Silicon is a strong competitor for the anode of the next generation of lithium-ion batteries, and ball-milled silicon has broad prospects as a low-cost method for preparing nano silicon. In order to match ball-milled silicon, it is imperative to develop better bonding agents with lower costs. Through adding amino silane coupling agent, the performance of ball-milling silicon anode is enhanced. This study explored the network structure formed by amino silane coupling agent with different chain lengths and polyacrylic acids. Herein, the crosslinked network prepared with 3-[2-(2-aminoethyl amino) ethyl amino] propyl-trimethoxysilane as coupling agent had the best performance, and the initial discharge capacity of the silicon anode prepared by this binder reached 3297.4 mAh·g−1 at a constant current density of 0.5A·g−1, the initial Coulomb efficiency reached 92.25%. After 100 cycles, the discharge capacity of anode was still maintained at 2229.5 mAh·g−1 with excellent charge/discharge performance.