钟厉,徐政,康俊,任凯翔.三维石墨烯晶体膜可控制备策略及其超级电容器的应用[J].表面技术,2025,54(11):32-49.
ZHONG Li,XU Zheng,KANG Jun,REN Kaixiang.Controllable Preparation Strategies of Advanced 3D Graphene Crystal Film and Its Application in Supercapacitor[J].Surface Technology,2025,54(11):32-49 |
| 三维石墨烯晶体膜可控制备策略及其超级电容器的应用 |
| Controllable Preparation Strategies of Advanced 3D Graphene Crystal Film and Its Application in Supercapacitor |
| 投稿时间：2024-12-11 修订日期：2025-02-18 |
| DOI：10.16490/j.cnki.issn.1001-3660.2025.11.003 |
| 中文关键词: 三维结构 石墨烯晶体 宏观厚度 薄膜电极 超级电容器 |
| 英文关键词:3D structure graphene crystal macro thickness film electrode supercapacitor |
| 基金项目:重庆市自然科学基金面上项目(cstc2020jcyj-msxmX0749);重庆市研究生联合培养基地项目(JDLHPYJD2020031);重庆市研究生导师团队建设项目(JDDSTD2019007); |
| 作者 | 单位 |
| 钟厉 | 重庆交通大学 机电与车辆工程学院，重庆 400074 |
| 徐政 | 重庆交通大学 机电与车辆工程学院，重庆 400074 |
| 康俊 | 中国科学技术大学 化学系，合肥 230026;中国科学院合肥物质科学研究院 固体物理研究所，合肥 230031 |
| 任凯翔 | 重庆交通大学 机电与车辆工程学院，重庆 400074 |
|
| Author | Institution |
| ZHONG Li | School of Mechatronics and Vehicle Engineering, Chongqing Jiaotong University, Chongqing 400074, China |
| XU Zheng | School of Mechatronics and Vehicle Engineering, Chongqing Jiaotong University, Chongqing 400074, China |
| KANG Jun | Department of Chemistry, University of Science and Technology of China, Hefei 230026, China;Institute of Solid-State Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China |
| REN Kaixiang | School of Mechatronics and Vehicle Engineering, Chongqing Jiaotong University, Chongqing 400074, China |
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| 中文摘要: |
| 三维石墨烯晶体膜具有高晶体质量、大比表面积和高导电性，成为理想的碳基超级电容器的电极材料。然而，传统石墨烯电极材料受限于表面活性位点数量和宏观尺度下的电化学体积效应，难以达到理论性能。为此，重点介绍通过高能束流(如CO2激光和高能电子束)诱导技术制备宏观厚度的三维石墨烯晶体膜，并探讨其修饰与复合方法。在此基础上，详细阐述CO2激光和高能电子束制备三维石墨烯晶体膜的基本原理及其可控制备策略。采用CO2激光，通过调节激光参数和前驱体材料，能够实现石墨烯晶体膜的厚度调控和结构优化。高能电子束具有高穿透力和低反射特性，能够在宏观尺度下制备均匀的三维石墨烯薄膜。此外，还介绍了通过非金属原子掺杂、金属氧化物和导电聚合物复合等方法，进一步提升三维石墨烯晶体膜的电化学性能等方面的研究内容。在超级电容器应用中，三维石墨烯晶体膜表现出优异的体积比电容和循环稳定性，具有广阔的应用前景。然而，随着厚度的增加，三维石墨烯晶体膜的体积效应和离子传输效率等问题仍需解决，提出通过构筑梯度孔道和优化孔隙结构来增强离子传输能力的解决方案。最后展望了三维石墨烯晶体膜在商用超级电容器中规模化应用的机遇与挑战。 |
| 英文摘要: |
| As a new type of electrochemical energy storage device, due to the excellent performance of small size, light weight, and high instantaneous energy, the supercapacitor plays an important role in the limited energy transit efficiency problem currently faced, and the key to achieve the performance advantage of supercapacitors lies in the optimized design of electrode material structure. Currently, graphene crystal film is one of the ideal supercapacitor electrode materials due to its high crystal quality, large specific surface area, and high conductivity. However, the traditional pyrolysis, chemical vapor deposition CVD, mechanical stripping, and hydrothermal reduction methods for the preparation of graphene crystal film have the drawbacks of complex process, high energy consumption, and high cost, and they are limited by the number of active sites on the surface of graphene and the macroscopic scale of electrochemistry. The traditional graphene electrode materials are still difficult to reach the theoretical value. Therefore, the development of 3D graphene crystal films with stronger bulk effect is achieved by choosing a simple, efficient, low-cost, and controllable preparation strategy. In recent years, the development of high-energy beam current-induced techniques for the preparation of macroscopic-thickness three-dimensional graphene crystal films has gradually attracted attention, and the prepared graphene materials not only maintain excellent crystal quality and rich pore structure, but also feature macroscopic thickness, exhibiting a more excellent bulk specific capacitance when used as electrode materials. Herein, the controllable preparation strategy of 3D graphene crystal films, the common schemes for modifying 3D graphene crystal films, and the recent research progress of their 3D graphene crystal film electrode materials applied in supercapacitors are presented. From the 3D graphene crystal film preparation strategy, the basic principles of various high-energy beam current induction techniques for the preparation of 3D graphene crystal film are described, and the controllable thickness of 3D graphene crystal film prepared by various strategies and the further precise regulation are analyzed. By summarizing the modification and composite methods of graphene crystal film in recent years and reviewing the application of 3D graphene crystal film in supercapacitors, it is concluded that the current macro-thickness 3D graphene electrodes need to be solved, and the opportunities and challenges that may be faced by the large-scale application of graphene electrodes in commercial supercapacitors are proposed. Controllable preparation strategies mainly include CO2 laser and high-energy electron beam preparation methods. In CO2 laser preparation method, through the patternable design of CO2 laser, the adjustable parameter and precursor are used to improve the cross-section thickness of the prepared graphene crystal film to achieve accurate adjustment. In high-energy electron beam preparation method, the electron beam of high kinetic energy, low reflective properties, and high penetration is used to make the three-dimensional graphene film in the macro-scale maintain a good overall uniformity, but its application in commercial supercapacitors may face challenges. The high-energy electron beam preparation method is mainly based on the high kinetic energy and low reflection characteristics of the electron beam, and the high penetration force makes the three-dimensional graphene film maintain a good overall uniformity in the macro scale, thus realizing the controllable preparation of the graphene crystal film. Due to the laser-induced 3D graphene crystal film with high conductivity, high crystallinity, adjustable macro-thickness, porous structure, and rich specific surface area, it is possible to scale up the application of 3D graphene crystal film with macro-thickness in commercial supercapacitors in the future. Currently, 3D graphene crystal films can be scanned in situ by high-energy beam current (laser beam or electron beam) to achieve controlled preparation of commercial polymer films, but as the thickness continues to accumulate, although the number of electrochemical reaction active sites has been significantly improved, the volume effect of the 3D graphene crystal film also reaches a peak in the charging process, which has been completed before ions can be delivered to the maximum depth of access. The problem of ineffective active sites has not yet been well solved, so two possible future solution strategies are proposed based on the above research progress. One is to construct orderly distributed gradient pores on the 3D graphene crystal film by drawing on the template method of pore fabrication or laser array pretreatment of precursors, so that the pores remain highly connected from the top of the electrode material to the bottom, and thus improved ion transfer efficiency is obtained. It is also possible to pre-treat commercial PI films with micro-pore arrays by lasers with smaller laser spots, and then prepare 3D graphene crystal films by in situ scanning with CO2 lasers, reserving top-down pore channels before the formation of graphene, and preserving the original hierarchical porous structure on the pore walls, which will ultimately lead to the improvement of the accessibility of ion transfer. It is hoped that solving the remaining problems of graphene crystal films can break through the performance limitations of graphene crystal films, and gradually push the supercapacitors made of graphene crystal film materials to the commercialization market. |
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