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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies

Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN 4 )-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm –2 at 0.7 V under HDV conditions (0.25 mgPt cm –2 and 250 kPa abs pressure) and retaining 1.20 A cm –2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. Importantly, the first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN 4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.

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

Extreme fast charge aging: Correlation between electrode scale and heterogeneous degradation in Ni-rich layered cathodes

Extreme fast charging (XFC) is a key requirement for the adoption of battery-based electric vehicles by the transportation sector. However, XFC has been shown to accelerate degradation, causing the capacity, life, and safety of batteries to deteriorate. There are no systematic studies in the open literature regarding aging modes in Ni-rich Li y Ni 0.a Mn 0.b Co 0.c O 2 (NMCabc) cathodes caused by fast charging. Herein, we report the effects of cathode composition and electrode loading in pouch cells containing NMC532, 622 and 811 paired with graphite and cycled under XFC conditions. The relative anisotropic volume change in the unit cell increases with Ni content in low-loading cells, while it levels up for all three NMC cathodes in high-loading cells because of substantial Li plating. The amounts of lithium plating and heterogeneity on the anode, determined by crystallographic phase quantification, were found to be correlated with electrode loading and cathode heterogeneity. The concentrations of the transition metals deposited on the anodes depend on NMCabc composition in a complex way. More particle cracking and surface degradation was found in NMC811. Here, the findings in this work provide a new understanding of the failure mechanisms and their practical implications for compositional tuning of future high-Ni NMCabc cathode materials during fast charging.

25 ENERGY STORAGE↗
DOE OSTI2026

Multiscale Cryo Electron Microscopy Reveals Interfacial Degradation and Stabilization in Battery Electrodes

Electrochemical interfaces are dynamic systems, evolving based on their local environment and reactant surface structures. The electrode-electrolyte interface in Li-ion batteries can be protective, limiting parasitic reactions with the electrolyte to passivate the surface [1]. Additionally, this interphase has an impact on the Li-ion transport through that layer based on its composition, bonding environment, and thickness. These parameters are challenging to collect and may vary depending on the electrode surface site investigated relative to its spatial position in a coin cell. This study will detail a multiscale cryogenic electron microscopy approach where millimeter-scale cross-sections through the coin cell batteries were made using a cryogenic stage within a fs-laser plasma focused ion beam (laser PFIB) with complementary energy dispersive X-ray spectroscopy able to detect variations in the composition at electrode interfaces [2]. Microscale cross-sectioning and lamella sample preparation of battery electrodes was conducted at the Center for Integrated Nanotechnologies using a Ga-ion focused ion beam (FIB) with air-free and cryo-transfer [3], followed by nanoscale mapping of composition and bonding within the CEI through cryo-scanning transmission electron microscopy (cryo-STEM) electron energy loss spectroscopy [4]. This multiscale approach enabled identification of millimeter-scale features of a battery stack with visualization of degradation in electrodes such as cracks in cathode particles, gas evolution, and SEI evolution; microscale interfacial characteristics, such as heterogeneity in the SEI or barrier layer and identification of electrolyte networks to the electrode surfaces; and nanoscale measurement of the CEI thickness, mapping of transition metal bonding within the cathode particles to identify loss of active materials, and identification of beneficial electrolyte additives incorporated into the CEI structure. This multiscale approach allows for a statistical understanding of the primary mechanisms and parasitic degradation pathways that impact performance by limiting the ion transport pathways within Li+ batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Degradation of Fuel Cell Membrane Electrode Assemblies from Buses Operated More than 25,000 h

This study investigates the performance losses and degradation of proton-exchange-membrane fuel-cell stacks taken from the Alameda Contra Costa Transit District (AC Transit) bus system (Alameda and Contra Costa counties, California, United States) that were operated for over 25,000 h. Here, we focus on the origin of differences in electrochemical performance between beginning-of-life (BOL) and end-of-life states as well as diagnostic data acquired during the lifetime of the buses. In doing so, we employ in- and ex- situ characterization methods such as polarization curves, electrochemical impedance spectroscopy, electron microscopy, and X-ray characterization. Uniform degradation of the catalyst layer including Pt agglomeration/migration and electrode thinning was observed in all of the post-teardown measurements compared to BOL materials resulting from years of field operation. Despite these changes, the measured post-teardown performance suggests a sufficient output for the expected load, which indicate factors other than degradation of the membrane-electrode assemblies (MEAs) are likely responsible for the decommissioning of the stacks. The findings indicate that these MEA materials can enable long lifetime in fuel-cell vehicles, if the MEAs are not subjected to adverse operating conditions. The results also highlight the need for more in-vehicle diagnostics to maximize the lifetime of fuel cell vehicle (FCV) powerplants.

25 ENERGY STORAGE↗
DOE OSTI2024

Theoretical Understanding of Effects of Operating Modes on the Performance Durability of Solid Oxide Cells: A Comparison between Potentiostatic and Galvanostatic Operations

In solid oxide cells (SOCs), the choice between galvanostatic (constant current) and potentiostatic (constant voltage) modes does not significantly affect the performance of SOCs as long as the cell components remain unchanged and intact. However, the degradation of cell components, which leads to changes in electrochemical and physical properties of the cell, elevates the importance of the selected operating mode. This paper aims to investigate the effects of galvanostatic and potentiostatic operating modes on the evolving properties of SOCs and their subsequent influence on performance durability. Employing non-equilibrium thermodynamic analysis, a crucial approach for understanding the degradation phenomena within an active electrochemical system, this study aims to provide in-depth insights into how these operating modes affect the longevity and efficacy of SOCs. Key findings include: In cases where oxygen electrode (OE) degradation is accelerated by higher partial pressure of oxygen ( p O 2 ), operating under constant voltage electrolysis can mitigate the high p O 2 at the OE|electrolyte (OE|EL) interface. Conversely, if OE degradation occurs more rapidly under a lower p O 2 , constant current electrolysis is more effective in suppressing degradation by achieving a high p O 2 at the OE|EL interface. For degradation of the fuel electrode (FE) due to higher p O 2 , constant current electrolysis is beneficial for more stable performance, which helps maintain low p O 2 at the FE|EL interface. When FE degradation is accelerated by lower p O 2 , constant voltage electrolysis can avert low p O 2 at the FE|EL interface. In practical scenarios, more complex degradation mechanisms come into play, especially when p O 2 significantly deviates from initial conditions. Degradation in one electrode can influence p O 2 in the other electrode, a phenomenon more pronounced in potentiostatic than in galvanostatic electrolysis.

Electrochemistry↗
DOE OSTI2026

Evaluating the Effects of Anode Porous Transport Layer on the Performance and Durability of Anion Exchange Membrane Electrolyzers

As anion exchange membrane systems have emerged as a competitive low temperature electrolysis technology, research has expanded to other components and device integration. In this study, nickel (Ni) and stainless steel (SS)-based porous transport layers (PTLs) are investigated in membrane electrode assemblies (MEAs). Compared to MEAs using Ni, the SS PTL shows higher performance due to less kinetics and residual loss and possibly due to a combination of iron mobility improving oxygen evolution reactivity and electron conduction pathways, as well as higher porosity increasing site access. Voltage decay rates of approximately 144 and 115 μV/h, respectively, for the Ni and SS PTLs are found, although the long-term durability and lifetime implications are convoluted. Voltage breakdown analysis confirms that both PTLs saw significant increases in residual loss possibly due to catalyst/PTL property changes that affected electronic, ionic, and mass transport pathways. For the Ni PTL, a higher proportion of the losses were due to cell kinetics; comparatively, more of the SS PTL losses were due to increases in the high frequency resistance. The experimental findings presented here provide insights on the impact of the PTL materials and their properties.

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

Binder-Free Cnt Cathodes for Li-O 2 Batteries with More Than One Life

Li-O 2 batteries (LOB) performance degradation ultimately occurs through the accumulation of discharge products and irreversible clogging of the porous electrode during the cycling. Electrode binder degradation in the presence of reduced oxygen species can result in additional coating of the conductive surface, exacerbating capacity fading. Herein, a facile method to fabricate free-standing is established, binder-free electrodes for LOBs in which multi-wall carbon nanotubes form cross-linked networks exhibiting high porosity, conductivity, and flexibility. These electrodes demonstrate high reproducibility upon cycling in LOBs. After cell death, efficient and inexpensive methods to wash away the accumulated discharge products are demonstrated, as reconditioning method. The second life usage of these electrodes is validated, without noticeable loss of performance. These findings aim to assist in the development of greener high energy density batteries while reducing manufacturing and recycling costs.

25 ENERGY STORAGE↗
DOE OSTI2022

High‐Performance and Durable Fuel Cells using Co/Sr‐Free Fluorite‐Based Mixed Conducting (Pr,Ce)O 2‐δ Cathode

Abstract A major challenge to overcome in demonstrating solid oxide fuel cells (SOFCs) to be suitable as efficient and environmentally friendly energy conversion devices capable of addressing pressing clean energy and environmental needs is to surmount chemical and thermo‐mechanical instabilities in their operational phase. To date, perovskite‐based mixed conducting cathodes, which include inherent Co and Sr elements for enhanced reactivity and conductivity, have been intensively studied. These Co/Sr‐based oxides, however, exhibit severe thermochemical expansion and suffer from Sr surface segregation, ultimately degrading the electrode performance. Here, high‐performance and durable SOFCs are demonstrated by employing a Co/Sr‐free fluorite‐based mixed conducting (Pr,Ce)O 2‐δ (PCO) cathode eminently compatible with fluorite‐based solid electrolytes. The nanocolumnar PCO electrode developed in this study provides not only a remarkable low level of electrode resistance (e.g., ≈0.05 Ω cm 2 at 600 °C) but also exceptional long‐term stability (e.g., a degradation rate 15 times slower compared to the state‐of‐the‐art La 0.6 Sr 0.4 CoO 3‐δ perovskite). The competitive peak power densities of an anode‐supported single cell with the PCO cathode are also successively achieved, recording a value of 0.92 W cm −2 at 600 °C. These findings herald the development of new Co/Sr‐free electrodes for SOFCs at intermediate temperatures.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2025

Characterizing Electrode Materials and Interfaces in Solid-State Batteries

Solid-state batteries (SSBs) could offer improved energy density and safety, but the evolution and degradation of electrode materials and interfaces within SSBs are distinct from conventional batteries with liquid electrolytes and represent a barrier to performance improvement. Over the past decade, a variety of imaging, scattering, and spectroscopic characterization methods has been developed or used for characterizing the unique aspects of materials in SSBs. These characterization efforts have yielded new understanding of the behavior of lithium metal anodes, alloy anodes, composite cathodes, and the interfaces of these various electrode materials with solid-state electrolytes (SSEs). This review provides a comprehensive overview of the characterization methods and strategies applied to SSBs, and it presents the mechanistic understanding of SSB materials and interfaces that has been derived from these methods. This knowledge has been critical for advancing SSB technology and will continue to guide the engineering of materials and interfaces toward practical performance.

25 ENERGY STORAGE↗
DOE OSTI2021

Evaluating temperature dependent degradation mechanisms of silicon-graphite electrodes and the effect of fluoroethylene carbonate electrolyte additive

Understanding and overcoming the relatively high rate of degradation observed with silicon (Si)-based anodes in lithium (Li)-ion batteries (LiBs) is crucial for developing cells with increased energy density. The capacity fade of Si-graphite (Gr) electrodes in electrolytes with and without 10 wt% fluoroethylene carbonate (FEC) is explored during cycling at temperatures of 25, 45, and 70 °C, focusing on the complex degradation modes arising from loss of active material, loss of Li inventory, and cell resistance growth. We first show the common half-cell testing cannot be used at elevated temperatures as the performance of Li metal overshadows the behavior of Si-Gr electrode. Symmetric cell configuration successfully eliminates the effect of foreign materials, and reveals that while the presence of FEC provides better passivation of Si, it also results in greater parasitic reactions at 70 °C and faster capacity fade. The electrolyte without FEC, on the other hand, shows higher capacity retention at 70 °C. Finally, we propose a multi-step test protocol which can successfully deconvolute the information on loss of Li inventory and of active material. By combining half-cell and symmetric cell test methods, we demonstrate that loss of active material is reduced at higher temperatures and the dominant mechanisms of capacity loss for Si-Gr electrodes at elevated temperatures is loss of Li inventory.

25 ENERGY STORAGE↗
DOE OSTI2025

Assessment of Blocking Contacts in Suppressing Polarization Effects in CsPbBr 3 Perovskite Detectors

The CsPbBr 3 perovskite has garnered significant attention as a room-temperature semiconductor for hard radiation detection due to straightforward synthesis, scalable crystal growth, low cost, and excellent energy resolution. However, despite these advantages, at ambient temperature, CsPbBr 3 devices may experience performance deterioration and irreversible failure due to “polarization” induced by electromigration of ions to electrical connections on the device. In this study, we tested several contact materials and their optimization deposition techniques to assess the stability of high-performance CsPbBr 3 γ-ray detectors. Metals, with low work functions (Ti, In, Sn, Sb, Pb, Bi, Al, Au, and TiC) and high-work-function (Au or Pt) contacts, were used to form different Schottky junctions using vacuum thermal evaporation, electron-beam evaporation, and sputtering methods. These detectors were tested in intermittent and continuous modes to assess their stability. Among the tested detectors, the Bi/CLB/Pt electrode configuration demonstrated superior stability, operating effectively for 11 months under periodic testing and 16 days under continuous testing. In contrast, other configurations functioned only for a few months under intermittent conditions. Upon incorporating a ~40-nm-thick TiC passivation layer on the anode side (Bi/TiC/CLB/Pt), the CLB device operated continuously for 36 days without degradation. In many cases, the failure mode of the devices was due to the degradation of the anode. Here, the chemical changes in the fresh and deteriorated anodes were characterized using scanning electron microscopy and energydispersive X-ray spectroscopy

CsPbBr3 perovskite↗
DOE OSTI2025

LiNi0.8Mn0.1Co0.1O2 Thin Films Prepared by Polymer-Assisted Deposition for the Study of Cathode-Electrolyte Interphases in Lithium-Ion Batteries

High-nickel layered oxide cathodes such as LiNi0.8Mn0.1Co0.1O2 (NMC811) are critical for next-generation lithium-ion batteries (LIBs) due to their superior energy density and reduced reliance on cobalt. However, many Ni-rich cathodes suffer from rapid capacity fade and structural instability originating from complex interfacial reactions at the cathode-electrolyte interface. Traditional composite electrodes exhibit degradation mechanisms that are challenging to quantitatively understand due to additives, including binders and carbon black. In this study, we demonstrate a new synthesis approach for binder- and additive-free NMC811 thin films using polymer-assisted deposition (PAD). PAD-NMC811 are model thin-film cathodes for investigating interfacial phenomena that can be obscured in composite cathodes. Structural and chemical characterization by X-ray diffraction, soft X-ray absorption spectroscopy, and atomic force microscopy show that PAD-NMC811 films possess high phase purity, crystallinity, chemical homogeneity, and morphological uniformity. Electrochemical analyses using cyclic voltammetry and galvanostatic cycling revealed electrochemical behavior consistent with that of composite electrodes, along with a moderate capacity fade indicative of cathode-electrolyte interphase (CEI) formation. Our findings illustrate the effectiveness of PAD synthesis of thin films tailored for detailed mechanistic studies, which offer critical insights into CEI evolution and cathode degradation pathways.

25 ENERGY STORAGE↗
DOE OSTI2020

Materials and Approaches for Mitigation of SOFC Cathode Degradation in SOFC Power Systems

Perovskites such as doped lanthanum manganite and cobaltite have been used successfully as a cathode material in SOFC power systems operating between 700-1000°C. The electrodes, however, remain prone to degradation in presence of Cr containing gas atmosphere under systems operating conditions. Cathode in SOFCs is considered as one of the largest contributors of electrochemical performance degradations, leading to significant increase in ohmic and non-ohmic losses as well as interfacial compound formation. These degradations are mostly irreversible due to permanent changes to chemical and morphological alterations in the electrodes, resulting in the blockage of triple phase boundary (TPB) sites and decrease in oxygen reduction reactions (ORR). Fundamental mechanistic understanding has been developed to elucidate the reaction pathways of electrode poisoning in electronically conducting electrodes (LSM) as well as mixed ionic and electronically conducting electrodes (LSCF). The overall goal of this program has been identification and development of cost effective solutions to mitigate electrode degradations under “real world” systems operating conditions. The overall technological innovations and impact from this work are: The research provides an understanding of the degradation mechanism and cost-effective approaches for implementation in SOFC systems; Develop mitigation processes utilizing low cost getters using conventional synthesis and fabrication route; Develop tailored high surface area powders and coatings for high Cr capture capacity under systems operating conditions; >Developed computational models to understand mechanistic behavior; Experimentally measure rate of Cr evaporation from chromia and alumina forming alloys under SOFC operating conditions; Developed conditions to minimize Cr evaporation from balance-of-plant alloys; This innovation will support the development of getter platform to capture both intrinsic and extrinsic impurities present in air; and, Applications under wide operating temperature range (500-900°C) as well for wide high-temperature electrochemical systems (SOFC, SOEC, and OTM). The work has been successfully developed, validated experimentally and implemented. Successful technology transfer of this knowledge with industrial partners has been accomplished and the getters have been independently tested and validated under their systems operating conditions. The innovation will also find application in related high temperature electrochemical systems such as OTM and SOEC for the prevention of Cr assisted performance degradation. The proposed approach for Cr capture can also be applied to oxy-combustion and other advanced combustion techniques for the reduction of Cr vapor in the exhaust gas stream. This fundamental knowledge gained also has led to the path forward for developing advanced getters for capturing more than one contaminant in air.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

First-Principles Thermodynamic Assessments of Sr-Containing Secondary Phase Formation in La1-xSrxMnO3±δ Perovskites for Solid Oxide Cell Applications

Sr-secondary phase formation is a potentially significant degradation mode threatening solid-oxide cell (SOC) commercial viability. A first-principles thermodynamic study was performed for rhombohedral perovskite (La1-xSrx) MnO3±δ (LSM) to assess its stability against Sr secondary phase formation in SOC applications. In this work, the Sr secondary phase formation reaction free energies were determined by combining ab initio lattice dynamics calculations for the solid phases and an ab initio thermodynamics approach for the gas phases. Furthermore, this approach goes beyond previous thermodynamic modeling studies by integrating first-principles based point-defect equilibria into the analyses. The modeling results indicate an increased tendency to form SrO oxide from LSM upon decreasing the oxygen partial pressure. Additionally, enhancing factors to form the Sr-related secondary phase from the associated SrO activity in LSM are further quantified by considering the equilibrium of SrO reacting with contaminant gas species as a function of temperature and gas pressure.

Defect and phase stability↗
DOE OSTI2022

Tuning Surface Acidity of Mixed Conducting Electrodes: Recovery of Si‐Induced Degradation of Oxygen Exchange Rate and Area Specific Resistance

Abstract Metal oxides are an important class of functional materials, and for many applications, ranging from solid oxide fuel/electrolysis cells, oxygen permeation membranes, and oxygen storage materials to gas sensors (semiconducting and electrolytic) and catalysts, the interaction between the surface and oxygen in the gas phase is central. Ubiquitous Si‐impurities are known to impede this interaction, commonly attributed to the formation of glassy blocking layers on the surface. Here, the surface oxygen exchange coefficient ( k chem ) is examined for Pr 0.1 Ce 0.9 O 2‐δ (PCO), a model mixed ionic electronic conductor, via electrical conductivity relaxation measurements, and the area‐specific resistance (ASR) by electrochemical impedance spectroscopy. It is demonstrated that even low silica levels, introduced by infiltration, depress k chem by a factor 4000, while the ASR increases 40‐fold and we attribute this to its acidity relative to that of PCO. The ability to fully regenerate the poisoned surface by the subsequent addition of basic Ca‐ or Li‐species is further shown. This ability to not only recover Si‐poisoned surfaces by tuning the relative surface acidity of an oxide surface, but subsequently outperform the pre‐poisoned response, promises to extend the operating life of materials and devices for which the catalytic oxygen/solid interface reaction is central.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Uncovering the Solvation Structure of LiPF 6 –Based Localized Saturated Electrolytes and Their Effect on LiNiO 2 –Based Lithium–Metal Batteries

Electrolytes play a critical role in stabilizing highly reactive lithium-metal anodes (LMAs) and high-voltage cathodes for rechargeable lithium-metal batteries (LMBs). Localized high concentration electrolytes (LHCEs) have achieved remarkable success in the context of LMBs. However, the state-of-the-art LHCEs are based on LiFSI salt, which is prohibitively expensive. Here, the utility of low-cost LiPF 6 salt in localized saturated electrolytes (LSEs) with a series of solvents and diluents in LMBs with cobalt-free LiNiO 2 cathode is systematically explored. Experimental and theoretical analyses reveal that the unique solvation structure formed not only changes the distribution of solvents and anions but also alters the atom–atom distances within them, leading to different reduction and oxidation stabilities compared to low-concentration electrolytes. In addition, LSEs help form LiF-rich interphase layers on the LMA and LiNiO 2 cathode, protecting the electrodes from degradation during cycling. Different LSEs also lead to differences in lithium plating morphology and impedance buildup during cycling, impacting the performance of LMBs. Finally, the solvent and diluent must be carefully selected for compatibility with a lithium salt when developing LHCEs and LSEs for LMBs.

25 ENERGY STORAGE↗