I have to second this. There is so much power in relational databases that is untapped by most developers. The best part about this is that, for the most part, this type of knowledge can apply to multiple databases.
Some specific things that I want to gain a deeper understanding of are window functions[0] and recursive CTEs[1]. In particular, I've used window functions to identify peaks in sensor data (e.g., finding spikes in temperature, water level, etc), which would otherwise require iterating through rows and maintaining a bunch of state. I've never actually written a recursive CTE, but I'm pretty sure it would simplify virtually anything dealing with a hierarchy.