Relations can be custom created in the designer using a PK field on either side of the tables.
In your case no PK is envolved in the relation, then you won't be able to define a relation at design time, and so you won't be able to add a field mapped on this relation.
But you can create a custom relation at runtime between any 2 fields in the database in order to make a JOIN needed for a query.
If I were in your shoes, I'd do the following:
In the database:
1- Create a View to capture the non-mutuable studentinformation without it's PK
In the LLBLGen Pro Designer:
2- Map it to LLBLGen Pro as an entity, and manually set the 'StudentNumber' as the PK.
3- Define a custom relation between both tables using the 'StudentNumber' field.