It doesn't matter whether the database is in use - Time Machine skips Outlook databases (regardless as to whether they're locked), and Outlook builds new ones after restoration of a user identity (eg, via system restore, or migration from backup).
I know what you're probably thinking about now, so don't take my word for it - hunt down a system with Outlook and Time Machine in use, ensure Outlook isn't running, trigger a backup, then search the result for the database file. How is this exclusion configured? I don't know, but nevertheless...
(Though it strikes me that this might've changed after, say, Outlook 2011. Couldn't say for sure. The linked article implies it's still a thing.)
What I do know is that prior to Outlook, Office for Mac offered Entourage - which also used a single database file, but stored all email-related data in it. Consider what happened when a user got an email - that database file changed, and Time Machine would include it in the next backup.
That is to say, on a regular basis Time Machine's hourly incremental backups would include the user's entire email collection. This led to backup drives being filled in fairly short periods of time.
Under Outlook, a single database file is still in use, and that file still gets quite large and changes often - but the actual email data is strewn across a set of much smaller files, the majority of which aren't affected when you eg get a new email. The database is no longer included in backups, solving the Entourage dilemma, and can be rebuilt in the event that a system restore is performed (by inspecting the separated email files, which of course are backed up).
The catch to all this is that the database rebuilding process is, in my somewhat limited experience, unreliable. I've seen it attempted on four different systems, and seen it succeed on only two of those - and without a working database, reading your emails becomes through Outlook becomes rather difficult.
Edit:
Mind you, I'd love to know where Time Machine's hidden exclusion list is kept. Presumably apps are able to alter it (just as they can tinker with the way Spotlight indexes certain files), and it'd be potentially handy to know what's on it.