It hasn't happened in anime, only in manga.
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First time Danzo appear is in Naruto Shippuden Episode 32
Source : Naruto.wikia.com
behind Danzo's mask is what Danzo absorbed out of Uchiha Shisui.
Episode 208
There are 220 Naruto episodes and 142(and counting) Naruto: Shippuuden episodes.
The first time he appears is episode 135 as a hologram
Well I'd say Naruto is stronger than Danzo because in manga 499 he learns how to control the kyubi. With that being said, if someone were to be able to control the demon fox back when minato (4th Hokage) was fighting him, minato would not have defeated the fox