Systematic Investigation of Binders for Silicon Anodes: Interactions of Binder with Silicon Particles and Electrolytes and Effects of Binders on Solid Electrolyte Interphase Formation

The effects of different binders, polyvinylidene difluoride (PVdF), poly(acrylic acid) (PAA), sodium carboxymethyl cellulose (CMC), and cross-linked PAA–CMC (c–PAA–CMC), on the cycling performance and solid electrolyte interphase (SEI) formation on silicon nanoparticle electrodes have been investigated. Electrodes composed of Si–PAA, Si–CMC, and Si–PAA–CMC exhibit a specific capacity ≥3000 mAh/g after 20 cycles while Si–PVdF electrodes have a rapid capacity fade to 1000 mAh/g after just 10 cycles. Infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS) reveal that PAA and CMC react with the surface of the Si nanoparticles during electrode fabrication. The fresh Si–CMC electrode has a thicker surface coating of SiOx than Si–PAA and Si–PAA–CMC electrodes, due to the formation of thicker SiOx during electrode preparation, which leads to lower cyclability. The carboxylic acid functional groups of the PAA binder are reactive toward the electrolyte, causing the decomposition of LiPF6 and dissolution of SiOx during the electrode wetting process. The PAA and CMC binder surface films are then electrochemically reduced during the first cycle to form a protective layer on Si. This layer effectively suppresses the decomposition of carbonate solvents during cycling resulting in a thin SEI. On the contrary, the Si–PVDF electrode has poor cycling performance and continuous reduction of carbonate solvents is observed resulting in the generation of a thicker SEI. Interestingly, the Lewis basic −CO2Na of CMC was found to scavenge HF in electrolyte.