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Don’t know that much about how btrfs works, just had a problem with the same symptoms as OP a while ago… Things started failing due to “no space left on device” despite df reporting several gigabytes available. Took a while to figure out what was going on but eventually found some stackoverflow/reddit post that told me to run the balance command and it worked. Just a single drive with btrfs, no raid.
A static website and Immich