CN109786623A - Improve the method and polymer coating diaphragm of polymer coating diaphragm ionic conductivity - Google Patents
Improve the method and polymer coating diaphragm of polymer coating diaphragm ionic conductivity Download PDFInfo
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Classifications
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
This application discloses a kind of methods and polymer coating diaphragm for improving polymer coating diaphragm ionic conductivity.The present processes coat at least one layer of graphene or graphite oxide ene coatings in thermoplastic resin membrane surface, and then the coated polymer slurry on graphene or graphite oxide ene coatings, is made polymer coating diaphragm；Alternatively, graphene or graphene oxide are added in polymer paste, it is directly coated on thermoplastic resin membrane surface.The present processes, it is creative that graphene or graphene oxide are introduced in polymer coating diaphragm, so that diaphragm is quite even better than the ionic conductivity of basement membrane after coated polymer coating with basement membrane.The introducing of graphene or graphene oxide, so that polymer coating diaphragm has more preferable thermally conductive and heat sinking function, the heat that can in time generate battery discharges, and reduces security risk, reduces energy consumption, extends battery life；Diaphragm electrolyte wellability is improved, excellent imbibition water retainability is made it have.
Description
Technical Field
The application relates to the field of battery diaphragm preparation methods, in particular to a method for improving the ionic conductivity of a polymer coating diaphragm and the polymer coating diaphragm.
Background
The polymer coating diaphragm, also called organic polymer coating diaphragm, is a composite diaphragm with a coating formed by coating an organic polymer coating on the surface of a conventional polyolefin microporous membrane, such as a polypropylene microporous membrane, a polyethylene microporous membrane and the like. The polymer coating diaphragm can improve the physical and chemical properties of the polyolefin microporous membrane through the organic polymer coating, for example, the heat resistance of the diaphragm is improved, the adhesive force between the diaphragm and a pole piece is improved, and the safety, the stability and other properties of the lithium ion battery are further improved.
The polymer coating diaphragm can improve the physical and chemical properties of the polyolefin microporous membrane; however, the coating slurry of the organic polymer coating may block part of micropores of the polyolefin microporous membrane, thereby causing a certain reduction in ionic conductivity of the polymer coating separator based on the polyolefin microporous membrane base membrane, and the reduction in ionic conductivity may deteriorate the cycle and rate performance of the battery. Therefore, the polymer coating diaphragm can only be used for digital products generally, but is difficult to be applied to products with higher requirements on battery performance, such as electric automobiles, energy storage power stations and the like.
Disclosure of Invention
An object of the present application is to provide a novel method of improving ionic conductivity of a polymer-coated separator, and a polymer-coated separator prepared thereby.
In order to achieve the purpose, the following technical scheme is adopted in the application:
one aspect of the application discloses a method for improving the ionic conductivity of a polymer coating diaphragm, which comprises the steps of improving the ionic conductivity of the polymer coating diaphragm by using graphene or graphene oxide; specifically, before the polymer slurry is coated on the surface of a thermoplastic resin base film, at least one graphene or graphene oxide coating is coated on the surface of the thermoplastic resin base film in advance, and then the polymer slurry is coated on the graphene or graphene oxide coating to prepare a polymer coating diaphragm; or adding graphene or graphene oxide into the polymer slurry, and directly coating the surface of the thermoplastic resin base film to prepare the polymer coating diaphragm.
The polymer coating diaphragm prepared by the method has the ion conductivity equivalent to or even superior to that of the base film; in addition, due to the good heat-conducting property of the graphene or the graphene oxide, the generated heat can be dissipated in time under the conditions of large current and high heat generation of the battery, so that the potential safety hazard is reduced, the energy consumption is effectively reduced, and the service life of the battery is prolonged; meanwhile, due to the super-hydrophobicity and super-lipophilicity of the graphene or the graphene oxide, the polymer coating diaphragm has good electrolyte wettability and excellent liquid absorption and retention performances.
Preferably, the graphene or graphene oxide is of a sheet structure, the fineness of the graphene or graphene oxide is more than 100 meshes, and the purity of the graphene or graphene oxide is more than 99.99%.
Preferably, the polymer slurry is further added with a pore-forming agent, wherein the pore-forming agent is at least one of deionized water, n-propanol, n-butanol, tripropylene glycol, cyclohexane, cyclohexanol, ethanol, acetic acid, ethyl acetate, dimethyl carbonate and diethyl ether.
The porosity of the polymer coating can be further improved by adding the pore-forming agent, and the influence of the polymer coating on the ionic conductivity is reduced; in addition, the polymer coating diaphragm contains graphene or graphene oxide, so that the ionic conductivity of the diaphragm can be effectively improved.
Preferably, the thermoplastic resin-based film is a polyolefin microporous film.
Preferably, the polyolefin microporous membrane is prepared from at least one of polyethylene, polypropylene, poly-1-butene and polypentene.
Preferably, the thermoplastic resin-based film has a thickness of 3 to 30 μm, a porosity of 20 to 60%, and a permeability value of 50 to 500s/100 mL.
It should be noted that the key point of the present application is to introduce graphene or graphene oxide into the polymer-coated separator, and as the base film, a base film used in a conventional polymer coating, such as a polyolefin microporous film, may be used.
Preferably, in the polymer syrup, the polymer is at least one of polyvinylidene fluoride, polyurethane, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyacrylamide, polymethyl acrylate, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, and polytetraethylene glycol diacrylate, or a copolymer thereof.
Preferably, the solvent used in the polymer syrup is at least one of acetone, tetrahydrofuran, methyl ethyl ketone, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl triamine, ethylene diamine, dimethylformamide and dimethylacetamide.
The application also discloses a preparation method of the polymer coating diaphragm, which comprises the following steps:
preparing polymer slurry, namely adding an organic polymer into a solvent, stirring and dissolving for 4-6 hours at the temperature of 40-80 ℃ to completely dissolve the organic polymer; then adding a pore-forming agent into the mixture, and stirring the mixture at room temperature for 1 to 2 hours to obtain polymer slurry;
preparing a graphite dispersion liquid, namely dispersing graphene or graphene oxide in a solvent, stirring at room temperature for 4-8 hours, then adding a binder, and continuously stirring for 0.5-1 hour to obtain the graphite dispersion liquid;
coating, namely coating the graphite dispersion liquid on the surface of a thermoplastic resin base film to form a graphite coating, and then coating polymer slurry on the graphite coating to prepare a polymer coating diaphragm; or mixing the graphite dispersion liquid and the polymer slurry to prepare mixed slurry, and coating the mixed slurry on the surface of the thermoplastic resin base film to prepare the polymer coating diaphragm.
It should be noted that, the preparation method of the polymer coating diaphragm of the present application is actually to prepare the polymer coating diaphragm by adopting the method for improving the ionic conductivity of the polymer coating diaphragm of the present application, and only each step of the polymer coating diaphragm is added to the process steps; other parts, such as polymers, pore formers, solvents, base films, graphene or graphene oxide, etc., may all refer to the method of improving the ionic conductivity of the polymer-coated separator herein.
Preferably, in the method for preparing a polymer-coated separator of the present application, the coating is performed by at least one of dip coating, micro-gravure printing, extrusion coating, roll coating, spin coating, and doctor blade coating.
Preferably, the weight ratio of the organic polymer to the graphene or the graphene oxide in the mixed slurry is 5-9: 1-5.
The other side of the application discloses the polymer coating diaphragm obtained by the method for improving the ionic conductivity of the polymer coating diaphragm or the preparation method of the polymer coating diaphragm.
Due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
according to the method for improving the ionic conductivity of the polymer coating diaphragm, the graphene or the graphene oxide is creatively introduced into the polymer coating diaphragm, so that the ionic conductivity of the polymer coating diaphragm is not reduced due to the fact that coating slurry blocks micropores of the base film after the polymer coating is coated, and the base film has the ionic conductivity which is equivalent to or even superior to that of the base film. In addition, due to the introduction of the graphene or the graphene oxide, on one hand, the polymer coating diaphragm has better heat conduction and heat dissipation functions, can release heat generated by the battery in time, reduces potential safety hazards, reduces energy consumption and prolongs the service life of the battery; on the other hand, the electrolyte wettability of the polymer coating is improved, so that the polymer coating has excellent liquid absorption and retention performances.
Drawings
FIG. 1 is a schematic structural view of a polymer-coated separator in an embodiment of the present application;
figure 2 is a schematic diagram of another polymer coated separator in an embodiment of the present application.
Detailed Description
The polymer coating membrane causes the micropores of the microporous membrane-based membrane to be partially blocked due to the introduction of the polymer coating, thereby causing the decrease of the ionic conductivity. The present invention provides for the incorporation of highly conductive graphene or graphene oxide in the polymer coating, for example by incorporating a graphene or graphene oxide coating between the polymer coating and the base film, or by incorporating graphene or graphene oxide directly in the polymer coating. In the first case, as shown in fig. 1, the polymer coating 13 is directly coated on the graphene or graphene oxide coating 12, and does not block the micropores of the base film 11, so that the ionic conductivity of the base film is not reduced. In the second case, as shown in fig. 2, graphene or graphene oxide is directly doped into the polymer coating 22, and the conductivity of graphene or graphene oxide is also utilized, so that the polymer coating has conductivity with certain capability, and thus, although the micropores of the base film 21 are partially blocked, the ion conductivity of the separator can be improved due to the conductivity. Both fig. 1 and fig. 2 are double coated, i.e. coated on both sides of the base film. In both cases, the polymer coating diaphragm does not cause the reduction of the ionic conductivity caused by the polymer coating, but has the ionic conductivity equivalent to or even superior to that of the base film.
The present application is described in further detail below with reference to specific embodiments and the attached drawings. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application.
Example 1
In this example, a 14 μm polypropylene microporous membrane was used as a thermoplastic resin base membrane, and graphene coating layers were applied to both surfaces of the base membrane, followed by polymer coating layers to prepare the polymer-coated separator of this example, as follows:
(1) preparation of slurry
1.07kg of polyvinylidene fluoride-hexafluoropropylene powder having an average particle diameter of 200nm was added to 58kg of acetone, and dissolved at 50 ℃ for 4 hours with stirring, and then 1.39kg of dimethyl carbonate was added to obtain a polyvinylidene fluoride-hexafluoropropylene acetone solution, i.e., the polymer slurry of this example.
Adding 1.07kg of graphite oxide into 58kg of acetone, emulsifying and dispersing for 6h, then adding 0.107kg of acrylic resin binder, and continuously stirring for 0.5h to obtain the acetone dispersion liquid of graphene.
(2) Coating of
The prepared slurry is respectively coated on two surfaces of a base film in a dipping coating mode, and the process flow is as follows: unreeling, coating, drying and reeling, wherein the coating thickness is 1 mu m per coating. In this example, graphene was coated on both sides, and then a polymer was coated on both sides of the graphene coating, to obtain a polymer-coated membrane having a total thickness of 18 μm.
Example 2
In this example, tests were conducted using the same thermoplastic resin base film as in example 1, the same polymer slurry and the same acetone dispersion liquid of graphene, except that in this example, the polymer slurry and the acetone dispersion liquid of graphene were mixed and applied as mixed slurry to both surfaces of the base film. The method comprises the following specific steps:
preparation of polymer slurry and acetone dispersion liquid of graphene referring to example 1, the polymer slurry and the acetone dispersion liquid of graphene were mixed according to the ratio of polyvinylidene fluoride-hexafluoropropylene: graphene of 10:1, and stirred for 1 hour to obtain a mixed slurry of the present example.
The prepared mixed slurry is coated on two surfaces of a base film in a dipping coating mode, and the process flow is as follows: unreeling, coating, drying and reeling, wherein the coating thickness is 2 mu m on each surface, and coating is carried out on two sides to obtain the polymer coating diaphragm with the total thickness of 18 mu m.
Example 3
This example is similar to example 2, and the thermoplastic resin-based film is the same as example 2, except that the weight ratio of polyvinylidene fluoride-hexafluoropropylene to graphene in the mixed slurry is 1:1, and the rest is the same as example 2. The method comprises the following specific steps:
preparation of polymer slurry and acetone dispersion liquid of graphene referring to example 1, the polymer slurry and the acetone dispersion liquid of graphene were mixed in a ratio of polyvinylidene fluoride-hexafluoropropylene to graphene of 1:1, and stirred for 1 hour to obtain a mixed slurry of the present example.
The prepared mixed slurry is coated on two surfaces of a base film in a dipping coating mode, and the process flow is as follows: unreeling, coating, drying and reeling, wherein the coating thickness is 2 mu m on each surface, and coating is carried out on two sides to obtain the polymer coating diaphragm with the total thickness of 18 mu m.
Comparative example 1
This example was tested using the same thermoplastic resin-based film and polymer paste as in example 1, except that the polymer paste was directly applied to the surface of the base film without adding graphene. The method comprises the following specific steps:
polymer paste formulation referring to example 1, the formulated polymer paste was coated on both surfaces of a base film by dip coating, and the process flow was: unreeling, coating, drying and reeling, wherein the coating thickness is 1 mu m on each surface, and coating is carried out on two sides to obtain the polymer coating diaphragm with the total thickness of 16 mu m.
Comparative example 2
This example was tested using the same thermoplastic resin-based film and acetone dispersion of graphene as in example 1, except that the acetone dispersion of graphene was directly applied to the surface of the base film to form a graphene coating layer, and no polymer was applied. The method comprises the following specific steps:
preparation of acetone dispersion solution of graphene referring to example 1, the prepared acetone dispersion solution of graphene is coated on both surfaces of a base film in a dip coating manner, and the process flow is as follows: unreeling, coating, drying and reeling, wherein the coating thickness is 1 mu m on each surface, and coating is carried out on two sides to obtain the coating diaphragm with the total thickness of 16 mu m.
The membranes of the above examples and comparative examples were tested for thickness, air permeability, ionic conductivity, liquid absorption rate and liquid retention rate, and the like, while the base membranes used in the examples and comparative examples were tested in the same manner to analyze the influence of the graphene introduction on the membranes. The method comprises the following specific steps:
the membrane thickness testing method is carried out by referring to GB/T6672-2001, a Mark thickness gauge with a flat head contact head is adopted for measurement, the gauge is calibrated and cleared before measurement, the contact surface is kept clean, one point is taken along the TD direction of the membrane every 5cm for measurement, and the average value of 5 points is measured to be the thickness of the membrane.
And (4) testing the air permeability, which is carried out by referring to GB/T458-.
And (3) testing the ionic conductivity, namely manufacturing a symmetrical battery by adopting an inert stainless steel electrode for testing, wherein the battery resistance is correspondingly increased along with the increase of the layer number of the diaphragm and is in a linear relation, and the corresponding slope is the diaphragm resistance. The diaphragm ionic conductivity calculation formula is as follows: σ S ═ d/(RS × a × 10); wherein,
σ S is the membrane ionic conductivity, unit: mS/cm;
d is the thickness of the separator, in units: mu m; measured by a thickness gauge;
RS is the diaphragm resistance, unit: omega;
a is the effective area of the diaphragm in the symmetrical battery, and the value is 6cm2；
Remarking: the denominator "10" is a dimension conversion ratio.
The liquid absorption rate and the liquid retention rate of the diaphragm are measured by weighing a coating film with the size of 10 multiplied by 10cm and the mass of the coating film is W0Immersing in the mixed solution of Ethylene Carbonate (EC) and Propylene Carbonate (PC) at room temperature at a ratio of 1:1, standing for 2h, sucking the electrolyte on the surface with filter paper, weighing, and recording the mass as W1Then continuously standing at room temperature for 10min, weighing again, and recording the mass as W2;
liquid absorption rate ═ W2-W0)/W0
Retention rate of (W)1-W2)/(W1-W0)
The results of the various performance tests are shown in table 1.
Table 1 base film and separator performance test results
| Item | Base film | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| Thickness (μm) | 14 | 16 | 16 | 18 | 18 | 18 |
| Breathability (s/100mL) | 180 | 234 | 200 | 260 | 230 | 220 |
| Ion conductivity (μ s/cm) | 1.5 | 1.0 | 1.7 | 1.1 | 1.3 | 1.6 |
| Liquid absorption Rate (%) | 30 | 150 | 210 | 200 | 176 | 198 |
| Liquid retention ratio (%) | 20 | 75 | 90 | 85 | 79 | 86 |
The results of table 1 show that the ionic conductivity is decreased after the polymer coating layer is coated on the surface of the base film, such as comparative example 1, which is significantly decreased with respect to the base film; however, after the graphene is added into the polymer coating, the decrease of the ionic conductivity is reduced, for example, in examples 1 to 3, the decrease of the ionic conductivity is significantly smaller than that in comparative example 1, and the decrease of the ionic conductivity is gradually reduced with the increase of the addition amount of the graphene, so that the ionic conductivity of the polymer coating membrane is equivalent to or even superior to that of the base membrane, for example, the ionic conductivity of example 3 is superior to that of the base membrane. In addition, if graphene is coated on the surface of the base film, although the ionic conductivity is improved, the problem that the graphene coating alone is easy to fall off due to the fact that the physicochemical property of the polymer coating is not provided is solved.
Example 4
The example was optimized and improved based on example 3, specifically, polymer slurries were prepared by adding different amounts and different types of pore-forming agents to the polymer slurries of example 3, and then coated into 18 μm polymer-coated membranes according to the method of example 3. The method comprises the following specific steps:
polymer syrup 1: to the polymer syrup of example 3 was added a dimethyl carbonate pore former in an amount of 2% by weight, the remainder being unchanged.
Polymer syrup 2: to the polymer syrup of example 3 was added dimethyl carbonate pore former in an amount of 3% by weight, the remainder being unchanged.
Polymer syrup 3: to the polymer syrup of example 3 was added a dimethyl carbonate pore former in an amount of 4% by total weight, with the remainder being unchanged.
Polymer syrup 4: to the polymer syrup of example 3 was added a dimethyl carbonate pore former in an amount of 5% by weight, the remainder being unchanged.
Polymer syrup 5: to the polymer slurry of example 3 was added deionized water pore former in an amount of 3% by weight, the remainder being unchanged.
Polymer syrup 6: to the polymer slurry of example 3 was added 3% by weight of n-propanol pore-forming agent, the remainder being unchanged.
Polymer syrup 7: to the polymer slurry of example 3 was added 3% by weight of cyclohexane pore former, the remainder being unchanged.
Polymer syrup 8: to the polymer syrup of example 3 was added 3% by weight of an acetic acid pore former, the remainder being unchanged.
Polymer syrup 9: to the polymer syrup of example 3, ethyl acetate pore former was added in an amount of 3% by weight, with the remainder being unchanged.
Polymer syrup 10: to the polymer slurry of example 3, a diethyl ether pore former was added in an amount of 3% by weight, with the remainder being unchanged.
The above 10 kinds of polymer slurries were coated with base films, respectively, to obtain 10 kinds of polymer-coated membranes having a thickness of 18 μm, which were labeled as membrane 1 to membrane 10, respectively, in this order. The membrane was subjected to the tests of thickness, air permeability, ionic conductivity, liquid absorption rate and liquid retention rate of the membrane according to the above methods, and the results are shown in table 2.
Table 2 membrane performance test results for different polymer slurries
The results in table 2 show that the addition of pore-forming agent to the polymer slurry can improve the porosity of the polymer coating, thereby improving the gas permeability and ionic conductivity of the polymer coating membrane, and the amount of pore-forming agent is effective in the range of 2% to 5%. In addition, the results of further experiments on the amount of the pore-forming agent in this example show that, generally, the amount of the pore-forming agent is in the range of 0.05% to 5% to improve the air permeability and the ionic conductivity to different degrees, too much pore-forming agent will cause larger pore defects in the polymer coating, and too little pore-forming agent will reduce the improvement effect accordingly. As for the type of pore-forming agent, other similar ones such as n-butanol, tripropylene glycol, cyclohexanol, ethanol and the like have a comparable effect in addition to the pore-forming agents used in the above respective tests.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended that the present application be limited to the specific embodiments thereof. It will be apparent to those skilled in the art from this disclosure that many more simple derivations or substitutions can be made without departing from the spirit of the disclosure.
Claims (10)
1. A method for improving the ionic conductivity of a polymer-coated separator, characterized by: the method comprises the steps of improving the ionic conductivity of the polymer coating diaphragm by using graphene or graphene oxide; in particular, the method comprises the following steps of,
before coating the polymer slurry on the surface of a thermoplastic resin base film, coating at least one layer of graphene or graphene oxide coating on the surface of the thermoplastic resin base film in advance, and then coating the polymer slurry on the graphene or graphene oxide coating to prepare a polymer coating diaphragm;
or adding graphene or graphene oxide into the polymer slurry, and directly coating the polymer slurry on the surface of the thermoplastic resin base film to prepare the polymer coating diaphragm.
2. The method of claim 1, wherein: the graphene or graphene oxide is of a sheet structure, the fineness of the graphene or graphene oxide is more than 100 meshes, and the purity of the graphene or graphene oxide is more than 99.99%.
3. The method of claim 1, wherein: the polymer slurry is also added with a pore-forming agent, wherein the pore-forming agent is at least one of deionized water, n-propanol, n-butanol, tripropylene glycol, cyclohexane, cyclohexanol, ethanol, acetic acid, ethyl acetate, dimethyl carbonate and diethyl ether.
4. A method according to any one of claims 1-3, characterized in that: the thermoplastic resin base film is a polyolefin microporous film;
preferably, the polyolefin microporous membrane is prepared from at least one of polyethylene, polypropylene, poly-1-butene and polypentene;
preferably, the thickness of the thermoplastic resin-based film is 3 to 30 μm, the porosity is 20 to 60%, and the air permeability value is 50 to 500s/100 mL.
5. A method according to any one of claims 1-3, characterized in that: in the polymer slurry, the polymer is at least one of polyvinylidene fluoride, polyurethane, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyacrylamide, polymethyl acrylate, polymethyl methacrylate, polyvinyl acetate, polyvinyl pyrrolidone and polytetraethylene glycol diacrylate, or a copolymer of the materials.
6. A method according to any one of claims 1-3, characterized in that: in the polymer slurry, the adopted solvent is at least one of acetone, tetrahydrofuran, methyl ethyl ketone, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl triamine, ethylenediamine, dimethylformamide and dimethylacetamide.
7. A preparation method of a polymer coating diaphragm is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
preparing polymer slurry, namely adding an organic polymer into a solvent, stirring and dissolving for 4-6 hours at the temperature of 40-80 ℃ to completely dissolve the organic polymer; then adding a pore-forming agent into the mixture, and stirring the mixture at room temperature for 1 to 2 hours to obtain polymer slurry;
preparing a graphite dispersion liquid, namely dispersing graphene or graphene oxide in a solvent, stirring at room temperature for 4-8 hours, then adding a binder, and continuously stirring for 0.5-1 hour to obtain the graphite dispersion liquid;
coating, namely coating the graphite dispersion liquid on the surface of a thermoplastic resin base film to form a graphite coating, and then coating polymer slurry on the graphite coating to prepare a polymer coating diaphragm; or mixing the graphite dispersion liquid and the polymer slurry to prepare mixed slurry, and coating the mixed slurry on the surface of the thermoplastic resin base film to prepare the polymer coating diaphragm.
8. The method of claim 7, wherein: the organic polymer is at least one of polyvinylidene fluoride, polyurethane, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyacrylamide, polymethyl acrylate, polymethyl methacrylate, polyvinyl acetate, polyvinyl pyrrolidone and polytetraethylene glycol diacrylate, or the copolymer of the materials;
preferably, the pore-forming agent is at least one of deionized water, n-propanol, n-butanol, tripropylene glycol, cyclohexane, cyclohexanol, ethanol, acetic acid, ethyl acetate, dimethyl carbonate and diethyl ether;
preferably, the solvent of the polymer syrup and the solvent of the graphite dispersion may repeatedly be at least one selected from the group consisting of acetone, tetrahydrofuran, methyl ethyl ketone, 1-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl triamine, ethylene diamine, dimethyl formamide, and dimethyl acetamide;
preferably, the thickness of the thermoplastic resin-based film is 3-30 μm, the porosity is 20-60%, and the air permeability value is 50-500s/100 mL; preferably, the thermoplastic resin-based film is a polyolefin microporous film; preferably, the polyolefin microporous membrane is prepared from at least one of polyethylene, polypropylene, poly-1-butene and polypentene.
9. The production method according to claim 7 or 8, characterized in that: the graphene or graphene oxide is of a sheet structure, the fineness of the graphene or graphene oxide is more than 100 meshes, and the purity of the graphene or graphene oxide is more than 99.99%;
preferably, the coating mode is at least one of dip coating, micro-gravure printing, extrusion coating, roll coating, spin coating and knife coating;
preferably, the weight ratio of the organic polymer to the graphene or the graphene oxide in the mixed slurry is 5-9: 1-5.
10. A polymer-coated separator obtained by the method according to any one of claims 1 to 6 or the production method according to any one of claims 7 to 9.
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