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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 37 records · Page 2

Synthesis and Crystallization of Atomic Layer Deposition β-Eucryptite LiAlSiO 4 Thin-Film Solid Electrolytes

Atomic layer deposition (ALD) was used to control the stoichiometry of thin lithium aluminosilicate films, thereby enabling crystallization into the ion-conducting β-eucryptite LiAlSiO 4 phase. Here, the rapid thermal annealed ALD film developed a well-defined epitaxial relationship to the silicon substrate: β-LiAlSiO4 ($1\bar{21}0$)||Si (100) and β-LiAlSiO 4 ($10\bar{10}$)||Si (001). The extrapolated room temperature ionic conductivity was found to be 1.2 × 10 –7 S/cm in the [$1\bar{21}0$] direction. Because of the unique 1-D channel along the c axis of β-LiAlSiO 4 , the epitaxial thin film has the potential to facilitate ionic transport if oriented with the c axis normal to the electrode surface, making it a promising electrolyte material for three-dimensional lithium-ion microbatteries.

25 ENERGY STORAGE↗

Lessons Learned Using in-situ TEM Liquid Corrosion of Al Alloys

Al and Al alloys are of interest in energy applications due to their strength and low weight [1] in addition to their electrochemical properties for aluminum-air batteries for energy storage [2]. However, Al alloys also are susceptible to corrosion in a variety of environments including liquid electrolytes and in solar panels [3], which has led to a great deal of research to understand and improve corrosion resistance in these materials. Al metal forms a native, passivating oxide layer in the presence of ambient air, which slows corrosion initiation. However, pitting still occurs as this protective layer breaks down in the presence of electrolytes. Thin metal Al films were used in these experiments to observe initiation and growth of pitting, which can be used as an approximation of corrosion initiation behavior in bulk samples.

alluminum alloys↗

Hybrid air revitalization system for a closed ecosystem

An air-revitalization concept is presented with experimental results to assess the practicality and applicability of the proposed system to extended-duration manned missions. The Hybrid Air Revitalization System (HARS) uses plants in a habitat to remove metabolic CO2 and moisture and produce oxygen and food. CO2 and O2 partial pressures, temperature, and humidity are regulated by means of electrochemical CO2 and O2 chemical separators and a moisture condenser separator. A cell-test facility is described in which the electrochemical CO2 removal processes are investigated with and without using H2. Performance is optimized by using 25-30 percent Teflon in the gas-diffusion-type electrode, employing a thin electrolyte matrix, operating at higher temperatures and lower dew points. The HARS concept is found to be a feasible approach to the electrochemical separation of CO2 and O2.

Lee, M. G.↗

Progress in High Power Density SOFC Material Development for Aerospace Applications

Solid oxide fuel cell (SOFC) systems for aircraft applications require order of magnitude increase in specific power density and long life under aircraft operating conditions. Advanced SOFC materials and fabrication processes are being developed at NASA GRC to increase specific power density and durability of SOFC cell and stack. Initial research efforts for increasing specific power density are directed toward increasing the operating temperature for the SOFC system and reducing the weight of the stack. While significant research is underway to develop anode supported SOFC system operating at temperatures in the range of 650 - 850 C for ground power generation applications, such temperatures may not yield the power densities required for aircraft applications. For electrode-supported cells, SOFC stacks with power densities greater than 1.0 W/sq cm are favorable at temperatures in excess of 900 C. The performance of various commercial and developmental anode supported cells is currently being evaluated in the temperature range of 900 to 1000 C to assess the performance gains and materials reliability. The results from these studies will be presented. Since metal interconnects developed for lower temperature operation are not practical at these high temperatures, advanced perovskite based ceramic interconnects with high electronic conductivity and lower sintering temperatures are being developed. Another option for increasing specific power density of SOFC stacks is to decrease the stack weight. Since the interconnect contributes to a significant portion of the stack weight, considerable weight benefits can be derived by decreasing its thickness. Eliminating the gas channels in the interconnect by engineering the pore structure in both anode and cathode can offer significant reduction in thickness of the ceramic interconnect material. New solid oxide fuel cells are being developed with porous engineered electrode supported structures with a 10 - 20 micron thin electrolyte. The performance data for advanced SOFC cells with engineered porosity in both electrodes will be presented.

Cable, Thomas L.↗

Regenerative Performance of the NASA Symmetrical Solid Oxide Fuel Cell Design

The NASA Glenn Research Center is developing both a novel cell design (BSC) and a novel ceramic fabrication technique to produce fuel cells predicted to exceed a specific power density of 1.0 kW/kg. The NASA Glenn cell design has taken a completely different approach among planar designs by removing the metal interconnect and returning to the use of a thin, doped LaCrO3 interconnect. The cell is structurally symmetrical. Both electrodes support the thin electrolyte and contain micro-channels for gas flow-- a geometry referred to as a bi-electrode supported cell or BSC. The cell characteristics have been demonstrated under both SOFC and SOE conditions. Electrolysis tests verify that this cell design operates at very high electrochemical voltage efficiencies (EVE) and high H2O conversion percentages, even at the low flow rates predicted for closed loop systems encountered in unmanned aerial vehicle (UAV) applications. For UAVs the volume, weight and the efficiency are critical as they determine the size of the water tank, the solar panel size, and other system requirements. For UAVs, regenerative solid oxide fuel cell stacks (RSOFC) use solar panels during daylight to generate power for electrolysis and then operate in fuel cell mode during the night to power the UAV and electronics. Recent studies, performed by NASA for a more electric commercial aircraft, evaluated SOFCs for auxiliary power units (APUs). System studies were also conducted for regenerative RSOFC systems. One common requirement for aerospace SOFCs and RSOFCs, determined independently in each application study, was the need for high specific power density and volume density, on the order of 1.0 kW/kg and greater than 1.0 kW/L. Until recently the best reported performance for SOFCs was 0.2 kW/kg or less for stacks. NASA Glenn is working to prototype the light weight, low volume BSC design for such high specific power aerospace applications.

Cable, Thomas L.↗

[Synthesis and Characterization of a Sugar Based Electrolyte for Thin-film Polymer Batteries]

The work performed during the current renewal period, March 1,1998 focused primarily on the synthesis and characterization of a sugar based electrolyte for thin-film polymer batteries. The initial phase of the project involved developing a suitable sugar to use as the monomer in the polymeric electrolyte synthesis. The monomer has been synthesized and characterized completely. Overall the yield of this material is high and it can be produced in relatively large quantity easily and in high purity. The scheme used for the preparation of the monomer is outlined along with pertinent yields.

Source record↗

Understanding slurry formulations to guide solution-processing of solid electrolytes

Scalable processing of thin solid electrolytes is crucial for engineering solid-state batteries with practical energy densities. To leverage existing battery production infrastructure, pathways for solution processing of solid electrolyte films must be investigated. Here, roll-to-roll compatible film preparation of aluminum-doped lithium lanthanum zirconate oxide was studied. Four slurry configurations accounting for different solvent properties and solid loadings were evaluated to investigate the ternary interactions within the dispersions. Rheological and coating stability analyses were carried out on the processed slurries. The analysis and characterization indicated that improved component interactions within the ethanol/toluene system result in homogenized distribution of the particles, binder, and plasticizer, and enable the extraction of free-standing thin films with thicknesses of 20 μm and large area (>15 in. 2 ). The drawbacks and opportunities of several protocols for high temperature sintering of the dried green films were investigated. This study highlights the importance of engineering dispersions during the development of processing protocols for solid electrolytes and provides guidelines for the best practices that can be leveraged for solution processing–based fabrications for a wide range of solid electrolyte materials.

25 ENERGY STORAGE↗

Method for forming thin composite solid electrolyte film for lithium batteries

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a co-solvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Nagasubramanian, Ganesan↗

Method for forming thin composite solid electrolyte film for lithium batteries

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a cosolvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Nagasubramanian, Ganesan↗

Tuned Reactivity at the Lithium Metal–Argyrodite Solid State Electrolyte Interphase

Thin intermetallic Li 2 Te–LiTe 3 bilayer (0.75 µm) derived from 2D tellurene stabilizes the solid electrolyte interphase (SEI) of lithium metal and argyrodite (LPSCl, Li 6 PS 5 Cl) solid-state electrolyte (SSE). Tellurene is loaded onto a standard battery separator and reacted with lithium through single-pass mechanical rolling or transferred directly to SSE surface by pressing. State-of-the-art electrochemical performance is achieved, e.g., symmetric cell stable for 300 cycles (1800 h) at 1 mA cm -2 and 3 mAh cm -2 (25% DOD, 60 µm foil). Cryo-stage focused ion beam (Cryo-FIB) sectioning and Raman mapping demonstrate that the Li 2 Te–LiTe 3 bilayer impedes SSE decomposition. The unmodified Li–LPSCl interphase is electrochemically unstable with a geometrically heterogeneous reduction decomposition reaction front that extends deep into the SSE. Decomposition drives voiding in Li metal due to its high flux to the reaction front, as well as voiding in the SSE due to the associated volume changes. Analysis of cycled SSE found no evidence for pristine (unreacted) lithium metal filaments/dendrites, implying failure driven by decomposition phases with sufficient electrical conductivity that span electrolyte thickness. In conclusion, DFT calculations clarify thermodynamic stability, interfacial adhesion, and electronic transport properties of interphases, while mesoscale modeling examines interrelations between reaction front heterogeneity (SEI heterogeneity), current distribution, and localized chemo-mechanical stresses.

25 ENERGY STORAGE↗

Nonflammable Lithium Metal Full Cells with Ultra-high Energy Density Based on Coordinated Carbonate Electrolytes

Coupling thin Li metal anodes with high-capacity/high-voltage cathodes such as LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is a promising way to increase lithium battery energy density. Yet, the realization of high-performance full cells remains a formidable challenge. Here, we demonstrate a new class of highly coordinated, nonflammable carbonate electrolytes based on lithium bis(fluorosulfonyl)imide (LiFSI) in propylene carbonate/fluoroethylene carbonate mixtures. Utilizing an optimal salt concentration (4 M LiFSI) of the electrolyte results in a unique coordination structure of Li + -FSI - -solvent cluster, which is critical for enabling the formation of stable interfaces on both the thin Li metal anode and high-voltage NCM811 cathode. Under highly demanding cell configuration and operating conditions (Li metal anode = 35 μm, areal capacity/charge voltage of NCM811 cathode = 4.8 mAh cm -2 /4.6 V, and anode excess capacity [relative to the cathode] = 0.83), the Li metal-based full cell provides exceptional electrochemical performance (energy densities = 679 Wh kg cell -1 /1,024 Wh L cell -1 ) coupled with nonflammability.

25 ENERGY STORAGE↗

Photopolymerized Electrolytes For Electrochromic Devices

Thin ion-conducting electrolyte films for use in electrochromic devices now fabricated relatively easily and quickly with any of class of improved formulations containing ultraviolet-polymerizable components. Formulations are liquids in their monomeric forms and self-supporting, transparent solids in their polymeric forms. Thin solid electrolytes form quickly and easily between electrode-bearing substrates. Film thus polymerized acts not only as solid electrolyte but also as glue holding laminate together: feature simplifies fabrication by reducing need for sealants and additional mechanical supports.

Cogan, Stuart↗

On the quality of tape-cast thin films of sulfide electrolytes for solid-state batteries

All-solid-state lithium batteries (ASSLBs) have the potential to increase energy density, improve safety, and allow for lower manufacturing costs compared to conventional, liquid-based Li-ion batteries. The thickness of solid electrolyte (SE) layer dictates the cell-level energy density and it is desirable to make the SE layer as thin as possible while maintaining uniformity and defect-free. Manufacturing a high- quality, thin sulfide SE layer at large-scale, however, is challenging. Previous studies have addressed the compatibility of materials used for manufacturing thin sulfide SE films, paving the way for further investigation of processing conditions and film quality. Here we report a strong correlation between the solid loading of dispersions and the quality of tape-casted thin sulfide SE films. We also demonstrate a method for quantifying the quality of thin SE films by observing both pin-hole defects and larger heterogeneous agglomerations of particles in the films. Our thin sulfide SE films containing ~5 wt% binder are defect-free and show similar ionic conductivity compared to a cold-pressed, binder-free, thick SE pellet, resulting in an ~11X reduction of area specific resistance. Here, this work on the solid loading of the dispersion used in a scalable tape casting process provides insight for manufacturing high-quality, thin sulfide SE films and to increase the cell-level energy density of ASSLB.

36 MATERIALS SCIENCE↗

Binder Effects on Processing, Mechanical Properties, and Performance of Thin Sulfide Solid‐State Electrolytes

All‐solid‐state batteries (ASSBs) offer enhanced safety and energy density compared to conventional lithium‐ion batteries by replacing flammable liquid electrolytes with solid‐state electrolytes (SSEs). Among SSEs, sulfide‐based electrolytes exhibit high ionic conductivity and mechanical deformability, making them promising candidates for next‐generation energy storage. However, their practical implementation is hindered by interfacial instability, mechanical brittleness, and challenges in fabricating ultrathin electrolyte membranes (<30 μm) with robust mechanical integrity. Here, this study systematically examines the influence of polymeric binders—polyisobutylene, hydrogenated nitrile butadiene rubber, and styrene–ethylene–butylene–styrene (SEBS)—on the structural, mechanical, and electrochemical performance of thin sulfide SSE membranes. Key findings reveal that SEBS enables the fabrication of ultrathin, uniform membranes, while binder elasticity significantly affects structural stability during cycling. Operando stack pressure measurements indicate that binder properties directly influence adhesion force for LPSCl particles, influencing their stabilizing cycling period. These results underscore the critical role of polymer binders beyond mechanical reinforcement, positioning them as essential design variables in sulfide SSE engineering. By linking binder chemistry to processability and electrochemical performance, this study provides insights into optimizing sulfide SSEs, advancing their commercial viability in ASSBs.

argyrodite sulfide electrolyte↗

Effect of hydration on morphology of thin phosphonate block copolymer electrolyte membranes studied by electron tomography

The morphological changes of phosphonate polypeptoid electrolyte membranes, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh m -b-pNpm n ), in hydrated and dry states were characterized by cryogenic transmission electron microscopy (cryo-TEM) and cryogenic electron tomography (cryo-ET). The analysis of 3D tomograms revealed that the pNeh 9 -b-pNpm 9 thin films absorbed a large amount of water, resulting in the formation of membranes that were nearly flat and giant multicompartment vesicles dispersed in the water phase. A simple lamellar phase appeared when the films were dried. In contrast, pNeh 18 -b-pNpm 18 thin films absorbed little water and formed small highly curved unilamellar and multilamellar vesicles. Water was located mainly outside the closely-packed vesicles. When water was removed by drying, the walls of adjacent vesicles collapsed to form honeycomb-like capsules. Here, the changes in domain size reflected changes in chain conformations. The pNpm9 blocks were saturated by water and fully extended, while pNpm 18 blocks were neither saturated by water nor fully extended. In addition, the thicknesses of hydrophobic blocks in the hydrated films of both pNeh 9 -b-pNpm 9 and pNeh 18 -b-pNpm 18 were smaller than those in the dry films, reflecting an increase of the average distance between the neighboring junctions of polypeptoid molecules.

36 MATERIALS SCIENCE↗

NASICON Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 Solid Electrolyte for an All‐Solid‐State Li‐Metal Battery

Abstract A thin solid electrolyte with a high Li + conductivity is used to separate the metallic lithium anode and the cathode in an all‐solid‐state Li‐metal battery. However, most solid Li‐ion electrolytes have a small electrochemical stability window, large interfacial resistance, and cannot block lithium‐dendrite growth when lithium is plated on charging of the cell. Mg 2+ stabilizes a rhombohedral NASICON‐structured solid electrolyte of the formula Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 (LMZP). This solid electrolyte has Li‐ion conductivity two orders of magnitude higher at 25 °C than that of the triclinic LiZr 2 (PO 4 ) 3 . 7 Li and 6 Li NMR confirm the Li‐ions in two different crystallographic sites of the NASICON framework with 85% of the Li‐ions having a relatively higher mobility than the other 15%. The anode–electrolyte interface is further investigated with symmetric Li/LMZP/Li cell testing, while the cathode–electrolyte interface is explored with an all‐solid‐state Li/LMZP/LiFePO 4 cell. The enhanced performance of these cells enabled by the Li 1.2 Mg 0.1 Zr 1.9 (PO 4 ) 3 solid electrolyte is stable upon repeated charge/discharge cycling.

Zhou, Qiongyu↗

(Invited) All-Solid-State Batteries Using Li 7 La 3 Zr 2 O 12 Garnet Electrolyte Framework

All-solid-state batteries (ASSB) using LLZO (variants of Li 7 La 3 Zr 2 O 12 ) garnet solid electrolyte with lithium metal anode potentially offer higher energy density and improved safety. Rational design of cell architecture as well as manufacturing scalability are key aspects to consider as the technology readiness level advances. A thick composite cathode layer attached to a thin solid electrolyte layer is desirable to obtain superior energy densities. Furthermore, the architecture within the composite cathode may be engineered to contain directional conduction paths of lithium ions or electrons for enhanced rate capabilities. Here, we demonstrate a functioning bulk-type LLZO based all-solid-state battery with a practical form factor incorporating the above described design concepts. Freeze-tape-casting (FTC), a scalable and environmentally friendly ceramic processing method, is used to construct 3D porous LLZO scaffolds composed of vertical arrays of LLZO walls. The thin solid-electrolyte layer is fabricated by tape-casting (TC). By sintering the stacks of FTC and TC green tapes, porous/dense bilayers and porous/dense/porous trilayers of LLZO frameworks are obtained. An ASSB was constructed using a porous/dense bilayer by infiltrating LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode powder and carbon black into the porous layer and adhering lithium metal foil to the dense side. We find it crucial to introduce a plastic crystal based soft solid electrolyte to the porous layer to electrochemically connect all cathode components, obviating the need for co-sintering to establish contact. The soft nature of the plastic crystal based solid-electrolyte may be able to accommodate the volume change of the cathode material as it cycles. In this device, which contained no liquid component, the initial discharge capacities were similar to those observed in a lithium ion battery configuration using the same cathode powder at C/10 rates.

25 ENERGY STORAGE↗