Fu Rusheng, Wu Yongkang, Fan Chongzhao, Long Zuxin, Shao Guangjie, Liu Zhaoping
Advanced Li-Ion Battery Engineering Laboratory and Key Laboratory of Graphene Technologies and Applications of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, P.R. China.
State Key Laboratory of Metastable Materials Science and Technology, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, 066004, P.R. China.
ChemSusChem. 2019 Jul 19;12(14):3377-3382. doi: 10.1002/cssc.201900541. Epub 2019 Jun 14.
The application of SiO anodes in Li-ion batteries is greatly restricted by its low initial coulombic efficiency (ICE). Usually, a pre-lithiation procedure is necessary to improve the ICE, but the available technologies are associated with safety issues. Metal (M)-mixed SiO shows great promise to address these issues by reactivating Li O through the reaction M+Li O→MO +Li , which is the inverse reaction to that occurring at MO anodes. Sn is found to be a good choice of metal for this concept. Nanoscale Sn-mixed SiO composites are prepared by mechanical milling. Sn forms an outstanding conductive phase, which boosts the reaction kinetics and also reactivates the Li O byproduct. Sn/SiO (1:2 w/w) delivers a significant improvement in ICE from 66.5 % to 85.5 %. A higher ICE value of >90 % is obtained when the Sn content is ≥50 wt %. However, additional electrolyte decomposition occurs, which is catalyzed by Sn. In addition, coarsening of the nano-Sn material reduces the inverse conversion reactivity of Sn/Li O and subsequently results in rapid capacity fading. The quantitative analysis indicates that, in contrast to transition metals, the alloying and dealloying nature of Sn gives a 50 % improvement in reversible capacity, attributed to Sn/Li O. This work gives a general strategy to choose metals for increasing the ICE of SiO and metal oxides.
SiO负极在锂离子电池中的应用因其较低的初始库仑效率(ICE)而受到极大限制。通常,需要进行预锂化程序来提高ICE,但现有技术存在安全问题。金属(M)混合的SiO有望通过M + Li₂O→MO + Li反应使Li₂O重新活化来解决这些问题,该反应是在MO负极上发生的反应的逆反应。发现Sn是适用于该概念的良好金属选择。通过机械球磨制备了纳米级Sn混合SiO复合材料。Sn形成了出色的导电相,这促进了反应动力学,还使Li₂O副产物重新活化。Sn/SiO(1:2 w/w)的ICE从66.5%显著提高到85.5%。当Sn含量≥50 wt%时,可获得>90%的更高ICE值。然而,会发生额外的电解质分解,这是由Sn催化的。此外,纳米Sn材料的粗化降低了Sn/Li₂O的逆转化反应活性,随后导致容量快速衰减。定量分析表明,与过渡金属相比,Sn的合金化和脱合金性质使可逆容量提高了50%,这归因于Sn/Li₂O。这项工作给出了一种选择金属以提高SiO和金属氧化物ICE的通用策略。