Poly(olefin)-Based Anion Exchange Membranes Prepared Using Ziegler-Natta Polymerization

Liang Zhu, Xuedi Yu, Xiong Peng, Tawanda Zimudzi, Nayan Saikia, Michael T. Kwasny, Shaofei Song, Douglas I. Kushner, Zhisheng Fu, Gregory N. Tew, William E. Mustain, Michael A. Yandrasits, Michael Anthony Hickner

Research output: Contribution to journalArticle

Abstract

Bromoalkyl-functionalized poly(olefin)s were synthesized by copolymerization of 4-(4-methylphenyl)-1-butene with 11-bromo-1-undecene using Ziegler-Natta polymerization. The resulting bromoalkyl-functionalized poly(olefin)s were converted to quaternary ammonium-containing anion-conductive copolymers by reacting the pendant bromoalkyl group with trimethylamine or a custom-synthesized tertiary amine containing pendant quaternary ammonium moieties. Poly(olefin)-based AEMs with three cations per side chain showed considerably higher hydroxide conductivities, up to 201 mS/cm at 80 °C in liquid water, compared to that of samples with only one cation per bromoalkyl site (68 mS/cm, 80 °C, liquid water), likely due to phase separation in the triple-cation structure. More importantly, triple-cation side-chain poly(olefin) AEMs exhibited higher hydroxide conductivity under relative humidity conditions (50%-100%) than typical AEMs based on benzyltrimethylammonium cations. The triple-cation the triple-cation side-chain poly(olefin)-based AEM exhibited an ionic conductivity as high as 115 mS/cm under 95% RH at 80 °C and 11 mS/cm under 50% RH at 80 °C. In addition to high ionic conductivity, the triple-cation side-chain poly(olefin) AEMs exhibited good chemical and dimensional stability. High retention of ionic conductivity (>85%) was observed for the samples in 1 M NaOH at 80 °C over 1000 h. Based on these high-performance poly(olefin) AEMs, a fuel cell with a peak power density of 0.94 W cm-2 (1.28 W cm-2 after iR correction) was achieved under H2/O2 at 70 °C. The results of this study suggest a new, low-cost, and scalable route for preparation of poly(olefin)-based AEMs for anion exchange membrane applications.

Original languageEnglish (US)
Pages (from-to)4030-4041
Number of pages12
JournalMacromolecules
Volume52
Issue number11
DOIs
StatePublished - Jun 11 2019

Fingerprint

Alkenes
Olefins
Anions
Cations
Ion exchange
Negative ions
Positive ions
Polymerization
Membranes
Ionic conductivity
Ammonium Compounds
Water
Dimensional stability
Chemical stability
Liquids
2-aminoethylmethacrylate
Butenes
Phase separation
Copolymerization
Amines

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Zhu, Liang ; Yu, Xuedi ; Peng, Xiong ; Zimudzi, Tawanda ; Saikia, Nayan ; Kwasny, Michael T. ; Song, Shaofei ; Kushner, Douglas I. ; Fu, Zhisheng ; Tew, Gregory N. ; Mustain, William E. ; Yandrasits, Michael A. ; Hickner, Michael Anthony. / Poly(olefin)-Based Anion Exchange Membranes Prepared Using Ziegler-Natta Polymerization. In: Macromolecules. 2019 ; Vol. 52, No. 11. pp. 4030-4041.
@article{81a284ec02f3493f9562229d95fce924,
title = "Poly(olefin)-Based Anion Exchange Membranes Prepared Using Ziegler-Natta Polymerization",
abstract = "Bromoalkyl-functionalized poly(olefin)s were synthesized by copolymerization of 4-(4-methylphenyl)-1-butene with 11-bromo-1-undecene using Ziegler-Natta polymerization. The resulting bromoalkyl-functionalized poly(olefin)s were converted to quaternary ammonium-containing anion-conductive copolymers by reacting the pendant bromoalkyl group with trimethylamine or a custom-synthesized tertiary amine containing pendant quaternary ammonium moieties. Poly(olefin)-based AEMs with three cations per side chain showed considerably higher hydroxide conductivities, up to 201 mS/cm at 80 °C in liquid water, compared to that of samples with only one cation per bromoalkyl site (68 mS/cm, 80 °C, liquid water), likely due to phase separation in the triple-cation structure. More importantly, triple-cation side-chain poly(olefin) AEMs exhibited higher hydroxide conductivity under relative humidity conditions (50{\%}-100{\%}) than typical AEMs based on benzyltrimethylammonium cations. The triple-cation the triple-cation side-chain poly(olefin)-based AEM exhibited an ionic conductivity as high as 115 mS/cm under 95{\%} RH at 80 °C and 11 mS/cm under 50{\%} RH at 80 °C. In addition to high ionic conductivity, the triple-cation side-chain poly(olefin) AEMs exhibited good chemical and dimensional stability. High retention of ionic conductivity (>85{\%}) was observed for the samples in 1 M NaOH at 80 °C over 1000 h. Based on these high-performance poly(olefin) AEMs, a fuel cell with a peak power density of 0.94 W cm-2 (1.28 W cm-2 after iR correction) was achieved under H2/O2 at 70 °C. The results of this study suggest a new, low-cost, and scalable route for preparation of poly(olefin)-based AEMs for anion exchange membrane applications.",
author = "Liang Zhu and Xuedi Yu and Xiong Peng and Tawanda Zimudzi and Nayan Saikia and Kwasny, {Michael T.} and Shaofei Song and Kushner, {Douglas I.} and Zhisheng Fu and Tew, {Gregory N.} and Mustain, {William E.} and Yandrasits, {Michael A.} and Hickner, {Michael Anthony}",
year = "2019",
month = "6",
day = "11",
doi = "10.1021/acs.macromol.8b02756",
language = "English (US)",
volume = "52",
pages = "4030--4041",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "11",

}

Zhu, L, Yu, X, Peng, X, Zimudzi, T, Saikia, N, Kwasny, MT, Song, S, Kushner, DI, Fu, Z, Tew, GN, Mustain, WE, Yandrasits, MA & Hickner, MA 2019, 'Poly(olefin)-Based Anion Exchange Membranes Prepared Using Ziegler-Natta Polymerization', Macromolecules, vol. 52, no. 11, pp. 4030-4041. https://doi.org/10.1021/acs.macromol.8b02756

Poly(olefin)-Based Anion Exchange Membranes Prepared Using Ziegler-Natta Polymerization. / Zhu, Liang; Yu, Xuedi; Peng, Xiong; Zimudzi, Tawanda; Saikia, Nayan; Kwasny, Michael T.; Song, Shaofei; Kushner, Douglas I.; Fu, Zhisheng; Tew, Gregory N.; Mustain, William E.; Yandrasits, Michael A.; Hickner, Michael Anthony.

In: Macromolecules, Vol. 52, No. 11, 11.06.2019, p. 4030-4041.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Poly(olefin)-Based Anion Exchange Membranes Prepared Using Ziegler-Natta Polymerization

AU - Zhu, Liang

AU - Yu, Xuedi

AU - Peng, Xiong

AU - Zimudzi, Tawanda

AU - Saikia, Nayan

AU - Kwasny, Michael T.

AU - Song, Shaofei

AU - Kushner, Douglas I.

AU - Fu, Zhisheng

AU - Tew, Gregory N.

AU - Mustain, William E.

AU - Yandrasits, Michael A.

AU - Hickner, Michael Anthony

PY - 2019/6/11

Y1 - 2019/6/11

N2 - Bromoalkyl-functionalized poly(olefin)s were synthesized by copolymerization of 4-(4-methylphenyl)-1-butene with 11-bromo-1-undecene using Ziegler-Natta polymerization. The resulting bromoalkyl-functionalized poly(olefin)s were converted to quaternary ammonium-containing anion-conductive copolymers by reacting the pendant bromoalkyl group with trimethylamine or a custom-synthesized tertiary amine containing pendant quaternary ammonium moieties. Poly(olefin)-based AEMs with three cations per side chain showed considerably higher hydroxide conductivities, up to 201 mS/cm at 80 °C in liquid water, compared to that of samples with only one cation per bromoalkyl site (68 mS/cm, 80 °C, liquid water), likely due to phase separation in the triple-cation structure. More importantly, triple-cation side-chain poly(olefin) AEMs exhibited higher hydroxide conductivity under relative humidity conditions (50%-100%) than typical AEMs based on benzyltrimethylammonium cations. The triple-cation the triple-cation side-chain poly(olefin)-based AEM exhibited an ionic conductivity as high as 115 mS/cm under 95% RH at 80 °C and 11 mS/cm under 50% RH at 80 °C. In addition to high ionic conductivity, the triple-cation side-chain poly(olefin) AEMs exhibited good chemical and dimensional stability. High retention of ionic conductivity (>85%) was observed for the samples in 1 M NaOH at 80 °C over 1000 h. Based on these high-performance poly(olefin) AEMs, a fuel cell with a peak power density of 0.94 W cm-2 (1.28 W cm-2 after iR correction) was achieved under H2/O2 at 70 °C. The results of this study suggest a new, low-cost, and scalable route for preparation of poly(olefin)-based AEMs for anion exchange membrane applications.

AB - Bromoalkyl-functionalized poly(olefin)s were synthesized by copolymerization of 4-(4-methylphenyl)-1-butene with 11-bromo-1-undecene using Ziegler-Natta polymerization. The resulting bromoalkyl-functionalized poly(olefin)s were converted to quaternary ammonium-containing anion-conductive copolymers by reacting the pendant bromoalkyl group with trimethylamine or a custom-synthesized tertiary amine containing pendant quaternary ammonium moieties. Poly(olefin)-based AEMs with three cations per side chain showed considerably higher hydroxide conductivities, up to 201 mS/cm at 80 °C in liquid water, compared to that of samples with only one cation per bromoalkyl site (68 mS/cm, 80 °C, liquid water), likely due to phase separation in the triple-cation structure. More importantly, triple-cation side-chain poly(olefin) AEMs exhibited higher hydroxide conductivity under relative humidity conditions (50%-100%) than typical AEMs based on benzyltrimethylammonium cations. The triple-cation the triple-cation side-chain poly(olefin)-based AEM exhibited an ionic conductivity as high as 115 mS/cm under 95% RH at 80 °C and 11 mS/cm under 50% RH at 80 °C. In addition to high ionic conductivity, the triple-cation side-chain poly(olefin) AEMs exhibited good chemical and dimensional stability. High retention of ionic conductivity (>85%) was observed for the samples in 1 M NaOH at 80 °C over 1000 h. Based on these high-performance poly(olefin) AEMs, a fuel cell with a peak power density of 0.94 W cm-2 (1.28 W cm-2 after iR correction) was achieved under H2/O2 at 70 °C. The results of this study suggest a new, low-cost, and scalable route for preparation of poly(olefin)-based AEMs for anion exchange membrane applications.

UR - http://www.scopus.com/inward/record.url?scp=85066467724&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85066467724&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.8b02756

DO - 10.1021/acs.macromol.8b02756

M3 - Article

AN - SCOPUS:85066467724

VL - 52

SP - 4030

EP - 4041

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 11

ER -