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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

A Comprehensive Analysis of the Interphasial and Structural Evolution over Long–Term Cycling of Ultrahigh–Nickel Cathodes in Lithium–Ion Batteries

Ultrahigh-Ni layered oxides hold great promise as high-energy-density cathodes at an affordable cost for lithium-ion batteries, yet their practical application is greatly hampered by the poor cyclability. Herein, by employing LiNi 0.94 Co 0.06 O 2 as a model cathode in a full-cell configuration, the interphasial and structural evolution processes of ultrahigh-Ni layered oxides are systematically investigated over the course of their service life (1500 cycles). By applying advanced analytic techniques (e.g., Li-isotope labeling, region-of-interest method), the dynamic chemical evolution on the cathode surface is revealed with spatial resolution, and the correlation between lattice distortion and cathode surface reactivity is established. Benefiting from in situ X-ray diffraction (XRD) analysis, the ultrahigh-Ni layered oxide is demonstrated to undergo dual-phase reaction mechanisms with huge lattice variation, which leads to a decrease in crystallinity and secondary particle pulverization. Furthermore, the critical impact of cathode surface reaction on the graphite anode–electrolyte interphase (AEI) is revealed at nanometer scale, and a universal chemical/physical evolution process of the AEI is illustrated, for the first time. Finally, the practical viability of ultrahigh-Ni layered oxides is demonstrated through Al-doping strategy. Finally, this work presents a comprehensive understanding of the structural and interphasial degradation of ultrahigh-Ni layered oxide cathodes for developing high-energy-density lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Electrochemical reactivity and passivation of organic electrolytes at spinel MgCrMnO 4 cathode interfaces for rechargeable high voltage magnesium-ion batteries

Magnesium transition metal oxides such as MgCr 2−x Mn x O 4 are promising high-voltage and high-capacity cathode materials for rechargeable magnesium batteries (RMBs). Understanding and improving the chemical and electrochemical stability of the cathode–electrolyte interface (CEI) has been the primary technical emphasis to enable this category of cathode materials, which has been significantly underexplored. Herein, in this study, we focus on investigating the fundamental mechanism of parasitic reactions at the charged surface of the high-voltage MgCrMnO 4 model cathode with different organic electrolytes. The aim is to reveal the underlying effect of anions and solvents responsible for the passivation behavior of the cathode by using three exemplary anions: [(CF 3 SO 2 ) 2 N] − (TFSI − ), Al[OC(CF 3 ) 3 ] 4 − (TPFA − ), and [CB 11 H 12 ] − (MC) and three solvents: diglyme (G2), triglyme (G3), and 3-methoxypropylamine (MPA). High precision leakage current measurements during potentiostatic hold reveal that the electrolyte solvent chemistry has a more profound impact than anion's on the passivation of the MgCrMnO 4 cathode surface during deintercalation of Mg 2+ . X-ray photoelectron spectroscopy exhibits the differences in CEI composition. Amine solvents like MPA show poor passivation due to a higher degree of solvent decomposition, while the thin and anion-derived CEI in glyme-based electrolytes is directly linked with the better passivation behavior on the cathode. Furthermore, we leverage the knowledge from these findings to modify the electrolyte structure by adding a solvent additive, with the goal of reducing the parasitic reaction.

25 ENERGY STORAGE↗
DOE OSTI2022

Facile Electrodeposition and Aging to Generate 3-Dimensional α-MnO 2 Battery Cathodes

Conventional tape casting forms 2-dimensional (2D) electrodes containing active material, conductive additive, and binder with restricted ion access as electrodes increase in thickness. To improve the transport properties, 3D architectures were developed using electrodeposition to ensure contact between the active material with the substrate, and provide enhanced electrolyte access. This paper investigates electrodeposition of cryptomelane ( α -MnO 2 ) as a model cathode material to efficiently accommodate (de)lithation and increase areal capacity vs conventional 2D coatings. Electodeposited samples on titantium (Ti) foil substrates were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) and show a linear increase of the average oxidation of Mn (3.5–3.8) and active mass loading (1.27–9.9 mg) with deposition and aging times (0–120 min). The initial deposition is amorphous and forms the crystalline material during the elevated temperature aging step. The active material, α -MnO 2 , was also deposited on C-cloth and these cathodes at deposition times of 3, 6, and 9 min deliver 9, 36, and 69% higher areal capacities, respectively, at 0.2 mA cm −2 compared to conventional 2D electrodes with a mass loading equal to the 3 min sample. These results demonstrate the benefit of α -MnO 2 within a porous architecture providing enhanced transport properties.

Electrochemistry↗
DOE OSTI2019

Probing Electrochemically Induced Structural Evolution and Oxygen Redox Reactions in Layered Lithium Iridate

In order to exploit electrochemical capacity beyond the traditionally-utilized transition metal redox reactions in lithium-metal-oxide cathode materials, it is necessary to understand the role that oxygen ions play in the charge compensation mech-anisms, i.e., to know the conditions triggering electron transfer on the oxygen ions and whether this transfer is correlated with battery capacity. Theoretical and experimental investigations of a model cathode material, Li-rich layered Li 2 IrO 3 , have been performed to study the structural and electronic changes induced by electrochemical delithiation in a lithium-ion cell. First-principles density functional theory (DFT) calculations were used to compute the voltage profile of a Li/Li 2-x IrO 3 cell at various states of charge, and the results were in good agreement with electrochemical data. Electron energy loss spectroscopy (EELS), X-ray absorption near-edge spectroscopy (XANES), resonant/non-resonant X-ray emission spectroscopy (XES), and first principles core-level spectra simulations using the Bethe Salpeter Equation (BSE) approach were used to probe the change in oxygen electronic states over the $x$ = 0 to 1.5 range. The correlated Ir M 3 -edge XANES and O K-edge XANES data provided evidence that oxygen hole states form during the early stage of delithiation at ~3.5 V due to the interaction between O $p$ and Ir $d$ states, with Ir oxidation being the dominant source of electrochemical capacity. At higher potentials, the charge capacity was predominantly attributed to oxidation of the O 2- ions. It is argued that the emergence of oxygen holes alone is not necessarily indicative of electrochemical capacity beyond transition metal oxidation, since oxygen hole states can appear as a result of enhanced mixing of O $p$ and Ir $d$ states. Prevailing mechanisms accounting for the oxygen redox mechanism in Li-rich materials were examined by theoretical and experimental X-ray spectroscopy; however, no unambiguous spectroscopic signatures of oxygen dimer interaction or non-bonding oxygen states were identified.

25 ENERGY STORAGE↗
DOE OSTI2020

How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode–Electrolyte Interface when Addressing Oxygen Redox

Sensitivity to the `bulk' oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes, Li 2 MnO 3 , Li-rich NMC, and NMC 442, that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Achieving high rate performance in hybrid pristine-recycled cathodes using model-informed electrode designs

Direct recycling lithium-ion battery cathodes, a process that retains the engineered oxide structures from end-of-life materials, presents a cost-effective and energy-efficient alternative to other battery recycling methods. However, while direct-recycled cathodes have demonstrated performance comparable to that of pristine materials at low cycling rates, their high-rate performance remains uncertain. Morphology changes in cathode particles, a main mode of degradation, directly impact rate performance by limiting surface kinetics and solid-phase diffusion. If direct recycling processes do not sufficiently restore pristine-like morphologies, the recycled materials may retain structural defects that hinder high-rate performance. The present work uses a physics-based pseudo-2D model to simulate hybrid electrodes with pristine and artificially “aged/recycled” NMC materials to investigate potential impacts of incorporating performance-limited aged cathode materials into cells. The study highlights how differences in transport and kinetic properties can influence rate capabilities in mixed electrodes — particularly in high-loading cells in high-demand applications. However, model results also reveal a possible mitigation strategy via dual-layer electrode architectures with lower-performing materials positioned near the current collector. Simulations of 4.0 mAh cm −2 cells cycled at 4C using a dual-layer architecture provided approximately 5%–30% more capacity in constant-current protocols compared to homogeneously blended electrode architectures with the same loadings and mixed-material compositions. These findings highlight the importance of strategic electrode design in minimizing potential performance losses and facilitating the integration of recycled materials into high-performance batteries, advancing sustainable and cost-effective battery manufacturing.

25 ENERGY STORAGE↗
DOE OSTI2024

Voltage Mining for (De)lithiation-Stabilized Cathodes and a Machine Learning Model for Li-Ion Cathode Voltage

Advances in lithium-metal anodes have inspired interest in discovery of Li-free cathodes, most of which are natively found in their charged state. This is in contrast to today's commercial lithium-ion battery cathodes, which are more stable in their discharged state. In this study, we combine calculated cathode voltage information from both categories of cathode materials, covering 5577 and 2423 total unique structure pairs, respectively. The resulting voltage distributions with respect to the redox pairs and anion types for both classes of compounds emphasize design principles for high-voltage cathodes, which favor later Period 4 transition metals in their higher oxidation states and more electronegative anions like fluorine or polyanion groups. Generally, cathodes that are found in their charged, delithiated state are shown to exhibit voltages lower than those that are most stable in their lithiated state, in agreement with thermodynamic expectations. Deviations from this trend are found to originate from different anion distributions between redox pairs. In addition, a machine learning model for voltage prediction based on chemical formulas is trained and shows state-of-the-art performance when compared to two established composition-based ML models for material properties predictions, Roost and CrabNet.

25 ENERGY STORAGE↗
DOE OSTI2017

Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi 0.61 Co 0.12 Mn 0.27 O 2 , over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtually atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.

25 ENERGY STORAGE↗
DOE OSTI2024

OPTIMIZATION OF COOLING DISTRIBUTION OF THE EIC SHC COOLER ERL

The Electron-Ion Collider (EIC) Hadron Storage Ring (HSR) will use strong hadron cooling to maintain the beam brightness and high luminosity during long collision ex?periments. An Energy Recovery Linac is used to deliver the high-current high-brightness electron beam for cooling. For the best cooling effect, the electron beam requires low emittance, small energy spread, and uniform longitudinal distribution. In this work, we simulate and optimize the longitudinal laser-beam distribution shaping at the photo?cathode, modeling space charge forces accurately. Machine parameters such as RF cavity phases are optimized in con?junction with the beam distribution using a genetic optimizer. We demonstrate improvement of the cooling distribution in key parameters.

Wang, N.↗
DOE OSTI2020

Physically Based Modeling of PEMFC Cathode Catalyst Layers: Effective Microstructure and Ionomer Structure–Property Relationship Impacts

Abstract This work presents a pseudo-two-dimensional proton exchange membrane fuel cell (PEMFC) model incorporating Nafion ionomer structure–property relationships in the cathode catalyst layer (CL) to capture and explain losses at low Pt loading. Structural data from neutron reflectometry and thin film Nafion conductivity measurements predict variations in the oxygen diffusion coefficient and ionic conductivity with changing CL ionomer thickness and Pt loading. By including these structure–property relationships, predicted polarization curves agree closely with previously published experimental data from cells with Pt loadings between 0.025 and 0.2 mg/cm2. Results demonstrate that structure–property relationships based on physically measurable ionomer and CL properties provide a feasible interpretation of PEMFC CL phenomena for a range of Pt loadings and help explain previously unaccounted-for losses at low Pt. Results also show that simulations must account for surface species coverage variations in order to properly capture the kinetic losses. Finally, results suggest that an increase in ionomer thickness surrounding the C/Pt surfaces may lead to improved cell performance due to improved ionic conductivity.

Electrochemistry↗
NASA NTRS2002

A Particle and Energy Balance Model of the Orificed Hollow Cathode

A particle and energy balance model of orificed hollow cathodes was developed to assist in cathode design. The model presented here is an ensemble of original work by the author and previous work by others. The processes in the orifice region are considered to be one of the primary drivers in determining cathode performance, since the current density was greatest in this volume (up to 1.6 x 10(exp 8) A/m2). The orifice model contains comparatively few free parameters, and its results are used to bound the free parameters for the insert model. Next, the insert region model is presented. The sensitivity of the results to the free parameters is assessed, and variation of the free parameters in the orifice dominates the calculated power consumption and plasma properties. The model predictions are compared to data from a low-current orificed hollow cathode. The predicted power consumption exceeds the experimental results. Estimates of the plasma properties in the insert region overlap Langmuir probe data, and the predicted orifice plasma suggests the presence of one or more double layers. Finally, the model is used to examine the operation of higher current cathodes.

Domonkos, Matthew T.↗
NASA NTRS1982

A model for mercury orificed hollow cathodes - Theory and experiment

A phenomenological model is developed which provides a qualitative description of the basic physical processes taking place within a mercury orifice hollow cathode. This model can be used to predict, to first order, the important cathode operating parameters such as emission length and insert temperature. By assuming an idealized ion production region within which most of the plasma processes are concentrated, the model can be expressed analytically as a simple set of equations which relate cathode dimensions and specifiable operating conditions, such as mass flow rate and discharge current, to such important parameters as insert temperature and plasma properties. A comparison of theoretical and experimental results shows that, if the excited state energy flux is neglected, the model provides relatively accurate predictions of emission length, emission surface temperature, plasma density, and fraction of discharge current due to volume ionization

Siegfried, D. E.↗
DOE OSTI2014

A one-dimensional model illustrating virtual-cathode formation in a novel coaxial virtual-cathode oscillator

A one-dimensional electrostatic sheet model of a coaxial geometry Virtual Cathode Oscillator (VCO) is presented. The cathode is centrally located and connects to a peripherally located plate electrode to form a resonant cavity, and is thus considered to be a novel design. Charge is modelled as concentric sheets about the cathode whose absolute position and velocity are determined as a function of time by solving the relativistic equations of motion. The model predicts the formation of a virtual cathode between the grid and plate electrodes for the case of a space-charge limited current. Setting the electron reflexing frequency (as a function of the grid potential) comparable with the cavity resonant frequency is predicted to improve the efficiency of microwave emission.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Establishing criteria for the transition from kinetic to fluid modeling in hollow cathode analysis

Hollow cathodes for plasma switch applications are investigated via 2D3V particle-in-cell simulations of the channel and plume region. The kinetic nature of the plasma within the channel is dependent on the thermalization rate of electrons, emitted from the insert. When Coulomb collisions occur at a much greater rate than ionization or excitation collisions, the electron energy distribution function rapidly relaxes to a Maxwellian and the plasma within the channel can be described accurately via a fluid model. In contrast, if inelastic processes are much faster than Coulomb collisions, then the electron energy distribution function in the channel exhibits a notable high-energy tail, and a kinetic treatment is required. This criterion is applied to hollow cathodes from the literature, revealing that a fluid approach is suitable for most electric propulsion applications, whereas a kinetic treatment can be more critical to accurate modeling of plasma switches.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS2004

Model of a Hollow Cathode Insert Plasma

A 2-D axisymmetric fluid model of the plasma in the insert region of a hollow cathode is presented. The level of sophistication included in the model is motivated in part by the need to determine quantitatively plasma fluxes to the emitter surface. The ultimate goal is to assess whether plasma effects can degrade the life of impregnated inserts beyond those documented throughout the 30-50 year history of vacuum cathode technologies. Results from simulations of a 1.2-cm diameter cathode operating at a discharge current of 25 A, and a gas flow rate of 5 sccm, suggest that approximately 10 A of electron current, and 3.5 A of ion current return to the emitter surface. The total emitted electron current computed by the model is about 35 A. Comparisons with plasma measurements suggest that anomalous heating of the plasma due to two-stream instabilities is possible near the orifice region. Solution to the heavy species energy equation, with classical transport and no viscous effects, predicts heavy species temperatures as high as 2640 K.

hollow cathodes↗
NASA NTRS2003

Model of hollow cathode operation and life limiting mechanisms

In this paper we apply results from the extensive traveling wave tube vacuum barium impregnated cathode literature to the hollow cathodes used in ion thrusters. We show that the observed space station cathode life is in general agreement with published barium evaporation rates.

hollow cathodes↗