Conversion Reaction of Nanoporous ZnO for Stable Electrochemical Cycling of Binderless Si Microparticle Composite Anode

Binderless, additiveless Si electrode design is developed where a nanoporous ZnO matrix is coated on a Si microparticle electrode to accommodate extreme Si volume expansion and facilitate stable electrochemical cycling. The conversion reaction of nanoporous ZnO forms an ionically and electrically conductive matrix of metallic Zn embedded in Li₂O that surrounds the Si microparticles. Upon lithiation, the porous Li₂O/Zn matrix expands with Si, preventing extensive pulverization, while Zn serves as active material to form Li_xZn to further enhance capacity. Electrodes with a Si mass loading of 1.5 mg/cm² were fabricated, and a high initial capacity of ∼3900 mAh/g was achieved with an excellent reversible capacity of ∼1500 mAh/g (areal capacity ∼1.7 mAh/cm²) beyond 200 cycles. A high first-cycle Coulombic efficiency was obtained owing to the conversion reaction of nanoporous ZnO, which is a notable feature in comparison to conventional Si anodes. Ex situ analyses confirmed that the nanoporous ZnO coating maintained the coalescence of SiMPs throughout extended cycling. Therefore, the Li₂O/Zn matrix derived from conversion-reacted nanoporous ZnO acted as an effective buffer to lithiation-induced stresses from volume expansion and served as a binder-like matrix that contributed to the overall electrode capacity and stability.