The Li-Ion cell would see the NiMH cell as a big resistor. If the NiMH cell discharges before the Li-Ion cell, it could reverse polarity on the NiMH cell. NiMH cells are safe, but I don't know if that's true when reverse voltage is applied. The NiMH cell wouldn't catch fire, but could burst putting excessive force and heat on the Li-Ion. Overheating or crushing a Li-Ion is hazardous since it can short internally resulting in fire.
If the Li-Ion cell discharges before the NiMH cell, the opposite will happen, the NiMH cell will see the Li-Ion cell as a big resistor. If the Li-Ion is not protected, voltage will reverse on the Li-Ion which would quickly destroy it.
Regardless of the technical reasons, mixing cells of two different types just doesn't sound safe based on common sense. Even mixing Li-Ions that are not matched is a bad idea.