Erik,
Let’s say you currently have two 6-volt, 100 Amp-Hour batteries wired in series to get 12 volts.
If you install a third in parallel with one of them you essentially will still have two batteries in series, but one will be 100 Amp-Hours and the other will be 200 Amp-Hours. As you use power from these TWO batteries (one 100 Amp-Hour and one 200 Amp-Hour) each battery will be providing half of the power because they are in series. When the 100 Amp-Hour battery is depleted, the other (200 Amp-Hour) battery will be only half-depleted. However, with one of the two batteries dead (the 100 Amp-Hour battery), you will be getting just 6 volts from the installation – no useable power.
This is exactly the same as when one battery goes dead in a flashlight that takes two batteries. You don’t get much light out of that flashlight, even though the other battery may be brand new. Flashlight batteries are in series, just like the 6-volt batteries in your RV.
If, instead of installing just one more battery, for a total of three, you install two more batteries, for a total of four, you will indeed double the capacity of your installation. You would have a pair of 6-volt batteries in parallel wired in series to another pair of 6-volt batteries that are also in parallel. This would create the equivalent of two 200 Amp-Hour batteries in series.
The bottom line is that three batteries would be worse than the two you have now, but four batteries will double your capacity.
Good luck,
– Loren