In situ synthesis of star copolymers consisting of a polyhedral oligomeric silsesquioxane core and poly(2,5-benzimidazole) arms for high-temperature proton exchange membrane fuel cells
Tao Li
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorFang Luo
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorCorresponding Author
Xudong Fu
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Correspondence
Qingting Liu and Xudong Fu, Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China.
Email: [email protected] (Q. L.) and Email: [email protected] (X. F.).
Search for more papers by this authorLanxin Li
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorJiayuan Min
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorRong Zhang
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorShengfei Hu
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorFeng Zhao
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Wuhan Troowin Power System Technology Co., Ltd., Wuhan, China
Search for more papers by this authorXiao Li
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Wuhan Troowin Power System Technology Co., Ltd., Wuhan, China
Search for more papers by this authorYanhua Zhang
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorXujin Bao
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Department of Materials, Loughborough University, Leicestershire, UK
Search for more papers by this authorCorresponding Author
Qingting Liu
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Correspondence
Qingting Liu and Xudong Fu, Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China.
Email: [email protected] (Q. L.) and Email: [email protected] (X. F.).
Search for more papers by this authorTao Li
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorFang Luo
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorCorresponding Author
Xudong Fu
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Correspondence
Qingting Liu and Xudong Fu, Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China.
Email: [email protected] (Q. L.) and Email: [email protected] (X. F.).
Search for more papers by this authorLanxin Li
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorJiayuan Min
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorRong Zhang
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorShengfei Hu
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorFeng Zhao
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Wuhan Troowin Power System Technology Co., Ltd., Wuhan, China
Search for more papers by this authorXiao Li
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Wuhan Troowin Power System Technology Co., Ltd., Wuhan, China
Search for more papers by this authorYanhua Zhang
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Search for more papers by this authorXujin Bao
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Department of Materials, Loughborough University, Leicestershire, UK
Search for more papers by this authorCorresponding Author
Qingting Liu
Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan, China
Correspondence
Qingting Liu and Xudong Fu, Hubei Provincial Key Laboratory of Green Materials for Light Industry, School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068, China.
Email: [email protected] (Q. L.) and Email: [email protected] (X. F.).
Search for more papers by this authorTao Li and Fang Luo contributed equally to this study.
Funding information: National Natural Science Foundation of China (NSFC), Grant/Award Numbers: 21905083, 51902096; Hubei Provincial R&D Foundation, Grant/Award Numbers: 2018CFB412, 201906A07, 2019CFB304; National Natural Science Foundation of China, Grant/Award Numbers: 51902096, 21905083
Summary
Star copolymers with good film-forming and mechanical properties were in situ synthesized for fabricating proton exchange membranes. The monomers of 3,4-diaminobenzoic acid were first grafted onto glycidyl-polyhedral oligomeric silsesquioxane (G-POSS) cores and then propagated to the poly(2,5-benzimidazole) (ABPBI) chains. The introduction of the star copolymer improves the movement of the ABPBI polymer chains, resulting in a lower internal viscosity and larger free volume that favor increased membrane flatness and absorbilities of water and phosphoric acid molecules, respectively. It was found that the star copolymers with 1.0 wt% of incorporated POSS (ABPBI-1.0POSS) had the best balance of the acid retentivity and film-forming property as well as mechanical properties that are desirable for proton exchange membranes without PA loss operating at high temperatures. The enhanced cell performance characteristics obtained using the ABPBI-1.0POSS-based membranes indicate that star copolymers are promising materials for use in high-temperature proton exchange membrane fuel cells.
Supporting Information
| Filename | Description |
|---|---|
| er5571-sup-0001-Supinfo.docxWord 2007 document , 1.1 MB | Appendix S1: Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
REFERENCES
- 1Lee YM. Fuel cells: operating flexibly. Nat Energy. 2016; 1: 16136. https://doi.org/10.1038/nenergy.2016.136.
- 2Li Q, Jensen JO, Savinell RF, Bjerrum NJ. High temperature proton exchange membranes based on polybenzimidazoles for fuel cells. Prog Polym Sci. 2009; 34: 449-477. https://doi.org/10.1016/j.progpolymsci.2008.12.003.
- 3Rosli R, Sulong AB, Daud WRW, et al. A review of high-temperature proton exchange membrane fuel cell (HT-PEMFC) system. Int J Hydrogen Energy. 2017; 42: 9293-9314. https://doi.org/10.1016/j.ijhydene.2016.06.211.
- 4Shaari N, Kamarudin SK. Recent advances in additive-enhanced polymer electrolyte membrane properties in fuel cell applications: an overview. Int J Energy Res. 2019; 43: 2756-2794. https://doi.org/10.1002/er.4348.
- 5Wang C, Wang S, Peng L, et al. Recent progress on the key materials and components for proton exchange membrane fuel cells in vehicle applications. Energies. 2016; 9: 603. https://doi.org/10.3390/en9080603.
- 6Kim AR, Gabunada JC, Yoo DJ. Amelioration in physicochemical properties and single cell performance of sulfonated poly(ether ether ketone) block copolymer composite membrane using sulfonated carbon nanotubes for intermediate humidity fuel cells. Int J Energy Res. 2019; 43: 2974-2989. https://doi.org/10.1002/er.4494.
- 7Liang H, Su H, Pollet BG, Pasupathi S. Development of membrane electrode assembly for high temperature proton exchange membrane fuel cell by catalyst coating membrane method. J Power Sources. 2015; 288: 121-127. https://doi.org/10.1016/j.jpowsour.2015.04.123.
- 8Wang S, Peng S, Li Z, et al. Comprehensive performance enhancement of polybenzimidazole based high temperature proton exchange membranes by doping with a novel intercalated proton conductor. Int J Hydrogen Energy. 2018; 43: 9994-10003. https://doi.org/10.1016/j.ijhydene.2018.04.089.
- 9Sun P, Li Z, Wang S, Yin X. Performance enhancement of polybenzimidazole based high temperature proton exchange membranes with multifunctional crosslinker and highly sulfonated polyaniline. J Membr Sci. 2018; 549: 660-669. https://doi.org/10.1016/j.memsci.2017.10.053.
- 10Mamlouk M, Scott K. Phosphoric acid-doped electrodes for a PBI polymer membrane fuel cell. Int J Energy Res. 2011; 35: 507-519. https://doi.org/10.1002/er.1708.
- 11Rath R, Kumar P, Unnikrishnan L, Mohanty S, Nayak SK. Current scenario of poly (2, 5-Benzimidazole)(ABPBI) as prospective PEM for application in HT-PEMFC. Polymer Rev. 2019; 60: 1-51. https://doi.org/10.1080/15583724.2019.1663211.
- 12Villa DC, Angioni S, Barco SD, Mustarelli P, Quartarone E. Polysulfonated fluoro-oxyPBI membranes for PEMFCs: an efficient strategy to achieve good fuel cell performances with low H3PO4 doping levels. Adv Energy Mater. 2014; 4: 1220-1225. https://doi.org/10.1002/aenm.201301949.
- 13Angioni S, Villa DC, Barco SD, et al. Polysulfonation of PBI-based membranes for HT-PEMFCs: a possible way to maintain high proton transport at a low H3PO4 doping level. J Mater Chem A. 2013; 2: 663-671. https://doi.org/10.1039/C3TA12200J.
- 14Shin DW, Guiver MD, Lee YM. Hydrocarbon-based polymer electrolyte membranes: importance of morphology on ion transport and membrane stability. Chem Rev. 2017; 117: 4759-4805. https://doi.org/10.1021/acs.chemrev.6b00586.
- 15Sun X, Simonsen SC, Norby T, Chatzitakis A. Composite membranes for high temperature PEM fuel cells and electrolysers: a critical review. Membranes. 2019; 9: 83. https://doi.org/10.3390/membranes9070083.
- 16Hooshyari K, Moradi M, Salarizadeh P. Novel nanocomposite membranes based on PBI and doped-perovskite nanoparticles as a strategy for improving PEMFC performance at high temperatures. Int J Energy Res. 2020; 44: 2617-2633. https://doi.org/10.1002/er.5001.
- 17Hu M, Li T, Neelakandan S, Wang L, Chen Y. Cross-linked polybenzimidazoles containing hyperbranched cross-linkers and quaternary ammoniums as high-temperature proton exchange membranes: enhanced stability and conductivity. J Membr Sci. 2020; 593: 117435. https://doi.org/10.1016/j.memsci.2019.117435.
- 18Li Q, Aili D, Hjuler HA, et al. High Temperature Polymer Electrolyte Membrane Fuel Cells. Cham: Springer; 2016.
10.1007/978-3-319-17082-4 Google Scholar
- 19Vijayakumar V, Kim K, Nam SY. Recent advances in polybenzimidazole (PBI)-based polymer electrolyte membranes for high temperature fuel cell applications. Appl Chem Eng. 2019; 30: 643-651. https://doi.org/10.14478/ace.2019.1080.
- 20Hadjichristidis N, Pitsikalis M, Iatrou H, et al. Polymers with star-related structures: synthesis, properties, and applications. Polym Sci A Comprehensive Ref. 2012; 6: 29-111. https://doi.org/10.1016/B978-0-444-53349-4.00161-8.
10.1016/B978-0-444-53349-4.00161-8 Google Scholar
- 21Fetters LJ, Kiss AD, Pearson DS, Quack GF, Vitus FJ. Rheological behavior of star-shaped polymers. Macromolecules. 1993; 26: 647-654. https://doi.org/10.1021/ma00056a015.
- 22Xie H, Tao D, Xiang X, Ou Y, Bai X, Wang L. Synthesis and properties of highly branched star-shaped sulfonated block poly(arylene ether)s as proton exchange membranes. J Membr Sci. 2015; 473: 226-236. https://doi.org/10.1016/j.memsci.2014.09.015.
- 23Liu D, Tao D, Ni J, Xiang X, Wang L, Xi J. Synthesis and properties of highly branched sulfonated poly (arylene ether) s with flexible alkylsulfonated side chains as proton exchange membranes. J Mater Chem C. 2016; 4: 1326-1335. https://doi.org/10.1039/C5TC04033G.
- 24Neelakandan S, Liu D, Wang L, Hu M, Wang L. Highly branched poly(arylene ether)/surface functionalized fullerene-based composite membrane electrolyte for DMFC applications. Int J Energy Res. 2019; 43: 3756-3767. https://doi.org/10.1002/er.4536.
- 25Hu M, Ni J, Zhang B, Neelakandan S, Wang L. Crosslinked polybenzimidazoles containing branching structure as membrane materials with excellent cell performance and durability for fuel cell applications. J Power Sources. 2018; 389: 222-229. https://doi.org/10.1016/j.jpowsour.2018.04.025.
- 26Liu Q, Quan S, Na N, et al. Novel octopus shaped organic–inorganic composite membranes for PEMFCs. Int J Hydrogen Energy. 2016; 41: 16160-16166. https://doi.org/10.1016/j.ijhydene.2016.05.078.
- 27Cordes DB, Lickiss PD, Rataboul F. Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chem Rev. 2010; 110: 2081-2173. https://doi.org/10.1021/cr900201r.
- 28Zhang F, Tu Z, Yu J, Li H, Huang C, Zhang H. Impregnation of imidazole functionalized polyhedral oligomeric silsesquioxane in polymer electrolyte membrane for elevated temperature fuel cells. RSC Adv. 2013; 3: 5438-5446. https://doi.org/10.1039/c3ra40640g.
- 29Pan H, Zhang Y, Pu H, Chang Z. Organic–inorganic hybrid proton exchange membrane based on polyhedral oligomeric silsesquioxanes and sulfonated polyimides containing benzimidazole. J Power Sources. 2014; 263: 195-202. https://doi.org/10.1016/j.jpowsour.2014.04.055.
- 30Aili D, Allward T, Alfaro SM, et al. Polybenzimidazole and sulfonated polyhedral oligosilsesquioxane composite membranes for high temperature polymer electrolyte membrane fuel cells. Electrochim Acta. 2014; 140: 182-190. https://doi.org/10.1016/j.electacta.2014.03.047.
- 31Zhang P, Li W, Wang L, et al. Polydopamine-modified sulfonated polyhedral oligomeric silsesquioxane: an appealing nanofiller to address the trade-off between conductivity and stabilities for proton exchange membrane. J Membr Sci. 2020; 596: 117734. https://doi.org/10.1016/j.memsci.2019.117734.
- 32Liu C, Wu Z, Xu Y, et al. Facile one-step fabrication of sulfonated polyhedral oligomeric silsesquioxane cross-linked poly(ether ether ketone) for proton exchange membranes. Polym Chem. 2018; 9: 3624-3632. https://doi.org/10.1039/c8py00650d.
- 33Zhang J, Chen F, Ma X, Guan X, Chen D, Hickner MA. Sulfonated polymers containing polyhedral oligomeric silsesquioxane (POSS) core for high performance proton exchange membranes. Int J Hydrogen Energy. 2015; 40: 7135-7143. https://doi.org/10.1016/j.ijhydene.2015.02.090.
- 34Martin S, Li Q, Steenberg T, Jensen JO. Binderless electrodes for high-temperature polymer electrolyte membrane fuel cells. J Power Sources. 2014; 272: 559-566. https://doi.org/10.1016/j.jpowsour.2014.08.112.
- 35Nag A, Ali MA, Watanabe M, et al. Dataset of various characterizations for novel bio-based plastic poly(benzoxazole-co-benzimidazole) with ultra-low dielectric constant. Data Brief. 2019; 25: 104114. https://doi.org/10.1016/j.dib.2019.104114.
- 36Acar SB, Ozcelik M, Uyar T, et al. Polyhedral oligomeric silsesquioxane-based hybrid networks obtained via thiol-epoxy click chemistry. Iran Polym J. 2017; 26: 405-411. https://doi.org/10.1007/s13726-017-0529-x.
- 37Wang Z, Chen Y, Chen S, et al. Preparation and characterization of a soy protein based bio-adhesive crosslinked by waterborne epoxy resin and polyacrylamide. RSC Adv. 2019; 9: 35273-35279. https://doi.org/10.1039/C9RA05931H.
- 38Tang Y, Wang B, Lu X, et al. Study on the synthesis and solubility of polybenzimidazole and derivatives. Mater Rep. 2009; 23: 21-24. https://doi.org/10.3321/j.issn:1005-023X.2009.06.007.
- 39Fang J, Lin X, Cai D, He N, Zhao J. Preparation and characterization of novel pyridine-containing polybenzimidazole membrane for high temperature proton exchange membrane fuel cells. J Membr Sci. 2016; 502: 29-36. https://doi.org/10.1016/j.memsci.2015.12.006.
- 40Asensio JA, Gómez-Romero P. Recent developments on proton conducting poly (2, 5-benzimidazole)(ABPBI) membranes for high temperature poly-mer electrolyte membrane fuel cells. Fuel Cells. 2005; 5: 336-343. https://doi.org/10.1002/fuce.200400081.
- 41Li S, Fried JR, Colebrook J, et al. Molecular simulations of neat, hydrated, and phosphoric acid-doped polybenzimidazoles. Part 1: poly(2,2′-m-phenylene-5,5′-bibenzimidazole) (PBI), poly(2,5-benzimidazole) (ABPBI), and poly(p-phenylene benzobisimidazole) (PBDI). Polymer. 2010; 51: 5640-5648. https://doi.org/10.1016/j.polymer.2010.09.021.
- 42Rewar AS, Chaudhari HD, Illathvalappil R, Sreekumar K, Kharul UK. New approach of blending polymeric ionic liquid with polybezimidazole (PBI) for enhancing physical and electrochemical properties. J Mater Chem A. 2014; 2: 14449-14458. https://doi.org/10.1039/C4TA02184C.
- 43Chiang Y-C, Tsai D-S, Liu Y-H, Chiang CW. PEM fuel cells of poly (2, 5-benzimidazole) ABPBI membrane electrolytes doped with phosphoric acid and metal phosphates. Mater Chem Phys. 2018; 216: 485-490. https://doi.org/10.1016/j.matchemphys.2018.06.035.
- 44Zhang X, Fu X, Yang S, et al. Design of sepiolite-supported ionogel-embedded composite membranes without proton carrier wastage for wide-temperature-range operation of proton exchange membrane fuel cells. J Mater Chem A. 2019; 7: 15288-15301. https://doi.org/10.1039/C9TA03666K.
- 45Su H, Xu Q, Chong J, Li H, Sita C, Pasupathi S. Eliminating micro-porous layer from gas diffusion electrode for use in high temperature polymer electrolyte membrane fuel cell. J Power Sources. 2017; 341: 302-308. https://doi.org/10.1016/j.jpowsour.2016.12.029.
- 46Devrim Y, Albostan A, Devrim H. Experimental investigation of CO tolerance in high temperature PEM fuel cells. Int J Hydrogen Energy. 2018; 43: 18672-18681. https://doi.org/10.1016/j.ijhydene.2018.05.085.
