Preparation and Performance of the Self-crosslinking Sulfonated Poly(ether ether ketone) Proton Exchange Membrane†

doi:10.7503/cjcu20180363

Abstract

Abstract:

Side chain type, sulfonated poly(ether ether ketone)(SPEEK) was prepared via free radical addition reaction using PEEK containning 3,3'-diallyl bisphenol A structural unit and 3-mercaptopropane-sulphonate. The structure and morphology of SPEEK membrane were characterized by Fourier transform infrared spectroscopy(FTIR), ¹H NMR, TGA and SEM. The SPEEK has high hydrophilic/hydrophobic phase separation. Water uptake, mechanical property, proton conductivity, VO²⁺ permeability and single cell performances were investigated in order to understand the relationship between morphology and property of the membranes. The vanadium ion VO²⁺ permeability through the SPFEK-4 membrane(IEC=2.12 mmol/g) is 1.54×10^-6 cm²/min, which is lower than that of Nafion membrane(6.04×10^-6 cm²/min). Tests of SPPEK-4 in vanadium redox batteries(VRB) demonstrate a comparable Columbic efficiency(CE) and energy efficiency(EE) to that of Nafion117 at 50 mA/cm², and the SPPEK-4 membrane exhibits stable performance in cell over 50 charge-discharge cycles.

Key words: Sulfonated poly(ether ether ketone) proton exchange membrane, Vanadium redox battery, Vanadium ion permeability, Crosslink

CLC Number:

O631

TrendMD:

CHEN Yuhan,HUANG Xuehong. Preparation and Performance of the Self-crosslinking Sulfonated Poly(ether ether ketone) Proton Exchange Membrane^†[J]. Chem. J. Chinese Universities, 2019, 40(2): 410.

Figures/Tables 16

Scheme 1 Synthesis of PEEK

Scheme 2 Synthesis of SPEEK

Fig.1 Structure of the cross-linking SPEEK

Fig.2 1H NMR spectra of PEEK(A) and SPEEK(B)Peaks a—f are corresponding to the positions of a—f in Scheme 1 and Fig.1.

Fig.3 SEM images(A, B) of cross-section and AFM image(C) of SPEEK-4 membrane

Fig.4 FTIR spectra of PEEK and SPEEKs membranesa. PEEK; b. SPEEK-2; c. SPEEK-3; d. SPEEK-4; e. SPEEK-5.

Fig.5 FTIR spectra of SPEEK-3 before(a) and after(b) UV curing

Fig.6 TG curves of PEEK(a), SPEEK-3(b) and SPEEK-4(c) membranes

Fig.7 Contact angle images(A) and contact angle and surface energy of series SPEEKs membranes for different reacting time(B)

Table 1 Water uptake, swelling ratio, proton conductivity, and VO2+ permeability of SPEEKs and Nafion 117

Membrane	IEC/ (mmol·g^-1)	Swelling ratio (%)	Water uptake (%)	Permeability of VO²⁺/ (cm²·min^-1)	δ/ (mS·cm^-1)	IEC loss(%)	Mass loss(%)
SPEEK-1	0.75	1.88	21.42	1.37×10^-7	0.73	4.7	3.1
SPEEK-2	1.23	2.72	31.99	8.36×10^-7	1.13	5.6	3.8
SPEEK-3	1.96	4.12	36.54	1.14×10^-6	1.34	6.3	4.4
SPEEK-4	2.12	6.45	43.90	1.54×10^-6	3.35	6.8	4.6
SPEEK-5	2.34	11.12	53.90	2.18×10^-6	4.81	7.2	5.5
Nafion117	0.91	11.50	18.80	6.04×10^-6	5.67	2.1	2.7

Table 2 Properties for the virgin polymers and the cross-linked polymers

Membrane	Tensile strength/MPa	Elongation at break(%)	Gel content (%)	Membrane	Tensile strength/MPa	Elongation at break(%)	Gel content (%)
SPEEK-1^*	22.19	8.37	-	SPEEK-1	26.84	4.78	49.3
SPEEK-2^*	18.03	5.32	-	SPEEK-2	22.01	2.94	36.7
SPEEK-3^*	15.05	3.54	-	SPEEK-3	17.58	1.46	11.2
SPEEK-4^*	12.35	1.63	-	SPEEK-4	13.22	0.97	6.9
SPEEK-5^*	10.28	0.78	-	SPEEK-5	10.21	0.76	0

Fig.8 Curves of VO2+ concentration versus time in the right reservoir of the permeation measuring device with SPEEKs and Nafion117 membranes

Fig.9 Discharge curves with different current densities of VRB single cell assembled with SPEEK-4(a), SPEEK-5(b) and Nafion117(c) membranesj/(mA·cm-2): (A) 20; (B) 30; (C) 40; (D) 50; (E) 60.

Fig.10 Effect of discharge current density on Columbic efficiency(CE) of VRB single cell assembled with SPEEK-4(a), SPEEK-5(b) and Nafion117(c) membranes

Fig.11 Charge-discharge cycling performance(50 mA/cm2) of the VRB single cell with SPEEK-4(A) and Nafion117(B) membranes

Fig.12 Open circuit voltage for SPEEK-3(a), SPEEK-4(b), SPEEK-5(c) and Nafion117(d) membranes versus time of the VRB single cell

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