CN116072884B - Composite porous current collector copper foil of lithium battery and preparation method thereof - Google Patents
Composite porous current collector copper foil of lithium battery and preparation method thereof Download PDFInfo
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- CN116072884B CN116072884B CN202310271348.3A CN202310271348A CN116072884B CN 116072884 B CN116072884 B CN 116072884B CN 202310271348 A CN202310271348 A CN 202310271348A CN 116072884 B CN116072884 B CN 116072884B
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- 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
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- H—ELECTRICITY
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- 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
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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
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/668—Composites of electroconductive material and synthetic resins
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- H—ELECTRICITY
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- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium battery composite porous current collector copper foil and a preparation method thereof, the preparation method comprises the steps of mixing a copper nitrate aqueous solution and polystyrene powder, adding a surfactant, stirring, defoaming, and uniformly mixing with absolute ethyl alcohol to obtain a suspension; paving a layer of absolute ethyl alcohol or acetone solvent film on a monocrystalline silicon substrate, and injecting the suspension onto the absolute ethyl alcohol or acetone solvent film; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid single-layer film attached to the monocrystalline silicon substrate is obtained and is transferred to absolute ethyl alcohol or acetone to float on the liquid surface; the PI film fixed on the carrier is used for fishing out the binary colloid single-layer film, the binary colloid single-layer film is dried, annealed in hydrogen after annealing in air, the PI film with the single-sided attached porous copper foil is prepared, the binary colloid single-layer film floating on the liquid surface is fished out after the PI film is turned over, and the steps of drying and annealing are repeated. The copper foil obtained by the preparation method is compact and uniform, and the prepared battery core has good circularity.
Description
Technical Field
The invention relates to the technical field of preparation and processing of lithium battery materials, in particular to a lithium battery composite porous current collector copper foil and a preparation method thereof.
Background
Lithium batteries are widely used in consumer electronics, power cells, energy storage, and other fields due to their stable cycle and high energy density. Meanwhile, due to the rapid development of electric automobiles, higher requirements are put on the safety, stability and energy density of lithium batteries. The lithium battery mainly comprises four parts, namely a positive electrode, a diaphragm, a negative electrode and a current collector. Current collectors are one of the main components of lithium batteries to maintain the transfer of electrical power between the electrodes and external circuitry, affecting the electrochemical performance of the battery.
In the lithium battery industry, copper foil and aluminum foil are commonly used as negative current collectors for lithium batteries as carriers for electrode materials, binders and conductive materials. The current negative electrode current collector mainly used is pure copper electrolytic copper foil with the thickness of about 6-9 mu m. The volume of the cathode material is also changed during the charge and discharge process of the battery. The copper foil used as the negative electrode current collector can be stretched and contracted continuously, and the negative electrode material can fall off to cause potential safety hazards such as capacity reduction, performance reduction, resistance increase, heat generation increase and the like. In addition, there is a risk of explosion of the battery after the battery is damaged due to dendrite growth, external force, and the like to cause thermal runaway. Therefore, the copper foil material needs to be modified to stabilize the battery capacity, improve the cycle performance and reduce the safety risk.
The composite current collector is of a sandwich structure of metal-high polymer material-metal, and a high polymer insulating material such as PET/PP/PI is used as a sandwich layer, and metal aluminum or metal copper is deposited on the upper surface and the lower surface of the sandwich structure. The composite current collector represented by the composite copper foil has the advantages of high safety, high specific energy, long service life, low cost, strong compatibility and the like, and is a good substitute material for the traditional lithium battery current collector (aluminum foil and copper foil). The expansion rate of the polymer layer in the middle of the composite copper foil is lower, the falling of active substances caused by metal shrinkage can be effectively reduced, and the cycle life of the battery is prolonged. Meanwhile, the high polymer material is heated to generate a circuit breaking effect, so that the influence factors of the puncture diaphragm are weakened, and the thermal runaway risk of the battery can be greatly reduced. The PET/PP/PI composite copper foil has good compatibility, can be matched with the existing battery system, and can reduce the weight of a current collector, increase the energy density of the battery and reduce the manufacturing cost by virtue of low density besides improving the safety of the battery.
The current preparation of the copper foil of the composite current collector is carried out by a 'two-step method' and a 'three-step method', and the process strategies of 'magnetron sputtering + water electroplating' and 'magnetron sputtering + vacuum plating + water electroplating' are adopted respectively. For example, the copper foil of the composite current collector is prepared by a 'two-step method', and a layer of metallic copper with the thickness of less than 100 nanometers is firstly subjected to magnetron sputtering on the surface of a high polymer layer, and a film is metallized; and then, thickening the copper layer to 1 micron by adopting a water electroplating mode, wherein the whole thickness of the composite copper foil is within 10 microns to replace the traditional electrolytic copper foil. For example, chinese patent application publication No. CN108531876a discloses a plating process for a lithium battery current collector, which is to plate a metal film on an ultrathin substrate to obtain a plating product with improved adhesion, and the process comprises the steps of plating a magnetic control film on the surface of the ultrathin substrate for 5-50nm, and then plating a water plating film for 600-1000nm; or the process flow is as follows, firstly adopting magnetic control plating film 5-50nm on the surface of the ultrathin substrate, then evaporating plating film 100-700nm, and finally plating film 100-800nm by water plating. The current difficulty in the manufacture of composite current collector copper foil is the close compounding and uniformity of organic polymers and inorganic metals. The non-uniformity of the magnetron sputtering copper plating can be amplified until the next step of water electroplating, so that the subsequent extensibility is problematic, and the yield is low. In addition, if the magnetic field and the electric field are not well controlled by magnetron sputtering, part of particle bombardment can cause damage to the polymer film. There is therefore an urgent need to develop a new non-destructive fabrication method for stable production of composite current collector copper foil.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a composite current collector copper foil in a nondestructive manner, which increases the composite bonding performance of an organic polymer and inorganic metal copper, improves the uniformity of the composite porous current collector copper foil and is used for enhancing the cycle performance of a prepared battery cell.
The invention solves the technical problems by the following technical means:
the preparation method of the lithium battery composite porous current collector copper foil comprises the following steps:
s1, mixing a copper nitrate aqueous solution and polystyrene powder to form a mixed solution, adding a surfactant, stirring to obtain a dispersion liquid, and defoaming to obtain a metal salt doped binary colloidal sphere stock solution; wherein the polystyrene powder has a particle size of < 1 μm;
s2, uniformly mixing the metal salt doped binary colloid pellet stock solution and absolute ethyl alcohol to prepare a metal salt doped binary colloid pellet suspension;
s3, uniformly spreading a layer of absolute ethyl alcohol solvent film or acetone solvent film on the monocrystalline silicon substrate, and then injecting the metal salt doped binary colloidal bead suspension onto the absolute ethyl alcohol solvent film or the acetone solvent film; after the solvent on the monocrystalline silicon substrate is volatilized, obtaining a binary colloid monolayer film attached to the monocrystalline silicon substrate;
s4, transferring the binary colloid single-layer film prepared by the method into absolute ethyl alcohol or acetone to enable the binary colloid single-layer film to float on the liquid surface; the PI film fixed on the carrier is used for fishing out the binary colloid single-layer film, and a semi-finished product with a single-sided adhesive colloid single-layer film is prepared;
s5, drying the semi-finished product of the single-sided adhesive colloid single-layer film, and annealing to obtain a PI film with a single-sided adhesive porous copper foil; wherein the annealing comprises annealing performed in an air atmosphere and annealing performed in a hydrogen atmosphere in sequence;
s6, turning over the PI film with the porous copper foil attached on one side, then fishing out the binary colloid single-layer film floating on the liquid surface in the S4, and repeating the S5 to obtain the lithium battery composite porous current collector copper foil.
Preferably, in S1, the mass ratio of copper nitrate to polystyrene powder in the copper nitrate aqueous solution is 10-20:20.
preferably, in S1, the copper nitrate aqueous solution has a mass fraction of copper nitrate of 20-40%; and mixing the copper nitrate aqueous solution and the polystyrene powder according to the mass ratio of 50:20 to form a mixed solution.
Preferably, in S1, the surfactant is one or a mixture of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, and sodium dodecyl diphenyl ether disulfonate.
Preferably, in S1, the copper nitrate aqueous solution is obtained by mixing copper nitrate and deionized water according to a mass ratio of 20-40:60-80 and stirring at a rotation speed of 400-800rpm until the copper nitrate aqueous solution is completely dissolved.
Preferably, in S1, the polystyrene powder has a particle size of 100 to 500nm.
Preferably, in S1, the mass of the surfactant is 0.5-2% of the mass of the mixed solution.
Preferably, in S2, the volume ratio of the metal salt doped binary colloidal bead stock solution to the absolute ethanol is 3-5:3-5.
Preferably, in S3, the dosage of the absolute ethyl alcohol or the acetone on the monocrystalline silicon substrate is 3-5mL/6 inch in the process of forming the absolute ethyl alcohol solvent film or the acetone solvent film; the volume ratio of the total volume of the metal salt doped binary colloidal sphere suspension to the volume of the absolute ethyl alcohol or acetone used is 20 mu L:3-5mL.
Preferably, in S5, the annealing performed in the air atmosphere means annealing in a tube furnace at 230-300 ℃ for 1-3 hours; the annealing is performed in a hydrogen atmosphere at a temperature of 300 ℃ for 1-3 hours.
Preferably, in S1, the stirring speed is 600rpm for 30min.
Preferably, in S4, the carrier is one of a stainless steel plate, an enamel glass plate, and an alumina plate.
Preferably, in S4, the PI film has a thickness of 6 μm and a size of 10cm×10cm.
Preferably, in S5, the temperature of the drying is 80 ℃ and the time is 30min.
The invention also provides a lithium battery composite porous current collector copper foil, which is prepared by adopting the preparation method of the lithium battery composite porous current collector copper foil.
The invention has the advantages that:
firstly, preparing a metal salt doped binary colloidal globule stock solution, and adding a surfactant to facilitate obtaining a dispersion liquid in the preparation process; then further preparing a metal salt doped binary colloid pellet suspension, then self-assembling through a soft template interface to prepare a binary colloid single-layer film, attaching the binary colloid single-layer film on the surface of the PI film through lossless transfer, and then drying and atmosphere-containing annealing to prepare the PI film with the single-sided attached porous copper foil. And repeating the film coating and annealing to obtain the double-sided composite porous current collector copper foil, and compounding by adopting a soft template interface self-assembly-lossless transfer technology to prepare the composite porous current collector copper foil. On one hand, the copper foil of the polymer layer is attached in a soft template attaching mode, so that the polymer layer is not easy to damage; on the other hand, the copper foil prepared by the soft template has a porous structure, so that the electron transmission capacity can be enhanced, and the energy density of the battery can be further increased.
The preparation method provided by the invention has the advantages of no damage to the polymer layer, simplified process, stable production performance of the copper foil for the composite current collector, tight composite of the obtained copper foil polymer layer and inorganic metal copper, good uniformity and good cycle performance of the battery core prepared by the copper foil.
Drawings
FIG. 1 is a flow chart of the preparation process of the composite porous current collector copper foil for lithium battery in example 1 of the invention;
FIG. 2 is a scanning electron microscope image of the composite porous current collector copper foil prepared in example 3 of the present invention;
FIG. 3 is a scanning electron microscope image of the composite porous current collector copper foil prepared in comparative example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of the composite porous current collector copper foil prepared in comparative example 1 of the present invention;
figure 5 is a scanning electron microscope image of a commercial composite copper foil used in the comparative test.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
FIG. 1 is a flow chart of the preparation process of the composite porous current collector copper foil for lithium battery in example 1 of the invention; referring to fig. 1, a method for preparing a lithium battery composite porous current collector copper foil comprises the following specific steps:
(1) Preparation of metal salt doped binary colloidal sphere stock solution
Mixing copper nitrate and deionized water according to a mass ratio of 40:60, and stirring at a rotating speed of 600rpm until the copper nitrate and the deionized water are completely dissolved to obtain a solution; mixing and stirring the solution and polystyrene powder (with the particle size of 100 nm) according to the mass ratio of 50:20 to form a mixed solution, adding sodium dodecyl benzene sulfonate accounting for 2% of the total mass of the mixed solution, stirring at 600rpm for 30min to obtain a dispersion, and defoaming to obtain a metal salt doped binary colloidal globule stock solution;
(2) Preparation of metal salt doped binary colloidal sphere suspension
Uniformly dispersing the prepared metal salt doped binary colloidal sphere stock solution and absolute ethyl alcohol in an ultrasonic way according to the volume ratio of 3:5 to prepare metal salt doped binary colloidal sphere suspension;
(3) Preparation of binary colloid monolayer film
Uniformly spreading a layer of absolute ethyl alcohol solvent film (the dosage of absolute ethyl alcohol is 4 mL) on a clean monocrystalline silicon substrate with the diameter of 6 inches, and then using a micropipette to inject uniformly dispersed metal salt doped binary colloidal small ball suspension (20 mu L) onto the absolute ethyl alcohol solvent film for multiple times, so that colloidal particles are diffused at an interface and self-assembled; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid monolayer film attached to the monocrystalline silicon substrate can be obtained;
(4) Attachment of binary colloid monolayer film
And slowly transferring the prepared binary colloid single-layer film into absolute ethyl alcohol to enable the binary colloid single-layer film to float on the liquid surface. Slowly extending a PI film (thickness 6 μm, size 10cm×10 cm) fixed on a stainless steel plate below the liquid level, and then pulling up to obtain a binary colloid single-layer film to obtain a semi-finished product with a single-sided adhesive colloid single-layer film;
(5) Preparation of PI film with porous copper foil attached on one side
And (3) putting the semi-finished product with the single-sided adhesive colloid monolayer film into an oven to be dried for 30min at 80 ℃ so that the adhesive colloid monolayer film is more tightly adhered. Annealing for 3 hours in an air atmosphere at 230 ℃ in a tube furnace, and annealing for 3 hours in a hydrogen atmosphere at 300 ℃ to prepare the PI film with the porous copper foil attached on one side;
(6) Preparation of double-sided composite porous current collector copper foil
Turning over the PI film with the porous copper foil attached on one side, and repeating the steps (3) - (5) to obtain the double-sided composite porous current collector copper foil, namely the lithium battery composite porous current collector copper foil.
Example 2
The preparation method of the lithium battery composite porous current collector copper foil comprises the following specific steps:
(1) Preparation of metal salt doped binary colloidal sphere stock solution
Mixing copper nitrate and deionized water according to a mass ratio of 20:80, and stirring at a rotating speed of 600rpm until the copper nitrate and the deionized water are completely dissolved to obtain a solution; mixing and stirring the solution and polystyrene powder (with the particle size of 200 nm) according to the mass ratio of 50:20 to form a mixed solution, adding sodium dodecyl sulfate accounting for 0.5% of the total mass of the mixed solution, stirring at 400rpm for 30min to obtain a dispersion, and defoaming to obtain a metal salt doped binary colloidal sphere stock solution;
(2) Preparation of metal salt doped binary colloidal sphere suspension
Uniformly dispersing the prepared metal salt doped binary colloidal sphere stock solution and absolute ethyl alcohol in an ultrasonic way according to the volume ratio of 4:4 to prepare metal salt doped binary colloidal sphere suspension;
(3) Preparation of binary colloid monolayer film
Uniformly spreading an acetone solvent film (the dosage of acetone is 3 mL) on a clean monocrystalline silicon substrate with the diameter of 6 inches, and then using a micropipette to inject uniformly dispersed metal salt doped binary colloidal bead suspension (20 mu L) onto the acetone solvent film for multiple times, so that colloidal particles are diffused at an interface and self-assembled; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid monolayer film attached to the monocrystalline silicon substrate can be obtained;
(4) Attachment of binary colloid monolayer film
And slowly transferring the binary colloid single-layer film prepared by the method into acetone to enable the binary colloid single-layer film to float on the liquid surface. Slowly extending a PI film (thickness 6 μm, size 10cm×10 cm) fixed on an enamel glass plate below the liquid level, and then pulling up to obtain a binary colloid single-layer film to obtain a semi-finished product with a single-sided adhesive colloid single-layer film;
(5) Preparation of PI film with porous copper foil attached on one side
And (3) putting the semi-finished product with the single-sided adhesive colloid monolayer film into an oven to be dried for 30min at 80 ℃ so that the adhesive colloid monolayer film is more tightly adhered. Annealing for 3 hours in an air atmosphere at 270 ℃ in a tube furnace, and annealing for 1 hour in a hydrogen atmosphere at 300 ℃ to prepare the PI film with the porous copper foil attached on one side;
(6) Preparation of double-sided composite porous current collector copper foil
Turning over the PI film with the porous copper foil attached on one side, and repeating the steps (3) - (5) to obtain the double-sided composite porous current collector copper foil, namely the lithium battery composite porous current collector copper foil.
Example 3
The preparation method of the lithium battery composite porous current collector copper foil comprises the following specific steps:
(1) Preparation of metal salt doped binary colloidal sphere stock solution
Mixing copper nitrate and deionized water according to a mass ratio of 30:70, and stirring at a rotating speed of 600rpm until the copper nitrate and the deionized water are completely dissolved to obtain a solution; mixing and stirring the solution and polystyrene powder (particle size 500 nm) according to a mass ratio of 50:20 to form a mixed solution, adding sodium dodecyl benzene sulfonate accounting for 1% of the total mass of the mixed solution, stirring at 600rpm for 30min to obtain a dispersion, and defoaming to obtain a metal salt doped binary colloidal globule stock solution;
(2) Preparation of metal salt doped binary colloidal sphere suspension
Uniformly dispersing the prepared metal salt doped binary colloidal sphere stock solution and absolute ethyl alcohol in an ultrasonic way according to the volume ratio of 3:5 to prepare metal salt doped binary colloidal sphere suspension;
(3) Preparation of binary colloid monolayer film
Uniformly spreading a layer of absolute ethyl alcohol solvent film (the dosage of absolute ethyl alcohol is 5 mL) on a clean monocrystalline silicon substrate with the diameter of 6 inches, and then using a micropipette to inject uniformly dispersed metal salt doped binary colloidal small ball suspension (20 mu L) onto the absolute ethyl alcohol solvent film for multiple times, so that colloidal particles are diffused at an interface and self-assembled; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid monolayer film attached to the monocrystalline silicon substrate can be obtained;
(4) Attachment of binary colloid monolayer film
And slowly transferring the binary colloid single-layer film prepared by the method into acetone to enable the binary colloid single-layer film to float on the liquid surface. Slowly extending a PI film (thickness 6 μm, size 10cm×10 cm) fixed on a stainless steel plate below the liquid level, and then pulling up to obtain a binary colloid single-layer film to obtain a semi-finished product with a single-sided adhesive colloid single-layer film;
(5) Preparation of PI film with porous copper foil attached on one side
And (3) putting the semi-finished product with the single-sided adhesive colloid monolayer film into an oven to be dried for 30min at 80 ℃ so that the adhesive colloid monolayer film is more tightly adhered. Annealing for 2 hours in an air atmosphere at 250 ℃ in a tube furnace, and annealing for 2 hours in a hydrogen atmosphere at 300 ℃ to prepare the PI film with the porous copper foil attached on one side;
(6) Preparation of double-sided composite porous current collector copper foil
Turning over the PI film with the porous copper foil attached on one side, and repeating the steps (3) - (5) to obtain the double-sided composite porous current collector copper foil, namely the lithium battery composite porous current collector copper foil.
Example 4
The preparation method of the lithium battery composite porous current collector copper foil comprises the following specific steps:
(1) Preparation of metal salt doped binary colloidal sphere stock solution
Mixing copper nitrate and deionized water according to a mass ratio of 20:80, and stirring at a rotating speed of 600rpm until the copper nitrate and the deionized water are completely dissolved to obtain a solution; mixing and stirring the solution and polystyrene powder (particle size 500 nm) according to a mass ratio of 50:20 to form a mixed solution, adding sodium dodecyl diphenyl oxide disulfonate accounting for 1% of the total mass of the mixed solution, stirring at 800rpm for 30min to obtain a dispersion, and defoaming to obtain a metal salt doped binary colloidal sphere stock solution;
(2) Preparation of metal salt doped binary colloidal sphere suspension
Uniformly dispersing the prepared metal salt doped binary colloidal sphere stock solution and absolute ethyl alcohol in an ultrasonic way according to the volume ratio of 5:3 to prepare metal salt doped binary colloidal sphere suspension;
(3) Preparation of binary colloid monolayer film
Uniformly spreading an acetone solvent film (the dosage of acetone is 4 mL) on a clean monocrystalline silicon substrate with the diameter of 6 inches, and then using a micropipette to inject uniformly dispersed metal salt doped binary colloidal bead suspension (20 mu L) onto the acetone solvent film for multiple times, so that colloidal particles are diffused at an interface and self-assembled; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid monolayer film attached to the monocrystalline silicon substrate can be obtained;
(4) Attachment of binary colloid monolayer film
And slowly transferring the prepared binary colloid single-layer film into absolute ethyl alcohol to enable the binary colloid single-layer film to float on the liquid surface. Slowly extending a PI film (thickness 6 μm, size 10cm multiplied by 10 cm) fixed on an alumina plate below the liquid level, and then pulling up to obtain a binary colloid single-layer film to obtain a semi-finished product with a single-sided adhesive colloid single-layer film;
(5) Preparation of PI film with porous copper foil attached on one side
And (3) putting the semi-finished product with the single-sided adhesive colloid monolayer film into an oven to be dried for 30min at 80 ℃ so that the adhesive colloid monolayer film is more tightly adhered. Annealing for 1h in an air atmosphere at 250 ℃ in a tube furnace, and annealing for 3h in a hydrogen atmosphere at 300 ℃ to prepare the PI film with the porous copper foil attached on one side;
(6) Preparation of double-sided composite porous current collector copper foil
Turning over the PI film with the porous copper foil attached on one side, and repeating the steps (3) - (5) to obtain the double-sided composite porous current collector copper foil, namely the lithium battery composite porous current collector copper foil.
Example 5
The preparation method of the lithium battery composite porous current collector copper foil comprises the following specific steps:
(1) Preparation of metal salt doped binary colloidal sphere stock solution
Mixing copper nitrate and deionized water according to a mass ratio of 40:60, and stirring at a rotating speed of 600rpm until the copper nitrate and the deionized water are completely dissolved to obtain a solution; mixing and stirring the solution and polystyrene powder (particle size 500 nm) according to a mass ratio of 50:20 to form a mixed solution, adding sodium dodecyl benzene sulfonate accounting for 1.5% of the total mass of the mixed solution, stirring at 600rpm for 30min to obtain a dispersion, and defoaming to obtain a metal salt doped binary colloidal sphere stock solution;
(2) Preparation of metal salt doped binary colloidal sphere suspension
Uniformly dispersing the prepared metal salt doped binary colloidal sphere stock solution and absolute ethyl alcohol in an ultrasonic way according to the volume ratio of 4:4 to prepare metal salt doped binary colloidal sphere suspension;
(3) Preparation of binary colloid monolayer film
Uniformly spreading a layer of absolute ethyl alcohol solvent film (the dosage of absolute ethyl alcohol is 5 mL) on a clean monocrystalline silicon substrate with the diameter of 6 inches, and then using a micropipette to inject uniformly dispersed metal salt doped binary colloidal small ball suspension (20 mu L) onto the absolute ethyl alcohol solvent film for multiple times, so that colloidal particles are diffused at an interface and self-assembled; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid monolayer film attached to the monocrystalline silicon substrate can be obtained;
(4) Attachment of binary colloid monolayer film
And slowly transferring the prepared binary colloid single-layer film into absolute ethyl alcohol to enable the binary colloid single-layer film to float on the liquid surface. Slowly extending a PI film (thickness 6 μm, size 10cm×10 cm) fixed on a stainless steel plate below the liquid level, and then pulling up to obtain a binary colloid single-layer film to obtain a semi-finished product with a single-sided adhesive colloid single-layer film;
(5) Preparation of PI film with porous copper foil attached on one side
And (3) putting the semi-finished product with the single-sided adhesive colloid monolayer film into an oven to be dried for 30min at 80 ℃ so that the adhesive colloid monolayer film is more tightly adhered. Annealing for 1h in an air atmosphere at 300 ℃ in a tube furnace, and annealing for 2h in a hydrogen atmosphere at 300 ℃ to prepare the PI film with the porous copper foil attached on one side;
(6) Preparation of double-sided composite porous current collector copper foil
Turning over the PI film with the porous copper foil attached on one side, and repeating the steps (3) - (5) to obtain the double-sided composite porous current collector copper foil, namely the lithium battery composite porous current collector copper foil.
Comparative example 1
Comparative example 1 also describes a method for preparing a lithium battery composite porous current collector copper foil, which is different from example 3 in that after preparing a semi-finished product with a single-sided adhesive colloid monolayer film, only conventional annealing in an air atmosphere is performed, and hydrogen atmosphere annealing is not performed, and specific steps include:
(1) Preparation of metal salt doped binary colloidal sphere stock solution
Mixing copper nitrate and deionized water according to a mass ratio of 30:70, and stirring at a rotating speed of 600rpm until the copper nitrate and the deionized water are completely dissolved to obtain a solution; mixing and stirring the solution and polystyrene powder (particle size 500 nm) according to a mass ratio of 50:20 to form a mixed solution, adding sodium dodecyl benzene sulfonate accounting for 1% of the total mass of the mixed solution, stirring at 600rpm for 30min to obtain a dispersion, and defoaming to obtain a metal salt doped binary colloidal globule stock solution;
(2) Preparation of metal salt doped binary colloidal sphere suspension
Uniformly dispersing the prepared metal salt doped binary colloidal sphere stock solution and absolute ethyl alcohol in an ultrasonic way according to the volume ratio of 3:5 to prepare metal salt doped binary colloidal sphere suspension;
(3) Preparation of binary colloid monolayer film
Uniformly spreading a layer of absolute ethyl alcohol solvent film (the dosage of absolute ethyl alcohol is 5 mL) on a clean monocrystalline silicon substrate with the diameter of 6 inches, and then using a micropipette to inject uniformly dispersed metal salt doped binary colloidal small ball suspension (20 mu L) onto the absolute ethyl alcohol solvent film for multiple times, so that colloidal particles are diffused at an interface and self-assembled; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid monolayer film attached to the monocrystalline silicon substrate can be obtained;
(4) Attachment of binary colloid monolayer film
And slowly transferring the binary colloid single-layer film prepared by the method into acetone to enable the binary colloid single-layer film to float on the liquid surface. Slowly extending a PI film (thickness 6 μm, size 10cm×10 cm) fixed on a stainless steel plate below the liquid level, and then pulling up to obtain a binary colloid single-layer film to obtain a semi-finished product with a single-sided adhesive colloid single-layer film;
(5) Preparation of PI film with porous copper oxide attached on one side
And (3) putting the semi-finished product with the single-sided adhesive colloid monolayer film into an oven to be dried for 30min at 80 ℃ so that the adhesive colloid monolayer film is more tightly adhered. Annealing for 2 hours in an air atmosphere at 250 ℃ in a tube furnace to prepare a PI film with copper oxide attached to one side;
(6) Preparation of double-sided composite porous current collector copper foil
Turning over the PI film with the copper oxide attached on one side, repeating the steps (3) - (5), and annealing for 2 hours in the hydrogen atmosphere with the temperature of 300 ℃ after the annealing is finished in the step (5), so as to obtain the double-sided composite porous current collector copper foil.
Comparative example 2
A preparation method of a lithium battery composite porous current collector copper foil selects polystyrene powder with larger particle size and a binary colloidal microsphere suspension doped with metal salt thereof, wherein the concentration of the metal salt in the binary colloidal microsphere suspension is higher, and the preparation method comprises the following specific steps:
(1) Preparation of metal salt doped binary colloidal sphere stock solution
Mixing copper nitrate and deionized water according to a mass ratio of 60:40, and stirring at a rotating speed of 600rpm until the copper nitrate and the deionized water are completely dissolved to obtain a solution; mixing and stirring the solution and polystyrene powder (particle size 1 μm) according to a mass ratio of 50:20 to form a mixed solution, adding sodium dodecyl benzene sulfonate accounting for 1% of the total mass of the mixed solution, stirring at 600rpm for 30min to obtain a dispersion, and defoaming to obtain a metal salt doped binary colloidal sphere stock solution;
(2) Preparation of metal salt doped binary colloidal sphere suspension
Uniformly dispersing the prepared metal salt doped binary colloidal sphere stock solution and absolute ethyl alcohol in an ultrasonic way according to the volume ratio of 5:3 to prepare metal salt doped binary colloidal sphere suspension;
(3) Preparation of binary colloid monolayer film
Uniformly spreading a layer of absolute ethyl alcohol solvent film (the dosage of absolute ethyl alcohol is 5 mL) on a clean monocrystalline silicon substrate with the diameter of 6 inches, and then using a micropipette to inject uniformly dispersed metal salt doped binary colloidal small ball suspension (20 mu L) onto the absolute ethyl alcohol solvent film for multiple times, so that colloidal particles are diffused at an interface and self-assembled; after the solvent on the monocrystalline silicon substrate is volatilized, a binary colloid monolayer film attached to the monocrystalline silicon substrate can be obtained;
(4) Attachment of binary colloid monolayer film
And slowly transferring the binary colloid single-layer film prepared by the method into acetone to enable the binary colloid single-layer film to float on the liquid surface. Slowly extending a PI film (thickness 6 μm, size 10cm×10 cm) fixed on a stainless steel plate below the liquid level, and then pulling up to obtain a binary colloid single-layer film to obtain a semi-finished product with a single-sided adhesive colloid single-layer film;
(5) Preparation of PI film with porous copper foil attached on one side
And (3) putting the semi-finished product with the single-sided adhesive colloid monolayer film into an oven to be dried for 30min at 80 ℃ so that the adhesive colloid monolayer film is more tightly adhered. Annealing for 2 hours in an air atmosphere at 250 ℃ in a tube furnace, and annealing for 2 hours in a hydrogen atmosphere at 300 ℃ to prepare the PI film with the porous copper foil attached on one side;
(6) Preparation of double-sided composite porous current collector copper foil
Turning over the PI film with the porous copper foil attached on one side, and repeating the steps (3) - (5) to obtain the double-sided composite porous current collector copper foil, namely the lithium battery composite porous current collector copper foil.
Lithium battery cell assembly and cell performance test:
and stamping the prepared composite current collector copper foil into a round pole piece with the diameter of 12mm on a sheet stamping machine. The commercial graphite and silicon carbon alloy are used as cathode materials, the metal lithium sheet is used as a symmetrical electrode, the circular electrode sheet prepared by the method is used as a current collector, and lithium hexafluorophosphate (LiPF 6) with the electrolyte of 1mol/L is dissolved in a EC, DMC, EMC (volume ratio of 1:1:1) mixed solvent. And respectively adding 20 mu L of electrolyte on the negative electrode and the diaphragm, wherein the total consumption of the electrolyte is 40 mu L, the diaphragm is polypropylene, and the gasket and the elastic sheet are both 304 stainless steel. The cell was prepared in a glove box filled with argon, sealed and left to stand for 24 hours for removal. Current collectors in the preparation of commercial comparative test cells were assembled using round pole pieces made of commercial composite copper foil (1 μm copper plated on both sides of a 6 μm PI film).
The cells prepared using the composite copper foils of examples 1-5, comparative examples 1-2 and commercial composite copper foils were tested for rate performance and cyclic capacity retention, using a New Wipe CT-4008T battery monitoring apparatus (5V, 10 mA).
Wherein the rate performance test conditions: testing at a voltage range of 0-3V, different currents (1C and 5C) and a room temperature of 25 ℃;
cycle life test conditions: and testing at the voltage range of 0-3V, the current of 1C and the room temperature of 25 ℃.
The test results are shown in the following table:
TABLE 1 results of Performance test of cells made from examples 1-5, comparative examples 1-2 and commercial composite copper foil
| 5C/1C volume retention | Volume retention rate of 2000 cycles 1C | |
| Example 1 | 99.45% | 97.17% |
| Example 2 | 99.33% | 96.40% |
| Example 3 | 99.84% | 98.25% |
| Example 4 | 99.37% | 96.08% |
| Example 5 | 99.15% | 97.74% |
| Comparative example 1 | 98.23% | 91.86% |
| Comparative example 2 | 98.54% | 92.68% |
| Commercial composite copper foil comparative test sample | 98.80% | 89.32% |
As can be seen from the results of Table 1, the 5C/1C capacity retention of the cells made using the inventive process composite copper foil is significantly improved compared to the 5C/1C capacity retention of the cells made using the commercial composite copper foil. The cell prepared by the composite copper foil of the invention is obviously superior to the cell prepared by the current mass production technology in terms of volume retention rate after 2000 times of circulation. As can be seen from comparison between fig. 2 and fig. 5, the composite copper foil prepared by the current mass production process is granular, has a compact network structure, is more excellent in electron transmission and adhesion performance with a substrate, and can still maintain a higher volume rate after repeated charge and discharge.
In addition, the performance of comparative examples 1 and 2 was reduced from that of other examples, and the reasons for this can be found from the comparison of fig. 2, 3 and 4. In the comparative example 2, the polystyrene powder with larger particle size and the metal salt doped binary colloidal pellet suspension thereof have higher concentration of the metal salt, and the copper foil layer is thicker due to superposition of two factors, so that cracks are generated in the subsequent drying and annealing; comparative example 1 the copper foil obtained by the secondary annealing of the PI thin film having the porous copper oxide adhered to one side was not excellent in the compactability, without performing the hydrogen atmosphere annealing after the semi-finished product having the colloidal single layer film adhered to one side was obtained. All of the above affect the electron transport performance, thereby causing the degradation of the cell cycle test performance.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a lithium battery composite porous current collector copper foil is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing a copper nitrate aqueous solution and polystyrene powder to form a mixed solution, adding a surfactant, stirring to obtain a dispersion liquid, and defoaming to obtain a metal salt doped binary colloidal sphere stock solution; wherein the polystyrene powder has a particle size of < 1 μm;
s2, uniformly mixing the metal salt doped binary colloid pellet stock solution and absolute ethyl alcohol to prepare a metal salt doped binary colloid pellet suspension;
s3, uniformly spreading a layer of absolute ethyl alcohol solvent film or acetone solvent film on the monocrystalline silicon substrate, and then injecting the metal salt doped binary colloidal bead suspension onto the absolute ethyl alcohol solvent film or the acetone solvent film; after the solvent on the monocrystalline silicon substrate is volatilized, obtaining a binary colloid monolayer film attached to the monocrystalline silicon substrate;
s4, transferring the binary colloid single-layer film prepared by the method into absolute ethyl alcohol or acetone to enable the binary colloid single-layer film to float on the liquid surface; the PI film fixed on the carrier is used for fishing out the binary colloid single-layer film, and a semi-finished product with a single-sided adhesive colloid single-layer film is prepared;
s5, drying the semi-finished product of the single-sided adhesive colloid single-layer film, and annealing to obtain a PI film with a single-sided adhesive porous copper foil; wherein the annealing comprises annealing performed in an air atmosphere and annealing performed in a hydrogen atmosphere in sequence;
s6, turning over the PI film with the porous copper foil attached on one side, then fishing out the binary colloid single-layer film floating on the liquid surface in the S4, and repeating the S5 to obtain the lithium battery composite porous current collector copper foil.
2. The method for preparing the lithium battery composite porous current collector copper foil according to claim 1, which is characterized in that: in S1, the mass ratio of the copper nitrate to the polystyrene powder in the copper nitrate aqueous solution is 10-20:20.
3. the method for preparing the lithium battery composite porous current collector copper foil according to claim 1, which is characterized in that: in S1, in the copper nitrate aqueous solution, the mass fraction of copper nitrate is 20-40%; and mixing the copper nitrate aqueous solution and the polystyrene powder according to the mass ratio of 50:20 to form a mixed solution.
4. The method for preparing the lithium battery composite porous current collector copper foil according to claim 1, which is characterized in that: in S1, the surfactant is one or a mixture of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and sodium dodecyl diphenyl ether disulfonate.
5. The method for preparing the lithium battery composite porous current collector copper foil according to claim 1, which is characterized in that: in S1, the particle size of the polystyrene powder is 100-500nm.
6. The method for preparing the lithium battery composite porous current collector copper foil according to claim 1, which is characterized in that: in S1, the mass of the surfactant is 0.5-2% of the mass of the mixed solution.
7. The method for preparing the lithium battery composite porous current collector copper foil according to claim 1, which is characterized in that: in S2, the volume ratio of the metal salt doped binary colloidal sphere stock solution to the absolute ethyl alcohol is 3-5:3-5.
8. The method for preparing the lithium battery composite porous current collector copper foil according to claim 1, which is characterized in that: in S3, in the process of forming the absolute ethyl alcohol solvent film or the acetone solvent film, the dosage of the absolute ethyl alcohol or the acetone on the monocrystalline silicon substrate is 3-5mL/6 inch; the volume ratio of the total volume of the metal salt doped binary colloidal sphere suspension to the volume of the absolute ethyl alcohol or acetone used is 20 mu L:3-5mL.
9. The method for preparing the lithium battery composite porous current collector copper foil according to any one of claims 1 to 8, wherein the method comprises the following steps: in S5, annealing in the air atmosphere means annealing for 1-3 hours at 230-300 ℃ in a tube furnace; the annealing is performed in a hydrogen atmosphere at a temperature of 300 ℃ for 1-3 hours.
10. The composite porous current collector copper foil of the lithium battery is characterized in that: the lithium battery composite porous current collector copper foil is prepared by adopting the preparation method of the lithium battery composite porous current collector copper foil according to any one of claims 1-9.
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