I hope someone else will take a look at this!
I think it is simply false to say E(z) = V/z, assuming E(z) means the z component of the electric field. Consider the situation where the point (x,y,z) = (1,0,0) relative to the charge q causing the field.
Then E(z) = V/z = V/0 = infinity.
The electric field will not be infinity at a position 1 meter away from the charge.
Your E = F/Q equation allows you to find the formula for E.
It assumes there is another charge, Q at the position we are interested in and F = kq*Q/r². Use E = F/Q to finish the job. And note that for the (1,0,0) example, the z component is not infinite.