Characteristic, structure, preparation and applications of soft and hard carbons

doi:10.11949/0438-1157.20230874

Abstract

Abstract:

In recent years, industries such as energy-saving, environmental protection, intelligent manufacturing and green low-carbon continue to develop, with the gradual implementation of the “14th Five-Year Plan” policy, carbon materials have played a crucial irreplaceable role. Soft and hard carbons have attracted wide attention from the scientific and industrial communities owing to their belongings to an important carbon material like graphite, graphene and nanocarbon. Thus, there is a vigorous growth in the development and utilization of soft and hard carbons in numerous fields such as new energy, new technology and ecological environment. First, the importance, research hotspots and historical development (in terms of professional terminology) of soft and hard carbons are introduced. The structure characteristics and classic structure models of soft and hard carbons are systematically summarized. Then, a comprehensive overview is focused on the preparation methods (e.g., gas-phase, liquid-phase and solid-phase carbonizations) and control means (including the rational selection of carbonaceous precursors), as well as regulating measures, thermal evolution laws and mutual transformation of microcrystalline structure. While giving a brief overview of the applications of soft/hard carbon in traditional fields, it also focuses on its applications in emerging fields such as energy storage and conversion, advanced catalytic materials, and efficient adsorption and environmental protection. Finally, a summary and outlook is presented on the research prospects and development trends of soft and hard carbons, offering an overall perspective for the design and development of soft and hard carbons with low-cost production, controllable fine-structure, adjustable excellent-performance, and high value-added and high-end applications.

Key words: soft and hard carbons, structure, model, control, preparation, application

摘要：

近年来，节能环保、智能制造和绿色低碳等行业持续发展壮大，伴随国家“十四五”政策逐步落实，炭材料起到了举足轻重和不可替代的作用。软/硬炭作为和石墨、石墨烯、纳米炭同等重要的一种炭材料，引起了科学界和产业界的广泛关注，目前在新能源、新技术和生态环境等领域的开发和应用方兴未艾。首先介绍了软/硬炭的重要性、研究热度及其专业术语的历史发展，并对其结构特性和经典结构模型进行了系统梳理；然后围绕软/硬炭的制备方法（气相、液相和固相炭化）及控制手段（包括碳质原料的合理选取）、微晶结构调控措施、高温衍变规律及相互转化进行了全面概括；简要概述软/硬炭在传统领域应用的同时，重点介绍了其在能源存储与转化、先进催化材料和高效吸附环保等新兴领域的应用；最后对软/硬炭的研发前景和发展趋势进行了总结和展望，为设计和开发低成本生产、精细结构及优异性能调控、高附加值和高端领域应用的软/硬炭提供了一个全面视角。

关键词: 软/硬炭, 结构, 模型, 控制, 制备, 应用

CLC Number:

TQ 127.1

Shuo LI, Zhepeng ZHAO, Zhengwei CUI, Guanming YUAN, Bin XU. Characteristic, structure, preparation and applications of soft and hard carbons[J]. CIESC Journal, 2023, 74(12): 4792-4809.

李烁, 赵哲鹏, 崔正威, 袁观明, 许斌. 软/硬炭的特性、结构、制备及应用[J]. 化工学报, 2023, 74(12): 4792-4809.

Figures/Tables 10

Fig.1 (a) Numbers of published articles on soft and hard carbons indexed by Web of Science; (b) Structure characteristics and applications of soft and hard carbons

Fig.2 A timeline showing eighty-year historic evolution of soft and hard carbons from 1942 to 2023

Fig.3 (a) Typical structure models of various carbon materials[32]； (b) Microcrystal structure characteristics of graphite, graphitizable soft carbon and non-graphitizable hard carbon[37-38]

Fig.4 Various structure models of soft and hard carbons in references

Fig.5 Structure models of different hard carbons[47-51]

Fig.6 Optical textures of mesophase liquid crystals (spheres and coalescence) are formed by heat treatment

Fig.7 Microcrystal evolution models of carbonaceous precursors during carbonization-graphitization process

Fig.8 (a) Structural changes of hardly and easily graphitized carbons during graphitization[83]； (b) Formation of hard carbon and its structure evolution as a function of temperature[84-85]

Fig.9 Composite types of soft and hard carbons

Table 1 Comprehensive comparison of soft and hard carbons in structure， preparation， properties and applications

项目	软炭	硬炭
结构特性	结构较为密实、硬度较小，石墨微晶较大、排列较为有序，易石墨化、缺陷较少	以多孔结构为主、硬度相对较大，石墨微晶较小、排列相对无序，难石墨化、缺陷较多
微观结构
代表种类	石油焦、针状焦、中间相炭微球、沥青基泡沫炭、中间相沥青基碳纤维、气相热解炭(石墨)	树脂(酚醛树脂、糠醛树脂等)炭、有机聚合物(聚丙烯腈、聚乙烯醇等)热解炭、生物质热解炭、炭黑(乙炔黑)
原料	石油沥青、煤沥青、重质油、稠环芳烃等	生物质、有机高分子聚合物、改性沥青、煤及其衍生物等
制备方法	气相炭化、液相炭化(主)、固相炭化	热解炭化、水热炭化、活化处理、氧化交联、静电纺丝、模板法
传统应用	导热材料、石墨电极、导电填料、耐磨材料、密封材料、增强材料	传统燃料、绝热材料、染料、耐火材料、电极材料、吸附剂
新兴应用	新型电池、超级电容器、电极材料、复合材料等	高效吸附材料、储氢材料、储能材料、新型电极、催化剂及载体等

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