If you don't have "Optimize Mac Storage" set with the iCloud Library then Yer_Man's recommendations will do the trick. But If you have "Optimize Mac Storage" enabled in Photos/iCloud settings you'll need to do the following;
1 - create a new library on the external drive where you will want to store the photos.
2 - set it to the System Photo Library and enable iCloud Library.
3 - DO NOT enable "Optimize Mac Storage"
4 - leave Photos open and in the background until the iCloud Library and completed it's download. Depending on the size of the library it could take up to a week or more. Leave the Mac on over night, do not sleep the Mac but just use the Screen Saver.
5 - when the download is completed disable iCloud Library and set the other library as the System Photo Library.