3.1 Sicherheit von Gefahrgutverpackungen und Batterien
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The potential release of hazardous substances from polymer-based products is currently in the focus of environmental policy. Environmental simulations are applied to expose such products to selected aging conditions and to investigate release processes. Commonly applied aging exposure types such as solar and UV radiation in combination with water contact, corrosive gases, and soil contact as well as expected general effects on polymers and additional ingredients of polymer-based products are described. The release of substances is based on mass-transfer processes to the material surfaces. Experimental approaches to investigate transport processes that are caused by water contact are presented. For tailoring the tests, relevant aging exposure types and release quantification methods must be combined appropriately. Several studies on the release of hazardous substances such as metals, polyaromatic hydrocarbons, flame retardants, antioxidants, and carbon nanotubes from polymers are summarized exemplarily. Differences between natural and artificial exposure tests are discussed and demonstrated for the release of flame retardants from several polymers and for biocides from paints. Requirements and limitations to apply results from short-term artificial environmental exposure tests to predict long-term environmental behavior of polymers are presented.
Porous carbons are promising anode materials for next generation lithium batteries due to their large lithium storage capacities. However, their highsloping capacity during lithiation and delithiation as well as capacity fading due to intense formation of solid electrolyte interphase (SEI) limit their gravimetric and volumetric energy densities. Herein we compare a microporous carbide-derived carbon material (MPC) as promising future anode for all solid-state batteries with a commercial high-performance hard carbon anode. The MPC obtains high and reversible lithiation capacities of 1000 mAh g−1carbon in half-cells exhibiting an extended plateau region near 0 V vs. Li/Li+ preferable for full-cell application. The well-defined microporosity of the MPC with a specific surface area of >1500 m2 g−1 combines well with the argyrodite-type electrolyte (Li6PS5Cl) suppressing extensive SEI formation to deliver high coulombic efficiencies. Preliminary full-cell measurements vs. nickel-rich NMC-cathodes (LiNi0.9Co0.05Mn0.05O2) provide a considerably improved average potential of 3.76 V leading to a projected energy density as high as 449 Wh kg−1 and reversible cycling for more than 60 cycles. 7Li Nuclear Magnetic Resonance spectroscopy was combined with ex-situ Small Angle X-ray Scattering to elucidate the storage mechanism of lithium inside the carbon matrix. The formation of extended quasi-metallic lithium clusters after electrochemical lithiation was revealed.
Täglich werden mehrere tausend Tonnen in Säcken verpackter Gefahrgüter über die Straßen transportiert. Laut den internationalen Gefahrgutvorschriften für den innerstaatlichen und grenzüberschreitenden Verkehr ADR müssen Gefahrgutsäcke aus Papier „staubdicht“ sein. Die Autobahnpolizei Münster wies bei einem Vortrag in der BAM darauf hin, dass im Rahmen polizeilicher LKW-Kontrollen Ladeflächen voller Staub vorgefunden wurden, ohne dass ein Defekt an einem Gefahrgutsack festgestellt werden konnte.
Ziel der Arbeit war es, eine Prüfkammer zu entwickeln, welche in der Lage ist, nach Fallversuchen mit Gefahrgutsäcken aus Papier den freigesetzten luftgetragenen Staub zu bestimmen. Eine anschließende Bewertung soll die gesundheitlichen Gefahren des entstandenen Aerosols aufzeigen. Durch die Auswertung erster Fallversuche wurde exemplarisch die „Dichtheit“ vorhandener Gefahrgutsäcke bestimmt und die Fraktionen der entstandenen Aerosole wurden mit den Arbeitsplatzgrenzwerten verglichen.
Im Zusammenhang mit den Untersuchungen zu den Möglichkeiten von gekühlten Transporten von Lithiumbatterien werden unterschiedliche Zerstörungsmethoden vorgestellt und diskutiert. Insbesondere wird dabei das neu entwickelte Nageltool und die vorläufigen Untersuchungen für den Einfluss von Ultratiefkühlung auf unbeschädigte Lithiumbatterien vorgestellt.
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.
Lithium batteries are the key technology for the successful implementation of the energy transition. Nevertheless, the consequences of thermal runaway of lithium batteries pose the greatest safety risk. In particular, the transport of damaged lithium batteries poses special challenges in order to minimize the effects of thermal runaway. By developing a precision nail test rig, the positive effects of cooling damaged lithium batteries can be investigated and safe transport temperatures identified.
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.
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.
Adopting X-ray computed tomography (XCT) for ex-situ characterization of battery materials has gained interest in the past decade. The main goal of this paper is to demonstrate the effectiveness of several X-ray computer tomography techniques to study commercial batteries. General guidelines are provided to select the most suitable imaging equipment and parameters for investigations of lithium-ion batteries, spanning the length scales from cell to electrode, down to particle level. Relevantly, such parameters would also be suitable for operando experiments.
Safety mechanisms and manufacturing inconsistencies at cell level as well as defects and inhomogeneity in cathode and anode is illustrated and quantified. Furthermore, relation of beam energy and sample-detector-distance on contrast retrieved from attenuation and phase shift is inspected using Synchrotron XCT.