论文标题
电解质溶液中具有非凸孔几何形状的多孔电极的电吸附诱导的变形:一项理论研究
Electrosorption-induced deformation of a porous electrode with non-convex pore geometry in electrolyte solutions: a theoretical study
论文作者
论文摘要
多孔碳是众所周知的电化学双层电容器发展的好候选者。主要是,许多常规碳是微孔的,通常通过裂缝几何形状的假设来很好地描述。但是,有一类碳与其他碳有明显不同的碳,即介孔碳。在这项工作中,我们研究了电吸附诱导的在具有平均场方法的非凸几何形状的CMK-3样中孔中的变形。该模型基于修改的泊松波尔兹曼方程,这些方程考虑了percus-yevick近似中硬球模型中离子的排除体积。我们假设变形是由两种效应引起的:电动双层在带电杆上的离子渗透压和静电相互作用。通过Maxwell应力张量计算后者,与改良的Poisson-Boltzmann方程一致。我们估计了类似CMK-3样材料的孔隙载模模量,并通过小角度中子散射(SAN)找到了与先前获得的值一致的一致。此外,我们研究了非凸孔几何形状中的差分电容,发现差分电容曲线的行为与平面电动双层获得的轮廓相似。也就是说,我们在相当高的电压和更明显的不对称性下获得了拥挤状态,而离子尺寸的差异增加。
Porous carbon is well known as a good candidate for the development of electrochemical double-layer capacitors. Predominantly, many conventional carbons are microporous and often well described by the assumption of slit pore geometry. However, there is a class of carbons that is significantly different from the others, namely templated mesoporous carbons. In this work, we study electrosorption-induced deformation in CMK-3-like mesopores having nonconvex geometry applying a mean-field approach. The model is based on the modified Poisson-Boltzmann equation taking into account the excluded volume of the ions within the hard-sphere model in the Percus-Yevick approximation. We assume that the deformation is caused by two effects: ion osmotic pressure and electrostatic interactions of the electric double layers on charged rods. The latter were calculated via the Maxwell stress tensor agreeing with the modified Poisson-Boltzmann equation. We estimated the pore-load modulus of the CMK-3-like material and found an agreement with the previously obtained values by small-angle neutron scattering (SANS). Additionally, we studied the differential capacitance in the non-convex pore geometry and found that the behavior of the differential capacitance profiles was similar to that of the profiles obtained for flat electric double layers. Namely, we obtained the crowding regime at rather high voltages and more pronounced profile asymmetry with increasing differences in the ionic sizes.