(I think) I ran into the same or similar problem you did - there's a partition for the debian OS + iso images of a fixed size (df shows it as /dev/mapper/pce-root -> / ) and all the reallocatable storage used by the VMs comes out of the rest.
Thing is it's hard to re-allocate this partition, and that's where all the iso images, and the backups go.
I tried to migrate a vm and boom - it filled up.
I tried to figure out how to reallocate it, but in the end, I found this (sort of hacky) solution documented:
https://pve.proxmox.com/wiki/Logical_Volume_Manager_(LVM)
basically:
# lvcreate -n vz -V 200G pve/data
# mkfs.ext4 /dev/pve/vz
# echo '/dev/pve/vz /var/lib/vz ext4 defaults 0 2' >> /etc/fstab
you migrate the stuff from /var/lib/vz to the new location and you have 200G for iso images/etc
Why this has to fight for storage from the root system, or why it's not easily expandable is a head-scratcher. I think it might be better to have a dedicated boot debian partition, a resizable/easily growable pve partition, then storage that can be allocated to vms/containers.
but yeah - that stopped me in my tracks, and when I'm doing it on a home machine you just don't have the time to chase this stuff down.