In Situ Constructing of Rigid-Soft Coupling Solid-Electrolyte Interphase on Silicon Electrode toward High-Performance Lithium Ion Batteries.

The application of Si anodes is hindered by some critical issues such as large volume changes of bare Si and fragile solid-electrolyte interface (SEI), resulting in low coulombic efficiency and rapid capacity decay. Herein, a multifunctional SEI film with high content of LiF is in situ constructed via the surface grafting of carbon-fluorine functionalized groups on silicon nanoparticles (SiNPs) during cycling. Mechanical study demonstrates that the incorporation of LiF with high modulus and unbroken carbon-fluorine groups with highly elastic guarantee the rigid-soft coupling SEI film on Si electrode. Furthermore, it is demonstrated that the rigid-soft coupling SEI film can effectively accommodate the volume expansion of Si nanoparticles during lithiation process, with the electrode expanding rate of only 114.16% after 100 cycles (263.87% for bare Si without surface modification). Afterward, with the aid of well-designed rigid-soft coupling SEI, the initial Coulomb efficiency of 89.8% is achieved, showing a reversible capacity of 1477 mAh g-1 after 200 cycles at 1.2 A g-1 . This work provides a simple and efficient solution that can potentially facilitate the practical application of Si anodes.

Manipulating Uniform Nucleation to Achieve Dendrite-Free Zn Anodes for Aqueous Zn-Ion Batteries.

The essence of Zn dendrite formation is ultimately derived from Zn nucleation and growth during the repeated Zn plating/stripping process. Here, the nucleation process of Zn has been analyzed using ex situ scanning electron microscopy to explore the formation of the initial Zn dendrite, demonstrating that the formation of tiny protrusions (the initial state of Zn dendrites) is caused by the inhomogeneity of Zn nucleation. Based on this, the uniform Zn nucleation is promoted by the Ni5Zn21 alloy coating (ZnNi) on the surface of Zn foil by electrodeposition, and the mechanism of ZnNi-promoted even nucleation is further analyzed with the assistance of density functional theory (DFT). The DFT results indicate that the ZnNi displays a stronger binding ability to Zn compared to the bare Zn, suggesting that Zn nuclei will preferentially form around ZnNi instead of continuing to grow on the surface of the initial Zn nuclei. Therefore, the designed Zn metal anode (Zn@ZnNi) can be ultra-stable for over 2200 h at a current density of 2 mA cm-2 in the symmetric cell. Even at a much higher current density of 20 mA cm-2, the extra-long life of over 2200 cycles (over 530 h) can be achieved. Moreover, the full cell with the Zn@ZnNi anode exhibits extra-long cycling performance for 500 cycles with a capacity of 207.7 mA h g-1 and 1100 cycles (148.5 mA h g-1) at a current density of 0.5 and 1 A g-1, respectively.