Ma Zi-Hui, Yang Tao, Song Yan, Tian Xiao-Dong, Liu Zheng-Yang, Gong Xiang-Jie, Liu Zhan-Jun
CAS Key Laboratory for Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.
CAS Key Laboratory for Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China.
J Colloid Interface Sci. 2024 May;661:436-449. doi: 10.1016/j.jcis.2024.01.141. Epub 2024 Jan 24.
Hyper cross-linked polymers (HCPs), as a key precursor of hard carbon (HC) anode materials, stand out because of their capacity for molecular-scale structural design and comparatively straightforward preparation techniques, which are not seen in other porous materials synthesized procedure. A novel synthesis method of HCPs is developed in this paper, which is through the incorporation of functional macromolecules, the structural control and heteroatom doping of the product has been achieved, thus augmenting its electrochemical performance in batteries. In this work, carbonized tetraphenylporphyrin zinc (TPP-Zn) doped HCP-based hard carbon (CTHCP) with stable structure was prepared by Friedel-Crafts reaction and carbonization by using naphthalene and trace TPP-Zn as monomers, dimethoxybenzene (DMB) as crosslinking agent and FeCl as catalyst. The introduction of TPP-Zn, a functional macromolecule with unique two-dimensional structure, realized the pore structure regulation and N doping of the raw carbonized HCP-based hard carbon (CHCP). The results showed that CTHCP had higher mesoporous volume, N content and wider layer spacing than CHCP. In addition, CTHCP anode exhibited excellent Li/Na storage performance, initial reversible capacity, rate performance and long cycle life. More amount of N-containing (N-5) active sites and mesoporous content in CTHCP anode was the main reason for the improvement of Na storage effect. While the increased interlayer spacing had a greater effect on the lithium storage capacity. This study uncovered the design rules of HC anode materials suitable for Li/Na batteries and provided a new idea for the preparation of high-performance HC anode materials.
超交联聚合物（HCPs）作为硬碳（HC）负极材料的关键前驱体，因其在分子尺度上的结构设计能力和相对简单的制备工艺而脱颖而出，这是其他多孔材料合成过程中所没有的。本文开发了一种新型的HCPs合成方法，通过引入功能大分子，实现了产物的结构控制和杂原子掺杂，从而提高了其在电池中的电化学性能。在这项工作中，以萘和微量四苯基卟啉锌（TPP-Zn）为单体，二甲氧基苯（DMB）为交联剂，FeCl为催化剂，通过傅克反应和碳化制备了结构稳定的碳化四苯基卟啉锌掺杂HCP基硬碳（CTHCP）。具有独特二维结构的功能大分子TPP-Zn的引入，实现了原始碳化HCP基硬碳（CHCP）的孔结构调控和N掺杂。结果表明，CTHCP比CHCP具有更高的中孔体积、N含量和更宽的层间距。此外，CTHCP负极表现出优异的Li/Na存储性能、初始可逆容量、倍率性能和长循环寿命。CTHCP负极中更多的含N（N-5）活性位点和中孔含量是Na存储效果改善的主要原因。而层间距的增加对锂存储容量有更大的影响。本研究揭示了适用于Li/Na电池的HC负极材料的设计规则，为高性能HC负极材料的制备提供了新思路。
