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You have to look at the amp hours (AH) for the batteries. In most cases you are going to get more AH out of two 6v batteries than 2 12v batteries. The big draw back to the 6v batteries is the weight.
As already mentioned adding a battery to your current setup will just pull the new battery down to the level of the old one. You are best to replace the old one when you add a new one. That is also why with diesels with multiple batteries it is recommend to replace all batteries even if only one is currently bad.
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