In Situ Raman Spectroscopy on Silicon Nanowire Anodes Integrated in Lithium Ion Batteries

Abstract

Rapid decay of silicon anodes during lithiation poses a significant challenge in application of silicon as an anode material in lithium ion batteries. In situ Raman spectroscopy is a powerful method to study the relationship between structural and electrochemical data during electrode cycling and to allow the observation of amorphous as well as liquid and transient species in a battery cell. Herein, we present in situ Raman spectroscopy on high capacity electrode using uncoated and carbon-coated silicon nanowires during first lithiation and delithiation cycle in an optimized lithium ion battery setup and complement the results with operando X-ray reflection diffraction measurements. During lithiation, we were able to detect a new Raman signal at 1859 cm −1 especially on uncoated silicon nanowires. The detailed in situ Raman measurement of the first lithiation/delithiation cycle allowed to differentiate between morphology changes of the electrode as well as interphase formation from electrolyte components.

Porous Si@SiOx@N‐Rich Carbon Nanofibers as Anode in Lithium‐Ion Batteries under High Temperature

“…When Li + was generally inserted, an intensified growth of the SEI film gave rise to the decreased intensity of the Si single. [25] With cycle processing, such a characteristic Raman peak disappeared in afterwards cycles (Figure 7b). No distinct peak shift could be found in the measured voltage range.…”

“…It is obvious that the intensity of the 1TO mode of Si decreased linearly, starting at a potential of 1.5 V at discharge state. When Li + was generally inserted, an intensified growth of the SEI film gave rise to the decreased intensity of the Si single . With cycle processing, such a characteristic Raman peak disappeared in afterwards cycles (Figure b).…”

Operando probing of Li-insertion into LiMn2O4cathodes by spectroscopic ellipsometry

“…[9][10][11][12][13] Despite these efforts, some of the most powerful techniques, such as isotopic ion exchange methods, 14 in situ TEM 14 and the collection of synchrotron radiation based techniques, 10,11,[15][16][17][18][19][20] are highly sophisticated limiting the straightforward access to essential information for developing highly performing batteries. In addition, a number of commonly available techniques have also been explored including X-ray diffraction, [21][22][23] atomic force microscopy (AFM), 5,24 Raman spectroscopy [25][26][27] and Fourier transform infrared (FTIR) spectroscopy 28,29 showing different advantages and limitations regarding spatial and time resolutions. On the other hand, despite the well-known capabilities of Spectroscopic Ellipsometry (SE) for the study of the properties of thin lm systems (including multi-layered devices), the use of this affordable technique in the eld of Lii is very limited 30 and, to the best of the authors' knowledge, it has never been implemented for real in operando measurements in the battery domain.…”

Derivation of Luminescent Mesoporous Silicon Nanocrystals from Biomass Rice Husks by Facile Magnesiothermic Reduction

“…As shown in Figure 3 b, the Raman spectra of all three samples revealed a similar feature of the typical Raman vibration modes from crystalline Si. Namely, the sharp peak at 519 cm −1 (i.e., the first-order transversal optical (TO) mode [ 18 , 57 , 58 ]) and the broad hump at 957 cm −1 (i.e., the second-order TO mode [ 18 , 57 , 58 ]) are clearly observable in all the samples, while no other Raman bands are visible. This demonstrates that the high-purity Si nanocrystals were effectively derived from the biomass RHs through the magnesiothermic reduction process.…”