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Exploring the electrochemical and physical stability of lithium-ion cells exposed to liquid nitrogen
(2024)
The transport and storage of lithium-ion (Li-ion) batteries — damaged or in an undefined state — is a major safety concern for regulatory institutions, transportation companies, and manufacturers. Since (electro)chemical reactivity is exponentially temperature-dependent, cooling such batteries is an obvious measure for increasing their safety.
The present study explores the effect of cryogenic freezing on the electrochemical and physical stability of Li-ion cells. For this purpose, three different types of cells were repeatedly exposed to liquid nitrogen (LN2).
Before and after each cooling cycle, electrical and electrochemical measurements were conducted to assess the impact of the individual freezing steps. While the electrochemical behavior of the cells did not change significantly upon exposure to LN2 , it became apparent that a non-negligible number of cells suffered from physical changes (swelling) and functional failures. The latter defect was found to be caused by the current interrupt device of the cylindrical cells. This safety mechanism is triggered by the overpressure of expanding nitrogen which enters the cells at cryogenic temperatures.
This study underlines that the widely accepted reversibility of LN2 -cooling on a material scale does not allow for a direct extrapolation toward the physical integrity of full cells. Since nitrogen enters the cell at cryogenic temperatures and expands upon rethermalization, it can cause an internal overpressure. This can, in turn, lead to mechanical damage to the cell. Consequently, a more appropriate temperature condition — less extreme than direct LN2 exposure — needs to be found
The ongoing geo-political conflicts and the increasing need for the implementation of measures to improve the energetic system sustainability are increasing the importance of tanks for storing cryogenic fluids in the energy industry. The most common example of cryogenic tank applications is the transport of natural gas and hydrogen in their liquid form (LNG and LH2 respectively) for which, considering the same transport volume cryogenic storage ensures significantly higher transport capacities with respect storage based solely on overpressure.
A common feature of all cryogenic transported fluids is that their condition must be maintained minimizing heat leaks from the environment as much as possible. This is achieved by the implementation of thermal super Insulations (TSI) systems based on e. g. rock wool, perlites, microspheres, multilayer insulations (MLI), and vacuum which have proven to be effective in applications. However, due to the relatively short period of use in some applications, the small number of documented incidents, and the still few investigations carried out in the field, the exploitation of such systems in the cryogenic fluids transport sector still suffers from insufficient knowledge about the course and consequences of incidents. Accidents involving collisions, fires, and their combination are quite common in the transportation sector and may generate extraordinary loads on the tank and its insulation system, eventually leading to tank failure.
The present study focuses on the behavior of TSI systems in tanks when it is exposed to an external heat source representative of a hydrocarbon fire scenario. This may cause an increase of the heat flux into a tank by several orders of magnitude with respect to normal design conditions, thus inducing severe and in the TSI, causing the rapid release of flammable gas and even resulting in a Boiling Liquide Expanding Vapour Explosion (BLEVE).
To study such scenarios a test rig was developed at BAM that allows testing of TSI at industrial conditions and enables subsequent analysis of TSI samples. This test rig considers the typical double-walled design of tanks for cryogenic fluids with vacuum and an additional insulating material in the interspace. Adjustable electrical heating elements simulate the fire on one side of the double wall. This process allows the implementation of repeatable heat loads of up to 100 kW/m². The other side of the double wall is represented by a fluid-supported heat exchanger, which allows the simulation of cold or cryogenic conditions in the test rig, and to determine the heat flux transmitted through the double wall. Thus, the test rig allows thermal loading and performance analysis of TSI samples at the same time.
In the presentation, the results of diverse tested TSI systems will be presented and discussed. As a result of this study, the list of advantages and disadvantages for the choice of tested TSI expands. Within the test, all samples degraded as a consequence of a hydrocarbon fire-orientated thermal load. Strong differences in the behavior of the tested TSI systems over temperature, location, and time were observed. Additionally, the tested MLI insulations were significantly more resistant to their base materials. These results are relevant for the design, the definition of national and international regulations, the Risk assessment, and the development of safety concepts for cryogenic tanks.
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
In this presentation safety aspects of hydrogen transportation are discussed. At first, the regulatory background and level of safety are presented. In the second part, the modelling of consequence due to sudden rupture of pressure receptacles is explained. Finally, the results are used to define a limit for consequence to enable an acceptable and safe transport of hydrogen.
Die Umweltwirkungen auf ein Material werden als Überlapp der Funktionskurven von Materialempfindlichkeit und einwirkenden Umweltparametern betrachtet. Wenn entweder die Empfindlichkeit oder die Beanspruchungen Null sind, ergibt sich auch keine Umweltwirkung und bei beidseitig Werten größer Null das jeweilige Produkt der beiden. Die Akkumulation der nicht-reversiblen Effekte über die Zeit und allen Eigenschaftsänderungen entspricht der Alterung des Materials für den jeweiligen Expositionszeitraum.
Die digitale Umweltsimulation gliedert sich hier in drei Teilaspekte. Ein erster, rein materialwissenschaftlicher Teil hat die Aufgabe, alle relevanten Materialempfindlichkeiten experimentell zu quantifizieren. Ein zweiter – unter Umständen numerischer Teil – hat die Aufgabe, das Bauteil und seine Einbaulage zu digitalisieren und aus den makroskopischen Umgebungsbedingungen die relevanten mikroklimatischen Umweltparameter für alle Oberflächen- oder Volumenelemente zu bestimmen. In einem dritten Teil werden die Einwirkungen über den betrachteten Zeitraum berechnet und kumuliert. Dieses Konzept, das auf den so genannten Expositions-Reaktions-Funktionen (ERF) basiert, wird an Beispielen der Photoxidation erläutert. Dieses Vorgehen wurde schon beim ViPQuali-Projekt als Numerische Umweltsimulation umgesetzt.
Überprüft werden muss das Modell unbedingt an einer realitätsnahen Validierungsbeanspruchung. Hier werden die ermittelten ERFs mit über den kompletten Beanspruchungszeitraum geloggten Umweltparametern gekoppelt, um die berechnete mit der experimentell erfahrenen Alterungswirkung zu vergleichen. Nur so kann sichergestellt sein, dass alle für die Anwendungsumgebung relevanten Materialempfindlichkeiten einbezogen wurden.
The BAM-GGR 016 explains the requirements of ADR, RID, ADN and IMDG for management systems for design, manufacturing, testing, documentation, use, maintenance, and inspection of packagings for package designs for the transport of radioactive material not requiring competent authority approval for all designs of exempted packages, packages type IP-1, IP-2, IP-3 and type A.
Die Umweltwirkungen auf ein Material werden als Überlapp der Funktionskurven von Materialempfindlichkeit und einwirkenden Umweltparametern betrachtet. Wenn entweder die Empfindlichkeit oder die Beanspruchungen Null sind, ergibt sich auch keine Umweltwirkung und bei beidseitig Werten größer Null das jeweilige Produkt der beiden. Die Akkumulation der nicht-reversiblen Effekte über die Zeit und allen Eigenschaftsänderungen entspricht der Alterung des Materials für den jeweiligen Expositionszeitraum.
Die digitale Umweltsimulation gliedert sich hier in drei Teilaspekte. Ein erster, rein materialwissenschaftlicher Teil hat die Aufgabe, alle relevanten Materialempfindlichkeiten experimentell zu quantifizieren. Ein zweiter – unter Umständen numerischer Teil – hat die Aufgabe, das Bauteil und seine Einbaulage zu digitalisieren und aus den makroskopischen Umgebungsbedingungen die relevanten mikroklimatischen Umweltparameter für alle Oberflächen- oder Volumenelemente zu bestimmen. In einem dritten Teil werden die Einwirkungen über den betrachteten Zeitraum berechnet und kumuliert. Dieses Konzept, das auf den so genannten Expositions-Reaktions-Funktionen (ERF) basiert, wird an Beispielen der Photoxidation erläutert. Dieses Vorgehen wurde schon beim ViPQuali-Projekt als Numerische Umweltsimulation umgesetzt.
Überprüft werden muss das Modell unbedingt an einer realitätsnahen Validierungsbeanspruchung. Hier werden die ermittelten ERFs mit über den kompletten Beanspruchungszeitraum geloggten Umweltparametern gekoppelt, um die berechnete mit der experimentell erfahrenen Alterungswirkung zu vergleichen. Nur so kann sichergestellt sein, dass alle für die Anwendungsumgebung relevanten Materialempfindlichkeiten einbezogen wurden.
A high precision nail‐penetration (NP) tool for characterizing the mechanically induced thermal‐runaway (TR) of lithium‐ion battery (LIB) cells in a defined range of temperatures down to −140 °C was developed. To understand the cell specific behavior at low temperatures aiming at the determination of safe handling conditions, different scenarios are analyzed. First, accuracy tests of the NP‐tool regarding motion and penetration depth are conducted with cylindrical cells at different temperatures. Thus, postmortem computer tomographic (CT) images are compared to the data measured with the newly integrated 3‐axis force sensor which is further combined with a high‐resolution position sensor. The herein developed setup allows evaluation of the NP‐metrics at an accuracy of ±1 pierced electrode layer without CT‐scans. Further NP examinations at 20 °C of fully charged cylindrical lithium nickel manganese cobalt oxide cells reveal a reproducible minimum damage as a reliable TR‐trigger. Moreover, NP‐tests at low temperature disclose a relation of the short circuit conductivity and TR‐reactions during subsequent rethermalization to room temperature. Finally, the implementation of a novel fixture for a controlled very fast cooling of LIB‐cells during critical damage opens the way to investigate the individual steps during a TR and, thus, to gain important information of the specific TR‐mechanism of different LIB‐cells.
The publication is an extended abstract on the modelling of the manufacturing process related residual stresses in type 4 pressure vessels for hydrogen storage. A 2D analytical model based on the classical laminate theory and a 3D finite element model are introduced. The calculated residual stress state after the filament winding process as well as the stress state in service are presented and discussed.
Abstract Hydrogenated nitrile butadiene rubber (HNBR) elastomer was thermo-oxidatively aged at different temperatures up to 150 °C. Fourier transform infrared spectroscopy (FTIR), compression stress relaxation (CSR) and international rubber hardness degree (IRHD) microhardness were used to characterise the chemo-mechanical changes of HNBR O-rings during thermo-oxidative ageing. FTIR shows the development of carbonyl, methyl and ester groups but the nitrile content was not affected by ageing. The effect of sample geometry during CSR was investigated. CSR data were converted through integrated kinetic laws. The conversion has proven its sensibility to detect heterogeneous ageing. This was confirmed by the IRHD measure-ments across the section of O-rings. The influence of compression during ageing was assessed through IRHD measurements across the section of compressed and uncom-pressed aged O-rings. The DLO effect was more pronounced in compressed O-rings. By applying the model of Wise et al., theoretical IRHD and oxidation profiles were determined on the basis of IRHD experimental data of compressed O-rings. Good agreements between the experimental and the theoretical IRHD profiles in the core region were obtained. However, near the edge, the theoretical IRHD values were overestimated.
EPDM, HNBR and FKM materials were exposed at 150 ◦C to air under atmospheric pressure and to hydrogen at 50 bar for different ageing times. All measurements after hydrogen exposure were conducted on samples in degassed condition to assess irreversible effects resulting from that exposure and to compare them to those after ageing in air. Density, hardness, tensile properties, compression set, and hydrogen permeability of all samples were analysed. In both ageing environments, HNBR exhibited the most significant changes of material properties.
However, for both EPDM and HNBR, considerably less severe ageing effects were observed under hydrogen in comparison to ageing in air. On the other hand, FKM showed about the same low level of deterioration in both ageing environments but exhibited poor resistance against damage due to rapid gas decompression in hydrogen environment that can lead to seal failure. The obtained results may serve as a guidance toward a better understanding for design and utilisation of elastomeric materials in future hydrogen infrastructure components.
Evaluation of Heat Fluxes in Fire Reference Test Conducted in BAM Propane Gas Fire Test Facility
(2024)
Packages for the transport of intermediate- and high-level radioactive waste are designed to withstand severe accidents. The International Atomic Energy Agency (IAEA) has established specific mechanical and thermal tests. Packages for the transport of radioactive material must withstand these tests to comply with the Regulations for the Safe Transport of Radioactive Materials IAEA [IAEA (2018)]. A fire reference package was developed with the primary objective to demonstrate that the fire meets the regulatory requirements. Another aim is to characterise the boundary conditions of the actual fire as input parameters for thermo-mechanical simulations. A simple method to characterise the boundary conditions of a real steady state fire with a fire reference package is presented. The thermal test mainly consists of a 30 minute fully engulfing 800°C pool fire or an equally severe fire, such as a propane gas fire. The fire reference tests are performed prior to the actual fire test with the real package. The heat fluxes into the package depend substantially on the fire characteristics and the surface temperature of the package. To investigate local and overall heat fluxes over a wide range of surface temperatures in this test facility a fire reference package was designed for repeated use. The fire reference package presented in this paper represents the outer geometry of a small transport container for radioactive material and is used as a device in civil engineering. It is designed as a closed steel sheet cylinder with a wall thickness of 10 mm, a length of 182 mm and a diameter of 102 mm. The package was instrumented with thermocouples and filled with heat resistant insulation material. Open-air fire tests were performed in a BAM propane gas fire test facility with the fire reference package. The measured temperatures are used to determine the changes of heat fluxes into the fire reference package in relation to the package surface temperature. The calculated heat fluxes allow its fitting to express the thermal exposure as simple mathematical boundary condition. Therefore, in a first approach, fire properties such as adiabatic surface temperature (AST) as proposed by Wickström et al. (2007), convection coefficient and emissivity are determined mathematically fitting the heat flux development presented in this paper. The evaluated results provide an initial picture of local fire characteristics of the conducted propane gas fire and are a further development of previous works from Feldkamp et al. (2020). The results can be used in thermal and thermo-mechanical models to simulate the load on the real transport package in fire. The test shows that the examined propane gas fire covers the IAEA-fire over a wide range of surface temperatures with the chosen test stand parameters.
Evaluation of Heat Fluxes in Fire Reference Test Conducted in BAM Propane Gas Fire Test Facility
(2024)
Packages for the transport of intermediate- and high-level radioactive waste are designed to withstand severe accidents. The International Atomic Energy Agency (IAEA) has established specific mechanical and thermal tests. Packages for the transport of radioactive material must withstand these tests to comply with the Regulations for the Safe Transport of Radioactive Materials IAEA [IAEA (2018)]. A fire reference package was developed with the primary objective to demonstrate that the fire meets the regulatory requirements. Another aim is to characterise the boundary conditions of the actual fire as input parameters for thermo-mechanical simulations. A simple method to characterise the boundary conditions of a real steady state fire with a fire reference package is presented. The thermal test mainly consists of a 30 minute fully engulfing 800°C pool fire or an equally severe fire, such as a propane gas fire. The fire reference tests are performed prior to the actual fire test with the real package. The heat fluxes into the package depend substantially on the fire characteristics and the surface temperature of the package. To investigate local and overall heat fluxes over a wide range of surface temperatures in this test facility a fire reference package was designed for repeated use. The fire reference package presented in this paper represents the outer geometry of a small transport container for radioactive material and is used as a device in civil engineering. It is designed as a closed steel sheet cylinder with a wall thickness of 10 mm, a length of 182 mm and a diameter of 102 mm. The package was instrumented with thermocouples and filled with heat resistant insulation material. Open-air fire tests were performed in a BAM propane gas fire test facility with the fire reference package. The measured temperatures are used to determine the changes of heat fluxes into the fire reference package in relation to the package surface temperature. The calculated heat fluxes allow its fitting to express the thermal exposure as simple mathematical boundary condition. Therefore, in a first approach, fire properties such as adiabatic surface temperature (AST) as proposed by Wickström et al. (2007), convection coefficient and emissivity are determined mathematically fitting the heat flux development presented in this paper. The evaluated results provide an initial picture of local fire characteristics of the conducted propane gas fire and are a further development of previous works from Feldkamp et al. (2020). The results can be used in thermal and thermo-mechanical models to simulate the load on the real transport package in fire. The test shows that the examined propane gas fire covers the IAEA-fire over a wide range of surface temperatures with the chosen test stand parameters.
Biofuels, particularly biodiesel, have gained significant attention as an alternative to traditional fossil fuels in recent years. Unlike diesel, which contains hundreds of compounds, biodiesel only contains a few compounds in the C16-C18 carbon chain. However, the use of biodiesel in automobile and transportation applications can result in problems of degradation or even damage in materials. Among the commonly used polymer materials, fluorocarbon (FKM) shows excellent performance and high stability and compatibility towards oil, diesel, ethanol, and other chemicals. FKM is a family of fluorocarbon-based fluoroelastomer materials, which provide excellent high-temperature and chemical stability compared to other elastomers. As a result, FKM is widely used in chemical processes such as petroleum refining, where it is used for sealings, pumps, and other components.
Mechanical stress often accelerates the failure of polymer materials. The aim of this research is to study the interaction between the sealing material FKM and biofuels B10 (heating oil with 10% biodiesel). The mechanical stress test was carried out in a special apparatus. Both mechanical and non-mechanical stress tests were conducted on specimens at 20, 40, and 70 °C for 28 days to document changes in mass, volume, and tensile properties. Both increasing temperature and mechanical stress have a significant effect on the tensile strength of the FKM polymer when exposed to B10. The combination of increasing temperature and mechanical stress induced rupture within 2 h. It was also established that FKM polymer with pre-exposure in B10 survived longer during mechanical stress compared to specimens exposed only to air. With the support of infrared (IR) spectroscopy, we were able to confirm the penetration of B10 into the FKM polymer.
Der Wasserstofftransport auf der Straße ist wichtig und wird wie der noch geringe Transport auf der Schiene weiter stark zunehmen. Die bisherige Effizienzsteigerungen sind über Werkstoff- und Designänderungen vom Vollstahl über umfangsumwickelte Stahl- bis zu Compositespeichern mit Kunststofflinern erfolgt.
Hinzu kam die auf Basis der BAM-GGR 022 an Vorbedingungen geknüpfte Prüffristverlängerung von 5 auf 10 Jahre. Die wiederkehrende Prüfung von großen Transporteinheiten bedeutet jedes Mal einen Stillstand von gut 8 Wochen. Entsprechend steht mit Blick auf die weitere Effizienzsteigerung die Reduktion des Prüfaufwands im Fokus.
Eine Effizienzsteigerung kann nach aktueller Rechtslage geschehen, indem die hydraulische Prüfung auf eine Gasdruckprüfung umgestellt wird. Dies könnte zukünftig mit geeigneten Arbeitsschutzmaßnahmen pneumatisch durchgeführt werden – auch ohne Rechtsänderung.
Ein deutlich größerer Schritt in Richtung Verbesserung des Aufwands- zu Nutzenverhältnis ließe sich erreichen, indem die zerstörungsfreie Prüfung nicht mehr nur als Arbeitsschutz-motiviertes, begleitendes, sondern als zentrales Prüfverfahren ausgebaut wird. Gerade wenn – wie für die Schallemissionsanalyse erwartet – eine relativ gute Abschätzung des Berstdruckes möglich ist, könnte auf die 100%-Prüfung verzichtet werden und bis zu einem kritischen Alter nur auf Stichprobenprüfung basieren, was allerdings erhebliche Rechtsänderung erfordert und auch neue Werkezuge der Informationsverwaltung.
Als Vorlage für einen praktischen Ansatz zur Rechtsänderungen inkl. Informationsverwaltung wird auf die SV 674 in Verbindung mit 6.2.3.5.3ff ADR/RID verwiesen. Dies kombiniert mit einer digitalen Lebenslaufakte, die auf der digitalen Qualitätssicherung (QI-digital) beruht, wäre ein mächtiges Werkzeug für eine Verbesserung des Aufwands- zu Nutzenverhältnis und so auch eine Lösung des mit der stark steigenden Anzahl der Transporteinheiten absehbaren Kapazitätsproblems in der wiederkehrenden Prüfung.
Bio-electrochemical CO2 conversion into organic products using precious-metal free electrocatalysts
(2024)
For the realization of a sustainable economy, it is of great importance to make use of CO2 for the production of multi-carbon organic chemicals used as feedstock in the chemical industry as well as carbon-neutral fuels (Varela et al. 2019). A promising approach is the electrochemical CO2 reduction followed by microbial conversion of the reduced products.
Die BAM-GGR 016 erläutert die Anforderungen des ADR, RID, ADN und IMDG hinsichtlich notwendiger Maßnahmen zum Qualitäts- und Alterungsmanagement bei der Auslegung, Herstellung, Prüfung, Dokumentation, Gebrauch, Wartung und Inspektion von nicht-zulassungspflichtigen Versandstücken für radioaktive Stoffe für alle Bauarten von freigestellten Versandstücken, Industrieversandstücken des Typs IP-1, IP-2 und IP-3 und Versandstücken des Typs A.
Acetogenic bacteria produce CO2-based chemicals in aqueous media by hydrogenotrophic conversion of CO2, but CO is the preferred carbon and electron source. Consequently, coupling CO2 electrolysis with bacterial fermentation within an integrated bio-electrocatalytical system (BES) is promising, if CO2 reduction catalysts are available for the generation of CO in the complex biotic electrolyte. A standard stirred-tank bioreactor was coupled to a zero-gap PEM electrolysis cell for CO2 conversion, allowing voltage control and separation of the anode in one single cell. The cathodic CO2 reduction and the competing hydrogen evolution enabled in-situ feeding of C. ragsdalei with CO and H2. Proof-of-concept was demonstrated in first batch processes with continuous CO2 gassing, as autotrophic growth and acetate formation was observed in the stirred BES in a voltage range of −2.4 to −3.0 V. The setup is suitable also for other bioelectrocatalytic reactions. Increased currents and lower overvoltages are however required. Atomically-dispersed M−N−C catalysts show promise, if degradation throughout autoclaving can be omitted. The development of selective and autoclavable catalysts resistant to contamination and electrode design for the complex electrolyte will enable efficient bioelectrocatalytic power-to-X systems based on the introduced BES.
The subject of permeation of hoses according to ISO 3821 for
hydrogen was discussed for a long time in ISO/TC 44/SC 8. The reason
is a considerable leakage of hydrogen diffused into the hose material
over the end face of the hose. Because of this unsolved, safety-related
problem of hoses sold on the market, measurements should be carried
out in order to be able to better assess the problem. BAM has declared
its attendance to provide a required fast solution to this issue.
In ultrasonic testing, material and structural properties of a specimen can be derived from the time-of-flight (ToF). Using signal features, such as the first peak or envelope maximum, to calculate the ToF is error-prone in multipath arrangements or dispersive and attenuating materials, which is not the case for the signal onset. Borrowing from seismology, researchers used the Akaike information criterion (AIC) picker to automatically determine onset times. The most commonly used formulation, Maeda's AIC picker, is reassessed and found to be based on inappropriate assumptions for signals often used in ultrasonic testing and dependent on arbitrary parameters. Consequently, an onset picker for ultrasonic through-transmission measurements is proposed, based on a spectral entropy criterion (SEC) to model the signal using the AIC framework. This SEC picker takes into account the spectral properties of the ultrasonic signal and is virtually free of arbitrary parameters. Synthetic and experimental data are used to compare the performance of SEC and AIC pickers. It is shown that the accuracy of onset picking is improved for densely sampled data.
The safety demonstration of heavy weight type B transport packages used for storing spent nuclear fuel (SNF) or radioactive waste is ensured by a combination of physical testing and numerical calculations. While experiments are performed in accordance with the IAEA regulations for selected drop scenarios, Finite-Element-Method (FEM) simulations are used to predict the most damaging case and to investigate additional drop positions. BAM as competent authority in Germany has performed different investigations of a welding seam for a typical large transport package made of A508 forged steel, where the bottom plate is welded to the cylindrical shell. The package has a mass of approx. 120 t. Results of physical drop tests with a full-scale model and accompanying preliminary FEM simulations are presented to determine the decisive stresses in the welding seam. A drop test only represents one set of a package and test parameters. A further parameter analysis is considered to account for allowable variations of packaging properties (e.g. resulting from the manufacturing process) and, based on IAEA requirements, the temperature dependence of the material behaviour. The results of the stress analyses from the drop test and the simulation form the basis and provide the input parameters for a fracture mechanics analysis. In addition to the IAEA specifications, further standards are taken into account for an in-depth investigation, see R6 [1], BS 7910 [2] and API 579-1/ASME FFS1 [3]. All the above-mentioned standards require a manufacturer-specific defect analysis with respect to size and position. Both result from the welding process and the following heat treatment regime. The maximum defect sizes are ensured with non-destructive test methods (such as ultrasonic or particle methods) as integral part of the manufacturing process of the welding seam. Another important parameter in the welding process is the residual stress (secondary stress). The combination of the primary and secondary stress determines the total stress in the welding seam. The most damaging case of the welding seam is determined and evaluated with help of the abovementioned standards and taking into account the IAEA requirements with respect to defect sizes, material properties, primary and residual stress, yield strength etc.
Experimental and numerical investigation of prestressed bolt connections under lateral displacements
(2022)
The containment system of transport packages for spent nuclear fuel and high-level waste usually includes bolted lids with metal gaskets. The packages are assessed to specific transport conditions which are specified in the IAEA safety standards SSR-6 (IAEA 2018). These transport conditions, especially the so-called accident conditions of transport, imply high dynamic loading on the lids and the bolt connections of the package. The response of the lid systems on the mechanical accident conditions is generally investigated by experimental drop tests or numerically, e.g., by finite element analyses. The interpretation of the drop test results for the verification of the numerical models is often not obvious due to the complex superposition of different effects in the real tests. BAM has started a research project to get a better understanding about the behavior of prestressed bolt connections under loadings typical for these drop tests. In this context an experimental test set-up was developed to investigate the response of a single bolt connection under a prescribed lateral displacement of clamped parts. The bolt is instrumented by strain gauges to get the pretensional, the torsional and the bending stress in the bolt shank. Furthermore, the lateral movement and the tilt of the bolt head is measured during the test. A finite element model of the test set-up has been created in Abaqus FEA (Simulia 2021). The very detailed instrumentation of the test set-up shall give the opportunity to investigate and validate the numerical model. The aim of this paper is to give an overview about the proposed research project and to present first results.
H2Safety@BAM
(2023)
BAM is part of the “Quality Infrastructure Digital” (QI Digital) initiative of the German Federal Ministry for Economic Affairs and Climate Action (BMWK). This initiative aims at coordinating a large cooperation project, “QI Digital” for making German and European quality management systems fit for the digital transformation. It is a fact that the digitization of new products and services is occurring much faster than quality management systems can be accordingly updated. Thus, the digital transformation of quality management is necessary to preserve the competitiveness of the German and European industries that stand for quality and safety in the global market. The Use Case “Reliable Hydrogen Refueling Station” of QI Digital aims at creating new solutions that are transferable to other technical systems and at further developing standards and technical rules as a contribution to technology transfer and innovation.
This lecture describes the history of hydrogen from the first scientific discoveries in the 18th century to the current technological and political developments for the market ramp-up of hydrogen technologies. The European policy framework for safe hydrogen technologies is explained comprehending the European Green Deal, European Climate Law, European Hydrogen Strategy, Clean Hydrogen Partnership, REPowerEU Plan, Renewable Energy Directive and its Delegated Act, Net Zero Industry Act, etc.
This lecture describes the history of hydrogen from the first scientific discoveries in the 18th century to the current technological and political developments for the market ramp-up of hydrogen technologies. The European policy framework for safe hydrogen technologies is explained comprehending the European Green Deal, European Climate Law, European Hydrogen Strategy, Clean Hydrogen Partnership, etc. Safety in hydrogen technologies is governed by international and European regulations and standards. An overview on regulatory bodies, technical committees, regulations, directives, standards, and technical guidelines with special attention on the BAM-GGR 021 is given in this lecture.
This lecture describes the history of hydrogen from the first scientific discoveries in the 18th century to the current technological and political developments for the market ramp-up of hydrogen technologies. The European policy framework for safe hydrogen technologies is explained comprehending the European Green Deal, European Climate Law, European Hydrogen Strategy, Clean Hydrogen Partnership, etc. Safety in hydrogen technologies is governed by international and European regulations and standards. An overview on regulatory bodies, technical committees, regulations, directives, standards, and technical guidelines with special attention on the BAM-GGR 021 is given in this lecture.
Lithium-ion batteries usually consist of numerous individual cells. There is ongoing discussion about enhancing sustainability by considering the replacement of heavily aged or damaged cells. Nevertheless, the planned replacement of individual cells poses significant challenges in ensuring the required reliability and safety of the refurbished device.
AbstractLithium‐ion cells connected in series are prone to an electrical safety risk called overdischarge. This paper presents a comprehensive investigation of the overdischarge phenomenon in lithium‐ion cells using operando nondestructive imaging. The study focuses on understanding the behavior of copper dissolution and deposition during overdischarge, which can lead to irreversible capacity loss and internal short‐circuits. By utilizing synchrotron X‐ray computed tomography (SXCT), the concentration of dissolved and deposited copper per surface area is quantified as a function of depth of discharge, confirming previous findings. The results also highlight for the first time a nonuniform distribution pattern for copper deposition on the cathode. This research provides insights for safer battery cell design.
Due to their increasing energy density, lithium-ion-batteries (LIBs) play a key role in the traffic energy transition. Regarding their safety behavior, the main challenge of LIB-cells remains the thermal runaway (TR) process. In situ/operando investigations of the TR on commercial cells is possible with radiographic and computer tomographic measurements. Nonetheless, high resolution visualization of the TR persists as a challenge due to the high progression speed of the TR-process itself. Generally, performing abuse tests at cryogenic temperatures allows to slow down or even prevent the TR. Nevertheless, not all abuse methods are suitable for TR investigations at low temperatures. Nail penetration is an appropriate option, however, contains numerous unknown parameters and therefore suffers regarding reproducibility.
Herein, a self-developed high precision nail-penetration-setup is introduced, approaching the necessary mechanically reproducibility with controlled temperatures down to -190°C. The setup allows the preparation of critically abused, however, at cryogenic temperatures stable LIB-cells. These cells were controlled rethermalized to room temperature during synchrotron x-ray computer tomography (SXCT) with a pixel size up to 0.7 μm. During this measurement, the temperature and voltage of the cell is monitored allowing the visualization of the initial internal cell reactions. This study reveals the relation between internal reactions and cell voltage. Finally, the developed set-up enables in-depth analysis of thermal runaway behavior down to material level for various commercial battery cells in the future.
Next to performance features, safety aspects of lithium-ion batteries (LIBs) are a crucial research field. The abuse/misuse of a LIB can trigger a chain of exothermic reactions on cell level. Hence, the cell temperature increases dramatically, causing the so-called thermal runaway (TR). Moreover, the TR of one cell can initiate the TR of adjacent cells leading to a TR-propagation. Due to the risk of a TR, special measures need to be applied while handling, storing, and transporting batteries. According to current transport regulations, all different types of lithium-ion and lithium metal cells/batteries (by means of cell format, cathode chemistry, etc.) require the same transport conditions regardless of the intensity of their reaction during abuse tests. To allow more differentiated transport requirements, the United Nations (UN) Subcommittee Transport of Dangerous Goods created an Informal Working Group (IWG) on the topic of a hazard-based classification of LIBs. BAM is one of nine laboratories working on the development of a respective classification scheme including appendant test protocols.
Herein, we discuss the latest results of our safety tests on commercial LIB-cells employing the test protocols developed in the UN-IWG. Single cell tests are analysed regarding different hazardous features during the TR, e.g., cell temperature, flame occurrence, and gas amount. Next to the general occurrence of a propagation, the propagation speed is analysed by propagation tests. In total, the presented results are gathered from over 200 tests. Next to the classification of the tested cells, the data set obtained is analysed in respect to the cells’ key features, such as cell energy, state of charge and cathode type. Generally, the presented results can increase the overall understanding of the TR-mechanism supporting the design of advanced safety measures on cell level in the future.
Lithium-ion batteries (LIBs) are essential for the electrification of vehicles and play an important role for stationary storage units needed for grid-balancing. Research groups all over the world work on the improvement of LIBs regarding an increase in energy density as well as cycle-life and a decrease in costs. Next to these research topics, a continuously uprising and crucial field is safety features of LIBs, which can be implemented at different levels, such as material, cell, battery and system level.
The abuse/misuse of a LIB can cause an internal release of heat which can trigger a chain of exothermic reactions on cell level. Hence, the cell temperature increases dramatically, causing the so-called thermal runaway (TR), possibly leading to flames and/or explosion of the cell. Moreover, the TR of one cell can initiate the TR of adjacent cells leading to a so-called propagation, possibly, causing the TR of the whole battery. Ideally, easily obtainable key features of a certain cell – such as cathode type, cell format, cell energy and state of charge (SOC) - could allow the prediction of its behaviour under abuse conditions. In the present study, we will discuss the latest result of our safety tests on cell level employing an external heater as TR-trigger. Single cell tests will be analysed regarding different hazardous features during the TR, e.g., cell temperature, occurrence of flames, peak pressure, gas amount and gas composition. Moreover, the possibility of a TR-propagation and the respective propagation speed will be gained from propagation tests utilizing six cells with identical SOC. In total, the study comprises over 200 tests on cell level. The gained data set is analysed in respect to the cell parameters, such as cell format, cell energy, SOC and the cathode type as well as the atmosphere (air vs. N2) present during the test. A special focus is put on the discussion of general conclusions linking cell parameters to TR-effects and propagation behaviour.
The findings regarding common conclusions between key features and TR-effects can enable a rather facile selection process of cells/batteries for certain applications according to specific safety targets. Moreover, it allows to choose cell-specific safety measures, suitable during operation. In further works, the study will be extended to end-of-first life cells yielding important conclusions regarding crucial safety aspects for the implementation of those cells in 2nd-life application. Generally, the presented results can increase the overall understanding of the TR mechanism supporting the design of advanced measures to enhance the safety on cell level in the future.
Lithium-ion battery (LIB) powered devices, such as laptops, mobile phones and power tools are ubiquitous in our daily lives. Moreover, LIBs are essential for the electrification of vehicles, and play an important role for stationary storage units needed for grid-balancing. The improvement of LIBs, in terms of increasing energy density as well as cycle-life and decreasing costs, is tackled by numerous research groups all over the world. In the last years, research regarding safety aspects has steadily gained more interest. The safety of LIBs can be implemented at different levels, such as material, cell, battery and system level.
The abuse/misuse of an LIB can lead to an internal increase in heat which can trigger a chain of exothermic reactions on cell level. Thus, the cell temperature increases dramatically causing the so-called thermal runaway (TR). This process can lead to flames and/or explosion of the cell. Furthermore, the TR of one cell can initiate the TR of adjacent cells causing the so-called propagation, possibly, leading to the TR of the whole battery.
Herein, we will show the latest result of our safety tests on cell level employing an external heater as TR-trigger. Regarding single cell tests, we will compare different hazardous features during the TR, e.g., cell temperature, occurrence of flames, peak pressure, and toxic gases, depending on the cell format, cell energy and the cathode type. The same cell parameters will be used to discuss the results of the propagation tests. Moreover, the influence of the state of charge (SOC) and the present atmosphere (air vs. N2) as well as the repeatability will be discussed. Overall, the study comprises over 180 tests on cell level.
The findings regarding the TR behaviour can be used to create a hazard-classification scheme of LIBs, e.g., allowing the definition of (cell type specific) conditions for a safe transport. Furthermore, the results can increase the general understanding of the TR mechanism promoting the development of advanced measures to enhance the safety on cell level in the future.
Deconvoluting the impact of early-life abuse conditions on the degradation of lithium-ion cells
(2023)
The successful repurposing of degraded lithium-ion (Li-ion) batteries in second-life applications is a vital step towards achieving a circular economy. While reusing aged Li-cells is a promising way of mitigating their overall environmental footprint, it is crucial to anticipate their future safety and performance characteristics . Unfortunately, predicting these properties is a cumbersome task, essentially caused by limited knowledge of the interference of different degradation modes in the cells’ first life.
To still enable estimating of these parameters from a current state, the present study systematically investigates the impacts of abusive conditions in an early phase of the cells’ life on their subsequent degradation behavior. For this purpose, individual Li-cells are initially stressed by different measures such as overcharging, deep-discharging, plating, and deliberate combinations of the aforementioned methods. Electrochemical performance indicators are monitored during subsequent cycling of the cells which provides insights into the interdependencies of different degradation modes induced by specific stress conditions. In this manner, it is clarified whether or not the total degradation can be determined by a convolution or a superposition of individual deterioration effects and, thus, be described as a multidimensional state function.
This knowledge will finally contribute to a better understanding of the performance and safety behavior of degraded Li-ion batteries which can help to successfully implement them into second-life applications.