分级多孔N, P共掺杂rGO改性隔膜增强锂硫电池的循环稳定性

doi:10.6023/A21030117

化学学报 ›› 2021, Vol. 79 ›› Issue (7): 941-947.DOI: 10.6023/A21030117 上一篇下一篇

研究论文

分级多孔N, P共掺杂rGO改性隔膜增强锂硫电池的循环稳定性

陈锋^a, 程晓琴^a, 赵振新^a, 王晓敏^a^,^b^,^*()

a 太原理工大学材料科学与工程学院太原 030024
b 太原理工大学新能源材料与器件山西省重点实验室太原 030024

投稿日期:2021-03-27 发布日期:2021-05-25
通讯作者: 王晓敏
基金资助:
国家自然科学基金(U1710256); 国家自然科学基金(U1810115); 国家自然科学基金(52072256); 山西省重点研发项目(201803D121038); 山西省科技重大专项(20181102018); 山西省科技重大专项(2181102019); 山西省科技重大专项(20191102004); 山西省科技重大专项(20201101016)

Hierarchical Porous N, P co-doped rGO Modified Separator to Enhance the Cycling Stability of Lithium-sulfur Batteries

Feng Chen^a, Xiaoqin Cheng^a, Zhenxin Zhao^a, Xiaomin Wang^a^,^b()

a College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
b Shanxi Key Laboratory of New Energy Materials and Devices, Taiyuan University of Technology, Taiyuan 030024, China

Received:2021-03-27 Published:2021-05-25
Contact: Xiaomin Wang
Supported by:
National Natural Science Foundation of China(U1710256); National Natural Science Foundation of China(U1810115); National Natural Science Foundation of China(52072256); Key Research and Development (R&D) Projects of Shanxi Province(201803D121038); Shanxi Science and Technology Major Project(20181102018); Shanxi Science and Technology Major Project(2181102019); Shanxi Science and Technology Major Project(20191102004); Shanxi Science and Technology Major Project(20201101016)

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1. Supporting Information-A21030117.pdf(877KB)

摘要/Abstract

多硫化物(LiPSs)的穿梭效应和低硫利用率会导致电池容量的快速衰减, 这严重阻碍了锂硫电池的商业化进程. 为了抑制LiPSs的穿梭效应和提高硫的利用率, 本工作采用一步高温还原法合成了具有分级多孔结构的N, P共掺杂还原氧化石墨烯(NPG), 并将其用于锂硫电池的隔膜改性. 高导电性NPG具有丰富的分级多孔结构, 提供了大量的LiPSs锚定位点和丰富的离子/电子传输通道, 实现了可溶性中间体的快速转化, 高效抑制了LiPSs的穿梭效应. 归因于以上优点, NPG改性聚丙烯隔膜(NPG/PP)能够有效抑制LiPSs的穿梭并提高硫的利用率. 结果表明, NPG/PP改性隔膜的电池展现出优异的循环性能(在1 C的电流密度下, 循环500圈以后容量仍保持在612.5 mAh•g^-1, 每圈的衰减仅为0.052%)和出色的倍率性能(在2 C的电流密度下容量仍保持在617.9 mAh•g^-1). 这种构建分级多孔N, P共掺杂rGO改性隔膜的思路为锂硫电池的研究提供了新的方向.

关键词: 锂硫电池, 多硫化物, N,P共掺杂rGO, 隔膜改性, 穿梭效应

Lithium-sulfur batteries with high energy density (2600 Wh•kg^-1) and theoretical capacity (1675 mAh•g^-1) have attracted much attention. Furthermore, as a cathode active material, sulfur has prominent advantages such as rich in natural resources, low cost and environmental friendliness. Attributed to the above merits, lithium-sulfur batteries deemed to be one of the most promising energy storage devices. However, poor utilization of sulfur and the shuttle effect of lithium polysulfides (LiPSs) causes dramatic capacity degradation, which severely restricts the commercial application of lithium-sulfur batteries. These problems are mainly attributed to the insulating nature of sulfur and its final discharge products (Li₂S₂/Li₂S), which reduces the sulfur utilization, as well as the poor adsorption capability and slow reaction kinetics, which give rise to the shuttle effect of soluble LiPSs. To solve the above problems, carbon materials are regarded as the most suitable cathode materials for lithium-sulfur batteries, because its superior electrical conductivity and rich porous structure can effectively improve the sulfur utilization and mitigate the shuttle effect of LiPSs. However, the shuttling of LiPSs is difficult to suppressed completely due to the weak adsorption interaction between nonpolar carbon materials and polar LiPSs. Based on this, heteroatom doping is beneficial to enrich the chemical adsorption sites of LiPSs in carbon materials, enhancing the interaction between carbon materials and LiPSs. Thus, the shuttle effect of LiPSs is efficiently suppressed and the cycle stability of lithium-sulfur batteries is improved. Hence, N, P co-doped reduced graphene oxide (NPG) with hierarchical porous structure was prepared by one-step high-temperature reduction method and used for the polypropylene (PP) separator modification of lithium-sulfur batteries. The highly conductive NPG with abundant hierarchical porous structure provides a large number of anchor sites for LiPSs and sufficient ion/electron transport channels, facilitating the conversion of the soluble intermediates and efficiently suppressing the shuttle effect of LiPSs. In consequence, the NPG/PP modified separator can effectively inhibit the shuttle of LiPSs and improve the sulfur utilization. The results show that the cells with NPG/PP modified separator exhibit excellent cycling performance (the degradation per cycle is only 0.052% and the capacity remains at 612.5 mAh•g^-1 after 500 cycles at 1 C) and excellent rate performance (high specific capacity of 617.9 mAh•g^-1 at 2 C). This idea of constructing hierarchical porous N, P co-doped rGO modified separators provides a new strategy for the study of lithium-sulfur battery.

Key words: lithium-sulfur battery, lithium polysulfide, NPG, modified separator, shuttle effect

引用此文

陈锋, 程晓琴, 赵振新, 王晓敏. 分级多孔N, P共掺杂rGO改性隔膜增强锂硫电池的循环稳定性[J]. 化学学报, 2021, 79(7): 941-947.

Feng Chen, Xiaoqin Cheng, Zhenxin Zhao, Xiaomin Wang. Hierarchical Porous N, P co-doped rGO Modified Separator to Enhance the Cycling Stability of Lithium-sulfur Batteries[J]. Acta Chimica Sinica, 2021, 79(7): 941-947.

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图/表 6

图1. NPG复合材料的制备示意图

Figure 1. Schematic illustration of the preparation of NPG composites

图2. (a, b) NPG的SEM图; (c) NPG的EDS图; (d, e) rGO的SEM图; (f) NPG, rGO和GO的XRD图

Figure 2. (a, b) SEM images of NPG; (c) EDS elemental mapping images of NPG; (d, e) SEM images of rGO; (f) XRD patterns of NPG, rGO and GO

图3. (a) NPG的XPS总谱图; XPS的高分辨谱图: (b) N 1s和 (c) P 2p; (d) NPG和rGO吸附Li2S6的光学图

Figure 3. (a) XPS spectra of NPG; the high-resolution XPS spectrum of (b) N 1s and (c) P 2p; (d) optical images the Li2S6 trapping by NPG and rGO

图4. (a) NPG和rGO的N2吸/脱附等温线; (b) NPG和rGO的孔径分布图; (c) NPG和rGO的拉曼谱图; (d) 科琴黑/硫(KB/S)的TGA

Figure 4. (a) Nitrogen adsorption/desorption isotherms a of NPG and rGO; (b) pore size distribution of NPG and rGO; (c) Raman spectra of NPG and rGO; (d) TGA of ketjen black/sulfur (KB/S)

图5. (a) NPG/PP、rGO/PP和PP在0.1 C下的CV曲线; (b) NPG/PP在0.1 C下前三圈的CV曲线; (c) NPG/PP, rGO/PP和PP的EIS图; (d) NPG和rGO作为工作电极的对称电池的CV曲线

Figure 5. (a) CV profiles of NPG/PP, rGO/PP and PP at a scan rate of 0.1 C; (b) first three turns of CV curves of NPG/PP at 0.1 C; (c) EIS profiles of NPG/PP, rGO/PP and PP separators; (d) CV curves for symmetric cells with NPG and rGO as working electrodes

图6. (a) 在0.1 C时的恒电流充放电曲线; (b) 不同电流密度下的倍率性能; (c) NPG/PP在0.1 C到2 C下的恒电流充放电曲线; (d) 不同装置的示意图; (f) 样品在1 C下的循环曲线

Figure 6. (a) Galvanostatic charge-discharge profiles at 0.1 C; (b) rate capabilities at different current densities; (c) galvanostatic charge-discharge profiles of NPG/PP at 0.1 C to 2 C; (d) schematic diagram of different devices; (f) cycling performance at 1 C

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分级多孔N, P共掺杂rGO改性隔膜增强锂硫电池的循环稳定性

Hierarchical Porous N, P co-doped rGO Modified Separator to Enhance the Cycling Stability of Lithium-sulfur Batteries

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