| As a green solvent and a new type of functional material,ionic liquid is a kind of salt contained of large volume organic cations and small volume of inorganic or organic anions.Combinating of chemistry,biomedicine,material science and based on the design of the structure,one or more functional groups are introduced into cation to make ionic liquid has a special function and characteristic.ILs has high conductivity,wide electrochemical window,high thermal stability,very low vapor pressure and non flammable properties,its application involves organic synthesis,dye sensitized solar cells,metal deposition and separation analysis and many other fields.In this paper,firstly,two types of functionalized ionic liquids containing ester groups were designed and synthesized based on the two aspects of ester based chain growth and ester based isomerization,it is functionalized ionic liquid containing ester group?[EPy][PF6]?and functionalized ionic liquid containing ester group 3-methyl pyridine?[EMPy][PF6]?.Next,we studied the effects of organic solvent ratio,ambient temperature and settling time on the grows of[EPy][PF6]and[EMPy][PF6]crystals and determine its optimum growth conditions.The structure of[EPy][PF6]and[EMPy][PF6]were characterized by IR and 1H NMR techniques.The thermal properties of[EPy][PF6]and[EMPy][PF6]were analyzed by differential scanning calorimetry and thermogravimetric analysis.The electrochemical stability of two kinds of ionic liquids and the variation of conductivity with ionic liquid concentration and temperature of ionic liquid organic solvent two element system were studied.Results show that[EPy][PF6]and[EMPy][PF6]have high thermal stability,wide electrochemical window and high conductivity,the electrochemical window is higher than 2 V,and the conductivity is higher than 1000?S·cm-1.Five new types of ester-based pyridine ionic liquid[EAPy][PF6],[EAMPy][PF6],[MeMPy][PF6],[n-C3EAPy][PF6],[i-C3EAPy][PF6]crystals have been successfully developed.The unit cell parameters,the structure of the supramolecular space network,the thermal properties and the electrical properties were systematically analyzed.The conductivity of two kinds of ionic liquid-organic solvent two element system increases with the increase of ionic liquid concentration and temperature.And the relationship between electrical conductivity and temperature is consistent with the behavior of Arrhenius.The activation energy of the conductive can be influenced by the growth of the ester group and the ester isomerization.In addition,solubility studies show that its polarity is close to that of alcohols and ketones.Finally,the[EPy][PF6]and[EMPy][PF6]are introduced into the soliquid system of PVA based electrolyte membrane.An ester based ionic liquid type PVA based electrolyte membrane with different structure and properties was prepared.Compared with the PVA based electrolyte membrane without ionic liquid,the thermal stability of ionic liquid type PVA based electrolyte membrane increase 46.9oC.The data of single crystal structure[EAPy][PF6],[EAMPy][PF6],[MeMPy][PF6],[n-C3EAPy][PF6],[i-C3EAPy][PF6]are as follows:The space group and crystal system of[EAPy][PF6]are C2/c and monoclinic,a=22.748?16??,b=6.204?4??,c=18.552?12??,?=90o,?=92.66?3?o,?=90o,Z=8,V=2615?3?A3,Dc=1.580 Mg/m3,?=0.280 mm-1,F?000?=1264.R1=0.0791,wR2=0.1777.The space group and crystal system of[EAMPy][PF6]are P2?1?2?1?2?1?and orthogonal,a=7.1265?17??,b=12.792?3??,c=15.327?3??,?=90o,?=90o,?=90o,Z=4,V=1397.2?6?A3,Dc=1.546 Mg/m3,?=0.265 mm-1,F?000?=664.R1=0.0641,?R2=0.16831.The space group and crystal system of[MeMPy][PF6]are P-1 and Triclinic,a=8.754?3??,b=8.780?3??,c=10.551?6??,?=103.589?7?o,?=100.965?7?o,?=117.956?5?o,Z=2,V=652.2?5?A3,Dc=1.584 Mg/m3,?=0.280 mm-1,F?000?=316.R1=0.0815,?R2=0.2261.The space group and crystal system of[n-C3EAPy][PF6]are P121/n1 and monoclinic,a=8.183?2??,b=13.156?5??,c=12.967?4??,?=90o,?=104.98?3?°,?=90o,Z=4,V=1348.5?8?A3,Dc=1.602 Mg/m3,?=0.275 mm-1,F?000?=664.R1=0.0837,wR2=0.2322.The space group and crystal system of[i-C3EAPy][PF6]are P1 and Triclinic,a=14.968?9??,b=6.457?4??,c=16.132?7??,?=122.39?4?o,Z=4,V=1316.6?14?A3,Dc=1.641 Mg/m3,?=0.282 mm-1,F?000?=664.R1=0.0653,wR2=0.1708. |
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