Yang Jing, Wang Bo, Jin Fan, Ning Yu, Luo Hao, Zhang Jian, Wang Fei, Wang Dianlong, Zhou Yu
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 150001 Harbin, China.
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China.
Nanoscale. 2020 Feb 20;12(7):4552-4561. doi: 10.1039/c9nr10491g.
Lithium-sulfur batteries are promising candidates for the next generation of energy storage systems owing to their high energy density, low toxicity and abundant reserves of sulfur. However, sulfur has poor conductivity, large volume change during charge/discharge, and more importantly, the intermediate polysulfide (Li2Sn, 3 ≤ n≤8) produced in the cycling process is easily soluble in the electrolyte resulting in the "shuttle effect", which have greatly limited the commercialization of lithium-sulfur batteries. Therefore, it is of great value to develop optimized sulfur cathode materials to improve electrode conductivity, buffer volume change and restrain the diffusion of polysulfide. In this work, we construct a V-MOF (MIL-47) derived V2O3@C hollow microcuboid with a hierarchical lasagna-like structure through hydrothermal synthesis followed by calcination, and employ it as a sulfur host for the first time. The fast anchoring of polysulfide by V2O3 nanoparticles and the high electronic conductivity of the 3D carbon framework can simultaneously inhibit the "shuttle effect" in the charge-discharge process and accelerate the kinetics of the redox process. Moreover, the special lasagna-like structure with appropriate voids generated during calcination not only provides many sites for sulfur loading, but also effectively alleviates the volume expansion problem during the electrochemical reaction. Therefore, the final fabricated sulfur cathode via the melt impregnation method exhibits good cycling stability (62.3% after 1000 cycles at 1C) and rate performance (663 mA h g-1 at 2C) at a relatively high sulfur loading of 3.7 mg cm-2.
锂硫电池因其高能量密度、低毒性和硫储量丰富,是下一代储能系统的理想候选者。然而,硫的导电性差,充放电过程中体积变化大,更重要的是,循环过程中产生的中间多硫化物(Li2Sn,3≤n≤8)易溶于电解液,导致“穿梭效应”,这极大地限制了锂硫电池的商业化。因此,开发优化的硫正极材料以提高电极导电性、缓冲体积变化并抑制多硫化物的扩散具有重要价值。在这项工作中,我们通过水热合成然后煅烧构建了一种具有分层千层饼状结构的V-MOF(MIL-47)衍生的V2O3@C空心微立方体,并首次将其用作硫宿主。V2O3纳米颗粒对多硫化物的快速锚定和3D碳框架的高电子导电性可以同时抑制充放电过程中的“穿梭效应”并加速氧化还原过程的动力学。此外,煅烧过程中产生的具有适当孔隙的特殊千层饼状结构不仅为硫负载提供了许多位点,还有效地缓解了电化学反应过程中的体积膨胀问题。因此,通过熔体浸渍法最终制备的硫正极在3.7 mg cm-2的相对高硫负载下表现出良好的循环稳定性(1C下1000次循环后为62.3%)和倍率性能(2C下为663 mA h g-1)。