低温燃料电池用聚(2,5-苯并咪唑)/磺化海泡石复合质子交换膜的制备与性能
|
摘要
采用原位法制备了一种适用于低温燃料电池的新型聚(2,5-苯并咪唑)/磺化海泡石(ABPBI/S-Sep)复合质子交换膜。对海泡石酸活化和磺化改性前后的化学结构、亲水性和分散性以及复合膜的形貌、吸水率、磷酸掺杂水平与质子传导率等性能进行了表征和测试。结果显示,所制备的S-Sep粒子在ABPBI聚合物基体中分散均匀,并能促进聚合物分子链的规整排布;与纯ABPBI膜相比,S-Sep粒子的添加显著增强了复合膜对水和磷酸的吸收和保留能力,且在相同或相近磷酸掺杂水平下,ABPBI/S-Sep复合膜的质子传导率显著提高。在40～90℃温度范围内,饱和湿度98%RH时复合膜的质子传导率与Nafion 212相当;在低湿度60%RH时,高磷酸掺杂水平的ABPBI/S-Sep复合膜质子传导率略低于98%RH的结果,但显著优于Nafion 212的质子传导性能。不同温湿度环境下的质子传导率结果表明S-Sep改性ABPBI复合膜具备低温环境使用的特点,可替代Nafion类全氟磺酸膜应用于低温质子交换膜燃料电池。
A novel poly(2,5-benzimidazole)/sulfonated sepiolite composite proton exchange membrane was prepared by in situ synthesis for application in low temperature fuel cells.The chemical structure,hydrophilicity and dispersibility of acid activated and sulfonated sepiolite as well as the morphology,water uptake,phosphoric acid doping level and proton conductivity of the composite membrane were characterized.The results show that sulfonated sepiolite(S-Sep)particles are dispersed uniformly in the ABPBI polymer matrix,and SSep particles can promote the regular arrangement of polymer molecular chains.The introduction of S-Sep particles into ABPBI matrix helps to significantly enhance the water and phosphoric acid absorption and retention abilities of the composite membrane compared to the virgin ABPBI membrane.With the same or similar phosphoric acid doping level,the proton conductivity of the ABPBI/S-Sep composite membrane is improved dramatically and is comparable to Nafion 212 at 40～90℃ under saturated humidity of 98%RH.Meanwhile,in a low humidity environment of 60%RH,the proton conductivity of high phosphoric acid doping level ABPBI/S-Sep composite membrane is slightly lower than the result of 98%RH but it is significantly better than that of Nafion212,indicating that S-Sep inorganic particles modified ABPBI membrane has the characteristics of applying in low temperature environment and has the prospect of replacing Nafion for low temperature PEMFCs.
A novel poly(2,5-benzimidazole)/sulfonated sepiolite composite proton exchange membrane was prepared by in situ synthesis for application in low temperature fuel cells.The chemical structure,hydrophilicity and dispersibility of acid activated and sulfonated sepiolite as well as the morphology,water uptake,phosphoric acid doping level and proton conductivity of the composite membrane were characterized.The results show that sulfonated sepiolite(S-Sep)particles are dispersed uniformly in the ABPBI polymer matrix,and SSep particles can promote the regular arrangement of polymer molecular chains.The introduction of S-Sep particles into ABPBI matrix helps to significantly enhance the water and phosphoric acid absorption and retention abilities of the composite membrane compared to the virgin ABPBI membrane.With the same or similar phosphoric acid doping level,the proton conductivity of the ABPBI/S-Sep composite membrane is improved dramatically and is comparable to Nafion 212 at 40～90℃ under saturated humidity of 98%RH.Meanwhile,in a low humidity environment of 60%RH,the proton conductivity of high phosphoric acid doping level ABPBI/S-Sep composite membrane is slightly lower than the result of 98%RH but it is significantly better than that of Nafion212,indicating that S-Sep inorganic particles modified ABPBI membrane has the characteristics of applying in low temperature environment and has the prospect of replacing Nafion for low temperature PEMFCs.
引文
[1] Kongstein O E,Berning T,Bφrresen B,et al.Polymer electrolyte fuel cells based on phosphoric acid doped polybenzimidazole(PBI)membranes[J].Energy,2007,32:418-422.
[2] Li Q F,He R H,Jensen J O,et al.Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100℃[J].Chem.Mater.,2003,15:4896-4915.
[3]龚春丽,管蓉,杨世芳,等.聚合物质子传导电解质膜的研究进展[J].高分子材料科学与工程,2005,21(2):42-46.Gong C L,Guang R,Yang S F,et al.Research progress on portonconducting polymer electrolyte membranes of fuel cells[J].Polymer Materials Science&Engineering,2005,21(2):42-46.
[4] Bao X J,Zhang F,Liu Q T,et al.Sulfonated poly(2,5-benzimidazole)(ABPBI)/MMT/ionic liquids composite membranes for high temperature PEM applications[J].Int.J.Hydrogen Energy,2015,40:16767-16774.
[5] Devrim Y,Devrim H,Eroglu I.Polybenzimidazole/SiO2hybrid membranes for high temperature proton exchange membrane fuel cells[J].Int.J.Hydrogen Energy,2016,41:10044-10052.
[6]孙权,倪娜,俞李帅,等.聚苯并咪唑基/八氨基笼状倍半硅氧烷复合电解质膜的制备与性能[J].高分子材料科学与工程,2016,32(12):20-25.Sun Q,Ni N,Yu L S,et al.Preparation and characterization of poly(2,5-benzimidazole)/octa ammonium polyhedral oligomeric silsesquioxane electrolyte composite membranes[J].Polymer Materials Science&Engineering,2016,32(12):20-25.
[7] Liu Q,Sun Q,Ni N,et al.Novel octopus shaped organicinorganic composite membranes for PEMFCs[J].Int.J.Hydrogen Energy,2016,41:16160-16166.
[8] Zhou C H,Li G L,Zhuang X Y,et al.Roles of texture and acidity of acid-activated sepiolite catalysts in gas-phase catalytic dehydration of glycerol to acrolein[J].Mol.Catal.,2017,434:219-231.
[9] Beauger C,Laine G,Burr A,et al.Nafion(R)-sepiolite composite membranes for improved proton exchange membrane fuel cell performance[J].J.Membr.Sci.,2013,430:167-179.
[10] Suarez M,Garcia-Rivas J,Garcia-Romero E,et al.Mineralogical characterisation and surface properties of sepiolite from Polatli(Turkey)[J].Appl.Clay Sci.,2016,131:124-130.
[11] Liang X F,Xu Y M,Sun G H,et al.Preparation and characterization of mercapto functionalized sepiolite and their application for sorption of lead and cadmium[J].Chem.Eng.J.,2011,174:436-444.
[12] Mao L L,Mishra A K,Kim N H,et al.Poly(2,5-benzimidazole)-silica nanocomposite membranes for high temperature proton exchange membrane fuel cell[J].J.Membr.Sci.,2012,411:91-98.
[13] Asensio J A,Borroós S,Goómez-Romero P,et al.Polymer electrolyte fuel cells based on phosphoric acid-impregnated poly(2,5-benzimidazole)membranes[J].J.Electrochem.Soc.,2004,151:A304-A310.
[14] Ozdemir Y,Uregen N,Devrim Y,et al.Polybenzimidazole based nanocomposite membranes with enhanced proton conductivity for high temperature PEM fuel cells[J].Int.J.Hydrogen Energy,2017,42:2648-2657.
[2] Li Q F,He R H,Jensen J O,et al.Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100℃[J].Chem.Mater.,2003,15:4896-4915.
[3]龚春丽,管蓉,杨世芳,等.聚合物质子传导电解质膜的研究进展[J].高分子材料科学与工程,2005,21(2):42-46.Gong C L,Guang R,Yang S F,et al.Research progress on portonconducting polymer electrolyte membranes of fuel cells[J].Polymer Materials Science&Engineering,2005,21(2):42-46.
[4] Bao X J,Zhang F,Liu Q T,et al.Sulfonated poly(2,5-benzimidazole)(ABPBI)/MMT/ionic liquids composite membranes for high temperature PEM applications[J].Int.J.Hydrogen Energy,2015,40:16767-16774.
[5] Devrim Y,Devrim H,Eroglu I.Polybenzimidazole/SiO2hybrid membranes for high temperature proton exchange membrane fuel cells[J].Int.J.Hydrogen Energy,2016,41:10044-10052.
[6]孙权,倪娜,俞李帅,等.聚苯并咪唑基/八氨基笼状倍半硅氧烷复合电解质膜的制备与性能[J].高分子材料科学与工程,2016,32(12):20-25.Sun Q,Ni N,Yu L S,et al.Preparation and characterization of poly(2,5-benzimidazole)/octa ammonium polyhedral oligomeric silsesquioxane electrolyte composite membranes[J].Polymer Materials Science&Engineering,2016,32(12):20-25.
[7] Liu Q,Sun Q,Ni N,et al.Novel octopus shaped organicinorganic composite membranes for PEMFCs[J].Int.J.Hydrogen Energy,2016,41:16160-16166.
[8] Zhou C H,Li G L,Zhuang X Y,et al.Roles of texture and acidity of acid-activated sepiolite catalysts in gas-phase catalytic dehydration of glycerol to acrolein[J].Mol.Catal.,2017,434:219-231.
[9] Beauger C,Laine G,Burr A,et al.Nafion(R)-sepiolite composite membranes for improved proton exchange membrane fuel cell performance[J].J.Membr.Sci.,2013,430:167-179.
[10] Suarez M,Garcia-Rivas J,Garcia-Romero E,et al.Mineralogical characterisation and surface properties of sepiolite from Polatli(Turkey)[J].Appl.Clay Sci.,2016,131:124-130.
[11] Liang X F,Xu Y M,Sun G H,et al.Preparation and characterization of mercapto functionalized sepiolite and their application for sorption of lead and cadmium[J].Chem.Eng.J.,2011,174:436-444.
[12] Mao L L,Mishra A K,Kim N H,et al.Poly(2,5-benzimidazole)-silica nanocomposite membranes for high temperature proton exchange membrane fuel cell[J].J.Membr.Sci.,2012,411:91-98.
[13] Asensio J A,Borroós S,Goómez-Romero P,et al.Polymer electrolyte fuel cells based on phosphoric acid-impregnated poly(2,5-benzimidazole)membranes[J].J.Electrochem.Soc.,2004,151:A304-A310.
[14] Ozdemir Y,Uregen N,Devrim Y,et al.Polybenzimidazole based nanocomposite membranes with enhanced proton conductivity for high temperature PEM fuel cells[J].Int.J.Hydrogen Energy,2017,42:2648-2657.