i think it is obvious to say that fish can't live in a tank of dechlor. with that said if u go a little over on the dechlor. no it won't hurt the fish u can add it basically when ever u think is best some people say before so say during it doesn't really matter.
There are a couple of ways to add dechlorinator, add to bucket of water or straight from the tap with a hose onto the tank.
I treat the whole tank before I put the water in. Chlorine will kill your fish faster than any ammonia.