It would seem to me that if the same thing is happening with two different batteries, one old one new, then it isn't the battery.
Its been my experience with my 2004 D2a, which I'ved had since new, that "13.9 to 14 volts with a peak of 14.1 a few times" is completely normal, unless it is charging a flatish batttery. I've never seen 14.8V (I have a dash mounted voltmeter) in my disco. Perhaps a fault in the alternator control circuitry.
So, if the brand new, fully charged battery discharged overnight then you must have a power leak somewhere. Perhaps in the dual battery controller or again in the alternator itself. If there's no leak, then the only thing I can think on is that there may be broken or loose connection between the battery and the starter motor.
If the voltmeter is reading 14V with the vehicle running, I think the squealing must be an unfortunate coincidence. My belt squeals only when I get dust on the belt having been off road. Get a hose and (gently) squirt the belt while the engine is running. If the squealing stops when you wet the belt, then its dust.

