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The math assumes the car travels 40 miles (62 km) before it runs out of battery power and then an additional 10 miles (on 0.2 gallons of gasoline) before running out of gas. So 50 miles on 0.2 gallons = 250 mpg, minus some lost energy recharging the battery and they arrive at the claim of 230 mpg.
So that is a nice claim, except the GM Volt won't actually go 230 miles. You will only go about 50 and then run completely out of battery and gasoline. And the time required to recharge the batteries is such that the $40,000 USD you paid for the car you will have a hunk of junk in your driveway that is constantly being charged, but rarely ever gets used.
And frankly why pay extra for a hybrid version of the car? Why not just stick to the standard electric version? Sure, the electric version can only go 40 miles, but the extra 10 miles just seems silly. So yes, the Volt hybrid goes 20% farther than the regular Volt... but what is the point if you are still restricted to very short distances like city driving only?
Also, if you are doing this for the environment... why not just take a bus, subway or cycle?
#1. The bus or subway is going that way anyway. Whether you take it or not it will still be using the energy to haul people back and forth.
#2. The average cyclist gets 15 mph (24 kph) and if you have a roadbike the average is about 18 mph (29 kph).
#3. About 35% of the electricity used to charge your GM Volt comes from coal power anyway, so unless you have 20 solar panels on your roof and you're charging it yourself (off the grid) you'd still be polluting for the sake of your motor.
Or you could wait a couple years for hydrogen filling stations and buy a hydrogen car, which is set to replace electric cars anyway. Hydrogen is more efficient way of running an electric motor. Way better than battery power.
Note: If someone were to invent a more powerful battery or a more efficient way to store energy they could rake in billions.
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