Design of metal-organic frameworks for improving pseudo-solid-state magnesium-ion electrolytes:Open metal sites,isoreticular expansion,and framework topology  

作　　者：Yun Zheng Junpo Guo De Ning Yike Huang Wen Lei Jing Li Jianding Li Götz Schuck Jingjun Shen Yan Guo Qi Zhang Hao Tian Hou Ian Huaiyu Shao 

机构地区：[1]Guangdong-Hong Kong-Macao Joint Laboratory for Photonic-Thermal-Electrical Energy Materials and Devices,Institute of Applied Physics and Materials Engineering,University of Macao,Avenida da Universidade,Macao 999078,China [2]Centre for Photonics Information and Energy Materials,Shenzhen Institutes of Advanced Technology,Chinese Academy of Sciences,Shenzhen 518055,China [3]The State Key Laboratory of Refractories and Metallurgy,Wuhan University of Science and Technology,Wuhan 430081,China [4]School of Science,Huzhou University,Huzhou 313000,China [5]Helmholtz-Center Berlin for Materials and Energy,Albert-Einstein-Street,Berlin 1512489,Germany [6]Cancer Center and Institute of Translational Medicine,Faculty of Health Sciences,University of Macao,Macao 999078,China

出　　处：《Journal of Materials Science & Technology》2023年第13期15-27,共13页材料科学技术（英文版）

基　　金：acknowledges the Guangdong-Hong Kong-Macao Joint Laboratory(Grant No.2019B121205001);the Macao Science and Technology Development Fund(FDCT)for funding(Project No.0098/2020/A2);this work was also partially supported by the Science and Technology Program of Guangdong Province of China(Grant No.2020A050515007);the Multi-Year Research Grant(MYRG)from University of Macao(Project No.MYRG2019-00055-IAPME);support by FDCT of Macao under Grants 0015/2021/AGJ and 0130/2019/A3;by the University of Macao under Grant MYRG2018-00088-IAPME.

摘　　要：The design criteria for metal-organic frameworks(MOFs)have been established by evaluating the rela-tionship between their key characteristics and magnesium-ion conductivity based on three types of sec-ondary building blocks(Zn_(4)O(CO_(2))_(6):MOF-5 and MOF-177;Cu_(2)(CO_(2))4:MOF-199,MOF-143,MOF-14,and MOF-399;Cu_(2)O_(2)(CO_(2))2:Cu-MOF-74)to achieve pseudo-solid-state magnesium-ion conduction.We found that open-metal sites and channel layouts play a pivotal role in promoting magnesium-ion transport dy-namics at reduced activation energy,transforming MOF scaffolds into ionic-channel analogs.X-ray ab-sorption spectroscopy combined with Raman and Fourier-transform infrared spectroscopy predicted the chemical environment,solvents,and anions that occupied coordinatively unsaturated metal sites.The chemical compositions of electrolytes determined by^(1)H-NMR(nuclear magnetic resonance)and organic elemental analysis confirmed that isoreticular expansion increases the molar percentage of charge carri-ers,providing high conductivity.The current research systematically reveals the impacts of different MOF characteristics on ionic conduction performance,paving the way for the construction of a new class of fast and selective multivalent-ion pseudo-solid electrolytes.

关 键 词：Magnesium conduction Magnesium battery Metal-organic frameworks Solid-state electrolytes Reticular chemistry 

分 类 号：TB34[一般工业技术—材料科学与工程]