Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

Yamamura, Tomoo; Shiokawa, Yoshinobu; Yamana, Hideaki; Moriyama, Hirotake

doi:10.1016/s0013-4686(02)00546-7

Cited by 100 publications

(84 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…In the case of uranium, electrode reactions of U(III)/U(IV) and U(V)/U(VI) are regarded as reversible or quasi-reversible in the absence of proton [2,3] which promotes the disproportionation reaction degrading U(V) to U(IV) and U(VI) [4,5]. By utilizing these two couples of fast reactions suppressing overvoltage at electrodes, uranium redox-flow battery with high efficiency has been proposed [3,6].…”

Section: Introductionmentioning

confidence: 99%

Electrolytic preparation, redox titration and stability of pentavalent state of uranyl tetraketonate in dimethyl sulfoxide

Shirasaki

Yamamura

Shiokawa

2006

Journal of Alloys and Compounds

View full text Add to dashboard Cite

Section: Introductionmentioning

confidence: 99%

Electrolytic preparation, redox titration and stability of pentavalent state of uranyl tetraketonate in dimethyl sulfoxide

Shirasaki

Yamamura

Shiokawa

2006

Journal of Alloys and Compounds

View full text Add to dashboard Cite

“…Au ranium redox-flow battery based on uranyl acetylacetonatewas proposed by Yamamura et al [265] Thesolubilities in acetonitrile (ACN), propylene carbonate (PC), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) were determined for uranium complexes with differently substituted b-diketonate ligands.T he highest solubility of more than 0.8 m was achieved for the complex with the fully fluorinated hexafluoro derivative [UO 2 (hfa) 2 ]. Thecauses for the higher solubility of hexafluoroacetylacetonate complexes were presumed to be structural changes of the complex during solvation.…”

mentioning

confidence: 99%

The Chemistry of Redox‐Flow Batteries

et al. 2015

View full text Add to dashboard Cite

The development of various redox-flow batteries for the storage of fluctuating renewable energy has intensified in recent years because of their peculiar ability to be scaled separately in terms of energy and power, and therefore potentially to reduce the costs of energy storage. This has resulted in a considerable increase in the number of publications on redox-flow batteries. This was a motivation to present a comprehensive and critical overview of the features of this type of batteries, focusing mainly on the chemistry of electrolytes and introducing a thorough systematic classification to reveal their potential for future development.

show abstract

“…1 In efforts to increase energy density or decrease active-species loading, researchers have targeted nonaqueous RFB chemistries, which can produce operating potentials outside the stability window of water. [2][3][4][5][6][7][8] Several nonaqueous chemistries are based on transition-metal-centered coordination complexes. 2,3,[6][7][8][9] Chromium acetylacetonate, or Cr(acac) 3 , appears especially promising as an RFB active species: it has five accessible redox states, and there is a wide voltage separation between the first reduced and first oxidized states of the neutral complex.…”

mentioning

confidence: 99%

Spectroelectrochemistry of Vanadium Acetylacetonate and Chromium Acetylacetonate for Symmetric Nonaqueous Flow Batteries

Saraidaridis

Bartlett

Monroe

2016

J. Electrochem. Soc.

View full text Add to dashboard Cite

Chromium acetylacetonate, or Cr(acac) 3 , is a promising active species for high-energy-density symmetric redox flow batteries because the neutral complex supports multiple charge-transfer reactions with widely separated redox potentials. Voltammetric and spectroelectrochemical measurements were performed to probe the mechanism of the first electrochemical disproportionation of Cr(acac) 3 -i.e., the cell reaction associated with the two redox couples immediately adjacent to the equilibrium potential of a freshly prepared nonaqueous Cr(acac) 3 solution. Substantially different limiting currents are observed for the positive and negative half-reactions, suggesting that at least one deviates from the similar outer-sphere single-electron transfer mechanisms proposed earlier. Spectroelectrochemical chronoamperometry suggests ligand dissociation in the negative reaction, and consequent structural reorganization of the Cr(acac) 3 complex. Vanadium acetylacetonate was investigated for comparison, and no ligand dissociation was observed. A negative half-reaction mechanism consistent with the voltammetric and spectroelectrochemical data is proposed, and used to rationalize observations of charge/discharge behavior in cycling Cr (acac) As researchers have identified the economic benefits that largescale energy storage delivers to the grid, research into redox flow batteries (RFBs) has expanded.1 In efforts to increase energy density or decrease active-species loading, researchers have targeted nonaqueous RFB chemistries, which can produce operating potentials outside the stability window of water.2-8 Several nonaqueous chemistries are based on transition-metal-centered coordination complexes. 2,3,[6][7][8][9] Chromium acetylacetonate, or Cr(acac) 3 , appears especially promising as an RFB active species: it has five accessible redox states, and there is a wide voltage separation between the first reduced and first oxidized states of the neutral complex. The Cr(acac) 3 complex has also been used for catalysis 10 and as a standard for atomic absorption spectra.11 Whereas vanadium acetylacetonate, or V(acac) 3 , appears to support outer-sphere electron transfer for both single-electron addition and withdrawal in certain nonaqueous electrolytes, and to undergo both charge exchanges with relatively facile kinetics, 12 the voltammetric response of Cr(acac) 3 is harder to interpret. Experimental efforts to clarify the electrochemistry of Cr(acac) 3 have been challenging because the reaction mechanism apparently varies with the choices of solvent, supporting electrolyte, and working electrode. 13-17The literature describing nonaqueous Cr(acac) 3 electrochemistry does not provide a consensus about the mechanisms for either the first reduction or first oxidation of the neutral complex. The electrochemical response during reduction depends heavily upon solvent, with different behavior observed in dimethylsulfoxide, 13,15,18,19 N,N-dimethylformamide, 15 dichloromethane, 14 acetonitrile, 15,17,20 and others. 15 Various mechanisms have...

show abstract

Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery

Cited by 100 publications

References 28 publications

Electrolytic preparation, redox titration and stability of pentavalent state of uranyl tetraketonate in dimethyl sulfoxide

Electrolytic preparation, redox titration and stability of pentavalent state of uranyl tetraketonate in dimethyl sulfoxide

The Chemistry of Redox‐Flow Batteries

Spectroelectrochemistry of Vanadium Acetylacetonate and Chromium Acetylacetonate for Symmetric Nonaqueous Flow Batteries

Contact Info

Product

Resources

About