Proton Exchange Membrane Based on the Star Shaped Block Copolymer with Well Connected Ionic Domain and Conductivity

doi:10.11901/1005.3093.2014.495

Chinese Journal of Materials Research

2015, Vol. 29

Issue (5): 337-345 DOI: 10.11901/1005.3093.2014.495

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Proton Exchange Membrane Based on the Star Shaped Block Copolymer with Well Connected Ionic Domain and Conductivity

Jie ZHANG,Fang CHEN(

),Xiaoyan MA(

),Beirong SHANG,Kun SUN

The Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education and the Key Laboratory of Polymer Science and Technology, School of Natural and Applied Science, Northwestern Polytechnical University, 710129, Xi’an, China

Cite this article:

Jie ZHANG,Fang CHEN,Xiaoyan MA,Beirong SHANG,Kun SUN. Proton Exchange Membrane Based on the Star Shaped Block Copolymer with Well Connected Ionic Domain and Conductivity. Chinese Journal of Materials Research, 2015, 29(5): 337-345.

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Abstract

Star shaped block copolymer POSS-(PMMA-b-PS)₈ was synthesized by a two step process of atom transfer radical polymerization (ATRP) with eight functionalized polyhedral oligomeric silisesquioxane POSS-(Cl)₈ as core and poly(methyl methacrylate-b-polystyrene) as arm. The POSS-(PMMA-b-PS)₈was then sulfonation treated to produce hybrid polymer POSS-(PMMA-b-SPS)₈, which was finally used as the polymer matrix for making proton exchange membranes (PEMs). The examination of conductivity as function of relative humidity for PEMs of high and low hydration status respectively indicated that with longer SPS block length exhibited higher proton conductivity for the PEMs of low hydration status with the same λ i.e. the number of water molecular coupled to sulfonic acid groups. TGA analysis showed that two kinds of PEM all exhibited higher water retention capacity and higher initial decomposition temperature. A well-connected ionic domains in PEM with longer SPS block could be observed by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The features of molecules motion of chain segments and spins relaxation time T₂ for the PEMs of low hydration status were analyzed by low field nuclear magnetic resonance, and it is found that the well connected ionic domains could be observed also in the PEMs with longer SPS block, which exhibited higher proton spin-diffusion coefficient, therewith higher proton conductivity by low relative humidity.

Key words: organic polymer materials PEM ATRP star shaped block copolymer POSS microstructure

Received: 13 September 2014

Fund: *Supported by National Natural Science Foundation of China No. 51103117, National Natural Science Foundation of Shaanxi Province Nos. 2013JQ2010 & 2013JM2012, NPU Fundamental Research Foundation No. 3102014JCQ01089.

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	Jie ZHANG
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	Xiaoyan MA
	Beirong SHANG
	Kun SUN

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https://www.cjmr.org/EN/10.11901/1005.3093.2014.495 OR https://www.cjmr.org/EN/Y2015/V29/I5/337

Fig.1 Synthesis scheme of POSS-(PMMA_m-b-SPS_n)₈

Fig.2 ¹H NMR spectra of POSS-(PMMA_m-b-PS_n)₈^a and POSS-(PMMA_m-b-PS_n)₈^b

Fig.3 GPC of POSS-(PMMA_m-b-PS_n)₈

Table 1 Molecular weight, distribution of molecular weight and ion exchange capacity for PEMs

Fig.4 Relationship between λ of membrane and humidity at 30℃

Fig.5 Relationship between proton conductivity(σ) of membrane and humidity in 30℃

Fig.6 Relationship between proton conductivity (σ) of POSS-(PMMA_m-b-SPS_n)₈ and hydrated number (λ)

Fig.7 TGA curves of water retention and thermal stability of PEMs (a) TGA curves of hydrated state PEM from room temperature to 160℃; (b) thermal decomposition of performance of hydration PEMs after all as shown in Fig.7 (a) heated and colded to room temperature

Fig.8 TEM ofPOSS-(PMMA₂₆-b-SPS₁₅₆)₈ (a) and POSS-(PMMA₁₆-b-SPS₂₀₀)₈ (b)

Fig.9 AFM of POSS-(PMMA₂₆-b-SPS₁₅₆)₈(a) and POSS-(PMMA₁₆-b-SPS₂₀₀)₈ (b)

Fig.10 Dotted line represents FIDs of two PEMs and solid line represent two-exponentially decaying fitting

Table 2 Relaxation time (T₂) of different phases of PEM and spin-diffusion coefficients (D(T_2r)) for rigid phase (SPS)

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