Quaternized membranes bearing zwitterionic groups for vanadium redox flow battery through a green route

Abstract Novel quaternized membranes with zwitterionic groups applied in all-vanadium redox flow battery (VRB) have been prepared using a solvent free strategy, which is environmentally-friendly and different from traditional methods using organic solvents as reaction media. It was performed by dissolving cardopolyetherketone (PEK-C) in monomers mixture of 4-vinylbenzyl chloride (VBC) and divinylbenzene (DVB), and then in situ polymerization to incorporate PEK-C into the network of poly (VBC–DVB). The resulting copolymer was immersed in dimethylamine (DMA) followed by 1,3-propane sultone (PS) aqueous solution to obtain the target quaternized membranes bearing zwitterionic groups ([ CH 2 N + (CH 3 ) 2 CH 2 CH 2 CH 2 SO 3 − ]), which greatly enhance the chain packing density, and consequently improve membrane stability. The optimized quaternized membrane with zwitterionic groups showed a 20% decrease in vanadium ion permeability as compared to the benchmark quaternized membrane without zwitterionic groups. It also possesses good mechanical strength even after immersion in VO 2+ solution for as long as 20 days. Comparing the commercial Nafion117 with the optimized membrane, the vanadium ion permeability sharply decreased from 10.80×10 −5  cm min −1 to 0.21×10 −5  cm min −1 while the coulombic and energy efficiency increased from 89.7% and 68.3% to 97.1% and 73.4% at 50 mA cm −2 , respectively. The present quaternized membrane with zwitterionic groups shows good characteristics for application in VRBs.

[1]  X. Jian,et al.  Poly(phthalazinone ether ketone ketone) anion exchange membranes with pyridinium as ion exchange groups for vanadium redox flow battery applications , 2013 .

[2]  Synthesis and characterization of novel cardo poly(aryl ether sulfone) bearing zwitterionic side groups for proton exchange membranes , 2011 .

[3]  Huamin Zhang,et al.  Ion exchange membranes for vanadium redox flow battery (VRB) applications , 2011 .

[4]  Xianfeng Li,et al.  Advanced charged membranes with highly symmetric spongy structures for vanadium flow battery application , 2013 .

[5]  Yung Chang,et al.  Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization. , 2011, ACS applied materials & interfaces.

[6]  D. Lin-Vien The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules , 1991 .

[7]  Sung-Gyu Park,et al.  Synthesis and characteristics of aminated vinylbenzyl chloride-co-styrene-co-hydroxyethyl acrylate anion-exchange membrane for redox flow battery applications , 2012 .

[8]  Jason Wu,et al.  High durable PEK-based anion exchange membrane for elevated temperature alkaline fuel cells , 2012 .

[9]  D. Macfarlane,et al.  The zwitterion effect in high-conductivity polyelectrolyte materials , 2004, Nature materials.

[10]  Xiaocheng Lin,et al.  Cross-linked anion exchange membranes for alkaline fuel cells synthesized using a solvent free strategy , 2013 .

[11]  Bin Li,et al.  Recent Progress in Redox Flow Battery Research and Development , 2012 .

[12]  R. C. King,et al.  Handbook of X Ray Photoelectron Spectroscopy: A Reference Book of Standard Spectra for Identification and Interpretation of Xps Data , 1995 .

[13]  Q. Zhang,et al.  Dehydration of acetic acid using sulfonation cardo polyetherketone (SPEK-C) membranes , 2008 .

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

[15]  X. Jian,et al.  Quaternized poly(phthalazinone ether ketone ketone) anion exchange membrane with low permeability of vanadium ions for vanadium redox flow battery application , 2012 .

[16]  Younian Liu,et al.  SPPEK/WO3 hybrid membrane fabricated via hydrothermal method for vanadium redox flow battery , 2012 .

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

[18]  Cong-jie Gao,et al.  AMOC Positron Annihilation Study of Zwitterionic Nanofiltration Membranes: Correlation between Fine Structure and Ultrahigh Permeability , 2013 .

[19]  K. Gleason,et al.  Ultrathin antifouling coatings with stable surface zwitterionic functionality by initiated chemical vapor deposition (iCVD). , 2012, Langmuir : the ACS journal of surfaces and colloids.

[20]  Li-ping Zhu,et al.  Surface zwitterionicalization of poly(vinylidene fluoride) porous membranes by post-reaction of the , 2011 .

[21]  Toraj Mohammadi,et al.  Preparation of sulfonated composite membrane for vanadium redox flow battery applications , 1995 .

[22]  M. Mench,et al.  Redox flow batteries: a review , 2011 .

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

[24]  Vijay Ramani,et al.  Polysulfone-based anion exchange membranes demonstrate excellent chemical stability and performance for the all-vanadium redox flow battery , 2013 .

[25]  Younian Liu,et al.  SPPEK/TPA composite membrane as a separator of vanadium redox flow battery , 2013 .

[26]  Jian Shen,et al.  Grafting of zwitterion from cellulose membranes via ATRP for improving blood compatibility. , 2009, Biomacromolecules.

[27]  Cheol-Hwi Ryu,et al.  Application of Psf–PPSS–TPA composite membrane in the all-vanadium redox flow battery , 2010 .

[28]  D. Briggs,et al.  High Resolution XPS of Organic Polymers: The Scienta ESCA300 Database , 1992 .

[29]  Zhao-Wu Tian,et al.  The preparation of a novel anion-exchange membrane and its application in all-vanadium redox batteries , 2012 .

[30]  Mahlon Wilson,et al.  Scientific aspects of polymer electrolyte fuel cell durability and degradation. , 2007, Chemical reviews.

[31]  Kevin L. Simmons,et al.  Nanoporous Polytetrafluoroethylene/Silica Composite Separator as a High‐Performance All‐Vanadium Redox Flow Battery Membrane , 2013 .

[32]  Jun Liu,et al.  Electrochemical energy storage for green grid. , 2011, Chemical reviews.

[33]  Anthony G. Fane,et al.  New All‐Vanadium Redox Flow Cell , 1986 .

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