Accelerating redox kinetics by ZIF-67 derived amorphous cobalt phosphide electrocatalyst for high-performance lithium-sulfur batteries

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引用次数: 7

Abstract

The feasibility of the commercialization of lithium-sulfur (Li-S) batteries is troubled by sluggish redox conversion kinetics and the shuttle effect of polysulfides. Herein, a zeolitic imidazolate framework derived amorphous CoP combined with carbon nanotubes conductive network composites (aCoP@CNTs) has been synthesized as an effective dual-electrocatalyst for accelerating the redox kinetics of polysulfides to prolong the lifespan of Li-S batteries. Compared with crystalline CoP, unsaturated Co atoms of aCoP@CNTs exhibit stronger chemical adsorption capacity for polysulfides and serve as catalytic centers to accelerate the conversion from soluble polysulfides to solid-state lithium sulfide. Meanwhile, the 3D porous conductive network not only facilitates ion/electron transportation but also forms a physical barrier to limit the migration of polysulfides. Benefiting from the above preponderances, the batteries with aCoP@CNTs modified interlayer exhibited excellent cycle stability (initial discharge capacity of 1227.9 mAh g-1 at 0.2 C), rate performance (795.9 mAh g-1 at 2.5 C), long-term cycle reliability (decay rate of 0.049% per cycle at 1 C over 1000 cycles), and superior high-loading performance (high initial discharge capacity of 886 mAh g-1 and 753.6 mAh g-1 at 1 C under high S loading of 3 mg cm-2 and 4 mg cm-2).
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ZIF-67衍生非晶磷化钴电催化剂加速高性能锂硫电池氧化还原动力学
锂硫电池商业化的可行性受到氧化还原转化动力学迟缓和多硫化物的穿梭效应的困扰。本文合成了一种由沸石基咪唑酸盐框架衍生的非晶态CoP与碳纳米管导电网络复合材料(aCoP@CNTs)作为有效的双电催化剂,用于加速多硫化物的氧化还原动力学,延长Li-S电池的寿命。与结晶CoP相比,aCoP@CNTs的不饱和Co原子对多硫化物表现出更强的化学吸附能力,并作为催化中心加速了可溶性多硫化物向固态硫化锂的转化。同时,三维多孔导电网络不仅促进了离子/电子的传输,而且形成了物理屏障,限制了多硫化物的迁移。受益于上述优势,电池与aCoP@CNTs改性层间表现出良好的循环稳定性(初始放电容量1227.9 mAh g1在0.2摄氏度),速率性能(795.9 mAh g - 1在2.5 C级),长期循环可靠性(每周期衰变率为0.049%在1 C / 1000周期),并分别优越性能(高的初始放电容量886 mAh g - 1和753.6级mAh g - 1在1 C级高的加载3毫克cm-2和4毫克cm-2)。
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