CN114709475A - Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof - Google Patents

Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof Download PDF

Info

Publication number
CN114709475A
CN114709475A CN202210302005.4A CN202210302005A CN114709475A CN 114709475 A CN114709475 A CN 114709475A CN 202210302005 A CN202210302005 A CN 202210302005A CN 114709475 A CN114709475 A CN 114709475A
Authority
CN
China
Prior art keywords
molecular sieve
polymer solid
imidazole framework
solid electrolyte
doped polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210302005.4A
Other languages
Chinese (zh)
Inventor
王朝阳
覃邓林
雷志文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202210302005.4A priority Critical patent/CN114709475A/en
Publication of CN114709475A publication Critical patent/CN114709475A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M2300/0082—Organic polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a molecular sieve imidazole framework doped polymer solid electrolyte and a preparation method thereof. The molecular sieve imidazole framework doped polymer solid electrolyte comprises a polymer body, and porous molecular sieve imidazole framework filler and lithium salt which adsorb ionic liquid. The porous molecular sieve imidazole framework filler adsorbing the ionic liquid can provide more lithium ion conducting passages for the polymer solid electrolyte and can also reduce the crystallinity of the polymer so as to improve the ionic conductivity of the polymer; meanwhile, the Lewis acid property of the surface of the molecular sieve imidazole framework filler can accelerate the dissociation of lithium salt in the electrolyte, is beneficial to the migration of lithium ions and improves the migration number of the lithium ions of the electrolyte. The preparation method is simple, efficient, easy for large-scale production and good in consistency, and can ensure the performance and quality stability of the prepared molecular sieve imidazole framework doped polymer solid electrolyte.

Description

Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof
Technical Field
The invention belongs to the technical field of solid lithium ion batteries, and particularly relates to a molecular sieve imidazole framework doped polymer solid electrolyte and a preparation method thereof.
Background
The lithium ion battery with the characteristics of high energy density, high power, long cycle life, no pollution and the like shows great development potential as a power source of the pure electric vehicle. As an important component of lithium ion batteries, electrolytes directly affect performance indexes such as capacity, safety, and cyclability of the batteries. At present, an organic liquid electrolyte containing lithium salt is used as the most common commercial electrolyte, although the lithium salt has good solubility and high ionic conductivity, the organic liquid electrolyte contains a large amount of volatile, flammable and easily-decomposed organic solvent, and the organic liquid electrolyte can be rapidly decomposed and release flammable gas under the conditions of short circuit, overcharge, thermal runaway and the like of a battery, so that the decomposition of positive and negative electrode materials is accelerated, the thermal runaway is caused, and spontaneous combustion or explosion is caused. The spontaneous combustion of Tesla electric vehicles and the fire accidents of domestic electric vehicles are related to the potential safety hazards of flammability and explosiveness of organic liquid electrolytes.
Compared with an organic liquid electrolyte, the solid electrolyte with strong flame retardant capability has the advantages of being difficult to burn, free of combustible liquid leakage, capable of eliminating electrolyte corrosion and the like, and can greatly improve the safety of the battery; also has good mechanical properties and effectively inhibits the dendritic growth of the lithium metal negative electrode; the assembly process of the battery is simplified, the battery space is effectively utilized, the weight of the battery can be reduced, the energy density and the production efficiency are improved, and the production cost is reduced. Therefore, the solid electrolyte can meet the requirement of high energy density of the lithium ion battery and meet the safety requirement.
At present, the research on the solid electrolyte of the polymer mainly made of polyethylene oxide (PEO) is more extensive and the commercial production is realized. The polymer solid electrolyte has the advantages of good interface compatibility, strong size processability, good flexibility, capability of well adapting to volume change in the charging and discharging process of electrode materials and the like, is beneficial to improving the safety of the lithium ion battery, and can also enable the lithium ion battery to develop towards the direction of miniaturization, light weight, high energy density and the like. However, the polymer solid electrolyte has low room temperature ionic conductivity (10)-6S/cm), it is difficult to effectively exert the battery capacity; the mechanical strength is low, and the growth of lithium dendrites is difficult to be effectively inhibited. The addition of the inorganic particle filler has been receiving much attention in order to improve electrochemical properties such as ionic conductivity of the polymer electrolyte. In improving polymer electrolysisIn electrochemical performance, the inorganic particle filler has three main functions: firstly, the winding of the chain is hindered, and the crystallization of the chain is reduced; secondly, the polar filler can play a role in promoting the dissociation of lithium salt; finally, the surface of the filler interacts with the chain, so that a rapid lithium ion conduction channel is formed. In recent years, TiO2，Ni3B2O3The addition of the nano particle filler increases the ionic conductivity of the polymer electrolyte to 10-5S/cm or more (Oxygen catalysts on surface of the TiO2 filters Li + reduction in PEO all-soluble-state electrolyte, 2022,28, 85-97; Lowering the operating temperature of PEO-based soluble-state electrolyte, 2022,29, 779-. The addition of porous Metal organic framework nanofillers such as HKUST and ZIF-8, which have better compatibility with polymers and larger specific surface area than pure solid inorganic nanofillers, can also further improve the ionic conductivity (Metal organic framework enabled given of multi-functional PEO-based dissolved polymer electrolytes. chemical Engineering Journal,2021,414,128702; expanded porous particulate organic framework work-8(ZIF-8) as an electron mediator for high-performance polymer (ethylene oxide) -based polymer electrolytes. nano Research,2020,13, 2259), but it is still difficult to satisfy the requirement of the solid state battery for ionic conductivity under room temperature conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a molecular sieve imidazole framework doped polymer solid electrolyte and a preparation method thereof, and aims to solve the technical problems of low ionic conductivity and poor mechanical properties of the conventional pure PEO polymer solid electrolyte. In order to improve the mechanical strength of PEO polymer electrolyte, the invention introduces rigid segment Polystyrene (PS) and takes polystyrene-polyethylene oxide copolymer (PS-PEO) as the bulk of polymer solid electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a molecular sieve imidazole framework doped polymer solid electrolyte. The electrolyte comprises a polymer body, molecular sieve imidazole framework inorganic nano particles and lithium salt, wherein the molecular sieve imidazole framework inorganic nano particles are doped in the polymer.
Further, the molecular sieve imidazole framework inorganic nano-filler is a molecular sieve imidazole framework 90(ZIF-90@ IL) for adsorbing ionic liquid, and the lithium salt is bis (trifluoromethyl) sulfonyl imide Lithium (LiTFSI), bis (fluoro) sulfonyl imide Lithium (LiFSI) or lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) The polymer body is a polystyrene-polyethylene oxide copolymer (PS-PEO).
Furthermore, the mass of the molecular sieve imidazole framework filler is 5-50% of the mass of the polymer body.
Further, the mass of the lithium salt is 20-100% of the mass of the polymer body.
Further, the mass content of the polyoxyethylene in the polystyrene-polyoxyethylene copolymer accounts for 10-90%.
The invention also provides a preparation method of the molecular sieve imidazole framework doped polymer solid electrolyte. The method comprises the following steps:
(1) firstly, dissolving lithium salt in 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide ionic liquid to obtain a solution 1, then dispersing porous inorganic nanoparticles ZIF-90 in the solution 1, standing at a high temperature for a period of time under a vacuum condition to obtain a mixed solution 2, cooling to room temperature, centrifugally separating the mixed solution 2, repeatedly cleaning, and drying to obtain solid powder ZIF-90@ IL.
(2) Sequentially adding ZIF-90@ IL obtained in the step (1) and lithium salt into an organic solvent to obtain a mixed solution 3, then adding a polymer body PS-PEO into the mixed solution 3 to obtain a mixed solution 4, dissolving the PS-PEO through magnetic stirring, casting the mixed solution 4 into a polytetrafluoroethylene mold, volatilizing and molding the solvent at room temperature under vacuum condition, and then heating and curing under vacuum condition to obtain the molecular sieve imidazole frame doped polymer solid electrolyte.
Further, in the step (1), the concentration of the lithium salt in the 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid is 0.2 mol/L-2 mol/L.
Further, in the step (1), the dosage ratio of the porous inorganic nano particle ZIF-90 to the 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonyl imide ionic liquid is 0.1 g/mL-0.5 g/mL.
Further, in the step (1), the temperature under the vacuum high-temperature condition is 80-180 ℃ and the time is 6-72 hours.
Further, in the step (2), the organic solvent includes at least one of 1, 3-dioxolane, tetrahydrofuran, dichloromethane, and N-methylpyrrolidone.
Furthermore, in the step (2), the dosage ratio of the organic solvent to the PS-PEO polymer bulk is 10 mL/g-100 mL/g.
Further, in the step (2), the temperature of the heating and curing treatment is 30-100 ℃, and the time is 3-30 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polymer body in the polymer solid electrolyte provided by the invention is a polystyrene-polyethylene oxide copolymer (PS-PEO), has more excellent mechanical properties compared with pure polyethylene oxide, and can better inhibit dendritic crystal growth.
(2) ZIF-90@ IL as an inorganic particulate filler can reduce the crystallinity of the polymer and thereby increase the ionic conductivity of the polymer electrolyte. Meanwhile, the surface of the ZIF-90@ IL particle has Lewis acid property, so that the dissociation of lithium salt can be accelerated, and more free lithium ions can be provided. The ionic liquid in the ZIF-90@ IL hole can provide a lithium ion transmission channel, and is beneficial to the migration of lithium ions, so that the ionic conductivity and the lithium ion migration number of the polymer solid electrolyte are improved. The ionic conductivity of the molecular sieve imidazole framework doped polymer solid electrolyte is 10-5～10-4S/cm, the transference number of lithium ions is as high as 0.45.
(3) The preparation method provided by the invention is simple and controllable, and can well uniformly disperse the inorganic particle filler in the polymer body; the preparation method can ensure the consistency of the structure and the performance of the molecular sieve imidazole framework doped polymer solid electrolyte, and is easy for large-scale production.
Drawings
FIG. 1 is a scanning electron micrograph of ZIF-90@ IL particles prepared in example 1;
FIG. 2 is a plot of elemental sulfur (S) spectra for ZIF-90@ IL particles prepared in example 1;
FIG. 3 is a scanning electron microscope plan view of a molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 1;
FIG. 4 is a graph of the molecular sieve imidazole framework doped polymer solid electrolyte zinc (Zn) element spectrum analysis prepared in example 1;
FIG. 5 is a scanning electron microscope cross-sectional view of a molecular sieve imidazole framework doped polymer solid state electrolyte prepared in example 1;
FIG. 6 is a cross-sectional zinc (Zn) element spectrum analysis diagram of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 1;
FIG. 7 shows an impedance spectrum and a constant current polarization spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 1 at room temperature;
FIG. 8 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 2 at room temperature;
FIG. 9 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 3 at room temperature;
FIG. 10 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 4 at room temperature;
FIG. 11 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 5 at room temperature;
fig. 12 is an impedance spectrum and a constant current polarization spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in comparative example 1 at room temperature.
Detailed Description
The present invention is described in further detail below with reference to examples, but the embodiments and the scope of the present invention are not limited thereto.
A molecular sieve imidazole framework doped polymer solid electrolyte and a preparation method thereof comprise the following steps:
1. firstly, dissolving 0.0574-0.574 g of LiTFSI in 1mL of 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid to obtain a solution 1, then dispersing 0.1-1 g of porous inorganic nanoparticles ZIF-90 in the solution 1, drying for 6-72 h at the temperature of 80-180 ℃ in vacuum to obtain a mixed solution 2, centrifugally separating the mixed solution 2, cleaning with anhydrous acetonitrile, and drying to obtain ZIF-90-coated ionic liquid solid powder (ZIF-90@ IL);
2. sequentially adding 0.02-0.2 g of ZIF-90@ IL and 0.08-0.4 g of lithium salt into 10mL of organic solvent to obtain a mixed solution 3, then adding 0.4g of PS-PEO into the mixed solution 3 to obtain a mixed solution 4, magnetically stirring to dissolve the PS-PEO, then casting the mixed solution 4 into a polytetrafluoroethylene mold, volatilizing and molding the solvent at room temperature under vacuum condition, and then drying and curing at 30-100 ℃ for 3-30 h under vacuum condition to obtain the molecular sieve imidazole frame doped polymer solid electrolyte.
The technical solution of the present invention will be specifically described below with reference to examples.
Example 1
1. Firstly, 0.0574g of LiTFSI is dissolved in 1mL of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ionic liquid to obtain a solution 1, then 0.1g of porous inorganic nanoparticles ZIF-90 are dispersed in the solution 1 and placed at the vacuum temperature of 120 ℃ for 12 hours to obtain a mixed solution 2, the mixed solution 2 is subjected to centrifugal separation and is washed by anhydrous acetonitrile, and solid powder ZIF-90@ IL is obtained after drying.
2. Sequentially adding 0.05g of ZIF-90@ IL and 0.1g of LiTFSI into 10mL of tetrahydrofuran to obtain a mixed solution 3, then adding 0.4g of PS-PEO into the mixed solution 3 to obtain a mixed solution 4, magnetically stirring to dissolve the PS-PEO, casting the mixed solution 4 into a polytetrafluoroethylene mold, volatilizing and molding the solvent at room temperature under vacuum condition, then placing the molded product into a vacuum state, and drying and curing the molded product at 60 ℃ for 5 hours to obtain the molecular sieve imidazole frame doped polymer solid electrolyte.
FIG. 1 is a scanning electron micrograph of ZIF-90@ IL particles prepared in example 1, which have a relatively uniform particle size distribution of 250-350 um; FIG. 2 is a plot of elemental sulfur (S) spectra of ZIF-90@ IL particles prepared in example 1, showing the successful preparation of ZIF-90@ IL from the effective distribution of S element in the solid powder for the proprietary ionic liquid.
Fig. 3 is a scanning electron microscope plan view of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 1, and it can be seen from fig. 3 that the surface of the composite electrolyte is very flat, has no obvious crystalline phase, can have good contact with the positive electrode and the negative electrode, and is beneficial to reducing the interface impedance of the battery; FIG. 4 is a graph of the molecular sieve imidazole framework doped polymer solid electrolyte zinc (Zn) element spectrum analysis prepared in example 1; the distribution of the Zn element in FIG. 4 reflects the relatively uniform distribution of the ZIF-90@ IL nanoparticles in the composite electrolyte.
FIG. 5 is a scanning electron microscope cross-sectional view of the solid electrolyte of the imidazole framework doped polymer of the molecular sieve prepared in example 1, and it can be seen from FIG. 5 that the thickness of the composite electrolyte is about 80 um; FIG. 6 is a cross-sectional zinc (Zn) element spectrum analysis diagram of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 1, and the distribution of Zn element in FIG. 6 can also reflect that ZIF-90@ IL nanoparticles are relatively uniformly distributed in the composite electrolyte.
Fig. 7 shows an impedance spectrum and a constant current polarization spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 1 at room temperature. Wherein, a in FIG. 7 is an impedance spectrum, and the room temperature ionic conductivity thereof is 4 × 10-4S/cm; fig. 7 b is a constant current polarization curve spectrum, and the transference number of lithium ions obtained is 0.45.
Example 2
1. Firstly, 0.1148g of LiFSI is dissolved in 1mL of 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid to obtain a solution 1, then 0.2g of porous inorganic nanoparticles ZIF-90 are dispersed in the solution 1 and placed at the temperature of 120 ℃ in vacuum for 6 hours to obtain a mixed solution 2, the mixed solution 2 is subjected to centrifugal separation and is washed by anhydrous acetonitrile, and solid powder ZIF-90@ IL is obtained after drying.
2. Sequentially adding 0.04g of ZIF-90@ IL and 0.15g of LiFSI into 10mL of dichloromethane to obtain a mixed solution 3, then adding 0.4g of PS-PEO into the mixed solution 3 to obtain a mixed solution 4, magnetically stirring to dissolve the PS-PEO, then casting the mixed solution 4 into a polytetrafluoroethylene mold, volatilizing and molding the solvent at room temperature under vacuum condition, then placing the molded product into a vacuum state, and drying and curing the molded product at 30 ℃ for 30 hours to obtain the molecular sieve imidazole frame doped polymer solid electrolyte.
FIG. 8 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 2 at room temperature, which can obtain a room temperature lithium ion conductivity of 6 × 10-5S/cm。
Example 3
1. Firstly, 0.574g of LiTFSI is dissolved in 1mL of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ionic liquid to obtain a solution 1, then 1g of porous inorganic nanoparticles ZIF-90 is dispersed in the solution 1 and placed under the condition of vacuum 180 ℃ for 6 hours to obtain a mixed solution 2, the mixed solution 2 is subjected to centrifugal separation and is washed by anhydrous acetonitrile, and solid powder ZIF-90@ IL is obtained after drying.
2. 0.2g ZIF-90@ IL and 0.2g LiClO4And sequentially adding the mixed solution into 10mL of tetrahydrofuran to obtain a mixed solution 3, then adding 0.4g of PS-PEO into the mixed solution 3 to obtain a mixed solution 4, dissolving the PS-PEO by magnetic stirring, casting the mixed solution 4 into a polytetrafluoroethylene mold, volatilizing and forming the solvent at room temperature under a vacuum condition, then placing the molded product in a vacuum state, and drying and curing the molded product at 100 ℃ for 3 hours to obtain the molecular sieve imidazole framework doped polymer solid electrolyte.
FIG. 9 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 3 at room temperature, and room temperature lithium ion conductivity thereof 2X 10 can be obtained-4S/cm。
Example 4
1. Firstly, 0.4g of LiTFSI is dissolved in 1mL of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt ionic liquid to obtain a solution 1, then 0.5g of porous inorganic nanoparticles ZIF-90 are dispersed in the solution 1 and placed at the vacuum condition of 80 ℃ for 72 hours to obtain a mixed solution 2, the mixed solution 2 is subjected to centrifugal separation and is washed by anhydrous acetonitrile, and solid powder ZIF-90@ IL is obtained after drying.
2. 0.15g ZIF-90@ IL and 0.15g LiPF6Sequentially adding into 10ml of N-methyl pyrrolidone to obtain a mixed solution 3, adding 0.4g of PS-PEO into the mixed solution 3 to obtain a mixed solution 4, and filteringAnd (3) after dissolving PS-PEO by magnetic stirring, casting the mixed solution 4 in a polytetrafluoroethylene mold, volatilizing and forming the solvent at room temperature under a vacuum condition, then placing the molded product in a vacuum state, and drying and curing the molded product at 80 ℃ for 10 hours to obtain the molecular sieve imidazole framework doped polymer solid electrolyte.
FIG. 10 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 4 at room temperature, which can obtain a room temperature lithium ion conductivity of 8 × 10-5S/cm。
Example 5
1. Firstly, 0.287g of LiTFSI is dissolved in 1mL of 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide ionic liquid to obtain a solution 1, then 0.2g of porous inorganic nanoparticles ZIF-90 are dispersed in the solution 1 and placed under the vacuum condition of 140 ℃ for 12 hours to obtain a mixed solution 2, the mixed solution 2 is subjected to centrifugal separation and is washed by anhydrous acetonitrile, and solid powder ZIF-90@ IL is obtained after drying.
2. Sequentially adding 0.02g of ZIF-90@ IL and 0.08g of LiTFSI into 10mL of tetrahydrofuran to obtain a mixed solution 3, then adding 0.4g of PS-PEO into the mixed solution 3 to obtain a mixed solution 4, magnetically stirring to dissolve the PS-PEO, casting the mixed solution 4 into a polytetrafluoroethylene mold, volatilizing and molding the solvent at room temperature under vacuum condition, then placing the molded product into a vacuum state, and drying and curing the molded product at 70 ℃ for 20 hours to obtain the molecular sieve imidazole frame doped polymer solid electrolyte.
FIG. 11 is an impedance spectrum of the molecular sieve imidazole framework doped polymer solid electrolyte prepared in example 5 at room temperature, which can obtain a lithium ion conductivity of 5 × 10 at room temperature-5S/cm。
Comparative example 1
Adding 0.1g of LiTFSI into 10mL of tetrahydrofuran to obtain a solution 1, then adding 0.4g of PS-PEO into the solution 1 to obtain a mixed solution 2, dissolving the PS-PEO by magnetic stirring, casting the mixed solution 2 into a polytetrafluoroethylene mold, volatilizing and molding the solvent at room temperature under vacuum condition, then placing the mold in a vacuum state, and drying and curing at 60 ℃ for 5 hours to obtain the molecular sieve imidazole frame doped polymer solid electrolyte.
FIG. 12 is a bar of pure PS-PEO polymer solid electrolyte prepared in comparative example 1 at room temperatureAn off-device impedance spectrogram and a constant current polarization spectrogram. Wherein, a in FIG. 12 is an impedance spectrum, which can be obtained to have a room temperature ionic conductivity of 6X 10-6S/cm; fig. 12 b is a constant current polarization curve spectrum, and the transference number of lithium ions obtained is 0.15. Results of example 1 (ionic conductivity 4X 10)-4S/cm; the lithium ion transport number is 0.45), compared with the pure PS-PEO polymer solid electrolyte, the molecular sieve imidazole framework doped polymer solid electrolyte prepared by the invention has higher ionic conductivity and larger lithium ion transport number.

Claims (10)

1. A molecular sieve imidazole framework doped polymer solid state electrolyte, characterized in that the polymer solid state electrolyte comprises a polymer body, a molecular sieve imidazole framework filler doped in the polymer, and a lithium salt; the polymer body is a polystyrene-polyoxyethylene copolymer.
2. The molecular sieve imidazole framework doped polymer solid-state electrolyte of claim 1, wherein the mass of the molecular sieve imidazole framework filler is 5% to 50% of the mass of the polymer bulk; the mass of the lithium salt is 20-100% of the mass of the polymer body.
3. The molecular sieve imidazole framework doped polymer solid state electrolyte of claim 1, wherein the molecular sieve imidazole framework filler is ZIF-90(ZIF-90@ IL) adsorbing an ionic liquid.
4. The molecular sieve imidazole framework doped polymer solid-state electrolyte according to claim 1, wherein the mass content of the polyethylene oxide segment in the polystyrene-polyethylene oxide copolymer is 10% to 90%.
5. The molecular sieve imidazole framework doped polymer solid-state electrolyte of claim 1, wherein the lithium salt comprises at least one of lithium bis (trifluoromethylsulfonate) imide, lithium bis (fluorosulfonyl) imide, lithium hexafluorophosphate, lithium perchlorate.
6. The method for preparing the molecular sieve imidazole framework doped polymer solid electrolyte as claimed in claim 1, characterized by comprising the following steps:
(1) firstly, dissolving lithium salt in 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonylimide ionic liquid to obtain a solution 1, then dispersing porous inorganic nanoparticles ZIF-90 in the solution 1, placing the solution under a vacuum high-temperature condition to obtain a mixed solution 2, centrifugally separating and cleaning the mixed solution 2, and drying to obtain solid powder ZIF-90@ IL;
(2) sequentially adding ZIF-90@ IL obtained in the step (1) and lithium salt into an organic solvent to obtain a mixed solution 3, then adding a polymer body PS-PEO into the mixed solution 3 to obtain a mixed solution 4, dissolving the PS-PEO through magnetic stirring, casting the mixed solution 4 into a polytetrafluoroethylene mold, volatilizing and molding the solvent at room temperature under vacuum condition, and then heating and curing under vacuum condition to obtain the molecular sieve imidazole frame doped polymer solid electrolyte.
7. The method for preparing the molecular sieve imidazole framework doped polymer solid electrolyte according to claim 6, wherein the concentration of the lithium salt in the 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt ionic liquid in the step (1) is 0.2 g/mL-2 mol/L; and/or the dosage ratio of the porous inorganic nano particle ZIF-90 to the 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide ionic liquid is 0.1 g/mL-0.5 g/mL.
8. The preparation method of the molecular sieve imidazole framework doped polymer solid electrolyte according to claim 6, wherein the temperature of the vacuum high temperature condition in the step (1) is 80-180 ℃ and the time is 6-72 h.
9. The method of claim 6, wherein the organic solvent of step (2) comprises at least one of 1, 3-dioxolane, tetrahydrofuran, dichloromethane, N-methylpyrrolidone; and/or the dosage ratio of the organic solvent to the PS-PEO polymer bulk is 10 mL/g-100 mL/g.
10. The method for preparing the molecular sieve imidazole framework doped polymer solid electrolyte according to any one of claims 6 to 9, wherein the temperature for heating and curing in the step (2) is 30 ℃ to 100 ℃ and the time is 3h to 30 h.
CN202210302005.4A 2022-03-25 2022-03-25 Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof Pending CN114709475A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210302005.4A CN114709475A (en) 2022-03-25 2022-03-25 Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210302005.4A CN114709475A (en) 2022-03-25 2022-03-25 Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114709475A true CN114709475A (en) 2022-07-05

Family

ID=82169974

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210302005.4A Pending CN114709475A (en) 2022-03-25 2022-03-25 Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114709475A (en)

Similar Documents

Publication Publication Date Title
JP5446309B2 (en) Gel electrolyte, battery using the same, method for using the same, and method for producing gel electrolyte
CN111697262A (en) Composite solid electrolyte, all-solid-state lithium ion battery and preparation method thereof
CN109360971B (en) Preparation method of microspherical manganese selenide/carbon composite material
CN106159325A (en) A kind of low temperature electrolyte for lithium ion battery and low-temperature lithium ion battery
WO2021189161A1 (en) All solid-state electrolyte composite based on functionalized metal-organic framework materials for li thoum secondary battery and method for manufacturing the same
CN111313083A (en) Composite solid electrolyte film and preparation and application thereof
CN113206288A (en) Composite solid electrolyte membrane based on titanium dioxide with surface defects as well as preparation method and application of composite solid electrolyte membrane
CN101702445B (en) Flame-retardant electrolyte for lithium ion batteries and preparation method and application thereof
CN110635116A (en) Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery
Narayanasamy et al. 2D MXenes for all-solid-state batteries: A comprehensive review
CN111786024B (en) Titanium oxygen cluster based solid polymer electrolyte and preparation method and application thereof
CN115411351A (en) Solid-state battery modified by ion/electron mixed conductive solid interface layer and preparation method thereof
CN115663393B (en) Chlorine-end-group MXene ink-based diaphragm for lithium metal battery and preparation method thereof
CN113991174B (en) Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof
CN113206292B (en) Polymer-based composite solid electrolyte and preparation method and application thereof
CN114709475A (en) Molecular sieve imidazole framework doped polymer solid electrolyte and preparation method thereof
CN114204118A (en) PVDF (polyvinylidene fluoride) -based composite solid electrolyte and preparation method thereof
CN110808410B (en) Solid electrolyte of lithium metal battery, preparation method and application thereof, and lithium metal battery
CN117913347B (en) CoNi-MOFs@NiPc modified PEO solid electrolyte and preparation method thereof
CN113517469B (en) Preparation method, product and application of single-phase compact polymer electrolyte
Yuan et al. Study of poly (organic palygorskite-methyl methacrylate)/poly (vinylidene fluoride-co-hexafluoropropylene) blended gel polymer electrolyte for lithium-ion batteries
CN114024027B (en) High-concentration electrolyte and preparation method and application thereof
CN112397771B (en) Solid electrolyte membrane, preparation method thereof and application thereof in solid lithium-sulfur battery
CN117525587A (en) Electrolyte additive, nonaqueous electrolyte, sodium secondary battery, and electric device
CN115911322A (en) Silicon-carbon negative electrode material for lithium ion battery, preparation method thereof and obtained product

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination