Supercritical CO2 fluid assisted synthesis of Si-Fe-Fe3O4-C composites and lithium storage performance
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摘要: 硅碳负极是未来锂离子电池材料发展的重点方向之一,本文针对传统球磨法制备硅碳负极复合不均匀、界面融合差等问题,提出了一种超临界二氧化碳(scCO2)流体介质球磨合成Si-Fe-Fe3O4-C复合材料的新方法。研究发现,纳米硅和中间相碳微球(MCMB)在scCO2介质球磨混合过程中,CO2和Fe反应先得到均匀分散的Si-FeCO3-C前驱体,然后FeCO3原位高温固相分解得到Si-Fe-Fe3O4-C复合材料。同时,在scCO2流体渗透下,MCMB剥离成石墨片,并与纳米硅和Fe-Fe3O4实现较好的界面融合,Fe-Fe3O4的引入显著提升了硅碳负极的储锂容量、循环稳定性和倍率性能,Si-Fe-Fe3O4-C复合材料在0.2 A·g−1下100次循环后可逆容量保持在1065 mA·h·g−1。本方法利用超临界流体渗透性好、扩散能力强等特点,合成工艺简便,容易工业化实施,具有商业化开发潜力。
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关键词:
- 硅碳负极 /
- 超临界流体 /
- CO2 /
- Si-Fe-Fe3O4-C复合材料 /
- 储锂性能
Abstract: Silicon-carbon anode is an important issue for the development of lithium-ion battery materials. Aiming at the problems of uneven combination and poor interfacial contact of silicon-carbon anode prepared by traditional ball milling, this paper proposes a new strategy to synthesize Si-Fe-Fe3O4-C composite by ball milling in supercritical carbon dioxide (scCO2) fluid medium. It is found that during the process of ball milling mixture of nano-silicon and mesophase carbon microspheres (MCMB) in the scCO2 medium, CO2 and Fe reacts firstly to form a uniformly dispersed Si-FeCO3-C precursor, and then in situ high temperature decomposition of FeCO3 solid phase results in final Si-Fe-Fe3O4-C product. Under the infiltration of scCO2 fluid, MCMB microspheres exfoliate into graphite flakes, and achieve ideal combination with nano-silicon and Fe-Fe3O4. The introduction of Fe-Fe3O4 in the composite has significantly improved the lithium storage capacity, cycle stability and rate performance of silicon-carbon anode, the synthesized Si-Fe-Fe3O4-C composite material maintains a reversible capacity of 1065 mA·h·g−1 after 100 cycles at 0.2 A·g−1. The method shows the merits of facile operation procedure, easy industrial production and potential commercial application basing on the supercritical fluid permeability and strong diffusion ability. -
表 1 Si-Fe-Fe3O4-C复合材料制备过程中的质量变化及计算结果
Table 1. Mass changes and calculation results during the preparation of Si-Fe-Fe3O4-C composite
Sample Nano Si/g MCMB/g Si-FeCO3-C/g Si-Fe-Fe3O4-C/g Fe/g Fe4O3/g Mass residual/wt% Si-Fe-Fe3O4-C (Si∶C=1∶1) 0.250 0.250 0.995 0.966 0.285 0.119 21.7 Si-Fe-Fe3O4-C (Si∶C=1∶4) 0.250 1.000 1.730 1.660 0.320 0.091 53.7 表 2 Si-Fe-Fe3O4-C复合材料各物相组成
Table 2. Phase composition of Si-Fe-Fe3O4-C composite
Sample Si/wt% C/wt% Fe/wt% Fe3O4/wt% Si-Fe-Fe3O4-C
(Si∶C=1∶1)29.06 29.06 29.51 12.36 Si-Fe-Fe3O4-C
(Si∶C=1∶4)15.05 60.21 19.25 5.49 -
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