High performance lithium-sulfur batteries using three-dimensional hierarchical porous carbons to host the sulfur
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摘要: 锂硫电池由于其高能量密度和低廉的价格,将在未来的储能领域得到广泛应用。然而,它面临许多挑战,特别是在硫的负载和可溶性多硫化物的穿梭效应方面。为了解决这些问题,本文设计了一种三维多级孔炭材料(3D-HPC)作为锂硫电池中硫的载体。采用模板法,在去除模板剂聚甲基丙烯酸甲酯和氧化锌后得到了三维多孔结构。电镜和BET测试表明相互连通的大孔道与大量的大尺寸介孔协同构成了三维导电碳网络。三维网络有利于离子和电子的转移,同时通过较大尺寸的孔缓解阴极的体积膨胀,多级孔通过毛细凝结抑制了穿梭效应。电化学测试结果表明,3D-HPC-S阴极具有良好的电化学性能。在实际环境中的测试结果显示0.2倍率下3D-HPC-S首次放电比容量为1 314.6 mAh·g−1,经100次循环后,容量保持率为69.13%。在0.5倍率下循环200次容量保持率为59.02%,平均库伦效率为98.16%。3D-HPC-S阴极有望进一步促进锂硫电池的商业化发展。Abstract: Lithium-sulfur batteries are promising for future energy storage because of their high-energy density and low price. However, they have many problems, especially the large volume change during cycling and the shuttle effect of the soluble polysulfides. To solve these problems, a three-dimensional porous carbon (3D-HPC) was investigated as the sulfur host of a lithium-sulfur battery. The 3D-HPC was prepared by a template method using polymethyl methacrylate and zinc oxide as the templates to form mesopores and macropores, respectively. The results showed that the interconnected macroporous channels and abundant large mesopores formed a three-dimensional conductive carbon network which is beneficial for electron/ion transfer and relieves the cathode volume change by the physical limiting effect. The pores alleviate the shuttle effect by the capillary condensation. A 3D-HPC-S composite used as the cathode has excellent electrochemical properties. The first discharge specific capacity of the 3D-HPC-S is 1 314.6 mAh g−1 at 0.2 C with a sulfur loading of 70%. After 100 cycles, the capacity retention rate is 69.13%. At 0.5 C, the capacity retention rate after 200 cycles is 59.02% and the average coulombic efficiency is 98.16%.
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Figure 4. CV of (a) 3D-HPC-1-S and (b) 3D-HPC-2-S cathodes between 3.0 V and 1.5 V with a scan rate of 1 mV s−1, (c) EIS spectra of the 3D-HPC-1-S and 3D-HPC-2-S cathodes before the cycle, (d) long-term cycling stabilities of the 3D-HPC-1-S cathode and 3D-HPC-2-S cathode over 100 cycles, charge-discharge profiles of (e) 3D-HPC-1 and (f) 3D-HPC-2 cathode at 0.5 C for 1st, 20th, 50th and 100th cycles.
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