Fe2C和氮共掺杂的具有有序孔道结构碳膜用于锂硫电池正极

doi:10.11949/0438-1157.20201163

摘要/Abstract

摘要：

利用定向冷冻-碳化法制备了Fe₂C、氮共掺杂的碳膜（Fe₂C/N-C）作为一体化电极用于锂硫电池。由于其兼具规则的导电网络和连通的离子扩散通道，可有效缓解活性物质硫及放电终端产物导电性差的问题，且孔道结构亦可有效缓冲充放电过程活性物质的体积膨胀效应。该膜结构有利于电子传递和锂离子扩散，掺杂的Fe₂C纳米颗粒对多硫化锂具有较强的吸附作用以及向放电终端产物转化的催化作用，有效抑制了多硫化物的“穿梭效应”，提高硫利用率，显著提升电池的综合性能和循环稳定性。Fe₂C/N-C电极在载流量1.1 mg·cm^-2、1.0 C电流密度下循环100圈后得到833.0 mA·h·g^-1的比容量、99.3%的库仑效率、每圈容量衰减率低至0.02%，在较高载硫量3.8 mg·cm^-2时，0.2 C下循环100圈仍能取得714.3 mA·h·g^-1的比容量。

关键词: 定向冷冻法, 金属碳化物, 膜, 纳米材料, 穿梭效应, 锂硫电池

Abstract:

A carbon film (Fe₂C /N-C) co-doped with Fe₂C and nitrogen was prepared by the directional freezing-carbonization method as an integrated electrode for lithium-sulfur batteries. Due to its regular conductive networks and well-connected ion diffusion channels, it can effectively alleviate the poor conductivity of the active substance sulfur and the final discharge products, meanwhile, the microporous structure can effectively buffer the volume expansion effect during the charging/discharging process. This membrane structure is conducive to electron transfer and lithium ion diffusion, coupled with the addition of Fe₂C which can provide the adsorption of lithium polysulfides (LiPSs) and the catalytic conversion of LiPSs to the final discharge products, the synergistic effect can effectively inhibit the “shuttle effect”, increase the sulfur utilization rate, and significantly improve the comprehensive performances and cycling stability of the batteries. Therefore, the Li-S batteries with Fe₂C/N-C/S as cathodes exhibit a high specific capacity of 833.0 mA·h·g^-1 at 1.0 C after 100 cycles with the coulombic efficiency of 99.3% and an extended cycling stability of 0.02% per cycle capacity decay at sulfur loading of 1.1 mg·cm^-2, even at a higher sulfur loading of 3.8 mg·cm^-2, the specific capacity of 714.3 mA·h·g^-1 can be obtained at 0.2 C after 100 cycles.

Key words: directional freezing, metal carbide, membranes, nanomaterials, shuttle effect, lithium-sulfur batteries

中图分类号:

O 646

那天成, 李祥村, 郭娇, 刘思远, 杨宏杰, 姜贺龙, 姜福林, 贺高红. Fe₂C和氮共掺杂的具有有序孔道结构碳膜用于锂硫电池正极[J]. 化工学报, 2021, 72(4): 2283-2292.

NA Tiancheng, LI Xiangcun, GUO Jiao, LIU Siyuan, YANG Hongjie, JIANG Helong, JIANG Fulin, HE Gaohong. Fe₂C hybrid nitrogen-doped carbon membranes with regular pore structure for integrated Li-S battery cathodes[J]. CIESC Journal, 2021, 72(4): 2283-2292.

图/表 10

图1 定向冷冻制膜流程和膜结构示意图及Fe3O4/PAN定向多孔复合膜、预氧化膜、碳化膜片实物图

Fig.1 Schematic of the process of the membrane prepared by directional freezing method and the structure of membrane, the photographs of the Fe3O4/PAN directional porous composite membrane, and the membranes after pre-oxidation and carbonization

图2 PAN膜、Fe3O4/PAN复合膜、Fe3O4微球及Fe2C/N-C、N-C膜的XRD谱图

Fig.2 XRD patterns of the PAN membrane, Fe3O4/PAN composite membrane, Fe3O4 microspheres and Fe2C/N-C, N-C membranes

图3 N-C和Fe2C/N-C膜的拉曼图

Fig.3 Raman shift of N-C and Fe2C/N-C membranes

图4 膜材料SEM图及元素分布

Fig.4 SEM and EDX elemental mapping images of membranes

图5 循环后放电状态下N-C/S和Fe2C/N-C/S电极的S 2p XPS谱图

Fig.5 S 2p XPS spectrum of N-C/S and Fe2C/N-C/S membrane as cathode in discharged state

图6 Fe2C/N-C/S和N-C/S电极在不同扫描速率下的循环伏安曲线

Fig.6 CV curves of Fe2C/N-C/S and N-C/S membrane electrodes at different scanning rates

图7 Fe2C/N-C/S和N-C/S电极在0.2 C和1.0 C下的充放电曲线

Fig.7 The charge-discharge curves of Fe2C/N-C/S and N-C/S membrane cathodes at 0.2 C and 1.0 C

图8 Fe2C/N-C/S和N-C/S电极在不同电流密度、不同载硫量下的循环性能

Fig.8 Cycling performance of Fe2C/N-C/S and N-C/S membrane cathodes at different current densities with different sulfur loadings

图9 Fe2C /N-C/S和N-C/S电极的倍率性能

Fig.9 Rate performance of Fe2C /N-C/S and N-C/S membrane cathodes

图10 Fe2C/N-C/S和N-C/S电极电池的交流阻抗曲线和拟合电路

Fig.10 EIS curves and the fitting curves of the cells with Fe2C/N-C/S and N-C/S membrane cathodes with the equivalent fitting circuit inside

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Fe₂C和氮共掺杂的具有有序孔道结构碳膜用于锂硫电池正极

Fe₂C hybrid nitrogen-doped carbon membranes with regular pore structure for integrated Li-S battery cathodes

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