I've never used a key file, only a 2-part passphrase (HW+my passphrase) or yubikey challenge/response.
Some of the cryptsetup options changed a few years ago. Might need to check that how-to with the current options available.
There are still 8 slots - 0-7.
Code:
luksAddKey <device> [<key file with new key>]
adds a new passphrase. An existing passphrase must be
supplied interactively or via --key-file. The new
passphrase to be added can be specified interactively
or read from the file given as positional argument.
<options> can be [--key-file, --keyfile-offset,
--keyfile-size, --new-keyfile-offset, --new-key-
file-size, --key-slot, --master-key-file,
--iter-time, --force-password].
Don't see any "of=" in the manpage here.
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