For the first time, a green lignin/silica nanocomposite (LSC) is introduced to the rechargeable hybrid aqueous Zn/LiMn2O4 battery (ReHAB) as additive in the cathode formulation. Lignin acts as a key role to regulate and control the structure of LSC, intending to enhance the stability of the ReHAB by improving the float charge performance while maintaining other electrochemical performances of the battery. The lignin/silica nanocomposites (LSCs) are characterized by X-ray diffraction, scanning electron microscopy, surface area and porosimetry analyzer, and transmission electron microscopy. The results show that amorphous, uniform and mesoporous LSC-1 is prepared at the mass ratio of 1:2 of lignin to silica. LSC-1 used as the cathode additive improves the float charge performance of ReHAB via decreasing the float charge capacity by 57%. To compensate the loss of conductivity caused by LSC-1 and increase the capacity of the battery, graphene (G) is added. Compared to the reference battery, battery using the cathode containing 3 wt% combined additive of LSC-1 and G at mass ratio of 1:1, has 50% lower float charge capacity, higher rate performance and better cyclability. Up to a discharge capacity of 95 mAh g−1 is still obtained after 300 cycles of 100% depth-of-discharge.