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The duplicate checker has a binary compare.
Ebooks are very rarely actual binary duplicates. You may as well run something like Dupeguru over your unadded books folder + Calibre's library and just sequester those books from your unadded books, and don't even add them.
But if you've ever used any of the Calibre features that touch the ebook internals, and there are quite a few, then you'll get few if any results.
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