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Enhancing the Performance of Poly(phthalazinone ether ketone)-Based Membranes Using a New Type of Functionalized TiO2 with Superior Proton Conductivity

  • Hossein Beydaghi*
    Hossein Beydaghi
    Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
    *Email: [email protected]
  • Ahmad Bagheri
    Ahmad Bagheri
    Department of Chemistry, Amirkabir University of Technology, 1599637111 Tehran, Iran
  • Parisa Salarizadeh
    Parisa Salarizadeh
    High-Temperature Fuel Cell Research Department, Vali-e-Asr University of Rafsanjan, 7718897111 Rafsanjan, Iran
  • Sepideh Kashefi
    Sepideh Kashefi
    Department of Chemical Engineering, Semnan University, 3513119111 Semnan, Iran
  • Khadijeh Hooshyari
    Khadijeh Hooshyari
    Department of Applied Chemistry, Faculty of Chemistry, Urmia University, 5756151818 Urmia, Iran
  • Ali Amoozadeh
    Ali Amoozadeh
    Department of Chemistry, Semnan University, 3513119111 Semnan, Iran
  • Taiebeh Shamsi
    Taiebeh Shamsi
    Department of Chemistry, Semnan University, 3513119111 Semnan, Iran
  • Francesco Bonaccorso*
    Francesco Bonaccorso
    Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
    BeDimensional SpA, Via Albisola 121, 16163 Genova, Italy
    *Email: [email protected]
  • , and 
  • Vittorio Pellegrini
    Vittorio Pellegrini
    Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy
    BeDimensional SpA, Via Albisola 121, 16163 Genova, Italy
Cite this: Ind. Eng. Chem. Res. 2020, 59, 14, 6589–6599
Publication Date (Web):March 13, 2020
https://doi.org/10.1021/acs.iecr.9b06813
Copyright © 2020 American Chemical Society
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Abstract

A novel, high-efficiency, and cost-effective series of sulfonated poly(phthalazinone ether ketone)/sulfonated titanium [email protected] [email protected] (SO3H−TiO2@[email protected]3H) nanocomposite membranes is designed to enhance the proton conductivity and methanol barrier of the proton exchange membrane (PEM). The nanocomposite membranes were prepared via a facile one-step process of the solution casting method. The presence of organic–inorganic SO3H–TiO2@[email protected]3H nanoparticles improved the performance of the nanocomposite membranes in terms of mechanical stability, proton conductivity, methanol permeability, and selectivity. We used toluene diisocyanate (TDI) as a linker to exploit the properties of sulfonated TiO2 and sulfonated ethylenediamine (EN-SO3H) nanoparticles. These nanoparticles act as Lewis and Brønsted acids simultaneously because of the presence of sulfonamide, TiO2, and SO3H groups, which increase the kinetics of the reaction between the membrane and electrode, improving the performance of the direct methanol fuel cell (DMFC). The DMFC, which is assembled using the nanocomposite membrane with 5 wt % SO3H–TiO2@[email protected]3H nanoparticle (MSN5) membrane, exhibited a maximum power density of 59.22 mW cm–2 during testing because of high proton conductivity and low methanol permeability. The MSN5 membrane is a promising PEM for DMFCs.

1. Introduction

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Recently, direct methanol fuel cells (DMFCs) have been widely used as promising power generation devices because of their simple structural design, low-temperature operation, and high efficiency. (1,2) Hydrogen or methanol are used as fuels, while air is used as an oxidant for portable applications. The consumption of methanol as the fuel in DMFC gives more advantages, compared to other fuels, such as flexibility of cell designing, reduced cost of the fuel management system, and the quick and safe refilling process of the fuel. (3) The slow kinetics of methanol oxidation reaction in the anode electrode and methanol cross-over through the membranes are important factors that could lead to a remarkable energy loss in DMFCs. (4,5) The proton exchange membrane (PEM), as the core component of DMFC, is required to have high proton conductivity, methanol barrier properties, suitable thermal, mechanical stability, and durability. (6−8) The most used PEM is the perfluorosulfonic acid (PFSA) ionomer (especially the Nafion membrane). (9,10) However, the environmental incompatibility, high cost production, high crossover of methanol, and decrease of proton conductivity with the increase of temperature have been critical challenges for the PFSA membranes. Therefore, in the past years, a strong research effort has been focused toward the preparation of new membranes with desirable properties as an alternative of the PFSA membrane (especially the Nafion membrane) for DMFCs.
In this context, some polymers have been processed to be sulfonated and used as alternative membranes to PFSA such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF), (11,12) polysulfone, (13) poly(ether ether ketone) (PEEK), (14−17) poly(ether sulfone), (18) sulfonated biopolymer, (19) and poly(phthalazinone ether ketone) (PPEK). (20,21) The introduction of sulfonated groups into polymeric chains creates specific proton transport channels in the structure of the membrane, improving the proton conductivity of the as-prepared PEMs. However, the proton conductivity of the sulfonated polymer is lower than the one of the Nafion membrane because of the lower acidity of −SO3H and less distinct phase separation between hydrophobic and hydrophilic domains. (22) To improve the performances of membranes, the addition of nanoparticles with good conductivity properties was investigated for the preparation of nanocomposite membranes as an alternative to the Nafion membrane. (10) In this context, different nanoparticles and nanosheets such as graphene-based nanosheets, (23,24) perovskite nanoparticles, (25,26) sulfonated tungsten trioxide, (20) and sulfonated nonporous silica (27) have been used to prepare nanocomposite membranes by our group.
Poly(aryl ether ketone)s-based membranes belong to the class of high-performance PEMs in DMFCs. (28) Among the poly(aryl ether ketone) polymers, PPEK has been extensively studied for its use in DMFCs because of the low methanol cross-over linked with the low hydrophilic/hydrophobic separation in the structure of the polymer. (20) The introduction of the rigid phenyl phthalazinone moiety into the polymer increases the intermolecular H-bond, leads to polymers with very high glass-transition temperature (as a class of thermoplastics) (>200 °C), excellent mechanical properties, and thermo-oxidative stability, and results in high dimensional stability and lower membrane swelling (MS) in PEMs. (29) For applications in DMFCs, it is desirable to modify PPEK still maintaining their properties, such as good water uptake, low electrical conductivity, high ionic conductivity, low fuel permeability, suitable mechanical properties, and high selectivity. (11) Compared to other conventional polymers used as the polymeric base of PEMs, less work has been done on PPEK. Liu et al., prepared a series of cross-linked anion exchange membranes based on quaternized PPEK. (30) The membranes have shown low MS (∼7%) and conductivity (0.028 S cm–1 at 30 °C) because of the cross-linking reaction. Hongwei et al. developed SPPEK membranes by electrospinning for their use in PEM fuel cells. (31) Recently, our group prepared SPPEK/SPVDF/sulfonated trioxide (SWO3) as suitable PEMs for DMFCs. (20) The results show that the presence of the sulfonated groups in the structure of SWO3 nanoparticles increases proton conductivity and selectivity of the as-prepared membranes. Sulfonated PPEK with ionic exchange groups (SO3H) can be prepared by the postsulfonation of PPEK. The proton conductivity is the most important parameter in the preparation of PEMs for different types of the polymeric fuel cell. The final performance of DMFC strictly depends on the conductivity of the membrane. The sulfonation determines an increase of water uptake, proton conductivity, MS, and methanol permeability. Therefore, to increase the proton conductivity, while maintaining low methanol permeability and swelling, the addition of an inorganic additive and preparation of nanocomposite membranes is a promising experimental route. (32)
The sulfonated titanium [email protected] [email protected] (SO3H–TiO2@[email protected]3H) nanoparticle is a suitable additive for the synthesis of PEMs. In the literature, the properties of sulfonated TiO2 as an attractive additive were investigated for the use in PEM of different types of fuel cells. (33−35) The hygroscopic nature and high surface area of TiO2 nanoparticles coupled with the formation of hydrogen bonding between functionalized groups of sulfonated TiO2 and polymer chains help improve water uptake, mechanical properties, and thermal stability of the as-prepared membranes. (33) Sulfonated groups of SO3H–TiO2 nanoparticles can increase the hydrophilic nature of these nanoparticles and improves water uptake, which is beneficial in improving proton transfer in the membrane structure. (35) The simultaneous use of sulfonated TiO2 and sulfonated ethylenediamine (EN-SO3H) is possible using toluene diisocyanate (TDI) as a linker. The TDI was used to establish a bridge between the surface of SO3H–TiO2 and EN-SO3H. The sulfonated groups of EN-SO3H support the H+ transport through proton exchange channels in the membrane structure, enhancing the proton conductivity. The increase in proton conductivity has an important role in improving the final performance of the DMFC. (27) In fact, in addition to the mentioned improvements, the sulfonamides act as an additional source of protons, which can be beneficial for the proton transfer across the membrane. It is well known that sulfonamides are good Brønsted acids. (36) Thus, the acidic properties of these nanoparticles can positively impact the kinetics of the reaction in membrane–electrode assembly (MEA) by decreasing the activation energy and reducing the methanol cross-over. This, in turn, increases the catalytic activity of the cathode catalyst, improving the final performance of DMFCs. The SO3H–TiO2@[email protected]3H nanoparticles act as Lewis and Brønsted acid simultaneously because of the presence of amide, TiO2, and SO3H groups, improving proton conductivity and mechanical stability of the as-prepared membranes. (37) The organic–inorganic structure of SO3H–TiO2@[email protected]3H nanoparticles combines different properties of an organic (ductility and flexibility) and inorganic (rigidity and stability) moiety in the as-prepared nanocomposite membranes, leading to the preparation of the ideal membrane for DMFC. (38)
In this work, we report the fabrication of a novel nanocomposite PEM based on SPPEK as the polymer matrix and SO3H–TiO2@[email protected]3H nanoparticles as a suitable organic–inorganic additive for use in DMFCs. The different SPPEK/SO3H–TiO2@[email protected]3H nanocomposite membranes were synthesized using the solution casting method. The SO3H–TiO2@[email protected]3H nanoparticles provide proton conductivity because of its sulfonated groups and the Grotthuss mechanism and can act as fillers in the structure of the membrane to decrease methanol permeability. (27) These as-prepared membranes show excellent selectivity and DMFC performance because of the high proton conductivity of SO3H–TiO2@[email protected]3H nanoparticles.

2. Experimental Section

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2.1. Materials

Sulfonated PPEK (SPPEK) was purchased from the FuMa-Tech company. TDI was of industrial grade. All other chemicals and solvents were purchased from Merck and used without any purification.

2.2. Synthesis of Nanoparticles

First, 1 g of titanium dioxide and 1.4 g of TDI were dissolved in 50 mL of pure toluene and sonicated in an ultrasound bath for 20 min and stirred for 6 h at 95 °C. The obtained powder was centrifuged. To eliminate the possible presence of TDI, the product was washed using toluene. Then, the product was dried at 80 °C for 24 h to obtained n-TiO2–TDI nanoparticles. (37)n-TiO2–TDI (1 g) was added to EN and stirred at 50 °C. After 24 h, the precipitated powder was separated by centrifugation and washed using acetone followed by drying at 110 °C. For the sulfonation reaction, 1 g of modified nanoparticles was dispersed in 15 mL of dichloromethane and 0.06 mL of chlorosulfonic acid was added dropwise to the dispersion at room temperature. Afterward, the dispersion was stirred for 2 h to eliminate the produced HCl gas. Finally, the dispersion was centrifuged, and the collected sediment was dried at 80 °C for 24 h. The schematic of the SO3H–TiO2@[email protected]3H nanoparticle synthesis procedure is shown in Figure 1.

Figure 1

Figure 1. Scheme for the synthesis of SO3H–TiO2@[email protected]3H nanoparticles.

2.3. Membrane Preparation

Two types of membranes of SPPEK and SPPEK/SO3H–TiO2@[email protected]3H were prepared and named MS and MSNx, respectively, in which x is the weight percentage of SO3H–TiO2@[email protected]3H nanoparticles in the structure of the nanocomposite membranes. For the preparation of the MS membrane, the appropriate amount of SPPEK was dissolved in dimethylacetamide (DMAc) under stirring at 60 °C, for 4 h to form 10 wt % solution. Afterward, the resulting solution was cast on a clean flat glass using a doctor blade and drying at 70 °C for 12 h and 120 °C for 2 h to remove residual solvents. For the preparation of MSNx membranes, after dissolving an appropriate amount of SPPEK in DMAc, the different weight percentages of SO3H–TiO2@[email protected]3H nanoparticles was added to the abovementioned solution and ultrasonicated for 1 h. The final dispersion was cast on a glass plate and drying at the same temperatures.

2.4. Characterization

Fourier transform infrared (FTIR) characterization of the nanocomposite membranes was carried out using a Bruker Equinox 55 FTIR Spectrometer at room temperature. The samples were tested from the wavenumber of 400–4000 cm–1. The X-ray diffraction (XRD) analysis of the samples was carried out using an Equinox 3000, by applying (a) a detected diffraction angle of 2θ, (b) a range of 15–65°, and (c) a fixed scan rate of 3° min–1. Scanning electron microscopy (SEM) images of the as-prepared PEM cross-section were taken on a TESCAN SEM. Before the test, the membranes were fractured in liquid nitrogen and coated with gold. The mechanical properties [tensile strength (TS) and elongation at break] of the prepared PEMs were determined using a SANTAM DBBP-100 testing machine with a tensile rate of 1 mm·min–1 at room temperature.
The water uptake of the as-prepared membranes was obtained by measuring the weight difference in wet and dry PEMs. First, the membranes were placed in distilled water for 12 h, the surface water was removed using paper, and the wet membrane was weighed (Ww). Afterward, the wet PEM was dried in the oven for 12 h and weighed (Wd). The water uptake (WU) is calculated using the equationin which Ww and Wd are the weight of the wet and dry membrasnes, respectively.
The swelling of the as-prepared membranes was measured using the same method and using the change of membrane area in the wet and dry membrane (Aw and Ad, respectively). The MS is calculated by
To investigate the oxidative stability of different membranes, the Fenton reagent (3 wt % H2O2 + 2 ppm FeSO4) was used at 80 °C. The prepared anhydrous membranes were placed in 30 mL of Fenton reagent until the membrane began to break.
The proton conductivity (σ) of different prepared membranes was calculated at different temperatures with a potentiostat/galvanostat electrochemical work station with four electrodes. The proton conductivity was calculated using a four-probe conductivity cell equipped with an AC impedance analyzer. The as-prepared membranes were soaked in deionized water for 12 h before the test. Bulk resistance (R) (Ω) was measured using the impedance plot obtained at an AC voltage of 50 mV in the frequency range of 0.1 Hz to 100 kHz. The proton conductivity of the samples was calculated as followsin which, L (cm) and A (cm2) are the distance between two electrodes and the surface area, respectively.
A diffusion cell containing two separate compartments, that were named A and B, was used for the calculation of methanol permeability (P, cm2 s–1). In order to calculate methanol permeability, the as-prepared membranes were placed between these two compartments. Methanol–water solution (1 M) was added to compartment A and also deionized water to compartment B. Methanol diffused through the thickness of the membrane from compartment A to B during stirring, and the methanol concentration in compartment B was measured using a density meter as a function of time because of concentration difference. The methanol permeability coefficient was calculated as follows
in which, VB (cm3), L (cm), A (cm2), CA (mol L–1), and CB (mol L–1) are the volume of compartment B, thickness of the sample, effective area of the sample, and the methanol concentration in compartments A and B, respectively.
For the calculation of proton conductivity and methanol permeability, the selectivity (S, S s cm–3) of prepared membranes was measured using the following equation

2.5. DMFC Performance

The MEA was prepared using the following procedure: the catalyst dispersion for the cathode was prepared by mixing the Pt/C catalyst (20 wt % of Pt), Nafion solution (5 wt %), deionized water, IPA, and glycerol. The obtained dispersion was then sonicated for 2 h to homogenize it. Pt–Ru/C (40:40:20) was used as the anode catalyst, mixed with a suitable amount of Nafion solution, IPA, and deionized water to get a homogeneous dispersion. The catalyst dispersions were painted onto carbon cloth (E-Tek, HT 2500-W) with the Pt and PtRu loading of 2 and 1 mg cm–2 for the anode and the cathode electrodes, respectively. Finally, the as-prepared PEM was hot-pressed between anode and cathode electrodes at 140 °C for 3 min to obtain MEA. Single active DMFC cell performance was carried out at room temperature, using 2 M methanol feed concentration.

3. Result and Discussion

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3.1. Characterization

The surface compositions and chemical structures of the nanoparticles and the different membranes were investigated via FTIR. Figure 2a shows the FTIR analysis for every step in the synthesis of SO3H–TiO2@[email protected]3H nanoparticles. In the spectrum of TiO2 nanoparticles, the characteristic peaks at 1622 and 3355 cm–1 confirm the presence of surface −OH stretching bands. Moreover, the wide peak below 1200 cm–1 may be attributed to Ti–O–Ti vibration in the structure of TiO2 nanoparticles. (39) The absorption bands at 1550 and 2243 cm–1 in the TDI spectrum is assigned to the existence of the phenyl ring and stretching vibration of N═C═O in the structure of TDI. (40) The successful synthesis of TiO2–TDI confirmed by the presence of the stretching vibration peaks of C═O and C–N in urethane bond at 1649 and 1595 cm–1 and two absorption peaks at 2266 and 1533 cm–1 assigned to the unreacted orthoisocyanate group and phenyl ring in the structure of TDI. (41) After adding EN to TiO2–TDI, the final structure was confirmed by the peak at 3260 cm–1, resulting from the presence of amino groups. Finally, sulfonation of nanoparticles with chlorosulfonic acid was verified using the wide band of the acidic group between 2800 and 3200 cm–1 and absorption peaks of 1033 and 1213 cm–1, which is assigned to O═S═O asymmetric and symmetric stretching and the stretching vibration of S═O on sulfonated groups, respectively. (42)

Figure 2

Figure 2. FTIR spectra of different prepared nanoparticles and membranes.

Chemical structures of the MS and MSN5 membranes were investigated, and the FTIR spectra are shown in Figure 2b. In the MS membrane, the peaks at around 1234 and 1479 cm–1 are related to the C–O–C and C–C bonds in the aromatic ring, respectively, and the peaks around 1585 and 1658 cm–1 represent the carbonyl groups and C═N bands in the structure of SPPEK, respectively. (43) Also, three absorption peaks at 1018, 1082, and 1144 cm–1 are related to the symmetric and asymmetric stretching vibration of O═S═O and stretching vibration of S═O, confirming the addition of sulfonated groups in the structure of the polymer. As shown in Figure 2b, after adding SO3H–TiO2@[email protected]3H nanoparticles to SPPEK, the intensity of sulfonated group-related peaks (1000–1150 cm–1) changed. This is related to the presence of sulfonated groups in the structure of SO3H–TiO2@[email protected]3H nanoparticles. In addition, the peak at ∼580 cm–1 in the MSN5 membrane may be assigned to the presence of Ti–O vibration in the structure of the nanocomposite membrane. (44)
The crystal nature of the SO3H–TiO2@[email protected]3H nanoparticles is verified using XRD analysis (Figure 3). Figure 3 shows diffraction peak (101), (103), (004), (112), (200), (105), (211), (204), (116), (220), (215), and (224) facets of the crystal planes of TiO2 nanoparticles which are in accordance with the JCPD 894921 standard for the crystalline phase of TiO2. As shown in Figure 3, the SO3H–TiO2@[email protected]3H nanoparticles show diffraction patterns similar to the ones of TiO2 nanoparticles. The addition of other organic materials (i.e., TDI and EN) and the sulfonate modification process do not change the phase of nanoparticles, and the crystal nature has been preserved.

Figure 3

Figure 3. Diffraction patterns of TiO2 (a) and SO3H–TiO2@[email protected]3H nanoparticles.

In order to illustrate the shape of SO3H–TiO2@[email protected]3H nanoparticles and the effect of adding organic materials and sulfonation reaction on the morphology of nanoparticles, SEM images of the nanoparticles were acquired, see Figure 4. Typically, some properties of small nanoparticles are determined by their size. (45)Figure 4a shows that the TiO2 nanoparticles have a spherical shape with an average particle size of 25 nm. According to the SEM image of TiO2@[email protected] nanoparticles, an increase in the average particle size to 80 nm is detected, which is due to the grafting of organic components onto the surface of TiO2 nanoparticles. The aggregation of SO3H–TiO2@[email protected]3H nanoparticles observed in Figure 4c is due to the functionalization process.

Figure 4

Figure 4. (a) SEM images of TiO2, (b) TiO2@[email protected], and (c) SO3H–TiO2@[email protected]3H nanoparticles.

Surface and cross-sectional images of MS and MSN5 membranes were shown in Figure 5a–d. The surface of the MS membrane (Figure 5a) is smoother than the nanocomposite membrane. This fact is due to the absence of SO3H–TiO2@[email protected]3H nanoparticles in the pristine membrane. From the cross-sectional SEM images, it is clear that both prepared membranes show homogeneous morphology without any cracks and holes. The uniform and homogeneous structure of the MSN5 membrane (Figure 5d) can be related to the high miscibility between SPPEK chains and SO3H–TiO2@[email protected]3H nanoparticles. EDX mapping images displayed in Figure 6 show the homogeneous distribution of nanoparticles in the as-prepared membranes. There is a more homogeneous dispersion of Ti in the MSN5 nanocomposite membrane compared to the other membranes. Also, the aggregation of SO3H–TiO2@[email protected]3H nanoparticles in the MSN5 membrane is evident in some regions.

Figure 5

Figure 5. Surface and cross-sectional images of (a,c) MS and (b,d) MSN5 membranes.

Figure 6

Figure 6. EDX mapping images of (a) MSN1, (b) MSN3, (c) MSN5, and (d) MSN7 membranes.

3.2. Water Uptake and Membrane Swelling

The water uptake and MS are two key parameters of membranes in DMFCs that have a huge impact on proton conductivity, mechanical stability, and durability of prepared membranes. It is desirable that prepared membranes should have high water uptake for proton conductivity and low MS for mechanical stability and durability. (46) In the as-prepared membranes, water molecules play the role of carriers, transferring proton and methanol by creating and breaking hydrogen bonding throughout the PEM. Figure 7 shows water uptake and MS of different prepared PEMs at temperatures in the 20–80 °C range. As shown in Figure 7a, the nanocomposite membranes have shown higher water uptake compared to the MS membrane. This behavior is ascribed to the hydrophilic nature of the SO3H–TiO2@[email protected]3H nanoparticles, absorption of water molecules with the formation of hydrogen bonding between functionalized groups of nanoparticles and free water molecules, and the creation of more acid sites to absorb free water. The results show that the water uptake on nanocomposite membranes increases with increasing the loading rate of nanoparticles from 1 to 7%. This is linked with the fact that the increase of the loading of SO3H–TiO2@[email protected]3H increases the hydrophilic region in the structure of nanocomposite membranes. Also the difference in morphology of the membrane influences the interconnections of the ionic cluster responsible for water retention. (47)

Figure 7

Figure 7. (a) Water uptake and (b) MS diagrams of different prepared PEMs at temperatures between 20 and 80 °C.

Dimensional stability is a vital parameter of the prepared membranes when used in MEA of DMFCs because it is critical for proper mass transfer and prevention of electrical contact in the MEA. (28) As shown in Figure 7b, unlike water uptake, the swelling of the different nanocomposite membranes are lower than pristine SPPEK, decreasing from 12.8 to 9.5% at room temperature with increasing the SO3H–TiO2@[email protected]3H nanoparticle content. This effect is likely due to the compact structure of nanocomposite membranes with the formation of hydrogen bonding between functionalized groups of nanoparticles and sulfonated groups of the polymer. Also, the complex structure of SO3H–TiO2@[email protected]3H nanoparticles could limit the motion of SPPEK chains, constraining the MS. (48) The results of Figure 7 show that both water uptake and MS increased with the temperature. These results may be due to the increase in mobility of free water molecules and SPPEK chains with increasing temperature from 20 to 80 °C, facilitating water absorption in the polymeric structure. (49) In general, the incorporation of SO3H–TiO2@[email protected]3H into the structure of nanocomposite membranes enhances water retention and dimensional stability, making the nanocomposite membranes more appealing for use in DMFCs.

3.3. Proton Conductivity

Proton conductivity is the most important property of PEM in DMFCs. According to the key role of water molecules on proton transfer in both the mechanism of Grotthuss and Vehicle, the water-friendly properties are the pillars of the movements of the protons in the structure of the membrane. The proton conductivity value of different PEMs in the absence and presence of SO3H–TiO2@[email protected]3H was measured at 20 °C and summarized in Table 1. As shown in Table 1, all nanocomposite membranes exhibited higher proton conductivity than the pristine SPPEK membrane. The addition of nanoparticles affects positively the structure of the membrane because of the improvement in the proton conductivity as a consequence of nanoparticle interaction (Figure 8). The transportation of the proton through the structure of PEM is via the hydrophilic regions, and thus, proton conductivity is directly linked with the water uptake. Thus, an increase of nanoparticles means more proton transfer, which is due to the hydrophilic nature of SO3H and TiO2 groups. (50) The hygroscopic nature of TiO2 nanoparticles leads to reserves of water molecules and creates water and proton conduction channels at the interface nanoparticles/polymeric chains. Also, according to the presence of TiO2, sulfamide, and SO3H groups in the structure of nanoparticles, the SO3H–TiO2@[email protected]3H nanoparticles act as Lewis and Brønsted acid simultaneously and improve proton conductivity of the nanocomposite membranes. Moreover, according to the key role of SO3H groups in the Grotthuss mechanism, the formation of hydrogen bonding between sulfonated groups of SO3H–TiO2@[email protected]3H nanoparticles and free water molecules available in the membrane leads to the more transfer of protons using the Grotthuss mechanism and increasing proton conductivity value in the membrane (Figure 8). (51) Furthermore, in the sulfonamide groups, there is an additional proton compared to sulfone ester and the hydrogen connected to nitrogen atom show acidic nature. Therefore, the proton transfer is easier at the presence of the prepared SO3H–TiO2@[email protected]3H nanoparticles. The reduction in proton conductivity of the MSN7 membrane may be due to the blocking of ion transport channels, resulting from aggregation tendency and the filling effect of nanoparticles on the polymer chains, see Figure 6d. (10)

Figure 8

Figure 8. Schematic of proton conductivity in the as-prepared nanocomposite membrane.

Table 1. Proton Conductivity, Methanol Permeability, and Selectivity of the Different Prepared Membranes at Room Temperature
membraneσ (S cm–1)P (cm2 S–1) × 10–7S (S s cm–3) × 104
MS0.0497.26.9
MSN10.0595.610.6
MSN30.0705.113.8
MSN50.0913.129.3
MSN70.0782.827.9
According to the proton conductivity–temperature relationship, the activation energy (Ea) that is the minimum energy required to proton passes from one functional group to another one and obtained using Arrhenius equation σ = A exp(−Ea/RT) was calculated and plotted in Figure 9. In the Arrhenius equation, A is a pre-exponential factor, R is the universal gas constant (J mol–1 K–1), and T is the temperature in kelvin. According to Arrhenius plots shown in Figure 9, the as-prepared PEMs exhibited an upward trend of the proton conductivity with the temperature. Increasing the mobility of water molecules and polymer chains at high temperatures increases the vacant spaces for proton transfer in the membrane. (52) Also, increasing the proton mobility at high temperatures has an influence on proton jumping from SO3H3O+ (Grotthuss mechanism). The results show that the PEM with 5 wt % SO3H–TiO2@[email protected]3H loading achieved the best proton conductivity at different temperatures. The MS, MSN1, MSN3, MSN5, and MSN7 membrane exhibits an ion transport Ea of 7.18, 6.32, 5.51, 4.49, and 5.19 kJ mol–1, respectively. The decay of Ea demonstrated the decreased energy barrier for proton transfer linked with the interaction between the sulfonamide and SO3H groups of nanoparticles and polymers. (53) Thus, the MSN5 nanocomposite membrane has the highest potential for use in higher temperature DMFC because of the lowest Ea value among all the different as-prepared membranes.

Figure 9

Figure 9. Arrhenius plots for proton conductivity at different temperatures.

3.4. Methanol Permeability and Selectivity

To demonstrate that the different as-prepared membranes can be used as the PEM for applications in DMFC, we investigated methanol permeability. The fuel cross-over through a membrane is an important challenge causing final performance degradation of DMFCs because the methanol can deteriorate the catalytic activity of the cathode toward oxygen reduction reaction, which determines a reduction in the DMFCs performance. (54) Then, the lower methanol cross-over of the membrane is a key requirement to improve the performance of DMFC. As aforementioned, SPPEK has attractive potential as a suitable PEM for DMFCs because of minimal hydrophilic/hydrophobic separation in the structure of the polymer that reduces methanol cross-over through the membrane. (20) The results of Table 1 show that the methanol permeability of nanocomposite membranes is lower than pristine SPPEK. The formation of hydrogen bonding between functionalized groups of nanoparticles and polymeric chains causes the compact structure of the membrane; subsequently, the methanol transport channels in the membrane are reduced, decreasing the methanol permeability of nanocomposite membranes. The formation of tighter hydrophilic domains with the addition of nanoparticles, which makes transport channels more obstructed, leads to the considerably lower methanol cross-over of nanocomposite membranes. (55) This is in good agreement with the results of MS of nanocomposite membranes. The methanol permeability of nanocomposite membranes was decreased from 5.6 × 10–7 to 2.8 × 10–7 cm2 S–1 with the addition of more SO3H–TiO2@[email protected]3H nanoparticles. The filling effect of SO3H–TiO2@[email protected]3H nanoparticles in the structure of polymeric chains that obstruct methanol transport channels upon nanocomposite membranes should be another reason for the decrease of methanol permeability.
To further investigate the performances of the different membranes, we measured, at room temperature, the selectivity of prepared membranes, see Table 1. High selectivity of the membrane represents a key performance parameter for DMFCs. (56) According to the results reported in Table 1, it is seen that compared to the MS membrane, the nanocomposite membranes show a significant improvement in selectivity. Among the different nanocomposite membranes, the MSN5 membrane shows the highest selectivity, that is, 4.5 times higher compared to the MS membrane because of their good proton conductivity and low methanol penetration. The combined analysis of three performance parameters (i.e., proton conductivity, methanol permeability, and MS) indicates that the MSN5 membrane can be considered as a potential candidate as the PEM of DFMC because of the high level of selectivity and improved mechanical/chemical stabilities.

3.5. Mechanical and Oxidative Stability

It was important for a prepared membrane to have favorable mechanical stability for the fabrication of the MEA and lifetime of DMFCs. The TS and elongation at break (Eb) of the MS membrane and different nanocomposite membranes were illustrated in Table 2. The SPPEK polymer with pendant phenyls and heterocyclic structures is rigid and has good mechanical properties. As shown in Table 2, the pristine SPPEK has TS of 45.5 MPa with Eb at 10.8% and with the addition of SO3H–TiO2@[email protected]3H nanoparticles, the nanocomposite membranes attained an improvement on the mechanical properties. The mechanical stability appeared to be very sensitive to the nanoparticle content, as the TS increased rapidly with the increase of the SO3H–TiO2@[email protected]3H percentage. This fact is due to the nanoparticles that are uniformly dispersed throughout the polymeric matrix, forming intermolecular hydrogen bonding with functionalized groups of the polymer. Therefore, the SO3H–TiO2@[email protected]3H content increase determined a more compact structure of the membrane and an increase in TS based on the interaction between the polymeric chains and functionalized groups of the nanoparticles. (57) Another explanation for the improvement of the TS in the nanocomposite membrane relies on the existence of the nitrogen moiety in the polymer structure that provides adhesion between the polymer and SO3H–TiO2@[email protected]3H nanoparticles. (31) Further increase in the 5 % wt of nanoparticle loading led to a slight decrease of the TS, which may be linked with the agglomeration of the SO3H–TiO2@[email protected]3H nanoparticles in the structure of the membrane. (58) According to the results reported in Table 2, an increase in the modulus of nanocomposite membranes is due to the formation of the rigid structure because of strong hydrogen bonding between SO3H–TiO2@[email protected]3H nanoparticles and SPPEK. (11) In addition, the results reported in Table 2 show that according to the rigid structure of nanoparticles, with the addition of SO3H–TiO2@[email protected]3H nanoparticles to SPPEK, the Eb of nanocomposite membranes decreases. The interactions between the nanoparticles and the polymer decrease the freedom of movement of the polymer chains in the structure of membranes and consequently cause to decrease flexibility and Eb of the nanocomposite membranes. By increasing the amount of the nanoparticles in the membrane, the Eb of the membrane decreases further.
Table 2. Tensile Strength, Elongation at Break, Modulus, and Oxidative Stability of the Prepared Membranes
membraneTS (MPa)Eb (%)modulus (MPa)oxidative stability (h)
MS45.510.810452.4
MSN148.610.411023.1
MSN350.29.811543.5
MSN553.69.112184.2
MSN752.48.812674.5
The oxidative stability of the membranes is one of the biggest issues for DMFCs. During the operation of DMFCs, hydroxyl (OH) and hydroperoxy (OOH) radicals are generated on both electrode sides. This process is ascribed to the degradation of H2O2 because of the incomplete reduction of oxygen, causing membrane ruin. (59) The time that the PEM could take to retain its shape before breaking, was recorded. As shown in Table 2, different nanocomposite membranes have higher oxidative stability than pristine SPPEK. The increase of the weight percentage of SO3H–TiO2@[email protected]3H nanoparticles in the membranes determines an improvement of the oxidative stability. The latter is directly related to MS. The membranes with large MS provide more chance for oxidative radicals (OH and OOH) to attack the polar groups of the polymer. (60,61) Therefore, MSN7 nanocomposite membranes show the best oxidative stability compared to other prepared membranes.

3.6. DMFC Test

To investigate the practical applications of membranes in DMFC operating conditions, different prepared membranes were used to measure the final performance of membranes in DMFC. The polarization curves of the as-prepared membranes, carried out in 2 M methanol solution and room temperature, are shown in Figure 10. The nanocomposite membranes show higher open-circuit voltage compared to the MS membrane, reflecting the low fuel cross-over in the nanocomposite membrane. (62) Methanol permeation as the fuel into the fabricated membranes causes an initial drop in voltage in the DMFC test. As seen in previous sections, the nanocomposite membranes exhibit several advantages such as higher proton conductivity, lower methanol permeability, and better selectivity compared to the MS membrane. Then, the nanocomposite membranes can be expected to exhibit better final performance than the MS membrane. Figure 10 shows the maximum power density of the MS membrane increased from 37.18 to 59.22 mW cm–2 with adding 5 wt % SO3H–TiO2@[email protected]3H nanoparticles. Also, the maximum current density of the MSN5 membrane was 267.36 mA cm–2, which is higher than the MS membrane (198.87 mA cm–2). The higher proton transfer of the nanocomposite membrane and lower methanol permeability due to compact structure increases the final performance of the nanocomposite membrane than the MS membrane. Also, in SO3H–TiO2@[email protected]3H nanoparticles, the sulfonamide groups could act as an additional excellent source of protons which could help the proton transfer across the membrane. It is well known that sulfonamides are Brønsted acids. (36) Thus, these properties can facilitate proton transfer in MEA and consequently can determine an increase of the final power density of DMFC. The results have shown that the MSN5 membrane exhibited the best maximum power density compared to the other nanocomposite membranes, which is due to better selectivity of this membrane compared to other membranes. According to the results of selectivity and power density, the MSN5 nanocomposite membrane shows potentiality for its use in DMFCs.

Figure 10

Figure 10. Polarization curves of different prepared membranes in 2 M methanol solution and room temperature.

4. Conclusions

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In this work, we assessed the potential of SPPEK-based membrane, added with organic–inorganic sulfonated titanium [email protected]@ethylenediamine (SO3H–TiO2@[email protected]3H) nanoparticles, in DMFCs. We investigated the loading dependence of the nanoparticles on the key parameters, such as water uptake, MS, morphology, proton conductivity, mechanical stability, and methanol permeability of the SPPEK-based membrane. Water uptake, MS, and methanol uptake of the as-prepared membranes are influenced by the increase of SO3H–TiO2@[email protected]3H nanoparticles. The methanol permeability results show that the addition of SO3H–TiO2@[email protected]3H nanoparticles acts as the barrier on the methanol cross-over, improving the selectivity of the nanocomposite membranes. The MSN5 nanocomposite membrane with the highest selectivity was selected for the DMFC test, showing a peak maximum power density of 59.22 mW cm–2 at room temperature. This value is higher than the one of Nafion 117 and SPPEK-based membranes under the same experimental conditions (see Table 3). The data reported in Table 3 show that the MSN5 membrane is a promising candidate for applications in DMFC.
Table 3. Comparison of the Different Properties of the MSN5 Membrane with SPPEK-Based Membranes and Nafion 117 Used in DMFC at 25 °C
membranesσ (S cm–1)P (cm2 s–1)S (S s–1 cm–3)PD (mW cm–2)refs
MSN50.0913.10 × 10–729.35 × 10459.22this work
SPPEK-dPa0.0143.50 × 10–842.40 × 104  (63)
SPPEK/PWAb0.0131.02 × 10–711.76 × 1043.79 (64)
SPPEK/SGNFc0.0542.79 × 10–719.35 × 104115.00d (32)
Nafion 1170.0902.40 × 10–63.75 × 10424.00 (9)
a

3,5-Diphenyl phthalazinone moieties.

b

Phosphotungstic acid.

c

Sulfonated graphite nanofibers.

d

Measured at 60 °C.

Author Information

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  • Corresponding Authors
  • Authors
    • Ahmad Bagheri - Department of Chemistry, Amirkabir University of Technology, 1599637111 Tehran, Iran
    • Parisa Salarizadeh - High-Temperature Fuel Cell Research Department, Vali-e-Asr University of Rafsanjan, 7718897111 Rafsanjan, Iran
    • Sepideh Kashefi - Department of Chemical Engineering, Semnan University, 3513119111 Semnan, Iran
    • Khadijeh Hooshyari - Department of Applied Chemistry, Faculty of Chemistry, Urmia University, 5756151818 Urmia, Iran
    • Ali Amoozadeh - Department of Chemistry, Semnan University, 3513119111 Semnan, Iran
    • Taiebeh Shamsi - Department of Chemistry, Semnan University, 3513119111 Semnan, Iran
    • Vittorio Pellegrini - Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, ItalyBeDimensional SpA, Via Albisola 121, 16163 Genova, Italy
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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MAECI (Minister of Foreign Affairs and International Cooperation) is gratefully acknowledged for the bilateral Italy–China GINSENG project.

References

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  • Abstract

    Figure 1

    Figure 1. Scheme for the synthesis of SO3H–TiO2@[email protected]3H nanoparticles.

    Figure 2

    Figure 2. FTIR spectra of different prepared nanoparticles and membranes.

    Figure 3

    Figure 3. Diffraction patterns of TiO2 (a) and SO3H–TiO2@[email protected]3H nanoparticles.

    Figure 4

    Figure 4. (a) SEM images of TiO2, (b) TiO2@[email protected], and (c) SO3H–TiO2@[email protected]3H nanoparticles.

    Figure 5

    Figure 5. Surface and cross-sectional images of (a,c) MS and (b,d) MSN5 membranes.

    Figure 6

    Figure 6. EDX mapping images of (a) MSN1, (b) MSN3, (c) MSN5, and (d) MSN7 membranes.

    Figure 7

    Figure 7. (a) Water uptake and (b) MS diagrams of different prepared PEMs at temperatures between 20 and 80 °C.

    Figure 8

    Figure 8. Schematic of proton conductivity in the as-prepared nanocomposite membrane.

    Figure 9

    Figure 9. Arrhenius plots for proton conductivity at different temperatures.

    Figure 10

    Figure 10. Polarization curves of different prepared membranes in 2 M methanol solution and room temperature.

  • References

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