Protecting groups in insertion chemistry: Site-selective positioning of lithium ions in intercalation hosts
Protecting groups in insertion chemistry: Site-selective positioning of lithium ions in intercalation hosts
复制标题
DOI：
10.1016/j.matt.2023.01.028
复制
发表时间：
2023-04-05
期刊：
影响因子：
18.9
通讯作者：
Banerjee，Sarbajit
中科院分区：
文献类型：
--
作者：
Handy，Joseph V.;Zaheer，Wasif;Banerjee，Sarbajit
功能化化学工具箱的不断扩大，用于选择性地将部分安装在底物的特定位点上，支撑着几乎所有现代有机和生物化学合成。同样，移动的客体离子在特定间隙位点中的安装以及它们沿沿着特定扩散路径的传输形成了现代锂（Li）离子电池电极的基础。许多插入宿主提供各种各样的可接近的间隙位点。然而，以原子精度对阳离子进行位点选择性定位仍然几乎完全未被探索。在这里，我们表明，通过破译网站偏好的共同/预插层阳离子，我们可以定位锂离子在四个不同的网站内的一维n-V2 O 5插入主机。使用拓扑化学来实现单晶到单晶的转变使得能够通过单晶X射线衍射对Li离子的选择性定位进行原子分辨率映射。我们的图像间隙的网站，被占领在高深度的放电，从而获得前所未有的结构洞察到“完全填充”的框架实现高能量密度嵌入电极的关键。
The expanding toolbox of functionalization chemistries for selectively installing moieties on specific sites of a substrate underpins almost all modern organic and biochemical syntheses. Likewise, the installation of mobile guest ions in specific interstitial sites and their transport along specific diffusion pathways forms the basis of modern lithium (Li)-ion battery electrodes. Many insertion hosts afford a diverse range of accessible interstitial sites. However, site-selective positioning of cations with atomic precision remains almost entirely unexplored. Here, we show that by deciphering site preferences of co/pre-intercalated cations, we can position Li ions in four distinct sites within a 1D ζ-V2O5insertion host. The use of topochemistry to effect single-crystal-to-single-crystal transformations enables atomic-resolution mapping of the selective positioning of Li ions through single-crystal X-ray diffraction. We image interstitial sites that are occupied at high depths of discharge, thereby obtaining unprecedented structural insight into "fully stuffed" frameworks critical for the realization of high-energy-density intercalation electrodes.