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Do I need a dweller in the storage room(s), or can I use the dweller elsewhere?
No, you do not need to have a dweller in a Storage Room. You might want to, in case of a fire or radroach invasion, but I wouldn't bother.
Putting a dweller in the storage room keeps them happy. Put high endurance dwellers in the storage room.
The storage room can be working as an empty one. The only reason you want to add dwellers inside is in case of an emergency starting in that spot, so you have people to take care of it.
Adding more dwellers adds NO benefits to your storage.