硅酸盐学报

聚吡咯修饰氧化铁纳米片改善锂硫电池性能

PDF下载

李舒楠 ¹ , 乔明涛 ¹ , 沈凯飞 ¹ , 张玉龙 ¹ , 司渭滨 ² , 雷琬莹 ¹ , 雷西萍 ¹

硅酸盐学报 | 研究论文 2024,52(5): 1664-1675

收起

硅酸盐学报 |研究论文 2024 , 52 (5) : 1664 -1675

聚吡咯修饰氧化铁纳米片改善锂硫电池性能

全屏

李舒楠¹, 乔明涛¹, 沈凯飞¹, 张玉龙¹, 司渭滨², 雷琬莹¹, 雷西萍¹

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．国网陕西省电力有限公司安康供电公司，陕西安康 725000

通讯作者:

乔明涛（1989—），博士，副教授。

作者简介:

李舒楠（2002—），男，硕士研究生。

Polypyrrole Modified Iron Oxide Nanosheets for Improving Li-S Battery Electrochemical Performance

Shunan LI¹, Mingtao QIAO¹, Kaifei SHEN¹, Yulong ZHANG¹, Weibin SI², Wanying LEI¹, Xiping LEI¹

Affiliations

^1.College of Materials Science and Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China

^2.State Grid Ankang Electric Power Supply Company, Ankang 725000, Shaanxi, China

Corresponding Author:

QIAO Mingtao (1989-), male, Ph.D., Professor. E-mail: mtqiao@xauat.edu.cn

LI Shunan (2002-), male, Master candidate. E-mail: lishunan@xauat.edu.cn

出版时间: 2024-05-20 doi: 10.14062/j.issn.0454-5648.20230779

文章导航

摘要

收起

采用酸刻蚀诱导的原位生长法在α-Fe₂O₃纳米片表面修饰聚吡咯，其中对甲苯磺酸起到刻蚀与掺杂的作用，Fe₂O₃纳米片表面被刻蚀出的Fe³⁺作为氧化剂，使得吡咯在Fe₂O₃纳米片表面聚合生长，对甲苯磺酸根作为对阴离子掺杂于聚吡咯分子结构中，得到Fe₂O₃@PPy复合纳米片。通过调节刻蚀环境与Fe₂O₃纳米片的投料量控制聚吡咯的修饰量，制得系列Fe₂O₃@PPy复合纳米片。当对甲苯磺酸和Fe₂O₃摩尔比为12∶1时，Fe₂O₃@PPy复合纳米片获得优异的电化学性能。1 C下的初始容量为468.7 mA·h·g^-1，循环500次后仍保持414.5 mA·h·g^-1的容量，容量保持率为86.2%，表现出良好的循环稳定性。该材料可应用于动力电池的开发。

关键词

三氧化二铁 / 聚吡咯 / 纳米片 / 原位生长 / 锂硫电池

Abstract

收起

Introduction

Lithium sulfur batteries have attracted recent attention as the secondary batteries with a high specific energy, a long lifespan, and a high safety. Inhibiting the shuttle effect of polysulfides and improving reaction kinetics become challenges. The chemical interactions between polar metal compounds and polysulfide ions (i.e., polarity polarity interactions, Lewis acid-base interactions, and sulfur bond chain reactions) have some advantages in inhibiting the shuttle effect of polysulfide ions. In addition, many metal compounds exhibit an electrocatalytic activity during the conversion of polysulfides, promoting the conversion rate of polysulfide ions during charging and discharging, suppressing the uneven deposition of insoluble sulfides Li₂S₂/Li₂S on the electrode surface, and thus achieving a goal of improving the utilization rate of active substances, inhibiting shuttle, and reducing the loss of active substances. The inherent conductive properties of conductive polymers are conducive to electron conduction, and their soft and elastic properties can effectively buffer the volume expansion of active substances during charge and discharge processes. The functional groups rich in them have a strong affinity for LiPSs and can inhibit shuttle effects. In this paper, Fe₂O₃@PPy composite materials were prepared via in-situ growth of polypyrrole on Fe₂O₃ nanosheets by acid etching.

Methods

Fe₂O₃ nanosheets were modified by a simple one-step method with polypyrrole to prepare high-performance lithium sulfur battery composite cathode materials. Fe₂O₃ nanosheets were placed in a solution of p-toluenesulfonic acid, and the surface was exposed to Fe³⁺ by acid etching. Fe³⁺ acted as an oxidant to promote the oxidation polymerization reaction of pyrrole monomers on the surface of the nanosheets. Also, p-toluenesulfonic acid was doped into the molecular structure of polypyrrole to obtain Fe₂O₃@PPy composite nanosheets. A series of Fe₂O₃@PPy composite nanosheets were prepared via adjusting the etching environment and the feeding amount of Fe₂O₃ nanosheets to control the modification amount of polypyrrole.

Results and discussion

The in-situ growth method induced by acid etching was used to modify the surface of α-Fe₂O₃ nanosheets with polypyrrole, in which p-toluenesulfonic acid played an etching and doping role. Fe³⁺ ion etched on the surface of Fe₂O₃ nanosheets is used as an oxidant, allowing pyrrole to polymerize and grow on the surface of Fe₂O₃ nanosheets. P-toluenesulfonic acid is doped into the molecular structure of polypyrrole as a para anion, resulting in Fe₂O₃@PPy composite nanosheets. The obtained Fe₂O₃@PPy nanocomposites combine the catalytic active sites exposed by Fe₂O₃ nanosheets with a high conductivity and a high specific surface area of polypyrrole. This increases the chemical adsorption of polysulfides and inhibits their shuttle, and accelerates the conversion of soluble LiPSs to insoluble products, greatly improving the utilization rate of sulfur, helping to improve the ion/electron transfer rate of nanosheets, and enhancing the reaction kinetics of electrode materials. Fe₂O₃ nanosheets form reinforced chemical bonds with LiPSs and promote the conversion of polysulfides, which effectively alleviates the shuttle effect of polysulfides, and improves the Coulomb efficiency, cycle stability and capacity retention of batteries. Polypyrrole enhances the conductivity of Fe₂O₃ nanosheets, their surface ion and electron conductivity, and improves Li⁺ diffusion kinetics. At a molar ratio of p-toluenesulfonic acid to Fe₂O₃ of 12∶1, Fe₂O₃@PPy composite nanosheets exhibit a superior electrochemical performance. The discharge specific capacities of the S@Fe₂O₃@PPy-3 cathode at 0.1, 0.2, 0.5 C and 1.0 C are 734.7, 576, 468.7 mA·h·g^-1 and 405.2 mA·h·g^-1, respectively. At a current density of 0.1C, S@Fe₂O₃@PPy-3 cathode can recover more reversible capacity with a discharge specific capacity of 519.5 mA·h·g^-1, having a superior rate performance. S@Fe₂O₃@PPy-3 provides an excellent cycling performance, maintaining a capacity of 414.5 mA·h·g^-1 even after 500 cycles at a high rate of 1 C with a capacity retention rate of 86.2%. This material can be used to the development of power batteries.

Conclusions

The synergistic effect of Fe₂O₃ and PPy on the electrochemical performance improvement of lithium sulfur batteries was effective. According to the change in the relative content of polypyrrole on the surface of Fe₂O₃ nanosheets, the conductivity of Fe₂O₃ nanosheets improved with the increase of polypyrrole content. However, the excess polypyrrole nanoparticles covered the surface of Fe₂O₃ nanosheets at the excessive polypyrrole, leading to a decrease in active sites and in battery performance. In summary, as a carrier for sublimation of sulfur, Fe₂O₃@PPy could promote the adsorption of polysulfides and alleviate their shuttle effect, improving the utilization rate of sulfur in lithium sulfur batteries.

Key words

iron oxide / polypyrrole / nanosheets / in situ growth / lithium-sulfur battery

引用本文

李舒楠, 乔明涛, 沈凯飞, 张玉龙, 司渭滨, 雷琬莹, 雷西萍. 聚吡咯修饰氧化铁纳米片改善锂硫电池性能. 硅酸盐学报, 2024 , 52 (5) : 1664 -1675 . DOI: 10.14062/j.issn.0454-5648.20230779

Shunan LI, Mingtao QIAO, Kaifei SHEN, Yulong ZHANG, Weibin SI, Wanying LEI, Xiping LEI. Polypyrrole Modified Iron Oxide Nanosheets for Improving Li-S Battery Electrochemical Performance[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (5) : 1664 -1675 . DOI: 10.14062/j.issn.0454-5648.20230779

基金

收起

国家自然科学基金青年项目(52302112)
陕西省教育厅重点科学研究计划项目(22JY037)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2024年第52卷第5期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20230779

接收时间：2023-10-10
首发时间：2026-10-22
出版时间：2024-05-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2023-10-10
修回日期：2023-11-03

基金

国家自然科学基金青年项目(52302112)

陕西省教育厅重点科学研究计划项目(22JY037)

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．国网陕西省电力有限公司安康供电公司，陕西安康 725000

通讯作者:

乔明涛（1989—），博士，副教授。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230779

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT