This question has frame challenge written all over it. As many of the comments point out, there are other more well established ways to help your humans survive.
For the main question regarding lithium: Yes?
The quoted article and related information does indicate the effects of nitrogen narcosis could be delayed. Additionally, lithium has been administered for long periods of time to people with bipolar disorder (lifetimes). This means its tolerated well. In the absence of research on humans at high pressures, it certainly seems possible. It is important to consider the side effects of lithium toxicity which is very close to the effective dose. Your risks may outweigh your rewards.
For your secondary question, the answer is Oxygen
Your workers are basically saturation divers working at a depth of about 40 meters on earth. This is a very manageable depth as saturation divers can go much deeper.
For very deep dives Heliox is used. This is a mixture of helium and oxygen. This is done to avoid nitrogen narcosis as helium in not reactive. However, for shallower dives of up to about 40 meters, you can use Nitrox. This is a mixture of nitrogen enriched with a higher concentration of oxygen, which for your atmosphere would be anything higher than 7%.
As your atmosphere has oxygen present, your workers would wear portable oxygen concentrators with a simple mask.
A POC system is functionally a nitrogen scrubber capable of consistently producing medical-grade oxygen of up to 90%.[10]
Even by creating a mix of about 21% O2, you probably couldn't stave off all symptoms of nitrogen narcosis and oxygen toxicity. However, 5atm is really not that much so these would be mild. Your humans could be exposed to it for a fairly long time (more than a day) before they need to step inside and "decompress".
Sources:
Saturation Divers
Oxygen Extraction
Portable Oxygen Concentrators