An Electrically Conducting Li-Ion Metal–Organic Framework
| Autor: | Tom Goossens, Darsi Rambabu, Jiande Wang, Deepak Gupta, Petru Apostol, Alae Eddine Lakraychi, Louis Sieuw, Alexandru Vlad, Géraldine Chanteux, Koen Robeyns |
|---|---|
| Přispěvatelé: | UCL - SST/IMCN/MOST - Molecular Chemistry, Materials and Catalysis |
| Rok vydání: | 2021 |
| Předmět: |
Chemistry
Ligand 02 engineering and technology General Chemistry 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Biochemistry Redox Catalysis Cathode 0104 chemical sciences law.invention Colloid and Surface Chemistry Transition metal Chemical engineering law Metal-organic framework 0210 nano-technology Lithium Cation Stoichiometry Topology (chemistry) |
| Zdroj: | Journal of the American Chemical Society, Vol. 143, no.30, p. 11641-11650 (2021) Journal of the American Chemical Society |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/jacs.1c04591 |
| Popis: | Metal–organic frameworks (MOFs) have emerged as an important, yet highly challenging class of electrochemical energy storage materials. The chemical principles for electroactive MOFs remain, however, poorly explored because precise chemical and structural control is mandatory. For instance, no anionic MOF with a lithium cation reservoir and reversible redox (like a conventional Li-ion cathode) has been synthesized to date. Herein, we report on electrically conducting Li-ion MOF cathodes with the generic formula Li2-M-DOBDC (wherein M = Mg2+ or Mn2+; DOBDC4– = 2,5-dioxido-1,4-benzenedicarboxylate), by rational control of the ligand to transition metal stoichiometry and secondary building unit (SBU) topology in the archetypal CPO-27. The accurate chemical and structural changes not only enable reversible redox but also induce a million-fold electrical conductivity increase by virtue of efficient electronic self-exchange facilitated by mix-in redox: 10–7 S/cm for Li2-Mn-DOBDC vs 10–13 S/cm for the isoreticular H2-Mn-DOBDC and Li2-Mg-DOBDC, or the Mn-CPO-27 compositional analogues. This particular SBU topology also considerably augments the redox potential of the DOBDC4– linker (from 2.4 V up to 3.2 V, vs Li+/Li0), a highly practical feature for Li-ion battery assembly and energy evaluation. As a particular cathode material, Li2-Mn-DOBDC displays an average discharge potential of 3.2 V vs Li+/Li0, demonstrates excellent capacity retention over 100 cycles, while also handling fast cycling rates, inherent to the intrinsic electronic conductivity. The Li2-M-DOBDC material validates the concept of reversible redox activity and electronic conductivity in MOFs by accommodating the ligand’s noncoordinating redox center through composition and SBU design. |
| Databáze: | OpenAIRE |
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