CN114069154A - Lithium battery coating diaphragm and preparation method thereof - Google Patents

Lithium battery coating diaphragm and preparation method thereof Download PDF

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CN114069154A
CN114069154A CN202111168746.XA CN202111168746A CN114069154A CN 114069154 A CN114069154 A CN 114069154A CN 202111168746 A CN202111168746 A CN 202111168746A CN 114069154 A CN114069154 A CN 114069154A
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solution
preparation
diaphragm
lithium battery
coating
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康卫民
隗立颖
程博闻
邓南平
丁玲
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Tianjin Polytechnic University
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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
    • 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
    • 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
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M50/431—Inorganic material
    • 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
    • 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a lithium battery coating diaphragm and a preparation method thereof. The coated membrane comprises a membrane substrate and a coating material, wherein the coating material comprises ZnF2The composite material comprises/ZnS heterostructure doped porous carbon nanofiber and a binder. The preparation method of the coating diaphragm comprises the following steps: 1) mixing solution of polyvinyl pyrrolidone, zinc acetate and polytetrafluoroethylene emulsionConfiguring; 2) electrostatic melt-blown spinning; 3) pre-oxidizing the prepared nascent fiber membrane; 4) carrying out hydrothermal reaction on the nano-fibers subjected to the pre-oxidation treatment; 5) carbonizing the nano-fibers after the hydrothermal reaction; 6) ZnF obtained after carbonization2And uniformly mixing the porous carbon nanofiber doped with the/ZnS heterostructure and a binder to prepare slurry and coating the slurry on the surface of the diaphragm. The coating diaphragm provided by the invention can effectively inhibit the growth of lithium dendrite in the lithium secondary battery, improves the safety performance of the battery and has important application prospect.

Description

Lithium battery coating diaphragm and preparation method thereof
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a lithium battery coating diaphragm and a preparation method thereof.
Background
Due to the rapid growth of personal electronic products, electric vehicles, energy storage systems, and the like, high-capacity rechargeable batteries such as lithium ion batteries, lithium oxygen batteries, and lithium sulfur batteries have received much attention from researchers. As an ideal final negative electrode material for lithium secondary batteries, lithium metal has numerous advantages, such as ultrahigh theoretical specific capacity (3860mAh g)-1) And the lowest redox electrochemical potential (-3.04V vs standard hydrogen electrode). However, severe volume expansion and uncontrolled lithium dendrite growth have hindered practical application of lithium metal anodes. In general, the growth of lithium dendrites is mainly caused by the non-uniformity of the spatial distribution of lithium ions across the electrode surface, the generation of which has a severe impact on battery life and safety. First, the high surface area of the lithium dendrites accelerates the consumption of lithium and electrolyte, resulting in a reduction in battery active material and a reduction in coulombic efficiency. At the same time, the growth of lithium dendrites also causes the production of "dead" lithium, resulting in an increase in the internal resistance of the battery. More seriously, lithium dendrites are highly apt to pierce the separator to cause short-circuiting of the battery. Therefore, it is very necessary to suppress the growth of lithium dendrites to improve the electrochemical performance and safety of the lithium secondary battery.
The separator, which is one of the basic and critical components of the battery, has a direct influence on the safety of the battery. The separator serves to separate the positive and negative electrodes, prevent electrons from freely passing through the battery, and allow ions in the electrolyte to freely pass between the positive and negative electrodes. The separators commonly used in lithium secondary batteries are polypropylene, polyethylene, and a composite of the two, and these polyolefin separators have been widely used due to their advantages of low cost, chemical stability, and high porosity. However, polyolefin separators also have inherent disadvantages such as poor thermal stability and low electrolyte wettability. In addition, the polyolefin separator hardly suppresses the growth of lithium dendrites in the lithium negative electrode, which eventually leads to a series of problems such as poor cycle stability and low rate performance of the battery.
In recent years, more and more researchers have inhibited the growth of lithium dendrites by modifying the separator. Studies have shown that the insertion of a functional interlayer between the separator and the lithium negative electrode can accommodate volume expansion and mitigate lithium dendrite growth during lithium plating/stripping. Among them, a three-dimensional carbon material having a nanostructure, such as carbon nanofiber, has been proven to be a promising material, and a 3D network structure having a large specific surface area can provide abundant ion paths and reduce local current density, thereby achieving a uniform flow of lithium ions and inhibiting growth of lithium dendrites. For example, Wang (Z.Wang, X.Wang, W.Sun, K.Sun, Dendrite-Free Lithium metals in High Performance Lithium-Sulfur Batteries with biofunctional Carbon Nanofiber Interlayers, electrochemical. acta.252(2017) 127-. Although the carbon nanofibers have made great progress in improving the stability of the lithium negative electrode, the action mechanism is based on physical regulation and the interaction with lithium ions is weak, so that the practical application of the carbon material still faces challenges, especially in a long-cycle process. Therefore, the development of a novel lithium secondary battery separator is one of the keys to improving the battery performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a lithium battery coating diaphragm and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the lithium battery coating diaphragm and the preparation method thereof are provided, and the preparation method comprises the following steps:
(1) preparation of spinning solution: dissolving 12-20% of polyvinylpyrrolidone in deionized water; slowly adding zinc acetate with the mass fraction of 6-10% into a polyvinylpyrrolidone aqueous solution, and stirring for 12 hours at normal temperature to obtain a mixed solution; and finally, adding 10-18 g of polytetrafluoroethylene emulsion into the mixed solution, and continuously stirring for 6 hours to obtain a spinning solution.
(2) Electrostatic melt-blown spinning: transferring the prepared spinning solution into a stainless steel nozzle with the inner diameter of 0.6-1.4 mm, and applying a certain air flow to the stainless steel nozzle, wherein the air flow pressure is 0.06-0.14 Mpa, and the spinning voltage is 20-40 kV; preparing the polyvinylpyrrolidone/zinc acetate/polytetrafluoroethylene nascent fiber.
(3) Pre-oxidation treatment: and (3) placing the prepared nascent fiber into a muffle furnace, heating to 200-280 ℃ at a heating rate of 2 ℃/min in an air atmosphere, preserving heat for 3h, and then cooling to room temperature.
(4) Hydrothermal reaction: dissolving 2-4% by mass of zinc acetate in deionized water, and placing a film subjected to pre-oxidation in an amount of 8-16% by mass into the solution to be stirred, wherein the solution is counted as a solution A; then adding an 18-26% dimethyl imidazole aqueous solution into the solution A to obtain a solution B; finally, adding a 10-14% water/ethanol mixed solution of thioacetamide into the solution B to obtain a solution C; and finally, transferring the mixed solution C into a hydrothermal reaction kettle, reacting for 6-14 h at 180 ℃, filtering the product after reaction for several times by using deionized water and absolute ethyl alcohol, and drying.
(5) Carbonizing: putting a sample obtained after the hydrothermal reaction into a tubular furnace, heating to 500-700 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, preserving heat for 2 hours, and then cooling to room temperature to obtain ZnF2the/ZnS heterostructure doped porous carbon nanofiber.
(6) Preparing and coating slurry: ZnF with the mass ratio of 2: 1-4: 12Uniformly mixing porous carbon nanofiber doped with a/ZnS heterostructure and a polyvinylidene fluoride adhesive, adding a certain amount of N-methyl pyrrolidone, fully stirring to prepare slurry, coating the slurry on a commercial diaphragm by using a scraper, and finally placing the coated diaphragm in an oven at 60 ℃ for vacuum drying for 24 hours.
Drawings
FIG. 1 shows ZnF of an embodiment of the present invention2Scanning electron microscope photos of/ZnS heterostructure doped porous carbon nanofibers.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
Example 1
A lithium battery coating diaphragm and a preparation method thereof are realized by the following steps in sequence:
(1) preparation of spinning solution: dissolving polyvinylpyrrolidone with the mass fraction of 12% in deionized water; slowly adding zinc acetate with the mass fraction of 6% into the polyvinylpyrrolidone aqueous solution, and stirring for 12 hours at normal temperature to obtain a mixed solution; and finally, adding 10g of polytetrafluoroethylene emulsion into the mixed solution, and continuously stirring for 6 hours to obtain a spinning solution.
(2) Electrostatic melt-blown spinning: transferring the prepared spinning solution into a stainless steel nozzle with the inner diameter of 0.6mm, and applying certain airflow to the stainless steel nozzle, wherein the airflow pressure is 0.06MPa, and the spinning voltage is 20 kV; preparing the polyvinylpyrrolidone/zinc acetate/polytetrafluoroethylene nascent fiber.
(3) Pre-oxidation treatment: and (3) putting the prepared nascent fiber into a muffle furnace, heating to 200 ℃ at the heating rate of 2 ℃/min in the air atmosphere, preserving the heat for 3h, and then cooling to the room temperature.
(4) Hydrothermal reaction: dissolving 2% by mass of zinc acetate in deionized water, placing the film subjected to pre-oxidation in a mass fraction of 8% in the solution, and stirring to obtain a solution A; then adding 18% dimethyl imidazole water solution into the solution A to obtain solution B; finally, adding a 10% water/ethanol mixed solution of thioacetamide into the solution B to obtain a solution C; and finally, transferring the mixed solution C into a hydrothermal reaction kettle to react for 6 hours at 180 ℃, filtering the product after the reaction for a plurality of times by using deionized water and absolute ethyl alcohol, and drying.
(5) Carbonizing: putting a sample obtained after the hydrothermal reaction into a tubular furnace, heating to 500 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, preserving heat for 2h, and then cooling to room temperature to obtain ZnF2the/ZnS heterostructure doped porous carbon nanofiber.
(6) Preparing and coating slurry: ZnF with the mass ratio of 2: 1 is added2Uniformly mixing porous carbon nanofiber doped with a/ZnS heterostructure and a polyvinylidene fluoride adhesive, adding a certain amount of N-methyl pyrrolidone, fully stirring to prepare slurry, coating the slurry on a commercial diaphragm by using a scraper, and finally placing the coated diaphragm in an oven at 60 ℃ for vacuum drying for 24 hours. .
Example 2
(1) Preparation of spinning solution: dissolving 14% of polyvinylpyrrolidone in deionized water: slowly adding 7% by mass of zinc acetate into the polyvinylpyrrolidone aqueous solution, and stirring for 12 hours at normal temperature to obtain a mixed solution; and finally, adding 12g of polytetrafluoroethylene emulsion into the mixed solution, and continuously stirring for 6 hours to obtain a spinning solution.
(2) Electrostatic melt-blown spinning: transferring the prepared spinning solution to a stainless steel nozzle with the inner diameter of 0.8mm, and applying certain airflow to the stainless steel nozzle, wherein the airflow pressure is 0.08Mpa, and the spinning voltage is 25 kV; preparing the polyvinylpyrrolidone/zinc acetate/polytetrafluoroethylene nascent fiber.
(3) Pre-oxidation treatment: and (3) putting the prepared nascent fiber into a muffle furnace, heating to 220 ℃ at a heating rate of 2 ℃/min in an air atmosphere, preserving heat for 3h, and then cooling to room temperature.
(4) Hydrothermal reaction: dissolving 2.5% by mass of zinc acetate in deionized water, placing a film which is pre-oxidized and 10% by mass of zinc acetate in the solution, and stirring to obtain a solution A; then adding 20% dimethyl imidazole water solution into the solution A to obtain solution B; finally, adding a 11% water/ethanol mixed solution of thioacetamide into the solution B to obtain a solution C; and finally, transferring the mixed solution C into a hydrothermal reaction kettle to react for 8 hours at 180 ℃, filtering the product after the reaction for a plurality of times by using deionized water and absolute ethyl alcohol, and drying.
(5) Carbonizing: putting a sample obtained after the hydrothermal reaction into a tubular furnace, heating to 550 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving heat for 2h, and then cooling to room temperature to obtain ZnF2/ZnS heterostructureDoped porous carbon nanofibers.
(6) Preparing and coating slurry: ZnF with the mass ratio of 2.5: 1 is added2Uniformly mixing porous carbon nanofiber doped with a/ZnS heterostructure and a polyvinylidene fluoride adhesive, adding a certain amount of N-methyl pyrrolidone, fully stirring to prepare slurry, coating the slurry on a commercial diaphragm by using a scraper, and finally placing the coated diaphragm in an oven at 60 ℃ for vacuum drying for 24 hours.
Example 3
(1) Preparation of spinning solution: dissolving polyvinylpyrrolidone with the mass fraction of 16% in deionized water; slowly adding 8% by mass of zinc acetate into the polyvinylpyrrolidone aqueous solution, and stirring for 12 hours at normal temperature to obtain a mixed solution; and finally, adding 14g of polytetrafluoroethylene emulsion into the mixed solution, and continuously stirring for 6 hours to obtain a spinning solution.
(2) Electrostatic melt-blown spinning: transferring the prepared spinning solution into a stainless steel nozzle with the inner diameter of 1.0mm, and applying certain airflow to the stainless steel nozzle, wherein the airflow pressure is 0.10Mpa, and the spinning voltage is 30 kV; preparing the polyvinylpyrrolidone/zinc acetate/polytetrafluoroethylene nascent fiber.
(3) Pre-oxidation treatment: and (3) putting the prepared nascent fiber into a muffle furnace, heating to 240 ℃ at a heating rate of 2 ℃/min in an air atmosphere, preserving heat for 3h, and then cooling to room temperature.
(4) Hydrothermal reaction: dissolving 3% by mass of zinc acetate in deionized water, and placing a pre-oxidized film with the mass fraction of 12% in the solution to be stirred to obtain a solution A; then adding a 22% dimethyl imidazole water solution into the solution A to obtain a solution B; finally, adding a 12% water/ethanol mixed solution of thioacetamide into the solution B to obtain a solution C; and finally, transferring the mixed solution C into a hydrothermal reaction kettle to react for 10 hours at 180 ℃, filtering the product after the reaction for a plurality of times by using deionized water and absolute ethyl alcohol, and drying.
(5) Carbonizing: putting a sample obtained after the hydrothermal reaction into a tubular furnace, heating to 600 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, preserving heat for 2h, and then cooling toAt room temperature to obtain ZnF2the/ZnS heterostructure doped porous carbon nanofiber.
(6) Preparing and coating slurry: ZnF with the mass ratio of 3: 1 is added2Uniformly mixing porous carbon nanofiber doped with a/ZnS heterostructure and a polyvinylidene fluoride adhesive, adding a certain amount of N-methyl pyrrolidone, fully stirring to prepare slurry, coating the slurry on a commercial diaphragm by using a scraper, and finally placing the coated diaphragm in an oven at 60 ℃ for vacuum drying for 24 hours.
Example 4
(1) Preparation of spinning solution: dissolving 18% by mass of polyvinylpyrrolidone in deionized water; slowly adding 9% zinc acetate into the polyvinylpyrrolidone aqueous solution, and stirring for 12h at normal temperature to obtain a mixed solution; and finally, adding 16g of polytetrafluoroethylene emulsion into the mixed solution, and continuously stirring for 6 hours to obtain a spinning solution.
(2) Electrostatic melt-blown spinning: transferring the prepared spinning solution into a stainless steel nozzle with the inner diameter of 1.2mm, and applying certain airflow to the stainless steel nozzle, wherein the airflow pressure is 0.12Mpa, and the spinning voltage is 35 kV; preparing the polyvinylpyrrolidone/zinc acetate/polytetrafluoroethylene nascent fiber.
(3) Pre-oxidation treatment: and (3) putting the prepared nascent fiber into a muffle furnace, heating to 260 ℃ at a heating rate of 2 ℃/min in an air atmosphere, preserving heat for 3h, and then cooling to room temperature.
(4) Hydrothermal reaction: dissolving 3.5% by mass of zinc acetate in deionized water, placing a film which is pre-oxidized and 14% by mass in the solution, and stirring to obtain a solution A; then adding 24% dimethyl imidazole water solution into the solution A to obtain solution B; finally, adding a 13% water/ethanol mixed solution of thioacetamide into the solution B to obtain a solution C; and finally, transferring the mixed solution C into a hydrothermal reaction kettle, reacting for 12 hours at 180 ℃, filtering the product after reaction for a plurality of times by using deionized water and absolute ethyl alcohol, and drying.
(5) Carbonizing: putting a sample obtained after the hydrothermal reaction into a tubular furnace, and heating at a heating rate of 2 ℃/min in a nitrogen atmosphereHeating to 650 ℃, preserving the heat for 2 hours, and then cooling to room temperature to obtain ZnF2the/ZnS heterostructure doped porous carbon nanofiber.
(6) Preparing and coating slurry: ZnF with the mass ratio of 3.5: 1 is added2Uniformly mixing porous carbon nanofiber doped with a/ZnS heterostructure and a polyvinylidene fluoride adhesive, adding a certain amount of N-methyl pyrrolidone, fully stirring to prepare slurry, coating the slurry on a commercial diaphragm by using a scraper, and finally placing the coated diaphragm in an oven at 60 ℃ for vacuum drying for 24 hours.
Example 5
(1) Preparation of spinning solution: dissolving 20% of polyvinylpyrrolidone in deionized water; slowly adding 10% by mass of zinc acetate into the polyvinylpyrrolidone aqueous solution, and stirring for 12 hours at normal temperature to obtain a mixed solution; and finally, adding 18g of polytetrafluoroethylene emulsion into the mixed solution, and continuously stirring for 6 hours to obtain a spinning solution.
(2) Electrostatic melt-blown spinning: transferring the prepared spinning solution into a stainless steel nozzle with the inner diameter of 1.4mm, and applying certain airflow to the stainless steel nozzle, wherein the airflow pressure is 0.14Mpa, and the spinning voltage is 40 kV; preparing the polyvinylpyrrolidone/zinc acetate/polytetrafluoroethylene nascent fiber.
(3) Pre-oxidation treatment: and (3) putting the prepared nascent fiber into a muffle furnace, heating to 280 ℃ at a heating rate of 2 ℃/min in an air atmosphere, preserving heat for 3h, and then cooling to room temperature.
(4) Hydrothermal reaction: dissolving zinc acetate with the mass fraction of 4% in deionized water, placing a film with the mass fraction of 16% after pre-oxidation in the solution, and stirring to obtain a solution A; then adding 26% dimethyl imidazole water solution into the solution A to obtain solution B; finally, adding a 14% water/ethanol mixed solution of thioacetamide into the solution B to obtain a solution C; and finally, transferring the mixed solution C into a hydrothermal reaction kettle to react for 14h at 180 ℃, filtering the product after reaction for a plurality of times by using deionized water and absolute ethyl alcohol, and drying.
(5) Carbonizing: putting a sample obtained after the hydrothermal reaction into a tubular furnace,heating to 700 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, preserving the heat for 2h, and then cooling to room temperature to obtain ZnF2the/ZnS heterostructure doped porous carbon nanofiber.
(6) Preparing and coating slurry: ZnF with the mass ratio of 4: 1 is added2Uniformly mixing porous carbon nanofiber doped with a/ZnS heterostructure and a polyvinylidene fluoride adhesive, adding a certain amount of N-methyl pyrrolidone, fully stirring to prepare slurry, coating the slurry on a commercial diaphragm by using a scraper, and finally placing the coated diaphragm in an oven at 60 ℃ for vacuum drying for 24 hours.

Claims (6)

1. A lithium battery coating diaphragm and a preparation method thereof are characterized in that the preparation of a spinning solution comprises the following specific steps: dissolving 12-20% of polyvinylpyrrolidone in deionized water; slowly adding zinc acetate with the mass fraction of 6-10% into a polyvinylpyrrolidone aqueous solution, and stirring for 12 hours at normal temperature to obtain a mixed solution; and finally, adding 10-18 g of polytetrafluoroethylene emulsion into the mixed solution, and continuously stirring for 6 hours to obtain a spinning solution.
2. The lithium battery coating diaphragm and the preparation method thereof as claimed in claim 1, wherein the specific steps of the electrostatic solution blow spinning are as follows: transferring the prepared spinning solution into a stainless steel nozzle with the inner diameter of 0.6-1.4 mm, and applying a certain air flow to the stainless steel nozzle, wherein the air flow pressure is 0.06-0.14 Mpa, and the spinning voltage is 20-40 kV; preparing the polyvinylpyrrolidone/zinc acetate/polytetrafluoroethylene nascent fiber.
3. The lithium battery coating separator and the preparation method thereof as claimed in claim 2, wherein the pre-oxidation treatment comprises the following specific steps: and (3) placing the prepared nascent fiber into a muffle furnace, heating to 200-280 ℃ at a heating rate of 2 ℃/min in an air atmosphere, preserving heat for 3h, and then cooling to room temperature.
4. The lithium battery coating separator and the preparation method thereof as claimed in claim 3, wherein the hydrothermal reaction comprises the following specific steps: dissolving 2-4% by mass of zinc acetate in deionized water, and placing a film subjected to pre-oxidation in an amount of 8-16% by mass into the solution to be stirred, wherein the solution is counted as a solution A; then adding an 18-26% dimethyl imidazole aqueous solution into the solution A to obtain a solution B; finally, adding a 10-14% water/ethanol mixed solution of thioacetamide into the solution B to obtain a solution C; and finally, transferring the mixed solution C into a hydrothermal reaction kettle, reacting for 6-14 h at 180 ℃, filtering the product after reaction for several times by using deionized water and absolute ethyl alcohol, and drying.
5. The lithium battery coating separator and the method for preparing the same as claimed in claim 4, wherein the carbonization comprises the following steps: putting a sample obtained after the hydrothermal reaction into a tubular furnace, heating to 500-700 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, preserving heat for 2 hours, and then cooling to room temperature to obtain ZnF2the/ZnS heterostructure doped porous carbon nanofiber.
6. The lithium battery coating separator as claimed in claim 5, wherein the slurry is prepared and coated by the following steps: ZnF with the mass ratio of 2: 1-4: 12Uniformly mixing porous carbon nanofiber doped with a/ZnS heterostructure and a polyvinylidene fluoride adhesive, adding a certain amount of N-methyl pyrrolidone, fully stirring to prepare slurry, coating the slurry on a commercial diaphragm by using a scraper, and finally placing the coated diaphragm in an oven at 60 ℃ for vacuum drying for 24 hours.
CN202111168746.XA 2021-10-08 2021-10-08 Lithium battery coating diaphragm and preparation method thereof Pending CN114069154A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784456A (en) * 2022-04-25 2022-07-22 江苏厚生新能源科技有限公司 Porous alumina fiber coated diaphragm and preparation method thereof
CN115000630A (en) * 2022-06-21 2022-09-02 江苏厚生新能源科技有限公司 Flame-retardant carbon fiber lithium ion battery diaphragm and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784456A (en) * 2022-04-25 2022-07-22 江苏厚生新能源科技有限公司 Porous alumina fiber coated diaphragm and preparation method thereof
CN114784456B (en) * 2022-04-25 2023-09-01 江苏厚生新能源科技有限公司 Porous alumina fiber coated diaphragm and preparation method thereof
CN115000630A (en) * 2022-06-21 2022-09-02 江苏厚生新能源科技有限公司 Flame-retardant carbon fiber lithium ion battery diaphragm and preparation method thereof
CN115000630B (en) * 2022-06-21 2023-09-01 江苏厚生新能源科技有限公司 Flame-retardant carbon fiber lithium ion battery diaphragm and preparation method thereof

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