Futamura Ryusuke, Iiyama Taku, Takasaki Yuma, Gogotsi Yury, Biggs Mark J, Salanne Mathieu, Ségalini Julie, Simon Patrice, Kaneko Katsumi
Center for Energy and Environmental Science, Shinshu University, 4-17-1, Wakasato, Nagano-City, 380-8553, Japan.
Faculty of Science, Department of Chemistry, Shinshu University, 3-1-1, Asahi, Matsumoto-City, 390-8621, Japan.
Nat Mater. 2017 Dec;16(12):1225-1232. doi: 10.1038/nmat4974. Epub 2017 Sep 18.
Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of a widely used ionic liquid (EMI-TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can accommodate only a single layer of ions. Instead, equally charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications.
离子液体由等量的正离子和负离子组成。在本体中,由于库仑有序排列,这些液体呈现电中性,即围绕中心离子形成交替电荷的离子壳层。人们对其受限状态下的结构了解甚少。这阻碍了离子液体在技术应用中的广泛应用。在此,我们通过散射实验来解析一种广泛使用的离子液体(EMI-TFSI)在被限制于纳米多孔碳内部时的结构。我们发现,当孔隙仅能容纳单层离子时,库仑有序排列会减弱。相反,由于碳孔壁中相反符号电势的诱导,会形成等电荷离子对。在施加外部电势的情况下,这种非库仑有序排列会进一步增强。这一发现为设计更好的电化学应用材料打开了大门。