N‑Type Polyoxadiazole Conductive Polymer Binders Derived High-Performance Silicon Anodes Enabled by Crosslinking Metal Cations

The dilemma of employing high-capacity battery materials and maintaining the electrodes’ electrical and mechanical integrity requires a unique binder system design. Polyoxadiazole (POD) is an n-type conductive polymer with excellent electronic and ionic conductive properties, which has acted as a silicon binder to achieve high specific capacity and rate performance. However, due to its linear structure, it cannot effectively alleviate the enormous volume change of silicon during the process of lithiation/delithiation, resulting in poor cycle stability. This paper systematically studied metal ion (i.e., Li+, Na+, Mg2+, Ca2+, and Sr2+)-crosslinked PODs as silicon anode binders. The results show that the ionic radius and valence state remarkably influence the polymer’s mechanical properties and the electrolyte’s infiltration. Electrochemical methods have thoroughly explored the effects of different ion crosslinks on the ionic and electronic conductivity of POD in the intrinsic and n-doped states. Attributed to the excellent mechanical strength and good elasticity, Ca-POD can better maintain the overall integrity of the electrode structure and conductive network, significantly improving the cycling stability of the silicon anode. The cell with such binders still retains a capacity of 1770.1 mA h g–1 after 100 cycles at 0.2 C, which is ∼285% that of the cell with the PAALi binder (620.6 mA h g–1). This novel strategy using metal-ion crosslinking polymer binders and the unique experimental design provides a new pathway of high-performance binders for next-generation rechargeable batteries.