Everything I have researched says that cervical dislocation is the most painless and FASTEST method. Quicker than CO2.
It is more difficult with large rats, so I don't recommend trying it without doing a little research, and being confident in your ability to act precisely and quickly, without hesitation, or things can go wrong and the animal will suffer.
I do agree with you though that this would have to be the quickest and most humane method if you can stomach it.