, though it has only been after the development of micro-testing based on Focused Ion Beam (FIB) sample manufacturing in that orders of magnitude smaller samples could really be investigated in a quantitative manner. In recent years, small scale mechanical testing techniques at a number of length scales has been developed for both unirradiated and irradiated (ion and neutron) materials. Technological advances made in this field have enabled ex-situ and in-situ transmission electron microscopy (TEM) and scanning electron microscopy (SEM) examination, thus leading to more accurate measurements as well as additional mechanistic information. A recent review of the benefits of these techniques show that these techniques are at a stage to tackle multi-scale ranges of materials investigations and can be utilized to obtain fundamental science-based understanding of nuclear materials. Considering the tremendous advances made, one can see how small-scale mechanical testing techniques combined with modeling can enable true small scale to bulk scale mechanical property correlations. However, for the engineering community to adapt this approach fully, one needs to demonstrate that a) that these techniques can produce results with high fidelity and reproducibility, b) generate engineering stress-strain data that one can utilize to understand bulk behavior, and c) generate new insight into relevant phenomena fostering the true understanding of radiation damage and microstructure in materials for nuclear applications. It is the objective of this proposal to bridge the length scale between macro- and micro- scale mechanical testing of unirradiated and irradiated materials. This involves the development and demonstration of procedures for multi-scale mechanical testing that enable high fidelity reproducibility of data and the generation bulk property data from small-scale mechanical tests. Through this, the proposal aims to enhance the confidence in the obtained data at the smaller length scales and enhance the insight provided from these techniques for bulk scale applications on both unirradiated and irradiated materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗