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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 73 records · Page 4

In-Situ FTIR Detection of Transition Metal (TM)-Ion Dissolution From Cathodes in Li-Ion Batteries

Transition metal (TM) ions, commonly Ni and Mn, play a crucial role in Li-ion battery cathodes as the reaction centers for rapid redox reactions. A major challenge with TM-based cathodes is capacity degradation, particularly at higher operating voltages. This degradation is closely linked to the dissolution of TMs from the cathode materials and their subsequent deposition on the anode. This process not only modifies the surface structure of the cathode but, more significantly, alters the SEI composition on the anode [1-2]. The dissolution of TMs cations into a liquid electrolyte from cathode materials, such as Mn-ion dissolution from Mn-rich cathode (LMR), is detrimental to the cycling performance of Li-ion batteries [3-4]. Much attention has been paid to this issue but there remains a lack of characterization techniques which can detect the TM-ion dissolution from the cathode during electrochemical measurements. In our study, we use in-situ ATR-FTIR as an effective technique to probe the TM-ion dissolution from the cathode. We have first demonstrated the detrimental effects of TM ions on the electrochemical performance of Li-ion batteries by adding a small amount of TM salt (50 mM Mn(PF6)) to the electrolyte of a Li-ion coin cell with LFP and graphite electrode. We observed a rapid capacity fade after the first delithiation cycle. To investigate TM ion dissolution, we established a baseline IR spectrum for various TM solvation states (such as Mn and Ni) by measuring concentration-dependent IR spectra. This baseline spectrum helps us detect TM ion dissolution during battery cycling. In this work, we discuss in detail the effect of TM ions on the electrochemical performance of Li-ion batteries and the detection of TM ions during battery cycling using in-situ FTIR spectroscopy. We will compare TM dissolution between coated and uncoated cathodes to examine the effect of cathode coatings to mitigate degradation due to TM dissolution and cross-over from cathode to anode. References: (1) Zhan, C.; Wu, T.; Lu, J.; Amine, K. Dissolution, migration, anddeposition of transition metal ions in Li-ion batteries exemplified byMn-based cathodes - a critical review. Energy Environ. Sci. 2018, 11,243-257. (2) Jung, R.; Linsenmann, F.; Thomas, R.; Wandt, J.; Solchenbach,S.; Maglia, F.; Stinner, C.; Tromp, M.; Gasteiger, H. A. Nickel,Manganese, and Cobalt Dissolution from Ni-Rich NMC and TheirEffects on NMC622-Graphite Cells. J. Electrochem. Soc. 2019, 166,A378-A389. (3) Zhao, L.; Chenard, E.; Capraz, O. O.; Sottos, N. R.; White, S.R. Direct Detection of Manganese Ions in Organic Electrolyte by UV-Vis Spectroscopy. J. Electrochem. Soc. 2018, 165, A345-A348 (4) Zhang, Y.; Hu, A.; Xia, D.; Hwang, S.; Sainio, S.; Nordlund, D.;Michel, F. M.; Moore, R. B.; Li, L.; Lin, F. Operando characterization and regulation of metal dissolution and redeposition dynamics nearbattery electrode surface. Nat. Nanotechnol. 2023, 18, 790.

25 ENERGY STORAGE↗

A study of the Lute Metering Structure

Two Metering Structure configurations were investigated. The first case was the traditional style metering structure which is larger than the outside diameter of the primary mirror. The second case investigated was the center support concept in which the outside diameter of the structure is less than the inside diameter of the primary mirror. Beryllium was used as the baseline material for this study. Four other materials were considered as candidates for the metering structure. These materials are: Graphite Epoxy, Aluminum, Titanium, and Invar. The loading conditions used for this study were estimated to be: Quasi Static: 6.0 G (all three directions); and Random Vibration: 30.0 G (applied 1 axis at a time). Taking advantage of symmetry, it was necessary to apply the lateral loading to only one axis. These loads were applied to both concepts and to all material configurations. The loadings as described above were based on the best available information and is felt to be adequate for this study since it was consistently used for all configurations. A load factor 2.00 was applied to both quasi static and random vibration loads. The allowable stresses are conservatively based yield strength of the material, except for the struts which are controlled by elastic stability. The stresses determined from each individual loading direction were conservatively combined by the absolute sum method.

Foreman, James W.↗

Silicon Anodes with Improved Calendar Life Enabled By Multivalent Additives

Silicon is widely recognized as the most promising upgrade for graphite anodes due to its much higher capacity, natural abundance, and ability to be directly applied in the slurry-based, roll-to-roll production lines. However, in addition to the fast capacity decay, silicon anodes also suffer from inferior calendar life in practical applications due to the unstable solid-electrode interface (SEI). Until now, strategies to effectively improve the calendar life by tailored SEIs remain largely unclear, especially in high-Si content, zero-graphite anodes. Here, silicon anodes with superior calendar life are developed by adding small concentrations of multivalent salts into the baseline electrolyte. The Ca additive reacts with the F ions in the electrolyte, forming a layer of nanocrystalline CaF 2 that is closely coated around the silicon particles. The CaF 2 -enabled new SEI is strong and dense, which effectively protects the silicon core from side reactions, leading to lower capacity decay after calendar aging at high voltage. More importantly, the Ca additive is effective universally for all available commercial silicon or SiO sources. This study provides a feasible and low-cost solution for developing silicon anodes with long calendar life, paving the way towards commercially viable silicon anodes.

25 ENERGY STORAGE↗

Coal to Carbon Fiber (C2CF) Continuous Processing for High Value Composites (Final Report)

Coal tar is a condensed and recovered by-product of the coking of metallurgical coal for steel production. The heaviest fraction of distilled coal tar is an isotropic pitch largely used as a binder in the manufacturing of carbonaceous electrodes for primary aluminum smelting and in electric arc furnaces. Coal tar pitch offers high carbon yield upon carbonization. In this project, a process to convert the domestically sourced isotropic coal tar pitch, containing very low particulates (QI = 0.32 wt.%), to form flow-domain mesophase pitch amenable for melt spinning into precursor (green) fibers for carbon fiber, was developed and optimized. The final reproducible processing developed is reviewed in this report, along with several characterizations of the mesophase pitch. A final definition of the characteristics of a ‘spinnable’ mesophase pitch is presented. With this mesophase pitch, reproducible and stable multifilament melt spinning was developed, producing green fiber tows with filament diameters of approximately 20 m. The multifilament melt spinning was the most challenging aspect of the project and required the most effort. The best practices learned from this project for melt spinning are reviewed in this report. Once spun, the green fibers were oxidatively stabilized, carbonized and graphitized under inert gas atmosphere to form the final carbon fibers. Given the relatively high softening point of the mesophase pitch, no issues of interfilament fusion were observed during batch oxidation, and subsequent batch carbonization and graphitization went smoothly in all cases. An ~ 80 wt.% conversion of the green fiber mass to final carbon fiber was achieved. After graphitization, the carbon fibers showed high tensile moduli (most were ~ 600 GPa, or 87 Msi) consistent with commercially-available high-performance pitch-based carbon fiber. However, tensile strength and strain to failure were comparatively low. Further work to reduce defects in and on the fiber surfaces would increase these properties. SEM imaging of the graphitic fiber textures is presented herein. Rudimentary composites were fabricated from the carbon fibers and characterized showing similar modulus to baseline composites fabricated with commercial carbon fiber. Finally, a basic economic analysis was done showing the potential to increase the value of the isotropic coal tar pitch by up to 13.6 to 136 times based on a carbon fiber value of $\$$5/lb to $\$$50/lb, respectively. Moreover, the site case study suggests that the coal tar from the single integrated steel mill could supply production of up to 16 kt/yr of carbon fiber. Finally, a technological gap analysis was done which shed light on remaining technical challenges. These challenges included: recovery and utilization of condensates from the mesophase pitch processing, further advancing and increasing stability of the multifilament melt spinning processing, optimization of the oxidation processing, defect reduction for increased carbon fiber strength, and the development of a weaving process towards carbon fiber fabrics. To maximize the coal value chain, the primary objectives of this project were to (a) develop and scale efficient processing technology for producing melt-spinnable mesophase pitch from isotropic coal tar pitch, (b) clarify and simplify tedious continuous fiber processing technologies (particularly multifilament melt spinning of mesophase pitch) towards the efficient production of high performance carbon fiber, and (c) demonstrate and characterize representative composite parts derived from the final carbon fiber. Immense progress was made on all 3 objectives and is detailed in this report.

01 COAL, LIGNITE, AND PEAT↗

Evaluation of Graph Analytics Frameworks Using the GAP Benchmark Suite

The analysis of connected data is an increasingly important application in high-performance computing. Such analyses can reveal fraudulent patterns in financial transactions, optimize telecommunications networks, predict information flow in social networks, etc. However, the landscape of graph analytics is highly diverse. Graph algorithms stress processor architectures differently, and no one graph can represent all topologies. Consequently, no single approach or framework is expected to be optimal for all graph analytics problems. To help make sense of this diverse landscape, we evaluated four approaches to graph analytics: GraphBLAS, Galois, BGL17, GraphIt; and compare them against hand-tuned implementations that take advantage of hardware features on our test platform. Graph- BLAS formulates graph analytics as sparse linear algebra. Galois provides syntactic constructs for data parallelism over irregular data structures. BGL17 is a generic C++ template library for implementing graph algorithms. GraphIt provides a domain- specific language to describe and optimize graph algorithms. We use the GAP Benchmark Suite to establish baseline performance and guide the side-by-side evaluation of each framework. GAP consists of 30 tests: six graph analytics algorithms (breadth- first search, single-source shortest path, PageRank, betweenness centrality, connected components, and triangle counting) run on five graphs, each with different topological characteristics (e.g., high diameter, skewed degree distribution, high average degree). High-performance reference implementations are included for each benchmark algorithm. Because a graph can be loaded into memory a number of ways (e.g., flat file on disk, compressed sparse format, data frames, retrieved from SQL or NoSQL databases), our evaluation focused on computational performance rather than I/O. Our results show the relative strengths of each framework.

Graph algorithms, Benchmarking, shared-memory prog↗

The Effect of Composition on the Surface Finish of PS400: A New High Temperature Solid Lubricant Coating

A new composite, multi-constituent, solid lubricant coating, NASA PS400, developed for high temperature tribological applications, exhibits a smoother surface finish after grinding and polishing than its predecessors PS200 and PS300. In this paper, the baseline composition of PS400 is modified to investigate each individual constituent s role on the achievable surface finish through a series of coating deposition, grinding, and polishing experiments. Furthermore, to explore the limits of compositional tailoring for improved tribological performance, several PS400 coatings were doped with additional solid lubricants (graphite, MoS2 and BN) and tribologically tested. The test results clearly showed that, compared to PS300 coatings, PS400 achieves a smoother surface finish via a reduced lubricant content. Coatings prepared with higher than the baseline level (10 wt%) of lubricants exhibited higher final surface roughness than the earlier generation PS300 coatings. Reducing or eliminating the one or both lubricants (fluorides or silver) did not further improve the surface finish suggesting that the current composition of PS400 is near optimal with respect to surface finish. Lastly, attempts to improve the poor initial room temperature tribological behavior of PS400 via the addition of traditional solid lubricants were unsuccessful. Based upon this work and earlier results it is expected that future research will concentrate on developing methods to produce a lubricious glaze on the rubbing surface during break in to ensure that low friction and wear are rapidly achieved.

DellaCorte, Christopher↗

Foam Spray Cooling Heat Transfer Performance Study

Previous studies have shown that spray cooling heat flux enhancement may be attained using enhanced surfaces. However, most enhanced surface spray cooling studies have been limited to extended and/or embedded surface structures. This study investigates the effect of foam on spray cooling heat flux. The foam used was graphite Poco Foam. The foam piece was attached to a copper block with a cross-sectional area of 2.0 cm(sup 2) using high thermal conductivity epoxy as the thermal interface material (TIM). Measurements were also obtained on a heater block with a flat surface for purposes of baseline comparison. A 2x2 nozzle array was used with PF-5060 as the working fluid. Thermal performance data was obtained under nominally degassed conditions (chamber pressure of 41.4 kPa). Results show that the highest heat flux (CHF) attained was 113 W/cm(sup 2) using the graphite Poco Foam.

Silk, E. A.↗

LBNF Target Complex Remote Handling

The Long Baseline Neutrino Facility (LBNF) near site at the Fermilab campus in Illinois, USA includes a target complex which houses a 1.5 – 1.8m long graphite neutrino production target, a pre-target baffle, three neutrino focusing horns (A,B,C), and a decay pipe 200m in length leading to an energy absorber / beam dump housed in an adjacent absorber building. The prompt dose rates are such that the Target Hall must be unoccupied while beam is on target. During maintenance periods, the Target Hall can be occupied by trained personnel. However, residual dose rates of activated components necessitate certain operations, such as the annual replacement of the target, be executed remotely by personnel located in a shielded room within the Target Hall. This presentation covers details designed into the infrastructure, equipment, and procedures to allow for successful execution of remote handling operations.

43 PARTICLE ACCELERATORS↗

Evaluation and prediction of long-term environmental effects of nonmetallic materials

The properties of a number of nonmetallic materials were evaluated experimentally in simulated space environments in order to develop models for accelerated test methods useful for predicting such behavioral changes. Graphite-epoxy composites were exposed to thermal cycling. Adhesive foam tapes were subjected to a vacuum environment. Metal-matrix composites were tested for baseline data. Predictive modeling designed to include strength and aging effects on composites, polymeric films, and metals under such space conditions (including the atomic oxygen environment) is discussed. The Korel 8031-00 high strength adhesive foam tape was shown to be superior to the other two tested.

Papazian, H.↗

Catalyst and electrode research for phosphoric acid fuel cells

An account is given of the development status of phosphoric acid fuel cells' high performance catalyst and electrode materials. Binary alloys have been identified which outperform the baseline platinum catalyst; it has also become apparent that pressurized operation is required to reach the desired efficiencies, calling in turn for the use of graphitized carbon blacks in the role of catalyst supports. Efforts to improve cell performance and reduce catalyst costs have led to the investigation of a class of organometallic cathode catalysts represented by the tetraazaannulenes, and a mixed catalyst which is a mixture of carbons catalyzed with an organometallic and a noble metal.

Antoine, A. C.↗

Reinforced Carbon Carbon (RCC) oxidation resistant material samples - Baseline coated, and baseline coated with tetraethyl orthosilicate (TEOS) impregnation

Reinforced carbon-carbon material specimens were machined from 19 and 33 ply flat panels which were fabricated and processed in accordance with the specifications and procedures accepted for the fabrication and processing of the leading edge structural subsystem (LESS) elements for the space shuttle orbiter. The specimens were then baseline coated and tetraethyl orthosilicate impregnated, as applicable, in accordance with the procedures and requirements of the appropriate LESS production specifications. Three heater bars were ATJ graphite silicon carbide coated with the Vought 'pack cementation' coating process, and three were stackpole grade 2020 graphite silicon carbide coated with the chemical vapor deposition process utilized by Vought in coating the LESS shell development program entry heater elements. Nondestructive test results are reported.

Gantz, E. E.↗

Monitoring of Ionic Silver Biocide with Capacitively-Coupled Contactless Conductivity Detection (C4D)

Monitoring of biocide dosing in spacecraft potable water systems is desirable to ensure dosing system operation and resultant microbial control. Electrolytic conductivity is linearly related to the concentration ionic silver (Ag+, the baseline biocide for future NASA missions) chemically dosed into highly purified water, and could serve as a proxy measurement. Traditional conductivity cells rely on immersed metal or graphite electrodes, which may potentially be subject to significant current-induced or auto-galvanic deposition of Ag+. Furthermore, oxide fouling may potentially induce measurement errors. Capacitively-coupled contactless conductivity detection (C4D) is a promising alternative. C4D uses electrodes placed outside an inert, non-conductive flow path, potentially mitigating such problems. We identified and purchased a commercial C4D system with claimed performance (conductivity range: 20 nS/cm to 4 µS/cm) appropriate for this application. We characterized the instrument’s performance with conductivity standards and Ag+ solutions. We began investigations considering practical and long-term detector operation, including potential current-induced deposition of conductive deposits at the tubing wall. In addition, we designed a side-stream flow system to provide liquid flow through the narrow tubing (1/16” outer diameter) required by the detector and characterized the performance of the combined C4D detector/flow system. Finally, we completed theoretical modeling of expected conductivity change with multiple dosing techniques and water chemistries.

Lance Dean Delzeit↗

Characterization of PMR polyimide resin and prepreg

Procedures for the chemical characterization of PMR-15 resin solutions and graphite-reinforced prepregs were developed, and a chemical data base was established. In addition, a basic understanding of PMR-15 resin chemistry was gained; this was translated into effective processing procedures for the production of high quality graphite composites. During the program the PMR monomers and selected model compounds representative of postulated PMR-15 solution chemistry were acquired and characterized. Based on these data, a baseline PMR-15 resin was formulated and evaluated for processing characteristics and composite properties. Commercially available PMR-15 resins were then obtained and chemically characterized. Composite panels were fabricated and evaluated.

Lindenmeyer, P. H.↗

Quantitative measurement of pebble fuel anisotropy using generalized ellipsometry

The renewed development of high-temperature gas-cooled reactors has created a need to modernize pebble fuel quality control methods. One important specification in these methods is the coefficient of thermal expansion (CTE) anisotropy, which reflects graphite grain alignment and affects fuel performance. This study investigates the feasibility of using two-modulator generalized ellipsometry microscopy (2-MGEM) as a potential surrogate metric for CTE anisotropy. Graphite matrix compacts with controlled levels of anisotropy were fabricated by varying pre-pressures during forming and were subsequently characterized using both optical dilatometry and 2-MGEM. Measured responses were compared to an isotropic reference pebble produced using an industrial manufacturing process to provide a practical baseline. The resulting measurements revealed a strong quantitative correlation between the CTE anisotropy ratio and the corresponding diattenuation ratio. However, propagated measurement uncertainties in the optical method were found to limit definitive pass/fail discrimination, highlighting the need for improved precision before qualification as a quality control tool. Still, the results establish a quantitative relationship between optical and CTE anisotropy and support further development of 2-MGEM as a potential surrogate method for evaluating graphite matrix anisotropy in pebble fuel manufacturing.

Raftery, Alicia [ORNL] (ORCID:0000000259076427)↗

Zinc-Doped High-Nickel, Low-Cobalt Layered Oxide Cathodes for High-Energy-Density Lithium-Ion Batteries

High-Ni layered oxides with Ni contents greater than 90% are promising cathode candidates for high-energy-density Li-ion batteries. However, drastic electrode-electrolyte reactions and mechanical degradation issues limit their cycle life and practical viability. We demonstrate here that LiNi 0.94 Co 0.04 Zn 0.02 O 1.99 (NCZ), obtained by incorporating 2 mol% Zn 2+ into an ultrahigh-Ni baseline cathode material LiNi 0.94 Co 0.06 O 2 (NC), delivers superior cell performance. NCZ retains 74% of the initial capacity after 500 cycles in full cell assembled with graphite anode, outperforming NC (62% retention). NCZ also possesses a higher average discharge voltage relative to NC with an outstanding average voltage retention of over 99% after 130 cycles in half cells. Bulk structural investigations unveil that Zn doping promotes a smoother phase transition, suppresses anisotropic lattice distortion, and maintains the mechanical integrity of cathode particles. Furthermore, NCZ shows an enhanced interphase stability after long-term cycling, in contrast to the seriously degraded surface chemistry in NC. Finally, this work provides a practically viable approach for designing higher-energy-density high-Ni layered oxide cathodes for lithium-ion batteries.

25 ENERGY STORAGE↗

Fuel cell systems for First Lunar Outpost-reactant storage option

The office of Space, DOE, appointed a Lunar Surface Power Working Group to review candidate systems for the First Lunar Outpost habitat. The working group met for a total of five days in the fall of 1992 and concluded that the candidate involving a photovoltaic unit, a fuel cell, a regenerator to recycle the reactants, and storage of oxygen and hydrogen gases was the most attractive for this application. Most of the volume (97 percent) and weight (63 percent) are taken up by the reactants and their storage tanks. Therefore, in my work for the Group, and in this report, I have concentrated on finding ways to reduce these volumes and weights. Three options were considered: (1) the baseline case considered in the preliminary system design, that of separate high pressure (200 bar) storage tanks; (2) the use of two of the descent storage propellant tanks wrapped with graphite fibers to increase the pressure capability; and (3) the use of cryogenic storage of reactants in the propellant tanks. The first option results in high storage tank mass and volume. The second option saves 90 percent of the volume by making use of the propellant tanks, but it has little if any weight advantages; the weight saved by not providing extra tanks for reactant storage is nearly entirely added back by the weight of the additional material (graphite fibers) to strengthen the propellant tanks. Use of the descent storage propellant tanks for storage of the fuel cell reactants as cryogenic liquids requires a gas liquefaction system. The weight of this system is expected to be less than that of the storage tanks but it would require development and testing to prove its reliability. The solar array would have to be 40 percent larger and the heat projection range would be 170 percent larger than for storage of reactants as high pressure gases. For a high power system (greater than 20 kW) the larger energy storage requirement would probably favor the cryogenic storage option.

Nelson, P. A.↗

LAMMR: A new generation satellite microwave radiometer - Its concepts and capabilities

Definition studies and baseline design are summarized for the proposed, and now discontinued, LAMMR. The instrument is an offset parabolic reflector with Cassegrain feeds. The three-meter aperture reflector, to be constructed using graphite-epoxy technology, rotates continuously at 0.833 rps. The scan drive subsystem includes momentum compensation for the rotating mass which includes the reflector, the support arm and Cassegrain subreflector, feed horns and radiometer. Two total power radiometers are recommended for each frequency, one each for horizontal and vertical polarizations. The selection plan, definition study specifications, LAMMR performance specifications, and predicted accuracies and resolutions after processing are shown.

Walton, W. T.↗