Actually you can do that. When adding extra batteries though for inverters to run appliances and power tools on though it's a good idea to use a battery isolator for the extra battery. The battery isolator lets you use one high amp alternator to charge all your batteries. If the one battery on the inverter or other high amp pulling accessories pulls down you still have the other battery charged that only runs your starter, lights, and vehicle ignition and accessories without pulling down both batteries that way. Ambulances, fire trucks, over the road trucks have been using battery isolators to do that for years now it's nothing new and does work well. Get a isolator that is rated a bit more than your alternator amps and the load you want to run on it.
http://www.colehersee.com/04resource/tec%5EBatt%20iso.htmYou probably don't need a alternator with 250 to 300 amps but they are out there and not cheap. An emergency vehicle with all those high amp flashing lights, cordless chargers, inverter, and other high amp drawing accesories won't work on one battery and a pissy ant 50 amp alternator.
http://www.nationsautoelectric.com/ecotech.html