应用阳离子开环聚合反应合成含二缩三乙二醇单甲醚侧链的梳形聚醚POE,并与高氯酸锂复配制成聚合物电解质.交流阻抗测试表明,当POE电解质内的氧锂比(O/L i)为20时,其电导率最高,室温下为10-4.43S/cm,80℃时则达到10-3.44S/cm.用DSC和XPS分别表征了链段运动能力和锂盐在POE中的溶解状态对电导率的影响.
A comb polymer was synthesized through cationic ring-opening polymerization starting from a monomer 3-hydroxymethyl-3-methyl-oxetane.The ion conductivity was measured by CHI660A electrochemical station under various lithium salt concentrations and various temperatures.The highest ion conductivity was recorded to be 10~(-4.43)S/cm at room temperature and 10~(-3.44)S/cm at 80 ℃.DSC results showed that the segment moves more difficultly with the increasing of lithium salts concentration.XPS found the existence of aggregating lithium ions in POE5 and POE10,and it suggested that POE20 had a suitable lithium concentration for polymer electrolyte.
[1]Fenton D E,Park J M,W right P V.Complexes of alkalimetal ions with poly(ethylene oxide)[J],Polymer,1973,14:589~589.
[2]REN Tian-B in,Huang X iao-B in,ZHAO X i-An,et al.Stud-ies on the ion states and ion transport mechanism of solidpolymer electrolyte[J].Acta Polymerica Sinica,2003,3:362.
[3]M iwa Y,Tsutsum i H,O ishi T.Novel polymer electrolytesbased on mono-and bis-oxrtane monomers with oligo(ethyl-ene oxide)units[J].E lectrochem istry,2002,70(4):264.
[4]Jankova K,Jannasch P,Hvilsted S.Ion conducting solidpolymer electrolytes based on polypentafluorostyrene-b-polyether-b-polypentafluorostyrene prepared by atom trans-fer rad ical polymerization[J].Journal ofMaterials Chem is-try,2004,14(19):2902.
[5]B lazquez E,Mustarelli P,Pasini D,et.al.Thermal andconductivity properties of poly(ethylene glycol)-based cy-clopolymers[J].Journal ofMaterials Chem istry,2004,14(16):2524.
[6]Jannasch P.Ion conducting electrolytes based on aggrega-ting comblike poly(propylene oxide)[J].polymer,2001,42:8 629~8 635.
[7]Itoh T,IkedaM,H irata N.Ionic conductivity of the hyper-branched polymer-lithium metal salt systems[J].Journal ofPower Sources,1999,81 82:824~829.
[8]N ishimoto A,W atanabe M,IkedaY,et al.H igh ionic con-ductivity of new polymer electrolytes based on high molecu-lar weight polyether comb polymers[J].E lectrochim icaActa,1998,43,(10~11):1 177~1 184.
[9]QI Li,LIN Yun-Q in,Jing X ia-B in,et al.Ionic conductivi-ty of novel comblike polymer electrolyte[J].Chem ical Re-search and Application,1998,10(4):356.
[10]DU Hong-Yan CHENG Hu,YANG Yong.Study on elec-trochem ical properties of PEO2based composite polymer e-lectrolytes[J].E lectrochem istry,2004,10(4):215~221.
[11]GU N ing-Yu,QIAN X in-M ing,ZHAO Feng,et al.Con-ductive behavior and ionic conductivity of composite poly-mer electrolytes[J].Chinese Journal of Analytical Chem-istry,2002,30(1):1~5.
[12]FANG B in,WANG X in-Ling,TANG X iao Zheng.The ap-plication and rectification of free volume theory in ionicconductivity of Poly(ethylene oxide)-Urethane salt com-plex[J].PolymerMaterials Science&Engineering,2003,19(1):199~204.
[13]ZHAO Feng,QIAN X in-M ing,WANG Er-Kang,et al.Advances in ionic conductive polymer electrolytes[J].Progress in Chem istry,2002,14(5):374~383.