Investigation of crossover processes in a unitized bidirectional vanadium/air redox flow battery

Abstract In this paper the losses in coulombic efficiency are investigated for a vanadium/air redox flow battery (VARFB) comprising a two-layered positive electrode. Ultraviolet/visible (UV/Vis) spectroscopy is used to monitor the concentrations c V 2 + and c V 3 + during operation. The most likely cause for the largest part of the coulombic losses is the permeation of oxygen from the positive to the negative electrode followed by an oxidation of V2+ to V3+. The total vanadium crossover is followed by inductively coupled plasma mass spectroscopy (ICP-MS) analysis of the positive electrolyte after one VARFB cycle. During one cycle 6% of the vanadium species initially present in the negative electrolyte are transferred to the positive electrolyte, which can account at most for 20% of the coulombic losses. The diffusion coefficients of V2+ and V3+ through Nafion® 117 are determined as D V 2 + , N 117 = 9.05 · 10 − 6  cm2 min−1 and D V 3 + , N 117 = 4.35 · 10 − 6  cm2 min−1 and are used to calculate vanadium crossover due to diffusion which allows differentiation between vanadium crossover due to diffusion and migration/electroosmotic convection. In order to optimize coulombic efficiency of VARFB, membranes need to be designed with reduced oxygen permeation and vanadium crossover.

[1]  Frank C. Walsh,et al.  Dynamic modelling of hydrogen evolution effects in the all-vanadium redox flow battery , 2010 .

[2]  J. Grunlan,et al.  Improving oxygen barrier and reducing moisture sensitivity of weak polyelectrolyte multilayer thin films with crosslinking , 2012 .

[3]  J. Jur,et al.  Measuring oxygen, carbon monoxide and hydrogen sulfide diffusion coefficient and solubility in Nafion membranes , 2009, 1108.2438.

[4]  Haisheng Chen,et al.  Progress in electrical energy storage system: A critical review , 2009 .

[5]  Göran Sundholm,et al.  In-situ measurements of gas permeability in fuel cell membranes using a cylindrical microelectrode , 2002 .

[6]  Dongjiang You,et al.  A simple model for the vanadium redox battery , 2009 .

[7]  Maria Skyllas-Kazacos,et al.  Novel vanadium chloride/polyhalide redox flow battery , 2003 .

[8]  B. Stevens,et al.  Hydrophobically modified polyelectrolyte for improved oxygen barrier in nanobrick wall multilayer thin films , 2014 .

[9]  G. Graff,et al.  A Stable Vanadium Redox‐Flow Battery with High Energy Density for Large‐Scale Energy Storage , 2011 .

[10]  Maria Skyllas-Kazacos,et al.  Modeling of vanadium ion diffusion across the ion exchange membrane in the vanadium redox battery , 2012 .

[11]  S. M. Greenlee,et al.  High gas barrier imparted by similarly charged multilayers in nanobrick wall thin films , 2014 .

[12]  John B Goodenough,et al.  Aqueous cathode for next-generation alkali-ion batteries. , 2011, Journal of the American Chemical Society.

[13]  Hansung Kim,et al.  Analysis of the Oxidation of the V(II) by Dissolved Oxygen Using UV-Visible Spectrophotometry in a Vanadium Redox Flow Battery , 2013 .

[14]  Zhenguo Yang,et al.  Structure and stability of hexa-aqua V(III) cations in vanadium redox flow battery electrolytes. , 2012, Physical chemistry chemical physics : PCCP.

[15]  D. Lundberg,et al.  A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state. , 2012, Inorganic chemistry.

[16]  Robert B. Moore,et al.  Effects of Hydrophilic and Hydrophobic Counterions on the Coulombic Interactions in Perfluorosulfonate Ionomers , 1995 .

[17]  C. Low,et al.  Progress in redox flow batteries, remaining challenges and their applications in energy storage , 2012 .

[18]  Shanfu Lu,et al.  Layer-by-layer self-assembly of Nafion–[CS–PWA] composite membranes with suppressed vanadium ion crossover for vanadium redox flow battery applications , 2014 .

[19]  Akeel A. Shah,et al.  The importance of key operational variables and electrolyte monitoring to the performance of an all vanadium redox flow battery , 2013 .

[20]  Jens Noack,et al.  Development and characterization of a 280 cm2 vanadium/oxygen fuel cell , 2014 .

[21]  Arvind R. Kalidindi,et al.  A Transient Vanadium Flow Battery Model Incorporating Vanadium Crossover and Water Transport through the Membrane , 2012 .

[22]  Lidiya Komsiyska,et al.  Study of an unitised bidirectional vanadium/air redox flow battery comprising a two-layered cathode , 2015 .

[23]  Huamin Zhang,et al.  The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium , 2014 .

[24]  S. Grigoriev,et al.  PEM water electrolyzers: From electrocatalysis to stack development , 2010 .

[25]  Qiang Ye,et al.  Effects of the electric field on ion crossover in vanadium redox flow batteries , 2015 .

[26]  Catherine Eysseric,et al.  Selective permeability of a perfluorosulphonic membrane to different valency cations. Ion-exchange isotherms and kinetic aspects , 1998 .

[27]  Maria Skyllas-Kazacos,et al.  State of charge monitoring methods for vanadium redox flow battery control , 2011 .

[28]  Toraj Mohammadi,et al.  Water transport study across commercial ion exchange membranes in the vanadium redox flow battery , 1997 .

[29]  D. N. Buckley,et al.  Towards Optical Monitoring of Vanadium Redox Flow Batteries (VRFBs): An Investigation of the Underlying Spectroscopy , 2014 .

[30]  Wei Wang,et al.  In-situ investigation of vanadium ion transport in redox flow battery , 2012 .

[31]  Qinghua Liu,et al.  High Performance Vanadium Redox Flow Batteries with Optimized Electrode Configuration and Membrane Selection , 2012 .

[32]  Curtis J. Bell,et al.  Determining Vanadium Concentrations Using the UV-Vis Response Method , 2015 .

[33]  Mike L. Perry,et al.  The Influence of Electric Field on Crossover in Redox-Flow Batteries , 2016 .

[34]  B. Stevens,et al.  Shift-Time Polyelectrolyte Multilayer Assembly: Fast Film Growth and High Gas Barrier with Fewer Layers by Adjusting Deposition Time. , 2014, ACS macro letters.

[35]  L. Zeng,et al.  Preparation of silica nanocomposite anion-exchange membranes with low vanadium-ion crossover for vanadium redox flow batteries , 2013 .

[36]  Zhenguo Yang,et al.  Spectroscopic investigations of the fouling process on Nafion membranes in vanadium redox flow batteries , 2011 .

[37]  Matthias Wessling,et al.  A polyelectrolyte membrane-based vanadium/air redox flow battery , 2011 .

[38]  Maria Skyllas-Kazacos,et al.  Progress in Flow Battery Research and Development , 2011 .

[39]  Xinping Qiu,et al.  Self-assembled polyelectrolyte multilayer modified Nafion membrane with suppressed vanadium ion crossover for vanadium redox flow batteries , 2008 .

[40]  D. N. Buckley,et al.  Factors Affecting Spectroscopic State-of-Charge Measurements of Positive and Negative Electrolytes in Vanadium Redox Flow Batteries , 2015 .

[41]  T. Zawodzinski,et al.  Hydrogen evolution at the negative electrode of the all-vanadium redox flow batteries , 2014 .

[42]  Huamin Zhang,et al.  Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery , 2014, Scientific Reports.

[43]  Xinping Qiu,et al.  State of charge monitoring for vanadium redox flow batteries by the transmission spectra of V(IV)/V(V) electrolytes , 2012, Journal of Applied Electrochemistry.

[44]  Jing Peng,et al.  Pre-irradiation grafting of styrene and maleic anhydride onto PVDF membrane and subsequent sulfonation for application in vanadium redox batteries , 2008 .

[45]  Maria Skyllas-Kazacos,et al.  Membrane stability studies for vanadium redox cell applications , 2004 .

[46]  Xinping Qiu,et al.  Nafion/organically modified silicate hybrids membrane for vanadium redox flow battery , 2009 .

[47]  King Jet Tseng,et al.  Extended dynamic model for ion diffusion in all-vanadium redox flow battery including the effects of temperature and bulk electrolyte transfer , 2014 .

[48]  Xinping Qiu,et al.  Influences of permeation of vanadium ions through PVDF-g-PSSA membranes on performances of vanadium redox flow batteries. , 2005, The journal of physical chemistry. B.

[49]  Maria Skyllas-Kazacos,et al.  Water transfer behaviour across cation exchange membranes in the vanadium redox battery , 2003 .

[50]  Bin Li,et al.  Capacity decay and remediation of nafion-based all-vanadium redox flow batteries. , 2013, ChemSusChem.

[51]  M. Falk,et al.  An infrared study of water–ion interactions in perfluorosulfonate (Nafion) membranes , 1984 .

[52]  Chenxi Sun,et al.  Investigations on transfer of water and vanadium ions across Nafion membrane in an operating vanadium redox flow battery , 2010 .

[53]  Yong Tae Park,et al.  Super Gas Barrier of All-Polymer Multilayer Thin Films , 2011 .

[54]  Chris Menictas,et al.  Performance of vanadium-oxygen redox fuel cell , 2011 .

[55]  Hansung Kim,et al.  Analysis of Concentration Polarization Using UV-Visible Spectrophotometry in a Vanadium Redox Flow Battery , 2014 .

[56]  H S White,et al.  Electrically facilitated molecular transport. Analysis of the relative contributions of diffusion, migration, and electroosmosis to solute transport in an ion-exchange membrane. , 2000, Analytical chemistry.

[57]  Frank C. Walsh,et al.  A dynamic performance model for redox-flow batteries involving soluble species , 2008 .

[58]  Qing Wang,et al.  Next‐Generation, High‐Energy‐Density Redox Flow Batteries , 2015 .

[59]  Xinping Qiu,et al.  Nafion/SiO2 hybrid membrane for vanadium redox flow battery , 2007 .