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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 289 records · Page 16

In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

Halide-based solid-state electrolytes (SSEs) are promising candidates for next-generation all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity and chemical stability. However, their poor interfacial compatibility with lithium metal anode and Li-In alloy significantly hinder practical application due to the requirement for a protective interlayer. In this study, a novel approach to overcome this limitation is presented by introducing iron (Fe) doping into Li 3 InCl 6 (LIC), which enables direct and stable contact with lithium-indium (Li-In) metal without a protective interlayer. Thermodynamic and computational analyses identified Fe 3+ as a suitable dopant based on its similar reduction potential to In 3+ and structural compatibility within the halide lattice. The synthesized 10 at. % Fe-doped LIC exhibits high phase purity, retained ionic conductivity, and notably improved interfacial stability. Full-cell tests using Fe-LIC achieve over 300 cycles with 80 % capacity retention. At the same time, symmetric Li-In/ Fe-LIC/ Li-In cells sustain over 500 h of operation, representing the first reported long-term cycling of LIC-based ASSLB without a protective interlayer. In conclusion, this work establishes Fe doping as an effective strategy to stabilize halide SSEs of In system against Li-In alloy, thereby simplifying cell architecture and advancing the development of safer, high-performance halide-based solid-state electrolytes.

Halide-based solid-state electrolytes↗

Electrolyte Compatible Separator Materials for Sodium-Ion Battery

Sodium-ion batteries (NIBs) have emerged as an alternative electrochemical energy storage to replace lithium-ion batteries (LIBs). Separator is one of the key components that dictates the cell performance of NIB. Significant progress has been made in electrolyte research, however for most cases glass fiber has been used as separator due to its remarkable electrolyte wettability despite its many disadvantages. In this study, we evaluated commercially available porous materials as separator material for NIB. Porous polyvinylidene fluoride (PVDF) membrane stands out as a universal separator which exhibits high compatibility with a wide range of electrolytes and electrodes and demonstrates high electrochemical stability evaluated in hard carbon/Na half cells and NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (NFM111)/hard carbon full cells. This research highlights the PVDF membrane as a viable separator for advancing NIB research, enabling the development of new electrolyte materials without the separator constraints of wetting limitations or excessive electrolyte consumption.

Wostoupal, Owen S. [Argonne National Laboratory (A↗

Correlation Between Microscopic Current Fluctuations Observed at Ultra-Microelectrodes and Macroscopic Bulk Electrolysis Performance in Redox-Active Microemulsions

Microemulsions (μEs) have been proposed as redox flow battery (RFB) electrolytes that maximize ionic conductivity and charge capacity by synergizing two immiscible phases. However, charge transfer during electrolysis in μEs is poorly understood. Here, we show that ultramicroelectrode electrolysis of ferrocene-loaded μEs –20%, 60%, and 90% water - reveals stochastic current fluctuations. These are differentiated in the scanning electrochemical microscopy (SECM) geometry, where power spectral density analysis showed distinct changes in the frequency contributions. SECM in the substrate generation-tip collection mode showed that fluctuations arise under mass-transfer control. Significant differences in the diffusion coefficient of ferrocene species were deducted from SECM approach curves, suggesting phase transfer behavior. Using bulk electrolysis, we calculated the charge accessibility and cycling behavior in the μEs. A decrease in the stochastic behavior of the μEs seems to correlate to a higher accessibility and cycling performance, with the 90% water μE displaying the best reversibility and the 60% the lowest. Altogether, these results suggest that Marangoni-type convection driven by concentration gradients and/or μE restructuring during charge transfer play a role in the electrochemical performance of μEs. This presents opportunities for screening and diagnosing the performance of these emerging RFB electrolytes.

25 ENERGY STORAGE↗

Studies on Methanol Crossover in Liquid-Feed Direct Methanol Pem Fuel Cells

The performance of liquid feed direct methanol fuel cells using various types of Nafion membranes as the solid polymer electrolyte have been studied. The rate of fuel crossover and electrical performance has been measured for cells with Nafion membranes of various thicknesses and equivalent weights. The crossover rate is found to decrease with increasing thickness and applied current. The dependence of crossover rate on current density can be understood in terms of a simple linear diffusion model which suggests that the crossover rate can be influenced by the electrode structure in addition to the membrane. The studies suggest that Nafion EW 1500 is a very promising alternate to Nafion EW 1100 for direct methanol fuel cells.

Methanol Pem Fuel↗

Observation of N-rich solid-electrolyte interphase by ToF-SIMS.

Formation of a stable solid electrolyte interphase (SEI) between lithium electrodes and electrolyte upon multiple charge/discharge cycles is crucial to a long-term lithium-ion battery performance. Addition of LiNO3 to lithium bis (fluorosulfonyl) imide/poly(ethylene oxide) (LiFSI/PEO) electrolyte leads to a durable SEI that is electrically insulating yet highly conductive to Li ions, chemically and electrochemically stable, physically uniform, and mechanically robust. ToF-SIMS was used here in combination with sputtering by a gaseous cluster ion beam (GCIB) to examine how the addition of a small proportion of LiNO3 to the LiFSI/PEO electrolyte affects the SEI composition. Negative ion ToF-SIMS spectra of the cycled samples display an intense m/z 26 peak associated with the SEI. Exact mass assignments and isotopic ratios indicate that this peak should be assigned as (CN-)-C-12, with little to no negative secondary ion signal arising from (LiF-)-Li-7. This CN- signal appears to arise from an N-rich portion of the SEI adjacent to the Li electrode that is depleted in LiF relative to the bulk electrolyte. The dearth of LiF- (and LiF+ from the positive ion spectra) is unexpected because LiF has been identified in the SEI in similar samples. Finally, GCIB sputtering indicates that the SEI adheres more strongly to the Li electrode than to the LiFSI/PEO electrolyte.

Shavandi, Seyedeh Reyhaneh↗

FCET Solid Oxide Fuel Cell Testing and Development (CRADA 526) (Final Report)

Pacific Northwest National Laboratory (PNNL) tested electrolyte coatings from Fuel Cell Enabling Technologies, Inc. (FCET) for use in solid oxide fuel cells (SOFCs). The key technology held by FCET is a process to deposit thin layers of oxide materials, less than 1 μm in thickness. The range of possible materials that can be deposited with their method is broad, but this project focused on the gadolinium-doped ceria (GDC) and yttria-stabilized zirconia (YSZ) electrolytes for SOFCs. Thin, gas tight electrolyte membranes have been a long-sought target in SOFC research. The thinner the electrolyte, the lower the cell resistance, and the higher performance of the cell (or the lower the operating temperature). A YSZ thickness of 1 μm would be a step change from the state-of-the-art, tape-cast electrolytes (~10 μm). An in-house prototype SOFC stack from FCET was first tested. The sealing geometry of the prototype stack was determined to be problematic, and testing shifted to button cells. Anode-supported solid oxide electrolysis cell (SOEC) button cells without an electrolyte layer were produced at PNNL and sent to FCET for coating with electrolyte. Three cells were tested with a gadolinium-doped ceria (GDC) electrolyte applied via spin coating. GDC was chosen for its conductivity at lower temperatures than YSZ. All three cells failed during initial reduction under hydrogen at 600°C. Testing then shifted to YSZ, which is the standard SOFC electrolyte. Several button cells were coated with YSZ and examined with scanning electron microscopy (SEM). A promising coating of ~1 mm thickness was observed under SEM. A similarly coated button cell was tested and failed similarly to previous tests during reduction at 600°C. The YSZ coating appeared dense and uniform in SEM analysis. The roughness of the underlying Ni/YSZ anode is on the order of 1 μm, and that may have compromised the gas-tightness of the coating. Further development is warranted to understand and refine the coating process. Thin YSZ applied via this spin-coating technique could be used as a low-cost, drop-in replacement in large-scale SOFC manufacturing processes, improving cell performance and lowering the cost per watt of SOFCs.

30 DIRECT ENERGY CONVERSION↗

Li/CFx Cells Optimized for Low-Temperature Operation

Some developments reported in prior NASA Tech Briefs articles on primary electrochemical power cells containing lithium anodes and fluorinated carbonaceous (CFx) cathodes have been combined to yield a product line of cells optimized for relatively-high-current operation at low temperatures at which commercial lithium-based cells become useless. These developments have involved modifications of the chemistry of commercial Li/CFx cells and batteries, which are not suitable for high-current and low-temperature applications because they are current-limited and their maximum discharge rates decrease with decreasing temperature. One of two developments that constitute the present combination is, itself, a combination of developments: (1) the use of sub-fluorinated carbonaceous (CFx wherein x<1) cathode material, (2) making the cathodes thinner than in most commercial units, and (3) using non-aqueous electrolytes formulated especially to enhance low-temperature performance. This combination of developments was described in more detail in High-Energy-Density, Low- Temperature Li/CFx Primary Cells (NPO-43219), NASA Tech Briefs, Vol. 31, No. 7 (July 2007), page 43. The other development included in the present combination is the use of an anion receptor as an electrolyte additive, as described in the immediately preceding article, "Additive for Low-Temperature Operation of Li-(CF)n Cells" (NPO- 43579). A typical cell according to the present combination of developments contains an anion-receptor additive solvated in an electrolyte that comprises LiBF4 dissolved at a concentration of 0.5 M in a mixture of four volume parts of 1,2 dimethoxyethane with one volume part of propylene carbonate. The proportion, x, of fluorine in the cathode in such a cell lies between 0.5 and 0.9. The best of such cells fabricated to date have exhibited discharge capacities as large as 0.6 A h per gram at a temperature of 50 C when discharged at a rate of C/5 (where C is the magnitude of the current, integrated for one hour, that would amount to the nominal charge capacity of a cell).

Smart, Marshall C.↗

Low Melting Temperature Gallium–Indium Liquid Metal Anode for Solid-State Li-Ion Batteries

Solid-state Li-ion batteries are attracting attention for their enhanced safety features, higher energy density, and broader operational temperature range compared to systems based on liquid electrolytes. However, current solid-state Li-ion batteries face performance challenges, such as suboptimal cycling and poor rate capabilities, often due to inadequate interfacial contact between the solid electrolyte and electrodes. To address this issue, we incorporated a gallium–indium (Ga–In) liquid metal as the anode in a solid-state Li-ion battery setup, employing Li 6 PS 5 Cl as the solid electrolyte. Operating at room temperature, this configuration achieved an initial capacity of 389 mAh g –1 and maintained 88% of this capacity after 30 cycles at a 0.05 C rate. It also demonstrated a capacity retention of 66% after 500 cycles at a 0.5 C rate. In comparison to solid anode materials, such as tin, the Ga–In liquid metal exhibited superior cycling stability and rate capacity, which is due to the self-healing and fluid properties of the alloy that ensure stable interfacial contact with solid electrolytes. In situ X-ray diffraction (XRD) and ex situ scanning electron microscope (SEM) analyses revealed that indium does not directly participate in the lithiation/delithiation process. Instead, it helps maintain the alloy’s low melting point, facilitating its return to a liquid state after delithiation. In a comparative analysis of stack pressure during cycling in cells utilizing Ga–In liquid metal and tin, the Ga–In liquid metal cell demonstrated an ability to buffer pressure increases associated with deformation. In conclusion, these findings suggest a promising approach for enhancing solid-state batteries by integrating liquid metal anodes, which improve interfacial contact and stability.

Alloys↗

Porous carbon from lignocellulosic biomass with emphasis on corn plant waste residue for energy storage

The rising global demand for sustainable energy storage materials has driven the search for environmentally friendly and cost-effective electrode options. Hydrothermal conversion of lignocellulosic biomass has gained attention due to its low energy requirements and operation at relatively low temperatures, presenting a green alternative to traditional thermochemical methods. The resulting solid product, hydrochar, has been used as an adsorbent and soil amendment; however, chemical/thermal treatment significantly enhances its physical properties. These structural modifications transform hydrochar into an effective porous carbon electrode, offering abundant sites for electrolyte ion transport, critical for high-performance devices like supercapacitors and batteries. This review first discusses various waste biomass and sustainable feedstocks available globally. It compares two primary thermochemical conversion techniques, pyrolysis and hydrothermal carbonization/liquefaction, and examines their respective solid products, biochar and hydrochar, analyzing differences in their physical and chemical characteristics. The focus is placed on hydrochar, summarizing activation methods to produce porous carbon suitable for energy storage applications. Additionally, this review will include a dedicated section on the application of porous carbon derived from corn plant waste residue, considering that corn is one of the most abundant crops grown worldwide, which makes it an important and promising source for sustainable porous carbon production. The role of machine learning models in optimizing hydrothermal processes to produce high-quality hydrochar is also discussed, emphasizing how data-driven approaches can streamline process development. Finally, the review identifies the current challenges and prospects for lignocellulosic biomass-derived porous carbon as a sustainable electrode material in next-generation energy storage technologies.

25 ENERGY STORAGE↗

Study of high performance alloy electroforming

Nickel-manganese alloy electrodeposits from an electrolyte containing more manganese ion than previously used is being evaluated at two bath operating temperatures with a great variety of pulse plating conditions. Saccharine was added as a stress reducing agent for the electroforming of several of the samples with highest manganese content. All specimens for mechanical property testing have been produced but are not through the various heat treatments as yet. One of the heat treatment will be at 343 C (650 F), the temperature at which the MCC outer electroformed nickel shell is stress relieved. A number of retainer specimens from prior work have been tested for hardness before and after heat treatment. There appears to be a fairly good correlation between hardness and mechanical properties. Comparison of representative mechanical properties with hardnesses are made for nickel-manganese electrodeposits and nickel-cobalt-manganese deposits.

Malone, G. A.↗

Advances in high temperature components for AMTEC (Alkali Metal Thermal-to-Electric Converter)

The basic performance of Alkali Metal Thermal-to-Electric Converter (AMTEC) cells is well understood, and quantitative modeling of the electrode performance has been carried out. Tests have been carried out to evaluate the high temperature performance of critical AMTEC components. Progress made in understanding the relative performance of AMTEC components, such as electrodes, electrolytes, working fluids, and seals, as device operating temperature is varied is discussed. Most metallic components are especially subject to corrosion in hot liquid alkali metals containing dissolved oxides. Stability issues of AMTEC components may be addressed by life testing, accelerated testing, and modeling based on known kinetic and thermochemical data.

Williams, R. M.↗

Exercise countermeasures for bed-rest deconditioning

The purpose for this 30-day bed rest study was to investigate the effects of short-term, high intensity isotonic and isokinetic exercise training on maintenance of working capacity (peak oxygen uptake), muscular strength and endurance, and on orthostatic tolerance, posture and gait. Other data were collected on muscle atrophy, bone mineralization and density, endocrine analyses concerning vasoactivity and fluid-electrolyte balance, muscle intermediary metabolism, and on performance and mood of the subjects. It was concluded that: The subjects maintained a relatively stable mood, high morale, and high esprit de corps throughout the study. Performance improved in nearly all tests in almost all the subjects. Isotonic training, as opposed to isokinetic exercise training, was associated more with decreasing levels of psychological tension, concentration, and motivation; and improvement in the quality of sleep. Working capacity (peak oxygen uptake) was maintained during bed rest with isotonic exercise training; it was not maintained with isokinetic or no exercise training. In general, there was no significant decrease in strength or endurance of arm or leg muscles during bed rest, in spite of some reduction in muscle size (atrophy) of some leg muscles. There was no effect of isotonic exercise training on orthostasis, since tilt-table tolerance was reduced similarly in all three groups following bed rest. Bed rest resulted in significant decreases of postural stability and self-selected step length, stride length, and walking velocity, which were not influenced by either exercise training regimen. Most pre-bed rest responses were restored by the fourth day of recovery.

Greenleaf, John↗

Surface treatment of a sulfide glass solid electrolyte layer

Chemically treating ionically conductive sulfide glass solid electrolyte separators or separator layers can improve performance. In particular, treatment involving chemically etching a surface or surface region of the sulfide glass separator to blunt, lessen or remove edge defects or surface flaws, and/or to enhance surface smoothness is cost effective, reliable and well suited for high production environments compared to physical methods of removing scratches or smoothing surfaces, such as mechanical grinding and polishing.

Visco, Steven J.↗

Enhanced cycling stability of Ni-rich Li-metal cells enabled by dual vinylene carbonate and tris(trimethylsilyl)borate electrolyte additives

NMC811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) and other high-Ni chemistries are promising cathode candidates for high-performance electric vehicles, owing to their high energy density and reduced cobalt content. However, their long-term cycling stability is hindered by surface degradation, particularly when paired with conventional electrolytes and a lithium metal anode. Electrolyte additives represent a practical approach to enhance interfacial stability and improve overall battery performance by promoting the formation of a robust electrolyte–electrode interphase (EEI). In this study, we revisit the effects of vinylene carbonate (VC) and tris(trimethylsilyl)borate (TMSB) additives on single-crystal SC-NMC811||Li cells. While TMSB only increases the open-circuit voltage and initial overpotential, it delivers superior capacity retention at C/3 compared to cells containing only VC or a dual additive system (VC and TMSB). Notably, under fast-charging conditions (1C, 2C, and 5C), the dual-additive system significantly outperforms other formulations, achieving markedly enhanced long-term capacity retention. Comprehensive electrochemical and spectroscopic analyses reveal that the VC/TMSB dual-additive system suppresses surface transition in NMC811, mitigates structural degradation by forming a thin, LiF-deficient cathode-electrolyte interface (CEI) layer. Moreover, they promote smooth and dense Li deposition and generate a LiF-deficient solid-electrolyte interphase (SEI). Consequently, the synergistic stabilization of both the CEI and SEI effectively limits the overall cell impedance growth during extended cycling. These findings provide key insights into co-additive strategies for engineering stable interfaces in high-energy Ni-rich Li-metal batteries.

36 MATERIALS SCIENCE↗

Assessing cathode–electrolyte interphases in batteries

The cathode-electrolyte interphase plays a pivotal role in determining the usable capacity and cycling stability of electrochemical cells, yet it is overshadowed by its counterpart, the solid-electrolyte interphase. This is primarily due to the prevalence of side reactions, particularly at low potentials on the negative electrode, especially in state-of-the-art Li-ion batteries where the charge cutoff voltage is limited. However, as the quest for high-energy battery technologies intensifies, there is a pressing need to advance the study of cathode-electrolyte interphase properties. Here, we present a comprehensive approach to analyse the cathode-electrolyte interphase in battery systems. We underscore the importance of employing model cathode materials and coin cell protocols to establish baseline performance. Additionally, we delve into the factors behind the inconsistent and occasionally controversial findings related to the cathode-electrolyte interphase. In conclusion, we also address the challenges and opportunities in characterizing and simulating the cathode-electrolyte interphase, offering potential solutions to enhance its relevance to real-world applications.

25 ENERGY STORAGE↗

Modeling Materials: Design for Planetary Entry, Electric Aircraft, and Beyond

NASA missions push the limits of what is possible. The development of high-performance materials must keep pace with the agency's demanding, cutting-edge applications. Researchers at NASA's Ames Research Center are performing multiscale computational modeling to accelerate development times and further the design of next-generation aerospace materials. Multiscale modeling combines several computationally intensive techniques ranging from the atomic level to the macroscale, passing output from one level as input to the next level. These methods are applicable to a wide variety of materials systems. For example: (a) Ultra-high-temperature ceramics for hypersonic aircraft-we utilized the full range of multiscale modeling to characterize thermal protection materials for faster, safer air- and spacecraft, (b) Planetary entry heat shields for space vehicles-we computed thermal and mechanical properties of ablative composites by combining several methods, from atomistic simulations to macroscale computations, (c) Advanced batteries for electric aircraft-we performed large-scale molecular dynamics simulations of advanced electrolytes for ultra-high-energy capacity batteries to enable long-distance electric aircraft service; and (d) Shape-memory alloys for high-efficiency aircraft-we used high-fidelity electronic structure calculations to determine phase diagrams in shape-memory transformations. Advances in high-performance computing have been critical to the development of multiscale materials modeling. We used nearly one million processor hours on NASA's Pleiades supercomputer to characterize electrolytes with a fidelity that would be otherwise impossible. For this and other projects, Pleiades enables us to push the physics and accuracy of our calculations to new levels.

Supercomputing↗

Development of Large-Format Lithium-Ion Cells with Silicon Anode and Low Flammable Electrolyte

NASA is developing safe, high energy and high capacity lithium-ion cell designs and batteries for future missions under NASAs Advanced Space Power System (ASPS) project. Advanced cell components, such as high specific capacity silicon anodes and low-flammable electrolytes have been developed for improving the cell specific energy and enhancing safety. To advance the technology readiness level, we have developed large-format flight-type hermetically sealed battery cells by incorporating high capacity silicon anodes, commercially available lithium nickel, cobalt, aluminum oxide (NCA) cathodes, and low-flammable electrolytes. In this report, we will present the performance results of these various battery cells. In addition, we will also discuss the post-test cell analysis results as well.

lithium-ion cell↗