Tschirschwitz Rico, Bernardy Christopher, Wagner Patrick, Rappsilber Tim, Liebner Christian, Hahn Sarah-K, Krause Ulrich
Bundesanstalt für Materialforschung und -prüfung (BAM) Unter den Eichen 87 12205 Berlin Germany
German Fire Protection Association (Vereinigung zur Förderung des Deutschen Brandschutzes e.V.-vfdb) Wolbecker Straße 237 48155 Münster Germany
RSC Adv. 2023 Jul 10;13(30):20761-20779. doi: 10.1039/d3ra02881j. eCollection 2023 Jul 7.
For a comprehensive safety assessment of stationary lithium-ion-battery applications, it is necessary to better understand the consequences of thermal runaway (TR). In this study, experimental tests comprising twelve TR experiments including four single-cell tests, two cell stack tests and six second-life module tests (2.65 kW h and 6.85 kW h) with an NMC-cathode under similar initial conditions were conducted. The temperature (direct at cells/modules and in near field), mass loss, cell/module voltage, and qualitative vent gas composition (Fourier transform infrared (FTIR) and diode laser spectroscopy (DLS) for HF) were measured. The results of the tests showed that the battery TR is accompanied by severe and in some cases violent chemical reactions. In most cases, TR was not accompanied by pre-gassing of the modules. Jet flames up to a length of 5 m and fragment throwing to distances to more than 30 m were detected. The TR of the tested modules was accompanied by significant mass loss of up to 82%. The maximum HF concentration measured was 76 ppm, whereby the measured HF concentrations in the module tests were not necessarily higher than that in the cell stack tests. Subsequently, an explosion of the released vent gas occurred in one of the tests, resulting in the intensification of the negative consequences. According to the evaluation of the gas measurements with regard to toxicity base on the "Acute Exposure Guideline Levels" (AEGL), there is some concern with regards to CO, which may be equally as important to consider as the release of HF.
为了对固定式锂离子电池应用进行全面的安全评估,有必要更好地了解热失控(TR)的后果。在本研究中,进行了包括十二次热失控实验的测试,其中包括四次单电池测试、两次电池组测试和六次二次利用模块测试(2.65 kW h和6.85 kW h),这些测试均采用镍锰钴(NMC)阴极,且初始条件相似。测量了温度(直接在电池/模块处及近场)、质量损失、电池/模块电压以及定性的排气成分(用于检测HF的傅里叶变换红外光谱(FTIR)和二极管激光光谱(DLS))。测试结果表明,电池热失控伴随着剧烈且在某些情况下甚至是猛烈的化学反应。在大多数情况下,热失控并未伴随着模块的预排气。检测到高达5米长的喷射火焰以及碎片抛射距离超过30米的情况。测试模块的热失控伴随着高达82%的显著质量损失。测得的最大HF浓度为76 ppm,其中模块测试中测得的HF浓度不一定高于电池组测试中的浓度。随后,在一次测试中发生了释放的排气爆炸,导致负面后果加剧。根据基于“急性暴露指导水平”(AEGL)对气体毒性测量结果的评估,对于CO存在一些担忧,其可能与HF的释放同样重要,值得考虑。