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Title: Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes

Abstract

An epoxy-crosslinked sulfonated poly(phenylene) copolymer composition used as proton exchange membranes, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cell, in electrode casting solutions and electrodes, and in sulfur dioxide electrolyzers. These improved membranes are tougher, have higher temperature capability, and lower SO.sub.2 crossover rates.

Inventors:
 [1];  [1];  [1];  [2]
  1. (Albuquerque, NM)
  2. (State College, PA)
Publication Date:
Research Org.:
Sandia Corporation (Albuquerque, NM)
Sponsoring Org.:
USDOE
OSTI Identifier:
1016126
Patent Number(s):
7,816,482
Application Number:
12/411,451
Assignee:
Sandia Corporation (Albuquerque, NM) SSO
DOE Contract Number:
AC04-94AL85000
Resource Type:
Patent
Country of Publication:
United States
Language:
English

Citation Formats

Hibbs, Michael, Fujimoto, Cy H., Norman, Kirsten, and Hickner, Michael A.. Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes. United States: N. p., 2010. Web.
Hibbs, Michael, Fujimoto, Cy H., Norman, Kirsten, & Hickner, Michael A.. Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes. United States.
Hibbs, Michael, Fujimoto, Cy H., Norman, Kirsten, and Hickner, Michael A.. 2010. "Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes". United States. doi:. https://www.osti.gov/servlets/purl/1016126.
@article{osti_1016126,
title = {Epoxy-crosslinked sulfonated poly (phenylene) copolymer proton exchange membranes},
author = {Hibbs, Michael and Fujimoto, Cy H. and Norman, Kirsten and Hickner, Michael A.},
abstractNote = {An epoxy-crosslinked sulfonated poly(phenylene) copolymer composition used as proton exchange membranes, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cell, in electrode casting solutions and electrodes, and in sulfur dioxide electrolyzers. These improved membranes are tougher, have higher temperature capability, and lower SO.sub.2 crossover rates.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2010,
month =
}

Patent:

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  • Improved multi-block sulfonated poly(phenylene) copolymer compositions, methods of making the same, and their use as proton exchange membranes (PEM) in hydrogen fuel cells, direct methanol fuel cells, in electrode casting solutions and electrodes. The multi-block architecture has defined, controllable hydrophobic and hydrophilic segments. These improved membranes have better ion transport (proton conductivity) and water swelling properties.
  • Permeation of ethylene and ethane is sulfonated poly(phenylene oxide), sulfonated bisphenol A polyarylethersulfone and sulfonated hexafluorobisphenol A polyarylethersulfone (6F-SPS) exchanged with Ag{sup +} ions were measured as a function of degree of sulfonation, temperature and trans membrane differential pressure. The data were compared with the permeation results for these membranes in acid form and alkaline metal salt form. Membranes exchanged with Ag{sup +} ions displayed enhanced etylene permeability and ethylene-ethane separation factors. The enhancement in transport of ethylene in ion exchange membranes is apparently related to an increase in ethylene solubility affected by complexation of ethylene with immobilized Ag{sup +}more » ions. A substantial increase in ethylene permeation rate and separation factor was observed when the feed gas was saturated with water vapors. Enhanced permeation/separation were attributed to an increase in the mobility of silver ions in water plasticized membranes. Membranes plasticized with glycerol exhibited high ethylene permeation rate and ethylene/ethane separation factors in dry feed gas streams that were comparable with permeation rates in water plasticized membranes.« less
  • A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.« less