Sergeev A V, Rudyak V Yu, Samodelkin R A, Kozhunova E Yu, Chertovich A V
Federal Research Center for Chemical Physics, Kosygina Street, 4 Building 1, Moscow 119991, Russian Federation.
Lomonosov Moscow State University, Faculty of Physics, Moscow 119991, Russia.
Soft Matter. 2025 Jan 15;21(3):411-417. doi: 10.1039/d4sm01199f.
Redox-active polymer gels are promising materials for various applications, such as energy conversion and storage systems, organic electronics, soft-robotics, sensors and others. This is in part due to the remarkable structural tunability of these materials. The gel may adopt different conformations depending on the crosslinking density, solvent temperature and other conditions. These parameters affect its behavior, including the dynamics of the charge transport between the redox groups grafted to the polymer subchains, which is of utmost importance for electrochemical applications. Here, we employed coarse-grained molecular dynamics simulation to investigate the impact of crosslinking, redox group content and solvent quality on both subchain mobility and charge transport speed. In particular, unexpected behavior of the system under the theta-solvent condition was found and analyzed. The obtained results provide useful guidelines to facilitate the best conditions for enhanced "redox induced" conductivity in polymer gels, which would help the development of redox-flow batteries and other electrochemical devices.
氧化还原活性聚合物凝胶是用于各种应用的有前途的材料，如能量转换和存储系统、有机电子学、软机器人技术、传感器等。这部分归因于这些材料显著的结构可调性。凝胶可能会根据交联密度、溶剂温度和其他条件采取不同的构象。这些参数会影响其行为，包括接枝到聚合物子链上的氧化还原基团之间的电荷传输动力学，这对电化学应用至关重要。在这里，我们采用粗粒度分子动力学模拟来研究交联、氧化还原基团含量和溶剂质量对亚链迁移率和电荷传输速度的影响。特别是，发现并分析了系统在θ溶剂条件下的意外行为。所得结果为促进聚合物凝胶中增强“氧化还原诱导”导电性的最佳条件提供了有用的指导方针，这将有助于氧化还原液流电池和其他电化学装置的开发。
