CN115172761A - Composite copper-based current collector and preparation method thereof, battery electrode and lithium ion battery - Google Patents
Composite copper-based current collector and preparation method thereof, battery electrode and lithium ion battery Download PDFInfo
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- CN115172761A CN115172761A CN202211096929.XA CN202211096929A CN115172761A CN 115172761 A CN115172761 A CN 115172761A CN 202211096929 A CN202211096929 A CN 202211096929A CN 115172761 A CN115172761 A CN 115172761A
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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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M4/80—Porous plates, e.g. sintered carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The disclosure provides a composite copper-based current collector, a preparation method thereof, a battery electrode and a lithium ion battery. The preparation method of the composite copper-based current collector comprises the following steps: dispersing the copper nanowires in a dispersing agent to form a copper nanowire dispersion liquid; spraying the copper nanowire dispersion liquid on a copper base layer, solidifying and sublimating the dispersing agent in a freeze drying mode, and removing the dispersing agent in the copper porous layer to form the copper porous layer with a porous structure; and depositing a reinforcing material on the copper porous layer by means of co-sputtering, wherein the reinforcing material comprises chromium and nickel. The preparation method of the composite copper-based current collector can ensure that the overall weight of the composite copper-based current collector is remarkably reduced to form a light composite copper-based current collector meeting the actual requirement.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a composite copper-based current collector and a preparation method thereof, a battery electrode and a lithium ion battery.
Background
Current collectors of lithium ion batteries currently commercialized are mainly conductive metal foils such as copper foil and aluminum foil, in which copper foil is generally used as lithiumNegative current collector of an ion battery. The density of copper is 8.6g/cm 3 The density of aluminum is 2.70 g/cm 3 The copper foil and the aluminum foil usually occupy 15% -50% of the total mass of the lithium ion battery. The current collector is generally a non-active component, and therefore reducing the mass fraction of the current collector in the battery is beneficial in increasing the overall specific energy of the battery. However, since the current collector plays a key role in the electronic transmission and mechanical support of the electrode material, the decrease in the mass of the current collector often means the decrease in the electrical conductivity and the decrease in the mechanical strength, and thus the mass ratio of the current collector is generally difficult to be effectively reduced. Researchers in the field are also trying to research some new lightweight current collectors, such as foam metal current collectors and carbon material current collectors. However, these current collectors generally suffer from poor mechanical properties or poor chemical stability to varying degrees.
Disclosure of Invention
In view of the above, in order to reduce the quality of the current collector while ensuring or improving the mechanical strength of the current collector, it is necessary to provide a method for preparing a composite copper-based current collector.
According to some embodiments of the present disclosure, a method of preparing a composite copper-based current collector includes the steps of:
dispersing the copper nanowires in a dispersing agent to form a copper nanowire dispersion liquid;
spraying the copper nanowire dispersion liquid on a copper base layer, solidifying and sublimating the dispersing agent in a freeze drying mode, and removing the dispersing agent in the copper porous layer to form the copper porous layer with a porous structure;
and depositing a reinforcing material on the copper porous layer by means of co-sputtering, wherein the reinforcing material comprises chromium and nickel.
In one embodiment of the present disclosure, the copper-based layer is disposed on a polymer film having a flame retardant material disposed therein.
In one embodiment of the present disclosure, the copper-based layer is disposed on the polymer film by a method comprising: treating the polymer film by adopting oxygen-containing plasma, and grafting hydrophilic functional groups on the surface of the polymer film; and depositing the copper-based layer on the surface of the polymer film.
In one embodiment of the present disclosure, the flame retardant material comprises one or more of triphenyl phosphate, trimethyl phosphate, tris (2, 3-dichloropropyl) phosphate, triethyl phosphate, a styrene-butadiene-based phosphate, and a polyphosphate.
In one of the embodiments of the present disclosure, the reinforcing material further includes at least one of silicon and aluminum.
In one of the embodiments of the present disclosure, the overall thickness of the deposited reinforcement material is 500nm to 2 μm.
According to still other embodiments of the present disclosure, there is also provided a composite copper-based current collector prepared by the preparation method described in any of the above embodiments.
According to still further embodiments of the present disclosure, there is also provided a battery electrode comprising an electrode active material and the composite copper-based current collector described in any of the above embodiments.
In one embodiment of the present disclosure, the battery electrode further includes an induction deposition layer, the electrode active material includes a black phosphorus film, the induction deposition layer is located on the composite copper-based current collector, the induction deposition layer includes a phosphorus-containing alloy for inducing deposition of the black phosphorus film, the black phosphorus film is formed on the induction deposition layer in a magnetron sputtering manner, and the black phosphorus film covers the composite copper-based current collector.
According to still other embodiments of the present disclosure, there is also provided a lithium ion battery, which includes a positive electrode, a separator, and a negative electrode, where the positive electrode is disposed opposite to the negative electrode, the separator is disposed between the positive electrode and the negative electrode, and at least one of the positive electrode and the negative electrode is the battery negative electrode in any of the above embodiments.
The preparation method of the composite copper-based current collector comprises the following steps: a porous copper layer having a porous structure is formed on a copper base layer by freeze-drying, and a reinforcing material comprising chromium and nickel is deposited on the porous copper layer by co-sputtering. Among them, the copper-based layer and the porous copper layer having a porous structure have a larger contact area than the copper foil, and thus can ensure electron conduction of the active material, but the mechanical properties of the porous copper layer temporarily fixed by freeze-drying are poor. Further, the reinforcing material comprising chromium and nickel is co-sputtered and deposited on the copper porous layer, so that a nichrome layer coated on the surface of the porous structure of the copper porous layer can be formed, and higher mechanical strength and hardness are provided, so that the mechanical performance of the copper-based layer and the copper porous layer are stabilized. And the density of nickel and chromium is lower than that of copper, and the porous structure in the copper porous layer is combined, so that the overall weight of the composite copper-based current collector can be obviously reduced on the whole current collector, and the light composite copper-based current collector meeting the actual requirement is formed.
Drawings
Fig. 1 shows a schematic step diagram of a method of making a composite copper-based current collector provided by the present disclosure;
fig. 2 illustrates a schematic structural view of a composite copper-based current collector provided by the present disclosure;
wherein the reference symbols and their meanings are as follows:
110. a copper base layer; 120. a porous layer of copper; 130. a polymer film; 140. a layer of reinforcing material.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. Preferred embodiments of the present invention are presented herein. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items, and "multiple" as used herein includes two or more items.
Herein, unless otherwise specified, the individual reaction steps may or may not be performed in the order indicated. For example, other steps may be included between the respective reaction steps, and the order may be appropriately changed between the reaction steps. As can be determined by the skilled person based on routine knowledge and experience.
According to some embodiments of the present disclosure, there is provided a method of manufacturing a composite copper-based current collector, including the steps of: dispersing the copper nanowires in a dispersing agent to form a copper nanowire dispersion liquid; spraying the copper nanowire dispersion liquid on a copper base layer, solidifying and sublimating the dispersing agent in a freeze drying mode, and removing the dispersing agent in the copper porous layer to form the copper porous layer with a porous structure; and depositing a reinforcing material on the copper porous layer by means of co-sputtering, wherein the reinforcing material comprises chromium and nickel.
It is understood that the copper-based layer may be a separate copper-based layer or a copper film prepared in advance on a supporting substrate. The copper-based layer is used for supporting the copper nanowire arranged above the copper-based layer on one hand and is also used for assisting in leading out electrons of the copper porous layer to an external circuit on the other hand.
It can be understood that the dispersant originally positioned between the adjacent copper nanowires can be removed by freeze drying, and the overall structure of the copper porous layer is not significantly changed by the freeze drying. After the dispersant is removed, a part of the space originally occupied by the dispersant forms pores in the copper porous layer to form the copper porous layer having a porous structure.
The copper foil in the traditional technology is a relatively dense copper metal film, and the overall quality of the copper foil is relatively heavy. In some current collectors newly developed at present, the foam metal current collector only changes a dense foil material into a porous material, and the mechanical property of the foam metal current collector is relatively poor. Although the carbon material current collectors have the advantage of light weight, the carbon materials are mainly supported by intermolecular forces, and the carbon material current collectors also have the problem of poor mechanical properties. In addition, many of the various composite materials have problems that they are not corrosion-resistant and they are easily peeled off from each other.
In the method for preparing a composite copper-based current collector provided in the above embodiments of the present disclosure, the copper-based layer and the copper porous layer having a porous structure have a larger contact area than the copper foil, so that electron conduction of the active material can be ensured, but the mechanical properties of the copper porous layer temporarily fixed by freeze-drying are poor. Further, the reinforcing material comprising chromium and nickel is co-sputtered and deposited on the copper porous layer, so that a nichrome layer coated on the surface of the porous structure of the copper porous layer can be formed, and higher mechanical strength and hardness are provided, so that the mechanical performance of the copper-based layer and the copper porous layer are stabilized. And the density of nickel and chromium is lower than that of copper, and the porous structure in the copper porous layer is combined, so that the overall weight of the composite copper-based current collector can be obviously reduced on the whole current collector, and the light composite copper-based current collector meeting the actual requirement is formed.
In order to facilitate understanding of the preparation method of the composite copper-based current collector provided by the present disclosure, reference is made to fig. 1, which shows an embodiment of the preparation method of the composite copper-based current collector, including steps S1 to S4.
And S1, providing a copper base layer.
The copper-based layer can be an independent layered copper material, and can also be a copper film layer arranged on a certain substrate.
In some examples of this embodiment, the copper-based layer has a thickness of 500nm to 3 μm. For example, the copper-based layer may have a thickness of 500nm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, or a range between any two of the foregoing thicknesses.
In some examples of this embodiment, the copper-based layer is disposed on a polymer film having a flame retardant material disposed therein. Through set up the copper basic unit on the polymer membrane, on the one hand the polymer membrane can play the effect of supporting the copper basic unit to make compound copper base current collector have certain toughness. On the other hand, the density of the polymer film is far lower than that of copper, so that the quality of the composite copper-based current collector can be remarkably reduced under the condition of the same thickness. On the other hand, the flame-retardant material is arranged in the polymer film, so that the fireproof safety of the current collector can be improved, and the lithium ion battery is particularly suitable for application scenes of high-capacity lithium ion batteries.
In some examples of this embodiment, the polymer film has a thickness of 2 μm to 10 μm.
In some examples of this embodiment, the flame retardant material may be selected from a phosphorus based flame retardant. Optionally, the flame retardant material comprises one or more of triphenyl phosphate, trimethyl phosphate, tris (2, 3-dichloropropyl) phosphate, triethyl phosphate, a styrene-butadiene based phosphate, and polyphosphate.
In some examples of this embodiment, the copper-based layer is disposed on the polymer film by a process comprising: processing the polymer film by using oxygen-containing plasma, and grafting a hydrophilic functional group on the surface of the polymer film; and depositing a copper base layer on the surface of the polymer film. The surface of the polymer film is treated by oxygen-containing plasma, and hydrophilic functional groups can be grafted on the surface of the polymer film, so that the adhesion of a subsequently prepared copper-based layer on the surface of the polymer film is increased, and the copper-based layer is prevented from falling off from the surface of the polymer film as far as possible.
In some examples of this embodiment, the manner of depositing the copper-based layer may be magnetron sputtering. In the preparation process of magnetron sputtering, the deposition pressure in the magnetron sputtering deposition chamber is optionally controlled at 10 -7 The power of the sputtering target is 200W to 500W below Torr.
And S2, preparing a copper porous layer with a porous structure on the copper base layer.
The mode for preparing the copper porous layer with the porous structure comprises the following steps: dispersing the copper nanowires in a dispersing agent to form a copper nanowire dispersion liquid; and spraying the copper nanowire dispersion liquid on the copper base layer, solidifying and sublimating the dispersing agent in a freeze drying mode, and removing the dispersing agent in the copper porous layer to form the copper porous layer with the porous structure.
In some examples of this embodiment, the copper nanowires have a diameter below 500 nm. Optionally, the diameter of the copper nanowire is from 20nm to 200nm. For example, the copper nanowires have a diameter of 20nm, 50nm, 80nm, 100nm, 150nm, 200nm, or a range therebetween.
In some examples of this embodiment, the dispersant may include water. The water between the copper nanowires can be firstly solidified to form tiny ice crystals in a freeze drying mode, and then the ice crystals are directly sublimated in a vacuumizing mode. The relative position between the copper nanowires and the overall physical structure of the copper nanowires are basically not influenced by the freeze drying mode, and pores exist among the copper nanowires to form a porous structure. During the freezing process of the dispersing agent, the temperature of the dispersing agent can be controlled to be reduced to below-20 ℃ so that the dispersing agent is solidified to form tiny ice crystals. In the step of subjecting the dispersant to the drying treatment, the current collector structure including the copper porous layer may be placed in a vacuum chamber, and the pressure of the gas in the vacuum chamber may be controlled to be 100Pa or less.
In some examples of this embodiment, the copper porous layer has an overall thickness of 2 μm to 10 μm. It is understood that, when the copper porous layer is formed, the thickness of the copper porous layer can be controlled by controlling the amount of the sprayed copper nanowire dispersion, or by freeze-drying and spraying the copper nanowire dispersion several times to obtain a copper porous layer having a higher thickness.
In some examples of this embodiment, the manner of spraying the copper nanowire dispersion may be knife coating, casting, inkjet printing, etc., as long as a film of the copper nanowire dispersion can be formed on the copper base layer.
A copper porous layer can be formed on the copper base layer in a freeze drying mode, and due to the fact that the copper porous layer has a porous structure and the copper nanowires can play a role in conducting electrons sufficiently, the density of the composite current collector can be reduced remarkably by introducing the copper porous layer under the condition that the conductive performance is guaranteed. The copper nanowires in the copper porous layer have a pore structure therebetween, and sufficient force is not applied between the copper nanowires. Therefore, although the density of the composite current collector can be remarkably reduced by introducing the copper porous layer, the problem of poor mechanical performance is also brought, and the method is not suitable for preparing the current collector. In order to overcome this problem, the method for manufacturing a composite copper-based current collector in this embodiment further includes step S3.
Step S3, depositing a reinforcing material on the copper porous layer.
Wherein the reinforcing material comprises chromium and nickel. The manner of depositing the reinforcing material on the porous layer of copper is co-sputter deposition. Chromium and nickel are simultaneously deposited on the copper porous layer by means of co-sputter deposition such that the reinforcement material at least partially forms a layer of reinforcement material on the copper porous layer.
Wherein, the nickel atom and the chromium atom deposited by the co-sputtering mode firstly nucleate on the surface of the copper nanowire and gradually form a nickel-chromium alloy film layer in the deposition process. Then, along with the deposition, the nickel-chromium alloy film layers on the surface layers of the plurality of copper nanowires are connected to form a nickel-chromium alloy layer which integrally covers the surface of the copper porous layer. Also, nickel atoms and chromium atoms may be deposited on the copper-based layer located at the bottom through the porous structure of the copper porous layer.
In some examples of this embodiment, the overall thickness of the deposited reinforcement material is 500nm to 2 μm. For example, the overall thickness of the deposited reinforcement material is 500nm, 1 μm, 1.5 μm, 2 μm, or a range therebetween.
In some examples of this embodiment, the deposition chamber pressure is controlled at 10 -7 The power of the sputtering target is 200W to 500W below Torr.
In some examples of this embodiment, the reinforcement material further comprises at least one of silicon and aluminum. Through setting up silicon and aluminium, can guarantee under the mechanical properties's of reinforcing material the circumstances for the reinforcing material layer still has corrosion-resistant effect.
In some examples of this embodiment, the mass ratio of chromium to nickel in the reinforcement is 1 to 1.
In some examples of this embodiment, after the deposition of the reinforcing material, a step of annealing the reinforcing material is further included to improve lattice defects in the reinforcing material layer and improve toughness of the reinforcing material layer, so that the prepared composite copper-based current collector has better mechanical properties.
In the co-sputtering process, the nickel atoms and the chromium atoms have high energy and can be embedded into crystal lattices on the surface layer of the copper nanowires, so that the bonding force between the copper nanowires and the nickel-chromium alloy film layer is high. The nickel-chromium alloy layer has higher integral mechanical strength and hardness, and can effectively stabilize the integral mechanical properties of the copper base layer and the copper porous layer. The nickel-chromium alloy layer also has higher conductivity, the contact between the nickel-chromium alloy layer prepared by co-sputtering and the copper porous layer is good, and the introduced nickel-chromium alloy layer does not obviously influence the conductivity of the copper porous layer and the copper base layer, so that the prepared composite copper-based current collector still has better conductivity.
It can be understood that through the steps S1-S3, the composite copper-based current collector which is in line with practical use can be prepared.
The embodiment of the disclosure also provides a composite copper-based current collector prepared by the preparation method of the composite copper-based current collector in the embodiment.
Referring to fig. 2, the composite copper-based current collector of this embodiment includes a copper-based layer 110, a copper porous layer 120, and a reinforcing material layer 140. Wherein the copper porous layer 120 has a porous structure therein, and the copper porous layer 120 is disposed on the copper base layer 110. The reinforcement layer 140 includes nichrome therein, and the reinforcement layer 140 entirely covers the copper porous layer 120 and the copper base layer 110.
In some examples of this embodiment, the copper-based layer 110 has a thickness of 500nm to 3 μm.
In some examples of this embodiment, the composite copper current collector further includes a polymer film 130, the copper-based layer 110 is disposed on the polymer film 130, and the flame retardant material is disposed in the polymer film 130.
In some examples of this embodiment, the polymer film 130 has a thickness of 2 μm to 10 μm.
In some examples of this embodiment, the copper porous layer 120 includes copper nanowires and a porous structure between the copper nanowires. Wherein optionally the diameter of the copper nanowires is below 500 nm. Further optionally, the diameter of the copper nanowire is from 20nm to 200nm.
In some examples of this embodiment, the copper porous layer 120 has an overall thickness of 2 μm to 10 μm.
In some examples of this embodiment, the overall thickness of the reinforcing material layer 140 is 500nm to 2 μm.
In some examples of this embodiment, the reinforcement material further comprises at least one of silicon and aluminum.
In some examples of this embodiment, the mass ratio of chromium to nickel in the reinforcement is 1 to 1.
Here, the manner of preparing the copper porous layer 120 is prepared according to step S2 in the above-described embodiment, and the manner of preparing the reinforcing material layer 140 is prepared according to step S3 in the above-described embodiment.
In the composite copper-based current collector provided in this embodiment of the present disclosure, a copper porous layer 120 is further disposed on the copper base layer 110, and a reinforcing material layer 140 is further disposed on the copper porous layer 120. By arranging the copper porous layer 120 and the copper base layer 110, the overall weight of the composite copper-based current collector can be reduced, and further arranging the reinforcing material layer 140 can ensure that the overall mechanical properties of the copper base layer 110 and the copper porous layer 120 are stable so as to be used as the composite copper-based current collector for practical use.
Yet another aspect of the present disclosure also provides a battery electrode including an electrode active material and a composite copper-based current collector as in the above embodiments.
In some examples of this embodiment, the electrode active material is a negative electrode active material of a lithium ion battery, and the battery electrode is a negative electrode.
In some examples of this embodiment, the electrode active material in the battery electrode comprises a black phosphorus thin film, and the battery electrode further comprises an induction deposition layer. The induction deposition layer is positioned on the composite copper-based current collector and comprises a phosphorus-containing alloy for inducing the deposition of the black phosphorus film, the black phosphorus film is formed on the induction deposition layer in a magnetron sputtering mode, and the black phosphorus film covers the composite copper-based current collector.
In the battery electrode, an induction deposition layer for inducing black phosphorus deposition is further arranged on the composite copper-based current collector, and a black phosphorus film is formed on the surface of the induction deposition layer in a magnetron sputtering mode so as to form the black phosphorus film directly growing on the surface of the current collector. The black phosphorus film grown by magnetron sputtering is complete and has pores. On one hand, the electron transmission capability in the layered black phosphorus film directly grown on the current collector is stronger, and the electron transmission capability in the black phosphorus film is ensured. Moreover, the electric contact area between the whole black phosphorus film and the current collector is larger, and the electronic conduction capability between the black phosphorus film and the current collector is ensured. More importantly, gaps exist in the black phosphorus film grown on the induced deposition layer through the magnetron sputtering process, so that the prepared black phosphorus film is loose under the condition of ensuring the integrity, the gaps can buffer the volume change of the black phosphorus film in the electrochemical reaction to a certain extent, and the condition that active substances fall off from the surface of the current collector due to repeated expansion and contraction is further relieved.
In addition, because the specific capacity of the black phosphorus thin film is high, in some examples of the embodiment, the copper-based layer in the composite copper-based current collector is arranged on the polymer film, and the flame retardant material is arranged in the polymer film, so that the safety of the battery electrode can be ensured as much as possible. Therefore, the battery electrode can not only reduce the mass ratio of the current collector, but also improve the specific energy and the safety of the battery electrode.
The inducing and depositing layer is used as a growth nucleation base material of the black phosphorus film, and when phosphorus atoms bombard from the phosphorus target material, the phosphorus atoms contact the inducing and depositing layer and take the inducing and depositing layer as a core for epitaxial growth. It will be appreciated that the exposed crystal plane of the material in which the layer is typically induced to deposit should be matched to one of the crystal planes of black phosphorus to facilitate epitaxial growth of the black phosphorus film.
In some examples of this embodiment, the black phosphorus thin film has a thickness of 1 μm to 50 μm. Wherein, optionally, the thickness of the black phosphorus film formed by deposition can be controlled to be 2-30 μm.
In some examples of this embodiment, the black phosphorus film surface also has laser ablation holes. The laser ablation method can directionally remove the black phosphorus at the ablated part, has strong controllability and limited damage to the black phosphorus film, and is enough to further form larger pores for accommodating volume change on the surface of the black phosphorus film so as to accommodate the volume change of the black phosphorus film in the charging and discharging processes.
The present disclosure also provides a method for preparing the battery electrode, which comprises the following steps:
forming an induced deposition layer on the composite copper-based current collector; and placing the current collector with the induced deposition layer in a magnetron sputtering cavity, and depositing on the induced deposition layer in a magnetron sputtering mode to form the black phosphorus film.
In some examples of this embodiment, after depositing to form the black phosphorus thin film, further comprising: and (3) adopting laser to ablate partial area on the black phosphorus film.
The present disclosure also provides a lithium ion battery, which includes a positive electrode, a diaphragm and a negative electrode, wherein the positive electrode and the negative electrode are oppositely disposed, the diaphragm is disposed between the positive electrode and the negative electrode, and the negative electrode is the battery negative electrode of the above embodiment.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the composite copper-based current collector is characterized by comprising the following steps of:
dispersing the copper nanowires in a dispersing agent to form a copper nanowire dispersion liquid;
spraying the copper nanowire dispersion liquid on a copper base layer, solidifying and sublimating the dispersing agent in a freeze drying mode, and removing the dispersing agent in the copper porous layer to form the copper porous layer with a porous structure;
and depositing a reinforcing material on the copper porous layer by means of co-sputtering, wherein the reinforcing material comprises chromium and nickel.
2. The method for preparing the composite copper-based current collector according to claim 1, wherein the copper-based layer is disposed on a polymer film, and a flame retardant material is disposed in the polymer film.
3. The method for preparing a composite copper-based current collector according to claim 2, wherein the copper-based layer is disposed on the polymer film by a method comprising:
treating the polymer film by adopting oxygen-containing plasma, and grafting hydrophilic functional groups on the surface of the polymer film; and depositing the copper-based layer on the surface of the polymer film.
4. The method for preparing the composite copper-based current collector according to claim 2, wherein the flame retardant material comprises one or more of triphenyl phosphate, trimethyl phosphate, tris (2, 3-dichloropropyl) phosphate, triethyl phosphate, butylbenzene-based phosphate esters and polyphosphate salts.
5. The method for preparing the composite copper-based current collector according to any one of claims 1 to 4, wherein the reinforcing material further comprises at least one of silicon and aluminum.
6. The method for preparing the composite copper-based current collector as claimed in any one of claims 1 to 4, wherein the overall thickness of the deposited reinforcing material is 500nm to 2 μm.
7. A composite copper-based current collector, which is prepared by the preparation method according to any one of claims 1 to 6.
8. A battery electrode comprising an electrode active material and the composite copper-based current collector of claim 7.
9. The battery electrode according to claim 8, further comprising an induction deposition layer, wherein the electrode active material comprises a black phosphorus film, the induction deposition layer is disposed on the composite copper-based current collector, the induction deposition layer comprises a phosphorus-containing alloy for inducing deposition of the black phosphorus film, the black phosphorus film is formed on the induction deposition layer in a magnetron sputtering manner, and the black phosphorus film covers the composite copper-based current collector.
10. A lithium ion battery comprising a positive electrode, a separator, and a negative electrode, wherein the positive electrode is disposed opposite to the negative electrode, the separator is disposed between the positive electrode and the negative electrode, and at least one of the positive electrode and the negative electrode is the battery electrode according to claim 8 or 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211096929.XA CN115172761B (en) | 2022-09-08 | 2022-09-08 | Composite copper-based current collector, preparation method thereof, battery electrode and lithium ion battery |
| PCT/CN2022/128600 WO2024050945A1 (en) | 2022-09-08 | 2022-10-31 | Composite copper-based current collector and preparation method therefor, battery electrode and lithium-ion battery |
Applications Claiming Priority (1)
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| CN202211096929.XA CN115172761B (en) | 2022-09-08 | 2022-09-08 | Composite copper-based current collector, preparation method thereof, battery electrode and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
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| CN115172761A true CN115172761A (en) | 2022-10-11 |
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| WO2024050945A1 (en) * | 2022-09-08 | 2024-03-14 | 深圳市汉嵙新材料技术有限公司 | Composite copper-based current collector and preparation method therefor, battery electrode and lithium-ion battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090269511A1 (en) * | 2008-04-25 | 2009-10-29 | Aruna Zhamu | Process for producing hybrid nano-filament electrodes for lithium batteries |
| CN102360949A (en) * | 2011-09-14 | 2012-02-22 | 中国第一汽车股份有限公司 | Current collector for flexible solid super capacitor and preparation method of current collector |
| CN102460782A (en) * | 2009-05-07 | 2012-05-16 | 安普雷斯股份有限公司 | Electrode including nanostructures for rechargeable cells |
| CN103173996A (en) * | 2013-04-07 | 2013-06-26 | 浙江理工大学 | Tough nanofiber structure of surface oriented growth nanorod and preparation method thereof |
| KR101858933B1 (en) * | 2017-12-29 | 2018-05-17 | 서울대학교산학협력단 | Heterogeneous metal nanowire electrode and preparing method thereof |
| CN110350200A (en) * | 2018-04-03 | 2019-10-18 | 山东玉皇盛世化工股份有限公司 | A kind of lithium ion battery three-dimensional Arrays of Copper Nanowires collector and preparation method thereof |
| CN111540610A (en) * | 2020-05-09 | 2020-08-14 | 中南大学 | Electrode material for super capacitor and preparation method and application thereof |
| CN111600036A (en) * | 2020-06-01 | 2020-08-28 | 南开大学 | Three-dimensional porous copper oxide modified copper foil for lithium metal battery current collector and preparation method and application thereof |
| CN114975863A (en) * | 2022-08-01 | 2022-08-30 | 深圳市汉嵙新材料技术有限公司 | Black phosphorus cathode, preparation method thereof and lithium ion battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108963266A (en) * | 2018-07-31 | 2018-12-07 | 邦泰宏图（深圳）科技有限责任公司 | A kind of collector of lithium ion battery and preparation method thereof |
| CN109638224B (en) * | 2018-11-29 | 2021-12-31 | 西交利物浦大学 | Preparation method and application of copper-carbon-silicon composite negative plate |
| CN109560256A (en) * | 2018-11-29 | 2019-04-02 | 西交利物浦大学 | The preparation method and applications of copper silicon composite cathode piece |
| CN111180735B (en) * | 2019-05-31 | 2021-05-07 | 宁德时代新能源科技股份有限公司 | Negative current collector, negative pole piece and electrochemical device |
| CN114156486A (en) * | 2021-10-29 | 2022-03-08 | 上海空间电源研究所 | Light-weight flame-retardant current collector, preparation method thereof, electrode and battery |
| CN115172761B (en) * | 2022-09-08 | 2022-11-22 | 深圳市汉嵙新材料技术有限公司 | Composite copper-based current collector, preparation method thereof, battery electrode and lithium ion battery |
-
2022
- 2022-09-08 CN CN202211096929.XA patent/CN115172761B/en active Active
- 2022-10-31 WO PCT/CN2022/128600 patent/WO2024050945A1/en unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090269511A1 (en) * | 2008-04-25 | 2009-10-29 | Aruna Zhamu | Process for producing hybrid nano-filament electrodes for lithium batteries |
| CN102460782A (en) * | 2009-05-07 | 2012-05-16 | 安普雷斯股份有限公司 | Electrode including nanostructures for rechargeable cells |
| CN102360949A (en) * | 2011-09-14 | 2012-02-22 | 中国第一汽车股份有限公司 | Current collector for flexible solid super capacitor and preparation method of current collector |
| CN103173996A (en) * | 2013-04-07 | 2013-06-26 | 浙江理工大学 | Tough nanofiber structure of surface oriented growth nanorod and preparation method thereof |
| KR101858933B1 (en) * | 2017-12-29 | 2018-05-17 | 서울대학교산학협력단 | Heterogeneous metal nanowire electrode and preparing method thereof |
| CN110350200A (en) * | 2018-04-03 | 2019-10-18 | 山东玉皇盛世化工股份有限公司 | A kind of lithium ion battery three-dimensional Arrays of Copper Nanowires collector and preparation method thereof |
| CN111540610A (en) * | 2020-05-09 | 2020-08-14 | 中南大学 | Electrode material for super capacitor and preparation method and application thereof |
| CN111600036A (en) * | 2020-06-01 | 2020-08-28 | 南开大学 | Three-dimensional porous copper oxide modified copper foil for lithium metal battery current collector and preparation method and application thereof |
| CN114975863A (en) * | 2022-08-01 | 2022-08-30 | 深圳市汉嵙新材料技术有限公司 | Black phosphorus cathode, preparation method thereof and lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024050945A1 (en) * | 2022-09-08 | 2024-03-14 | 深圳市汉嵙新材料技术有限公司 | Composite copper-based current collector and preparation method therefor, battery electrode and lithium-ion battery |
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| CN115172761B (en) | 2022-11-22 |
| WO2024050945A1 (en) | 2024-03-14 |
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