Proton Conducting Polymer Electrolytes for
Electrochemical Capacitors
H. Gao, Q.Tian and K. Lian
Department of Materials Science and Engineering, University of Toronto, Toronto, Ont.,
Canada M5S 3E4
Solid polymer electrolytes containing phosphotungstic acid (PWA)
and/or silicotungstic acid (SiWA) blended in polyvinyl alcohol
(PVA) were investigated. The polymer electrolyte with a mixed
PWA and SiWA had a synergistic effect on its proton conductivity
over that of pure PVA-PWA or PVA-SiWA electrolytes. When
adding a small amount of polyacrylic acid (PAA), a further
increase in proton conductivity was obtained. Electrochemical and
structural analyses were conducted on these electrolytes as well.
Introduction
Solid-polymer electrolytes are important enabling materials for energy storage devices,
such as batteries and electrochemical capacitors (EC), which require high energy density,
high power density, and thin and flexible form factors. However, the conductivities of
polymer electrolytes are typically a few orders of magnitude lower than that of their
liquid counterparts. Moreover, the ionic conductivities of many proton conducting
polymer electrolytes such as Nafion and its derivatives depend strongly on the relative
humidity (RH) and temperature [1,2], which is not desirable for electrochemical energy
storage devices that operate in an ambient environment.
Solid electrolytes using poly(vinyl alcohol) (PVA) and heteropoly acids (HPA) have
been demonstrated for solid-state ECs and showed promising conductivities and stability
[3]. In previous studies, we have demonstrated that PVA and silicotungstic acid (SiWA)
can form a solid film with a conductivity of 0.01 S/cm which was implemented in an EC
[3]. We further optimized the conductivities by adjusting the ratio of PWA and SiWA in
PVA matrix and obtained a synergistic effect with a conductivity of ca. 0.013 S/cm,
exceeding that of pure PVA-PWA or PVA-SiWA solid electrolytes [4]. The objectives of
the current study are: a) to further optimize PVA-HPA polymer electrolytes through HPA
loading and additives and, b) to develop an understanding of the mechanism of the proton
conduction in the solid polymer electrolyte.
Experimental
Two precursors were prepared by mixing a PVA solution (PVA, Aldrich MW = 125,000)
with a heteropoly acid solution, either H
4
SiW
12
O
40
·xH
2
O (SiWA, alfa aesar) or
H
3
PW
12
O
40
·xH
2
O (PWA, alfa aesar). The precursor solutions were composed of 32.5%
SiWA or PWA, 1.5% PVA, and 66% de-ionized water (all in wt. %). The PVA-PWA and
PVA-SiWA precursors were combined in equal volumes for a mixed polymer electrolyte
(we henceforth refer to this mixture as PVA-Mix). In addition, a 0.02 wt. % of
polyacrylic acid (PAA) was added to PVA solution as additive in some cases. The matrix
ECS Transactions, 28 (8) 77-82 (2010)
10.1149/1.3490684 © The Electrochemical Society
77
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