The only fully supported thing is to have the main repository on one disk,
and .git/annex on another. Only commands that move data in/out of the annex
will need to copy it across devices.
There is only partial support for putting arbitrary subdirectories of
.git/annex on different devices. For one thing, but this can require more
copies to be done. For example, when .git/annex/tmp is on one device, and
.git/annex/journal on another, every journal write involves a call to
mv(1). Also, there are a few places that make hard links between various
subdirectories of .git/annex with createLink, that are not handled.
In the common case without cross-device, the new moveFile is actually
faster than renameFile, avoiding an unncessary stat to check that a file
(not a directory) is being moved. Of course if a cross-device move is
needed, it is as slow as mv(1) of the data.