I don't know if it's the absolute fastest since I've never timed it, but robocopy is, hands down, a much more robust, useful tool than xcopy. I've never really done anything with the powershell tool.
Xcopy and Copy-Item may be single threaded. Robocopy by default uses 8 threads to copy 8 files simultaneously (you can increase the thread count up to the number of your physical cores). But obviously the storage medium should be able to handle writing files in parallel. If you are reading from and writing to an SSD, Robocopy may potentially perform the fastest. I would suggest timing the copying of some folder with a large number of variable sized files. Do Robocopy first. Reboot. Then try Xcopy. As soon as the time exceeds 30 seconds more, abort it, reboot and finally test copy-item.
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