CN110854429A - Particle composite membrane coated polymer electrolyte and preparation method thereof - Google Patents

Particle composite membrane coated polymer electrolyte and preparation method thereof Download PDF

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CN110854429A
CN110854429A CN201911126448.7A CN201911126448A CN110854429A CN 110854429 A CN110854429 A CN 110854429A CN 201911126448 A CN201911126448 A CN 201911126448A CN 110854429 A CN110854429 A CN 110854429A
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particle composite
polymer electrolyte
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nano particle
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陈庆
李国松
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Chengdu New Keli Chemical Science 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
    • H01M10/056—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • 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
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a polymer electrolyte coated by a particle composite membrane and a preparation method thereof, belonging to the technical field of lithium ion battery electrolytes. The technical problem to be solved by the invention is to provide a preparation method of a particle composite membrane coated polymer electrolyte. The method comprises the steps of preparing a nano particle composite adhesive by sequentially carrying out polyvinylidene fluoride-tetrafluoropropene and inorganic nano particle ultrasound, and coating a polycarbonate electrolyte matrix with the nano particle composite adhesive by equidistant electrostatic spraying to prepare the particle composite film coated polymer electrolyte material. The polycarbonate electrolyte material is coated by the nano particle composite film, so that the compatibility of an electrolyte and an electrode interface is improved, the mechanical strength and an electrochemical window are improved, and the reduction of the internal resistance of a lithium battery and the improvement of the rate capability are facilitated; the nano particle composite film is thin, the using amount of the inorganic nano particles is less, the cost is further reduced, and the promotion of industrial production is facilitated.

Description

Particle composite membrane coated polymer electrolyte and preparation method thereof
Technical Field
The invention relates to a polymer electrolyte coated by a particle composite membrane and a preparation method thereof, belonging to the technical field of lithium ion battery electrolytes.
Background
With the progress of science and technology, people have entered the digital information era, portable intelligent digital products have developed rapidly, and various intelligent devices such as smart phones, notebook computers, audio devices, game machines, and the like, come out endlessly. On the other hand, the petroleum resources are gradually exhausted, the influence of automobile exhaust on the ecological environment is increasingly remarkable, the environmental awareness of people is continuously enhanced, and the electric automobile is increasingly popular. The lithium ion battery has the advantages of high voltage, high specific energy, long charging and discharging service life, no memory effect, no pollution, quick charging, low self-discharging rate and the like, and is a source of energy of electronic intelligent products and electric automobiles.
In recent years, requirements on safety, energy density and the like of lithium ion batteries of consumer electronic products, electric automobiles and the like are continuously improved, and the lithium ion batteries of the traditional liquid organic electrolyte have potential safety hazards of electrolyte leakage, volatilization, combustion, explosion and the like caused by collision and even easy short circuit. The solid electrolyte is used as a high-safety electrolyte system, has the unique advantages of avoiding short circuit inside the battery, preventing the leakage of the electrolyte, containing no flammable and explosive components and the like, and the development of the solid electrolyte lithium ion battery is a necessary trend. The solid electrolyte is used for replacing the liquid electrolyte, which is a great progress in the development of the lithium ion battery, and the lithium ion battery has the obvious characteristics that the safety performance of the battery is improved, the lithium ion battery is easy to process into a film and can be made into a full-plastic structure, so that the lithium ion battery can be manufactured into ultrathin batteries with various shapes; the lithium ion battery electrode can well adapt to the volume change of the electrode in the charging and discharging processes of the battery, and has better chemical and electrochemical stability, so that the lithium ion battery electrode has great superiority in the application of novel high-energy lithium batteries and electrochemistry.
The solid polymer electrolyte has the advantages of good processability, good flexibility, easy realization of industrial production, stable interface compatibility, capability of better adapting to volume change in the charge and discharge processes of electrode materials and the like, and is considered to be the most ideal electrolyte for developing high-energy all-solid batteries. However, due to the higher crystallinity of the polymer matrix, the conductivity at room temperature is lower, and the electrochemical window is narrower, which limits the practical application. Therefore, improvements are needed.
The Chinese patent application No. 201910422565.1 discloses an all-solid-state polymer solid electrolyte and a preparation method thereof, wherein the all-solid-state polymer solid electrolyte comprises an inorganic filler, PEO and lithium salt, and the inorganic filler comprises MoSi2Or MoSi2And inorganic oxides. By adding MoSi to PEO2The PEO polymer solid electrolyte has excellent thermal stability, the conductivity of the PEO polymer solid electrolyte is improved, the compatibility of the polymer solid electrolyte and an electrode is improved, the impedance of an interface between the polymer solid electrolyte and the electrode is reduced, the cycle performance of a battery is improved, and the PEO-TiO is improved2Conductivity of the polymer solid electrolyte.
The Chinese patent with application number 201810374629.0 discloses a preparation method of a composite all-solid-state polymer electrolyte membrane, which comprises the following steps: stirring and mixing the carbonate functional vinyl monomer, the polyether structural monomer and a solvent in an inert gas atmosphere, then adding an initiator, reacting in the inert gas atmosphere, drying and purifying to obtain a carbonate functional vinyl copolymer; adding the obtained carbonate functionalized vinyl copolymer and inorganic filler or fast ion conductor into a solvent, stirring and mixing uniformly, adding lithium salt, and stirring to obtain a uniformly mixed solution; and uniformly coating the mixed solution on a mould, and drying in vacuum to evaporate the solvent to obtain the composite all-solid polymer electrolyte membrane. The electrolyte membrane has the advantages of better liquid retention rate, higher lithium ion conductivity, more superior mechanical property, good machining property, better electrochemical stability and better application prospect.
In summary, nanoparticles are mainly blended and doped in polymers to improve the lithium ion conductivity and the electrochemical window; however, the improvement effect of the interfacial compatibility of the polymer and the electrode is still poor, which causes the problems of high internal resistance, poor rate capability and the like of the lithium battery, and in addition, the blending of a large amount of nano particles in the polymer electrolyte has high cost, which restricts the industrial production of the nano particles in the lithium battery electrolyte.
Disclosure of Invention
Aiming at the defects of poor electrode interface compatibility, high cost and the like of the blended nano particles in the conventional polymer electrolyte, the invention provides a particle composite film coated polymer electrolyte and a preparation method thereof.
The first technical problem solved by the invention is to provide a preparation method of a particle composite membrane coated polymer electrolyte.
The preparation method of the particle composite membrane coated polymer electrolyte comprises the following steps:
a. preparing nano particle composite glue: mixing polyvinylidene fluoride-tetrafluoropropene, inorganic nanoparticles and N-methyl pyrrolidone, and carrying out ultrasonic treatment for 1-3 hours at 20-30 kHz to obtain a nanoparticle composite adhesive;
b. preparation of polymer electrolyte base membrane: extruding polycarbonate and lithium salt by a screw to form a polymer electrolyte base film; (ii) a
c. Spraying: and c, spraying the nano particle composite adhesive obtained in the step a on the surface of the polymer electrolyte base film obtained in the step b to form a nano particle composite adhesive film, and drying to obtain the polymer electrolyte coated with the particle composite film, wherein the spraying is carried out by adopting an electrostatic spray gun, the gun mouth of the spray gun rotates at a constant speed, the distance between the gun mouth of the spray gun and the polymer electrolyte base film is 100-140 mm, the voltage of the electrostatic spray gun is 50-70 kV, and the spraying time is 12-18 s.
The preparation method of the particle composite membrane coated polymer electrolyte comprises the steps of ultrasonically preparing a nano particle composite adhesive from polyvinylidene fluoride-tetrafluoropropene and inorganic nano particles, and mixing polycarbonate and lithium salt to obtain a polymer electrolyte base membrane; by equidistant electrostatic spraying, the polycarbonate electrolyte matrix is coated by the nano particle composite adhesive to prepare the nano particle composite film coated polymer electrolyte material, so that the compatibility of the electrolyte and an electrode interface is improved, the mechanical strength and the electrochemical window are improved, and the reduction of the internal resistance of a lithium battery and the improvement of the rate capability are facilitated.
In the step a, mixing polyvinylidene fluoride-tetrafluoropropene, inorganic nanoparticles and N-methyl pyrrolidone, and carrying out ultrasonic treatment for 1-3 hours at 20-30 kHz to obtain the nanoparticle composite adhesive.
The inorganic nanoparticles can be inorganic nanoparticles commonly used in the art, and preferably, the inorganic nanoparticles are titanium dioxide (TiO)2) Aluminum oxide (Al)2O3) Lithium titanate (Li)2TiO3) And barium titanate (BaTiO)3) At least one of (1).
The polyvinylidene fluoride-tetrafluoropropene is a copolymer of vinylidene fluoride and 2,3,3, 3-tetrafluoropropene, and the copolymer can be obtained by adopting a conventional polymerization method in the field, for example, the polyvinylidene fluoride-tetrafluoropropene can be obtained by adopting an emulsion polymerization method. The invention has no requirement on the proportion of synthetic monomers of the copolymer, namely vinylidene fluoride and 2,3,3, 3-tetrafluoropropene, and the monomer proportion commonly used in the field can achieve the aim of the invention. Preferably, in the polyvinylidene fluoride-tetrafluoropropene, the molar ratio of the vinylidene fluoride unit to the 2,3,3, 3-tetrafluoropropene unit is 0.1-10: 1.
The proportion of the polyvinylidene fluoride-tetrafluoropropene, the inorganic nanoparticles and the N-methyl pyrrolidone influences the viscosity of the composite adhesive and further influences the subsequent spraying effect, and preferably, the proportion is 70-80 parts by weight of the polyvinylidene fluoride-tetrafluoropropene, 20-30 parts by weight of the inorganic nanoparticles and 100-300 parts by weight of the N-methyl pyrrolidone.
The ultrasonic treatment in the step a is mainly used for uniformly mixing to obtain the nano particle composite glue with uniform texture. Preferably, in the step, 25kHz ultrasound is carried out for 2 h.
In the step b, extruding the polycarbonate and the lithium salt by using a conventional screw to form a film; typically, extrusion into a sheet at 100 ℃ in a single screw forms a sheet that is stretched to ultimately form the polymer electrolyte based membrane.
Polycarbonate is a high molecular polymer having a carbonate group in its molecular chain, and is a matrix material of a polymer electrolyte in the present invention. Polycarbonates commonly used in the art are suitable for use in the present invention, and preferably, the polycarbonate is at least one of polytrimethylene carbonate, polyethylene carbonate, and polypropylene carbonate.
The addition of lithium salt to the matrix material has no special requirement on the type of lithium salt, and lithium salts commonly used in the art are also suitable for the present invention, and preferably, the lithium salt is at least one of lithium tetrafluoroborate, lithium trifluoromethanesulfonate and lithium bis (oxalato) borate.
Preferably, in the step b, 70 to 85 parts by weight of polycarbonate and 15 to 30 parts by weight of lithium salt are calculated.
And c, spraying the nano particle composite adhesive obtained in the step a on the surface of the polymer electrolyte base film obtained in the step b by adopting equidistant electrostatic spraying, and drying to obtain the particle composite film coated polymer electrolyte. The polycarbonate electrolyte matrix is coated by the nano composite film, so that the compatibility of the electrolyte and an electrode interface can be improved, and the mechanical strength and the electrochemical window of the electrolyte are further improved.
And c, spraying by using an electrostatic spray gun, wherein the electrostatic spray gun has no special requirement, a common electrostatic spray gun sold in the market can be adopted, and the electrostatic spray gun only needs to ensure that the gun nozzle of the spray gun rotates at a constant speed, the distance between the gun nozzle and the polymer electrolyte base film is 100-140 mm, and the voltage of the electrostatic spray gun is 50-70 kV.
The thickness of the sprayed nanoparticle composite adhesive film will affect the performance of the electrolyte material. The nano particle composite adhesive film is thin and cannot be completely coated or the coating thickness is too small, so that the aim of improving the mechanical property and the ionic conductivity of the nano particle composite adhesive film cannot be achieved, the thicker the nano particle composite adhesive film is, the higher the mechanical strength is, but the higher the cost is, and the thicker the film is, the transmission path of lithium ions in the electrolyte coating layer can be enlarged, so that the ionic conductivity of the lithium ions is seriously influenced. Therefore, in the step c, the thickness of the nanoparticle composite adhesive film is preferably 50-100 nm. The particle composite membrane in the thickness range coats the polymer electrolyte material, and the mechanical property and the electrochemical property are better.
After spraying, drying can be carried out by adopting a conventional drying method, and in the step c, the drying adopts the step of fast curing of the sprayed layer at the instant high temperature of 200 ℃ without influencing the electrolyte of the inner layer.
The invention also provides a polymer electrolyte coated by the particle composite membrane.
The particle composite film-coated polymer electrolyte is prepared by the preparation method of the particle composite film-coated polymer electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, the polyvinylidene fluoride-tetrafluoropropene and the inorganic nanoparticles are sequentially subjected to ultrasonic preparation of the nanoparticle composite adhesive, and then the polycarbonate electrolyte matrix is coated with the nanoparticle composite adhesive through equidistant electrostatic spraying to prepare the particle composite film coated polymer electrolyte material. The polycarbonate electrolyte material is coated by the nano particle composite film, so that the compatibility of an electrolyte and an electrode interface is improved, the mechanical strength and an electrochemical window are improved, and the reduction of the internal resistance of a lithium battery and the improvement of the rate capability are facilitated; the nano particle composite film is thin, the using amount of the inorganic nano particles is less, the cost is further reduced, and the promotion of industrial production is facilitated.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
1. Preparing nano particle composite glue: 70g of polyvinylidene fluoride-tetrafluoropropene and 30g of nano TiO2Adding the nano particles into 200g N-methyl pyrrolidone organic solvent, and carrying out ultrasonic treatment for 2h at the frequency of 25kHZ to obtain the nano particle composite glue.
2. Preparation of polymer electrolyte base membrane: adding 85g of polytrimethylene carbonate and 30g of lithium tetrafluoroborate into a single-screw extruder, carrying out extrusion molding at 100 ℃, forming a sheet through a die head, and further stretching to form a polymer electrolyte base film with the thickness of 80 mu m;
3. spraying and compounding: fixing a polymer electrolyte base film on a carrier, spraying nano particle composite glue by an electrostatic spray gun, enabling a gun nozzle of the spray gun to rotate at a constant speed, enabling the distance between the gun nozzle and a base body to be 120mm, maintaining the voltage of the electrostatic spray gun at 60KV, and controlling the spraying time to be 15 s; and (3) uniformly spraying a composite particle adhesive film with the thickness of 50nm on the surface of the polymer electrolyte base film, and drying at the instantaneous temperature of 200 ℃ to obtain the particle film-coated polymer composite electrolyte film material.
And (3) performance detection:
(1) the maximum load of vertical puncture of the electrolyte membrane material was tested with a hemispherical needle having a diameter of 1 mm. The test conditions are as follows: test speed: 20 mm/min. The test results are shown in Table 1.
(2) The electrolyte membrane is clamped by a stainless steel plate, the AC impedance spectrum of the electrolyte membrane is tested by using an Autolab PGSTAT302N electrochemical workstation, and the ionic conductivity of the membrane material is calculated. The test results are shown in Table 1.
(3) The electrolyte membrane obtained in the example was assembled with LiFePO4/Li to form a test cell, and the capacity after 200 cycles at 0.1C was 159 mA · h/g. Because the good electrode is compatible with electrolyte, the cycle performance of the battery is favorably improved.
Example 2
1. Preparation of polymer electrolyte base membrane: adding 70g of polyethylene carbonate and 15g of lithium trifluoromethanesulfonate into a single-screw extruder, extruding and molding at 100 ℃, forming a sheet through a die head, and further stretching to form a polymer electrolyte base film with the thickness of 80 mu m;
2. preparing nano particle composite glue: 80g of polyvinylidene fluoride-tetrafluoropropene and 30g of nano Al2O3Adding the nano particles into a 300g N-methylpyrrolidone organic solvent, and carrying out ultrasonic treatment for 3h at the frequency of 20kHZ to obtain the nano particle composite adhesive.
3. Spraying and compounding: fixing a polymer electrolyte base film on a carrier, spraying nano particle composite glue by an electrostatic spray gun, enabling a gun nozzle of the spray gun to rotate at a constant speed, enabling the distance between the gun nozzle and a base body to be 100mm, maintaining the voltage of the electrostatic spray gun at 50KV, and controlling the spraying time to be 18 s; and (3) uniformly spraying a composite particle adhesive film with the thickness of 60nm on the surface of the polymer electrolyte base film, and drying at the instantaneous temperature of 200 ℃ to obtain the particle film-coated polymer composite electrolyte material.
The puncture strength and ionic conductivity were measured by the methods described in example 1, and the results are shown in Table 1.
Example 3
1. Preparing nano particle composite glue: 70g of polyvinylidene fluoride-tetrafluoropropene and 20g of nano Li2TiO3Adding the nano particles into 100g N-methyl pyrrolidone organic solvent, and carrying out ultrasonic treatment for 1h at the frequency of 30kHZ to obtain the nano particle composite adhesive.
2. Preparation of polymer electrolyte base membrane: adding 80g of polypropylene carbonate and 20g of lithium bis (oxalato) borate into a single-screw extruder, carrying out extrusion molding at 100 ℃, forming a sheet through a die head, and further stretching to form a polymer electrolyte base film with the thickness of 80 mu m;
3. spraying and compounding: fixing a polymer electrolyte base film on a carrying platform, spraying nano particle composite glue by an electrostatic spray gun, enabling a gun nozzle of the spray gun to rotate at a constant speed, enabling the distance between the gun nozzle and a base body to be 140mm, maintaining the voltage of the electrostatic spray gun at 70KV, and controlling the spraying time to be 12 s; and (3) uniformly spraying a composite particle adhesive film with the thickness of 50nm on the surface of the polymer electrolyte base film, and drying at the instantaneous temperature of 200 ℃ to obtain the particle film-coated polymer composite electrolyte material.
The puncture strength and ionic conductivity were measured by the methods described in example 1, and the results are shown in Table 1.
Example 4
1. Preparing nano particle composite glue: 75g of polyvinylidene fluoride-tetrafluoropropene and 25g of nano BaTiO3Adding the nano particles into 200g N-methyl pyrrolidone organic solvent, and carrying out ultrasonic treatment for 2h at the frequency of 25kHZ to obtain the nano particle composite glue.
2. Preparation of polymer electrolyte base membrane: adding 85g of polypropylene carbonate and 30g of lithium tetrafluoroborate into a single-screw extruder, extruding and molding at 100 ℃, forming a sheet through a die head, and further stretching to form a polymer electrolyte base film with the thickness of 80 microns;
3. spraying and compounding: fixing a polymer electrolyte base film on a carrier, spraying nano particle composite glue by an electrostatic spray gun, enabling a gun nozzle of the spray gun to rotate at a constant speed, enabling the distance between the gun nozzle and a base body to be 130mm, maintaining the voltage of the electrostatic spray gun at 60KV, and controlling the spraying time to be 16 s; and (3) uniformly spraying a composite particle adhesive film with the thickness of 55nm on the surface of the polymer electrolyte base film, and drying at the instantaneous temperature of 200 ℃ to obtain the particle film-coated polymer composite electrolyte material.
The puncture strength and ionic conductivity were measured by the methods described in example 1, and the results are shown in Table 1.
Example 5
1. Preparing nano particle composite glue: 78g of polyvinylidene fluoride-tetrafluoropropene and 24g of nano TiO2Adding the nano particles into 200g N-methyl pyrrolidone organic solvent, and carrying out ultrasonic treatment for 2h at the frequency of 25kHZ to obtain the nano particle composite glue.
2. Preparation of polymer electrolyte base membrane: adding 85g of polytrimethylene carbonate, 10g of lithium tetrafluoroborate and 15g of lithium trifluoromethanesulfonate into a single-screw extruder, carrying out extrusion molding at 100 ℃, forming a sheet through a die head, and further stretching to form a polymer electrolyte base film with the thickness of 80 mu m;
3. spraying and compounding: fixing a polymer electrolyte base film on a carrier, spraying nano particle composite glue by an electrostatic spray gun, enabling a gun nozzle of the spray gun to rotate at a constant speed, enabling the distance between the gun nozzle and a base body to be 110mm, maintaining the voltage of the electrostatic spray gun at 60KV, and controlling the spraying time to be 14 s; and (3) uniformly spraying a composite particle adhesive film with the thickness of 50nm on the surface of the polymer electrolyte base film, and drying at the instantaneous temperature of 200 ℃ to obtain the particle film-coated polymer composite electrolyte material.
The puncture strength and ionic conductivity were measured by the methods described in example 1, and the results are shown in Table 1.
Comparative example 1
Comparative example 1 compared to example 1, the electrolyte membrane obtained without spraying the nanoparticle composite gel was assembled with LiFePO4/Li to form a test cell with a capacity of 102 mA · h/g after 200 cycles at 0.1C. Because the interface modification of the electrolyte is not carried out, the compatibility and the permeability of the electrode and the electrolyte are poor, and the cycle performance of the battery is poor.
The puncture strength and ionic conductivity were measured by the methods described in example 1, and the results are shown in Table 1.
As can be seen from Table 1, since inorganic nanoparticles are not added as a coating layer, the mechanical properties of the polymer of the surface coating layer are poor, and the puncture strength thereof is significantly reduced.
TABLE 1
Numbering Puncture Strength (gf) Ion conductivity (S/cm)
Example 1 274 4.77*10-4
Example 2 277 3.51*10-4
Example 3 263 4.65*10-4
Example 4 268 3.61*10-4
Example 5 271 5.70*10-4
Comparative example 1 162 4.85*10-5

Claims (9)

1. A preparation method of a polymer electrolyte coated by a particle composite membrane is characterized by comprising the following steps:
a. preparing nano particle composite glue: mixing polyvinylidene fluoride-tetrafluoropropene, inorganic nanoparticles and N-methyl pyrrolidone, and carrying out ultrasonic treatment for 1-3 hours at 20-30 kHz to obtain a nanoparticle composite adhesive;
b. preparation of polymer electrolyte base membrane: extruding polycarbonate and lithium salt by a screw to form a polymer electrolyte base film;
c. spraying: and c, spraying the nano particle composite adhesive obtained in the step a on the surface of the polymer electrolyte base film obtained in the step b to form a nano particle composite adhesive film, and drying to obtain the polymer electrolyte coated with the particle composite film, wherein the spraying is carried out by adopting an electrostatic spray gun, the gun mouth of the spray gun rotates at a constant speed, the distance between the gun mouth of the spray gun and the polymer electrolyte base film is 100-140 mm, the voltage of the electrostatic spray gun is 50-70 kV, and the spraying time is 12-18 s.
2. The method for preparing a polymer electrolyte coated with a particle composite film according to claim 1, wherein: in the step a, the inorganic nano particles are TiO2、Al2O3、Li2TiO3And BaTiO3At least one of (1).
3. The method for preparing a polymer electrolyte coated with a particle composite film according to claim 1, wherein: in the step a, 70-80 parts of polyvinylidene fluoride-tetrafluoropropene, 20-30 parts of inorganic nanoparticles and 100-300 parts of N-methylpyrrolidone by weight.
4. The method for preparing a polymer electrolyte coated with a particle composite film according to claim 1, wherein: in the step a, 25kHz ultrasonic treatment is carried out for 2 h.
5. The method for preparing a polymer electrolyte coated with a particle composite film according to claim 1, wherein: in the step b, the polycarbonate is at least one of polytrimethylene carbonate, polyethylene carbonate and polypropylene carbonate; the lithium salt is at least one of lithium tetrafluoroborate, lithium trifluoromethanesulfonate and lithium bis (oxalate) borate.
6. The method for preparing a polymer electrolyte coated with a particle composite film according to claim 1, wherein: in the step b, 70-85 parts of polycarbonate and 15-30 parts of lithium salt by weight.
7. The method for preparing a polymer electrolyte coated with a particle composite film according to claim 1, wherein: in the step c, the thickness of the nano particle composite adhesive film is 50-100 nm.
8. The method for preparing a polymer electrolyte coated with a particle composite film according to claim 1, wherein: in the step c, instantaneous high temperature of 200 ℃ is adopted for drying.
9. A particle composite film-coated polymer electrolyte characterized in that: the particle composite membrane coated polymer electrolyte is prepared by the preparation method of the particle composite membrane coated polymer electrolyte according to any one of claims 1 to 8.
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CN111969252A (en) * 2020-08-31 2020-11-20 蜂巢能源科技有限公司 Solid-state battery and method for manufacturing same
WO2022054540A1 (en) * 2020-09-09 2022-03-17 ダイキン工業株式会社 Solid secondary battery binding agent, solid secondary battery slurry, method for forming solid secondary battery layer, and solid secondary battery
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CN113903985B (en) * 2021-09-17 2024-02-23 海南大学 Solid electrolyte buffer layer and preparation method thereof
CN115678000A (en) * 2022-10-31 2023-02-03 华中科技大学 Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method
CN115678000B (en) * 2022-10-31 2023-12-05 华中科技大学 Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method

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