Interaction of the ionic liquid [BMP][TFSA] with rutile TiO2(110) and coadsorbed lithium.
Interaction of the ionic liquid [BMP][TFSA] with rutile TiO2(110) and coadsorbed lithium.
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离子液体[BMP][TFSA]与金红石TiO2(110)和共吸附锂的相互作用。
DOI：
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
R. Behm
中科院分区：
文献类型：
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作者：
B. Uhl;M. Hekmatfar;F. Buchner;R. Behm
旨在对电极上的过程有基本的了解|锂离子电池中离子液体界面，研究了离子液体N-丁基-N-甲基吡咯烷鎓双用X-射线衍射法研究了还原金红石型TiO 2（110）（1 × 1）表面的三氟甲磺酰亚胺[BMP][TFSA]和Li的相互作用，以及在超高真空（UHV）条件下[BMP][TFSA]和Li在TiO 2（110）表面上的相互作用。射线光电子能谱和扫描隧道显微镜。在80 K和340 K之间，[BMP][TFSA]以分子形式吸附在表面上，在较高温度下观察到分解，产生诸如Sad、Fad和TiNx的产物。的分解模式进行比较，以理论为基础的建议。少量的Li甚至在80 K下嵌入到TiO 2（110）中，形成Li（+）和Ti（3+）物种。在近表面区域中的化学计量对应于Li 7 Ti 5 O 12。对于几个单层范围内的较高覆盖率，部分Li保留在表面上，形成Li 2 O覆盖层。在300 K时，Ti（3+）物种变得足够移动的扩散到块体中。Li后沉积在[BMP][TFSA]覆盖的TiO 2（110）表面上在80 K下导致两个竞争反应，Li嵌入和与IL的反应，导致IL的分解。在升温时，在低T下形成的Ti（3+）通过与IL吸附层和中间分解产物反应而被消耗。[BMP][TFSA]（300 K）在预覆盖有Li 2 O/Li 7 Ti 5 O 12层的表面上的后沉积导致[BMP][TFSA]与Li（+）和Ti（3+）物质的部分反应，该反应在较高温度下完成。
Aiming at a fundamental understanding of the processes at the electrode|ionic liquid interface in Li ion batteries, we investigated the interaction of the ionic liquid n-butyl-n-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [BMP][TFSA] and of Li with a reduced rutile TiO2(110) (1 × 1) surface as well as the interaction between [BMP][TFSA] and Li on the TiO2(110) surface under ultrahigh vacuum (UHV) conditions by X-ray photoelectron spectroscopy and scanning tunnelling microscopy. Between 80 K and 340 K [BMP][TFSA] adsorbs molecularly on the surface and at higher temperatures decomposition is observed, resulting in products such as Sad, Fad and TiNx. The decomposition pattern is compared to proposals based on theory. Small amounts of Li intercalate even at 80 K into TiO2(110), forming Li(+) and Ti(3+) species. The stoichiometry in the near surface region corresponds to Li7Ti5O12. For higher coverages in the range of several monolayers part of the Li remains on the surface, forming a Li2O cover layer. At 300 K, Ti(3+) species become sufficiently mobile to diffuse into the bulk. Li post-deposition on a [BMP][TFSA] covered TiO2(110) surface at 80 K results in two competing reactions, Li intercalation and reaction with the IL, resulting in the decomposition of the IL. Upon warming up, the Ti(3+) formed at low T is consumed by reaction with the IL adlayer and intermediate decomposition products. Post-deposition of [BMP][TFSA] (300 K) on a surface pre-covered with a Li2O/Li7Ti5O12 layer results in the partial reaction of [BMP][TFSA] with the Li(+) and Ti(3+) species, which gets completed at higher temperatures.