Hamilton Sara T, Feric Tony G, Bhattacharyya Sahana, Cantillo Nelly M, Greenbaum Steven G, Zawodzinski Thomas A, Park Ah-Hyung Alissa
Department of Earth and Environmental Engineering, Columbia University, New York, New York 10027, United States.
Lenfest Center for Sustainable Energy, The Earth Institute, Columbia University, New York, New York 10027, United States.
JACS Au. 2022 Mar 2;2(3):590-600. doi: 10.1021/jacsau.1c00410. eCollection 2022 Mar 28.
As renewable energy is rapidly integrated into the grid, the challenge has become storing intermittent renewable electricity. Technologies including flow batteries and CO conversion to dense energy carriers are promising storage options for renewable electricity. To achieve this technological advancement, the development of next generation electrolyte materials that can increase the energy density of flow batteries and combine CO capture and conversion is desired. Liquid-like nanoparticle organic hybrid materials (NOHMs) composed of an inorganic core with a tethered polymeric canopy (e.g., polyetheramine (HPE)) have a capability to bind chemical species of interest including CO and redox-active species. In this study, the unique response of NOHM-I-HPE-based electrolytes to salt addition was investigated, including the effects on solution viscosity and structural configurations of the polymeric canopy, impacting transport behaviors. The addition of 0.1 M NaCl drastically lowered the viscosity of NOHM-based electrolytes by up to 90%, reduced the hydrodynamic diameter of NOHM-I-HPE, and increased its self-diffusion coefficient, while the ionic strength did not alter the behaviors of untethered HPE. This study is the first to fundamentally discern the changes in polymer configurations of NOHMs induced by salt addition and provides a comprehensive understanding of the effect of ionic stimulus on their bulk transport properties and local dynamics. These insights could be ultimately employed to tailor transport properties for a range of electrochemical applications.
随着可再生能源迅速并入电网，挑战已变成储存间歇性的可再生电力。包括液流电池以及将一氧化碳转化为高密度能量载体在内的技术，是储存可再生电力的有前景的选择。为实现这一技术进步，需要开发能够提高液流电池能量密度并结合一氧化碳捕获与转化的下一代电解质材料。由带有连接聚合物冠层（例如聚醚胺（HPE））的无机核心组成的类液体纳米颗粒有机杂化材料（NOHM），具有结合包括一氧化碳和氧化还原活性物质在内的目标化学物质的能力。在本研究中，研究了基于NOHM-I-HPE的电解质对添加盐的独特响应，包括对溶液粘度和聚合物冠层结构构型的影响，这些影响会影响传输行为。添加0.1 M氯化钠可使基于NOHM的电解质粘度大幅降低高达90%，减小NOHM-I-HPE的流体动力学直径，并增加其自扩散系数，而离子强度并未改变未连接的HPE的行为。本研究首次从根本上辨别了添加盐引起的NOHM聚合物构型变化，并全面理解了离子刺激对其整体传输性质和局部动力学的影响。这些见解最终可用于为一系列电化学应用定制传输性质。
