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静电纺聚酰亚胺-AlO隔膜的原位热安全性表明,在锂离子电池热失控事件中,其放热能量比聚丙烯少。

In Situ Thermal Safety Aspect of the Electrospun Polyimide-AlO Separator Reveals Less Exothermic Heat Energies Than Polypropylene at the Thermal Runaway Event of Lithium-Ion Batteries.

作者信息

Palanisamy Manikandan, Lin Keng-Wei, Lo Chieh-Tsung, Pol Vilas G

机构信息

Davidson School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United States.

Department of Mechanical, Aerospace, and Biomedical Engineering, University of Tennessee, Knoxville, Tennessee 37996, United States.

出版信息

ACS Appl Mater Interfaces. 2022 Jun 22;14(24):28310-28320. doi: 10.1021/acsami.2c07780. Epub 2022 Jun 10.

DOI:10.1021/acsami.2c07780
PMID:35687749
Abstract

Polyimide-AlO membranes are developed as a direct alternative to current polyolefin separators by the electrospinning technique and their chemical structures confirm the carbonyl group with the presence of asymmetric and symmetric stretching and bending vibrations at 1778, 1720, and 720 cm and stretching vibration at 1373 cm for the imide group. Porous nanofiber architecture morphology is realized with a nanofiber thickness of ∼200 nm and shows an ultrasmooth surface and >1 μm pore size in the architecture, built with the chemical constituents of carbon, nitrogen, aluminum, and oxygen elements. The galvanostatic cycling study of the Li/PI-AlO/LiFePO lithium cell delivers stable charge-discharge capacities of 144/143 mAh g at 0.2 C and 110/100 mAh g at 1 C for 1-100 cycles. The fabricated MCMB/PI-AlO/LiFePO lithium-ion full-cell reveals less charge transfer resistance of ∼ 25 Ω and yields stable charge-discharge capacities of 125/119 mAh g. The thermogravimetric curve for the PI-AlO separator discloses thermal stability up to 525 °C, and the differential scanning calorimetric curve shows a straight line until 300 °C and depicts high thermal stability than the PP separator. In situ multimode calorimetry analysis of the MCMB/PP/LiFePO full-cell showed a pronounced exothermic peak at 225 °C with a higher released heat energy of 211 J g at the thermal runaway event, while the MCMB/PI-AlO/LiFePO full-cell revealed an almost 8-fold less exothermic released heat energy of 25 J g than the Celgard polypropylene separator, which was because the MCMB anode and LiFePO cathode can be mechanically isolated without any additional separator's melting and burning reactions, as a fire-suppressant separator for lithium-ion batteries.

摘要

通过静电纺丝技术制备了聚酰亚胺 - 氧化铝(Polyimide - AlO)膜,作为当前聚烯烃隔膜的直接替代品,其化学结构通过在1778、1720和720 cm处存在不对称和对称拉伸及弯曲振动以及在1373 cm处存在酰亚胺基团的拉伸振动来证实羰基的存在。实现了多孔纳米纤维结构形态,纳米纤维厚度约为200 nm,表面超光滑,结构中的孔径大于1μm,由碳、氮、铝和氧元素的化学成分构成。Li/PI - AlO/LiFePO锂电池的恒电流循环研究表明,在0.2 C下1 - 100次循环的稳定充放电容量为144/143 mAh g,在1 C下为110/100 mAh g。制备的MCMB/PI - AlO/LiFePO锂离子全电池显示出约25Ω的较低电荷转移电阻,稳定充放电容量为125/119 mAh g。PI - AlO隔膜的热重曲线表明其热稳定性高达525°C,差示扫描量热曲线显示在300°C之前为直线,且比聚丙烯(PP)隔膜具有更高的热稳定性。MCMB/PP/LiFePO全电池的原位多模式量热分析表明,在热失控事件中,在225°C出现明显的放热峰,释放的热能较高,为211 J g,而MCMB/PI - AlO/LiFePO全电池显示出的放热释放热能比Celgard聚丙烯隔膜少近8倍,为25 J g,这是因为MCMB阳极和LiFePO阴极可以机械隔离,无需任何额外隔膜的熔化和燃烧反应,作为锂离子电池的阻燃隔膜。

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