LiPF6 is a contact irritant, PF5 it decomposes to is a gas, and also a respiratory irritant, and HF PH5 decomposes in the air is a dangerous poisonous acid.
This is what everybody visiting a lithium battery factory is told on safety orientation. In case there is fire in the factory, run, preferably until you are few blocks away.
If enough hot aqueous LF6 in solvent gets on the skin, you will get a chemical burn. In worst case, the same thing as HF poisoning will happen (it pulls electrolytes out of blood, and then death from heart failure.)