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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

Phase-field model for diffusion-induced grain boundary migration: An application to battery electrodes

Diffusion-induced grain boundary migration is a phenomenon in which a grain boundary moves in response to the driving forces generated by diffusing solute species. For example, diffusing solute species change the atomic volume in the host material, either by filling a vacancy with a misfitting solute atom or by expanding host lattices through interstitial diffusion. These volume changes are inhomogeneous and are stored as elastic energy in the material that drives grain boundaries. In this paper, we introduce our previously developed Cahn-Hilliard–phase-field-crystal model (CH-PFC) as a computational tool to investigate diffusion-induced grain boundary migration in crystalline materials. This multiscale phase-field model couples the composition field of a diffusing species with the crystallographic texture of a host material. We apply the CH-PFC model to battery electrodes and investigate whether interstitial solute diffusion induces grain growth in FePO 4 /LiFePO 4 electrodes. To this end, we compute grain growth in 60 FePO 4 electrodes by conducting two parallel trials: In the first trial, we cycle the electrode and calculate diffusion-induced grain growth. In the second trial, we do not cycle the electrode and calculate curvature-driven grain growth. We find a statistically significant grain growth in the cycled electrodes and negligible grain growth in the noncycled electrodes. Altogether, we show that the CH-PFC model not only predicts electrode microstructures as a function of the Li composition, but also predicts the crystallographic features of an electrode during battery operation.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Probing microstructure and electrolyte concentration dependent cell chemistry via operando small angle neutron scattering

The key to understanding the cycling mechanism of lithium-ion battery electrodes is to develop methods to monitor the dynamic cell chemistry, but the complexity of the problem has continued to pose an obstacle. Here we describe the use of operando small-angle neutron scattering (SANS) to show directly how the use of concentrated LiTFSI electrolyte in Li/ordered mesoporous carbon (OMC) half-cells influences the mechanism of solid electrolyte interphase (SEI) formation, lithium intercalation, and carbon framework expansion. We find that a complex interplay between the viscosity, lithium solvation shell and electrode microstructure in the concentrated 4 M electrolyte changes the dynamics of SEI formation and pore filling at a given applied potential. Both the filling of micropores and co-intercalation are found to drive the expansion of the carbon framework. Lithium-rich reduction products form at much higher potentials in the micropores of the 4 M electrolyte system, while on mesopore surfaces the lithium-rich salts form quickly before giving way to carbonaceous products. As a result, this study reveals operando SANS as a unique method for providing microstructure dependent information on the dynamics of electrochemical processes.

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

Low-Tortuosity Thick Electrodes with Active Materials Gradient Design for Enhanced Energy Storage

The ever-growing energy demand of modern society calls for the development of high-loading and high-energy-density batteries, and substantial research efforts are required to optimize electrode microstructures for improved energy storage. Low-tortuosity architecture proves effective in promoting charge transport kinetics in thick electrodes; however, heterogeneous electrochemical mass transport along the depth direction is inevitable, especially at high C-rates. In this work, we create an active material gradient in low-tortuosity electrodes along ion-transport direction to compensate for uneven reaction kinetics and the nonuniform lithiation/delithiation process in thick electrodes. The gradual decrease of active material concentration from the separator to the current collector reduces the integrated ion diffusion distance and accelerates the electrochemical reaction kinetics, leading to improved rate capabilities. Further, the structure advantages combining low-tortuosity pores and active material gradient offer high mass loading (60 mg cm –2 ) and enhanced performance. Comprehensive understanding of the effect of active material gradient architecture on electrode kinetics has been elucidated by electrochemical characterization and simulations, which can be useful for development of batteries with high-energy/power densities.

25 ENERGY STORAGE↗
DOE OSTI2020

Microstructural Evolution and ORR Activity of Nanocolumnar Platinum Thin Films with Different Mass Loadings Grown by High Pressure Sputtering

Nanocolumnar platinum thin films (Pt-TFs) with different Pt mass loadings were grown by high pressure sputtering (HIPS) and investigated as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte membrane fuel cell applications. Mass loading was controlled by changing the sputter deposition time. A cauliflower-like columnar microstructure was achieved by depositing the Pt-TFs onto a microporous layer (MPL)-like surface composed of carbon particles in order to mimic catalyst-coated gas diffusion electrodes. Microstructural evolution of HIPS Pt-TFs and their ORR activity were investigated. Electrochemical characterization of the nanocolumnar Pt-TFs was performed by cyclic voltammetry and rotating disk electrode measurements on Pt-TF/MPL-like-layer/glassy-carbon samples in an aqueous perchloric acid electrolyte. The electrochemically active surface area increased from 18 to 39 m 2 g –1 as the Pt mass loading was decreased. Specific activity of the films was similar (~600 μA cm –2 ) for all Pt mass loadings, due to the similar nanoparticle sizes of ~5 nm as observed by transmission electron microscopy and X-ray diffraction. Furthermore, mass activity of the films increased from 0.11 to 0.26 A mg –1 as the Pt mass loading was decreased, which is an indication of the effective Pt utilization and better access through the catalyst layer at lower Pt mass loadings.

08 HYDROGEN↗
DOE OSTI2020

Enabling fast charging of lithium-ion batteries through secondary- /dual- pore network: Part I - Analytical diffusion model

Battery performance is strongly correlated with electrode microstructural properties. Enabling fast charging of lithium-ion batteries requires improved through-plane ionic diffusion that can be achieved through, among other strategies, structured electrodes with a secondary- or dual-pore network (SPN). In this work, an analytical model investigates the impact of such an SPN on ionic diffusion with a composite electrode, considering various pore-channel geometries and comparing to standard electrodes with identical gravimetric- and volumetric-specific theoretical capacities. Relevant SPN design parameters and tortuosity coefficients are identified according to three optimization objectives that aim to balance the improved overall through-plane diffusion, thanks to the coarse aligned channels, and degraded in-plane diffusion because of the porous matrix densification required to maintain gravimetric- and volumetric-specific theoretical capacities. The model indicates that a relatively low amount of SPN is required and that electrodes with high through-plane tortuosity and low in-plane tortuosity benefit most from such architecture.

25 ENERGY STORAGE↗
DOE OSTI2024

Voltage and temperature effects on low cobalt lithium-ion battery cathode degradation

Degradation of low cobalt lithium-ion cathodes was tested using a full factorial combination of upper cut-off voltage (4.0 V and 4.3 V vs. Li/Li + ) and operating temperature (25 °C and 60 °C). Half-cell batteries were analyzed with electrochemical and microstructural characterization methods. Electrochemical performance was assessed with galvanostatic cycling, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) supported by distribution of relaxation times (DRT) analysis. Electrode microstructure was characterized with scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) imaging. Higher cut-off voltage cycling shows presence of NiO x formation, a low diffusivity rock-salt phase, in both CV and XRD data. XRD patterns confirmed that the rock-salt phase was beginning to form at the low cut-off voltage at high temperature, but in much lower intensity than at the high cut-off voltage. Higher temperature accelerates degradation processes at both voltages. Degradation factors at high temperature include NiO x formation, cathode material dissolution, and electrolyte decomposition. SEM analysis suggests that supporting phases may isolate and disconnect active material particles reducing capacity retention and battery life cycle. DRT analysis and XANES imaging show that both high temperature samples revealed a NiO x phase based on an increased diffusive impedance and a visible shift in the XANES spectra. The low cut-off voltage, high temperature sample showed a split peak and shift to lower energies indicating early formation of the NiO x phase. The diffusive impedance, which hinders intercalation and deintercalation, is driven by the formation of the NiO x phase. While primarily driven by cut-off voltage, elevated temperature also contributes to this degradation mechanism.

electrochemical impedance spectroscopy↗
DOE OSTI2022

Artificial intelligence inferred microstructural properties from voltage–capacity curves

Abstract The quantification of microstructural properties to optimize battery design and performance, to maintain product quality, or to track the degradation of LIBs remains expensive and slow when performed through currently used characterization approaches. In this paper, a convolution neural network-based deep learning approach (CNN) is reported to infer electrode microstructural properties from the inexpensive, easy to measure cell voltage versus capacity data. The developed framework combines two CNN models to balance the bias and variance of the overall predictions. As an example application, the method was demonstrated against porous electrode theory-generated voltage versus capacity plots. For the graphite|LiMn $$_2$$ 2 O $$_4$$ 4 chemistry, each voltage curve was parameterized as a function of the cathode microstructure tortuosity and area density, delivering CNN predictions of Bruggeman’s exponent and shape factor with 0.97 $$R^2$$ R 2 score within 2 s each, enabling to distinguish between different types of particle morphologies, anisotropies, and particle alignments. The developed neural network model can readily accelerate the processing-properties-performance and degradation characteristics of the existing and emerging LIB chemistries.

25 ENERGY STORAGE↗
DOE OSTI2024

Manufacturing of Fabric Electrodes using a High-Throughput Screening Platform for Redox Flow Batteries

The objective of this project is to establish a new manufacturing methodology with machine learning- based high-throughput screening for the design and development of hierarchical structured, high-performance fabric electrodes for redox flow batteries (RFBs). The end goal of the project is to design and manufacture fabric electrodes for RFB applications that can provide 250 mA/cm2 current density operation for 100-cycles with 80% average energy efficiency. This was accomplished by first examining the structure-performance-property linkages of the electrodes provided by our partner, AvCarb. The electrodes’ microstructure was characterized by determining their pore size distribution, tortuosity, specific surface area, and porosity. The ohmic, charge transfer and mass transfer resistances were then calculated using electrochemical impedance spectroscopy. Carbon cloth electrodes showed the greatest resistance, which was dominated by charge transfer resistance, which we believe is related to the surface functionalization. Full cell cycling was used in order to determine the area specific resistance and energy efficiency of the cells. All of this experimental data and the results of the mathematical model (to increase the amount of inputs with parametric sweeping) were used to develop a machine learning-based model for the design of high-performance fabric electrodes. Using the results from the machine learning tool, optimized electrodes were fabricated by AvCarb. The ohmic, charge transfer and mass transfer resistances for these new electrodes were measured, and both performed better than any of the initial samples which had been provided by AvCarb.

25 ENERGY STORAGE↗
DOE OSTI2025

Microstructure Scale Lithium-Ion Battery Modeling: Part II. On In-Plane Heterogeneities and the Mechanisms that Regulate Them

Li-ion batteries performance and degradation are typically modeled at the macroscopic scale, that is neglecting in-plane heterogeneities that can arise from non-uniform electrode microstructures. Herein, a microstructure scale electrochemical model is used to quantify the impact of microstructure heterogeneity on cell performance during fast charging. The model predicts the electrolyte and solid concentration in-plane standard deviation can reach, respectively, ≈200 mol·m −3 and 6–7 kmol·m −3 locally. Further, the intercalation current density in-plane relative standard deviation can reach extremely high values, around 100% in the cathode and well above 100% in the anode graphite. These denote highly non-uniform lithiation rates and material utilization within each slice of the microstructure along the cell thickness. Non-uniform curvatures, at the particle scale (surface roughness) and between particles (size distribution), were found to initiate these in-plane heterogeneities, while an OCP-induced mechanism subsequently regulates them. The present model provides new insights into small length scale heterogeneity impact on battery performance not available with standard macro-scale/P2D modeling.

25 ENERGY STORAGE↗
DOE OSTI2020

Effects of bubbles on the electrochemical behavior of hydrogen-evolving Si microwire arrays oriented against gravity

The size-distribution, coverage, electrochemical impedance, and mass-transport properties of H 2 gas-bubble films were measured for both planar and microwire-array platinized n + -Si cathodes performing the hydrogen-evolution reaction in 0.50 M H 2 SO 4 (aq). Inverted, planar n + -Si/Ti/Pt cathodes produced large, stationary bubbles which contributed to substantial increases in ohmic potential drops. In contrast, regardless of orientation, microwire array n + -Si/Ti/Pt cathodes exhibited a smaller layer of bubbles on the surface, and the formation of bubbles did not substantially increase the steady-state overpotential for H 2 (g) production. Experiments using an electroactive tracer species indicated that even when oriented against gravity, bubbles enhanced mass transport at the electrode surface. Microconvection due to growing and coalescing bubbles dominated effects due to macroconvection of gliding bubbles on Si microwire array cathodes. Electrodes that maintained a large number of small bubbles on the surface simultaneously exhibited low concentrations of dissolved hydrogen and small ohmic potential drops, thus exhibiting the lowest steady-state overpotentials. The results indicate that microstructured electrodes can operate acceptably for unassisted solar-driven water splitting in the absence of external convection and can function regardless of the orientation of the electrode with respect to the gravitational force vector.

25 ENERGY STORAGE↗
DOE OSTI2019

Electrochemically-Driven Phase Transformations in Battery Compounds (Final Technical Report)

Ion-insertion compounds for advanced batteries frequently exhibit phase transformations as the concentration of the working ion varies. Under the large electrochemical driving forces inherent to practical use, systems are often driven far from equilibrium and exhibit phase transition behavior not seen in other materials. An improved understanding of phase transformation pathways in electrode materials upon cycling will lead to new materials design concepts and electrochemical duty cycle management strategies that improve capacity utilization at high charge/discharge rates, reduce voltage and capacity hysteresis, and extend battery life. The main goal of this project is to develop a predictive understanding of the phase transition behavior of battery compounds when electrochemically driven far from equilibrium through a combined experimental- theoretical approach. Research focuses on elucidating how the phase transition behaviors in a diverse group of selected model systems (olivines, lithium metal, etc.) are regulated by various factors including transformation strains, plasticity, metastable transformation pathways, electrode microstructure, surface reaction and ion diffusion kinetics, and what are the unique features of phase transitions in battery compounds. To this end, operando X-ray-based characterization techniques are applied to interrogate the structure and composition evolution of electrode materials and interfaces at nano- and meso-scales. Mesoscale modeling techniques such as phase-field simulation are employed to shed light on the experimental observations and establish a unified framework for describing phase transition behaviors in battery compounds.

25 ENERGY STORAGE↗
DOE OSTI2022

Numerical modeling of ion transport and adsorption in porous media: A pore-scale study for capacitive deionization desalination

In this report a pore-scale model is presented to simulate the dynamic ion transport and adsorption processes in porous electrodes used for capacitive deionization (CDI). The Stokes equation governing water flow is solved using the lattice Boltzmann method and Nernst-Planck equation describing ion transport is solved using the finite volume method. The ion adsorption process is considered at the surface of carbon electrodes. After validation against analytical solutions and published results, the model is used to study the coupled water flow, ion transport and adsorption in both two-dimensional and three-dimensional porous CDI electrodes at the pore scale. The effect of electrode microstructure, electrical potential and flow velocity on the adsorption processes is quantitatively investigated, and the relative importance of various parameters is determined. The presented model can be a powerful numerical tool to quantitatively analyze ion transport and adsorption in porous electrodes, and may provide useful information for the design and optimization of CDI electrodes and operating conditions for desired desalination efficiency, water throughput and cost.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

An immersed interface method for microstructure-scale electrochemical battery models: numerical formulation and performance portable implementation

We present the numerical formulation, verification, and performance portable implementation of an immersed interface method for microstructure scale electrochemical modeling of batteries. The innovation in this approach is the resolution of chemical species and electrostatic potential discontinuities at active interfaces without the use of interface conforming unstructured grids. A unified formulation on Cartesian grids for all domains (electrodes and electrolyte) is used with interfacial flux conditions applied using volume fraction or “color” function gradients. We have developed one dimensional and two dimensional test cases with analytic solutions for electrochemical modeling using which we verified the consistency and accuracy of our scheme. Our solver is also validated against solutions from a macroscale model and an unstructured multi-subdomain solver for a full lithium ion cell. We then demonstrated the utility of our solver on an image-based complex battery electrode microstructure at high charging rate. Our technique also exhibits good scalability on distributed memory architectures using central processing units (CPU), with problem sizes up to 1.8 billion degrees of freedom and with 5400 ranks. Initial performance studies of our open-source performance portable solver showed about 70 times speed up using a graphics processing unit (GPU) compared to single compute core for a problem with 4 million cells.

25 ENERGY STORAGE↗
DOE OSTI2025

Depth-Resolved Lithiated Gradients in Pristine and Laser-Ablated Anodes During Fast Charging

Laser ablating 3D electrode microstructures is a technique to improve Li-ion battery fast-charge performance. This technique has been theoretically proposed and electrochemically validated previously in the literature. The fundamental principle underlying laser ablation is that the ablated features reduce Li-ion transport pathways, improving access to the electrode active material near the current collector. This, in turn, promotes more homogeneous electrode utilization. The present study seeks to directly affirm the physics attributed to laser ablation using operando high-speed synchrotron X-ray diffraction. In this study, depth-resolved graphite lithiation gradients are measured operando during high-rate (15 min) charging. The depth-resolved lithiation dynamics of both ablated and non-ablated anodes are compared. The results highlight that the laser-ablated graphite electrode has notably more homogeneous utilization as compared to the non-ablated electrode. Additionally, the ablated electrode has a significant delay in reaching the maximum graphite lithiation at the separator, indicating less propensity for lithium plating. During low rate delithiation/discharge (2 hr), the two cells' lithiation gradients converge. Notably, a calibrated physics-based electrochemical model accurately reflects experimental findings, suggesting the potential to use pseudo-4D models not only to optimize laser ablation parameters in fast-charge capable electrodes but also to guide fast charging protocols that avoid lithium plating.

25 ENERGY STORAGE↗
DOE OSTI2020

Elucidating the Role of Ionomer in the Performance of Platinum Group Metal-free Catalyst Layer via in situ Electrochemical Diagnostics

The ionomer content in platinum group metal (PGM)-free polymer electrolyte fuel cell (PEFC) cathode catalyst layer (CCL) plays an important role in the electrode gas transport properties, proton conductivity, and hence, membrane electrode assembly (MEA) performance. In this work, the ionomer content in the CCL is varied, influencing electrode microstructure by altering porosity, tortuosity, as well as ionomer distribution and coverage of the catalyst particles. A novel technique consisting of a H 2 pump, combined with a Pt black sensor layer, is used to measure the bulk mass transport resistance of a series of PGM-free CCL prepared with different ionomer contents. The values for bulk electrode mass transport resistance are contrasted with electrode proton transport resistance in the cathode catalyst layer, establishing a clearly defined trade-off between two key performance limiting phenomena and identifying a need for novel PGM-free electrode fabrication strategies.

25 ENERGY STORAGE↗
DOE OSTI2020

Correlative electron and ion beam analysis of the electrochemical performances of LiV 3 O 8 cathode films as a function of microstructures

Degradation mechanisms in LiV 3 O 8 cathode films (~500 nm) with different initial microstructures i.e., globular nanocrystals in amorphous matrix and needle-like nanocrystals, synthesized by annealing the cathodes at 150 °C and 300 °C for 6 h are studied by Transmission Electron Microscopy (TEM) and Auger Electron Spectroscopy (AES). In addition, a unique in-situ combination of TEM and Secondary Ion Mass Spectrometry (SIMS) imaging techniques, namely Parallel Ion and Electron beam Spectrometry (PIES) is carried out to measure the 3D distribution of V and Li with nanoscale resolution. These characterization studies focus on correlating the pre- and post-cycling microstructure to observed electrochemical performance. The LiV 3 O 8 cathode film with needle-like nanocrystals (300 °C) shows a higher initial capacity but it degrades rapidly compared to the film with globular nanocrystals embedded in amorphous matrix (150 °C). We observed that LiV 3 O 8 films with needle-like nanocrystals are more susceptible to cathode decohesion and vanadium dissolution than the films with globular nanocrystals embedded in amorphous matrix, explaining the differences in their electrochemical performance. The findings from this study have relevance to the development of thin film electrode microstructures for high capacity and cyclic stability.

25 ENERGY STORAGE↗
DOE OSTI2025

Enhancing surface activity and durability in triple conducting electrode for protonic ceramic electrochemical cells

With the material system operating at lower temperatures, protonic ceramic electrochemical cells (PCECs) can offer high energy efficiency and reliable performance for both power generation and hydrogen production, making them a promising technology for reversible energy cycling. However, PCEC faces technical challenges, particularly regarding electrode activity and durability under high current density operations. To address these challenges, we introduce a nano-architecture oxygen electrode characterized by high porosity and triple conductivity, designed to enhance catalytic activity and interfacial stability through a self-assembly approach, while maintaining scalability. Electrochemical cells incorporating this advanced electrode demonstrate robust performance, achieving a peak power density of 1.50 W cm −2 at 600 °C in fuel cell mode and a current density of 5.04 A cm −2 at 1.60 V in electrolysis mode, with enhanced stability on transient operations and thermal cycles. The underlying mechanisms are closely related to the improved surface activity and mass transfer due to the dual features of the electrode structure. Additionally, the enhanced interfacial bonding between the oxygen electrode and electrolyte contributes to increased durability and thermomechanical integrity. This study underscores the critical importance of optimizing electrode microstructure to achieve a balance between surface activity and durability.

Protonic Ceramic Electrochemical Cells↗