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All I can say is that I have successfully copied my complete Calibre eBook library with about 13K books each typically in 3 or 4 formats and an associated calibre2opds catalog (totalling around 100K files and 32GB) without issues using an Explorer Copy/Paste although it took a very long time to copy.
I now use the (free) Microsoft RichCopy tool to keep my live Calibre library synced with my backup copy as that minimizes the number of files that need copying. I have also in the past used XCOPY with the option to only copy changed files set. The problem with XCOPY was that it would not remove files from the target that were no longer in my source, whereas RichCopy does if you have the Purge option set. Both of these options are MUCH faster than using Windows Explorer to do the copy.
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