CN111732677A - Imidazolyl star-shaped polymerized ionic liquid all-solid-state electrolyte and preparation method thereof - Google Patents

Imidazolyl star-shaped polymerized ionic liquid all-solid-state electrolyte and preparation method thereof Download PDF

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CN111732677A
CN111732677A CN202010530149.6A CN202010530149A CN111732677A CN 111732677 A CN111732677 A CN 111732677A CN 202010530149 A CN202010530149 A CN 202010530149A CN 111732677 A CN111732677 A CN 111732677A
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ionic liquid
star
imidazolyl
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谢泽辉
杨勇
凌灿辉
陈梦玲
周洋
李瑞靖
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Nanjing University of Science and Technology
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Abstract

The invention discloses an imidazolyl star-shaped polymerized ionic liquid all-solid-state electrolyte and a preparation method thereof, and the preparation method comprises the following steps: a) pentaerythritol and 2-bromine isobutyryl bromide are reacted to prepare the four-arm macromolecular initiator, hydroxyethyl acrylate is initiated to polymerize to obtain a four-arm branched polymer, and then two-step substitution reaction, imidazole group introduction and ion exchange are carried out to obtain the productB) mixing the imidazolyl star-shaped polymerized ionic liquid with lithium salt, and preparing the star-shaped polymerized ionic liquid all-solid electrolyte by a solution casting method, wherein the room-temperature conductivity of the solid electrolyte can reach 4.57 × 10‑5S cm‑1The transference number of lithium ions is 0.31, the electrochemical window reaches 4.8V, and the method has a large application potential.

Description

Imidazolyl star-shaped polymerized ionic liquid all-solid-state electrolyte and preparation method thereof
Technical Field
The invention relates to an imidazolyl star-shaped polymerized ionic liquid all-solid-state electrolyte and a preparation method thereof, and belongs to the technical field of solid-state energy storage.
Background
The electrolyte of the traditional lithium battery adopts liquid organic compounds, and has the defects of easy leakage, easy combustion, easy volatilization and the like. In some special cases, such as: during overcharge, high-rate and heavy-current charge and discharge of the battery, the electrolyte can be leaked, even the battery deforms, and further safety problems such as short circuit and explosion can be caused. Therefore, the development of an all-solid electrolyte with higher safety performance to replace a liquid electrolyte is a preferred method for fundamentally solving the safety problem of the lithium ion battery. Solid electrolytes can be divided into two categories by composition: gel polymer electrolytes and all-solid-state polymer electrolytes. The gel polymer electrolyte can not completely eliminate the problems of decomposition, flammability and the like of the traditional lithium battery due to the existence of the liquid plasticizer, so the application of the gel polymer electrolyte still has a safety problem. Compared with the former, the all-solid-state electrolyte has relatively high thermal stability and low flammability, and can realize the processing of an ultrathin polymer diaphragm, thereby improving the energy density of the battery. Although all-solid-state electrolytes still have the defects of low conductivity, large interface impedance and the like, modification of all-solid-state electrolytes by various modification technologies is a currently very popular research direction.
Chinese patent CN110474089A discloses an all-solid-state electrolyte and a preparation method thereof, wherein silane, polyethylene glycol and polyethylene glycol monomethyl ether are synthesized into a cross-linked polymer, and then the cross-linked polymer is mixed with lithium salt and acetone to obtain solid polymer slurry, and the solid polymer slurry is sprayed on prepared anode and cathode materials and assembled to prepare the all-solid-state lithium ion battery. The technical scheme is more complicated in the manufacturing process of the battery, still adopts graphite as a negative electrode material, and has limitation in the improvement of the energy density of the battery. The Chinese invention patent CN109608592A adopts 1-vinyl-3-methylimidazole bistrifluoromethylsulfonyl imide as a monomer, dissolves in a PEO and lithium salt system, and then adds a crosslinking agent PEGDA and an initiator AIBN to prepare the polymeric ionic liquid solid electrolyte. The ionic liquid structure can effectively promote the ion migration in the solid electrolyte, but the ionic conductivity in the all-solid electrolyte needs to be further improved so as to meet the requirement of a high-performance battery.
Disclosure of Invention
The invention aims to provide an imidazolyl star-shaped polymer ionic liquid all-solid-state electrolyte and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the imidazolyl star-shaped polymerized ionic liquid all-solid-state electrolyte is composed of lithium salt, a solvent and an imidazolyl star-shaped polymerized ionic liquid I, wherein the imidazolyl star-shaped polymerized ionic liquid I has the following structure:
Figure BDA0002535086630000021
wherein R is1The structure is as follows:
Figure BDA0002535086630000022
Figure BDA0002535086630000023
PF6 -,ClO4 -in the above-mentioned manner, the first and second substrates are,
preference is given to
Figure BDA0002535086630000024
R2The structure is as follows:
Figure BDA0002535086630000025
m is 1-6, preferably m is 1, 2, 3;
the synthesis method of the star-shaped polymerized ionic liquid comprises the following steps:
(1) in the nitrogen atmosphere, pentaerythritol, 2-bromine isobutyryl bromide and triethylamine are subjected to acylation reaction to prepare a four-arm macroinitiator IbIn the step (2) of (a),
Figure BDA0002535086630000031
(2) the initiator IbThe four-arm branched polymer I is prepared by atom transfer radical polymerization of a copper-based catalyst, a ligand and a hydroxyethyl acrylate monomer under the condition of nitrogencIn the step (2) of (a),
Figure BDA0002535086630000032
(3) mixing polymer IcBromine substitution reaction is carried out with trimethyl bromosilane to prepare four-arm polymeric ionic liquid bromo intermediate IdIn the step (2) of (a),
Figure BDA0002535086630000033
(4) bromo intermediate IdPerforming ion exchange reaction with imidazolyl homologues to obtain imidazolyl star-shaped polymerized ionic liquid intermediate IeIn the step (2) of (a),
Figure BDA0002535086630000041
(5) mixing I obtained in the fourth stepeWith lithium salts LiR1Carrying out ion exchange reaction to obtain imidazolyl star-shaped polymerized ionic liquid I,
Figure BDA0002535086630000042
further, in the step (1), the molar ratio of pentaerythritol, 2-bromoisobutyryl bromide and triethylamine is 1:8: 8; the solvent used in the reaction system is tetrahydrofuran.
Further, in the step (2), the copper-based catalyst is selected from one of CuBr and CuCl; the ligand is selected from any one of N, N, N' -pentamethyldiethylenetriamine, tri (2-dimethylaminoethyl) amine, 1,4,7,10, 10-hexamethyltriethylenetetramine and 2, 2-bipyridine; initiator IbThe molar ratio of the copper-based catalyst, the ligand and the hydroxyethyl acrylate is 1:3:10: 100.
Further, in the step (3), a polymer IcThe mass ratio of the catalyst to the trimethyl bromosilane is 1: 4.
Further, in the step (4), a polymer IdThe mass ratio of the 1-methylimidazole homologue to the 1-methylimidazole homologue is 1: 3.
Further, in the step (5), a lithium salt LiR1Is LiTFSI or LiCF3SO3、LiClO4、LiBF4、 LiPF6And lithium perfluorobutylsulfonate, intermediate IeThe mass ratio of the lithium salt to the lithium salt is 1: 1.5.
The star-shaped polymerized ionic liquid all-solid-state electrolyte is prepared by adopting multi-arm branched structure polymerized ionic liquid as a substrate, adding lithium salt and adopting a solution casting method, and specifically comprises the following steps: dissolving the imidazolyl star-shaped polymerized ionic liquid I and lithium salt in a solvent, uniformly stirring at room temperature, placing the obtained mixed solution in a mold, volatilizing the solvent, and drying in vacuum to obtain the all-solid-state electrolyte.
Further, the lithium salt is LiTFSI or LiCF3SO3、LiClO4、LiBF4、LiPF6And lithium perfluorobutylsulfonate; the mass ratio of the imidazolyl star-shaped polymerized ionic liquid I to the lithium salt is 1: 0.2; the solvent is acetonitrile.
Compared with the prior art, the invention has the following advantages:
(1) the polymer ionic liquid is used as the main body of the polymer electrolyte, has the characteristic of high ionic conductivity, and has high safety due to high thermal stability and low inflammability of the polymer electrolyte.
(2) The preparation method adopts an atom transfer radical polymerization technology, has mild reaction conditions, and can prepare the polymer at room temperature. Compared with the traditional free radical polymerization, the molecular weight of the polymer is controllable, the molecular weight distribution is narrower, and the performance regulation is more convenient.
(3) The star-shaped four-arm branched structure is designed and constructed, the crystallinity of the polymer is reduced, the glass transition temperature is reduced, and the migration and transportation of lithium ions can be promoted. The multi-arm polymer with the flexible support can be tightly adhered to the surface of the electrode, and is more favorable for realizing good contact of an electrode-electrolyte interface.
Drawings
FIG. 1 shows the NMR spectra of imidazolyl star-shaped polymeric ionic liquid prepared in example 1.
FIG. 2 is an IR spectrum of an imidazolyl star-shaped polymeric ionic liquid prepared in example 1.
FIG. 3 shows an imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte entity prepared in example 1.
FIG. 4 is a differential scanning calorimetry curve of the all-solid-state electrolyte of the imidazolyl star-shaped polymeric ionic liquid prepared in example 1.
FIG. 5 is an Arrhenius curve of the ionic conductivity of the all-solid-state electrolyte of the imidazolyl star-shaped polymeric ionic liquid prepared in example 1.
FIG. 6 is a chronoamperometric curve and an AC impedance spectrum of the imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte prepared in example 1.
FIG. 7 is a linear sweep voltammogram of the imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte prepared in example 1.
FIG. 8 is a first charge-discharge curve diagram of the imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte prepared in example 1.
Detailed Description
The invention discloses an imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte, which is further detailed in the following by combining with an embodiment and a drawing.
Example 1: (R)1Is composed of
Figure BDA0002535086630000061
R2Is composed of
Figure BDA0002535086630000062
)
1.36g of pentaerythritol, 18.4g of 2-bromoisobutyryl bromide and 8g of triethylamine were added to a 100ml three-necked flask containing 40ml of tetrahydrofuran under dry nitrogen filling, the mixture was stirred at room temperature for 24 hours, the reaction product was transferred to a separatory funnel, and 350ml of CH was added2Cl2Extraction was performed with 10% HCl, 5% NaHCO, respectively3And repeatedly washing with deionized water. The resulting organic phase was dried over anhydrous magnesium sulfate, filtered to remove the desiccant and then dried under reduced pressure to give a white powder product. Recrystallizing the product with methanol to obtain four-arm macroinitiator (FIBr)4)2.8 g. 0.05g of FIBr was taken4This was added to the flask with 10g of hydroxyethyl acrylate monomer and 0.112g of bipyridine under nitrogen bubbling, and after half an hour, 0.05g of CuBr was added and reacted under heating at 80 ℃ under nitrogen for 2 hours. And after the reaction is finished, transferring the mixture into a dialysis bag for dialysis and purification, and changing deionized water at regular intervals for dialysis for 48 hours. After completion of dialysis, lyophilization was carried out to obtain 3g of a four-arm branched polymer. 3g of a four-arm branched polymer were dissolved with 10ml of trimethylbromosilane in 30ml of CH under nitrogen2Cl2And cooling to 0 ℃, slowly raising the temperature to room temperature, reacting in a 100ml single-neck flask for 24 hours, filtering the obtained purple black mixture after the reaction is finished to remove residual solid by suction, and recrystallizing with low-temperature methanol to obtain 2.7g of pure white flocculent four-arm branched polymeric ionic liquid bromo-compound. 2.7g of four-arm branched polymeric ionic liquid bromo-compound was dissolved in 10ml of tetrahydrofuran, 8ml of 1-methylimidazole was added, and a yellow block was obtained after refluxing for 3 hours. And drying the residual tetrahydrofuran in the flask, dissolving the blocky substance by using methanol, and recrystallizing for three times by using tetrahydrofuran to obtain the imidazolyl bromo-ionic liquid. Finally, 4.5g of LiTFSI was added, reacted for 24 hours and then filtered to obtain white flocculent solidsThe body was then washed repeatedly 5 times with deionized water to remove residual LiBr until AgNO was added3The solution appeared white turbidity, and 3.2g of imidazolyl star-shaped polymerized ionic liquid was obtained.
0.1g of imidazolyl star-shaped polymeric ionic liquid was dissolved in 2ml of acetonitrile, 0.02g of LiTFSI was added thereto, and the mixture was stirred at room temperature for 24 hours to obtain a clear solution. Then casting the imidazole-based star-shaped polymerized ionic liquid in a polytetrafluoroethylene mold with the diameter of 20mm, volatilizing the solvent, carrying out vacuum drying at 60 ℃ for 12h, and then transferring to a glove box for storage to obtain the imidazole-based star-shaped polymerized ionic liquid all-solid-state electrolyte. Using LiFePO4The lithium ion battery is a positive electrode material, the Li sheet is a negative electrode material, the imidazolyl star-shaped polymerized ionic liquid all-solid-state electrolyte is a diaphragm, an LIR2016 button cell is assembled in a glove box, and a test is carried out at 0.1 ℃ by adopting a LAND cell test system. As shown in FIG. 8, the initial specific discharge capacity of the imidazolyl star-shaped polymerized ionic liquid-based all-solid-state electrolyte battery can reach 153mAh g-1。
Fig. 1 is a hydrogen nuclear magnetic resonance spectrum of the imidazolyl star-shaped polymerized ionic liquid, and no carbon-carbon double bond peaks appear at 1.4ppm and 2.1 ppm, which proves that the double bonds in HEA are polymerized. Proton signals for imidazolium cations appeared at 7.6ppm and 9.2 ppm. And 4.4ppm, 4.2ppm and 3.8 ppm are-O-CH, respectively2-，-N-CH2-and-N-CH3Further proving that the product is the target composition. In addition, the base line in the figure is flat, no obvious miscellaneous peak exists, and the imidazolyl star-shaped polymerized ionic liquid has no error in structure and high purity. FIG. 2 is an infrared spectrum of an imidazolyl star-shaped polymerized ionic liquid. At 1650 cm-1The characteristic peak of C-C disappears, which indicates that the double bond of HEA monomer is polymerized more completely. At 1740cm-1The characteristic peak at (A) belongs to carbonyl, 3150cm-1And 2950cm-1Respectively belong to the stretching vibration of C-H in imidazole ring and saturated group. Furthermore, 1350cm-1The absorption peak of (a) can be assigned as a C-N stretching vibration. TFSI－Can exist by being at 1130cm-1、1050cm-1、740cm-1And 567cm-1And (c) was confirmed, which is consistent with the previous literature values.FIG. 3 is a photo of an imidazole-based star-shaped polymerized ionic liquid electrolyte, and it can be seen that the polymer has good film-forming properties, and the film surface has a certain viscosity, which is beneficial to better contact with an electrode interface. As can be seen from FIG. 4, the glass transition temperature T of the imidazolyl star-shaped polymeric ionic liquid electrolytegThe room-temperature conductivity of the imidazolyl star-shaped polymeric ionic liquid electrolyte is 4.57 × 10 as can be seen from FIG. 5-5S cm-1The conductivity was improved due to the improved electrode-electrolyte interface, and was shown to increase with increasing temperature, reaching a conductivity of 4.95 × 10 at 60 ℃-4S cm-1. It can be seen from the figure that the logarithmic value of the conductivity and the reciprocal of the temperature show a good linear relationship, which conforms to the Arrhenius equation. From FIG. 6, it can be seen that the ionic migration number of the imidazolyl star-shaped polymeric ionic liquid electrolyte is 0.31. The electrochemical window of the imidazolyl star-shaped polymeric ionic liquid electrolyte obtained from FIG. 7 is more than 4.8V, and can meet the requirements of lithium batteries.
Example 2: (R)1Is composed of
Figure BDA0002535086630000071
R2Is composed of
Figure BDA0002535086630000072
)
Under the condition of nitrogen, 1.36g of pentaerythritol, 18.4g of 2-bromine isobutyryl bromide and 8g of triethylamine are added into 40ml of tetrahydrofuran, the mixture is stirred and reacted for 24 hours at room temperature, and 350ml of CH is added into the product after the reaction2Cl2Extraction was performed with 10% HCl, 5% NaHCO, respectively3And repeatedly washing with deionized water. The resulting organic phase was dried over anhydrous magnesium sulfate and dried by spinning under reduced pressure to give a white powdery product. Recrystallizing the product with methanol to obtain four-arm macroinitiator (FIBr)4)2.8 g. Take 0.05g of FIBr4This was charged into a flask with 10g of hydroxyethyl acrylate monomer and 0.112g of bipyridine under nitrogen bubbling, and after half an hour, 0.05g of CuBr was added and reacted under heating at 80 ℃ under nitrogen for 2 hours. Dialyzing and purifying after the reaction is finished, and exchanging and removing ions for a certain timeWater, and dialyzing for 48 h. After completion of dialysis, lyophilization was carried out to obtain 3g of a four-arm branched polymer. 3g of a four-arm branched polymer were dissolved with 10ml of trimethylbromosilane in 30ml of CH under nitrogen2Cl2The reaction solution was reacted in a 100ml single-neck flask for 24 hours, after the reaction was completed, the residual solid was removed by suction filtration, and recrystallized from methanol to obtain 2.7g of a four-arm branched polymeric ionic liquid bromo-compound. Dissolving 2.7g of four-arm branched polymeric ionic liquid brominated compound in 10ml of tetrahydrofuran, adding 8ml of 1-ethylimidazole, refluxing for 3h, drying the residual tetrahydrofuran after the reflux is finished, dissolving a blocky substance by using methanol, and recrystallizing for three times by using tetrahydrofuran to obtain the imidazolyl brominated ionic liquid. Finally, 4.5g of LiTFSI was added, reacted for 24h and filtered to obtain a white flocculent solid, which was then washed repeatedly with deionized water until AgNO was added3The solution appeared white turbidity, and 3.2g of imidazolyl star-shaped polymerized ionic liquid was obtained.
0.1g of imidazolyl star-shaped polymeric ionic liquid was dissolved in 2ml of acetonitrile, 0.02g of LiTFSI was added thereto, and the mixture was stirred at room temperature for 24 hours to obtain a clear solution. The imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte is prepared by casting the imidazole star-shaped polymerized ionic liquid in a polytetrafluoroethylene mold with the diameter of 20mm, volatilizing a solvent, carrying out vacuum drying for 12h at the temperature of 60 ℃, and then transferring the imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte into a glove box for storage.
Example 3: (R)1Is composed of
Figure BDA0002535086630000081
R2Is composed of
Figure BDA0002535086630000082
)
Under the condition of nitrogen, 1.36g of pentaerythritol, 18.4g of 2-bromine isobutyryl bromide and 8g of triethylamine are added into 40ml of tetrahydrofuran, the mixture is stirred and reacted for 24 hours at room temperature, and 350ml of CH is added into the product after the reaction2Cl2Extraction was performed with 10% HCl, 5% NaHCO, respectively3And repeatedly washing with deionized water. The resulting organic phase was dried over anhydrous magnesium sulfate and dried by spinning under reduced pressure to give a white powdery product. Recrystallizing the product by adopting methanol to obtain the four-arm macromoleculeInitiator (FIBr)4)2.8 g. Take 0.05g of FIBr4This was charged into a flask with 10g of hydroxyethyl acrylate monomer and 0.112g of bipyridine under nitrogen bubbling, and after half an hour, 0.05g of CuBr was added and reacted under heating at 80 ℃ under nitrogen for 2 hours. After the reaction, the mixture was purified by dialysis and then freeze-dried to obtain 3g of a four-arm branched polymer. 3g of a four-arm branched polymer were dissolved with 10ml of trimethylbromosilane in 30ml of CH under nitrogen2Cl2And (3) reacting for 24 hours, filtering to remove residual solid after the reaction is finished, and recrystallizing with methanol to obtain 2.7g of the four-arm branched polymeric ionic liquid bromo-compound. Dissolving 2.7g of the compound in 10ml of tetrahydrofuran, adding 8ml of 1-methylimidazole, refluxing for 3h, drying the residual tetrahydrofuran after the reaction is finished, dissolving the tetrahydrofuran in methanol, and recrystallizing the tetrahydrofuran for three times to obtain the imidazolyl bromo-ionic liquid. Finally, 4g of LiPF were added6After 24 hours of reaction, white flocculent solid is obtained by filtration, and then is repeatedly washed by deionized water until AgNO is added3The solution appeared white turbidity, and 3g of imidazolyl star-shaped polymerized ionic liquid was obtained.
0.1g of imidazolyl star-shaped polymeric ionic liquid was dissolved in 2ml of acetonitrile, and 0.018g of LiPF was added6Stirring at room temperature for 24h gave a clear solution. The imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte is prepared by casting the imidazole star-shaped polymerized ionic liquid in a polytetrafluoroethylene mold with the diameter of 20mm, volatilizing a solvent, carrying out vacuum drying for 12h at the temperature of 60 ℃, and then transferring the imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte into a glove box for storage.
Example 4: (R)1Is composed of
Figure BDA0002535086630000091
R2Is composed of
Figure BDA0002535086630000092
)
Under the condition of nitrogen, 1.36g of pentaerythritol, 18.4g of 2-bromine isobutyryl bromide and 8g of triethylamine are added into 40ml of tetrahydrofuran, the mixture is stirred and reacted for 24 hours at room temperature, 350ml of CH is added into the product after the reaction2Cl2Extraction was performed with 10% HCl, 5% NaHCO, respectively3And toAnd repeatedly washing with ionized water. The obtained organic phase is dried by anhydrous magnesium sulfate and is dried by spinning under reduced pressure to obtain a product. Recrystallizing the product with methanol to obtain four-arm macroinitiator (FIBr)4)2.8 g. 0.05g of FIBr was taken4It was mixed with 10g of hydroxyethyl acrylate monomer and 0.112g of bipyridine under nitrogen, and after half an hour, 0.05g of CuBr was added and reacted under heating at 80 ℃ under nitrogen for 2 hours. After the reaction, 3g of a four-arm branched polymer was obtained by dialysis purification and freeze-drying. 3g of polymer and 10ml of trimethylbromosilane are dissolved in 30ml of CH under nitrogen2Cl2After 24 hours of reaction, the residual solid was removed by suction filtration and recrystallized from methanol to obtain 2.7g of a four-arm branched polymeric ionic liquid bromo-compound. Dissolving 2.7g of the compound in 10ml of tetrahydrofuran, adding 8ml of 1-ethylimidazole, refluxing for 3h, drying the residual tetrahydrofuran after the reaction is finished, dissolving the tetrahydrofuran in methanol, and recrystallizing the tetrahydrofuran for three times to obtain the imidazolyl bromo-ionic liquid. Finally, 4g LiCF were added3SO3After 24h of reaction, the solid was filtered and washed repeatedly with deionized water until AgNO was added3The solution appeared white turbidity, and 3g of imidazolyl star-shaped polymerized ionic liquid was obtained.
0.1g of imidazolyl star-shaped polymeric ionic liquid was dissolved in 2ml of acetonitrile, and 0.018g of LiCF was added3SO3Stirring at room temperature for 24h gave a clear solution. The imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte is prepared by casting the imidazole star-shaped polymerized ionic liquid in a polytetrafluoroethylene mold with the diameter of 20mm, volatilizing a solvent, carrying out vacuum drying for 12h at the temperature of 60 ℃, and then transferring the imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte into a glove box for storage.
Example 5: (R)1Is composed of
Figure BDA0002535086630000101
R2Is composed of
Figure BDA0002535086630000102
)
1.36g of pentaerythritol, 18.4g of 2-bromoisobutyryl bromide and 8g of triethylamine were added to 40ml of tetrahydrofuran under nitrogen, and the mixture was stirred at room temperatureThe reaction product is added with 350ml CH after 24h2Cl2Extraction was performed with 10% HCl, 5% NaHCO, respectively3And repeatedly washing with deionized water. The obtained organic phase is dried by anhydrous magnesium sulfate and is dried by spinning under reduced pressure to obtain a product. Recrystallizing the product with methanol to obtain four-arm macroinitiator (FIBr)4)2.8 g. 0.05g of FIBr was taken4It was mixed with 10g of hydroxyethyl acrylate monomer and 0.112g of bipyridine under nitrogen, and after half an hour, 0.05g of CuBr was added and reacted under heating at 80 ℃ under nitrogen for 2 hours. After the reaction, 3g of a four-arm branched polymer was obtained by dialysis purification and freeze-drying. 3g of polymer and 10ml of trimethylbromosilane are dissolved in 30ml of CH under nitrogen2Cl2And reacting for 24 hours, filtering by suction to remove residual solid, and recrystallizing by using methanol to obtain 2.7g of the four-arm branched polymeric ionic liquid brominated compound. 2.7g of this compound were dissolved in 10ml of tetrahydrofuran, and 8ml of 1-propylimidazole was added thereto and refluxed for 3 hours. Drying the residual tetrahydrofuran, dissolving the tetrahydrofuran by using methanol, and recrystallizing the tetrahydrofuran for three times to obtain the imidazolyl bromo-ionic liquid. Finally, 4.5g of LiTFSI was added, reacted for 24h and filtered to obtain a solid, which was repeatedly washed with deionized water until AgNO was added3The solution appeared white turbidity, and 3g of imidazolyl star-shaped polymerized ionic liquid was obtained.
0.1g of imidazolyl star-shaped polymeric ionic liquid was dissolved in 2ml of acetonitrile, 0.02g of LiTFSI was added thereto, and the mixture was stirred at room temperature for 24 hours to obtain a clear solution. The imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte is prepared by casting the imidazole star-shaped polymerized ionic liquid in a polytetrafluoroethylene mold with the diameter of 20mm, volatilizing a solvent, carrying out vacuum drying for 12h at the temperature of 60 ℃, and then transferring the imidazole star-shaped polymerized ionic liquid all-solid-state electrolyte into a glove box for storage.
Since the implementation effect of the imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte prepared in examples 2-5 is similar to that of the imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte prepared in example 1, no description is given here.

Claims (10)

1. An imidazolyl star-shaped polymerized ionic liquid is characterized in that the structural formula is shown as a formula (I):
Figure FDA0002535086620000011
wherein R is1The structure is as follows:
Figure FDA0002535086620000012
Figure FDA0002535086620000013
PF6 -,ClO4 -in the above-mentioned manner, the first and second substrates are,
R2the structure is as follows:
Figure FDA0002535086620000014
m is 1 to 6.
2. The preparation method of the imidazolyl star-shaped polymeric ionic liquid of claim 1, which comprises the following steps:
(1) under the condition of nitrogen, pentaerythritol, 2-bromine isobutyryl bromide and triethylamine are subjected to acylation reaction to prepare four-arm initiator IbIn the step (2) of (a),
Figure FDA0002535086620000015
(2) the initiator IbThe four-arm branched polymer I is prepared by atom transfer radical polymerization of a copper-based catalyst, a ligand and a hydroxyethyl acrylate monomer under the condition of nitrogencIn the step (2) of (a),
Figure FDA0002535086620000021
(3) will IcBromine substitution reaction is carried out with trimethyl bromosilane to prepare four-arm polymeric ionic liquid bromo intermediate IdIn the step (2) of (a),
Figure FDA0002535086620000022
(4) will IdPerforming ion exchange reaction with imidazolyl homologues to obtain imidazolyl star-shaped polymerized ionic liquid IeIn the step (2) of (a),
Figure FDA0002535086620000023
(5) will IePerforming ion exchange reaction with lithium salt to obtain imidazolyl star-shaped polymerized ionic liquid I,
Figure FDA0002535086620000024
3. the method according to claim 2, wherein in step (1), the molar ratio of pentaerythritol, 2-bromoisobutyryl bromide and triethylamine is 1:8: 8; the solvent of the reaction system is tetrahydrofuran.
4. The method according to claim 2, wherein in the step (2), the copper-based catalyst is one selected from the group consisting of CuBr and CuCl; the ligand is selected from one of N, N, N' -pentamethyldiethylenetriamine, tri (2-dimethylaminoethyl) amine, 1,4,7,10, 10-hexamethyltriethylenetetramine and 2, 2-bipyridine; initiator IbThe molar ratio of the copper-based catalyst, the ligand and the hydroxyethyl acrylate is 1:3:10: 100.
5. The method according to claim 2, wherein in step (3), IcThe mass ratio of the catalyst to the trimethyl bromosilane is 1: 4.
6. The method according to claim 2, wherein in the step (4), IdThe mass ratio of the 1-methylimidazole homologue to the 1-methylimidazole homologue is 1: 3.
7. The method of claim 2, wherein in step (5), the lithium salt is LiTFSI or LiCF3SO3、LiClO4、LiBF4、LiPF6And lithium perfluorobutylsulfonate, IeThe mass ratio of the lithium salt to the lithium salt is 1: 1.5.
8. The imidazolyl star-shaped polymeric ionic liquid all-solid-state electrolyte is prepared from the imidazolyl star-shaped polymeric ionic liquid as claimed in claim 1, a lithium salt and a solvent through a solution casting method.
9. The all-solid electrolyte of claim 8, wherein the lithium salt is LiTFSI, LiCF3SO3、LiBF4、LiClO4、LiPF6And lithium perfluorobutylsulfonate.
10. The all-solid-state electrolyte of claim 8, wherein the mass ratio of the imidazolyl star polymeric ionic liquid to the lithium salt is 1: 0.2.
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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN107579277A (en) * 2017-08-14 2018-01-12 南京理工大学 Three arm branched polymeric ionic liquid gel electrolyte and preparation method thereof
CN109286040A (en) * 2018-08-03 2019-01-29 南京理工大学 Four arm branched polymeric ionic liquid gel electrolyte membrances and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107579277A (en) * 2017-08-14 2018-01-12 南京理工大学 Three arm branched polymeric ionic liquid gel electrolyte and preparation method thereof
CN109286040A (en) * 2018-08-03 2019-01-29 南京理工大学 Four arm branched polymeric ionic liquid gel electrolyte membrances and preparation method thereof

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