Definitely not Gil-Galad. Probably Fëanor with Fingolfin a close second. Eärendil killed Ancalagon the Black, but not by himself.
Fëanor fought at least two Balrogs plus other forces of Morgoth probably by himself. Fingolfin fought Morgoth one-on-one. Ecthelion of Gondolin who slew Gothmog and Glorfindel who also slew a Balrog are high on the list.