Synthesis, Structure, and Pressure-Induced Polymerization of Li3Fe(CN)6 Accompanied with Enhanced Conductivity

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• 作者：Kuo Li ; Haiyan Zheng ; Takanori Hattori ; Asami Sano-Furukawa ; Christopher A. Tulk ; Jamie Molaison ; Mikhail Feygenson ; Ilia N. Ivanov ; Wenge Yang ; Ho-kwang Mao
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 7, 2015
• 年：2015
• 卷：54
• 期：23
• 页码：11276-11282
• 全文大小：463K
• ISSN：1520-510X

文摘

Pressure-induced polymerization of charged triple-bond monomers like acetylide and cyanide could lead to formation of a conductive metal鈥揷arbon network composite, thus providing a new route to synthesize inorganic/organic conductors with tunable composition and properties. The industry application of this promising synthetic method is mainly limited by the reaction pressure needed, which is often too high to be reached for gram amounts of sample. Here we successfully synthesized highly conductive Li₃Fe(CN)₆ at maximum pressure around 5 GPa and used in situ diagnostic tools to follow the structural and functional transformations of the sample, including in situ X-ray and neutron diffraction and Raman and impedance spectroscopy, along with the neutron pair distribution function measurement on the recovered sample. The cyanide anions start to react around 1 GPa and bond to each other irreversibly at around 5 GPa, which are the lowest reaction pressures in all known metal cyanides and within the technologically achievable pressure range for industrial production. The conductivity of the polymer is above 10^鈥? S路cm^鈥?, which reaches the range of conductive polymers. This investigation suggests that the pressure-induced polymerization route is practicable for synthesizing some types of functional conductive materials for industrial use, and further research like doping and heating can hence be motivated to synthesize novel materials under lower pressure and with better performances.