Characterization of a Recyclate‐Based MgO‐Steel Composite As‐Sintered Inert Anode Candidate After Exposure to Cryolite Electrolysis

The replacement of consumable carbon anodes with oxygen‐evolving inert, carbon‐free anodes is a key technological challenge for decarbonizing primary aluminum production. While metallic, ceramic, and cermet anodes have been extensively studied, the use of recycled raw materials remains largely unexplored. In this work, composite cermet anodes consisting of 60 vol% AISI 316L stainless steel and 40 vol% recycled MgO from spent refractories were developed and tested under galvanostatic Hall–Héroult electrolysis conditions in cryolite at 1000°C. The as‐sintered composites exhibited stable cell voltage (3.2–3.3 V) over 2 h of operation. Postexperiment SEM/EDS/EBSD analyses revealed a multilayered structure with protective Fe‐oxide, Al/Cr spinel formation, corroded Mg‐F‐rich phases, and cryolite infiltration extending beyond 2 mm depth. While the 316L steel matrix showed relative stability, the recycled MgO fraction proved chemically reactive, generating porosity and acting as the primary pathway for melt intrusion and secondary Al 2 O 3 precipitation. Complementary static contact corrosion tests (CCTs) confirmed rapid fluorination of MgO, whereas steel grains remained intact.