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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Elucidating Lithium Alloying-Induced Degradation Evolution in High-Capacity Electrodes

Alloy electrode materials offer high capacity in lithium ion batteries; however, they exhibit rapid degradation resulting in particle disintegration and electrochemical performance decay. Here in this study, the evolution of lithium alloying induced degradation due to electrochemo-mechanical interactions is examined based on a multi-pronged electrochemical and microstructural analysis. Copper-tin (Cu 6 Sn 5 ) is chosen as an exemplary alloy electrode material. Electrodes with compositional variations were fabricated and electrochemical performance was examined under varying conditions including voltage window, C-rate, and short- and long-term cycling. Morphology and composition analyses of pristine and cycled electrodes were conducted using micrography and spectroscopy techniques. Alloying induced electrode microstructural evolution was probed using X-ray microtomography. The rapid capacity fading was found to be caused by mechanical degradation of the electrode. Driving the electrode to a lower potential (E ≈ 0.2 V vs. Li/Li + ) induced Li-Sn alloy formation and provided the characteristic large capacity; however, this led to a large volume expansion and active particle cracking and disintegration. Copper expulsion was found to be a consequence of the alloy formation; however, it was not the primary contributor to the dramatic electrochemical performance decay.

25 ENERGY STORAGE↗
DOE OSTI2022

Nanoscale Three-Dimensional Imaging of Degradation in Composite Si-Containing Anodes

The use of silicon (Si) in next-generation lithium-ion battery (LIB) anodes has the potential to dramatically improve electrochemical performance over current LIB graphite (Gr) anodes, due to silicon’s higher specific capacity.1 However, widespread implementation of Si-containing anodes is inhibited by issues such as significant Si volume expansion during lithiation and an unstable solid-electrolyte interphase (SEI), resulting in unreliable performance and poor cycle life. Currently, composite anodes with both Si and graphite active materials are used to increase capacity and mitigate some of the limitations associated with Si. In composite electrodes with a heterogeneous distribution of components with varying electrical properties (including Si, Gr, conductive carbon additive, and binder), it is important to understand the local distribution of each component to correlate with electrochemical processes, particularly localized degradation and heterogeneous aging, and to optimize performance. To investigate Si-containing composite anodes in the nanoscale, we use scanning spreading resistance microscopy (SSRM), a form of scanning probe microscopy (SPM) that probes local electronic resistivity. By examining the intrinsic electronic resistivity contrast between the anode components, separate phases can be distinguished and understood within the composite structure.2 This work studies the effect of electrochemical cycling in two different electrolytes on component distribution and aging by comparing the electrical and structural evolution of composite Si-graphite electrodes and SEI before and after charge-discharge cycling. 1. W. J. Zhang. A review of the electrochemical performance of alloy anodes for lithium-ion batteries J. Power Sources 196 13–24 (2011). 2. C. Stetson, Z. Huey, A. Downard, Z. Li, B. To, A. Zakutayev, C.-S. Jiang, M. Al-Jassim, D. Finegan, S.-D. Han and S. DeCaluwe: Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries. ACS Nano Letters Accepted (2020).

ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2024

When and Where Lithium Plating Occurs, Its Correlation with Microstructure Heterogeneity, and the Mechanisms That Initiate and Self-Regulate Electrochemical Heterogeneity (A02-0444)

A microstructure scale electrochemical LIB model was used to investigate lithium plating onset, material non-uniform utilization, and in-plane heterogeneities for an NMC-graphite full cell. Model predicts active material particle surface roughness and size distribution (respectively, non-uniform curvature within and between particles) initiate in-plane heterogeneity, and that particle size heterogeneity at the separator interface controls the lithium plating preferential deposition ("Where"). These in-plane heterogeneities are then exacerbated by through-plane heterogeneities induced at fast charge as electrolyte depletion occurs and concentrates intercalation reaction near the anode-separator interface. Also, magnitude and occurrence of lithium plating is controlled by effective, or macroscale, microstructure parameters ("When"). As local states of charge start to diverge between nearby active material regions, overpotential differences induced by OCP difference kick in and contribute to reduce these SOC local heterogeneities. However, for staged materials such as graphite, with OCP profile alternating between plateaus and varying regions, this balancing mechanism is, respectively, inactive and active. This leads to a dynamic, non-monotonic, in-plane heterogeneity time evolution for state of charge and Faraday current density, for which their respective in-plane heterogeneity magnitude alternates. Such behavior has been modeled both for the whole electrode at the microstructure scale and at the particle scale. In-plane heterogeneities are usually considered to be detrimental, as they result in material non-uniform utilization (i.e., under and over stressed regions) and earlier degradations. However, this work provides a more granular approach as it discriminates between a harmful in-plane heterogeneity (non-uniform curvature) that triggers SOC in-plane heterogeneity, and a beneficial in-plane heterogeneity (Faraday current density) that contributes to reduce SOC in-plane heterogeneity. This work comprehensively explains the mechanisms that initiate, exacerbate, and regulate heterogeneity at the microstructure scale, while providing some design suggestions to reduce both in-plane and through-plane heterogeneities, as summarized in the graphical abstract.

ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2021

Effect of Nanoscale Ce 0.8 Gd 0.2 O 2–δ Infiltrant and Steam Content on Ni–(Y 2 O 3 ) 0.08 (ZrO 2 ) 0.92 Fuel Electrode Degradation during High-Temperature Electrolysis

Studies of Ni–yttria-stabilized zirconia (YSZ) fuel electrode degradation mechanisms in solid oxide electrolysis cells (SOECs) are complicated by the different possible Ni–YSZ microstructures and compositions, and the variations in the H 2 /H 2 O ratio encountered in an electrolysis stack. Here, in this study, we describe a life testing scheme aimed at providing survey results on degradation as a function of the H 2 O–H 2 composition, with life tests carried out at five different steam contents from 90% to 10%. A Ni–YSZ-supported symmetric cell geometry is employed both with and without infiltrated nanoscale gadolinia-doped ceria (GDC). Impedance spectroscopy is utilized to observe changes in electrochemical characteristics during the life test, and a transmission-line-based equivalent circuit is used to model the data. Post-test electrode microstructures were observed. The results suggest that the GDC infiltrant reduces the electrode polarization resistance and provides more stable electrode polarization over a range of conditions.

08 HYDROGEN↗
DOE OSTI2022

Precision surface modification of solid oxide fuel cells via layer-by-layer surface sol–gel deposition

While solid oxide fuel cells (SOFCs) are a promising technology for a clean and sustainable future, their commercialization is hindered by limited durability and performance. Here, we report our findings on the application of a layer-by-layer surface sol–gel (SSG) coating of catalysts to dramatically enhance the electro-catalytic activity and durability of SOFC cathodes. The SSG process is capable of penetrating and preserving complex backbone microstructures of porous electrodes, creating highly conformal coatings of controlled morphology, while tailoring the composition of the surface to improve catalytic properties and durability. For example, the application of an SSG coating of PrO x to a La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3–δ (LSCF) cathode has reduced the polarization resistance from 1.136 to 0.117 Ω cm 2 at 600 °C and the degradation rate from 1.13 × 10 –3 to 2.67 × 10 –4 Ω cm 2 h –1 at 650 °C. In addition, a continuous improvement in electrode performance is demonstrated as the thickness of the coating is increased, corresponding to the linear addition of catalyst. Furthermore, this first application of the SSG technique to SOFC systems opens the door for the controlled surface modification of porous components in electrochemical systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Electrolysis Performance Improvement Concept Study (EPICS) flight experiment phase C/D

The overall purpose of the Electrolysis Performance Improvement Concept Study flight experiment is to demonstrate and validate in a microgravity environment the Static Feed Electrolyzer concept as well as investigate the effect of microgravity on water electrolysis performance. The scope of the experiment includes variations in microstructural characteristics of electrodes and current densities in a static feed electrolysis cell configuration. The results of the flight experiment will be used to improve efficiency of the static feed electrolysis process and other electrochemical regenerative life support processes by reducing power and expanding the operational range. Specific technologies that will benefit include water electrolysis for propulsion, energy storage, life support, extravehicular activity, in-space manufacturing and in-space science in addition to other electrochemical regenerative life support technologies such as electrochemical carbon dioxide and oxygen separation, electrochemical oxygen compression and water vapor electrolysis. The Electrolysis Performance Improvement Concept Study flight experiment design incorporates two primary hardware assemblies: the Mechanical/Electrochemical Assembly and the Control/Monitor Instrumentation. The Mechanical/Electrochemical Assembly contains three separate integrated electrolysis cells along with supporting pressure and temperature control components. The Control/Monitor Instrumentation controls the operation of the experiment via the Mechanical/Electrochemical Assembly components and provides for monitoring and control of critical parameters and storage of experimental data.

Schubert, F. H.↗
DOE OSTI2021

Large-Area Lithium Electrode Sub-Assemblies (LESAs) Protected by Self Forming Microstructured Polymer-Inorganic Single-Ion Conducting Composites (Final Report)

The aim of this project is to realize a low-cost, safe, reversible, high-areal capacity lithium metal electrode though the use of scalable, low-cost Lithium Electrode Sub-Assembly (LESA). At its core, the LESA applies novel polymer scaffolds to nanostructure inorganic ionic materials into high-conductivity composites that stabilize lithium anodes during high-rate, high-capacity cycling in lithium metal batteries. Fundamental investigations from this project identified a newly defined region of stability for composites with respect to the shear modulus and lithium molar volume ratio which have been broadly applied in the scientific literature for a multitude of different systems. The advancements achieved in this field have furthered the fundamental understanding of lithium metal electrode chemistry and degradation mechanisms and resulted in a lithium metal anode with improved cycle life.

25 ENERGY STORAGE↗
DOE OSTI2025

Laser ablation of high-loading Li-ion battery electrodes improves accessible capacity and cycle life for Behind-the-Meter Storage

Adoption of Behind-the-Meter Storage (BTMS) requires design of batteries that enable high safety, long cycle life, and low cost at the system level. Pairing Li 4 Ti 5 O 12 (LTO) with LiMn 2 O 4 (LMO) achieves targets related to safety and cycle life, but these materials' low energy densities contribute to higher cost at the system scale. Increasing electrode loading is a simple approach to improve energy density, but comes with a trade-off in electrode utilization due to long, tortuous Li + diffusion pathways. Here, laser ablation is used to microstructure (pattern) high-loading electrodes to enhance electrode performance through improved Li + diffusion pathways. Four cell types, comprising combinations of standard or patterned anode and cathode, were prepared to evaluate the effects of laser ablation at each electrode. A rate test shows that patterning electrodes enhances active material utilization at ≳1C rates. Patterning the cathode yields the most benefit, as cells with a patterned cathode demonstrate a ~20% higher accessible capacity than those without at 1.4C. Additionally, 1C capacity retention of cells with patterned cathode (91% through 3000 cycles) is significantly improved over cells with only the anode patterned (64%) and non-patterned electrodes (50%). Characterization of post-mortem cells before and after refreshing their electrolyte suggests that 1C capacity retention is improved by mitigation of electrode "dry-out". We hypothesize that the microstructure acts as a reservoir of additional electrolyte, or a path for gas to escape, so that active material remains wetted throughout long-term cycling, and/or the microstructure may reduce localized, gas-forming overpotentials in the high-loading electrode.

25 ENERGY STORAGE↗
DOE OSTI2026

Passivation‐Induced Species Dynamics and Microstructural Evolution in Solid‐State Lithium–Sulfur Cathodes

Solid-state lithium–sulfur (SSLS) batteries offer high theoretical energy density, yet their practical viability is hindered by poor sulfur utilization and limited rechargeability. At the core of this challenge lies the passivating nature of Li 2 S, which restricts ionic and electronic transport, suppresses interfacial activity, and severely impedes the reversibility of electrochemical reactions. In this study, we elucidate the mechanistic origins of these limitations by resolving how charge and discharge species form, grow, and spatially evolve within the cathode microstructure under varied current densities and electrode compositions. By resolving the species distribution at the particle scale and coupling it with Raman spectroscopy and X-ray diffraction, we demonstrate how Li 2 S formation induces localized surface passivation that progressively limits electrochemical accessibility within the cathode microstructure. Sulfur utilization is found to be strongly governed by the interplay between sulfur loading, residual porosity, and interfacial architecture. High sulfur contents result in buried, electrochemically isolated domains due to poor solid electrolyte (SE) percolation, while low sulfur contents trigger SE degradation via parasitic reactions. The resulting sulfur-porosity maps delineate the mechanistic boundaries between reversible and transport-limited regimes, offering actionable design guidance for SSLS cathodes with enhanced sulfur utilization.

electrode microstructure↗
DOE OSTI2019

Determination of Thermodynamic Properties of Si-B Alloys

This study establishes the thermodynamic properties of the Si-B binary alloy system. The electromotive force (emf) as a function of temperature (823 K to 923 K) was measured using solid-state electrochemical cells, represented as(−) Pt,Ar/{Si∥CaF_2∥} {Si−B(alloy)}/Ar,Pt(+) Using the experimental emf data obtained from the solid-state heterogeneous phase equilibrium, the activities of Si and B in Si-B alloys were calculated. The integral Gibbs energy of mixing (ΔG{sup M}) of alloys were calculated from the activity of Si and B. A large negative deviation from ideality was found for the integral Gibbs energy of mixing (ΔG{sup M}) of the binary Si-B system. From the activities of Si and B, the Gibbs energies of formation (ΔG{sub f}{sup 0}) of phases present were calculated. The ΔG{sub f}{sup 0} of SiB{sub 3}, the most thermodynamically stable phase, was calculated as − 13.13 ± 0.19 kJ/mole-atoms at 923 K. The heterogeneous phases and microstructure after the equilibrium study of the electrode were characterized using XRD, SEM, and EDS analyses.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Forming more and sharper sensing protrusions on graphene-based electrodes through annealing

A better understanding of the microstructure, physicochemical properties, and sensing behavior of an electrode is critical in developing quick, high sensitivity, and robust electrochemical sensors. Here, in this study, a single electrode was fabricated with self-prepared graphene ink through a drop-cast process followed with a subsequent annealing treatment. The graphene ink-based electrodes were characterized through AFM, contact angle, FTIR, impedance spectra, Raman, and SEM to understand annealing treatment effects. The dynamic response of the electrode to humidity, and vapors of ethanol, propanol, or acetone was measured using a four-point probe station in a closed chamber. The annealing treatment increased the conductivity of the electrode and improved its sensing performance by forming more and sharper protrusions on the electrode surface. These unique surface protrusions suggest that the annealed graphene ink-based electrodes hold great potential in developing high-performance electrochemical sensors.

42 ENGINEERING↗
DOE OSTI2019

Atomic layer deposition in porous electrodes: A pore-scale modeling study

Coating porous electrodes of Li-ion batteries with functional materials by atomic layer deposition (ALD) can enhance their capacity stability. Because of the complex microstructure of the porous electrodes, predicting the required exposure time of the precursors for achieving a desired coating and the coating characteristics for a given exposure time remains difficult. Here, a three-dimensional (3D) pore-scale lattice Boltzmann model is developed to investigate the reactive transport processes during the ALD of reconstructed electrodes and to assess the accuracy of one-dimensional (1D) mean-field models. The effects of the hierarchical structure of pores and their connectivity on the coating process of ALD are investigated and the detailed coating characteristics in the electrodes are resolved. Electrodes with smaller pore sizes requires a longer exposure time to achieve full coating. At the same depth within an electrode, the smaller pores are coated more slowly than the wider pores (especially at high Damkohler numbers) and the coating speed of well-connected pores are faster than that of poorly connected pores. Furthermore, simulations also reveal that the 1D mean-field model can capture the average coating characteristics reasonably well when pores in the electrodes are well connected but may perform poorly if the pores are poorly connected.

25 ENERGY STORAGE↗
DOE OSTI2022

Interplay of Electrode Heterogeneity and Lithium Plating

Lateral microstructure heterogeneity in anodes is known to induce nonuniform current density, state of charge, and lithium plating. This means that such electrode heterogeneity can limit the fast charging of lithium-ion batteries. In this work, a combination of experiments and simulation is employed to understand the effect of mm scale lateral heterogeneity on cell aging. A previously developed model was extended to efficiently simulate SEI formation and Li plating for independent regions of an electrode. The model consists of three parallel regions each described under a P2D framework and with a distinct ionic resistance and possibly active material loading. The results suggest that during fast charge when the active material is uniformly distributed across the three regions, the region with the highest resistance reaches the end of life sooner than the other regions. There is also positive feedback from Li metal filling the pores near the separator interface that further accelerates lithium plating. Lastly, when there is a non-uniform active material distribution associated with the ionic resistance heterogeneity, tight competition between regions can occur, leading to less overall lithium plating and plating that is more uniform between regions.

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

Dynamic In‐Plane Heterogeneous and Inverted Response of Graphite to Fast Charging and Discharging Conditions in Lithium‐Ion Pouch Cells

Solutions for improving fast charging of lithium‐ion batteries have largely focused on alleviating through‐plane lithiation gradients while little is understood about in‐plane heterogeneities and how to resolve them. Herein, high‐speed synchrotron X‐ray diffraction (XRD) resolves graphite lithiation spatially and temporally during 6 C charging and 2 C discharging. At every point during operation, considerable differences in the state of lithiation across the pouch cell are present. Some regions are more responsive to operation than others, reaching full lithiation early during charge and full delithiation during discharge. Other regions within the cell never fully delithiate during discharge, despite a prolonged voltage hold at 2.8 V. Using time‐resolved XRD data, the calculated local current density (mA cm −2 ) at the graphite surface shows an unexpected occurrence of local inverted current densities where regions of graphite are observed to delithiate during charging and lithiate during discharging. A pseudo‐3D model is developed for the graphite electrode with spatially varying microstructural tortuosity to show how microstructural heterogeneity could influence spatial charge dynamics. The model could not predict the complex in‐plane charge behavior observed within the cell. Consequently physics‐based charging protocols based on homogeneous electrode assumptions may underestimate the local variations in charge dynamics and occurrence of lithium plating.

25 ENERGY STORAGE↗
DOE OSTI2025

Microstructure-based modeling of inner oxygen pressure in solid oxide electrolysis cells: Analysis of electrode delamination and mitigation

One major degradation mechanism during long-term operation of solid oxide electrolysis cells (SOECs) is delamination of oxygen electrodes (OEs). The driving force for the electrode delamination could be the generated high inner oxygen pressure near the electrode-electrolyte interface during operation. However, the effects of transport properties and electrode thickness on the inner oxygen partial pressure are not well understood. Here a microstructure-based electrochemical model, which includes the conduction of electrons and oxygen ions coupled with Butler-Volmer-type chemical reactions at triple-phase-boundaries (TPBs), is employed to investigate the oxygen pressure in lanthanum strontium manganate (LSM)-based SOECs. The model is applied to both two-dimensional (2D) prototype microstructures and three-dimensional (3D) realistic microstructures, and the oxygen pressure is analyzed as a function of transport properties and electrode thickness under both potentiostatic and galvanostatic operations. The simulation results suggest strategies to suppress electrode delamination. The simulation results are compared to an analytical solution, and the discrepancies are attributed to the Butler-Volmer-type kinetics included in the microstructure-based model.

25 ENERGY STORAGE↗