If you think for a few seconds about it you will recognize that this is true. When a path is passed in, LabVIEW has at every call to verify that the path has not changed in respect to the last call. That is not a lot of CPU cycles for a single call but can add up if you call many Call Library Nodes like that especially in loops. So if the dll name doesn't really change, it's a lot better to use the library name in the configuration dialog, as there LabVIEW only will evaluate the path once at load time and afterwards never again.
If it wouldn't do this check the performance of the Call Library node would be abominable bad, since loading and unloading of DLLs is really a performance killer, where this code comparison is just a micro delay in comparison.
If I would have to have a guess, using a not changing diagram path adds up maybe 100us, maybe a bit more, but compare that to the overhead of the Call Library node itself which is in the range of single us. Comparison of paths on equality is the most expensive comparison operation, as you only can determine equality if you have compared every single element and character in them. Unequality has on average half the execution time, since you can break out of the comparison at the first occurrence of a difference.