A Fluorine‐Free Binder with Organic–Inorganic Crosslinked Networks Enabling Structural Stability of Ni‐Rich Layered Cathodes in Lithium‐Ion Batteries

Abstract Although the high‐energy Ni‐rich layered cathodes suffer from undesirable surface reactions with the electrolyte, the polyvinylidene fluoride (PVDF) binder has a limitation on surface stabilization because of its weak affinity and low adhesion/cohesion. Here, it is demonstrated that the novel fluorine‐free and hydroxyl‐rich siloxane nanohybrid (SNH) binder can enhance the electrochemical performances of LiNi _0.8 Mn _0.1 Co _0.1 O ₂ cathode (NCM811) via successful surface stabilization. The high silanol content in the SNH binder enhances the affinity to both NCM811 and conductive agent, facilitating uniform electron/ion pathways with high mass loading, improved shear thinning, and superior mechanical properties. Moreover, the fluorine‐free organic‐inorganic hybrid structure prevents the dissolution of transition metals, active material structural changes, and electrolyte interaction, leading to greatly enhanced cyclability of the SNH‐based NCM811 electrode (≈81.9% in half‐cell; ≈87.82% in full‐cell after 200 cycles) compared to PVDF‐based NCM811 electrode (≈58.8% in half‐cell; ≈61.24% in full‐cell after 200 cycles). Various analyses also indicate that the application of the fluorine‐free SNH binder successfully stabilizes both the surface and bulk structure of the NCM811 cathode during charge/discharge. The binder design represents a straightforward yet highly effective approach to achieving remarkably prolonged cyclability in lithium‐ion batteries, surpassing the performance of other fluorine‐based or polymer‐based binders.