Mrcapcom
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Some characters have moves that make them invunerable for a short time, for example your 2 of your Tier 2's (Sharon and Elsa) have invunerability on their 3rd and 5th skills respectively.
Your other Tier 2 (Silk) has a different kind of protection called a guard hit. It's a shield that will protect your character for a specific amount of hits.
So with characters that have activated defenses like that you need to make sure you are triggering those abilities *every time they come off cooldown*, using these moves is priority number one. If you max your skill cooldown stat (50%) then you can keep these moves active almost the entire time.
As for I-Frames, that's a little harder to explain as the game doesn't give any indicator of what moves have them. But basically it's a move that has either part of the animation or the whole animation which puts the character in an invulnerable state. Sticking with your characters, for example Sharon Rogers 4th skill (with uniform) is an I-Frame when she lifts off into the air and shoots the beam down. Silk's second skill is an I-Frame start to finish. In general (though not always), if a character goes airborne as part of the animation you will be invulnerable during that. You can time these moves to avoid damage.
Awesome so if you max skill cooldown by going where? I remember you could pay to move stats along but I forgot where and also can't that mess you up? Like mess with the stats or is it something I should always spec in?