CN115304710A - Ionic liquid-based copolymer gel electrolyte and preparation method thereof - Google Patents

Ionic liquid-based copolymer gel electrolyte and preparation method thereof Download PDF

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CN115304710A
CN115304710A CN202211046008.2A CN202211046008A CN115304710A CN 115304710 A CN115304710 A CN 115304710A CN 202211046008 A CN202211046008 A CN 202211046008A CN 115304710 A CN115304710 A CN 115304710A
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房大维
文静宜
刘娜
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Liaoning University
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Abstract

The invention relates to the technical field of electrolyte materials, in particular to an ionic liquid based copolymer gel electrolyte and a preparation method thereof. The method comprises the following steps: firstly, hydroxyl functionalized vinyl imidazole bromide ionic liquid monomers are synthesized, hydroxyl functionalized vinyl imidazole bromide ionic liquid monomers with different anions are prepared by adopting an ion exchange method, and the hydroxyl functionalized vinyl imidazole bromide ionic liquid monomers and a certain amount of methacrylic acid monomers undergo free radical copolymerization under the action of an initiator, so that the conductive gel electrolyte with different microstructures and properties and using polyion liquid as a matrix is prepared. According to the invention, an ester group-containing flexible unit and an anion with a larger ionic radius are introduced into the main chain of the ionic liquid-based copolymer, and the synergistic effect of the flexible unit and the anion can improve the mobility of the polymer, so that the ionic conductivity and the mechanical property of the material are improved. The ionic liquid-based copolymer electrolyte provided by the invention provides a new research direction for designing advanced polymer electrolytes.

Description

Ionic liquid-based copolymer gel electrolyte and preparation method thereof
Technical Field
The invention relates to the technical field of electrolyte materials, in particular to an ionic liquid based copolymer gel electrolyte and a preparation method thereof.
Background
With the rapid development of wearable electronic devices, energy storage devices with high energy density have attracted extensive attention in recent years in academia and industry. The conventional liquid electrolyte is likely to cause a serious safety problem in that lithium dendrite is easily generated during charge and discharge to pierce a separator to cause a short circuit, and in that the electrolyte is likely to leak during bending deformation. The flexible electrolyte has a good application prospect in the fields of functional materials, energy batteries and the like due to the reliable mechanical property and good self-healing property.
The Ionic Liquid (ILs) has the advantages of high ionic conductivity, difficult combustion, good thermal stability and electrochemical stability, low volatility and the like, and is an ideal choice for replacing the traditional organic liquid electrolyte. Furthermore, ILs can also be linked to polymer networks by covalent bonds or can synthesize gel polymers, i.e. polyionic liquids (PILs), from themselves as monomers. PILs not only inherit the advantages of monomeric ILs (flame retardancy, thermal stability and electrochemical stability), but also maintain the strong mechanical toughness of the polymer. However, the ionic conductivity of common PILs is relatively lower than the corresponding ILs, resulting in a decrease in the overall performance of the assembled device.
Disclosure of Invention
The invention aims to provide an ionic liquid-based copolymer gel electrolyte and a preparation method thereof, wherein the glass transition temperature (T) of a polymer can be effectively reduced by introducing a monomer containing rich ester groups and anions with larger ionic radius into a PILs (Poly-L-phenyleneisophthalamide) main chain g ) And the movement of polymer chains is promoted, so that the polymer electrolyte with high ionic conductivity, good electrochemical stability and excellent mechanical properties is obtained.
In order to realize the purpose, the technical scheme of the invention is as follows:
an ionic liquid-based copolymer gel electrolyte is prepared by the following steps:
(1) Synthesis of hydroxy functionalized vinyl imidazole bromide monomer: adding bromoalkyl alcohol, 1-vinyl imidazole and a certain amount of acetonitrile solvent into an anhydrous and oxygen-free reaction container in sequence, replacing gas with a double-row pipe for multiple times to ensure that a three-neck flask is finally and completely in a nitrogen atmosphere, reacting, washing a product with an organic solvent for multiple times, evaporating to dryness to be viscous by using a rotary evaporator, and drying in vacuum to constant weight;
(2) Carrying out anion exchange on the ionic liquid obtained in the step (1): respectively dissolving the hydroxyl functionalized vinyl imidazole bromide monomer prepared in the step (1) and lithium salt in distilled water by adopting an ion exchange method, carrying out ion exchange reaction, carrying out multiple times of extraction by using an organic solvent after the reaction is finished, removing the organic solvent to obtain an oily substance, and drying in vacuum to constant weight to obtain hydroxyl functionalized vinyl imidazole salt ionic liquids of different anions;
(3) Preparation of ionic liquid-based copolymer gel electrolyte: simultaneously dissolving one of methacrylic acid monomers, methacrylate monomers, acrylic acid monomers and acrylate monomers and the hydroxyl functionalized vinyl imidazole bromide monomer prepared in the step (1) or the hydroxyl functionalized vinyl imidazole salt ionic liquid prepared in the step (2) and an initiator in a certain amount of dried polymeric organic solvent, carrying out polymerization reaction under the condition of nitrogen, filtering a generated precipitate after the reaction is finished, repeatedly washing the precipitate for several times by using the organic solvent, further purifying the precipitate by a Soxhlet extraction method, dissolving the purified precipitate by using the organic solvent, transferring the purified precipitate into a mold, drying the precipitate in vacuum, and forming to obtain the ester group functionalized ionic liquid based copolymer gel electrolyte.
In the ionic liquid-based copolymer gel electrolyte, the alkyl bromide in the step (1) is one or more of 2-bromoethanol, 3-bromo-1-propanol, 4-bromo-1-butanol, 6-bromo-1-hexanol and 8-bromo-1-octanol.
In the ionic liquid-based copolymer gel electrolyte, in the step (1), the molar ratio of the brominated alkyl alcohol to the 1-vinylimidazole is 1-1.2.
In the ionic liquid based copolymer gel electrolyte, in the step (2), the molar ratio of the hydroxyl functionalized vinyl imidazole bromide monomer to the lithium salt is 1.1-1.3, and the ion exchange reaction is carried out for 24 hours at 25 ℃.
In the ionic liquid based copolymer gel electrolyte, in the step (2), the ion exchange reaction is performedShould be anionic from Br - Switched to TFSI - 、FSI - 、PF 6 - 、BF 4 - To (3) is provided.
In the ionic liquid based copolymer gel electrolyte, in the step (3), the molar ratio of the methacrylic monomer or the methacrylate ester monomer or the acrylic monomer or the acrylate ester monomer to the hydroxyl functionalized vinyl imidazolium salt monomer is 1 to 50.
In the ionic liquid based copolymer gel electrolyte, in the step (3), the initiator is azobisisobutyronitrile, and the initiator accounts for 0.5 to 1 percent of the total molar amount of the monomers.
In the ionic liquid based copolymer gel electrolyte, in the step (3), the polymerization organic solvent is an organic solvent with a boiling point of 80-120 ℃; the washing organic solvent is an organic solvent with a boiling point of 40-90 ℃.
In the step (3), the polymerization reaction is carried out by placing the reaction device in a pre-heated 70 ℃ oil bath for 24 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the ionic liquid based copolymer gel electrolyte provided by the invention successfully prepares the novel high-performance conductive gel electrolyte by a simple one-pot method under the condition of not using a cross-linking agent, has the advantages of simplicity and good repeatability, and is hopefully applied to a plurality of important fields of flexible electronic products, super capacitors, lithium batteries and the like.
2. According to the preparation method of the ionic liquid based copolymer gel electrolyte, provided by the invention, a series of gel electrolytes with different microstructures and properties and taking polyion liquid as a matrix are prepared by regulating and controlling the anionic structure, the type and the proportion of the comonomer. Compared with PILs homopolymer electrolyte, the PILs copolymer electrolyte has higher ionic conductivity, excellent mechanical property and good self-healing capability, and can provide new insight for developing advanced high-safety polymer electrolyte.
3. According to the preparation method of the ionic liquid-based copolymer gel electrolyte, after anions with larger radius are introduced through ion exchange, due to the fact that the interaction of ionic bonds and ion-dipole bonds between the copolymers is weak, physical crosslinking among polymer chains is reduced, and the glass transition temperature (T) is caused g ) Reduce and greatly improve the mobility of polymer chains.
Drawings
FIG. 1 shows the NMR spectrum of 1-vinyl-3-hydroxyethyl imidazolium bromide monomer ([ VIL-OH ] [ Br ]).
FIG. 2 is a NMR chart of 1-vinyl-3-hydroxyethylimidazolium bromide monomer ([ VIL-OH ] [ Br ]).
FIG. 3 is a Fourier transform infrared spectrum of 1-vinyl-3-hydroxyethylimidazolium bromide monomer ([ VIL-OH ] [ Br ]).
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples describing preferred embodiments of the invention, but it is to be understood that these descriptions are intended only to further illustrate the features and advantages of the invention and are not intended to limit the scope of the claims which follow.
Example 1 free radical copolymerization of vinylimidazolium salt ionic liquids with methyl acrylate (BA) (one) preparation method is as follows:
(1) Synthesis of [ VIL-OH ] [ Br ]: adding 110mmol of 2-bromoethanol, 100mmol of 1-vinyl imidazole and 10mL of acetonitrile solvent into an anhydrous and oxygen-free reaction container in sequence, replacing gas with a double-row pipe for multiple times, enabling a three-neck flask to be finally and completely in a nitrogen atmosphere, reacting, washing a product with ethyl acetate for multiple times, evaporating to be thick by using a rotary evaporator, and drying in vacuum to constant weight;
(2) Carrying out anion exchange on the ionic liquid obtained in the step (1): respectively dissolving the prepared [ VIL-OH ] [ Br ] and lithium bistrifluoromethanesulfonylimide (LiTFSI) in distilled water by adopting an ion exchange method, wherein the molar ratio of the [ VIL-OH ] [ Br ] to the lithium bistrifluoromethanesulfonylimide (LiTFSI) is 1.2, carrying out ion exchange at 25 ℃ for 24 hours, carrying out multiple extraction on ethyl acetate after reaction is finished, removing an organic solvent to obtain an oily substance, and carrying out vacuum drying at 60 ℃ to constant weight to obtain 1-vinyl-3-hydroxyethyl imidazole bistrifluoromethanesulfonylimide salt ([ VIL-OH ] [ TFSI ]);
(3) With [ VIL-OH][TFSI][ molar ratio of BA 1 ]][TFSI]50mmol BA, 1mmol AIBN initiator and 5mL toluene, stirred vigorously at 70 ℃ for 24h. And after the polymerization process is finished, filtering the generated precipitate, repeatedly washing the precipitate for a plurality of times by using ethyl acetate, further purifying the precipitate by using a Soxhlet extraction method, dissolving the purified precipitate by using an organic solvent, transferring the purified precipitate into a mold of a 1mm sheet, and finally drying the purified precipitate in a vacuum oven at 60 ℃ for 24 hours to obtain the conductive gel electrolyte sheet with the thickness of 1 mm. The performance test is carried out, the tensile strength of the conductive gel is 1.8MPa, the elongation at break is 260 percent, and the ionic conductivity is 3.34 +/-0.08 mS cm -1 。
Example 2 radical copolymerization of vinylimidazolium ionic liquids with Ethyl Acrylate (EA) (one) the preparation method is as follows:
(1) Synthesis of [ VIL-OH ] [ Br ]: adding 110mmol of 2-bromoethanol, 100mmol of 1-vinyl imidazole and 10mL of acetonitrile solvent into an anhydrous and oxygen-free reaction container in sequence, replacing gas with a double-row pipe for multiple times, enabling a three-neck flask to be finally and completely in a nitrogen atmosphere, reacting, washing a product with ethyl acetate for multiple times, evaporating to be thick by using a rotary evaporator, and drying in vacuum to constant weight;
(2) Carrying out anion exchange on the ionic liquid obtained in the step (1): respectively dissolving the prepared [ VIL-OH ] [ Br ] and lithium bistrifluoromethanesulfonylimide (LiTFSI) in distilled water by adopting an ion exchange method, wherein the molar ratio of the [ VIL-OH ] [ Br ] to the lithium bistrifluoromethanesulfonylimide (LiTFSI) is 1.2, carrying out ion exchange at 25 ℃ for 24h, carrying out multiple extraction with ethyl acetate after the reaction is finished, removing an organic solvent to obtain an oily substance, and carrying out vacuum drying at 60 ℃ to constant weight to obtain 1-vinyl-3-hydroxyethyl imidazole bistrifluoromethanesulfonylimide salt ([ VIL-OH ] [ TFSI ]);
(3) With [ VIL-OH][TFSI][ 1/EA ] in an ampoule bottle dried without water and oxygen, 50mmol of [ 2 VIL-OH ] was added in this order][TFSI]50mmol EA, 1mmol AIBN initiator and 5mL toluene, stirred vigorously at 70 ℃ for 24h. After the polymerization process, the precipitate formed is filtered and washed several times with ethyl acetate and subjected to Soxhlet extractionFurther purifying, dissolving with organic solvent, transferring into a mold of 1mm sheet, and drying in a vacuum oven at 60 deg.C for 24h to obtain conductive gel electrolyte sheet with thickness of 1 mm. The performance test is carried out, the tensile strength of the conductive gel is 1.7MPa, the elongation at break is 255%, and the ionic conductivity is 3.18 +/-0.12 mS cm -1 。
Example 3 radical copolymerization of vinylimidazolium salt ionic liquids with Methyl Methacrylate (MMA) (one) the preparation method is as follows:
(1) [ VIL-OH ] [ Br ] Synthesis: adding 110mmol of 2-bromoethanol, 100mmol of 1-vinyl imidazole and 10mL of acetonitrile solvent into an anhydrous and oxygen-free reaction container in sequence, replacing gas with a double-row pipe for multiple times, enabling a three-neck flask to be finally and completely in a nitrogen atmosphere, reacting, washing a product with ethyl acetate for multiple times, evaporating to be thick by using a rotary evaporator, and drying in vacuum to constant weight;
(2) Carrying out anion exchange on the ionic liquid obtained in the step (1): respectively dissolving the prepared [ VIL-OH ] [ Br ] and lithium bistrifluoromethanesulfonylimide (LiTFSI) in distilled water by adopting an ion exchange method, wherein the molar ratio of the [ VIL-OH ] [ Br ] to the lithium bistrifluoromethanesulfonylimide (LiTFSI) is 1.2, carrying out ion exchange at 25 ℃ for 24 hours, carrying out multiple extraction on ethyl acetate after reaction is finished, removing an organic solvent to obtain an oily substance, and carrying out vacuum drying at 60 ℃ to constant weight to obtain 1-vinyl-3-hydroxyethyl imidazole bistrifluoromethanesulfonylimide salt ([ VIL-OH ] [ TFSI ]);
(3) With [ VIL-OH][TFSI][ 1 molar ratio of MMA ]][TFSI]50mmol MMA, 1mmol AIBN initiator and 5mL toluene are stirred vigorously at 70 ℃ for 24h. And after the polymerization process is finished, filtering the generated precipitate, repeatedly washing the precipitate by ethyl acetate for a plurality of times, further purifying the precipitate by a Soxhlet extraction method, dissolving the precipitate by using an organic solvent after the purification, transferring the precipitate into a mould with a sheet thickness of 1mm, and finally drying the mould in a vacuum oven at 60 ℃ for 24 hours to obtain the conductive gel electrolyte sheet with the thickness of 1 mm. The performance test is carried out, the tensile strength of the conductive gel is 1.3MPa, the elongation at break is 172 percent, and the ionic conductivity is 1.88 +/-0.45 mS cm -1 。
Example 4 radical copolymerization of vinylimidazolium salt ionic liquids with Ethyl Methacrylate (EMA) (one) the preparation method is as follows:
(1) [ VIL-OH ] [ Br ] Synthesis: adding 110mmol of 2-bromoethanol, 100mmol of 1-vinyl imidazole and 10mL of acetonitrile solvent into an anhydrous and oxygen-free reaction container in sequence, replacing gas with a double-row pipe for multiple times, enabling a three-neck flask to be finally and completely in a nitrogen atmosphere, reacting, washing a product with ethyl acetate for multiple times, evaporating to be thick by using a rotary evaporator, and drying in vacuum to constant weight;
(2) Carrying out anion exchange on the ionic liquid obtained in the step (1): respectively dissolving the prepared [ VIL-OH ] [ Br ] and lithium bistrifluoromethanesulfonylimide (LiTFSI) in distilled water by adopting an ion exchange method, wherein the molar ratio of the [ VIL-OH ] [ Br ] to the lithium bistrifluoromethanesulfonylimide (LiTFSI) is 1.2, carrying out ion exchange at 25 ℃ for 24h, carrying out multiple extraction with ethyl acetate after the reaction is finished, removing an organic solvent to obtain an oily substance, and carrying out vacuum drying at 60 ℃ to constant weight to obtain 1-vinyl-3-hydroxyethyl imidazole bistrifluoromethanesulfonylimide salt ([ VIL-OH ] [ TFSI ]);
(3) With [ VIL-OH][TFSI][ EMA ] in a molar ratio of 1][TFSI]50mmol EMA, 1mmol AIBN initiator and 5mL toluene, stirred vigorously at 70 ℃ for 24h. And after the polymerization process is finished, filtering the generated precipitate, repeatedly washing the precipitate for a plurality of times by using ethyl acetate, further purifying the precipitate by using a Soxhlet extraction method, dissolving the purified precipitate by using an organic solvent, transferring the purified precipitate into a mold of a 1mm sheet, and finally drying the purified precipitate in a vacuum oven at 60 ℃ for 24 hours to obtain the conductive gel electrolyte sheet with the thickness of 1 mm. The performance test is carried out, the tensile strength of the conductive gel is 1.3MPa, the breaking elongation is 176 percent, and the ionic conductivity is 1.57 +/-0.31 mS cm -1 。
Comparative example 1 free radical homopolymerization of vinylimidazolium ionic liquids
The preparation method comprises the following steps:
sequentially adding 100mmol of [ VIL-OH ] in an anhydrous and oxygen-free dried ampoule bottle][TFSI]1mmol AIBN initiator and 5mL toluene, stirring vigorously at 70 deg.C for 24h, filtering the precipitate, washing with ethyl acetate repeatedly for several times, further purifying by Soxhlet extraction, and purifying with organic solventThe solvent was dissolved and transferred to a mold of a 1mm sheet, and finally dried in a vacuum oven at 60 ℃ for 24 hours to obtain a conductive gel electrolyte sheet having a thickness of 1 mm. The performance test is carried out, the tensile strength of the conductive gel is 1.1MPa, the elongation at break is 194 percent, and the ionic conductivity is 0.24 +/-0.03 mS cm -1 。
Example 5 characterization
The hydroxyl functionalized 1-vinyl-3-hydroxyethyl imidazole bromide salt monomer is characterized by means of nuclear magnetic resonance hydrogen spectrum, nuclear magnetic resonance carbon spectrum and Fourier transform infrared spectrum, and the results are shown in figures 1-3.
FIG. 1 is a NMR spectrum of 1-vinyl-3-hydroxyethylimidazolium bromide monomer. 1 H NMR(500MHz,DMSO-d 6 ,298K),δ:9.67(s,1H,N-CH＝N),8.30(s,1H,N-CH＝CH-N),7.95(s,1H,N-CH＝CH-N),7.38(dd,J＝15.7,8.8Hz,1H,＝CH-N),6.02(dd,J＝15.7,2.4Hz,1H,＝CH 2 ),5.39(d,J＝8.7Hz,1H,＝CH 2 ),4.29(s,2H,-CH 2 -),3.74(s,2H,-CH 2 -O).
FIG. 2 is a carbon nuclear magnetic resonance spectrum of 1-vinyl-3-hydroxyethylimidazolium bromide monomer. 13 C NMR(126MHz,DMSO-d 6 ,298K),δ:135.70,128.91,123.80,119.10,108.87,59.22,52.18.
The above characterization confirmed the successful synthesis of 1-vinyl-3-hydroxyethylimidazolium bromide monomer.
FIG. 3 is a Fourier transform infrared spectrum of 1-vinyl-3-hydroxyethyl imidazolium bromide monomer, as shown in the following table.
Figure BDA0003822423900000061
The above characterization confirmed the successful synthesis of 1-vinyl-3-hydroxyethylimidazolium bromide monomer.

Claims (9)

1. The ionic liquid-based copolymer gel electrolyte is characterized in that the preparation method comprises the following steps:
(1) Synthesis of hydroxy functionalized vinyl imidazole bromide salt monomer: adding bromoalkyl alcohol, 1-vinyl imidazole and a certain amount of acetonitrile solvent into an anhydrous and oxygen-free reaction container in sequence, replacing gas with a double-row pipe for multiple times to ensure that a three-neck flask is finally and completely in a nitrogen atmosphere, reacting, washing a product with an organic solvent for multiple times, evaporating to dryness to be viscous by using a rotary evaporator, and drying in vacuum to constant weight;
(2) Carrying out anion exchange on the ionic liquid obtained in the step (1): respectively dissolving the hydroxyl functionalized vinyl imidazole bromide monomer prepared in the step (1) and lithium salt in distilled water by adopting an ion exchange method, carrying out ion exchange reaction, carrying out multiple times of extraction by using an organic solvent after the reaction is finished, removing the organic solvent to obtain an oily substance, and drying in vacuum to constant weight to obtain hydroxyl functionalized vinyl imidazole salt ionic liquids of different anions;
(3) Preparation of ionic liquid-based copolymer gel electrolyte: dissolving one of methacrylic acid monomers, methacrylic acid ester monomers, acrylic acid monomers and acrylic acid ester monomers and the hydroxyl functionalized vinyl imidazolium bromide monomer prepared in the step (1) or the hydroxyl functionalized vinyl imidazolium ionic liquid prepared in the step (2) and an initiator in a certain amount of dried polymeric organic solvent at the same time, carrying out polymerization reaction under the condition of nitrogen, filtering generated precipitates after the reaction is finished, repeatedly washing the precipitates for a plurality of times by using the organic solvent, further purifying the precipitates by a Soxhlet extraction method, dissolving the purified precipitates by using the organic solvent, transferring the precipitates into a mold, drying the precipitates in vacuum, and forming the ester group functionalized ionic liquid based copolymer gel electrolyte.
2. The ionic liquid-based copolymer gel electrolyte of claim 1, wherein in step (1), the alkyl bromide is one or more of 2-bromoethanol, 3-bromo-1-propanol, 4-bromo-1-butanol, 6-bromo-1-hexanol, and 8-bromo-1-octanol.
3. The ionic liquid-based copolymer gel electrolyte of claim 1, wherein in the step (1), the molar ratio of the brominated alkyl alcohol to the 1-vinylimidazole is 1-1.2.
4. The ionic liquid based copolymer gel electrolyte as claimed in claim 1, wherein in the step (2), the molar ratio of the hydroxyl functionalized vinyl imidazole bromide monomer to the lithium salt is 1.1-1.3, and the ion exchange reaction is carried out at 25 ℃ for 24h.
5. The ionic liquid-based copolymer gel electrolyte of claim 1, wherein in the step (2), the ion exchange reaction is anion from Br - Switched to TFSI - 、FSI - 、PF 6 - 、BF 4 - One kind of (1).
6. The ionic liquid-based copolymer gel electrolyte of claim 1, wherein in step (3), the molar ratio of the methacrylic monomer or the methacrylate monomer or the acrylic monomer or the acrylate monomer to the hydroxyl-functionalized vinylimidazolium salt monomer is 1.
7. The ionic liquid-based copolymer gel electrolyte as claimed in claim 1, wherein in the step (3), the initiator is azobisisobutyronitrile, and the initiator accounts for 0.5 to 1 percent of the total molar amount of the monomers.
8. The ionic liquid-based copolymer gel electrolyte of claim 1, wherein in the step (3), the polymeric organic solvent is an organic solvent having a boiling point of 80 to 120 ℃; the washing organic solvent is an organic solvent with a boiling point of 40-90 ℃.
9. The ionic liquid based copolymer gel electrolyte as claimed in claim 1, wherein in the step (3), the polymerization reaction is carried out by placing the reaction apparatus in an oil bath kettle preheated in advance at 70 ℃ for 24 hours.
CN202211046008.2A 2022-08-30 2022-08-30 Ionic liquid-based copolymer gel electrolyte and preparation method thereof Pending CN115304710A (en)

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