CN113185695B - Polyether sulfone single-ion polymer and single-ion gel polymer electrolyte - Google Patents

Polyether sulfone single-ion polymer and single-ion gel polymer electrolyte Download PDF

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CN113185695B
CN113185695B CN202110392601.1A CN202110392601A CN113185695B CN 113185695 B CN113185695 B CN 113185695B CN 202110392601 A CN202110392601 A CN 202110392601A CN 113185695 B CN113185695 B CN 113185695B
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polyether sulfone
ion
lithium
polymer
pes
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CN113185695A (en
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呼微
尤莹雪
梁笑笑
杜新伟
赵麒
刘佰军
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Jilin Dongchi New Energy Technology Co ltd
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Changchun University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a polyether sulfone single-ion polymer, the chemical structure of which is shown as formula (I). Firstly, polyether sulfone containing methoxyl is prepared; then demethylating the polyether sulfone containing the methoxyl group by boron tribromide; and finally, reacting the hydroxyl-containing polyether sulfone with organic lithium salt 3-chloropropane sulfonyl (trifluoromethanesulfonyl) imide to obtain the polyether sulfone single-ion polymer. Because anions are fixed on a polyether sulfone matrix, only Li is contained in the system + And (4) moving. The lithium bissulfonylimide part has low ion dissociation domain energy, promotes the dissociation and transmission of lithium ions, provides more lithium sources, ensures the high lithium ion conductivity of the system, and improves the Li of electrolyte + The number of transitions; thereby improving the electrochemical performance and stability of the battery. The invention also providesProvides a single ion gel polymer electrolyte, which is prepared by blending polyether sulfone single ion polymer and functional polymer, casting and soaking. The prepared single-ion gel polymer electrolyte has excellent and stable battery performance and can be widely applied to the field of lithium ion batteries and lithium metal batteries.

Description

Polyether sulfone single-ion polymer and single-ion gel polymer electrolyte
Technical Field
The invention belongs to the technical field of lithium battery application, and particularly relates to a polyether sulfone single-ion gel polymer and a single-ion gel polymer electrolyte prepared from the same.
Background
The modern civilization development encounters a bottleneck and solves the problems due to the excessive consumption of fossil energy, atmospheric pollution and global warming
One approach is to develop and effectively utilize green energy. Lithium ion batteries are advantageous in terms of specific energy density, cost and safety
The advantages of the surfaces become one of the focuses of people. At present, Lithium Ion Batteries (LIBs) are widely used in portable electronic devices such as mobile phones and notebook computers, electric vehicles and large-scale power storage systems, and play an important role in daily life. The traditional lithium ion battery is composed of a liquid organic electrolyte, a diaphragm, a positive electrode, a negative electrode and the like. However, the commercial liquid electrolyte LIBs, which are currently most widely used, have serious safety problems, such as liquid leakage, flammability, and explosiveness. The development of novel separators and the research of polymer electrolytes become hot topics of the current lithium ion battery technology.
Single-ion polymer electrolyte (SIPE) is formed by fixing anionic groups on a polymer or an inorganic framework in a covalent bond mode through chemical bonds, so that only lithium ions in the system move. Lithium ions can be deposited more uniformly in the charging and discharging process, and the formation of lithium dendrites is relieved. Meanwhile, the leakage problem of the electrolyte in the lithium ion battery can be solved, and the safety of the lithium ion battery is improved. Therefore, the SIPE is adopted to replace the traditional diaphragm, so that the problem of lithium dendrite can be solved to a certain extent, and the battery performance and the safety of the lithium ion battery are improved.
As is well known, polyphenylene oxide is a special engineering plastic and has the advantages of excellent mechanical properties, high temperature resistance, chemical stability, flame retardancy and the like, so that the polyphenylene oxide can be used as a next-generation diaphragm material. Chinese patent CN 101916836 a uses polysulfone engineering plastics and polyvinylpyrrolidone as raw materials, and after dissolving the raw materials in a solvent, the raw materials are blended, coated and cast into a film, and then an electrolyte solution containing lower alcohol is used to perform hydrophilization treatment on the film to prepare a polymer diaphragm for an aqueous solution electrochemical device. The blend film has excellent chemical and thermal stability, but the membrane has poor film forming uniformity and limited porosity. The Chinese patent CN 103000851A adopts an electrostatic spinning technology to prepare the polysulfone nanofiber membrane, and the polysulfone nanofiber membrane has the advantages of tear resistance, high temperature resistance and high pressure resistance, and has good uniformity and high porosity.
In summary, the separator prepared from polyethersulfone adopts small-molecule lithium salt as lithium source. In the charging and discharging process of the battery, concentration polarization can be generated due to the difference of the moving speed of anions and cations, and the stability of the battery is influenced. Meanwhile, the reduction of the transference number of the lithium ions accelerates the growth of lithium dendrites, further affects the performance of the battery, and even causes safety accidents such as explosion and the like.
Disclosure of Invention
In order to solve the technical problems, the invention tries to graft lithium salt on a rigid polymer with good thermal stability to prepare a single-ion polymer, so that the obtained single-ion gel polymer electrolyte can reduce concentration polarization generated in the charging and discharging process of the battery and improve the safety performance and the cycle performance of the battery. The invention aims to provide a polyether sulfone single-ion polymer and a polyether sulfone single-ion gel polymer electrolyte prepared from the polyether sulfone single-ion polymer.
The polyether sulfone single-ion polymer shown in the formula (I) has the following chemical structure:
Figure RE-GDA0003114763630000021
wherein:
Figure RE-GDA0003114763630000022
m＝2～4；
R 2 ＝-H，
Figure RE-GDA0003114763630000023
m＝2～4。
the invention also provides a preparation method of the polyether sulfone single ion polymer shown in the formula (I), and the synthesis route is shown as follows:
Figure RE-GDA0003114763630000024
further, the preparation method of the polyethersulfone single-ion polymer shown in formula (i) comprises the following steps:
(i) under the protection of inert gas, mixing lithium hydroxide and trifluoromethanesulfonamide, adding the mixture into anhydrous acetonitrile, adding 3-chloropropane sulfonyl chloride in an ice water bath, reacting at normal temperature, filtering, performing rotary evaporation, and recrystallizing to obtain 3-chloropropane sulfonyl (trifluoromethanesulfonyl) imide Lithium (LiPSI);
(ii) under the protection of inert gas, mixing 2-Methoxy Hydroquinone (MHQ) and 4, 4' -difluoro diphenylsulfone (FPS), adding a catalyst, a solvent and an azeotropic dehydrating agent, stirring and heating to 140-170 ℃ for reaction for 12 hours to obtain a viscous solution, then precipitating the viscous solution into distilled water, cooling, crushing a product, washing by using deionized water and ethanol, and drying to obtain methoxy polyether sulfone (PES-OCH) 3 ）;
(iii) Under the protection of inert gas, PES-OCH obtained in the step (ii) 3 Dissolving in anhydrous chloroform, adding chloroform solution containing boron tribromide at-40 deg.C, reacting at room temperature for 12 hr, precipitating with ethanol, washing with deionized water and ethanol, and drying to obtain hydroxy-containing polyethersulfone (PES-OH);
(iv) and (4) under the protection of inert gas, dissolving PES-OH obtained in the step (iii) in anhydrous dimethyl sulfoxide (DMSO), adding LiH, heating and stirring, adding the LiCPSI obtained in the step (i), and heating to react to obtain the polyether sulfone single ion polymer (PES-LiCPI) shown in the formula (I).
Preferably, the molar ratio of the trifluoromethanesulfonamide to the 3-chloropropane sulfonyl chloride to the LiOH in the step (i) is 1-1.5: 1-1.5; the reaction time is 18-48 h. The recrystallization solvent is not particularly limited, and dichloromethane may be selected.
Preferably, the molar ratio of MHQ to FPS in step (ii) is 1:1 to 1.2.
(iii) the catalyst in step (ii) is selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine; the solvent is selected from N-methyl pyrrolidone, N-dimethylformamide, dimethyl sulfoxide or sulfolane; the azeotropic dehydrating agent is at least one of dimethylbenzene, chlorobenzene or toluene.
Preferably, PES-OCH in step (iii) 3 The molar ratio of the boron tribromide to the boron tribromide is 1: 3-6; the concentration of the boron tribromide solution is 5-20%.
Preferably, the concentration of PES-OH in DMSO in step (iv) is 5-10%, and the molar ratio of PES-OH to LiCPSI is 1: 1-2.
And (iv) heating the mixture to 60-100 ℃ under the protection of inert gas, and precipitating the reaction solution in ethyl acetate.
The invention also provides a gel polymer electrolyte comprising the polyether sulfone single ion polymer shown in the formula (I).
Preferably, the gel polymer electrolyte further comprises a functional polymer, which may be selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), preferably polyvinylidene fluoride-hexafluoropropylene.
The preparation of the gel polymer electrolyte comprises the following steps:
(v) preparing 5-10 wt% solution of the polyether sulfone single ion polymer and the functional polymer in the formula (I), dripping the solution on a plate by a tape casting method, drying at 80-120 ℃, taking off the plate, and soaking in a plasticizer to obtain the gel polymer electrolyte membrane.
The solvent of the solution is selected from one of anhydrous N, N-dimethyl pyrrolidone (NMP), anhydrous dimethyl sulfoxide (DMSO), N, N-dimethyl acetamide (DMAC) or N, N-dimethyl formamide (DMF); the concentration of the solution is preferably 6 to 7 wt%.
The mass ratio of the polyether sulfone single ion polymer to the functional polymer is 1: 0.4-1, and preferably 1: 0.66.
The substrate is selected from flat glass plates, tetrafluoro plates, and preferably glass plates.
The plasticizer is at least one of dimethyl carbonate (DMC), gamma-butyrolactone (GBL), Propylene Carbonate (PC), diethyl carbonate (DEC), Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC); the soaking time is 20-60 min.
Preferably, the plasticizer is a compound of ethylene carbonate/propylene carbonate with the volume ratio of 0.5-2:0.5-2, preferably 1-1.5: 1-1.5.
The invention also provides a lithium ion battery which comprises a positive electrode, a negative electrode and the gel polymer electrolyte membrane.
The anode is selected from LiFePO 4 ，LiCoO 2 ，LiMn 2 O 4 And the negative electrode is selected from a lithium sheet.
The preparation method of the gel polymer electrolyte based on the polyether sulfone with the specific structure and the organic lithium salt has the following beneficial effects that:
(1) selecting a specific monomer and preparing polyether sulfone with a specific structure, and effectively improving the heat resistance of the electrolyte by using the polyether sulfone as a matrix;
(2) the organic lithium salt 3-chloropropane sulfonyl (trifluoromethanesulfonyl) imide Lithium (LiCPSI) with high dissociation degree is prepared, so that lithium ions are more easily dissociated, and the lithium ions are grafted on polyether sulfone to fix anions on a polymer matrix, so that only the lithium ions in a system move, and the electrochemical performance and the stability of the battery are improved. The prepared electrolyte material has excellent comprehensive performance, and the thermal stability and the electrochemical performance of the electrolyte material are optimized;
(3) the gel polymer electrolyte prepared by the invention has excellent electrochemical performance, the long-cycle stability of the assembled battery is good, and the capacity retention rate of the battery is more than 98% after the battery runs for 100 circles.
Drawings
FIG. 1 is a schematic representation of LiPSI prepared in example 1 1 HNMR atlas.
FIG. 2 is PES-OCH prepared in example 2 3 And PES-OH prepared in example 3 1 HNMR atlas.
FIG. 3 is a graph of PES-LiCPSI prepared in example 4 1 HNMR atlas.
FIG. 4 is a thermogravimetric analysis of a polyethersulfone single-ion gel polymer electrolyte of example 5.
Fig. 5 is the tensile test results of the polyethersulfone single-ion gel polymer electrolyte of example 5.
Fig. 6 is a graph of bulk impedance of the polyethersulfone single-ion gel polymer electrolyte of example 5.
Fig. 7 is a diagram of the electrochemical window of the polyethersulfone single-ion gel polymer electrolyte of example 5.
Fig. 8 is the cell cycle performance at different rates at room temperature for a lithium ion battery assembled with the polyethersulfone single-ion gel polymer electrolyte of example 6.
Fig. 9 shows the battery cycle performance of the lithium ion battery assembled with the polyethersulfone single-ion gel polymer electrolyte of example 6, wherein the charge-discharge current density of the lithium ion battery is 0.2C at room temperature.
FIG. 10 is the first charge-discharge diagram of the lithium ion battery assembled with the polyethersulfone single-ion gel polymer electrolyte in example 6, wherein the charge-discharge current density of the lithium ion battery is 0.2C at room temperature
Detailed Description
The technical solution of the present invention is clearly and completely described below with reference to specific embodiments. Of course, the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 13 preparation of lithium Chloropropanesulfonyl (Trifluoromethanesulfonyl) imide (LiPSI)
20 mmol (2.9818 g) of trifluoromethylsulfonamide and 40 mmol (0.9572 g) of LiOH were added to 20 ml of anhydrous acetonitrile under nitrogen atmosphere, and 20 mmol (3.541 g) of 3-chloropropanesulfonyl chloride were added to the ice-water bath. Subsequently, the reaction was carried out at normal temperature for 24 hours, acetonitrile was removed by rotary evaporation, and solid 3-chloropropanesulfonyl (trifluoromethanesulfonyl) imide Lithium (LiCPSI) was recrystallized from dichloromethane and filtered to obtain 7.4125g of white solid.
Example 2 methoxy-containing polyethersulfone (PES-OCH) 3 ) Preparation of (2)
5.6056 g of 2-Methoxy Hydroquinone (MHQ), 10.17 g of 4, 4' -difluoro diphenyl sulfone (FPS), 6.624 g of anhydrous potassium carbonate, 50 mL of sulfolane (TMS) and 18 mL of toluene are sequentially added into a three-neck flask provided with a mechanical stirrer, a nitrogen inlet pipe, a thermometer and a water separator, nitrogen is introduced into the three-neck flask, the mixture is stirred and heated to 140 ℃ and 170 ℃ to react for 12 hours to obtain viscous solution, the viscous solution is added into distilled water, the product is crushed after cooling, and is washed by deionized water and ethanol and dried to obtain methoxy polyether sulfone (PES-OCH) 3 ）。
EXAMPLE 3 preparation of hydroxy-containing polyethersulfone (PES-OH)
In a three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, a thermometer and a water separator, 6 g of PES-OCH obtained in example 2 were placed 3 Dissolving in anhydrous chloroform, dropwise adding 60 ml of chloroform solution containing 10% boron tribromide at-40 ℃, reacting at normal temperature for 12h, precipitating in ethanol, washing with deionized water and ethanol, and drying to obtain the hydroxyl-containing polyether sulfone (PES-OH).
EXAMPLE 4 preparation of polyethersulfone Mono-ion Polymer (PES-LiCPSI)
2g of PES-OH obtained in example 3 was dissolved in 40 ml of anhydrous DMSO under a nitrogen atmosphere, followed by addition of an excess of LiH, reaction was carried out at 70 ℃ for 3 hours, then 1.85 g of LiPSI obtained in example 1 was dissolved in 15ml of anhydrous DMSO, the solution was added to the reaction mixture, the reaction was stirred with nitrogen for 48 hours, the reaction mixture was poured into ethyl acetate, the liquid was removed by filtration, and the resulting solid was dried under vacuum for use.
EXAMPLE 5 preparation of polyethersulfone Single ion gel Polymer electrolyte (PES-GPE)
A mass of 0.399 g PES-LiCPSI was dissolved in 10.5 mL of NMP solvent and dissolved by sonication. And after the polyether sulfone single-ion gel polymer electrolyte is completely dissolved, adding 0.266 g of PVDF-HFP, performing ultrasonic treatment, filtering impurities by using 400-mesh filter cloth after the polymer is completely dissolved and uniformly dispersed, casting the mixture on a clean glass plate, performing vacuum drying at 100 ℃ for 48 hours, cooling, taking out the mixture, removing the polyether sulfone single-ion polymer electrolyte from the glass plate, cutting the mixture into a circle with the diameter of 16 mm, and finally soaking the circle in EC/PC (v/v, 1: 1) for 30 min to obtain the polyether sulfone single-ion gel polymer electrolyte (PES-GPE).
Example 6 preparation of Battery
(1) 1.6 g of LiFePO were respectively taken 4 Dissolving 0.2g of acetylene black and 0.2g of PVDF in NMP, uniformly stirring, coating the obtained slurry on aluminum foil paper, cutting into pieces, and drying to obtain a positive plate;
(2) taking the gel polymer electrolyte (PES-GPE) prepared in example 5, taking the positive plate prepared in the step (1), and assembling the positive plate into Li/PES-GPE/LiFePO according to the sequence of the positive shell, the positive plate, the gel polymer electrolyte, the lithium plate, the gasket and the elastic sheet 4 The half cell of (1).
Characterization analysis
FIG. 1 is a schematic representation of lithium 3-chloropropanesulfonyl (trifluoromethanesulfonyl) imide (LiCPSI) prepared in example 1 1 HNMR atlas. The nuclear magnetic characterization results of LiCPSI are as follows: by usingd 6 -DMSO dissolves LiPSI, and the structure is detected by nuclear magnetic hydrogen spectrum, and the result is shown in the attached figure 1: the characteristic peak at 3.74 ppm was the proton resonance by methylene H1 bonded to a chlorine atom, the characteristic peak at 3.10ppm was the proton resonance by methylene H3 bonded to lithium trifluoromethanesulfonimide, and the characteristic peak at 2.15 ppm was the proton resonance by methylene H2. Thus, it was confirmed that LiCPSI was successfully prepared.
FIG. 2 is the polyether sulfone containing methoxy group (PES-OCH) prepared in example 2 3 ) And of the hydroxy-containing polyethersulfone (PES-OH) prepared in example 3 1 HNMR atlas. By usingd 6 -DMSO dissolution of PES-OCH 3 And PES-OH, the structure of which is detected by nuclear magnetic hydrogen spectrum, and the result is shown in the attached figure 2: the peaks at 6.6-8.0 ppm correspond to protons on the benzene ring. from-OCH 3 The proton resonance generated by the group disappeared at 3.7 ppm, while a new peak appeared at 10.1 ppm, attributable to the proton resonance generated from the-OH group, demonstrating a complete demethylation reaction. Further, the integral ratio of H4 to H6 is close to the theoretical value.
FIG. 3 is a drawing of a polyethersulfone monoanionic polymer (PES-LiCPSI) prepared in example 4 1 HNMR atlas. By d 6 PES-LiCPSI dissolved by DMSO, and the structure of the PES-LiCPSI is detected by nuclear magnetic hydrogen spectroscopy, and the result is shown in the attached figure 3: the peak at 6.5-8.1 ppm corresponds to the proton on the benzene ring, the characteristic peak at 4.38 ppm is the proton resonance generated by the methylene group H6 linked to the oxygen atom on the polymer branch, the characteristic peak at 3.45 ppm is the proton resonance generated by the methylene group H8 linked to the lithium trifluoromethanesulfonimide on the polymer branch, and the characteristic peak at 2.95 ppm is the proton resonance generated by the methylene group H7 on the polymer branch. The grafting ratio according to the integrated ratio of LiPSI was 15%.
Analysis of thermal stability
The thermogravimetric analysis result of the polyether sulfone single-ion polymer electrolyte prepared in example 5 is shown in fig. 4, and the polymer electrolyte is 5% weight loss at 297 ℃ and 10% weight loss at 335 ℃, and shows good thermal stability.
Analysis of mechanical Properties
The polyether sulfone single ion polymer electrolyte prepared in example 5 was cut into a dumbbell, and subjected to tensile test on an Shimadzu AG-I1 KN universal tester, and the results are shown in FIG. 5, in which the elongation at break was 8.3% and the tensile strength was 48 MPa. The good mechanical strength can prevent the lithium dendrite generated in the charging and discharging process of the battery from piercing the electrolyte membrane, and the safety of the battery is ensured.
Properties of polyether sulfone single ion gel polymer electrolyte
(1) Example 5 ionic conductivity test of polyethersulfone Mono-Ionic gel Polymer electrolyte
The ionic conductivity was measured using ac impedance. A dried electrolyte membrane with a diameter of 1.6 cm was soaked in EC/PC (1/1, v/v) and placed in a stainless steel jig to construct a stainless steel/electrolyte/stainless steel structured plugged cell whose impedance was measured using an electrochemical workstation using the formula: σ = L/SR b Calculating the ionic conductivity, wherein σ is the ionic conductivity of the electrolyte, L is the thickness of the electrolyte, S is the area of the electrolyte, R b Is the resistance of the electrolyte at room temperature. As shown in FIG. 6 and Table 2, the bulk impedance of the polyethersulfone single-ion gel polymer electrolyte at room temperature was 43. omega. and the ionic conductivity was calculated to be 8.1X 10 -5 S cm -1 。
Table 2 shows the thickness, bulk resistance, effective area of contact of the electrolyte with the steel sheet, and ionic conductivity data of PES-GPE prepared in example 5
TABLE 1
Example 5 Thickness (μm) Body impedance (omega) Effective area (cm) of contact of electrolyte with steel sheet -2 ) Ion conductivity (S cm) -1 )
PES-GPE 68 43 1.96 8.1×10 -5
(2) Example 5 polyethersulfone single ion gel Polymer electrolyte Ionic electrochemical Window test
The electrochemical window was measured using linear sweep voltammetry. The polyether sulfone single-ion gel electrolyte obtained in example 5 is placed between a stainless steel sheet and a lithium sheet to construct a battery with a stainless steel/electrolyte/lithium sheet structure, and an electrochemical stability window of the battery is measured by using an electrochemical workstation. The results are shown in fig. 7, the electrochemical window of the polyethersulfone single ion gel polymer electrolyte is 4.4V at room temperature, which indicates that the polyethersulfone single ion gel polymer electrolyte does not decompose within 4.4V.
(3) Cell performance test of a polyether sulfone single ion gel polymer electrolyte Assembly in example 6
And (3) testing the rate capability and the cycle capability of the battery by using a battery performance testing cycle tester (BTS-4000). The rate test result of the battery at room temperature is shown in fig. 8, and the specific discharge capacity of 0.1C is 138 mAh g -1 0.2C has a specific discharge capacity of 128 mAh g -1 0.5C specific discharge capacity of 109 mAh g -1 And the specific discharge capacity of 1C is 78 mAh g -1 After high-rate circulation, the battery returns to 0.1C, and the discharge specific capacity of the battery is still kept at 138 mAh g -1 There is no attenuation. The cycle test results are shown in FIG. 9, 100 cycles are tested at 0.2C rate, and the specific discharge capacity is kept at 128 mAh g -1 The coulombic efficiency can be kept to be nearly 100%, and the capacity retention rate is 99%. FIG. 10 is the first charge-discharge diagram of the battery at 0.2C, and it can be seen that the specific charge capacity of the battery at the first turn is 131 mAh g -1 The specific discharge capacity is 126 mAh g -1 The first coulombic efficiency is 96%, and the polarization voltage is 193 mV, which indicates that the internal resistance of the battery is small. The above results indicate that the battery has good cycle stability.
The gel polymer electrolyte provided by the invention has good specific discharge capacity and high coulombic efficiency, and is attributed to the chemical structure and composition thereof, the special structure of the lithium bissulfonylimide in the single-ion polymer, wherein the electron delocalization of nitrogen atoms is realized by-SO with strong electron-withdrawing capability 2 -N (-) -SO 2 -CF 3 Radical reinforcement of Li + More readily dissociates and provides a source of lithium. The above structure and composition contribute to good electrochemical performance of the electrolyte. In conclusion, the lithium ion battery assembled by the polyether sulfone single-ion gel polymer electrolyte prepared by the method has excellent battery performance and good commercial popularization prospect.

Claims (10)

1. A polyethersulfone monoanionic polymer having the formula:
Figure FDA0003750103780000011
wherein:
Figure FDA0003750103780000012
2. the preparation method of the polyether sulfone single ion polymer shown in the formula (I) in the claim 1 has the following synthetic route:
(i)
Figure FDA0003750103780000013
(ii)
Figure FDA0003750103780000014
(iii)
Figure FDA0003750103780000015
(iv)
Figure FDA0003750103780000016
3. the method of claim 2, comprising the steps of:
(i) adding lithium hydroxide and trifluoromethanesulfonamide into anhydrous acetonitrile, adding 3-chloropropane sulfonyl chloride in an ice-water bath, reacting at normal temperature, filtering, performing rotary evaporation, and recrystallizing to obtain 3-chloropropane sulfonyl (trifluoromethanesulfonyl) imide lithium LiCPSI;
(ii) mixing 2-methoxy hydroquinone and 4, 4' -difluoro diphenyl sulfone, adding catalyst, solvent and azeotropic dehydrating agent, stirring and heatingReacting at 140 deg.C for 4h, further reacting at 155 deg.C for 18h to obtain viscous solution, precipitating the viscous solution into distilled water, cooling, pulverizing, washing with deionized water and ethanol, and drying to obtain PES-OCH containing methoxyl polyethersulfone 3 ；
(iii) (iii) subjecting the PES-OCH obtained in step (ii) to 3 Dissolving in anhydrous chloroform, adding a chloroform solution containing boron tribromide at-40 ℃, reacting at normal temperature for 12h, precipitating in ethanol, washing with deionized water and ethanol, and drying to obtain hydroxyl-containing polyether sulfone (PES-OH);
(iv) and (5) dissolving the PES-OH obtained in the step (iii) in anhydrous dimethyl sulfoxide (DMSO), adding LiH, heating and stirring, adding the LiPSI obtained in the step (i), and heating to react to obtain the PES-LiPSI shown in the formula (I).
4. The process according to claim 3, wherein the molar ratio of trifluoromethanesulfonamide, 3-chloropropanesulfonyl chloride and LiOH in step (i) is 1-1.5: 1-1.5.
5. The process of claim 3, wherein the molar ratio of 2-methoxyhydroquinone to 4, 4' -difluorodiphenyl sulfone in step (ii) is 1:1 to 1.2.
6. The process according to claim 3, wherein PES-OCH in step (iii) 3 The molar ratio of the boron tribromide to the boron tribromide is 1: 3-6; the concentration of the boron tribromide solution is 5-20%.
7. A gel polymer electrolyte, which comprises the polyether sulfone single ion polymer as described in claim 1 or the polyether sulfone single ion polymer prepared by the preparation method as described in any one of claims 2 to 6.
8. The gel polymer electrolyte of claim 7, further comprising a functional polymer selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA).
9. The method for preparing the gel polymer electrolyte as claimed in claim 7 or 8, comprising the steps of:
preparing a 5-10 wt% solution from the polyether sulfone single ion polymer of the formula (I) in claim 1 or the polyether sulfone single ion polymer prepared by the preparation method in any one of claims 2-6 and a functional polymer, dripping the solution on a plate by a tape casting method, drying at 80-120 ℃, peeling off the plate, and soaking in a plasticizer to obtain the gel polymer electrolyte; the mass ratio of the polyether sulfone single ion polymer to the functional polymer is 1: 0.4-1.
10. A lithium ion battery comprising a positive electrode, a negative electrode, and the gel polymer electrolyte of claim 7 or 8.
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