journal article·2019-01

High proton conductivity polybenzimidazole proton exchange membrane based on phosphotungstic acid-anchored nano-Kevlar fibers

Xiao-Bing Yang, Ling-Hui Meng, Xu-Lei Sui, Zhen-Bo Wang

Journal of Materials Science· Volume 54· Issue 2
Publisher page

Abstract

A novel polybenzimidazole (PBI) proton exchange membrane based on phosphotungstic acid (PWA)-anchored nano-Kevlar fibers (NKFs) has been successfully prepared by solution casting. Employing NKFs instead of frequently used oxide support as anchoring agent has effectively conquered the problem of the poor interface compatibility between the inorganic component and the polymer, resulting in the excellent dispersion of PWA in the matrix and providing favorable conditions for the formation of consecutive proton transport channels. The as-obtained PBI/NKFs@PWA membrane exhibits proton conductivities as high as 0.029 and 0.051 S cm−1 at 20 and 80 °C without extra humidity, respectively. And benefit from the undetectable leakage of PWA, the proton conductivity retention could achieve 93.16% within 500 h. Simultaneously, the methanol barrier property of the hybrid membrane is far beyond Nafion, indicating a membrane selectivity of 12.08 × 104 S (s cm−3), which is 8.21 times higher than that of Nafion 115. The hybrid membrane allowed for sufficient proton conductivity, robust stability, lower methanol permeability, as well as low cost compared with Nafion, shows great potential for direct methanol fuel cell applications.
Source: openaire · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Fuel Cells and Related Materials · Membrane-based Ion Separation Techniques · Electrocatalysts for Energy Conversion

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References (65)

Show source-provided references
1. Heinzel A, Steele BCH (2001) Materials for fuel-cell technologies. Nature 414:345–35210.1038/35104620 ↗
2. Çelik SÜ, Bozkurt A, Hosseini SS (2012) Alternatives toward proton conductive anhydrous membranes for fuel cells: heterocyclic protogenic solvents comprising polymer electrolytes. Prog Polym Sci 37:1265–129110.1016/j.progpolymsci.2011.11.006 ↗
3. Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath JE (2004) Alternative polymer systems for proton exchange membranes (PEMs). Chem Rev 104:4587–461210.1021/cr020711a ↗
4. Feng K, Tang B, Wu P (2015) Ammonia-assisted dehydrofluorination between PVDF and Nafion for highly selective and low-cost proton exchange membranes: a possible way to further strengthen the commercialization of Nafion. J Mater Chem A 3:12609–1261510.1039/C5TA02855H ↗
5. Wu L, Zhang Z, Ran J, Zhou D, Li C, Xu T (2013) Advances in proton-exchange membranes for fuel cells: an overview on proton conductive channels (PCCs). Phys Chem Chem Phys 3:4870–488710.1039/c3cp50296a ↗
6. Bose S, Kuila T, Nguyen TXH, Kim NH, Lau K, Lee JH (2011) Polymer membranes for high temperature proton exchange membrane fuel cell: recent advances and challenges. Prog Polym Sci 37:813–84310.1016/j.progpolymsci.2011.01.003 ↗
7. Park CH, Lee CH, Guiver MD, Lee YM (2011) Sulfonated hydrocarbon membranes for medium-temperature and low-humidity proton exchange membrane fuel cells (PEMFCs). Prog Polym Sci 37:1443–149810.1016/j.progpolymsci.2011.06.001 ↗
8. Lim Y, Seo D, Lee S, Jang H, Ju H, Jo A, Kim D, Kim W (2014) High efficiency of proton transport by clustering nanochannels in multi-sulfonated propeller-like nonplanar hexaphenylbenzene poly(ether sulfone)s. Int J Hydrog Energy 39:2756–276610.1016/j.ijhydene.2013.05.165 ↗
9. Wang B, Tseng CK, Shih C, Pai Y, Kuo H, Lue SJ (2014) Polytetrafluoroethylene (PTFE)/silane cross-linked sulfonated poly(styrene–ethylene/butylene–styrene) (sSEBS) composite membrane for direct alcohol and formic acid fuel cells. J Membr Sci 464:43–5410.1016/j.memsci.2014.03.076 ↗
10. Tripathi BP, Shahi VK (2011) Organic–inorganic nanocomposite polymer electrolyte membranes for fuel cell applications. Prog Polym Sci 36:945–97910.1016/j.progpolymsci.2010.12.005 ↗
11. Yang J, Li Q, Cleemann LN, Jensen JO, Pan C, Bjerrum NJ, He R (2013) Crosslinked hexafluoropropylidene polybenzimidazole membranes with chloromethyl polysulfone for fuel cell applications. Adv Energy Mater 3:622–63010.1002/aenm.201200710 ↗
12. Li Q, Jensen JO, Savinell RF, Bjerrum NJ (2009) High temperature proton exchange membranes based on polybenzimidazoles for fuel cells. Prog Polym Sci 34:449–47710.1016/j.progpolymsci.2008.12.003 ↗
13. Weng D, Wainright JS, Landau U, Savinell RF (1996) Electro-osmotic drag coefficient of water and methanol in polymer electrolytes at elevated temperatures. J Electrochem Soc 143:1259–126310.1149/1.1836626 ↗
14. Zhang H, Shen PK (2012) Recent development of polymer electrolyte membranes for fuel cells. Chem Rev 112:2780–283210.1021/cr200035s ↗
15. Diaz LA, Abuin GC, Corti HR (2012) Methanol sorption and permeability in Nafion and acid-doped PBI and ABPBI membranes. J Membr Sci 411:35–4410.1016/j.memsci.2012.04.013 ↗
16. Mondal S, Soam S, Kundu PP (2015) Reduction of methanol crossover and improved electrical efficiency in direct methanol fuel cell by the formation of a thin layer on Nafion 117 membrane: effect of dip-coating of a blend of sulphonated PVDF-co-HFP and PBI. J Membr Sci 474:140–14710.1016/j.memsci.2014.09.023 ↗
17. Gu T, Shimpalee S, Van Zee JW, Chen CY, Lin CW (2010) A study of water adsorption and desorption by a PBI–H3PO4 membrane electrode assembly. J Power Sources 195:8194–819710.1016/j.jpowsour.2010.06.063 ↗
18. Lin H, Tang T, Hu C, Yu TL (2012) Poly(benzimidazole)/silica-ethyl-phosphoric acid hybrid membranes for proton exchange membrane fuel cells. J Power Sources 201:72–8010.1016/j.jpowsour.2011.10.110 ↗
19. Rikukawa M, Sanui K (2000) Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers. Prog Polym Sci 25:1463–150210.1016/S0079-6700(00)00032-0 ↗
20. Asensio JA, Gómez-Romero P (2005) Recent developments on proton conducting poly(2,5-benzimidazole) (ABPBI) membranes for high temperature polymer electrolyte membrane fuel cells. Fuel Cells 5:336–34310.1002/fuce.200400081 ↗
21. Villa DC, Angioni S, Barco SD, Mustarelli P, Quartarone E (2014) Polysulfonated fluoro-oxyPBI membranes for PEMFCs: an efficient strategy to achieve good fuel cell performances with low H3PO4 doping levels. Adv Energy Mater 4:130194910.1002/aenm.201301949 ↗
22. Nawn G, Pace G, Lavina S, Vezzù K, Negro E, Bertasi F, Polizzi S, Noto VD (2014) Interplay between composition, structure, and properties of new H3PO4-doped PBI4N-HfO2 nanocomposite membranes for high-temperature proton exchange membrane fuel cells. Macromolecules 48:15–2710.1021/ma5018956 ↗
23. Özdemir Y, Özkan N, Devrim Y (2017) Fabrication and characterization of cross-linked polybenzimidazole based membranes for high temperature PEM fuel cells. Electrochim Acta 245:1–1310.1016/j.electacta.2017.05.111 ↗
24. Maity S, Jana T (2014) Polybenzimidazole block copolymers for fuel cell: synthesis and studies of block length effects on nanophase separation, mechanical properties, and proton conductivity of PEM. ACS Appl Mater Interfaces 6:6851–686410.1021/am500668c ↗
25. Jahangiri S, Aravi İ, Işıkel Şanlı L, Menceloğlu YZ, Özden-Yenigün E (2018) Fabrication and optimization of proton conductive polybenzimidazole electrospun nanofiber membranes. Polym Adv Technol 29:594–60210.1002/pat.4169 ↗
26. Li Q, He R, Jensen JO, Bjerrum NJ (2003) Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100 °C. Chem Mater 15:4896–491510.1021/cm0310519 ↗
27. Martínez-Morlanes MJ, Martos AM, Várez A, Levenfeld B (2015) Synthesis and characterization of novel hybrid polysulfone/silica membranes doped with phosphomolybdic acid for fuel cell applications. J Membr Sci 492:371–37910.1016/j.memsci.2015.05.031 ↗
28. Bose AB, Gopu S, Li W (2014) Enhancement of proton exchange membrane fuel cells performance at elevated temperatures and lower humidities by incorporating immobilized phosphotungstic acid in electrodes. J Power Sources 263:217–22210.1016/j.jpowsour.2014.04.043 ↗
29. Zhang B, Cao Y, Li Z, Wu H, Yin Y, Cao L, He X, Jiang Z (2017) Proton exchange nanohybrid membranes with high phosphotungstic acid loading within metal-organic frameworks for PEMFC applications. Electrochim Acta 240:186–19410.1016/j.electacta.2017.04.087 ↗
30. Amirinejad M, Madaeni SS, Navarra MA, Rafiee E, Scrosati B (2011) Preparation and characterization of phosphotungstic acid-derived salt/Nafion nanocomposite membranes for proton exchange membrane fuel cells. J Power Sources 196:988–99810.1016/j.jpowsour.2010.08.062 ↗
31. Lu S, Xu X, Zhang J, Peng S, Liang D, Wang H, Xiang Y (2014) A self-anchored phosphotungstic acid hybrid proton exchange membrane achieved via one-step synthesis. Adv Energy Mater 4:140084210.1002/aenm.201400842 ↗
32. Rao S, Xiu R, Si J, Lu S, Yang M, Xiang Y (2014) In situ synthesis of nanocomposite membranes: comprehensive improvement strategy for Direct Methanol Fuel Cells. Chemsuschem 7:822–82810.1002/cssc.201301060 ↗
33. Du Y, Yang P, Zhou S, Li J, Du X, Lei J (2018) Direct synthesis of ordered meso/macrostructured phosphotungstic acid/SiO2 by EISA method and its catalytic performance of fuel oil. Mater Res Bull 97:42–4810.1016/j.materresbull.2017.08.034 ↗
34. Lu S, Wang D, Jiang SP, Xiang Y, Lu J, Zeng J (2010) HPW/MCM-41 phosphotungstic acid/mesoporous silica composites as novel proton-exchange membranes for elevated-temperature fuel cells. Adv Mater 22:971–97610.1002/adma.200903091 ↗
35. Huang D, Wang YJ, Yang LM, Luo GS (2006) Direct synthesis of mesoporous TiO2 modified with phosphotungstic acid under template-free condition. Micropor Mesopor Mat 96:301–30610.1016/j.micromeso.2006.06.040 ↗
36. Sacca A, Carbone A, Pedicini R, Marrony M, Barrera R, Elomaa M, Passalacqua E (2008) Phosphotungstic acid supported on a nanopowdered ZrO2 as a filler in Nafion-based membranes for polymer electrolyte fuel cells. Fuel Cells 8:225–23510.1002/fuce.200800009 ↗
37. Hasani-Sadrabadi MM, Dashtimoghadam E, Majedi FS, VanDersarl JJ, Bertsch A, Renaud P, Jacob KI (2016) Ionic nanopeapods: next-generation proton conducting membranes based on phosphotungstic acid filled carbon nanotube. Nano Energy 23:114–12110.1016/j.nanoen.2016.01.024 ↗
38. Leroux F, Taviot-Guého C (2005) Fine tuning between organic and inorganic host structure: new trends in layered double hydroxide hybrid assemblies. J Mater Chem 15:362810.1039/b505014f ↗
39. Sakhno OV, Goldenberg LM, Stumpe J, Smirnova TN (2007) Surface modified ZrO2 and TiO2 nanoparticles embedded in organic photopolymers for highly effective and UV-stable volume holograms. Nanotechnology 18:105704–10571010.1088/0957-4484/18/10/105704 ↗
40. Zou H, Wu S, Shen J (2008) Polymer/silica nanocomposites: preparation, characterization, properties, and applications. Chem Rev 108:3893–395710.1021/cr068035q ↗
41. Mishra AK, Bose S, Kuila T, Kim NH, Lee JH (2012) Silicate-based polymer-nanocomposite membranes for polymer electrolyte membrane fuel cells. Prog Polym Sci 37:842–86910.1016/j.progpolymsci.2011.11.002 ↗
42. Abouzari-lotf E, Nasef MM, Ghassemi H, Zakeri M, Ahmad A, Abdollahi Y (2015) Improved methanol barrier property of Nafion hybrid membrane by incorporating nanofibrous interlayer self-immobilized with high level of phosphotungstic acid. ACS Appl Mater Interfaces 7:17008–1701510.1021/acsami.5b02268 ↗
43. Abouzari-lotf E, Jacob MV, Ghassemi H, Ahmad A, Nasef MM, Zakeri M, Mehdipour-Ataei S (2016) Enhancement of fuel cell performance with less-water dependent composite membranes having polyoxometalate anchored nanofibrous interlayer. J Power Sources 326:482–48910.1016/j.jpowsour.2016.07.027 ↗
44. Jia W, Feng K, Tang B, Wu P (2015) β-Cyclodextrin modified silica nanoparticles for Nafion based proton exchange membranes with significantly enhanced transport properties. J Mater Chem A 3:15607–1561510.1039/C5TA03381K ↗
45. Xu X, Wang H, Lu S, Peng S, Xiang Y (2016) A phosphotungstic acid self-anchored hybrid proton exchange membrane for direct methanol fuel cells. RSC Adv 6:43049–4305510.1039/C6RA07318B ↗
46. Banerjee S, Kar KK (2016) Aluminum-substituted phosphotungstic acid/sulfonated poly ether ether ketone nanocomposite membrane with reduced leaching and improved proton conductivity. High Perform Polym 28:1043–105810.1177/0954008315614984 ↗
47. Zhong S, Cui X, Gao Y, Liu W, Dou S (2014) Fabrication and properties of poly(vinyl alcohol)-based polymer electrolyte membranes for direct methanol fuel cell applications. Int J Hydrog Energy 39:17857–1786410.1016/j.ijhydene.2014.08.040 ↗
48. Wu Q, Wang H, Lu S, Xu X, Liang D, Xiang Y (2016) Novel methanol-blocking proton exchange membrane achieved via self-anchoring phosphotungstic acid into chitosan membrane with submicro-pores. J Membr Sci 500:203–21010.1016/j.memsci.2015.11.019 ↗
49. Ogawa T, Kamiguchi K, Tamaki T, Imai H, Yamaguchi T (2014) Differentiating Grotthuss proton conduction mechanisms by nuclear magnetic resonance spectroscopic analysis of frozen samples. Anal Chem 86:9362–936610.1021/ac5021485 ↗
50. Chen Y, Thorn M, Christensen S, Versek C, Poe A, Hayward RC, Tuominen MT, Thayumanavan S (2010) Enhancement of anhydrous proton transport by supramolecular nanochannels in comb polymers. Nat Chem 2:503–50810.1038/nchem.629 ↗
51. Rao Z, Feng K, Tang B, Wu P (2017) Construction of well interconnected metal-organic framework structure for effectively promoting proton conductivity of proton exchange membrane. J Membr Sci 533:160–17010.1016/j.memsci.2017.03.031 ↗
52. Ogawa T, Aonuma T, Tamaki T, Ohashi H, Ushiyama H, Yamashita K, Yamaguchi T (2014) The proton conduction mechanism in a material consisting of packed acids. Chem Sci 5:4878–488710.1039/C4SC00952E ↗
53. Vuilleumier R, Borgis D (2012) Hopping along hydrogen bonds. Nat Chem 4:432–43310.1038/nchem.1365 ↗
54. Wei Y, Shang Y, Ni C, Zhang H, Li X, Liu B, Men Y, Zhang M, Hu W (2017) Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes. Appl Surf Sci 416:996–100610.1016/j.apsusc.2017.04.190 ↗
55. Matsuki Y, Iwamoto M, Mita K, Shigemi K, Matsunaga S, Oiki S (2016) Rectified proton grotthuss conduction across a long water-wire in the test nanotube of the polytheonamide B channel. J Am Chem Soc 138:4168–417710.1021/jacs.5b13377 ↗
56. Benhabbour SR, Chapman RP, Scharfenberger G, Meyer WH, Goward GR (2005) Study of imidazole-based proton-conducting composite materials using solid-state NMR. Chem Mater 17:1605–161210.1021/cm048301l ↗
57. Liu J, Li X, Wu J, Dai Z, Song X (2016) Structural transformation of an imidazolium-templated two-dimensional aluminophosphate and its proton conduction under anhydrous conditions. Mater Lett 184:119–12210.1016/j.matlet.2016.08.001 ↗
58. Lage LG, Delgado PG, Kawan Y (2004) Thermal stability and decomposition of Nafion® membranes with different cations using high-resolution thermogravimetry. J Therm Anal Cal 75:521–53010.1023/B:JTAN.0000027142.21928.c7 ↗
59. Hasani-Sadrabadi MM, Dashtimoghadam E, Majedi FS, Moaddel H, Bertsch A, Renaud P (2013) Superacid-doped polybenzimidazole-decorated carbon nanotubes: a novel high-performance proton exchange nanocomposite membrane. Nanoscale 5:11710–1171710.1039/c3nr02886k ↗
60. Bhavsar RS, Kumbharkar SC, Rewar AS, Kharul UK (2014) Polybenzimidazole based film forming polymeric ionic liquids: synthesis and effects of cation–anion variation on their physical properties. Polym Chem 5:4083–409610.1039/c3py01709e ↗
61. Baker AM, Wang L, Johnson WB, Prasad AK, Advani SG (2014) Nafion membranes reinforced with ceria-coated multiwall carbon nanotubes for improved mechanical and chemical durability in polymer electrolyte membrane fuel cells. J Phys Chem C 118:26796–2680210.1021/jp5078399 ↗
62. Li Y, Wang H, Wu Q, Xu X, Lu S, Xiang Y (2017) A poly(vinyl alcohol)-based composite membrane with immobilized phosphotungstic acid molecules for direct methanol fuel cells. Electrochim Acta 224:369–37710.1016/j.electacta.2016.12.076 ↗
63. He Q, Zheng J, Zhang S (2014) Preparation and characterization of high performance sulfonated poly(p-phenylene-co-aryl ether ketone) membranes for direct methanol fuel cells. J Power Sources 260:317–32510.1016/j.jpowsour.2014.03.028 ↗
64. Devi AU, Divya K, Divya D, Saraswathi MSA, Nagendran A (2018) Highly selective and methanol resistant polypyrrole laminated SPVdFco-HFP/PWA proton exchange membranes for DMFC applications. Mater Chem Phys 212:533–54210.1016/j.matchemphys.2018.03.086 ↗
65. Yang CW, Chen CC, Chen KH, Cheng S (2017) Effect of pore-directing agents in SBA-15 nanoparticles on the performance of Nafion®/SBA-15n composite membranes for DMFC. J Membr Sci 526:106–11710.1016/j.memsci.2016.11.054 ↗