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Ex stands for Extension, in essence an addon for NPCScan and what it does is this: it injections many rare spawns not automatically added by the addon itself, and makes sure you are alerted no mater the level of the rare mob!
It's an experimental addon but it works. You can clean the existing database and then install the NPCs, or you can pick to only install missing NPC and leave the database as it is. If you are afraid then use the "Install only" option.
The slash command to open up the menu is:
/npcscanex or /scanex
Note that each character keep their own list of NPCs to track, meaning you need to install the database on each new character, and re-install when a new update is released. It's not so bad if you take a look at the "/npcscanex auto" command, it helps you update automatically!