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Gaseous inhibitors are used in many industries for the explosion prevention of combustible dusts, mitigating the potential hazard to humans, properties and environments. This work experimentally and theoretically studied the inerting effect of gaseous inhibitors on the ignition process of dust clouds in O2/N2/CO2 atmospheres, with an emphasis on the role of the CO2/N2 ratio. 10 different combustible carbonaceous dusts were selected, including grain dust, biomass dust and coal dust. Experimental results showed that the inhibition effect of CO2/N2 is closely related to the ignition mechanism of dust clouds. Specifically, a higher ratio of CO2/N2 yields a stronger inhibition effect on the ignition process of dust samples with relatively low volatile matter contents predominated by heterogeneous ignition. In addition, two novel steady-state ignition mechanism models were developed to interpret the experimental observations. Maxwell-Stefan equations were used to describe the diffusivity in the ternary O2/N2/CO2 gas mixtures. The analytical results were in good agreement with the experimental data of the minimum ignition temperature of dust cloud (MITC) in oxygen-lean atmospheres. The mechanism modelling can be used to estimate the critical ignition temperature of all carbonaceous dust clouds with a wide range of volatile matter content under different inert atmospheres, which will provide a reference for the explosion hazard assessment of dust posed by a hot surface in the process industries.
The number of cars which use a battery for propulsion, like BEV (battery electric vehicle) or PHEV (plug-in hybrid electric vehicle), is increasing. Following, the probability of these car types being involved in car accidents will increase. In a worst-case accident scenario, the installed batteries could go under thermal runaway (TR). A TR could be initiated by various causes, e.g., high temperatures from outside, mechanical damage of the cells/modules/batteries or internal and external short circuits. During such an event, large amounts of heat and toxic and/or flammable gases are released. This poses a great hazard to people and property in the immediate vicinity. The paper describes a large-scale test series on the lithium-ion battery TR consequences of automobile cells and modules up to E = 6.85 kWh. Near field temperatures of ΔT > 800°C in a distance of l = 2 m were measured. During an overcharge test, fragment throwing distances of l > 30 m were detected. Subsequent gas explosions of the released gases were documented. Hydrogen fluoride (HF) was measured in all tests, from cell to module. The highestmeasured concentration was cHF = 76 ppm, which is significantly higher than the 30-min-level for AEGL 2 (acute exposure guideline level 2). Based on the experimentally determined consequences, concrete measures for the accident analysis are subsequently drawn.
Elektrische Energiespeicher können unter bestimmten Bedingungen thermisch Durchgehen. Dies ist mit der Freisetzung von großen Mengen an Wärme sowie toxischen und/oder brennbaren Gasen assoziiert. Um die potenziellen Auswirkungen des thermischen Durchgehens zu quantifizieren, wurden Versuche mit Zellen und Modulen mit einem Energieinhalt von bis zu E = 6,85 kWh durchgeführt. Es wurden verschiedene Kenngrößen, wie z.B. Temperatur, Spannung, Massenabbrand, qualitative Gaszusammensetzung sowie Fragmente, messtechnisch erfasst und ausgewertet. Die Ergebnisse können sowohl für Bemessungen im vorbeugenden baulichen Brandschutz als auch in der Prozess- und Anlagensicherheit verwendet werden. Ebenso können sie in Konzept des abwehrenden Brandschutzes integriert werden.
Thermal runaway reactions were studied in arrangements from single battery cells with energy capacities of 2.5 Ah (9.25 Wh) to battery modules up to 6.85 kWh. All cells were pouch cells of the Li-ion NMC type and the modules were composed of such. Abuse was triggered either by overcharging or thermally by attaching a heat source (heating plate or glow plug) to the cells. Experiments with single cells or assemblies of two to four cells were undertaken in closed
autoclaves.
Samples of the gas released from the cells during the runaway were extracted and analysed using a Fourier-transformed infrared spectrometer (FTIR). In some experiments pressure peaks up to 7 bar (g) were observed which could not be explained by the gas release alone. Obviously, secondary explosions took place.
Thermal runaway propagation was studied with and without an insulation layer between the battery cells. Several materials and combinations of them were tested as insulations: hollow glass spheres (Pyrobubbles®), phase change materials (PCM) and intumescent materials. Experiments showed that already layers of 10 to 20 mm of insulation effectively prevented the propagation of a thermal runaway. In addition to the experiments, a mathematical model was developed for studying numerically the heat transfer through arrangements of multiple battery cells and also the effect of insulation layers. This model was implemented into the commercial finite-element software package COMSOL Multiphysics®. The simulations confirmed the experimental findings that already
quite thin insulation layers between cells or modules effectively delay or even suppress the propagation of the thermal runaway.
Die Transformation der Energienutzung von konventionellen zu erneuerbaren Quellen führt dazu, dass zukünftig mehr Energie effizient zwischengespeichert werden muss. Eine Möglichkeit der elektrochemischen Zwischenspeicherung bieten Lithium-Ionen-Batterien. Hierfür können ausgemusterte Automobilantriebsbatterien verwendet werden. Erfüllen sie die hohen Anforderungen des mobilen Bereichs nicht mehr, haben sie oftmals noch eine ausreichende Kapazität und Leistungsfähigkeit für die stationäre Zwischenspeicherung.
Neben der Verwendung der Batterien im größeren Maßstab, z.B. bei Energieversorgern, werden durch den vermehrten Einsatz von Photovoltaik-Anlagen in Ein- und Mehrfamilienhäusern verstärkt Zwischenspeicher für Privathaushalte nachgefragt. Dies birgt auch für Einsatzkräfte neue Herausforderungen in der Gefahrenabwehr.
Im vom Bundesministerium für Bildung und Forschung (BMBF) geförderten Verbundprojekt „SEE-2L – Sicherheit elektrochemischer Energiespeicher in Second Life Anwendungen“ wurden Versuche mit Second Life Modulen durchgeführt. Verbundpartner im Projekt waren neben der vfdb die Otto-von-Guericke-Universität Magdeburg und die Bundesanstalt für Materialforschung und -prüfung. Zudem war das Institut der Feuerwehr Nordrhein-Westfalen eingebunden.
Die durchgeführten Versuche bilden eine Grundlage für die Einordnung der Batteriespeicher, z.B. aus Sicht des baulichen Brandschutzes, zur Methodik der Brandbekämpfung oder zur Risikobewertung hinsichtlich der Prozess- und Anlagensicherheit.
Im Beitrag werden die Versuchsergebnisse vorgestellt und Ansätze für deren Anwendung gezeigt. Um die gewonnenen Erkenntnisse zu vermitteln, wurde im Projekt zudem ein Schulungskonzept für Einsätze mit Lithium-Ionen-Technologien erarbeitet, das im Beitrag präsentiert wird. Es besteht aus theoretischen und praktischen Anteilen, sodass bei den Feuerwehren praxisnah aus- bzw. fortgebildet werden kann.
Thermal runaway and explosibility of the gas release from 18650 sodium-ion cells of NFM chemistry
(2025)
The present study investigates the thermal runaway behaviour and explosibility of the gas mixture released from sodium-ion batteries (SIBs). A total of 30 tests comprising two test series were performed using 18650 SIBs with a NaNi1/3Fe1/3Mn1/3O2 (NFM) chemistry. The cells of SOC level = 0 %, 25 %, 50 %, 75 % and 100 % were subjected to thermal abuse inside a 10 L pressurized reaction vessel. In test series 1, the tests were performed in an air atmosphere. In test series 2, an inert atmosphere was used. First, the total amount of gas released from the SIBs was calculated based on the temperature and pressure measured in the reaction vessel. Subsequently, a gas composition analysis was performed using a Fourier-transformed infrared (FTIR) spectrometer. This study revealed that the thermal runaway in SIBs could be categorized into four phases. At the onset of thermal runaway, the thermal runaway-induced explosion of the cells resulted in a rate of temperature rise ranging from 2 K/s to 70 K/s. The investigation further revealed a peak reaction temperature of 415 ◦C and a maximum pressure of 4 bar could be reached at thermal runaway in the 10 L vessel. The gas release of up to 5 ± 0.3 L (4 ± 0.2 L/Ah, 1.3 ± 0.1 L/Wh) from test series 1 and 2.4 ± 0.2 L (2 ± 0.1 L/Ah, 0.53 ± 0.04 L/Wh) from test series 2 showed a dependence on SOC and failure environment used. By applying Le Chatelier's mixing rule, the measured gas release from the air atmosphere showed a calculated lower explosion limit and upper explosion limit values of 4.8 % and 24 % in volume fraction, respectively.