Luffy Uses Ryuo For The First Time [One Piece]
In what episode does Luffy use Ryuo Haki for the first time?
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Episode Summary:
Big Mom invades the Prisoner Mine in search of Red-Bean Soup (or Oshiruko) but is challenged by Queen. Queen however got over powered by Big Mom. After finding the pot with the Red-Bean Soup, Big Mom realizes that it is empty, this sends her in rage ad attacks Luffy who unknowingly admitted he was the one that ate all the soup. With the fighting ring now destroyed they are now out of bounds and the timer for the collar to activate starts. finding himself in this desperate situation, Luffy attempts to remove the collars with Haki and manages to activate Ryuo for the first time. He crushes both his and Hyogoro collar and throws them away before they could explode. Wanting to further Luffy’s Ryūō training, Hyogoro forces Luffy to defend him from Big Mom. 
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