Optimizing Si-Dominant Anodes in High-Energy Li-Ion Batteries with a Binary Binder System: Exploring Impacts on Adhesion, Cohesion, and Electrochemical Performance

Abstract

Silicon anode stands out as a promising game-changer for Li-ion batteries (LIBs) due to its remarkable gravimetric and volumetric capacities, boasting 4200 mAh/g1 and 2200 mAh/cm3, respectively. In addition, its operating voltage of 0.4 V vs Li/Li+, abundant availability, and environmental friendliness make Si a strong candidate to revolutionize energy densities in the next-generation high-performance LIBs. However, challenges arise during lithiation as silicon undergoes an expansion of ~300% of its initial volume, leading to a cascade of detrimental effects on the electrode.1 The micron-sized silicon particles tend to pulverize, and resulting in fragmented silicon particles that become electrically isolated. Such volume variations compromise the adhesion of the Si electrode to the current collector. Furthermore, the repetitive expansion and shrinkage cycles contribute to cohesive failure within the electrode. Collectively, these factors considerably diminish the electrochemical performance and lifespan of Si anodes. Consequently, these challenges have placed major constraints on the utilization of silicon, making it currently viable only at levels below 10 wt% in LIB anodes, thereby impacting the commercial feasibility of Si-dominant anodes in high-energy LIBs.Such challenges in Si anodes impose strict demands on the binder, requiring it to maintain intimate contact between electrode components and to the current collector and preserve the integrity of ion and electron transport channels during frequent volume changes upon cycling. Obviously, the traditional binders like PVDF or carboxymethylcellulose (CMC)/Styrene-butadiene rubber (SBR) are not suitable options for addressing these specific challenges.Many approaches have been explored to address such requirements including increased crosslinking, different binding functionalities, adhesion promoters, etc.2 In this study, we investigate a binder system comprising two key components: (i) an acrylic acid-based polymer enriched with a high concentration of carboxyl groups. This component not only forms effective bonds with the silicon surface but also fosters interactions with other polar species, facilitating the self-healing properties. (ii) Incorporating a styrene-butadiene-based polymer, renowned for its exceptional flexibility, improves adhesion and enhances the tensile properties of the electrode, particularly in response to volume expansion challenges. We evaluated the characteristics of the binders and electrode properties, including adhesion to the current collector, cohesion within the electrode, and binder distribution. These properties were subsequently correlated with the initial columbic efficiencies (IEC) and electrode cycle life in Si-dominant/NMC811 cells. We show that there is an optimal binder ratio that achieves the desired adhesion and significantly enhances cohesive strength, leading to improved cycling stability compared to a single binder system.