Ion-Cross-Linking-Promoted High-Performance Si/PEDOT:PSS Electrodes: The Importance of Cations’ Ionic Potential and Softness Parameters

PSS has been studied as a silicon-based binder due to its inherent superior electricity and electrochemical stability. However, it cannot effectively alleviate the huge volume changes of silicon during lithiation/delithiation due to its linear structure, resulting in poor cycling stability. Ion-cross-linking is a usual method to cross-link linear polymers into 3D structures. In this paper, multivalent cations of the 5th period and Group 2 cross-linked PEDOT:PSS were applied as silicon anode binders and studied systematically. It was found that the variation trend of viscosity and conductivity of PEDOT:PSS after cross-linking was consistent with that of ionic potential and softness parameters of multivalent cations. The mesostructure of a binder after cross-linking is influenced by the solubility product constant of sulfites or hydroxides of cations and the growth characteristics of crystals. An Sn4+-cross-linked binder displayed increased viscosity and electrical conductivity and higher reduced modulus and hardness due to its positive softness parameter and higher ion potential. The Si electrode with the Sn4+-cross-linked binder showed improved cycling stability (1876.4 mAh g-1 compared with 1068.4 mAh g-1 of the electrode with the pure PEDOT:PSS binder after 100 cycles) and superior rate capability (∼800 mAh g-1 at an ultrahigh current density of 8.0 A g-1).