Although, we would love to see such a large network being built with eXo Social, our initial target is more tens of thousands, rather than millions. Because, yes, we focus on enterprise environment primarily.
We intend to make some measurements and scalability testing in the coming months. We'll share result when available.
About persistence, exo Social uses eXo JCR as the persistence engine. Note that eXo JCR uses a relational database for storage by default, but is possible to write your own storage engine based on a nosql engine.