Physicochemical Characterization of Morpholinium Cation Based Protic Ionic Liquids Used As Electrolytes

被引:70
作者
Brigouleix, Catherine [1 ]
Anouti, Meriem [1 ]
Jacquemin, Johan [1 ]
Caillon-Caravanier, Magali [1 ]
Galiano, Herve [2 ]
Lemordant, Daniel [1 ]
机构
[1] Univ Tours, Lab PCMB EA 4244, Equipe Chim Phys Interfaces & Milieux Electrolyt, F-37200 Tours, France
[2] CEA, LE RIPAULT, Lab Synth & Transformat Polymeres, F-37260 Monts, France
关键词
MOLTEN-SALTS; 1-BUTYL-3-METHYLIMIDAZOLIUM TETRAFLUOROBORATE; ETHYLAMMONIUM NITRATE; NONIONIC SURFACTANT; VAPOR-PRESSURE; PHASE-BEHAVIOR; FUSED SALT; TEMPERATURE; HEXAFLUOROPHOSPHATE; VISCOSITY;
D O I
10.1021/jp906917v
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
New protic ionic liquids (PILs) based on the morpholinium, N-methylmorpholinium, and N-ethyl morpholinium cations have been synthesized through a simple and atom-economic neutralization reaction between N-alkyl morpholine and formic acid. Their densities, refractive indices, thermal properties, and electrochemical windows have been measured. The temperature dependence of their dynamic viscosity and ionic conductivity have also been determined. The results allow us to classify them according to a classical Walden diagram and to evaluate their "fragility". In addition, morpholinium based PILs exhibit a large electrochemical window as compared to other protic ionic liquids (up 2.91 V) and possess relatively high ionic conductivities of 10-16.8 mS.cm(-1) at 25 degrees C and 21-29 mS.cm(-1) at 100 degrees C, and a residual conductivity close to 1.0 mS.cm(-1) at - 15 degrees C. PIL-water Mixtures exhibit high ionic conductivities up to 65 mS.cm(-1) at 25 degrees C and 120 mS.cm(-1) at 100 degrees C for morpholinium formate with water weight fraction w(w) = 0.6. Morpholinium based PILs studied in this work have a low cost and low toxicity, are good ionic liquids, and prove extremely fragile. They have wide applicable perspectives as electrolytes for fuel cell devices, thermal transfer fluids, and acid-catalyzed reaction media as replacements of conventional solvents.
引用
收藏
页码:1757 / 1766
页数:10
相关论文
共 83 条
[31]   Formation of amphiphile self-assembly phases in protic ionic liquids [J].
Greaves, Tamar L. ;
Weerawardena, Asoka ;
Fong, Celesta ;
Drummond, Calum J. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2007, 111 (16) :4082-4088
[32]   Many protic ionic liquids mediate hydrocarbon-solvent interactions and promote amphiphile self-assembly [J].
Greaves, Tamar L. ;
Weerawardena, Asoka ;
Fong, Celesta ;
Drummond, Calum J. .
LANGMUIR, 2007, 23 (02) :402-404
[33]   Protic ionic liquids: Solvents with tunable phase behavior and physicochemical properties [J].
Greaves, Tamar L. ;
Weerawardena, Asoka ;
Fong, Celesta ;
Krodkiewska, Irena ;
Drummond, Calum J. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (45) :22479-22487
[34]   RECOMMENDATIONS ON REPORTING ELECTRODE-POTENTIALS IN NON-AQUEOUS SOLVENTS [J].
GRITZNER, G ;
KUTA, J .
PURE AND APPLIED CHEMISTRY, 1982, 54 (08) :1527-1532
[35]   RECOMMENDATIONS ON REPORTING ELECTRODE-POTENTIALS IN NONAQUEOUS SOLVENTS (RECOMMENDATIONS 1983) [J].
GRITZNER, G ;
KUTA, J .
PURE AND APPLIED CHEMISTRY, 1984, 56 (04) :461-466
[36]   Room temperature ionic liquids of alkylimidazolium cations and fluoroanions [J].
Hagiwara, R ;
Ito, Y .
JOURNAL OF FLUORINE CHEMISTRY, 2000, 105 (02) :221-227
[37]   Temperature and pressure dependence of the viscosity of the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate: Viscosity and density relationships in ionic liquids [J].
Harris, Kenneth R. ;
Kanakubo, Mitsuhiro ;
Woolf, Lawrence A. .
JOURNAL OF CHEMICAL AND ENGINEERING DATA, 2007, 52 (06) :2425-2430
[38]   Self-assembly of block copolymer micelles in an ionic liquid [J].
He, YY ;
Li, ZB ;
Simone, P ;
Lodge, TP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (08) :2745-2750
[39]  
Hirschfelder JO, 1964, Molecular theory of gases and liquids, V165
[40]   Strong and fragile liquids - A brief critique [J].
Hodge, IM .
JOURNAL OF NON-CRYSTALLINE SOLIDS, 1996, 202 (1-2) :164-172