I once had a chat about this with a good friend. The library is your book shelves. The home screen is your coffee table - big glossy covers and text, and one-tap quick access.
On a more practical level, the home screen always shows books in the order they've last been opened whereas in the library you could be in different collections with different sort orders. So the last book(s) read might not be on top and would be harder to access.
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