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

Abstract

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 tomore » more advances in maintaining the cycle life of RFBs in the future.« less

Authors:
 [1];  [1];  [1];  [2]
  1. Department of Mechanical, Materials and Aerospace Engineering, Illinois Institute of Technology, Chicago Illinois 60616 USA
  2. Energy Storage and Conversion Energy Materials, Pacific Northwest National Laboratory, Richland WA 99352 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1372987
Report Number(s):
PNNL-SA-126496
Journal ID: ISSN 1864-5631; TE1400000
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 1864-5631
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Shamie, Jack S., Liu, Caihong, Shaw, Leon L., and Sprenkle, Vincent L. New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries. United States: N. p., 2016. Web. doi:10.1002/cssc.201601126.
Shamie, Jack S., Liu, Caihong, Shaw, Leon L., & Sprenkle, Vincent L. New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries. United States. doi:10.1002/cssc.201601126.
Shamie, Jack S., Liu, Caihong, Shaw, Leon L., and Sprenkle, Vincent L. Thu . "New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries". United States. doi:10.1002/cssc.201601126.
@article{osti_1372987,
title = {New Mechanism for the Reduction of Vanadyl Acetylacetonate to Vanadium Acetylacetonate for Room Temperature Flow Batteries},
author = {Shamie, Jack S. and Liu, Caihong and Shaw, Leon L. and Sprenkle, Vincent L.},
abstractNote = {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.},
doi = {10.1002/cssc.201601126},
journal = {ChemSusChem},
issn = {1864-5631},
number = 3,
volume = 10,
place = {United States},
year = {2016},
month = {12}
}

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