The old White's TM-808 had a cave locator feature, which would basically detect large "open spaces" within the ground, mountain, etc.
Sunn also made one.
I have used thermal photography a few times, but with that, the conditions have to be right. Little "fissures" or vents in cave systems can either pull in air, or release air. Generally, air flows up in the winter time, and mostly flows down in the summer. This is because the air temp inside caves is pretty steady, at around mid 40's or so. If the temp outside is warm (in summer), the cool air inside a cave will condense, and "suck in" the outside air from the top-side, releasing it toward the bottom somewhere. If the outside temp is colder, the warmer air is sucked in at the bottom, heats up a little, and flows upward, out through vents toward the top....
If the temp is around the same, you won't see much happening.
So, you kind of have to keep that in mind, but you can take a picture of an entire mountain face, and see some of these things happening, locating possible cave systems.
I've also used thermal guns (I use two Raytek models all the time). This works pretty good if you have an idea about general locations. It just takes awhile, and you have to be pretty close (within 20 feet or so), and the infrared dot is pretty small. But, they are very accurate.