Sounds like your wife has a gen2 so you've experimented? 40 miles sounds about right at 75-80mph.That's the debate I'm in.
My commute to work is 60 miles, almost all freeway driving at 75-80 mph.
So the Gen II Volt ends up getting about 40 miles of electric before switching to gas.
The i3 should be able to make the entire journey on electric.
According to the EPA, the gen2 highway EV range is 49 miles, and the used 60AHr i3 REx has a highway EV range of 66 miles. So if the gen2 Volt at 75-80mph is down to 40 miles, then the i3 REx is down to 54 miles, so its not quite going to make it either. That means you'll be buying a gallon of premium gas every 4-5 days to top off your 1.9 gallon tank, which sounds like an unexpected hassle. Also, for the i3 REx, 80mph using the ICE is possibly beyond it's limits.
Of course, at 75-80mph, 20 miles ICE daily, you'd probably be filling up the Volt every two weeks or so its not tons better. I guess your best bet is to find an L2 charger at work, and then either the Volt or the REx would work for you. Since you're in California, there are also several 100 mile pure EV's that might work for you as well.