硅酸盐学报

原位硒化法制备NiSe/Mo₁₅Se₁₉电极材料及其在超级电容器中的应用

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郑佳红 , 白昕

硅酸盐学报 | 研究论文 2024,52(1): 65-74

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硅酸盐学报 |研究论文 2024 , 52 (1) : 65 -74

原位硒化法制备NiSe/Mo₁₅Se₁₉电极材料及其在超级电容器中的应用

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郑佳红, 白昕

作者信息

长安大学材料科学与工程学院，西安 710021

作者简介:

郑佳红（1983—），女，博士，副教授。

Preparation of NiSe/Mo₁₅Se₁₉ Electrode Materials by in-situ Selenization and Their Application in Supercapacitors

Jiahong ZHENG, Xin BAI

Affiliations

School of Materials Science and Engineering, Chang'an University, Xi'an 710061, China

ZHENG Jiahong (1983-), female, Ph.D., Associate Professor. E-mail: jhzheng@chd.ed

出版时间: 2024-01-20 doi: 10.14062/j.issn.0454-5648.20230241

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摘要

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开发高性能、高效的电极材料对提高混合超级电容器的能量密度具有重要意义。以泡沫镍为基底，制备了NiSe/Mo₁₅Se₁₉复合材料，系统地研究了不同镍钼摩尔比例对其电化学性能的影响。当n（Ni）∶n（Mo）=2∶1（摩比）时，NiSe/Mo₁₅Se₁₉复合材料的电化学性能最优，在1A/g电流密度下，样品比电容为940.9 F/g。此外，该电极材料具有良好的倍率性能和循环稳定性。由NiSe/Mo₁₅Se₁₉和活性炭（AC）制成的NiSe/Mo₁₅Se₁₉//AC混合型超级电容器（ASC）表现出较高的能量（46.5 W·h/kg）和功率密度（800 W/kg），表明NiSe/Mo₁₅Se₁₉复合材料在未来储能器件研究领域具有潜在的应用价值。

关键词

过渡金属硒化物 / 超级电容器 / 电化学性能

Abstract

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Introduction

It is necessary to explore efficient and environmentally friendly energy storage devices due to the rapid consumption of fossil fuels and increasing environmental pollution. Among various energy storage devices, supercapacitors have some advantages of high power density, short charging and discharging time, good cycle stability, safety and reliability. The related studies focused on transition metal oxides and sulfides. However, their conductivity and cycle stability are rather poor. Compared with transition metal oxides and sulfides, transition metal selenides as an advanced multifunctional material dominate the field of energy storage and conversion by virtue of their high theoretical capacity, good electrical conductivity, and good cycling stability. Also, the coexistence of different metal cations with multiple valence leaps enables multiple redox reactions and enriches structural defects, and the coupling between the bimetals favors the regulation of the electronic structure and improved electrical conductivity, resulting in better electrochemical activity than monometallic selenides. Transition metal selenide electrodes for electrochemical studies are usually prepared with polymer binders by conventional slurry coating methods, which increases the dead volume of the active transition metal selenide surface and decreases the contact with the electrolyte. Therefore, transition metal selenides can be designed and prepared on a conductive substrate with an ideal porous network to obtain better charge storage performance. In this paper, NiMo precursor was firstly synthesized on a nickel foam substrate by a hydrothermal method, and then NiSe/Mo₁₅Se₁₉ electrode materials were prepared via in-situ selenation reaction of this precursor with Se powder. In addition, the effect of NiMo ratio on their electrochemical properties was also investigated.

Methods

A 2 cm × 4 cm nickel foam (NF) substrate was firstly pretreated with 2 mol/L HCl, acetone, anhydrous ethanol and deionized water, and then 6 mmol of Ni(NO₃)₂-6H₂O and 3 mmol of Na₂MoO₄-2H₂O were dissolved in 60 mL of deionized water. The dissolved mixture and 1 block of pre-treated NF were added into a PTFE-lined reactor, and the hydrothermal reaction was carried out at 150 ℃ for 5 h. The effect of nickel and molybdenum molar ratio (i.e., 1∶1 and 3∶1) on the electrochemical performance was investigated. Finally, the precursor and 0.13 g of Se powder were placed at the two ends of a quartz boat into a tube furnace in Ar gas as a protective gas at 350 ℃ for 2 h. After natural cooling, NiSe/Mo₁₅Se₁₉ was obtained. The crystal structure of the samples was determined by a model D8AA25 X-ray diffractometer (XRD, Bruker). The microstructure of the samples was observed using a model S-4800 scanning electron microscope (SEM, Hitachi Co., Japan). The morphology, lattice, and lattice spacing of the samples were analyzed by a model F30G2 transmission electron microscope (TEM, Tecnai). The molecular structure, elemental valence states and chemical bonding were analyzed by a model Xi+ X-ray photoelectron spectroscope (XPS, ESCALAB). The electrochemical properties of the samples in the three-electrode system and the two-electrode system were tested by a model CHI660E electrochemical workstation (Chenhua Co., China) under an electrolyte of 6 mol/L KOH. Three-electrode measurements were carried out using Pt as a counter electrode and saturated calomel as a reference electrode. The ASC devices were made with NiSe/Mo₁₅Se₁₉ as a positive electrode and activated carbon (AC) as a negative electrode in the two-electrode system.

Results and discussion

The SEM images show that the Ni∶Mo molar ratio has an effect on the morphology of the samples. When the Ni∶Mo molar ratio is 1∶1, the sample morphology is the coexistence of flower-like microspheres composed of nanorods and nanosheets, and the disorganized molecular pore arrangement is not conducive to the flow of electrolyte ions. The diameter of the microspheres composed of nanosheets is approximately 1 μm, the thicknesses of the nanosheets are 30-40 nm, the diameters of the nanorods are 150-200 nm, and the length of the nanorods is approximately 2 μm. When the Ni∶Mo molar ratio is 2∶1, the morphology of the sample is nanorods, and they are grown vertically oriented on the NF substrate, with the lengths of the nanorods of 1.0-1.5 μm, and the diameters of the nanorods of 50-120 nm. At the Ni∶ Mo molar ratio of 3∶1, the morphology of the sample is flower-like microspheres composed of nanosheets, the diameters of the microspheres are 1.5-2.0 μm, and the thicknesses of the nanosheets are 20-30 nm. The electrochemical test shows that the sample has the optimum electrochemical performance when the molar ratio of Ni∶Mo is 2∶1. The specific capacitance of the sample is 940.9 F/g at the current density of 1 A/g, and the specific capacitance of the sample is 940.9 F/g when the current density increases from 1 A/g to 10 A/g. The electrode with n(Ni)∶ n(Mo) of 2∶1 still maintains a specific capacitance of 75.5% when the current density increases from 1 A/g to 10 A/g. This is since the rod-like nanostructure possesses a large specific surface area, thus providing more active sites for the electrochemical reaction and being beneficial to the energy storage device. From the TEM images, NiSe/Mo₁₅Se₁₉ nanorods have a porous structure due to the release of gases during the calcination process. This unique porous structure can provide more transport channels for electrolyte ions and a large number of active sites in the Faraday reaction.

Conclusions

NiSe/Mo₁₅Se₁₉ composites had an optimum electrochemical performance at a Ni∶Mo molar ratio of 2∶1. The sample-specific capacitance was 940.9 F·g^-1 at a current density of 1 A·g^-1. In addition, this electrode material exhibited good multiplication properties and cycling stability. The NiSe/Mo₁₅Se₁₉//AC hybrid supercapacitor (ASC) made from NiSe/Mo₁₅Se₁₉ and activated carbon (AC) had a high energy (i.e., 46.5 Wh·kg^-1) and a power density (i.e., 800 W·kg^-1), indicating that NiSe/Mo₁₅Se₁₉ composites have a promising application potential in energy storage devices.

Key words

transition metal selenide / supercapacitor / electrochemical performance

引用本文

郑佳红, 白昕. 原位硒化法制备NiSe/Mo₁₅Se₁₉电极材料及其在超级电容器中的应用. 硅酸盐学报, 2024 , 52 (1) : 65 -74 . DOI: 10.14062/j.issn.0454-5648.20230241

Jiahong ZHENG, Xin BAI. Preparation of NiSe/Mo₁₅Se₁₉ Electrode Materials by in-situ Selenization and Their Application in Supercapacitors[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (1) : 65 -74 . DOI: 10.14062/j.issn.0454-5648.20230241

基金

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陕西省自然科学专项基金(2020JM-221)
陕西省重点研发项目(2022GY-358)
长安大学中央高校基本科研业务费专项资金资助(300102310203; 300102311405; 300102312405; 300102312406)
大学生创新创业训练计划项目(s202210710247; X202310710415)

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2024年第52卷第1期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230241

接收时间：2023-04-12
首发时间：2026-10-22
出版时间：2024-01-20

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收稿日期：2023-04-12
修回日期：2023-06-27

基金

陕西省自然科学专项基金(2020JM-221)

陕西省重点研发项目(2022GY-358)

长安大学中央高校基本科研业务费专项资金资助(300102310203; 300102311405; 300102312405; 300102312406)

大学生创新创业训练计划项目(s202210710247; X202310710415)

作者信息

长安大学材料科学与工程学院，西安 710021

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230241

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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

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