Note that some OnStar services are disabled after a length of time. Remote Start via OnStar app may continue to work, but you may not be able to use the app to open the door. The "time after which some OnStar services are disabled" seems to have expanded from 5 to 10 days over the years (it’s unclear if it remains 5 days for some model years, and 10 days for newer models, or if it is now 10 days for all models for that issue):
The 2012-2016 Volt owner manual says: "Some OnStar services are disabled after five days. OnStar cannot perform Remote Door Unlock or Stolen Vehicle Assistance after the vehicle has been off continuously for five days. After five days, OnStar can contact Roadside Assistance and a locksmith to help gain access to the vehicle."
The 2017-2019 Volt owner manual says: "OnStar cannot perform Remote Door Unlock or Stolen Vehicle Assistance after the vehicle has been off continuously for 10 days without an ignition cycle. If the vehicle has not been started for 10 days, OnStar can contact Roadside Assistance or a locksmith to help gain access to the vehicle."
If you are at the car with fob in hand, you should be able to open the door via fob... and, this makes me wonder, could you use the app for a Remote Start after 10 days, have that count as "an ignition cycle," and then use the app for a Remote Door Unlock?
But, of course, if the reason you need to use the app is because you locked your fob inside the car when you parked it those many days ago, then you also can’t use the app for a Remote Start ("Conditions in which a remote start may not occur include: The RKE transmitter is in the vehicle...").