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Spectroscopic Characterization of the SEI Layer Formed on Lithium Metal Electrodes in Phosphonium Bis(fluorosulfonyl)imide Ionic Liquid Electrolytes

机译:在鏻双(氟磺酰基)酰亚胺离子液体电解质中形成锂金属电极上形成的SEI层的光谱表征

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摘要

The Chemical composition of the solid electrolyte interphase (SEJ) layer formed on the surface of lithium metal electrodes cycled in phosphonium bis(florosulfonyl)imide ionic liquid (IL) electroytes are characterized by magic angle spinning nuclear magnetic resonance (MAS NMR), X-ray photoelectron spectroscopy (XPS), fourier transformed infrared spectroscopy, and electrochemical impedance spectroscopy. A multiphase layered structure is revealed, which is shown to reamin relatively unchanged during extended cycling (up to 250 cycles at 1.5 mA.cm(-2), 3 mA h.cm(-2), 50 degrees C). The main components detected by MAS NMR and XPS agter several hundreds of cycles are LiF and breakdown products from the bis(flourosufonyl)imide anion including Li2S. Similarities in chemical composition are observed in the case of the dilute (0.5 mol.kg(-1) of Li salf in IL) and the highly concentrated (3.8 mol.kg(-1) of Li salt in IL) electrolyte during cycling. The concentrated system is found to promote the formation of a thicker and more uniform SEI with larger amounts of reduced species from the anion. These SEI features are thought to facilitate more stable and efficient Li cycling and a reduced rendency for dendrite formation.
机译:在膦酸钯(Florosulfonyl)离子液体(IL)电极中循环的锂金属电极表面上形成的固体电解质相互异位(SEJ)层的化学组成是通过魔法角旋转核磁共振(MAS NMR),X-射线光电子体光谱(XPS),傅里叶变换红外光谱和电化学阻抗光谱。揭示了多相分层结构,其显示在延长的循环期间相对不变的铰型(在1.5 mA.CM(-2),3mA HCM(-2),50℃)中相对不变(最多250个循环。 MAS NMR和XPS活化剂检测的主要成分数百次循环是来自包括Li2s的双(蜡磺酰基)Imide阴离子的LiF和击穿产品。在循环期间,在IL的稀释(0.5mol.kg(-1)Li Salf的Li Salf的稀释(0.5mol.kg(-1)的Li Salf的情况下,观察到化学成分的相似性。发现浓缩系统促进较厚且更均匀的SEI的形成,并且来自阴离子的较大量的物种。这些SEI的特征被认为促进更稳定和高效的锂循环和枝晶形成的延续率。

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