Title

Composite Polymer Electrolyte Membranes with Ultrahigh Ion Selectivity for Redox Flow Batteries

Alternative Title

산화 환원 흐름전지를 위한 초고이온선택성의 고분자 전해질 복합막

DGIST Authors

Md. Abdul Aziz ; Sangaraju Shanmugam ; Soonhyun Kim

Advisor

상가라쥬 샨무감

Co-Advisor(s)

Soonhyun Kim

Issued Date

2021

Awarded Date

2021/02

Citation

Md. Abdul Aziz. (2021). Composite Polymer Electrolyte Membranes with Ultrahigh Ion Selectivity for Redox Flow Batteries. doi: 10.22677/thesis.200000364276

Type

Thesis

Subject

Redox flow battery, composite membrane, Nafion, proton conductivity, permeability, ion selectivity, 산화환원 흐름전지, 복합막, 나피온, 수소이온전도도, 투과성, 이온선택성

Table Of Contents

CHAPTER I. INTRODUCTION 1
1.1 Theoretical background 1
1.2 The fundamental of redox flow battery (RFB) 2
1.3 RFB types and energy production capability 3
1.4 Problem description and current understanding 6
1.5 Development of membranes for vanadium redox flow battery (VRFB) 7
1.5.1. Cation exchange membrane 7
1.5.1.1 Perfluorosulfonic acid membrane (Nafion®) 8
1.5.1.2 Nafion/filler composite membrane 9
1.5.1.3 Hydrocarbon polymer membrane 12
1.5.1.4 Hydrocarbon polymer composite membrane 13
1.5.2 Anion exchange membranes 17
1.5.3 Amphoteric ion exchange membranes (AIEMs) 19
1.6 Motivation and goal of this dissertation 21
CHAPTER II. EXPERIMENTAL METHODOLOGY 24
2.1 Materials 24
2.2 Preparation of graphene oxide (GO) and sulfonated graphene oxide (sGO) 24
2.3 Preparation of metal oxide nanotubes (ZrO2NT, TiO2NT and TiZrO4NT) 25
2.4 Synthesis of sulfonated poly(ether ketone sulfone) (SPEKS) block copolymer 26
2.4.1 Synthesis of hydrophilic oligomer 26
2.4.2 Synthesis of hydrophobic oligomer 26
2.4.3 Synthesis of block copolymer (SPEKS) 27
2.5 Synthesis of sulfonated poly(arylene ether ketone) (SPAEK) block copolymer 27
2.5.1 Synthesis of hydrophilic oligomer 27
2.5.2 Synthesis of hydrophobic oligomer 28
2.5.3 Synthesis of block copolymer (SPAEK) 28
2.6 Preparation of composite membrane 28
2.6.1 SPEKS/sulfonated graphene oxide (sGO) composite membrane 28
2.6.2 SPAEK/ZrO2 nanotubes (ZrO2NT) composite membrane 29
2.6.3 Nafion-metal oxide nanotubes composite membranes 29
2.7 Preparation of H6[CoW12O40] 30
2.8 Characterization techniques 30
2.8.1 Water uptake, swelling degree, ion exchange capacity (IEC) and oxidative stability 31
2.8.2 Proton conductivity 32
2.8.3 Measurements of VO2+ and [CoW12O40]6- permeability, and ion selectivity 32
2.8.4 Measurements of redox flow battery performance 33
CHAPTER III. SULFONATED POLY(ETHER KETONE SULFONE) COMPOSITE MEMBRANE (SPEKS/sGO) FOR VANADIUM REDOX FLOW BATTERY 35
3.1 Introduction 35
3.2 Results and discussion 37
3.2.1 Characterization of sGO and SPEKS/sGO composite membrane 37
3.2.2 Proton/vanadium selectivity measurements 50
3.2.3 VRFB performance 53
3.3 Summary 64
CHAPTER IV. SULFONATED POLY(ARYLENE ETHER KETONE) COMPOSITE MEMBRANE (SPAEK/ZrO2NT) FOR VANADIUM REDOX FLOW BATTERY 65
4.1 Introduction 65
4.2 Results and discussion 66
4.2.1 Characterization of SPAEK/ZrO2NT composite membrane 66
4.2.2 VO2+ permeability and ion selectivity measurements 72
4.2.3 VRFB performance 74
4.3 Summary 84
CHAPTER V. NAFION DECORATED WITH TiZrO4 NANOTUBES COMPOSITE MEMBRANE (NAFION/TiZrO4NT) FOR VANADIUM REDOX FLOW BATTERY 85
5.1 Introduction 85
5.2 Results and discussion 86
5.2.1 Characterization of metal oxide nanotubes and Nafion composite membranes 86
5.2.2 Ion selectivity measurements of Nafion composite membranes 97
5.2.3 VRFB Performance 99
5.3 Summary 108
CHAPTER VI. NAFION/TiZrO4NT COMPOSITE MEMBRANE FOR POLYOXOMETALATE REDOX FLOW BATTERY 109
6.1 Introduction 109
6.2 Results and discussion 110
6.2.1 Characterization and electrochemical activity of H6[CoW12O40] 110
6.2.2 Measurements of H+/[CoW12O40]6- selectivity 114
6.2.3 H6[CoW12O40] RFB performance 117
6.3 Summary 130
CHAPTER VII. CONCLUSIONS 131
REFERENCES 133

URI

http://dgist.dcollection.net/common/orgView/200000364276
http://hdl.handle.net/20.500.11750/16688

DOI

10.22677/thesis.200000364276

Degree

Doctor

Department

Energy Science & Engineering

Publisher

DGIST

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