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Polyoxometalate-Incorporated Metallapillararene/Metallacalixarene Metal-Organic Frameworks as Anode Materials for Lithium Ion Batteries

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journal contribution
posted on 23.06.2017 by Xi-Ya Yang, Tao Wei, Ji-Sen Li, Ning Sheng, Pei-Pei Zhu, Jing-Quan Sha, Tong Wang, Ya-Qian Lan
A series of remarkable crystalline compounds containing metallapillararene/metallacalixarene metal-organic frameworks (MOFs), [Ag5(pyttz)3·Cl·(H2O)]­[H3SiMo12O40]·3H2O (1), [Ag5(trz)6]­[H5SiMo12O40] (2), [Ag5(trz)6]­[H5GeMo12O40] (3), and [Ag5(trz)6]­[H4PW12O40] (4) (pyttz = 3-(pyrid-4-yl)-5-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolyl, trz = 1,2,4-triazole), have been obtained by using a simple one-step hydrothermal reaction of silver nitrate, pyttz for 1 and trz for 24, and Keggin type polyoxometalates (POMs). Crystal analysis reveals that Keggin POMs have been successfully incorporated in the windows of the metallapillararene/metallacalixarene MOFs in compounds 14. In addition, the Keggin silicomolybdenate-based hybrid compounds 1 and 2 were used as anode materials in lithium ion batteries (LIBs), which exhibited promising electrochemical performance with the first discharge capacities of 1344 mAh g–1 for 1 and 1452 mAh g–1 for 2, and this stabilized at 520 mAh g–1 for 1 and 570 mAh g–1 for 2 after 100 cycles at a current density of 100 mA g–1. The performances are better than that of (NBu4)4[SiMo12O40] matrix and commercial graphite anodes.