CN109755644B - Gel composite polymer electrolyte membrane, preparation method thereof and lithium ion battery - Google Patents
Gel composite polymer electrolyte membrane, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
A method for preparing a gel composite polymer electrolyte membrane, comprising the steps of: mixing the silicon dioxide nano-particles, ethanol and water to form a mixed solution; heating the mixed solution to 65-85 ℃ under an acidic condition, adding a coupling agent for reaction under a heat preservation condition, and then separating, washing and drying to obtain modified silicon dioxide nano particles; mixing the modified silicon dioxide nano-particles with a linear polymer, polyethylene glycol diacrylate, polyethylene glycol methyl ether acrylate, a photoinitiator and a solvent to prepare a precursor solution; forming the precursor solution on a supporting body and carrying out ultraviolet curing to prepare a composite polymer film, wherein the composite polymer film is of a semi-interpenetrating network structure; and immersing the composite polymer film into an electrolyte, and absorbing the electrolyte to saturation to obtain a gel composite polymer electrolyte film. The invention also provides a gel composite polymer electrolyte membrane and a lithium ion battery.
Description
Technical Field
The invention relates to the field of polymer gel electrolyte for lithium secondary batteries, in particular to a gel composite polymer electrolyte membrane with a semi-interpenetrating structure, a preparation method thereof and a lithium ion battery using the gel composite polymer electrolyte membrane.
Background
Currently, a graphitized carbon material is generally adopted as a negative electrode of a commercial lithium ion battery, and the theoretical capacity of the lithium ion battery is only 372mAh g-1In order to further improve the capacity of the lithium ion battery, the lithium metal is adopted as the cathode, so that the lithium ion battery has a wide application prospect. The metallic lithium has the highest theoretical specific capacity of 3860mAh g-1However, the method has not been commercialized in a large scale, because the following problems have not been effectively solved: (1) in the process of charging and discharging, because lithium metal has strong reducibility, the lithium metal is easy to react with the electrolyte continuously, the electrolyte is consumed continuously, and a continuously thickened interface layer is generated at the interface of the lithium metal and the electrolyte, so that the capacity of the battery is attenuated quickly. (2) Due to the tip effect, lithium ions tend to deposit unevenly on the surface of the metallic lithium negative electrode, resulting in the generation of a large amount of lithium dendrites and "dead lithium", which cannot be expectedThe controlled lithium dendrite growth can pierce through the diaphragm to cause the short circuit of the battery, and the battery combustion or even explosion is caused, thereby bringing great safety problems.
The gel polymer electrolyte can effectively solve a series of problems caused by the lithium metal cathode, has good electrochemical stability, is not easy to react with metal lithium, can generate a stable solid electrolyte interface film, and improves the coulombic efficiency of the battery. The lithium metal negative electrode can be well attached, and the compact structure can guide the uniform deposition of lithium ions on the surface of the lithium metal negative electrode to a certain extent. However, at present, the ionic conductivity and mechanical properties of the gel polymer electrolyte are still difficult to satisfy practical commercial application, the linear gel polymer electrolyte is easily dissolved in a liquid electrolyte to cause short circuit, and the addition of a cross-linking agent to form a cross-linked polymer can improve the dimensional stability and mechanical strength of the gel polymer electrolyte, but can bring about a significant reduction in the ionic conductivity to cause a reduction in the performance of the battery. In addition, the traditional preparation process of the gel polymer electrolyte usually takes a long time and is not beneficial to large-scale production.
Disclosure of Invention
In order to solve the technical problems, the invention provides a gel composite polymer electrolyte membrane with a semi-interpenetrating network structure and a preparation method thereof, the process is quick and simple, the ionic conductivity is high, the mechanical property is excellent, and a lithium ion battery assembled by the gel composite polymer electrolyte membrane has excellent electrochemical property and stable cycle.
A method for preparing a gel composite polymer electrolyte membrane, comprising the steps of:
mixing the silicon dioxide nano-particles, ethanol and water to form a mixed solution;
heating the mixed solution to 65-85 ℃ under an acidic condition, adding a coupling agent for reaction under a heat preservation condition, and then separating, washing and drying to obtain modified silicon dioxide nano particles;
mixing the modified silicon dioxide nano-particles with a linear polymer, polyethylene glycol diacrylate, polyethylene glycol methyl ether acrylate, a photoinitiator and a solvent to prepare a precursor solution;
forming the precursor solution on a supporting body and carrying out ultraviolet curing to prepare a composite polymer film, wherein the composite polymer film is of a semi-interpenetrating network structure; and
and immersing the composite polymer membrane into an electrolyte, and absorbing the electrolyte until the electrolyte is saturated to obtain the gel composite polymer electrolyte membrane.
A gel composite polymer electrolyte membrane having a semi-interpenetrating network structure prepared by the above preparation method.
The lithium ion battery comprises a positive electrode, a negative electrode and the gel composite polymer electrolyte membrane prepared by the preparation method, wherein the gel composite polymer electrolyte membrane has a semi-interpenetrating network structure.
The gel composite polymer electrolyte membrane prepared by the preparation method of the gel composite polymer electrolyte membrane has a semi-interpenetrating network structure, and can effectively improve the mechanical property of the gel composite polymer electrolyte membrane. The preparation method also utilizes the chemical action between the functional group on the surface of the nano filler and the polymer monomer, and introduces the silica nanoparticles grafted on the surface as a cross-linking agent, so as to further effectively improve the mechanical property of the gel composite polymer electrolyte membrane and effectively improve the ionic conductivity and the electrochemical stability of the gel composite polymer electrolyte membrane. In addition, the composite polymer film is prepared by utilizing an ultraviolet curing mode, and the method has the advantage of quick and simple film forming.
Drawings
Fig. 1 is a schematic flow chart of a method for manufacturing a gel composite polymer electrolyte membrane according to an embodiment of the present invention.
FIG. 2 is a transmission electron microscope photograph of the modified silica nanoparticles prepared in example 1.
Fig. 3 is a schematic view of the internal structure of the semi-interpenetrating network structure composite polymer film prepared in this example 1.
Fig. 4 is a scanning electron microscope of the composite polymer film of semi-interpenetrating network structure prepared in example 1.
Fig. 5 is a stress-strain curve of the tensile test performed on the composite polymer film of the semi-interpenetrating network structure prepared in example 1.
Fig. 6 is a graph showing the temperature dependence of the ion conductivity of the composite polymer film with a semi-interpenetrating network structure prepared in example 1 and the electrolyte-compounded polypropylene separator.
Fig. 7 is a cyclic voltammogram measured for an electrochemical stability window of the semi-interpenetrating network structure composite polymer electrolyte membrane prepared in example 1.
FIG. 8 shows the 1C cycle performance at 25 ℃ of the button cell prepared in example 1.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The names of technical means used in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention.
The embodiments described below and the features of the embodiments can be combined with each other without conflict.
Referring to fig. 1, the present invention provides a method for preparing a gel composite polymer electrolyte membrane applied to a lithium ion battery, which includes the following steps:
step S1, mixing the silica nanoparticles, ethanol, and water to form a mixed solution, in which the silica nanoparticles are dispersed.
In the present embodiment, the silica nanoparticles have a particle diameter of 10nm to 100 nm. Preferably, the particle size of the silica nanoparticles is 15nm to 30 nm.
In the mixed solution, the volume ratio of ethanol to water is 19: 1-3: 1, and the concentration of the silicon dioxide nanoparticles is 0.5-10 mg/mL.
And step S2, heating the mixed solution under an acidic condition, adding a coupling agent under a heat preservation condition while stirring for reaction, continuously stirring until the reaction is finished, and separating, washing and drying to obtain the modified silicon dioxide nano particles.
In the embodiment, the pH value of the mixed solution is adjusted to 2-5, the mixed solution is heated to 65-85 ℃, and the reaction time is 3-10 hours. Preferably, the pH of the mixture is adjusted to 4, and the mixture is heated to 75 ℃. Under the acidic condition, the coupling agent and the silicon dioxide nano-particles can react conveniently to prepare the modified silicon dioxide nano-particles.
Specifically, the pH of the mixed solution may be adjusted by an organic acid, which may be selected from, but not limited to, formic acid, acetic acid, citric acid, benzoic acid, oxalic acid, and the like.
The coupling agent can be a silane coupling agent with a double bond at the tail end, and the mass of the coupling agent is 3-10% of that of the silica nanoparticles.
In this embodiment, the washing may specifically include washing with pure water after sequentially washing with solutions having gradually decreasing alcohol-water ratios. The solution with the gradually reduced alcohol-water ratio is adopted for washing in sequence, so that the uniform coating of the coupling agent on the surface of the silicon dioxide nano-particles is facilitated. In other embodiments, the washing may be performed directly with pure water.
The drying can be drying under vacuum condition, or other drying modes.
Step S3, mixing the modified silicon dioxide nano-particles with a linear polymer, polyethylene glycol diacrylate (PEGDA), polyethylene glycol methyl ether acrylate, a photoinitiator and a solvent to prepare a precursor solution.
Wherein the linear polymer may be a high molecular weight linear polyethylene oxide or poly (vinylidene fluoride-co-hexafluoropropylene). In the present embodiment, "high molecular weight" means a number average molecular weight of 100000 or more.
In the precursor solution except the solvent, the mass percentage of the modified silicon dioxide nano particles is 2-10%, the mass percentage of the linear polymer is 10-30%, and the mass percentage of the photoinitiator is 1-5%.
In the present embodiment, the number average molecular weight (Mn) of the polyethylene glycol diacrylate is 500 to 2000. The number average molecular weight (Mn) of the polyethylene glycol methyl ether acrylate is 300-1000. Preferably, the molar ratio of the polyethylene glycol diacrylate to the polyethylene glycol methyl ether acrylate is 1: 4-2: 1.
The photoinitiator may be a free radical photoinitiator. The solvent is an organic solvent with a boiling point below 100 ℃ or a volatilization rate above 1 (n-butyl acetate method), can dissolve the linear polymer, and can be selected from one of acetone and tetrahydrofuran. The content of the solvent in the precursor solution is only required to dissolve the linear polymer, the polyethylene glycol diacrylate, the polyethylene glycol methyl ether acrylate and the photoinitiator.
And step S4, forming the precursor solution on a supporting body and carrying out ultraviolet light curing to obtain a composite polymer film. Wherein, the composite polymer film is in a semi-interpenetrating network structure.
In this embodiment, the precursor solution is placed between two glass plates and then cured by ultraviolet light. The ultraviolet curing time is 1-10 minutes, and the wavelength range of the ultraviolet is 200-400 nm. Preferably, the wavelength of the ultraviolet light during ultraviolet light curing is 254nm or 365 nm.
In this embodiment, the composite polymer film has a thickness of 70 to 150 micrometers.
The polyethylene glycol diacrylate and the polyethylene glycol methyl ether acrylate are favorable for forming a comb-shaped composite polyethylene oxide network during ultraviolet curing.
Step S5, immersing the composite polymer membrane in an electrolyte, and absorbing the electrolyte to saturation to obtain a gel composite polymer electrolyte membrane.
The electrolyte includes a lithium salt and a solvent. In this embodiment, the lithium salt is dissolved in the solvent.
The lithium salt includes, but is not limited to, at least one of lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium tetrafluoroborate, or lithium bistrifluorosulfonylimide. In the electrolyte, the concentration of the lithium salt is 0.6-1.2 mol/L.
The solvent includes, but is not limited to, at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, propylene carbonate, and ethylene glycol dimethyl ether.
The gel composite polymer electrolyte membrane prepared by the preparation method of the gel composite polymer electrolyte membrane has a semi-interpenetrating network structure, and can effectively improve the mechanical property of the gel composite polymer electrolyte membrane. The preparation method also utilizes the chemical action between the functional group on the surface of the nano filler and the polymer monomer, and introduces the silica nanoparticles grafted on the surface as a cross-linking agent, so as to further effectively improve the mechanical property of the gel composite polymer electrolyte membrane and effectively improve the ionic conductivity and the electrochemical stability of the gel composite polymer electrolyte membrane. In addition, the composite polymer film is prepared by utilizing an ultraviolet curing mode, and the method has the advantage of quick and simple film forming.
The invention is further illustrated by the following examples.
Example 1
Mixing 300mg of silicon dioxide nanoparticles with the particle size of 15nm, 90mL of ethanol and 10mL of deionized water, stirring for 1 minute, and performing ultrasonic dispersion at room temperature for 30 minutes to obtain a mixed solution.
Adding oxalic acid into the mixed solution to adjust the pH value to 4, heating the mixed solution to 75 ℃, dropwise adding 30mg of gamma-Methacryloxypropyltrimethoxysilane (MPS) while stirring under the condition of heat preservation, continuously stirring for reacting for 4 hours, separating, washing for three times by deionized water, and performing vacuum drying at 60 ℃ for 12 hours to obtain the modified silicon dioxide nano-particles.
200mg of the above-mentioned modified silica nanoparticles, 1g of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP, weight average molecular weight Mw 400000), 1.02g of polyethylene glycol diacrylate (Mn 700, U.), 2.78g of polyethylene glycol methyl ether acrylate (Mn 480), 0.08g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 5mL of acetone were mixed uniformly to prepare a precursor solution.
And (3) placing the precursor solution between two glass plates, and curing for 2 minutes under the ultraviolet light with the wavelength of 365nm to prepare the composite polymer film with the semi-interpenetrating network structure.
And (3) immersing the composite polymer membrane into electrolyte and absorbing the electrolyte until the electrolyte is saturated to prepare the gel composite polymer electrolyte membrane. The electrolyte is prepared by dissolving lithium hexafluorophosphate in a mixed solvent consisting of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in a volume ratio of 1:1: 1. Wherein the concentration of the lithium hexafluorophosphate in the electrolyte is 1 mol/L.
The gel composite polymer electrolyte membrane is applied to a lithium ion battery, wherein a lithium plate is used as a negative electrode, a lithium iron phosphate plate is used as a positive electrode, and the gel composite polymer electrolyte membrane electrolyte is used as an electrolyte. The lithium iron phosphate pole piece is prepared by mixing and coating active substances, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 on an aluminum foil to form a film, and punching the film into a sheet with the diameter of 12 mm. The lithium ion battery was assembled in a glove box under argon atmosphere, maintaining the moisture and oxygen content in the glove box below 10 ppm. The assembled button cell is in the model number CR 2030.
The lithium ion battery is subjected to constant-current charge and discharge performance test on an LAND battery test system (provided by Wuhan blue electronics Co., Ltd.), and the measured charge and discharge multiplying power is 1C, and the charge and discharge cutoff voltage is 2.4V-4.2V vs Li/Li+。
FIG. 2 is a transmission electron microscope photograph of the modified silica nanoparticles prepared in example 1. It can be seen that the surface of the modified silica nanoparticle is coated with a film layer with a thickness of several nanometers.
Fig. 3 is a schematic view of the internal structure of the semi-interpenetrating network structure composite polymer film prepared in this example 1. Wherein the poly (vinylidene fluoride-co-hexafluoropropylene) isA heavy straight chain network, polyethylene glycol diacrylate, polyethylene glycol methyl ether acrylate and silicon dioxide nano-particles with the surface grafted with gamma-methacryloxypropyl trimethoxy silane are crosslinked by double bonds to form PEO-SiO2The two networks are mutually interpenetrated in the polymerization process, so as to form the composite polymer film with the semi-interpenetrating network structure.
Fig. 4 is a scanning electron microscope of the composite polymer film of semi-interpenetrating network structure prepared in example 1. It can be seen that the structure of the composite polymer film of the semi-interpenetrating network structure is uniform and dense.
Fig. 5 is a stress-strain curve of the tensile test performed on the composite polymer film of the semi-interpenetrating network structure prepared in example 1. It can be seen that the semi-interpenetrating network structure composite polymer film has a mechanical strength of 7.01Mpa and a breaking strain of 248.3%. Compared with the traditional linear polymer, the semi-interpenetrating network structure of the composite polymer membrane with the semi-interpenetrating network structure can effectively enhance the rigidity of the polymer membrane, and meanwhile, the graft modified silicon dioxide which plays the role of a cross-linking agent can improve the overall flexibility of the polymer membrane to a certain degree by mutual cross-linking of relatively soft silicon-oxygen-carbon bonds and the PEO-based polymer.
Fig. 6 is a graph showing the temperature dependence of the ion conductivity of the composite polymer film with a semi-interpenetrating network structure prepared in example 1 and the electrolyte-compounded polypropylene separator. It can be seen that the ionic conductivity of the gel composite polymer electrolyte membrane at room temperature was 2.71 x 10-3S/cm. The compact semi-interpenetrating network structure of the gel composite polymer electrolyte membrane can prevent the migration of lithium salt cations with large volume to a certain extent, so that the migration number of lithium ions is increased, and the introduction of the graft modified silicon dioxide nanoparticles enhances the flexibility of a polymer chain segment and is beneficial to the transmission of lithium ions, so that the ionic conductivity of the gel composite polymer electrolyte membrane is several times of that of an electrolyte matched with a polypropylene diaphragm.
FIG. 7 shows cyclic voltammetry for electrochemical stability window test of composite polymer electrolyte membrane with semi-interpenetrating network structure prepared in example 1Curve line. As can be seen, the electrochemical stability window of the composite polymer electrolyte membrane with the semi-interpenetrating network structure is 5V vs Li/Li+。
FIG. 8 shows the 1C cycle performance at 25 ℃ of the button cell prepared in example 1. (in FIG. 8)
Example 2
Mixing 500mg of silicon dioxide nanoparticles with the particle size of 50nm, 80mL of ethanol and 20mL of deionized water, stirring for 1 minute, and performing ultrasonic dispersion for 30 minutes at room temperature to obtain a mixed solution.
Adding oxalic acid into the mixed solution to adjust the pH value to 3, heating the mixed solution to 85 ℃, dropwise adding 25mg of gamma-methacryloxypropyltrimethoxysilane while stirring under the condition of heat preservation, continuously stirring for reacting for 3 hours, separating, washing for three times by deionized water, and performing vacuum drying at 60 ℃ for 12 hours to prepare the modified silicon dioxide nano-particles.
200mg of the modified silica nanoparticles, 1g of poly (vinylidene fluoride-co-hexafluoropropylene) (weight average molecular weight Mw of 100000), 1.02g of polyethylene glycol diacrylate (Mn of 700), 2.78g of polyethylene glycol methyl ether acrylate (Mn of 480), 0.08g of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 5mL of acetone were mixed uniformly to prepare a precursor solution.
And (3) placing the precursor solution between two glass plates, and curing for 2 minutes under the ultraviolet light with the wavelength of 365nm to prepare the composite polymer film with the semi-interpenetrating network structure.
And (3) immersing the composite polymer membrane into electrolyte and absorbing the electrolyte until the electrolyte is saturated to prepare the gel composite polymer electrolyte membrane. The electrolyte is prepared by dissolving lithium hexafluorophosphate in a mixed solvent consisting of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1. Wherein the concentration of the lithium hexafluorophosphate in the electrolyte is 0.6 mol/L.
Example 3
Mixing 500mg of silicon dioxide nanoparticles with the particle size of 15nm, 95mL of ethanol and 5mL of deionized water, stirring for 1 minute, and performing ultrasonic dispersion at room temperature for 30 minutes to obtain a mixed solution.
Adding oxalic acid into the mixed solution to adjust the pH value to 4, heating the mixed solution to 85 ℃, dropwise adding 50mg of gamma-methacryloxypropyltrimethoxysilane while stirring under the condition of heat preservation, continuously stirring for reaction for 10 hours, separating, washing for three times by deionized water, and performing vacuum drying at 60 ℃ for 12 hours to prepare the modified silicon dioxide nano-particles.
200mg of the modified silica nanoparticles, 1g of poly (vinylidene fluoride-co-hexafluoropropylene) (weight average molecular weight Mw 400000), 1.8g of polyethylene glycol diacrylate (Mn 700), 2g of polyethylene glycol methyl ether acrylate (Mn 480), 0.1g of 1-hydroxy-cyclohexyl-phenyl ketone and 5mL of acetone were mixed uniformly to prepare a precursor solution.
And (3) placing the precursor solution between two glass plates, and curing for 3 minutes under ultraviolet light with the wavelength of 256nm to prepare the composite polymer film with the semi-interpenetrating network structure.
And (3) immersing the composite polymer membrane into electrolyte and absorbing the electrolyte until the electrolyte is saturated to prepare the gel composite polymer electrolyte membrane. The electrolyte is prepared by dissolving lithium hexafluorophosphate in a mixed solvent consisting of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1. Wherein the concentration of the lithium hexafluorophosphate in the electrolyte is 0.8 mol/L.
Example 4
Mixing 100mg of silicon dioxide nanoparticles with the particle size of 15nm, 60mL of ethanol and 20mL of deionized water, stirring for 1 minute, and performing ultrasonic dispersion at room temperature for 30 minutes to obtain a mixed solution.
Adding oxalic acid into the mixed solution to adjust the pH value to 5, heating the mixed solution to 70 ℃, dropwise adding 10mg of gamma-methacryloxypropyltrimethoxysilane while stirring under the condition of heat preservation, continuously stirring for reacting for 4 hours, separating, washing for three times by deionized water, and performing vacuum drying at 60 ℃ for 12 hours to prepare the modified silicon dioxide nano-particles.
200mg of the above-mentioned modified silica nanoparticles, 1g of poly (vinylidene fluoride-co-hexafluoropropylene) (weight average molecular weight Mw is 200000), 1.9g of polyethylene glycol diacrylate (Mn is 2000,), 1.9g of polyethylene glycol methyl ether acrylate (Mn is 950), 0.06g of 1-hydroxy-cyclohexyl-phenyl ketone and 5mL of acetone were mixed uniformly to prepare a precursor solution.
And (3) placing the precursor solution between two glass plates, and curing for 1 minute under ultraviolet light with the wavelength of 256nm to prepare the composite polymer film with the semi-interpenetrating network structure.
And (3) immersing the composite polymer membrane into electrolyte and absorbing the electrolyte until the electrolyte is saturated to prepare the gel composite polymer electrolyte membrane. The electrolyte is prepared by dissolving lithium hexafluorophosphate in a mixed solvent consisting of ethylene carbonate and ethyl methyl carbonate in a volume ratio of 1: 1. Wherein the concentration of the lithium hexafluorophosphate in the electrolyte is 1 mol/L.
In addition, it is obvious to those skilled in the art that other various corresponding changes and modifications can be made according to the technical idea of the present invention, and all such changes and modifications should fall within the scope of the claims of the present invention.
Claims (13)
1. A method for preparing a gel composite polymer electrolyte membrane, comprising the steps of:
mixing the silicon dioxide nano-particles, ethanol and water to form a mixed solution;
heating the mixed solution to 65-85 ℃ under an acidic condition, adding a coupling agent under a heat preservation condition for reaction, separating, washing and drying to obtain modified silicon dioxide nano particles, wherein the washing is sequentially carried out by adopting solutions with gradually reduced alcohol-water ratios;
mixing the modified silicon dioxide nano-particles with a linear polymer, polyethylene glycol diacrylate, polyethylene glycol methyl ether acrylate, a photoinitiator and a solvent to prepare a precursor solution;
forming the precursor solution on a supporting body and carrying out ultraviolet curing to prepare a composite polymer film, wherein the composite polymer film is of a semi-interpenetrating network structure; and
and immersing the composite polymer membrane into an electrolyte, and absorbing the electrolyte until the electrolyte is saturated to obtain the gel composite polymer electrolyte membrane.
2. The method for producing a gel composite polymer electrolyte membrane according to claim 1, wherein a volume ratio of ethanol to water in the mixed solution is 19:1 to 3: 1.
3. The method for preparing a gel composite polymer electrolyte membrane according to claim 1, wherein the silica nanoparticles have a particle size of 10nm to 100 nm.
4. The method for producing a gel composite polymer electrolyte membrane according to claim 1, wherein the acidic condition is that the pH of the mixed solution is 2 to 5.
5. The method for producing a gel composite polymer electrolyte membrane according to claim 1, wherein the reaction time of the mixed solution and the coupling agent is 3 to 10 hours.
6. The method for preparing a gel composite polymer electrolyte membrane according to claim 1, wherein the linear polymer is linear polyethylene oxide having a number average molecular weight of 100000 or more or poly (vinylidene fluoride-co-hexafluoropropylene) having a number average molecular weight of 100000 or more.
7. The method for preparing a gel composite polymer electrolyte membrane according to claim 1, wherein the modified silica nanoparticles are contained in an amount of 2 to 10% by mass, the linear polymer is contained in an amount of 10 to 30% by mass, and the photoinitiator is contained in an amount of 1 to 5% by mass in the precursor solution excluding the solvent.
8. The method for preparing a gel composite polymer electrolyte membrane according to claim 1, wherein the number average molecular weight of the polyethylene glycol diacrylate is 500 to 2000, the number average molecular weight of the polyethylene glycol methyl ether acrylate is 300 to 1000, and the molar ratio of the polyethylene glycol diacrylate to the polyethylene glycol methyl ether acrylate is 1:4 to 2: 1.
9. The method of preparing a gel composite polymer electrolyte membrane according to claim 1, wherein the photoinitiator is a radical photoinitiator.
10. The method for preparing a gel composite polymer electrolyte membrane according to claim 1, wherein the ultraviolet curing time is 1 minute to 10 minutes, and the wavelength of the ultraviolet light during the ultraviolet curing is 200nm to 400 nm.
11. The method of preparing a gel composite polymer electrolyte membrane according to claim 1, wherein the electrolyte solution includes a lithium salt and a plasticizer, the lithium salt includes at least one of lithium bistrifluoromethanesulfonylimide, lithium hexafluorophosphate, lithium tetrafluoroborate or lithium bistrifluorosulfonylimide, the plasticizer includes at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, propylene carbonate and ethylene glycol dimethyl ether, and the concentration of the lithium salt in the electrolyte solution is 0.6mol/L to 1.2 mol/L.
12. A gel composite polymer electrolyte membrane having a semi-interpenetrating network structure, prepared by the preparation method according to any one of claims 1 to 11.
13. A lithium ion battery comprises a positive electrode and a negative electrode, and is characterized in that: the lithium ion battery further comprises a gel composite polymer electrolyte membrane prepared by the preparation method according to any one of claims 1 to 11, wherein the gel composite polymer electrolyte membrane has a semi-interpenetrating network structure.
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