Adding 2nd drive for raid without reinstalling PVE, possible?

Did you install on ZFS? If so, then it is not too hard. Follow the guide on how to replace a failed boot drive but instead of a zpool replace you run zpool attach <current disk part3> <additional disk part3>

eg: zpool attach /dev/disk/by-id/<current disk>-part3 /dev/disk/by-id/<aditional disk>-part3
 
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