Has Kaido the Conqueror's Haki
Has Ace mastered any haki skills?
Yes, Ace owned Haoshoku Haki.
According to Portgas D. Ace's article on the One Piece Wiki:
Although not depicted in the main storyline, it was revealed in a flashback that Ace Haoshoku owned Haki, over which he had no conscious control at the time. Ace first demonstrated the ability at the age of 10 when he knocked the Bluejam Pirates crew unconscious after a fit of rage (only Bluejam himself remained conscious when Haki was released and was a senior East Blue player at the time). Just as Luffy used his haki to take out a crowd of Kuja warriors, Ace used his haki to take out the attacking members of Bluejam's pirate crew.
Ace was first shown to know about this when, during the battle at Marineford, he saw Luffy unknowingly unleash his haki and say, "You too?" He has never been seen with Haki except in his childhood.
Ace unleashed Haoshoku Haki in chapter 587 ...
... and Bluejam's pirate crew after they were hit by Aces Haki.
He may have developed and mastered other types of haki as well, but they are not shown in the manga. After all, he was the 2nd division commander of the Whitebeard Pirates and had the power of D.
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