纺织学报 ›› 2024, Vol. 45 ›› Issue (06): 210-218.doi: 10.13475/j.fzxb.20221204802

• 综合述评 • 上一篇    下一篇

生物质基碳气凝胶及其在储能器件中应用研究进展

高志浩1,2, 宁新1,2,3, 明津法1,2,3()   

  1. 1.青岛大学 纺织服装学院, 山东 青岛 266071
    2.青岛大学 非织造材料与产业用纺织品创新研究院,山东 青岛 266071
    3.特型非织造材料山东省工程研究中心, 山东 青岛 266071
  • 收稿日期:2022-12-27 修回日期:2023-07-25 出版日期:2024-06-15 发布日期:2024-06-15
  • 通讯作者: 明津法(1984—),男,副教授,博士。主要研究方向为非织造新材料开发。E-mail: mingjinfa@qdu.edu.cn。
  • 作者简介:高志浩(1998—),男,博士生。主要研究方向为微纳米纤维的绿色制造及功能化技术。
  • 基金资助:
    生物多糖纤维成形与生态纺织国家重点实验室课题(RZ2000003348);生物多糖纤维成形与生态纺织国家重点实验室课题(ZDKT202109)

Research progress in biomass-based carbon aerogels in energy storage device

GAO Zhihao1,2, NING Xin1,2,3, MING Jinfa1,2,3()   

  1. 1. College of Textile & Clothing, Qingdao University, Qingdao, Shandong 266071, China
    2. Industrial Research Institute for Specialty Nonwoven Materials, Qingdao University, Qingdao, Shandong 266071, China
    3. Shandong Engineering Research Center for Specialty Nonwoven Materials, Qingdao, Shandong 266071, China
  • Received:2022-12-27 Revised:2023-07-25 Published:2024-06-15 Online:2024-06-15

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摘要：

为提高生物质基碳气凝胶的电化学性能,促进其在储能领域的产业化应用,对储能器件领域用生物质基碳气凝胶材料进行了系统评述。首先介绍了目前制备生物质基碳气凝胶的主要方法,即凝胶炭化法、水热炭化法和直接炭化法,并对比分析了3种方法的优缺点。分别总结了3类生物质基碳气凝胶在超级电容器和锂离子电池等储能器件中的最新研究进展,包括未经改性的纯生物质基碳气凝胶以及通过金属掺杂和杂原子掺杂改性的复合生物质基碳气凝胶,并重点阐述了其材料设计和微观结构与电化学性能之间的关系。最后在对研究现状进行深入分析的基础上,展望了生物质基碳气凝胶未来的研究方向和发展前景,指出提高原料利用率、改善整体环保性以及调控结构性能将会成为今后的热点方向,而生物质基碳气凝胶也势必将作为一种新型的绿色电化学能源材料而得到蓬勃发展。

关键词: 生物质基碳气凝胶, 储能器件, 材料设计, 微观结构, 电化学性能

Abstract:

Significance With the increasing scarcity of oil, coal and other resources, the development of green and efficient energy storage materials has gradually become the focus of relevant research. Carbon aerogels have been recognized as one of the most promising candidate for energy storage materials due to its high porosity, low density, good electrical conductivity and high temperature resistance. Biomass materials are the most cost-effective, environmentally friendly and sustainable precursors for fabricating carbon aerogels. The preparation of biomass-based carbon aerogel and its application in the field of energy storage have attracted much research attention in the recent years. The release of China's "carbon peak and carbon neutralization" strategy further promotes its research and application. To foster the development of biomass-based carbon aerogels, a systematically overview on biomass-based carbon aerogels for energy storage devices was carried.

Progress Based on the differences in raw material form, the preparation methods of biomass-based carbon aerogel are summarized as gel carbonization, hydrothermal carbonization and direct carbonization. Three preparation methods including the technological process, application range and advantages/disadvantages are compared and analyzed. At present, there are biomass-based carbon aerogels which are widely used, namely unmodified pure biomass-based carbon aerogels and composite biomass-based carbon aerogels modified by metal doping and heteroatom doping. This work summarizes the latest research progress in energy storage devices such as supercapacitors and lithium-ion batteries. Material design and microstructure are the main factors affecting the electrochemical performance of biomass-based carbon aerogel. Suitable doping and uniform nanostructure will help to improve its comprehensive performance. The energy storage device using this biomass-based carbon aerogel as the electrode shows superior rate capability and cycling performance during the test. In addition, relevant studies have shown that biomass-based carbon aerogels can also be used as electrodes for fuel cells, zinc-air batteries, and lithium-sulfur batteries. Some researchers attempted to use it to modify the battery separator and have achieved certain results.

Conclusion and Prospect As a new type of functional aerogel, biomass-based carbon aerogels possess excellent properties of aerogel (high specific surface area, high porosity and low density), carbon materials (heat resistance and electrical conductivity) and biomass materials (economical and biodegradable). Based on these advantages, biomass-based carbon aerogel has been preliminarily applied in supercapacitors and some secondary batteries. In recent years, it has becomes one of the hotspot research fields in energy storage materials. Innovative research methods and theories are constantly emerging around the functional preparation, material characterization and product application of biomass-based carbon aerogels. However, there are still some uncertainties and challenges in the process of industrial production and application of biomass-based carbon aerogels. Future research can be focussed on the following aspects. ① Development of new biomass precursors with more attention to be paided to the utilization rate of biomass materials and the impact of raw materials on the structure and properties of carbon aerogel. ② Innovation and improvement of the preparation process of biomass-based carbon aerogels, aiming for large-scale production of carbon aerogels with uniform structure and excellent performance on the basis of reducing cost and energy consumption. ③ Replacement of man-made materials with natural renewable materials (such as silk fibroin extracted from cocoon silk), in forming the combination with biomass-based carbon aerogel, so as to improve the overall environmental protection of energy storage devices. ④ Further exploration into the influence mechanism of production process including composite process on biomass-based carbon aerogels to achieve controllable optimization of the microstructure and comprehensive properties of carbon aerogels so as to expand application into more prospective emerging material fields.

Key words: biomass-based carbon aerogel, energy storage device, material design, microstructure, electrochemical performance

中图分类号: 

  • TQ352.7

图1

生物质基碳气凝胶的前驱体来源"

表1

凝胶炭化法的主要步骤及机制"

过程 机制
溶解/提取 原料溶解于溶剂体系中,在不改变其化学结构的前提下,破坏分子链非晶区结构从而改变物质晶型,
最终通过提取获得微/纳米纤维素分散液
溶胶-凝胶[10] 均匀分布的凝胶基元借助聚合反应形成相互交联的三维网络结构
干燥[11] 超临界干燥 通过加压和升温使溶剂成为超临界态的流体,以此来降低气液界面的表面张力,从而保持凝胶原本的结构
冷冻干燥 凝胶中的溶剂被冷冻成冰晶,在之后的真空干燥过程中升华消失
常压干燥 将湿凝胶或前驱体溶液置于大气压下直接干燥
炭化 在气凝胶三维多孔结构的基础上,通过炭化处理形成高度无序的无定型碳以及石墨结构

图2

不同生物质基碳气凝胶的制备过程"

表2

超级电容器用生物质基碳气凝胶性能参数"

电极材料 制备方法① 比表面积/
(m2·g-1)		 比电容/
(F·g-1)		 倍率性能②/% 循环性能③/% 文献
棉花 直接炭化法 2 307 283 (1 A/g) 79 (1~100 A/g) 97 (4 A/g(2 000圈)) [17]
藤条 水热炭化法 2 436 221 (0.5 A/g) 80 (0.5~20 A/g) 100 (5 A/g(10 000圈)) [18]
RGO/竹纤维素 凝胶炭化法 1 957 351 (10 mV/s) 90 (10~200 mV/s) 99 (5 A/g(5 000圈)) [19]
MnOx/萝卜 水热炭化法 203 557 (1 A/g) 43 (0.5~10 A/g) 48 (10 A/g(10 000圈)) [20]
NiCo2S4/废西瓜皮 水热炭化法 56 1 019 (1 A/g) 74 (0.5~20 A/g) 87 (10 A/g(10 000圈)) [21]
Fe3O4/西瓜 水热炭化法 - 333 (1 A/g) 39 (5~100 mV/s) 96 (1 A/g(1 000圈)) [22]
Fe3O4/壳聚糖 凝胶炭化法 - 316 (0.5 A/g) 56 (0.5~20 A/g) 83 (5 A/g(5 000圈)) [23]
氮掺杂甲壳素 水热炭化法 2 540 249 (1 A/g) 66 (1~10 A/g) 98 (2 A/g(15 000圈)) [24]
氧氮掺杂海藻酸钠 凝胶炭化法 1 695 342 (2 A/g) 69 (0.5~3 A/g) 96 (1.5 A/g(2 000圈)) [25]
磷掺杂松果 水热炭化法 1 176 228 (10 mV/s) 33 (2~200 mV/s) - [27]
硫磷掺杂废马铃薯皮 凝胶炭化法 1 912 323 (1 A/g) 65 (1~15 A/g) 98 (10 A/g(5 000圈)) [28]
氮掺杂壳聚糖 凝胶炭化法 2 529 267 (1 A/g) 86 (0.5~10 A/g) 100 (5 A/g(10 000圈)) [30]

表3

锂离子电池用生物质基碳气凝胶性能参数"

电极材料 制备方法① 比表面积/
(m2·g-1)		 孔径大
小/nm		 倍率性能②/
(mA·h·g -1)		 循环性能③/(mA·h·g-1) 文献
桉木浆 凝胶炭化法 489 - 416~219 (2~20 A/g) 409 (1 A/g(1 000圈)) [31]
MnO2/海藻酸钠 凝胶炭化法 210 1.8-10 574~33 (0.1~1 A/g) 490 (0.2 A/g(120圈)) [33]
氮掺杂红藻 水热炭化法 2 290 1.5-4 320~220 (2~10 A/g) 572 (1 A/g(600圈)) [34]
氮掺杂竹纤维素 凝胶炭化法 696 0.5-5 631~289 (1~20 A/g) 651 (1 A/g(1 000圈)) [35]
氮掺杂海藻酸钠 凝胶炭化法 2 136 3.5 550~190 (0.37~7.4 A/g) 550 (0.37 A/g(300圈)) [37]
Fe3O4/褐藻 水热炭化法 297 <5 1570~615 (0.1~4 A/g) 1 176 (1 A/g(200圈)) [38]

图3

不同生物质基碳气凝胶的相关作用机制"

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