锂硒电池ZIF-L衍生氮掺杂碳纳米片/碳布自支撑电极的电化学性能研究

doi:10.15541/jim20240027

无机材料学报 ›› 2024, Vol. 39 ›› Issue (9): 1013-1021.DOI: 10.15541/jim20240027

锂硒电池ZIF-L衍生氮掺杂碳纳米片/碳布自支撑电极的电化学性能研究

荀道祥¹(), 罗序维¹, 周明冉¹, 何佳乐¹, 冉茂进¹^,², 胡执一¹^,², 李昱¹()

1.武汉理工大学材料复合新技术国家重点实验室, 武汉 430070
2.武汉理工大学纳微结构研究中心, 武汉 430070

收稿日期:2024-01-11 修回日期:2024-03-19 出版日期:2024-09-20 网络出版日期:2024-05-08
通讯作者: 李昱, 教授. E-mail: yu.li@whut.edu.cn
作者简介:荀道祥(1998-), 男, 硕士研究生. E-mail: xundaoxiang@whut.edu.cn
基金资助:
国家自然科学基金(U22B6011);国家自然科学基金(22275142);国家自然科学基金(52103285);111引智计划(B20002);湖北省自然科学基金(2020CFB416)

ZIF-L Derived Nitrogen-doped Carbon Nanosheets/Carbon Cloth Self-supported Electrode for Lithium-selenium Battery

XUN Daoxiang¹(), LUO Xuwei¹, ZHOU Mingran¹, HE Jiale¹, RAN Maojin¹^,², HU Zhiyi¹^,², LI Yu¹()

1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
2. Nanostructure Research Centre (NRC), Wuhan University of Technology, Wuhan 430070, China

Received:2024-01-11 Revised:2024-03-19 Published:2024-09-20 Online:2024-05-08
Contact: LI Yu, professor. E-mail: yu.li@whut.edu.cn
About author:XUN Daoxiang (1998-), male, Master candidate. E-mail: xundaoxiang@whut.edu.cn
Supported by:
National Natural Science Foundation of China(U22B6011);National Natural Science Foundation of China(22275142);National Natural Science Foundation of China(52103285);The 111 National Project(B20002);Natural Science Foundation of Hubei Province(2020CFB416)

摘要/Abstract

摘要：

硒(Se)因其较高的体积比容量(3253 mAh·cm^-3)和电子电导率(1×10^-5 S·m^-1)而成为新一代锂硒(Li-Se)电池储能材料。针对其反应过程中体积膨胀较大、容量衰减较快以及活性物质利用率低等问题, 本研究通过在碳布(CC)上生长二维Zn基金属有机框架(ZIF-L)并碳化, 设计了一种ZIF-L衍生氮掺杂碳纳米片/硒自支撑复合材料(Se@NC/CC)用于锂硒电池研究。ZIF-L碳化形成的氮掺杂碳纳米片中丰富的微孔结构有效缓解了反应过程中的体积膨胀, 掺杂N原子有利于吸附反应过程中的Li₂Se, 减少活性物质损失。特别地, Se@NC/CC电极中Se和C之间存在强的化学键作用, 在一定程度上也可以减少活性物质损失, 提高整体性能稳定性。电化学测试表明, 在0.5C(1.0C=675 mAh·g^-1)电流密度下, Se@NC/CC电极的初始放电比容量为574 mAh·g^-1, 展现出高初始放电比容量; 电流密度为2.0C时, 初始放电比容量为453.3 mAh·g^-1, 循环500圈后仍然具有406.2 mAh·g^-1的容量; 同时也表现出了良好的倍率性能, 与文献报道相比有较明显的优势。本研究设计的柔性自支撑硒电极为先进碱金属-硒电池的硒宿主材料设计提供了新的研究思路。

关键词: 锂硒电池, 碳布, 自支撑, ZIF-L材料, 碳纳米片

Abstract:

Selenium (Se) is considered as a new generation energy storage material of lithium-selenium (Li-Se) battery due to its high volume specific capacity (3253 mAh·cm^-3) and high electronic conductivity (1×10^-5 S·m^-1). To address the problems of volume expansion, fast capacity decay, and low utilization of active materials during its charging-discharging process, a ZIF-L derived nitrogen-doped nanosheets/selenium (Se@NC/CC) flexible self-supported composite electrode is designed in this study for lithium-selenium battery by growing two-dimensional zinc-based metallic organic framework (ZIF-L) on carbon cloth (CC). The rich microporous structure in the nitrogen-doped carbon nanosheets can effectively alleviate the volume expansion during the reaction process, and the doping of heteroatoms N helps to adsorb Li₂Se and reduce the loss of active substances. In particular, it is found that there is strong chemical bonding between Se and C in the Se@NC/CC electrode, which also helps to reduce the loss of active materials and improve the performance. Electrochemical results show that the initial discharge specific capacity of the Se@NC/CC electrode is 574 mAh·g^-1 at a current density of 0.5C (1.0C=675 mAh·g^-1), demonstrating a high initial discharge specific capacity. At a current density of 2.0C, the initial discharge specific capacity is 453.3 mAh·g^-1, which maintains at 406.2 mAh·g^-1 after cycling for 500 cycles and it also displays excellent rate performance compared to literature. Such a flexible self-supported selenium cathode designed in this study provides a new research route on the design of selenium host materials for advanced alkali metal-selenium batteries.

Key words: lithium-selenium battery, carbon cloth, self-supporting, ZIF-L, carbon nanosheet

中图分类号:

TQ174

荀道祥, 罗序维, 周明冉, 何佳乐, 冉茂进, 胡执一, 李昱. 锂硒电池ZIF-L衍生氮掺杂碳纳米片/碳布自支撑电极的电化学性能研究[J]. 无机材料学报, 2024, 39(9): 1013-1021.

XUN Daoxiang, LUO Xuwei, ZHOU Mingran, HE Jiale, RAN Maojin, HU Zhiyi, LI Yu. ZIF-L Derived Nitrogen-doped Carbon Nanosheets/Carbon Cloth Self-supported Electrode for Lithium-selenium Battery[J]. Journal of Inorganic Materials, 2024, 39(9): 1013-1021.

图/表 9

图1 Se@NC/CC合成示意图以及各样品SEM照片

Fig. 1 Schematic of the synthesis of Se@NC/CC and SEM images of each sample (a) Schematic of the synthesis of Se@NC/CC; (b-g) SEM images of (b) ZIF-L/CC, (c) NC/CC, (d) Se@NC/CC, (e) CC, (f) PCC, and (g) Se@PCC; (h-k) EDX mappings of Se@PCC

图2 各样品的XRD、Raman和热重图谱

Fig. 2 XRD, Raman and thermogravimetric profiles of each sample (a) XRD patterns of the precursors ZIF-L and ZIF-L/CC; (b) XRD patterns of NC/CC and PCC before and after selenium filling; (c) Raman spectra of Se@NC/CC and Se@PCC; (d) TG curves of Se@NC/CC and Se@PCC

图3 各样品的N2吸附-脱附等温曲线及孔径分布图

Fig. 3 N2 adsorption-desorption isotherms and pore size distribution of each sample (a) N2 adsorption-desorption isotherms of NC/CC and Se@NC/CC and corresponding (b) pore size distribution; (c) N2 adsorption-desorption isotherms of PCC and Se@PCC and corresponding (d) pore size distribution

图4 Se@NC/CC的TEM照片

Fig. 4 TEM images of Se@NC/CC (a) TEM image of Se@NC/CC; (b) High-resolution transmission electron microscope (HRTEM) image of Se@NC/CC; (c-f) EDX mappings of C, N, and Se in Se@NC/CC

图5 两种电极的XPS图谱

Fig. 5 XPS patterns of two electrodes (a) Total, and (b-d) high-resolution (b) C1s, (c) Se3d and (d) N1s XPS spectra of Se@NC/CC composites; (e, f) High-resolution (e) C1s and (f) Se3d XPS spectra of of Se@PCC composites

图6 两种电极的电化学性能

Fig. 6 Electrochemical performances of two electrodes (a, b) CV curves, (c) EIS profiles, (d, e) charge-discharge curves and (f) rate performance of (a, d) Se@NC/CC and (b, e) Se@PCC

图7 Se@NC/CC和Se@PCC电极在(a) 0.5C, (b) 1.0C和(c) 2.0C下的循环性能

Fig. 7 Cycling performance of Se@NC/CC and Se@PCC electrodes at (a) 0.5C, (b) 1.0C and (c) 2.0C

图8 Se@NC/CC电极循环后的SEM照片及机理示意图

Fig. 8 SEM images of Se@NC/CC electrode after cycling and corresponding mechanism diagram (a) Typical SEM image of the Se@NC/CC electrode after 100 cycles at 0.5C; (b) Typical SEM enlarged image of the Se@NC/CC electrode after 100 cycles at 0.5C; (c) Microscopic mechanism of the Se@NC/CC electrode

表1 硒碳复合材料电化学性能比较

Table 1 Comparison of electrochemical properties of selenium-carbon composites

Host material	Current density	Cycle number	Reversible capacity/ (mAh·g^-1)	Ref.
Se@NC/CC	0.5C	100	516	This work
Se@NC/CC	2.0C	500	406.2	This work
NiS₂-HPC/Se	0.5C	200	533	[37]
Se@NMC-Co	0.2C	100	419	[38]
Se@S-NOHPC	0.2C	200	367	[39]
ZnCo-NC/Se	2.0C	1000	428	[40]
Ni-NC/Se	2.0C	500	301	[20]

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锂硒电池ZIF-L衍生氮掺杂碳纳米片/碳布自支撑电极的电化学性能研究

ZIF-L Derived Nitrogen-doped Carbon Nanosheets/Carbon Cloth Self-supported Electrode for Lithium-selenium Battery

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