Windows only supports drive letters A through Z.
However, it isn't necessary for a drive (other than the boot, system and pagefile drive, and perhaps CD/DVD drives and similar) to have a letter; drives can instead be accessed by mounting them as folders in another drive (e.g. C:\Array\Drive27, C:\Array\Drive28, etc) and furthermore itself DrivePool can have drives form part of a pool without being lettered or mounted at all.
To add/remove drive letters or mount drives as folders in other drives, use Windows Disk Management: right-click a volume and click Change Drive Letters and Paths...
Late edit for future readers: DON'T mount them as folders inside the pool drive itself, nor inside a poolpart folder. That risks a recursive loop, which would be bad.