CN114725394A - Electron-rich negative current collector, preparation method thereof, electrode plate and battery - Google Patents

Electron-rich negative current collector, preparation method thereof, electrode plate and battery Download PDF

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Publication number
CN114725394A
CN114725394A CN202210414363.4A CN202210414363A CN114725394A CN 114725394 A CN114725394 A CN 114725394A CN 202210414363 A CN202210414363 A CN 202210414363A CN 114725394 A CN114725394 A CN 114725394A
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electron
current collector
layer
copper
rich
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王成豪
李学法
张国平
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Jiangyin Nali New Material Technology Co Ltd
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Jiangyin Nali New Material Technology Co Ltd
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Priority to CN202210414363.4A priority Critical patent/CN114725394A/en
Priority to PCT/CN2022/095416 priority patent/WO2023201844A1/en
Publication of CN114725394A publication Critical patent/CN114725394A/en
Priority to PCT/CN2023/089504 priority patent/WO2023202666A1/en
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the technical field of new materials, in particular to an electron-rich negative current collector, a preparation method thereof, an electrode plate and a battery. The invention arranges the charge quantity distribution of 200eV/mm on the surface of the polymer base material layer2～500eV/mm2The electron-rich nano copper layer can effectively prevent the oxidation of copper without additionally adding a zinc or chromium oxidation resistant layer, greatly reduces the interface resistance between different metal layers in the prior art, and improves the performance of a current collectorThe step of galvanizing or chrome plating on the surface of the copper-containing current collector is omitted, the production cost is effectively reduced, and the pollution to the environment is less and more environment-friendly; in addition, the polymer and metal composite is adopted, so that the energy density of the current collector is effectively improved, and compared with the traditional current collector made of all metals, the battery is lighter and thinner.

Description

Electron-rich negative current collector, preparation method thereof, electrode plate and battery
Technical Field
The invention relates to the technical field of new materials, in particular to an electron-rich negative current collector, a preparation method thereof, an electrode plate and a battery.
Background
Due to its good conductivity and low price, copper metal is widely used for preparing negative current collectors of non-aqueous secondary batteries such as lithium batteries. However, since copper is very easily oxidized in air, and the performance thereof is affected, the copper-containing negative electrode current collector needs to be subjected to an oxidation preventing treatment during processing. In the traditional technology, the copper negative current collector is subjected to anti-oxidation treatment by plating a layer of zinc or chromium on the surface of the copper negative current collector to serve as a barrier layer so as to isolate the contact between copper and air, and the storage life of the copper negative current collector is prolonged to about 3 months. However, the use of zinc and chromium not only causes the increase of production cost, but also causes the increase of interface resistance between the current collector and the pole piece, which causes the increase of internal resistance of the battery and influences the capacity and cycle performance of the battery; moreover, galvanizing and chrome plating can generate more industrial wastewater, especially chrome plating, can cause serious environmental pollution due to toxicity, and does not accord with the new concept of green environmental protection.
In addition, conventional negative current collectors are often made entirely of metal, but the metal density is high, resulting in a battery that weighs more and has a lower energy density for an equal volume.
Disclosure of Invention
Therefore, the electron-rich negative electrode current collector which has the advantages of small environmental pollution, small interface resistance, high energy density and good oxidation resistance during production, the preparation method thereof, the electrode plate and the battery are needed to be provided.
In one aspect of the invention, an electron-rich negative electrode current collector is provided, which comprises a polymer substrate layer and two nano copper layers arranged on two sides of the polymer substrate layer;
the nano copper layer is a film layer formed by depositing copper nanoparticles, the nano copper layer is provided with electrons, and the charge quantity distribution of the nano copper layer is 200eV/mm2～500eV/mm2。
In some embodiments, the nano copper layer has a particle size of 10nm to 50 nm.
In some embodiments, the material of the polymeric substrate layer includes one or more of polyethylene terephthalate, polyethylene, polypropylene, and polymethylpentene.
In some embodiments, the starting material of the polymeric substrate layer has a weight average molecular weight of 1000kDa to 1500 kDa.
In some embodiments, the surface roughness of the polymeric substrate layer is from 150nm to 200 nm.
In some embodiments, the electron rich negative current collector has a thickness of 3 μm to 30 μm.
In some embodiments, the polymeric substrate layer has a thickness of 1 μm to 25 μm.
In some embodiments, the thicknesses of the two nano copper layers are each independently selected from 10nm to 3 μm.
In some embodiments, a non-nano copper layer is further present between the polymer substrate layer and at least one side of the nano copper layer, the thickness of the nano copper layer is 10nm to 50nm, and the thickness of the non-nano copper layer is 0.25 μm to 2.99 μm.
In another aspect of the present invention, there is also provided a method for preparing the electron-rich negative electrode current collector, comprising the following steps:
providing the polymer base material layer, and plating electron-rich copper nanoparticles on two sides of the polymer base material layer by a vacuum magnetron sputtering method to obtain two nano copper layers;
the preparation method of the electron-rich copper nanoparticles comprises the following steps:
is prepared from [ Gd2C]2+·2e-Mixing electret, bivalent copper salt and alcohol solvent, reacting at 60-100 deg.C, and magnetic substance reacting2C]2+·2e-Electret adsorption, transferring the rest reaction system, carrying out solid-liquid separation, collecting the solid phase and drying.
In some embodiments, the reaction time in the preparation of the electron-rich copper nanoparticles is 40min to 60 min.
In some embodiments, the vacuum magnetron sputtering comprises the steps of: preparing the electron-rich copper nanoparticles into a target material, and fixing the target material on the surface of the copper nanoparticlesThe polymer substrate layer is arranged on the anode of the magnetron sputtering instrument; vacuumizing the magnetron sputtering instrument until the vacuum degree is less than or equal to 5 multiplied by 10-2And after Pa, filling 1-10 Pa of non-reactive gas, applying a voltage of 2500-3500V between the cathode and the anode to enable atoms in the target material to fly to the anode under the action of an electric field, and depositing on the surface of the polymer base material layer to obtain the nano copper layer.
In another aspect of the present invention, there is provided an electrode sheet comprising the electron-rich negative electrode current collector of any one of the foregoing embodiments.
The invention also provides a battery which comprises the electrode pole piece.
The invention arranges the charge quantity distribution of 200eV/mm on the surface of the polymer base material layer2～500eV/mm2The electron-rich nano copper layer can effectively prevent the oxidation of copper, and a zinc or chromium oxidation resistant layer is not required to be additionally added, so that the interface resistance between different metal layers in the traditional technology is greatly reduced, the performance of the current collector is improved, the step of carrying out zinc plating or chromium plating on the surface of the copper-containing current collector is omitted, the production cost is effectively reduced, the pollution to the environment is less, and the environment is more environment-friendly; in addition, the polymer and metal composite is adopted, so that the energy density of the current collector is effectively improved, and the battery is lighter and thinner compared with the traditional current collector made of all metals.
By reacting [ Gd ]2C]2+·2e-The electret and the cupric salt precursor are used for preparing electron-rich copper nanoparticles through a spontaneous electron transfer way, the charge quantity of the surface of the copper nanoparticles can be controlled under certain reaction conditions, so that the charge distribution of a nano copper layer is further controlled, no additional stabilizer needs to be added in the reaction, the prepared copper nanoparticles have good dispersibility and simple post-treatment, the electret can be transferred through a magnet, conventional solid-liquid separation, drying and other steps are carried out, the electron-rich copper nanoparticles can be obtained, the nanoparticles can be deposited on the surface of a polymer substrate layer through vacuum magnetron sputtering to form a film, and the electron-rich antioxidant negative current collector is obtained. The whole preparation method is simple and controllable, and is easy for industrializationAnd (4) producing.
The electrode pole piece is prepared by adopting the negative current collector, so that the energy density is high, the interface resistance is small, and the performance of the electrode pole piece can be effectively improved; the battery is prepared by adopting the electrode plate containing the negative current collector, so that the capacity and the cycle performance of the battery can be effectively improved.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention are, unless otherwise specified, the final concentrations. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
In the present invention, the "non-reactive gas" refers to a gas that does not affect deposition film formation and does not react with a target in magnetron sputtering, and may be an inert gas such as argon, for example.
In one aspect of the invention, an electron-rich negative current collector is provided, which comprises a polymer substrate layer and two nano copper layers arranged on two sides of the polymer substrate layer;
wherein the nano copper layer is a film layer formed by depositing copper nanoparticles, the nano copper layer is provided with electrons, and the charge quantity distribution of the nano copper layer is 200eV/mm2～500eV/mm2。
By arranging a charge quantity distribution of 200eV/mm on the surface of the polymer base material layer2～500eV/mm2The electron-rich nano copper layer can effectively prevent the oxidation of copper, does not need to additionally increase a zinc or chromium oxidation resistant layer, and has a storage life of 7 months, which is longer than that of 3 months in the prior art adopting the zinc or chromium oxidation resistant layer; moreover, different metals in the traditional technology are greatly reducedThe interface resistance between layers improves the performance of the current collector, reduces the step of galvanizing or chrome plating on the surface of the copper-containing current collector, effectively reduces the production cost, and has less pollution to the environment and more environmental protection; in addition, the polymer and metal composite is adopted, so that the energy density of the current collector is effectively improved, and the battery is lighter and thinner compared with the traditional current collector made of all metals. Generally, the invention provides a negative current collector with better oxidation resistance and better comprehensive performance, the puncture strength of the negative current collector is more than or equal to 50gf, and the tensile strength MD is more than or equal to 150MPa, and the TD is more than or equal to 150 MPa; the elongation MD is more than or equal to 10 percent, and the TD is more than or equal to 10 percent; the surface roughness Rz is less than or equal to 2.5 mu m; the sheet resistance of both surfaces is less than or equal to 38m omega, and the peeling force between the nano copper layer and the polymer substrate layer is more than or equal to 2N/m.
In some embodiments, the charge distribution of the nano-copper layer may be, for example, 320eV/mm2～380eV/mm2And, for example, 200eV/mm2、250eV/mm2、300eV/mm2、350eV/mm2、400eV/mm2Or 450eV/mm2. The charge distribution of the nano copper layer directly influences the performance of the negative current collector, so that on one hand, the sufficient charge can effectively improve the oxidation resistance of the nano copper layer and can also effectively reduce the resistance of the current collector; on the other hand, the excessive charge amount may cause the nano copper layer to be excessively electrostatic, and the nano copper layer may be contaminated during the storage process, thereby affecting the performance. Therefore, the contradiction among the oxidation resistance, the conductivity and the static problem can be well balanced only by the proper charge quantity range, and the comprehensive performance of the current collector is improved to the maximum extent.
In some embodiments, the copper nanoparticles have a particle size of 10nm to 50nm in the nano copper layer. The particle size of the copper nanoparticles may be, for example, 28nm to 43nm, or, for example, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, or 45 nm. The particle size control of copper nanoparticles is in suitable scope, can make the technology degree of difficulty reasonable, and the closely knit degree of the nanometer copper layer that makes is higher to make the nanometer copper layer can possess sufficient electric charge quantity in order to realize anti-oxidant effect, and mechanical strength is also higher, is favorable to promoting the security of battery.
In some embodiments, the material of the polymeric substrate layer includes one or more of polyethylene terephthalate, polyethylene, polypropylene, and polymethylpentene. The low-density polymers such as polyethylene terephthalate, polyethylene, polypropylene, polymethylpentene and the like are adopted, so that the density of the prepared negative electrode current collector is lower, and the energy density of the battery is further improved.
In some embodiments, the starting material for the polymeric substrate layer has a weight average molecular weight of 1000kDa to 1500 kDa. The weight average molecular weight of the starting material of the polymeric substrate layer may be, for example, 1100kDa, 1200kDa, 1300kDa or 1400 kDa. The appropriate weight average molecular weight enables the strength and the density of the polymer base material layer to be more balanced, and the comprehensive performance of the current collector is further improved.
In some embodiments, the surface roughness of the polymeric substrate layer is from 150nm to 200 nm. The surface roughness of the polymeric substrate layer may be, for example, 155nm, 160nm, 165nm, 170nm, 175nm, 180nm, 185nm, 190nm, or 195 nm. The polymer substrate layer has proper roughness, can be tightly combined with the nano copper layer, and avoids the peeling between layers.
In some embodiments, the electron rich negative current collector has a thickness of 3 μm to 30 μm. The thickness of the electron-rich negative electrode current collector may be, for example, 6 μm to 24 μm, or, for example, 5 μm, 10 μm, 15 μm, 20 μm, or 25 μm.
In some embodiments, the polymeric substrate layer has a thickness of 1 μm to 25 μm. The thickness of the polymer substrate layer may be, for example, 4 μm to 20 μm, or, for example, 5 μm, 10 μm, or 15 μm.
In some embodiments, the thicknesses of the two nano-copper layers are each independently selected from 10nm to 3 μm. Further, the thicknesses of the two nano copper layers can be, for example, independently selected from 0.5 μm to 2.5 μm, and can also be, for example, independently selected from 0.4 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm, 2.0 μm, 2.4 μm, 2.6 μm, or 2.8 μm.
In some embodiments, a non-nano copper layer is further present between the polymer substrate layer and the nano copper layer on at least one side, the nano copper layer has a thickness of 10nm to 50nm, and the non-nano copper layer has a thickness of 0.25 μm to 2.99 μm. The main purpose of the nano copper layer in the invention is to replace the traditional zinc or chromium layer as an antioxidation layer, therefore, in order to further reduce the cost, part of the nano copper layer in the scheme can be replaced by the common non-nano copper layer to play the basic electron collecting function, and the thickness of the nano copper layer playing the antioxidation role is maintained between 10nm and 50 nm. In this case, the thickness of the nano copper layer may be, for example, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm or 45nm, and the thickness of the non-nano copper layer may be, for example, 0.3 μm, 0.5 μm, 0.7 μm, 0.9 μm, 1.1 μm, 1.3 μm, 1.5 μm, 1.7 μm, 1.9 μm, 2.1 μm, 2.3 μm, 2.5 μm, 2.7 μm or 2.9 μm.
In some embodiments, the non-nanocopper layer is prepared by: copper material with the purity of more than 99.9 percent, water and sulfuric acid are mixed to prepare copper sulfate electrolyte, and then divalent copper in the copper sulfate electrolyte is reduced into a copper simple substance in an electroplating mode to prepare the non-nano copper layer. The copper layer prepared by the method has high purity, good quality and good bonding degree with the polymer base material layer.
In another aspect of the present invention, there is also provided a method for preparing the electron-rich negative electrode current collector, comprising the following steps:
providing a polymer base material layer, plating electron-rich copper nanoparticles on two sides of the polymer base material layer by a vacuum magnetron sputtering method to prepare two nano copper layers;
the preparation method of the electron-rich copper nanoparticles comprises the following steps:
is prepared from [ Gd2C]2+·2e-Mixing electret, bivalent copper salt and alcohol solvent, reacting at 60-120 deg.C, and magnetic substance reacting2C]2+·2e-Electret adsorption, transferring the rest reaction system, carrying out solid-liquid separation, collecting the solid phase and drying. Preferably, the magnetic substance is a magnet.
By reacting [ Gd2C]2+·2e-The electret and the cupric salt precursor are used for preparing the electron-rich copper nano-particles through a spontaneous electron transfer way, and the surface of the copper nano-particles can be controlled under certain reaction conditionsThe charge quantity of the surface is controlled, so that the charge distribution of the nano copper layer is further controlled, no additional stabilizer is needed to be added in the reaction, the prepared copper nanoparticles are good in dispersibility and simple in post-treatment, the electret can be transferred through a magnet, conventional solid-liquid separation, drying and other steps are carried out, the copper nanoparticles rich in electrons can be obtained, and the nanoparticles can be deposited on the surface of the polymer base material layer through vacuum magnetron sputtering to form a film, so that the electron-rich antioxidant negative current collector is obtained. The whole preparation method is simple and controllable, and is easy for industrial production.
An electret, i.e. a permanent magnet, is a dielectric material that itself carries an electric charge, and the electric charge is nearly permanent. In the present invention by using [ Gd ]2C]2+·2e-The electret can reduce a bivalent copper precursor into a nano copper simple substance with a proper particle size, and transfer electrons to the surface of nano copper to enable the nano copper to have negative charges, so that the electret has oxidation resistance. [ Gd ] used in the present invention2C]2+·2e-The electret may be prepared by reference to the following preparation method: under the protection of argon, Gd metal sheet (99.9%) and graphite are prepared according to the molar ratio of 2:1 by an electric arc melting method; to ensure uniformity, the cooling and melting process can be repeated three times; after smelting, the [ Gd ] is added2C]2+·2e-Transferring the cast ingot into a glove box, grinding to remove surface oxide layer, and grinding into powder to obtain [ Gd2C]2+·2e-An electret.
In some embodiments, the divalent copper salt may be, for example, one or more of copper chloride, copper sulfate, and copper nitrate, with copper chloride being preferred.
In some embodiments, the alcoholic solvent may be, for example, hexanol, ethanol, or isopropanol, with hexanol being preferred.
In some embodiments, the reaction temperature may also be, for example, 70 ℃, 90 ℃, 100 ℃, or 110 ℃. Preferably, the reaction temperature is 80 ℃, and the proper reaction temperature can ensure that the particle size of the nano-copper formed by the reduction of the bivalent copper is more proper.
In some embodiments, [ Gd ]2C]2+·2e-Electret and divalent copperThe ratio of the amount of salt to the amount of salt is (1.5-2.5): 1, preferably 2: 1.
In some embodiments, the concentration of the cupric salt in the alcoholic solvent is 0.05mol/L to 0.15mol/L, preferably 0.1 mol/L.
The spontaneous electron transfer can be better controlled by proper concentration and proper electret, namely the mole ratio of the cupric salt precursor, so that the copper nanoparticles can take proper electron quantity.
In some embodiments, the reaction time in the preparation of the electron-rich copper nanoparticles is 40min to 60 min. Further, the reaction time may be, for example, 45min, 50min or 55 min. The appropriate reaction time can enable the surface of the nano copper to carry appropriate number of electrons, so that the surface charge quantity distribution of the prepared nano copper layer can be further more appropriate.
In some embodiments, vacuum magnetron sputtering comprises the steps of: preparing the copper nano particles rich in electrons into a target material, fixing the target material on a cathode of a magnetron sputtering instrument, and placing a polymer substrate layer on an anode of the magnetron sputtering instrument; vacuumizing the magnetron sputtering instrument until the vacuum degree is less than or equal to 5 multiplied by 10-2And after Pa, filling 1-10 Pa of non-reactive gas, and applying 2500-3500V of voltage between the cathode and the anode to make atoms in the target fly to the anode under the action of an electric field, and depositing on the surface of the polymer substrate layer to obtain the nano copper layer. Further, the pressure of the non-reactive gas may be, for example, 2Pa, 4Pa, 6Pa, or 8Pa, and the voltage between the cathode and the anode may be, for example, 2750V, 3000V, or 3250V. The prepared nano copper layer has more proper charge quantity distribution by proper magnetron sputtering parameters, so that the negative current collector has good oxidation resistance and is not too large in static electricity.
In some embodiments, the unwinding tension for providing the polymer substrate layer may be, for example, 6N to 25N, and may also be, for example, 8N, 10N, 12N, 14N, 16N, 18N, 20N, 22N, or 24N.
In some embodiments, the tension for winding the electron-rich negative electrode current collector may be, for example, 4N to 15N, and may also be, for example, 6N, 8N, 10N, 12N, or 14N.
In some embodiments, the unwinding and/or winding speed may be, for example, 25m/min to 35m/min, or, for example, 30 m/min.
The quality of the negative current collector can be further improved by proper winding and unwinding tension and speed. In another aspect of the present invention, there is also provided an electrode sheet comprising the electron-rich negative electrode current collector of any one of the foregoing embodiments.
The invention also provides a battery, which comprises the electrode pole piece.
The electrode pole piece is prepared by adopting the negative current collector, so that the energy density is high, the interface resistance is small, and the performance of the electrode pole piece can be effectively improved; the battery is prepared by adopting the electrode pole piece containing the negative current collector, so that the capacity and the cycle performance of the battery can be effectively improved.
The present invention will be described in further detail with reference to specific examples and comparative examples. Experimental parameters not described in the following specific examples are preferably referred to the guidelines given in the present application, and may be referred to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by the manufacturer. It is understood that the following examples are specific to the particular apparatus and materials used, and in other embodiments, are not limited thereto; the weight of the related components mentioned in the embodiments of the present specification may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the embodiments of the present specification according to the present specification. Specifically, the weight described in the description of the embodiments of the present invention may be a mass unit known in the chemical engineering field, such as μ g, mg, g, kg, etc.
[Gd2C]2+·2e-Preparing an electret: under the protection of argon, Gd metal sheet (99.9%) and graphite are prepared according to the molar ratio of 2:1 by an electric arc melting method; to ensure uniformity, the cooling and melting process can be repeated three times; after smelting, the [ Gd ] is added2C]2+·2e-Transferring the cast ingot into a glove box, grinding to remove surface oxide layer, and grinding into powderForm [ Gd ] to obtain2C]2+·2e-An electret.
Example 1
(1) 1mmol of [ Gd ]2C]2+·2e-Electret, 0.5mmol of cupric chloride mixed with 5mL of hexanol, reacted at 80 ℃ for 50min, then [ Gd ] was reacted with a magnet2C]2+·2e-Electret adsorbing, performing solid-liquid separation on the residual reaction system, collecting a solid phase, and drying to obtain copper nanoparticles with the average particle size of 30 nm;
(2) preparing the copper nanoparticles prepared in the step (1) into a target material, fixing the target material on a cathode of a magnetron sputtering instrument, and placing a polyethylene terephthalate substrate layer (with the weight average molecular weight of 100000Da and the surface roughness of 150nm) with the thickness of 4 microns on an anode of the magnetron sputtering instrument; vacuumizing the magnetron sputtering instrument until the vacuum degree is less than or equal to 5 multiplied by 10-2Introducing 10Pa argon after Pa, applying 3000V voltage between the cathode and the anode to make atoms in the target fly to the anode under the action of an electric field, and depositing on one surface of the polyethylene terephthalate substrate layer to form a layer with the thickness of 1 μm and the charge amount distribution of 350eV/mm2The nano copper layer; repeating the above steps to form another surface of the polyethylene terephthalate substrate layer with thickness of 1 μm and charge amount distribution of 350eV/mm2Preparing an electron-rich negative current collector by using the nano copper layer;
(3) and (3) rolling and storing the electron-rich negative current collector prepared in the step (2) by adopting a rolling tension of 6N and a rolling speed of 30 m/min.
Example 2
Substantially in accordance with example 1, except that the reaction temperature in step (1) was adjusted to 60 ℃ so that the average particle diameter of the copper nanoparticles was 45 nm.
Example 3
Substantially in accordance with example 1, except that the reaction time of step (1) was adjusted to 60min to obtain a charge amount distribution of the nano-copper layer obtained in step (2) of 450eV/mm2。
Example 4
The method is basically consistent with the embodiment 1, and has the difference that a part of common non-nano copper target materials are adopted to replace nano copper target materials, and the prepared electron-rich cathode current collector has the following structures in sequence: a nano copper layer with the thickness of 10nm, a non-nano copper layer with the thickness of 0.99 mu m, a polyethylene terephthalate substrate layer with the thickness of 4 mu m, a non-nano copper layer with the thickness of 0.99 mu m and a nano copper layer with the thickness of 10 nm.
Example 5
(1) 1mmol of [ Gd ]2C]2+·2e-Electret, 0.5mmol of cupric chloride mixed with 5mL of hexanol, reacted at 120 ℃ for 45min, then [ Gd ] was added with magnet2C]2+·2e-Electret adsorbing, carrying out solid-liquid separation on the rest reaction system, collecting the solid phase, and drying to obtain copper nanoparticles with the average particle size of 10 nm;
(2) preparing the copper nanoparticles prepared in the step (1) into a target material, fixing the target material on a cathode of a magnetron sputtering instrument, and placing a polypropylene substrate layer (with the weight-average molecular weight of 150000Da and the surface roughness of 200nm) with the thickness of 8 microns on an anode of the magnetron sputtering instrument; vacuumizing the magnetron sputtering instrument to the vacuum degree of less than or equal to 5 multiplied by 10-2Introducing 10Pa argon gas after Pa, applying 3000V voltage between the cathode and the anode to make atoms in the target fly to the anode under the action of electric field, and depositing on one surface of the polypropylene substrate layer to form a layer with thickness of 0.5 μm and charge amount distribution of 250eV/mm2The nano copper layer; repeating the above steps to form another surface of the polypropylene substrate layer with a thickness of 0.5 μm and a charge amount distribution of 250eV/mm2Preparing an electron-rich cathode current collector;
(3) and (3) rolling and storing the electron-rich negative current collector prepared in the step (2) by adopting a rolling tension of 6N and a rolling speed of 30 m/min.
Comparative example 1
Substantially in accordance with example 1, except that the reaction time of step (1) was adjusted to 100min so that the charge amount distribution of the nano-copper layer obtained in step (2) was 600eV/mm2。
Comparative example 2
Substantially in accordance with example 1, except that the reaction time of step (1) was adjusted to 20min so that the nano-copper layer obtained in step (2) had a charge amount distribution of 100eV/mm2。
Comparative example 3
Substantially in accordance with example 1, except that the reaction temperature in step (1) was adjusted to 55 ℃ so that the average particle diameter of copper nanoparticles was 60 nm.
Comparative example 4
Substantially the same as in example 1 except that the voltage in the step (2) was adjusted to 4500V.
Comparative example 5
In substantial agreement with example 4, except that two 10nm thick nanocopper layers were replaced with two protective layers, respectively, the protective layers consisted of a 7nm thick barrier layer of metallic zinc and a 3nm thick oxidation resistant layer of metallic chromium.
Performance characterization and testing:
respectively carrying out basic characterization and the following tests on the composite current collectors prepared in the embodiments and the comparative examples according to the GB/T36363-2018 standard, wherein the oxidation resistance test can be observed by naked eyes, the oxidized copper foil gradually turns red, and the oxidized copper foil turns black when continuously oxidized; the structure of the 100Ah lithium battery used is as follows: the positive electrode is an NCM811 ternary material, the negative electrode is graphite, the electrolyte is a liquid lithium salt solution of lithium hexafluorophosphate, the diaphragm is a wet-process PE diaphragm, and the whole battery is a soft package aluminum plastic film shell battery. The results obtained are shown in Table 1:
(1) surface static measurement
(2) Measurement of tensile Strength and elongation
(3) Puncture strength measurement
(4) Roughness measurement
(5) Sheet resistance measurement
(6) Oxidation resistance test
(7) Internal resistance measurement (100Ah lithium battery)
(8) Energy density measurement (100Ah lithium battery)
TABLE 1
Figure BDA0003604886880000141
As can be seen from table 1, the negative electrode current collectors prepared in examples 1 to 5 have moderate surface static electricity, have good oxidation resistance, start to oxidize in 200 days or more, and have good basic properties such as mechanical strength and energy density. Compared with the preferred embodiment 1, the embodiment 2 has the advantages that the copper nanoparticles with a slightly larger particle size can reduce the strength of the current collector to a certain degree, the roughness is slightly increased, and the energy density is lower due to the reduction of the compactness to a certain degree; in example 3, the charge amount is slightly high, the improvement of the antioxidation performance is limited, but the surface static electricity is higher, the storage difficulty is slightly high, and the sheet resistance of the two surfaces can be different due to improper storage; in the embodiment 4, a common non-nano copper layer is adopted to replace part of nano copper, so that the cost is obviously reduced, but various performances are also reduced to a certain degree;
in comparative examples 1 and 2, the surface static electricity is too large to be stored due to improper charge distribution and too high charge distribution, and the sheet resistance difference between the two surfaces is large; if the charge distribution is too low, the oxidation resistance of the current collector is obviously reduced; in the comparative example 3, the average particle size of the copper nanoparticles is too large, which has certain influence on the oxidation resistance and other basic performances of the current collector; in comparative example 4, excessive voltage in step (2) may cause loss of electrons on the surface of the current collector, resulting in too low charge distribution, which may affect oxidation resistance and may also adversely affect mechanical properties; comparative example 5 adopts a conventional method using zinc as a barrier layer and chromium as an oxidation preventing layer, not only oxidation resistance is inferior to each example, but also electrical properties are not good due to the presence of interface resistance, and elongation is also poor due to poor integrity of the materials used together.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the invention is subject to the appended claims, and the description can be used for explaining the contents of the claims.

Claims (10)

1. The electron-rich negative current collector is characterized by comprising a polymer base material layer and two nano copper layers arranged on two sides of the polymer base material layer;
the nano copper layer is a film layer formed by depositing copper nanoparticles, the nano copper layer is provided with electrons, and the charge quantity distribution of the nano copper layer is 200eV/mm2～500eV/mm2。
2. The electron rich negative electrode current collector of claim 1, wherein the nano copper layer has a particle size of copper nanoparticles ranging from 10nm to 50 nm.
3. The electron rich negative electrode current collector of claim 1, wherein the material of the polymer substrate layer comprises one or more of polyethylene terephthalate, polyethylene, polypropylene, and polymethylpentene; and/or
The surface roughness of the polymer base material layer is 150 nm-200 nm.
4. The electron rich negative electrode current collector of claim 3, wherein the weight average molecular weight of the starting material of the polymeric substrate layer is from 1000kDa to 1500 kDa.
5. The electron rich negative electrode current collector according to any one of claims 1 to 4, wherein the thickness of the electron rich negative electrode current collector is 3 μm to 30 μm; and/or
The thickness of the polymer base material layer is 1-25 μm; and/or
The thicknesses of the two nano copper layers are respectively and independently selected from 10 nm-3 mu m.
6. The electron-rich negative electrode current collector as claimed in any one of claims 1 to 4, wherein a non-nano copper layer is further present between the polymer substrate layer and the nano copper layer on at least one side, the thickness of the nano copper layer is 10nm to 50nm, and the thickness of the non-nano copper layer is 0.25 μm to 2.99 μm.
7. The method for preparing an electron-rich negative electrode current collector as claimed in any one of claims 1 to 6, comprising the steps of:
providing the polymer base material layer, and plating electron-rich copper nanoparticles on two sides of the polymer base material layer by a vacuum magnetron sputtering method to obtain two nano copper layers;
the preparation method of the electron-rich copper nanoparticles comprises the following steps:
is prepared from [ Gd2C]2+·2e-Mixing electret, bivalent copper salt and alcohol solvent, reacting at 60-100 deg.C, and magnetic substance reacting2C]2+·2e-Electret adsorption, transferring the rest reaction system, carrying out solid-liquid separation, collecting the solid phase and drying.
8. The method according to claim 7, wherein in the preparation of the electron-rich copper nanoparticles, the reaction time is 40 to 60 min; and/or
The vacuum magnetron sputtering comprises the following steps: preparing the electron-rich copper nanoparticles into a target material, fixing the target material on a cathode of a magnetron sputtering instrument, and placing the polymer substrate layer on an anode of the magnetron sputtering instrument; vacuumizing the magnetron sputtering instrument to the vacuum degree of less than or equal to 5 multiplied by 10-2And after Pa, filling 1-10 Pa of non-reactive gas, applying a voltage of 2500-3500V between the cathode and the anode to enable atoms in the target material to fly to the anode under the action of an electric field, and depositing on the surface of the polymer base material layer to obtain the nano copper layer.
9. An electrode sheet comprising the electron-rich negative electrode current collector according to any one of claims 1 to 6.
10. A battery comprising the electrode sheet of claim 9.
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