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Updated: Jun 13, 2025
Author Spotlight: Accelerating Discovery in Microporous Material Chemistry
Published on: October 6, 2023
d-Orbital Induced Electronic Structure Reconfiguration toward Manipulating Electron Transfer Pathways of
Shuqiang Jiao1,2, Xue Han3, Xudong Bu1
1State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metal, Lanzhou University of Technology, Lanzhou, 730050, P. R. China.
Abstract:
The positive electrodes of non-aqueous aluminum ion batteries (AIBs) frequently encounter significant issues, for instance, low capacity in graphite (mechanism: anion de/intercalation and large electrode deformation induced) and poor stability in inorganic positive electrodes (mechanism: multi-electron redox reaction and dissolution of active materials induced). Here, metallo-porphyrin compounds (employed Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ as the ion centers) are introduced to effectively enhance both the cycling stability and reversible capacity due to the formation of stable conjugated metal-organic coordination and presence of axially coordinated active sites, respectively. With the regulation of electronic energy levels, the d-orbitals in the redox reactions and electron transfer pathways can be rearranged. The 5,10,15,20-tetraphenyl-21H,23H-porphine nickle(II) (NiTPP) presents the highest specific capacity (177.1 mAh g-1), with an increment of 32.1% and 77.1% in comparison with the capacities of H2TPP and graphite, respectively, which offers a new route for developing high-capacity positive electrodes for stable AIBs.
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