Multi-electron reaction and fast Al ion diffusion of 8-MnO2 cathode materials in rechargeable aluminum batteries via first-principle calculations

Rechargeable aluminum batteries with multi -electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO2 are not clear. Hence, based on the first -principles calculations, key influencing factors of slow Al -ions diffusion are narrow pathways, unstable Al -O bonds and Mn3 + type polaron have been identified by investigating four types of 8-MnO2 (O3, O'3, P2 and T1). Although Al insert into 8-MnO2 leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO2 keeps the long (spacious pathways) and stable (2.007-2.030A) Al -O bonds resulting in the lower energy barrier of Al diffusion of 0.56 eV. By eliminated the influence of Mn3 + (low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 eV in P2 type, confirming the obviously effect of Mn3 + polaron. On the contrary, although the T1 type MnO2 has the sluggish of Al -ions diffusion, the larger interlayer spacing of Mn-Mn layer, causing by H2O could assist Al -ions diffusion. Furthermore, it's worth to notice that the multilayer 8-MnO2 achieves multi -electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2 (1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO2 should keep more P2 -type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage. (c) 2024 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.