Construction of sub micro-nano-structured silicon based anode for lithium-ion batteries.

The significant volume change experienced by silicon (Si) anodes during lithiation/delithiation cycles often triggers mechanical-electrochemical failures, undermining their utility in high-energy-density lithium-ion batteries (LIBs). Herein, we propose a sub micro-nano-structured Si based material to address the persistent challenge of mechanic-electrochemical coupling issue during cycling. The mesoporous Si-based composite submicrospheres (M-Si/SiO2/CS) with a high Si/SiO2content of 84.6 wt.% is prepared by magnesiothermic reduction of mesoporous SiO2submicrospheres followed by carbon coating process. M-Si/SiO2/CS anode can maintain a high specific capacity of 740 mAh g-1at 0.5 A g-1after 100 cycles with a lower electrode thickness swelling rate of 63%, and exhibits a good long-term cycling stability of 570 mAh g-1at 1 A g-1after 250 cycles. This remarkable Li-storage performance can be attributed to the synergistic effects of the hierarchical structure and SiO2frameworks. The spherical structure mitigates stress/strain caused by the lithiation/delithiation, while the internal mesopores provide buffer space for Si expansion and obviously shorten the diffusion path for electrolyte/ions. Additionally, the amorphous SiO2matrix not only servers as support for structure stability, but also facilitates the rapid formation of a stable solid electrolyte interphase layer. This unique architecture offers a potential model for designing high-performance Si-based anode for LIBs.

Economic synthesis of sub-micron brick-like Al-MOF with designed pore distribution for lithium-ion battery anodes with high initial Coulombic efficiency and cycle stability.

Metal-organic frameworks (MOFs) have exhibited great potential for lithium-ion batteries (LIBs). However, to date, it is difficult to fabricate MOF electrode materials with regular shape and rational pore distribution by an economic approach, and the currently achieved MOF electrode materials usually have a relatively low initial Coulombic efficiency and poor cycle stability, which is not satisfactory for practical application. In this study, by using the recycled AlCl3 solution after dealloying treatment of Al-Si alloy, an evenly distributed brick-like Al-MOF with sub-micron size and rational pore distribution was synthesized for the first time. Because of the larger size and more macropores, the as-prepared Al-MOF electrode exhibits superior initial Coulombic efficiency as high as 96.6% for LIB anodes. Moreover, on account of the irregular crystal defects at the edge of the designed macropores, which result from unstable connection between the inorganic nodes (AlO6 octahedral cluster) and the organic linkers (PTA) and result in the formation of spherical nano-sized particles with better structural stability, the electrode materials show excellent cycle stability with discharge attenuation rate of 0.051%. The electrochemical performance considerably outperforms that of reported Al-MOF anodes and some representative MOF anodes in other studies. The robust realization of high initial Coulombic efficiency and cycle stability defines a critical step to capturing the full potential of MOF electrode materials in practical LIBs.