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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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Probing Thermal Stability of Li-Ion Battery Ni-Rich Layered Oxide Cathodes by means of Operando Gas Analysis and Neutron Diffraction

Thermal stability is a crucial parameter that must be considered within the overall performance metrics of Ni-rich layered oxide cathodes. While the intrinsic structural stability of the cathode materials under thermal conditions is important, it is also critical to consider their reaction with electrolytes. In this study, operando gas analysis, ex situ neutron diffraction, and differential scanning calorimetry were combined to give a broader picture of the thermal stability of Ni-rich NMC cathodes. Li 1– x Ni 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite materials with four different states of charge were investigated with and without the presence of an electrolyte. It has been found that electrolyte can greatly accelerate both the structural and thermal decomposition of the cathode materials. A higher state of charge will also make cathode materials more susceptible to thermal shock. Without an electrolyte, O 2 release inducing a structural change from layered to rock salt was the major observation during thermal runaway. However, all samples retained some levels of layered structure after annealing up to 300 °C without the electrolyte. In comparison, almost all the O3-type layered phase transformed to the rock-salt phase for the cathode materials heated with the electrolyte at the same experimental conditions. Moreover, the amount of CO 2 increased by nearly two orders of magnitude when annealing cathode materials with electrolyte in operando gas analysis experiments. More delithiated NMC811 samples released larger amounts of CO 2 at earlier onset temperatures, resonating well with the differential scanning calorimetry (DSC) results showing that more delithiated samples release more heat during thermal shock.

25 ENERGY STORAGE↗
DOE OSTI2021

Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

The high-voltage, cobalt-free spinel cathode LiNi 0.5 Mn 1.5 O 4 (LNMO) is receiving extensive attention for lithium-ion batteries due to its low cost, high operating voltage and energy density, superior power density, and good thermal stability. However, its high operating voltage hampers its stability with commercial electrolytes and makes its practical viability challenging. We present here a Mn-rich LNMO cathode to encourage the disordering of Mn and Ni in the lattice and the incorporation of a small dose of Fe into Mn-rich LNMO (Fe-LNMO) to improve the cycling stability. The introduction of Fe further increases the cation disorder between Mn and Ni, thus enabling a better rate capability. Electron energy loss spectroscopy analysis indicates that Fe is concentrated on the surface, and X-ray photoelectron spectroscopy analysis shows that Fe-LNMO alleviates the aggressive reaction between the cathode surface and the electrolyte, thus stabilizing the interface and cycle life. Furthermore, a full cell assembled with a graphite anode with an areal capacity of 3 mA h cm –2 displays a capacity retention of 90% over 300 cycles. Furthermore, the present work demonstrates an effective way to promote cation disordering and lower the surface reactivity of LNMO with the electrolyte, thereby enhancing the conductivity, stabilizing the cathode–electrolyte interphase, and making LNMO promising for practical applications.

25 ENERGY STORAGE↗
DOE OSTI2018

Modified Coprecipitation Synthesis of Mesostructure-Controlled Li-Rich Layered Oxides for Minimizing Voltage Degradation

In this work, modified carbonate coprecipitation synthesis without addition of chelating agent is introduced to obtain mesostructure-controlled Li-rich layered oxides. The designed mesostructure for target material Li 1.2 Ni 0.2 Mn 0.6 O 2 has uniformly dispersed spherical secondary particles with size around 3 μm. These micrometer-sized particles consist of self-assembled crystallites with size of ~150 nm. This unique design not only decreases the surface area compared with the sample with dispersive particles, but also increases overall structural mechanical stability compared with the sample with larger dense secondary particles as observed by transmission X-ray microscope. As a result, the voltage decay and capacity loss during long-term cycling have been minimized to a large extent. Our findings clearly demonstrate that mesostructure design of Li-rich layered oxides play a key role in optimizing this class of cathode materials. Surprisingly, the voltage fading issue can be partially mitigated by such an approach.

25 ENERGY STORAGE↗
DOE OSTI2019

Synthesis of Ni-Rich Thin-Film Cathode as Model System for Lithium Ion Batteries

We demonstrate a process to prepare model electrodes of the Ni-rich layered compound LiNi 0.6 Mn 0.2 Co 0.2 O 2 . These thin-film cathodes are compared with the composite materials to demonstrate the system is a viable platform for isolating interfacial phenomena between the electrolyte and active material without the influence of binders and conductive additives. The appropriate choice of heterolayers was found to influence the preferential orientation of the (101) and (104) planes relative to the (003) plane of the layered R-3m crystal structure, enhancing Li + diffusion and improving electrochemical performance. The addition of a Co interlayer between the Pt current collecting layer and alumina substrate increased the (101) and (104) texturing of the 500 nm Ni-rich film and allowed cells to deliver greater than 50% of their theoretical capacity. This work provides an architecture for isolating complex mechanisms of active materials that suffer from surface reconstruction and degradation in electrochemical cells.

25 ENERGY STORAGE↗
DOE OSTI2023

High-Performance Layered Ni-Rich Cathode Materials Enabled by Stress-Resistant Nanosheets

Here, layered O3-type transition metal oxides are promising cathode candidates for high-energy-density Li-ion batteries. However, the structural instability at the highly delithiated state and low kinetics at the fully lithiated state are arduous challenges to overcome. Here, a facile approach is developed to make secondary particles of Ni-rich materials with nanosheet primary grains. Because the alignment of the primary grains reduces internal stress buildup within the particle during charge-discharge and provides straightforward paths for Li transport, the as-synthesized Ni-rich materials do not undergo cracking upon cycling with higher overall Li + ion diffusion rates. Specifically, a LiNi 0.75 Co 0.14 Mn 0.11 O 2 cathode with nanosheet grains delivers a high reversible capacity of 206 mAh g -1 and shows ultrahigh cycling stability, e.g., 98% capacity retention over 500 cycles in a full cell with a graphite anode.

25 ENERGY STORAGE↗
DOE OSTI2019

Quantification of Anionic Redox Chemistry in a Prototype Na-Rich Layered Oxide

Harnessing anionic redox reactions is of prime importance for boosting the capacity of sodium-ion batteries (NIBs). However, quantifying the cyclability of anionic redox reactions is still challenging. Herein, we conduct a qualitative and quantitative investigation of the cationic and anionic redox reactions of a prototype Na-rich layered oxide, namely, Na 3 RuO 4 , by a combination of bulk-sensitive X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering. We unequivocally reveal that both Ru cations and oxygen anions are involved in the charge compensation process of Na 3 RuO 4 . Ru redox is highly reversible over extended electrochemical cycles, while the cyclability of lattice oxygen redox gradually decreases with the retention of only 36% after 30 cycles, which is mainly responsible for the capacity fading of Na 3 RuO 4 . Finally, our findings provide deeper insights into the complex oxygen redox mechanism, which plays a decisive role for designing high-energy Na-rich electrode materials for NIBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Tuning Oxygen Redox Reaction through the Inductive Effect with Proton Insertion in Li-Rich Oxides

As a parent compound of Li-rich electrodes, Li 2 MnO 3 exhibits high capacity during the initial charge; however, it suffers notoriously low Coulombic efficiency due to oxygen and surface activities. Here, we successfully optimize the oxygen activities toward reversible oxygen redox reactions by intentionally introducing protons into lithium octahedral vacancies in the Li 2 MnO 3 system with its original structural integrity maintained. Combining structural probes, theoretical calculations, and resonant inelastic X-ray scattering results, a moderate coupling between the introduced protons and lattice oxygen at the oxidized state is revealed, which stabilizes the oxygen activities during charging. Such a coupling leads to an unprecedented initial Coulombic efficiency (99.2%) with a greatly improved discharge capacity of 302 mAh g -1 in the protonated Li 2 MnO 3 electrodes. These findings directly demonstrate an effective concept for controlling oxygen activities in Li-rich systems, which is critical for developing high-energy cathodes in batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Conformal PEDOT Coating Enables Ultra-High-Voltage and High-Temperature Operation for Single-Crystal Ni-Rich Cathodes

Single-crystal Ni-rich Li[Ni x Mn y Co 1-x-y ]O 2 (SC-NMC) cathodes represent a promising approach to mitigate the cracking issue of conventional polycrystalline cathodes. However, many reported SC-NMC cathodes still suffer from unsatisfactory cycling stability, particularly under high charge cutoff voltage and/or elevated temperature. Herein, we report an ultraconformal and durable poly(3,4-ethylenedioxythiophene) (PEDOT) coating for SC-NMC cathodes using an oxidative chemical vapor deposition (oCVD) technique, which significantly improves their high-voltage (4.6 V) and high-temperature operation resiliency. The PEDOT coated SC LiNi 0.83 Mn 0.1 Co 0.07 O 2 (SC-NMC83) delivers an impressive capacity retention rate of 96.7% and 89.5% after 100 and 200 cycles, respectively. Significantly, even after calendar aging at 45 degrees C and 4.6 V, the coated cathode can still retain 85.3% (in comparison with 59.6% for the bare one) of the initial capacity after 100 cycles at a 0.5 C rate. Synchrotron X-ray experiments and interface characterization collectively reveal that the conformal PEDOT coating not only effectively stabilizes the crystallographic structure and maintains the integrity of the particles but also significantly suppresses the electrolyte's corrosion, resulting in improved electrochemical/thermal stability. Our findings highlight the promise of an oCVD PEDOT coating for single-crystal Ni-rich cathodes to meet the grand challenge of high-energy batteries under extreme conditions.

25 ENERGY STORAGE↗
DOE OSTI2025

Modulating Surface Anionic Redox Chemistry toward Highly Stable Li-Rich Cathodes with Negligible Oxygen Loss

Low initial Coulombic efficiency and severe capacity/voltage fading during cycling caused by serious irreversible oxygen release, especially in the initial cycle, and resultantly induced unstable electrode/electrolyte interfacial chemistry, largely prohibit the commercial application of high-capacity Li-rich layered oxide cathodes (LLOs). Here, in this work, a dual reductive gas interface cotreatment strategy is applied to regulate the lattice oxygen redox activity and reversibility with a multiple defective structure design including Li/O/TM (TM = transition metal) vacancies and the intrinsic TM doping as well as a full-surface protective layer, which can suppress the irreversible TM migration and then undesirable phase transformation, resisting the corrosion of electrolyte during cycling effectively. Importantly, the introduced reversible SO 3 2- /SO 4 2- redox couple that provides extra capacity compensation could alleviate the distortion of oxygen-central octahedral structure and structural collapse caused by immoderate oxygen oxidation. Thus, the lattice oxygen redox chemistry is optimized, with negligible oxygen loss during the initial cycle. And the designed AS-LLO cathode with greatly enhanced structure stability shows high-capacity retentions of 99.2% at 0.3C after 100 cycles and 82.4% even after 1000 cycles at 5C. This work provides a guideline for manipulating the oxygen redox chemistry to achieve long-lifespan Li-rich layered oxide cathodes for high-energy-density lithium batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Boosting the cycling stability of Ni-rich layered oxide cathode by dry coating of ultrastable Li 3 V 2 (PO 4 ) 3 nanoparticles

Nickel (Ni)-rich layered oxides such as LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) represent one of the most promising candidates for next-generation high-energy lithium-ion batteries (LIBs). However, the pristine Ni-rich cathode materials usually suffer from poor structural stability during cycling. In this work, we demonstrate a simple but effective approach to improve the cycling stability of the NCM622 cathode by dry coating of ultrastable Li 3 V 2 (PO 4 ) 3 -carbon (LVP-C) nanoparticles, which leads to a robust composite cathode (NCM622/LVP-C) without sacrificing the specific energy density compared with pristine NCM622. The optimal NCM622/LVP-C composite presents a high specific capacity of 162 mA h g -1 at 0.5 C and excellent cycling performance with 85.0% capacity retention after 200 cycles at 2 C, higher than that of the pristine NCM622 (67.6%). Systematic characterization confirms that the LVP-C protective layer can effectively reduce the side reactions, restrict the cation mixing of NCM622 and improve its structural stability. Moreover, the NCM622/LVP-C||graphite full cells also show a commercial-level capacity of 3.2 mA h cm -2 and much improved cycling stability compared with NCM622/LVP-C||graphite full cells, indicating the great promise for low-cost, high-capacity and long-life LIBs.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Recent activities for β-decay half-lives and β-delayed neutron emission of very neutron-rich isotopes

Beta-delayed neutron (βn) emitters play an important, two-fold role in the stellar nucleosynthesis of heavy elements in the 'rapid neutron-capture process' (r process). On one hand they lead to a detour of the material β-decaying back to stability. On the other hand, the released neutrons increase the neutron-to-seed ratio, and are re-captured during the freeze-out phase and thus influence the final solar r-abundance curve. A large fraction of the isotopes inside the r-process reaction path are not yet experimentally accessible and are located in the (experimental) 'Terra Incognita'. With the next generation of fragmentation and ISOL facilities presently being built or already in operation, one of the main motivation of all projects is the investigation of these very neutron-rich isotopes. A short overview of one of the planned programs to measure βn-emitters at the limits of the presently know isotopes, the BRIKEN campaign (Beta delayed neutron emission measurements at RIKEN) will be given. Presently, about 600 β-delayed one-neutron emitters are accessible, but only for a third of them experimental data are available. Reaching more neutron-rich isotopes means also that multiple neutron-emission becomes the dominant decay mechanism. About 460 β-delayed two-, three-or four-neutron emitters are identified up to now but for only 30 of them experimental data about the neutron branching ratios are available, most of them in the light mass region below A=30. The International Atomic and Energy Agency (IAEA) has identified the urgency and picked up this topic recently in a 'Coordinated Research Project' on a 'Reference Database for Beta-Delayed Neutron Emission Data'. This project will review, compile, and evaluate the existing data for neutron-branching ratios and half-lives of β-delayed neutron emitters and help to ensure a reliable database for the future discoveries of new isotopes and help to constrain astrophysical and theoretical models.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2015

From laser particle acceleration to the synthesis of extremely neutron rich isotopes via the novel fission-fusion mechanism

High-power, short pulse lasers have emerged in the last decade as attractive tools for accelerating charged particles (electrons, ions) to high energies over mm-scale acceleration lengths, thus promising to rival conventional acceleration techniques in the years ahead. In the first part of the article, the principles of laser-plasma interaction as well as the techniques and the current status of the acceleration of electron and ion beams will be briefly introduced. In particular with the upcoming next generation of multi-PW class laser systems, such as the one under construction for the ELI-Nuclear Physics project in Bucharest (ELI-NP), very efficient acceleration mechanisms for brilliant ion beams like radiation pressure acceleration (RPA) come into reach. Here, ultra-dense ion beams reaching solid-state density can be accelerated from thin target foils, exceeding the density of conventionally accelerated ion beams by about 14 orders of magnitude. This unique property of laser-accelerated ion beams can be exploited to explore the scenario of a new reaction mechanism called ‘fission-fusion’, which will be introduced in the second part of the article. Accelerating fissile species (e.g. {sup 232}Th) towards a second layer of the same material will lead to fission both of the beam-like and target-like particles. Due to the close to solid-state density of the accelerated ion bunches, fusion may occur between neutron-rich (light) fission products. This may open an access path towards extremely neutron-rich nuclides in the vicinity of the N=126 waiting point of the astrophysical r process. ‘Waiting points’ at closed nucleon shells play a crucial role in controlling the reaction rates. However, since most of the pathway of heavy-element formation via the rapid-neutron capture process (r-process) runs in ‘terra incognita’ of the nuclear landscape, in particular the waiting point at N=126 is yet unexplored and will remain largely inaccessible to conventional nuclear reaction schemes even at next-generation radioactive beam facilities, underlining the attractive perspectives offered, e.g., by ELI-NP.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Co-free gradient lithium-rich cathode for high-energy batteries with optimized cyclability

Lithium-rich layered oxides (LLOs) hold the promise for high-energy battery cathodes. However, its application has been hindered by voltage decay associated with irreversible reactions at high voltages despite decades of intensive efforts. Here, we first theoretically studied the molecular orbitals of Mn-based Li-rich configurations. We found that the π-bond ring formed within the LiMn 6 structure could participate in stable redox reactions as one unit, but Co could disrupt its symmetry. We thus designed and synthesized Co-free concentration-gradient LLOs (CF-CG-LLOs) materials. The combination of concentration gradient and Co removal leads to exceptional capacity retention without any fading over 100 cycles of the pouch cell. More importantly, it exhibits an extraordinarily low voltage decay of 0.15 mV/cycle, accompanied by a high Coulombic efficiency of 99.86%. This concept and demonstration of CF-CG-LLO cathodes reveal a viable avenue toward low-cost, high-energy-density battery cathodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Changes of deformed shell gaps at N ~ 100 in light rare-earth, neutron-rich nuclei

There have been compelling evidences indicating that deformed single-particle states in neutron- rich regions are different from those in the stable region. It was pointed out that for the light rare- earth (60Nd, 62Sm, and 64Gd), neutron-rich (N = 98-102) nuclei, the Woods-Saxon potential, the Nilsson modified oscillator potential with "universal" parameters, and the folded Yukawa potential all failed to describe the correct ordering of neutron single-particle states. The location and size of deformed shell gaps in this mass region are under current debate. We propose a modification for the "standard" Nilsson parameters of Bengtsson and Ragnarsson introduced in 1985. The proposed N-dependent spin-orbit interaction brings an effect of the tensor force for the deformed potential, which causes dynamic changes in deformed shell gaps with neutron number and deformation. By applying the modified Nilsson parameters to generate deformed bases for the Projected Shell Model, we demonstrate that the calculation can explain consistently the current experimental data, including the ground state configuration in odd-neutron nuclei, upbending of the yrast moment of inertia at higher spins and the energies of 2-quasineutron 6- and 4- isomers in even-even nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Enhanced dynamics in fusion of neutron-rich oxygen nuclei at above-barrier energies

Above-barrier fusion cross sections for an isotopic chain of oxygen isotopes with A = 16 –19 incident on a C 12 target are presented. Experimental data are compared with both static and dynamical microscopic calculations. Here, these calculations are unable to explain the ≈ 37 % increase in the average above-barrier fusion cross section observed for O 19 as compared to β -stable oxygen isotopes. This result suggests that for neutron-rich nuclei existing time-dependent Hartree-Fock calculations underpredict the role of dynamics at near-barrier energies. High-quality measurement of above-barrier fusion for an isotopic chain of increasingly neutron-rich nuclei offers an effective means to probe this fusion dynamics.

6 ≤ A ≤ 19↗
DOE OSTI2019

Stabilizing Li-rich NMC Materials by Using Precursor Salts with Acetate and Nitrate Anions for Li-ion Batteries

Lithium-rich layered oxide cathode materials of Li 1.2 Mn 0.5100 Ni 0.2175 Co 0.0725 O 2 have been synthesized using metal salts with acetate and nitrate anions as precursors in glycerol solvent. The effects of the precursor metal salts on particle size, morphology, cationic ordering, and ultimately, the electrode performance of the cathode powders have been studied. It was demonstrated that the use of cornstarch as a gelling agent with nitrate-based metal salts results in a reduction of particle size, leading to higher surface area and initial discharge capacity. However, the cornstarch gelling effect was minimized when acetate salts were used. As observed in the Fourier-transform infrared spectroscopy analysis, cornstarch can react with acetates to form acetyl groups during the synthesis, effectively preventing the cornstarch gel from capping the particles, thus leading to larger particles. A tradeoff was found when nitrate and acetate salts were mixed in the synthesis. It was shown that the new cathode powder has the best cationic ordering and capacity retention, promising a much stable Li-rich cathode material for lithium-ion batteries.

25 ENERGY STORAGE↗
NASA NTRS1995

Stable loop in the crystal structure of the intercalated four-stranded cytosine-rich metazoan telomere

In most metazoans, the telomeric cytosine-rich strand repeating sequence is d(TAACCC). The crystal structure of this sequence was solved to 1.9-A resolution. Four strands associate via the cytosine-containing parts to form a four-stranded intercalated structure held together by C.C+ hydrogen bonds. The base-paired strands are parallel to each other, and the two duplexes are intercalated into each other in opposite orientations. One TAA end forms a highly stabilized loop with the 5' thymine Hoogsteen-base-paired to the third adenine. The 5' end of this loop is in close proximity to the 3' end of one of the other intercalated cytosine strands. Instead of being entirely in a DNA duplex, this structure suggests the possibility of an alternative conformation for the cytosine-rich telomere strands.

NASA Discipline Exobiology↗
DOE OSTI2021

Hydration‐Induced β‐Sheet Crosslinking of α‐Helical‐Rich Spider Prey‐Wrapping Silk

Abstract Due to its moderate strength (≈700 MPa) and impressive extensibility before breaking (≈60–80%), orb‐weaving spider aciniform (AC) prey‐wrapping silks are actually the toughest of the spider silks but are remarkably understudied. The previous results indicate that native AC silk fibers are an α‐helix rich coiled‐coil/β‐sheet hybrid nanofiber, and that conversion of disordered or helical domains to β‐sheet aggregates is surprisingly minimal and overall β‐sheet content is low (≈15%). In this work, it is demonstrated through scanning electron microscopy that native AC silk fibers undergo matted cross‐linking upon exposure to moisture that increases silk stiffness. The unique molecular mechanism of water‐induced cross‐linking is revealed with solid‐state NMR (SSNMR) methods; water‐induced morphological changes are correlated with an increase in AC silk protein β‐sheet content, and additionally a minor unfolding of coiled‐coil regions is observed. Continued and increased β‐sheet cross‐linking is observed upon application of mechanical shear. The size of these β‐sheet domains to be 4–6 nm using Wide‐Line Separation SSNMR is determined. The observation that merely water treatment can be used to convert a protein‐based material from a flexible/extensible α‐helix‐rich fiber to a rigid crossed‐linked β‐sheet mat is a novel observation that should provide new avenues in bioinspired materials design.

Stengel, Dillan↗