多孔石墨烯薄膜结构优化及其电容性能研究

钟厉, 廖声朝, 康俊, 韩西

表面技术 ›› 2025, Vol. 54 ›› Issue (4) : 221-232.

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表面技术 ›› 2025, Vol. 54 ›› Issue (4) : 221-232. DOI: 10.16490/j.cnki.issn.1001-3660.2025.04.018
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多孔石墨烯薄膜结构优化及其电容性能研究

  • 钟厉1, 廖声朝1, 康俊2, 韩西3
作者信息 +

Structure Optimization and Capacitive Properties of Porous Graphene Films

  • ZHONG Li1, LIAO Shengzhao1, KANG Jun2, HAN Xi3
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文章历史 +

摘要

目的 解决多孔石墨烯薄膜作为电极时离子传输受阻碍的问题。方法 提出一种先将石墨烯前驱体预碳化处理,随后利用多步激光刻蚀方法来优化所制备的多孔石墨烯薄膜结构的方法,对石墨烯薄膜的表面形貌、晶体质量、湿润性和电化学性能进行表征,并探索其在电化学储能器件中的应用。结果 将石墨烯前驱体在300 ℃的温度下预碳化处理2 h后,可以使其在后续的激光刻蚀处理中形成具有稳定结构的石墨烯薄膜材料,这与预碳化导致前驱体中的有机小分子分解,使内部交联程度更高有关,从而在CO2激光的重复作用下保持良好的基底稳定性。拉曼光谱的分析结果表明,预碳化处理后的样品在激光重复刻蚀的过程中可以对石墨烯结构优化过程进行直接观测,且在温度300 ℃下处理后具有更宽的演化范围。SEM扫描电子显微镜的表征结果显示,300 ℃预碳化后前驱体衍生的石墨烯薄膜具有典型的三维网络多孔结构,形成天然的离子传输通道。此外,电阻行为分析结果表明石墨烯薄膜具有一定程度的晶体缺陷能获得更优异的离子传输能力,促进电化学反应的发生,在1 mol/L的H2SO4电解质中面积比电容为124.6 mF/cm2,将其组装成微型电化学储能器件后也保持了优异的储电能力和循环稳定性。结论 通过优化多孔石墨烯薄膜的结构来解决离子传输问题,进而获得显著提高的电化学性能,为制备兼具高储电能力和优异稳定性的电极材料提供了设计思路。

Abstract

With the increasing demand of energy, high energy storage and excellent conversion efficiency are urgently needed by energy storage devices. Therefore, the research of electrochemical energy storage devices with both high energy density and high-power density is still a challenge. To further improve the capacity of electrochemical energy storage devices, more precise material science analysis has been conducted on electrochemical energy storage, revealing that the performance of electrochemical energy storage devices is related to the structure of electrode materials. Nowadays, a plenty of studies have found that three-dimensional porous graphene with macro thickness is one of the ideal electrode materials for electrochemical energy storage devices. Due to the strict experimental conditions and preparation technology, the crystal quality and pore connectivity of porous graphene as electrode materials are still worthy of further improvement. Commercial phenolic resin (PR) is one of the ideal precursors for the preparation of porous carbon materials due to its high carbon residue rate. The phenolic resin is pretreated at high temperature to obtain a stable structure, and then the optimized pore structure and crystal quality are expected to be obtained on the phenolic resin derived graphene films by low energy laser etching, thus significantly improving the electrochemical properties. Besides, laser induced technology for the preparation of graphene materials has gradually become the mainstream way for the preparation of porous graphene due to its simple method, rapid synthesis, low cost, and low environmental pollution characteristics. However, the limited ions transport efficiency still remains. In this work, under the above condition, the graphene precursor was carbonized in advance, and then the structure of the porous graphene films was optimized by low-energy multi-step laser etching. The surface morphology, crystal quality, wettability and electrochemical properties of the prepared graphene films were characterized. The pre-carbonization of the graphene precursor for 2 h at 300 ℃ could improve the stability of the graphene film material prepared in the subsequent multi-step laser treatment. The pre-carbonization process caused the decomposition of small organic molecules in the precursor, and the internal cross-linking degree became higher, which could better cope with the repeated etching of CO2 laser. The results of Raman spectroscopy revealed that the graphene structure optimization process could be directly observed in the process of low energy laser repeated etching, which was of great significance for screening the optimal graphene film structure. SEM images demonstrated that the pre-carbonized carbon precursor derived graphene films at 300 ℃ had a typical three- dimensional network porous structure, which provided a reliable structure for efficient ion transport. During the electrochemical performance test, the area specific capacitance reached 124.6 mF/cm2 in 1 mol/L H2SO4 solution, and excellent storage capacity and cycle stability were maintained after assembly into a MSC device. In this paper, the ion transport problem is improved by optimizing the structure of porous graphene films, and the electrochemical performance is significantly improved, which is important for the design of graphene electrode with both high electrical storage capacity and excellent stability.

关键词

多孔石墨烯薄膜;结构优化;预碳化处理;多步激光刻蚀;电容性能

Key words

porous graphene films; structure optimization; pre-carbonization process; multi-step laser etching; capacitive performance

引用本文

导出引用
钟厉, 廖声朝, 康俊, 韩西. 多孔石墨烯薄膜结构优化及其电容性能研究[J]. 表面技术. 2025, 54(4): 221-232
ZHONG Li, LIAO Shengzhao, KANG Jun, HAN Xi. Structure Optimization and Capacitive Properties of Porous Graphene Films[J]. Surface Technology. 2025, 54(4): 221-232

基金

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)

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