I have successfully run a 96v system at home for about four years. Never had as much as a tingle from it either, but then I am an old fart with very dry skin.
On the other hand, I once helped a mate launch his aluminium power boat from the beach. I was up to my knees in salt water and had wet hands.
With one hand clutching the gunnel, I accidentally came into direct contact with the twelve volt battery with my second hand. That was quite a belt I will never forget.
So its not so much the voltage as the current that can flow that gets you.
Anyhow, back to 96 volts. It has advantages from the wiring and efficiency point of view, but there are a lot of extra battery cells to keep an eye on.
As already stated, there is very little equipment out there designed to run directly with 96 volts dc.
While I am quite happy with my own 96v system, If I was building a boat I would go for 48 volts, and be pretty afraid of it, given my past experience with only 12v. But you asked the question, and those are my feelings on the subject.
Positive ground will corrode your hull. Negative ground will corrode your wiring. Up to you to decide, but most things are designed for negative ground these days, especially with an inboard engine.