磺化聚醚砜/二硫化钼复合膜在甲醇燃料电池中的应用
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摘要
在甲醇燃料电池应用中,磺化聚醚砜(SPES)质子膜高的磺化度不仅会带来高质子传导率,更容易带来严重的甲醇渗透问题与溶胀问题。针对这一矛盾,本文将片状的二硫化钼(MoS_2)与SPES共混,制备了一系列不同MoS_2含量的SPES/MoS_2复合膜。红外光谱测试表征了复合膜的结构,结果表明复合膜已成功制备,且MoS_2的添加未引起聚合物结构的变化。热失重曲线表明复合膜在300℃仍能保持稳定,完全可以满足使用要求。在力学性能测试中,当MoS_2添加量为SPES质量的4%时,复合膜的拉伸强度提高了20%,尺寸稳定性提高了33.7%。添加的MoS_2提高了复合膜的阻醇性能,使质子选择性比Nafion 117提高了4倍。
In the application of methanol fuel cell, the high sulfonation degree of sulfonated polyethersulfone(SPES) proton membrane will not only bring about high proton conductivity, but also lead to serious methanol permeability and swelling problems. In view of this contradiction, by blending sheet-like molybdenum disulfide(MoS_2) with SPES, a series of SPES/MoS_2 composite membranes with different MoS_2 contents were prepared. The structure of the composite membranes was characterized by infrared spectroscopy. The results show that SPES was successfully prepared. The thermogravimetric curves show that the composite film can remain stable at 300 ℃ and can fully meet the requirements of application. In the mechanical properties test, when the MoS_2 content is 4% of the SPES mass, the tensile strength and dimensional stability of the composite film are increased by 20% and 33.7%, respectively. The addition of MoS_2 improves the methanol resistance of the composite membranes and makes the proton selectivity four times higher than that of Nafion 117.
In the application of methanol fuel cell, the high sulfonation degree of sulfonated polyethersulfone(SPES) proton membrane will not only bring about high proton conductivity, but also lead to serious methanol permeability and swelling problems. In view of this contradiction, by blending sheet-like molybdenum disulfide(MoS_2) with SPES, a series of SPES/MoS_2 composite membranes with different MoS_2 contents were prepared. The structure of the composite membranes was characterized by infrared spectroscopy. The results show that SPES was successfully prepared. The thermogravimetric curves show that the composite film can remain stable at 300 ℃ and can fully meet the requirements of application. In the mechanical properties test, when the MoS_2 content is 4% of the SPES mass, the tensile strength and dimensional stability of the composite film are increased by 20% and 33.7%, respectively. The addition of MoS_2 improves the methanol resistance of the composite membranes and makes the proton selectivity four times higher than that of Nafion 117.
引文
[1] Hickner M,Ghassemi H,Kim Y,et al.Alternative polymer systems for proton exchange membranes (PEMs) [J].Chem.Rev.,2004,104:4587-4612.
[2] Rikukawa M,Sanui K.Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers [J].Prog.Polym.Sci.,2000,25:1463-1502.
[3] 王哲,吕鑫,隋秀鹏,等.磺化聚芳醚酮砜/PVA复合质子交换膜的制备与性能[J].高分子材料科学与工程,2012,28(10):141-144.Wang Z,Lü X,Sui X P,et al.Sulfonated poly(arylene ether ketone sulfone)/PVA composite proton exchange membranes [J].Polymer Materials Science & Engineering,2012,28(10):141-144.
[4] Gu S,He G H,Wu X M,et al.Preparation and characteristics of crosslinked sulfonated poly(phthalazinone ether sulfone ketone) with poly(vinyl alcohol) for proton exchange membrane [J].J.Membr.Sci.,2008,312:48-58.
[5] Feng K,Tang B B,Wu P Y.Selective growth of MoS2 for proton exchange membranes with extremely high selectivity [J].Appl.Mater.Interfaces,2013,5:13042-13049.
[6] 项昭保,霍丹群,候长军,等.聚醚砜的磺化改性[J].重庆大学学报,2002,25(10):117-120.Xiang S B,Huo D Q,Huo C J,et al.Sulfonation of polyethersulfone for modification [J].Journal of Chongqing University,2002,25(10):117-120.
[7] 宁永成.有机化合物结构鉴定与有机波谱学[M].北京:科学出版社,2000:495-497.
[8] 辛勤,熊光,高兴涛,等.Mo/Al2O3催化剂中钼配位结构的原位红外和拉曼光谱表征[J].光散射学报,1998(Z1):132-134.Xin Q,Xiong G,Gao X T,et al.In-situ infrared and Raman spectroscopic characterization of molybdenum coordination structure in Mo/Al2O3 catalysts [J].The Journal of Light Scattering,1998(Z1):132-134.
[9] Li J C,Zhang Y P,Zhang S,et al.Sulfonated polyimide/s-MoS2 composite membrane with high proton selectivity and good stability for vanadium redox flow battery [J].J.Membr.Sci.,2015,490:179-189.
[10] Peng S G,Niu Y P,Fan X J,et al.Enhancement of mechanical and tribological properties in ring-opening metathesis polymerization functionalized molybdenum disulfide/polydicyclopentadiene nanocomposites [J].J.Appl.Polym.Sci.,2013,129:1045-1052.
[11] Zhou K Q,Jiang S H,Bao C L,et al.Preparation of poly(vinyl alcohol) nanocomposites with molybdenum disulfide (MoS2):structural characteristics and markedly enhanced properties [J].RSC Adv.,2012,2:11695-11703.
[12] Tsenga C Y,Yea Y S,Josepha J,et al.Tuning transport properties by manipulating the phase segregation of tetramethyldisiloxane segments in modified polyimide electrolytes [J].J.Power Sources,2011,196:3470-3478.
[2] Rikukawa M,Sanui K.Proton-conducting polymer electrolyte membranes based on hydrocarbon polymers [J].Prog.Polym.Sci.,2000,25:1463-1502.
[3] 王哲,吕鑫,隋秀鹏,等.磺化聚芳醚酮砜/PVA复合质子交换膜的制备与性能[J].高分子材料科学与工程,2012,28(10):141-144.Wang Z,Lü X,Sui X P,et al.Sulfonated poly(arylene ether ketone sulfone)/PVA composite proton exchange membranes [J].Polymer Materials Science & Engineering,2012,28(10):141-144.
[4] Gu S,He G H,Wu X M,et al.Preparation and characteristics of crosslinked sulfonated poly(phthalazinone ether sulfone ketone) with poly(vinyl alcohol) for proton exchange membrane [J].J.Membr.Sci.,2008,312:48-58.
[5] Feng K,Tang B B,Wu P Y.Selective growth of MoS2 for proton exchange membranes with extremely high selectivity [J].Appl.Mater.Interfaces,2013,5:13042-13049.
[6] 项昭保,霍丹群,候长军,等.聚醚砜的磺化改性[J].重庆大学学报,2002,25(10):117-120.Xiang S B,Huo D Q,Huo C J,et al.Sulfonation of polyethersulfone for modification [J].Journal of Chongqing University,2002,25(10):117-120.
[7] 宁永成.有机化合物结构鉴定与有机波谱学[M].北京:科学出版社,2000:495-497.
[8] 辛勤,熊光,高兴涛,等.Mo/Al2O3催化剂中钼配位结构的原位红外和拉曼光谱表征[J].光散射学报,1998(Z1):132-134.Xin Q,Xiong G,Gao X T,et al.In-situ infrared and Raman spectroscopic characterization of molybdenum coordination structure in Mo/Al2O3 catalysts [J].The Journal of Light Scattering,1998(Z1):132-134.
[9] Li J C,Zhang Y P,Zhang S,et al.Sulfonated polyimide/s-MoS2 composite membrane with high proton selectivity and good stability for vanadium redox flow battery [J].J.Membr.Sci.,2015,490:179-189.
[10] Peng S G,Niu Y P,Fan X J,et al.Enhancement of mechanical and tribological properties in ring-opening metathesis polymerization functionalized molybdenum disulfide/polydicyclopentadiene nanocomposites [J].J.Appl.Polym.Sci.,2013,129:1045-1052.
[11] Zhou K Q,Jiang S H,Bao C L,et al.Preparation of poly(vinyl alcohol) nanocomposites with molybdenum disulfide (MoS2):structural characteristics and markedly enhanced properties [J].RSC Adv.,2012,2:11695-11703.
[12] Tsenga C Y,Yea Y S,Josepha J,et al.Tuning transport properties by manipulating the phase segregation of tetramethyldisiloxane segments in modified polyimide electrolytes [J].J.Power Sources,2011,196:3470-3478.
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