This is something I have looked into for many years (about 8). I know people HATE when i bring this up, but it goes very well with this topic. I breed feeder rats (no imbreeding, I'm ubber picky as I do give some away as pets). I feed live & dead. I once thought drowning was painless & thats how I killed my feeders many years ago... I soon realized that not only was it painful, but the animal was being scared to death in the process. I then held off on killing them until I found a better way. I read info online & talked to my Bio & Chem teachers. We all disscussed this in great detail for a long time.
Besides dying in your sleep, freezing to death is the next best way. But it has to be done right. There needs to be shaving or someway for the animal to keep its feet warm as frost bite is painful! What happeneds is that hypothermia sets in. What that does, is it slows the body down, which then makes the animal fall asleep until death happeneds.