OK, this is an issue I can actually speak to from direct experience:
Back in my Battlebot days I used to have SMALL CO2 tanks filled at the local paintball place. (4oz, 8oz, and 20oz paintball-marker sized tanks).
On one occasion the counter-jockey overfilled a 4oz tank. Standard filling procedure for PB tanks is to partially fill then vent the tank to chill it so that it can be properly filled with a measured mass of liquid CO2 (leaving appropriate headspace for the gas-over-liquid volume at room temperature.) As I drove home from the PB store, the overfilled tank warmed back to ambient temperature while sitting on the passenger seat of my car and the safety burst disk blew.
Aside from the shock of the sound of a blown disc, the car was nearly INSTANTLY filled with condensed water vapor and CO2. Luckily I was on a straight, non-busy road and I have "auto-down" power windows, so I was able to quickly open all four windows in the vehicle and attempt to pull over and vent the "fog".
Later calculations showed that the C02 concentration might have been enough to cause harm, but I can certainly say that the more immediate danger was the sudden release of a cryogenic gas in an enclosed space.
CO2 will not "explode", but the sudden boiling of the liquid is EXTREMELY endothermic and potentially violent just the same. Admittedly, I was potentially negligent in transporting the tank sitting on the passenger seat, but even secured this tank would have vented due to overfilling. Raising the temperature of the tank (such as in a hot car) will result in a similar effect, especially if the tank is at or near the "full" level of liquid/gas volume.
Again, I will point out that this reaction occurred with a 4oz tank, basically the smallest refillable tank you can buy. (I have smaller custom tanks for my smallest robots, but that's another thing). If the venting CO2 liquid/gas mix had sprayed onto exposed skin, tissue damage was a real possibility. If the gas volume had been higher, or if the tank had taken longer to "empty", I might not have been able to vent the gasses from the cabin in a safe way. If the relative humidity had been higher that day, I might have created an even thicker "fog" which could have further obscured visibility while driving down the road.
In summary, I am now much more careful when transporting CO2. Whenever possible I leave my small tanks empty until I arrive and I would NEVER carry a refill station or other large volume of CO2 within the passenger compartment of a vehicle. Also, I haven't checked the MSDS on liquid CO2 lately, but I'm pretty sure when I last leased a CO2 refill tank, I had to sign a "training" document that basically said I promised only to transport the tank properly secured in an open-air vehicle, etc.