New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

doi:10.1002/cssc.201601126

New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries

Journal Article · Wed Dec 28 23:00:00 EST 2016 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.201601126· OSTI ID:1372987

Shamie, Jack S. ^[1]; Liu, Caihong ^[1]; Shaw, Leon L. ^[1]; Sprenkle, Vincent L. ^[2]

Department of Mechanical, Materials and Aerospace Engineering, Illinois Institute of Technology, Chicago Illinois 60616 USA
Energy Storage and Conversion Energy Materials, Pacific Northwest National Laboratory, Richland WA 99352 USA

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac)2, to vanadium acetylacetonate, V(acac)3, is introduced. V(acac)3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac)2. In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H+), the reduction can take place between 2.25 and 1.5 V versus Na/Na+ via a one-electron-transfer reduction. This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na–Cs alloy as the anode. The in situ recovery of V(acac)3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V3+/V4+ and V2+/V3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac)3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future.

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1372987

Report Number(s):: PNNL-SA--126496; TE1400000

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 3 Vol. 10; ISSN 1864-5631

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

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