SPES/SiO_2杂化纳米纤维复合质子交换膜的制备与性能
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摘要
提出了一种利用杂化纳米纤维来制备高性能质子交换膜的方法,首先采用溶液喷射纺丝技术纺制了SPES/Si O2杂化纳米纤维,再通过溶液浸渍法制备了SPES/Si O2/Nafion复合质子交换膜,并研究了其热稳定性、吸水性能、溶胀性能、质子传导性能以及甲醇渗透性能等.结果表明,杂化纳米纤维的引入明显改善了Nafion膜的热性能、尺寸稳定性,并大大提高了其质子传导性能.TG数据表明复合膜的热稳定性相比于Nafion膜得到了极大改善.复合膜溶胀率均比Nafion膜的小,SPES/Si O2/Nafion-5,SPES/Si O2/Nafion-15和SPES/Si O2/Nafion-25在80℃溶胀率仅为14.9%,15.84%和17.2%,但是复合膜的溶胀率随着Si O2含量的增加而增大.复合膜电导率随Si O2含量的增加呈先增大后减小的规律,Si O2含量为15%的复合膜在80℃、100%湿度条件下,质子导电率可达到0.154 S/cm.其阻醇性能也得到了极大改善,Si O2含量为25%的复合膜相比于Nafion膜其甲醇渗透率降低了55.3%.因此SPES/Si O2杂化纳米纤维复合质子交换膜可以作为一种新型质子交换膜应用于燃料电池中.
Sulfonated poly( ether sulfone)( SPES) / Silica( Si O2) nanofibers were prepared by solution blowing process,and impregnated to Nafion matrix to prepare SPES / Si O2/ Nafion composite proton exchange membranes( PEMs). The characteristics of the composite membrane,such as morphology,thermal stability,proton conductivity and performance of membrane as PEMs,were investigated. The results showed that the introduction of solution-blown nanofibers to composite membranes significantly improved properties of Nafion.The TG results showed all the composite membranes had better thermal stability than pure Nafion. Swelling ratios of all the composite membranes were lower than that of pure Nafion,and those of SPES / Si O2/ Nafion-5,SPES / Si O2/ Nafion-15 and SPES / Si O2/ Nafion-25 were 14. 9%,15. 84% and 17. 2% at 80 ℃,respectively.However,the swelling ratios of composite membranes increased with the increase of Si O2 content in nanofiber.Proton conductivity of the composite membranes increased first and then decreased with the increase of Si O2 content,and the membrane containing 15% Si O2 could get 0. 154 S / cm at 80 ℃ and 100% humidity. Besides,the methanol resistance was also greatly improved,methanol permeability of the composite membrane containing 25% Si O2 decreased by 55. 3% compared to that of Nafion. Therefore,the composite membrane containing hybrid SPES / Si O2 nanofibers can be considered as a promising PEM for fuel cell applications.
Sulfonated poly( ether sulfone)( SPES) / Silica( Si O2) nanofibers were prepared by solution blowing process,and impregnated to Nafion matrix to prepare SPES / Si O2/ Nafion composite proton exchange membranes( PEMs). The characteristics of the composite membrane,such as morphology,thermal stability,proton conductivity and performance of membrane as PEMs,were investigated. The results showed that the introduction of solution-blown nanofibers to composite membranes significantly improved properties of Nafion.The TG results showed all the composite membranes had better thermal stability than pure Nafion. Swelling ratios of all the composite membranes were lower than that of pure Nafion,and those of SPES / Si O2/ Nafion-5,SPES / Si O2/ Nafion-15 and SPES / Si O2/ Nafion-25 were 14. 9%,15. 84% and 17. 2% at 80 ℃,respectively.However,the swelling ratios of composite membranes increased with the increase of Si O2 content in nanofiber.Proton conductivity of the composite membranes increased first and then decreased with the increase of Si O2 content,and the membrane containing 15% Si O2 could get 0. 154 S / cm at 80 ℃ and 100% humidity. Besides,the methanol resistance was also greatly improved,methanol permeability of the composite membrane containing 25% Si O2 decreased by 55. 3% compared to that of Nafion. Therefore,the composite membrane containing hybrid SPES / Si O2 nanofibers can be considered as a promising PEM for fuel cell applications.
引文
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15 Gao Qijun(高启君),Wang Yuxin(王宇新),Lv Xiaolong(吕晓龙).Acta Polymerica Sinica(高分子学报),2012,(6):640~647
16 Luo Jujie(罗居杰),Wang Shuanjin(王拴紧),Xiao Min(肖敏),Han Dongmei(韩东梅),Meng Yuezhong(孟跃中).Polymer Materials Science And Engineering(高分子材料科学与工程),2011,(4):117~120
17 Fang Yong(方勇),Miao Ruiying(苗睿瑛),Wang Tongtao(王同涛),Wang Xindong(王新东),Fang Shibi(方世璧).Acta Polymerica Sinica(高分子学报),2009,(10):992~1006
18 Jiang Shudong(蒋淑冬),Liao Shiqin(廖师琴),Wei Qufu(魏取福),Huang Fenglin(黄锋林),Ma Zhen(马震),Huang Bin(黄彬).New Chemical Materials(化工新型材料),2011,(10):48~50+137
2 Takemori R,Kawakami H.J Power Sources,2010,195(18):5957~5961
3 Divona M.,Ahmed Z,Bejjitto S,Lenci A,Traversa E,Licoccia S.J Membrane Sci,2007.296(1-2):156~161
4 Wen S,Gong C,Tsen W,Shu Y C,Tsai F C.Int J Hydrogen Energy,2009,34(21):8982~8991
5 Lee J R,Kim N Y,Lee M S,Lee S Y.J Membrane Sci,2011.367(1-2):265~272
6 Li H,Liu Y.J Mater Chem A,2014,2(11):3783~3793
7 Wang L,Advani S G,Prasad A K.Electrochim Acta.2013,105:530~534
8 Xu X L,Li L,Wang H,Li X J,Zhuang X P.RSC Adv,2015,5(7):4934~4940
9 Zhuang X P,Yang X C,Shi L,Cheng B W,Guan K T,Kang W M.Carbohyd Polym,2012,90(2):982~987
10 Lee C M,Jo S M,Choi J H,Baek K Y,Truong Y B,Kyratzis I L,Shul Y G.J Mater Sci,2013,48(10):3665~3671
11 NAM S E,Kim S O,Kang Y K,Lee J W,Lee K H.J Membrane Sci,2008,322:466~474
12 ZHANG J,Zhou Z.J Power Sources,2007,31:721~724
13 Zhang Chunxue(张春雪),Yuan Xiaoyan(袁晓燕),Wu Lili(邬丽丽),Sheng Jing(盛京).Acta Polymerica Sinica(高分子学报),2006,(2):294~297
14 Ke C C,Li X J,Shen Q,Qu S G,Shao Z G,Yi B L.Int J Hydrogen Energy,2011,36(5):3606~3613
15 Gao Qijun(高启君),Wang Yuxin(王宇新),Lv Xiaolong(吕晓龙).Acta Polymerica Sinica(高分子学报),2012,(6):640~647
16 Luo Jujie(罗居杰),Wang Shuanjin(王拴紧),Xiao Min(肖敏),Han Dongmei(韩东梅),Meng Yuezhong(孟跃中).Polymer Materials Science And Engineering(高分子材料科学与工程),2011,(4):117~120
17 Fang Yong(方勇),Miao Ruiying(苗睿瑛),Wang Tongtao(王同涛),Wang Xindong(王新东),Fang Shibi(方世璧).Acta Polymerica Sinica(高分子学报),2009,(10):992~1006
18 Jiang Shudong(蒋淑冬),Liao Shiqin(廖师琴),Wei Qufu(魏取福),Huang Fenglin(黄锋林),Ma Zhen(马震),Huang Bin(黄彬).New Chemical Materials(化工新型材料),2011,(10):48~50+137