CN114976482A - Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery - Google Patents

Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery Download PDF

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CN114976482A
CN114976482A CN202210462178.2A CN202210462178A CN114976482A CN 114976482 A CN114976482 A CN 114976482A CN 202210462178 A CN202210462178 A CN 202210462178A CN 114976482 A CN114976482 A CN 114976482A
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lithium
sulfur battery
prepolymer
base film
diaphragm
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张强
武鹏
闫崇
温雪飞
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Shanxi Research Institute for Clean Energy of Tsinghua University
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Shanxi Research Institute for Clean Energy of Tsinghua 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/403—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
    • 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)
  • Secondary Cells (AREA)

Abstract

The application discloses a lithium-sulfur battery diaphragm, a preparation method thereof and a lithium-sulfur battery, wherein the lithium-sulfur battery diaphragm comprises a base film and a high molecular polymer loaded on the surface of the base film, and the high molecular polymer comprises one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane. On one hand, oxygen, chlorine and other atoms are introduced together with the high molecular polymer, so that the lithium-sulfur battery diaphragm can realize the adsorption of polysulfide, the shuttle effect of polysulfide is obviously improved, and the utilization rate of active sulfur is improved; on the other hand, the diaphragm modified by the high molecular polymer can effectively improve the wettability of the electrolyte, so that the rapid transmission and uniform distribution of lithium ions are realized, the interface impedance of the electrode is reduced, and the cycle life and the rate capability of the battery are improved.

Description

Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery
Technical Field
The application relates to the technical field of lithium-sulfur batteries, in particular to a lithium-sulfur battery diaphragm, a preparation method of the lithium-sulfur battery diaphragm and a lithium-sulfur battery.
Background
Since the commercial application of the lithium ion battery was realized in the 90 s of the 20 th century, the communication and traffic modes of people are innovated, and the development of portable cameras, mobile phones, notebook computers and recent electric automobiles is promoted. But the mass energy density and power of the energy storage device still cannot meet the future requirement of people for energy storage. As the actual energy density of lithium ion batteries gradually approaches the theoretical attainable limit value, it is imperative to research a novel electrochemical energy storage system with energy density higher than that of lithium ion batteries, and among many energy storage systems replacing lithium ion batteries, lithium sulfur batteries are the next generation battery system which is the most practical and promising at present.
The diaphragm is used as one of key components in a battery system, and plays roles of isolating the positive electrode and the negative electrode and preventing short circuit in the battery. Besides the functions of electronic insulation and mechanical isolation, the diaphragm also has the following characteristics of good chemical and electrochemical stability and capability of resisting the corrosion of electrolyte and electrode materials; good electrolyte wettability and enough liquid absorption and moisture retention capacity; good mechanical property, so as to prevent short circuit caused by piercing of burrs, dendrites or foreign matters; good thermal stability; has certain aperture and porosity, ensures low resistance and high ionic conductivity, and has good permeability to lithium ions.
Lithium-sulfur battery separators, such as porous Polyethylene (PE) and polypropylene (PP) films, are widely used in lithium ion secondary batteries due to their mature fabrication process, low bulk impedance, and excellent chemical stability. In a lithium-sulfur battery system, due to the shuttle effect, the adoption of the conventional polymer diaphragm often results in lower discharge capacity and coulombic efficiency, and the superiority of the lithium-sulfur battery cannot be fully realized.
Disclosure of Invention
The application provides a lithium-sulfur battery diaphragm, a preparation method thereof and a lithium-sulfur battery, and aims to solve the problem that the traditional lithium-sulfur battery diaphragm causes poor cycle performance of the lithium-sulfur battery.
In one aspect, the embodiment of the present application provides a lithium-sulfur battery separator, which includes a base film, and a high molecular polymer loaded on the surface of the base film, where the high molecular polymer includes one or more of polyethylene oxide, polyethylene glycol, dimethyl ether of polyethylene glycol, polyvinyl chloride, and poly 1, 3-dioxolane.
Optionally, the lithium sulfur battery separator has a thickness of 10 to 40 μm, wherein the base film has a thickness of 5 to 20 μm.
In another aspect, an embodiment of the present application provides a method for preparing a lithium sulfur battery separator, including the steps of:
and carrying out self-polymerization reaction on a high-molecular monomer on the surface of the base film to obtain the lithium-sulfur battery diaphragm loaded with a high-molecular polymer, wherein the high-molecular polymer comprises one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane.
Optionally, the self-polymerization reaction comprises: mixing the high molecular monomer with a catalyst or an initiator to obtain a prepolymer; coating the prepolymer on the surface of the base film, and polymerizing under a heating condition.
Alternatively, the self-polymerization reaction of polyethylene oxide comprises: stirring ethylene oxide and a catalyst at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
Optionally, the self-polymerization of the polyethylene glycol comprises: stirring ethylene oxide, ethylene glycol and a catalyst at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
Alternatively, the self-polymerization reaction of the polyethylene glycol dimethyl ether comprises: stirring ethylene oxide, dimethyl ether and a catalyst at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
Optionally, the self-polymerization reaction of polyvinyl chloride comprises: stirring vinyl chloride and a catalyst at 60-70 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 75-85 ℃.
Alternatively, the self-polymerization of the poly 1, 3-dioxolane comprises: stirring 1, 3-dioxolane and an initiator at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
In another aspect, embodiments of the present application provide a lithium-sulfur battery, which includes a sulfur positive electrode, a lithium negative electrode, an electrolyte, and the above-mentioned lithium-sulfur battery separator or the lithium-sulfur battery separator prepared by the above-mentioned method.
In the lithium-sulfur battery diaphragm provided by the application, on one hand, a high molecular polymer (one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane) is loaded on the surface of a base film, and atoms such as oxygen, chlorine and the like are introduced along with the high molecular polymer, so that the diaphragm can realize the adsorption of polysulfide, the shuttle effect of the polysulfide is obviously improved, and the utilization rate of active sulfur is improved; on the other hand, the diaphragm modified by the high molecular polymer can effectively improve the wettability of the electrolyte, so that the rapid transmission and uniform distribution of lithium ions are realized, the interface impedance of the electrode is reduced, and the cycle life and the rate capability of the battery are improved.
The preparation method of the lithium-sulfur battery diaphragm is low in cost, the prepared lithium-sulfur battery diaphragm system is stable, the shuttle effect of polysulfide in the lithium-sulfur battery can be effectively improved, and the wettability of electrolyte can be preferentially improved.
Drawings
Features, advantages and technical effects of exemplary embodiments of the present application will be described below with reference to the accompanying drawings.
Fig. 1 is a schematic structural view of a separator for a lithium sulfur battery of the present application.
In the drawings:
1-a base film; 2-high molecular polymer.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "a plurality" of "one or more" means two or more.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through lists of examples, which examples can be used in various combinations. In various embodiments, the lists are provided as representative groups and should not be construed as exhaustive.
Conventional lithium-sulfur battery separators, such as porous Polyethylene (PE) and polypropylene (PP) films, are widely used in lithium ion secondary batteries due to their mature fabrication process, low bulk impedance, and excellent chemical stability. In a lithium-sulfur battery system, due to the shuttle effect, the adoption of the conventional polymer diaphragm often results in lower discharge capacity and coulombic efficiency, and the superiority of the lithium-sulfur battery cannot be fully realized.
The applicant finds that the overall performance of the lithium-sulfur battery can be effectively improved by reasonably designing and modifying the traditional diaphragm material in a functional manner, such as optimizing the pore structure, introducing electrostatic repulsion to realize specific ion conduction, enhancing the characteristic adsorption effect on polysulfide to improve the redox reaction rate of active substances, and the like, and provides a way for realizing the practicability of the high-energy-density lithium-sulfur battery.
Lithium-sulfur battery diaphragm
The embodiment of the first aspect of the application provides a lithium-sulfur battery diaphragm, which comprises a base film and a high molecular polymer loaded on the surface of the base film, wherein the high molecular polymer comprises one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane.
Polyethylene oxide is a crystalline, thermoplastic, water-soluble polymer with a linear, regular, helical structure. Polyethylene glycol is a high molecular polymer, has good water solubility, good intermiscibility with a plurality of organic components, and excellent lubricity, moisture retention, dispersibility and adhesiveness. The polyethylene glycol dimethyl ether has the advantages of stable chemical property, good thermal stability, small volatilization loss, high boiling point, low freezing point, low vapor pressure and the like, and is an excellent organic solvent. Polyvinyl chloride is a polymer obtained by polymerizing Vinyl Chloride Monomer (VCM) by an initiator such as peroxide and azo compound, or by a radical polymerization mechanism under the action of light and heat. Poly-1, 3-dioxolane is an excellent organic solvent, and is commonly used as a solvent for oils and fats, an extractant, an electrolytic solvent for lithium batteries, and a chlorine-based solvent stabilizer.
In the examples of the present application, high molecular polymers are carried on both upper and lower surfaces of the base film.
In embodiments of the present application, the base film comprises a polyethylene or polypropylene base film.
According to the embodiment of the application, a high molecular polymer (one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane) is attached to the surface of a base membrane, and oxygen, chlorine and other atoms are introduced together with the high molecular polymer, so that the diaphragm can realize the adsorption of polysulfide, the shuttle effect of the polysulfide is obviously improved, and the utilization rate of active sulfur is improved; on the other hand, the diaphragm modified by the high molecular polymer can effectively improve the wettability of the electrolyte, so that the rapid transmission and uniform distribution of lithium ions are realized, the interface impedance of the electrode is reduced, and the cycle life and the rate capability of the battery are improved.
In an embodiment of the present application, the lithium-sulfur battery separator has a thickness of 10 to 40 μm, wherein the base film has a thickness of 5 to 20 μm.
According to the embodiment of the application, the thickness of the upper and lower layers of high molecular polymer is 5-20 μm, and the thickness of the single layer of high molecular polymer is 2.5-10 μm. For example, the thickness of the monolayer polymer is 2.5. mu.m, 3. mu.m, 4. mu.m, 5. mu.m, 6. mu.m, 7. mu.m, 8. mu.m, 9. mu.m, or 10 μm. The thickness of the monolayer polymer may be any combination of the above ranges. The high molecular polymer with the thickness can obviously improve the shuttling effect of polysulfide and improve the utilization rate of active sulfur.
Preparation method of lithium-sulfur battery diaphragm
In a second aspect, the present application provides a method for preparing a lithium-sulfur battery separator, including the following steps:
and carrying out self-polymerization reaction on a high-molecular monomer on the surface of the base film to obtain the lithium-sulfur battery diaphragm loaded with a high-molecular polymer, wherein the high-molecular polymer comprises one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane.
In the examples of the present application, the high molecular monomer refers to a high molecular monomer of the following high molecular polymer: polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane.
According to the embodiment of the application, after the high molecular monomer is subjected to self-polymerization reaction on the base film, the lithium-sulfur battery diaphragm loaded with the high molecular polymer is obtained, and the high molecular polymer is uniformly distributed on the base film and is tightly combined. The thickness of the monolayer high molecular polymer is 2.5-10 μm. For example, the thickness of the monolayer polymer is 2.5. mu.m, 3. mu.m, 4. mu.m, 5. mu.m, 6. mu.m, 7. mu.m, 8. mu.m, 9. mu.m, or 10 μm. The thickness of the monolayer polymer may be any combination of the above ranges.
In embodiments herein, the self-polymerization reaction comprises: mixing the high molecular monomer with a catalyst or an initiator to obtain a prepolymer; coating the prepolymer on the surface of the base film, and polymerizing under a heating condition.
According to the examples herein, the rate of reaction once polymerization occurs is very fast. In the application, the purpose of mixing the high molecular monomer with the catalyst or the initiator to obtain the prepolymer is to prepare the high molecular monomer into slurry with a low conversion rate, and then to continue to complete the polymerization reaction on the base film after the preparation is convenient.
In the examples herein, the self-polymerization reaction of polyethylene oxide comprises: stirring ethylene oxide and a catalyst at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
In some embodiments, the polyethylene oxide modified diaphragm is prepared by ring-opening polymerization of ethylene oxide under the action of a heterogeneous catalyst, and is divided into two stages, wherein in the first stage, high-molecular monomer ethylene oxide and the corresponding catalyst are stirred at 10-20 ℃, in the second stage, a prepolymer is coated on the surface of a base film, and the polymerization temperature in the second stage is controlled at 35-40 ℃.
In embodiments herein, the self-polymerization reaction of polyethylene glycol comprises: stirring ethylene oxide, ethylene glycol and a catalyst at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
In some embodiments, the polyethylene glycol modified membrane is prepared by performing consecutive condensation on ethylene glycol and ethylene oxide to obtain polyethylene glycol, the polyethylene glycol is divided into two stages, the first stage is to stir high-molecular monomer ethylene oxide, ethylene glycol and corresponding catalysts at 10-20 ℃, the second stage is to coat the prepolymer on the surface of a base membrane, and the polymerization temperature of the second stage is controlled at 35-40 ℃.
In embodiments herein, the self-polymerization reaction of dimethyl ethers of polyethylene glycol comprises: stirring ethylene oxide, dimethyl ether and a catalyst at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
In some embodiments, the polyethylene glycol dimethyl ether modified membrane is prepared by directly preparing ethylene oxide and dimethyl ether under the action of a catalyst and is divided into two stages, wherein in the first stage, high-molecular monomer ethylene oxide, dimethyl ether and the corresponding catalyst are stirred at 10-20 ℃, in the second stage, a prepolymer is coated on the surface of a base membrane, and the polymerization temperature in the second stage is controlled at 35-40 ℃.
In embodiments of the present application, the self-polymerization reaction of polyvinyl chloride comprises: stirring vinyl chloride and a catalyst at 60-70 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 75-85 ℃.
In some embodiments, the polyvinyl chloride modified membrane is divided into two stages, wherein in the first stage, high-molecular monomer vinyl chloride and a corresponding catalyst are intensively stirred at 60-70 ℃, in the second stage, a prepolymer is coated on the surface of a base membrane, and the polymerization temperature in the second stage is controlled to be about 80 ℃.
In the examples of the present application, the self-polymerization of poly 1, 3-dioxolane comprises: stirring 1, 3-dioxolane and an initiator at 10-20 ℃ to obtain a prepolymer; coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
In some embodiments, the 1, 3-dioxolane modified membrane is prepared by a poly-1, 3-dioxolane modified membrane, and the initiator triggers the 1, 3-dioxolane ring-opening polymerization, and is divided into two stages, wherein in the first stage, the 1, 3-dioxolane as a high molecular monomer and the corresponding initiator are stirred at 10-20 ℃, in the second stage, the prepolymer is coated on the surface of a base membrane, and the polymerization temperature in the second stage is controlled at 35-40 ℃.
According to the embodiment of the application, the method for preparing the lithium-sulfur battery diaphragm can be used for preparing the lithium-sulfur battery diaphragm of the embodiment of the first aspect, and the obtained lithium-sulfur battery diaphragm is stable in system, can effectively improve the shuttling effect of polysulfide in a lithium-sulfur battery, and can also preferably improve the wettability of an electrolyte.
Lithium-sulfur battery
In a third aspect of the present application, there is provided a lithium-sulfur battery, including a sulfur positive electrode, a lithium negative electrode, an electrolyte, and the lithium-sulfur battery separator provided in the first aspect of the present application or the lithium-sulfur battery separator prepared by the method provided in the second aspect of the present application.
In some embodiments, the sulfur positive electrode of the lithium sulfur battery employs a carbon material composite system, a polymer composite system, or a metal compound composite system.
In some embodiments, the electrolyte system adopts 1, 3-dioxolane/glycol dimethyl ether with the volume ratio of 1 (0.1-10).
In some embodiments, the lithium salt in the electrolyte is bis (trifluoromethyl) sulfonyl imide lithium, and the concentration of the lithium salt is 1.0-3.0 mol/L.
The lithium-sulfur battery containing the lithium-sulfur battery diaphragm can realize rapid transmission and uniform distribution of lithium ions, can reduce the interface impedance of an electrode, has good cycle life and rate capability, and is expected to be applied to rechargeable batteries of portable electronic products, electric tools, electric automobiles and the like.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrative only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1
The embodiment provides a lithium-sulfur battery diaphragm, and a preparation method of the lithium-sulfur battery diaphragm comprises the following steps:
a method for preparing polyethylene oxide modified diaphragm, preparing high molecular polymerization monomer ethylene oxide, aldehyde content is less than 30ppm, water content is less than 100ppm, and catalyst, stirring and polymerizing ethylene oxide in 20L enamel kettle. And (3) pre-polymerizing at the temperature of 10-20 ℃ for 1 hour, and then coating the pre-polymer on the surface of the single-layer polyolefin diaphragm in a suspension coating, coating and other ways, wherein the polymerization temperature is 35-40 ℃ and the polymerization time is 4 hours. Finally, the thickness of the composite diaphragm is measured to be 10-40 mu m.
Example 2
The embodiment provides a lithium-sulfur battery separator, and a preparation method thereof comprises the following steps:
a process for preparing polyethylene glycol modified diaphragm includes such steps as preparing high-molecular polymerized monomer (epoxy ethane, aldehyde content less than 30ppm, water content less than 100 ppm), glycol and catalyst, and stirring polymerizing in 20L enamel reactor. And (3) pre-polymerizing at the temperature of 10-20 ℃ for 1 hour, and then coating the pre-polymer on the surface of the single-layer polyolefin diaphragm in a suspension coating, coating and other ways, wherein the polymerization temperature is 35-40 ℃ and the polymerization time is 4 hours. Finally, the thickness of the composite diaphragm is measured to be 10-40 mu m.
Example 3
The embodiment provides a lithium-sulfur battery separator, and a preparation method thereof comprises the following steps:
a process for preparing the modified polyethylene glycol dimethyl ether diaphragm includes such steps as preparing high-molecular epoxy ethane monomer whose aldehyde content is less than 30ppm and water content is less than 100ppm, dimethyl ether and catalyst, and stirring in 20-L enamel reactor for polymerizing. And (3) pre-polymerizing at the temperature of 10-20 ℃ for 1 hour, and then coating the pre-polymer on the surface of the single-layer polyolefin diaphragm in a suspension coating, coating and other ways, wherein the polymerization temperature is 35-40 ℃ and the polymerization time is 4 hours. And finally measuring the thickness of the composite diaphragm to be 10-40 mu m.
Example 4
The embodiment provides a lithium-sulfur battery separator, and a preparation method thereof comprises the following steps:
the preparation method of polyvinyl chloride modified diaphragm is characterized by that it prepares high-molecular polymerization monomer vinyl chloride and catalyst, and makes them undergo the process of stirring polymerization in 20L enamel still. And (3) pre-polymerizing at the temperature of 60-70 ℃ for 1 hour, and then coating the pre-polymer on the surface of the single-layer polyolefin diaphragm in a suspension coating, coating and other ways, wherein the polymerization temperature is 80 ℃ and the polymerization time is 4 hours. Finally, the thickness of the composite diaphragm is measured to be 10-40 mu m.
Example 5
The embodiment provides a lithium-sulfur battery separator, and a preparation method thereof comprises the following steps:
the preparation method of the poly 1, 3-dioxolane modified diaphragm comprises the steps of preparing a high polymer monomer 1, 3-dioxolane and a catalyst, and carrying out stirring polymerization in a 20-liter enamel kettle. And (3) pre-polymerizing at the temperature of 10-20 ℃ for 1 hour, and then coating the pre-polymer on the surface of the single-layer polyolefin diaphragm in a suspension coating, coating and other ways, wherein the polymerization temperature is 35-40 ℃ and the polymerization time is 4 hours. Finally, the thickness of the composite diaphragm is measured to be 10-40 mu m.
Comparative example
Comparative example 1
The present comparative example provides a single layer polypropylene lithium sulfur battery separator.
The separators of examples 1 to 5 and comparative example 1 were assembled into a lithium sulfur pouch cell using 4mg/cm 2 Sulfur surface loaded sulfur-carbon positive electrode wherein sulfur: carbon black: PVDF (polyvinylidene fluoride) is 75:15:10, the negative electrode is metallic lithium, and the dosage ratio of electrolyte DOL/DME is 1: 1, 1mol/L LiTFSI, and the steps of packaging, standing, formation, aging, secondary packaging, pre-circulation and the like are carried out to obtain the battery to be tested, wherein the test result is shown in Table 1.
TABLE 1 test results of examples 1-5 and comparative example 1
Figure BDA0003622530160000091
Comparing the capacity retention rate after 200 cycles, the data of examples 1-6 have higher charging capacity in a fixed time, and the capacity retention rate after 200 cycles is higher.
While the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims (10)

1. The lithium-sulfur battery diaphragm is characterized by comprising a base film and a high molecular polymer loaded on the surface of the base film, wherein the high molecular polymer comprises one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane.
2. The lithium sulfur battery separator according to claim 1, wherein the thickness of the lithium sulfur battery separator is 10 to 40 μm, and wherein the thickness of the base film is 5 to 20 μm.
3. A preparation method of a lithium-sulfur battery diaphragm is characterized by comprising the following steps:
and carrying out self-polymerization reaction on a high-molecular monomer on the surface of the base film to obtain the lithium-sulfur battery diaphragm loaded with a high-molecular polymer, wherein the high-molecular polymer comprises one or more of polyethylene oxide, polyethylene glycol dimethyl ether, polyvinyl chloride and poly 1, 3-dioxolane.
4. The method of preparing the lithium-sulfur battery separator according to claim 3, wherein the self-polymerization reaction comprises:
mixing the high molecular monomer with a catalyst or an initiator to obtain a prepolymer;
coating the prepolymer on the surface of the base film, and polymerizing under a heating condition.
5. The method of manufacturing a lithium sulfur battery separator according to claim 3, wherein the self-polymerization reaction of polyethylene oxide comprises:
stirring ethylene oxide and a catalyst at 10-20 ℃ to obtain a prepolymer;
coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
6. The method of preparing the lithium-sulfur battery separator according to claim 3, wherein the self-polymerization reaction of the polyethylene glycol comprises:
stirring ethylene oxide, ethylene glycol and a catalyst at 10-20 ℃ to obtain a prepolymer;
coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
7. The method for preparing the separator for the lithium-sulfur battery according to claim 3, wherein the self-polymerization reaction of the dimethyl ether of polyethylene glycol comprises:
stirring ethylene oxide, dimethyl ether and a catalyst at 10-20 ℃ to obtain a prepolymer;
coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
8. The method of claim 3, wherein the self-polymerization of the polyvinyl chloride comprises:
stirring chloroethylene and a catalyst at the temperature of 60-70 ℃ to obtain a prepolymer;
and coating the prepolymer on the surface of a base film, and polymerizing at 75-85 ℃.
9. The method of claim 3, wherein the self-polymerization of the poly 1, 3-dioxolane comprises:
stirring 1, 3-dioxolane and an initiator at 10-20 ℃ to obtain a prepolymer;
coating the prepolymer on the surface of a base film, and polymerizing at 35-40 ℃.
10. A lithium-sulfur battery comprising a sulfur positive electrode, a lithium negative electrode, an electrolyte, and the lithium-sulfur battery separator according to claim 1 or 2 or the lithium-sulfur battery separator prepared by the method according to any one of claims 3 to 9.
CN202210462178.2A 2022-04-28 2022-04-28 Lithium-sulfur battery diaphragm, preparation method thereof and lithium-sulfur battery Pending CN114976482A (en)

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