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As far as I know, once, in episode 66, and because (if you don't mind spoilers) they landed on a island filled with barouqes works agents, who tricked them by getting them to drink until they passed out, and Zoro woke up and had to kill all of the billions that where there, and Luffy was confused, thinking that he killed them for no reason, causing them to fight. Hope that helped!

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