磺化聚醚醚酮/石墨烯类流体复合质子交换膜的制备及性能
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摘要
采用离子交换法制备了有机含量高达80%且无褶皱的石墨烯类流体(SF-GF)。将SF-GF加入到磺化聚醚醚酮(SPEEK)基体中,通过溶液浇铸法制备了磺化聚醚醚酮/石墨烯类流体(SPEEK/SF-GF)有机-无机复合质子交换膜,并对其尺寸稳定性、氧化稳定性、力学性能、质子传导率及微观形貌进行了测试与表征。结果表明,2%的SF-GF能够均匀地分散在SPEEK基体中,且与基体界面黏接较强,复合质子交换膜的尺寸稳定性、氧化稳定性、力学性能都有较大的提升,同时在80℃时2%SF-GF添加量的SPEEK/SF-GF复合膜质子传导率达到0.18 S/cm,复合膜表现出较好的综合性能。
In this paper, the unfolded solvent-free grapheme fluids(SF-GF) with the organic content as high as 80% were prepared by the ion exchange method. The as-prepared SF-GF was incorporated into the sulfonated poly(ether ether ketone)(SPEEK) matrix to prepare sulfonated poly(ether ether ketone)/solvent-free grapheme fluids(SPEEK/SF-GF) composite membranes through the solution casting method. The dimensional stability, oxidation stability, mechanical properties, proton conductivity and microstructure of the SPEEK/SF-GF composite membranes were measured. The results show that the 2% content of SF-GF could uniformly disperse in the SPEEK matrix and enhance the interface adhesion between GC-GF and SPEEK, which lead to the improvement in the dimensional stability, oxidation stability and mechanical properties of the SPEEK/SF-GF composite membranes. Moreover, the proton conductivity of the SPEEK/SF-GF composite membrane with 2% SF-GF loading reaches to the maximum value of 0.18 S/cm at 80 ℃, the SPEEK/SF-GF composite membranes exhibit a favorable comprehensive performance.
In this paper, the unfolded solvent-free grapheme fluids(SF-GF) with the organic content as high as 80% were prepared by the ion exchange method. The as-prepared SF-GF was incorporated into the sulfonated poly(ether ether ketone)(SPEEK) matrix to prepare sulfonated poly(ether ether ketone)/solvent-free grapheme fluids(SPEEK/SF-GF) composite membranes through the solution casting method. The dimensional stability, oxidation stability, mechanical properties, proton conductivity and microstructure of the SPEEK/SF-GF composite membranes were measured. The results show that the 2% content of SF-GF could uniformly disperse in the SPEEK matrix and enhance the interface adhesion between GC-GF and SPEEK, which lead to the improvement in the dimensional stability, oxidation stability and mechanical properties of the SPEEK/SF-GF composite membranes. Moreover, the proton conductivity of the SPEEK/SF-GF composite membrane with 2% SF-GF loading reaches to the maximum value of 0.18 S/cm at 80 ℃, the SPEEK/SF-GF composite membranes exhibit a favorable comprehensive performance.
引文
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[3] Cai H L,Shao K,Zhong S L,et al.Properties of composite membranes based on sulfonated poly(ether ether ketone)s (SPEEK)/phenoxy resin (PHR) for direct methanol fuel cells[J].J.Membr.Sci.,2007,297:162-173.
[4] Mohtar S S,Ismail A F,Matsuura T.Preparation and characterization of SPEEK/MMT-STA composite membrane for DMFC application[J].J.Membr.Sci.,2011,371:10-19.
[5] Iulianelli A,Basile A.Sulfonated PEEK-based polymers in PEMFC and DMFC applications:a review[J].Int.J.Hydrogen Energy,2012,37:15241-15255.
[6] 薛艳红,傅荣强,徐铜文.磺化聚醚醚酮与壳聚糖共混制备直接甲醇燃料电池用质子交换膜[J].高分子学报,2010(3):285-291.Xue Y H,Fu R Q,Xu T W.Preparation of SPEEK and SPEEK/chitosan composite proton exchange membranes for application in direct methanol fuel cells[J].Acta Polymerica Sinica,2010(3):285-291.
[7] 蔡雨泉,黄绵延,王宇新,等.DMFC用磺化聚醚醚酮/聚苯胺共混型质子交换膜的研究[J].高分子材料科学与工程,2007,23(1):246-249.Cai Y Q,Huang M Y,Wang Y X,et al.Sulfonated polyether ether ketone/polyaniline membranes for direct methanol fuel cells[J].Polymer Materials Science & Engineering,2007,23(1):246-249.
[8] 张高文,周震涛.SPEEK/SiO2复合型质子交换膜的结构与性能[J].高分子材料科学与工程,2007,23(2):124-127.Zhang G W,Zhou Z T.Structure and property of SPEEK/SiO2 composite proton exchange membranes[J].Polymer Materials Science and Engineering,2007,23(2):124-127.
[9] 张耀霞,朱秀玲,蹇锡高.磺化聚芳醚酮酮的制备及磷酸硼复合膜的性能[J].材料研究学报,2009,23(2):215-219.Zhang Y X,Zhu X L,Jian X G.Preparation of sulfonated poly(phthalazinone ether ketone ketone) and properties of the composite membranes SPPEKK/BPO4[J].Chinese Journal of Materials Research,2009,23(2):215-219.
[10] Hasani-Sadrabadi M M,Dashtimoghadam E,Sarikhani K,et al.Electrochemical investigation of sulfonated poly(ether ether ketone)/clay nanocomposite membranes for moderate temperature fuel cell applications[J].J.Power Sources,2010,195:2450-2456.
[11] 谢卫刚,赵东林,景磊,等.石墨烯/环氧树脂复合材料的制备与力学性能[J].高分子材料科学与工程,2012,28(9):129-132.Xie W G,Zhao D L,Jing L,et al.Preparation and mechanical properties of graphene reinforced epoxy resin matrix composites[J].Polymer Materials Science & Engineering,2012,28(9):129-132.
[12] Robert J Y,Ian A K,Lei G,et al.The mechanics of graphene nanocomposites:a review[J].Compos.Sci.Technol.,2012,12:1459-1476.
[13] Gong C L,Zheng X,Liu H,et al.A new strategy for designing high-performance sulfonated poly(ether ether ketone) polymer electrolyte membranes using inorganic proton conductor-functionalized carbon nanotubes[J].J.Power Sources,2016,325:453-64.