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Though it's largely for morale purposes (most boats operate in depths that if they sank would crush them), the reason for exhaling when escaping from a sunken boat is so that your lungs don't explode.
Sea pressure compresses air in the lungs, and that air expands as the person moves to shallow water. If you don't exhale as you head for the surface, you risk the air expanding in your lungs as the sea pressure decreases, rupturing the lungs and killing you.
It's not just for those in a disabled boat; the technique is also taught to divers in basic Scuba classes.
It's one thing if you're on the surface and hold your breath and then dive down; in that case, air at sea level is being compressed as you go deeper, and the volume will be the same once you return to the surface. For divers and those in submarines, the air is equalized to the ambient sea pressure at the depth in question, so the air expands as you go shallower.
Submariners are taught how to do this in Submarine School. Though I don't believe they use them anymore, we used to train in the old 100' water towers, where you entered at 100' and then rose to the surface, exhaling all the way.
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