Poly(ether ether ketone) Proton Exchange Membrane Containing Bisphenol Fluorene Unit for Vanadium Redox Flow Battery Application

doi:10.11944/j.issn.1000-0518.2020.08.200022

Chinese Journal of Applied Chemistry ›› 2020, Vol. 37 ›› Issue (8): 912-922.DOI: 10.11944/j.issn.1000-0518.2020.08.200022

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Poly(ether ether ketone) Proton Exchange Membrane Containing Bisphenol Fluorene Unit for Vanadium Redox Flow Battery Application

SONG Xun, JIA Yuting, ZHANG Jieling, NING Jinfeng, ZUO Haiyan, HUANG Xuehong^*

Key Laboratory of Polymer Science,College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350007,China

Published:2020-08-01 Online:2020-08-07
Contact: HUANG Xuehong, professor; Tel:0591-83465353; E-mail:xhhuang64@fjnu.edu.cn; Research interests:the molecular design of ion exchange membranes for fuel cells
Supported by:
Natural Science Foundation of Fujian Province(No.2017J01407), and the Fujian Normal University College Students′ Innovative Entrepreneurial Training Plan(No.S201910394023, No.202010394020)

Abstract

Abstract: Poly(ether ether ketone) (PEEK) containing methyl groups was synthesized by the aromatic nucleophilic polycondensation reaction of bisphenol fluorene unit, 4,4′-(Hexafluoroisopropylidene)diphenol, and 4,4′-difluoro-benzophenone. Poly(ether ether ketone) proton exchange membranes were post-sulfonated using concentrated sulfuric acid to give highly proton conductive sulfonic fluorenyl groups (SF-PEEK). The structure and morphology of SF-PEEK membranes were characterized by Fourier transform infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance spectroscopy (¹H NMR), thermal gravimetric analyzer (TGA), atomic force microscope (AFM) and scanning electron microscopy (SEM). The SF-PEEK membranes have strong hydrophilic/hydrophobic phase separation. The conductivity of the SF80-PFEK608 membrane (IEC=1.97 mmol/g) is 4.15×10^-2 S/cm which is lower than that of Nafion membrane (5.67×10^-2 S/cm). SF-PEEK membranes show much lower vanadium ions permeability (3.15×10^-7~1.48×10^-6 cm²/min) than that of Nafion 117 membrane (7.04×10^-6cm²/min). As a result, the self-discharge duration of the vanadium redox flow battery (VRFB) cell with SF80-PEEK608 membrane (90 h) is longer than that of VRFB cell with Nafion 117 membrane (57 h). Furthermore, the VRFB cell with SF80-PEEK608 (IEC=1.97 mmol/g) membrane exhibits higher coulombic efficiency of 80.9% compare with that of VRFB cell with Nafion 117 membrane (coulombic efficiency of 78.8%) at current density of 40 mA/cm². The results indicate that SF-PEEK membrane is high-performance and low-cost alternative membrane for VRFB application.

Key words: polyether ether ketone proton exchange membrane, vanadium redox battery, vanadium ion permeability, conductivity, bisphenol fluorene unit

SONG Xun, JIA Yuting, ZHANG Jieling, NING Jinfeng, ZUO Haiyan, HUANG Xuehong. Poly(ether ether ketone) Proton Exchange Membrane Containing Bisphenol Fluorene Unit for Vanadium Redox Flow Battery Application[J]. Chinese Journal of Applied Chemistry, 2020, 37(8): 912-922.

References

[1] Wang W,Luo Q T,Li B,et al. Recent Progress in Redox Flow Battery Research and Development[J]. Adv Funct Mat,2013,23(8):970-986.
[2] Ulaganathan M,Aravindan V,Yan Q,et al. Recent Advancements in All-Aanadium Redox Flow Batteries[J]. Adv Mater Interfaces,2016,3(1):1-22.
[3] Sum E,Skyllas-Kazacos M. A Study of the V(II)/V(III) Redox Couple for Redox Flow Cell Applications[J]. J Power Sources,1985,15:179-190.
[4] Zeng L,Ye J Y,Zhang J H,et al. A Promising SPEEK/MCM Composite Membrane for Highly Effcient Vanadium Redox Fow Battery[J]. Surf Coat Technol,2019,358(2):167-172.
[5] Ye J Y,Cheng Y H,Sun L D,et al. A Green SPEEK/lignin Composite Membrane with High Ion Selectivity for Vanadium Redox Flow Battery[J]. J Membr Sci,2019,572:110-118.
[6] Ulaganathan M,Jain A,Aravindan V,et al. Bio-mass Derived Mesoporous Carbon as Superior Electrode in All Vanadium Redox Flow Battery with Multicouple Reactions[J]. J Power Sources,2015,274:846-850.
[7] Tian S,Meng Y,Hay A S,et al. Membranes from Poly(aryl ether)-Based Ionomers Containing Randomly Distributed Nanoclusters of 6 or 12 Sulfonic Acid Groups[J]. Macromolecules,2009,42(4):1153-1160.
[8] Zhang S H,Zhang B G,Xing D B,et al. Poly(phthalazinone ether ketone ketone) Anion Exchange Membranes with Pyridinium as Ion Exchange Groups for Vanadium Redox Flow Battery Applications[J]. J Mater Chem A,2013,1(39):12246-12254.
[9] Kausar N,Mousa A,Skyllas-Kazacos M. The Effect of Additives on the High-Temperature Stability of the Vanadium Redox Flow Battery Positive Electrolytes[J]. ChemElectroChem,2016,3(2):276-282.
[10] Wang G,Lee K H,Lee W H,et al. Durable Sulfonated Poly(benzothiazole-co-benzimidazole) Proton Exchange Membranes[J]. Macromolecules,2014,47(18):6355-6364.
[11] Yee R S,Zhang K,Ladewig B P,et al. The Effects of Sulfonated Poly(ether ether ketone) Ion Exchange Preparation Conditions on Membrane Properties[J]. Membranes,2013,3(3):182-95.
[12] Winardi S,Raghu S C,Oo M O,et al. Sulfonated Poly(ether ether ketone)-Based Proton Exchange Membranes for Vanadium Redox Battery Applications[J]. J Membr Sci,2014,450:313-322.
[13] Oh K,Ketpang K,Kim H,et al. Synthesis of Sulfonated Poly(arylene ether ketone) Block Copolymers for Proton Exchange Membrane Fuel Cells[J]. J Membr Sci,2016,507:135-142.
[14] Assumma L,Nguyen H D,Iojoiu C,et al. Effects of Block Length and Membrane Processing Conditions on the Morphology and Properties of Perfluorosulfonated Poly(arylene ether sulfone) Multiblock Copolymer Membranes for PEMFC[J]. ACS Appl Mater Interfaces,2015,7(25):13808-13820.
[15] Maity S,Jana T. Polybenzimidazole Block Copolymers for Fuel Cell:Synthesis and Studies of Block Length Effects on Nanophase Separation, Mechanical Properties and Proton Conductivity of PEM[J]. ACS Appl Mater Interfaces,2014,6(9):6851-64.
[16] Li N,Wang C,Lee S Y,et al. Enhancement of Proton Transport by Nanochannels in Comb-shaped Copoly(arylene ether sulfone)s[J]. Angew Chem,2011,123(39):9324-9327.
[17] Cui M,Zhang Z,Yuan T,et al. Proton-conducting Membranes Based on Side-Chain-Type Sulfonated Poly(ether ketone/ether benzimidazole)s via One-Pot Condensation[J]. J Membr Sci,2014,465:100-106.
[18] Chen D Y,Wang S J,Xiao M,et al. Preparation and Properties of Sulfonated Poly(fluorenyl ether ketone) Membrane for Vanadium Redox Flow Battery Application[J]. J Power Sources,2010,195:2089-2095.
[19] Zhang H W,Shen P K. Advances in the High Performance Polymer Electrolyte Membranes for Fuel Cells[J]. Chem Soc Rev,2012,41(6):2382-94.
[20] Pang J H,Feng S N,Yu Y Y,et al. Poly(aryl ether ketone) Containing Flexible tetra-Sulfonated Side Chains as Proton Exchange Membranes[J]. Polym Chem,2014,5(4):1477-1486.
[21] Wang B L,Cai Z Z,Zhang N,et al. Fully Aromatic Naphthalene-Based Sulfonated Poly(arylene ether ketone)s with Flexible Sulfoalkyl Groups as Polymer Electrolyte Membranes[J]. RSC Adv,2015,1(5):536-544.
[22] Li N,Leng Y,Hickner M A,et al. Highly Stable, Anion Conductive, Comb-Shaped Copolymers for Alkaline Fuel Cells[J]. J Am Chem Soc,2013,135(27):10124-10133.
[23] Kim D S,Kim Y S,Guiver M D,et al. Highly Fluorinated Comb-Shaped Copolymer as Proton Exchange Membranes(PEMs):Fuel Cell Performance[J]. J Power Sources,2008,182:100-105.
[24] Chen D Y,Wang S J,Xiao M,et al. Preparation and Properties of Sulfonated Poly(fluorenyl ether ketone) Membrane for Vanadium Redox Flow Battery Application[J]. J Power Sources,2010,195:2089-2095.
[25]. Wang C,Li N,Shin D W,et al. Fluorene-Based Poly(arylene ether sulfone)s Containing Clustered Flexible Pendant Sulfonic Acids as Proton Exchange Membranes[J]. Macromolecules,2011,44(18):7296-7306.
[26] Luo J J,Wang S J,Xiao M,et al. Fluorene-Containing Block Sulfonated Poly(ether ether ketone) as Proton-Exchange Membrane for PEM Fuel Cell Application[J]. Eur Polym J,2010,46(8):1736-1744.
[27] Matsumura S,Hlil A R,Lepiller C,et al. Ionomers for Proton Exchange Membrane Fuel Cells with Sulfonic Acid Groups on the End Groups: Novel Branched Poly(ether-ketone)s[J]. Macromolecules,2008,41(2):281-284.
[28] Chen D Y,Wang S J,Xiao M,et al. Synthesis of Sulfonated Poly(fluorenyl ether thioether ketone)s with Bulky-Block Structure and Its Application in Vanadium Redox Flow Battery[J]. Polymer,2011,52(23):5312-5319.
[29] Wu H L,Ma C C M,Liu F Y,et al. Preparation and Characterization of Poly(ether sulfone)/Sulfonated Poly(ether ether ketone) Blend Membranes[J]. Eur Polym J,2006,42(7):1688-1695.
[30] Sun J,Shi D,Zhong H,et al. Investigations on the Self-discharge Process in Vanadium Flow Battery[J]. J Power Sources,2015,294:562-568.
[31] Chen D Y,Wang S N,Xiao M,et al. Synthesis and Characterization of Novel Sulfonated Poly(arylene thioether) Ionomers for Vanadiumredox Flow Battery Applications[J]. Energy Environ Sci,2010,3(5):622-628.
[32] Chen D,Wang S,Xiao M,et al. Sulfonated Poly(fluorenyl ether ketone) Membrane with Embedded Silica Rich Layer and Enhanced Proton Selectivity for Vanadium Redox Flow Battery[J]. J Power Sources,2010,195:7701-7708.
[33] Aaron D S,Liu Q,Tang Z,et al. Dramatic Performance Gains in Vanadium Redox Flow Batteries Through Modified Cell Architecture[J]. J Power Sources,2012,206:450-453.
[34] Chen D,Hickner M A,Agar E,et al. Optimized Anion Exchange Membranes for Vanadium Redox Flow Batteries[J]. ACS Appl Mater Interfaces,2013,5(15):7559-66.
[35] Chen D,Hickner M A,Agar E,et al. Optimizing Membrane Thickness for Vanadium Redox Flow Batteries[J]. J Membr Sci,2013,437:108-113.
[36] Liu Q H,Grim G M,Papandrew A B,et al. High Performance Vanadium Redox Flow Batteries with Optimized Electrode Configuration and Membrane Selection[J]. J Electrochem Soc,2012,159(8):1246-1252.
[37] Chen D,Kim S,Li L,et al. Stable Fluorinated Sulfonated Poly(arylene ether) Membranes for Vanadium Redox Flow Batteries[J]. RSC Adv,2012,2(24):8087-8094.
[38] Kjeang E,Michel R,Harrington D A,et al. A Microfluidic Fuel Cell with Flow-Through Porous Electrodes[J]. J Am Chem Soc,2008,130(12):4000-4006.

Poly(ether ether ketone) Proton Exchange Membrane Containing Bisphenol Fluorene Unit for Vanadium Redox Flow Battery Application

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