School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444, China.
Nanoscale. 2020 Jan 23;12(3):1697-1706. doi: 10.1039/c9nr08075a.
In this work, we demonstrate an interesting structural phase transition from SnS2/reduced graphene oxide to SnS/sulfur-doped graphene at a moderate calcination temperature of 500 °C under an inert atmosphere. It is discovered that SnS2 chemically bound to rGO with a weakened C-S bond is easier to break and decompose into SnS, whereas it is difficult for pure-phase crystalline SnS2 to experience phase transformation at this temperature. Moreover, the thin-layered structure of SnS2 and rGO is an important factor for the effective doping of the dissociated Sx into graphene. Density functional theory calculations also reveal the feasibility of the structural phase transition process. Morphology characterization shows that partial SnS maintains the original nanosheet structure (∼100 nm) and the others are decomposed into tiny nanoparticles (10-20 nm). A high S-doping amount reduces the irreversible lithium storage sites on graphene, and the first coulombic efficiency is as high as 81.7%. In addition, thin-layered and small-sized SnS can alleviate the structural damage caused by volume expansion and shrinkage; therefore, a high specific capacity of 893.9 mA h g-1 is retained after 100 cycles.
在这项工作中,我们在惰性气氛中,于 500°C 的适中煅烧温度下,证明了 SnS2/还原氧化石墨烯向 SnS/硫掺杂石墨烯的有趣结构相变。研究发现,与 rGO 以较弱的 C-S 键化学结合的 SnS2 更容易断裂和分解为 SnS,而纯相结晶 SnS2 很难在该温度下经历相变。此外,SnS2 和 rGO 的薄层结构是将分离的 Sx 有效掺杂到石墨烯中的重要因素。密度泛函理论计算也揭示了结构相变过程的可行性。形貌表征表明,部分 SnS 保持了原始纳米片结构(~100nm),其余部分分解成微小纳米颗粒(10-20nm)。高硫掺杂量减少了石墨烯上不可逆的锂存储位点,首次库仑效率高达 81.7%。此外,薄而小的 SnS 可以缓解体积膨胀和收缩引起的结构损坏;因此,在 100 次循环后仍保持 893.9mAhg-1 的高比容量。