CN117276683A - Quasi-solid polymer fiber electrolyte and preparation method and application thereof - Google Patents

Quasi-solid polymer fiber electrolyte and preparation method and application thereof Download PDF

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Publication number
CN117276683A
CN117276683A CN202311557705.9A CN202311557705A CN117276683A CN 117276683 A CN117276683 A CN 117276683A CN 202311557705 A CN202311557705 A CN 202311557705A CN 117276683 A CN117276683 A CN 117276683A
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polymer fiber
quasi
electrolyte
few
solid polymer
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韩炜
李栋栋
李俊志
李是鳞
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Jilin Jianeng Sodium Electric Technology Co ltd
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Jilin Jianeng Sodium Electric Technology Co ltd
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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
    • H01M10/058—Construction or manufacture
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures

Abstract

The invention belongs to the technical field of sodium ion batteries, and provides a quasi-solid polymer fiber electrolyte, a preparation method and application thereof. According to the preparation method, a few-layer MXene material, a polymer and an organic solvent are mixed to obtain an electrostatic spinning precursor dispersion liquid; carrying out electrostatic spinning on the electrostatic spinning precursor dispersion liquid to obtain a polymer fiber film precursor; and drying the polymer fiber film precursor to obtain the quasi-solid polymer fiber electrolyte. According to the invention, a few-layer MXene material is introduced, so that the ion conductivity of the quasi-solid polymer fiber electrolyte is improved, and when the quasi-solid polymer fiber electrolyte is applied to a sodium ion battery, the internal resistance of the sodium ion battery is reduced, so that the quasi-solid polymer fiber electrolyte, an NVP sodium ion battery anode and a sodium ion battery assembled by sodium sheets can realize stable circulation under different current densities, namely, the electrochemical performance of the sodium ion battery is improved; and the solid electrolyte is not easy to leak, so that the safety is high.

Description

Quasi-solid polymer fiber electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a quasi-solid polymer fiber electrolyte and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) are the currently dominant energy storage technology, powering portable electronics and automobiles. However, global lithium resources are in shortage and distributed unevenly, and the cost of lithium ion batteries is increasing with the increasing demand for lithium ion battery technology. Sodium Ion Batteries (SIBs) are one of the best alternative power sources for portable electronic devices, automobiles, and grid storage applications due to their low cost and greater reserves than lithium. Similar to the composition of lithium ion batteries, sodium batteries also include a positive electrode, a negative electrode, and an electrolyte. In recent years, polymer electrolytes have been greatly favored in energy storage applications because they can reduce the volume of the electrode during electrochemical storage and accommodate cell designs of various shapes. In addition, the use of the polymer electrolyte can minimize problems such as electrolyte leakage. However, polymer electrolytes also have some disadvantages such as low room temperature conductivity and poor interfacial resistance. Accordingly, various proposals have been made to develop a polymer electrolyte having good room temperature high conductivity and stable interface properties between the electrode and the electrolyte. In order to overcome the above problems, a liquid electrolyte is added to a polymer film to form a gel polymer electrolyte having both solid electrolyte and liquid electrolyte characteristics. Among gel polymer electrolytes, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polyacrylonitrile (PAN), and polymethyl methacrylate (PMMA) are widely used as polymer matrices. Among them, PVDF-HFP is attracting attention because of its amorphous nature and having the characteristics of high ionic conductivity at room temperature, strong chemical resistance, high thermal stability, strong flexibility, etc.
The polyvinylidene fluoride-co-hexafluoropropylene is used as a polymer matrix to prepare a polymer fiber film by an electrostatic spinning method, and the polymer fiber film is prepared by the electrostatic spinning method, so that certain requirements on the concentration, viscosity and conductivity of a precursor solution are met; in addition, the voltage of the electrospinning also affects the diameter of the fibers and the voids of the film. In addition, the PVDF-HFP fiber gel prepared by the prior art still has room for improvement in ionic conductivity.
Disclosure of Invention
In view of the above, the present invention is directed to a quasi-solid polymer fiber electrolyte, and a preparation method and application thereof. The quasi-solid polymer fiber electrolyte prepared by the preparation method provided by the invention has higher ionic conductivity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of quasi-solid polymer fiber electrolyte, which comprises the following steps:
mixing a few-layer MXene material, a polymer and an organic solvent to obtain an electrostatic spinning precursor dispersion liquid;
carrying out electrostatic spinning on the electrostatic spinning precursor dispersion liquid to obtain a polymer fiber film precursor;
drying the polymer fiber film precursor to obtain the quasi-solid polymer fiber electrolyte;
the few-layer MXene material is Ti 3 C 2 T x 、Nb 2 CT x 、V 4 C 3 T x And TiVCT x One or more of the following;
the polymer is one or more of polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene, polyacrylonitrile and polymethyl methacrylate;
the mass ratio of the few-layer MXene material to the polymer is (0-10): 100, the mass of the few-layer MXene material is not 0.
Preferably, the organic solvent is N, N-dimethylformamide or an N, N-dimethylformamide-acetone mixed solvent;
the dosage ratio of the few-layer MXene material to the organic solvent is 8-56 mg:5mL.
Preferably, the mixing of the few layers of MXene material, polymer and organic solvent comprises: stirring, mixing and ultrasonically dispersing the few-layer MXene material and the organic solvent in sequence to obtain MXene material dispersion liquid; heating, stirring and mixing the MXene material dispersion liquid and the polymer;
the rotation speed of stirring and mixing is 200-300 rpm, and the time is 1-2 hours; the working power of the ultrasonic dispersion is 200-500W, and the time is 1-2 h; the temperature of heating, stirring and mixing is 60-80 ℃, the rotating speed is 200-300 rpm, and the time is 1-4 hours.
Preferably, the parameters of the electrospinning include: the propelling speed of the injection pump of the spinning machine is 0.5-1 mL/h, the specification of the needle head of the injection pump of the spinning machine is 1.2X38 mm, the working environment humidity of the spinning machine is 30%, the working voltage of the spinning machine is 10-20 kV, the distance between the needle head of the injection pump of the spinning machine and the roller receiver is 10-20 cm, and the rotating speed of the roller receiver is 400-1000 rpm.
Preferably, the drying temperature is 60-80 ℃ and the drying time is 8-12 hours.
The invention also provides the quasi-solid polymer fiber electrolyte prepared by the preparation method.
The invention also provides application of the quasi-solid polymer fiber electrolyte in sodium ion batteries.
The invention provides a preparation method of quasi-solid polymer fiber electrolyte, which comprises the following steps: mixing a few-layer MXene material, a polymer and an organic solvent to obtain an electrostatic spinning precursor dispersion liquid; carrying out electrostatic spinning on the electrostatic spinning precursor dispersion liquid to obtain a polymer fiber film precursor; drying the polymer fiber film precursor to obtain the quasi-solid polymer fiber electrolyte; the few-layer MXene material is Ti 3 C 2 T x 、Nb 2 CT x 、V 4 C 3 T x And TiVCT x One or more of the following; the polymer is polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoroOne or more of propylene, polyacrylonitrile, and polymethyl methacrylate; the mass ratio of the few-layer MXene material to the polymer is (0-10): 100, the mass of the few-layer MXene material is not 0.
The invention introduces a few layers of MXene materials, improves the ion conductivity of the quasi-solid polymer fiber electrolyte, reduces the internal resistance of the sodium ion battery when the quasi-solid polymer fiber electrolyte is applied to the sodium ion battery, and ensures that the quasi-solid polymer fiber electrolyte and Na 3 V 2 (PO 4 ) 3 The positive electrode of the (NVP) sodium ion battery and the sodium ion battery assembled by the sodium sheets can realize stable circulation under different current densities, namely, the electrochemical performance of the sodium ion battery is improved; and the solid electrolyte is not easy to leak, so that the safety is high.
Drawings
FIG. 1 is a graph showing the cycle performance of a quasi-solid polymer fiber electrolyte assembled full cell obtained in example 1;
FIG. 2 is a graph showing the cycle performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in example 2;
FIG. 3 is a graph showing the cycling performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in example 3;
FIG. 4 is a graph showing the cycling performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in example 4;
FIG. 5 is a graph showing the cycle performance of a quasi-solid polymer fiber electrolyte assembled full cell obtained in comparative example 1;
FIG. 6 is an XRD pattern of the quasi-solid polymer fiber electrolyte obtained in example 2;
FIG. 7 is an SEM image of a quasi-solid polymer fiber electrolyte obtained in example 2;
FIG. 8 is a graph showing the conductivity of the quasi-solid polymer fiber electrolytes obtained in examples 1 to 4 and comparative example 1.
Detailed Description
The invention provides a preparation method of quasi-solid polymer fiber electrolyte, which comprises the following steps:
mixing a few-layer MXene material, a polymer and an organic solvent to obtain an electrostatic spinning precursor dispersion liquid;
carrying out electrostatic spinning on the electrostatic spinning precursor dispersion liquid to obtain a polymer fiber film precursor;
drying the polymer fiber film precursor to obtain the quasi-solid polymer fiber electrolyte;
the few-layer MXene material is Ti 3 C 2 T x 、Nb 2 CT x 、V 4 C 3 T x And TiVCT x One or more of the following;
the polymer is one or more of polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene, polyacrylonitrile and polymethyl methacrylate;
the mass ratio of the few-layer MXene material to the polymer is (0-10): 100, the mass of the few-layer MXene material is not 0.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention mixes a few-layer MXene material, a polymer and an organic solvent to obtain an electrostatic spinning precursor dispersion liquid.
In the invention, the few-layer MXene material is Ti 3 C 2 T x 、Nb 2 CT x 、V 4 C 3 T x And TiVCT x One or more of the following.
In the present invention, the polymer is one or more of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polyacrylonitrile (PAN), and polymethyl methacrylate (PMMA).
In the present invention, the organic solvent is preferably N, N-Dimethylformamide (DMF) or an N, N-dimethylformamide-acetone mixed solvent, and more preferably N, N-Dimethylformamide (DMF).
In the invention, the mass ratio of the few-layer MXene material to the polymer is (0-10): 100, wherein the mass of the few-layer MXene material is not 0, and is preferably 0.1-10: 100, more preferably 1 to 7:100, more preferably 3 to 5:100.
in the invention, the dosage ratio of the few-layer MXene material to the organic solvent is preferably 8-56 mg:5mL.
In the present invention, the mixing of the minor layer of MXene material, the polymer and the organic solvent preferably comprises: stirring, mixing and ultrasonically dispersing the few-layer MXene material and the organic solvent in sequence to obtain MXene material dispersion liquid; the MXene material dispersion and the polymer are heated, stirred and mixed.
In the invention, the rotation speed of stirring and mixing is preferably 200-300 rpm, and the time is preferably 1-2 h. In the invention, the working power of ultrasonic dispersion is preferably 200-500W, more preferably 300-400W, and the time is preferably 1-2 h. In the present invention, the ultrasonic dispersion is preferably performed in a cell pulverizer. In the invention, the temperature of the heating, stirring and mixing is preferably 60-80 ℃, more preferably 70 ℃, the rotating speed is preferably 200-300 rpm, and the time is preferably 1-4 h.
After the mixing, the invention preferably further comprises standing at room temperature until naturally cooling.
After the electrostatic spinning precursor dispersion liquid is obtained, the invention carries out electrostatic spinning on the electrostatic spinning precursor dispersion liquid to obtain the polymer fiber film precursor.
In the present invention, the parameters of the electrospinning include: the advancing speed of the injection pump of the spinning machine is preferably 0.5-1 mL/h, more preferably 0.6-0.9 mL/h, and even more preferably 0.7-0.8 mL/h; the syringe pump of the spinning machine is preferably a medical syringe, the capacity of the medical syringe is preferably 10mL, the specification of the needle head of the syringe pump of the spinning machine is preferably 1.2X138 mm, the humidity of the working environment of the spinning machine is preferably 25% -60%, more preferably 30% -50%, the working voltage of the spinning machine is preferably 10-20 kV, the distance between the needle head of the syringe pump of the spinning machine and a roller receiver is preferably 10-20 cm, the surface of the roller receiver is preferably coated with copper foil or aluminum foil, and the rotating speed of the roller receiver is preferably 400-1000 rpm.
After the polymer fiber film precursor is obtained, the polymer fiber film precursor is dried to obtain the quasi-solid polymer fiber electrolyte.
In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 70 ℃; the time is preferably 8-12 hours. In the present invention, the drying is preferably performed in a vacuum drying oven.
The invention also provides the quasi-solid polymer fiber electrolyte prepared by the preparation method.
The invention also provides application of the quasi-solid polymer fiber electrolyte in sodium ion batteries.
The application mode of the quasi-solid polymer fiber electrolyte in the sodium ion battery is not particularly limited, and the quasi-solid polymer fiber electrolyte can be set by a person skilled in the art according to actual conditions.
The quasi-solid polymer fiber electrolyte, the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Will be 8mg (few layer Ti) 3 C 2 T x MXene to PVDF-HFP mass ratio of 1/100) of the few layers Ti 3 C 2 T x MXene is dispersed in 5mL of organic solvent DMF and stirred for 1h in a stirring table with the rotating speed of 250 rpm; then moving the mixture into a cell grinder, performing ultrasonic dispersion at the power of 300W for 1h to obtain MXene dispersion liquid; 0.8g of PVDF-HFP was added as a polymer to the MXene dispersion, stirred at 250rpm in a heated stirring table at 70℃for 1 hour, and allowed to stand to room temperature to obtain an electrostatic spinning precursor dispersion.
Transferring the electrostatic spinning precursor dispersion liquid into an electrostatic spinning injection pump; the injection pump is a medical injector with the volume of 10mL, and the specification of the needle head of the medical injector is 1.2 multiplied by 38mm; installing a syringe pump on an electrostatic spinning machine, and pushing the syringe pump at a speed of 0.8mL/h; the working environment humidity of the electrostatic spinning machine is 30%, the working voltage is 12kV, a roller type receiver is used, the surface of the roller type receiver is coated with aluminum foil and rotates at 400rpm, and the distance between the roller type receiver and a syringe pump needle is 15cm; and after the electrostatic spinning is finished, collecting the polymer fiber film precursor from the aluminum foil outside the drum-type receiver.
Drying the polymer fiber film precursor in a vacuum drying oven at 60 ℃ for 8 hours to remove the organic solvent remained in the precursor; after drying, a quasi-solid polymer fiber electrolyte for sodium ion batteries is obtained.
Example 2
Will be 24mg (few layer Ti) 3 C 2 T x 3/100 MXene to PVDF-HFP) of the reduced layer Ti 3 C 2 T x MXene is dispersed in 5mL of organic solvent DMF and stirred for 1h in a stirring table with the rotating speed of 250 rpm; then moving the mixture into a cell grinder, performing ultrasonic dispersion at the power of 300W for 1h to obtain MXene dispersion liquid; 0.8g of PVDF-HFP was added as a polymer to the MXene dispersion, stirred at 250rpm in a heated stirring table at 70℃for 1 hour, and allowed to stand to room temperature to obtain an electrostatic spinning precursor dispersion.
Transferring the electrostatic spinning precursor dispersion liquid into an electrostatic spinning injection pump; the injection pump is a medical injector with the volume of 10mL, and the specification of the needle head of the medical injector is 1.2 multiplied by 38mm; installing a syringe pump on an electrostatic spinning machine, and pushing the syringe pump at a speed of 0.8mL/h; the working environment humidity of the electrostatic spinning machine is 30%, the working voltage is 12kV, a roller type receiver is used, the surface of the roller type receiver is coated with aluminum foil and rotates at 400rpm, and the distance between the roller type receiver and a syringe pump needle is 15cm; and after the electrostatic spinning is finished, collecting the polymer fiber film precursor from the aluminum foil outside the drum-type receiver.
Drying the polymer fiber film precursor in a vacuum drying oven at 60 ℃ for 8 hours to remove the organic solvent remained in the precursor; after drying, a quasi-solid polymer fiber electrolyte for sodium ion batteries is obtained.
Example 3
Will be 40mg (few layer Ti) 3 C 2 T x MXene to PVDF-HFP mass ratio of 5/100) of the few layers Ti 3 C 2 T x MXene dispersed in 5mLStirring in DMF as the organic solvent in a stirring table with the rotating speed of 250rpm for 1h; then moving the mixture into a cell grinder, performing ultrasonic dispersion at the power of 300W for 1h to obtain MXene dispersion liquid; 0.8g of PVDF-HFP was added as a polymer to the MXene dispersion, stirred at 250rpm in a heated stirring station at 70℃for 1 hour, and allowed to stand to room temperature to obtain a polymer fiber film precursor.
Transferring the polymer fiber film precursor into an electrostatic spinning injection pump; the injection pump is a medical injector with the volume of 10mL, and the specification of the needle head of the medical injector is 1.2 multiplied by 38mm; installing a syringe pump on an electrostatic spinning machine, and pushing the syringe pump at a speed of 0.8mL/h; the working environment humidity of the electrostatic spinning machine is 30%, the working voltage is 12kV, a roller type receiver is used, the surface of the roller type receiver is coated with aluminum foil and rotates at 400rpm, and the distance between the roller type receiver and a syringe pump needle is 15cm; and after the electrostatic spinning is finished, collecting the polymer fiber film precursor from the aluminum foil outside the drum-type receiver.
Drying the polymer fiber film precursor in a vacuum drying oven at 60 ℃ for 8h to remove the organic solvent remaining in the precursor; after drying, a quasi-solid polymer fiber electrolyte for sodium ion batteries is obtained.
Example 4
Will be 56mg (few layer Ti) 3 C 2 T x MXene to PVDF-HFP mass ratio of 7/100) of the few layers Ti 3 C 2 T x Dispersing MXene in 5mL of organic solvent DMF, stirring for 1h in a stirring table with the rotating speed of 250rpm, then moving into a cell grinder, and performing ultrasonic dispersion with the power of 300W for 1h to obtain MXene dispersion; 0.8g of PVDF-HFP was added as a polymer to the MXene dispersion, stirred at 250rpm in a heated stirring table at 70℃for 1 hour, and allowed to stand to room temperature to obtain an electrostatic spinning precursor dispersion.
Transferring the electrostatic spinning precursor dispersion liquid into an electrostatic spinning injection pump; the injection pump is a medical injector with the volume of 10mL, and the specification of the needle head of the medical injector is 1.2 multiplied by 38mm; installing a syringe pump on an electrostatic spinning machine, and pushing the syringe pump at a speed of 0.8mL/h; the working environment humidity of the electrostatic spinning machine is 30%, the working voltage is 12kV, a roller type receiver is used, the surface of the roller type receiver is coated with aluminum foil and rotates at 400rpm, and the distance between the roller type receiver and a syringe pump needle is 15cm; and after the electrostatic spinning is finished, collecting the polymer fiber film precursor from the aluminum foil outside the drum-type receiver.
Drying the polymer fiber film precursor in a vacuum drying oven at 60 ℃ for 8 hours to remove the organic solvent remained in the precursor; after drying, a quasi-solid polymer fiber electrolyte for sodium ion batteries is obtained.
Comparative example 1
The differences from example 1 are: does not add less layer of Ti 3 C 2 T x MXene。
Test example 1
Cutting the quasi-solid polymer fiber electrolyte for sodium ion battery obtained in examples 1-4 and comparative example 1 according to the requirement, assembling the quasi-solid electrolyte, a positive electrode, a negative electrode and accessories into a button type full battery, wherein the positive electrode is a self-supporting electrode for sodium ion battery positive electrode, the negative electrode is a metal sodium sheet, and the electrolyte is 1M NaClO 4 Dissolved in a mixed solution of ethylene carbonate and diethyl carbonate (EC/DEC) in a volume ratio of 1:1, and contains 5% by mass of fluoroethylene carbonate.
The obtained full cells were tested, and the obtained performance diagrams are shown in fig. 1 to 5.
Fig. 1 is a graph showing the cycle performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in example 1, as can be seen from fig. 1: it has a long and stable plateau during the first five cycles and it still has a specific capacity of >95mAh/g after 5 cycles.
Fig. 2 is a graph showing the cycle performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in example 2, as can be seen from fig. 2: it has a long and stable plateau during the first five cycles and it still has a specific capacity of >100mAh/g after 5 cycles.
Fig. 3 is a graph showing the cycle performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in example 3, as can be seen from fig. 3: it has a long and stable plateau during the first five cycles and it still has a specific capacity of >105mAh/g after 5 cycles.
Fig. 4 is a graph showing the cycle performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in example 4, as can be seen from fig. 4: it has a long and stable plateau during the first five cycles and it remains >90mAh/g after 5 cycles.
Fig. 5 is a graph showing the cycle performance of the quasi-solid polymer fiber electrolyte assembled full cell obtained in comparative example 1, as can be seen from fig. 5: it has a long and stable plateau during the first five cycles and it remains >95mAh/g after 5 cycles.
Test example 2
The quasi-solid polymer fiber electrolyte for sodium ion battery obtained in example 2 was subjected to X-ray diffraction test, and the obtained XRD pattern was shown in fig. 6. As can be seen from FIG. 6, the XRD pattern exhibits a very pronounced characteristic peak around 7℃and 20℃both of which are Ti 3 C 2 T x Common characteristic peaks of MXene.
Test example 3
The quasi-solid polymer fiber electrolyte for sodium ion battery obtained in example 2 was subjected to scanning electron microscope test, and the obtained SEM image is shown in fig. 7. As can be seen from FIG. 7, a large number of carbon nanofibers having a diameter of about 1 μm are loaded with flake-like Ti 3 C 2 T x The MXene structure is characterized in that carbon nanofibers are interconnected to form a carbon nanofiber net, so that the carbon nanofiber net becomes a skeleton of the self-supporting structure of the material, and meanwhile, the material can be responsible for the task of efficiently conducting carriers between the anode and the cathode.
Test example 4
The conductivities of the quasi-solid polymer fiber electrolytes obtained in examples 1 to 4 and comparative example 1 were measured by an alternating current impedance method, the results are shown in fig. 8, and the inset in fig. 8 is a partial enlarged view; as can be seen from fig. 8: the sodium ion battery added with a small amount of MXene has excellent electrochemical performance, greatly improves the ion conductivity of the sodium ion battery, and reduces the internal resistance of the battery.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. A method for preparing a quasi-solid polymer fibrous electrolyte, comprising the steps of:
mixing a few-layer MXene material, a polymer and an organic solvent to obtain an electrostatic spinning precursor dispersion liquid;
carrying out electrostatic spinning on the electrostatic spinning precursor dispersion liquid to obtain a polymer fiber film precursor;
drying the polymer fiber film precursor to obtain the quasi-solid polymer fiber electrolyte;
the few-layer MXene material is Ti 3 C 2 T x 、Nb 2 CT x 、V 4 C 3 T x And TiVCT x One or more of the following;
the polymer is one or more of polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene, polyacrylonitrile and polymethyl methacrylate;
the mass ratio of the few-layer MXene material to the polymer is (0-10): 100, the mass of the few-layer MXene material is not 0.
2. The preparation method according to claim 1, wherein the organic solvent is N, N-dimethylformamide or an N, N-dimethylformamide-acetone mixed solvent;
the dosage ratio of the few-layer MXene material to the organic solvent is 8-56 mg:5mL.
3. The method of claim 1, wherein mixing the few layers of MXene material, polymer and organic solvent comprises: stirring, mixing and ultrasonically dispersing the few-layer MXene material and the organic solvent in sequence to obtain MXene material dispersion liquid; heating, stirring and mixing the MXene material dispersion liquid and the polymer;
the rotation speed of stirring and mixing is 200-300 rpm, and the time is 1-2 hours; the working power of the ultrasonic dispersion is 200-500W, and the time is 1-2 h; the temperature of heating, stirring and mixing is 60-80 ℃, the rotating speed is 200-300 rpm, and the time is 1-4 hours.
4. The method according to claim 1, wherein the parameters of the electrospinning include: the propelling speed of the injection pump of the spinning machine is 0.5-1 mL/h, the specification of the needle head of the injection pump of the spinning machine is 1.2X38 mm, the working environment humidity of the spinning machine is 25% -60%, the working voltage of the spinning machine is 10-20 kV, the distance between the needle head of the injection pump of the spinning machine and the roller receiver is 10-20 cm, and the rotating speed of the roller receiver is 400-1000 rpm.
5. The method according to claim 1, wherein the drying temperature is 60-80 ℃ and the drying time is 8-12 hours.
6. A quasi-solid polymer fiber electrolyte prepared by the method according to any one of claims 1 to 5.
7. Use of the quasi-solid polymer fiber electrolyte of claim 6 in a sodium ion battery.
CN202311557705.9A 2023-11-22 2023-11-22 Quasi-solid polymer fiber electrolyte and preparation method and application thereof Pending CN117276683A (en)

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