CN112054211A - Negative current collector and preparation method and application thereof - Google Patents
Negative current collector and preparation method and application thereof Download PDFInfo
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- CN112054211A CN112054211A CN202011042975.2A CN202011042975A CN112054211A CN 112054211 A CN112054211 A CN 112054211A CN 202011042975 A CN202011042975 A CN 202011042975A CN 112054211 A CN112054211 A CN 112054211A
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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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/76—Containers for holding the active material, e.g. tubes, capsules
- H01M4/765—Tubular type or pencil type electrodes; tubular or multitubular sheaths or covers of insulating material for said tubular-type electrodes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention provides a negative current collector and a preparation method and application thereof. The invention provides a negative current collector, which comprises a metal layer and a conductive layer arranged on the upper surface and/or the lower surface of the metal layer; the conductive layer comprises a bonding agent and a metal tube, wherein the metal tube comprises a first metal layer on an inner layer and a second metal layer on an outer layer, the first metal layer comprises a lithium-philic metal, and the second metal layer comprises a lithium-phobic metal. The negative current collector comprises the metal tube, an effective lithium storage space can be provided in the metal tube, the metal tube structure with the inner lithium-philic layer and the outer lithium-phobic layer can induce the metal lithium to be deposited in the metal tube, and the uniformity of metal lithium deposition is improved, so that the cycle performance and the safety performance of a lithium ion battery are improved.
Description
Technical Field
The invention relates to a negative current collector and a preparation method and application thereof, and relates to the technical field of lithium ion batteries.
Background
A lithium ion battery is a secondary battery that is very widely used. At present, graphite is used as a common negative electrode material of the lithium ion battery, but the improvement of the energy density of the lithium ion battery faces a bottleneck due to the lower specific capacity of the graphite.
The metal lithium has higher specific capacity, and the energy density of the lithium ion battery can be obviously improved by using the metal lithium as the negative electrode material of the lithium ion battery. However, in the charging process of the lithium ion battery, the problem of uneven deposition of the metal lithium negative electrode exists, so that the cycle performance and the safety performance of the lithium ion battery are poor, and the application of the metal lithium negative electrode in the lithium ion battery is influenced.
Disclosure of Invention
The invention provides a negative current collector and a preparation method thereof, which are used for solving the problem of uneven deposition of a lithium metal negative electrode in the charging process of a lithium ion battery.
The invention provides a negative current collector, which comprises a metal layer and a conductive layer arranged on the upper surface and/or the lower surface of the metal layer;
the conductive layer comprises a bonding agent and a metal tube, wherein the metal tube comprises a first metal layer on an inner layer and a second metal layer on an outer layer, the first metal layer comprises a lithium-philic metal, and the second metal layer comprises a lithium-phobic metal.
The invention provides a negative current collector, which comprises a metal layer and a conductive layer arranged on the upper surface and/or the lower surface of the metal layer, wherein the metal layer is a metal foil material commonly used by the negative current collector, and the conductive layer can be arranged on the upper surface or the lower surface of the metal layer or arranged on the upper surface and the lower surface of the metal layer at the same time, for example, fig. 1 is a schematic structural diagram of the negative current collector provided by an embodiment of the invention, as shown in fig. 1, the negative current collector comprises a metal layer 1 and conductive layers 2 arranged on the upper surface and the lower surface of the metal layer 1, and a person skilled in the art can arrange the positions of the conductive layers according to actual; the conductive layer includes a binder and a metal tube, wherein the metal tube has a hollow tubular structure, an inner layer of the metal tube is a first metal layer including a lithium-philic metal, an outer layer of the metal tube is a second metal layer including a lithium-phobic metal, fig. 2 is a schematic structural diagram of a cross section of the metal tube according to an embodiment of the present invention, as shown in fig. 2, the metal tube has a hollow tubular structure, an inner layer of the metal tube is a first metal layer 3 including a lithium-philic metal, and an outer layer of the metal tube is a second metal layer 4 including a lithium-phobic metal, it should be noted that the cross section of the metal tube provided by the present invention is not limited to the circular shape shown in fig. 2, and the cross section of the metal tube may have any shape such as a rectangular shape, a. The negative current collector comprises the metal tube, an effective lithium storage space can be provided in the metal tube, the metal tube structure with the inner lithium-philic layer and the outer lithium-phobic layer can induce the metal lithium to be deposited in the metal tube, and the uniformity of metal lithium deposition is improved, so that the cycle performance and the safety performance of a lithium ion battery are improved.
In a specific embodiment, in order to further improve the conductivity of the negative electrode current collector, a conductive agent may be added to the conductive layer, i.e., the conductive layer includes a binder, a metal tube, and a conductive agent.
The skilled person can select the material of the negative current collector according to the prior art and in combination with the actual preparation needs, in particular:
the metal layer can be a metal foil commonly used in the negative current collector in the prior art, such as copper and nickel;
the binder is one or more of polythiophene, polypyrrole, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polystyrene, polyacrylamide, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, nitrile rubber, polyethylene oxide, polyvinylpyrrolidone, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, carboxypropyl cellulose, ethyl cellulose, polyethylene oxide, sodium carboxymethylcellulose (CMC) and styrene butadiene latex (SBR).
The lithium-philic metal and the lithium-phobic metal can be judged according to the contact angle between the metal and the molten liquid metal lithium, specifically, the contact angle theta between the lithium-philic metal and the molten liquid metal lithium is less than or equal to 90 degrees, and the contact angle theta between the lithium-phobic metal and the molten liquid metal lithium is more than or equal to 110 degrees.
Specifically, the lithium-philic metal is one or more of aluminum, silver, gold, indium, zinc, tin, bismuth, gallium, germanium and antimony.
The lithium-phobic metal is one or more of copper, nickel and iron.
The invention further tests the contact angles of part of the lithium-philic metal and the lithium-phobic metal with the molten liquid metal lithium to illustrate the relationship between the contact angles and the lithium-philic or lithium-phobic performance of the metal, wherein the test method comprises the following steps: melting metal lithium at 300 ℃ in an argon atmosphere glove box, then dripping the molten metal lithium on the surface of a foil material of metal to be detected, controlling the temperature of the metal foil to be constant at 300 ℃ through a heating table, and then measuring the contact angle of the molten liquid metal lithium on the surface of the metal foil by using a contact angle measuring instrument with reference to a contact angle measuring method in a GBT 30693-; the test results are shown in table 1:
TABLE 1 contact angle of metal foil with molten liquid metal lithium
| Contact angle (°) | Lithium-philic and lithium-phobic properties | |
| Copper (Cu) | 140 | Lyophobic lithium |
| Nickel (II) | 131 | Lyophobic lithium |
| Iron | 134 | Lyophobic lithium |
| Silver (Ag) | 42 | Lithium-philic |
| Indium (In) | 38 | Lithium-philic |
| Aluminium | 55 | Lithium-philic |
| Zinc | 46 | Lithium-philic |
| Tin (Sn) | 51 | Lithium-philic |
| Bismuth (III) | 43 | Lithium-philic |
Because the metal tube is of a hollow tubular structure, in the preparation process, the fiber can be used as a template, lithium-philic metal and lithium-phobic metal are sequentially deposited on the surface of the fiber template to obtain a first metal layer and a second metal layer, and finally the fiber template is removed to obtain the metal tube.
Wherein, the fiber template can be one of magnesium oxide nano fiber, zinc oxide nano fiber, polyacrylonitrile fiber, polycaprolactone fiber and polyvinyl alcohol fiber.
In order to further improve the comprehensive performance of the lithium ion battery, a fiber template with the diameter of 10-2000nm and the length of 0.1-10 μm can be selected in the preparation process of the metal tube, namely, the inner diameter of the metal tube is 10-2000nm and the length of the metal tube is 0.1-10 μm.
The deposition can adopt a common physical vapor deposition, sputtering or electroplating method to sequentially deposit lithium-philic metal and lithium-phobic metal on the surface of the fiber template to obtain a first metal layer and a second metal layer.
In the preparation process of the metal tube, the thicknesses of the first metal layer and the second metal layer can be controlled by controlling the deposition time or other process parameters, and particularly, the total thickness of the first metal layer and the second metal layer is 10-2000 nm.
Wherein the thickness of the first metal layer is 1-1999 nm.
The thickness of the second metal layer is 1-1999 nm.
And finally, removing the fiber template through chemical reaction or high-temperature calcination or solvent cleaning and the like to obtain the metal tube with the lithium-philic inner layer and the lithium-phobic outer layer.
In a specific embodiment, firstly, taking magnesium oxide nano-fiber with the fiber diameter of 100nm and the fiber length of 1 μm as a fiber template, putting metal silver into an evaporation boat, and depositing the metal silver on the surface of the magnesium oxide nano-fiber by using a vacuum coating machine to obtain a first metal layer; secondly, replacing the evaporation boat, putting in metal copper, and continuously depositing the metal copper on the surface of the first metal layer to obtain a second metal layer; finally, soaking the magnesium oxide nanofiber after film coating with 1mol/L hydrochloric acid, then washing with deionized water and drying to obtain a metal tube, wherein fig. 3 is an SEM image of the metal tube provided by one embodiment of the invention, as shown in fig. 3, the metal tube is a hollow tubular structure, the inner layer of the metal tube is a first metal layer comprising lithium-philic metallic silver, and the outer layer of the metal tube is a second metal layer comprising lithium-phobic metallic copper.
When the conductive layer includes a conductive agent, the conductive agent may be one or more of carbon black, carbon nanotubes, carbon fibers, graphene.
After selecting the corresponding conductive layer material, dispersing the binder and the metal tube or the binder, the metal tube and the conductive agent in a solvent, uniformly mixing to obtain conductive layer slurry, and coating the slurry on the upper surface and/or the lower surface of the metal layer to obtain the negative current collector.
Wherein, the binder, the metal tube and the conductive agent are selected as described above, and the solvent is one or more of water, N-methylpyrrolidone (NMP), N, N-Dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), toluene and xylene.
The applicant researches and discovers that the cycle performance of the lithium ion battery is gradually improved along with the gradual improvement of the mass fraction of the metal tube in the negative current collector, and in order to further improve the cycle performance of the lithium ion battery, the mass fractions of the metal tube and the binder or the mass fractions of the metal tube, the binder and the conductive agent are kept within a certain range, and specifically, the mass of the metal tube is 80-99.9% of the total mass of the conductive layer; the mass of the binder is 0.1-20% of the total mass of the conductive layer; the mass of the conductive agent is 0.1-20% of the total mass of the conductive layer, and the metal tube, the binder and the conductive agent can be reasonably matched according to the mass percentage content and the actual preparation requirement by the technical personnel in the field.
The skilled person knows that the thicknesses of the metal layer and the conductive layer have a great influence on the performance of the lithium ion battery, and in order to further improve the performance of the lithium ion battery, the invention further defines the thicknesses of the metal layer and the conductive layer: specifically, the thickness of the conductive layer is 1-50 μm; the thickness of the metal layer is 1-20 μm.
In summary, the invention provides a negative current collector, which includes a metal tube, an effective lithium storage space can be provided inside the metal tube, and the structure of the metal tube with an inner layer being lithium-philic and an outer layer being lithium-phobic can induce the metal lithium to deposit inside the metal tube, so as to improve the uniformity of the metal lithium deposition, thereby improving the cycle performance and the safety performance of the lithium ion battery.
The second aspect of the present invention provides a method for preparing any one of the above negative electrode current collectors, including the steps of:
sequentially depositing lithium-philic metal and lithium-phobic metal on the surface of the fiber template to obtain a first metal layer and a second metal layer, and removing the fiber template to obtain a metal tube; and then mixing the metal pipe and a binder to obtain conductive layer slurry, and coating the conductive layer slurry on the upper surface and/or the lower surface of the metal layer to obtain the negative electrode current collector.
The invention provides a preparation method of a negative current collector, which comprises the steps of firstly, taking fibers as a template, sequentially depositing lithium-philic metal and lithium-phobic metal on the surface of the fiber template to obtain a first metal layer and a second metal layer, and finally removing the fiber template to obtain a metal tube; and secondly, mixing the prepared metal tube with a binder to obtain conductive layer slurry, and coating the conductive layer slurry on the upper surface and/or the lower surface of the metal layer to obtain a negative electrode current collector.
In one embodiment, the materials of the fiber template, the lithium-philic metal, the lithium-phobic metal, and the binder are as previously described.
Depositing lithium-philic metal on the surface of the fiber template by adopting a common physical vapor deposition, sputtering or electroplating method to obtain a first metal layer, depositing lithium-phobic metal on the surface of the first metal layer to obtain a second metal layer, and removing the fiber template by chemical reaction or high-temperature calcination or solvent cleaning and the like to obtain the metal tube with the lithium-philic inner layer and the lithium-phobic outer layer.
The preparation method of the conducting layer slurry can be prepared according to the prior art, and specifically, the prepared metal tube and the binder are dispersed in a solvent, the conducting layer slurry is obtained by uniformly mixing, and the conducting layer slurry is coated on the upper surface and/or the lower surface of the metal layer to prepare the negative electrode current collector.
In a third aspect, the invention provides a lithium ion battery, which includes any one of the negative electrode current collectors.
The invention provides a lithium ion battery, which is characterized in that a negative plate is prepared on the basis of the negative current collector provided by the invention, specifically, a person skilled in the art can deposit partial metal lithium in the prepared metal tube of the negative current collector, the deposition method can be carried out according to the conventional technical means, but the thickness d of the metal lithium deposited on the inner wall of the metal tube is not more than 1/2 of the inner diameter of the metal tube, and then the negative plate deposited with the metal lithium is matched with a positive plate, a diaphragm and electrolyte to prepare the lithium ion battery; or, the lithium ion battery can be prepared by directly taking a negative electrode current collector without metal lithium as a negative electrode plate and then matching with a lithium-removable positive electrode material without depositing the metal lithium in the metal tube.
According to the lithium ion battery provided by the invention, the negative current collector comprises the metal tube, an effective lithium storage space can be provided in the metal tube, and the metal tube structure with the inner lithium-philic layer and the outer lithium-phobic layer can induce the metal lithium to be deposited in the metal tube, so that the uniformity of metal lithium deposition is improved, and the lithium ion battery has better cycle performance and safety performance.
The implementation of the invention has at least the following advantages:
1. the invention provides a negative current collector which comprises a metal tube, wherein an effective lithium storage space can be provided in the metal tube, and the structure of the metal tube with an inner lithium-philic layer and an outer lithium-phobic layer can induce metal lithium to be deposited in the metal tube, so that the uniformity of metal lithium deposition is improved, and the cycle performance and the safety performance of a lithium ion battery are improved.
2. The lithium ion battery provided by the invention has better cycle performance and safety performance.
Drawings
Fig. 1 is a schematic structural diagram of a negative electrode current collector according to an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a metal tube according to an embodiment of the present invention;
fig. 3 is an SEM image of a metal tube according to an embodiment of the present invention.
Description of reference numerals:
1-a metal layer; 2-a conductive layer; 3-a first metal layer; 4-second metal layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The negative current collector provided by the embodiment comprises a copper foil and conductive layers arranged on the upper surface and the lower surface of the copper foil, wherein the conductive layers comprise 90 parts by mass of a metal tube and 10 parts by mass of a binder SBR, a first metal layer on the inner layer of the metal tube comprises metal silver, and a second metal layer on the outer layer comprises metal copper.
The thickness of the copper foil was 6 μm, the thickness of the conductive layer was 30 μm, the inner diameter of the metal tube was 100nm, the thickness of the first metal layer was 20nm, the thickness of the second metal layer was 500nm, and the length of the metal tube was 1 μm.
The preparation method of the current collector provided by the embodiment includes:
1. taking 1 g of magnesium oxide nano fiber with the fiber diameter of 100nm and the fiber length of 1 mu m, putting metal silver into an evaporation boat, and depositing the metal silver on the surface of the magnesium oxide nano fiber by using a vacuum coating machine (a vacuum coating machine produced by Beijing Taikono science and technology Co., Ltd., the same below) to obtain a first metal layer;
wherein, the coating process parameters are as follows: the deposition current was 100A, and the vacuum chamber vacuum degree was 8X 10-5Pa, the coating time is 2min, and the coating thickness is 20 nm.
2. Replacing the evaporation boat, putting metal copper in the evaporation boat, and continuously depositing the metal copper on the surface of the first metal layer to obtain a second metal layer;
wherein, the coating process parameters are as follows: the deposition current was 150A, and the vacuum chamber had a vacuum degree of 1X 10-5Pa, the coating time is 20min, and the coating thickness is 500 nm.
3. Soaking the coated magnesium oxide nano-fiber with 1mol/L hydrochloric acid for 12h, washing with deionized water for 3 times, baking at 120 ℃ for 4h, and completely drying to obtain a metal tube, wherein a Scanning Electron Microscope (SEM) image of the metal tube is shown in FIG. 3.
4. And dispersing 90 parts by mass of a metal pipe and 10 parts by mass of a binder SBR in 50 parts by mass of solvent water, uniformly mixing to obtain conductive layer slurry, coating the conductive layer slurry on the upper surface and the lower surface of a copper foil, and drying the solvent to obtain a negative current collector.
The preparation method of the negative electrode plate provided by the embodiment comprises the following steps: electroplating the prepared negative current collector by using a direct current power supply LW3080KD special for electroplating produced by Longwei electronic technology Co., Ltd, Dongguan: putting a negative current collector and a metal lithium sheet into a plating bath, connecting the negative current collector with a negative electrode of a direct current power supply, connecting the metal lithium sheet with a positive electrode of the direct current power supply, and injecting 1mol/L LiPF into the plating bath6(the volume ratio of the solvent EC to DMC is 1:1) to immerse the electrolyte into the negative current collector and the metal lithium sheet, setting the direct current power supply to be in a constant current working mode, setting the current to be 0.1A, continuing electroplating for 1min, taking out the negative current collector, and cleaning with DMC solution to obtain the negative sheet.
The preparation method of the lithium ion battery provided by the embodiment comprises the following steps: the negative electrode sheet was matched with a positive electrode sheet (4.4V lithium cobaltate, Beijing Dangsheng materials science and technology Co., Ltd., surface density of the sheet was 18mg/cm2The compacted density of the pole piece is 4.14g/cm3) The lithium ion battery C1 is prepared from a Polyethylene (PE) porous diaphragm (a wet diaphragm ND12 produced by Shanghai Enjie New Material science and technology Limited, with the thickness of 10 μm) and an electrolyte (an electrolyte of type LBC445B33 of Shenzhen New Zezhou Pont science and technology Limited).
Example 2
The negative electrode current collector provided in this example can be referred to example 1 except that the inner diameter of the metal tube is 50nm and the length of the metal tube is 0.5 μm.
The current collector provided in this example can be prepared by referring to example 1, except that the fiber template is a magnesium oxide nanofiber with a diameter of 50nm and a length of 0.5 μm.
A lithium ion battery C2 was produced in the same manner as in example 1.
Example 3
The negative electrode current collector provided in this example can be referred to example 1 except that the inner diameter of the metal tube is 200nm and the length of the metal tube is 2 μm.
The current collector provided in this example can be prepared by referring to example 1, except that the fiber template is a magnesium oxide nanofiber with a diameter of 200nm and a length of 2 μm.
A lithium ion battery C3 was produced in the same manner as in example 1.
Example 4
The negative electrode current collector provided in this embodiment can be referred to in example 1, except that the second metal layer of the outer layer of the metal tube includes copper metal, the thickness of the second metal layer is 1500nm, the inner diameter of the metal tube is 2000nm, and the length of the metal tube is 10 μm.
The current collector provided in this example can be prepared by referring to example 1, except that,
1. the fiber template is polyvinyl alcohol fiber with the diameter of 2000nm and the length of 10 mu m;
2. prolonging the film coating time to 60min, wherein the film coating thickness is 1500 nm;
3. soaking the coated polyvinyl alcohol fiber in hot water at 100 ℃ for 4h, filtering, washing with hot water at 100 ℃ for 3 times, and drying at 100 ℃ to obtain the metal tube.
A lithium ion battery C4 was produced in the same manner as in example 1.
Example 5
The negative electrode current collector provided in this embodiment can be referred to in embodiment 1, except that the first metal layer on the inner layer of the metal tube comprises aluminum metal, the thickness of the first metal layer is 28nm, the inner diameter of the metal tube is 1500nm, and the length of the metal tube is 8 μm.
The current collector provided in this example can be prepared by referring to example 1, except that,
1. the fiber template is polyvinyl alcohol fiber with the diameter of 1500nm and the length of 8 mu m; the coating time is shortened to 1min, and the coating thickness is 28 nm;
3. soaking the coated polyvinyl alcohol fiber in hot water at 100 ℃ for 4h, filtering, washing with hot water at 100 ℃ for 3 times, and drying at 100 ℃ to obtain the metal tube.
A lithium ion battery C5 was produced in the same manner as in example 1.
Example 6
The negative electrode current collector provided in this example may be referred to example 1 except that the conductive layer includes 80 parts by mass of the metal tube and 20 parts by mass of the binder SBR.
The current collector provided in this example was prepared by referring to example 1, except that 80 parts by mass of the metal tube and 20 parts by mass of the binder SBR were included in the conductive layer slurry.
A lithium ion battery C6 was produced in the same manner as in example 1.
Example 7
The negative electrode current collector provided in this example can be referred to example 1 except that the conductive layer includes 99.9 parts by mass of the metal tube and 0.1 parts by mass of the binder SBR.
The current collector provided in this example was prepared by referring to example 1, except that 99.9 parts by mass of the metal tube and 0.1 part by mass of the binder SBR were dispersed in 10 parts by mass of the solvent water.
A lithium ion battery C7 was produced in the same manner as in example 1.
Example 8
The negative electrode current collector provided in this example can be referred to example 1 except that the conductive layer includes 90 parts by mass of the metal tube, 5 parts by mass of the binder SBR, and 5 parts by mass of the conductive agent carbon black.
The current collector provided in this example was prepared by referring to example 1, except that 90 parts by mass of the metal pipe, 5 parts by mass of the binder SBR, and 5 parts by mass of the conductive agent carbon black were dispersed in 100 parts by mass of water to obtain a conductive layer slurry.
A lithium ion battery C8 was produced in the same manner as in example 1.
Example 9
The negative electrode current collector provided in this example can be referred to example 1 except that the conductive layer includes 80 parts by mass of the metal tube, 19.9 parts by mass of the binder SBR, and 0.1 parts by mass of the conductive agent carbon nanotube.
The current collector provided in this example was prepared by referring to example 1, except that 80 parts by mass of a metal tube, 19.9 parts by mass of a binder SBR, and 0.1 part by mass of a conductive agent carbon nanotube were dispersed in 100 parts by mass of water to obtain a conductive layer slurry.
A lithium ion battery C9 was produced in the same manner as in example 1.
Example 10
The negative electrode current collector provided in this example can be referred to example 1 except that the conductive layer includes 80 parts by mass of the metal tube, 19 parts by mass of the binder SBR, and 1 part by mass of the conductive agent carbon fiber.
The current collector provided in this example was prepared by referring to example 8, except that 80 parts by mass of the metal tube, 19 parts by mass of the binder SBR, and 1 part by mass of the conductive agent carbon fiber were dispersed in 100 parts by mass of water to obtain a conductive layer slurry.
A lithium ion battery C10 was produced in the same manner as in example 1.
Example 11
The negative electrode current collector provided in this example can be referred to example 1 except that the conductive layer includes 99.8 parts by mass of the metal tube, 0.1 parts by mass of the binder SBR, and 0.1 parts by mass of the conductive agent graphene.
The current collector provided in this example was prepared by referring to example 8, except that 99.8 parts by mass of a metal tube, 0.1 part by mass of SBR as a binder, and 0.1 part by mass of graphene as a conductive agent were dispersed in 100 parts by mass of water to obtain a conductive layer slurry.
A lithium ion battery C11 was produced in the same manner as in example 1.
Example 12
The negative electrode current collector provided in this example can be referred to example 1 except that the conductive layer includes 90 parts by mass of the metal tube and 10 parts by mass of the binder PVDF.
The current collector provided in this example was prepared by referring to example 1, except that 90 parts by mass of the metal tube and 10 parts by mass of PVDF as a binder were dispersed in 50 parts by mass of NMP to obtain conductive layer slurry.
A lithium ion battery C12 was produced in the same manner as in example 1.
Example 13
The negative electrode current collector provided in the present example may be referred to example 1 except that the conductive layer includes 90 parts by mass of the metal tube and 10 parts by mass of the binder acrylic resin.
The current collector provided in this embodiment may be prepared by referring to example 1, except that the binder is an acrylic resin.
A lithium ion battery C13 was produced in the same manner as in example 1.
Example 14
The negative electrode current collector provided in this embodiment can refer to embodiment 1, except that the second metal layer of the outer layer of the metal tube includes metal nickel, and the thickness of the second metal layer is 420 nm.
The preparation method of the current collector provided in this embodiment can refer to embodiment 1, and the difference is that the nickel plating time is 17min, and the nickel plating thickness is 420 nm.
A lithium ion battery C14 was produced in the same manner as in example 1.
Example 15
The negative electrode current collector provided in this embodiment can refer to embodiment 1, except that the second metal layer of the outer layer of the metal tube includes metal bismuth, and the thickness of the second metal layer is 20 nm.
The preparation method of the current collector provided in this embodiment can refer to embodiment 1, and the difference is that the bismuth plating process parameters are as follows: the deposition current was 85A, and the vacuum chamber vacuum degree was 9X 10-5Pa, the coating time is 1min, and the thickness of the plated bismuth is 20 nm.
A lithium ion battery C15 was produced in the same manner as in example 1.
Example 16
The negative electrode current collector provided in this embodiment can be referred to in embodiment 1.
The preparation method of the current collector provided in this embodiment can refer to embodiment 1, and the difference is that the fiber template is zinc oxide nanofiber.
A lithium ion battery C16 was produced in the same manner as in example 1.
Example 17
The negative electrode current collector provided in this embodiment can refer to embodiment 1, except that the first metal layer of the inner layer of the metal tube includes indium metal, and the second metal layer of the outer layer includes iron metal. The inner diameter of the metal tube was 1000nm and the length of the metal tube was 5 μm.
The preparation method of the current collector provided by the embodiment includes:
1. taking 1 g of polyacrylonitrile fiber with the fiber diameter of 1000nm and the fiber length of 5 microns, putting metal indium into an evaporation boat, and depositing the metal indium on the surface of the polyacrylonitrile fiber by using a vacuum coating machine to obtain a first metal layer;
wherein, the coating process parameters are as follows: the deposition current was 75A, and the vacuum chamber vacuum degree was 3X 10-5Pa, the coating time is 1min, and the coating thickness is 20 nm.
2. Replacing the evaporation boat, putting metal iron, and continuously depositing the metal iron on the surface of the first metal layer to obtain a second metal layer;
wherein, the coating process parameters are as follows: the deposition current was 160A, and the vacuum chamber had a degree of vacuum of 1X 10-5Pa, the coating time is 50min, and the coating thickness is 500 nm.
3. Soaking the coated polyacrylonitrile fiber in DMF for 12h, washing with DMF for 3 times, baking at 180 deg.C for 4h, and oven drying to obtain the metal tube.
4. And dispersing 90 parts by mass of a metal pipe and 10 parts by mass of a binder SBR in 50 parts by mass of solvent water, uniformly mixing to obtain conductive layer slurry, coating the conductive layer slurry on the upper surface and the lower surface of a copper foil, and drying the solvent to obtain a negative current collector.
A lithium ion battery C17 was produced in the same manner as in example 1.
Example 18
The present embodiment provides a negative electrode current collector as defined in example 17, except that the second metal layer of the outer layer of the metal tube comprises sn-zn alloy (22% by mass of sn).
The method for preparing the current collector provided in this embodiment can be referred to in example 17, except that the fiber template is polycaprolactone fiber, and the tin-zinc plating process is performedThe parameters are as follows: the deposition current was 95A, and the vacuum chamber was 2X 10 in vacuum degree-5Pa。
A lithium ion battery C18 was produced in the same manner as in example 1.
Example 19
The negative electrode current collector provided in example 1 was directly used as a negative electrode sheet, and a positive electrode sheet, a Polyethylene (PE) porous separator, and an electrolyte were used in combination to prepare a lithium ion battery C19, where the positive electrode sheet, the Polyethylene (PE) porous separator, and the electrolyte were the same as in example 1.
Comparative example 1
The negative electrode current collector provided by this comparative example can be referred to example 1 except that the metal tube includes only a metallic copper layer having a thickness of 500 nm.
The method for preparing the negative electrode current collector provided by the comparative example comprises the following steps:
1. taking 1 g of magnesium oxide nano fiber with the fiber diameter of 100nm and the fiber length of 1 mu m, putting metal copper into an evaporation boat, and depositing the metal copper on the surface of the magnesium oxide nano fiber by using a vacuum coating machine to obtain a metal copper layer;
wherein, the coating process parameters are as follows: the deposition current was 150A, and the vacuum chamber had a vacuum degree of 1X 10-5Pa, the coating time is 20min, and the coating thickness is 500 nm.
2. Soaking the magnesium oxide nano-fiber after film coating in 1mol/L hydrochloric acid for 12h, then washing with deionized water for 3 times, baking at 120 ℃ for 4h, and completely drying to obtain the metal tube only comprising a metal copper layer.
3. And dispersing 90 parts by mass of a metal pipe and 10 parts by mass of a binder SBR in 50 parts by mass of solvent water, uniformly mixing to obtain conductive layer slurry, coating the conductive layer slurry on the upper surface and the lower surface of a copper foil, and drying the solvent to obtain a negative current collector.
A lithium ion battery a1 was produced in the same manner as in example 1.
Comparative example 2
The negative electrode current collector provided by the present comparative example may be referred to comparative example 1 except that the metal tube includes only the metallic silver layer.
Comparative exampleThe preparation method of the negative current collector can refer to comparative example 1, and the difference is that the coating process parameters are that the evaporation current is 100A, and the vacuum degree of a vacuum chamber is 8 multiplied by 10-5Pa, the coating time is 50min, and the coating thickness is 500 nm.
A lithium ion battery a2 was produced in the same manner as in example 1.
Comparative example 3
The negative electrode current collector provided by this comparative example includes a copper foil and conductive layers disposed on the upper and lower surfaces of the copper foil, the conductive layers including 90 parts by mass of copper fibers and 10 parts by mass of binder SBR, wherein the copper fibers have a diameter of 600nm and a length of 1 μm.
A lithium ion battery a3 was produced in the same manner as in example 1.
Comparative example 4
The negative electrode current collector provided by the present comparative example includes a copper foil and conductive layers disposed on the upper and lower surfaces of the copper foil, the conductive layers including 90 parts by mass of silver fibers and 10 parts by mass of binder SBR, wherein the silver fibers have a diameter of 600nm and a length of 1 μm.
A lithium ion battery a4 was produced in the same manner as in example 1.
Comparative example 5
The negative electrode current collector provided by this comparative example can be referred to example 1, except that the first metal layer of the inner layer of the metal tube includes metallic copper, and the second metal layer of the outer layer includes metallic silver.
The method for preparing the negative electrode current collector provided by the comparative example comprises the following steps:
1. taking 1 g of magnesium oxide nano fiber with the fiber diameter of 100nm and the fiber length of 1 mu m, putting metal copper into an evaporation boat, and depositing the metal copper on the surface of the magnesium oxide nano fiber by using a vacuum coating machine to obtain a first metal layer;
wherein, the coating process parameters are as follows: the deposition current was 150A, and the vacuum chamber had a vacuum degree of 1X 10-5Pa, the coating time is 20min, and the coating thickness is 500 nm.
2. Replacing the evaporation boat, putting metal silver in the evaporation boat, and continuously depositing the metal silver on the surface of the first metal layer by a vacuum evaporation coating method to obtain a second metal layer;
wherein, the coating process parameters are as follows: the deposition current was 100A, and the vacuum chamber vacuum degree was 8X 10-5Pa, the coating time is 2min, and the coating thickness is 20 nm.
3. Soaking the magnesium oxide nano-fiber after film coating in 1mol/L hydrochloric acid for 12h, then washing with deionized water for 3 times, baking at 120 ℃ for 4h, and completely drying to obtain the metal tube with the outer layer of metal silver and the inner layer of metal copper.
4. And dispersing 90 parts by mass of a metal pipe and 10 parts by mass of a binder SBR in 50 parts by mass of solvent water, uniformly mixing to obtain conductive layer slurry, coating the conductive layer slurry on the upper surface and the lower surface of a copper foil, and drying the solvent to obtain a negative current collector.
A lithium ion battery a5 was produced in the same manner as in example 1.
The present invention tests the cycle performance and safety performance of the lithium ion batteries provided in examples 1 to 19 and comparative examples 1 to 5, and the test results are shown in table 1:
the cycle performance test method comprises the following steps: the cycle performance of the lithium ion battery is tested by referring to a test method in GB/T18287-2013 standard, and the cycle test conditions are as follows: 25 ℃ and 0.5C/0.5C (the upper limit voltage is set to 4.4V, and the lower limit voltage is set to 3.0V);
the safety performance testing method comprises the following steps: the safety performance of the battery is tested according to the GB/T31485-.
Table 1 results of performance tests of lithium ion batteries prepared in examples 1 to 19 and comparative examples 1 to 5
As can be seen from table 1, the cycle life and the safety test pass rate of the lithium ion battery C1-C19 prepared on the basis of the negative electrode current collector provided in this embodiment are both higher than those of a1-a5, and therefore, the negative electrode current collector provided by the present invention can significantly improve the cycle performance and the safety performance of the lithium ion battery.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A negative current collector is characterized by comprising a metal layer and a conductive layer arranged on the upper surface and/or the lower surface of the metal layer;
the conductive layer comprises a bonding agent and a metal tube, wherein the metal tube comprises a first metal layer on an inner layer and a second metal layer on an outer layer, the first metal layer comprises a lithium-philic metal, and the second metal layer comprises a lithium-phobic metal.
2. The negative electrode current collector of claim 1, wherein the conductive layer further comprises a conductive agent.
3. The negative electrode current collector of claim 1 or 2, wherein the lithium-philic metal is one or more of aluminum, silver, gold, indium, zinc, tin, bismuth, gallium, germanium, antimony.
4. The negative electrode current collector of claim 1 or 2, wherein the lithium-phobic metal is one or more of copper, nickel, iron.
5. The negative electrode current collector as claimed in any one of claims 1 to 4, wherein the inner diameter of the metal tube is 10 to 2000 nm.
6. The negative electrode current collector of any one of claims 1 to 4, wherein the total thickness of the first metal layer and the second metal layer is 10 to 2000 nm.
7. The negative electrode current collector as claimed in any one of claims 1 to 4, wherein the length of the metal tube is 0.1 to 10 μm.
8. The negative electrode current collector as claimed in any one of claims 1 to 4, wherein the thickness of the conductive layer is 1 to 50 μm.
9. A method for preparing a negative electrode current collector according to any one of claims 1 to 8, comprising the steps of:
sequentially depositing lithium-philic metal and lithium-phobic metal on the surface of the fiber template to obtain a first metal layer and a second metal layer, and removing the fiber template to obtain a metal tube; and then mixing the metal pipe and a binder to obtain conductive layer slurry, and coating the conductive layer slurry on the upper surface and/or the lower surface of the metal layer to obtain the negative electrode current collector.
10. A lithium ion battery comprising the negative electrode current collector of any one of claims 1 to 8.
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