The growth of population and the limited supply of fossil fuels have forced the world to seek for new kinds of alternative energy sources which are abundant, renewable, efficient, secure and pollution-free. In this regard, hydrogen is generally considered as a potential candidate. However, it is a great challenge to find hydrogen storage materials with large hydrogen gravimetric density under ambient thermodynamic conditions. The most effective way to improve the hydrogen storage capacity is to decorate the pure nanomaterials with transition metals, alkaline metals, and alkaline earth metals. The generalized gradient approximation based on density functional theory is used to study the hydrogen storage capacity of the expanded sandwich structure graphene-2Li-graphene. It is calculated that the structure with the Li atom located above the face site of the hexagonal ring of the graphene has the maximum binding energy (1.19 eV), which is less than the experimental cohesive energy of bulk Li (1.63 eV). However, the calculated binding energy values of the Li atom to the upper and lower graphene layer are both 3.43 eV, which is much larger than the experimental cohesive energy value of bulk Li, so it can prevent the Li atoms from clustering between graphene layers. Each Li atom in the graphene-2Li-graphene structure can adsorb 3 H ₂molecules at most. Thus, the hydrogen gravimetric density of graphene-2(Li-3H ₂)-graphene is 10.20 wt.%, which had far exceeded the gravimetric density of the target value of 5.5 wt.% by the year 2017 specified by the US Department of Energy. The average adsorption energy values of H ₂adsorbed per Li are 0.37, 0.17, and 0.12 eV respectively for 1−3 H ₂molecules, which are between the physical adsorption and chemical adsorption(0.1−0.8 eV), therefore, it can realize the reversible adsorption of hydrogen. Each Li atom can adsorb 3 H ₂molecules at most by the electronic polarization interaction. The dynamic calculations and GFRF calculations show that the interlayer Li atom doped double-layer graphene has good reversible adsorption performance for hydrogen. This research can provide a good research idea for developing good hydrogen storage materials and theoretical basis for experimental worker. These findings can suggest a way to design hydrogen storage materials under the near-ambient conditions.