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An easy (but perhaps cheating) answer: The relative entropy $S(A||B)$diverges when $A$ has support over the kernel of $B$ (e.g., wikipedia). Now, the kernel of $B=|0\rangle^{\otimes n}\langle 0|^{\otimes n}$ is everything other than $|0\rangle^{\otimes n}$, i.e., $\mathbb{I}-|0\rangle^{\otimes n}\langle 0|^{\otimes n}$! For the inequality to be meaningful, ...