PVDF增强咪唑功能化聚芳醚酮膜的制备与研究
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摘要
研究了一种新型耐高温聚合物电解质膜的制备方法.以聚偏氟乙烯(PVDF)为增强材料,以甲基咪唑功能化聚芳醚酮(MeIm-PAEK)为基体材料,通过两者共混制备了具有较高电导率和良好尺寸稳定性的膜材料,并研究膜材料组分对膜材料性能的影响.1H NMR证实了咪唑基团的接枝成功.磷酸掺杂实验表明:甲基咪唑的功能化,使MeIm-PAEK膜具备较强的吸附磷酸能力;随着咪唑基团接枝度的增加,MeImPAEK膜的磷酸掺杂含量显著增加.通过与PVDF复合,显著地改善MeIm-PAEK膜在高温下、高浓度磷酸掺杂后的尺寸稳定性. 70MeIm-PAEK/PVDF复合膜经85%磷酸溶液掺杂后,膜材料的磷酸掺杂质量分数为226%,体积溶胀率为248%,180℃不加湿条件下的电导率为0. 141 S/cm,适合做高温聚合物电解质膜材料.
Novel polymer electrolyte membranes of thermostability with superior conductivity and improved dimensional stability have been proposed based on poly(vinylidene fluoride)(PVDF)blended with methylimidazolium poly(aryl ether ketone)(MeIm-PAEK). The relationship between the properties and chemical components of membranes has been investigated.1 H NMR spectra have confirmed the successful reaction of the imidazole function. Acid doping measurement indicates that grafting imidazole groups into PAEK makes the PAEK absorb phosphoric acid and the acid doping content increase with the increase of imidazole groups 'grafting degree. The dimensional stability of MeIm-PAEK membranes in the concentrated phosphoric acid solution under elevated temperatures can be improved by blending PVDF. The70 MeIm-PAEK/PVDF membrane achieves an acid doping content of 226% and volume swelling of 248% after being immersed in the 85% phosphoric acid solution. This acid doped membrane exhibits a conductivity as high as 0. 141 S/cm at 180 ℃ without humidifying.
Novel polymer electrolyte membranes of thermostability with superior conductivity and improved dimensional stability have been proposed based on poly(vinylidene fluoride)(PVDF)blended with methylimidazolium poly(aryl ether ketone)(MeIm-PAEK). The relationship between the properties and chemical components of membranes has been investigated.1 H NMR spectra have confirmed the successful reaction of the imidazole function. Acid doping measurement indicates that grafting imidazole groups into PAEK makes the PAEK absorb phosphoric acid and the acid doping content increase with the increase of imidazole groups 'grafting degree. The dimensional stability of MeIm-PAEK membranes in the concentrated phosphoric acid solution under elevated temperatures can be improved by blending PVDF. The70 MeIm-PAEK/PVDF membrane achieves an acid doping content of 226% and volume swelling of 248% after being immersed in the 85% phosphoric acid solution. This acid doped membrane exhibits a conductivity as high as 0. 141 S/cm at 180 ℃ without humidifying.
引文
[1] Li Q,Jensena J O,Savinell R F,et al. High temperature proton exchange membranes based on polybenzimidazoles for fuel cells[J]. Progress in Polymer Science,2009,34(5):449-477.
[2] Aili D,Zhang J,Jakobsen M T D,et al. Exceptional durability enhancement of PA/PBI based polymer electrolyte membrane fuel cells for high temperature operation at 200oC[J]. Journal of Materials Chemistry A,2016,4(11):4019-4024.
[3] Quartarone E,Mustarelli P. Polymer fuel cells based on polybenzimidazole/H3PO4[J]. Energy&Environmental Science,2012,5(4):6436-6444.
[4]杨景帅,李雪源,徐一鑫,等.循环伏安法测定聚苯并咪唑膜电解质甲醇透过率[J].东北大学学报(自然科学版),2015,36(5):757-760.(Yang Jing-shuai, Li Xue-yuan, Xu Yi-xin, et al.M easurement of the methanol permeability of polybenzimidazole membrane electrolytes w ith cyclic voltammetry[J]. Journal of Northeastern University(Natural Science),2015,36(5):757-760.)
[5] Yang J S,Gao L P,Wang J,et al. Strengthening phosphoric acid doped polybenzimidazole membranes w ith siloxane netw orks for using as high temperature proton exchange membranes[J]. Macromolecular Chemistry and Physics,2017,218(10):1700009.
[6] Ma W,Zhao C,Yang J,et al. Cross-linked aromatic cationic polymer electrolytes w ith enhanced stability for high temperature fuel cell applications[J]. Energy&Environmental Science,2012,5(6):7617-7625.
[7] Yang J S,Li Q F,Jensen J O,et al. Phosphoric acid doped imidazolium polysulfone membranes for high temperature proton exchange membrane fuel cells[J]. Journal of Power Sources,2012,205:114-121.
[8] Ma Y L,Wainright J S,Litt M H,et al. Conductivity of PBI membranes for high-temperature polymer electrolyte fuel cells[J]. Journal of The Electrochemical Society,2004,151(1):A8-A16.
[9] Yang J S,Aili D,Li Q F,et al. Benzimidazole grafted polybenzimidazoles for proton exchange membrane fuel cells[J]. Polymer Chemistry,2013,4(17):4768-4775.
[10] Guo Z,Xu X,Xiang Y,et al. New anhydrous proton exchange membranes for high-temperature fuel cells based on PVDF-PVP blended polymers[J]. Journal of Materials Chemistry A,2015,3(1):148-155.
[2] Aili D,Zhang J,Jakobsen M T D,et al. Exceptional durability enhancement of PA/PBI based polymer electrolyte membrane fuel cells for high temperature operation at 200oC[J]. Journal of Materials Chemistry A,2016,4(11):4019-4024.
[3] Quartarone E,Mustarelli P. Polymer fuel cells based on polybenzimidazole/H3PO4[J]. Energy&Environmental Science,2012,5(4):6436-6444.
[4]杨景帅,李雪源,徐一鑫,等.循环伏安法测定聚苯并咪唑膜电解质甲醇透过率[J].东北大学学报(自然科学版),2015,36(5):757-760.(Yang Jing-shuai, Li Xue-yuan, Xu Yi-xin, et al.M easurement of the methanol permeability of polybenzimidazole membrane electrolytes w ith cyclic voltammetry[J]. Journal of Northeastern University(Natural Science),2015,36(5):757-760.)
[5] Yang J S,Gao L P,Wang J,et al. Strengthening phosphoric acid doped polybenzimidazole membranes w ith siloxane netw orks for using as high temperature proton exchange membranes[J]. Macromolecular Chemistry and Physics,2017,218(10):1700009.
[6] Ma W,Zhao C,Yang J,et al. Cross-linked aromatic cationic polymer electrolytes w ith enhanced stability for high temperature fuel cell applications[J]. Energy&Environmental Science,2012,5(6):7617-7625.
[7] Yang J S,Li Q F,Jensen J O,et al. Phosphoric acid doped imidazolium polysulfone membranes for high temperature proton exchange membrane fuel cells[J]. Journal of Power Sources,2012,205:114-121.
[8] Ma Y L,Wainright J S,Litt M H,et al. Conductivity of PBI membranes for high-temperature polymer electrolyte fuel cells[J]. Journal of The Electrochemical Society,2004,151(1):A8-A16.
[9] Yang J S,Aili D,Li Q F,et al. Benzimidazole grafted polybenzimidazoles for proton exchange membrane fuel cells[J]. Polymer Chemistry,2013,4(17):4768-4775.
[10] Guo Z,Xu X,Xiang Y,et al. New anhydrous proton exchange membranes for high-temperature fuel cells based on PVDF-PVP blended polymers[J]. Journal of Materials Chemistry A,2015,3(1):148-155.