Slimy, sorry but both CR2016 and CR2032 are 3v lithium cells.
The number refers to the size of the cell: 20mm diameter, 1.6 or 3.2 mm thick. So you can fit two CR 2016 in the same holder that a single 2032 fits into. However 2xCR2016 will give you 6V which is not recommended if the electronics is expecting 3V from a single 2032.
I think some keys have two CR2016 and some have a single CR2032. The only way to be sure is to take the fob apart. I think it's older keys that have 6V electronics, but both my Toledos (2001 and 2004) had/have 1xCR2032 keys.
I had some fun changing my key battery recently,
as described in this thread. The key indicated that the cell was dying by flashing the red LED constantly. I can't see it doing that for too long on a dead cell, though. Fortunately for me it happened while I was out in the car - came back to it, remote wouldn't work, scratch head, look at keyfob: ooooh, look a that

Used the key in the lock to get into the car.
The keyfob does not need to be resynchronised to the alarm in my experience.
The keyfob is a radio-frequency remote control for the alarm system and central locking, which is one of two separate systems that restrict your ability to get into the car and start it. The other is the immobiliser, which uses a transponder build into the keyblade half of the key and is also present in the "dumb" key (which has no buttons: you have to use the key in the door lock to get in). The transponder uses no battery, it is energised and read by a coil surrounding the ignition key barrel.