制备了含有烷基磺酸侧链的聚磷腈(PFSPP),对氧化石墨烯进行改性制备了季铵盐化氧化石墨烯(QGO),通过共混法制备了QGO/PFSPP质子交换复合膜。通过对复合膜的吸水率、溶胀度、抗氧化性和电化学性能测试,表明复合膜的吸水率和溶胀度都低于纯PFSPP膜;并且具有较优异的抗氧化性能。复合膜PFS-3-QGO在80℃条件下具有最高的质子传导率,为0.09S/cm。研究结果表明,具有稳定性能的复合膜QGO/PFSPP可以作为质子交换膜的潜在备选材料。
Polyphosphazene containing alkyl sulfonic acid side chains (PFSPP) was prepared,quaternized graphene oxide (QGO) was further prepared by modifying graphene oxide.Subsequently,a series of novel alkylsulfonic acid polyphosphazene-based hybrid membranes (PFS-x-QGO) containing QGO (QGO/PFSPP) were obtained by blending.The water uptake,swelling ratio,oxidative stabilities and proton conductivities of QGO/PFSPP were measured.The test results showed that all composite membranes exhibited lower swelling ratio and water uptake than that of pure PFSPP membrane;moreover,they displayed high oxidative stabilities.The highest proton conductivity rate of SP-3-QGO composite membrane was about 0.09S/cm at 80℃.All the results indicated that the composite membranes with excellent stabilization were the potential candidate materials for proton exchange membranes.
[1] Hickner M A,Ghassemi H,Kim Y S,et al.Alternative polymer systems for proton exchange membranes[J].Chemical Reviews,2004,104(10):4587-4612.
[2] Souzy R,Ameduri B.Functional fluoropolymers for fuel cell membranes[J].Progressin Polymer Science,2005,30:644-687.
[3] Mauritz K A,Moore R B.State of understanding of nafion[J].Chemical Reviews,2004,104(10):4535-4585.
[4] Wang J L,Song Y L,Zhang C,et al.Alternating copolymer of sulfonated poly(ether ether ketone-benzimidazole)s (SPEEK-BI) bearing acid and base moieties[J].Macromolecular Chemistryand Physics,2008,209(14):1495-1502.
[5] 宋勋,贾玉婷,张睫灵,等.磺化双酚芴型聚醚醚酮质子交换膜的制备及其在钒流电池中的应用[J].应用化学,2020,37(8):912-922.
[6] Bae B,Miyatake K,Watanabe M.Effect of the hydrophobic component on the properties of sulfonated poly(arylene ether sulfone)s[J].Macromolecules,2009,42:1873-1880.
[7] Lee K H,Lee S Y,Shin D W,et al.Structural influence of hydrophobic diamine in sulfonated poly(sulfide sulfone imide) copolymers on medium temperature PEM fuel cell[J].Polymer,2014,55:1317-1326.
[8] He M L,Xu H L,Dong Y,et al.Synthesis and characterization of sulfonated polyphosphazene-graft-polystyrene copolymers for proton exchange membranes[J].Chinese Journalof Polymer Science,2014,32:151-162.
[9] Fu F Y,Xu H L,Dong Y,et al.Design of polyphosphazene-based graft copolystyrenes with alkylsulfonatebranch chains for proton exchange membranes[J].Journal of Membrane Science,2015,489:119-128.
[10] Luo T W,Zhang Y X,Xu H L,et al.Highly conductive proton exchange membranes from sulfonated polyphosphazene-graft-copolystyrenes doped with sulfonated single-walled carbon nanotubes[J].Journal of Membrane Science,2016,514:527-536.
[11] Yadav R,Subhash A,Chemmenchery N,et al.Graphene and graphene oxide for fuel cell technology[J].Industrial & Engineering Chemistry Research,2018,57(29):9333-9350.
[12] Cai Y B,Yue Z Y,Xu S A.A novel polybenzimidazole composite modified by sulfonated graphene oxide for high temperature proton exchange membrane fuel cells in anhydrous atmosphere[J].Journalof Applied Polymer Science,2017,134(25):44986.
[13] Ravi K,Mamlouk M,Scott K.Sulfonated polyether ether ketone-sulfonated graphene oxide composite membranes for polymer electrolyte fuel cells[J].RSC Advances,2014,4(2):617-623.
[14] Üregen N,Pehlivanoglu K,Özdemir Y,et al.Development of polybenzimidazole/graphene oxide composite membranes for high temperature PEM fuel cells[J].International Journalof Hydrogen Enegy,2017,42(4):2636-2647.
[15] Zhao Y X,Fu Y Q,Hu B,et al.Quaternized graphene oxide modified ionic cross-linked sulfonated polymer electrolyte composite proton exchange membranes with enhanced properties[J].Solid State Ionics,2016,294:43-53.
[16] Liu L D,Tong C Y,He Y,et al.Enhanced properties of quaternized graphenes reinforced polysulfone based composite anion exchange membranes for alkaline fuel cell[J].Journal of Membrane Science,2015,487:99-108.
[17] Allcock H R.Chemistry and applications of polyphosphazenes[M].New York:Wiley-Interscience,2003:145.
[18] Hummers W S,Offeman R E.Preparation of graphitic oxide[J].Journalof the American Chemistry Society,1958,80:1339.
[19] Zawodzinski T A,Neeman M,Sillerud L O,et al.Determination of water diffusion coefficients in perfluorosulfonate ionomeric membranes[J].Journal of Physical Chemistry,1991,95(15):6040-6044.
基金资助
河北省高等学校科学研究项目(BJ2019206);大学生科技创新能力培育专项(22E50258D);衡水学院高层次人才科研启动基金项目(2018GC10);衡水学院高层次人才科研启动基金项目(2019GC10);河北省重点研发计划自筹项目(18214321)
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