A little more detail if you like-
Onii can end with 3 different Japanese honourifics, -San, -Chan, or -Sama.
-San is the basic ending for the basic big bro.
-Chan is a more compassionate ending for Onii if you really love your big brother and feel emotionally attached to him greatly
-Sama is a bit of a formal ending for big brother, nothing too special.
Download audio sample : Onii-Chan