They are SO much faster and easier to cary than a frame pump. A 12g will do ~90psi, a 16g ~120 you can buy the co2 at Wally-world in boxes of 25 (12g) for cheap. I love mine, so little effort to fix flats (the only better way is to play dumb and get someone else to do it for you).
I swear by CO2. When I'm already sweating from the ride and pulling the tire off the rim (I'm stupid, btw... I don't carry tire levers) it's such a relief to see the tire inflate instantly. I carry two 16-gram cylinders, and an Innovations Air Chuck SL in my jersey. The things work beautifully! With the spare tube in another pocket, I don't even have to keep a bag on my bike. The 16g will inflate my 23c to 110 with air to spare.
If the decision is between a mini-pump and CO2, the choice is obvious to me. A larger mini-pump or frame pump might make more sense on multi-day excursions, or situations where you will be isolated from support.