D and L are not driving gears, but level settings for regen. You can change them while moving.
The Wikipedia article on the Gen 2 Volt has a sidebar with specs for the 2017 Volt. There it says the battery is 18.4 kWh, 14 kWh usable. There are several factors the car’s system uses to determine when it is time to "switch to gas" as the car is moving down the road, so the 14.5 kWh you noted is within a reasonable variable range for a full depletion.
Note that the energy usage display of kWh Used is not a meter reading, but a net estimate of grid power used less regen put back into the battery. If you drive down a long hill, for example, you may notice this number decreases as regen is put back into the battery. The "net" calculation allows the "fully depleted" reading to remain fairly consistent, representing the amount of usable power in a fully charged battery.
For more information on the kWh Used display, check out forum moderator Steverino’s kWh Used vs. Battery Degradation FAQ:
kWh Used vs. Battery Degradation FAQ
As to how far you could drive a Gen 2 Volt on a single charge, consider the impact of downhill regen on mileage (i.e., regen is not counted as fuel when calculating fuel mileage): you are on a plateau, where one road makes a long descent into the valley far below. Charge your Gen 2 Volt, then unplug and drive around the plateau until just before the ev range estimate drops to 0 (at window sticker ratings, the display might now read: 52.9 Electric Miles/13.9 kWh Used). You’re now at the edge of the plateau and start the long descent. Let’s say the downhill drive is 10.1 miles and it’s steep and long enough for regen to fully recharge your battery. When you reach the valley floor, the display reads 63.0 Electric Miles / 0 kWh Used.
You now drive around the valley floor another 53 ev miles, and the car finally runs out of battery power and switches to gas. Your display now reads: 116.0 Electric Miles / 14.0 kWh Used, 232 MPGe
Do you really believe you just drove 116 ev miles on only the 14.0 of grid power you put into the battery when you charged it at the top of the mesa?