Have a single 3.6hybrid and 2x 8.2kw batteries. The system has been working perfectly, bar a few minor hickups. We heat water, dishwasher, washer, etc by solar in the day, surplus going to battery for evening/night. Last two months have only drawn 2kw of daytime electric (economy 7) and average of 15kw nightime. The nightime was topup, for daytime use, to allow for two periods of 3days poor solar energy.
We are a heavy usage household, but this configuration works for the majority of the year. From November through to March we switch to everything reset for night usage and batteries charged on cheap rate for daytime use. We still required approx 60kw daytime in Jan and 30kw in February.
When we had the system installed it didn't make financial sense to have a third battery to cover this additional requirement. It would only be of any use for about 4months a year, charging overnight to ensure full daytime supply. The rest of the year it would just fill with the surplus solar, but we would have no use for it! The two 8.2 batteries was the way to go for us, allowing that extra capacity that also means you don't have to micro manage your system as much.
I am tied in to a good economy 7 rate till next September, but will have to re-evaluate the situation once I know what my future rates are likely to be.
I would have no hesitation adding the second battery, as others have said it just appears as one 16.4kw battery on the apps and they both charge/discharge in unison.