Spectacular Spider-Man #90 features the first appearance of Spider-Man's black costume.  This book was released the same month, but a week or two after Amazing Spider-Man #252 so technically some consider it tied for the second appearance of the black costume (with Marvel Team-Up #141, which was released the same day).  Black Cat also appears.  This book is graded 9.6 NM+ with white pages by CGC.  Color, gloss, and alignment are excellent.