High temperature proton exchange membranes with enhanced proton conductivities at low humidity and high temperature based on polymer blends and block copolymers of poly(1,3-cyclohexadiene) and poly(ethylene glycol)

Deng, Shawn; Hassan, Mohammad K.; Nalawade, Amol; Perry, Kelly A.; More, Karren L.; Mauritz, Kenneth A.; McDonnell, Marshall T.; Keffer, David J.; Mays, Jimmy W.

doi:10.1016/j.polymer.2015.09.033

Title: High temperature proton exchange membranes with enhanced proton conductivities at low humidity and high temperature based on polymer blends and block copolymers of poly(1,3-cyclohexadiene) and poly(ethylene glycol)

Journal Article · Wed Sep 16 00:00:00 EDT 2015 · Polymer

DOI:https://doi.org/10.1016/j.polymer.2015.09.033· OSTI ID:1324149

Deng, Shawn ^[1]; Hassan, Mohammad K. ^[2]; Nalawade, Amol ^[2]; Perry, Kelly A. ^[3]; More, Karren L. ^[3]; Mauritz, Kenneth A. ^[2]; McDonnell, Marshall T. ^[4]; Keffer, David J. ^[5]; Mays, Jimmy W. ^[6]

Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
Univ. of Southern Mississippi, Hattiesburg, MS (United States). School of Polymers and High Performance Materials
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

Hot (at 120 °C) and dry (20% relative humidity) operating conditions benefit fuel cell designs based on proton exchange membranes (PEMs) and hydrogen due to simplified system design and increasing tolerance to fuel impurities. In this paper, presented are preparation, partial characterization, and multi-scale modeling of such PEMs based on cross-linked, sulfonated poly(1,3-cyclohexadiene) (xsPCHD) blends and block copolymers with poly(ethylene glycol) (PEG). These low cost materials have proton conductivities 18 times that of current industry standard Nafion at hot, dry operating conditions. Among the membranes studied, the blend xsPCHD-PEG PEM displayed the highest proton conductivity, which exhibits a morphology with higher connectivity of the hydrophilic domain throughout the membrane. Simulation and modeling provide a molecular level understanding of distribution of PEG within this hydrophilic domain and its relation to proton conductivities. Finally, this study demonstrates enhancement of proton conductivity at high temperature and low relative humidity by incorporation of PEG and optimized sulfonation conditions.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Contributing Organization:: Univ. of Southern Mississippi, Hattiesburg, MS (United States)

Grant/Contract Number:: FG36-06GO16037; FG36-08GO88106; FG02-05ER15723; DGE-0801470; EPS-1004083; OCI 07-11134.5

OSTI ID:: 1324149

Alternate ID(s):: OSTI ID: 1254775

Journal Information:: Polymer, Vol. 77; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 9 works

Citation information provided by
Web of Science

References (64)

Two Fuel Cell Cars In Every Garage? Mathias, Mark F.; Makharia, Rohit; Gasteiger, Hubert A. The Electrochemical Society Interface, Vol. 14, Issue 3 https://doi.org/10.1149/2.F05053IF	journal	September 2005
On the development of proton conducting materials for technological applications Kreuer, K. D. Solid State Ionics, Vol. 97, Issue 1-4 https://doi.org/10.1016/S0167-2738(97)00082-9	journal	May 1997
The Grotthuss mechanism Agmon, Noam Chemical Physics Letters, Vol. 244, Issue 5-6 https://doi.org/10.1016/0009-2614(95)00905-J	journal	October 1995
Transport in Proton Conductors for Fuel-Cell Applications: Simulations, Elementary Reactions, and Phenomenology Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020715f	journal	October 2004
Evaluation of a Sol-Gel Derived Nafion/Silica Hybrid Membrane for Proton Electrolyte Membrane Fuel Cell Applications: I. Proton Conductivity and Water Content Miyake, N.; Wainright, J. S.; Savinell, R. F. Journal of The Electrochemical Society, Vol. 148, Issue 8 https://doi.org/10.1149/1.1383071	journal	January 2001
Investigation of PEMFC operation above 100 °C employing perfluorosulfonic acid silicon oxide composite membranes Adjemian, K. T.; Srinivasan, S.; Benziger, J. Journal of Power Sources, Vol. 109, Issue 2 https://doi.org/10.1016/S0378-7753(02)00086-1	journal	July 2002
Atomistic Simulation of Water Percolation and Proton Hopping in Nafion Fuel Cell Membrane Devanathan, Ram; Venkatnathan, Arun; Rousseau, Roger The Journal of Physical Chemistry B, Vol. 114, Issue 43 https://doi.org/10.1021/jp103398b	journal	November 2010
Probing Selected Morphological Models of Hydrated Nafion Using Large-Scale Molecular Dynamics Simulations Knox, Craig K.; Voth, Gregory A. The Journal of Physical Chemistry B, Vol. 114, Issue 9 https://doi.org/10.1021/jp9112409	journal	March 2010
Toward a Predictive Understanding of Water and Charge Transport in Proton Exchange Membranes Esai Selvan, Myvizhi; Calvo-Muñoz, Elisa; Keffer, David J. The Journal of Physical Chemistry B, Vol. 115, Issue 12 https://doi.org/10.1021/jp1115004	journal	March 2011
Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C Li, Qingfeng; He, Ronghuan; Jensen, Jens Oluf Chemistry of Materials, Vol. 15, Issue 26 https://doi.org/10.1021/cm0310519	journal	December 2003
Physical properties and supermolecular structure of perfluorinated ion-containing (nafion) polymers Yeo, Swee Chye; Eisenberg, A. Journal of Applied Polymer Science, Vol. 21, Issue 4 https://doi.org/10.1002/app.1977.070210401	journal	April 1977
Application of coupled thermal analysis techniques to thermodynamic studies of water interactions with a compressible ionic polymer matrix Escoubes, M.; Pineri, M.; Robens, E. Thermochimica Acta, Vol. 82, Issue 1 https://doi.org/10.1016/0040-6031(84)87283-4	journal	December 1984
Influence of temperature and humidity on the mechanical properties of Nafion® 117 polymer electrolyte membrane: Mechanical Properties of Nafion® 117 Bauer, F.; Denneler, S.; Willert-Porada, M. Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 7 https://doi.org/10.1002/polb.20367	journal	February 2005
The effect of equivalent weight, temperature, cationic forms, sorbates, and nanoinorganic additives on the sorption behavior of Nafion® Jalani, Nikhil H.; Datta, Ravindra Journal of Membrane Science, Vol. 264, Issue 1-2 https://doi.org/10.1016/j.memsci.2005.04.047	journal	November 2005
State of Understanding of Nafion Mauritz, Kenneth A.; Moore, Robert B. Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr0207123	journal	October 2004
Recent developments in high-temperature proton conducting polymer electrolyte membranes Jannasch, Patric Current Opinion in Colloid & Interface Science, Vol. 8, Issue 1 https://doi.org/10.1016/S1359-0294(03)00006-2	journal	March 2003
Non-Fluorinated Polymer Materials for Proton Exchange Membrane Fuel Cells Rozière, Jacques; Jones, Deborah J. Annual Review of Materials Research, Vol. 33, Issue 1 https://doi.org/10.1146/annurev.matsci.33.022702.154657	journal	August 2003
Poly(arylene ether) Ionomers Containing Sulfofluorenyl Groups for Fuel Cell Applications Chikashige, Yohei; Chikyu, Yoshiki; Miyatake, Kenji Macromolecules, Vol. 38, Issue 16 https://doi.org/10.1021/ma050856u	journal	August 2005
Novel Sulfonated Poly(arylene ether): A Proton Conductive Polymer Electrolyte Designed for Fuel Cells Miyatake, Kenji; Chikashige, Yohei; Watanabe, Masahiro Macromolecules, Vol. 36, Issue 26 https://doi.org/10.1021/ma035452l	journal	November 2003
Sulfonated Poly(aryl ether ketone)s Containing the Hexafluoroisopropylidene Diphenyl Moiety Prepared by Direct Copolymerization, as Proton Exchange Membranes for Fuel Cell Application ^† Xing, Peixiang; Robertson, Gilles P.; Guiver, Michael D. Macromolecules, Vol. 37, Issue 21 https://doi.org/10.1021/ma0494941	journal	October 2004
Synthesis and properties of a polyimide containing pendant sulfophenoxypropoxy groups Miyatake, Kenji; Yasuda, Tomohiro; Hirai, Michiko Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 1 https://doi.org/10.1002/pola.21816	journal	January 2006
Tuned Polymer Electrolyte Membranes Based on Aromatic Polyethers for Fuel Cell Applications Miyatake, Kenji; Chikashige, Yohei; Higuchi, Eiji Journal of the American Chemical Society, Vol. 129, Issue 13 https://doi.org/10.1021/ja0672526	journal	April 2007
Synthesis and properties of sulfonated polyimides from homologous sulfonated diamines bearing bis(aminophenoxyphenyl)sulfone Chen, Shouwen; Yin, Yan; Kita, Hidetoshi Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 13 https://doi.org/10.1002/pola.22036	journal	January 2007
Synthesis and Properties of Sulfonated Poly[bis(benzimidazobenzisoquinolinones)] as Hydrolytically and Thermooxidatively Stable Proton Conducting Ionomers Li, Nanwen; Zhang, Suobo; Liu, Jia Macromolecules, Vol. 41, Issue 12 https://doi.org/10.1021/ma800119y	journal	May 2008
Polymers Containing Di(1 H -benzo[ d ]imidazol-2-yl)arene Moieties: Polymerization via N−C Coupling Reactions Hlil, Antisar R.; Matsumura, Sumiko; Hay, Allan S. Macromolecules, Vol. 41, Issue 6 https://doi.org/10.1021/ma702596x	journal	March 2008
Synthesis and properties of soluble sulfonated polybenzimidazoles from 3,3′-disulfonate-4,4′-dicarboxylbiphenyl as proton exchange membranes Kang, Sen; Zhang, Chunjie; Xiao, Guyu Journal of Membrane Science, Vol. 334, Issue 1-2 https://doi.org/10.1016/j.memsci.2009.02.021	journal	May 2009
Sulfonated Polybenzimidazoles for High Temperature PEM Fuel Cells Mader, Jordan A.; Benicewicz, Brian C. Macromolecules, Vol. 43, Issue 16 https://doi.org/10.1021/ma1009098	journal	August 2010
Thermally crosslinked sulfonated polyethersulfone proton exchange membranes for direct methanol fuel cells Chul Gil, Seung; Chul Kim, Jin; Ahn, Dahee Journal of Membrane Science, Vol. 417-418 https://doi.org/10.1016/j.memsci.2012.05.064	journal	November 2012
Poly(sulfonated phenylene)-block-poly(arylene ether sulfone) copolymer for polymer electrolyte fuel cell application Chen, Shouwen; Chen, Kangcheng; Zhang, Xuan Polymer, Vol. 54, Issue 1 https://doi.org/10.1016/j.polymer.2012.10.058	journal	January 2013
Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers Li, Nanwen; Guiver, Michael D. Macromolecules, Vol. 47, Issue 7 https://doi.org/10.1021/ma402254h	journal	February 2014
Synthesis of Sulfonic Acid-Containing Polybenzoxazine for Proton Exchange Membrane in Direct Methanol Fuel Cells Yao, Bingjian; Yan, Xiuling; Ding, Yi Macromolecules, Vol. 47, Issue 3 https://doi.org/10.1021/ma4020214	journal	January 2014
Cross-Linked Sulfonated Poly(arylene ether sulfone) Membranes Formed by in Situ Casting and Click Reaction for Applications in Fuel Cells Ko, Taeyun; Kim, Kihyun; Jung, Bo-Kyung Macromolecules, Vol. 48, Issue 4 https://doi.org/10.1021/ma5021616	journal	January 2015
A comparative study of phosphoric acid-doped m -PBI membranes A. Perry, Kelly; L. More, Karren; Andrew Payzant, E. Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1 https://doi.org/10.1002/polb.23403	journal	October 2013
NMR, conductivity and neutron scattering investigation of ionic dynamics in the anhydrous polymer protonic conductor PEO(H3PO4)x) Donoso, P. Solid State Ionics, Vol. 28-30 https://doi.org/10.1016/0167-2738(88)90313-X	journal	September 1988
Enhanced ionic conductivity of poly(ethylene imine) phosphate Senadeera, G. Solid State Ionics, Vol. 85, Issue 1-4 https://doi.org/10.1016/0167-2738(96)00038-0	journal	May 1996
Proton-conductive polyimides consisting of naphthalenediimide and sulfonated units alternately segmented by long aliphatic spacers Zhang, Zhenghui; Xu, Tongwen Journal of Materials Chemistry A, Vol. 2, Issue 30 https://doi.org/10.1039/C4TA00942H	journal	January 2014
Recent Development of Polymer Electrolyte Membranes for Fuel Cells Zhang, Hongwei; Shen, Pei Kang Chemical Reviews, Vol. 112, Issue 5 https://doi.org/10.1021/cr200035s	journal	February 2012
Hydrocarbon-based fuel cell membranes: Sulfonated crosslinked poly(1,3-cyclohexadiene) membranes for high temperature polymer electrolyte fuel cells Deng, Suxiang; Hassan, Mohammad K.; Mauritz, Kenneth A. Polymer, Vol. 73 https://doi.org/10.1016/j.polymer.2015.07.030	journal	September 2015
Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation Borup, Rod; Meyers, Jeremy; Pivovar, Bryan Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr050182l	journal	October 2007
Hydrocarbon polymers containing six-membered rings in the main chain. Microstructure and properties of poly(1,3-cyclohexadiene) Natori, Itaru; Imaizumi, Kimio; Yamagishi, Hideyuki Journal of Polymer Science Part B: Polymer Physics, Vol. 36, Issue 10 https://doi.org/10.1002/(SICI)1099-0488(19980730)36:10<1657::AID-POLB7>3.0.CO;2-M	journal	July 1998
Soluble polystyrene‐block‐poly(p‐phenylene) block copolymers prepared from polystyrene‐block‐poly(1,3‐cyclohexadiene) precursors. Study of the aromatization process Zhong, Xing Fu; François, Bernard Die Makromolekulare Chemie, Vol. 192, Issue 10, p. 2277-2291 https://doi.org/10.1002/macp.1991.021921008	journal	October 1991
Architecturally and Chemically Modified Poly(1,3-cyclohexadiene) Huang, Tianzi; Zhou, Hongliang; Hong, Kunlun Macromolecular Chemistry and Physics, Vol. 209, Issue 3 https://doi.org/10.1002/macp.200700409	journal	February 2008
A New Fluorinated Polymer Having Two Connected Rings in the Main Chain: Synthesis and Characterization of Fluorinated Poly(1,3-cyclohexadiene) Huang, Tianzi; Messman, Jamie M.; Mays, Jimmy W. Macromolecules, Vol. 41, Issue 1 https://doi.org/10.1021/ma0718043	journal	January 2008
1,3-Cyclohexadiene Polymers. 1. Anionic Polymerization Hong, Kunlun; Mays, Jimmy W. Macromolecules, Vol. 34, Issue 4 https://doi.org/10.1021/ma0015626	journal	February 2001
Conductivity Dependence of PEG Content in an Anhydrous Proton Conducting Sol−Gel Electrolyte Ghosh, Braja D.; Lott, Kyle F.; Ritchie, Jason E. Chemistry of Materials, Vol. 17, Issue 3 https://doi.org/10.1021/cm0486969	journal	February 2005
Synthesis and characterization of sulfonated poly(acrylene ether sulfones) Johnson, B. C.; Yilgör, İ.; Tran, C. Journal of Polymer Science: Polymer Chemistry Edition, Vol. 22, Issue 3 https://doi.org/10.1002/pol.1984.170220320	journal	March 1984
Thermostable ionomeric filled membrane for H2/O2 fuel cell Baradie, B.; Poinsignon, C.; Sanchez, J. Y. Journal of Power Sources, Vol. 74, Issue 1 https://doi.org/10.1016/S0378-7753(97)02816-4	journal	July 1998
Sulfonation of polysulfones: Suitability of the sulfonated materials for asymmetric membrane preparation Blanco, J. F.; Nguyen, Q. T.; Schaetzel, P. Journal of Applied Polymer Science, Vol. 84, Issue 13 https://doi.org/10.1002/app.10536	journal	April 2002
Sulfonation and subsequent rections of ethylidene norbornane and dihydrodicyclopentadiene. The chemistry of some small molecule models for EPDM rubbers Thaler, Warren A. Journal of Polymer Science: Polymer Chemistry Edition, Vol. 20, Issue 3 https://doi.org/10.1002/pol.1982.170200323	journal	March 1982
Proton Conduction Mechanisms at Low Degrees of Hydration in Sulfonic Acid–Based Polymer Electrolyte Membranes Paddison, S. J. Annual Review of Materials Research, Vol. 33, Issue 1 https://doi.org/10.1146/annurev.matsci.33.022702.155102	journal	August 2003
Reactive Molecular Dynamics Study of Proton Transport in Polymer Electrolyte Membranes Selvan, Myvizhi Esai; Keffer, David J.; Cui, Shengting The Journal of Physical Chemistry C, Vol. 115, Issue 38 https://doi.org/10.1021/jp203443c	journal	September 2011
Synthesis and characterization of sulfonated‐fluorinated, hydrophilic‐hydrophobic multiblock copolymers for proton exchange membranes Yu, Xiang; Roy, Abhishek; Dunn, Stuart Journal of Polymer Science Part A: Polymer Chemistry, Vol. 47, Issue 4 https://doi.org/10.1002/pola.23194	journal	January 2009
A coarse-grained model for polyethylene glycol polymer Wang, Qifei; Keffer, David J.; Nicholson, Donald M. The Journal of Chemical Physics, Vol. 135, Issue 21 https://doi.org/10.1063/1.3664623	journal	December 2011
Multi-scale models for cross-linked sulfonated poly (1, 3-cyclohexadiene) polymer Wang, Qifei; Keffer, David J.; Deng, Suxiang Polymer, Vol. 53, Issue 7 https://doi.org/10.1016/j.polymer.2012.02.005	journal	March 2012
Atomistic and Coarse-Grained Molecular Dynamics Simulation of a Cross-Linked Sulfonated Poly(1,3-cyclohexadiene)-Based Proton Exchange Membrane Wang, Qifei; Suraweera, Nethika S.; Keffer, David J. Macromolecules, Vol. 45, Issue 16 https://doi.org/10.1021/ma300383z	journal	July 2012
Structure and Diffusion in Cross-Linked and Sulfonated Poly(1,3-cyclohexadiene)/Polyethylene Glycol-Based Proton Exchange Membranes Wang, Qifei; Keffer, David J.; Deng, Suxiang The Journal of Physical Chemistry C, Vol. 117, Issue 10 https://doi.org/10.1021/jp309793z	journal	March 2013
Structure and proton transport in proton exchange membranes based on cross-linked sulfonated poly (1, 3-cyclohexadiene) with varying local acid environment Wang, Qifei; Keffer, David J.; Deng, Suxiang Polymer, Vol. 54, Issue 9 https://doi.org/10.1016/j.polymer.2013.03.018	journal	April 2013
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996
Estimation of the ion conductivity of a PEO-based polyelectrolyte system by molecular modeling Ennari, J. Polymer, Vol. 42, Issue 19 https://doi.org/10.1016/S0032-3861(01)00311-1	journal	September 2001
Photopolymerizable sulfonated poly(ethylene glycol) proton exchange membranes for microfluidic and fuel cell applications Nearingburg, B.; Elias, A. L. Journal of Membrane Science, Vol. 389 https://doi.org/10.1016/j.memsci.2011.10.024	journal	February 2012
Oxidation and epoxidation of poly(1,3-cyclohexadiene) Williamson, D. T.; Mather, B. D.; Long, T. E. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 41, Issue 1 https://doi.org/10.1002/pola.10551	journal	December 2002
Thermal Degradation of Poly(1,3-cyclohexadiene) and its Dehydrogenated Derivatives: Influence of a Controlled Microstructure Natori, Itaru; Natori, Shizue Macromolecular Chemistry and Physics, Vol. 207, Issue 15 https://doi.org/10.1002/macp.200600183	journal	August 2006
Hyperbranched fluoropolymer and linear poly(ethylene glycol) based amphiphilic crosslinked networks as efficient antifouling coatings: An insight into the surface compositions, topographies, and morphologies Gudipati, Chakravarthy S.; Greenlief, C. Michael; Johnson, Jeremiah A. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 24 https://doi.org/10.1002/pola.20466	journal	January 2004
Fuel Cell Membrane Characterizations Kim, Yu Seung; Lee, Kwan-Soo Polymer Reviews, Vol. 55, Issue 2 https://doi.org/10.1080/15583724.2015.1011275	journal	April 2015

Cited By (1)

Reactive molecular dynamics simulations of an excess proton in polyethylene glycol-water solutions McDonnell, Marshall T.; Keffer, David J. Molecular Simulation, Vol. 45, Issue 4-5 https://doi.org/10.1080/08927022.2018.1557328	journal	December 2018

Similar Records

Poly(cyclohexadiene)-Based Polymer Electrolyte Membranes for Fuel Cell Applications

Technical Report · Mon Mar 07 00:00:00 EST 2011 · OSTI ID:1324149

Mays, Jimmy W

High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

Technical Report · Thu Jun 03 00:00:00 EDT 2010 · OSTI ID:1324149

McGrath, James E; Baird, Donald G

Alternate Fuel Cell Membranes for Energy Independence

Technical Report · Tue Dec 18 00:00:00 EST 2012 · OSTI ID:1324149

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Proton exchange membrane
Poly(ethylene glycol)
Poly(1
3-cyclohexadiene)
fuel-cell applications
electrolyte membranes
sulfonated polybenzimidazoles
fluorinated polymer
molecular dynamics

Title: High temperature proton exchange membranes with enhanced proton conductivities at low humidity and high temperature based on polymer blends and block copolymers of poly(1,3-cyclohexadiene) and poly(ethylene glycol)

Citation Formats

References (64)

Cited By (1)

Similar Records

Related Subjects