Preparation， Structure and Properties of Crystalline Homo-Polystyrene/Hydrogenated Poly（styrene-b-butadiene-b-styrene） Anion Exchange Membrane

doi:10.19894/j.issn.1000-0518.230005

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (6): 833-844.DOI: 10.19894/j.issn.1000-0518.230005

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Preparation， Structure and Properties of Crystalline Homo-Polystyrene/Hydrogenated Poly（styrene-b-butadiene-b-styrene） Anion Exchange Membrane

Fu-Lin WANG, Zhong-Fu ZHAO(), Yi-Ming LIANG, Jian-En HUANG, Chun-Qing ZHANG()

State Key Laboratory of Fine Chemicals，School of Chemical Engineering，Dalian University of Technology，Dalian 116024，Chain

Received:2023-01-09 Accepted:2023-04-06 Published:2023-06-01 Online:2023-06-27
Contact: Zhong-Fu ZHAO,Chun-Qing ZHANG
About author:zhangcq@dlut.edu.cn
zfzhao@dlut.edu.cn；

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Abstract

Abstract:

Composite anion exchange membranes （AEMs） supported by crystalline poly（ethylene-co-butadiene） phase are prepared from low molecular mass homo-polystyrene （hPS） and hydrogenated poly?（styrene-b-butadiene-b-styrene）（HSBS） by chloromethylation， quaternization and alkalization. The composition， structure and properties of the composite membranes are adjusted by the amount of hPS. The results show that with the increase of hPS content， the tensile strength decreases， the Young′s modulus increases significantly from 14.68 MPa to 69.35 MPa， water uptake （WU） increases from 17.9% to 54.3%， and swelling ratio （SR） increases only from 4.1% to 10.2%. With the support of HSBS crystal structure， the mechanical properties and dimensional stability of the system are better than other poly（styrene-b-（ethylene-co-butylene）-b-styrene）（SEBS） based AEMs. Meanwhile， the distance between AEMs′ crystalline micro regions increases， the ion transport channel broadens， the ion exchange capacity （IEC） increases from 0.82 mmol/g to 1.94 mmol/g， and the alkali resistance stability is enhanced. However， because the compatibility of hPS in HSBS is restricted by PS content， CHM-OH-8∶2 has the best ion transport performance （101.3 mS/cm@80 ℃）， which is much higher than SEBS system with the same PS content. Its open circuit voltage at 70 ℃ is 0.970 V， and the power density of 299 mW/cm² is achieved at a current density of 188 mA/cm².

Key words: Poly（styrene-b-butadiene-b-styrene）, Low molecular mass homo-polystyrene, Anion exchange membrane

CLC Number:

O632.1

Fu-Lin WANG, Zhong-Fu ZHAO, Yi-Ming LIANG, Jian-En HUANG, Chun-Qing ZHANG. Preparation， Structure and Properties of Crystalline Homo-Polystyrene/Hydrogenated Poly（styrene-b-butadiene-b-styrene） Anion Exchange Membrane[J]. Chinese Journal of Applied Chemistry, 2023, 40(6): 833-844.

Figures/Tables 12

Fig.1 Synthesis route of HSBS/hPS composite AEMs

Fig.2 （A） 1H NMR and （B） DSC spectra of SBS and HSBS

Fig.3 1H NMR spectra of hPS， CM-hPS （A）， and HSBS， CM-HSBS （B）

Fig.4 FT-IR spectra of hPS， CM-hPS， HSBS， CM-HSBS， CHM-Cl-6：4 （A）， and CHM-OH-x：y （B）

Fig.5 （A） SAXS curves of CHM-OH-x∶y（x∶y=10∶0， 8∶2， 6∶4）； AFM phase images of CHM-OH-10∶0（B），CHM-OH-8∶2（C）， and CHM-OH-6∶4 （D）

Table 1 Thermo and mechanical performances of AEMs

Membrane	w（PS） ^a /%	Δα₁/%	Δα₂/%	T_s/MPa	Elongation at break/%	Young's modulus/MPa
CHM-OH-10∶0	18.3	3.9	13.9	24.48	497.05	14.68
CHM-OH-9∶1	23.3	4.6	15.3	18.51	447.7	28.32
CHM-OH-8∶2	28.3	5.3	17.5	13.27	409.24	38.85
CHM-OH-7∶3	33.3	5.8	18.1	12.08	364.43	46.58
CHM-OH-6∶4	38.3	6.1	20.3	10.94	345.32	69.35

Fig.6 （A） TGA curves and （B） stress-strain relationship diagram of AEMs

Table 2 IEC， WU， SR and ionic conductivity of AEMs

Membranes	IEC ^a /（mmol·g^-1）	σ^b /（mS·cm^-1）	WU ^c /%	SR ^c /%	Ref.
CHM-OH-10∶0	0.82	80.6	10.1	2.9	This work
CHM-OH-9∶1	1.35	71.1	15.6	3.8	This work
CHM-OH-8∶2	1.79	101.3	17.9	4.1	This work
CHM-OH-7∶3	1.89	85.4	18.4	4.9	This work
CHM-OH-6∶4	1.94	68.6	25.8	5.4	This work
SEBS-PMAI	3.55	95.4	172.0	42.7	［2］
SEBS-C16D100	1.59	57.5	85.6	14.7	［20］
SEBSC6-Pip	0.48	57.7	31.0	12.1	［21］
xTQA50-PPO-SEBS	1.43	89.9	67.2	9.1	［28］
70C16-SEBS-TMHDA	1.65	72.1	40.7	6.8	［38］
SEBS-CH₂-QHQA-1.5	0.69	43.2	4.78	1.43	［39］

Fig.7 （A） WU and （B） SR of AEMs as a function of temperature

Fig.8 Ionic conductivity vs temperature curves （A）， and the linear fitting of ln σ and 1000/T （B） for the AEMs

Fig.9 Ionic conductivity remaining for AEMs after soaking in NaOH aqueous solution （2 mol/L） at 60 ℃ for various times

Fig.10 Polarization and power density curve （A） and high frequency resistance curve （B） of H2/O2 single cell assembled by CHM-OH-8∶2 at 70 ℃

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Preparation， Structure and Properties of Crystalline Homo-Polystyrene/Hydrogenated Poly（styrene-b-butadiene-b-styrene） Anion Exchange Membrane

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