NH4+扩层MoS2的制备及其储锌性能研究

doi:10.15541/jim20220242

无机材料学报 ›› 2023, Vol. 38 ›› Issue (1): 79-86.DOI: 10.15541/jim20220242

NH₄⁺扩层MoS₂的制备及其储锌性能研究

李涛¹(), 曹鹏飞¹, 胡力涛¹, 夏勇¹, 陈一¹, 刘跃军¹, 孙翱魁¹^,²()

1.湖南工业大学包装与材料工程学院, 株洲 412007
2.中南大学冶金与环境学院, 长沙 410083

收稿日期:2022-04-23 修回日期:2022-05-31 出版日期:2022-06-16 网络出版日期:2022-06-16
通讯作者: 孙翱魁, 副教授. E-mail: aksun@hut.edu.cn
作者简介:李涛(1998-), 男, 硕士研究生. E-mail: 17404200515@stu.hut.edu.cn
基金资助:
湖南省自然科学基金(2021JJ30215);湖南省教育厅科学研究项目(21A0363)

NH₄⁺ Assisted Interlayer-expansion of MoS₂: Preparation and Its Zinc Storage Performance

LI Tao¹(), CAO Pengfei¹, HU Litao¹, XIA Yong¹, CHEN Yi¹, LIU Yuejun¹, SUN Aokui¹^,²()

1. School of Packaging and Materials Engineering, Hunan University of Technology, Zhuzhou 412007, China
2. School of Metallurgy and Environment, Central South University, Changsha 410083, China

Received:2022-04-23 Revised:2022-05-31 Published:2022-06-16 Online:2022-06-16
Contact: SUN Aokui, associate professor. E-mail: aksun@hut.edu.cn
About author:LI Tao (1998-), male, Master candidate. E-mail: 17404200515@stu.hut.edu.cn
Supported by:
Hunan Provincial Natural Science Foundation(2021JJ30215);Scientific Research Project of Hunan Provincial Department of Education(21A0363)

摘要/Abstract

摘要：

二硫化钼(MoS₂)作为水系锌离子电池的正极材料, 受到锌离子(Zn²⁺)与主体框架之间的强静电相互作用表现出缓慢的反应动力学。并且MoS₂的层间距较窄难以嵌入大尺寸水合Zn²⁺, 导致MoS₂电极呈现出较低的放电比容量。本研究通过一种简单的氨水辅助水热法制备了NH₄⁺扩层的二硫化钼(MoS₂-N)电极, 氨水分解产生的氨气在促进硫代乙酰胺水解和提供还原性S^2-的同时, 还会产生大量NH₄⁺作为插层离子, 将MoS₂的层间距由0.62 nm扩展至0.92 nm, 进而大大降低了Zn²⁺嵌入能垒(改性电极的电荷转移电阻R_ct低至35 Ω)。当电流密度为0.1 A·g^-1时, MoS₂-N电极的初始放电比容量相比未扩层的MoS₂电极提高了1倍, 高达149.9 mAh·g⁻¹。同时在1.0 A·g^-1电流密度下放电比容量稳定在110 mAh·g^-1左右, 循环200圈后库仑效率将近100%。本研究提出的氨水辅助扩层法, 丰富了提升MoS₂电化学性能的改性策略, 为后续的正极材料开发提供了新的思路。

关键词: MoS₂, 氨水辅助扩层, 正极材料, 水系锌离子电池, 二维材料

Abstract:

Suffering from strong electrostatic interactions between divalent Zn²⁺ and host framework, molybdenum disulfide exhibits slow reaction kinetics as cathode for aqueous zinc-ion batteries. The narrow layer spacing of MoS₂ is difficulty in accommodating large size insertion of hydrated Zn²⁺, resulting in a lower discharge specific capacity. Here, NH₄⁺ expanded MoS₂-N was prepared by a simple ammonia-assisted hydrothermal. The result showed that the ammonia promoted hydrolysis of thioacetamide to provide reduced S^2- and generated a large amount of NH₄⁺ as intercalating particles. These particles expanded the layer spacing of pristine MoS₂ from 0.62 nm to 0.92 nm, greatly reducing the Zn²⁺ inserting energy barrier (with its charge transfer resistance of MoS₂-N only 35 Ω), and increased the discharge specific capacity to 149.9 mAh·g⁻¹ at the current density of 0.1 A·g^-1, 2 times that of MoS₂ electrode without NH₄⁺expansion. Consequently, it exhibited a stable discharge capacity of about 110 mAh·g^-1 at the current density of 1.0 A·g^-1 with nearly 100% Coulombic efficiency after 200 cycles. The approach of ammonia-assisted layer expansion proposed in this study enriches the modification strategy to enhance the electrochemical performance of MoS₂ and provides a new idea for subsequent cathode development.

Key words: MoS₂, ammonia-assisted interlayer-expansion, cathode material, aqueous zinc ion battery, 2D material

中图分类号:

TQ174

李涛, 曹鹏飞, 胡力涛, 夏勇, 陈一, 刘跃军, 孙翱魁. NH₄⁺扩层MoS₂的制备及其储锌性能研究[J]. 无机材料学报, 2023, 38(1): 79-86.

LI Tao, CAO Pengfei, HU Litao, XIA Yong, CHEN Yi, LIU Yuejun, SUN Aokui. NH₄⁺ Assisted Interlayer-expansion of MoS₂: Preparation and Its Zinc Storage Performance[J]. Journal of Inorganic Materials, 2023, 38(1): 79-86.

图/表 8

图S1 NH4+扩层的MoS2-N结构图

Fig. S1 Structure diagram of MoS2-N with NH4+ expanded layer

图1 (a)MoS2-N和p-MoS2的XRD图谱和(b)MoS2-N的拉曼光谱

Fig. 1 (a) XRD patterns of MoS2-N and p-MoS2 and (b) Raman spectrum of MoS2-N

图2 MoS2-N的(a)XPS总谱, (b)高分辨率Mo3d, (c)S2p和(d) N1s XPS谱

Fig. 2 (a) Total survey, (b) Mo3d, (c) S2p and (d) N1s high resolution XPS spectra of MoS2-N

图3 (a)p-MoS2的SEM照片, MoS2-N的(b)SEM、(c, d)TEM和(e)HRTEM照片

Fig. 3 (a) SEM image of p-MoS2; (b) SEM, (c, d) TEM and (e) HRTEM images of MoS2-N

图4 (a) MoS2-N和(b) p-MoS2在不同电流密度下的恒电流充放电曲线, (c) MoS2-N和p-MoS2在不同电流密度下的倍率性能和(d)在1.0 A·g−1下的循环性能

Fig. 4 GCD curves under different current densities of (a) MoS2-N and (b) p-MoS2, (c) rate capabilities under different current densities and (d) cyclic performance at 1.0 A·g−1 of MoS2-N and p-MoS2 Colorful figures are available on website

图S2 (a) A-MoS2-N的恒电流充放电曲线, (b)倍率性能和(c)在0.1 A·g-1下的循环性能

Fig. S2 (a) GCD curves, (b) rate capability under different current densities and (c) cyclic performance at 1.0 A·g-1 of A-MoS2-N

图5 储能机理分析

Fig. 5 Analysis of energy storage mechanism (a) CV curves at different scan rates from 0.2 to 1.0 mV·s−1; (b) Fitting lines of lgi vs. lgv; (c) Fitting lines of v1/2 vs. i/v1/2; (d) Histogram of capacitive-controlled (blue) and diffusion controlled (orange) distributions at different scan rates for of MoS2-N electrode Colorful figures are available on website

图S3 (a) MoS2-N和p-MoS2在不同循环圈数下的Nyquist图谱; MoS2-N在不同放电深度的(b)异位XRD图谱，以及(c) Zn2p和(d) Mo3d异位XPS高分辨率谱图

Fig. S3 (a) Nyquist plots of MoS2-N and p-MoS2 under different cycles, (b) ex-situ XRD patterns and ex-situ XPS high resolution spectra of (c) Zn2p, (d) Mo3d of MoS2-N electrode collected at different charge/discharge depths

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NH₄⁺扩层MoS₂的制备及其储锌性能研究

NH₄⁺ Assisted Interlayer-expansion of MoS₂: Preparation and Its Zinc Storage Performance

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