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Fabrication of highly selective SPVDF-co-HFP/APTES-SiO2/Nafion nanocomposite membranes for PEM fuel cells

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Abstract

Polyelectrolyte membrane (PEM) with improved proton conductivity and low methanol crossover are highly desirable for direct methanol fuel cells (DMFCs). Herein, the prime goal is to fabricate a ternary hybrid nanocomposite PEM by incorporating low-cost silane functionalized silica nanoparticles (AMPS) nanoparticles into the mixture of Nafion and PVDF-co-HFP, followed by sulfonation with chlorosulfonic acid which has not been reported by any earlier studies. Various physicochemical characterizations including FTIR, TGA, XRD, FESEM-EDS have been performed for the confirmation of formed sulfonated PVDF-co-HFP-AMPS-Nafion (SPAN) membranes. The initial studies including water/methanol uptake, swelling ratios, contact angle and improved ion exchange capacity (0.65 meq. g−1) confirms the hydrophilic and ion exchange properties of the SPAN membranes. The combination of highly hydrophobic partially fluorinated polymer along with hydrophilic AMPS and sulfonic acid moieties have resulted in significant improvement in proton conductivities (1.0 × 10–1 S.cm−1) and optimum methanol permeability values (8.79 × 10–7 cm2s−1) thereby exhibiting a better membrane selectivity value of 1.18 × 105 S.scm−3. Therefore, these unique SPAN membranes have the potentiality to be employed in methanol fuel cells.

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Data availability

The raw/processed data required to reproduce these findings cannot be shared at this time as the data also forms part of an ongoing study.

Abbreviations

APTES:

3-(Aminopropyl) triethoxysilane

AMPS:

APTES-modified pristine SiO2 nanoparticles

CA:

Contact Angle

DMF:

Dimethylformamide

DMFC:

Direct Methanol Fuel Cell

FC:

Fuel Cell

FE-SEM:

Field emission scanning electron microscope

GC:

Gas Chromatography

IC:

Ionic Conductivity

IEC:

Ion Exchange Capacity

MC:

Methanol Crossover

MEA:

Membrane Electrode Assembly

MP:

Methanol Permeability

MS:

Membrane Selectivity

MU:

Methanol Uptake

PAN:

PVDF-co-HFP-APTES-SiO2–Nafion (PAN) membrane

PEM:

Proton Exchange Membrane

PEMFC:

Polymer Electrolyte Membrane Fuel Cell

PVDF-co-HFP:

Poly(vinylidene fluoride-co-hexafluoropropylene)

SPAN:

Sulfonated PVDF-co-HFP-APTES-SiO2–Nafion membrane

SPC:

Sulfonated PVDF-co-HFP membrane

TGA:

Thermogravimetric Analysis

UTM:

Universal testing machine

WU:

Water Uptake

XRD:

X-ray powder diffraction

EDS:

Energy dispersive X-ray analysis

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Acknowledgements

R. R. gratefully acknowledges the Department of Science & Technology (DST), Government of India, for providing the fellowship (DST/INSPIRE Fellowship/2017/IF170468). The authors would like to thank MNIT-JAIPUR, INDIA, for FESEM-EDS characterization and also acknowledge Dr. Sarada Srinivasan Pati and Bhabani Shankar Panda, SPCB-Bhubaneswar, Odisha for the GC analysis.

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Authors and Affiliations

  1. School for Advanced Research in Polymers (SARP), Laboratory for Advanced Research in Polymeric Materials (LARPM), Central Institute of Petrochemicals Engineering & Technology (CIPET), Bhubaneswar, Odisha, India

    Rosalin Rath, Piyush Kumar, Lakshmi Unnikrishnan, Smita Mohanty & Sanjay K. Nayak

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  1. Rosalin Rath
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  2. Piyush Kumar
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Correspondence to Rosalin Rath.

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Highlights

• A new hybrid solid nanocomposite membrane consisting of PVDF-co-HFP-APTES-SiO2-Nafion has been designed.

• The membranes have the highest proton conductivity at elevated temperature (1.58 × 10–1 S.cm−1 at 85 °C).

• The methanol crossover has been reduced by 87.44% and selectivity is improved by 777% than the Nafion membranes.

• The membranes have a reduced methanol crossover value (8.76 × 10–7 cm2s−1) and higher selectivity ratio (1.15 × 105 S.scm−3).

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Rath, R., Kumar, P., Unnikrishnan, L. et al. Fabrication of highly selective SPVDF-co-HFP/APTES-SiO2/Nafion nanocomposite membranes for PEM fuel cells. J Polym Res 30, 135 (2023). https://doi.org/10.1007/s10965-023-03509-9

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