Here we report a Li-metal-free full battery, using interlayer-expanded V6O13 ultra-thin nanosheets and prelithiated graphite for cathodes and anodes, respectively. This full Li-ion battery exhibits a superior specific capacity of 233mAhg−1 at a current density of 100mAg−1 and 91% capacity retention after 500 cycles. Our first-principle calculations reveal that the interlayer-expansion is induced by the interaction between V6O13 and water which breaks interlayer V-O bonds and forms hydroxyls. The unique structure provides short lithium-ion diffusion path, excellent charge transport, abundant binding sites and volume flexibility for Li+ intercalation/deintercalation, thus leading to high capability (280mAhg−1) and cycling performance (capacity retain 96.1% at 2.4Ag−1 for 1000 cycles). Using novel prelithiation process, the Li-metal-free full cells with high controllability and performance is expected to contribute significantly to the development of safe, green, and powerful energy storage devices.