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A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

ABSTRACT: Silver vanadium oxide (Ag2V4O11, SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag2VO2PO4, SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

SUBMITTER: Bock DC

PROVIDER: S-EPMC4389686 | biostudies-literature | 2013 Jun

REPOSITORIES: biostudies-literature

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A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

Bock David C DC Marschilok Amy C AC Takeuchi Kenneth J KJ Takeuchi Esther S ES

Journal of power sources 20130601

Silver vanadium oxide (Ag2V4O11, SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag2VO2PO4, SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most ...[more]

PMID: 25866437

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Project description:A core component of energy storage systems like vanadium redox flow batteries (VRFB) is the polymer electrolyte membrane (PEM). In this work, the frequently used perfluorosulfonic-acid (PFSA) membrane Nafion™ 117 and a novel poly (vinylidene difluoride) (PVDF)-based membrane are investigated. A well-known problem in VRFBs is the vanadium permeation through the membrane. The consequence of this so-called vanadium crossover is a severe loss of capacity. For a better understanding of vanadium transport in membranes, the uptake of vanadium ions from electrolytes containing Vdimer(IV-V) and for comparison also V(II), V(III), V(IV), and V(V) by both membranes was studied. UV/VIS spectroscopy, X-ray absorption near edge structure spectroscopy (XANES), total reflection X-ray fluorescence spectroscopy (TXRF), inductively coupled plasma optical emission spectrometry (ICP-OES), and micro X-ray fluorescence spectroscopy (microXRF) were used to determine the vanadium concentrations and the species inside the membrane. The results strongly support that Vdimer(IV-V), a dimer formed from V(IV) and V(V), enters the nanoscopic water-body of Nafion™ 117 as such. This is interesting, because as of now, only the individual ions V(IV) and V(V) were considered to be transported through the membrane. Additionally, it was found that the Vdimer(IV-V) dimer partly dissociates to the individual ions in the novel PVDF-based membrane. The Vdimer(IV-V) dimer concentration in Nafion™ was determined and compared to those of the other species. After three days of equilibration time, the concentration of the dimer is the lowest compared to the monomeric vanadium species. The concentration of vanadium in terms of the relative uptake λ = n(V)/n(SO3) are as follows: V(II) [λ = 0.155] > V(III) [λ = 0.137] > V(IV) [λ = 0.124] > V(V) [λ = 0.053] > Vdimer(IV-V) [λ = 0.039]. The results show that the Vdimer(IV-V) dimer needs to be considered in addition to the other monomeric species to properly describe the transport of vanadium through Nafion™ in VRFBs.

Dataset Information

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

Publications

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

Similar Datasets

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