We study the onset of dissipation in an atomic Josephson junction between Fermi superfluids in the molecular Bose-Einstein condensation limit of strong attraction. Our simulations identify the critical population imbalance and the maximum Josephson current delimiting dissipationless and dissipative transport, in quantitative agreement with recent experiments. We unambiguously link dissipation to vortex ring nucleation and dynamics, demonstrating that quantum phase slips are responsible for the observed resistive current. Our work directly connects microscopic features with macroscopic dissipative transport, providing a comprehensive description of vortex ring dynamics in three-dimensional inhomogeneous constricted superfluids at zero and finite temperatures.