The relationship between the diffusivity and electrochemical characteristics of lithium secondary battery with the modified Si anode material prepared in HF/$AgNO_3$ solution was investigated. The crystallographic structure and images of the modified porous Si and modified Si/Cu was examined using the X-ray diffraction, BET and SEM. To examine the effect of metal composite and pore size distribution according to chemical etching on the electrochemical characterization, the electrodes for half cells were prepared with the modified Si, modified Si/Cu, and modified Si/Cu annealed with $600^{circ}C$. Our results showed that the chemical diffusivity of lithium ions was related to structure and resistance of Si/Cu composite anode material. The lithium diffusivity in modified silicon compound calculated from the CV was at the range of $1{ imes}10^{-12}$ to $9{ imes}10^{-16}cm^2/s$. The effects of modified silicon structure and resistance on the cycling efficiency were significant.