When you are moving from a traditional homedirectory based environment to Onedrive for Business, O365Migrator is the best free tool out there to assist you.
O365Migrator will provision, authorize, clean up and upload. It is everything you need to move from homedirectories to Onedrive for Business in one simple free tool.
If, for some reason, you want to see which domains in your exchange organisation are not being used (not registered in the ProxyAddresses fields of your users), use below snippet in the Exchange Powershell Module.
Note: this does NOT (yet) check for domains used in Public Folders or Mail Contacts.
Recently I wrote a small (login) script to automatically configure the Next Generation Onedrive for Business client with the proper tenant and no user interaction (except for a one-time login). This reduces user impact when migrating to Onedrive for Business.
This script is an addition to O365Datacleaner and will allow you to run the original script over many target locations simultaneously, using a CSV file as input.
This is the simplest and most reliable method currently available to make, for example, all the data on your fileservers spread out over homedirectories completely compliant with Onedrive for Business or Sharepoint Online’s requirements.