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Most likely. Until the library becomes corrupted or the disk crash, and you have to create a new calibre library.
Most likely it is an integer that is at least 32 bits large. So when you have added something like 2,147,483,647 books (or possibly the double amount if the integer is unsigned) something unforseen might happen. Or not. If you continuously add one book per second to calibre it would take at least 68 years before that limit is reached. By that time calibre will most likely have been updated to handle larger integers, if it doesn't already.
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