Just had same problem. Using Xcode 8.3.3 and wanted to use AppIcon in Assests catalogue. Tried all sorts of Stack Overflow answers without success.
Finally learned about a deep clean step from Ken/Apple Forum:
- removed all icon files, whether from resources (delete - trash) or appicon file (select - remove selected items); removed even assets folder
- deep cleaned (Use the Product menu w/option key pressed, then choose to 'clean build folder')
- added a new asset catalogue and called it "Assets" right clicked in Assets folder and added new app icon set - changed that one in inspector to be for iOS >=7
- triple
checked all my icon files OUTSIDE of Xcode (all were already png files of right resolution, but some had still colour profile attached from photoshop elements or did have indexed colour instead of RGB profile. so I made sure I only save a png file without colour profile and from a background layer) - not sure that was necessary
- archived the build from Product menu
- validated and uploaded the build from Window - Organizer