Tip Effect‐Driven Charge Transport Enhancement in Silicon‐Carbon Anodes for All‐Solid‐State Lithium‐Ion Batteries

Abstract Despite its pronounced impact on mass transport and local energy field modulation, the tip effect remains an underexplored strategy in the design of solid‐state batteries. Here, a radial vertical graphene (RVG)‐encapsulated silicon anode (RVG@Si‐V) that strategically leverages the tip effect to modulate interfacial charge transport and direct the formation of solid electrolyte interphases (SEI) in all‐solid‐state lithium‐ion batteries (ASSLIBs) is reported. The sharp geometry of RVG induces localized electric field enhancement at the electrode‐electrolyte interfaces, which promotes charge accumulation and facilitates field‐driven electrolyte decomposition toward thin and LiF‐rich SEI formation. The structure‐field coupling effectively overcomes the long‐standing challenge of sluggish charge transfer kinetics at electrode‐electrolyte interfaces and contributes to improved rate capability and long‐term cycling stability. Electrochemical characterizations reveal that RVG@Si‐V delivers excellent rate performance (940.9 mAh g −1 , 5 A g −1 ) and capacity retention compared to its planar graphene (PG) counterpart (PG@Si‐V) without the tip effect, retaining 76.6% of its capacity after 500 cycles at 3 A g −1 . This work demonstrates a previously underexplored but highly effective strategy of employing the tip effect to modulate interfacial charge transport and SEI formation in solid‐state battery systems, offering critical insights toward the development of high‐performance Si anodes for advanced ASSLIBs.