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At least 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Multiscale Characterization of Electrode-Induced Degradation in Perovskite Solar Cells

The stability of metal-halide-perovskite (MHP) solar cells must be understood and improved for the commercial viability of MHP technologies. Here, we apply multiscale characterization methods to study degradation modes, specifically electrode corrosion, for p-i-n MHP partial device stacks and full devices that are stored in the dark under an inert atmosphere. Our multiscale characterization approaches include full-device electro-optical performance using current-voltage (JV) curves and spatial imaging with electroluminescence (EL) and photoluminescence (PL). We further correlate interface properties using cross-sectional Kelvin probe force microscopy, which maps the nanoscale electric field properties, and electron microscopy, which demonstrates structural and chemical features. Devices stored as a full device stack degrade primarily by metal (Ag) electrode diffusion into the absorber, with formation of AgI byproducts and Ag accumulation near the indium tin oxide (ITO) contact. This causes decomposition of the perovskite absorber domains, loss of the potential drop at the electron transport layer (ETL)/perovskite interface near the metal contact, and increased equivalent resistance at the perovskite/hole transport layer (HTL) interface near the ITO contact. The devices stored without metal show a different degradation pathway dominated by corrosion of the ITO, creating voids at the ITO electrode surface with diffusion of In and Sn into the absorber. We conclude that metal electrode-induced degradation is the most severe degradation pathway under dark storage, but that ITO corrosion and absorber instability must also be mitigated. We further demonstrate mitigation of these degradation pathways by changes to the device stack, including a SnO x blocking layer at the ETL side and replacing ITO with FTO at the HTL side. These results provide a useful demonstration of specific dark degradation pathways at each electrode interface, as well as a unique multiscale example that links degradation of chemical, structural, and electrical interface properties to the full-device electro-optical characteristics.

14 SOLAR ENERGY↗
DOE OSTI2021

Formation of Surface Impurities on Lithium–Nickel–Manganese–Cobalt Oxides in the Presence of CO 2 and H 2 O

Surface impurities involving parasitic reactions and gas evolution contribute to the degradation of high Ni content LiNi x Mn y Co z O 2 (NMC) cathode materials. The transient kinetic technique of Temporal Analysis of Products (TAP), density functional theory, and infrared spectroscopy have been used to study the formation of surface impurities on varying nickel content NMC materials (NMC811, NMC622, NMC532, NMC433, NMC111) in the presence of CO 2 and H 2 O. CO 2 reactivity on a clean surface as characterized by CO 2 conversion rate in the TAP reactor follows the order: NMC811 > NMC622 > NMC532 > NMC433 > NMC111. The capacity of CO 2 uptake follows a different order: NMC532 > NMC433 > NMC622 > NMC811 > NMC111. Moisture pretreatment slows down the direct CO 2 adsorption process and creates additional active sites for CO 2 adsorption. Electronic structure calculations predict that the (012) surface is more reactive than the ($10\bar{1}4$) surface for CO 2 and H 2 O adsorption. CO 2 adsorption leading to carbonate formation is exothermic with formation of ion pairs. The average CO 2 binding energies on the different materials follow the CO 2 reactivity order. Water hydroxylates the (012) surface and surface OH groups favor bicarbonate formation. Water creates more active sites for CO 2 adsorption on the ($10\bar{1}4$) surface due to hydrogen bonding. The composition of surface impurities formed in ambient air exposure is dependent on water concentration and the percentage of different crystal planes. Different surface reactivities suggest that battery performance degradation due to surface impurities can be mitigated by precise control of the dominant surfaces in NMC materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Radiation Induced Degradation of the White Thermal Control Paints Z-93 and Z-93P

This paper details a comparison analysis of the zinc oxide pigmented white thermal control paints Z-93 and Z-93P. Both paints were simultaneously exposed to combined space environmental effects and analyzed using an in-vacuo reflectance technique. The dose applied to the paints was approximately equivalent to 5 years in a geosynchronous orbit. This comparison analysis showed that Z-93P is an acceptable substitute for Z-93. Irradiated samples of Z-93 and Z-93P were subjected to additional exposures of ultraviolet (UV) radiation and analyzed using the in-vacuo reflectance technique to investigate UV activated reflectance recovery. Both samples showed minimal UV activated reflectance recovery after an additional 190 equivalent sun hour (ESH) exposure. Reflectance response utilizing nitrogen as a repressurizing gas instead of air was also investigated. This investigation found the rates of reflectance recovery when repressurized with nitrogen are slower than when repressurized with air.

Edwards, D. L.↗
NASA NTRS1996

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in the neat resin, and anisotropic diffusion effects in the composites, are identified through the use of specimens with different aspect ratios. The data is used with the model to determine reaction coefficients and effective diffusion coefficients. The empirical and analytical correlations confirm the preliminary model results which suggest that mass loss at lower temperatures is dominated by oxidative reactions and that these reaction are limited by diffusion of oxygen from the surface. The mechanism-based model is able to successfully capture the basic physics of the degradation phenomena under a wide range of test conditions. The analysis-based test design is successful in separating out oxidative, thermal, and diffusion effects to allow the determination of material coefficients. This success confirms the basic picture of the process; however, a more complete understanding of some aspects of the physics are required before truly predictive capability can be achieved.

Cunningham, Ronan A.↗
NASA NTRS1997

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects in the neat resin, and anisotropic diffusion effects in the composites, are identified through the use of specimens with different aspect ratios. The data is used with the model to determine reaction coefficients and effective diffusion coefficients. The empirical and analytical correlations confirm the preliminary model results which suggest that mass loss at lower temperatures is dominated by oxidative reactions and that these reaction are limited by diffusion of oxygen from the surface. The mechanism-based model is able to successfully capture the basic physics of the degradation phenomena under a wide range of test conditions. The analysis-based test design is successful in separating out oxidative, thermal, and diffusion effects to allow the determination of material coefficients. This success confirms the basic picture of the process; however, a more complete understanding of some aspects of the physics are required before truly predictive capability can be achieved.

Cunningham, Ronan A.↗
DOE OSTI2020

High-efficiency, air-stable manganese–iron oxide nanoparticle-pigmented solar selective absorber coatings toward concentrating solar power systems operating at 750 °C

Solar selective absorber coating with long-term thermal stability at high temperatures ≥750 °C in air is an important component to reduce the levelized cost of energy (LCOE) of concentrating solar power (CSP) systems toward 50% power efficiency and dispatchable solar electricity. Conventionally, solar spectral selectivity requires multilayer-interference coatings implemented by stringently controlled vacuum deposition, and these coatings degrade significantly at >700 °C in air. Herein, we established a quantitative design approach and demonstrated a proof-of-concept air-stable, manganese–iron oxide nanoparticle (NP)-pigmented solar selective coatings with a high solar absorptance of ~93%, a relatively low thermal emittance of ~52%, and an optical-to-thermal energy conversion efficiency >89% under 1,000× solar concentration at 750 °C toward Generation 3 CSP systems. These coatings demonstrate spectral selectivity using cost-effective spray coating approach, a notable improvement over conventional vacuum-deposited, multilayer solar selective coatings for low-cost, high-efficiency solar thermal receivers. In contrast to the thermal degradation of spectrally non-selective benchmark Pyromark 2500 coatings at 750 °C in air, the solar absorptance of the MnFe 2 O 4 -pigmented coatings on stainless steel 310 (SS 310) substrates is increased to ~92.9% and the optical-to-thermal energy conversion efficiency is improved to 89.7% after serving at 750 °C in air for 700 h. X-ray diffraction results reveal that this improvement is due to the transformation of MnFe 2 O 4 NPs into more thermodynamically stable, non-stoichiometric manganese-rich manganese ferrite and iron-rich manganese–iron oxide phases after 500 h aging at 750 °C. For >1,000 h-endurance testing at 750 °C in air and the subsequent 19 day-night thermal cycling between 750 °C (12 h/cycle) and 25 °C (12 h/cycle) on SS 310 substrates, the thermal degradation is mainly due to the CrO x microflake formation from SS 310 substrates rather than the coatings, which can be suppressed by preoxidizing the surface of SS 310. With lower emittance matrix material and further optimization of pigment NP stoichiometry, concentration, and coating thickness, it is promising to achieve an optimized thermal efficiency ≥92.5% with long-term thermal stability at 750 °C for Generation 3 CSP systems.

14 SOLAR ENERGY↗
DOE OSTI2022

Electron beam treatment for the removal of 1,4-dioxane in water and wastewater

Electron beam (e-beam) treatment uses accelerated electrons to form oxidizing and reducing radicals when applied to water without the use of external chemicals. In this study, electron beam treatment was used to degrade 1,4-dioxane in several water matrices. Removal improved in the progressively cleaner water matrices and removals as high as 94% to 99% were observed at a dose of 2.3 kGy in secondary effluent. 1,4-dioxane removal was confirmed to be primarily through hydroxyl radical oxidation. The calculated electrical energy per order was found to be 0.53, 0.26, and 0.08 kWh/m 3 /order for secondary effluent (Avg. total organic carbon (TOC) 9.25 mg/L), granular activated carbon effluent (TOC 3.46 mg/L), and ultrapure water, respectively, with a 70% generation and transfer efficiency applied.

1,4-dioxane↗
DOE OSTI2024

Phase-field modeling of thermally-grown oxide and damage evolution in environmental barrier coatings

Silicon carbide-based ceramic matrix composites protected by environmental barrier coatings (EBCs) present a promising materials solution for next-generation gas turbines. Developing more robust and efficient EBCs is therefore of significant technological importance. During the service in high-temperature oxidative environments, there is a thermally grown oxide (TGO) layer, spontaneously formed in the EBC system. TGO is recognized as a critical factor for the degradation and failure of EBCs, yet the detailed mechanisms of TGO growth and its effect on EBC failure remain unclear. In this study we develop a comprehensive chemo-mechano-phase-field model to simulate growth of the TGO in EBCs, factoring in creep and deformation, and especially the cracking behaviors. The volume expansion due to TGO growth and the resulting large inelastic deformation are addressed by using our recently developed, so-called incremental realization of inelastic deformation (IRID) algorithm, in combination with an adapted Hu-Chen spectral solver for elasticity. Simulations of TGO growth are performed considering different growth modes of TGOs determined mainly by the ratio of oxidant permeability in the topcoat to that in the TGO itself. Large-scale three-dimensional (3D) simulations are performed to model the formation of interconnecting vertical/channel cracks (often called ‘mud cracks’). The simulated crack morphology are in excellent agreement with the experimental observations from the literature. The simulations also provide insights into the cracking of EBCs and its dependence on the structure and constituent properties of the coating system. Furthermore, these results demonstrate the developed damage model can be a useful tool for design of more durable EBCs.

Cracking↗
DOE OSTI2025

Roles of surface Mn(III) and MgOH + /CaOH + complexation in photochemically assisted Mn 2+ oxidation and Todorokite formation

Todorokite, a Mn oxide phase commonly found in seafloor Mn nodules, is one of the most abundant Mn oxides in nature and has wide applications in environmental engineering, including heavy metal remediation, contaminant adsorption for water purification, and catalysis for organic pollutant degradation. However, traditional abiotic formation of todorokite reported to date typically requires high temperature, pressure, and pH outside circumneutral conditions, or involves several days of phase transformations from precursor phases. In this study, we demonstrate rapid todorokite formation within 6 h via photochemically assisted oxidation of Mn 2+ (aq) in the presence of Mg 2+ or Ca 2+ , notably at ambient temperature and pressure. The concentrations of aqueous MgOH + and CaOH + , as well as the pH (initial 9 or 6), had significant collective influences on the crystalline phases of the formed Mn oxide solids. The proportions of the Mn oxidation states (IV, III, and II) and the extent of Mn(III) surface complexation with MgOH + or CaOH + controlled the crystalline phases (todorokite, feitknechtite, and birnessite) and the extent of cation incorporation into the resulting Mn oxide solids. Specifically, the oxidation state of Mn influenced the crystallization of different Mn oxide phases, and the formed Mn(III) complexed with MgOH + or CaOH + facilitated the formation of todorokite, along with cation incorporation. X-ray pair distribution function analysis revealed that incorporated Mg species were located at the inside corner sites of the 5 × 3 MnO 6 octahedral tunnel structure of todorokite, suggesting complexation between MgOH + and Mn(III) at the corners of the tunnel. Furthermore, this study provides novel insights into the elusive formation of todorokite and its potential for applications in advanced water treatment and environmental remediation.

Abiotic Mn2+ oxidation↗
DOE OSTI2021

Evaluating efficacy of different UV-stabilizers/absorbers in reducing UV-degradation of lignin

Abstract Susceptibility of wood to UV degradation decreases the service life of wood products outdoors. Organic UV absorbers (UVAs) and hindered amine light stabilizers (HALSs), as well as inorganic UVAs, are added to coatings to improve the UV stability of coated-wood products. Although about 85% of UV radiation is absorbed by lignin in the wood, it is unclear which UV stabilizers can minimize lignin degradation. In this study, the photodegradation of softwood organosolv lignin was monitored over 35 days of UV exposure. Changes in lignin properties were assessed using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and phosphorus-31 nuclear magnetic resonance spectroscopy ( 31 P NMR). It was found that the aromatic rings of lignin underwent significant degradation, resulting in increased glass transition temperature and molecular weight of lignin. Subsequently, 18 different additives were mixed with lignin and exposed to UV irradiation. The analysis of samples before and after UV exposure with FTIR revealed that inorganic UVAs (cerium oxide and zinc oxide) and a mixture of organic UVAs and HALSs (T-479/T-292, T-5248, and T-5333) were the most effective additives in reducing lignin degradation. This study can help coating scientists to formulate more durable transparent exterior wood coatings.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Long Term Degradation of LSM Based SOFC Cathodes: Use of a Proven Accelerated Test Regimen

The overall goals of the program were: • To understand the microstructural basis of long-term performance loss in solid oxide fuel cells (SOFCs) with cathodes based on lanthanum strontium manganite (LSM, (La 1–x Sr x ) 1–yM nO 3±z ); • To develop strategies for optimizing LSM–based cathodes that achieve improved long-term performance, while exhibiting microstructural and chemical stability, for commercial fuel cell systems. The research project carried out accelerated testing of SOFCs with LSM-based cathodes of selected compositions. After intervals of accelerated testing (and control tests using non-accelerated conditions), the cells underwent extensive microstructural characterization to determine the physical and chemical changes in the cells. By analysis of a) the results of the testing, b) the observed microstructural changes, and c) the differences in these correlations between different cathode compositions and test durations, the research: • Identified a correlation between microstructural change and performance loss: specifically, between decrease of three-phase boundary (TPB) density and increase of area specific re-sistance (ASR) during operation; • Identified a cathode composition parameter — Mn excess, defined as 1/(1–y) in (La 1–x Sr x ) 1–y MnO 3±z ) — and how it affects TPB density, ASR and change of cell performance over time.

08 HYDROGEN↗
DOE OSTI2024

Reliability of Copper Inverse Opal Surfaces for Extreme-Heat-Flux Micro-Coolers in Low-Global-Warming-Potential Refrigerant R-1233zd Pool Boiling Experiments

This presentation provides a brief snapshot of the InterPACK paper InterPACK2023-113781. The paper explores copper inverse opal (CIO) surface reliability in pool boiling experiments in water and a new, low-global-warming-potential (GWP = 1) hydrofluoroolefin (HFO) refrigerant R-1233zd. The CIO-based structure is intended to develop enhanced two-phase heat transfer surfaces for extreme-heat-flux (approximately 1 kW/cm2) micro-coolers. In this study, a limited number of pool boiling experiments were performed using water and HFO-1233zd fluid, and the reliability of the CIO-based surfaces was evaluated. Critical heat flux (CHF) values in HFO-1233zd at 40 Degrees Celsius to 45 Degrees Celsius saturation temperatures and the corresponding saturation pressures were also measured. The CHF values with the refrigerant are significantly lower compared to those with water, but the refrigerant allows for a wider usable temperature range in the end application of the micro-coolers and is not limited to data centers with controlled ambient conditions. Reliability experiments with CIO surface samples - involving pool boiling with water on the CIO surfaces for approximately 48 hours and with HFO-1233zd for 144 hours - showed no structural degradation of the enhanced surface or any significant performance drop in heat transfer coefficients. The CIO surface samples in water were oxidized, most likely due to the presence of air in water and in the experimental vessel.

critical heat flux↗
DOE OSTI2023

Operational and scaling-up barriers of SOEC and mitigation strategies to boost H 2 production- a comprehensive review

Solid oxide electrolysis cells (SOECs) proffer a flexible and environmentally friendly solution to reduce CO 2 emissions and/or produce H 2 fuel for various applications. Here, the integration of this technology with renewable energy systems makes them even more promising in realizing a near-perpetual green energy infrastructure in the near future. SOEC technology has achieved stupendous improvement in recent years, and some of the limiting factors to the commercialization of this technology have been explored. It is, therefore, necessary to have a succinct outlook of the different factors that contribute to the recent developments in SOEC technology. The current work presents a comprehensive review of the state-of-the-art SOEC component materials and their degradation mechanisms, SOEC modeling essentials and efficiencies, and the scalability of SOECs. Although SOEC is considered a highly promising technology and sufficient multifaceted research has been done, yet not been widely commercialized. Despite the improvement to mitigate degradation of the SOEC materials, a large share of the degradation concerns sprang from charge transfer reaction at the triple-phase boundaries of the H 2 -electrode. Part of which can be improved by microkinetic modeling of these materials supported by their characterization to give insight into their development. Some other directions for the future in advancing this technology toward the commercialization stage are thoroughly addressed.

08 HYDROGEN↗
DOE OSTI2021

Activating Layered Metal Oxide Nanomaterials via Structural Engineering as Biodegradable Nanoagents for Photothermal Cancer Therapy

Layered metal oxides including MoO 3 and WO 3 have been widely explored for biological applications owing to their excellent biocompatibility, low toxicity, and easy preparation. However, they normally exhibit weak or negligible near-infrared (NIR) absorption and thus are inefficient for photo-induced biomedical applications. Herein, the structural engineering of layered MoO 3 and WO 3 nanostructures is first reported to activate their NIR-II absorption for efficient photothermal cancer therapy in the NIR-II window. White-colored micrometre-long MoO 3 nanobelts are transformed into blue-colored short, thin, defective, interlayer gap-expanded MoO 3–x nanobelts with a strong NIR-II absorption via the simple lithium treatment. The blue MoO 3–x nanobelts exhibit a large extinction coefficient of 18.2 L g –1 cm –1 and high photothermal conversion efficiency of 46.9% at 1064 nm. After surface modification, the MoO 3–x nanobelts can be used as a robust nanoagent for photoacoustic imaging-guided photothermal therapy to achieve efficient cancer cell ablation and tumor eradication under irradiation by a 1064 nm laser. Importantly, the biodegradable MoO 3–x nanobelts can be rapidly degraded and excreted from body. We report the study highlights that the structural engineering of layered metal oxides is a powerful strategy to tune their properties and thus boost their performances in given applications.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Supercritical water desalination and oxidation (SCWDO): Effectiveness on complex solutions, technoeconomic, and CO 2 impact for produced water treatment

The modern energy-economy is increasingly causing the production of highly saline brines, including from produced water. Supercritical water desalination can concentrate and extract minerals from these brines, but the effects of mixed salt interactions, organic degradation with additives, and the technology's economics are not well understood at supercritical condition. The present study evaluated and experimentally studied an integrated supercritical water desalination and oxidation (SCWDO) process for treating real-produced water samples from oil/natural gas field. The complex interactions between the various anions and cations in produced water were extensively evaluated. Most of the divalent and trivalent ions were extracted below 250 °C while the majority of the monovalent salt were removed between 380 to 410 °C. The treated real produced water was of drinking water quality, with <500 mg/l of total dissolved solid (TDS) and with 100% organics removal. Furthermore, the heat liberated during the organic oxidation could be utilized internally and for electricity generation for enhanced the energy efficiency and lower cost of produced water treatment. With system optimization, the proposed SCWDO process can essentially be made a net zero energy process. A novel process flow diagram for the commercial scale self-powered hybrid SCWDO technology was proposed as a cost-effective produced water treatment to mitigate the environmental crises. Techno-economic analysis showed that produced water treatment cost with SCWDO can be reduced to 2–3 $/m 3 and can be up to 60 % cheaper to traditional deep well reinjection. Additionally, the proposed SCWDO process could achieve net negative CO 2 emission.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Electrolyte Reactivity at the Charged Ni-Rich Cathode Interface and Degradation in Li-Ion Batteries

The chemical and electrochemical reactions at the positive electrode–electrolyte interface in Li-ion batteries are hugely influential on cycle life and safety. Ni-rich layered transition metal oxides exhibit higher interfacial reactivity than their lower Ni-content analogues, reacting via mechanisms that are poorly understood. Here, we study the pivotal role of the electrolyte solvent, specifically cyclic ethylene carbonate (EC) and linear ethyl methyl carbonate (EMC), in determining the interfacial reactivity at charged LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC111) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes by using both single-solvent model electrolytes and the mixed solvents used in commercial cells. While NMC111 exhibits similar parasitic currents with EC-containing and EC-free electrolytes during high voltage holds in NMC/Li 4 Ti 5 O 12 (LTO) cells, this is not the case for NMC811. Online gas analysis reveals that the solvent-dependent reactivity for Ni-rich cathodes is related to the extent of lattice oxygen release and accompanying electrolyte decomposition, which is higher for EC-containing than EC-free electrolytes. Combined findings from electrochemical impedance spectroscopy (EIS), TEM, solution NMR, ICP, and XPS reveal that the electrolyte solvent has a profound impact on the degradation of the Ni-rich cathode and the electrolyte. Higher lattice oxygen release with EC-containing electrolytes is coupled with higher cathode interfacial impedance, a thicker oxygen-deficient rock-salt surface reconstruction layer, more electrolyte solvent and salt breakdown, and higher amounts of transition metal dissolution. These processes are suppressed in the EC-free electrolyte, highlighting the incompatibility between Ni-rich cathodes and conventional electrolyte solvents. Finally, new mechanistic insights into the chemical oxidation pathways of electrolyte solvents and, critically, the knock-on chemical and electrochemical reactions that further degrade the electrolyte and electrodes curtailing battery lifetime are provided.

25 ENERGY STORAGE↗
NASA NTRS2015

Formaldehyde Production from Isoprene Oxidation Across NOx Regimes

The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= 27 NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast U.S., we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1 - 2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9), while background HCHO increases by more than a factor of 2 (from 1.5 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D chemical box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models under-estimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or under-estimated hydroxyl radical concentrations. Moreover, we find that the total organic peroxy radical production rate is essentially independent of NOx, as the increase in oxidizing capacity with NOx is largely balanced by a decrease in VOC reactivity. Thus, the observed NOx dependence of HCHO mainly reflects the changing fate of organic peroxy radicals.

VOC↗
DOE OSTI2021

Investigation of $\gamma$-irradiated polyvinylidene fluoride and its acute toxicity

Polyvinylidene fluoride (PVDF) is an industrial polymer with many applications. The EPR spectrum of polyvinylidene fluoride (PVDF) irradiated by γ-rays at low temperature (-196°C) provides evidence for the presence of radicals formed by loss of a fluorine atom from PVDF, and polyenyl radicals. Polyenyl radicals dominate in the polymer irradiated at room temperature. Peroxide radicals formed as a result of oxidation of primary free radicals by atmospheric oxygen are observed in the EPR spectrum of a polymer irradiated in air, or when air is introduced to a polymer irradiated in a vacuum. Carbonization and oxidation of γ-irradiated PVDF were observed in the XPS spectrum. A model for polymer degradation based on correlated G3(MP2) molecular orbital theory electronic structure calculations is described in this report. The presence of HF in the products and a low yield of products with the composition CxFyHz indicate the absence of noticeable thermal destruction of the main polymer chain upon heating to 220°C of both the initial and γ-irradiated PVDF. Although any HF released during the PVDF dehydrofluorination would be toxic, a study of the acute toxicity of γ-irradiated PVDF showed that the polymer does not exhibit toxicity after a single intragastric route of administration to mice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗