LAUSR

Free‐standing and foldable electrodes with high energy density and long lifespan have recently elicited attention on the development of lithium‐ion batteries (LIBs) for flexible electronic devices. However, both low energy density and slow kinetics in cycling impede their practical applications. In this work, a free‐standing and binder‐free N, O‐codoped 3D vertical graphene carbon nanofibers electrode with ultra‐high silicon content (VGAs@Si@CNFs) is developed via electrospinning, subsequent thermal treatment, and chemical vapor deposition processes. The as‐prepared VGAs@Si@CNFs electrode exhibits excellent conductivity and flexibility because of the high graphitized carbon nanofiber network and abundant vertical graphene arrays. Such 3D all‐carbon architecture can be fabulous for providing a conductive and mechanically robust network, further improving the kinetics and restraining the volume expansion of Si NPs, especially with an ultra‐high Si content (>90 wt%). As a result, the VGAs@Si@CNFs composite demonstrates a superior specific capacity (3619.5 mAh g−1 at 0.05 A g−1), ultralong lifespan, and outstanding rate capability (1093.1 mAh g−1 after 1500 cycles at 8 A g−1) as a free‐standing anode for LIBs. It is believed that this work offers an exciting method for developing free‐standing and high‐energy‐density electrodes for other energy storage devices.