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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Understanding Reactivities of Ni-rich Li[NixMnyCo1-x-y]O2 Single-Crystal Cathode Materials

While Ni-rich Li[NixMnyCo1-x-y]O2 (NMC, x ? 0.8) compounds are considered the most promising cathode materials for high-energy lithium-ion batteries (LIBs), a significant challenge is the higher reactivities caused by the increased Ni content, especially under high-voltage operation conditions. In the present study, we synthesize three single-crystal NMC (SC-NMC) samples with the same particle size and morphology: LiNi0.8Mn0.1Co0.1O2 (NMC811), LiNi0.80Mn0.15Co0.05O2 (NMC80155) and LiNi0.85Mn0.10Co0.05O2 (NMC85105). By systematically varying the composition while controlling other properties, the role of each transition metal during air exposure, thermal treatment and long-term cycling is clearly demonstrated. We reveal that while higher Ni content leads to an overall increased reactivities, the presence of Mn provides a stabilizing effect on thermal, structural and chemical properties. In the absence of cycling-induced particle cracking, surface reconstruction is shown to be the dominating contributor to cathode capacity fade. Our study provides key insights needed for the development of better-performing Ni-rich NMC cathode materials.

Kim, Minkyung↗
DOE OSTI2022

Stability Enhancement and Microstructural Modification of Ni-Rich Cathodes via Halide Doping

In this study, elemental doping is an effective strategy to modify surface and bulk chemistry in NMC cathode materials. By adding small amounts of lithium halide salts during the calcination process, the Ni-rich NMC811 cathode is doped with Br, Cl, or F halogens. The dopant type has a significant impact on the lithiation process and heavily influences the final cathode porosity and surface morphology. Utilizing a variety of electrochemical, surface, and bulk characterization techniques, it is demonstrated that an initial content of 5 mol % LiBr or LiCl in the lithium source is effective in improving capacity retention while also providing excellent rate performance. The improvements are attributed to a substantial increase in specific surface area, the formation of a stable cathode electrolyte interface (CEI) layer, and suppressed surface reconstruction. In addition, the particle microstructure is better equipped to handle cyclic volume changes with increased values of critical crack lengths. Overall, it is demonstrated that anion doping via the addition of lithium halide salts is a facile approach toward Ni-rich NMC modification for enhanced cathode performance.

25 ENERGY STORAGE↗
DOE OSTI2020

Hydrogen Evolution on Restructured B-Rich WB: Metastable Surface States and Isolated Active Sites

Borides have been recently identified to be a class of earth-abundant and low-cost materials that are surprisingly active toward oxidative dehydrogenation and hydrogen evolution reaction (HER) catalysis. Here, we explain from first-principles calculations the HER activity of WB, an industrial material known for its superior physical properties and chemical inertness. We find that, compared to bulk termination, a major surface reconstruction takes place, leading to the off-stoichiometric B-rich surface termination that contains the active sites. The hydrogen adsorbate configurations are further investigated under various adsorbate coverages. Many competing configurations appear to be accessible in reaction conditions, and thus, a grand canonical ensemble is established to describe the catalytic system. A phase diagram of adsorbate coverages is constructed as a function of pH and the applied potential. A complex reaction network is presented based on the ensemble-averaged reaction rates, and the electrocatalytic activities are evaluated under different overpotentials. Here, the major contributors to the activity are found to be a few metastable surface states with a distinct electronic structure that are only accessible at high adsorbate coverages in reaction conditions. In addition, while the activity of the dominant active site is nearly the same as that on the unreconstructed WB, the B-rich formations play an important role of isolating the active sites and preventing the passivation of the surface with H 2 bubble formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Local A-Site Phase Segregation Leads to Cs-Rich Regions Showing Accelerated Photodegradation in Mixed-Cation Perovskite Semiconductor Films

We use hyperspectral photoluminescence microscopy to study compositional heterogeneity and its influence on the stability of mixed-cation (formamindinium (FA) and cesium) FA 1-x Cs x Pb(I 0.9 Br 0.1 ) 3 lead halide perovskites with different Cs contents. We observe substantial microscale heterogeneity in the photoluminescence. By correlating photoluminescence maps with time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging, we show that the redder-photoluminescence regions of the perovskite film are associated with Cs-rich compositions. X-ray diffraction measurement and confocal Raman spectroscopy provide evidence for the presence of d-phase CsPbI x Br 3-x in these regions. Photo-aging tests show that these Cs-rich clusters undergo faster photoluminescence decay than the rest of the film. These observations highlight the importance of local heterogeneities and their influence on the stability of halide perovskite semiconductors being studied for optoelectronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Investigating the Role π -Rich Solvents Play in the Growth of Cesium Lead Bromide Nanocrystals

In this report, the role that a high-boiling-point solvent type plays on the nucleation and growth, morphology, and crystal-phase transformation of cesium lead bromide nanocrystals (CsPbBr 3 ) is studied. The CsPbBr 3 products were compared between a one-pot growth mechanism at room temperature (RT) versus a hot-injection mechanism (HI) control using dibenzyl ether (DBE), diphenyl ether (DPE), dioctyl ether (DOE), or 1- octadecene (ODE). The coordination between these solvents and the PbBr 2 salt precursors resulted in different plumbate [PbSBr n ] 2−n precursors being formed. The S-to-Pb 2+ coordination within [PbSBr n ] 2−n was probed by UV−vis and solvent-phase 207 Pb NMR, both of which showed considerable coordination between [PbSBr n ] 2−n and the π-rich DBE and DPE, whose reactivity affected CsPbBr 3 growth. The effect was more pronounced for CsPbBr 3 prepared via RT, where the morphology was tunable, with π-rich solvents producing thin rod-like CsPbB r3 with a blue emission, compared to the green-emitting thicker platelets formed via HI. While XRD showed crystalline products for both RT and HI, with orthorhombic and cubic forms, respectively, the RT products had considerable surface defects, as was indicated by lower quantum yields, and to understand this the photoluminescent lifetimes were measured by time-correlated single photon counting.

207Pb NMR↗
DOE OSTI2020

Probing the Thermal-Driven Structural and Chemical Degradation of Ni-Rich Layered Cathodes by Co/Mn Exchange

The intrinsic poor thermal stability of layered LiNi x Co y Mn 1-x-y O 2 (NCM) cathodes and the exothermic side reactions triggered by the associated oxygen release are the main safety threats for their large-scale implantation. In NCM family, it is widely accepted that Ni is the stability troublemaker, while Mn has long been considered as a structure stabilizer, whereas the role of Co remains elusive. Here, via Co/Mn exchange in Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 cathode, we demonstrate that, the chemical and structural stability of the deep delithiated NCM cathodes are significantly affected by Co, rather than the widely reported Mn. Operando synchrotron X-ray characterization coupling with in situ mass spectrometry reveal that the Co 4+ reduces prior to the reduction of Ni 4+ , and could thus prolong the Ni migration by occupying the tetrahedra sites, and hence postpone the oxygen release and thermal failure. In contrast, the Mn itself is stable, but barely stabilizes the Ni 4+ . Our results highlight the importance of evaluating the intrinsic role of compositional tuning on Ni-rich/Co-free layered oxide cathode materials to guarantee the safe operation of high-energy Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Exceptional Electron-Rich Heteroaromatic Pentacycle for Ultralow Band Gap Conjugated Polymers and Photothermal Therapy

Stable redox-active conjugated molecules with exceptional electron-donating abilities are key components for the design and synthesis of ultralow band gap conjugated polymers. While hallmark electron-rich examples such as pentacene derivatives have been thoroughly explored, their poor air stability has hampered their broad incorporation into conjugated polymers for practical applications. Herein, we describe the synthesis of the electron-rich, fused pentacyclic pyrazino[2,3-b:5,6-b’]diindolizine (PDIz) motif and detail its optical and redox behavior. The PDIz ring system exhibits a lower oxidation potential and a reduced optical band gap than the isoelectronic pentacene while retaining greater air stability in both solution and the solid state. The enhanced stability and electron density, together with readily installed solubilizing groups and polymerization handles, allow for the use of the PDIz motif in the synthesis of a series of conjugated polymers with band gaps as small as 0.71 eV. Importantly; the tunable absorbance throughout the biologically relevant near-infrared I and II regions enables the use of these PDIz-based polymers as efficient photothermal therapeutic reagents for laser ablation of cancer cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Coherent Strain-Inhibiting Phase Construction of Lithium-Rich Manganese-Based Oxide Toward High Mechanochemical Stability

A layered lithium-rich manganese-based oxide cathode, containing $R\overline{3}m$ (LiTMO 2 , TM = Mn, Ni, Co) and $C2/m$ (Li 2 MnO 3 ) nanodomains, utilizes both transition metals and oxygen redox to yield substantial energy density. However, the inherent heterogeneous nature and distinct nanodomain redox chemistries of layered lithium-rich oxides will inevitably cause pernicious lattice strain and structural displacement, which can hardly be eliminated by conventional doping or coating strategies and result in accelerated performance decay. Herein, we incorporate a strain-inhibiting perovskite phase coherently grown within the layered structure to effectively restrain the displacement and lattice strain during uneven Li-ion extraction. The enhanced mechanochemical stability of the designed cathode benefits the persistent structure and reversible oxygen redox, thereby achieving high initial Coulombic efficiency and stable cycling and voltage profiles. In conclusion, our approach of lattice engineering alleviates the strain and displacement caused by inhomogeneous reactivity between heterogeneous nanodomains and promotes the development of advanced cathode materials with long durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Local Cation-Ordered Superlattice Stabilizing Ni-Rich Single-Crystalline Cathodes

Ni-rich single-crystalline cathodes are pivotal for advancing lithium-ion battery technology due to their high energy density and mechanical stability. However, Ni-rich single-crystalline particles face intrinsic structural heterogeneity due to excessively high sintering temperature required to shape micron-sized morphologies─typically over 150 °C above the polycrystalline optimum, leading to rapid electrochemical decay and unsatisfied rate performance that hinder their practical application. Here, in this work, we propose a lithium-deficient presintering strategy to synthesize cation-ordered single-crystalline LiNi 0.83 Co 0.12 Mn 0.05 O 2 (S-NCM83), effectively minimizing lattice chemical heterogeneity and defect formation. The resulting cation-ordered percolation network enhances the structural stability of the bulk, reduces the energy barrier for Li + migration, and stabilizes Li + diffusion pathways. Consequently, S-NCM83 demonstrates significantly improved cycling stability across various operating temperatures and achieves exceptional rate performance, delivering 206 mAh g –1 at 0.1 C and 170 mAh g –1 at 5 C, without requiring surface coatings or doping. This work introduces a universal strategy to address the long-standing structural instability issues in single-crystalline cathodes, paving the way for simplified and scalable approaches to long-life and high-energy lithium-ion batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Rapid Mineral Precipitation During Shear Fracturing of Carbonate-Rich Shales

Target subsurface reservoirs for emerging low-carbon energy technologies and geologic carbon sequestration typically have low permeability and thus rely heavily on fluid transport through natural and induced fracture networks. Sustainable development of these systems requires deeper understanding of how geochemically mediated deformation impacts fracture microstructure and permeability evolution, particularly with respect to geochemical reactions between pore fluids and the host rock. Here, a series of triaxial direct shear experiments was designed to evaluate how fractures generated at subsurface conditions respond to penetration of reactive fluids with a focus on the role of mineral precipitation. Calcite-rich shale cores were directly sheared under 3.5 MPa confining pressure using BaCl 2 -rich solutions as a working fluid. Experiments were conducted within an X-ray computed tomography (xCT) scanner to capture 4-D evolution of fracture geometry and precipitate growth. Three shear tests evidenced nonuniform precipitation of barium carbonates (BaCO 3 ) along through-going fractures, where the extent of precipitation increased with increasing calcite content. Precipitates were strongly localized within fracture networks due to mineral, geochemical, and structural heterogeneities and generally concentrated in smaller apertures where rock:water ratios were highest. The combination of elevated fluid saturation and reactive surface area created in freshly activated fractures drove near-immediate mineral precipitation that led to an 80% permeability reduction and significant flow obstruction in the most reactive core. While most previous studies have focused on mixing-induced precipitation, this work demonstrates that fluid–rock interactions can trigger precipitation-induced permeability alterations that can initiate or mitigate risks associated with subsurface energy systems.

58 GEOSCIENCES↗
DOE OSTI2025

Thermoelastic Properties of Iron-Rich Ringwoodite and the Deep Mantle Aerotherm of Mars

The Martian mantle is considered to have a higher Fe/Mg ratio than the Earth's mantle. Ringwoodite, γ-(Mg,Fe) 2 SiO 4 , is likely the dominant polymorph of olivine in the core-mantle boundary (CMB) region of Mars. We synthesized anhydrous iron-rich ringwoodite with molar Mg/(Mg + Fe) = 0.44 and determined its thermal equation of state up to 35 GPa and 750 K by synchrotron X-ray diffraction. Using a third order Birch-Murnaghan equation of state, we obtain K T0 = 182 (3) GPa, K' = 4.6 (2), and α 0 = 3.18 (6) × 10 -5 K -1 . Using these results and an updated mineralogical model with an iron-rich composition of Mg/(Mg + Fe) = 0.75 for the Martian mantle, we estimate ~1900 K for the temperature of the D1000 seismic discontinuity inside Mars. The resulting adiabat predicts a warm aerotherm, which could explain the presence of partial melt at the CMB of Mars recently detected with seismic data from the 2019 InSight mission.

58 GEOSCIENCES↗
DOE OSTI2021

In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes

High nickel content in LiNi x Co y Mn z O 2 (NCM, x ≥ 0.8, x + y + z = 1) layered cathode material allows high specific energy density in lithium-ion batteries (LIBs). However, Ni-rich NCM cathodes suffer from performance degradation, mechanical and structural instability upon prolonged cell cycling. Although the use of single-crystal Ni-rich NCM can mitigate these drawbacks, the ion-diffusion in large single-crystal particles hamper its rate capability. Herein, we report a strategy to construct an in situ Li 1.4 Y 0.4 Ti 1.6 (PO 4 ) 3 (LYTP) ion/electron conductive network which interconnects single-crystal LiNi 0.88 Co 0.09 Mn 0.03 O 2 (SC-NCM88) particles. The LYTP network facilitates the lithium-ion transport between SC-NCM88 particles, mitigates mechanical instability and prevents detrimental crystalline phase transformation. When used in combination with a Li metal anode, the LYTP-containing SC-NCM88-based cathode enables a coin cell capacity of 130 mAh g -1 after 500 cycles at 5 C rate in the 2.75-4.4 V range at 25 °C. Tests in Li-ion pouch cell configuration (i.e., graphite used as negative electrode active material) demonstrate capacity retention of 85% after 1000 cycles at 0.5 C in the 2.75-4.4 V range at 25 °C for the LYTP-containing SC-NCM88-based positive electrode.

25 ENERGY STORAGE↗
DOE OSTI2022

Enabling high energy lithium metal batteries via single-crystal Ni-rich cathode material co-doping strategy

High-capacity Ni-rich layered oxides are promising cathode materials for secondary lithium-based battery systems. However, their structural instability detrimentally affects the battery performance during cell cycling. Here, we report an Al/Zr co-doped single-crystalline LiNi<:sub>0.88 Co 0.09 Mn 0.03 O 2 (SNCM) cathode material to circumvent the instability issue. We found that soluble Al ions are adequately incorporated in the SNCM lattice while the less soluble Zr ions are prone to aggregate in the outer SNCM surface layer. The synergistic effect of Al/Zr co-doping in SNCM lattice improve the Li-ion mobility, relief the internal strain, and suppress the Li/Ni cation mixing upon cycling at high cut-off voltage. These features improve the cathode rate capability and structural stabilization during prolonged cell cycling. In particular, the Zr-rich surface enables the formation of stable cathode-electrolyte interphase, which prevent SNCM from unwanted reactions with the non-aqueous fluorinated liquid electrolyte solution and avoid Ni dissolution. To prove the practical application of the Al/Zr co-doped SNCM, we assembled a 10.8 Ah pouch cell (using a 100 μm thick Li metal anode) capable of delivering initial specific energy of 504.5 Wh kg- 1 at 0.1 °C and 25 °C.

25 ENERGY STORAGE↗
DOE OSTI2022

Trans-crustal structural control of CO 2 -rich extensional magmatic systems revealed at Mount Erebus Antarctica

Erebus volcano, Antarctica, with its persistent phonolite lava lake, is a classic example of an evolved, CO 2 -rich rift volcano. Seismic studies provide limited images of the magmatic system. Here we show using magnetotelluric data that a steep, melt-related conduit of low electrical resistivity originating in the upper mantle undergoes pronounced lateral re-orientation in the deep crust before reaching shallower magmatic storage and the summit lava lake. The lateral turn represents a structural fault-valve controlling episodic flow of magma and CO 2 vapour, which replenish and heat the high level phonolite differentiation zone. This magmatic valve lies within an inferred, east-west structural trend forming part of an accommodation zone across the southern termination of the Terror Rift, providing a dilatant magma pathway. Unlike H 2 O-rich subduction arc volcanoes, CO 2 -dominated Erebus geophysically shows continuous magmatic structure to shallow crustal depths of < 1 km, as the melt does not experience decompression-related volatile supersaturation and viscous stalling.

58 GEOSCIENCES↗
DOE OSTI2022

Effect of the grain arrangements on the thermal stability of polycrystalline nickel-rich lithium-based battery cathodes

One of the most challenging aspects of developing high-energy lithium-based batteries is the structural and (electro)chemical stability of Ni-rich active cathode materials at thermally-abused and prolonged cell cycling conditions. Here, we report in situ physicochemical characterizations to improve the fundamental understanding of the degradation mechanism of charged polycrystalline Ni-rich cathodes at elevated temperatures (e.g., ≥ 40 °C). Using multiple microscopy, scattering, thermal, and electrochemical probes, we decouple the major contributors for the thermal instability from intertwined factors. Our research work demonstrates that the grain microstructures play an essential role in the thermal stability of polycrystalline lithium-based positive battery electrodes. We also show that the oxygen release, a crucial process during battery thermal runaway, can be regulated by engineering grain arrangements. Furthermore, the grain arrangements can also modulate the macroscopic crystallographic transformation pattern and oxygen diffusion length in layered oxide cathode materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Incorporation of 16 O-rich anhydrous silicates in the protolith of highly hydrated asteroid Ryugu

The abundant phyllosilicate and carbonate minerals characterizing most of the returned particles from asteroid Ryugu suggest a history of extensive aqueous alteration on its parent body, similar to the rare mineralogically altered, but chemically primitive, CI (Ivuna-type) chondrite meteorites. Particle C0009 differs mineralogically from other Ryugu particles examined so far by containing anhydrous silicates at a level of ~0.5 vol%, and thus can help shed light on the unaltered original materials that constituted Ryugu’s protolith. In situ oxygen isotope measurements of the most Mg-rich olivine and pyroxene in C0009 reveal two populations of Δ 17 O: –25‰ to –15‰ and –8‰ to –3‰. The former and the latter populations correlate well with silicate morphologies similar to those seen in amoeboid olivine aggregates and chondrule phenocrysts, respectively, both of which are abundant in less aqueously altered carbonaceous chondrites. Here, this result also highlights the presence of olivine with Δ 17 O close to the solar value in either a CI chondrite or an asteroid with CI-chondrite characteristics, and provides strong evidence that amoeboid olivine aggregates and Mg-rich chondrules accreted into Ryugu’s protolith. Our data also raise the possibility that the protoliths of CI and other carbonaceous chondrites incorporated similar anhydrous silicates.

58 GEOSCIENCES↗
DOE OSTI2025

Abundant ammonia and nitrogen-rich soluble organic matter in samples from asteroid (101955) Bennu

Organic matter in meteorites reveals clues about early Solar System chemistry and the origin of molecules important to life, but terrestrial exposure complicates interpretation. Samples returned from the B-type asteroid Bennu by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer mission enabled us to study pristine carbonaceous astromaterial without uncontrolled exposure to Earth’s biosphere. Here we show that Bennu samples are volatile rich, with more carbon, nitrogen and ammonia than samples from asteroid Ryugu and most meteorites. Nitrogen-15 isotopic enrichments indicate that ammonia and other N-containing soluble molecules formed in a cold molecular cloud or the outer protoplanetary disk. We detected amino acids (including 14 of the 20 used in terrestrial biology), amines, formaldehyde, carboxylic acids, polycyclic aromatic hydrocarbons and N-heterocycles (including all five nucleobases found in DNA and RNA), along with ~10,000 N-bearing chemical species. All chiral non-protein amino acids were racemic or nearly so, implying that terrestrial life’s left-handed chirality may not be due to bias in prebiotic molecules delivered by impacts. The relative abundances of amino acids and other soluble organics suggest formation and alteration by low-temperature reactions, possibly in NH 3 -rich fluids. Bennu’s parent asteroid developed in or accreted ices from a reservoir in the outer Solar System where ammonia ice was stable.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

In situ formed partially disordered phases as earth-abundant Mn-rich cathode materials

Abstract Earth-abundant cathode materials are urgently needed to enable scaling of the Li-ion industry to multiply terawatt hours of annual production, necessitating reconsideration of how good cathode materials can be obtained. Irreversible transition metal migration and phase transformations in Li-ion cathodes are typically believed to be detrimental because they may trigger voltage hysteresis, poor kinetics and capacity degradation. Here we challenge this conventional consensus by reporting an unusual phase transformation from disordered Li- and Mn-rich rock salts to a new phase (named δ ), which displays partial spinel-like ordering with short coherence length and exhibits high energy density and rate capability. Unlike other Mn-based cathodes, the δ phase exhibits almost no voltage fade upon cycling. We identify the driving force and kinetics of this in situ cathode formation and establish design guidelines for Li- and Mn-rich compositions that combine high energy density, high rate capability and good cyclability, thereby enabling Mn-based energy storage.

25 ENERGY STORAGE↗