The emerging era of supramolecular polymeric binders in silicon anodes

Silicon (Si) anode is among the most promising candidates for the next-generation high-capacity electrodes in Li-ion batteries owing to its unparalleled theoretical capacity (4200 mA h g^-1 for Li_4.4Si) that is approximately 10 times higher than that of commercialized graphitic anodes (372 mA h g^-1 for LiC₆). The battery community has witnessed substantial advances in research on new polymeric binders for silicon anodes mainly due to the shortcomings of conventional binders such as polyvinylidene difluoride (PVDF) to address problems caused by the massive volume change of Si (300%) upon (de)lithiation. Unlike conventional battery electrodes, polymeric binders have been shown to play an active role in silicon anodes to alleviate various capacity decay pathways. While the initial focus in binder research was primarily to maintain the electrode morphology, it has been recently shown that polymeric binders can in fact help to stabilize cracked Si microparticles along with the solid-electrolyte-interphase (SEI) layer, thus substantially improving the electrochemical performance. In this review article, we aim to provide an in-depth analysis and molecular-level design principles of polymeric binders for silicon anodes in terms of their chemical structure, superstructure, and supramolecular interactions to achieve good electrochemical performance. We further highlight that supramolecular chemistry offers practical tools to address challenging problems associated with emerging electrode materials in rechargeable batteries.