If you replaced the alternator's pulley with a smaller one, the alternator would spin faster at a given engine RPM. However, it would increase the load on the engine due to the reduced mechanical advantage.I can put an underdrive pulley on it which would make it spin faster so it would require less power to get more out of it.
If you installed a larger pulley, it would decrease the alternator's RPM for a given engine RPM, but it would decrease the load on the engine due to the increase in mechanical advantage.