Coordinatively Cross-Linked Binders for Silicon-Based Electrodes for Li-Ion Batteries: Beneficial Impact on Mechanical Properties and Electrochemical Performance

A simple and versatile preparation of Zn(II)-poly(carboxylates) reticulated binders by the addition of Zn(II) precursors (ZnSO₄, ZnO, or Zn(NO₃)₂) into a preoptimized poly(carboxylic acids) binder solution is proposed. These binders lead systematically to a significantly improved electrochemical performance when used for the formulation of silicon-based negative electrodes. The formation of carboxylate-Zn(II) coordination bonds formation is investigated by rheology and FTIR and NMR spectroscopies. Mechanical characterizations reveal that the coordinated binder offers a better electrode coating cohesion and adhesion to the current collector, as well as higher hardness and elastic modulus, which are even preserved in the presence of a carbonate solvent (i.e., in battery operation conditions). Ultimately, as shown from operando dilatometry experiments, the electrode expansion during lithiation is reduced, mitigating electrode mechanical failure. Such coordinatively reticulated electrodes outperform their uncoordinated counterparts with an improved capacity retention of over 30% after 60 cycles.