ZHONG Li,XU Zheng,KANG Jun,REN Kaixiang.Controllable Preparation Strategies of Advanced 3D Graphene Crystal Film and Its Application in Supercapacitor[J],54(11):32-49
Controllable Preparation Strategies of Advanced 3D Graphene Crystal Film and Its Application in Supercapacitor
Received:December 11, 2024  Revised:February 18, 2025
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DOI:10.16490/j.cnki.issn.1001-3660.2025.11.003
KeyWord:3D structure  graphene crystal  macro thickness  film electrode  supercapacitor
           
AuthorInstitution
ZHONG Li School of Mechatronics and Vehicle Engineering, Chongqing Jiaotong University, Chongqing , China
XU Zheng School of Mechatronics and Vehicle Engineering, Chongqing Jiaotong University, Chongqing , China
KANG Jun Department of Chemistry, University of Science and Technology of China, Hefei , China;Institute of Solid-State Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei , China
REN Kaixiang School of Mechatronics and Vehicle Engineering, Chongqing Jiaotong University, Chongqing , China
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Abstract:
      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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