Glibin, V. P.

Pupkevich, V. R.

BSU Digital Library

 72 
Synthesis and transport properties of phosphorylated polyvinyl alcohol mem-
branes for redox Fe3+/H2 flow cell  
V. P. Glibin, V. R. Pupkevich 
Western University, London, ON N6A 5B9, Canada, 
 e-mail: vassili.glibin@gmail.com 
Fuel cells redox flow batteries are used in the electrochemical energy conversion and elec-
trical energy storage technologies [1–3]. A hybrid Fe3+/H2 redox flow system is very promising 
among those and the polyvinyl alcohol-based membranes are believed to be components of this 
system. 
A novel method for preparation of phosphorylated polyvinyl alcohol (p-PVA) membranes 
was developed and used to synthesize a series of membranes with different degree of phosphory-
lation (4–9 w. % of phosphorus). The optimal mass ratio of PVA : H3PO2 was found to be 4 : 1, 
while the optimal curing time was 3 h at a temperature of 120 oC. The membranes possessed 
good mechanical robustness and chemical stability in acidic media. A method, based on “diatom-
ic approximation” and combined with the Badger’s rule and Brown’s bond valence concept,  was  
developed  to  estimate  the  chemical  bonds  frequencies  with  an  accuracy  of  20–25 cm–1 
and was used to interpret the IR-spectra of the membranes. The possibble pathway of PVA 
phosphorylation leading to formation of P–C bonds and various chemical functionalities was 
suggested.  
The water flux (6.08∙10–2 g∙cm-2∙h-1) and permeability of ferric ions (3.5∙10–5 cm2∙ min–1) 
were comparable to those of commercial Nafion 117 membrane. The dependence of the proton 
conductivity on the concentration of H2SO4 at 22 
oC was studied and the intrinsic proton conduc-
tivity of the p-PVA membrane (5.5∙10–3 S∙cm–1) was determined. The partial charges on oxygen 
atoms in structural linkages were calculated and the results indicate on the Grotthuss mechanism 
of proton transport. The increased density of negative charges on oxygen atoms in structural 
linkages results in extra hydrogen bonding within the p-PVA matrix and affects not only proton 
conductivity, but also water flux trough the membrane and other transport properties. The doping 
of p-PVA membrane with 2NH2SO4 increases the proton conductivity to the value close to the 
conductivity of commercial Selemion HSF membrane. 
 
References 
1. D.S. Scott. Int. J. Hydrogen Energy. (2011) 36: 9401. 
2. G. Kear, A.A. Shah, F.C. Walsh. Int. J. Energy Res. (2012) 36: 1105. 
3. D.G. Karamanev, V.R. Pupkevich, H. Hojjati. Bio-fuel Cell System. U.S. Patent; US 201100040909 A 
1, 2010.  


Synthesis and transport properties of phosphorylated polyvinyl alcohol mem-branes for redox Fe3+/H2 flow cell

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Synthesis and transport properties of phosphorylated polyvinyl alcohol mem-branes for redox Fe3+/H2 flow cell

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