National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University , Nanjing 210093, China.
Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University , Suzhou 215123, China.
Nano Lett. 2015 Sep 9;15(9):5750-4. doi: 10.1021/acs.nanolett.5b01698. Epub 2015 Aug 13.
Silicon, one of the most promising candidates as lithium-ion battery anode, has attracted much attention due to its high theoretical capacity, abundant existence, and mature infrastructure. Recently, Si nanostructures-based lithium-ion battery anode, with sophisticated structure designs and process development, has made significant progress. However, low cost and scalable processes to produce these Si nanostructures remained as a challenge, which limits the widespread applications. Herein, we demonstrate that Si nanoparticles with controlled size can be massively produced directly from low grade Si sources through a scalable high energy mechanical milling process. In addition, we systematically studied Si nanoparticles produced from two major low grade Si sources, metallurgical silicon (∼99 wt % Si, $1/kg) and ferrosilicon (∼83 wt % Si, $0.6/kg). It is found that nanoparticles produced from ferrosilicon sources contain FeSi2, which can serve as a buffer layer to alleviate the mechanical fractures of volume expansion, whereas nanoparticles from metallurgical Si sources have higher capacity and better kinetic properties because of higher purity and better electronic transport properties. Ferrosilicon nanoparticles and metallurgical Si nanoparticles demonstrate over 100 stable deep cycling after carbon coating with the reversible capacities of 1360 mAh g(-1) and 1205 mAh g(-1), respectively. Therefore, our approach provides a new strategy for cost-effective, energy-efficient, large scale synthesis of functional Si electrode materials.
硅作为锂离子电池阳极的最有前途的候选材料之一,由于其高理论容量、丰富的存在和成熟的基础设施而受到广泛关注。最近,基于 Si 纳米结构的锂离子电池阳极,通过复杂的结构设计和工艺开发,取得了重大进展。然而,生产这些 Si 纳米结构的低成本和可扩展工艺仍然是一个挑战,这限制了其广泛应用。在此,我们证明可以通过可扩展的高能机械研磨工艺,直接从低品位硅源大规模生产具有可控尺寸的 Si 纳米颗粒。此外,我们系统地研究了两种主要的低品位硅源(冶金硅(约 99wt%Si,$1/kg)和硅铁(约 83wt%Si,$0.6/kg))生产的 Si 纳米颗粒。研究发现,硅铁源生产的纳米颗粒中含有 FeSi2,它可以作为缓冲层来缓解体积膨胀引起的机械断裂,而冶金硅源生产的纳米颗粒由于纯度更高、电子传输性能更好,具有更高的容量和更好的动力学性能。经过碳涂层后,硅铁纳米颗粒和冶金硅纳米颗粒分别具有超过 100 次的稳定深循环,可逆容量分别为 1360 mAh/g 和 1205 mAh/g。因此,我们的方法为具有成本效益、节能和大规模合成功能性 Si 电极材料提供了一种新策略。