you dont unlock him but you do help him in the middle of the game
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There will be a cut scene where Batman and Mr Freeze talk then a ninja breaks out of a glass case. You follow her blood trail and put a tracking system on her back. Robin comes, gives you the Line Launcher and you go off to Wonder City
It's unlocked at a certain point in the game. I can't really remember when it's unlocked but i know it's early in the game before you make it to mr. freeze. i think you get it after you escape the church
Main Characters: Batman (Obviously) Harley Quinn The Joker Robin Catwoman The Riddler Azrael Talia Al Ghul Ra's Al Ghul Bane Killer Croc Poison Ivy The Penguin Two Face Victor Zsasz Mr Freeze And that's about it :)
Penguin, The Riddler, Joker, Two-Face, Harley Quinn, Ra's al Ghul, Bane, Deadshot, Mad Hatter, Mr Freeze, Poison Ivy, Solomon Grundy, Clayface, Zsasz, Hush and Hugo Strange.
apart from general thugs, villians include Joker, Harley Quinn, Penguin, Riddler, Mr Freeze, Two Face, Hugo Strange, Clayface, Solomon Grundy, Ras al ghul, Bane Poison Ivy, Mad Hatter and two very short apperances by Black Mask and Killer Croc.