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用于水系镍锌电池高面积能量密度的MOF-74家族的原位合成

In Situ Synthesis of MOF-74 Family for High Areal Energy Density of Aqueous Nickel-Zinc Batteries.

作者信息

Chen Tingting, Wang Fanfan, Cao Shuai, Bai Yang, Zheng Shasha, Li Wenting, Zhang Songtao, Hu Shu-Xian, Pang Huan

机构信息

School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu, 225009, P. R. China.

School of Mathematics and Physics, University of Science and Technology Beijing, Beijing, 100083, P. R. China.

出版信息

Adv Mater. 2022 Jul;34(30):e2201779. doi: 10.1002/adma.202201779. Epub 2022 Jun 17.

Abstract

Limited by single metal active sites and low electrical conductivity, designing nickel-based metal-organic framework (MOF) materials with high capacity and high energy density remains a challenge. Herein, a series of bi/multimetallic MOF-74 family materials in situ grown on carbon cloth (CC) by doping M ions in Ni-MOF-74 is fabricated: NiM-MOF@CC (M = Mn , Co , Cu , Zn , Al , Fe ), and NiCoM-MOF@CC (M = Mn , Zn , Al , Fe ). The type and ratio of doping metal ions can be adjusted while the original topology is preserved. Different metal ions are confirmed by X-ray absorption fine structure (XAFS). Furthermore, these Ni-based MOF electrodes are directly utilized as cathodes for aqueous nickel-zinc batteries (NZBs). Among all the as-prepared electrodes, NiCo-MOF@CC-3 (NCM@CC-3), with an optimized Co/Ni ratio of 1:1, exhibits the best electrical conductivity, which is according to the density functional theory (DFT) theoretical calculations. The NCM@CC-3//Zn@CC battery achieves a high specific capacity of 1.77 mAh cm , a high areal energy density of 2.97 mWh cm , and high cycling stability of 83% capacity retention rate after 6000 cycles. The synthetic strategy based on the coordination effect of metal ions and the concept of binder-free electrodes provide a new direction for the synthesis of high-performance materials in the energy-storage field.

摘要

受限于单一金属活性位点和低电导率,设计具有高容量和高能量密度的镍基金属有机框架(MOF)材料仍然是一项挑战。在此,通过在Ni-MOF-74中掺杂M离子,制备了一系列原位生长在碳布(CC)上的双金属/多金属MOF-74家族材料:NiM-MOF@CC(M = Mn、Co、Cu、Zn、Al、Fe)和NiCoM-MOF@CC(M = Mn、Zn、Al、Fe)。在保留原始拓扑结构的同时,可以调节掺杂金属离子的类型和比例。通过X射线吸收精细结构(XAFS)确认了不同的金属离子。此外,这些镍基MOF电极直接用作水系镍锌电池(NZB)的阴极。在所有制备的电极中,具有优化的Co/Ni比为1:1的NiCo-MOF@CC-3(NCM@CC-3)表现出最佳的电导率,这与密度泛函理论(DFT)理论计算结果一致。NCM@CC-3//Zn@CC电池实现了1.77 mAh cm的高比容量、2.97 mWh cm的高面积能量密度以及6000次循环后83%容量保持率的高循环稳定性。基于金属离子配位效应和无粘结剂电极概念的合成策略为储能领域高性能材料的合成提供了新方向。

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