能源存储与转化用微纳超结构碳：现状与建议

doi:10.3981/j.issn.2097-0781.2024.03.008

前瞻科技 ›› 2024, Vol. 3 ›› Issue (3): 97-110.DOI: 10.3981/j.issn.2097-0781.2024.03.008

能源存储与转化用微纳超结构碳：现状与建议

程醒^,^*(), 李曈^,^*(), 司知蠢, 干林, 吕伟, 康飞宇^†()

清华大学深圳国际研究生院，深圳 518000

收稿日期:2024-06-24 修回日期:2024-07-01 出版日期:2024-09-20 发布日期:2024-09-18
通讯作者: †
作者简介:程醒，博士。主要从事高镍正极材料结构改性及匹配聚合物固态电解质等研究。电子信箱：chengxing@sz.tsinghua.edu.cn。
李瞳，博士研究生。主要从事碳材料在锂金属负极中的应用等研究。电子信箱：li-t21@mails.tsinghua.edu.cn。
康飞宇，教授。主要从事储能用碳材料和先进电池研究。解决了天然石墨应用于锂离子微观结构调控和易解理的难题，推动了天然石墨负极和石墨烯应用于锂离子电池的产业化进程；发明了水系锌离子电池，开拓了高安全性多价态金属离子二次电池研发领域；建立了介电耦合陶瓷固态电解质构建策略，为固态电池产业化提供了解决方案。获国家技术发明奖二等奖、教育部自然科学奖一等奖、广东省自然科学奖一等奖、中国建材学会技术发明奖一等奖、中国炭素杰出成就奖、广东省丁颖科技奖和深圳市市长奖。2018—2023年连续入选科睿唯安高被引科学家。出版专著8部，发表论文500余篇，授权发明专利190件。电子信箱：fykang@tsinghua.edu.cn。
* 对论文具有同等贡献
基金资助:
深圳市杰出人才项目;国家重点研发计划(2014CB932400)

Status and Prospect on Micro-nano Superstructured Carbon for Energy Storage and Conversion

CHENG Xing^,^*(), LI Tong^,^*(), SI Zhichun, GAN Lin, LÜ Wei, KANG Feiyu^†()

Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen 518000, China

Received:2024-06-24 Revised:2024-07-01 Online:2024-09-20 Published:2024-09-18
Contact: †
About author:* Equivalent contribution author

摘要/Abstract

摘要：

碳材料作为电极材料或关键组分在诸多能源存储与转化器件中发挥着不可或缺的作用。然而，传统碳材料存在的结构单一、富含缺陷和织构无序等问题严重制约了相关器件性能的提升，难以满足新能源和电动汽车产业的快速发展需求。针对上述问题，文章提出了微纳超结构碳的概念和设计思想，采用结构纳米化、复合化、有序化设计和功能导向组装，构建碳材料跨越“纳-微-宏”的多层次孔道、多尺度网络、多组分界面，获得具有“精准定制、层次有序、厚密联通、多相耦合”基本特征的微纳超结构碳。同时，文章全面综述了微纳超结构碳材料在能源存储与转换器件中应用的国内外最新研究进展，涵盖了锂/钠离子电池、超级电容器、固态电池、水系电池以及氢能转换技术等关键领域，并对未来储能用碳材料的发展方向和应用模式作出展望。

关键词: 微纳超结构碳材料, 能源存储与转换, 锂/钠离子电池, 超级电容器, 燃料电池

Abstract:

Carbon materials are indispensable as electrode materials or key components in energy storage and conversion devices. However, traditional carbon materials suffer from simple structure, massive defects, and disordered texture, which restrict the performance of related devices, making it difficult to meet the rapid development of the new energy and electric vehicle industries. To address the above issues, this review proposed the concept and design principle of micro-nano superstructured carbon. By nanocomposite structure, ordered design, and function-oriented assembly, carbon materials with hierarchical pores, multi-scale networks, and multi-component interfaces across nano-micro-macro scales were constructed. In addition, micro-nano superstructured carbon featuring precise customization, hierarchical order, thick and dense connectivity, and multiphase coupling was obtained. The research progress in the application of micro-nano superstructured carbon materials in energy storage and conversion devices in China and abroad was reviewed, covering key fields such as lithium/sodium ion batteries, supercapacitors, solid-state batteries, aqueous batteries, and hydrogen energy conversion technology. In addition, the future development direction and application mode of carbon materials for energy storage were introduced.

Key words: micro-nano superstructured carbon material, energy storage and conversion, lithium/sodium ion batteries, supercapacitor, fuel cell

程醒, 李曈, 司知蠢, 干林, 吕伟, 康飞宇. 能源存储与转化用微纳超结构碳：现状与建议[J]. 前瞻科技, 2024, 3(3): 97-110.

CHENG Xing, LI Tong, SI Zhichun, GAN Lin, LÜ Wei, KANG Feiyu. Status and Prospect on Micro-nano Superstructured Carbon for Energy Storage and Conversion[J]. Science and Technology Foresight, 2024, 3(3): 97-110.

图/表 7

图1 微纳超结构碳基础模型的模块化

Fig. 1 Modularization of basic model of micro-nano superstructured carbon

图2 筛分型碳孔结构调控和作用机制示意图

Fig. 2 Regulation and mechanism of sieve-type carbon pore structure

图3 包含高电容（>6.8 mA·h/cm2）的LiNi0.9Co0.05Mn0.05O2 （NMC）正极、硫化物固态电解质和不需要过量锂的Ag-C纳米复合负极层组成

Fig. 3 Structure composed of high-capacitance (>6.8 mA·h/cm2) LiNi0.9Co0.05Mn0.05O2 (NMC) cathode electrode, sulfide solid electrolyte, and Ag-C nanocomposite anode electrode requiring no excessive lithium

图4 以稳定的锌负极为目标的三维分层结构石墨烯矩阵设计示意图 Zn沉积在裸Zn（a）、纵向三维石墨烯矩阵（b）和径向三维石墨烯矩阵（c）上。

Fig. 4 Three-dimensional layered graphene matrix for stabling zinc anode electrode

图5 面向燃料电池低Pt催化剂的微纳米碳载体材料设计图（a）表示不同碳载体（Vulcan与HSC碳）中Pt催化剂空间分布的STEM电子三维重构（表示处于孔道内部的Pt，表示暴露于载体表面的Pt）；图（b）表示通过设计具有合适孔道深度的新型介孔碳载体优化Pt催化剂（，分别表示较高活性和较低活性）与Nafion离子聚合物（）的界面结构。

Fig. 5 Design of micro-nano carbon material for low Pt catalysts in fuel cells

图6 面向燃料电池非贵金属催化剂的微纳米碳载体材料设计图（a）和图（b）表示采用MOF为前驱体结合模板法制备的Fe-N-C单原子催化剂及其在燃料电池中的电子/质子/物质输运过程示意图；图（c）表示碳载体表面负载Fe单原子催化剂的高分辨STEM图；图（d）表示调制Fe单原子与碳载体之间的配位结构实现高稳定性的非贵金属催化剂。

Fig. 6 Design of micro-nano carbon material for non-precious metal catalysts in fuel cells

图7 面向电解水制氢的“亲水/疏气”多孔碳基电极材料设计图（a）表示传统电极催化表面，气泡的黏附导致催化活性位点被覆盖；图（b）表示通过微纳米尺度的超亲水/疏气多孔碳基电极设计，有效减小气泡的黏附，显著提升析氢反应的催化性能。

Fig. 7 Design of “hydrophilic/hydrophobic” porous carbon electrode for hydrogen production by water electrolysis

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能源存储与转化用微纳超结构碳：现状与建议

Status and Prospect on Micro-nano Superstructured Carbon for Energy Storage and Conversion

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