I suspect the play they're making is that putting millions of new Discover cards out there will be a tipping point, pressuring the remaining merchants who don't take it, as a play to break the Visa/MC duopoly.
This could be not that hard to pull off. American Express historically was less accepted because of their high fees, but I don't think Discover has or had that problem.
Maybe I just don't use it enough but I can really only remember one time in the last ~15 years that I've tried to use my Discover card and been told they don't take Discover. I wonder if there's a geographical component, or if certain industries are less likely to take anything other than Visa/MC?