Encapsulating a Responsive Hydrogel Core for Void Space Modulation in High-Stability Graphene-Wrapped Silicon Anodes

Due to its formidably high theoretical capacity (3590 mAh/g at room temperature), silicon (Si) is expected to replace graphite as the dominant anode for higher energy density lithium (Li)-ion batteries. However, stability issues stemming from silicon's significant volume expansion (∼300%) upon lithiation have slowed down commercialization. Herein, we report the design of a scalable process to engineer core-shell structures capable of buffering this volume expansion, which utilize a core made up of a poly(ethylene oxide)-carboxymethyl cellulose hydrogel and silicon protected by a crumpled graphene shell. The volume expansion of the hydrogel upon exposure to water creates a void space between the Si-Si and Si-rGO interfaces within the core when the gel dries. Unlike sacrificial spacers, the dehydrated hydrogel remains in the core and acts as an elastic Li-ion conductor, which improves the stability and high rate performance. The optimized composite electrodes retain ∼81.7% of their initial capacity (1055 mAh/(grGO+gel+Si)) after 320 cycles when an active material loading of 1 mg/cm2 is used. At more practical mass loadings (2.5 mg/cm2), the electrodes achieve 2.04 mAh/cm2 and retain 79% of this capacity after 200 cycles against a lithium half-cell. Full cells assembled using a lithium ion phosphate cathode lose only 6.7% of their initial capacity over 100 cycles, demonstrating the potential of this nanocomposite anode for use in next-generation Li-ion batteries.