Electrode-polymer interfaces dictate many of the properties of thin films such as capacitance, the electric field experienced by polymers, and charge transport. However, structure and dynamics of charged polymers near electrodes remain poorly understood, especially in the high concentration limit representative of the melts. To develop an understanding of electric field–induced transformations of electrode-polymer interfaces, we have studied electrified interfaces of an imidazolium-based polymerized ionic liquid (PolyIL) using combinations of broadband dielectric spectroscopy, specular neutron reflectivity, and simulations based on the Rayleigh’s dissipation function formalism. Overall, we obtained the camel-shaped dependence of the capacitance on applied voltage, which originated from the responses of an adsorbed polymer layer to applied voltages. This work provides additional insights related to the effects of molecular weight in affecting structure and properties of electrode-polymer interfaces, which are essential for designing next-generation energy storage and harvesting devices.

电极与聚合物的界面决定了薄膜的许多特性，例如电容，聚合物所经历的电场以及电荷传输。然而，对电极附近带电聚合物的结构和动力学的了解仍然很少，特别是在代表熔体的高浓度极限中。为了了解电场诱导的电极-聚合物界面的转变，我们结合了宽带介电谱，镜面中子反射率和基于瑞利耗散的模拟，研究了咪唑基聚合离子液体（PolyIL）的带电界面功能形式主义。总体而言，我们获得了电容对施加电压的骆驼形依赖性，这取决于吸附的聚合物层对施加电压的响应。