Synchronising is the preferred way to backup library and is highly recommended. This should be done as well as backing up your library so you effectively have two back ups if anything ever goes wrong.
How to sync your library
Go to Edit> Preferences> Sync> Click 'Enable Sync'.

Click on Sign Up and follow the steps to create an EndNote account (or link to an existing Endnote Web account)

Only one library can be used – so make it your main library. If you already have references in an EndNote Online account they will also go into your library (make sure you want this!)