薄膜厚度对α-SiOx薄膜负极电化学性能的影响

doi:10.15541/jim20180227

摘要/Abstract

摘要：

近年来, SiO_x作为锂离子电池负极, 由于其良好的循环稳定性、较大的容量以及对成分调控的可行性, 引起了广泛的关注。以往的许多研究都集中在阐明氧含量对SiO_x负极的影响, 尺寸效应对性能的影响规律很少被研究。此工作研究了不同厚度的薄膜型SiO_x负极材料的电化学性能。溅射制备SiO_x电极的Si/O比值为0.7、膜厚为450 nm时, 电极初始库仑效率(ICE)为71.68%、容量保持率92.01%。以上的最优性能主要归功于电荷转移电阻低、SEI层形成减少和循环过程中电极的结构稳定性。研究表明, 作为LIBs负极, 控制SiO_x负极的厚度可以有效改善电极材料的电化学性能。

关键词: SiO_x薄膜负极, 薄膜厚度, 循环稳定性, 容量, 锂离子电池

Abstract:

SiO_x anodes of lithium ion batteries have attracted considerable attention in recent years, due to their cycle stability, large capacity, and feasibility on composition manipulation. Many previous works have focused on clarifying the influences of oxygen contents on SiO_x based anodes. However, the size effect is still far from understanding. Herein, the size effect on electrochemical properties of SiO_x with thin-film type anodes in different thickness was investigated. It is found that the SiO_x electrodes prepared by sputtering is of a Si/O ratio of 0.7 and exhibits the highest initial Coulombic efficiency (ICE) of 71.68% and the highest capacity retention of 92.01% when the film thickness being 450 nm, compared with those in other thickness. The best performance under such intriguing thickness-performance relationship is attributed to the low charge transfer resistance, formation of the reduced SEI layer and good electrode integrity upon cycling, as evidenced by SEM images and EIS collected during cycling. These results indicate that as anodes of LIBs, the SiO_x anodes with controlled size can greatly improve the electrochemical performance.

Key words: SiO_x thin-film anodes, film thickness, cycle stability, capacity, lithium-ion batteries

中图分类号:

TQ174

孟祥鲁, 霍翰宇, 郭向欣, 董绍明. 薄膜厚度对α-SiO_x薄膜负极电化学性能的影响[J]. 无机材料学报, 2018, 33(10): 1141-1146.

MENG Xiang-Lu, HUO Han-Yu, GUO Xiang-Xin, DONG Shao-Ming. Influence of Film Thickness on the Electrochemical Performance of α-SiO_x Thin-film Anodes[J]. Journal of Inorganic Materials, 2018, 33(10): 1141-1146.

图/表 6

Fig. 1 Characterization of the deposited SiOx film electrodes. (a) The typical surface morphology of SiO0.7 thin film deposited on rough Cu foil; (b) Cross section SEM image of the SiO0.7 thin film deposited on Si wafer; (c) XRD patterns of the SiO0.7 thin films with a thickness of 450 nm; (d) Raman spectra of as-deposited SiO0.7 with a thickness of 450 nm; (e) XPS Si 2p spectral of the SiO0.7 thin films with a thickness of 450 nm, which is fitted by using five Si peaks

Fig. 2 The 1st cycle charge-discharge curves of SiO0.7 film electrodes with different thickness of 90 nm, 270 nm, 450 nm and 630 nm

Fig. 3 Cyclic voltammograms of SiO0.7 film electrode with thickness of (a) 90 nm and (b) 450 nm of the 1st, 2nd, 3rd, 4th and 5th cycle at a scan rate of 0.05 mV•s-1 in the potential range of 0.01 V-1.5 V

Fig. 4 Electrochemical performances of SiO0.7 film anodes with different thickness(a) Cycle performance of SiO0.7 thin film anodes with different thickness at the current density of 0.2C; (b,c) The Nyquist plots of the SiO0.7 thin film anodes with different thickness after (b) the 1st cycle and (c) the 200th cycle; (d-g) Surface morphologies of the 200th-cycled SiO0.7 thin film anodes with thickness of 90 nm, 270 nm, 450 nm, and 630 nm

Fig. S1 (a) The galvanostatic discharge-charge voltage profiles of the SiO0.7 anodes with a thickness of 450 nm of 1st, 10th, 100th, 200th and 300th cycle and (b) the dQ/dV differential curve of the first cycle profile of the SiO0.7 anodes with a thickness of 450 nm

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