分子工程化可持续制备多元素掺杂的分级多孔碳材料用于高性能锌离子存储  

Molecular engineering toward sustainable development of multiple-doped hierarchical porous carbons for superior zinc ion storage

作　　者：刘明权 吴锋 冯鑫 王亚辉 郑路敏 李新 李莹 巩玉腾 白莹 吴川 Mingquan Liu;Feng Wu;Xin Feng;Yahui Wang;Lumin Zheng;Xin Li;Ying Li;Yuteng Gong;Ying Bai;Chuan Wu(School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China;Yangtze Delta Region Academy of Beijing Institute of Technology,Jiaxing 314019,China;School of Aeronautical Engineering,Jiangxi Institute of Economic Administrators,Nanchang 330088,China)

机构地区：[1]School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China [2]Yangtze Delta Region Academy of Beijing Institute of Technology,Jiaxing 314019,China [3]School of Aeronautical Engineering,Jiangxi Institute of Economic Administrators,Nanchang 330088,China

出　　处：《Science China Materials》2023年第2期541-555,共15页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(21975026);the Science and Technology Program of Guangdong Province(2020B0909030004);the Graduate Interdisciplinary Innovation Project of Yangtze Delta Region Academy of Beijing Institute of Technology(Jiaxing,GIIP2021-002)。

摘　　要：具备低价、优异倍率性能、长寿命、高安全性的水系锌离子混合电容器(ZHSCs)是理想的下一代能量存储器件.高比表面积、多级孔、富缺陷的掺杂分级多孔碳(HD-HPCs)是非常有前景的ZHSCs正极材料.但是,可持续且可控原位构筑同时具备多种结构组分优势的HDHPCs仍然面临挑战.本文提出一种新的分子工程化策略,即直接碳化富含多种异质原子的超分子前驱体,便可实现原位构筑多元掺杂HDHPCs.该绿色可持续策略具有多种优势,包括不需要额外的成孔技术、活化剂、模板剂、以及复杂且危险的清洗过程.由于富杂原子超分子前驱体具有较高的活性,高温碳化过程中杂原子以及邻近杂原子的碳原子很容易从碳骨架中脱离,形成丰富的微介孔结构.因此,活性结构与组分优化后的正极材料在水系ZHSCs中0.5和20 A g^(-1)下容量分别达到139.2和88.9 mA h g^(-1),在准固态ZHSCs中0.5 A g^(-1)下容量也能够达到111.5 mA h g^(-1).此外,水系和准固态ZHSCs也具备高能量和功率密度,以及长循环稳定性.理论计算表明多原子掺杂能够协同提升碳材料的导电性,且降低锌离子与碳之间的相互作用能垒,因而提升锌离子的吸附性能.本工作为直接制备HD-HPCs及其电化学储能应用提供了新思路.Aqueous Zn-ion hybrid supercapacitors(ZHSCs)hold great potential as next-generation energy storage devices due to their low cost,excellent rate capability,long cycling life,and high safety.Heteroatom-doped hierarchical porous carbons(HD-HPCs)with integrated high specific surface area,multiscale pores,and abundant defects have been regarded as promising cathode materials for ZHSCs.However,the in situ architecture of HD-HPCs with these multiple advantages via a sustainable and controllable method remains an arduous challenge.Herein,a novel molecular engineering strategy was proposed for the in situ construction of N/P/O-doped HD-HPCs via the direct carbonization of multiple-heteroatom-rich hypermolecules.Such a strategy has multiple advantages,including the exclusion of pore-making techniques,activation agents,templates,and complicated and hazard washing processes,demonstrating its green and sustainable properties.The highly active multiple-heteroatom-rich hypermolecular precursors contributed to the formation of abundant micro/mesopores due to the self-abscission of heteroatoms and heteroatom-contiguous carbon atoms at high carbonization temperatures.Consequently,these active structural/compositional features endowed the optimal cathodes with outstanding storage capacities of 139.2 and 88.9 mA h g^(-1)at 0.5 and 20 A g^(-1)for aqueous ZHSCs,respectively.They also delivered a superior storage performance in quasi-solid ZHSCs(QS-ZHSCs)with a high specific capacity of 111.5 mA h g^(-1)at 0.5 A g^(-1).Superior energy/power densities and long cycling stability were also achieved for aqueous and QS-ZHSCs.The theoretical calculation confirmed the synergetic effects of multiple-atom doping on enhancing the electronic conductivity and reducing the energy barrier between Zn ions and carbon,which promote the Zn-ion adsorption capability.These findings shed fresh light on the straightforward manufacture of superior HD-HPCs for electrochemical energy storage.

关 键 词：正极材料 电化学储能 混合电容器 锌离子 工程化 存储器件 结构组分 杂原子 

分 类 号：TM912[电气工程—电力电子与电力传动]