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Results for “Surface Instability”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Avoiding surface instability and slurry jamming in simultaneous multilayer coating of structured particulate films

Simultaneous multilayer coating techniques are widely known, but their industrial application remains limited to narrow market sectors. One barrier to adoption may be the mismatch between industries that are familiar with such processes but have no need, and industries that have need but are not familiar. Moreover, there are application-specific technical challenges to developing multilayer-coating processes. In this article, we describe our resolution of two specific issues in simultaneous multilayer coating of all aqueous highly loaded slurries for new and emerging energy applications. The first issue is particle jamming (associated with Shear-thickening) of the highly loaded slurries in the die internals, which we alleviated by adding small amounts of viscosity modifiers without reducing the solid loading. The second issue is a Marangoni-driven surface instability that resembles top layer de-wetting, which we solved by carefully selecting surfactants to tune the dynamic surface tensions of each slurry. Both issues were resolved early in a step-wise development, saving significant development cost which in our case was driven by expensive materials.

08 HYDROGEN↗
DOE OSTI2025

Mechanistic Insights into the Surface Instabilities of TiNb 2 O 7, a High‐Power Li‐Ion Anode

TiNb 2 O 7 (TNO) is a promising Li-ion battery anode for high-power applications, such as implantable medical devices and heavy-duty equipment. Hailed as being safe due to its elevated operating potential near 1.6 V, TNO has long been assumed to be highly stable in the carbonate-based electrolytes used in Li-ion batteries. Herein, all mechanisms occurring at the surface of both TNO and Nd-doped TNO are identified, and both materials in fact show significant gassing. CO 2 is even released at open circuit conditions, demonstrating the poor chemical stability of the material in the electrolyte even prior to battery operation. Such extreme instability is a critical safety concern. In addition, it was found that Ti dissolves from the surface of TNO particles at low voltage (below 1.4 V vs Li), and in fact deposits on the counter electrode. Ti further inside TNO particles then diffuses to the Ti-poor surface during discharge. Partial carbon-coating as a mitigating measure has also been tested and found to exacerbate these processes. The findings identify novel reactions occurring within TNO, and clearly highlight the need to stabilize the surfaces of TNO in order to prevent such aggressive deterioration at the surface of the particles.

25 ENERGY STORAGE↗
DOE OSTI2023

Single monkey-saddle singularity of a Fermi surface and its instabilities

Fermi surfaces can undergo sharp transitions under smooth changes of parameters. Such transitions can have a topological character, as is the case when a higher-order singularity, one that requires cubic or higher-order terms to describe the electronic dispersion near the singularity, develops at the transition. When time-reversal and inversion symmetries are present, odd singularities can only appear in pairs within the Brillouin zone. In this case, the combination of the enhanced density of states that accompanies these singularities and the nesting between the pairs of singularities leads to interaction-driven instabilities. Here, we present examples of single n = 3 (monkey-saddle) singularities when time-reversal and inversion symmetries are broken. We then turn to the question of what instabilities are possible when the singularities are isolated. For spinful electrons, we find that the inclusion of repulsive interactions destroys any isolated monkey-saddle singularity present in the noninteracting spectrum by developing Stoner or Lifshitz instabilities. In contrast, for spinless electrons and at the mean-field level, we show that an isolated monkey-saddle singularity can be stabilized in the presence of short-range repulsive interactions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results

Recent studies have suggested that Co-free, Ni-rich layered cathodes (e.g., doped LiNiO2) can provide promising battery performance for practical applications. However, these layered cathodes suffer from significant surface instability during various stages of the sample history, which generates inherent challenges for achieving stable battery performance and obtaining statistically representative characterization results. To reliably report the surface chemistry of these materials, delicate controls of stepwise sample preparation are required. In this study, we aim to reveal how the surface chemistry of LiNiO2 based materials changes with various environments, including human exhalation, sample storage, sample preparation, electrochemistry cycling, and surface doping. Our results demonstrate that the surface of these materials is highly reactive and prone to alter at various stages of sample handling and characterization. The sensitive surface could impact the interpretation of the surface chemical and structural information, including surface carbonate formation, transition metal reduction and dissolution, and surface reconstruction. Importantly, the heterogeneity of the surface degradation calls for a consolidation of nanoscale, high-resolution characterization, and ensemble-averaged methods in order to improve statistical representation. Furthermore, the doping chemistry can effectively mitigate the surface degradation and improve overall battery performance due to the enhanced surface oxygen retention. Our study highlights the necessity of strict measurements through complementary characterizations at multiple length scales to eliminate unintentional biased conclusions.

surface chemistry, Co-free Ni-rich cathodes, Istab↗
DOE OSTI2021

Origin of the quasi-quantized Hall effect in ZrTe 5

The quantum Hall effect (QHE) is traditionally considered to be a purely two-dimensional (2D) phenomenon. Recently, however, a three-dimensional (3D) version of the QHE was reported in the Dirac semimetal ZrTe 5 . It was proposed to arise from a magnetic-field-driven Fermi surface instability, transforming the original 3D electron system into a stack of 2D sheets. Here, we report thermodynamic, spectroscopic, thermoelectric and charge transport measurements on such ZrTe 5 samples. The measured properties: magnetization, ultrasound propagation, scanning tunneling spectroscopy, and Raman spectroscopy, show no signatures of a Fermi surface instability, consistent with in-field single crystal X-ray diffraction. Instead, a direct comparison of the experimental data with linear response calculations based on an effective 3D Dirac Hamiltonian suggests that the quasi-quantization of the observed Hall response emerges from the interplay of the intrinsic properties of the ZrTe 5 electronic structure and its Dirac-type semi-metallic character.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Measurement of Ehrlich-Schwoebel barrier contribution to the self-organized formation of ordered surface patterns on Ge(001)

Normal-incidence 1-keV Ar + ion bombardment leads to amorphization and ultrasmoothing of Ge at room temperature, but at elevated temperatures the Ge surface remains crystalline and is unstable to the formation of self-organized nanoscale patterns of ordered pyramid-shaped pits. The physical phenomenon distinguishing the high-temperature patterning from room-temperature ultrasmoothing is believed to be a surface instability due to the Ehrlich-Schwoebel barrier for diffusing vacancies and adatoms, which is not present on the amorphous material. This real-time grazing-incidence small-angle x-ray scattering study compares smoothing of a prepatterned Ge sample at room temperature with patterning of an initially flat Ge sample at an elevated temperature. In both experiments, when the nanoscale structures are relatively small in height, the average kinetics can be explained by a linear theory. Furthermore, the linear theory coefficients, indicating surface stability or instability, were extracted for both experiments. A comparison between the two measurements allows estimation of the contribution of the Ehrlich-Schwoebel barrier to the self-organized formation of ordered nanoscale patterns on crystalline Ge surfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Mitigation of rapid capacity decay in silicon-LiNi 0.6 Mn 0.2 Co 0.2 O 2 full batteries

Silicon (Si)-based materials have been considered as the most promising anode materials for high-energy-density lithium-ion batteries because of their higher storage capacity and similar operating voltage, as compared to the commercial graphite (Gr) anode. But the use of Si anodes including silicon-graphite (Si-Gr) blended anodes often leads to rapid capacity decay in Si-Gr/LiNixMnyCo z O 2 (x+y+z=1) full cells, which has been attributed to surface instability of the Si component. In addition to stabilizing the surface, this work investigates the potential of the Si-Gr blended anodes in a full-cell configuration and its impact on the capacity contribution from active components. Using dQ/dV plots of the full cells, a powerful but simple-to-implement differential potential approach is developed to decouple the capacity contribution and degradation from the graphite and silicon components. Data collected from three-electrode cells confirm the results from the differential potential approach, which suggests a voltage slippage to a higher voltage at the blended anode side. Additionally, the voltage slippage causes a reduced utilization of the Gr component and exacerbates side reactions between the Si-Gr anode and carbonate electrolytes. Furthermore, based on these failure mechanisms, we adopted a mitigation strategy to tune the open circuit voltage of the prelithiated anode while stabilizing the surface. As a result, the full cells with the modified Si-Gr anodes (mass loading, 2.5 mAh/cm 2 ) offer a highly reversible full-cell energy density of 390 Wh/kg (based on the mass of both anode and cathode materials in a full cell) with a cycling CE of 99.9% over 200 cycles.

25 ENERGY STORAGE↗
DOE OSTI2026

Charge density wave in a band insulator

Charge-density-wave implies a periodic modulation of the charge density. Typically observed in metallic systems, charge-density-wave arise from Fermi surface instabilities, resulting in the total or partial gapping of the Fermi surface. Here, we present experimental evidence for a charge-density wave state emerging in a band insulator which has no Fermi surface. The bulk and surface of our material platform, 𝛂-Bi 4 Br 4 , is gapped over the entire Brillouin zone. Through topographic and spectroscopic imaging at low temperatures, we unveil an unexpected unidirectional charge modulation in 𝛂-Bi 4 Br 4 , breaking the lattice translation symmetry. The charge-density-wave develops at temperatures below 40 K and adds an energy gap atop the existing insulating gap of 𝛂-Bi 4 Br 4 . Furthermore, our transport measurements reveal nonlinear electrical conduction, a phenomenon conventionally associated with the sliding or phason mode of incommensurate charge-density-waves. These unusual observations represent a different type of charge-density-wave

Phase transitions and critical phenomena↗
DOE OSTI2021

Nanoscale dynamics during self-organized ion beam patterning of Si. II. Kr + bombardment

Understanding the self-organized ion beam nanopatterning of elemental semiconductors, particularly silicon, is of intrinsic scientific and technological interest. This is the second component of a two-part coherent x-ray scattering and x-ray photon correlation spectroscopy (XPCS) investigation of the kinetics and fluctuation dynamics of nanoscale ripple development on silicon during 1 keV Ar + (part I) and Kr + bombardment at 65° polar angle. Here it is found that the ion-enhanced viscous flow relaxation is essentially equal for Kr + -induced patterning as previously found for Ar + patterning despite the difference in ion masses. However, the magnitude of the surface curvature-dependent roughening rate in the early-stage kinetics is larger for Kr + than for Ar + , consistent with expectations that the heavier ion gives an increased mass redistributive contribution to the initial surface instability. As with the Ar + case, fluctuation dynamics in the late stage show a peak in correlation times at the length scale corresponding to the dominant structural feature on the surface—the ripples. Finally, it is shown that speckle motion during the surface evolution can be analyzed to determine spatial inhomogeneities in erosion rate and ripple velocity. This allows the direction and speed of ripple motion to be measured in a real time experiment. In the present case, ripple motion is found to be into the projected direction of the ion source, in contrast to expectations from an existing sputter erosion driven model with parameters derived from binary collision approximation simulations.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In–Depth Analysis of the Degradation Mechanisms of High–Nickel, Low/No–Cobalt Layered Oxide Cathodes for Lithium–Ion Batteries

A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi 0.883 Co 0.053 Al 0.064 O 2 (NCA-89) leads to a loss of active material and an increase in surface area, thereby exacerbating structural and surface instabilities, accelerating impedance and polarization growth, and ultimately reducing their capacity retentions. LiNi 0.89 Mn 0.044 Co 0.042 Al 0.013 Mg 0.011 O 2 (NMCAM-89) and NMA-89 experience subdued surface reactions and maintain spherical particle structures, both of which are conducive to their capacity retentions during long-term cycling. Furthermore, this investigation offers insights into how specific transition-metal ions dictate the electrochemical stability of high-Ni layered oxide cathode materials, highlights the benefit of Mn-Al combination in NMA-89, and presents potential strategies to further enhance the performance of this novel class of cathode materials.

degradation mechanisms↗
DOE OSTI2021

Identification of a low-energy metastable 1 T -type phase for monolayer VSe 2

Elucidating the polymorphism of transition metal dichalcogenide layers and the interplay between structure and properties is a key challenge for the application of these materials. We identify a low-energy metastable phase of monolayer VSe 2 and elucidate its magnetic and electronic properties. This structure is distinct from the previously identified charge density wave (CDW) phase. However, while having rather distinct properties it is very close in energy to the CDW phase and is likely to be realized in experiments. Importantly, local bonding instabilities, as characterized by reconstruction of the electronic structure over a wide energy range, are important for this distortion, which includes both V off-centering in the octahedral coordination cages and a partial disproportionation into two distinct types of V. The phase does not have a ferromagnetic ground state. Furthermore, the results show that the physics of 1T–VSe 2 are richer than previously known with an interplay of Fermi surface instabilities and local bonding effects.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Order-disorder charge density wave instability in the kagome metal (Cs,Rb)V 3 Sb 5

The origin of the charge density wave phases in the kagome metal compound AV 3 Sb 5 is still under great scrutiny. Here, we combine diffuse and inelastic x-ray scattering to identify a 3-dimensional precursor of the charge order at the L point that condenses into a CDW through a first order phase transition. The quasi-elastic critical scattering indicates that the dominant contribution to the diffuse precursor is the elastic central peak without phonon softening. However, the inelastic spectra show a small broadening of the Einstein-type phonon mode on approaching T CDW . Our results point to the situation where the Fermi surface instability at the L point is of order-disorder type with critical growth of quasi-static domains. The experimental data indicate that the CDW consists on an alternating Star of David and trihexagonal distortions and its dynamics goes beyond the classical weak-coupling scenario and is discussed within strong-electron phonon coupling and non-adiabatic models.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials

High-nickel content cathode materials offer high energy density. However, the structural and surface instability may cause poor capacity retention and thermal stability of them. To circumvent this problem, nickel concentration-gradient materials have been developed to enhance high-nickel content cathode materials’ thermal and cycling stability. Even though promising, the fundamental mechanism of the nickel concentration gradient’s stabilization effect remains elusive because it is inseparable from nickel’s valence gradient effect. To isolate nickel’s valence gradient effect and understand its fundamental stabilization mechanism, we design and synthesize a LiNi 0.8 Mn 0.1 Co 0.1 O 2 material that is compositionally uniform and has a hierarchical valence gradient. The nickel valence gradient material shows superior cycling and thermal stability than the conventional one. The result suggests creating an oxidation state gradient that hides the more capacitive but less stable Ni 3+ away from the secondary particle surfaces is a viable principle towards the optimization of high-nickel content cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2021

Core–Multishell-Structured Digital-Gradient Cathode Materials with Enhanced Mechanical and Electrochemical Durability

Ni-rich cathode materials provide high energy density, but their structural and surface instability limits their cyclability and thermal stability. As one of the approaches to mitigate this problem, cathode materials comprising Ni-rich high-capacity core wrapped in Mn-rich multiple shells are produced successfully. In contrast to the conventional batch-type process for concentration-gradient materials, a digital-gradient cascade coprecipitation process described here achieves the improvements in productivity and quality consistency needed to move toward large-scale manufacturing. The core-multishell cathode materials produced in this manner not only have longer cycle life and improved rate performance compared to homogeneous Ni-rich cathode materials having the same overall composition, but also show remarkably enhanced thermal stability and low impedance growth characteristics. In a novel attempt to determine the correlation between the mechanical properties of the core-multishell cathode particles and their electrochemical cyclabilities, their breaking force and elasticity were successfully measured using a statistical approach, which indicates that a cathode particle with stable surface composition as well as high breaking force has improved capacity retention and durability. These results guide the realization of long life and high thermal stability in Ni-rich cathode materials through heterogeneous particle engineering.

25 ENERGY STORAGE↗
DOE OSTI2023

Demarcating the Impact of Electrolytes on High–Nickel Cathodes and Lithium–Metal Anode

The ever-growing demand for low-cost, high-energy-density lithium-ion batteries (LIBs) makes high-nickel layered oxide cathodes, especially LiNiO 2 (LNO), one of the most appealing candidates. However, poor structural and surface instability that leads to a short cycle life remains a formidable challenge. Herein, a systematic investigation of LNO performance in two different electrolytes (a conventional carbonate-based LP57 electrolyte and an ether-based localized high-concentration electrolyte (LHCE)) with different charge cut-off voltages is presented. These findings show that the cathode-electrolyte reactivity is the main factor dictating the performance degradation of LNO at high voltages rather than bulk integrity. While LHCE can provide good stability beyond 4.2 V with a robust, uniform solid–electrolyte interphase (SEI) layer on the Li-metal anode, there is no significant difference in cyclability at 4.15 V (96% capacity retention after 200 cycles) for both LP57 and LHCE. From LNO symmetric cells, carbonate-based electrolyte is found to be good for LNO stability while ether-based electrolyte is beneficial toward Li-metal anode. Furthermore, a suitable electrolyte or a low cut-off voltage is necessary to maintain a decent cycle life. Altogether, this work highlights the impact of electrolyte and cut-off voltage on LNO and Li-metal, which can help guide the development of cells based on LNO.

25 ENERGY STORAGE↗
DOE OSTI2024

Effects of Calcination Conditions on the Structural and Electrochemical Behaviors of High‐Nickel, Cobalt‐Free LiNi 0.9 Mn 0.1 O 2 Cathode

Abstract Eliminating cobalt from high‐nickel layered oxide cathodes lowers the cost of lithium‐ion batteries for electric vehicles. However, cobalt‐free cathodes with high Mn 4+ and Ni 2+ contents are prone to Li/Ni mixing after synthesis, potentially compromising battery energy density, rate capability, and cycling stability. Without cobalt facilitating cation ordering in the layered structure, the degree of Li/Ni mixing in cobalt‐free cathodes depends heavily on the calcination conditions. In this study, a systematic exploration of calcination temperatures and LiOH ratio for LiNi 0.9 Mn 0.1 O 2 (NM‐90) provides detailed insights into the optimal synthesis conditions for high‐capacity cobalt‐free cathodes with extended cycle life. Surprisingly, high Li/Ni mixing does not necessarily lead to poor cycling stability whereas low Li/Ni mixing does not guarantee a long cycle life. More importantly, although excessive calcination temperature can further decrease Li/Ni mixing, it does not necessarily enhance capacity. Instead, the pernicious effects from the H2 → H3 phase transition are amplified due to a pronounced two‐phase reaction. An extensive suite of chemical and structural characterization methods uncovers a correlation between elevated calcination temperature, phase transformation, cation ordering, and capacity fading behavior: “overcooking” high‐nickel, cobalt‐free cathodes induce structural arrangement toward that of LiNiO 2 , with exacerbated lattice distortion and surface instability accelerating capacity fade.

Lee, Steven↗
DOE OSTI2022

Experimentally validated high-fidelity simulations of a liquid jet in supersonic crossflow

Here, utilizing recent advancements in computational schemes for compressible, multiphase flows, this work features a parametric study of a pure liquid jet in supersonic crossflow that involves simulating the atomization process for four values of momentum-flux ratio. These simulations are validated against experimental results measured with high-speed X-ray imaging, which confirm the accuracy of the numerical approach. Also, the effect of numerical resolution on some flow behavior is investigated, revealing convergence of the jet shape and surface instability wavelength. Analysis of the resulting sprays includes statistical descriptions of the liquid distribution, liquid structures created through breakup, interfacial instabilities, and dominant flow features. As the flowrate increases, the spray penetrates further, it becomes more disperse, and less liquid impacts the wall, but the droplet size distribution changes little. The wavelength of instabilities on the windward side of the jet diverges from measured trends in subsonic crossflows. In a visualization of the time-averaged flow, counter-rotating vortices are observed along the jet core and in the wake, affecting the process of primary atomization and early droplet trajectories.

42 ENGINEERING↗
DOE OSTI2024

Anharmonic strong-coupling effects at the origin of the charge density wave in CsV 3 Sb 5

The formation of charge density waves is a long-standing open problem, particularly in dimensions higher than one. Various observations in the vanadium antimonides discovered recently further underpin this notion. Here, we study the Kagome metal CsV3Sb5 using polarized inelastic light scattering and density functional theory calculations. We observe a significant gap anisotropy with 2Δ max /κ B T CDW ≈ 20, far beyond the prediction of mean-field theory. The analysis of the A 1g and E 2g phonons, including those emerging below T CDW , indicates strong phonon-phonon coupling, presumably mediated by a strong electron-phonon interaction. Similarly, the asymmetric Fano-type lineshape of the A 1g amplitude mode suggests strong electron-phonon coupling below T CDW . The large electronic gap, the enhanced anharmonic phonon-phonon coupling, and the Fano shape of the amplitude mode combined are more supportive of a strong-coupling phonon-driven charge density wave transition than of a Fermi surface instability or an exotic mechanism in CsV 3 Sb 5 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗