CN118027287A - Preparation method and application of liquid crystal polymer-based solid single-ion conductor film - Google Patents

Preparation method and application of liquid crystal polymer-based solid single-ion conductor film Download PDF

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CN118027287A
CN118027287A CN202410170445.8A CN202410170445A CN118027287A CN 118027287 A CN118027287 A CN 118027287A CN 202410170445 A CN202410170445 A CN 202410170445A CN 118027287 A CN118027287 A CN 118027287A
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liquid crystal
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film
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ion conductor
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李艺
彭慧
杨永刚
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Suzhou University
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Abstract

The invention discloses a preparation method and application of a liquid crystal polymer-based solid single-ion conductor film. According to the invention, the liquid crystal polymer is used as a solid electrolyte main body material, and the lithium salt is grafted on the liquid crystal polymer to obtain a single ion conductor, so that the liquid crystal electrolyte film with ordered ion channels is obtained.

Description

Preparation method and application of liquid crystal polymer-based solid single-ion conductor film
Technical Field
The invention relates to the field of preparation of liquid crystal polymer films, in particular to a preparation method and application of a liquid crystal polymer-based solid single-ion conductor film.
Background
Organic liquids and gel electrolytes are commonly used in commercial lithium ion batteries. These electrolytes present themselves with the risk of leakage, evaporation and volatile. To overcome these problems, a nonvolatile electrolyte having high ionic conductivity is required. Inorganic solid electrolytes are one of the promising candidates. However, most inorganic solid electrolytes have problems of low ionic conductivity, poor processability, poor interfacial compatibility with electrode materials, and the like. Solid polymer electrolytes are of great interest because of their good mechanical properties and interfacial contact. In this case, the nanostructured liquid crystals can be used as a new electrolyte because they have nanochannels that can efficiently transport lithium ions between electrodes. The single lithium ion conductive electrolyte is characterized in that anions are fixed on a polymer framework through a capturing agent or anchored on the polymer framework, so that the migration number of lithium is increased, and lithium dendrites generated by severe concentration polarization effect of a double-ion conductor can be avoided.
The patent 'a preparation method of an eight-arm liquid crystal block copolymer composite electrolyte' (CN 107256981B) proposes that the eight-arm liquid crystal block copolymer is added to perform microscopic regulation and control on a composite membrane to obtain a composite all-solid-state polymer electrolyte with good mechanical property and stable electrochemical property, but the problem of low lithium migration number of the liquid crystal electrolyte is still not improved. Therefore, there is an urgent need to develop a single ion, ordered arrangement liquid crystal polymer-based solid electrolyte film.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a liquid crystal polymer film with high migration number and conductivity; the polymer film provides an ordered channel for ion transmission by utilizing the ordered structure of liquid crystal, so as to improve the lithium migration number. And the polymer film is prepared by polymerizing a lithium ion conductor and liquid crystal, so that anions of the lithium ion conductor are fixed in the polymer, and further lithium ions are released to obtain the single ion conductor film with high lithium migration number.
In order to solve the technical problems, the first aspect of the present invention provides a preparation method of a liquid crystal polymer-based solid single ion conductor film, which specifically comprises the following steps:
s1, dissolving a trifluoromethyl sulfonimide salt derivative, a photoinitiator and liquid crystal in an organic solution to obtain a mixed solution; both the trifluoromethyl sulfimide salt derivative and the liquid crystal contain carbon-carbon double bonds;
s2, carrying out photo-curing reaction on the mixed solution to obtain the solid single-ion conductor film.
Further, in S1, a leveling agent is added to the organic solvent to form a mixed solution.
Further, in S1, the mass of the trifluoromethyl sulfonyl imide salt derivative and the liquid crystal accounts for 15-20% of the mass of the mixed solution; preferably 18.8%.
Further, in S1, the trifluoromethylsulfonyl imide salt derivative: liquid crystal: the mass ratio of the photoinitiator is (10-20): (74-84): 6.
Further, in S1, the structural formula of the trifluoromethylsulfonyl imide derivative is:
R 1 is Wherein X is-H, -F, -Br or-I;
the R 1 is preferably M is Li, na or K, preferably Li.
Further, the liquid crystal is nematic liquid crystal.
Further, in S1, the structural formula of the nematic liquid crystal is:
Wherein: n ranges from 2 to 10, preferably from 4 to 8, more preferably from 4 to 6;
A is In said A, R is-CH 3, -Cl, -F or-COOCH 3, R is preferably-CH 3.
Preferably, the liquid crystal is 242 and/or C6M.
Further, in S1, the photoinitiator is selected from one or more of 907, 369, 184, 1173, BDK; more preferably 907 and/or 369; the structural formula is as follows:
Further, in S1, the organic solvent is selected from one or more of cyclohexanone, cyclopentanone, ethyl acetate, N-dimethylacetamide, tetrahydrofuran, acetone, dichloromethane, N-methylpyrrolidone; one or more of cyclohexanone, cyclopentanone, ethyl acetate are preferred.
Further, in S1, the leveling agent is a fluorocarbon polymer compound; preferably 3600.
Further, in S2, the photo-curing reaction specifically uses a mercury lamp for curing, where the power of the mercury lamp is 800-1200W, preferably 1000W; the curing time is 10-120s; preferably 30s.
Further, in S2, the mixed solution is poured on a polytetrafluoroethylene mould, and after the bubbles are removed, the solvent is dried and then the photo-curing reaction is carried out.
In a second aspect, the present invention provides a liquid crystal film prepared by the preparation method of the first aspect.
The third aspect of the invention provides an application of the liquid crystal film prepared by the preparation method of the first aspect in a battery.
The invention has the beneficial effects that:
1. the solid single-ion conductor film prepared by the method has higher lithium migration number and ion conductivity; in the curing process, a liquid crystal polymer is used as a solid electrolyte main body material, and lithium salt is grafted on the liquid crystal polymer to obtain a single ion conductor, so that the liquid crystal electrolyte film with ordered ion channels is obtained.
2. The preparation method of the liquid crystal film is simple, the operation is convenient, the raw materials are easy to obtain, and the liquid crystal film has no pollution.
Drawings
FIG. 1 is a diagram of the lithium ion conduction mechanism of the prepared liquid crystal polymer-based Shan Lizi conductor;
FIG. 2 is an optical photograph of the liquid crystal polymer-based Shan Lizi conductor separator N1 prepared in example 4;
FIG. 3 is a polarized image at 85℃of the liquid crystal mixtures prepared in examples 4-6; (a) is the picture of example 4, (b) is the picture of example 5, and (c) is the picture of example 6;
FIG. 4 is an infrared test of the liquid crystal polymer-based Shan Lizi conductor film prepared in example 4 before and after curing;
FIG. 5 is a thermal decomposition temperature test of the liquid crystal polymer-based Shan Lizi conductor film prepared in example 4;
FIG. 6 is an ionic conductivity test of the liquid crystal polymer-based Shan Lizi conductor film prepared in example 4;
FIG. 7 is a lithium migration count test of the liquid crystal polymer-based Shan Lizi conductor film prepared in example 4;
FIG. 8 is a graph of the cycling performance of the assembled LiFePO 4// Li button cell at 0.1C for the liquid crystal polymer based Shan Lizi conductor film prepared in example 4;
FIG. 9 is a polarized image at 85℃of the liquid crystal mixture prepared in comparative example 1.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In some preferred embodiments, a polarizing optical microscope is equipped with LINKAM LTS420 hotplate test material polarizing material at Leica Microsystems CMS GmbH; testing infrared with VERTEX 70,70 fourier transform infrared spectrometer; testing the alternating current impedance with a CHI660D electrochemical workstation; the stability of the lithium battery was tested using a CT2003A type Land test system.
Example 1
This example relates to a process for the preparation of lithium 3- (methacryloxy) propane-1-trifluoromethylsulfonimide (LiMTFSI); the molecular formula of LiMTFSI is
(1) 5.0G of anhydrous potassium 3- (methacryloxy) propane-1-sulfonate was weighed into a three-necked flask and purged with nitrogen. 8.33ml of anhydrous tetrahydrofuran and 0.567ml of DMF were added by syringe. The ice bath is cooled to 0-1 ℃, 13.3g of thionyl chloride is added under stirring, the mixture is reacted for 1h at 0-1 ℃, then the mixture is poured into 66.67ml of ice water, and the reaction is carried out for 12h at room temperature. The upper aqueous layer was poured off, and the lower oil layer was diluted with 26.27ml of dichloromethane, washed 6 times with 8.33ml of water and dried over anhydrous magnesium sulfate. Rotary evaporation at 40 ℃ gave a yellow oil after removal of dichloromethane.
(2) 2.433G of trifluoromethanesulfonamide was weighed into a three-necked flask, purged with nitrogen, and 13.33ml of anhydrous tetrahydrofuran and 3.63g of anhydrous triethylamine were added to the flask via syringe. 3.7g of the yellow oil in step (1) was diluted with 5ml of anhydrous tetrahydrofuran and dropped into the flask. After 1h at 0 ℃, 1h at room temperature, the resulting precipitate was removed by filtration and the solvent was removed by evaporation. The evaporated margarine was washed 4 times with 11.67ml of water in another 30ml of dichloromethane and dried over anhydrous magnesium sulfate. The dichloromethane was evaporated at room temperature to give a yellow transparent oil.
(3) The resulting 3.27g oil was diluted with 10ml of anhydrous tetrahydrofuran. 0.086g of lithium hydride was weighed into a three-necked flask and purged with nitrogen. 15ml of anhydrous tetrahydrofuran was added at 0℃and then the diluted solution was dropped thereinto, followed by reaction at room temperature for 2 hours. Unreacted lithium hydride was removed by filtration, and the filtrate was washed 3 times with 6.67ml of hexane. The resulting solution was evaporated under reduced pressure at room temperature and then recrystallized from dried dichloromethane to give a white LiMTFSI solid.
Example 2
This example relates to a method for preparing lithium p-styrene trifluoromethylsulfonyl imide (LiSTFSI); the molecular formula of LiSTFSI is
(1) And taking a clean three-neck flask, and pumping and filling nitrogen. 4ml of oxalyl chloride, 0.1546ml of DMF and 55ml of ultra-dry acetonitrile were added in sequence using a syringe and stirred for 6h under ice-bath conditions. Then slowly adding 8g of sodium p-styryl sulfonate into the solution, strictly controlling the adding speed in the adding process to avoid the phenomenon of too strong reaction, stirring the obtained mixed solution for 36 hours under the condition of nitrogen protection and room temperature, separating the obtained brown solution containing sodium chloride precipitate by a suction filtration device, and storing and cooling the brown filtrate to 0 ℃ for later use.
(2) 5.78G of trifluoromethylsulfonamide and 1.58g of 4-Dimethylaminopyridine (DMAP) were weighed into a three-necked flask, and the apparatus was purged with nitrogen. 16.2ml of triethylamine and 45ml of ultra-dry acetonitrile were added in sequence with a syringe and stirred at room temperature for 2h until the solids were all dissolved and cooled to 0℃in an ice bath. The p-styrenesulfonyl chloride synthesized in the previous step was taken out and slowly dropped into the above solution by using a syringe, and stirred vigorously at room temperature for 22 hours. Then, the mixture was subjected to rotary evaporation under vacuum, 70ml of methylene chloride was added to dissolve the product, and the mixture was washed twice with 40ml of 4% sodium bicarbonate solution, and finally washed twice with 40ml of 1M hydrochloric acid to obtain a methylene chloride solution in which the product was dissolved. And weighing 3g of potassium carbonate to prepare a saturated solution, pouring the saturated solution of the potassium carbonate into a dichloromethane solution in which the product is dissolved, stirring the mixed solution for 2 hours to obtain a suspension, centrifuging to collect precipitate, drying the precipitate in an oven at 60 ℃ for 8 hours, and recrystallizing the collected pale yellow solid with deionized water to obtain pure potassium p-styrene trifluoromethylsulfonyl imide (KSTFSI).
(3) 2G KSTFSI and a three-neck flask are weighed, and nitrogen is introduced to enable the device to be in a nitrogen atmosphere. 80ml of ultra-dry acetonitrile was added by syringe and stirred until completely dissolved. Equimolar lithium perchlorate is weighed, dissolved in ultra-dry acetonitrile, and the lithium perchlorate solution is added dropwise to KSTFSI solution, stirred overnight. The resulting suspension was filtered through a PTFE filter head having a pore size of 0.22 μm to remove potassium perchlorate precipitate, the acetonitrile solvent was removed by spin evaporation under vacuum, and the resulting solid was dried at 50℃for 8 hours in a vacuum oven to give LiSTFSI.
Example 3
The embodiment relates to a preparation method of a lithium triflimide salt; the molecular formula of the trifluoromethyl sulfonimide lithium salt is
The specific preparation method comprises the following steps: liSTFSI prepared in example 2 was placed in an eggplant-type bottle, to which concentrated nitric acid and concentrated sulfuric acid (LiSTFSI: HNO 3：H2SO4 molar ratio 1:1:1) were added, and stirred slowly at 60 ℃ for 2h. After the reaction, the mixture was cooled in a cooler, and the product was filtered off, washed with ice-cold nitric acid, washed with water several times, and dried. Adding the dry product and bromine water (the molar ratio is 1:1) into a three-necked flask, weighing a proper amount of iron powder as a catalyst, sealing the three-necked flask, inserting one end of the three-necked flask into a guide pipe, placing the other end of the three-necked flask on the water surface, and slightly boiling the solution in the reaction process to generate white smoke. After the reaction, the liquid in the three-necked flask was poured into a lithium hydroxide solution to be washed, and a white lithium trifluoromethylsulfonyl imide salt was obtained.
Example 4
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
(1) 80mg LiMTFSI mg of liquid crystal 242, 24mg of photoinitiator 907, 1.28g of cyclohexanone, 0.32g of ethyl acetate and 8mg of flatting agent 3600 are weighed and uniformly mixed to obtain a liquid crystal mixed liquid. The LiMTFSI: liquid crystal 242: the mass ratio of the photoinitiator 907 was 20:74:6
(2) Pouring the liquid crystal mixed solution on a polytetrafluoroethylene mould, removing bubbles, putting the liquid crystal mixed solution into a 100 ℃ oven for 15min to dry the solvent, taking out the solvent, putting the solvent into a 80 ℃ hot table for heat preservation for 3-5 min, and rapidly putting the solvent into a 1000W mercury lamp for photo-curing for 30s to obtain the polymer film.
Example 5
This example relates to a process for the preparation of a polymer film, which differs from example 4 only in step (1): 40mg LiMTFSI mg of liquid crystal 242, 336mg of photoinitiator 907, 1.28g of cyclohexanone, 0.32g of ethyl acetate and 8mg of flatting agent 3600 are weighed and uniformly mixed to obtain liquid crystal mixed liquid.
Example 6
This example relates to a process for the preparation of a polymer film, which differs from example 4 only in step (1): 60mg LiMTFSI mg of liquid crystal 242, 316mg of photoinitiator 907, 1.28g of cyclohexanone, 0.32g of ethyl acetate and 8mg of flatting agent 3600 are weighed respectively and uniformly mixed to obtain liquid crystal mixed liquid.
Example 7
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
(1) 80mg LiSTFSI mg of liquid crystal 242, 24mg of photoinitiator 907, 1.28g of cyclohexanone, 0.32g of ethyl acetate and 8mg of flatting agent 3600 are weighed and uniformly mixed to obtain a liquid crystal mixed liquid.
(2) Pouring the liquid crystal mixed solution on a polytetrafluoroethylene mould, removing bubbles, putting the liquid crystal mixed solution into a 100 ℃ oven for 15min to dry the solvent, taking out the solvent, putting the solvent into a 80 ℃ hot table for heat preservation for 3-5 min, and rapidly putting the solvent into a 1000W mercury lamp for photo-curing for 30s to obtain the polymer film.
Example 8
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
This embodiment differs from embodiment 1 only in that the photoinitiator 907 in (1) is replaced by a photoinitiator 369.
Example 9
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
this embodiment differs from embodiment 1 only in that the liquid crystal 242 in (1) is replaced with a liquid crystal C6M.
Example 10
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
This example differs from example 1 only in that 1.28g of cyclohexanone and 0.32g of ethyl acetate in (1) were replaced with 1.28g of cyclopentanone and 0.32g of cyclohexanone.
Example 11
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
This embodiment differs from embodiment 2 only in that the photoinitiator 907 in (1) is replaced by a photoinitiator 369.
Example 12
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
this embodiment differs from embodiment 2 only in that the liquid crystal 242 in (1) is replaced with a liquid crystal C6M.
Example 13
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
This example differs from example 2 only in that 1.28g of cyclohexanone and 0.32g of ethyl acetate in (1) were replaced with 1.28g of cyclopentanone and 0.32g of cyclohexanone.
Example 14
The embodiment relates to a method for assembling a lithium ion battery by using a polymer film as a diaphragm, which comprises the following specific steps:
the polymer film prepared in example 4 was immersed in an electrolyte having EC: dmc=1:1, and a lithium ion battery was assembled using LiFePO 4 as the positive electrode and lithium metal as the negative electrode. Wherein the positive electrode LiFePO 4 is prepared by mixing 80wt% of LiFePO 4, 10wt% of conductive carbon black (Super P) and 10wt% of polyvinylidene fluoride (PVDF), then uniformly coating the resulting slurry on a copper foil, and cutting it into wafers having a diameter of 14mm after vacuum drying. And sequentially stacking and packaging the anode sheet LiFePO 4, the polymer film soaked by the electrolyte and the lithium sheet in the CR2032 button cell in a glove box filled with inert gas.
Comparative example 1
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
(1) 120mg LiMTFSI mg of liquid crystal 242, 24mg of photoinitiator 907, 1.28g of cyclohexanone, 0.32g of ethyl acetate and 8mg of flatting agent are weighed and uniformly mixed to obtain a liquid crystal mixed liquid.
(2) Pouring the liquid crystal mixed solution on a polytetrafluoroethylene mould, removing bubbles, putting the liquid crystal mixed solution into a 100 ℃ oven for 15min to dry the solvent, taking out the solvent, putting the solvent into a 80 ℃ hot table for heat preservation for 3-5 min, and rapidly putting the solvent into a 1000W mercury lamp for photo-curing for 30s to obtain the polymer film.
Comparative example 2
The embodiment relates to a preparation method of a polymer film, which comprises the following specific steps:
(1) 376mg of liquid crystal 242, 24mg of photoinitiator 907, 1.28g of cyclohexanone, 0.32g of ethyl acetate and 8mg of flatting agent are respectively weighed and uniformly mixed to obtain a liquid crystal mixture.
(2) Sucking 0.1-0.3 ml of liquid crystal mixture by using a 1ml syringe, spreading a commercial diaphragm Celgard 2325 of a lithium ion battery on a table top, inserting an organic filter head into one section of the syringe, filtering and coating the liquid crystal mixture on the Celgard 2325, placing a wire rod at the upper end of the Celgard 2325 liquid crystal mixture, and uniformly and slowly scraping and coating by force to uniformly spread the wire rod on the Celgard 2325. And then the coated film is put into a 100 ℃ oven for 3min to dry the solvent, taken out and put into a 80 ℃ hot table for heat preservation for 3-5 min, and quickly put into a mercury lamp for photo-curing, thus obtaining the polymer film.
(3) 5Ml of the electrolyte (EC: dmc=1:1) was weighed into a reagent bottle, liMTFSI mg was weighed into the bottle, and the solution was stirred to be dissolved and mixed uniformly. And (3) punching a wafer (diameter is 16 mm) on the prepared polymer film on a punching machine, and immersing the wafer in the prepared electrolyte for 2 hours under the protection of inert gas to obtain the lithium ion battery diaphragm.
Test example 1
The mechanism diagram of the prepared liquid crystal polymer film transmitted to lithium ions is shown in fig. 1: the liquid crystal polymer is used as a main body material of the solid electrolyte, and lithium salt is grafted on the liquid crystal polymer to obtain a single ion conductor, so that the liquid crystal electrolyte film with ordered ion channels is obtained. As shown in fig. 2, the surface of the prepared film is flat and uniform, and the texture is compact; when the content of the lithium salt is at a certain concentration, the liquid crystal mixture has a good schlieren structure (as shown in fig. 3). However, when the content of the lithium salt is increased, as shown in fig. 9, the liquid crystal and the lithium salt are not well mixed together.
As shown in FIG. 4, the characteristic band of the cured acrylate disappeared at 1400cm -1、800cm-1, indicating that the polymerization of the lithium salt and the liquid crystal took place. As shown in fig. 5, the thermal decomposition temperature of the prepared polymer-based single ion conductor is 200 ℃, which indicates that the obtained polymer film has good thermodynamic stability.
To further compare the properties of the liquid crystal polymer films prepared according to the present application, the separators prepared in example 4 and comparative example 2 were compared in terms of room temperature ionic conductivity and lithium migration number, and the results are shown in table 1:
TABLE 1
The results show that although the ionic conductivity of the double ionic conductor prepared in comparative example 2 is higher than that of the single ionic conductor, the liquid crystal single ionic polymer prepared by grafting liquid crystal with lithium salt has a higher lithium migration number than that of the double ionic liquid crystal polymer (fig. 6, 7).
The performance of the separator prepared in example 4 in a button cell of lithium iron phosphate is shown in fig. 8, and the results show that: the button cell LiFePO 4// Li has good capacity and coulombic efficiency at 0.1C, and provides a certain practical significance for the application of the single-ion liquid crystal polymer diaphragm in the cell.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.

Claims (10)

1. The preparation method of the liquid crystal polymer-based solid single-ion conductor film is characterized by comprising the following steps of:
s1, dissolving a trifluoromethyl sulfonimide salt derivative, a photoinitiator and liquid crystal in an organic solution to obtain a mixed solution; both the trifluoromethyl sulfimide salt derivative and the liquid crystal contain carbon-carbon double bonds;
s2, carrying out photo-curing reaction on the mixed solution to obtain the solid single-ion conductor film.
2. The method of claim 1, wherein the step of S2 further comprises pouring the mixed solution onto a polytetrafluoroethylene mold, removing bubbles, drying the solvent, and performing a photo-curing reaction.
3. The method of claim 1, wherein the trifluoromethylsulfonyl imide salt derivative has the structural formula:
wherein R 1 is Wherein X is-H, -F, -Br or-I; m is Li, na or K.
4. The method of claim 1, wherein the liquid crystal is a nematic liquid crystal having the formula:
wherein: n is an integer ranging from 2 to 10;
A is
R in A is-CH 3, -Cl, -F or-COOCH 3.
5. The preparation method according to claim 1, wherein the sum of the mass of the trifluoromethanesulfonyl imide derivative and the mass of the liquid crystal is 15-20% of the mass of the mixed solution.
6. The method of preparation of claim 1, wherein the derivative of trifluoromethylsulfonyl imide salt: liquid crystal: the mass ratio of the photoinitiator is (10-20): (74-84): 6.
7. The preparation method according to claim 1, wherein the organic solvent is one or more selected from cyclohexanone, cyclopentanone, ethyl acetate, N-dimethylacetamide, tetrahydrofuran, acetone, dichloromethane, and N-methylpyrrolidone.
8. The method of claim 1, wherein the leveling agent is a fluorocarbon polymer.
9. A film prepared by the method of any one of claims 1-8.
10. Use of the film of claim 9 in a battery.
CN202410170445.8A 2024-02-06 2024-02-06 Preparation method and application of liquid crystal polymer-based solid single-ion conductor film Pending CN118027287A (en)

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