CN103408496A - Bis-imidazole ionic crystal and preparation method thereof - Google Patents
Bis-imidazole ionic crystal and preparation method thereof Download PDFInfo
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- CN103408496A CN103408496A CN2013103198626A CN201310319862A CN103408496A CN 103408496 A CN103408496 A CN 103408496A CN 2013103198626 A CN2013103198626 A CN 2013103198626A CN 201310319862 A CN201310319862 A CN 201310319862A CN 103408496 A CN103408496 A CN 103408496A
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Abstract
The present invention relates to a kind of bis-imidazole ionic crystal, its general formula of the chemical structures are as follows:
Or
, in which: one of X Cl, Br, I, one of Y BF4, TFSI, PF6, the integer that q is 0 to 5. The bis-imidazole ionic crystal that the present invention synthesizes, relative to single imidazole type ionic crystals, its conductivity (~ 10-5S/cm) with higher, and the method for preparing the bis-imidazole ionic crystal is easy to operate, is conducive to commercially produce, have a extensive future.
Description
Technical field
The present invention relates to a kind of ionic crystal, be specifically related to a kind of pair of imidazole type ionic crystal and preparation method thereof.
Background technology
Ionic crystal be by positive and negative ion by a certain percentage by ionic linkage in conjunction with the crystal formed, conventional ionic crystal is such as NaCl, CaCl
2And so on inorganic salt.Along with the deepening continuously and develop of organic synthesis mechanism, technology, increasing organic ionic crystal just constantly is synthesized out, has enriched kind and the definition of ionic crystal, has widened its Application Areas.
Due to the organic ionic crystal have advantages of thermally-stabilised good, specific conductivity is high, be solid does not leak etc., they are as a kind of composition of solid electrolyte or accurate solid electrolyte, be widely used in solar cell, ultracapacitor, lithium ion battery equal energy source device, can overcome the shortcomings such as the leakage of liquid electrolyte easy firing, volatile, difficult encapsulation, high toxicity, poor stability, so the organic ionic crystal causes scientific worker's extensive concern just gradually.
Publication number is that the Chinese invention patent of CN 102592832A discloses a kind of single imidazole type ionic crystal, and uses it for and prepare the solar cell solid state electrolyte.Yet should list imidazole type ionic crystal specific conductivity lower, be approximately 1 * 10
-6S/cm, the solid state electrolyte that utilizes this list imidazole type ionic crystal to prepare is applied in dye sensitization solar battery to reach 4.45% electricity conversion.Therefore the ionic crystal of necessary synthetic novelty, improve its specific conductivity, thereby improve the energy device performance that contains this ionic crystal, constantly advances towards the industrialization direction.
Summary of the invention
The objective of the invention is to provide in order to overcome the deficiencies in the prior art a kind of two imidazole type ionic crystals with high conductance.
For solving above technical problem, a kind of technical scheme that the present invention takes is: a kind of pair of imidazole type ionic crystal is characterized in that: its chemical structure of general formula is:
Wherein: X is a kind of in Cl, Br, I, and q is 0 to 5 integer.
Optimally, described X replaces with Y, and wherein Y is BF
4, TFSI, PF
6In a kind of.
The present invention also provides the preparation method of a kind of pair of imidazole type ionic crystal, and it comprises the following steps:
(1) in reaction vessel, add successively acetone,
,
, K
2CO
3, under 60 ~ 80 ℃, protection of inert gas, to react and filter to get filtrate after 10 ~ 15 hours, filtrate obtains product a through rotary evaporation, sherwood oil recrystallization;
(2) in another reaction vessel, add successively acetonitrile,
, imidazoles, KOH, at room temperature react after 10 ~ 20 hours and filter to get filtrate, filtrate obtains product b through rotary evaporation, deionized water recrystallization;
(3) product a is added drop-wise in the acetone soln of product b, 30 ~ 50 ℃ of lower condensing reflux reactions 10 ~ 15 hours, rotary evaporation was removed acetone, with ethyl acetate and ether, repeatedly washs respectively, after drying, obtains product c;
(4) product c is dissolved in to acetonitrile, adds
, KOH, at room temperature react after 10 ~ 20 hours and filter to get filtrate, rotary evaporation is removed acetonitrile, more repeatedly washs with ethyl acetate and ether, after drying product d;
Wherein product d is
, described X is a kind of in Cl, Br, I, q is 0 to 5 integer.
Optimally, it also comprises step (5), and described step (5) is: product d is soluble in water, add LiY to carry out ion-exchange, stirring reaction filtered collecting precipitation to producing precipitation in 5 ~ 10 hours, with deionized water, repeatedly wash, the dry product e that obtains, described Y is BF
4, TFSI, PF
6In a kind of.
Optimally, in described step (3), the mol ratio of product a and product b is 1:1 ~ 3.
Because technique scheme is used, the present invention compared with prior art has following advantages: the present invention has synthesized a kind of new two imidazole type ionic crystals, on the one hand by its chemical structure, introducing the crystal primitive, can increase its scattering of light effect, in its chemical structure, introduce on the other hand two imidazole groups, can improve its specific conductivity (~ 10
-5And it is simple to operate to prepare the method for this pair imidazole type ionic crystal, is conducive to commercially produce, and has a extensive future S/cm).
The accompanying drawing explanation
Fig. 1 is the preparation flow figure of the two imidazole type ionic crystals of the present invention;
Fig. 2 is the nuclear magnetic spectrogram of two imidazole type ionic crystals of preparation in embodiment 1.
Embodiment
Embodiment 1
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add successively 20mL acetone, 15mmol bis-butyl iodides, 10mmol
, 20mmol K
2CO
3, under 60 ℃, protection of inert gas, to react and filter to get filtrate after 15 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization
(2) in another reaction vessel, add successively 20mL acetonitrile, 10mmol bis-butyl iodides, 25mmol imidazoles, 35mmol KOH, at room temperature react after 10 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization
(3) by 10mmol
Be added drop-wise to 30mmol
Acetone (20mL) solution in, 30 ℃ of lower condensing refluxes reactions 10 hours, rotary evaporation was removed acetone, respectively with ethyl acetate and ether washing three times, after drying
(4) by 10mmol
Be dissolved in the 20ml acetonitrile, add 12mmol methyl iodide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation is removed acetonitrile, then washs three times with ethyl acetate and ether, after drying
.
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add successively 20mL acetone, 15mmol bis-butyl iodides, 10mmol
, 20mmol K
2CO
3, under 80 ℃, protection of inert gas, to react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization
(2) in another reaction vessel, add successively 20mL acetonitrile, 10mmol bis-butyl iodides, 25mmol imidazoles, 35mmol KOH, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization
(3) by 10mmol
Be added drop-wise to 30mmol
Acetone (20mL) solution in, 30 ℃ of lower condensing refluxes reactions 10 hours, rotary evaporation was removed acetone, respectively with ethyl acetate and ether washing three times, after drying
(4) by 10mmol
Be dissolved in the 20ml acetonitrile, add 12mmol butyl iodide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation is removed acetonitrile, then washs three times with ethyl acetate and ether, after drying
.
Embodiment 3
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add successively 20mL acetone, 15mmol bis-butyl iodides, 10mmol
, 20mmol K
2CO
3, under 80 ℃, protection of inert gas, to react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization
(2) in another reaction vessel, add successively 20mL acetonitrile, 10mmol bis-butyl iodides, 25mmol imidazoles, 35mmol KOH, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization
(3) by 10mmol
Be added drop-wise to 30mmol
Acetone (20mL) solution in, 30 ℃ of lower condensing refluxes reactions 10 hours, rotary evaporation was removed acetone, respectively with ethyl acetate and ether washing three times, after drying
(4) by 10mmol
Be dissolved in the 20ml acetonitrile, add 12mmol iodohexane, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation is removed acetonitrile, then washs three times with ethyl acetate and ether, after drying
.
Embodiment 4
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add successively 20mL acetone, 15mmol dibromobutane, 10mmol
, 20mmol K
2CO
3, under 80 ℃, protection of inert gas, to react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization
(2) in another reaction vessel, add successively 20mL acetonitrile, 10mmol dibromobutane, 25mmol imidazoles, 35mmol KOH, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization
(3) by 10mmol
Be added drop-wise to 30mmol
Acetone (20mL) solution in, 30 ℃ of lower condensing refluxes reactions 10 hours, rotary evaporation was removed acetone, respectively with ethyl acetate and ether washing three times, after drying
(4) by 10mmol
Be dissolved in the 20ml acetonitrile, add 12mmol n-butyl bromide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation is removed acetonitrile, then washs three times with ethyl acetate and ether, after drying
.
Embodiment 5
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
(1) in reaction vessel, add successively 20mL acetone, 15mmol dibromobutane, 10mmol
, 20mmol K
2CO
3, under 80 ℃, protection of inert gas, to react and filter to get filtrate after 20 hours, filtrate obtains through rotary evaporation, sherwood oil recrystallization
(2) in another reaction vessel, add successively 20mL acetonitrile, 10mmol dibromobutane, 25mmol imidazoles, 35mmol KOH, at room temperature react after 15 hours and filter to get filtrate, filtrate obtains through rotary evaporation, deionized water recrystallization
(3) by 10mmol
Be added drop-wise to 30mmol
Acetone (20mL) solution in, 30 ℃ of lower condensing refluxes reactions 10 hours, rotary evaporation was removed acetone, respectively with ethyl acetate and ether washing three times, after drying
(4) by 10mmol
Be dissolved in the 20ml acetonitrile, add 12mmol n-butyl bromide, 10 mmol KOH, at room temperature react after 10 hours and filter to get filtrate, rotary evaporation is removed acetonitrile, then washs three times with ethyl acetate and ether, after drying
(5) by 10mmol
Be dissolved in 10mL water, add 12mmol LiBF
4Carry out ion-exchange, stirring reaction filtered collecting precipitation to producing precipitation in 5 hours, used deionized water wash three times, dry
This example provides the preparation method of a kind of pair of imidazole type ionic crystal, as shown in Figure 1, comprises the following steps:
Get in 10mmol embodiment 4 preparation
Be dissolved in 10mL water, add 12mmol pair of fluoroform sulfimide lithiums (LiTFSI) to carry out ion-exchange, stirring reaction filtered collecting precipitation to producing precipitation in 10 hours, used deionized water wash three times, dry
.
Test example 1
Two imidazole type ionic crystals and Comparative Examples ionic crystal prepared by embodiment 1-6 carry out the specific conductivity test, concrete steps are as follows: described ionic crystal is placed in to tabletting machine, under 10 ~ 20MPa, be pressed into the thin slice of 1cm*1cm, these thin slices are clipped in respectively between two stainless steel electrodes, the contact area that makes thin slice and stainless steel electrode is 1cm*1cm, with two-probe method, be connected on electrochemical workstation and test, the results are shown in Table shown in 1, wherein the chemical structural formula of Comparative Examples ionic crystal is respectively
,
Two imidazole type ionic crystal specific conductivity test results prepared by table 1 embodiment 1-6
The high order of magnitude of specific conductivity of single imidazole type ionic crystal in the equal Comparative Examples of specific conductivity of two imidazole type ionic crystals in the present invention as can be seen from Table 1, be suitable for preparing the ionogen of energy device more, can improve the performance of corresponding energy device.
Above-described embodiment only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (8)
2. according to claim 1 pair of imidazole type ionic crystal, it is characterized in that: described X replaces with Y, and wherein Y is BF
4, TFSI, PF
6In a kind of.
3. the preparation method of two imidazole type ionic crystals, it is characterized in that: it comprises the following steps:
(1) in reaction vessel, add successively acetone,
,
, K
2CO
3, under 60 ~ 80 ℃, protection of inert gas, to react and filter to get filtrate after 10 ~ 15 hours, filtrate obtains product a through rotary evaporation, sherwood oil recrystallization;
(2) in another reaction vessel, add successively acetonitrile,
, imidazoles, KOH, at room temperature react after 10 ~ 20 hours and filter to get filtrate, filtrate obtains product b through rotary evaporation, deionized water recrystallization;
(3) product a is added drop-wise in the acetone soln of product b, 30 ~ 50 ℃ of lower condensing reflux reactions 10 ~ 15 hours, rotary evaporation was removed acetone, with ethyl acetate and ether, repeatedly washs respectively, after drying, obtains product c;
(4) product c is dissolved in to acetonitrile, adds
, KOH, at room temperature react after 10 ~ 20 hours and filter to get filtrate, rotary evaporation is removed acetonitrile, more repeatedly washs with ethyl acetate and ether, after drying product d;
4. the preparation method of according to claim 3 pair of imidazole type ionic crystal, it is characterized in that: it also comprises step (5), described step (5) is: product d is soluble in water, add LiY to carry out ion-exchange, stirring reaction filtered collecting precipitation to producing precipitation in 5 ~ 10 hours, repeatedly washed with deionized water, the dry product e that obtains, described Y is BF
4, TFSI, PF
6In a kind of.
7. the preparation method of according to claim 3 pair of imidazole type ionic crystal, it is characterized in that: in described step (3), the mol ratio of product a and product b is 1:1 ~ 3.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2481202A1 (en) * | 2002-04-05 | 2003-10-23 | University Of South Alabama | Functionalized ionic liquids, and methods of use thereof |
WO2008115250A2 (en) * | 2006-07-03 | 2008-09-25 | Matheson Tri-Gas, Inc. | Fluid storage and purification method and system using ionic liquid in particular di-imidazolium cation |
CN102568834A (en) * | 2011-11-14 | 2012-07-11 | 江苏德威新材料股份有限公司 | Electrolyte used for dye-sensitized solar cell and preparation method thereof |
CN102592832A (en) * | 2012-03-15 | 2012-07-18 | 苏州大学 | Solid electrolyte for solar cell based on ionic crystal |
-
2013
- 2013-07-26 CN CN201310319862.6A patent/CN103408496B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2481202A1 (en) * | 2002-04-05 | 2003-10-23 | University Of South Alabama | Functionalized ionic liquids, and methods of use thereof |
WO2008115250A2 (en) * | 2006-07-03 | 2008-09-25 | Matheson Tri-Gas, Inc. | Fluid storage and purification method and system using ionic liquid in particular di-imidazolium cation |
CN102568834A (en) * | 2011-11-14 | 2012-07-11 | 江苏德威新材料股份有限公司 | Electrolyte used for dye-sensitized solar cell and preparation method thereof |
CN102592832A (en) * | 2012-03-15 | 2012-07-18 | 苏州大学 | Solid electrolyte for solar cell based on ionic crystal |
Non-Patent Citations (1)
Title |
---|
XIAOJIAN CHEN等: "Bis-imidazolium based poly(ionic liquid) electrolytes for quasi-solid-state dye-sensitized solar cells", 《J. MATER. CHEM.》, vol. 22, 13 July 2012 (2012-07-13), pages 18018 - 18024 * |
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