CN111430721A - Composite electrode and preparation method and application thereof - Google Patents

Composite electrode and preparation method and application thereof Download PDF

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Publication number
CN111430721A
CN111430721A CN202010115119.9A CN202010115119A CN111430721A CN 111430721 A CN111430721 A CN 111430721A CN 202010115119 A CN202010115119 A CN 202010115119A CN 111430721 A CN111430721 A CN 111430721A
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current collector
carbon nanotube
carbon
composite electrode
nanotube film
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孙洋洋
刘静
马可新
其他发明人请求不公开姓名
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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

Abstract

The invention discloses a composite electrode and a preparation method and application thereof. The composite electrode includes: the carbon nanotube film current collector, the electrode material layer and the metal layer. The electrode material layer is arranged on at least part of the surface of the carbon nanotube film current collector; the metal layer is arranged on at least part of the surface of the carbon nano tube film current collector, which is far away from the electrode material layer. The composite electrode has the advantages of the carbon nanotube film current collector and the metal current collector, effectively overcomes the defects of the carbon nanotube film current collector and the metal current collector, and has wide application prospect.

Description

Composite electrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a composite electrode and a preparation method and application thereof.
Background
With the gradual consumption of traditional energy and the excessive dependence of modern society on energy, energy problems and environmental problems force people to find new green energy and increase the strength of research on new energy storage and conversion forms. The battery is a tool for achieving the purpose of energy storage by means of mutual conversion of electric energy and chemical energy, and is a hotspot of research in the field of new energy. Lithium ion batteries have been increasingly widely studied and applied in the fields of power and energy storage due to their high energy density, excellent cycle and rate performance, etc. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, electrolyte, a diaphragm, a binder, a conductive agent, a current collector and the like, wherein the current collector not only bears active substances, but also has the function of concentrating micro current generated by the positive electrode to form larger current and then outputting the larger current to the outside, and is an indispensable structural component in the lithium ion battery.
The current collector is required to have the characteristics of good conductivity, good ductility, high tensile strength, good chemical and electrochemical stability, capability of keeping good compatibility and bonding force with the positive active material and the like, and the current collector has great influence on the performance of the lithium ion battery such as internal resistance, efficiency, circulation, stability, multiplying power and the like. Aluminum foil and copper foil have been the most commonly used current collectors for positive and negative electrodes in lithium ion batteries because of their advantages such as high conductivity, suitable electrochemical stability, and low cost. However, as the conventional current collector, the aluminum foil and the copper foil have more problems in practical application due to the material itself, and cannot completely meet the requirement of the lithium ion battery on higher performance. For example, metal foils have the disadvantages of high potential, easy oxidation, high mass density, poor corrosion resistance, poor binding force with active substances, low potential lithium intercalation, and the like, and the service life and the performance of the battery are seriously influenced.
In the traditional lithium ion battery electrode, additives such as a conductive agent, a binder and the like are respectively added into positive and negative active substances for homogenate, and finally, the homogenate is uniformly coated on aluminum foil and copper foil current collectors and dried to obtain a positive pole piece and a negative pole piece. However, with the increasing requirements of human and society on new energy, the conventional positive plate and negative plate using aluminum foil and copper foil as current collectors have been unable to meet the requirements of lithium ion batteries. With the rapid development of technology, a number of novel carbon-based current collectors have been reported, such as carbon nanofiber mats, bucky papers, graphene papers, and the like. These carbon-based materials can improve the mass energy density to some extent, but have disadvantages such as low volumetric energy density, poor mechanical strength, and unsatisfactory electrical conductivity. At present, the main problem of the carbon-based current collector is focused on how to effectively construct a film material with excellent physical structure, mechanical property and electrical conductivity.
The carbon nano tube is taken as an ideal conductive agent which is most commonly used in the lithium ion battery, and the unique geometric structure and the electronic energy band of the carbon nano tube greatly improve the ion conduction and the electronic conduction of a cell. The carbon nano tube has excellent mechanical property, electrical property and thermal property due to the larger length-diameter ratio and the unique one-dimensional structure, so that the carbon nano tube film formed by aggregation by taking the carbon nano tube as a basic material attracts social wide attention as a novel carbon-based current collector. The carbon nanotube film as a current collector has the following advantages: (1) the conductive network can be effectively formed, and the conductive network has excellent conductive performance and better mechanical strength; (2) the wettability of the electrolyte can be improved, an ion channel is increased, and the ion transmission performance of the battery is improved; (3) the lower density can effectively improve the energy density and the capacity of the battery; (4) the binding force between the active material and the battery is increased, an electronic path is increased, the contact resistance is reduced, and the service life and the cycle performance of the battery are improved. For example, patent CN103715394A discloses a lithium ion battery positive electrode and a preparation method thereof, wherein a carbon nanotube macroscopic tube is prepared into a carbon nanotube film current collector, and a positive electrode material layer is coated to form an electrode. The preparation process of the carbon nanotube film comprises the steps of preparing a film layer with the thickness of about 0.2-100 mu m by using the surface tension of an ethanol solution of a glass substrate, drying the film layer, coating a positive electrode material on the film layer, drying the film layer on a glass substrate, and then removing the film layer by using a scraper and the like to obtain the pole piece. The method can realize discontinuous production to a certain extent and improve the battery capacity by about 15 percent. But the defects of complex preparation process, incapability of continuous production, poor conductivity in the direction parallel to the film, unobvious increase of volume energy density and the like in the utilization of the existing carbon nanotube film exist. Therefore, the development of a preparation method of a current collector or an electrode which has great help for improving the volume energy density and the mass energy density of the battery and has great improvement on the conductivity, the safety, the circulation, the capacity and the like has great significance for the development of the lithium ion battery.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a composite electrode, a method for its preparation and its use. The composite electrode has the advantages of the carbon nanotube film current collector and the metal current collector, effectively overcomes the defects of the carbon nanotube film current collector and the metal current collector, and has wide application prospect.
In one aspect of the invention, a composite electrode is provided. According to an embodiment of the invention, the composite electrode comprises: a carbon nanotube film current collector; the electrode material layer is arranged on at least part of the surface of the carbon nanotube film current collector; and the metal layer is arranged on at least part of the surface of the carbon nanotube film current collector, which is far away from the electrode material layer.
In the research of the lithium battery electrode, the inventor finds that the traditional metal current collector has the defects of high potential, easy oxidation, high mass density, poor corrosion resistance, poor binding force with active substances, low potential lithium intercalation and the like, and the service life and the performance of the battery are seriously influenced. The main problem of the novel carbon current collector is how to effectively construct a film material with excellent physical structure, mechanical property and electrical conductivity. The carbon nanotube film is used as the optimal material of the carbon-based current collector, and still has the defects of complex preparation process, difficult continuous production, poor conductivity in the direction parallel to the film, unobvious improvement of volume energy density and the like.
Aiming at the advantages and disadvantages of the traditional metal current collector and the carbon nano tube film current collector, the invention designs the composite electrode which improves the performances of the carbon nano tube film in the aspects of conductivity, mechanical strength, electrochemical performance and the like by evaporating metal. The metal layer solves the main problems of low conductivity and low strength of the carbon nanotube film current collector, and greatly reduces the surface resistance of the material. And the metal layer is formed by evaporation, when the metal layer is formed on the carbon nano tube film current collector, a part of metal can enter the carbon nano tube film, and the bit resistance between the electrode material and the current collector is effectively improved.
Thus, a composite electrode according to embodiments of the present invention may have at least one advantage selected from the following:
(1) the composite electrode has the characteristic of deformability, has better wettability to electrode slurry and larger contact area, and ensures that stronger bonding force and lower contact resistance are obtained between a current collector and the electrode slurry, and meanwhile, electron transfer and ion transmission channels are improved;
(2) the composite electrode greatly improves the energy per unit mass and volume under the premise of considering the whole mass and volume;
(3) the composite electrode solves the problems that the traditional current collector is high in potential, easy to oxidize, high in mass density, poor in active substance binding force, low in volume energy density, poor in mechanical strength, low in conductivity and the like;
(4) the lithium ion battery prepared by the composite electrode has the advantages of high energy density, good rate capability, long service life and good cycle and low-temperature performance;
(5) the composite electrode is a novel carbon nanotube film electrode modified by vapor plating metal, has the advantages of high production efficiency, good uniformity and integrity of a pole piece and the like, and can meet the requirements of industrial production;
(6) the laminated square-shell lithium ion battery prepared by the composite electrode has high first efficiency, excellent gram capacity exertion and good cycle performance. And has better low-temperature characteristic and cycle safety, and no gas is generated after 30 days of storage at 60 ℃.
In addition, the composite electrode according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, the carbon nanotube thin film current collector is formed of at least one selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, aligned carbon nanotubes, non-aligned carbon nanotubes, and functionalized carbon nanotubes.
In some embodiments of the present invention, the metal layer is formed of at least one selected from Cu, Al, Ag, Fe, Zn, Mn, Au, Ni, Mg.
In some embodiments of the present invention, the thickness of the carbon nanotube thin film current collector is 10nm to 100 μm.
In some embodiments of the present invention, the metal layer has a thickness of 10nm to 8 μm.
In another aspect of the invention, the invention provides a method of making the composite electrode of the above embodiments. According to an embodiment of the invention, the method comprises: (1) mixing the carbon nano tube with a dispersant and a solvent to obtain a carbon nano tube dispersion liquid; (2) spraying the carbon nano tube dispersion liquid onto a vacuum suction filtration platform paved with a filter membrane, and removing the dispersing agent and the solvent through vacuum negative pressure to obtain a carbon nano tube film; (3) carrying out first drying treatment on the carbon nanotube film to obtain a carbon nanotube film current collector; (4) applying an electrode material to at least part of the surface of the carbon nanotube film current collector and performing second drying treatment to obtain an electrode material layer; (5) and removing the filter membrane, and applying a metal material to at least part of the surface of the carbon nanotube film current collector away from the electrode material layer by an electron beam evaporation method to obtain a metal layer.
According to the method for preparing the composite electrode, the preparation of the carbon nano tube film current collector, the coating of the electrode slurry and the modification of the evaporation plating metal are creatively combined, the complete carbon nano tube film current collector can be prepared by a vacuum injection method and a vacuum suction filtration method, and the film thickness is easy to control. In the step of preparing the carbon nanotube film current collector, the existence of the filter membrane can ensure the continuous productivity and appearance integrity of the current collector, and effectively improve the production efficiency and the yield. The composite electrode prepared by the method has the advantages of the carbon nanotube film current collector and the metal current collector, effectively overcomes the defects of the carbon nanotube film current collector and the metal current collector, and has wide application prospect.
In addition, the method for manufacturing a composite electrode according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, in the step (1), the concentration of the carbon nanotube dispersion is 0.1 to 20 wt%.
In some embodiments of the present invention, the dispersant is added in an amount of 0 to 5.0 wt%.
In some embodiments of the invention, in the step (2), the carbon nanotube dispersion is sprayed onto a vacuum filtration platform paved with a filter membrane at a pressure of 0.1-5.0 MPa, and the dispersant and the solvent are removed by a vacuum negative pressure of-0.5-0.01 MPa, so as to obtain the carbon nanotube film.
In some embodiments of the present invention, the filter membrane is formed of at least one selected from a cellulose ester-based material, a polysulfone-based material, a polyolefin-based material, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, ceramic, glass, metal, alumina, and zirconia.
In some embodiments of the present invention, the first drying treatment is performed at 40 to 90 ℃ for 0.5 to 6.0 hours.
In some embodiments of the present invention, the second drying process is performed at 40 to 120 ℃ for 2 to 40 min.
In yet another aspect of the present invention, a lithium ion battery is presented. According to an embodiment of the present invention, the lithium ion battery includes the composite electrode of the above embodiment. Thus, the lithium ion battery has all the features and advantages described above for the composite electrode, and thus, the description thereof is omitted. In general, the lithium ion battery has excellent electrochemical performance.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a flow diagram of a method of making a composite electrode according to one embodiment of the present invention;
fig. 2 is a flow chart of a method of making a composite electrode according to yet another embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a composite electrode is provided. According to an embodiment of the invention, the composite electrode comprises: the carbon nanotube film current collector, the electrode material layer and the metal layer. The electrode material layer is arranged on at least part of the surface of the carbon nanotube film current collector; the metal layer is arranged on at least part of the surface of the carbon nano tube film current collector, which is far away from the electrode material layer.
According to some embodiments of the present invention, the carbon nanotube thin film current collector may be formed of at least one selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, aligned carbon nanotubes, non-aligned carbon nanotubes, and functionalized carbon nanotubes.
According to some embodiments of the present invention, the metal layer may be formed of at least one selected from Cu, Al, Ag, Fe, Zn, Mn, Au, Ni, and Mg.
According to some embodiments of the present invention, the thickness of the carbon nanotube thin film current collector may be 10nm to 100 μm, for example, 10nm, 50nm, 100nm, 200nm, 500nm, 1 μm, 10 μm, 20 μm, 50 μm, 100 μm, and the like. By controlling the thickness of the carbon nanotube film current collector within the above range, the mechanical property and the conductivity of the carbon nanotube film current collector can be further improved.
According to some embodiments of the present invention, the thickness of the metal layer may be 10nm to 8 μm, for example, 10nm, 50nm, 100nm, 200nm, 500nm, 1 μm, 2 μm, 5 μm, 8 μm, and the like. Therefore, the mechanical property and the conductivity of the composite electrode can be further improved.
The specific kind of the electrode material layer is not particularly limited, and may be formed using an electrode material commonly used in the art, and may be a positive electrode material or a negative electrode material. According to some embodiments of the present invention, the electrode material may include an electrode active material (a positive electrode active material or a negative electrode active material), a conductive agent, a binder, and the like. When the composite electrode is applied as a positive electrode, the positive active material in the electrode material can be one, two or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt oxide and lithium nickel manganese oxide, and the content of the positive active material can be 80-99.5 wt%; the conductive agent can be one, two or more of carbon black, carbon nano tubes, carbon nano fibers, graphene, graphite, carbon filaments and the like, and the content of the conductive agent can be 0.1-10 wt%; the binder can be one, two or more of polyvinylidene fluoride, styrene butadiene rubber, fluorinated rubber, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, polyolefins and the like, and the content of the binder can be 0.4-10 wt%. When the composite electrode is applied as a negative electrode, the negative active substance in the electrode material can be one, two or more of natural graphite, artificial graphite, disordered carbon, carbon-containing compounds, non-carbon negative electrode materials and the like, and the content of the negative active substance can be 82-90 wt%; the conductive agent can be one, two or more of carbon black, carbon nano tubes, carbon nano fibers, graphene, graphite, carbon filaments and the like, and the content of the conductive agent can be 0.1-8 wt%; the binder can be one or two or more of styrene butadiene rubber, fluorinated rubber, sodium carboxymethylcellulose, hydroxymethyl cellulose, polyvinyl alcohol, dimethyl diallyl ammonium chloride, polymethyl methacrylate, polytetrafluoroethylene, olefins and the like, and the usage amount of the binder can be 0.2-10 wt%.
In another aspect of the invention, the invention provides a method of making the composite electrode of the above embodiments. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: preparation of carbon nanotube Dispersion
In this step, the carbon nanotube is mixed with a dispersant and a solvent to obtain a carbon nanotube dispersion liquid.
According to some embodiments of the present invention, the concentration of the carbon nanotube dispersion may be 0.1 to 20 wt%, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, etc. Therefore, the concentration of the carbon nanotube dispersion liquid is suitable, and the thickness of the carbon nanotube film prepared subsequently is easy to control.
According to some embodiments of the present invention, the above-mentioned dispersant may be added in an amount of 0 to 5.0 wt%, for example, 0 wt%, 0.1 wt%, 0.5 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 5.0 wt%, etc. This can further improve the stability of the carbon nanotube dispersion, and further improve the uniformity of the film obtained by the preparation. In some embodiments, the dispersant is added in an amount of 0 wt%, i.e., no dispersant is added, whereby this step is mixing the carbon nanotubes with a solvent to obtain a carbon nanotube dispersion, and no treatment of the dispersant is involved in the subsequent steps.
According to some embodiments of the present invention, the carbon nanotube thin film current collector may be formed of at least one selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, aligned carbon nanotubes, non-aligned carbon nanotubes, and functionalized carbon nanotubes.
According to some embodiments of the present invention, the dispersant may be selected from sodium polyacrylate and the like commonly used in the art.
According to some embodiments of the present invention, the solvent may be one, two or more selected from water, ethanol, isopropanol, N-butanol, ethylene glycol, N-methylpyrrolidone, acetone, toluene, methanol, acetonitrile, ethyl acetate, and the like.
S200: preparation of carbon nanotube film
In the step, the carbon nanotube dispersion liquid is sprayed on a vacuum suction filtration platform paved with a filter membrane, and the dispersant and the solvent are removed through vacuum negative pressure to obtain the carbon nanotube film. According to the embodiment of the present invention, the thickness of the prepared carbon nanotube thin film precursor can be controlled by controlling the concentration of the carbon nanotube dispersion, the number of spraying times, the spraying speed, and other parameters. Further, the carbon nanotube film can be obtained by extracting the dispersant and the solvent.
According to some embodiments of the present invention, the carbon nanotube dispersion may be sprayed onto a vacuum filtration platform with a filter membrane laid thereon at a pressure of 0.1 to 5.0MPa, and the dispersant and the solvent may be removed by a vacuum negative pressure of-0.5 to-0.01 MPa, thereby obtaining the carbon nanotube film. Therefore, the uniformity and the integrity of the prepared carbon nanotube film can be further improved.
According to some embodiments of the present invention, the filter membrane may be formed of at least one selected from a cellulose ester-based material, a polysulfone-based material, a polyolefin-based material, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, ceramic, glass, metal, alumina, and zirconia.
S300: first drying treatment
In the step, the carbon nanotube film is subjected to first drying treatment to obtain a carbon nanotube film current collector.
According to some embodiments of the present invention, the first drying process may be performed at 40 to 90 ℃ for 0.5 to 6.0 hours. Specifically, the drying temperature may be 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the like, and the drying time may be 0.5h, 1h, 2h, 3h, 4h, 6h and the like. By performing the first drying treatment under the above conditions, the drying effect of the carbon nanotube film can be further improved.
S400: second drying treatment
In the step, the electrode material is applied to at least part of the surface of the carbon nanotube film current collector and is subjected to second drying treatment, so that an electrode material layer is obtained.
According to some embodiments of the present invention, the second drying process may be performed at 40 to 120 ℃ for 2 to 40 min. Specifically, the drying temperature may be 40 ℃, 60 ℃, 80 ℃, 90 ℃, 100 ℃, 120 ℃ and the like, and the drying time may be 2min, 5min, 10min, 20min, 30min, 40min and the like. By performing the second drying treatment under the above-described conditions, the drying effect of the electrode material can be further improved.
The electrode material may be a positive electrode material or a negative electrode material. According to some embodiments of the present invention, the electrode material may include an electrode active material (a positive electrode active material or a negative electrode active material), a conductive agent, a binder, and the like. For the positive electrode material, the positive active material in the electrode material can be one, two or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium nickel cobalt oxide and lithium nickel manganese oxide, and the content of the positive active material can be 80-99.5 wt%; the conductive agent can be one, two or more of carbon black, carbon nano tubes, carbon nano fibers, graphene, graphite, carbon filaments and the like, and the content of the conductive agent can be 0.1-10 wt%; the binder can be one, two or more of polyvinylidene fluoride, styrene butadiene rubber, fluorinated rubber, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, polyolefins and the like, and the content of the binder can be 0.4-10 wt%. In addition, N-methyl pyrrolidone is used for adjusting the viscosity of the electrode material to be 1000-9000 mPas and the solid content to be 40-90%. For the negative electrode material, the negative active material in the electrode material can be one, two or more of natural graphite, artificial graphite, disordered carbon, carbon-containing compounds, non-carbon negative electrode materials and the like, and the content of the negative active material can be 82-90 wt%; the conductive agent can be one, two or more of carbon black, carbon nano tubes, carbon nano fibers, graphene, graphite, carbon filaments and the like, and the content of the conductive agent can be 0.1-8 wt%; the binder can be one or two or more of styrene butadiene rubber, fluorinated rubber, sodium carboxymethylcellulose, hydroxymethyl cellulose, polyvinyl alcohol, dimethyl diallyl ammonium chloride, polymethyl methacrylate, polytetrafluoroethylene, olefins and the like, and the usage amount of the binder can be 0.2-10 wt%. In addition, the viscosity of the electrode material is adjusted to be 500-5000 mPa & s by using water, and the solid content is 10-60%.
Further, the surface density of the obtained electrode material is 18.0-62.0 mg/cm through second drying treatment2。
S500: removing the filter membrane, evaporating to obtain a metal layer
In the step, the filter membrane is removed, and the metal material is applied to at least part of the surface of the carbon nanotube film current collector away from the electrode material layer through an electron beam evaporation method to obtain the metal layer. Specifically, the specific operating conditions of the electron beam evaporation method are not particularly limited, and those skilled in the art can select the operating conditions according to actual needs.
In addition, it should be noted that all the features and advantages described above for the "composite electrode" are also applicable to the "method for preparing a composite electrode", and are not described in detail herein.
In yet another aspect of the present invention, a lithium ion battery is presented. According to an embodiment of the present invention, the lithium ion battery includes the composite electrode of the above embodiment. Thus, the lithium ion battery has all the features and advantages described above for the composite electrode, and thus, the description thereof is omitted. In general, the lithium ion battery has excellent electrochemical performance.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Referring to fig. 2, a metal vapor deposition modified carbon nanotube thin film electrode (in fig. 2, 1 is a carbon nanotube dispersion liquid, 2 is an injection gun, 3 is a vacuum filtration platform, 4 is a filter membrane, 5 is a carbon nanotube thin film current collector, 6 is an electrode slurry, 7 is a carbon nanotube thin film electrode, and 8 is a metal vapor deposition modified carbon nanotube thin film electrode) is prepared.
Preparing 5.0 wt% solid content ethanol dispersion of multi-walled carbon nano-tubes, dispersing agent is 1.5 wt% sodium polyacrylate, after fully ultrasonic dispersing and stirring, uniformly spraying the solution on a polypropylene filter membrane by a vacuum spray gun under the pressure of 0.8 MPa. After repeated and uniform spraying twice, the thickness of the carbon nano tube film is 0.2 mu m, and the carbon nano tube film is dried for 0.5h at the temperature of 40 ℃.
The positive electrode slurry (solid content 62 wt%; viscosity 6500 mPa.s; N-methylpyrrolidone) of NCM811(96.5 wt%) + carbon black conductive agent (2.5 wt%) + carbon nanotube conductive agent (0.5 wt%) + binder (0.5 wt%) was uniformly coated onto the carbon nanotube thin film current collector using a doctor blade process, with a design areal density of 32.4mg/cm2And then dried by air blowing at 45 ℃ for 0.5 h. And removing the filter membrane after drying, and forming a copper particle metal layer with the thickness of 100nm by using Cu as a modified metal on the surface of the current collector which is not coated with the active material by adopting an electron beam evaporation method.
The negative electrode slurry was natural graphite (97.0 wt%) + conductive carbon black (2.0 wt%) + binder (1 wt%) (solid content 47 wt%; viscosity 2500mPa · s; water). The slurry is coated on the front surface of the carbon nano tube film current collector by adopting a scraping coating process, and the surface density is 29.5mg/cm2And after drying, removing the filter membrane, and forming an aluminum particle metal layer with the thickness of 120nm by using an electron beam evaporation method on the surface of the current collector which is not coated with the active material and using A as a modified metal.
Finally, preparing pole pieces by die cutting and rolling, and assembling the pole pieces into the 5 A.h soft package battery by a lamination method. The first efficiency of the battery is more than 99.8 percent, and the 0.33C discharging gram capacity is 295.4 mA.h/g; 50% DOD discharge DCIR is 0.34m Ω; the capacity retention rate at low temperature of minus 20 ℃ is 85.1 percent; the retention rate of 3C-time discharge capacity is 95.9%; after 1500 cycles of high temperature of 45 ℃ and 100 percent DOD, the capacity retention rate reaches up to 90.1 percent.
Example 2
Referring to fig. 2, a metal vapor deposition modified carbon nanotube thin film electrode is prepared.
Preparing 5.0 wt% solid content ethanol dispersion of multi-walled carbon nano-tubes, dispersing agent is 1.5 wt% sodium polyacrylate, after fully ultrasonic dispersing and stirring, uniformly spraying the dispersion on a polyvinylidene fluoride filter membrane by a vacuum spray gun under the pressure of 0.8 MPa. After repeated and uniform spraying twice, the thickness of the carbon nano tube film is 0.5 mu m, and the carbon nano tube film is dried for 0.5h at the temperature of 40 ℃.
NCM811(96.5 wt%) + carbon black conductive agent (2.5 wt%) + carbon nanotube conductive agent (0.5 wt%) + binder (0.5 wt%) was added to the positive electrode slurry (solid solution)Content 62 wt%; viscosity 6500 mPas; n-methyl pyrrolidone) is uniformly coated on the carbon nano tube film current collector by adopting a scraper type process, and the designed surface density is 32.4mg/cm2And then dried by air blowing at 45 ℃ for 0.5 h. And removing the filter membrane after drying, and forming a copper particle metal layer with the thickness of 100nm by using Cu as a modified metal on the surface of the current collector which is not coated with the active material by adopting an electron beam evaporation method.
The negative electrode slurry was natural graphite (97.0 wt%) + conductive carbon black (2.0 wt%) + binder (1 wt%) (solid content 47 wt%; viscosity 2500mPa · s; water). The slurry is coated on the front surface of the carbon nano tube film current collector by adopting a scraping coating process, and the surface density is 29.5mg/cm2And after drying, removing the filter membrane, and forming an aluminum particle metal layer with the thickness of 120nm by using an electron beam evaporation method on the surface of the current collector which is not coated with the active material and using A as a modified metal.
Finally, preparing pole pieces by die cutting and rolling, and assembling the pole pieces into the 5 A.h soft package battery by a lamination method. The first effect of the battery is more than 99.4 percent, and the 0.33C discharging gram capacity is 299.5 mA.h/g; 50% DOD discharge DCIR was 0.37m Ω; the capacity retention rate at low temperature of minus 20 ℃ is 85.4 percent; the retention rate of 3C-time discharge capacity is 95.3%; after 1500 cycles of high temperature of 45 ℃ and 100 percent DOD, the capacity retention rate reaches up to 90.2 percent.
Example 3
Referring to fig. 2, a metal vapor deposition modified carbon nanotube thin film electrode is prepared.
Preparing 5.0 wt% solid content ethanol dispersion of multi-walled carbon nano-tubes, dispersing agent is 1.5 wt% sodium polyacrylate, after fully ultrasonic dispersing and stirring, uniformly spraying the dispersion on a polyvinylidene fluoride filter membrane by a vacuum spray gun under the pressure of 0.8 MPa. After repeated and uniform spraying twice, the thickness of the carbon nano tube film is 1.0 mu m, and the carbon nano tube film is dried for 0.5h at the temperature of 40 ℃.
The positive electrode slurry (solid content 62 wt%; viscosity 6500 mPa.s; N-methylpyrrolidone) of NCM811(96.5 wt%) + carbon black conductive agent (2.5 wt%) + carbon nanotube conductive agent (0.5 wt%) + binder (0.5 wt%) was uniformly coated onto the carbon nanotube thin film current collector using a doctor blade process, with a design areal density of 32.4mg/cm2Then blowing at 45 deg.CDrying for 0.5 h. And removing the filter membrane after drying, and forming a copper particle metal layer with the thickness of 100nm by using Cu as a modified metal on the surface of the current collector which is not coated with the active material by adopting an electron beam evaporation method.
The negative electrode slurry was natural graphite (97.0 wt%) + conductive carbon black (2.0 wt%) + binder (1 wt%) (solid content 47 wt%; viscosity 2500mPa · s; water). The slurry is coated on the front surface of the carbon nano tube film current collector by adopting a scraping coating process, and the surface density is 29.5mg/cm2And after drying, removing the filter membrane, and forming an aluminum particle metal layer with the thickness of 120nm by using an electron beam evaporation method on the surface of the current collector which is not coated with the active material and using A as a modified metal.
Finally, preparing pole pieces by die cutting and rolling, and assembling the pole pieces into the 5 A.h soft package battery by a lamination method. The first effect of the battery is more than 99.4 percent, and the 0.33C discharging gram capacity is 301 mA.h/g; 50% DOD discharge DCIR was 0.5m Ω; the capacity retention rate at low temperature of minus 20 ℃ is 85.5 percent; the retention rate of 3C-time discharge capacity is 95.2%; after 1500 cycles of high temperature 100% DOD at 45 ℃, the capacity retention rate is up to 89.9%.
Example 4
Referring to fig. 2, a metal vapor deposition modified carbon nanotube thin film electrode is prepared.
Preparing 5.0 wt% solid content ethanol dispersion of multi-walled carbon nano-tubes, dispersing agent is 1.5 wt% sodium polyacrylate, after fully ultrasonic dispersing and stirring, uniformly spraying the dispersion on a polyvinylidene fluoride filter membrane by a vacuum spray gun under the pressure of 0.8 MPa. After repeated and uniform spraying twice, the thickness of the carbon nano tube film is 6.0 mu m, and the carbon nano tube film is dried for 0.5h at the temperature of 40 ℃.
The positive electrode slurry (solid content 62 wt%; viscosity 6500 mPa.s; N-methylpyrrolidone) of NCM811(96.5 wt%) + carbon black conductive agent (2.5 wt%) + carbon nanotube conductive agent (0.5 wt%) + binder (0.5 wt%) was uniformly coated onto the carbon nanotube thin film current collector using a doctor blade process, with a design areal density of 32.4mg/cm2And then dried by air blowing at 45 ℃ for 0.5 h. And removing the filter membrane after drying, and forming a copper particle metal layer with the thickness of 100nm by using Cu as a modified metal on the surface of the current collector which is not coated with the active material by adopting an electron beam evaporation method.
The negative electrode slurry was natural graphite (97.0 wt%) + conductive carbon black (2.0 wt%) + binder (1 wt%) (solid content 47 wt%; viscosity 2500mPa · s; water). The slurry is coated on the front surface of the carbon nano tube film current collector by adopting a scraping coating process, and the surface density is 29.5mg/cm2And after drying, removing the filter membrane, and forming an aluminum particle metal layer with the thickness of 120nm by using an electron beam evaporation method on the surface of the current collector which is not coated with the active material and using A as a modified metal.
Finally, preparing pole pieces by die cutting and rolling, and assembling the pole pieces into the 5 A.h soft package battery by a lamination method. The first efficiency of the battery is more than 95.4 percent, and the 0.33C discharging gram capacity is 299.7 mA.h/g; 50% DOD discharge DCIR was 2.2m Ω; the capacity retention rate at low temperature of minus 20 ℃ is 86.2 percent; the retention rate of 3C-time discharge capacity is 96.7%; after 1500 cycles of high temperature 100% DOD at 45 ℃, the capacity retention rate is up to 91.2%.
Example 5
Referring to fig. 2, a metal vapor deposition modified carbon nanotube thin film electrode is prepared.
Preparing 5.0 wt% solid content ethanol dispersion of multi-walled carbon nano-tubes, dispersing agent is 1.5 wt% sodium polyacrylate, after fully ultrasonic dispersing and stirring, uniformly spraying the dispersion on a polyvinylidene fluoride filter membrane by a vacuum spray gun under the pressure of 0.8 MPa. After repeated and uniform spraying twice, the thickness of the carbon nano tube film is 1.0 mu m, and the carbon nano tube film is dried for 0.5h at the temperature of 40 ℃.
The positive electrode slurry (solid content 62 wt%; viscosity 6500 mPa.s; N-methylpyrrolidone) of NCM811(96.5 wt%) + carbon black conductive agent (2.5 wt%) + carbon nanotube conductive agent (0.5 wt%) + binder (0.5 wt%) was uniformly coated onto the carbon nanotube thin film current collector using a doctor blade process, with a design areal density of 32.4mg/cm2And then dried by air blowing at 45 ℃ for 0.5 h. And removing the filter membrane after drying, and forming a copper particle metal layer with the thickness of 50nm by using Cu as a modified metal on the surface of the current collector which is not coated with the active material by adopting an electron beam evaporation method.
The negative electrode slurry was natural graphite (97.0 wt%) + conductive carbon black (2.0 wt%) + binder (1 wt%) (solid content 47 wt%; viscosity 2500mPa · s; water). The slurry is also coated by a doctor blade coating processThe surface density of the carbon nano tube film current collector is 29.5mg/cm2And after drying, removing the filter membrane, and forming an aluminum particle metal layer with the thickness of 120nm by using an electron beam evaporation method on the surface of the current collector which is not coated with the active material and using A as a modified metal.
Finally, preparing pole pieces by die cutting and rolling, and assembling the pole pieces into the 5 A.h soft package battery by a lamination method. The first effect of the battery is more than 99.1 percent, and the 0.33C discharging gram capacity is 293.7 mA.h/g; 50% DOD discharge DCIR was 1.45m Ω; the capacity retention rate at low temperature of minus 20 ℃ is 79.9 percent; the retention rate of 3C-time discharge capacity is 93.1%; after 1500 cycles of high temperature of 45 ℃ and 100 percent DOD, the capacity retention rate is as high as 80.4 percent.
Example 6
Referring to fig. 2, a metal vapor deposition modified carbon nanotube thin film electrode is prepared.
Preparing 5.0 wt% solid content ethanol dispersion of multi-walled carbon nano-tubes, dispersing agent is 1.5 wt% sodium polyacrylate, after fully ultrasonic dispersing and stirring, uniformly spraying the dispersion on a polyvinylidene fluoride filter membrane by a vacuum spray gun under the pressure of 0.8 MPa. After repeated and uniform spraying twice, the thickness of the carbon nano tube film is 1.0 mu m, and the carbon nano tube film is dried for 0.5h at the temperature of 40 ℃.
The positive electrode slurry (solid content 62 wt%; viscosity 6500 mPa.s; N-methylpyrrolidone) of NCM811(96.5 wt%) + carbon black conductive agent (2.5 wt%) + carbon nanotube conductive agent (0.5 wt%) + binder (0.5 wt%) was uniformly coated onto the carbon nanotube thin film current collector using a doctor blade process, with a design areal density of 32.4mg/cm2And then dried by air blowing at 45 ℃ for 0.5 h. And removing the filter membrane after drying, and forming a copper particle metal layer with the thickness of 180nm by using Cu as a modified metal on the surface of the current collector which is not coated with the active material by adopting an electron beam evaporation method.
The negative electrode slurry was natural graphite (97.0 wt%) + conductive carbon black (2.0 wt%) + binder (1 wt%) (solid content 47 wt%; viscosity 2500mPa · s; water). The slurry is coated on the front surface of the carbon nano tube film current collector by adopting a scraping coating process, and the surface density is 29.5mg/cm2Drying, removing the filter membrane, using A as modified metal on the surface of the current collector which is not coated with active material, and adopting electron beam evaporation methodAnd forming an aluminum particle metal layer with the thickness of 120 nm.
Finally, preparing pole pieces by die cutting and rolling, and assembling the pole pieces into the 5 A.h soft package battery by a lamination method. The first efficiency of the battery is more than 95.9 percent, and the 0.33C discharging gram capacity is 302.6 mA.h/g; 50% DOD discharge DCIR is 0.42m Ω; the capacity retention rate at low temperature of minus 20 ℃ is 89.4 percent; the retention rate of 3C-time discharge capacity is 96.3%; after 1500 cycles of high temperature 100% DOD at 45 ℃, the capacity retention rate reaches up to 90.7%.
The test results of the battery cells prepared in examples 1 to 6 are summarized in table 1, where a is the thickness (in μm) of the carbon nanotube film current collector, B is the thickness (in nm) of the metal layer, C is the first efficiency (%), D is the 0.33C gram discharge capacity (in mA · H/G), E is the 50% DOD discharge DCIR (in m Ω), F is the-20 ℃ low-temperature capacity retention (%), G is the 3C-fold discharge capacity retention (%), and H is the capacity retention (%) after 100% DOD1500 cycles at 45 ℃.
TABLE 1
Figure BDA0002391257350000121
As can be seen from the experimental results in table 1, increasing the thickness of the carbon nanotube film current collector is not beneficial to improving the electrical performance of the battery, and when the thickness of the carbon nanotube film current collector reaches 1 μm, it can provide sufficient mechanical support for the electrode. Increasing the thickness of the modified metal layer reduces the DCIR to a certain extent, but after the plating layer is continuously increased, the DCIR changes little, the retention rate of gram capacity and low-temperature capacity is increased and weakened, and the high-temperature improvement is not good. The thickness of the carbon nano tube film is 1 mu m, and the electrical property and the comprehensive processing property are optimal when the thickness of the coating is 100 nm.
The carbon nano film as a novel carbon-based current collector has incomparable advantages of a metal current collector in the aspects of energy density, flexibility and the like. The method aims at the determination that the traditional carbon-based current collector has poor processability, is determined after a film layer and the like, and is modified by a metal evaporation method after being combined with an electrode preparation process. The composite electrode has the advantages of convenient operation, continuous production, low cost, high cell energy density, excellent electrical performance and obvious effect in the fields of power batteries, 3C batteries and even flexible foldable batteries.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A composite electrode, comprising:
a carbon nanotube film current collector;
the electrode material layer is arranged on at least part of the surface of the carbon nanotube film current collector;
and the metal layer is arranged on at least part of the surface of the carbon nanotube film current collector, which is far away from the electrode material layer.
2. The composite electrode of claim 1, wherein the carbon nanotube thin film current collector is formed from at least one selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, aligned carbon nanotubes, non-aligned carbon nanotubes, functionalized carbon nanotubes.
3. The composite electrode according to claim 1, wherein the metal layer is formed of at least one selected from Cu, Al, Ag, Fe, Zn, Mn, Au, Ni, Mg.
4. The composite electrode according to claim 1, wherein the thickness of the carbon nanotube thin film current collector is 10nm to 100 μm.
5. The composite electrode according to claim 1, wherein the metal layer has a thickness of 10nm to 8 μm.
6. A method of making a composite electrode according to any one of claims 1 to 5, comprising:
(1) mixing the carbon nano tube with a dispersant and a solvent to obtain a carbon nano tube dispersion liquid;
(2) spraying the carbon nano tube dispersion liquid onto a vacuum suction filtration platform paved with a filter membrane, and removing the dispersing agent and the solvent through vacuum negative pressure to obtain a carbon nano tube film;
(3) carrying out first drying treatment on the carbon nanotube film to obtain a carbon nanotube film current collector;
(4) applying an electrode material to at least part of the surface of the carbon nanotube film current collector and performing second drying treatment to obtain an electrode material layer;
(5) and removing the filter membrane, and applying a metal material to at least part of the surface of the carbon nanotube film current collector away from the electrode material layer by an electron beam evaporation method to obtain a metal layer.
7. The method according to claim 6, wherein in the step (1), the concentration of the carbon nanotube dispersion is 0.1 to 20 wt%;
optionally, the addition amount of the dispersing agent is 0-5.0 wt%.
8. The method as claimed in claim 6, wherein in the step (2), the carbon nanotube dispersion liquid is sprayed onto a vacuum filtration platform paved with a filter membrane at a pressure of 0.1 to 5.0MPa, and the dispersant and the solvent are removed by a vacuum negative pressure of-0.5 to-0.01 MPa to obtain the carbon nanotube film;
optionally, the filter membrane is formed by at least one selected from cellulose ester materials, polysulfone materials, polyolefin materials, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, ceramics, glass, metal, alumina and zirconia.
9. The method according to claim 6, wherein the first drying treatment is carried out at 40-90 ℃ for 0.5-6.0 h;
optionally, the second drying treatment is carried out at 40-120 ℃ for 2-40 min.
10. A lithium ion battery, comprising: a composite electrode as claimed in any one of claims 1 to 5.
CN202010115119.9A 2020-02-25 2020-02-25 Composite electrode and preparation method and application thereof Pending CN111430721A (en)

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