CN112133873A - Manganese-cobalt oxide modified composite diaphragm and preparation method and application thereof - Google Patents

Manganese-cobalt oxide modified composite diaphragm and preparation method and application thereof Download PDF

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CN112133873A
CN112133873A CN202011021911.4A CN202011021911A CN112133873A CN 112133873 A CN112133873 A CN 112133873A CN 202011021911 A CN202011021911 A CN 202011021911A CN 112133873 A CN112133873 A CN 112133873A
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manganese
cobalt oxide
modified composite
soluble
lithium
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CN112133873B (en
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刘佳
谢海明
丛丽娜
刘军
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Northeast Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0241—Composites
    • H01M8/0243—Composites in the form of mixtures
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention belongs to the technical field of battery materials, and particularly relates to a manganese-cobalt oxide modified composite diaphragm and a preparation method and application thereof. The manganese cobalt oxide modified composite diaphragm provided by the invention comprises a film substrate and a composite diaphragm covered on the surface of the film substrateA porous coating layer; the porous coating comprises nano cage-shaped manganese cobalt oxide, a conductive carbon material and a binder. In the invention, the nanometer cage-shaped manganese cobalt oxide is beneficial to promoting the redox couple reaction kinetic process of redox mediator LiI in the lithium-oxygen battery and improving Li2O2The decomposition efficiency of (a) promotes the cycle efficiency of the battery; can also effectively adsorb I3 ‑Thereby achieving the purpose of inhibiting the shuttle flying effect in the lithium-oxygen battery, improving the cycle stability of the battery and prolonging the service life of the battery; the conductive carbon can provide an electron conductive channel for the manganese-cobalt oxide, improve the conductivity and the lithium ion mobility, and ensure the I trapped by the manganese-cobalt oxide3 ‑And (4) reusing.

Description

Manganese-cobalt oxide modified composite diaphragm and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a manganese-cobalt oxide modified composite diaphragm and a preparation method and application thereof.
Background
The lithium-oxygen battery is a novel electrochemical energy storage system which takes electrochemical synthesis and decomposition of lithium peroxide as a main reaction mechanism and has ultrahigh theoretical energy density (11400 Wh-kg)-1) Has extremely high application prospect. However, the intrinsic reaction kinetics of the decomposition process of lithium peroxide is delayed due to the self insulation property of the lithium peroxide and insolubility of the lithium peroxide with an organic solvent, so that the battery has the defects of high overpotential, low cycle performance, limited rate performance and the like, and the practical application of the lithium-oxygen battery is severely restricted.
In recent years, although the addition of solid-phase catalysts is thought to improve the kinetics, a great deal of research has found that solid-phase catalysts have difficulty in maintaining high catalytic capacity over many cycles of the cell, which is directly related to the coverage of their active sites by lithium peroxide. The development of redox mediators is thought to completely avoid this problem, and by effectively transferring the charge transport at the solid/solid interface to that at the liquid/solid interface, the interfacial charge penetration resistance of the oxygen electrode can be reduced, and the catalytic reaction can be promoted to proceed continuously, thereby achieving the purpose of reducing the polarization phenomenon of the battery and prolonging the cycle life of the battery.
Currently, lithium iodide (LiI) is used as a redox mediator, and much attention is paid to the most suitable redox potential pair, and the action mechanism is as follows: i is-Losing electrons and oxidizing them to I3 -Or I2，I3 -Or I2Free between the electrode surface and the lithium peroxide by the electrolyteShuttling, effectively promoting lithium peroxide decomposition (Li)2O2+I3 -→O2+I-+Li+Or 3I2+Li2O2→2Li++2I3 -+O2). However, soluble I3 -Or I2Inevitably, the lithium ion battery anode can migrate from the anode to the surface of the lithium cathode to generate side reaction with the lithium anode, so that the continuous consumption of LiI and the continuous corrosion of metallic lithium are caused, namely the shuttle flying effect is generated; in addition, theoretically, the reaction kinetics of promoting the redox couple conversion of LiI is also beneficial to the decomposition reaction process of lithium peroxide and to improve the decomposition of lithium peroxide, but a strategy for catalyzing the redox mediator couple conversion kinetics is still lacking so far.
The method has the advantages of inhibiting the shuttle flying effect, improving the conversion kinetics of the redox mediator, and having important significance for prolonging the service life of the lithium-oxygen battery and improving the cycle performance of the lithium-oxygen battery.
Disclosure of Invention
In view of the above, the present invention provides a manganese-cobalt oxide modified composite separator, which can effectively inhibit the "shuttle effect" in a lithium-oxygen battery, and improve the kinetic conversion of the redox couple of redox mediator lithium iodide, and improve the decomposition efficiency of lithium peroxide, thereby improving the lifetime of the lithium-oxygen battery and improving the cycle performance of the lithium-oxygen battery.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a manganese cobalt oxide modified composite diaphragm, which comprises a membrane substrate and a porous coating covering the surface of the membrane substrate; the porous coating comprises nano cage-shaped manganese cobalt oxide, a conductive carbon material and a binder.
Preferably, the mass ratio of the nano cage-shaped manganese cobalt oxide to the conductive carbon material to the binder is (0.1-2): (0.1-2): 1.
preferably, the conductive carbon material comprises one or more of acetylene black, porous carbon, graphene and carbon nanotubes; the binder comprises one or more of polytetrafluoroethylene, styrene butadiene rubber, polyvinylidene fluoride and carboxymethyl cellulose.
Preferably, the thickness of the porous coating is 5-20 μm.
The invention also provides a preparation method of the manganese cobalt oxide modified composite diaphragm, which comprises the following steps:
mixing nano cage-shaped manganese cobalt oxide, a conductive carbon material, a binder and an organic solvent to obtain a coating suspension;
and coating the coating suspension liquid on one surface of the film substrate, and drying to obtain the manganese cobalt oxide modified composite diaphragm.
Preferably, the preparation method of the nano cage-shaped manganese cobalt oxide comprises the following steps:
mixing a soluble manganese source, polyvinylpyrrolidone, deionized water and absolute ethyl alcohol to obtain a manganese-containing solution;
and mixing the manganese-containing solution and a soluble cobalt source, carrying out precipitation reaction, and sequentially carrying out primary drying and heat treatment on the obtained precipitate to obtain the nano cage-shaped manganese-cobalt oxide.
Preferably, the soluble manganese source comprises manganese acetate tetrahydrate, manganese acetate tetrahydrate or manganese nitrate; the soluble cobalt source comprises potassium hexacyanocobaltate, sodium hexacyanocobaltate or zinc hexacyanocobaltate.
Preferably, the molar ratio of the soluble manganese source to the soluble cobalt source is (0.1-10): 1.
preferably, the K value of the polyvinylpyrrolidone is 25-90.
The invention also provides the application of the manganese-cobalt oxide modified composite diaphragm in the technical scheme or the manganese-cobalt oxide modified composite diaphragm prepared by the preparation method in the technical scheme in a lithium-oxygen battery.
The invention provides a manganese cobalt oxide modified composite diaphragm, which comprises a membrane substrate and a porous coating covering the surface of the membrane substrate; the porous coating comprises nano cage-shaped manganese cobalt oxide, a conductive carbon material and a binder. In the invention, the nanometer cage-shaped manganese cobalt oxide is beneficial to promoting the lithium-oxygen batteryThe dynamic process of redox couple reaction of intermediate redox mediator LiI is improved2O2The decomposition efficiency of (a) promotes the cycle efficiency of the battery; can also effectively adsorb I3 -Thereby achieving the purpose of inhibiting the shuttle flying effect in the lithium-oxygen battery, improving the cycle stability of the battery and prolonging the service life of the battery; the conductive carbon material can provide an electron conductive channel for the manganese-cobalt oxide, improve the conductivity and the lithium ion mobility, and ensure the I trapped by the manganese-cobalt oxide3 -And (4) reusing.
The test result of the embodiment shows that after 500 cycles, the charging voltage of the lithium-oxygen battery obtained by adopting the manganese-cobalt oxide modified composite diaphragm as the diaphragm is only 3.3V vs. Li/Li+High cycle stability and long service life.
Drawings
FIG. 1 is an SEM photograph of nano-cage manganese cobalt oxide obtained in example 1;
FIG. 2 is a TEM photograph of the nanocage manganese cobalt oxide obtained in example 1;
FIG. 3 is a BET test chart of the nanocage manganese cobalt oxide obtained in example 1, wherein an interpolation chart is a pore size distribution chart;
FIG. 4 is an SEM image of a manganese cobalt oxide-modified composite separator obtained in example 1;
FIG. 5 is a photograph of a cross-section of a manganese cobalt oxide-modified composite separator obtained in example 1;
FIG. 6 is a graph of cycle performance for application example 1;
FIG. 7 is a graph of cycling performance for application example 2;
fig. 8 is a graph of cycle performance for comparative example 1.
Detailed Description
The invention provides a manganese cobalt oxide modified composite diaphragm, which comprises a membrane substrate and a porous coating covering the surface of the membrane substrate; the porous coating comprises nano cage-shaped manganese cobalt oxide, a conductive carbon material and a binder.
In the invention, the manganese cobalt oxide modified composite diaphragm comprises a film substrate. In the present invention, the film substrate is preferably Polyethylene (PE) or polypropylene (PP). In the present invention, the thickness of the film substrate is preferably 5 to 40 μm, more preferably 10 to 30 μm, and most preferably 20 μm.
In the present invention, the porous coating layer includes nanocage manganese cobalt oxide, a conductive carbon material, and a binder.
In the invention, the particle size of the nano cage-shaped manganese cobalt oxide is preferably 300-800 nm, and more preferably 400-700 nm; the specific surface area is preferably 60-180 m2(ii)/g, more preferably 80 to 170m2(ii) in terms of/g. In the invention, the nano cage-shaped manganese cobalt oxide is preferably composed of manganese cobalt oxide nanoparticles; the size of the manganese cobalt oxide nanoparticles is preferably 3-20 nm, and more preferably 5-18 nm.
In the present invention, the preparation method of the nanocage manganese cobalt oxide preferably comprises the following steps:
mixing a soluble manganese source, polyvinylpyrrolidone, deionized water and absolute ethyl alcohol to obtain a manganese-containing solution;
and mixing the manganese-containing solution and a soluble cobalt source, carrying out precipitation reaction, and sequentially carrying out primary drying and heat treatment on the obtained precipitate to obtain the nano cage-shaped manganese-cobalt oxide.
The method comprises the step of mixing a soluble manganese source, polyvinylpyrrolidone, deionized water and absolute ethyl alcohol to obtain a manganese-containing solution.
In the present invention, the soluble manganese source preferably comprises manganese acetate tetrahydrate, manganese acetate tetrahydrate or manganese nitrate. In the invention, the K value of the polyvinylpyrrolidone is preferably 25-90, and more preferably 25, 30, 60 or 90. In the invention, the molar ratio of the soluble manganese source to the polyvinylpyrrolidone is preferably (1-100): 1, more preferably (20 to 60): 1. in the invention, the volume ratio of the deionized water to the absolute ethyl alcohol is preferably (0.05-2): 1, more preferably (0.2 to 2): 1. in the invention, the molar ratio of the soluble manganese source to the absolute ethyl alcohol is preferably (0.0005-0.5): 1, more preferably (0.005 to 0.35): 1.
the invention preferably mixes the mixed system composed of the soluble manganese source and the polyvinylpyrrolidone with the solution composed of deionized water and absolute ethyl alcohol; the mixing is preferably carried out under stirring; in the invention, the stirring temperature is preferably room temperature, specifically, 18-40 ℃; the stirring time is not particularly limited, and the manganese-containing solution obtained after mixing is clarified.
After the manganese-containing solution is obtained, the manganese-containing solution and a soluble cobalt source are mixed for precipitation reaction, and the obtained precipitate is sequentially subjected to preliminary drying and heat treatment to obtain the nano cage-shaped manganese cobalt oxide.
In the present invention, the soluble cobalt source preferably comprises potassium hexacyanocobaltate, sodium hexacyanocobaltate or zinc hexacyanocobaltate, more preferably potassium hexacyanocobaltate. In the present invention, the soluble cobalt source is preferably provided in the form of an aqueous solution; the concentration of the water solution of the soluble cobalt source is preferably 0.01-0.8 mol/L, and more preferably 0.1-0.7 mol/L. In the invention, the molar ratio of the soluble manganese source to the soluble cobalt source is preferably (0.1-10): 1, more preferably (1 to 9): 1.
in the invention, the temperature of the precipitation reaction is preferably room temperature, and specifically, 18-40 ℃; the time of the precipitation reaction is preferably 24 h. In the present invention, the precipitation reaction is preferably carried out under a condition of standing. In the present invention, the precipitation reaction forms Mn3[Co(CN)6]2·nH2And (4) O precursor.
In the present invention, the temperature of the preliminary drying is preferably 60 ℃; the time is preferably 2 to 48 hours, and more preferably 10 to 36 hours. In the present invention, the primary drying apparatus is preferably an oven. Before primary drying, the precipitation obtained by the precipitation reaction is preferably washed by water and ethanol in sequence; the water washing and the ethanol washing are not particularly limited, and the unreacted ions adhered to the surface of the precipitate are removed.
In the invention, the temperature of the heat treatment is preferably 90-700 ℃, and more preferably 300-600 ℃; the time is preferably 2 to 72 hours, and more preferably 2 to 24 hours.The heating rate for heating to the heat treatment temperature is preferably 2 to 20 ℃/min, more preferably 4 to 15 ℃/min, and most preferably 5 ℃/min. In the present invention, the atmosphere of the heat treatment is preferably an air atmosphere. In the present invention, the heat treatment apparatus is preferably a muffle furnace. In the present invention, the manganese cobalt oxide has a chemical composition of MnxCo3-xO4Wherein x has a value of 0<x<3; the manganese cobalt oxide is black powder.
In the present invention, the conductive carbon material preferably includes one or more of acetylene black, porous carbon, graphene, and carbon nanotubes. The source of the conductive carbon material in the present invention is not particularly limited, and any one known to those skilled in the art may be used, and specifically, any one known to those skilled in the art may be used.
In the present invention, the binder preferably includes one or more of polytetrafluoroethylene, Styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF), and carboxymethyl cellulose (CMC). The source of the binder is not particularly limited in the present invention, and any known source to those skilled in the art may be used, and specifically, any commercially available source known to those skilled in the art may be used.
In the invention, the mass ratio of the nano cage-shaped manganese cobalt oxide to the conductive carbon material to the binder is preferably (0.1-2): (0.1-2): 1, more preferably (0.5 to 1.5): (0.5-1.5): 1. in the invention, the thickness of the porous coating is preferably 5-20 μm, and more preferably 8-17 μm.
The invention also provides a preparation method of the manganese cobalt oxide modified composite diaphragm, which comprises the following steps:
mixing nano cage-shaped manganese cobalt oxide, a conductive carbon material, a binder and an organic solvent to obtain a coating suspension;
and coating the coating suspension liquid on one surface of the film substrate, and drying to obtain the manganese cobalt oxide modified composite diaphragm.
The invention mixes the nanometer cage manganese cobalt oxide, the conductive carbon material, the binder and the organic solvent to obtain the coating suspension.
According to the invention, the nano cage-shaped manganese cobalt oxide, the conductive carbon material and the binder are preferably mixed, and then the obtained porous coating mixture is mixed with the organic solvent.
In the present invention, the nano cage-shaped manganese cobalt oxide, the conductive carbon material and the binder are the same as the conductive carbon and the binder in the manganese cobalt oxide in the above technical solution, and are not described herein again.
The mixing mode of the nano cage-shaped manganese cobalt oxide, the conductive carbon material and the binder is not particularly limited, and the mixing mode known to those skilled in the art can be adopted, specifically, ball milling is adopted. In the invention, the rotation of the ball mill is preferably 600-3000 rpm, more preferably 1000-2500 rpm; the time is preferably 4 to 48 hours, and more preferably 10 to 36 hours.
In the present invention, the organic solvent is preferably one or more of acetone, N-methylpyrrolidone, and isopropanol.
In the invention, the solid content of the coating suspension is preferably 25-75%, and more preferably 35-65%.
The mixing method of the porous coating mixture and the solvent is not particularly limited in the present invention, and the mixing method known to those skilled in the art may be adopted, specifically, stirring. In the invention, the stirring speed is preferably 100-500 rpm, more preferably 150-450 rpm; the time is preferably 2 to 8 hours, and more preferably 3 to 7 hours.
After the coating suspension liquid is obtained, the coating suspension liquid is coated on one surface of the film substrate, and the coating suspension liquid is dried to obtain the manganese cobalt oxide modified composite diaphragm.
In the present invention, the film substrate is preferably Polyethylene (PE) or polypropylene (PP). In the present invention, the thickness of the film substrate is preferably 20 μm.
In the invention, the coating amount of the coating suspension on one side of the film substrate is preferably 0.9-1.1 mg/cm2More preferably 0.95 to 1.05mg/cm2. In the present invention, the coating is preferably performed by a dip coating method, a blade coating method, or a spray coating method.
In the invention, the drying temperature is preferably 50-100 ℃, and more preferably 60-90 ℃; the time is preferably 2 to 48 hours, and more preferably 5 to 24 hours.
The invention also provides the application of the manganese-cobalt oxide modified composite diaphragm in the technical scheme or the manganese-cobalt oxide modified composite diaphragm prepared by the preparation method in the technical scheme in a lithium-oxygen battery.
In the present invention, the application preferably includes: and assembling the manganese-cobalt oxide modified composite diaphragm serving as a diaphragm between the anode and the cathode to obtain the lithium-oxygen battery. In the present invention, the method for preparing the positive electrode (oxygen electrode) of the lithium-oxygen battery preferably includes the steps of: mixing porous carbon, polyvinylidene fluoride (PVDF) and N-methyl pyrrolidone (NMP) to obtain anode slurry, and coating the anode slurry on carbon paper to obtain the anode. In the embodiment of the present invention, the mass ratio of the porous carbon and PVDF is preferably 9: 1. the amount of NMP used in the present invention is not particularly limited, and those known to those skilled in the art can be used. The carbon paper is not particularly limited, and the carbon paper known by the technicians in the field can be adopted, specifically, the thickness of the carbon paper is preferably 0.20-0.22 mm, and more preferably 0.205-0.215 mm; the density is preferably 0.83g/cm3(ii) a The resistivity is preferably 5.5 m.OMEGA.cm2(ii) a Preferred bending radius>15 cm. In the invention, the coating amount of the slurry on the carbon paper is preferably 0.1-1.2 mg/cm2More preferably 0.5 to 1mg/cm2。
In the present invention, the negative electrode (counter electrode) of the lithium-oxygen battery is a lithium sheet.
In the invention, the electrolyte of the lithium-oxygen battery is preferably a lithium bis (trifluoromethyl) sulfonimide (LiTFSI) organic electrolyte containing LiI; the organic solvent in the electrolyte is preferably triethylene glycol dimethyl ether (TEGDME). The concentration of the electrolyte is not particularly limited in the present invention, and the electrolyte concentration known to those skilled in the art may be used.
In order to further illustrate the present invention, the manganese cobalt oxide modified composite separator and the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing 0.22g of manganese acetate tetrahydrate and 1.5g of polyvinylpyrrolidone K30, adding 90mL of a mixed solution of deionized water and absolute ethyl alcohol (the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution is 0.5: 1), and stirring at room temperature to obtain a clear manganese-containing solution; mixing the obtained manganese-containing solution with 60mL of potassium hexacyanocobaltate aqueous solution with the concentration of 0.008mol/L, standing at room temperature for precipitation reaction for 24 hours to obtain white precipitate, washing the obtained precipitate with water and ethanol in sequence, primarily drying in a 60 ℃ oven for 8 hours, and then transferring to a muffle furnace for heat treatment at 400 ℃ for 2 hours to obtain black nano cage-shaped manganese cobalt oxide;
and (3) mixing the obtained nano cage-shaped manganese cobalt oxide, porous carbon and PVDF according to a mass ratio of 3: 4: 3, mixing, and performing ball milling for 8 hours at the rotating speed of 850rpm to obtain a porous coating mixture; stirring 10g of the porous coating mixture and 20g of NMP for 8 hours at 350rpm to obtain a coating suspension;
coating one side of the obtained coating suspension liquid on the surface of a PE film with the thickness of 20 mu m, wherein the coating amount of the coating suspension liquid on the PE film is 0.9-1.1 mg/cm2And placing the PE film coated with the coating suspension in a vacuum drying oven, and drying at 70 ℃ for 12h to obtain the manganese-cobalt oxide modified composite diaphragm.
Scanning electron microscope tests are carried out on the nano cage-shaped manganese cobalt oxide obtained in example 1, and the SEM image is shown in figure 1. As can be seen from fig. 1, the manganese cobalt oxide obtained in the present example has a cubic structure in which a large number of primary particles of several tens of nanometers are deposited.
The nanocage manganese cobalt oxide obtained in example 1 was subjected to transmission electron microscopy and the TEM image obtained is shown in FIG. 2. As can be seen from FIG. 2, the manganese cobalt oxide obtained in this example has a three-dimensional hollow nanocage-like micro-morphology with an edge length of about 300 nm.
The nano cage manganese cobalt oxide obtained in example 1 was subjected to BET test, and the BET test pattern obtained is shown in fig. 3, wherein the inset in fig. 3 is a pore size distribution diagram. As can be seen from FIG. 3, the manganese cobalt oxide obtained in the present embodiment has a mesoporous structure and a pore size distribution range of 1 to 80 nm.
Scanning electron microscope tests are carried out on the manganese cobalt oxide modified composite diaphragm obtained in example 1, and an SEM image is shown in figure 4. As can be seen from fig. 4, in the manganese cobalt oxide modified composite diaphragm provided by the invention, the manganese cobalt oxide and the porous carbon material are uniformly distributed, and the manganese cobalt oxide still maintains a complete cubic structure.
The cross section of the manganese cobalt oxide modified composite diaphragm obtained in example 1 was subjected to a scanning electron microscope test, and the obtained cross section photograph is shown in fig. 5. As can be seen from fig. 5, the thickness of the porous coating in the manganese cobalt oxide modified composite separator was about 8 μm.
Example 2
Mixing 0.29g of tetrahydrate manganese acetate and 1.5g of polyvinylpyrrolidone K30, adding 90mL of a mixed solution of deionized water and absolute ethyl alcohol (the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution is 0.25: 1), and stirring at room temperature to obtain a clear manganese-containing solution; mixing the obtained manganese-containing solution with 60mL of potassium hexacyanocobaltate aqueous solution with the concentration of 0.008mol/L, standing at room temperature for precipitation reaction for 24 hours to obtain white precipitate, washing the obtained precipitate with water and ethanol in sequence, primarily drying in a 60 ℃ oven for 12 hours, and then transferring to a muffle furnace for heat treatment at 350 ℃ for 6 hours to obtain black nano cage-shaped manganese cobalt oxide;
and (3) mixing the obtained nano cage-shaped manganese cobalt oxide, the carbon nano tube and PVDF according to the mass ratio of 1: 6: 3, mixing, and performing ball milling for 8 hours at the rotating speed of 800rpm to obtain a porous coating mixture; stirring 10g of the porous coating mixture and 20g of NMP for 4h under the condition of 400rpm to obtain a coating suspension;
coating one side of the obtained coating suspension liquid on the surface of a PE film with the thickness of 20 mu m, wherein the coating amount of the coating suspension liquid on the PE film is 0.9-1.1 mg/cm2The PE film coated with the coating suspension was placed in a vacuum drying oven,and drying at 60 ℃ for 18h to obtain the manganese cobalt oxide modified composite diaphragm.
Example 3
Mixing 0.22g of manganese acetate tetrahydrate and 1.5g of polyvinylpyrrolidone K30, adding 90mL of a mixed solution of deionized water and absolute ethyl alcohol (the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution is 1: 1), and stirring at room temperature to obtain a clear manganese-containing solution; mixing the obtained manganese-containing solution with 60mL of potassium hexacyanocobaltate aqueous solution with the concentration of 0.008mol/L, standing at room temperature for precipitation reaction for 24 hours to obtain white precipitate, washing the obtained precipitate with water and ethanol in sequence, primarily drying in an oven at 80 ℃ for 8 hours, and then transferring to a muffle furnace for heat treatment at 550 ℃ for 1.5 hours to obtain black nano cage-shaped manganese cobalt oxide;
and (3) mixing the obtained nano cage-shaped manganese cobalt oxide, acetylene black and SBR according to a mass ratio of 6: 1: 3, mixing, and carrying out ball milling for 16h at the rotating speed of 1000rpm to obtain a porous coating mixture; stirring 10g of the porous coating mixture and 20g of isopropanol for 6h under the condition of 400rpm to obtain a coating suspension;
coating one side of the obtained coating suspension liquid on the surface of a PE film with the thickness of 20 mu m, wherein the coating amount of the coating suspension liquid on the PE film is 0.9-1.1 mg/cm2And placing the PE film coated with the coating suspension in a vacuum drying oven, and drying at 60 ℃ for 12h to obtain the manganese-cobalt oxide modified composite diaphragm.
Example 4
Mixing 0.21g of manganese nitrate and 0.9g of polyvinylpyrrolidone K60, adding 90mL of a mixed solution of deionized water and absolute ethyl alcohol (the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution is 2: 1), and stirring at room temperature to obtain a clear manganese-containing solution; mixing the obtained manganese-containing solution with 60mL of potassium hexacyanocobaltate aqueous solution with the concentration of 0.008mol/L, standing at room temperature for precipitation reaction for 24 hours to obtain white precipitate, washing the obtained precipitate with water and ethanol in sequence, primarily drying in an oven at 80 ℃ for 12 hours, and then transferring to a muffle furnace for heat treatment at 500 ℃ for 2 hours to obtain black nano cage-shaped manganese cobalt oxide;
and (3) mixing the obtained nano cage-shaped manganese cobalt oxide, conductive carbon and PVDF according to the mass ratio of 2: 5: 3, mixing, wherein the conductive carbon is mixed according to the mass ratio of 1: 1, ball-milling the mixture of the acetylene black and the graphene for 8 hours at the rotating speed of 1200rpm to obtain a porous coating mixture; stirring 10g of porous coating mixture and 20g of acetone for 6h under the condition of 400rpm to obtain a coating suspension;
coating one side of the obtained coating suspension liquid on the surface of a PE film with the thickness of 20 mu m, wherein the coating amount of the coating suspension liquid on the PE film is 0.9-1.1 mg/cm2And placing the PE film coated with the coating suspension in a vacuum drying oven, and drying for 48 hours at 70 ℃ to obtain the manganese-cobalt oxide modified composite diaphragm.
Comparative example 1
A PE film having a thickness of 20 μm was provided.
Application example 1
Mixing porous carbon and PVDF according to a mass ratio of 9: 1, mixing the mixture in NMP, coating the mixture on carbon paper to serve as an oxygen electrode, taking a metal lithium sheet as a counter electrode, taking a manganese-cobalt oxide modified composite diaphragm prepared in example 1 as a diaphragm, taking 1mol/L LiTFSI (organic solvent TEGDME) containing 50mmol/L LiI as an organic electrolyte, and assembling the diaphragm into a button lithium-oxygen battery in a glove box protected by high-purity argon.
In a glove box protected by pure oxygen, a Land battery testing system is adopted to perform constant current charge and discharge testing on the obtained lithium-oxygen battery, and the set testing conditions are as follows: under the constant temperature of 25 ℃, the current density is 200mA/g, the specific capacity is limited to 1000mAh/g (calculated by taking the mass of a carbon material in the oxygen battery as a reference), and the potential range is 2.3-4.0V vs. Li/Li+。
The resulting cycle performance is shown in FIG. 6. As can be seen from FIG. 6, the current density is 200mA/g, the capacity is limited to 1000mAh/g, and the potential range is 2.3-4.0V vs. Li/Li+Under the condition, the lithium-oxygen battery containing the manganese-cobalt oxide modified composite diaphragm can stably circulate 507 times and still keep about 3.3V vs+The charging voltage of (2) shows good cycle stability and has a long life.
Application example 2
The manganese cobalt oxide modified composite diaphragm prepared in the embodiment 4 is used as a diaphragm, and other technical means are the same as those of the application example 1, so that the button lithium-oxygen battery is assembled.
And (3) according to the test method of the application example 1, carrying out a cycle performance test on the button lithium-oxygen battery obtained in the application example 2, and obtaining a cycle performance graph shown in figure 7.
Comparative application example 1
The PE diaphragm of the comparative example 1 is used as a diaphragm, and other technical means are the same as those of the application example 1, so that the button lithium-oxygen battery is assembled.
The cycling performance of the button lithium-oxygen battery obtained in comparative application example 1 was tested in accordance with the testing method of application example 1, and the obtained cycling performance graph is shown in fig. 8.
As can be seen from comparison of fig. 7 to 8, compared with the lithium-oxygen battery using only the PE separator as the separator, the cycle stability of the lithium-oxygen battery containing the manganese-cobalt oxide modified composite separator is greatly improved. The reason is analyzed, on one hand, the manganese cobalt oxide accelerates the dynamic reaction of the LiI redox couple, so that the cycle efficiency of the lithium peroxide is improved, and on the other hand, the manganese cobalt oxide modified composite diaphragm provided by the invention can effectively inhibit the shuttle effect and prolong the service life of the battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A manganese cobalt oxide modified composite diaphragm comprises a film substrate and a porous coating covering the surface of the film substrate; the porous coating comprises nano cage-shaped manganese cobalt oxide, a conductive carbon material and a binder.
2. The manganese-cobalt oxide-modified composite separator according to claim 1, wherein the mass ratio of the nanocage manganese-cobalt oxide to the conductive carbon material to the binder is (0.1-2): (0.1-2): 1.
3. the manganese cobalt oxide-modified composite separator according to claim 1 or 2, wherein the conductive carbon material comprises one or more of acetylene black, porous carbon, graphene, and carbon nanotubes; the binder comprises one or more of polytetrafluoroethylene, styrene butadiene rubber, polyvinylidene fluoride and carboxymethyl cellulose.
4. The manganese-cobalt oxide-modified composite separator according to claim 1 or 2, wherein the thickness of the porous coating layer is 5 to 20 μm.
5. The preparation method of the manganese cobalt oxide modified composite diaphragm of any one of claims 1 to 4, comprising the following steps:
mixing nano cage-shaped manganese cobalt oxide, a conductive carbon material, a binder and an organic solvent to obtain a coating suspension;
and coating the coating suspension liquid on one surface of the film substrate, and drying to obtain the manganese cobalt oxide modified composite diaphragm.
6. The preparation method of claim 5, wherein the preparation method of the nanocage manganese cobalt oxide comprises the following steps:
mixing a soluble manganese source, polyvinylpyrrolidone, deionized water and absolute ethyl alcohol to obtain a manganese-containing solution;
and mixing the manganese-containing solution and a soluble cobalt source, carrying out precipitation reaction, and sequentially carrying out primary drying and heat treatment on the obtained precipitate to obtain the nano cage-shaped manganese-cobalt oxide.
7. The method of claim 6, wherein the soluble manganese source comprises manganese acetate tetrahydrate, or manganese nitrate; the soluble cobalt source comprises potassium hexacyanocobaltate, sodium hexacyanocobaltate or zinc hexacyanocobaltate.
8. The preparation method according to claim 6 or 7, wherein the molar ratio of the soluble manganese source to the soluble cobalt source is (0.1-10) based on manganese in the soluble manganese source and cobalt in the soluble cobalt salt: 1.
9. the method according to claim 6, wherein the polyvinylpyrrolidone has a K value of 25 to 90.
10. Use of the manganese cobalt oxide-modified composite separator according to any one of claims 1 to 4 or the manganese cobalt oxide-modified composite separator prepared by the preparation method according to any one of claims 5 to 9 in a lithium-oxygen battery.
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