Let $A,B$ be positive matrices on a finite-dimensional space, and suppose that $A+B=I$. In the special case of $A,B$ being projectors, we know that this implies that they must be orthogonal, as shown for example here and links therein.
Can something be said about the more general case of $A,B\ge0$?
If $A,B$ have orthogonal support, it is not hard to see that they must each equal the identity on their supports. We can therefore, I think, restrict ourselves to consider only the cases in which $\operatorname{im}(A)=\operatorname{im}(B)$, as we know that the restriction of the operators on every subspace in which only one of the two acts equals the identity (more precisely, one of the two operators will act like the identity and the other like $0$).