I haven't tried this, but I can't see why it wouldn't work.
By default, the Photo Library inside of your /Users/Pictures/ is set to be the 'System Photos Library' (You can see this by choosing 'Photos-Preferences-iCloud' (This will be important)
First of all, make sure the Photo Library on your system is complete, and set to Optimise Storage.
Close Photos, reopen while holding the Option key and choose to 'Create New Library'. Save this to your External Drive.
When this new Photo Library opens it will be empty. Go into 'Photos-Preferences-' and choose 'Use as System Photo Library' (This step may require a relaunch to complete). You should then be able to go to the 'iCloud' tab and choose to enable the iCloud Photo Library and choose 'Download Originals'
The 'System Photo Library' is the one that will automatically update with new Photos from your iCloud Photo Library, so you will need to switch this setting when you want to use the other Photo Library (while holding Option on opening Photos).
This means that you will have to switch the 'System Photo Library' back and forth, and generally I'd leave it set for the Optimised Photo Library (even after you've just downloaded and set the Originals one), just to that it will be nice and up to date.
I'm hoping the setting for 'Download Originals/Optimised' is a setting within the Library, as opposed to a Photo setting, or else it will be a headache. The only other option would be to have the Originals/Optimised Libraries in different logins, but then that would get a little messy!
Hope this is something to try
