Crosslinked poly(acrylic acid) enhances adhesion and electrochemical performance of Si anodes in Li-ion batteries

Water-soluble binders such as poly (acrylic acid) (PAA) possess many advantages in the slurry and electrode preparation due to their low-cost and environmental friendliness. However, due to the linear nature of these binders, they are susceptible to slide under the continuous volume variation of Si-containing anodes during cycling. Therefore, a three-dimensional (3D) interconnected polymeric network is required to provide robust mechanical adhesion with the Si particles to maintain the electrode integrity for excellent cycle stability. Here, pentaerythritol (PER) is used as a crosslinking agent to connect the linear PAA binder to enhance its adhesion strength for Si anodes, which is systematically confirmed using Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric (TG) measurements. Si electrodes with crosslinked PAA-PER binder show enhanced adhesion and elasticity, exhibiting a more robust electrode integrity than purely PAA-based Si electrodes. Galvanostatic cycling shows that Si-PAA-5%PER electrodes maintain a higher discharge capacity of 514.3 mAh g$^{-1}$ (after 10 cycles) for micro-sized and 1502.1 mAh g$^{-1}$ (after 105 cycles) for nano-sized Si particles compared to 257.6 mAh g-1 and 1413.9 mAh g$^{-1}$ for micro- and nano-sized Si in Si-PAA electrodes, respectively. XPS analyses on cycled electrodes confirmed that crosslinked PAA-PER binder has no negative effects on the SEI formation and its functionality in Si electrodes. SEM cross-sections reveal that Si-PAA-5%PER electrodes show reduced electrode thickness variation (micro-/nano-: 114.2%/182.2%) than that of Si-PAA electrodes (micro-/nano-: 134.1%/212.0%) after cycling, which indicates that crosslinked PAA-PER binder can enhance the electrode integrity due to its 3D interconnected network. This work provides meaningful insight into the exploration of novel binders and their impact on the SEI formation and functionality, especially for high-capacity alloy-type anode materials