Composite Polymer Electrolyte Membranes based on Nafion and Modified PVDF Electrospun Nanofiber Mats

Abstract

We fabricated the nanofiber composite membranes by impregnating Nafion into the modified polyvinylidene fluoride(PVDF) electrospinning nanofiber mat for proton exchange membrane fuel cells applications. The hydrophobic PVDF nanofibers mat became to the hydrophilic state by alkali treatment for the full embedding of Nafion into the PVDF network. The fabricated composite membranes exhibit significantly enhanced thermal stabilities, swelling resistance, and observably improved mechanical property compared to the pristine Nafion membrane. When the content of PVDF nanofiber mat is 15.1wt% in the membrane, the proton conductivity of the nanofiber composite membrane is nearly equal to that of pristine Nafion membrane with the same condition. The experimental results show that the prepared composite membrane can be used as a promising polyelectrolyte membrane for fuel cell applications.

Keywords

proton exchange membrane / hydrophilic treatment / PVDF / electrospinning

References

[1] Devanathan R. Recent Developments in Proton Exchange Membranes for Fuel Cells[J]. Energ. Environ. Sci., 2008, 1: 101-119.

[2] Zhang HW, Shen PK. Recent Development of Polymer Electrolyte Membranes for Fuel Cells[J]. Chem. Rev., 2012, 112: 2 780-2 832.

[3] Mauritz KA, Moore RB. State of Understanding of Nafion[J]. Chem. Rev., 2004, 104: 4 535-4 586.

[4] Lou LD, Pu HT. Preparation and Properties of Proton Exchange Membranes based on Nafion and Phosphonic Acid-functionalized Hollow Silica Spheres[J]. Int. J. Hydrogen Energy, 2011, 36: 3 123-3 130.

[5] Lipman TE, Edwards JL, Kammen DM. Fuel Cell System Economics: Comparing the Costs of Generating Power with Stationary and Motor Vehicle PEM Fuel Cell Systems[J]. Energy Policy, 2004, 32(1): 101-125.

[6] Debruijn FA, Dam VAT, Janssen GJM. Review: Durability and Degradation Issues of PEM Fuel Cell Components[J]. Fuel Cells, 2008, 8: 3-22.

[7] Daud WRW, Rosli RE, Majlan EH, et al. PEM Fuel Cell System Control: A Review[J]. Renewable Energy, 2017, 113: 620-638.

[8] Shen M, Meuleman W, Scott K. The Characteristics of Power Generation of Static State Fuel Cells[J]. J. Power Sources, 2003, 115(2): 203-209.

[9] Ramya K, Velayutham G, Subramaniam C, et al. Effect of Solvents on the Characteristics of Nafion/PTFE Composite Membranes for Fuel Cell Applications[J]. J. Power Sources, 2006, 160: 10-17.

[10] Yin C, Li J, Zhou Y, et al. Enhancement in Proton Conductivity and Thermal Stability in Nafion Membranes Induced by Incorporation of Sulfonated Carbon Nanotubes[J]. ACSAppl. Mater. Interfaces, 2018, 10: 14 026-14 035.

[11] Pang J, Jin X, Wang Y, et al. Fluorinated Poly(Arylene Ether Ketone) Containing Pendent Hexasulfophenyl for Proton Exchange Membrane[J]. J. Membrane Sci., 2015, 492: 67-76.

[12] Won M, Kwon S, Kim TH. High Performance Blend Membranes based on Sulfonated Poly(arylene Ether Sulfone) and Poly(p-benzimidazole) for PEMFC Applications[J]. J. Ind. Eng. Chem., 2015, 29: 104-111.

[13] Song JM, Woo HS, Sohn JY, et al. 12HPW/Meso-SiO₂ Nanocomposite CSPEEK Membranes for Proton Exchange Membrane Fuel Cells[J]. J. Ind. Eng. Chem., 2016, 36: 132-138.

[14] Lin HL, Hsieh YS, Chiu CW, et al. Durability and Stability Test of Proton Exchange Membrane Fuel Cells Prepared from Polybenzimidazole/poly(Tetrafluoro Ethylene) Composite Membrane[J]. J. Power Sources, 2009, 193: 170-174.

[15] Liu QT, Ni N, Sun Q, et al. Poly (2,5-benzimidazole)/TriSilanol-Phenyl PCSS Composite Membranes for Intermediate Temperature PEM Fuel Cells[J]. J. Wuhan Unvi. Techn., 2018, 33(1): 212-220.

[16] Santiago EI, Isidoro RA, Dresch MA, et al. Nafion-TiCC Hybrid Electrolytes for Stable Cperation of PEM Fuel Cells at High Temperature[J]. Electrochim. Acta, 2009, 54: 4 111-4 117.

[17] So SY, Kim SC, Lee SY. In Situ Hybrid Nafion SiO₂-O₅ Proton Conductors for High-temperature and Low-humidity Proton Exchange Membrane Fuel Cells[J]. J.Memb. Sci., 2010, 360: 210-216.

[18] Tang HL, Wang XE, Pan M, et al. Fabrication and Characterization of Improved PFSA/ePTFE Composite Polymer Electrolyte Membranes[J]. J.Memb. Sci., 2007, 306: 298-306.

[19] Liao Y, Loh CH, Tian M, et al. Progress in Electrospun Polymeric Nanofibrous Membranes for Water Treatment: Fabrication, Modification and Applications[J]. Prog. Polym. Sci., 2018, 77: 69-94.

[20] Cavaliere S, Subianto S, Savych I, et al. Electrospinning: Designed Architectures for Energy Conversion and Storage Devices[J]. Energy Environ. Sci., 2011, 4(12): 4 761-4 785.

[21] Sood R, Cavaliere S, Jones DJ, et al. Electrospun Nanofiber Composite Polymer Electrolyte Fuel Cell and Electrolysis Membranes[J]. Nano Energy, 2016, 26: 729-745.

[22] Yao YF, Guo BK, Ji LW, et al. Highly Proton Conductive Electrolyte Membranes: Fiber-induced Long-range Ionic Channels, Electrochemistry Communications[J]. Electrochemistry Communications, 2011, 13: 1 005-1 008.

[23] Zhang SK, He GH, Gong X, et al. Electrospun Nanofiber Enhanced Sulfonated Poly (Phthalazinone Ether Sulfone Ketone) Composite Proton Exchange Membranes[J]. J. Memb. Sci., 2015, 493: 58-65.

[24] Zhu X, Zhang H, Liang Y, et al. Challenging Reinforced Composite Polymer Electrolyte Membranes Based on Disulfonated Poly(Arylene Ether Sulfone)- Impregnated Expanded PTFE for Fuel Cell Applications[J]. J. Mater. Chem., 2007, 17: 386-397.

[25] Bi C, Zhang H, Zhang Y, et al. Hydrophilic Treatment Poly(Tetrafluoroethylene) Reinforced Sulfonated Poly(Ether Ether Ketone) Composite Membrane for Proton Exchange Membrane Fuel Cell Application[J]. J. Power Sources, 2009, 194: 838-842.