In Situ X-Ray Photoelectron Spectroscopy for All-Solid-State Batteries: Analysis of Lithiation and Delithiation Reactions of Silicon Thin-Film Electrode
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E-Article
Title:
In Situ X-Ray Photoelectron Spectroscopy for All-Solid-State Batteries: Analysis of Lithiation and Delithiation Reactions of Silicon Thin-Film Electrode
Description:
Si is an attractive anode material for next-generation lithium batteries including all-solid-state batteries because it has a high theoretical capacity density (4200 mAh g-1). However, Si suffers from the irreversible capacity loss related to the severe volume expansion/shrinkage during the lithiation/delithiation processes. In liquid-type batteries, the main cause of the capacity loss is the continuous formation/decomposition of the solid electrolyte interphase (SEI) on the Si anodes [1]. However, the capacity loss of the Si anode is also regarded as a serious issue even in all-solid-state batteries without using electrolyte solution. Thus, a fundamental understanding of the lithiation/delithiation reactions of the Si anode is important to solve the problem. X-ray photoelectron spectroscopy (XPS) enables us to analyze the elemental composition, oxidation states, and electronic structure of the sample surface. In situelectrochemical XPS, which can measure the same position of a sample under the operational condition for batteries, allows a stepwise analysis of the reactions without interference from variation and inhomogeneity of samples [2]. Here, lithiation/delithiation reactions of an amorphous Si electrode in a thin-film cell is investigated by using an XPS apparatus equipped with an applying voltage system [3]. The amorphous Si with a thickness of about 100 nm is formed on the Li6.6La3Zr1.6Ta0. 4O12 (LLZT) sheet by radio-frequency magnetron sputtering, and the Cu is further coated on the sputtered Si layer by DC sputtering. During the Cu deposition, a stainless-steel stencil mask is used to yield an uncoated amorphous Si part with a diameter of about 2 mm as an analytical region for the XPS measurements. The Li metal layer is thermally deposited on the other side of LLZT. After the thin-film cell with the final structure of [Cu/Si(100 nm)/LLZT(500 µm)/Li metal(1.3 µm)] is connected to the sample holder in an Ar-filled glove box, it is transferred to the XPS apparatus by using a vacuum suitcase to prevent from exposing to open air. The cell is cycled between 0.01 and 1.2 V at 0.02C (1.245 µA) in UHV chamber of the XPS apparatus. The Si surface is observed by XPS before/after the lithiation/delithiation processes. The galvanostatic potential profiles show that the capacity for the first lithiation and delithiation processes is 3160 and 2977 mAh g-1, respectively. A broad Li 1s peak appears after the first lithiation process, confirming the Li insertion to the Si electrode. According to the peak fitting, the Li 1s peak is composed of lithium-silicide (LixSi), Li2O, and Li2CO3. The Li2O and Li2CO3 are possibly formed by the reaction of the lithium-silicide surface with a trace amount of residual gas from the vacuum chamber and LLZT. The Li2O and Li2CO3 contribute to the irreversible capacity loss because these components remain even after the subsequent delithiation process. In the Si 2p region, peaks originated from bulk Si (Si0) at 99.1 eV and Si suboxide (SiOx) at 101.9 eV are shifted to lower binding energy side. These peak shifts indicate the formation of lithium-silicide (LixSi) and lithium-silicate (Li4SiO4) due to the insertion of Li ions to each layer. Based on the calculation using the peak intensities and known physical parameters, it is proposed that the Si electrode has a surface structure of [Li2O (2.5 nm)/Li4SiO4 (0.9 nm)/LixSi] at this state. In addition, the composition of the LixSi is estimated to be Li3.27Si from the charge integration and the thickness of each layer. After the subsequent delithiation process, the Li4SiO4 peak remains in the same position. In contrast to the immobility of the Li4SiO4 peak, the LixSi peak is shifted back to the higher binding energy side, but it does not completely return to the original position of the Si0 peak. The composition of the lithium-silicide phase at this state is estimated to be Li0.14Si. Therefore, Li trapped in Li0.14Si and formation of Li4SiO4, Li2O, and Li2CO3 contribute to the irreversible capacity loss of the Si electrode. References: [1] Y. Xu, K. Wood, J. Coyle, C. Engtrakul, G. Teeter, C. Stoldt, A. Burrell, A. Zakutayev, J. Phys. Chem. C, 123 (2019) 13219-13224. [2] X.H. Wu, C. Villevieille, P. Novak, M. El Kazzi, J. Mater. Chem. A, 8 (2020) 5138-5146. [3] R. Endo, T. Ohnishi, K. Takada, T. Masuda, submitted (2020).