If you're running to mated/balanced identical batteries in parallel (not series) in an unregulated box mod what it does is split the load of the atomizer equally between the two making the workload much easier for the batteries. If you run in parallel you still max out at 4.2 volts with freshly charged batteries but since each battery is only doing half the work you can (in theory) build lower than you could with only a single battery because only half of the amps for the load is coming from each battery doubling your amp limit (in theory). This is how you get double the mah life from using two batteries as well because you have to batteries sharing the load equally.
If you run unregulated in series (stacking the batteries as it's more commonly referred to as,) you have double the voltage (8.4 volts fully charged) but have the amp limit as if you were running a single battery as well as the same mah as if you were running a single battery because you have two batteries now working together to push out twice the power in the same amount of time as if you had just one.
hope that helps