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Synthesis of Zeolite-Nafion Composite

Membranes for Electrical Storage Batteries

Research sponsored
by the UC WISE
program and the U.S.
National Science
Foundation (CBET1263860)

Fiona Shaw, Ruidong Yang, Ioannis Michos, Junhang Dong

Cincinnati, OH, Department of Chemical Engineering



A composite membrane made of Nafion

and zeolite nanocrystals was synthesized and
the effects of the changes to the drying
procedure during the membrane formation
process were investigated. The parameters of
the drying process that were studied were the
drying temperature and the use of a 17-hour
delay period before the vacuum drying
started. It was found that both the drying
temperature and the pre-drying delay period
had significant effects on the membrane
microstructure and consequently its
performance as an ion separator.

Six sample membranes with a composition of

Nafion polymer and MFI- type zeolite
nanocrystals were synthesized to test the
effect of drying procedure. The membranes
were dried at varying temperatures, and after
the components were mixed and poured into
the cast, they were either immediately sealed
in the vacuum oven or had a 17 hour delay
period. Below are the names and descriptions
of the six samples.

Shown below are images of two of the
membrane samples, taken using a Scanning
Electron Microscope. The pre-settling delay
period in drying consistently resulted in a
thinner, more compact zeolite layer, but it also
had unexpected effects on the other
characteristics of the membrane.

The widespread implementation of renewable
energy sources depends on developing more
efficient electrical storage technology.
Vanadium redox flow batteries (VRFBs) are
very promising in this field, but they suffer
from self-discharge due to metal ion
crossover. RFBs consist of an anode and
cathode, both filled with electrolyte solution
and separated by a semi-permeable
membrane. The job of the membrane is to
allow for the flow of protons from one side to
another to complete the reaction that powers
the battery while effectively containing the
metal ion solution. New membrane
technology has led to a polymer-zeolite
composite that has increased performance
within the VRFB. To further improve proton
selectivity of the membranes, we hope to
determine whether the drying conditions of
the composite affect morphology or
performance within the cell.

Ion Permeation Tests

To determine whether the drying procedure
influences the membrane structure and
performance as ion separator, the samples
were examined for ion permeation,
morphology, and electrical resistance in a
VFRB. Ion permeation was tested using the
setup shown below. The concentration of
protons (measured using a pH probe) and
vanadyl metal ions (using UV-Vis
Spectroscopy) were plotted over time in the
graphs to the right.

Ion Permeation
While the more compact zeolite layer reduced
vanadyl ion flow and so minimized electrolyte
solution crossover, it also decreased proton flow.
As the main purpose of the membrane is to allow
for the flow of protons, the decrease in proton
conductivity is something that could seriously
impact the battery performance.
Below is a table of resistance measurements for
the six samples tested. It was found that the
drying temperature was more of a factor in the
resistance than the delay period.

Resistance (Ohms)

F1 - 25C, No pre-settling


F2 - 25C, 17 hour pre-settling


F3 - 80C, No pre-settling


F4 - 80C, 17 hour pre-settling


F5 - 40C, No pre-settling


F6 - 40C, 17 hour pre-settling


While it was determined that a delay in the
drying procedure produced a thinner, more
compact zeolite layer, this alteration also
affected the resistance and overall proton
selectivity negatively. It was also determined
that the 80 drying temperature had the most
favorable ratio of proton to vanadyl ion flow.

Zhi Xu, I. Michos, X. Wang, R. Yang, X. Gu, J. Dong,
Zeolite Ion Exchange Membrane for Redox Flow Battery.
Chem. Commun. 50 (2014) 2416-2419.
R. Yang, Z. Xu, S. Yang, L. Li, A. Angelopoulos, J. Dong,
Nonionic Zeolite Membrane as Potential Ion Separator in
Redox-Flow Battery. J. Membr. Sci. 450 (2014) 12-17.