Ion-selective copper hexacyanoferrate with an open-framework structure enables high-voltage aqueous mixed-ion batteries
Ion-selective copper hexacyanoferrate with an open-framework structure enables high-voltage aqueous mixed-ion batteries
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具有开放框架结构的离子选择性六氰基铁酸铜可实现高压水性混合离子电池
DOI：
10.1039/c7ta04172a
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发表时间：
2017-08-28
影响因子：
11.9
通讯作者：
Liu, Zhaoping
中科院分区：
文献类型：
--
作者：
Jiang, Ping;Shao, Hezhu;Liu, Zhaoping
在“M+/N+-双穿梭机”（AMIB）上运行的不易燃且低成本的水性电池在大规模公用电网应用中提供了巨大的机会。本文首次以六氰合铁酸铜（CuHCFs）为正极材料，TiP_2O_7和NaTi_2（PO_4）（3）为负极材料，制备了一系列高电压AMIB（>1.23 V）。其中，CuHCF/NaTi 2（PO 4）（3）作为超级电容器具有高功率密度（3006 W kg（-1）），但能量密度更高（56 W h kg（-1））。通过多种表征技术结合从头计算，碱金属阳离子在CuHCF的嵌入化学被揭示。随着离子尺寸的增加，最稳定的间隙位点从面心位点（24 d）变为体心位点（8 c）。碱金属离子的嵌入电压顺序为：K+ > Na+ > Li+。同时，它们之间的离子选择性遵循相同的顺序作为嵌入电压，这占较高的电压输出的AMIB相比，在一个梭上运行的水溶液电池。
Non-flammable and low-cost aqueous batteries operating on "M+/N+-dual shuttles" (AMIB) offer great opportunities in large-scale utility grid applications. Here, for the first time, we demonstrate a series of high-voltage AMIB (>1.23 V) based on open-framework copper hexacyanoferrates (CuHCFs) as cathode materials, and TiP2O7 & NaTi2(PO4)(3) as anode materials. Among them, CuHCF/NaTi2(PO4)(3) possesses high power density as an ultra-capacitor (3006 W kg(-1)), but with a higher energy density (56 W h kg(-1)). Through multiple characterization techniques combined with ab initio calculations, the intercalation chemistry of alkali cations in CuHCF is revealed. With increasing ionic size, the most stable interstitial site changes from the face-centered site (24d) to the body-centered site (8c). The intercalation voltage for the alkali cations follows the order: K+ > Na+ > Li+. Meanwhile, the ion-selectivity among them follows the same order as the intercalation voltage, which accounts for the higher voltage outputs of AMIB in contrast to aqueous batteries operating on one shuttle.