Preparation and Properties of Filling-type Sulfonated Poly(arylene ether sulfone)/Poly(ether sulfone) Composite Membranes with Microporous Structures†

doi:10.7503/cjcu20180785

Abstract

Abstract:

A series of filling-type composite polymer exchange membranes was prepared based on sulfonated poly(arylene ether sulfones)(SPAES) and poly(ether sulfone)s(PES), and the properties including water uptake, dimensional change, thermal-mechanical properties, proton conductivity, methanol permeability and chemical stability were evaluated. Firstly, a series of microporous composite proton exchange membranes(Sx-y, x refers to the sulfonation degree of the SPAES copolymers, y refers to the mass ratio(20%—40%) of SPAES copolymers) was fabricated via immersion phase inversion method from PES and SPAES copolymers with sulfonation degree of 30%(S30), 40%(S40) and 50%(S50). Then, the corresponding filling-type composite polymer exchange membranes(Sx-y+F50) were prepared by filling S50 in the Sx-y micropores by vacuum filtration. The results indicate that the Sx-y membranes, despite of the rather low ion exchange capacity(IEC), all display fairly high proton conductivity, fine mechanical strength, excellent chemical stability and rather low methanol permeability. After filling with S50, the corresponding Sx-y+F50 membranes exhibit improved IEC and proton conductivity, lowered methanol permeability, and maintain high mechanical strength and chemical stability. The S30-40+F50 membrane(IEC=0.69 mmol/g) shows the best comprehensive properties: proton conductivity of 50.4 mS/cm at 90 ℃ in water; mass loss of 8.2% and proton conductivity loss of 9% by aging in water at 140 ℃ for 24 h, and mass loss of 0.66% by soaking in Fenton reagent(3% H₂O₂, 20 mg/L FeSO₄) at 80 ℃ for 1 h; methanol permeability of 6.8×10^-8 cm²/s. The filling-type composite proton exchange membranes are promising candidates for fuel cell applications.

Key words: Fuel cell, Immersion phase transformation, Filling-type composite proton exchange membrane, Sulfonated poly(arylene ether sulfone), Poly(ether sulfone), Proton conductivity

CLC Number:

O631

TrendMD:

ZHU Yuxin,HARAGIRIMANA Alphonse,LU Yao,BUREGEYA Ingabire Providence,NING Cong,LI Na,HU Zhaoxia,CHEN Shouwen. Preparation and Properties of Filling-type Sulfonated Poly(arylene ether sulfone)/Poly(ether sulfone) Composite Membranes with Microporous Structures^†[J]. Chem. J. Chinese Universities, 2019, 40(5): 1051.

Figures/Tables 8

References 14

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Sample	IEC^a/ (mmol·g^-1)	WU(%)		SR(%)	σ/(mS·cm^-1)		Mass loss^b(%)
Sample	IEC^a/ (mmol·g^-1)	30 ℃	80 ℃	30 ℃	30 ℃	90 ℃	Mass loss^b(%)
S30-20	0.21	64.1±5.0	198.4±12.6	0.20±0.01	5.0±0.2	16.2±0.4	0.20
S30-30	0.36	86.2±7.0	209.8±12.8	0.90±0.07	10.1±0.3	26.7±0.8	0
S30-40	0.42	91.3±11.3	205.9±11.8	1.70±0.07	16.0±0.5	32.1±1.4	0
S40-20	0.30	83.3±6.8	161.7±11.4	0.43±0.05	6.3±0.2	24.8±1.2	0.07
S40-30	0.41	116.6±12.5	226.5±13.5	1.22±0.09	9.9±0.2	37.0±1.6	0.15
S40-40	0.58	122.8±7.1	201.6±12.3	2.15±0.10	16.9±0.6	32.1±1.5	0.20
S50-20	0.32	102.8±8.3	244.8±15.4	0.58±0.06	7.7±0.3	19.2±0.6	0.05
S50-30	0.51	136.2±9.5	270.4±17.5	1.39±0.10	1.5±0.1	5.8±0.1	0.13
S50-40	0.69	151.1±13.9	283.2±18.6	3.50±0.14	5.4±0.1	8.7±0.2	0.17
S30-20+F50	0.29	46.2±2.8	186.3±11.9	0.24±0.03	8.0±0.4	41.3±1.6	0.58
S30-30+F50	0.84	50.8±3.4	196.2±12.5	0.97±0.07	26.6±0.9	43.2±1.7	0.62
S30-40+F50	0.69	55.6±3.5	188.7±12.1	1.80±0.09	28.0±1.2	50.4±2.2	0.66
S40-20+F50	0.58	48.8±2.9	148.6±8.9	0.54±0.04	13.1±0.6	30.1±1.4	0.67
S40-30+F50	0.60	72.9±4.4	210.6±12.6	2.56±0.12	18.5±0.7	40.2±1.5	0.75
S40-40+F50	0.66	87.7±4.7	187.4±11.6	4.47±0.31	18.0±0.7	33.3±1.4	0.87
S50-20+F50	0.67	92.4±6.5	222.4±13.4	0.78±0.04	16.9±0.6	28.6±0.9	1.01
S50-30+F50	0.72	93.7±6.8	262.1±14.5	1.88±0.16	5.1±0.2	12.1±0.6	1.19
S50-40+F50	0.78	98.2±7.3	277.8±14.8	3.85±0.22	8.8±0.3	14.1±0.8	0.98

Sample	IEC^a/ (mmol·g^-1)	WU(%)		SR(%)	σ/(mS·cm^-1)		Mass loss^b(%)
Sample	IEC^a/ (mmol·g^-1)	30 ℃	80 ℃	30 ℃	30 ℃	90 ℃	Mass loss^b(%)
S30-20	0.21	64.1±5.0	198.4±12.6	0.20±0.01	5.0±0.2	16.2±0.4	0.20
S30-30	0.36	86.2±7.0	209.8±12.8	0.90±0.07	10.1±0.3	26.7±0.8	0
S30-40	0.42	91.3±11.3	205.9±11.8	1.70±0.07	16.0±0.5	32.1±1.4	0
S40-20	0.30	83.3±6.8	161.7±11.4	0.43±0.05	6.3±0.2	24.8±1.2	0.07
S40-30	0.41	116.6±12.5	226.5±13.5	1.22±0.09	9.9±0.2	37.0±1.6	0.15
S40-40	0.58	122.8±7.1	201.6±12.3	2.15±0.10	16.9±0.6	32.1±1.5	0.20
S50-20	0.32	102.8±8.3	244.8±15.4	0.58±0.06	7.7±0.3	19.2±0.6	0.05
S50-30	0.51	136.2±9.5	270.4±17.5	1.39±0.10	1.5±0.1	5.8±0.1	0.13
S50-40	0.69	151.1±13.9	283.2±18.6	3.50±0.14	5.4±0.1	8.7±0.2	0.17
S30-20+F50	0.29	46.2±2.8	186.3±11.9	0.24±0.03	8.0±0.4	41.3±1.6	0.58
S30-30+F50	0.84	50.8±3.4	196.2±12.5	0.97±0.07	26.6±0.9	43.2±1.7	0.62
S30-40+F50	0.69	55.6±3.5	188.7±12.1	1.80±0.09	28.0±1.2	50.4±2.2	0.66
S40-20+F50	0.58	48.8±2.9	148.6±8.9	0.54±0.04	13.1±0.6	30.1±1.4	0.67
S40-30+F50	0.60	72.9±4.4	210.6±12.6	2.56±0.12	18.5±0.7	40.2±1.5	0.75
S40-40+F50	0.66	87.7±4.7	187.4±11.6	4.47±0.31	18.0±0.7	33.3±1.4	0.87
S50-20+F50	0.67	92.4±6.5	222.4±13.4	0.78±0.04	16.9±0.6	28.6±0.9	1.01
S50-30+F50	0.72	93.7±6.8	262.1±14.5	1.88±0.16	5.1±0.2	12.1±0.6	1.19
S50-40+F50	0.78	98.2±7.3	277.8±14.8	3.85±0.22	8.8±0.3	14.1±0.8	0.98

Code	Mass loss(%)	IEC/(mmol·g^-1)		σ/(mS·cm^-1)(30 ℃)
Code	Mass loss(%)	0 h	24 h	0 h	24 h
S30-20+F50	6.3	0.29	0.21	18.0±0.5	16.7±0.5
S30-30+F50	7.5	0.84	0.39	26.6±0.9	20.4±0.8
S30-40+F50	8.2	0.69	0.47	28.0±1.2	25.6±0.9
S40-20+F50	3.2	0.58	0.35	13.1±0.4	11.1±0.6
S40-30+F50	5.4	0.60	0.33	18.5±0.7	16.8±0.8
S40-40+F50	21.5	0.66	0.58	18.0±0.9	10.7±0.5
S50-20+F50	10.6	0.67	0.30	16.9±0.8	9.2±0.4
S50-30+F50	8.9	0.72	0.46	6.8±0.5	5.2±0.3
S50-40+F50	17.8	0.78	0.62	8.8±0.6	8.1±0.3

Code	Mass loss(%)	IEC/(mmol·g^-1)		σ/(mS·cm^-1)(30 ℃)
Code	Mass loss(%)	0 h	24 h	0 h	24 h
S30-20+F50	6.3	0.29	0.21	18.0±0.5	16.7±0.5
S30-30+F50	7.5	0.84	0.39	26.6±0.9	20.4±0.8
S30-40+F50	8.2	0.69	0.47	28.0±1.2	25.6±0.9
S40-20+F50	3.2	0.58	0.35	13.1±0.4	11.1±0.6
S40-30+F50	5.4	0.60	0.33	18.5±0.7	16.8±0.8
S40-40+F50	21.5	0.66	0.58	18.0±0.9	10.7±0.5
S50-20+F50	10.6	0.67	0.30	16.9±0.8	9.2±0.4
S50-30+F50	8.9	0.72	0.46	6.8±0.5	5.2±0.3
S50-40+F50	17.8	0.78	0.62	8.8±0.6	8.1±0.3

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