Space-confined construction of nitrogen-rich cobalt porphyrin-derived nanoparticulates anchored on activated carbon for high-current lithium thionyl chloride battery
Space-confined construction of nitrogen-rich cobalt porphyrin-derived nanoparticulates anchored on activated carbon for high-current lithium thionyl chloride battery
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DOI：
10.1016/j.electacta.2020.136543
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发表时间：
2020-09
影响因子：
6.6
通讯作者：
Kang Li;Zhanwei Xu;Qianqian Liu;Zhi Li;Xiaoxian Wang;Jun Zhang;Jianfeng Zhu
中科院分区：
文献类型：
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作者：
Kang Li;Zhanwei Xu;Qianqian Liu;Zhi Li;Xiaoxian Wang;Jun Zhang;Jianfeng Zhu
基于锂金属阳极的一次电池因其高容量和能量密度而受到越来越多的关注，但实现电池大电流化仍面临SOCl 2反应速率低、阻抗大等挑战。为解决上述问题，采用原位固相合成法制备了富氮钴卟啉衍生纳米颗粒锚定在功能活性炭（NCA）上的空间受限结构复合材料，作为碳阴极的催化剂。在分子水平上，钴卟啉衍生物的钴原子与功能活性炭的含氧官能团形成C-O-Co键，进一步增强了π-π共轭体系。值得注意的是，所得到的NCA复合材料表现出最长的大电流（大于25 mA/cm 2）放电时间，高达37 min，容量约为19.18 mAh，占其总容量的88.5%。同时，NCA复合物催化的电池内阻（24.06 Ω）比未加催化剂的电池低0.40倍，循环伏安法的还原峰最大，约为2.357 V，表明NCA复合物电极具有良好的催化活性。这是由于NCA复合材料的载体活性炭通过调节碳阴极的孔隙率降低了电池的内阻，负载的CoTAP纳米颗粒提高了SOCl 2的还原速率。
Primary batteries based on lithium metal anodes have been attracting increasing attention due to their high capacity and energy density, but the implementation high-current of battery still faces many challenges, such as low reaction rate of SOCl2and large impedance. Space-confined construction of nitrogen-rich cobalt porphyrin-derived nanoparticulates anchored on functional-activated carbon (NCA) composites were prepared byin situsolid phase synthesis as catalysts of carbon cathode to address these issues. On the molecular level, the π-π conjugate system is further enhanced by forming C–O–Co bond between the Co atoms of cobalt porphyrin derivatives and the oxygen-containing functional groups of functional-activated carbon. Significantly, the resulting NCA composites exhibit the longest high-current (above 25 mA/cm2) discharge time, up to 37 min, and the capacity is about 19.18 mAh, accounting for 88.5% of its total capacity. Meanwhile, the internal resistance of the battery catalyzed by the NCA composites (24.06 Ω) is 0.40 times lower than that without catalysts, and the reduction peak of cyclic voltammetry is the largest about 2.357 V, showing that the electrode with NCA composites has good catalytic activity. All this is due to the fact that the carrier activated carbon of the NCA composites reduces the internal resistance of the battery by regulating the porosity of the carbon cathode, and the loaded CoTAP nanoparticulates improve the reduction rate of SOCl2.