I was queried the backup history, when I am getting 'NUL' for physical_device_name. Is logshipping going out of sync due to this?
Yes correct, someone is running command line backup database db_name to disk='nul' which makes SQL Server think that you are actually taking backup but since you would have specified NUL (Single L) the backup goes into kind of space which immediately deleted it, it like NUL which you use in Unix which deletes anything written on it. So SQL Server thinks you took backup and stored and OTOH you lost it in NUL and this log backup is not moved to secondary server hence LS breaks.
You need to find this process and STOP it, its NOT needed at all