skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Highly Stable Anion Exchange Membranes for High-Voltage Redox-Flow Batteries

Abstract

In this work, multiple polymer backbones were screened for oxidation resistance and multiple chemistries were explored for tethering tris(2,4,6-trimethylphenyl)phosphonium (9MeTTP +) to the selected polymer backbones. A new tethering strategy through brominated 9MeTTP+ cation was developed and used to obtain the desired 9MeTTP +-functionalized polysulfone (PSf) and hexafluoro polybenzimidazole (F 6PBI) polymer. The crosslinked 9MeTTP+-functionalized hexafluoro polybenzimidazole (9MeTTP-F 6PBI) polymer demonstrated excellent oxidation stability that met the go-no-go milestone of the first year. However, large-scale bromination inevitably involved multi-bromination products, which led to polymer crosslinking in the next tethering. A new synthesis strategy with diiodobutane as linker was developed to overcome the crosslinking problem. The prepared 9MeTTP +-F 6PBI membrane without crosslinking showed only 3.58% water uptake and less than 1 mS/cm OH - conductivity in water at 20°C, possibly due to the hydrophobic 9MeTTP + cation. In order to improve the conductivity, hydrophilic tris(2,4,6-trimethoxylphenyl)phosphonium (9MeOTTP+) cation was tethered to an F 6PBI backbone, and a 9MeOTTP +-F 6PBI PTFE reinforced membrane was prepared with 17.4% water uptake to increase the mechanical strength and durability in cerium (IV) solution. A 9MeOTTP+-F 6PBI PTFE reinforced membrane had less than 20% conductivity loss during an accelerated stability test in 0.5 M ceriummore » (IV) and 1.3 M HClO 4 at 55°C for 100 hours. Moreover, a 9MeOTTP +-F 6PBI PTFE reinforced membrane had more than double the lifetime of commercial FAS-30 and FAB-PK-130 AEMs during an accelerated stability test in 0.5 M cerium (IV) and 1.3 M HClO 4 at 55°C. Low area specific resistance (ASR) of a 9MeOTTP +-F 6PBI PTFE reinforced membrane in the sulfuric acid system was also achieved due to the high acid doping ability of the polymer structure. The cationic 9MeOTTP +-F 6PBI PTFE reinforced membrane shows a cerium (IV) permeability that is 27-fold lower than that of Nafion 212. Excellent voltage and energy efficiencies with a 9MeOTTP +-F 6PBI PTFE reinforced membrane were demonstrated in an all-vanadium redox flow battery (VRFB).« less

Authors:
 [1]
  1. Univ. of Delaware, Newark, DE (United States)
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1422516
Report Number(s):
DOE-U Delaware-EE0006964
DOE Contract Number:  
EE0006964
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Membrane, hydroxide exchange membrane, flow battery, oxidation resistant

Citation Formats

Yan, Yushan. Highly Stable Anion Exchange Membranes for High-Voltage Redox-Flow Batteries. United States: N. p., 2018. Web. doi:10.2172/1422516.
Yan, Yushan. Highly Stable Anion Exchange Membranes for High-Voltage Redox-Flow Batteries. United States. doi:10.2172/1422516.
Yan, Yushan. Mon . "Highly Stable Anion Exchange Membranes for High-Voltage Redox-Flow Batteries". United States. doi:10.2172/1422516. https://www.osti.gov/servlets/purl/1422516.
@article{osti_1422516,
title = {Highly Stable Anion Exchange Membranes for High-Voltage Redox-Flow Batteries},
author = {Yan, Yushan},
abstractNote = {In this work, multiple polymer backbones were screened for oxidation resistance and multiple chemistries were explored for tethering tris(2,4,6-trimethylphenyl)phosphonium (9MeTTP+) to the selected polymer backbones. A new tethering strategy through brominated 9MeTTP+ cation was developed and used to obtain the desired 9MeTTP+-functionalized polysulfone (PSf) and hexafluoro polybenzimidazole (F6PBI) polymer. The crosslinked 9MeTTP+-functionalized hexafluoro polybenzimidazole (9MeTTP-F6PBI) polymer demonstrated excellent oxidation stability that met the go-no-go milestone of the first year. However, large-scale bromination inevitably involved multi-bromination products, which led to polymer crosslinking in the next tethering. A new synthesis strategy with diiodobutane as linker was developed to overcome the crosslinking problem. The prepared 9MeTTP+-F6PBI membrane without crosslinking showed only 3.58% water uptake and less than 1 mS/cm OH- conductivity in water at 20°C, possibly due to the hydrophobic 9MeTTP+ cation. In order to improve the conductivity, hydrophilic tris(2,4,6-trimethoxylphenyl)phosphonium (9MeOTTP+) cation was tethered to an F6PBI backbone, and a 9MeOTTP+-F6PBI PTFE reinforced membrane was prepared with 17.4% water uptake to increase the mechanical strength and durability in cerium (IV) solution. A 9MeOTTP+-F6PBI PTFE reinforced membrane had less than 20% conductivity loss during an accelerated stability test in 0.5 M cerium (IV) and 1.3 M HClO4 at 55°C for 100 hours. Moreover, a 9MeOTTP+-F6PBI PTFE reinforced membrane had more than double the lifetime of commercial FAS-30 and FAB-PK-130 AEMs during an accelerated stability test in 0.5 M cerium (IV) and 1.3 M HClO4 at 55°C. Low area specific resistance (ASR) of a 9MeOTTP+-F6PBI PTFE reinforced membrane in the sulfuric acid system was also achieved due to the high acid doping ability of the polymer structure. The cationic 9MeOTTP+-F6PBI PTFE reinforced membrane shows a cerium (IV) permeability that is 27-fold lower than that of Nafion 212. Excellent voltage and energy efficiencies with a 9MeOTTP+-F6PBI PTFE reinforced membrane were demonstrated in an all-vanadium redox flow battery (VRFB).},
doi = {10.2172/1422516},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Feb 26 00:00:00 EST 2018},
month = {Mon Feb 26 00:00:00 EST 2018}
}

Technical Report:

Save / Share: