硅氧材料的膨胀性能研究和改善
收稿日期: 2021-08-12
修回日期: 2021-08-27
网络出版日期: 2021-09-17
Study and Improvement on Expansion Property of Silicon Oxide
Received date: 2021-08-12
Revised date: 2021-08-27
Online published: 2021-09-17
本文利用自行搭建的原位膨胀率测试装置,系统研究了硅氧和石墨-硅氧混合材料的膨胀特点和机理。混合品的膨胀行为受石墨和硅氧两种材料共同影响,通过充放电曲线对比方法,我们计算出了混合品在各荷电态下石墨和硅氧组分的容量贡献比例,发现首圈和第2圈脱锂/去锂化的前期,石墨材料发挥的容量为主,放电到36% SOC时硅氧材料开始去锂化发挥容量,因此混合品放电至该SOC时膨胀率急剧减小;第2圈嵌锂/锂化过程在40% ~ 50% SOC区间,硅氧材料几乎未发挥容量,因此该区间混合品的膨胀率变化较小。硅氧材料循环过程中不可逆膨胀持续增长,可逆膨胀率的降低幅度超过不可逆膨胀的增长,因此其整体膨胀率在循环第3圈后呈现小幅度降低的特点。基于以上研究,我们从表面包覆、预锂量和材料粒径等方面对硅氧材料进行工艺改善,有效降低了材料的不可逆膨胀。
谯渭川 , 李芳儒 , 肖瑾林 , 屈丽娟 , 赵晓 , 张梦 , 庞春雷 , 李子坤 , 任建国 , 贺雪琴 . 硅氧材料的膨胀性能研究和改善[J]. 电化学, 2022 , 28(5) : 2108121 . DOI: 10.13208/j.electrochem.210812
The silicon-based anode materials have the potential to meet the ever-increasing demand for energy density in lithium-ion batteries market owing to their high theoretical specific capacity. Unfortunately, their commercialization was hindered by the continuous volume expansion. Herein, the expansion characteristics and corresponding mechanism of the silicon oxide and graphite-silicon oxide composites were investigated by in-situ displacement detection systematically. The results showed that the expansion property was improved by material process modifications. During the de/lithiation processes of graphite, the expansion ratio in 30% ~ 50% SOC changed little because of the small interlayer spacing variation of the intercalated graphite. Unlike the graphite anode, there was no obvious platform in the expansion ratio curve of silicon oxide except for the first lithiation process. As for the graphite-silicon oxide composite, the expansion ratio was influenced by two-component materials. In order to figure out how the expansion ratio of the composite changed, the capacity contributions of graphite and silicon oxide at various states of charge were calculated. It was found that the graphite dominated the initial stage of the first and second delithiation processes, while delithiation of silicon oxide started from 36% SOC, leading to the steep decline of the expansion ratio curves. During the second lithiation process, the capacity of the first 20% SOC mainly came from silicon oxide, after which the capacity proportion of graphite increased gradually. In 40% ~ 50% SOC region, the capacity contribution of silicon oxide was negligible, resulting in the reduction of expansion increase rate. The calculated capacity contribution of the component materials corresponded to the evaluation of expansion ratio, indicating the reliability of the calculation method, which could be applied in other graphite-silicon oxide composites with different proportions. The irreversible expansion of graphite mainly occurred at the first three charges processes, while the irreversible expansion of silicon oxide increased significantly over all cycling processes. The reversible expansion of silicon oxide decreased gradually as the capacity fading. And the total expansion of silicon oxide tended to be decreased from the third cycle because the decrement of reversible expansion surpassed the increment of irreversible expansion. Finally, the expansion ratio especially the irreversible expansion of silicon oxide was effectively reduced by optimizing the surface coating, prelithiation and particle size. These results could provide favorable guidance for developing high-performance silicon-based anode materials with stable structure and low expansion ratio.
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