Unconventional Charge Transport in MgCr2O4 and Implications for Battery Intercalation Hosts

Ion transport in solid-state cathode materials prescribes a fundamental limit to the rates batteries can operate; therefore, an accurate understanding of ion transport is a critical missing piece to enable new battery technologies, such as magnesium batteries. Based on our conventional understanding of lithium-ion materials, MgCr₂O₄ is a promising magnesium-ion cathode material given its high capacity, high voltage against an Mg anode, and acceptable computed diffusion barriers. Electrochemical examinations of MgCr₂O₄, however, reveal significant energetic limitations. Motivated by these disparate observations; herein, we examine long-range ion transport by electrically polarizing dense pellets of MgCr₂O₄. Our conventional understanding of ion transport in battery cathode materials, e.g., Nernst-Einstein conduction, cannot explain the measured response since it neglects frictional interactions between mobile species and their nonideal free energies. We propose an extended theory that incorporates these interactions and reduces to the Nernst-Einstein conduction under dilute conditions. This theory describes the measured response, and we report the first study of long-range ion transport behavior in MgCr₂O₄. We conclusively show that the Mg chemical diffusivity is comparable to lithium-ion electrode materials, whereas the total conductivity is rate-limiting. Given these differences, energy storage in MgCr₂O₄ is limited by particle-scale voltage drops, unlike lithium-ion particles that are limited by concentration gradients. Future materials design efforts should consider the interspecies interactions described in this extended theory, particularly with respect to multivalent-ion systems and their resultant effects on continuum transport properties.