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Abstract This study demonstrates fluorine‐free cross‐linked (meth)acrylate polymers as alternatives to polyvinylidene fluoride (PVDF) in LiNi_0.33Mn_0.33Co_0.33O₂(NMC111) cathodes. We determine the effects of thermal initiator content, polymer content, and curing environment for two polymer chemistries: a flexible acrylate polymer, and a stiff methacrylate polymer. Electrodes are manufactured and tested for final electrochemical performance and mechanical properties. The results show that the flexible acrylate polymer exhibits higher rate capability compared to the stiff methacrylate polymer because calendering fractures the brittle network of stiff polymer. Electrode adhesion to the current collector and cohesion between particles are found to be a strong function of thermal initiator ratio and oxygen inhibition. Furthermore, there exists an optimal binder concentration that maximizes rate capability performance. Under the right conditions, the two polymers exhibit comparable performance to PVDF electrodes. These results provide important implications for designing cross‐linked polymers as cathode binder alternatives to PVDF. 

The viscosity and microstructure of Li-ion battery slurries and the performance of the resulting electrodes have been shown to depend on the mixing protocol. This work applies rheology to understand the impact of shear during mixing and polymer molecular weight on slurry microstructure and electrode performance. Mixing protocols of different shear intensity are applied to slurries of LiNi0.33Mn0.33Co0.33O2 (NMC), carbon black (CB), and polyvinyldiene difluoride (PVDF) in N-methyl-2-pyrrolidinone (NMP), using both high-molecular-weight (HMW) and low-molecular-weight (LMW) PVDF. Slurries of both polymers are observed to form colloidal gels under high-shear mixing, even though unfavorable interactions between high molecular weight PVDF and CB should prevent this microstructure from forming. Theoretical analysis and experimental results show that increasing shear rate during the polymer and particle mixing steps causes polymer scission to decrease the polymer molecular weight and allow colloidal gelation. In general, electrodes made from high molecular weight PVDF generally show increased rate capability. However, high shear rates lead to increased cell variability, possibly due to the heterogeneities introduced by polymer scission.