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摘要: 锂离子电池商用负极材料石墨比容量低,难以满足市场需求,金属有机骨架材料(metal-organic framework materials,MOFs)具有可调控的结构、较大的表面积和可调节的孔径,可用作下一代电化学储能器件,引起广泛研究。本文综述了金属(Fe、Co、Zn、Mn、Cu)基金属有机骨架及其衍生物的合成,重点介绍了以金属有机骨架材料为前驱体制备过渡金属氧化物(transition metal oxide,TMO)/C作为锂离子电池负极材料的研究进展,并对其发展方向进行了展望。Abstract: The graphite as the commercial anode material for lithium-ion batteries shows the low specific capacity, which is difficult to meet the market demand. The metal-organic framework materials (MOFs) have the tunable structure, large surface area, and adjustable pore size, which can be used as the next generation of electrochemical energy storage devices, causing the extensive research. The synthesis of the metal (Fe, Co, Zn, Mn, Cu)-based metal organic frameworks and the derivatives were introduced in this paper, the research progress on the preparation of transition metal oxide (TMO)/C as the anode materials for lithium-ion batteries was focused, using MOFs as the precursors, and the development direction was prospected.
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图 1 前驱体GO/ZIF-67(a)和G/Co3O4复合材料(b)显微形貌、G/Co3O4和Co3O4电极在100 mA·g−1电流密度下前三圈放电/充电曲线(c)以及在200 mA·g−1的循环图(d)[17]
Figure 1. Microstructures of GO/ZIF-67 precursor (a) and G/Co3O4 (b), the discharge/charge curves of G/Co3O4 and Co3O4 at the current density of 100 mA·g−1 for the first three cycles (c), and the cycling properties of G/Co3O4 and Co3O4 at 200 mA·g−1 (d)[17]
图 3 空心多孔ZnO/C制备工艺流程(a)、空心多孔ZnO/C显微形貌(b)以及在电流密度为100 mA·g−1时空心多孔ZnO/C、空心多孔ZnO和商用ZnO的循环性能(c)[20]
Figure 3. Schematic diagram of hollow porous ZnO/C preparation process (a), microstructure of hollow porous ZnO/C (b), and cycling properties of hollow porous ZnO/C, hollow porous ZnO, and commercial ZnO at 100 mA·g−1 (c)[20]
表 1 MOFs衍生锂离子电池负极材料
Table 1. MOFs-derived anode materials for lithium-ion batteries
MOFs前驱体 产物 电流密度 / (mA·g−1) 可逆容量 / (mA·h·g−1) 循环次数 参考文献 Co-MOF Co3O4/C 200 1052 60 [15] Co-MOF Co3O4/C 1000 601.0 500 [16] ZIF-67 G/Co3O4 200 714.0 200 [17] Fe-MOF C-Fe3O4 100 975.0 50 [18] Fe-ZIF Fe2O3@N-C 100 861.0 100 [19] MOF-5 ZnO/C 100 750.0 100 [20] Ppy-ZIF-8 ZnO/C 250 526.0 500 [21] Zn-BTC ZnO/C 100 919.0 100 [22] ZnO@ZIF-8 ZnO/C 2000 351.0 — [23] MOF-5 ZnO@C/CNT 100 758.0 100 [24] Mn-BTC MnO@C 3825 596.3 1000 [26] Mn-PBI MnO/C−N 300 1085.0 100 [27] Mn-BDC MnO/C@rGO 100 1536.4 100 [29] Cu-MOF CuOx-rGO 200 1490.0 220 [31] Cu-BTC CuO@C 100 1024.0 100 [32] [Cu(BTC)2]n-MOF CuO/C 100 510.5 200 [33] Cu-MOF CuO/C 100 789.0 200 [34] Cu-MOF CuO@C 1000 410.0 1000 [35] MIL-125@ZIF-67 Co3O4/TiO2 1000 838.6 600 [36] ZIF-67 Co3O4@Co3V2O8 100 948.0 100 [37] ZIF-67 Co3O4@TiO2 100 1057.0 100 [38] MOF-74-FeCo Co3O4-CoFe2O4 100 940.0 80 [39] ZnCo-MOF ZnO/ZnCo2O4/C 500 669.0 250 [40] GO/Zn-Co-ZIF/Ni rGO/ZnCo2O4-ZnO-C/Ni 100 1184.4 150 [42] -
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