普鲁士蓝
电导率
材料科学
电子结构
密度泛函理论
化学物理
半导体
离子键合
兴奋剂
金属
锰
带隙
电化学
电子能带结构
有效质量(弹簧-质量系统)
载流子
电子
化学
离子
凝聚态物理
光电子学
计算化学
物理化学
电极
有机化学
物理
冶金
量子力学
作者
Kevin Hurlbutt,Feliciano Giustino,Mauro Pasta,George Volonakis
标识
DOI:10.1021/acs.chemmater.1c02183
摘要
Metal hexacyanometallates, or Prussian blue analogs (PBAs), are active materials in important electrochemical technologies, including next-generation sodium- and potassium-ion batteries. They have tunable properties, including reduction potential, ionic conductivity, and color. However, little is known about their electronic conductivities. In this work, we use density-functional theory to model the electronic structure and to explore the likely electron-conduction mechanism in three promising cathodes (manganese, iron, and cobalt hexacyanoferrate) in each of three oxidation states. First, we demonstrate that hybrid functionals reliably reproduce experimentally observed spin configurations and geometric phase changes. We confirm these materials are semiconductors or insulators with band gaps ranging from 1.90 eV up to 4.94 eV. We further identify that for most of the compounds, the electronic band edges originate from carbon-coordinated iron orbitals, suggesting that doping at the carbon-coordinated site may strongly affect carrier conductivity. Finally, we calculate charge-carrier effective masses, which we find are very heavy. This study is an important foundation for making electronic conductivity a tunable PBA material property.
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