Facile regulation of carbon framework from the microporous to low-porous via molecular crosslinker design and enhanced Na storage

Facile regulation of carbon framework from the microporous to low-porous via molecular crosslinker design and enhanced Na storage
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通过分子交联剂设计和增强的钠储存轻松调节碳骨架从微孔到低孔

DOI:
10.1016/j.carbon.2020.05.081
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发表时间:
2020-10
期刊:
影响因子:
10.9
通讯作者:
Stefan Kaskel
Stefan Kaskel
中科院分区:
材料科学2区
文献类型:
--
作者:
Fei Xu;Haojie Han;Yuqian Qiu;En Zhang;Hlib Repich;Changzhen Qu;Huiwu Yu;Hongqiang Wang;Stefan Kaskel

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通过分子设计方法将碳框架从微孔到无孔的合理操作是有趣但具有挑战性的。在这里,我们报告了一个通用的策略,通过在聚苯乙烯(PS)前体中精心设计的分子交联剂,将微孔碳骨架转化为低孔骨架。通过Scholl反应在PS中直接偶联苯环产生具有低孔骨架的超交联PS衍生碳,而通过溶剂编织策略将亚甲基交联剂插入PS中导致微孔碳骨架。结果表明,亚甲基交联剂的功能作为分子尺度的软模板,促进微孔,而直接连接PS链促进芳构化,并减轻热解过程中的异构体的形成。由相似的前体和热解条件得到的不同的碳骨架为结构-性能关系的研究提供了一个有趣的平台,初步例证了钠离子存储的应用。低孔隙率碳由于其低表面积和增强的Na插入到伪石墨微晶结构中而显示出较高的初始库仑效率和上级容量。目前的协议开辟了新的途径,在分子水平上灵活的碳框架孔隙率操纵,并将引发进一步的努力,为低孔隙率的碳在能量存储。
Rational manipulation of the carbon framework from the microporous to nonporous via a molecular design approach is interesting but challenging. Herein, we report a versatile strategy for transforming the microporous carbon framework to the low porous one by an elaborate molecular crosslinker design in the polystyrene (PS) precursor. Direct coupling of benzene rings in PS via Scholl reaction yields hypercrosslinked PS-derived carbon with low porous framework, while insertion of methylene crosslinker into PS via a solvent knitting strategy leads to microporous carbon framework. The results show that methylene crosslinker functions as molecular-scale soft templates for facilitating micropores, whereas direct linking PS chains promotes aromatization and mitigates micropore formation during the pyrolysis. The distinct carbon frameworks derived from similar precursor and pyrolysis condition provide an intriguing platform for structure-property relationship study, as preliminarily exemplified by the application in Na ion storage. The low-porosity carbon shows higher initial Coulombic efficiency and superior capacity thanks to its low surface area and enhanced Na insertion into pseudo-graphitic microcrystal structure. The present protocol opens up new avenues towards flexible carbon framework porosity manipulation at molecular level and would trigger further efforts for low-porosity carbons in energy storage.
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