硅酸盐学报

水滑石超级电容器电极材料层间距调控研究进展

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王晓亮 ¹ , 高靖淞 ¹ , 宋晓琦 ¹ , 张一波 ¹ , 潘奎 ¹ , 王宏伟 ¹ , 郭力歌 ¹ , 李盼盼 ¹ , 刘忆 ² , 黄传辉 ² , 杨绍斌 ¹

硅酸盐学报 | 综合评述 2024,52(6): 2162-2174

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硅酸盐学报 |综合评述 2024 , 52 (6) : 2162 -2174

水滑石超级电容器电极材料层间距调控研究进展

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王晓亮¹, 高靖淞¹, 宋晓琦¹, 张一波¹, 潘奎¹, 王宏伟¹, 郭力歌¹, 李盼盼¹, 刘忆², 黄传辉², 杨绍斌¹

作者信息

^1．辽宁工程技术大学材料科学与工程学院，辽宁省地矿工程特种材料专业技术创新中心，辽宁省矿物高值化与储能材料重点实验室，辽宁阜新 123000

^2．徐州工程学院机电工程学院，江苏徐州 221111

作者简介:

王晓亮（1980—），男，博士，教授。

Research Progress on Layered Double Hydroxide Electrode Materials for Supercapacitors

Xiaoliang WANG¹, Jingsong GAO¹, Xiaoqi SONG¹, Yibo ZHANG¹, Kui PAN¹, Hongwei WANG¹, Lige GUO¹, Panpan LI¹, Yi LIU², Chuanhui HUANG², Shaobin YANG¹

Affiliations

^1.School of Materials Science and Engineering, Liaoning Technical University, Geology and Mineral Engineering Special Materials Professional Technology Innovation Center of Liaoning Province, Key Laboratory of Mineral High Value Conversion and Energy Storage Materials of Liaoning Province, Fuxin 123000, Liaoning, China

^2.School of Mechanical and Electrical Engineering, Xuzhou Institute of Technology, Xuzhou 221111, Jiangsu, China

WANG Xiaoliang (1980-), male, Ph.D., Professor. E-mail: ningke@163.com

出版时间: 2024-06-20 doi: 10.14062/j.issn.0454-5648.20230722

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摘要

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水滑石具有二维层状结构和高理论比电容，在超级电容器电极材料领域崭露头角。通过调控层间距，提高水滑石层间电化学活性位点利用率，降低离子传输阻力，成为水滑石等二维电极材料常用而有效的结构调控方法。近年来，水滑石层间距调控和电容性能研究报道迅速增加，但至今关于水滑石层间距调控提升电容性能的综述文章依然很少。因此，本文对水滑石的结构和储能机理进行了介绍，系统对比评述了离子交换法和一步合成方法调控层间距的优缺点，深入对比并总结了客体插层、金属阳离子配比调控、插层及水滑石载量调控等方法对水滑石层间距、成分、结构和电容性能的影响研究的进展情况，梳理出了调控层间距提升电容性能的常用方法和电容性能提升的内在机制，为推进水滑石电极材料的深入研究和应用发挥重要作用。

关键词

水滑石 / 超级电容器电极材料 / 层间距调控 / 电容性能

Abstract

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Supercapacitors have attracted recent attention because of their high power density, fast charging and discharging capability, long cycle life, and good stability. However, the generally low energy density of supercapacitors restricts their applications. The electrode material is the most critical part in the supercapacitor and significantly affects the performance. In recent years, a rational design of electrode materials is proved to be an effective way to improve the capacitance performance of supercapacitors. Among many electrode materials, layered double hydroxide (i.e., hydrotalcite and hydrotalcite-like) has the advantages of adjustable morphology and composition, high theoretical specific capacitance, low cost, easy synthesis and considerable energy density and power density, etc., and emerges in the field of supercapacitor electrode materials. The unique two-dimensional structure of the layered double hydroxide (LDH) and its energy storage mode through electrolyte ions embedded and dislodged in the interlayer dictate that an interlayer spacing modulation is an effective method to improve its capacitance performance. Enhancing the utilization of electrochemically active sites between LDH layers and reducing the ion transport velocity resistance via regulating the layer spacing become a commonly used and effective structural modulation method for two-dimensional electrode materials such as LDH.

This review summarized the research progress on the application of LDH interlayer spacing regulation in the field of supercapacitors, introduced the structure of LDH, the energy storage mechanism, and the advantages of LDH as an electrode material, and described the influencing factors and the advantages and disadvantages about the interlayer spacing regulation from the two different perspectives of the ion-exchange method and the one-step synthesis method, respectively. The target anion intercalation in the two methods concerns the anion charge density and anion concentration in the reaction system. The interlayer spacing values of different guest intercalated LDH, such as inorganic anions, organic anions, and molecules, were discussed. The factors affecting interlayer spacing and capacitance performance were summarized. A small interlayer spacing significantly inhibits ion diffusion and charge transport, which is not conducive to achieving a high capacitance performance. Organic anion intercalation is more likely to achieve a larger interlayer spacing and a higher capacitance performance. Appropriate interlayer objects and interlayer spacing are crucial for achieving a high capacitance performance. The influence of metal cations ratio on the interlayer spacing and capacitance performance was evaluated, and three methods for regulating metal cations were summarized. The ratio of divalent and trivalent cations in the synthesis process can be adjusted to achieve the control of positive charge concentration in the basal layer and the control of interlayer force, thus controlling the interlayer spacing. The oxidation of divalent cations during or after synthesis is controlled to achieve a positive charge density. Selecting cations of different radii to synthesize LDH affects the distribution of basal layer charges, thereby affecting the interlayer spacing. This review elaborated on the method of adding intercalation agents during the process of regulating interlayer spacing, which can simultaneously increase the interlayer spacing and load mass, and is of great significance for obtaining high load and high capacitance electrodes. This review outlined common methods for improving capacitance performance by regulating interlayer spacing and the underlying mechanisms for improving the capacitance performance, playing an important role in promoting the in-depth research and application of LDH electrode materials.

Summary and prospects

Some prospects for future development were provided. In the future, with the continuous development of precise temperature control, uniform, and rapid heating synthesis technologies such as microwave synthesis, the combination of artificial intelligence control technology and synthesis equipment, the advancement of multi index observation in-situ experimental technology, and the precise observation and control of synthesis heating rate, temperature field, and concentration field are effective ways to achieve precise synthesis of hydrotalcite and precise control of interlayer spacing. And it is expected to achieve precise control of the types, quantities, and layout of interlayer objects according to demand. The influences of interlayer object types, quantities, arrangement attitudes, and pores on the electrolyte ion transport, and the related mechanism on the interlayer active site electrochemical reactions, and the related mechanism on the interlayer spacing and layer structure evolution can be investigated more accurately. The combination of multi-index observation in-situ synthesis experimental technology with the first-principles, molecular dynamics, and machine learning simulation methods can be ultilized to analyze the microstructure, electrochemical reactions, and other processes.

Key words

layered double hydroxide / supercapacitor / interlayer spacing regulation / capacitor performance

引用本文

王晓亮, 高靖淞, 宋晓琦, 张一波, 潘奎, 王宏伟, 郭力歌, 李盼盼, 刘忆, 黄传辉, 杨绍斌. 水滑石超级电容器电极材料层间距调控研究进展. 硅酸盐学报, 2024 , 52 (6) : 2162 -2174 . DOI: 10.14062/j.issn.0454-5648.20230722

Xiaoliang WANG, Jingsong GAO, Xiaoqi SONG, Yibo ZHANG, Kui PAN, Hongwei WANG, Lige GUO, Panpan LI, Yi LIU, Chuanhui HUANG, Shaobin YANG. Research Progress on Layered Double Hydroxide Electrode Materials for Supercapacitors[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (6) : 2162 -2174 . DOI: 10.14062/j.issn.0454-5648.20230722

基金

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国家自然科学基金(51974152)

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2024年第52卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230722

接收时间：2023-09-20
首发时间：2026-10-22
出版时间：2024-06-20

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收稿日期：2023-09-20
修回日期：2023-11-02

基金

国家自然科学基金(51974152)

作者信息

^1．辽宁工程技术大学材料科学与工程学院，辽宁省地矿工程特种材料专业技术创新中心，辽宁省矿物高值化与储能材料重点实验室，辽宁阜新 123000

^2．徐州工程学院机电工程学院，江苏徐州 221111

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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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