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SYNTHESIS AND CHARACTERIZATION OF CATIONIC MEMBRANES WITH POLY(INDENE)
SULPHONATED POLYELECTROLYTE FOR FUEL CELL APPLICATION
1* Hannah Corrêa de M. M. Thomaz,1 João Víctor M.R. de Souza, 1 Alexandre Furtado Ferreira, 1 Fábio José Bento Brum
1Universidade Federal Fluminense, Avenida dos Trabalhadores, 420, Vila Santa Cecília, 27255-125 Volta Redonda, RJ, Brazil.
ABSTRACT
In this work, results of the synthesis and characterization of cationic hydrocarbon membranes with application in
fuel cells will be presented. Semi-interpenetrating membranes based on PVA with sulfonated aromatic electrolyte
polymer were prepared. In the polarization tests in a fuel cell prototype, the membrane with the best result obtained
the value of open circuit potential and power equal to and , respectively, very close values when
compared to Nafion®, an industrial membrane that reaches and , respectively, thus proving the
applicability of the synthesized membrane in fuel cells.
Keywords: Electrolyte Polymers, Fuel Cells, Membranes, Polarization Curve
INTRODUCTION
Hydrocarbon electrolyte polymers have been good substitutes for the Nafion® membrane due to their low-cost
synthesis, ease of insertion of hydrophilic groups, good proton conductivity and high chemical stability in some
cases [1-4]. This work presents a new sulfonated indene-based electrolyte polymer applied in the synthesis of
membranes with semi-interpenetrating structure, semi-IPNs, based on poly (vinyl alcohol) crosslinked with different
crosslinking agents and tested in a fuel cell prototype.
MATERIALS AND METHODS
Poly (vinyl alcohol) - PVA Sigma Aldrich PM 130,000 g/mol and degree of hydrolysis 99% and ethanol Sigma
Aldrich 98% were used in the synthesis of the membranes. The crosslinking agents used were Sigma Aldrich 99%
citric acid, Sigma Aldrich 50% sulfosuccinic acid, Sigma Aldrich 50% 4-sulfophthalic acid. Poly(indene) sulfonated
electrolyte polymer (SPInd) was synthesized as described by Brum and Colab [3–5]. Membranes were prepared by
mixing 1.0 grams of PVA, 30% by weight of the crosslinking agents and 40% by weight of the SPInd polymer
electrolyte [3,4]. For the characterization of the membranes, the following tests were performed: ion exchange
capacity (IEC) at room temperature; degree of swelling at room temperature for 24 hours; degree of hydration;
electrochemical impedance spectroscopy with humidified samples (sample area: 1.5 cm 2) [3,4]. In the fuel cell test,
a hydrogen pressure of 1.5 psi and 3.0 psi of oxygen, cell area of 5.8 cm2 and platinum catalyst 0.5 mg/cm2 were
used.
Units and Equations
Evaluation of the degree of swelling (WU): the degree of swelling measures the water absorption capacity of the
membranes. The previously dried membrane sample is weighed and immersed in distilled water at room
temperature for 24 hours, then it is removed from the aqueous medium, lightly dried to remove excess water, and
weighed again. The value of the degree of swelling is calculated by the difference between then.
Ion exchange capacity (IEC): indicates the number of moles of the ion in 1.0 g of polymer. To perform this method,
conventional titration is used, later the sample is placed in 1M NaCl solution for 24 hours. Then titrated with a
0.05M NaOH solution and using Eq. (1). Where VNaOH is the volume of NaOH solution used to reach the
equivalence point in the titration, M NaOH is the molar concentration of the NaOH solution and M sample is the mass
of the sample, in grams:
IEC (VNaOH xM NaOH ) / M sample (1)
molecules per an acidic
hydrophilic group by Eq. (2).
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IEC (%swelling ) /(18 / IEC) (2)
Ionic conductivity (EIS): evaluates the resistance profile of isolated membranes and membranes in the prototype. It
relates the ionic conductivity ( ) with the film thickness (I), the cross-sectional area (A) of the analyzed material,
and the material resistance (R), the latter determined by electrochemical impedance spectroscopy (EIS), given by
Eq.3. To perform this method, the membranes were conditioned in deionized water for 1h:
(1 / R) x(1 / A) (3)
RESULTS AND DISCUSSION
Table 1 presents the values of ion exchange capacity, degree of swelling and hydration, and the description of
each synthesized membrane. The only variation in the formulation of the membranes was the crosslinking agents.
Membranes crosslinked with citric acid will be called M-AC, those with sulfophthalic acid (M-ASF) and sulfosuccinic
acid (M-ASS).
Table 1. Values of ion exchange capacity, degree of swelling and hydration of synthesized membranes
Membranes IEC (mEq/g) Thickness (cm) Swelling degree (%) Hydration degree
M-AC 1.3 0.021 206 8.803
M-ASF 1.5 0.022 100 3,704
M-ASS 1.4 0.022 121 4.801
It can be seen that the IEC values were practically unchanged, but on the other hand, in the swelling values a
significant variation is observed. This fact is attributed to the acidic character of the hydrophilic sulfonic groups (-
SO3H) having a strong influence as a catalyst in membrane esterification reactions, and crosslinking reactions [1,4].
The M-AC membrane has a hydrophilic carboxylic group (-COOH) and this fact explains the high swelling degree
value, since the carboxylic acid group has a lower acidic character compared to the sulfonic group (BRUM, 2013).
The values of the degree of hydration are almost double for the membrane with (-COOH), while those with group (-
SO3H) had little difference. The M-ASF membrane has an aromatic group in its composition, and this group
confers greater rigidity to the polymeric structure, which justifies the differences in swelling and hydration values of
this membrane when compared to the M-ASF membrane.
Table 2 presents the results of the electrochemical impedance test. Citric acid and sulfosuccinic acid present a
linear carbonic chain structure, with their major difference being the hydrophilic groups. This fact is observed by the
proximity of the electrolyte resistance values, but with very different values in relation to conductivity.
Table 2. Resistance and conductivity values obtained by impedance
Membranes Resistance (ohm) Conductivity (S/cm)*
M-AC 9.20
M-ASF 10.5
M-ASS 3.47
Nafion® 1.94
*1.5 cm2 area electrodes
From the resistance values it is observed that the M-ASS membrane presented the lowest value and, when
compared to the M-AC membrane, the difference between the resistance values reaches more than 250%. This is
due to the low ionic strength of the carboxylic groups, which is proven by the values of degree of hydration
presented (Table 1). The M-ASF membrane, which presents only sulfonic hydrophilic groups in its composition,
presented the highest resistance value and the lowest conductivity. This fact is associated with the presence of
aromatic groups in the composition of this membrane from the structure of SPInd and the crosslinking agent
sulfophthalic acid [1]. The aromatic groups tend to rearrange themselves in structures in the form of a half ladder
and make the polymeric structure more rigid, thus impairing the ionic transport [3,4].
Figure 1 shows the polarization curves of the synthesized membranes obtained from the fuel cell performance test
[2]. It can be seen that all the electrode/membrane/electrode sets presented the same open circuit value, around
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0.8V, therefore, it is evident in the test only the influence of the tested membrane. The membrane that came
closest to the Nafion® reference (power 9.20 x10 -2 W) was the HC (power 7.49 x10-2 W) crosslinked with
sulfosuccinic acid.
Fig.1. Polarization Curves of M-AC, M-ASF, M-ASS and Nafion® membranes
This result is corroborated by the conductivity values presented in Table 2. Although the HB membrane (power
5.56 x10-2 W) has in its composition only hydrophilic sulfonic groups, what may have influenced the reduction of
proton transport was the presence of aromatic rings leaving the molecular structure of the semi-interpenetrating
network more rigid, which impaired the transport of H3O+ species. Even with the presence of the polymer
electrolyte SPInd, the HA membrane (power 2.31 x10-2 W) showed low performance compared to the other
membranes.
CONCLUSIONS
Semi-interpenetrating PVA-based cationic membranes with poly(indene) sulfonated electrolyte polymer were
prepared and presented homogeneous and stable films. The IEC values, degree of swelling and degree of
hydration confirmed the esterification reaction and the structural differences between the membranes presented.
Citric acid, sulfophthalic acid and sulfosuccinic acid were good crosslinking agents. The membrane that showed
the best performance in a fuel cell test was the HC, crosslinked with sulfosuccinic acid.
REFERENCES
1. C.Y Wong et al., “Development of Poly(Vinyl Alcohol) – Based Polymecs as Proton Exchange Membranes and Challenges
in Fuell Cell Application: A Review,” Polym. Rev., vol. 60, no.1, pp. 171-202, 2020, doi: 10.1080/15583724.2019.1641514.
2. Costa, L.A.T, Aguiar, L.C.V, Gomes, A. S, F.J.B. Brum. “Characterization of PVA and phenol salt modified tin dioxide
cationic membranes” Inernational Journal of Hydrogen Energy, doi: 10.1016/j.ijhydene.2021.12.074.
3. F.J.B. Brum, F.G.Zanatta, E.S.Marczynski, M.M.C. Forte, and B. Pollet, “Synthesis and characterization of a new
sulphonated hydrocarbon polymer for application as a solid proton-conducting electrolyte,” Solid State Ionics, vol. 263, pp.
62-70, 2014, doi: 10.1016/j.ssi.2014.05.009
4. F.J.B. Brum, “Membranas catiônicas a base de poli(indeno) sulfonado/PVA para uso como eletrolito em célula a
combustível tipo PEMFC,” 2013.
5. F.J.B. Brum, F.N. Lau, and M.M.C. Forte, “Synthesis of hydrocarbon polymers by cationic polymerization and their thermal
properties,” Des. Monomers Polym., vol.16, no. 0, pp. 291-301, 2013, doi: 10.1080/15685551.2012.747145
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