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Investigation of Cubic Fe 4 M 4 Frameworks for Application in Nonaqueous Energy Storage
Author(s) -
VanGelder Lauren E.,
Schreiber Eric,
Wind MarieLouise,
Limberg Christian,
Matson Ellen M.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903360
Subject(s) - tungstate , redox , electrochemistry , faraday efficiency , materials science , electron transfer , molybdenum , energy storage , sulfide , chemical engineering , flow battery , electrode , chemistry , combinatorial chemistry , inorganic chemistry , thermodynamics , metallurgy , physics , power (physics) , electrolyte , engineering
Multimetallic complexes have recently seen increased attention as next‐generation charge carriers for nonaqueous redox flow batteries. Herein, we report the electrochemical performance of a molecular iron–molybdenum oxido complex, {[(Me 3 TACN)Fe][ μ ‐(MoO 4 κ 3 O , O ′, O “)]} 4 (Fe 4 Mo 4 O 16 ). In symmetric battery charging schematics, Fe 4 Mo 4 O 16 facilitates reversible two‐electron storage with coulombic efficiencies >99 % over 100 cycles (5 days) with no molecular decomposition and minimal capacity fade. Energy efficiency throughout cycling remained high (∼82 %), as a result of the rapid electron‐transfer kinetics observed for each of the complex's four redox events. We also report the synthesis of the analogous synthetic frameworks featuring tungstate vertices or bridging‐sulfide moieties, revealing key observations relevant to structure–function relationships and design criteria for these types of heterometallic ensembles.