If they are both standard 12v batteries but one is showing a higher voltage than the other the higher one will drop and the lower one will rise. In other words the voltage of both will change until they reach equilibrium.
- If the voltage is different because one battery is faulty it could fully discharge the good battery damaging it.
- If the voltage is different because one battery fully charged while the other one is fully discharged it is not ideal because there will be a lot of current flow between the batteries and you will get a significant spark as you connect them. Although car batteries are quite robust and should cope with this why risk it if you can avoid it.
- If you are adding another battery to give you more capacity it would be a good idea to charge both batteries before linking them. I have run a twin battery set up in a 4WD and used an isolation switch so that I could never flatten the starter battery when camping and using power for lighting and refrigeration.
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