Uysal Ahmet, Zhou Hua, Feng Guang, Lee Sang Soo, Li Song, Cummings Peter T, Fulvio Pasquale F, Dai Sheng, McDonough John K, Gogotsi Yury, Fenter Paul
Chemical Science and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
J Phys Condens Matter. 2015 Jan 28;27(3):032101. doi: 10.1088/0953-8984/27/3/032101. Epub 2014 Dec 5.
It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. We used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene-RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can be described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. The potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (∼0.15 eV).
众所周知,室温离子液体(RTILs)在带电界面处通常会形成电荷分离的层状结构,即阳离子富集层和阴离子富集层交替排列。然而,人们对这种层状结构对施加电势随时间变化的动态响应了解甚少。我们使用原位实时X射线反射率来研究基于咪唑鎓的RTIL在带电外延石墨烯上的电势循环过程中电势依赖的双电层(EDL)结构随温度的变化。结果表明,石墨烯-RTIL界面结构是双稳态的,其中任何中间电势下的EDL结构都可以由两种极端电势结构的组合来描述,这两种结构的比例会根据施加电势的极性和大小而变化。这一情况得到了在各种静态电势下通过全原子分子动力学模拟得到的EDL结构的支持。两种结构之间的电势驱动转变的特征是宽度增加,但作为温度的函数,滞后幅度大致固定。结果与由能量势垒(约0.15电子伏特)分隔的不同阴离子和阳离子吸附结构的共存相一致。