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The animation starts once you press A. If the animation has started, you can stop it by pressing B. If you're away while the animation is starting and you can't press B, your Pokémon evolves.

I'm not a big fan of the Z-Moves, so those Crystals have stayed in my bag during the whole game. I hope playing competitively without them is possible too, I just really don't want to use them ^^;