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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Rapid charging made practical in graphite-based lithium batteries: surface-acoustic wave turbulent electrolyte mixing to overcome diffusion limited charging rates [Final Report]

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer’s depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li+ ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles. 0.1. Turbulent acoustic streaming mixes the electrolyte during charging—even with separator Our proposed 100-MHz SAW device used to recirculate the electrolyte is compatible with lithium- ion battery electrochemistry, as it is made in our lab of single-crystal lithium niobate. Their solution is straightforward to drive from a DC power source alongside the signal provided during battery charging. The device is only needed during charging and does not consume power dur- ing battery discharge. Uniquely, SAW generates extreme accelerations of over 1 billion meters per second squared in the fluid, driving turbulent mixing from centimeter to submicron length scales, even through the porous separator materials that tend to be used in batteries, all while avoiding interfering with the anode’s solid electrolyte interphase layer that forms during use. By employing novel fluid mechanics, the investigators are proposing a new direction for battery research away from direct use of materials science and electrochemistry. The chemistry agnostic solution may be employed in any battery chemistry that makes use of liquid electrolytes, providing a broader transformative benefit to the battery research community. They are to produce a series of prismatic and 20700-cell sized 2 Ah batteries capable of being charged and discharged at least 500 times without more than 20% loss in battery capacity, and to provide analysis tools useful to the battery research and development community for adopting this approach for other battery chemistries and configurations.

25 ENERGY STORAGE↗
DOE OSTI2021

Rapid Charging Made Practical in Graphite-Based Lithium Batteries: Surface-Acoustic Wave Turbulent Electrolyte Mixing to Overcome Diffusion Limited Charging Rates

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer's depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles.

25 ENERGY STORAGE↗
DOE OSTI2021

Application of electron backscatter diffraction techniques to quantify effects of aging on sub-grain and spatial heterogeneity in NMC cathodes

Identification and evaluation of structural heterogeneity in spent cathode materials is crucial to developing appropriate remediation strategies for novel recycling processes. Native heterogeneities may be exacerbated during the cell's operational lifetime, as sub-particle-scale variations induce anisotropic expansion and contraction upon cycling. Structural transformations resulting from repeated cycling and calendar aging predominantly occur at the secondary particle surface and at the grain boundaries (GBs) between primary particles. However, the diffusion and stress build up around and across GBs are poorly understood. In this study, electron backscatter diffraction (EBSD) is employed to track sub-grain lattice structure across a statistically relevant number of Li(Ni0.33Mn0.33Co0.33)O2 (NMC-111) particles. Specifically, differences in lattice misorientation – measured as the deviation from the grain's average orientation – are tracked as a function of position within the electrode (near current collector, middle, and near separator) and as a function of electrochemical cycling. Further, a novel method of structural analysis is developed, offering insight into sub-grain diffusion behavior by comparing lattice misorientation near the grain boundary versus in the grain bulk. The present results suggest that electrode-scale spatial heterogeneity in lattice structure is induced by initial manufacturing conditions, and that radial gradients in lattice misorientation evolve at the primary particle scale with repeated electrochemical cycling.

25 ENERGY STORAGE↗
DOE OSTI2023

Stabilized lithium metal oxide electrode material and method of preparation

A stabilized lithium metal oxide cathode material comprises microparticles of lithium metal oxide in which individual particles thereof a core of lithium metal oxide and a coating of a different lithium metal oxide surrounding the core. There is an interface layer between the cores and the coatings in which there are gradients of metal ions in the direction of coating to core. The materials are made by a three stage process involving coprecipitating precursor metal hydroxide core particles at a controlled pH; coprecipitating a different metal hydroxide coating on the particles without controlling the pH; and then calcining the resulting coated precursor particles with lithium hydroxide to form the stabilized lithium metal oxide material.

Lipson, Albert L.↗
DOE OSTI2024

Stabilized lithium metal oxide electrode material and method of preparation

A stabilized lithium metal oxide cathode material comprises microparticles of lithium metal oxide in which individual particles thereof a core of lithium metal oxide and a coating of a different lithium metal oxide surrounding the core. There is an interface layer between the cores and the coatings in which there are gradients of metal ions in the direction of coating to core. The materials are made by a three stage process involving coprecipitating precursor metal hydroxide core particles at a controlled pH; coprecipitating a different metal hydroxide coating on the particles without controlling the pH; and then calcining the resulting coated precursor particles with lithium hydroxide to form the stabilized lithium metal oxide material.

Lipson, Albert L.↗
DOE OSTI2021

Efficient Hydrogen Delivery for Microbial Electrosynthesis via 3D-Printed Cathodes

The efficient delivery of electrochemically in situ produced H 2 can be a key advantage of microbial electrosynthesis over traditional gas fermentation. However, the technical details of how to supply large amounts of electric current per volume in a biocompatible manner remain unresolved. Here, we explored for the first time the flexibility of complex 3D-printed custom electrodes to fine tune H 2 delivery during microbial electrosynthesis. Using a model system for H 2 -mediated electromethanogenesis comprised of 3D fabricated carbon aerogel cathodes plated with nickel-molybdenum and Methanococcus maripaludis, we showed that novel 3D-printed cathodes facilitated sustained and efficient electromethanogenesis from electricity and CO 2 at an unprecedented volumetric production rate of 2.2 L CH4 /L catholyte /day and at a coulombic efficiency of 99%. Importantly, our experiments revealed that the efficiency of this process strongly depends on the current density. At identical total current supplied, larger surface area cathodes enabled higher methane production and minimized escape of H 2 . Specifically, low current density (<1 mA/cm 2 ) enabled by high surface area cathodes was found to be critical for fast start-up times of the microbial culture, stable steady state performance, and high coulombic efficiencies. Our data demonstrate that 3D-printing of electrodes presents a promising design tool to mitigate effects of bubble formation and local pH gradients within the boundary layer and, thus, resolve key critical limitations for in situ electron delivery in microbial electrosynthesis.

03 NATURAL GAS↗
DOE OSTI2026

Electro-chemo-mechanically Driven Ni Exsolution from (Pr,Ce,Ni)O 2−δ : Controlled Nucleation Density and Enhanced Electrode Kinetics

In situ exsolution of metal nanoparticles is a promising strategy to prepare electrocatalysts with enhanced activity and resistance to agglomeration for efficient chemical transformations and energy conversion. Achieving a high nucleation density of nanoparticles under mild conditions and understanding how to tailor the process is important for performance of these electrodes in electrochemical cells. In this work, we demonstrate facile exsolution of Ni nanoparticles using fluorite-structured (Pr,Ce)O 2−δ as the support oxide, driven by electrochemical potential and aided by the metastability of Ni in the solid solution (elastic driving force). We prepare single-phase oriented thin films of (Pr,Ce,Ni)O 2−δ (NPCO) on (Zr,Y)O 2−δ (YSZ) substrates by pulsed laser deposition. With the aid of a high-throughput electrochemical cell that provides a lateral gradient in Nernst voltage, we apply in situ near-ambient pressure synchrotron X-ray photoelectron spectroscopy and ex situ atomic force microscopy to investigate the impact of electrochemical potential on Ni nucleation density. We find that metallic Ni can be successfully exsolved at 550 °C upon cathodic biasing in 20 mTorr O 2 , and its nucleation density increases with increasing electrochemical driving force/decreasing oxygen chemical potential. We further evaluate the electrochemical performance under highly reducing (fuel electrode) conditions by electrochemical impedance spectroscopy. With the exsolved Ni nanoparticles, the surface exchange coefficient of the NPCO is found to be ∼4× higher than for PCO without exsolution. This work confirms mixed conducting fluorites as beneficial host lattices for facile transition-metal exsolution and suggests the possibility for constructing an all ceria-based electrochemical cell with PCO serving as both the cathode and the anode.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Excellent performance of 650 MHz single-cell niobium cavity after electropolishing

Electropolishing process and cathodes have undergone modification and optimization for both low- and high-beta 650 MHz five-cell niobium cavities for PIP-II. Cavities treated with these modified electropolishing conditions exhibited smooth surfaces and good performance in baseline tests. Nonetheless, due to administrative constraints on project cavities, maximum gradient performance testing was not conducted. This paper presents a study conducted on a single-cell 650 MHz cavity utilizing the optimized electropolishing conditions, highlighting the maximum performance attained for this specific cavity. The cavity tested at 2 K in a vertical cryostat reached a superior accelerating field gradient of 53.3 MV/m at Q0 of 1.6x1010, which is the highest gradient attained for this type of large-sized cavities.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Rotating spokes, potential hump and modulated ionization in radio frequency magnetron discharges

Here, in this work, the transition from the gradient drift instability (GDI) into an m = 1 rotating spoke in the radio frequency magnetron discharge was studied by means of the two-dimensional axial-azimuthal (z–y) particle-in-cell/Monte Carlo collision method. The kinetic model combined with the linear analysis of the perturbation revealed that the cathode sheath (axial) electric field E z triggers the GDI, deforming the local potential until the instability condition is not fulfilled and the fluctuation growth stops in which moment the instability becomes saturated. The potential deformation consequently leads to the formation of the potential hump, surrounding which the azimuthal electric field E y is present. The saturation level of E y was found to be synchronized with and proportional to the time-changing voltage applied at the cathode, resulting in the RF-modulation of the electron heating in the E y due to $\nabla B$ drift. In the saturated stage of the instability, it was shown that the rotation velocity and direction of the spoke present in the simulations agree well with the experimental observation (Panjan 2019 J. Appl. Phys.125 203303). In the instability linear stage, the instability mode wavelength and the growth rate were also found to be in good agreement with the prediction of the GDI linear fluid theory.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Atomic-Level Understanding of Surface Reconstruction Based on Li[Ni x Mn y Co 1–x–y ]O 2 Single-Crystal Studies

The stability of cathode particle surfaces that are directly exposed to the electrolyte is one of the most crucial and determining factors for cathode performance at high operating voltages. Theory has predicted a strong dependence of surface stability on chemical compositions as well as surface facets of layered oxides, yet conflicting results on the correlations exist as most experimental studies focus on cycled secondary particles recovered from composite electrodes. Here, we synthesize well-formed Li[Ni x Mn y Co 1–x–y ]O 2 (NMC) single-crystal samples, carefully define pristine surface properties, and then monitor their evolution with cycling. Atomic-resolution scanning transmission electron microscopy (STEM) imaging and electron energy loss spectroscopy (EELS) analysis show the formation of a surface reconstruction layer (SRL) as well as an extended surface reduction layer on pristine, Li-permeable non-(001) surfaces, even before cycling. We reveal a transition region with chemical gradient, in which the layered structure gradually densifies and eventually transforms into the SRL on the top surface. Contrary to these observations, no SRL is observed on pristine, Li-impermeable (001) surfaces, revealing the facet-dependent nature of surface reconstructions during particle synthesis. Upon electrochemical cycling, significant composition-and facet-dependent SRL growth is observed. The driving force and mechanism for surface reconstruction are further discussed. The present study provides insights into the origin as well as the nature of SRLs, highlighting the significance of surface engineering in cathode material optimization.

25 ENERGY STORAGE↗
DOE OSTI2022

Toward Emittance Measurements at 11.7 GHz Short-Pulse High-Gradient RF Gun

A short pulse high gradient RF gun has been recently tested at Argonne Wakefield Accelerator (AWA) facility. The carried-out test showed that the 1,5-cell gun was able to inject 3 MeV, up to 100 pC bunches at room tem-perature being fed by 9 ns up to 300 MW 11.7 GHz puls-es. The cathode field was as high as about 400 MV/m. So high field is aimed to mitigate repealing Coulomb forces substantially. In accordance with simulations the emit-tance could be as low as less than 0.2 mcm. To obtain so low emittance in the experiment, the gun is assumed to be equipped with a downstream linac to be fed from the same power extractor as the gun itself. Here we report design of the RF power distribution system splitting RF power among the gun and the linac, results of low-power tests, and emittance measurement plans for upcoming new experiment at AWA.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Probing how Ti- and Nb-substitution affect the stability and improve the electrochemical performance of β- and ε-LiVOPO 4

LiVOPO 4 is a promising next-generation multi-electron cathode material, boasting a theoretical capacity of 305 mA h g -1 , significantly higher than any commercially used Li-ion battery cathode material. However, the material still faces several limitations, including the difficulty in attaining the full theoretical capacity at higher rates and capacity fade over several cycles. Here, in this paper, we show that Ti- and Nb-substitution can be used to improve the thermal stability and electrochemical performance of LiVOPO 4 . We show through in situ heating with XRD and a novel gradient heating technique that both Ti- and Nb-substitution cause β-LiVOPO 4 to be stabilized relative to ε-LiVOPO 4 . This is due to transition-metal substitution, which increases the O-vacancy formation energies, pushing the β → ε transition to higher temperatures. We show that it is still possible to synthesize pure-phase ε-LiVOPO 4 through the use of high temperatures to generate these O-vacancies. We show that even 1% of Ti- or Nb-substitution can improve the initial capacity and long term cycling capability of LiVOPO 4 by improving the high-voltage capacity and reducing the capacity fade in both the high- and low-voltage regions. This is due to the overall improved Li + ion diffusion which is caused by an improved charge-transfer resistance during cycling.

25 ENERGY STORAGE↗
DOE OSTI2025

Azimuthal and axial structures in 3D particle-in-cell simulation of Penning discharge

We report the results of a 3D particle-in-cell simulation of cylindrical Penning discharge with the axial magnetic field in the so-called reflex configuration, where the cathode and anti-cathode are biased to the same negative potential. The discharge is supported by thermal electron emission from the cathode. Electron and ion collisions, including ionization, are fully accounted for. The emphasis is on a specific regime in which the plasma potential at the center of the discharge is positive with respect to the chamber walls, serving as an anode. Spatial and temporal scales of the observed azimuthal and axial fluctuations and structures are characterized. It is suggested that azimuthal structures are caused by the dissipative gradient-drift instability. We find that the axial fluctuations related to the plasma-beam instabilities are weakly correlated with the azimuthal perturbations of the density, so that the azimuthal modes rotate as a whole and do not show any axial shear. The behavior of the electric potential is more involved, demonstrating intermittent standing wave and propagating structures in the axial direction that modulate the electron transport, producing the standing wave pattern (along the z-direction) in the radial electron flux.

3D PIC simulation of discharge↗
DOE OSTI2025

Modeling Structured Electrodes and Graded Porosity for Improving Discharge Rate Capability in Ultra-Thick Graphite|LiNi 0.6 Mn 0.2 Co 0.2 O 2 Batteries

Long-range electric vehicles (EVs) require high-energy-density batteries that also meet the power demands of high current charge and discharge. Ultra-thick (>100 μm) Lithium-ion battery electrodes are critical to enable this need, but slow ion transport in conventional uniform electrodes (UEs) reduces battery capacity at increasing charge/discharge rates. We present a 3D computational analysis on the impact of structured electrode (SE) and graded electrode (GE) geometries on the discharge rate capability of ultra-thick graphite|LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC-622) battery cells based on the footprint of a commercial EV pouch cell. SE cathodes with either a “grid” or “line” geometry and GEs with two layers of porosity were modeled. Based on the results of 230 models, we found that the electrolyte volume fraction is a key parameter that impacts capacity improvements in UEs, GEs, and SEs at 2 C–6 C discharge rates. SEs have the greatest discharge rate capability, outperforming GEs and UEs due to reduced Lithium-ion concentration gradients across the electrode thickness, which mitigates electrolyte depletion at high rates. The best SE model has a “grid” geometry with gravimetric and volumetric energy density improvements of 0.9%–4% at C/2–2 C and 18%–24% at 4 C–6 C relative to UEs.

25 ENERGY STORAGE↗
DOE OSTI2025

Interplay between electron localization, magnetic order, and Jahn-Teller distortion dictates LiMnO2 phase stability

The development of manganese (Mn)-rich cathodes for Li-ion batteries promises to alleviate potential supply chain bottlenecks in battery manufacturing. Fundamental challenges in Mn-rich cathodes arise from phenomena such as structural changes due to cooperative Jahn-Teller (JT) distortions of in octahedral environments, Mn migration, and phase transformations to spinel-like order, all of which affect the electrochemical performance. These physically complex phenomena motivate an re-examination of the Li-Mn-O rock-salt space, with a focus on the thermodynamics of the prototypical, polymorphs. It is found that the generalized gradient approximation (GGA-PBEsol) and meta-GGA ( ) density functionals with empirically fitted on-site Hubbard corrections yield spurious stable phases for , such as predicting a phase with -like order ( ) to be the ground state instead of the orthorhombic (Pmmn) phase, which is the experimentally known ground state. Accounting for antiferromagnetic order in each structure is shown to have a substantial effect on the total energies and resulting phase stability. By using hybrid-GGA (HSE06) and GGA with self-consistent Hubbard parameters (on-site and inter-site ) calculated from linear response theory, the experimentally observed phase stability trends are recovered. The calculated on-site between Mn- states in the experimentally observed orthorhombic, layered, and spinel phases are significantly smaller than in and disordered layered structures, by within GGA. The smaller values of are shown to be correlated with a collinear ordering of JT distortions, in which all orbitals are oriented in the same direction. This cooperative JT effect can lead to greater electron delocalization from Mn along the states due to increased Mn-O covalency, which contributes to the greater electronic stability compared to the phases with noncollinear JT arrangements. The structures with collinear ordering of JT distortions also generate greater vibrational entropy, which helps stabilize these phases at high temperature. These phases are shown to be strongly insulating with large calculated band gaps , which are computed using HSE06 and .

Kam, Ronald L↗
DOE OSTI2020

Mapping Competitive Reduction upon Charging in LiNi 0.8 Co 0.15 Al 0.05 O 2 Primary Particles

Side reactions involving surface reduction play a critical role in the failure of LiNi 0.8 Co 0.15 Al 0.05 O 2 to reach its theoretical capacity as a cathode material for Li-ion batteries. While macroscopic consequences are known, the underlying nanoscopic mechanisms are not fully elucidated. By coupling X-ray spectroscopy with several X-ray microscopy modalities, we have spatially resolved the extent of Ni oxidation at several states of charge and uncovered heterogeneity that is hidden when considering ensemble measurements alone. The use of morphologically controlled particles enabled high-resolution imaging of these materials, uncovering gradients of Ni oxidation states within individual primary particles. At high states of charge, these gradients revealed regions of possible oxygen deficiency extending deeper into the particle than previously observed. Surface-sensitive X-ray coupled scanning tunneling microscopy allows oxidation states to be measured at the material's surface, showing predominantly Ni II in the first atomic layer and mixtures of Ni II with Ni III /Ni IV already appearing 1.5 nm into the particle. These results reveal the subtle interplay between irreversible surface transformations and the bulk reactions that ultimately define function, which will refine strategies of surface passivation that are key to overcoming current performance limitations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

High Throughput Laser Processing for Enhanced Battery Performance and Manufacturing

For widespread adoption of electric vehicles, lithium-ion batteries (LiBs) need to achieve energy densities of >275 Wh/kg, cell costs less than $100/kWh, and charge to more than 80% capacity within 15 minutes. Recently, it has been shown that introducing a secondary pore network in thick battery electrodes enables higher extracted capacity without a severe reduction in charge/discharge rate performance. Secondary pore networks consisting of ordered arrays of microstructures reduce tortuosity of Li+-ion transport deep into the thick electrodes, diminishing detrimental concentration gradients within the cell. Ultrafast (femtosecond)-pulsed laser ablation is a promising method to introduce such micro pores or channels in thick battery electrodes as it allows for precise control of pattern geometries, results in minimal damage to the electrode, and can be introduced into existing roll-to-roll electrode manufacturing lines. We have explored laser patterning to create secondary pore networks in a variety of battery electrode materials for both anode and cathode applications and characterized the laser-material interaction parameters. In addition, advanced materials characterization techniques (SEM-EDS, XRD) were used to explore whether ultrafast laser ablation affects the remaining electrode materials' morphology and structure. Furthermore, we have translated lab-scale laser ablation to high-throughput roll-to-roll processing at industrially relevant scales. Finally, we worked with Argonne National Laboratory, developers of the battery cost-analysis package BatPac, to estimate the additional manufacturing costs (CapEx and OpEx) for incorporation of laser-ablation processing to current battery electrode manufacturing. We estimate that ultrafast laser processing will add only -$1kWh, which for considerable improvements in cell performance, creates a compelling case for industry adoption.

battery↗
DOE OSTI2024

Liquid-like solid-state diffusion of lithium ions in super-halide-rich argyrodite

The development of solid electrolytes with high ionic conductivity is essential for advancing safer, high-energy-density solid-state batteries, where lithium site distribution in the sublattice strongly affects ion transport. Here, we report a super-halide-rich argyrodite, Li 5.3 PS 4.3 Cl 1.7 , with remarkable room-temperature ionic conductivity (11.4 ± 0.7 mS cm -1 ) due to population of two additional interstitial lithium sites induced by vacancy redistribution. Prominent lithium density between lithium sites and elevated atomic displacement parameters indicate liquid-like diffusive behavior resembling sublattice melting. Combining electrochemical impedance spectroscopy, pulsed-field gradient NMR, and T 1 relaxation methods, we demonstrate that the augmented conductivity partly arises from a low energy barrier (0.08 eV) at the local scale, attributed to a three-site lithium distribution that drives correlated lithium dynamics. This work advances our understanding of the structure-dynamics interplay in super-halide-rich argyrodites, and highlighting their potential as solid-state battery electrolytes in cells with a coated single-crystal NMC82 cathode that achieve 170 mAh/g capacity at a 0.2 C rate .

25 ENERGY STORAGE↗