Synthesis of hybrid layered electrode materials via chemical pre-intercalation of linear organic molecules
Synthesis of hybrid layered electrode materials via chemical pre-intercalation of linear organic molecules
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通过线性有机分子化学预插层合成混合层状电极材料
DOI：
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发表时间：
2018
期刊：
影响因子：
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通讯作者：
E. Pomerantseva
中科院分区：
文献类型：
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作者：
Mallory Clites;E. Pomerantseva
化学预插层是一种低温、可规模化的合成方法，其利用溶胶-凝胶工艺来形成具有插入在层之间的带正电荷的物质的层状氧化物。我们已经表明，这种方法可以用于成功地将Li+、Na+、K+、Mg 2+和Ca 2+离子插入双层钒氧化物（δ V2 O 5）的晶体结构中。1通过这种离子插入，δ-MgxV 2 O 5的层间距（M=Li、Na、K、Mg和Ca）结构可以控制在9.6 μ m至100 μ m之间。（δ-KxV 2 O 5）和13.4 μ m（δ-MgxV 2 O 5）。1此外，δ-MgxV 2 O 5相获得的扩展间距对应于Li-和Na-离子电池中增加的电化学稳定性。[1]虽然该研究确定了扩展的层间距与循环过程中改善的电化学稳定性之间的相关性，但离子的化学预嵌入不允许扩展超过δ-MgxV 2 O 5结构所表现出的扩展。在这项工作中，我们表明，进一步扩大层间距可以通过预插层的带正电的线性，有机阳离子。我们报道了具有一维纳米带形态的无机/有机杂化材料的合成。通过XRD和TEM分析证实了杂化物的层状结构。用十六烷基三甲基铵离子（CTA+）预插层的δ-V2 O 5显示了所有样品的层间距（31 μ m），比通过预插层无机离子实现的最大层间距大两倍以上。研究了碳链长度和带正电荷的氮末端对层间距和电化学稳定性的影响，阳离子（DMO+）上的两个N-末端导致预插层相的电化学稳定性增加。
Chemical pre-intercalation is a low-temperature, scalable synthesis method that utilizes a sol-gel process to form layered oxides with positively-charged species inserted between the layers. We have shown that this approach can be used to successfully intercalate Li+ , Na+ , K+ , Mg2+, and Ca2+ ions into the crystal structure of bilayered vanadium oxide (δV2O5).1 Through this ion-intercalation, the interlayer spacing of the δ-MgxV2O5 (M=Li, Na, K, Mg, and Ca) structure can be controlled between 9.6 Å (δ-KxV2O5) and 13.4 Å (δ-MgxV2O5).1 Moreover, the expanded spacing achieved for the δ-MgxV2O5 phase corresponded to increased electrochemical stability in both Li- and Na-ion cells.[1] While this study identified a correlation between expanded interlayer spacing and improved electrochemical stability over cycling, chemical pre-intercalation of ions does not allow for expansion beyond that exhibited by the δ-MgxV2O5 structure. In this work, we show that further expansion of the interlayer spacing can be achieved via pre-intercalation of positivelycharged linear, organic cations. We report synthesis of hybrid inorganic/organic materials with a 1D nanobelt morphology. The layered structure of the hybrids is confirmed by both XRD and TEM analysis. δ-V2O5 preintercalated with cetyltrimethylammonia ions, CTA+ , demonstrated the interlayer spacings of all samples (31 Å), more than twice larger than the largest interlayer spacing achieved via pre-intercalation of inorganic ions. The effects of carbon chainlength and positively charged nitrogen termini on the interlayer spacing and electrochemical stability is investigated, with two N-termini on the cation (DMO+) resulting in increased electrochemical stability of the preintercalated phase.