Particle Dynamics Electromechanical Model of a Cathode Microstructure in All-Solid-State Batteries
Explore the source record for details and available documents.
Solid-state battery↗
SEARCH · Search NASA
Results for “Cathode modeling”
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Theoretical model of a hollow cathode plasma for the assessment of insert and keeper lifetimes
Two theoretical models have been developed to aid the design of hollow cathodes for high power Ion and Hall propulsion that will last longer and perform better.
hollow cathode↗
3D Particle-In-Cell Model of Axis-I: Cathode to Target Single-Code Development for Scorpius
Presentation summary: We are validating the Cathode-to-Target PIC model for Scorpius using Axis-I data and envelope codes. Results include particle transport and phase-space information. Future Work: Charge neutralization and ion focusing via target interactions, (example on next slide) investigation of misalignments of solenoid and accelerating gap fields, and investigation of chromatic effects due to pulsed power fluctuations. The bottom line is determining the impact on spot size.
43 PARTICLE ACCELERATORS↗
Modeling Co-Extruded Cathodes for High Energy Lithium-Ion Batteries
Utilizing an existing macro-homogeneous porous electrode model developed by John Newman, this talk presents the potential energy density gains that can be realized in lithium-ion battery electrodes fabricated with co-extrusion (CoEx) technology. CoEx uses carefully engineered fluidic channels to cause multiple streams of dissimilar fluids to impart shape to one another. The result is a high-speed, continuous deposition process that can create fine linear structures much smaller than the smallest physical feature within the printhead. By eliminating the small channels necessary for conventional extrusion and injection processes, CoEx is able to deposit highly loaded and viscous pastes at high line speeds under reasonable operating pressures. The CoEx process is capable of direct deposition of features as small as 10 μm with aspect ratios of 5 or greater, and print speeds > 80 ft/min. We conduct an analysis on two-dimensional cathode cross-sections in COMSOL and present the electrochemical performance results, including calculated volumetric energy capacity for Lithium Nickel Manganese Cobalt Oxide (NMC) co-extruded cathodes, in the presence of a lithium metal anode, polymer separator and ethylene carbonate–diethyl carbonate (EC:DEC) liquid electrolyte. The impact of structured electrodes on cell performance is investigated by varying the physical distribution of a fixed amount of cathode mass over a space of dimensions which can be fabricated by CoEx. By systematically varying the thickness and aspect ratio of the electrode structures, we present an optimal subset of geometries and design rules for co-extruded geometries. Modeling results demonstrate that NMC CoEx cathodes, on the order of 125-200 µm thick, can garner an improvement in material utilization and in turn capacity through the addition of fine width electrolyte channels or highly conductive electrode regions. We also present initial experimental results on CoEx NMC cathode structures.
25 ENERGY STORAGE↗
Pulsed Laser Deposition and Characterization of Heteroepitaxial LiMn 2 O 4 /La 0.5 Sr 0.5 CoO 3 Bilayer Thin Films as Model Lithium Ion Battery Cathodes
Epitaxial LiMn 2 O 4 (LMO)/La 0.5 Sr 0.5 CoO 3 (LSCO) bilayer thin films were grown on single crystalline SrTiO 3 (STO) (111) substrates as model lithium ion battery cathodes. The LSCO layer was used as an electrically conducting buffer layer for electrochemical testing. The LMO and LSCO layers were both epitaxial, with sub-nano flat LMO/LSCO interfaces as seen by X-ray diffraction, synchrotron X-ray scattering, and high-resolution transmission electron microscopy (HRTEM), but with a large LMO surface roughness due to the relatively large lattice mismatch with LSCO. Three-dimensional islands and depressions were formed on the strain-relaxed LMO layer, and misfit dislocations at the LMO/LSCO interface were discerned through HRTEM imaging, suggesting a Stranski–Krastanov (SK) mode thin-film growth. A crystalline structural change from cubic spinel at the LMO surface and interior to tetragonal oxygen-deficient LMO at the LMO/LSCO interface was examined. Furthermore, electrochemical tests along with in situ synchrotron X-ray scattering measurements on the epitaxial LMO/LSCO bilayers showed a significant loss of capacity after the first cycle, which was attributed to an electrical conductivity loss of the LSCO buffer layer due to irreversible lattice oxygen loss.
25 ENERGY STORAGE↗
Quantitative Analysis and Prediction of Thermal Runaway Metrics of High-Nickel Oxide Cathodes by Machine Learning Models
The pursuit of higher energy density in lithium-ion batteries has made high-nickel (Ni) layered oxides leading cathode candidates for next-generation electric vehicles. However, their poor thermal stability, particularly at Ni contents ≥ 90%, increases the risk of cathode-initiated thermal runaway. Furthermore, we present a data-driven framework combining linear and nonlinear machine learning models to predict key thermal runaway descriptors from a high-throughput differential scanning calorimetry database. With cathode composition and state of charge (SOC) as input features, the ensemble model accurately predicts peak temperature, heat release, and peak heat flow. SHAP analysis identifies Ni content and SOC as the dominant factors controlling thermal runaway temperature, while SOC primarily governs heat release and peak heat flow. Al, Mg, and Mn improve thermal stability by strengthening metal–oxygen bonding and delaying structural transformation, whereas B mainly reduces heat release through surface passivation. Validation with a new cathode composition confirms accurate prediction of SOC-dependent thermal runaway behavior and critical SOC.
25 ENERGY STORAGE↗
Meshfree Methods for Modeling Chemo-Mechanical Cathode Cracking in Li-Ion Batteries
Through repeated charging and discharging, the electrodes of a Li-ion battery experience cyclic loading causing swelling and contraction due to the movement of lithium, also known as intercalation. This research focuses specifically on the chemo-mechanical cracking in the cathode. Because cathode particles are comprised of many randomly-oriented grains, which have highly anisotropic material properties, the expansion and contraction is very non-uniform. As a result, stress concentrations tend to form between grains, which necessitates the modeling of crack propagation largely along grain boundaries. Chemo-mechanical models are simulated mainly by two methods: the cohesive zone model (CZM) and the continuous damage model (CDM). The CZM is more accurate at capturing the sharp discontinuities of a crack but is very computationally expensive and intractable for large-scale models as a result. Conversely, the CDM is easily computed but not well-suited to easily allow for discontinuous field variables, which are inherent across a crack. This study aims to improve the CDM's ability to capture discontinuous cracks. Current versions of the CDM use the finite element method (FEM), which is one of the most widely used approaches for spatial discretization. This research investigates the use of the Reproducing Kernel Particle Method (RKPM), a meshfree method, for spatial discretization and aims to achieve a chemo-mechanical crack propagation model that achieves both intermediate accuracy and computational time between a CDM and CZM. To gain a better understanding of how the meshfree model compares to the current FEM model in capturing cathode crack propagation, further investigation is needed.
cathode cracking↗
Electro-reduction of organics on metal cathodes: A multiscale-modeling study of benzaldehyde on Au (111)
Here, we present a multiscale modeling study on the electro-reduction of benzaldehyde (BZY) on Au(111) under realistic electrochemical conditions. To model the electrochemical cell, we adopt a capacitor model in which complex solvents are confined between a Au cathode and a carbon anode. Classical molecular dynamics simulations reveal that electrode charge density and the presence of alcohol show strong effects on the density, adsorption geometry and dynamics of benzaldehyde on the Au electrode. Under charging conditions, the surface concentration of benzaldehyde on the Au electrode decreases, while the content of other species increases. Finally, we proposed a scheme that correlates the electric current running through the Au/solvent interface with the applied bias. This study provides a molecular level understanding of how solvent composition, in this case water/alcohol content, controls the activity of electrocatalytic hydrogenation
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Multi-variable mathematical models for the air-cathode microbial fuel cell system
This research adopted the version control system into the model construction for the single chamber air-cathode microbial fuel cell (MFC) system, to understand the interrelation of biological, chemical, and electrochemical reactions. The anodic steady state model was used to consider the chemical species diffusion and electric migration influence to the MFC performance. In the cathodic steady state model, the mass transport and reactions in a multi-layer, abiotic cathode and multi-bacteria cathode biofilm were simulated. Transport of hydroxide was assumed for cathodic pH change. This assumption is an alternative to the typical notion of proton consumption during oxygen reduction to explain elevated cathode pH. The cathodic steady state model provided the power density and polarization curve performance results that can be compared to an experimental MFC system. Another aspect we considered was the relative contributions of platinum catalyst and microbes on the cathode to the oxygen reduction reaction (ORR). We found simulation results showed that the biocatalyst in a cathode that includes a Pt/C catalyst likely plays a minor role in ORR, contributing up to 8% of the total power calculated by the models.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A phenomenological model for orificed hollow cathodes
A quartz hollow tube cathode was used to determine the operating conditions within a mercury orificed hollow cathode. Insert temperature profiles, cathode current distributions, plasma properties profile, and internal pressure-mass flow rate results are summarized and used in a phenomenological model which qualitatively describes electron emission and plasma production processes taking place within the cathode. By defining an idealized ion production region within which most of the plasma processes are concentrated, this model is 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 emission surface temperature and internal plasma properties. Key aspects of the model are examined.
Siegfried, D. E.↗
Interpreting Ionic Conductivity for Polymer Electrolyte Fuel Cell Catalyst Layers with Electrochemical Impedance Spectroscopy and Transmission Line Modeling
A cathode catalyst layer containing optimally distributed ionomer is critical to reduce the platinum loading and increase its utilization in polymer electrolyte fuel cells. Here, electrochemical impedance spectroscopy (EIS) was used to measure effective ionic conductivity of pseudo catalyst layers (PCLs) at a relative humidity (RH) range of 50%-120%. These results are compared to previous work using the hydrogen pump (HP) method. EIS effective ionic conductivity results reported here are higher than those from the HP because in the HP set-up ionic pathways must be effectively connected through the PCL to be counted, whereas in the EIS measurement, ionomer segments that are in contact with the membrane but are not effectively connected all the way through the PCL can be detected. Double layer capacitances and effective ionic conductivities of Pt/C catalyst layers with various supports and ionomer to carbon (I/C) ratios were studied. High surface area carbon support resulted in a lower effective ionic conductivity compared to the graphitized carbon support due to worse ionomer dispersion. Effective ionic conductivities of Pt/C layers were compared to that of PCLs. On average, effective ionic conductivities of Pt/C layers were higher than PCLs because of possible carbon agglomeratio n within the PCLs.
25 ENERGY STORAGE↗
Modeling Lithium Diffusion in Battery Cathodes Considering Chemo-Mechanically Induced Damage
This talk will present a 3D, continuum-level damage model for simulating Lithium diffusion within generated Li_{x}Ni_{0.5}Mn_{0.3}Co_{0.2} (NMC 532) secondary cathode particles. The primary motivation of the particle-level model is to inform cathode-particle design and determine charging profiles that reduce cathode fracture. The model considers NMC 532 secondary particles containing an agglomeration of anisotropic, randomly oriented grains. The model predicts that secondary-particle fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. The model predicts that small secondary-particles with large grains develop significantly less damage than larger secondary particles with small grains. Finally, the model predicts most of the chemo-mechanical damage accumulates in the first high-rate cycles. This chemo-mechanical “damage saturation” effect indicates that initial secondary-particle fracture occurs within the first few cycles, while long-term cathode degradation is not solely chemo-mechanically induced.
47 OTHER INSTRUMENTATION↗
A pseudo-two-dimensional (P2D) model for FeS 2 conversion cathode batteries
Conversion cathode materials are gaining interest for secondary batteries due to their high theoretical energy and power density. However, practical application as a secondary battery material is currently limited by practical issues such as poor cyclability. To better understand these materials, we have, for this study, developed a pseudo-two-dimensional model for conversion cathodes. We apply this model to FeS 2 – a material that undergoes intercalation followed by conversion during discharge. The model is derived from the half-cell Doyle–Fuller–Newman model with additional loss terms added to reflect the converted shell resistance as the reaction progresses. We also account for polydisperse active material particles by incorporating a variable active surface area and effective particle radius. Using the model, we show that the leading loss mechanisms for FeS 2 are associated with solid-state diffusion and electrical transport limitations through the converted shell material. The polydisperse simulations are also compared to a monodisperse system, and we show that polydispersity has very little effect on the intercalation behavior yet leads to capacity loss during the conversion reaction. Finally, we provide the code as an open-source Python Battery Mathematical Modeling (PyBaMM) model that can be used to identify performance limitations for other conversion cathode materials.
25 ENERGY STORAGE↗
Coupling of multiscale imaging analysis and computational modeling for understanding thick cathode degradation mechanisms
Here, using a thick NMC811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) electrode as an example, we present a macro- to nanoscale 2D and 3D imaging analysis approach coupled with 4D (space + time) computational modeling to probe its degradation mechanism in a lithium-ion battery cell. Particle cracking increases and contact loss between particles and carbon-binder domain are observed to correlate with the cell degradation. This study unravels that the reaction heterogeneity within the thick cathode caused by the unbalanced electron conduction is the main cause of the battery degradation over cycling. The increased heterogeneity in the system will entail more cathode regions where the degree of active material utilization is uneven, leading to higher probabilities of particle cracking. These findings shed light on the crucial role of the electronic and ionic transportation networks in the performance deterioration of the thick cathode. They also provide guidance for cathode architecture optimization and performance improvement.
25 ENERGY STORAGE↗
Modeling Intercalation Chemistry with Multiredox Reactions by Sparse Lattice Models in Disordered Rocksalt Cathodes
Modern battery materials can contain many elements with substantial site disorder, and their configurational state has been shown to be critical for their performance. The intercalation voltage profile is a critical parameter to evaluate the performance of energy storage. The application of commonly used cluster expansion techniques to model the intercalation thermodynamics of such systems ab initio is challenged by the combinatorial increase in configurational degrees of freedom as the number of species grows. Such challenges necessitate the efficient generation of lattice models without overfitting and proper sampling of the configurational space under the requirement of charge balance in ionic systems. In this work, we introduce a combined approach that addresses these challenges by (1) constructing a robust cluster expansion Hamiltonian using the sparse regression technique, including -norm regularization and structural hierarchy; and (2) implementing semigrand-canonical Monte Carlo to sample charge-balanced ionic configurations using the table-exchange method and an ensemble average approach. These techniques are applied to a disordered rocksalt oxyfluoride (LMNOF) that is part of a family of promising earth-abundant cathode materials. The simulated voltage profile is found to be in good agreement with experimental data and particularly provides a clear demonstration of the and oxygen contributions to the redox potential as a function of content.
25 ENERGY STORAGE↗
Electrical characterization and an equivalent circuit model of a microhollow cathode discharge reactor
This paper reports the electrical characterization and an equivalent circuit of a microhollow cathode discharge (MHCD) reactor in the self-pulsing regime. A MHCD reactor was prototyped for air plasma generation, and its current-voltage characteristics were measured experimentally in the self-pulsing regime for applied voltages from 2000 to 3000 V. The reactor was modeled as a capacitor in parallel with a variable resistor. A stray capacitance was also introduced to the circuit model to represent the capacitance of the circuit elements in the experimental setup. The values of the resistor and capacitors were recovered from experimental data, and the proposed circuit model was validated with independent experiments. Experimental data showed that increasing the applied voltage increased the current, self-pulsing frequency and average power consumption of the reactor, while it decreased the peak voltage. The maximum and the minimum voltages obtained using the model were in agreement with the experimental data within 2.5%, whereas the differences between peak current values were less than 1%. At all applied voltages, the equivalent circuit model was able to accurately represent the peak and average power consumption as well as the self-pulsing frequency within the experimental uncertainty. Although the results shown in this paper was for atmospheric air pressures, the proposed equivalent circuit model of the MHCD reactor could be generalized for other gases at different pressures.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Advanced space propulsion thruster research
Experiments showed that stray magnetic fields can adversely affect the capacity of a hollow cathode neutralizer to couple to an ion beam. Magnetic field strength at the neutralizer cathode orifice is a crucial factor influencing the coupling voltage. The effects of electrostatic accelerator grid aperture diameters on the ion current extraction capabilities were examined experimentally to describe the divergence, deflection, and current extraction capabilities of grids with the screen and accelerator apertures displaced relative to one another. Experiments performed in orificed, mercury hollow cathodes support the model of field enhanced thermionic electron mission from cathode inserts. Tests supported the validity of a thermal model of the cathode insert. A theoretical justification of a Saha equation model relating cathode plasma properties is presented. Experiments suggest that ion loss rates to discharge chamber walls can be controlled. A series of new discharge chamber magnetic field configurations were generated in the flexible magnetic field thruster and their effect on performance was examined. A technique used in the thruster to measure ion currents to discharge chamber walls is described. Using these ion currents the fraction of ions produced that are extracted from the discharge chamber and the energy cost of plasma ions are computed.
Wilbur, P. J.↗
Communication — Modeling polymer-electrolyte fuel-cell agglomerates with double-trap kinetics
A new semi-analytical agglomerate model is presented for polymer-electrolyte fuel-cell cathodes. The model uses double-trap kinetics for the oxygen-reduction reaction, which can capture the observed potential-dependent coverage and Tafel-slope changes. An iterative semi-analytical approach is used to obtain reaction rate constants from the double-trap kinetics, oxygen concentration at the agglomerate surface, and overall agglomerate reaction rate. The analytical method can predict reaction rates within 2% of the numerically simulated values for a wide range of oxygen concentrations, overpotentials, and agglomerate sizes, while saving simulation time compared to a fully numerical approach.
36 MATERIALS SCIENCE↗