I would also suggest to use UV-Vis-IR technique. You can determine the wavelength of the cut-off in your spectrum and calculate the band gap from the following equation:E = h*c/λ, where E is in Joules, so you can easily switch to eV taking into account that 1eV = 1.6 X 10-19 Joules. h is Planks constant, c is the speed of light, and λ is the cut-off wavelength.
Thanks for all of the responses. I will like to determine the band gap by uv vis spectroscopy also, but there is a difference between optical band gap and electrical band gap. Thats why I want to know the electrochemical route also.