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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2018

Coupled Thermomechanical Micromechanics Modeling of the Influence of Thermally Grown Oxide Layer in an Environmental Barrier Coating System

Environmental Barrier Coatings (EBCs) have emerged as a promising means of protecting critical components for high temperature applications (e.g., aircraft engines). EBCs are often used to protect an underlying material (substrate) from extreme thermal/chemical environments. However, systems that utilize EBCs are susceptible to a number of failure modes including oxidation/delamination. Environmental Barrier Coatings (EBCs) have emerged as a promising means of protecting silicon based ceramic matrix composite (CMC) components for high temperature applications (e.g., aircraft engines). EBCs are often used to protect an underlying material (substrate) such as silicon carbide from extreme thermal/chemical environments. In a typical CMC/EBC system, an EBC may or may not be adhered to an underlying substrate with a bond coat (e.g., silicon). Irrespective, systems that utilize EBCs are susceptible to a number of failure modes including oxidation/delamination, recession, chemical attack and dissolution, thermo-mechanical degradation, erosion, and foreign object damage. Current work at NASA Glenn Research Center is aimed at addressing these failure modes in EBC systems and developing robust analysis tools to aid in the design process. The Higher-Order Theory for Functionally Graded Materials (HOTFGM), a precursor to the High-Fidelity Generalized Method of Cells micromechanics approach, was developed to investigate the coupled thermo-mechanical behavior of functionally graded composites and will be used herein to assess the development and growth of a low-stiffness thermally grown oxide (TGO) layer in EBC/CMC systems without a silicon bond coat. To accomplish this a sensitivity study is conducted to examine the influence of uniformly and non-uniformly grown oxide layer on the associated driving forces leading to mechanical failure (spallation) of EBC layer when subjected to isothermal loading, recession, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object damage. Current work at NASA Glenn Research Center is aimed at addressing these failure modes in EBC systems and developing robust analysis tools to aid in the design process. The Higher-Order Theory for Functionally Graded Materials (HOTFGM), a precursor to the High-Fidelity Generalized Method of Cells micromechanics approach, was developed to investigate the coupled thermo-mechanical behavior of functionally graded composites (Aboudi et al., 1999, Composites B). For example, HOTFGM was previously used (Arnold et al, 1995, NASA CP 10178, paper 34), to assess interlaminar stresses (including free edge effects) in a substrate with a thermal barrier coating (TBC). In this study, HOTFGM micromechanics analyses will be used to assess the development and growth of a low-stiffness thermally grown oxide (TGO) layer between a silicon carbide substrate and a ytterbium disilicate EBC. In order to realistically simulate TGO growth, an evolution law will be incorporated into HOTFGM. In addition, the effect of TGO roughness will be explored consistent with previous TBC work (Pindera et al., 2000. Material Science and Engineering, A284, pp. 158-175). This model represents a first step in developing a robust analysis tool that can ultimately be used to design durable EBC systems. Additional failure modes will be considered as part of a future work.

environmental barrier coating↗
DOE OSTI2022

Native lattice strain induced structural earthquake in sodium layered oxide cathodes

Abstract High-voltage operation is essential for the energy and power densities of battery cathode materials, but its stabilization remains a universal challenge. To date, the degradation origin has been mostly attributed to cycling-initiated structural deformation while the effect of native crystallographic defects induced during the sophisticated synthesis process has been significantly overlooked. Here, using in situ synchrotron X-ray probes and advanced transmission electron microscopy to probe the solid-state synthesis and charge/discharge process of sodium layered oxide cathodes, we reveal that quenching-induced native lattice strain plays an overwhelming role in the catastrophic capacity degradation of sodium layered cathodes, which runs counter to conventional perception—phase transition and cathode interfacial reactions. We observe that the spontaneous relaxation of native lattice strain is responsible for the structural earthquake (e.g., dislocation, stacking faults and fragmentation) of sodium layered cathodes during cycling, which is unexpectedly not regulated by the voltage window but is strongly coupled with charge/discharge temperature and rate. Our findings resolve the controversial understanding on the degradation origin of cathode materials and highlight the importance of eliminating intrinsic crystallographic defects to guarantee superior cycling stability at high voltages.

25 ENERGY STORAGE↗
DOE OSTI2023

Low cobalt layered oxide materials for lithium ion battery electrodes

Stabilized layered lithium metal oxide cathode materials are described which include excess lithium, Ni, Mn, and at least one other metal ion. The materials comprise a layered LiMO 2 -type material in which M comprises a combination of Ni, Mn, and at least one other metal ion that includes less than about 6 mol % Co; and which has about 1 to 6 percent excess lithium. In one embodiment, the stabilized lithium metal oxide cathode material comprises a composition having the empirical formula xLi 2 MnO 3 ·(1−x)LiNi 0.5+δ/2 Mn 0.5−δ Co δ/2 O 2 , wherein 0 1+3y [Ni a Mn b M′ c ] 1−y O 2 , wherein M′ is one of more metal selected from the group consisting of Co, Al, Fe, Mg, and Ti; 0<y≤0.02; 0.85≤a≤0.96; 0.03≤b≤0.1; and 0.01≤c≤0.1.

Croy, Jason R.↗
NASA NTRS1983

A critical study of the role of the surface oxide layer in titanium bonding

Scanning electron microscope/X-ray photoelectron spectroscopy (SEM/XPS) analysis of fractured adhesively bonded Ti 6-4 samples is discussed. The text adhesives incuded NR 056X polyimide, polypheylquinoxaline (PPQ), and LARC-13 polyimide. Differentiation between cohesive and interfacial failure was based on the absence of presence of a Ti 2p XPS photopeak. In addition, the surface oxide layer on Ti-(6A1-4V) adherends is characterized and bond strength and durability are addressed. Bond durability in various environmental conditions is discussed.

Dias, S.↗
DOE OSTI2021

Octahedral rotations in Ruddlesden-Popper layered oxides under pressure from first principles

The combination of reduced dimensionality and tunable structural distortions in layered perovskite oxides makes these materials ideal platforms for designing novel properties and functionalities. One example is hybrid improper ferroelectricity in n = 2 Ruddlesden-Popper oxides, where the combination of a layered crystal structure and rotations of the metal-oxide octahedra break symmetry and induce a polarization. Precisely controlling the octahedral rotation distortions, for example by the application of hydrostatic pressure, provides a pathway to tune and optimize the properties of these materials. Here we combine group theoretic methods, density functional theory calculations, and Landau theory analysis to investigate how octahedral rotations respond to pressure in the hybrid improper ferroelectrics Sr 3 Zr 2 O 7 , Ca 3 Ti 2 O 7 , and Sr 3 Sn 2 O 7 . We find that factors that are known to control the pressure response of ABO 3 perovskites—the formal charge of the A- and B-site cations, tolerance factor, and B-site chemistry—also impact the pressure response of these layered perovskites. We also show that coupling between the octahedral rotation and strain order parameters plays a key role in determining the overall pressure response. Despite some similarities, we find that these layered perovskites display a distinct pressure response compared to their ABO 3 perovskite analogs. By identifying trends and underlying mechanisms that control octahedral rotations in Ruddlesden-Popper oxides under pressure, this work lays the foundation for tailoring the structure and properties of these materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

What is the Role of Nb in Nickel-Rich Layered Oxide Cathodes for Lithium-Ion Batteries?

Nickel-rich layered metal oxide LiNi 1–y–z Mn y Co z O 2 (1 – y – z ≥ 0.8) materials are the most promising cathodes for next-generation lithium-ion batteries in electric vehicles. However, they lose more than 10% of their capacity on the first cycle, and interfacial/structural instability causes capacity fading. Coating and substitution are possible direct and effective solutions to solve these challenges. In this Letter, Nb coating and Nb substitution on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is easily produced through a scalable wet chemistry method followed by sintering from 400 to 800 °C. A Li-free Nb oxide treatment is found to remove surface impurities forming a LiNbO 3 /Li 3 NbO 4 surface coating, to reduce the first capacity loss and to improve the rate performance. Furthermore, Nb substitution stabilizes the structure, as evidenced by less heat evolution on heating, thus providing better long cycling stability with a 93.2% capacity retention after 250 cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Asynchronous domain dynamics and equilibration in layered oxide battery cathode

To improve lithium-ion battery technology, it is essential to probe and comprehend the microscopic dynamic processes that occur in a real-world composite electrode under operating conditions. The primary and secondary particles are the structural building blocks of battery cathode electrodes. Their dynamic inconsistency has profound but not well-understood impacts. In this research, we combine operando coherent multi-crystal diffraction and optical microscopy to examine the chemical dynamics in local domains of layered oxide cathode. Our results not only pinpoint the asynchronicity of the lithium (de)intercalation at the sub-particle level, but also reveal sophisticated diffusion kinetics and reaction patterns, involving various localized processes, e.g., chemical onset, reaction front propagation, domains equilibration, particle deformation and motion. These observations shed new lights onto the activation and degradation mechanisms of state-of-the-art battery cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2023

Emergent Magnetism with Continuous Control in the Ultrahigh-Conductivity Layered Oxide PdCoO 2

The current challenge to realizing continuously tunable magnetism lies in our inability to systematically change properties, such as valence, spin, and orbital degrees of freedom, as well as crystallographic geometry. Here, we demonstrate that ferromagnetism can be externally turned on with the application of low-energy helium implantation and can be subsequently erased and returned to the pristine state via annealing. We find that this high level of continuous control is made possible by targeting magnetic metastability in the ultrahigh-conductivity, nonmagnetic layered oxide PdCoO 2 where local lattice distortions generated by helium implantation induce the emergence of a net moment on the surrounding transition metal octahedral sites. These highly localized moments communicate through the itinerant metal states, which trigger the onset of percolated long-range ferromagnetism. The ability to continuously tune competing interactions enables tailoring precise magnetic and magnetotransport responses in an ultrahigh-conductivity film and will be critical to applications across spintronics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS2018

Coupled Thermo-Mechanical Micromechanics Modeling of the Influence of Thermally Grown Oxide Layer in an Environmental Barrier Coating System

Environmental Barrier Coatings (EBCs) have emerged as a promising means of protecting silicon based ceramic matrix composite (CMC) components for high temperature applications (e.g., aircraft engines). EBCs are often used to protect an underlying material (substrate) such as silicon carbide from extreme thermal/chemical environments. In a typical CMC/EBC system, an EBC may or may not be adhered to an underlying substrate with a bond coat (e.g., silicon). Irrespective, systems that utilize EBCs are susceptible to a number of failure modes including oxidation/delamination, recession, chemical attack and dissolution, thermomechanical degradation, erosion, and foreign object damage. Current work at NASA Glenn Research Center is aimed at addressing these failure modes in EBC systems and developing robust analysis tools to aid in the design process. The Higher-Order Theory for Functionally Graded Materials (HOTFGM), a precursor to the High-Fidelity Generalized Method of Cells micromechanics approach, was developed to investigate the coupled thermo-mechanical behavior of functionally graded composites and will be used herein to assess the development and growth of a low-stiffness thermally grown oxide (TGO) layer in EBC/CMC systems without a silicon bond coat. To accomplish this a sensitivity study is conducted to examine the influence of uniformly and nonuniformly grown oxide layer on the associated driving forces leading to mechanical failure (spallation) of EBC layer when subjected to isothermal loading.

thermally grown oxide↗
DOE OSTI2020

Consequences of long-term water exposure for bulk crystal structure and surface composition/chemistry of nickel-rich layered oxide materials for Li-ion batteries

Water exposure of layered nickel-rich transition metal oxide electrodes, widely used in high-energy lithium-ion batteries, has detrimental effects on the electrochemical performance, which complicates electrode handling and prevents implementation of environmentally benign aqueous processing procedures. Elucidating the degradation mechanisms in play may help rationally mitigate/circumvent key challenges. Here, the bulk structural consequences of long-term (>2.5 years) deuterated water (D2O) exposure of intercalation materials with compositions Li x Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) and Li x Ni 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) are studied by neutron powder diffraction (NPD). Detailed inspection of the NPD data reveals gradual formation of a secondary crystalline phase in all exposed samples, not previously reported for this system. This unknown phase forms faster in liquid- compared to vapor-exposed compounds. Structural modelling of the NPD data shows a stable level of Li/Ni anti-site defects and does not indicate any significant changes in lattice parameters or hydrogen-lithium (D + /Li + ) exchange in the structure. Consequently, the secondary phase formation must take place via transformation rather than modification of the parent material. X-ray photoelectron spectroscopy data indicate formation of LiHCO 3 /Li 2 CO 3 at the surface and a Li-deficient oxide in the sub-surface region of the pristine compounds, and the presence of adsorbed water and transition metal hydroxides at the exposed sample surfaces.

25 ENERGY STORAGE↗
DOE OSTI2024

Achieving a high-performance sodium-ion pouch cell by regulating intergrowth structures in a layered oxide cathode with anionic redox

In P2-type layered transition metal (TM) oxides, which are typical cathode materials for Na-ion batteries, the presence of Li within the TM layer could lead to the formation of specific Na–O–Li configurations that trigger additional oxygen redox at high charging voltages. However, the prismatic-type (P-type) to octahedral-type (O-type) phase transition and irreversible TM migration could be simultaneously aggravated in high state of charge, resulting in structural distortion. Here we demonstrate that excessive desodiation of P2-Na 0.67 Li 0.1 Fe 0.37 Mn 0.53 O 2 (NLFMO) induces the formation of neighbouring O-type stacking faults with an intergrowth structure (that is, interlacing of O- and P-type layers), which leads to out-of-lattice Li migration and irreversible oxygen loss. We show that, by controlling the depth of charge to tailor the intergrowth structure, a P-type stacking state can be uniformly interspersed between the O-type stacking state, thereby avoiding neighbouring O-type stacking faults. Adjusting the O/P intergrowth structure leads to both reversible migration of Li/TM ions and reversible anionic redox in the NLFMO cathode. In conclusion, we thereby achieve a high-performance pouch cell (with an energy density of 165 W h kg −1 based on the entire weight of the cell) with both cationic and anionic redox activities.

25 ENERGY STORAGE↗
DOE OSTI2022

Pinhole‐Free Ultrathin Silicon Oxide Layer by Ozone‐Dissolved Deionized Water

The pinhole‐free silicon oxide (SiO x ) layer grown using dissolved ozone in deionized water (DI‐O 3 ) is demonstrated. An ultrathin SiO x layer of thickness 1.53 nm ± 1.5% is grown on silicon wafer using 7 ppm DI‐O 3 . A four‐step methodology, including 25 wt% aq. tetramethylammonium hydroxide (TMAH) solution at 80 °C, is employed to magnify the pinhole signatures in the underlying silicon and visualized with dark‐field optical microscopy (DFOM) and scanning electron microscopy (SEM). The DFOM images show spots on the surface of wafer that originate from airborne particles, contamination, etc. SEM images reveal the absence of etch pits in silicon even after etching of SiO x /silicon in TMAH for 300 s. The minority carrier lifetime and interface states density in AlO x ‐capped SiO x /Si structure are ≥2 ms at carrier density of 1 × 10 15 cm −3 and less than 2 × 10 11 cm −2 eV −1 , respectively.

42 ENGINEERING↗
DOE OSTI2024

Stabilized Oxygen Vacancy Chemistry toward High-Performance Layered Oxide Cathodes for Sodium-Ion Batteries

Anionic redox has emerged as a transformative paradigm for high-energy layered transition-metal (TM) oxide cathodes, but it is usually accompanied by the formation of anionic redox-mediated oxygen vacancies (OVs) due to irreversible oxygen release. Additionally, external factor-induced OVs (defined as intrinsic OVs) also play a pivotal role in the physicochemical properties of layered TM oxides. However, an in-depth understanding of the interplay between intrinsic and anionic redox-mediated OVs and the corresponding regulation mechanism of the dynamic evolution of OVs is still missing. Herein, we disclose the strong interrelationship between these OVs and demonstrate that the presence of intrinsic OVs in the TMO2 layers could induce weak integrity of the TM-O frameworks and unlock additional diffusion paths to trigger the generation and migration of anionic redox-mediated OVs. Accordingly, an OV stabilization strategy is proposed by deliberately introducing high-valence Nb5+, which could serve as an important building block in anchoring the oxygen sublattice and preventing the formation of a percolating OV migration network, thereby suppressing the formation/diffusion of anionic redox-mediated OVs. Consequently, superb structural integrity and improved electrochemical performance with reversible anionic redox chemistry are achieved. This work advances our understanding of the role of OVs for developing high-performance energy storage systems utilizing anionic redox.

anionic redox↗
DOE OSTI2022

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na 0.72 Mn 0.75 Li 0.24 X 0.01 O 2 (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 Whkg -1 based on the cathode mass) deliver the capacity retention of 83% for P2- Na 0.72 Mn 0.75 Li 0.24 Si 0.01 O 2 and 66% for P2-Na 0.72 Mn 0.75 Li 0.24 Ti 0.01 O 2 after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers new composition towards developing high performance low-cost cathodes for Na-ion batteries and highlights the unique role of Ti/Si ions.

25 ENERGY STORAGE↗
DOE OSTI2020

Ultralow-Strain Zn-Substituted Layered Oxide Cathode with Suppressed P2–O2 Transition for Stable Sodium Ion Storage

Layered transition metal oxides have drawn much attention as a promising candidate cathode material for sodium-ion batteries. However, their performance degradation originating from strains and lattice phase transitions remains a critical challenge. Herein, a high-concentration Zn-substituted Na x MnO 2 cathode with strongly suppressed P2–O2 transition is investigated, which exhibits a volume change as low as 1.0% in the charge/discharge process. Additionally, such ultralow strain characteristics ensure a stable host for sodium ion storage, which significantly improves the cycling stability and rate capability of the cathode material. Also, the strong coupling between the highly reversible capacity and the doping content of Zn in Na x MnO 2 is investigated. It is suggested that a reversible anionic redox reaction can be effectively triggered by Zn ions and is also highly dependent on the Zn content. Such an ion doping strategy could shed light on the design and construction of stable and high-capacity sodium ion host.

25 ENERGY STORAGE↗
DOE OSTI2021

Tuning local chemistry of P2 layered-oxide cathode for high energy and long cycles of sodium-ion battery

Layered transition-metal oxides have attracted intensive interest for cathode materials of sodium-ion batteries. However, they are hindered by the limited capacity and inferior phase transition due to the gliding of transition-metal layers upon Na + extraction and insertion in the cathode materials. Here, we report that the large-sized K + is riveted in the prismatic Na + sites of P2-Na 0.612 K 0.056 MnO 2 to enable more thermodynamically favorable Na + vacancies. The Mn-O bonds are reinforced to reduce phase transition during charge and discharge. 0.901 Na + per formula are reversibly extracted and inserted, in which only the two-phase transition of P2 ↔ P’2 occurs at low voltages. It exhibits the highest specific capacity of 240.5 mAh g -1 and energy density of 654 Wh kg -1 based on the redox of Mn 3+ /Mn 4+ , and a capacity retention of 98.2% after 100 cycles. This investigation will shed lights on the tuneable chemical environments of transition-metal oxides for advanced cathode materials and promote the development of sodium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Electro-Optical Stability in Gallium Magnesium Zinc Oxide Layers for CdTe Solar Cells

In CdTe solar cells, the emitter electron density, bandgap, and band alignment can be tuned by adjusting alloy composition and stoichiometry in gallium magnesium zinc oxide (GMZO) layers, thereby allowing for critical front interface engineering. For example, computational modeling indicates efficiency can change from 7% to 25% by adjusting these buffer properties even with fixed CdSeTe and CdTe material properties. However, the GMZO as-deposited electro-optical properties can shift during subsequent CdTe deposition, CdCl 2 annealing, and solar cell operation. Here, we examine these changes by sputtering GMZO films on glass, and measuring the electron density before and after post-deposition treatments over a range of temperatures and different ambients. We then compare GMZO to SnO 2 and MZO. The addition of Ga to MgZnO is found to have profound effects on both the electron density and electro-optical stability that should be advantageous for CdTe solar cells.

41 EE - Solar Energy Technologies Office (EE-4S)↗
DOE OSTI2024

Coupling Anionic Oxygen Redox with Selenium for Stable High‐Voltage Sodium Layered Oxide Cathodes

Utilizing anion redox reaction is crucial for developing the next generation of high-energy density, low-cost sodium-ion batteries. However, the irreversible oxygen redox reaction in Na-ion layered cathodes, which leads to voltage fading and reduced overall lifespan, has hindered their practical application. In this study, selenium is incorporated as a synergistic redox active center of oxygen to improve the stability of Na-ion cathodes. The redesigned cathode maintains stable voltage by demonstrating reversible oxygen redox while significantly suppressing the redox activity of manganese. The anionic redox contribution capacity of the selenium-doped Na 0.6 Li 0.2 Mn 0.8 O 2 cathode remains as high as 84% after 50 cycles, while the pristine Na 0.6 Li 0.2 Mn 0.8 O 2 cathode experiences a reduction to 39% of its initial capacity. The X-ray photoelectron spectroscopy data and computational analysis further revealed that selenium doping participates in redox as Se +4/5 which stabilizes the charged state and increases the energy step for O─O dimerization, thus improving the stability and lifespan of Na 0.6 Li 0.2 Mn 0.8 O 2 cathodes. In conclusion, the findings highlight the potential of redox coupling design to address the issue of voltage fade caused by irreversible anionic redox.

25 ENERGY STORAGE↗