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You don't want to boil your battery unless you have a charger that is designed to do an equalizing charge and most car battery chargers don't do that, they just do a float charge, much safer for the battery.
The only advantage to the higher voltage is that the starter spins a little faster, I don't think this will help your gas mileage and the battery is not going to have that much "extra" energy in it from being over charged, the advantage that you will get from charging the battery before you drive is that your battery might last you 20 years (if you don't boil it!) and that your alternator isn't going to have to work as hard to make up for a part charged battery because it was sitting over night.
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