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It's going to depend a lot on what you mean by highway driving. Solo driving at 80? Drafting safely at 55?
My commute involves driving 60-65 and some city (80% state highway). I'll get about 42-46 miles on my 2014 before the gas engine kicks in. Spring/summer driving with the AC on enough that I'm not uncomfortable. Engine only, I get a little over 40mpg on road trips.
Earlier Volts without "hold" mode still have "mountain" mode. This doesn't let the battery fall below 50%. You can even use it to charge with the engine to 50% if the battery is low, but this is inefficient.
I put together a calculator to compare operating costs for gas, hybrid, plug in hybrid, and full electric. I can give you an output if you give me some info for electric rates, fuel cost, and estimated mpg/range. I think the Volt website has something similar.
The first 40 electric miles are going to be much cheaper than gas, your oil changes significantly less frequent, and the Volt has quite a bit more power. I think the Prius starts to make more sense with 100+ mile round trip.
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