Wang Deping,Hu Wenming,Fan Wufeng,Xia Xiaohong,Liu Junqiang,Liu Hongbo
Metal-organic frameworks (MOFs) have attracted numerous attentions as anode materials for lithium-ion batteries (LIBs) owing to their unique tunable structures. However, utilizing MOFs in electrochemical devices has been hampered by the inferior electrical conductivity and poor stability that dominate the cycling stability and rate performance of electrodes. Herein, a Ni-PTA/graphene hybrid with porous spherical structure has been successfully constructed by interconnected needle-like Ni-MOFs nanocrystals after the introduction of amine functionalized graphene (NG). The conductivity and structural stability of the composites have been greatly improved due to the chemical bonds formed between the N -containing graphene and the MOFs. When used as anode materials for LIBs, the synthesized Ni-PTA/NG composite shows a superior Li storage with a reversible capacity of 1585 mAh g −1 at a current density of 200 mA g −1 . In addition, Ni-PTA/NG composite demonstrates an ameliorative rate performance (340 mAh g −1 at 5 A g −1 ) and long-term cyclability (570 mAh g −1 at 1 A g −1 after 420 repeated cycles), significantly higher than traditional graphene/MOF composite materials. The novel method in this work paves a new way to form 3D structure by using NG to induce MOF germination, which may be extended to preparing other metal/metal oxides materials for electrochemical energy-storage systems.
A new energetic MOFs , {[Ni 2 (C 2 H 5 N 5 ) 2 (C 3 H 2 O 4 ) 2 (H 2 O)]·3H 2 O} n (Hdatrz (C 2 H 5 N 5 ) = 3,5-diamino-1,2,4-triazole, H 2 mal (C 3 H 4 O 4 ) = malonic acid), has been synthesized and characterized by element analysis, chemical analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analysis confirmed that the compound featured a 2D layer structure with dinuclear Ni(II) unit. Thermal analysis demonstrated that the compound after dehydration have good thermostability with decomposition temperature up to 633 K. The non-isothermal kinetics for the compound was studied by Kissinger’s and Ozawa’s methods. The Arrhenius equation of initial thermal decomposition process of compound can be expressed as ln k = 55.89 − 332.01 × 10 3 / RT . Furthermore, a reasonable thermochemical cycle was designed based on the preparation reaction of the compound, and standard molar enthalpy of dissolution of reactants and products were measured by RD496-2000 calorimeter. Finally, the standard molar enthalpy of formation of the compound was determined to be −(2766.3 ± 2.3) kJ · mol −1 in accordance with Hess’s law. In addition, the specific heat capacity of the compound at T = 298.15 K was determined to be 1.42 ± 0.11 J · K −1 · g −1 by RD496-2000 calorimeter.
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