CN114914629A - Flame-retardant composite diaphragm and preparation method and application thereof - Google Patents
Flame-retardant composite diaphragm and preparation method and application thereof Download PDFInfo
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- CN114914629A CN114914629A CN202210569895.5A CN202210569895A CN114914629A CN 114914629 A CN114914629 A CN 114914629A CN 202210569895 A CN202210569895 A CN 202210569895A CN 114914629 A CN114914629 A CN 114914629A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- General Chemical & Material Sciences (AREA)
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- Cell Separators (AREA)
Abstract
The invention discloses a flame-retardant composite diaphragm and a preparation method and application thereof, wherein the composite diaphragm is composed of a composite fiber membrane prepared by a coaxial electrostatic spinning method; the composite fiber membrane comprises a hollow cylindrical shell layer and a flame-retardant core material distributed in the hollow cylindrical shell layer; the hollow columnar shell layer is made of a high polymer material, and the flame-retardant core material is a liquid flame retardant. The flame-retardant composite diaphragm can ensure that the electrochemical performance of the lithium ion battery is not influenced, and when the battery is subjected to conditions such as needling, extrusion or overcharging to cause thermal runaway inside the battery, the high polymer material can be heated, melted and broken, so that the liquid flame retardant can be released, the thermal runaway process of the battery can be effectively blocked, and the safety performance of the battery is improved. Meanwhile, the flame-retardant composite diaphragm prepared by the invention has excellent mechanical property and thermal stability, has larger gap and ensures the liquid absorption rate of the electrolyte. The method for preparing the flame-retardant composite diaphragm is quick and simple, and is convenient for large-scale popularization and application.
Description
Technical Field
The invention belongs to the technical field of composite diaphragms, and particularly relates to a flame-retardant composite diaphragm and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in portable electronic devices such as mobile phones and notebook computers, new energy vehicles such as electric vehicles, and energy storage fields due to their advantages such as high energy density and long cycle life. In recent years, people have higher and higher requirements on energy density of lithium ion batteries, but the safety performance of the lithium ion batteries faces a great challenge, and because the lithium ion batteries are subjected to thermal runaway caused by external severe conditions such as high temperature, extrusion, overcharge and the like, the batteries are ignited and even exploded, and the life and property safety of users is seriously affected. Especially for a power battery with larger capacity, it is very important to synchronously improve the safety performance.
The diaphragm material is one of four main materials of the lithium ion battery, plays the roles of isolating the short circuit caused by the contact of a positive electrode and a negative electrode and providing a lithium ion transmission channel, and directly influences the electrochemical performance and the safety performance of the battery. The lithium ion battery diaphragm commonly used in the market at present is mainly a single-layer Polyethylene (PE), polypropylene (PP) or PP/PE/PP three-layer composite diaphragm, has certain thermal shutdown performance, but has poor thermal stability, and can generate obvious size shrinkage when the temperature is higher than 120 ℃, thereby possibly causing short circuit inside the battery and finally causing fire and even explosion. Especially for new energy electric vehicles and energy storage which adopt large-capacity lithium batteries as driving force, the potential safety hazard is very large, so that the lithium ion battery diaphragm with higher safety performance needs to be researched and developed on the premise of ensuring that the electrochemical performance is not influenced.
In order to improve the safety performance of the lithium ion battery, the prior art adjusts the electrolyte formula, for example, a flame retardant additive is added into the electrolyte, but the electrochemical performance of the battery is often sacrificed by the method. Further, chinese patent publication No. CN104466186A discloses that a microcapsule technology is adopted to coat a liquid flame retardant in microcapsules, and coat the microcapsules on the surface of a positive electrode material or disperse the microcapsules in the positive electrode material, and when thermal runaway occurs in a battery, the microcapsules melt and cover the surface of the positive electrode material, and release the liquid flame retardant to prevent the battery from burning or exploding. However, this method increases the internal resistance of the positive electrode, because the microcapsule is not conductive, which leads to the increase of the internal resistance of the battery, which is very disadvantageous for the power battery.
Disclosure of Invention
In view of the above, the invention aims to provide a flame-retardant composite diaphragm, a preparation method and an application thereof, wherein the flame-retardant composite diaphragm has good mechanical properties and high porosity, and can improve the safety performance of a battery on the basis of not sacrificing the electrochemical performance. The composite diaphragm which takes the flame retardant as a core material and the polymer material as a shell material is formed by wrapping the liquid flame retardant with the polymer material, thermal runaway occurs in the battery to melt and crack the shell layer, the liquid flame retardant is released, the combustion and even explosion of the battery can be effectively reduced, and the composite diaphragm is particularly suitable for lithium ion power batteries.
In order to achieve the purpose, the invention adopts the technical scheme that:
a flame-retardant composite diaphragm is composed of a composite fiber membrane prepared by a coaxial electrostatic spinning method; the composite fiber membrane comprises a hollow cylindrical shell layer and a flame-retardant core material distributed in the hollow cylindrical shell layer; the hollow columnar shell layer is made of a high polymer material, and the flame-retardant core material is a liquid flame retardant. Further preferably, the thickness of the hollow cylindrical shell is 2-3 μm; the inner diameter of the hollow cylindrical shell is 1-4 mu m; the high polymer material is a polyolefin material, and the melting point of the high polymer material is 110-200 ℃; the polyolefin material is at least one of low-density polyethylene, polypropylene and polystyrene. The liquid flame retardant is at least one of phosphate flame retardant, phosphite flame retardant and phosphazene flame retardant.
The invention also aims to provide application of the flame-retardant composite separator, which is used for lithium ion battery separators.
The invention also provides a preparation method of the flame-retardant composite diaphragm, which is prepared by a coaxial electrostatic spinning method and comprises the following steps:
(1) selecting at least one liquid flame retardant from a phosphate flame retardant, a phosphite flame retardant and a phosphazene flame retardant as a spinning solution A;
(2) mixing at least one polymer material of low-density polyethylene, polypropylene and polystyrene with a solvent, and heating at 150-220 ℃ to obtain a melt in a molten state as a spinning solution B. Preferably, the solvent is at least one of white oil, liquid paraffin and mineral vegetable oil; the mass ratio of the high polymer material to the solvent is 1: (1.5-2);
(3) and (3) injecting the spinning solution A obtained in the step (1) into an inner needle injector in a coaxial electrostatic spinning device, and injecting the spinning solution B prepared in the step (2) into an outer needle injector in the coaxial electrostatic spinning device to start electrostatic spinning. Preferably, the electrostatic spinning process comprises the following steps: the aperture of the inner needle injector is 0.3-0.8mm, the aperture of the outer needle is 0.5-1mm, the spinning voltage is 10-30kV, the distance between the needle and the receiver is 5-25cm, the spinning temperature is 20-60 ℃, and the spinning humidity is 20-45%.
(4) And cleaning the collected material by using an acetone solution, and then drying to obtain the dry composite diaphragm. Preferably, the drying is performed under vacuum; the drying temperature is 30-100 ℃ and the drying time is 10-24 h.
(5) Cutting the dried composite diaphragm into a required shape, carrying out hot pressing treatment, and drying to obtain a final product. Preferably, the hot pressing treatment process comprises the following steps: the temperature is 50-100 ℃, the temperature is kept for 0.5-1h, and the pressure is 2-6 MPa.
The invention has the beneficial effects that:
the composite diaphragm prepared by a coaxial electrostatic spinning method is used as a lithium ion flame-retardant diaphragm, a high polymer material with a specific melting point is used as a shell material, a liquid flame retardant is used as a core material, and the electrochemical performance of the composite diaphragm is not affected when a lithium ion battery normally works; when the lithium ion battery is subjected to conditions such as needling, extrusion or overcharge to cause thermal runaway inside the lithium ion battery, the high molecular polymer shell layer can be melted and broken by heating, and the liquid flame retardant serving as the core material can be released. The liquid flame retardant is a phosphorus compound, and when the liquid flame retardant is combusted, the phosphorus compound is decomposed to generate a non-combustible liquid film of phosphoric acid, the boiling point of the non-combustible liquid film can reach 300 ℃, so that the liquid flame retardant can effectively isolate external air and heat and has a good flame retardant effect; meanwhile, the phosphoric acid is further dehydrated to generate metaphosphoric acid, and the metaphosphoric acid is further polymerized to generate polymetaphosphoric acid. In the process, the covering layer generated by phosphoric acid plays a covering effect, and the generated polymetaphosphoric acid is strong acid and is a strong dehydrating agent, so that the high molecular polymer is dehydrated and carbonized, the combustion process mode of the high molecular polymer is changed, and a carbon film is formed on the surface of the high molecular polymer to isolate air, so that a stronger flame retardant effect is exerted, the thermal runaway process of the lithium ion battery can be effectively blocked, and the safety performance of the battery is improved. Meanwhile, the composite diaphragm prepared by the invention has excellent mechanical property and thermal stability, has larger gap, and ensures the liquid absorption rate of the electrolyte.
The composite diaphragm provided by the invention has simple preparation process, the liquid flame retardant is liquid, can be directly injected into equipment for preparation, can reduce the production energy consumption and cost, is convenient for large-scale commercial application, and has very important significance and reference value for improving the safety performance of a power battery, especially a high-energy-density ternary battery system.
Drawings
FIG. 1 is a scanning electron microscope image of a composite diaphragm prepared by an electrospinning method according to the present invention;
FIG. 2 is a schematic cross-sectional view of a composite fiber membrane;
reference numerals: 1-flame-retardant core material and 2-hollow cylindrical shell layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the accompanying drawings and detailed description. It is emphasized that the embodiments described in this application are required for the purpose of illustrating the invention and are part of the invention. Based on the embodiments in the present invention, those skilled in the art can freely combine the embodiments described below to form new embodiments without making creative efforts, and all of them are within the protection scope of the present invention.
Referring to fig. 1 and 2, a flame retardant composite separator is composed of a composite fiber membrane prepared by a coaxial electrospinning method; the composite fiber membrane comprises a hollow cylindrical shell layer 2 and a flame-retardant core material 1 distributed in the hollow cylindrical shell layer; the hollow columnar shell layer 2 is made of a high polymer material, and the flame-retardant core material 1 is a liquid flame retardant.
Example 1
Taking triethyl phosphate as spinning solution A; mixing low-density polyethylene powder and white oil according to mass ratio m Polyethylene ：m White oil 1: 2, mixing, and heating at 180 ℃ to obtain a melt in a molten state as a spinning solution B; injecting the spinning solution A into an inner needle injector of a coaxial electrostatic spinning device, and injecting the spinning solution B into an outer needle injector of the coaxial electrostatic spinning device for electrostatic spinning; the aperture of the inner needle is 0.3mm, the aperture of the outer needle is 0.5mm, the spinning voltage is 13kV, aluminum foil paper is used as a receiver, the distance between the needle and the receiver is 15cm, and the humidity is 30-45%; cleaning the collected non-woven membrane by acetone solution, drying at 80 ℃ under vacuum condition to obtain a dry composite fiber membrane, cutting into a required shape, and carrying out hot pressing treatment at 100 ℃ to obtain the lithium ion battery flame-retardant composite diaphragm
Example 2
Taking triethyl phosphate as spinning solution A; mixing low-density polypropylene powder and white oil according to mass ratio m Polypropylene ：m White oil 1: 2, mixing, and heating at 210 ℃ to obtain a melt in a molten state as a spinning solution B; injecting the spinning solution A into an inner needle injector of a coaxial electrostatic spinning device, and injecting the spinning solution B into an outer needle injector of the coaxial electrostatic spinning device to carry out electrostatic spinning; the aperture of the inner needle is 0.4mm, the aperture of the outer needle is 0.7mm, the spinning voltage is 15kV, aluminum foil paper is used as a receiver, the distance between the needle and the receiver is 13cm, and the humidity is 25-40%; and cleaning the collected non-woven membrane by using an acetone solution, drying at a high temperature of 70 ℃ under a vacuum condition to obtain a dry composite fiber membrane, cutting into a required shape, and performing hot-pressing treatment at a hot-pressing temperature of 90 ℃ to obtain the lithium ion battery flame-retardant composite diaphragm.
Example 3
Taking triethyl phosphate as spinning solution A; will be lowThe weight ratio m of the density polyethylene powder, the polypropylene powder and the white oil Polyethylene ：m Polypropylene ：m White oil 1: 1: 4, mixing, and heating at 200 ℃ to obtain a melt in a molten state as a spinning solution B; injecting the spinning solution A into an inner needle injector of a coaxial electrostatic spinning device, and injecting the spinning solution B into an outer needle injector of the coaxial electrostatic spinning device to carry out electrostatic spinning; the aperture of the inner needle is 0.5mm, the aperture of the outer needle is 0.8mm, the spinning voltage is 20kV, aluminum foil paper is used as a receiver, the distance between the needle and the receiver is 18cm, and the humidity is 30-40%; and cleaning the collected non-woven membrane by using an acetone solution, drying at a high temperature of 70 ℃ under a vacuum condition to obtain a dry composite fiber membrane, cutting into a required shape, and performing hot-pressing treatment at a hot-pressing temperature of 90 ℃ to obtain the lithium ion battery flame-retardant composite diaphragm.
Example 4
Taking triethyl phosphate as spinning solution A; mixing low-density polypropylene powder and white oil according to mass ratio m Polypropylene ：m White oil 1: 1.5, mixing, and heating at 220 ℃ to obtain a melt in a molten state as a spinning solution B; injecting the spinning solution A into an inner needle injector of a coaxial electrostatic spinning device, and injecting the spinning solution B into an outer needle injector of the coaxial electrostatic spinning device to carry out electrostatic spinning; the aperture of the inner needle is 0.6mm, the aperture of the outer needle is 0.8mm, the spinning voltage is 22kV, aluminum foil paper is used as a receiver, the distance between the needle and the receiver is 20cm, and the humidity is 30-45%; and cleaning the collected non-woven membrane by using an acetone solution, drying at a high temperature of 70 ℃ under a vacuum condition to obtain a dry composite fiber membrane, cutting into a required shape, and performing hot-pressing treatment at a hot-pressing temperature of 80 ℃ to obtain the lithium ion battery flame-retardant composite diaphragm.
Comparative example 1
The commercial polypropylene lithium battery diaphragm is used as a comparison to illustrate relevant performance parameters of the flame-retardant composite diaphragm.
The invention measures the basic performance parameters of film thickness, porosity, liquid absorption rate, tensile strength and heat shrinkage rate of different diaphragms in the above examples 1-4 and the comparative example 1, and the test method is as follows:
1. film thickness test: and (3) testing the thicknesses of different diaphragms by using a micrometer, randomly sampling 5 points on a sample, and taking an average value.
2. And (3) porosity testing: and (3) soaking the diaphragm in the n-butyl alcohol solution for 4 hours, sucking the n-butyl alcohol on the surface of the diaphragm by using filter paper before weighing, and weighing the mass of the diaphragm again. The porosity P of the separator is Δ m/(ρ × V) × 100%. Wherein, the delta m is the mass difference before and after the membrane is soaked, and the rho is the density of n-butyl alcohol and is equal to 0.81g/cm 3 And V is the volume of the diaphragm.
3. And (3) testing the liquid absorption rate: the separator was immersed in the electrolyte for 10 hours to saturate the electrolyte in the separator, and the mass of the separator before and after the absorption of the electrolyte was measured, respectively, and the liquid absorption rate EU of the separator was ═ W-Wo)/Wo × 100%. Where Wo and W absorb the mass of the separator before and after the electrolyte.
4. And (3) testing tensile strength: a sample with the width of 15mm +/-0.1 mm is adopted, the initial distance of the clamp is set to be 65mm +/-5 mm, and the test speed is 100mm/min +/-10 mm/min. The tensile breaking strength calculation formula is as follows: δ is F/(L × d), where δ is the tensile strength, F is the sample tensile load, L is the specimen width, and d is the specimen width.
5. Testing the thermal shrinkage rate: : 5 pieces of a 100mm X100 mm sample were cut out, treated in a vacuum oven at a temperature of 120 ℃ for 1 hour, and then measured for longitudinal dimension. The heat shrinkage Δ L is (L0L)/L0 × 100%, L being the longitudinal length after heating, and L0 being the longitudinal length before heating, in mm.
The test results are detailed in table 1.
TABLE 1 lithium ion battery separator Performance test results
Where MD is a machine direction stretched membrane and TD is a transverse direction stretched membrane.
The test results in table 1 show that the flame-retardant composite diaphragm prepared by the method provided by the invention has high porosity and liquid absorption rate, good mechanical strength and good heat resistance, and is a lithium ion battery diaphragm with excellent performance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and design concepts of the present invention are equivalent to or changed within the technical scope of the present invention.
Claims (10)
1. A flame retardant composite separator characterized by: consists of a composite fiber membrane prepared by a coaxial electrostatic spinning method; the composite fiber membrane comprises a hollow cylindrical shell layer and a flame-retardant core material distributed in the hollow cylindrical shell layer; the hollow columnar shell layer is made of a high polymer material, and the flame-retardant core material is a liquid flame retardant.
2. The flame retardant composite separator membrane of claim 1, wherein: the thickness of the hollow cylindrical shell layer is 2-3 mu m; the inner diameter of the hollow cylindrical shell layer is 1-4 mu m.
3. The flame retardant composite separator membrane of claim 1, wherein: the high polymer material is a polyolefin material, and the melting point of the high polymer material is 110-200 ℃; the polyolefin material is at least one of low-density polyethylene, polypropylene and polystyrene.
4. The flame retardant composite separator membrane of claim 1, wherein: the liquid flame retardant is at least one of phosphate flame retardant, phosphite flame retardant and phosphazene flame retardant.
5. Use of a flame retardant composite separator as claimed in any one of claims 1 to 4 wherein: it is used for lithium ion battery separators.
6. The method of preparing a flame retardant composite separator according to any one of claims 1 to 4, wherein: prepared by a coaxial electrostatic spinning method, comprising the following steps:
(1) selecting at least one liquid flame retardant from a phosphate flame retardant, a phosphite flame retardant and a phosphazene flame retardant as a spinning solution A;
(2) mixing a high polymer material with a solvent, and then heating at the temperature of 150-220 ℃ to obtain a melt in a molten state as spinning solution B;
(3) injecting the spinning solution A in the step (1) into an inner needle injector in a coaxial electrostatic spinning device, injecting the spinning solution B prepared in the step (2) into an outer needle injector in the coaxial electrostatic spinning device, and starting electrostatic spinning;
(4) cleaning the collected materials by an acetone solution, and then drying to obtain a dry composite diaphragm;
(5) cutting the dried composite diaphragm into a required shape, carrying out hot pressing treatment, and drying to obtain a final product.
7. The method for preparing the flame-retardant composite separator according to claim 6, characterized in that: in the step (2), the solvent is at least one of white oil, liquid paraffin and mineral vegetable oil; the mass ratio of the high polymer material to the solvent is 1: (1.5-2).
8. The method for preparing the flame-retardant composite separator according to claim 6, characterized in that: in the step (3), the electrostatic spinning process comprises the following steps: the bore diameter of the inner needle injector is 0.3-0.8mm, the bore diameter of the outer needle is 0.5-1mm, the spinning voltage is 10-30kV, the distance between the needle and the receiver is 5-25cm, and the spinning humidity is 20-45%.
9. The method for preparing the flame-retardant composite separator according to claim 6, characterized in that: in the step (4), the drying is finished under the vacuum condition, and the drying temperature is 30-100 ℃.
10. The method for preparing the flame-retardant composite separator according to claim 6, characterized in that: in the step (5), the temperature of the hot pressing treatment is 50-100 ℃.
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| CN202210569895.5A CN114914629A (en) | 2022-05-24 | 2022-05-24 | Flame-retardant composite diaphragm and preparation method and application thereof |
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| CN202210569895.5A CN114914629A (en) | 2022-05-24 | 2022-05-24 | Flame-retardant composite diaphragm and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742733A (en) * | 2016-03-01 | 2016-07-06 | 湖南立方新能源科技有限责任公司 | Method for enhancing safety of lithium-ion battery |
| CN109473603A (en) * | 2017-09-07 | 2019-03-15 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof and lithium battery |
| CN109873108A (en) * | 2019-03-12 | 2019-06-11 | 芜湖天弋能源科技有限公司 | A kind of fire-retardant diaphragm of lithium ion battery and preparation method thereof |
| CN111987275A (en) * | 2020-09-01 | 2020-11-24 | 厦门大学 | Preparation method and preparation device of lithium ion battery diaphragm |
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2022
- 2022-05-24 CN CN202210569895.5A patent/CN114914629A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105742733A (en) * | 2016-03-01 | 2016-07-06 | 湖南立方新能源科技有限责任公司 | Method for enhancing safety of lithium-ion battery |
| CN109473603A (en) * | 2017-09-07 | 2019-03-15 | 比亚迪股份有限公司 | Battery diaphragm and preparation method thereof and lithium battery |
| CN109873108A (en) * | 2019-03-12 | 2019-06-11 | 芜湖天弋能源科技有限公司 | A kind of fire-retardant diaphragm of lithium ion battery and preparation method thereof |
| CN111987275A (en) * | 2020-09-01 | 2020-11-24 | 厦门大学 | Preparation method and preparation device of lithium ion battery diaphragm |
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