CN109103499B - Polymer electrolyte and preparation method and application thereof - Google Patents
Polymer electrolyte and preparation method and application thereof Download PDFInfo
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- CN109103499B CN109103499B CN201710470352.7A CN201710470352A CN109103499B CN 109103499 B CN109103499 B CN 109103499B CN 201710470352 A CN201710470352 A CN 201710470352A CN 109103499 B CN109103499 B CN 109103499B
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a polymer electrolyte, a preparation method and application thereof. The polymer electrolyte comprises three structural units, namely a structural unit A, a structural unit B and a structural unit C, and is solid at room temperature. The polymer electrolyte disclosed by the invention comprises three structural units, namely a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a lithium ion providing unit; the structural unit B is a lithium ion conducting unit; the structural unit C is a polymer structure supporting unit, provides certain mechanical strength for the polymer electrolyte and has a lithium ion transmission function; the structural unit A, the structural unit B and the structural unit C are connected with each other by single bonds, the mechanical property and the flexibility of the polymer electrolyte are good, and the polymer electrolyte can be changed continuously according to the change of external force, so that the influence on lithium ion transmission is reduced, the uniformity of current density is maintained, and the growth of lithium dendrites is effectively inhibited.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a polymer electrolyte and a preparation method and application thereof.
Background
Lithium is more suitable as a negative electrode material for lithium batteries than carbon because of its higher theoretical specific energy. During the cycle charge and discharge of the lithium battery, uneven deposition of lithium on the negative electrode of the lithium sheet occurs due to non-uniform diffusion density of ions in the electrolyte, and such continuous aggregate deposition can generate a structure, namely lithium dendrite, which is more prominent than other deposited layers. The generation of lithium dendrites not only can cause the overall performance of the lithium battery to be greatly reduced, but also can cause serious consequences such as internal short circuit of the battery, thermal runaway and even explosion.
In order to solve the safety hazard caused by lithium dendrites, researchers have also tried from several aspects, such as: replacing electrolyte, adding effective additives into the electrolyte and the like. Among them, the selection of solid polymer electrolyte to replace the existing liquid electrolyte is one of the major research points at present. It is desired to enhance interfacial stability and improve safety by using the SEI film interface composed of metallic lithium and a polymer electrolyte film. The stability and uniformity of the SEI film are related to the quantity and uniformity of formed lithium ions, and in the current solid polymer electrolyte technology, lithium salt is usually added into the polymer electrolyte as a lithium ion source, so that the dispersion degree of the lithium salt in a polymer cannot be ensured, and the uniformity of current density in a lithium battery is influenced; meanwhile, the existing solid polymer electrolytes are composite polymer electrolytes formed by compounding a plurality of polymers, and the problems of structural collapse and phase separation are easy to occur. The above factors cause the conventional polymer electrolyte to be ineffective in suppressing the growth of lithium dendrites.
Disclosure of Invention
The invention aims to provide a polymer electrolyte, so as to solve the problem that the conventional polymer electrolyte has poor effect on inhibiting the growth of lithium dendrites.
The second object of the present invention is to provide a method for preparing the above polymer electrolyte.
The third purpose of the invention is to provide the application of the polymer electrolyte in the lithium ion battery.
In order to achieve the above purpose, the polymer electrolyte of the present invention adopts the following technical scheme:
a polymer electrolyte comprises three structural units, namely a structural unit A, a structural unit B and a structural unit C, wherein the structural formula of the structural unit A is shown as a formula 1:
the structural formula of the structural unit B is shown as formula 2:
in the formula 2, the value of m is an integer of 7-16;
the structural formula of the structural unit C is shown as formula 3:
in the formula 3, n is an integer of 7-20; the polymer electrolyte is solid at room temperature.
The polymer electrolyte disclosed by the invention has three structural units, namely a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is a lithium ion providing unit and can provide stable and uniform lithium ions for the polymer electrolyte, and the structural unit A adopts a lithium phosphate structure, so that the structure has smaller dissociation energy, the lithium ions are easy to dissociate, and the quantity of the lithium ions in the polymer electrolyte is increased; the structural unit B is a lithium ion conduction unit, and the conduction rate of lithium ions is increased; the structural unit C is a polymer structure supporting unit, provides certain mechanical strength for the polymer electrolyte and has a lithium ion transmission function; the structural units A, B and C are connected by themselves or with each other by a single bond. The polymer electrolyte has good mechanical property and flexibility, and can be continuously changed according to the change of external force, thereby reducing the influence on lithium ion transmission, maintaining the uniformity of current density, and effectively inhibiting the growth of lithium dendrite.
In the structural unit A, the phosphorus group also has good flame retardant property, when the phosphorus-containing high polymer is heated or combusted, the phosphorus group in the system can be decomposed to generate oxyacid of phosphorus, so that a stable polymer is formed, a diaphragm is formed on the surface of a base material, and the combustion-supporting gas is prevented from contacting with combustible materials; meanwhile, oxyacid of phosphorus and hydroxyl compound can generate carbonization reaction of endothermic dehydration to generate a large amount of coke which covers the surface of the high polymer to prevent the further combustion of the high polymer, and the dehydration reaction needs to absorb a large amount of heat to delay the combustion rate.
Preferably, in the polymer electrolyte, the ratio of the average polymerization degrees of the structural unit a, the structural unit B, and the structural unit C is (1 to 4): 1: 1.
preferably, the polymer electrolyte has a thermal decomposition temperature of 300 to 500 ℃.
When the polymer electrolyte is used as a solid electrolyte for a lithium battery, the polymer electrolyte has good conductivity and mechanical property, and the uniformity of current density is good in the charging and discharging process, so that the growth of lithium dendrites can be effectively inhibited, and the possibility of using a lithium sheet as a negative electrode of the lithium battery is greatly enhanced. Under the above preferred parameters, the polymer electrolyte of the present invention contains a lithium ion providing unit, a lithium ion conducting unit and a polymer structure supporting unit at the same time, and no other supporting film and lithium salt need to be introduced, thereby avoiding the defect of macroscopic phase separation which may occur in the composite polymer electrolyte and significantly improving the performance of the polymer electrolyte.
The preparation method of the polymer electrolyte comprises the following steps:
1) dissolving 5-norbornene-2-dimethyl phosphate, 5-norbornene-2-polyethylene glycol monomethyl ether and bis-norbornene grafted polyethylene glycol in a solvent, and reacting under a Grubbs second-generation catalyst to prepare a polymer A;
2) carrying out reduction reaction on the polymer A and trimethyl bromosilane in a solvent, and then adding methanol for reaction to prepare a polymer B;
3) reacting the polymer B and lithium bistrifluoromethanesulfonimide in a solvent to prepare a polymer C;
4) and (3) carrying out hydrogenation reaction on the polymer C to obtain the catalyst.
In the step 1), the solvent is dichloromethane. The reaction end point is determined by the conversion of the system color from pink to dark brown. 5-norbornene-2-dimethylphosphate: molar ratio of Grubbs second generation catalyst 150: 1.
in the step 2), the solvent is dichloromethane. The reduction reaction is carried out for 16-20 h at room temperature; the reaction is carried out for 24 to 30 hours at room temperature after the methanol is added. The molar ratio of the phosphate ester unit, the trimethyl bromosilane and the methanol in the polymer A is 1:2: 4.
In the step 3), the solvent is dimethylformamide. The reaction temperature is 85-95 ℃, and the reaction time is 24-30 h.
In the step 4), the temperature of the hydrogenation reaction is 140-160 ℃, and the pressure is 4-5 Mpa. The time of the hydrogenation reaction is 24-30 h.
The preparation method of the polymer electrolyte has simple process flow, is easy to realize automatic control, and has excellent conductivity and mechanical property and good application prospect in lithium batteries.
The application of the polymer electrolyte in a lithium battery is as follows: the lithium ion battery can be directly used as a solid electrolyte to combine with a positive plate and a negative plate to form the lithium ion battery, has good cycle charge and discharge performance, can effectively inhibit the growth of lithium dendrites, and has excellent safety performance.
Drawings
FIG. 1 is a stress-strain curve of a polymer electrolyte and a polymer C according to example 1 of the present invention;
FIG. 2 is a comparison of optical photographs of the polymer electrolyte of example 1 before and after heat treatment;
FIG. 3 is a TG curve of the polymer electrolyte of example 1;
FIG. 4 is a cycle test chart at 120 ℃ and 0.2C rate after the polymer electrolyte of example 1 is assembled to be buckled;
FIG. 5 is a graph of lithium dendrite growth over time for a Li/Li battery system employing polymer C;
fig. 6 is a lithium dendrite growth for a Li/Li battery system employing the polymer electrolyte of example 1.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
Example 1
The polymer electrolyte of this example was prepared by the following steps:
1) 5.66mg of Grubbs was dissolved in 1.33mL of dichloromethane to obtain a catalyst solution;
dissolving 202mg of 5-norbornene-2-dimethylphosphate (M1), 187mg of 5-norbornene-2-polyethylene glycol monomethyl ether (M2), and 100mg of bis-norbornene-grafted polyethylene glycol (M3) in 30mL of dichloromethane to obtain a monomer solution;
mixing the catalyst solution and the monomer solution, stirring and reacting for 10 hours at room temperature, adding vinyl ether to terminate the reaction when the system is converted from pink to dark brown, and distilling under reduced pressure to remove the solvent to obtain a polymer A;
2) respectively dissolving the polymer A and the trimethyl bromosilane in 5mL of dichloromethane, mixing the two dissolved solutions, reacting at room temperature for 16h, and adding methanol (the molar ratio of 5-norbornene-2-dimethyl phosphate to trimethyl bromosilane to methanol is 1:2: 4) stirring and reacting for 24 hours at room temperature, and evaporating the solvent to obtain a polymer B;
3) under the protection of nitrogen, 2.349g of polymer B and 0.287g of lithium bistrifluoromethanesulfonylimide (LITFSI) are dissolved in 20mL of dimethylformamide, then the mixture is stirred and reacted for 24 hours at 90 ℃, and the solvent is evaporated under reduced pressure to obtain a polymer C;
4) adding the polymer C into a high-pressure hydrogenation reaction kettle, introducing nitrogen, relieving pressure after pressure test is qualified, then introducing hydrogen until the pressure in the kettle reaches 4MPa, maintaining the pressure for 30min to confirm that the sealing performance is good, heating to 150 ℃, carrying out hydrogenation reaction for 25h, then cooling to room temperature, relieving pressure, taking out a hydrogenation reaction product, and drying in a vacuum drying oven at 30 ℃ and 0.08MPa for 10h to obtain the polymer electrolyte.
The reaction scheme in this example is as follows:
in the polymer electrolyte obtained in this example, the ratio of the average polymerization degrees of the structural unit a (m ═ 16), the structural unit B (n ═ 9), and the structural unit C was 4:1:1, and the initial thermal decomposition temperature was 355.6 ℃; the ion conductivity reaches 0.21ms/cm through detection.
The polymer electrolyte of the embodiment is used for manufacturing the button cell, and is cut into a circular sheet shape in an argon glove box according to a positive electrode shell and LiFePO4The polymer electrolyte, the lithium sheet, the gasket and the negative electrode shell are assembled in sequence, and the assembled electricity is sealed by a sealing machine so as to facilitate subsequent detection.
Example 2
The polymer electrolyte of this example was prepared substantially in the same manner as in example 1, except that in step 1), the amounts of M1, M2, and M3 added were 202mg, 236mg, and 339mg, respectively, and that M1: molar ratio of Grubbs second generation catalyst 150: 1; in the step 2), the reduction reaction is carried out at room temperature for 18 hours by stirring, and after methanol is added, the reaction is carried out at room temperature for 28 hours by stirring; in the step 3), stirring and reacting for 30h at 85 ℃; in the step 4), hydrogenation reaction is carried out for 24 hours at 140 ℃ and 4.5 MPa.
The polymer electrolyte obtained in example 2 had an initial thermal decomposition temperature of 356.8 ℃, and the ratio of the average polymerization degrees of the structural unit a (m ═ 10), the structural unit B (n ═ 15), and the structural unit C was 2:1: 1.
Example 3
The polymer electrolyte of this example was prepared substantially in the same manner as in example 1, except that in step 1), the amounts of M1, M2, and M3 added were 202mg, 340mg, and 370mg, respectively, M1: molar ratio of Grubbs second generation catalyst 150: 1; in the step 2), the reduction reaction is carried out at room temperature for 20 hours by stirring, and after methanol is added, the reaction is carried out at room temperature for 30 hours by stirring; in the step 3), stirring and reacting for 28h at 95 ℃; in the step 4), hydrogenation reaction is carried out for 24 hours at 160 ℃ and under 5.0 MPa.
The polymer electrolyte obtained in example 2 had an initial thermal decomposition temperature of 360.2 ℃, and the ratio of the average polymerization degrees of the structural unit a (m ═ 7), the structural unit B (n ═ 8), and the structural unit C was 1:1: 1.
Test example 1
This test example examined the mechanical properties and thermal stability of the polymer electrolyte of example 1. Example 1, step 3), polymer C was formed into a film, and a polymer electrolyte membrane was obtained through step 4), and the results of mechanical property measurements are shown in fig. 1 and the results of thermal property measurements are shown in fig. 2 and 3.
In the stress-strain graph of FIG. 1, the mechanical properties of the polymer electrolyte obtained in example 1 were further improved as compared with that of unhydrogenated polymer C, and the deformation amount thereof was not more than 4% under the pressure condition of less than 8 MPa; FIG. 2 is a comparative photograph of a polymer electrolyte after heat treatment at 150 ℃ for 2 hours, and it can be seen that no significant volume expansion occurs before and after the heat treatment; the TG curve of the polymer electrolyte as shown in fig. 3, which has an initial thermal decomposition temperature of 355.6 ℃, shows good thermal stability; the flame test shows that the polymer electrolyte also has good flame retardance.
Test example 2
This test example examined the electrochemical performance of the lithium ion battery of example 1. Fig. 4 shows that the discharge capacity of the battery hardly decayed when the charge/discharge test was performed at 120 ℃ and 0.2C rate, and was always maintained at a high level, showing good charge/discharge performance.
Test example 3
In this test example, a Li/Li battery system (denoted as Li/Polymer C/Li pseudo battery, Li/Polymer electrolyte/Li pseudo battery) was assembled from the polymer C and the polymer electrolyte of example 1 at 0.2mA cm-2The growth of lithium dendrites on two simulated cells was observed by comparison with an optical microscope at the current of (1), and the results are shown in fig. 5 and 6. As can be seen from FIG. 5, the growth of the lithium dendrite is faster along with the extension of the polarization time, and the length of the lithium dendrite can reach about 0.1mm after polarization for 20 h; after polarization for 60h, the length of the lithium dendrite can reach about 0.35 mm; instead, the polymer of example 1 was usedThe simulation battery made of the compound electrolyte is polarized for 600h, and no obvious lithium dendrite phenomenon is observed, so that the polymer electrolyte has an obvious effect on inhibiting the growth of the lithium dendrite and has a good application prospect in a solid electrolyte battery.
Claims (10)
1. The polymer electrolyte is characterized by comprising three structural units, namely a structural unit A, a structural unit B and a structural unit C, wherein the structural formula of the structural unit A is shown as the formula 1:
the structural formula of the structural unit B is shown as formula 2:
in the formula 2, the value of m is an integer of 7-16;
the structural formula of the structural unit C is shown as formula 3:
in the formula 3, n is an integer of 7-20; the polymer electrolyte is solid at room temperature.
2. The polymer electrolyte according to claim 1, wherein the ratio of the average polymerization degrees of the structural unit A, the structural unit B and the structural unit C is (1 to 4): 1: 1.
3. the polymer electrolyte according to claim 1 or 2, wherein the polymer electrolyte has a thermal decomposition temperature of 300 to 500 ℃.
4. A method for preparing the polymer electrolyte according to claim 1, comprising the steps of:
1) dissolving 5-norbornene-2-dimethyl phosphate, 5-norbornene-2-polyethylene glycol monomethyl ether and bis-norbornene grafted polyethylene glycol in a solvent, and reacting under a Grubbs second-generation catalyst to prepare a polymer A;
2) carrying out reduction reaction on the polymer A and trimethyl bromosilane in a solvent, and then adding methanol for reaction to prepare a polymer B;
3) reacting the polymer B and lithium bistrifluoromethanesulfonimide in a solvent to prepare a polymer C;
4) and (3) carrying out hydrogenation reaction on the polymer C to obtain the catalyst.
5. The method of preparing a polymer electrolyte according to claim 4, wherein the reduction reaction in the step 2) is carried out at room temperature for 16 to 20 hours.
6. The method for preparing a polymer electrolyte according to claim 4 or 5, wherein the reaction is carried out at room temperature for 24 to 30 hours after adding methanol in step 2).
7. The method of claim 4, wherein the reaction temperature in step 3) is 85 to 95 ℃ and the reaction time is 24 to 30 hours.
8. The method of claim 4, wherein the hydrogenation reaction in step 4) is carried out at a temperature of 140 to 160 ℃ and a pressure of 4 to 5 MPa.
9. The method of claim 8, wherein the hydrogenation reaction time in the step 4) is 24 to 30 hours.
10. Use of the polymer electrolyte of claim 1 in a lithium ion battery.
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| US11075407B2 (en) | 2019-03-15 | 2021-07-27 | Robert Bosch Gmbh | Grafted polyesters as electrolytes for lithium ion batteries |
Citations (3)
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|---|---|---|---|---|
| CN101728575A (en) * | 2008-10-29 | 2010-06-09 | 三星电子株式会社 | Electrolyte composition and catalyst ink used to form solid electrolyte membrane |
| CN103288712A (en) * | 2012-03-02 | 2013-09-11 | 华东师范大学 | Norbornene monomer, as well as polymer and preparation method thereof |
| CN104693423A (en) * | 2015-02-02 | 2015-06-10 | 华东师范大学 | Cross-linkable high dielectric norbornene copolymer and norbornene cross-linked polymer and preparation methods thereof |
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| CN101728575A (en) * | 2008-10-29 | 2010-06-09 | 三星电子株式会社 | Electrolyte composition and catalyst ink used to form solid electrolyte membrane |
| CN103288712A (en) * | 2012-03-02 | 2013-09-11 | 华东师范大学 | Norbornene monomer, as well as polymer and preparation method thereof |
| CN104693423A (en) * | 2015-02-02 | 2015-06-10 | 华东师范大学 | Cross-linkable high dielectric norbornene copolymer and norbornene cross-linked polymer and preparation methods thereof |
| CN104693423B (en) * | 2015-02-02 | 2017-04-19 | 华东师范大学 | Cross-linkable high dielectric norbornene copolymer and norbornene cross-linked polymer and preparation methods thereof |
Non-Patent Citations (1)
| Title |
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| "Multifunctional macromolecular design as self-standingelectrolyte for high-temperature single-ion lithium";WANG Y等;《J Appl Electrochem》;20161219;第238-239页 * |
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