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Results for “Degradation mechanism”

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 19 records

Fundamental Investigations of Mechanical and Chemical Degradation Mechanisms in Lithium Ion Battery Materials (Final Technical Report)

The objective of our effort under the DOE EPSCoR Implementation grant is to establish a comprehensive and internationally recognized research program at Brown University and University of Rhode Island in understanding degradation mechanisms and to improve the cycle and calendar life of lithium ion battery (LIB) materials. A series of basic investigations are undertaken to characterize the mechanical and chemical degradation mechanisms, which can help enable new higher capacity and longer lasting electrode designs. Controlling mechanical and chemical degradation is the primary challenge in developing the next generation of higher energy density batteries. The development of failure resistant battery microstructures will require a fundamental understanding of the evolution of stress, deformation, damage, and electrochemistry in battery materials during cyclic charging and discharging. In addition, controlling the reactions at the electrode/electrolyte interface is critical for the formation of a stable SEI layer. We address these issues through a combination of controlled experiments on model battery materials and practical composite electrodes, together with multi-scale computations. Our effort is organized into three focus areas that encompass many critical challenges in Lithium Ion Battery Technologies: (i) Mechanical properties, fracture and damage in electrode materials; (ii) Chemistry and Mechanics of Solid Electrolyte Interphase (SEI); (iii) Mechanical and Chemical Integrity of Solid-Solid Interfaces in Practical Electrodes.

25 ENERGY STORAGE↗

Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells

Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) has been a strategic research topic for proton exchange membrane (PEM) fuel cells. Present state-of-art PGM-free ORR catalysts are Fe, N co-doped carbon (Fe-N-C) catalysts, which unfortunately exhibit instability concerns. Herein, we report a stable atomically dispersed Co, N co-doped carbon (Co-N-C) catalyst with high Co content of 1.0 at% and the active site, i.e., the coordination of Co, is CoN2+2 in nature. The Co-N-C catalyst demonstrated high ORR activity comparable to, and high stability over 3 times better than, that of the Fe-N-C catalyst. It also achieved a high activity of 22 mA cm2 at 0.9 ViR-free and a power density of 0.61 W cm-2 under 1.0 bar H2/O2. Further, we identify two main degradation mechanisms of the PGM-free catalysts: catalyst oxidation by H2O2/radicals and demetalation. The improved stability of Co-N-C relative to Fe-N-C is attributed to less Fenton-reactive nature of Co and significantly enhanced resistance to demetalation of Co-N-C.

Xie, Xiaohong↗

In–Depth Analysis of the Degradation Mechanisms of High–Nickel, Low/No–Cobalt Layered Oxide Cathodes for Lithium–Ion Batteries

A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi 0.883 Co 0.053 Al 0.064 O 2 (NCA-89) leads to a loss of active material and an increase in surface area, thereby exacerbating structural and surface instabilities, accelerating impedance and polarization growth, and ultimately reducing their capacity retentions. LiNi 0.89 Mn 0.044 Co 0.042 Al 0.013 Mg 0.011 O 2 (NMCAM-89) and NMA-89 experience subdued surface reactions and maintain spherical particle structures, both of which are conducive to their capacity retentions during long-term cycling. Furthermore, this investigation offers insights into how specific transition-metal ions dictate the electrochemical stability of high-Ni layered oxide cathode materials, highlights the benefit of Mn-Al combination in NMA-89, and presents potential strategies to further enhance the performance of this novel class of cathode materials.

degradation mechanisms↗

Investigation of degradation mechanisms in composite matrices

Degradation mechanisms were investigated for graphite/polysulfone and graphite/epoxy laminates exposed to ultraviolet and high-energy electron radiations in vacuum up to 960 equivalent sun hours and 10 to the ninth power rads respectively. Based on GC and combined GC/MS analysis of volatile by-products evolved during irradiation, several free radical mechanisms of composite degradation were identified. The radiation resistance of different matrices was compared in terms of G values and quantum yields for gas formation. All the composite materials evaluated show high electron radiation stability and relatively low ultraviolet stability as indicated by low G values and high quantum for gas formation. Mechanical property measurements of irradiated samples did not reveal significant changes, with the possible exception of UV exposed polysulfone laminates. Hydrogen and methane were identified as the main by-products of irradiation, along with unexpectedly high levels of CO and CO2.

Giori, C.↗

Radiation Degradation Mechanisms in Laser Diodes

Degradation mechanisms are investigated for laser diodes fabricated with different materials and wavelengths between 660 and 1550 nm. A new approach is developed that evaluates degradation below the laser threshold to determine the radiation-induced recombination density. This allows mechanisms at high injection, such as Auger recombination, to be separated from low-injection damage. New results show that AlGaInP lasers in the visible region are nearly an order of magnitude more resistant to radiation than devices fabricated with AlGaAs or AlGaAsP at longer wavelengths.

laser degradation↗

Computational Elucidation of Mechanical Degradation in NMC Cathodes: Impact on Cell Performance

Next-generation lithium ion batteries are expected to demonstrate superior energy and power density with longer cycle life for successful electrification of the automobile, aviation, and marine industries. Adoption of lithium metal anodes with solid electrolytes can help to achieve that goal given that the dendrite-related issues are solved eventually. Another possibility is to use Ni-rich high-capacity NMC cathode materials with liquid and/or solid electrolytes, which presently experiences rapid capacity fade while charged to higher voltages. Several mechanical and chemical degradation mechanisms are active within these NMC-based cathode particles. Recent experimental research activities attempted to correlate the mechanical damage with the capacity fade experienced by Ni-rich LiNi x Mn y Co z O 2 (x+y+z = 1) (NMC) cathodes. Here, a computational framework is developed in this study capable of quantifying the evolution of inter primary particle and cathode/electrolyte interfacial fracture experienced by the poly- and single-crystalline NMC cathodes during charge/discharge operation. Influences of mechanical degradation on the overall cell capacity, while operating with liquid and/or solid electrolytes, are successfully characterized. Decreasing the size of the cathode primary particles, or the size of the single-crystalline cathodes, can mitigate the overall mechanical degradation, and subsequent capacity fade, experienced by NMC cathodes. The developed theoretical methodology can help the engineers and scientists to better understand the mechanical degradation mechanism prevalent in Ni-rich NMC cathodes and build superior lithium ion-based energy storage devices for the application in next-generation devices.

25 ENERGY STORAGE↗

Environment assisted degradation mechanisms in aluminum-lithium alloys

Section 1 of this report records the progress achieved on NASA-LaRC Grant NAG-1-745 (Environment Assisted Degradation Mechanisms in Al-Li Alloys), and is based on research conducted during the period April 1 to November 30, 1987. A discussion of work proposed for the project's second year is included. Section 2 provides an overview of the need for research on the mechanisms of environmental-mechanical degradation of advanced aerospace alloys based on aluminum and lithium. This research is to provide NASA with the basis necessary to permit metallurgical optimization of alloy performance and engineering design with respect to damage tolerance, long term durability and reliability. Section 3 reports on damage localization mechanisms in aqueous chloride corrosion fatigue of aluminum-lithium alloys. Section 4 reports on progress made on measurements and mechanisms of localized aqueous corrosion in aluminum-lithium alloys. Section 5 provides a detailed technical proposal for research on environmental degradation of Al-Li alloys, and the effect of hydrogen in this.

Gangloff, Richard P.↗

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.↗

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.↗

Degradation mechanisms in thermal barrier coatings

The degradation mechanism in thermal barrier coating systems subjected to prolonged heating in air as well as to thermal cycling was studied. Bond coat oxidation was found to be the most important reason for degradation. The oxidation produced NiO as well as Al?O? in one set of samples, but the variation in initial coating structure made it difficult to resolve systematic differences between isothermally heated and thermally cycled samples. However, the contribution to degradation from changes in substrate composition seemed less in the cycled sample.

Shinde, S. L.↗

Network Models of Active Degradation Mechanisms and Pathways for Service Life Prediction of Indoor and Outdoor PV Modules

ct: PV service lifetime prediction (SLP) enables accurate calculation of levelized cost of energy (LCOE), which is crucial to rationalizing PV investment and installation. However, SLP is challeging since PV reliability in the field is affected by many combined factors, including various environmental stresses and module quality. In order to map out the active degradation mechanisms and pathways that best resemble real world conditions, we introduce the framework of a study protocol and use network models fitted to data, to enable analysis and SLP of complex PV systems with multiple active degradation mechanisms. The study protocol is the experimental design, including module variants and different exposure conditions, selection of evaluation methods, time-series data acquisition and training of network models to these data. We present SLP of minimodules in the lab and PV systems in the field. For lab SLP, minimodules with 8 variants based on manufacturer, architecture, and encapsulation were prepared and aged in modified damp heat with or without full spectrum light exposure. Stepwise I-V and Suns-Voc data acquisition tracks changes in electrical properties including Rs,IV, Isc,IV, Vmp,PIV providing insights into power loss of minimodules. Network structural equation modeling (netSEM) was utilized to construct degradation pathway models that identify active degradation mechanisms and predict power loss over time. For field SLP, datastreams of Pmp values and I-V curve datastreams of two types of modules installed in three distinctly different Köppen-Geiger climate zones for 9 years were acquired. With power loss modes corresponding to uniform current loss (ΔPIsc), recombination (ΔPVoc), series resistance (ΔPRs), and current mismatch (ΔPImis) determined, the performance loss rates (PLR) were determined using PVplr. We show how to establish a study protocol framework to ensure appropriate parametric variations and valid data collection from the variants of your complex systems. Then the data-driven netSEM model fitting provides a comprehensive mapping of multiple active degradation mechanisms, and accurate service life prediction.

network model, degradation, photovoltaic, solar↗

Degradation mechanisms and partial shading of glass-backsheet and double-glass photovoltaic modules in three climate zones determined by remote monitoring of time-series current–voltage and power datastreams

Degradation and partial shading impact the long-term reliability and power production of photovoltaic (PV) modules and power plants. Time-series power (P mp ) and current–voltage (I-V) curve datastreams from PV modules enable a remote diagnostic approach to quantify active degradation mechanisms and identify partial shading. We study three to nine years of these datastreams, including 3.6 million P mp I-V curves and 36 million values, from eight PV modules, four each of double-glass and glass-backsheet module architectures, located in three distinctly different Köppen-Geiger climate zones, to determine the module’s performance loss rates (PLR), identify active degradation mechanisms and power loss modes, along with partial shading by local objects. Considering both module architectures, PLR results indicate that the BSh climate zone is the most aggressive for module degradation, while the Alpine ET zone is the mildest climate. PLR of double-glass modules located in BWh and BSh climate zones are different due to the significantly greater uniform current loss (ΔP Isc ) for double-glass modules in BSh, at a 5% significance level. Power loss for four out of five modules located in the BWh and BSh climates are dominated by uniform current degradation. Statistical analysis of multistep I-V curves detects partial shading experienced by three studied modules with details of the shading profile, the shading Poynting vector diagram for the obstacle’s relative position, shading scenarios, and duration. Lastly, this work demonstrates how remote monitoring and diagnosis of P mp & I-V time-series of modules can provide quantitative operations and maintenance insights into system performance, degradation mechanisms, and shading.

14 SOLAR ENERGY↗

The Work of Mechanical Degradation in Elongating Polymer Melts

Molecular dynamics simulations are used to study the mechanical degradation of well-entangled polymer melts during uniaxial extensional flow. Simulations measure the transient rise in extensional stresses and relate them to the molecular alignment and scission of chain backbones. Intermolecular entanglements couple chain scission in space and time, making degradation sensitive to deformation history and strain rate in ways not displayed by dilute polymer solutions. The rate of chain scission is nonmonotonic and peaks at strains corresponding to the maximum extensibility of entanglement segments but prior to the full extension of chain backbones. We measure a specific work per scission event w* and decompose it into separate contributions associated with chain alignment, chemical bond breaking, and scission-induced plasticity. We find chain scission in melts requires activating plastic dissipation that is multiple orders of magnitude larger than the chemical work required to break a covalent backbone bond. Our findings underscore the critical need to consider bulk polymer mechanics and rheology in designing efficient mechanical degradation and mechanochemical processes.

36 MATERIALS SCIENCE↗

Dependence of adhesion on degradation mechanisms of ethylene co-vinyl acetate encapsulants over the lifetime of photovoltaic modules

The long-term reliability of encapsulation has a critical impact on the overall cost and effectiveness of photovoltaic modules. An often overlooked but important element of this reliability concerns adhesive degradation of the encapsulant, which results in delamination. This work critically examines the degradation mechanisms – deacetylation, β-scission, and hydrolytic depolymerization – primarily responsible for adhesion loss in ethylene co-vinyl acetate (EVA) encapsulants to provide evidence and clarity regarding the contribution of these mechanisms to the adhesive degradation over the lifetime of a module. EVA samples obtained from mini-modules exposed in two sets of controlled, accelerated conditions – with and without ultraviolet (UV) radiation – are characterized to find specific evidence for the proposed degradation mechanisms. The mini-modules were exposed up to 10,000 h, which represents up to 15–20 years in the field. Results affirm that initially, deacetylation dominates the degradation before scission takes over, followed by hydrolytic depolymerization. Additional analysis highlights the climacteric interdependency between deacetylation and hydrolytic depolymerization as it relates to eventual delamination, where deacetylation products catalyze interfacial hydrolysis reactions. Furthermore, effects occurring at a given interface are isolated, explicitly providing evidence for how these mechanisms are nonuniform throughout the thickness of the EVA. Results demonstrate that the EVA that interfaces with the glass as opposed to the cell experiences increased levels of degradation, explaining why this initially stronger interface becomes the preferential interface for delamination after longer periods of exposure. Additionally, elevated temperatures alone are shown to induce limited migration of sodium ions across the glass/EVA interface.

36 MATERIALS SCIENCE↗