CN103408496A - Bis-imidazole ionic crystal and preparation method thereof - Google Patents

Bis-imidazole ionic crystal and preparation method thereof Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
product
ionic crystal
imidazole type
type ionic
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2013103198626A
Other languages
Chinese (zh)
Other versions
CN103408496B (en
Inventor
赵杰
丛姗
邹贵付
曹梦瑜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201310319862.6A priority Critical patent/CN103408496B/en
Publication of CN103408496A publication Critical patent/CN103408496A/en
Application granted granted Critical
Publication of CN103408496B publication Critical patent/CN103408496B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The present invention relates to a kind of bis-imidazole ionic crystal, its general formula of the chemical structures are as follows: Or
Figure 800366DEST_PATH_IMAGE002
, 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

A kind of pair of imidazole type ionic crystal and preparation method thereof
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:
Figure 2013103198626100002DEST_PATH_IMAGE001
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,
Figure 2013103198626100002DEST_PATH_IMAGE002
, , 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,
Figure 2013103198626100002DEST_PATH_IMAGE004
, 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
Figure 2013103198626100002DEST_PATH_IMAGE005
, 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 (1),
Figure 195808DEST_PATH_IMAGE003
With
Figure 913228DEST_PATH_IMAGE002
Mol ratio be 1:1 ~ 1.5.
Optimally, in described step (2),
Figure 121487DEST_PATH_IMAGE002
With the mol ratio of imidazoles be 1:2 ~ 3.
Optimally, in described step (3), the mol ratio of product a and product b is 1:1 ~ 3.
Optimally, in described step (4), product c with
Figure 935859DEST_PATH_IMAGE005
Mol ratio be 1:1 ~ 2.
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
Figure 2013103198626100002DEST_PATH_IMAGE006
, 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
Figure 2013103198626100002DEST_PATH_IMAGE007
(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
Figure 2013103198626100002DEST_PATH_IMAGE008
(3) by 10mmol
Figure 2013103198626100002DEST_PATH_IMAGE009
Be added drop-wise to 30mmol
Figure 2013103198626100002DEST_PATH_IMAGE010
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
Figure 2013103198626100002DEST_PATH_IMAGE011
(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
Figure 2013103198626100002DEST_PATH_IMAGE012
.
Embodiment 2
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
Figure 835475DEST_PATH_IMAGE006
, 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
Figure 34375DEST_PATH_IMAGE007
(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
Figure 516303DEST_PATH_IMAGE008
(3) by 10mmol
Figure 509667DEST_PATH_IMAGE009
Be added drop-wise to 30mmol
Figure 326313DEST_PATH_IMAGE010
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
Figure 63325DEST_PATH_IMAGE011
(4) by 10mmol
Figure 586710DEST_PATH_IMAGE011
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
Figure 2013103198626100002DEST_PATH_IMAGE013
.
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
Figure 829604DEST_PATH_IMAGE006
, 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
Figure 133546DEST_PATH_IMAGE007
(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
Figure 408669DEST_PATH_IMAGE008
(3) by 10mmol
Figure 52140DEST_PATH_IMAGE009
Be added drop-wise to 30mmol
Figure 200356DEST_PATH_IMAGE010
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
Figure 929278DEST_PATH_IMAGE011
(4) by 10mmol
Figure 70409DEST_PATH_IMAGE011
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
Figure 2013103198626100002DEST_PATH_IMAGE014
.
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
Figure 568386DEST_PATH_IMAGE006
, 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
Figure 2013103198626100002DEST_PATH_IMAGE015
(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
Figure 144294DEST_PATH_IMAGE008
(3) by 10mmol Be added drop-wise to 30mmol
Figure 39754DEST_PATH_IMAGE010
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
Figure 2013103198626100002DEST_PATH_IMAGE016
(4) by 10mmol
Figure 205288DEST_PATH_IMAGE016
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
Figure 2013103198626100002DEST_PATH_IMAGE017
.
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
Figure 648087DEST_PATH_IMAGE015
(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
Figure 881754DEST_PATH_IMAGE008
(3) by 10mmol
Figure 354323DEST_PATH_IMAGE015
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
Figure 455320DEST_PATH_IMAGE016
(4) by 10mmol
Figure 492678DEST_PATH_IMAGE016
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
Figure 554175DEST_PATH_IMAGE017
(5) by 10mmol
Figure 900842DEST_PATH_IMAGE017
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
Embodiment 6
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
Figure 123489DEST_PATH_IMAGE017
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
Figure DEST_PATH_IMAGE019
.
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
Figure 483242DEST_PATH_IMAGE001
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)

1. two imidazole type ionic crystal, it is characterized in that: its chemical structure of general formula is:
Figure 2013103198626100001DEST_PATH_IMAGE001
Wherein: X is a kind of in Cl, Br, I, and q is 0 to 5 integer.
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,
Figure 873347DEST_PATH_IMAGE002
,
Figure 2013103198626100001DEST_PATH_IMAGE003
, 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,
Figure 9930DEST_PATH_IMAGE004
, 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
Figure 2013103198626100001DEST_PATH_IMAGE005
, 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
Figure 554175DEST_PATH_IMAGE001
, described X is a kind of in Cl, Br, I, q is 0 to 5 integer.
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.
5. the preparation method of according to claim 3 pair of imidazole type ionic crystal is characterized in that: in described step (1),
Figure 485222DEST_PATH_IMAGE003
With
Figure 177234DEST_PATH_IMAGE002
Mol ratio be 1:1 ~ 1.5.
6. the preparation method of according to claim 3 pair of imidazole type ionic crystal is characterized in that: in described step (2),
Figure 849000DEST_PATH_IMAGE002
With the mol ratio of imidazoles be 1:2 ~ 3.
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.
8. the preparation method of according to claim 3 pair of imidazole type ionic crystal is characterized in that: in described step (4), product c with
Figure 310068DEST_PATH_IMAGE005
Mol ratio be 1:1 ~ 2.
CN201310319862.6A 2013-07-26 2013-07-26 A kind of two imidazole type ionic crystal and preparation method thereof Expired - Fee Related CN103408496B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310319862.6A CN103408496B (en) 2013-07-26 2013-07-26 A kind of two imidazole type ionic crystal and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310319862.6A CN103408496B (en) 2013-07-26 2013-07-26 A kind of two imidazole type ionic crystal and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103408496A true CN103408496A (en) 2013-11-27
CN103408496B CN103408496B (en) 2015-10-21

Family

ID=49601553

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310319862.6A Expired - Fee Related CN103408496B (en) 2013-07-26 2013-07-26 A kind of two imidazole type ionic crystal and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103408496B (en)

Citations (4)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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 *

Also Published As

Publication number Publication date
CN103408496B (en) 2015-10-21

Similar Documents

Publication Publication Date Title
Huang et al. Ultrastable zinc anodes enabled by anti-dehydration ionic liquid polymer electrolyte for aqueous Zn batteries
Xu et al. Additive-containing ionic liquid electrolytes for secondary lithium battery
CN101901692B (en) Solar cell gel electrolyte and preparation method and application thereof
CN102592832B (en) Solid electrolyte for solar cell based on ionic crystal
CN106410148B (en) A kind of high-performance kalium ion battery negative electrode material and the electrolyte to match
CN107534180A (en) Nonaqueous electrolyte magnesium system secondary cell
CN103413682A (en) Quasi-solid electrolyte for solar cell based on double-imidazole type ionic crystal
CN103965141A (en) Pyrrolidine ionic liquid, and preparation method, electrolyte and capacitor thereof
CN110407724A (en) A kind of double ion is to ionic liquid and preparation method thereof
CN102568834A (en) Electrolyte used for dye-sensitized solar cell and preparation method thereof
CN102780034B (en) Ionic liquid electrolyte and preparation method and application thereof
CN102952097B (en) Double-centre piperazine ionic liquid, and preparation method and application thereof
CN104016419A (en) Method for preparing three-dimensional flower-shaped CoS hierarchy counter electrode of dye-sensitized solar cell
CN103387571B (en) Bi-imidazole type benzimidazole ionic liquid and preparation method thereof
CN103408496B (en) A kind of two imidazole type ionic crystal and preparation method thereof
CN103794818A (en) Pyrroles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof
CN103732587B (en) Two centers bipyridine cation class ionic liquid and its preparation method and application
CN102592831B (en) Cobalt ion liquid redox couple and preparation and application thereof
CN101887802B (en) Quasi-solid electrolyte used for dye-sensitized solar cell and preparation method thereof
CN113540563B (en) Additive and modification method of lithium battery electrolyte
CN103489645A (en) Gel electrolyte for DSSC and preparation method of gel electrolyte
CN111525186B (en) All-solid-state polymer electrolyte based on zwitterionic liquid modified polyvinyl alcohol and preparation method thereof
CN111116388A (en) Preparation method of polyether-based ionic liquid, preparation method and application of high-voltage electrolyte
CN103450610A (en) Gel polymer electrolyte membrane, and preparation method and application thereof
CN103887069B (en) A kind of electrolyte based on ionic liquid metal complex and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20151021

Termination date: 20180726

CF01 Termination of patent right due to non-payment of annual fee