CN111180790B - Polymer electrolyte, preparation method thereof and solid-state lithium-air battery - Google Patents

Polymer electrolyte, preparation method thereof and solid-state lithium-air battery Download PDF

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CN111180790B
CN111180790B CN202010005029.4A CN202010005029A CN111180790B CN 111180790 B CN111180790 B CN 111180790B CN 202010005029 A CN202010005029 A CN 202010005029A CN 111180790 B CN111180790 B CN 111180790B
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lithium
polymer electrolyte
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ionic liquid
air battery
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CN111180790A (en
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曹元成
张炜鑫
吴林
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Huazhong University of Science and Technology
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell 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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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a polymer electrolyte, a preparation method thereof and a solid-state lithium-air battery. Preparing a metal-organic framework material by adopting a solvothermal method, and mixing the metal-organic framework material with a lithium-containing ionic liquid to obtain a composite filler; and then taking the polyether polyurethane elastomer as a matrix, and mixing the polyether polyurethane elastomer with the composite filler to obtain the polymer electrolyte. The polymer electrolyte has excellent conductivity and stability, and when the polymer electrolyte is used in a solid lithium-air battery, the safety and the stability of the solid lithium-air battery can be effectively improved, and the solid lithium-air battery can keep better charge and discharge performance and cycle performance so as to meet the requirements of practical application. Through the mode, the composite filler can be loaded on the polyether polyurethane elastomer, and the prepared polymer electrolyte has better conductivity and mechanical property by utilizing the soft segment and the hard segment of the polyether polyurethane elastomer, so that the conductivity and the stability of the polymer electrolyte are effectively improved.

Description

Polymer electrolyte, preparation method thereof and solid-state lithium-air battery
Technical Field
The invention relates to the technical field of lithium-air batteries, in particular to a polymer electrolyte, a preparation method thereof and a solid-state lithium-air battery.
Background
Over the past decade, lithium ion batteries have grown in length, ranging from small portable electronic devices to large power systems. However, the energy density of the lithium ion battery is limited at present, so that the lithium ion battery cannot meet the requirement of long-distance running of the electric automobile when being applied to an electric system in the electric automobile. For this reason, lithium-air batteries having higher theoretical energy density have been receiving attention, but since organic liquid electrolytes have fluidity, the electrolyte in lithium-air batteries using organic liquid electrolytes is liable to leak, so that lithium-air batteries face serious safety problems when actually used. Accordingly, solid-state lithium-air batteries using a solid electrolyte have attracted increasing attention.
Solid-state lithium-air batteries use solid-state electrolytes instead of organic liquid-state electrolytes, so that safety is greatly improved, but the solid-state electrolytes also bring about the problems of poor self-stability, low conductivity and the like. Therefore, research into solid electrolytes is necessary to improve the performance of solid lithium-air batteries. Patent publication No. CN107039680A provides a solid electrolyte comprising an ionic liquid, a lithium salt, inorganic particles and a polymer for improving the cycle characteristics of a lithium-air battery. However, the range of raw materials provided by the patent is too wide, and the selection of different types of raw materials has a great influence on the performance of the lithium-air battery produced, so that how to select appropriate types of raw materials, especially the types of inorganic particles and polymers, and to study the preparation methods thereof is the focus of the current study.
In inorganic particles, a metal-organic framework material is a typical nano porous material, is generated by coordination self-assembly of metal ion clusters and organic ligands, can provide ideal accommodating space for various guest species, and is an ideal electrolyte filler. Patent publication No. CN108878970A provides a composite polymer solid electrolyte, a solid-state lithium battery, and a method for producing the same, in which a metal-organic framework structure is mixed with a lithium-containing ionic liquid, and polyethylene oxide and lithium bistrifluoromethanesulfonylimide are added to the metal-organic framework structure to which the lithium-containing ionic liquid is adsorbed, thereby producing a composite polymer solid electrolyte. However, the patent uses polyethylene oxide as a polymer, is only suitable for lithium ion batteries to a certain extent, and cannot be applied to lithium air batteries because the product lithium peroxide in the lithium air batteries reacts with polyethylene oxide, thereby causing polyethylene oxide failure. In this regard, there is still a need to research the kind of polymer matrix and select a material that can resist the corrosion of lithium peroxide and has better conductivity so as to maintain the excellent cycling stability of the lithium air battery.
In view of the above, there is still a need for a polymer electrolyte, a method for preparing the same, and a solid-state lithium-air battery, which are capable of preparing a polymer electrolyte with high stability and good conductivity by using more suitable raw materials and processes, and applying the polymer electrolyte to a solid-state lithium-air battery to improve the performance of the solid-state lithium-air battery.
Disclosure of Invention
The present invention is directed to solve the above problems, and an object of the present invention is to provide a polymer electrolyte, a method for preparing the same, and a solid-state lithium-air battery, in which a nano-porous composite filler is prepared by using an adsorption effect of a metal-organic framework material on a lithium-containing ionic liquid, and a polymer electrolyte based on a polyether polyurethane elastomer is prepared by using the nano-porous composite filler, so that the polymer electrolyte has excellent conductivity and stability; the prepared polymer electrolyte is used in a solid lithium-air battery, so that the safety and the stability of the solid lithium-air battery are improved to meet the requirements of practical application.
In order to achieve the above object, the present invention provides a method for preparing a polymer electrolyte, comprising the steps of:
s1, preparing the metal-organic framework material by adopting a solvothermal method;
s2, dissolving lithium salt in the ionic liquid, and heating to remove water to obtain lithium-containing ionic liquid; mixing the metal-organic framework material prepared in the step S1 with the lithium-containing ionic liquid according to a preset mass ratio, and heating and stirring to obtain a composite filler;
s3, dissolving the polyether polyurethane elastomer in an organic solvent, adding the composite filler obtained in the step S2, and fully stirring to obtain a homogeneous solution; and uniformly coating the homogeneous solution on a polytetrafluoroethylene plate, and drying until the organic solvent is completely volatilized to obtain the polymer electrolyte.
Further, in step S1, the metal-organic framework material is prepared as follows:
mixing hafnium chloride and terephthalic acid according to a molar ratio of 1:2, adding the mixture into N, N-dimethylformamide, adding hydrochloric acid after full dissolution, stirring uniformly, transferring the mixed solution into a reaction kettle, setting the heating temperature to be 100-150 ℃ and the heating time to be 20-28 h, and filtering, washing, activating and drying the product after full reaction to obtain the metal-organic framework material.
Further, in step S2, the concentration of the lithium-containing ionic liquid is 1-3 mol/L, and the preset mass ratio of the metal-organic framework material to the lithium-containing ionic liquid is (0.5-1): 1.
Further, in step S3, the mass fraction of the composite filler in the polymer electrolyte is 10% to 60%.
Further, in step S2, the heating temperature of the heating and stirring is 110-130 ℃, and the heating and stirring time is 10-14 h.
Further, in step S2, the lithium salt is one or more of lithium bistrifluoromethanesulfonimide, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimidazole, lithium trifluoromethanesulfonate, lithium hexafluoroarsenate, lithium bisoxalateborate, lithium tetrafluoroborate, and lithium perchlorate; the ionic liquid is one or a mixture of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide, 1-butyl-3-methylimidazole tetrafluoroboric acid, N-methyl-N-propyl pyrrole bistrifluoromethylsulfonyl imide and 1-butyl-4 methylpyridine bistrifluoromethylsulfonyl imide.
Further, in step S3, the organic solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, and anhydrous acetonitrile.
In order to achieve the above object, the present invention also provides a polymer electrolyte prepared according to any one of the above technical solutions.
The invention also provides a solid-state lithium-air battery, which comprises a positive electrode, a negative electrode and the polymer electrolyte; the positive electrode is an air electrode, and the negative electrode is a lithium metal sheet.
Further, the air electrode is foamed nickel loaded with commercial carbon nanotubes, and the preparation method comprises the following steps: the preparation method comprises the steps of uniformly mixing commercial carbon nanotubes, polytetrafluoroethylene emulsion and N-methyl pyrrolidone, stirring the mixture by using a grease homogenizing machine to prepare slurry, and spraying the slurry on foamed nickel by using a spray gun with the caliber of 0.1-0.5 mm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention prepares the nano-porous composite filler by preparing the metal-organic framework material and utilizing the adsorption effect of the metal-organic framework material on the lithium-containing ionic liquid, and prepares the polymer electrolyte based on the polyether polyurethane elastomer by mixing the nano-porous composite filler with the polyether polyurethane elastomer. The polymer electrolyte has excellent conductivity and stability, and when the polymer electrolyte is used in a solid lithium-air battery, the safety and the stability of the solid lithium-air battery can be effectively improved, and the solid lithium-air battery can keep better charge and discharge performance and cycle performance so as to meet the requirements of practical application.
2. The metal-organic framework material with excellent dispersibility is prepared by a simple solvothermal method, and is a nanocrystal and has high specific surface area and stability; meanwhile, the lithium-containing ionic liquid used in the invention is not easy to volatilize and burn, and when the lithium-containing ionic liquid is mixed with the metal-organic framework material prepared in the invention, the porous structure of the metal-organic framework material can adsorb the lithium-containing ionic liquid, so that the ion-movable nano-structure composite filler is obtained. The composite filler can not only hinder the chain segment recombination of the polyether type polyurethane elastomer, but also play a role in inhibiting the crystallization of the polyether type polyurethane elastomer and effectively improve the ionic conductivity of the polymer electrolyte; the dissociation of lithium salt can be promoted, the concentration of carriers is increased, and the mobility of lithium ions is improved; meanwhile, when the polymer electrolyte provided by the invention is used in a solid-state lithium-air battery, the composite filler in the polymer electrolyte can also play a role in protecting a lithium cathode, so that the long-term stability of a lithium electrode is improved.
3. The invention selects the polyether polyurethane elastomer as the matrix of the polymer electrolyte, and can comprehensively improve the performance of the polymer electrolyte by utilizing the soft segment and the hard segment of the polyether polyurethane elastomer. Wherein, the soft segment of the polyether polyurethane elastomer is polyhydric alcohol containing ether bond, and can inhibit the combination of anion and cation by generating complex reaction with lithium salt, thereby enhancing the ion transmission capability and improving the ionic conductivity; the hard segment of the polyether polyurethane elastomer is mainly isocyanate which can generate a crosslinking point so as to keep good mechanical property and film-forming property. Meanwhile, the composite filler is mixed with the polyether type polyurethane elastomer, so that the composite filler is loaded on the polyether type polyurethane elastomer, and the mechanical property of the polyether type polyurethane elastomer can be further improved by utilizing the composite filler, so that the prepared polymer electrolyte is not easy to damage and has higher stability. In addition, the polyether polyurethane elastomer selected by the invention does not react with lithium peroxide, can resist the corrosion of the lithium peroxide, has good conductivity, and can ensure that the prepared lithium-air battery keeps excellent cycling stability.
4. The solid lithium-air battery provided by the invention contains the polymer electrolyte provided by the invention, so that the safety and the stability of the solid lithium-air battery can be effectively improved, and the solid lithium-air battery can keep better charge-discharge performance and cycle performance. In addition, the polytetrafluoroethylene emulsion is added in the preparation process of the air electrode in the solid-state lithium-air battery, so that the side reaction caused by the fact that water invades a catalytic interface can be effectively prevented, and the washing of the electrolyte on the catalyst can be effectively resisted by utilizing the property that the polytetrafluoroethylene emulsion is insoluble in the electrolyte, so that the stability of the electrode is maintained, and the stability of the solid-state lithium-air battery is further improved.
Drawings
FIG. 1 is a scanning electron micrograph of a composite filler prepared in example 1 of the present invention at magnification of 20000 times;
FIG. 2 is a scanning electron microscope image at 1000 times magnification of a polymer electrolyte prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a polymer electrolyte prepared in example 1 of the present invention at 20000 times magnification;
fig. 4 is a charge-discharge curve of a solid-state lithium-air battery prepared in example 2 of the present invention;
fig. 5 is a cycle test chart of the solid-state lithium-air battery prepared in example 2 of the present invention.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention. It is to be understood that the described embodiments are merely a few 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 any inventive step, are within the scope of the present invention.
The invention provides a preparation method of a polymer electrolyte, which comprises the following steps:
s1, preparing the metal-organic framework material by adopting a solvothermal method;
s2, dissolving lithium salt in the ionic liquid, and heating to remove water to obtain lithium-containing ionic liquid; mixing the metal-organic framework material prepared in the step S1 with the lithium-containing ionic liquid according to a preset mass ratio, and heating and stirring to obtain a composite filler;
s3, dissolving the polyether polyurethane elastomer in an organic solvent, adding the composite filler obtained in the step S2, and fully stirring to obtain a homogeneous solution; and uniformly coating the homogeneous solution on a polytetrafluoroethylene plate, and drying until the organic solvent is completely volatilized to obtain the polymer electrolyte.
In step S1, the metal-organic framework material is prepared as follows:
mixing hafnium chloride and terephthalic acid according to a molar ratio of 1:2, adding the mixture into N, N-dimethylformamide, adding hydrochloric acid after full dissolution, stirring uniformly, transferring the mixed solution into a reaction kettle, setting the heating temperature to be 100-150 ℃ and the heating time to be 20-28 h, and filtering, washing, activating and drying the product after full reaction to obtain the metal-organic framework material.
In step S2, the concentration of the lithium-containing ionic liquid is 1-3 mol/L, and the preset mass ratio of the metal-organic framework material to the lithium-containing ionic liquid is (0.5-1): 1.
In step S3, the mass fraction of the composite filler in the polymer electrolyte is 10% to 60%.
In step S2, the heating temperature of the heating and stirring is 110-130 ℃, and the heating time is 10-14 h.
In step S2, the lithium salt is one or more of lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimidazole, lithium trifluoromethanesulfonate, lithium hexafluoroarsenate, lithium bisoxalateborate, lithium tetrafluoroborate, and lithium perchlorate; the ionic liquid is one or a mixture of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide, 1-butyl-3-methylimidazole tetrafluoroboric acid, N-methyl-N-propyl pyrrole bistrifluoromethylsulfonyl imide and 1-butyl-4 methylpyridine bistrifluoromethylsulfonyl imide.
In step S3, the organic solvent is one of N, N-dimethylformamide, N-methylpyrrolidone, and anhydrous acetonitrile.
The invention also provides a polymer electrolyte prepared according to any one of the technical schemes.
The invention also provides a solid-state lithium-air battery, which comprises a positive electrode, a negative electrode and the polymer electrolyte; the positive electrode is an air electrode, and the negative electrode is a lithium metal sheet.
The air electrode is foamed nickel loaded with commercial carbon nano tubes, and the preparation method comprises the following steps: the preparation method comprises the steps of uniformly mixing commercial carbon nanotubes, polytetrafluoroethylene emulsion and N-methyl pyrrolidone, stirring the mixture by using a grease homogenizing machine to prepare slurry, and spraying the slurry on foamed nickel by using a spray gun with the caliber of 0.1-0.5 mm.
The polymer electrolyte, the method for preparing the same, and the solid lithium-air electrode according to the present invention will be described with reference to examples, comparative examples, and the accompanying drawings.
Example 1
The embodiment provides a preparation method of a polymer electrolyte, which comprises the following steps:
s1 preparation of metal-organic framework material by solvothermal method
Hafnium chloride (1.281g, 4mmol) and terephthalic acid (1.32g, 8mmol) were ultrasonically dissolved in 24mL of N, N-Dimethylformamide (DMF) at room temperature, and 0.665mL of hydrochloric acid having a concentration of 12mol/L was added to generate more crystal nuclei, and after ultrasonic stirring dissolution, the mixed solution was transferred to a 100mL autoclave lined with polytetrafluoroethylene. Then the reaction kettle is put into a baking oven with program temperature control, and the temperature is controlled at 1 ℃ for min-1The temperature rising speed of (1) is increased from room temperature to 120 ℃, and after 24 hours of reaction, the temperature is increased to 1 ℃ for min-1Cool to room temperature. The product was filtered to give a white solid, which was treated with N, N-dimethylAnd leaching by formamide and acetone for three times, and activating and drying to obtain the metal-organic framework material.
S2 preparation of composite filler
Dissolving lithium bistrifluoromethanesulfonimide (LiTFSI) in an ionic solution 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide (EMIM TFSI) to prepare a solution of 2mol/L, heating to 120 ℃, keeping for 12h, and removing moisture to obtain a lithium-containing deionized solution. And mixing the metal-organic framework material obtained in the step S1 with the lithium ion-containing solution according to the mass ratio of 0.75:1, heating and stirring, setting the heating temperature to 120 ℃, keeping the temperature and stirring for 12 hours to obtain the composite filler.
S3 preparation of polymer electrolyte
5g of polyether urethane elastomer (TPU) was slowly added to 50mL of N, N-Dimethylformamide (DMF) and stirred for 12h, then 5g of the composite filler obtained in step S2 was slowly added and stirred for 12h to form a transparent homogeneous solution. Then, the homogeneous solution was uniformly coated on a teflon plate with a doctor blade having a certain thickness, and then it was dried in an oven at 60 ℃ until DMF was completely volatilized, to obtain a polymer electrolyte.
The scanning electron microscope image of the composite filler obtained in step S2 in this example is shown in fig. 1, and as can be seen from fig. 1, the particle size of the metal-organic framework material in the composite filler is small, and the metal-organic framework material is uniformly dispersed as a whole, which indicates that the metal-organic framework material prepared in this example has a large specific surface area and good dispersibility, and can absorb a lithium-containing ionic liquid.
The corresponding scanning electron micrographs of the polymer electrolyte prepared in this example at magnifications of 1000 and 20000 are shown in FIG. 2 and FIG. 3, respectively. As can be seen from fig. 2 and 3, the composite filler is uniformly loaded in the polymer matrix, which shows that in the polymer electrolyte provided by this embodiment, the polyether polyurethane elastomer and the composite filler are uniformly mixed, so that the polymer electrolyte has uniform and stable performance.
Example 2
This example provides a solid-state lithium-air battery comprising a positive electrode, a negative electrode, and the polymer electrolyte prepared in example 1. Wherein, the positive electrode is an air electrode, and the negative electrode is a lithium metal sheet.
The air electrode is foamed nickel loaded with commercial carbon nano tubes, and the preparation method comprises the following steps: uniformly mixing 90mg of commercial carbon nano tube, 5mg of polytetrafluoroethylene emulsion and 10mL of N-methyl pyrrolidone, stirring by using a grease homogenizing machine to prepare slurry, and spraying the slurry on foamed nickel by using a spray gun with the caliber of 0.3 mm.
The electrical properties of the solid-state lithium-air battery provided in this example were tested, and the charge-discharge curve and the cycle test chart are shown in fig. 3 and fig. 4, respectively.
In fig. 3, a curve a represents a change curve of voltage with test time, a curve b represents a change curve of current with test time, the test time is a discharging stage from 0 to 30 hours, and 30 to 50 hours are charging stages. As can be seen from FIG. 3, during the discharging process, the voltage is slowly reduced to 2V, and the current is kept stable at 0.35 mA; after the charging process is switched, the voltage changes to about 3.75V and slowly rises to 4.5V, and the current changes to 1.3mA and then keeps stable; the voltage and current change conditions in the whole charging and discharging process accord with the change rule of a normal battery, and the change rule shows that the solid-state lithium-air battery provided by the embodiment can be normally used and meets the requirements of practical application.
In fig. 4, a curve a represents a voltage variation with a test time, and a curve b represents a current variation with a test time. As can be seen from fig. 4, the voltage and the current both change periodically and regularly with the change of the test time, which indicates that the solid-state lithium-air battery provided by this embodiment has good cycling stability.
Examples 3 to 8
Examples 3 to 8 provide a method for preparing a polymer electrolyte, which is different from example 1 in that the concentration of the lithium-containing ionic liquid, the mass ratio of the metal-organic framework material to the lithium-containing ionic liquid in step S2, or the mass fraction of the composite filler in the polymer electrolyte in step S3 is changed, and the remaining steps are the same as example 1 and are not repeated herein. The relevant parameters corresponding to the embodiments are shown in table 1.
TABLE 1 relevant parameters in Steps S2, S3 in example 1 and examples 3 to 8
Figure BDA0002354942000000081
Figure BDA0002354942000000091
The conductivity of the polymer electrolytes prepared in examples 1 and 3 to 8 was measured at a temperature of 30 ℃, and the results are shown in table 2.
TABLE 2 conductivity of Polymer electrolytes prepared in example 1 and examples 3 to 8
Examples Electrical conductivity (10)-4S/cm)
Example 1 82
Example 3 6
Example 4 151
Example 5 24
Example 6 73
Example 7 0.6
Example 8 116
As can be seen from tables 1 and 2: changing the concentration of the lithium-containing ionic liquid, the mass ratio of the metal-organic framework material to the lithium-containing ionic liquid, or the mass fraction of the composite filler can have an effect on the conductivity of the finally prepared polymer electrolyte.
Comparing example 1 with examples 3-4 and examples 7-8, it can be seen that the ionic conductivity of the finally prepared polymer electrolyte gradually increases with the increase of the concentration of the lithium-containing ionic liquid or the mass fraction of the composite filler; however, in the actual production process, when the concentration of the ionic liquid and the mass fraction of the filler are too high, the mechanical strength of the final composite electrolyte membrane is affected to some extent. Therefore, in order to enable the prepared polymer electrolyte to have higher conductivity and mechanical strength, the concentration of the lithium-containing ionic liquid is preferably 1-3 mol/L, and the mass fraction of the composite filler in the polymer electrolyte is preferably 10-60%.
Comparing the example 1 with the examples 5 to 6, it can be seen that, as the content of the metal-organic framework material in the composite filler increases, the conductivity of the prepared polymer electrolyte increases first and then decreases, which indicates that the conductivity is improved by the combined action of the metal-organic framework material and the lithium-containing ionic liquid, and the conductivity of the prepared polymer electrolyte is affected by too high or too low content of the metal-organic framework material. Therefore, the mass ratio of the metal-organic framework material to the lithium-containing ionic liquid is preferably (0.5-1): 1.
Comparative example 1
Comparative example 1 provides a method for preparing a polymer electrolyte, which is different from example 1 in that the polyether polyurethane elastomer in step S3 is changed to polyethylene oxide, and the remaining steps are the same as example 1 and thus are not described again.
The conductivity of the polymer electrolyte prepared in comparative example 1 was measured to be 26X 10-4S/cm。
Compared with the embodiment 1, the invention can show that the polyether polyurethane elastomer is selected as the polymer electrolyte matrix, the soft segment of the polyether polyurethane elastomer can be used for enhancing the ion transmission capability and improving the ionic conductivity, and the hard segment of the polyether polyurethane elastomer is used for generating crosslinking points to improve the mechanical property and the film forming property, so that the prepared polymer electrolyte has more excellent conductivity and stability.
It should be noted that, in the preparation method of the polymer electrolyte provided by the present invention, the lithium salt may be one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imidazole, lithium trifluoromethanesulfonate, lithium hexafluoroarsenate, lithium bis (oxalato) borate, lithium tetrafluoroborate, and lithium perchlorate; the ionic liquid can be one or more of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide, 1-butyl-3-methylimidazole tetrafluoroboric acid, N-methyl-N-propyl pyrrole bistrifluoromethylsulfonyl imide and 1-butyl-4 methylpyridine bistrifluoromethylsulfonyl imide; the organic solvent in step S3 may be one or more of N, N-dimethylformamide, N-methylpyrrolidone, and anhydrous acetonitrile.
In addition, in the step S1, the heating temperature of the reaction kettle can be adjusted between 100 ℃ and 150 ℃ according to actual conditions, and the heating time can be adjusted between 20 h and 28 h; in step S2, the heating temperature during the heating and stirring process can be adjusted between 110 ℃ and 130 ℃ according to practical situations, and the heating and stirring time can be adjusted between 10 h and 14h, both of which belong to the protection scope of the present invention.
In summary, the invention discloses a polymer electrolyte, a preparation method thereof and a solid-state lithium-air battery. Preparing a metal-organic framework material by adopting a solvothermal method, and mixing the metal-organic framework material with a lithium-containing ionic liquid to obtain a composite filler; and then taking the polyether polyurethane elastomer as a matrix, and mixing the polyether polyurethane elastomer with the composite filler to obtain the polymer electrolyte. The polymer electrolyte has excellent conductivity and stability, and when the polymer electrolyte is used in a solid lithium-air battery, the safety and the stability of the solid lithium-air battery can be effectively improved, and the solid lithium-air battery can keep better charge and discharge performance and cycle performance so as to meet the requirements of practical application. Through the mode, the composite filler with the nano-porous structure can be prepared by utilizing the adsorption effect of the metal-organic framework material on the lithium-containing ionic liquid, the composite filler is loaded on the polyether polyurethane elastomer, and the prepared polymer electrolyte has better conductivity and mechanical property by utilizing the soft segment and the hard segment of the polyether polyurethane elastomer, so that the conductivity and the stability of the polymer electrolyte are effectively improved, and the solid lithium-air battery containing the polymer electrolyte can be safely and stably used.
The above description is only for the purpose of illustrating the technical solutions of the present invention and is not intended to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; all the equivalent structures or equivalent processes performed by using the contents of the specification and the drawings of the invention, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (9)

1. A method for preparing a polymer electrolyte, comprising the steps of:
s1, preparing the metal-organic framework material by adopting a solvothermal method;
s2, dissolving lithium salt in the ionic liquid, and heating to remove water to obtain lithium-containing ionic liquid; mixing the metal-organic framework material prepared in the step S1 with the lithium-containing ionic liquid according to a preset mass ratio, and heating and stirring to obtain a composite filler;
s3, dissolving the polyether polyurethane elastomer in an organic solvent, adding the composite filler obtained in the step S2, and fully stirring to obtain a homogeneous solution; uniformly coating the homogeneous solution on a polytetrafluoroethylene plate, and drying until the organic solvent is completely volatilized to obtain a polymer electrolyte; the mass fraction of the composite filler in the polymer electrolyte is 10-60%.
2. The method for producing a polymer electrolyte according to claim 1, wherein: in step S1, the metal-organic framework material is prepared as follows:
mixing hafnium chloride and terephthalic acid according to a molar ratio of 1:2, adding the mixture into N, N-dimethylformamide, adding hydrochloric acid after full dissolution, stirring uniformly, transferring the mixed solution into a reaction kettle, setting the heating temperature to be 100-150 ℃ and the heating time to be 20-28 h, and filtering, washing, activating and drying the product after full reaction to obtain the metal-organic framework material.
3. The method for producing a polymer electrolyte according to claim 1, wherein: in step S2, the concentration of the lithium-containing ionic liquid is 1-3 mol/L, and the preset mass ratio of the metal-organic framework material to the lithium-containing ionic liquid is (0.5-1): 1.
4. The method for producing a polymer electrolyte according to claim 1, wherein: in step S2, the heating temperature of the heating and stirring is 110-130 ℃, and the heating time is 10-14 h.
5. The method for producing a polymer electrolyte according to claim 1, wherein: in step S2, the lithium salt is one or more of lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium bistrifluoromethanesulfonylimidazole, lithium trifluoromethanesulfonate, lithium hexafluoroarsenate, lithium bisoxalateborate, lithium tetrafluoroborate, and lithium perchlorate; the ionic liquid is one or a mixture of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide, 1-butyl-3-methylimidazole tetrafluoroboric acid, N-methyl-N-propyl pyrrole bistrifluoromethylsulfonyl imide and 1-butyl-4 methylpyridine bistrifluoromethylsulfonyl imide.
6. The method for producing a polymer electrolyte according to claim 1, wherein: in step S3, the organic solvent is one of N, N-dimethylformamide, N-methylpyrrolidone, and anhydrous acetonitrile.
7. A polymer electrolyte characterized by: the polymer electrolyte is prepared by the preparation method of any one of claims 1 to 6.
8. A solid state lithium-air battery, characterized by: comprising a positive electrode, a negative electrode and the polymer electrolyte according to claim 7; the positive electrode is an air electrode, and the negative electrode is a lithium metal sheet.
9. A solid state lithium-air battery as claimed in claim 8, wherein: the air electrode is foamed nickel loaded with commercial carbon nano tubes, and the preparation method comprises the following steps: the preparation method comprises the steps of uniformly mixing commercial carbon nanotubes, polytetrafluoroethylene emulsion and N-methyl pyrrolidone, stirring the mixture by using a grease homogenizing machine to prepare slurry, and spraying the slurry on foamed nickel by using a spray gun with the caliber of 0.1-0.5 mm.
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