Game consoles, and back in the day most MS-DOS, Amiga and Atari Games that only used hardware directly with OS services could in retrospective be considered some form of unikernels.
Amiga games used to be written such that they would boot the computer from floppy.
It's from an era before ubiquitous MMUs, even in IBM mainframes. It therefore was structured as a library OS, with even less separation between it and the application code than even MSDOS and it's applications.
Transaction Processing Facility: A Guide for Application Programmers by R. Jason Martin is a decent book I'd recommend on the subject.
I believe Cisco had an unikernel running on Vmware for SDN vSwitches.
Makes sense: you "only" need to move packets from some vLan to another vLan/vNic after applying policies... and you can forget about supporting hardware modules alien to you.
The automotive domain definitely use them (e.g., Open Synergy and others), since their efficiency means they consume fewer resources on ECUs, and their relatively small Trusted Computing Base (TCB) not only reduces exploits but also means certification is cheaper/faster.