A single belt will be unlikely to slip unless you sap down the battery a great deal by having every accessory on at once ,or use a winch for a long hard pull...having double batteries will ease the load on the alternator by allowing them to be the main power source,and the alternator wont have to max out to keep both charged,just maintain their fully charged status..
You can get double grooved v pulleys for the alternator,its finding the correct engine and water pump pulley setups to allow double grooved ones to be used that will prove hard to get--there are many more serpentine setups in boneyards now than any V belt driven alternators,its been since '87 they went to serpentine..