CN117476946A - Composite current collector and manufacturing method thereof, composite pole piece and manufacturing method thereof, and lithium battery - Google Patents
Composite current collector and manufacturing method thereof, composite pole piece and manufacturing method thereof, and lithium battery Download PDFInfo
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- CN117476946A CN117476946A CN202311361671.6A CN202311361671A CN117476946A CN 117476946 A CN117476946 A CN 117476946A CN 202311361671 A CN202311361671 A CN 202311361671A CN 117476946 A CN117476946 A CN 117476946A
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 239000007769 metal material Substances 0.000 claims abstract description 216
- 239000000758 substrate Substances 0.000 claims abstract description 99
- 239000011149 active material Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims description 42
- -1 polyethylene terephthalate Polymers 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 21
- 239000007773 negative electrode material Substances 0.000 claims description 21
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- 238000000034 method Methods 0.000 claims description 12
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- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 8
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- 238000007740 vapor deposition Methods 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 6
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- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
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- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
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- 229920002978 Vinylon Polymers 0.000 claims description 4
- 239000005025 cast polypropylene Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
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- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
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- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
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- 239000010949 copper Substances 0.000 description 23
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
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- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
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- 238000007738 vacuum evaporation Methods 0.000 description 2
- 229910018182 Al—Cu Inorganic materials 0.000 description 1
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- 229910021383 artificial graphite Inorganic materials 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The present disclosure provides a composite current collector and a method of manufacturing the same, a composite pole piece and a method of manufacturing the same, and a lithium battery, the composite current collector including: a substrate layer; the first metal material layer is arranged on one side of the substrate layer, and one side of the first metal material layer, which is far away from the substrate layer, is configured to be coated with a first active material; and a second metal material layer disposed on a side of the substrate layer away from the first metal material layer, the side of the second metal material layer away from the substrate layer being configured to be coated with a second active material, the second active material being of opposite polarity to the first active material.
Description
Cross Reference to Related Applications
The present disclosure claims priority to 2022, 12, 23, application number 202211667775.5, the entire contents of which are incorporated herein by reference.
Technical Field
The disclosure relates to the technical field of lithium batteries, in particular to a composite current collector and a manufacturing method thereof, a composite pole piece and a manufacturing method thereof, and a lithium battery.
Background
Lithium ion batteries, abbreviated as lithium batteries, are widely used in human daily life as a kind of efficient energy storage device. The traditional lithium ion battery cell internally comprises a pair of positive plate and negative plate, and the positive plate and the negative plate are stacked in multiple layers or wound to realize battery cells with different capacities. In the traditional lithium ion battery, the volume of an active material part for effectively storing energy is small, and the volumes of a positive electrode current collector in a positive electrode plate and a negative electrode current collector in a negative electrode plate are large, so that the effective energy volume ratio of the lithium ion battery is low.
Disclosure of Invention
The invention aims to provide a composite current collector and a manufacturing method thereof, a composite pole piece and a manufacturing method thereof and a lithium battery, which can solve the technical problem of low effective energy volume ratio of the current lithium battery.
Embodiments of the present disclosure provide a composite current collector for a lithium battery, the composite current collector including:
a substrate layer;
the first metal material layer is arranged on one side of the substrate layer, and one side of the first metal material layer, which is far away from the substrate layer, is configured to be coated with a first active material; and
the second metal material layer is arranged on one side, far away from the first metal material layer, of the substrate layer, and one side, far away from the substrate layer, of the second metal material layer is configured to be coated with a second active material, and the polarity of the second active material is opposite to that of the first active material.
In some embodiments, the first metal material layer comprises:
a first sub-metal material layer disposed on the one side of the base material layer; and
and the second sub-metal material layer is arranged on one side of the first sub-metal material layer away from the base material layer, and one side of the second sub-metal material layer away from the first sub-metal material layer is configured to be coated with the first active material.
In some embodiments, the orthographic projection of the first sub-metallic material layer onto the substrate layer coincides with the orthographic projection of the second sub-metallic material layer onto the substrate layer.
In some embodiments, the substrate layer is made of one or more selected from polyethylene terephthalate, o-phenylphenol, cast polypropylene, polyimide polyvinyl chloride, polybutylene terephthalate, polyethylene naphthalate, polyether ether ketone, polyamide, polyethylene glycol, polyamide imide, polycarbonate, cyclic polyolefin, polyphenylene sulfide, polyvinyl acetate, polytetrafluoroethylene, polymethylene naphthalene, polyvinylidene fluoride, polyethylene naphthalate, polypropylene carbonate, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-co-trifluorochloroethylene, silicone, vinylon, polypropylene, polyethylene, polystyrene, polyether nitrile, polyurethane, polyphenylene oxide, polyester, and polysulfone and derivatives thereof.
In some embodiments, the substrate layer has a thickness of 4 to 8 μm.
In some embodiments, the material of either of the first metal material layer and the second metal material layer is selected from one or more of Ni, ti, cu, ag, au, pt, fe, co, cr, W, mo, al, mg, K, na, ca, sr, ba, si, ge, sb, pb, in and Zn.
In some embodiments, the material of the first sub-metal material layer comprises Al and the material of the second sub-metal material layer comprises Cu.
In some embodiments, the first sub-metal material layer has a thickness of 0.2-2 μm and the second sub-metal material layer has a thickness of 0.1-2 μm.
In some embodiments, the material of the second metal material layer includes Al, and the thickness of the second metal material layer is 0.3 to 4 μm.
In some embodiments, at least one of the first sub-metal material layer and the second sub-metal material layer is formed using one or more selected from evaporation, deposition, and sputtering.
In some embodiments, the second metal material layer is formed using one or more selected from evaporation, deposition, and sputtering.
In some embodiments, the first active material comprises a negative active material and the second active material comprises a positive active material.
Some embodiments of the present disclosure provide a composite pole piece comprising:
the composite current collector described in the foregoing embodiment;
the first active material layer is arranged on one side of the metal material layer away from the substrate layer; and
the second active material layer is arranged on one side of the two metal material layers away from the base material layer.
Some embodiments of the present disclosure provide a lithium battery, including the composite pole piece described in the foregoing embodiments.
Some embodiments of the present disclosure provide a method of manufacturing a composite current collector, the method comprising:
providing a substrate layer;
forming a first metal material layer on the substrate layer, wherein one side of the first metal material layer, which is far away from the substrate layer, is configured to be coated with a first active material; and
and forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein one side of the second metal material layer far away from the substrate layer is configured to be coated with a second active material, and the polarity of the second active material is opposite to that of the first active material.
In some embodiments, forming a first metal material layer on the substrate layer includes:
forming a first sub-metal material layer on one side of the substrate layer; and
a second sub-metal material layer is formed on a side of the first sub-metal material layer away from the substrate layer, the side of the second sub-metal material layer away from the first sub-metal material layer being configured to coat the first active material.
In some embodiments, the orthographic projection of the first sub-metallic material layer onto the substrate layer coincides with the orthographic projection of the second sub-metallic material layer onto the substrate layer.
In some embodiments, forming a first sub-metal material layer on one side of the substrate layer includes:
and forming an Al first sub-metal material layer on one side of the substrate layer by adopting one or more selected from vapor deposition, deposition and sputtering.
In some embodiments, forming a second sub-metal material layer on a side of the first sub-metal material layer remote from the substrate layer comprises:
and forming a Cu second sub-metal material layer on one side of the first sub-metal material layer far away from the substrate layer by adopting one or more selected from vapor deposition, deposition and sputtering.
In some embodiments, forming a second metal material layer on a side of the substrate layer remote from the first metal material layer includes:
and forming an Al second metal material layer on one side of the substrate layer far away from the first metal material layer by adopting one or more selected from vapor deposition, deposition and sputtering.
Some embodiments of the present disclosure provide a method of manufacturing a composite pole piece, comprising:
the method for manufacturing a composite current collector according to the foregoing embodiment;
coating a first active material on one side of the first metal material layer away from the substrate layer; and
and coating a second active material on one side of the second metal material layer far away from the substrate layer.
Compared with the related art, the embodiment of the disclosure has the following technical effects:
the two sides of the composite current collector can be coated with the positive electrode active material and the negative electrode active material respectively, so that a composite pole piece can be formed, and the thickness of the composite current collector of the composite pole piece is very thin compared with that of the positive electrode current collector of the positive electrode piece and the negative electrode current collector of the negative electrode piece of a conventional lithium battery, and can be used for improving the effective energy volume ratio of the lithium battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the disclosure and together with the description, serve to explain the principles of the disclosure. It will be apparent to those of ordinary skill in the art that the drawings in the following description are merely examples of the disclosure and that other drawings may be derived from them without undue effort. In the drawings:
fig. 1 is a schematic structural diagram of a composite current collector provided in some embodiments of the present disclosure;
fig. 2 is a schematic structural diagram of a composite pole piece provided in some embodiments of the present disclosure;
FIG. 3 is a method of manufacturing a composite current collector provided in some embodiments of the present disclosure;
FIG. 4 is a flowchart showing the step S20 in FIG. 3; and
fig. 5 is a flow chart of a method of manufacturing a composite pole piece provided by some embodiments of the present disclosure.
Detailed Description
For the purpose of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the drawings, in which it is apparent that the embodiments described are only some, but not all embodiments of the disclosure. Based on the embodiments in this disclosure, all other embodiments that a person of ordinary skill in the art would obtain without making any inventive effort are within the scope of protection of this disclosure.
The terminology used in the embodiments of the disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used in this disclosure of embodiments and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise, the "plurality" generally includes at least two.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
It should be understood that although the terms first, second, third, etc. may be used in embodiments of the present disclosure, these should not be limited to these terms. These terms are only used to distinguish one from another. For example, a first may also be referred to as a second, and similarly, a second may also be referred to as a first, without departing from the scope of embodiments of the present disclosure.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or apparatus. Without further limitation, an element defined by the phrase "comprising" does not exclude the presence of other like elements in a commodity or device comprising such element.
In the related art, a lithium battery generally comprises a positive electrode plate and a negative electrode plate, and the positive electrode plate and the negative electrode plate realize battery cells with different capacities through multilayer superposition or positive electrode winding. The positive electrode sheet generally includes a positive electrode current collector and positive electrode active materials coated on both sides of the positive electrode current collector. The positive current collector typically employs aluminum foil, which is typically 10 to 15 microns thick. The negative electrode sheet generally includes a negative electrode current collector and a negative electrode active material coated on both sides of the negative electrode current collector. The negative current collector typically employs copper foil, which is typically 4.5 to 9 microns thick. The positive electrode active material is coated on two sides of an aluminum foil, and then the positive electrode plate is manufactured after baking, rolling, slitting and die cutting, and the negative electrode active material is coated on two sides of a copper foil, and then the negative electrode plate is manufactured after baking, rolling, slitting and die cutting. And then sequentially superposing or winding the negative plate/the diaphragm/the positive plate to form the battery core of the lithium battery. In the battery cell of a lithium battery, positive electrode active materials and negative electrode active materials play a role in energy storage. The positive current collector and the negative current collector only play a role in conducting electricity, but do not play a role in energy storage, and the positive current collector and the negative current collector occupy a considerable volume, so that the effective energy volume ratio of the lithium battery is low, and the lithium battery is not beneficial to miniaturization.
An embodiment of the present disclosure provides a composite current collector for a lithium battery, including: a substrate layer; the first metal material layer is arranged on one side of the substrate layer, and one side of the first metal material layer, which is far away from the substrate layer, is configured to be coated with a first active material; and a second metal material layer disposed on a side of the substrate layer away from the first metal material layer, the side of the second metal material layer away from the substrate layer being configured to be coated with a second active material, the second active material being of opposite polarity to the first active material.
The two sides of the composite current collector can be coated with the positive electrode active material and the negative electrode active material respectively, so that a composite pole piece can be formed, and the thickness of the composite current collector of the composite pole piece is very thin compared with that of the positive electrode current collector of the positive electrode piece and that of the negative electrode current collector of the negative electrode piece, and the composite current collector can be used for improving the effective energy volume ratio of a lithium battery.
Alternative embodiments of the present disclosure are described in detail below with reference to the drawings.
Fig. 1 is a schematic structural diagram of a composite current collector according to some embodiments of the present disclosure, and as shown in fig. 1, an embodiment of the present disclosure provides a composite current collector 100 for a lithium battery, where the composite current collector 100 includes a substrate layer 30, a first metal material layer 10, and a second metal material layer 20.
Specifically, the substrate layer, for example, a high molecular polymer substrate layer, has good insulating properties, and can be made very thin. The first metal material layer 10 is disposed on a side of the substrate layer 30, such as the underside shown in fig. 1, and the side of the first metal material layer 10 remote from the substrate layer 30 is configured to be coated with a first active material. A second metal material layer 20 is provided on a side of the substrate layer 30 remote from the first metal material layer 10, the side of the second metal material layer 20 remote from the substrate layer 30 being configured to be coated with a second active material, the second active material being of opposite polarity to the first active material. The first active material is, for example, one of a positive electrode active material and a negative electrode active material, and the second active material is, for example, the other of the positive electrode active material and the negative electrode active material.
The composite current collector in the embodiment of the disclosure may form the first metal material layer and the second metal material layer on two sides of the high polymer substrate layer by using a film forming process, and thus the formed composite current collector may have a very thin thickness. The two sides of the composite current collector can be coated with the positive electrode active material and the negative electrode active material respectively to form a composite pole piece, the thickness of the formed composite pole piece can be made very thin, the cost-increasing ratio of the positive electrode active material and the negative electrode active material for energy storage is increased, and the improvement of the effective energy volume ratio of the lithium battery is facilitated.
In some embodiments, as shown in fig. 1, the first metal material layer 10 includes a first sub metal material layer 11 and a second sub metal material layer 12 stacked. The first sub-metal material layer 11 is arranged on one side of the substrate layer 30, for example the lower side shown in fig. 1. A second sub-metal material layer 12 is provided on a side of the first sub-metal material layer 11 remote from the substrate layer 30, the side of the second sub-metal material layer 12 remote from the first sub-metal material layer 11 being configured to be coated with the first active material.
As described above, the first metal material layer 10 may employ a plurality of metal film layers, for example, 2 or more layers. In some embodiments, the material of the first sub-metal material layer 11 is, for example, al, and the material of the second sub-metal material layer 12 is, for example, cu. The second sub-metallic material layer 12 of Cu is typically used to coat a first active material, such as a negative active material. Because of the high cost of Cu, forming the Cu second sub-metal material layer 12 directly on the base material layer 30 to form a predetermined film thickness results in high cost, and the Al first sub-metal material layer 11 may be formed on the base material layer 30 at a low cost, and then forming the Cu second sub-metal material layer 12 at a low thickness on a side of the Al first sub-metal material layer 11 away from the base material layer 30, thereby reducing the manufacturing cost. In some cases, the second sub-metal material layer 12 for carrying the first active material may not be easily formed on some specific substrate layers 30, and thus, the first sub-metal material layer 11 that is easily formed on the substrate layers 30 may be formed first, and then the second sub-metal material layer 12 may be formed on a side of the first sub-metal material layer 11 away from the substrate layers 30, so that stability of the composite current collector structure is ensured.
In some embodiments, as shown in fig. 1, the orthographic projection of the first sub-metallic material layer 11 onto the substrate layer 30 coincides with the orthographic projection of the second sub-metallic material layer 12 onto the substrate layer 30. The second sub-metal material layer 12 substantially completely covers the first sub-metal material layer 11. The side of the second sub-metal material layer 12 remote from said first sub-metal material layer 11 is used for coating the first active material.
In some embodiments, the material of the substrate layer 30 may be a high polymer material with insulating properties, and may form a thin film layer with stable structure. The material of the substrate layer 30 may be, for example, one or more selected from polyethylene terephthalate, o-phenylphenol, cast polypropylene, polyimide polyvinylchloride, polybutylene terephthalate, polyethylene naphthalate, polyether ether ketone, polyamide, polyethylene glycol, polyamide imide, polycarbonate, cyclic polyolefin, polyphenylene sulfide, polyvinyl acetate, polytetrafluoroethylene, polymethylene naphthalene, polyvinylidene fluoride, polyethylene naphthalate, polypropylene carbonate, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-co-chlorotrifluoroethylene, silicone, vinylon, polypropylene, polyethylene, polystyrene, polyether nitrile, polyurethane, polyphenylene oxide, polyester, polysulfone, and derivatives thereof.
In some embodiments, the substrate layer 30 may be made of polyethylene terephthalate (PET) or O-phenylphenol (OPP) material, so that better insulation property and structural stability can be obtained, and the manufacturing cost is low.
In some embodiments, the substrate layer 30 has a thickness of 4 to 8 μm, for example 5 to 7 μm. The substrate layer 30 needs to be thinned as much as possible while ensuring its insulating properties and structural stability to improve the effective energy-to-volume ratio of the lithium ion battery.
In some embodiments, the material of either of the first metal material layer and the second metal material layer is selected from one or more of Ni, ti, cu, ag, au, pt, fe, co, cr, W, mo, al, mg, K, na, ca, sr, ba, si, ge, sb, pb, in and Zn. The first and second metal material layers are coated with a first active material and a second active material, respectively, both of which require good electrical conductivity for smooth charge flow therethrough.
In some embodiments, as shown in fig. 1, the material of the first sub-metal material layer 11 includes Al, and the material of the second sub-metal material layer 12 includes Cu. The surface of the second sub-metal material layer 12 on the side remote from the first sub-metal material layer 11 is coated with a first active material, such as a negative electrode active material.
The Cu resource is abundant, the price is low, and the film layer has certain ductility, which is beneficial to the winding of the composite current collector in the process of manufacturing the lithium battery. Cu is relatively stable in air itself, does not substantially react in dry air, but has a low oxidation potential and is easily oxidized at a high potential, so Cu is more suitable for coating a negative electrode active material than a positive electrode active material. In some embodiments, the first metal material layer 10 may form a single film layer using Cu.
The Al resources are more abundant, the price is lower than Cu, the price is also good, and the Al resources can be tightly stacked with the Cu film, and in some embodiments of the present disclosure, as shown in fig. 1, the first metal material layer 10 adopts a double-layer structure, so as to ensure the conductive effect and further reduce the cost.
In some embodiments, as shown in fig. 1, the thickness of the first sub-metal material layer 11 is 0.2-2 μm, for example 1 μm. The thickness of the second sub-metal material layer is 0.1-2 μm, for example 1 μm. The overall thickness of the first metal material layer 10 needs to be reduced as much as possible while ensuring its conductive properties, ductility, and structural stability, so as to improve the effective energy-to-volume ratio of the lithium ion battery.
In some embodiments, as shown in fig. 1, the material of the second metal material layer includes Al, and the thickness of the second metal material layer is 0.3 to 4 μm, for example, 2 μm. As shown before, the Al resource is abundant, the price is very low, and the film layer has certain ductility, which is beneficial to the winding of the composite current collector in the process of manufacturing the lithium battery. Al is relatively stable in air, does not substantially react in dry air, has a high oxidation potential, and is not easily oxidized at a high potential, so that Al is suitable for coating a positive electrode active material. The second metal material layer 20 may be formed as a single film layer using Al. The overall thickness of the second metal material layer 20 needs to be reduced as much as possible while ensuring its conductive properties, ductility, and structural stability, so as to improve the effective energy-to-volume ratio of the lithium ion battery.
In some embodiments, as shown in fig. 1, at least one of the first sub-metal material layer 11 and the second sub-metal material 12 is formed using one or more selected from evaporation, deposition, and sputtering. The second metal material layer 20 is formed using one or more selected from evaporation, deposition, and sputtering.
Specifically, the evaporation may include vacuum evaporation, ion plating, etc., the deposition may include chemical vapor deposition, plasma vapor deposition, atomic layer deposition, pulse laser deposition, etc., and the sputtering may include radio frequency sputtering, magnetron sputtering, reactive sputtering, etc.
The sheet resistance of the first metal material layer 10 was 33mΩ/≡, which indicates that the conductivity of the first metal material layer 10 formed by the first metal material layer 11 and the second metal material layer 12 was good.
In some embodiments, the first active material comprises a negative active material and the second active material comprises a positive active material. The positive electrode active material includes, for example, lithium-containing transition metal oxides, phosphides such as LiCoO2, liFePO4, and the like, and the negative electrode active material includes, for example, carbon materials such as artificial graphite, natural graphite, mesophase carbon microspheres, petroleum coke, carbon fibers, pyrolytic resin carbon, and the like.
Fig. 2 is a schematic structural diagram of a composite pole piece provided in some embodiments of the present disclosure. As shown in fig. 2, some embodiments of the present disclosure provide a composite pole piece 1000, the composite pole piece 1000 including the composite current collector 100 of the previous embodiments, the first active material layer 41, and the second active material layer 42.
The specific structure of the composite current collector 100 has been described in detail in the foregoing embodiments, and will not be described in detail herein.
The first active material layer 41 is provided on a side of the first metal material layer 10 away from the base material layer 30, and is formed, for example, by coating a negative electrode active material slurry on a side of the first metal material layer 10 away from the base material layer 30, specifically, a negative electrode active material slurry is formed, for example, by a coating process on a side of the second sub metal material layer 12 away from the first sub metal material layer 11. Coating processes include, for example, spraying, printing, roll coating, spin coating, and the like.
The second active material layer 42 is disposed on a side of the bi-metallic material layer 20 remote from the substrate layer 30. Which is formed, for example, by coating the side of the first metal material layer 20 remote from the base material layer 30 with a positive electrode active material slurry.
In the composite pole piece provided by the disclosure, the thickness of the composite current collector is very thin compared with that of the positive current collector of the positive pole piece and the negative current collector of the negative pole piece of the conventional lithium battery, and the composite pole piece can be used for improving the effective energy volume ratio of the lithium battery.
The present disclosure also provides a lithium battery, including the composite pole piece provided in the foregoing embodiment, where the composite pole piece may form a battery core of the lithium battery in a conventional stacking manner or a winding manner, and further wrap the protective case to form the lithium battery. Because the thickness of the combined current collector is very thin compared with the positive current collector of the positive plate and the negative current collector of the negative plate of the conventional lithium battery, the lithium battery provided by the disclosure can have better effective energy-volume ratio.
Some embodiments of the present disclosure further provide a method for manufacturing a composite current collector, and fig. 3 is a schematic diagram illustrating a method for manufacturing a composite current collector according to some embodiments of the present disclosure. As shown in fig. 3, the manufacturing method of the composite current collector includes the steps of:
s10: a substrate layer is provided.
Specifically, the material of the substrate layer may be a high polymer material with insulating properties, and a thin film layer with stable structure and thin thickness may be formed. The material of the substrate layer may be, for example, one or more selected from polyethylene terephthalate, o-phenylphenol, cast polypropylene, polyimide polyvinylchloride, polybutylene terephthalate, polyethylene naphthalate, polyether ether ketone, polyamide, polyethylene glycol, polyamide imide, polycarbonate, cyclic polyolefin, polyphenylene sulfide, polyvinyl acetate, polytetrafluoroethylene, polymethylene naphthalene, polyvinylidene fluoride, polyethylene naphthalate, polypropylene carbonate, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-co-chlorotrifluoroethylene, silicone, vinylon, polypropylene, polyethylene, polystyrene, polyether nitrile, polyurethane, polyphenylene oxide, polyester, polysulfone, and derivatives thereof. The substrate layer may be purchased or produced by itself.
S20: a first metal material layer is formed on the substrate layer, the first metal material layer being configured to coat a first active material on a side of the substrate layer remote from the substrate layer.
The material of the first metal material layer is selected from one or more of Ni, ti, cu, ag, au, pt, fe, co, cr, W, mo, al, mg, K, na, ca, sr, ba, si, ge, sb, pb, in and Zn. Specifically, in some embodiments, the first metal material layer may be formed using Cu as a single film layer. The Cu resource is abundant, the price is low, and the film layer has certain ductility, which is beneficial to the winding of the composite current collector in the process of manufacturing the lithium battery. Cu is relatively stable in air itself, does not substantially react in dry air, but has a low oxidation potential and is easily oxidized at a high potential, so Cu is more suitable for coating a negative electrode active material than a positive electrode active material.
S30: and forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein one side of the second metal material layer far away from the substrate layer is configured to be coated with a second active material, and the polarity of the second active material is opposite to that of the first active material.
The material of the second metal material layer is selected from one or more of Ni, ti, cu, ag, au, pt, fe, co, cr, W, mo, al, mg, K, na, ca, sr, ba, si, ge, sb, pb, in and Zn. Specifically, in some embodiments, the second metal material layer may employ Al as a single film layer to form the first metal material layer. Al resources are rich, the price is very cheap, and the film layer has certain ductility, which is beneficial to the winding of the composite current collector in the process of manufacturing the lithium battery. Al is relatively stable in air, does not substantially react in dry air, has a high oxidation potential, and is not easily oxidized at a high potential, so that Al is suitable for coating a positive electrode active material.
Fig. 4 is a specific flowchart of step S20 in fig. 3, and in some embodiments, step S20 includes the following steps:
s21: and forming a first sub-metal material layer on one side of the substrate layer.
Specifically, in some embodiments, the material of the first sub-metal material layer includes Al, and the thickness of the first sub-metal material layer is 0.2 to 2 μm, for example, 1 μm.
S22: a second sub-metal material layer is formed on a side of the first sub-metal material layer away from the substrate layer, the side of the second sub-metal material layer away from the first sub-metal material layer being configured to coat the first active material.
Specifically, in some embodiments, the material of the second sub-metal material layer includes Cu, and the thickness of the second sub-metal material layer is 0.1 to 2 μm, for example, 1 μm.
Because Al resources are richer, the price is lower than that of Cu, the Al-Cu composite film has good conductivity, can be tightly overlapped with a Cu film, and can adopt a double-layer film formed by overlapping Al and Cu to replace a single film layer formed by Cu, thereby further reducing the cost.
The overall thickness of the first metal material layer needs to be reduced as much as possible under the condition of ensuring the conductive property, the ductility and the structural stability of the first metal material layer so as to improve the effective energy-volume ratio of the lithium ion battery.
In some embodiments, the orthographic projection of the first sub-metallic material layer onto the substrate layer coincides with the orthographic projection of the second sub-metallic material layer onto the substrate layer. The second sub-metal material layer substantially completely covers the first sub-metal material layer. The side of the second sub-metal material layer remote from the first sub-metal material layer is used for coating the first active material.
In some embodiments, in step S21, an Al-based first sub-metal material layer is formed on one side of the base material layer using one or more selected from evaporation, deposition, and sputtering.
In some embodiments, in step S22, a Cu-based second sub-metal material layer is formed on a side of the first sub-metal material layer remote from the substrate layer using one or more selected from evaporation, deposition, and sputtering.
In some embodiments, in step S30, an Al-based second metal material layer is formed on a side of the base material layer remote from the first metal material layer using one or more selected from evaporation, deposition, and sputtering.
Specifically, the evaporation may include vacuum evaporation, ion plating, etc., the deposition may include chemical vapor deposition, plasma vapor deposition, atomic layer deposition, pulse laser deposition, etc., and the sputtering may include radio frequency sputtering, magnetron sputtering, reactive sputtering, etc.
Some embodiments of the present disclosure further provide a method for manufacturing a composite pole piece, and fig. 5 is a flowchart of the method for manufacturing a composite pole piece provided by some embodiments of the present disclosure. The manufacturing method of the composite pole piece comprises the following steps of:
s510 provides a composite current collector;
specifically, the manufacturing method of the composite current collector provided in the foregoing embodiment may be used to manufacture the composite current collector, which is not described herein.
S520: coating a first active material on one side of the first metal material layer away from the substrate layer;
specifically, a first active material slurry, such as a negative electrode active material slurry, is applied to a side of the first metal material layer remote from the base material layer to form a first active material layer, such as a negative electrode active material layer. Coating processes include, for example, spraying, printing, roll coating, spin coating, and the like.
S530: and coating a second active material on one side of the second metal material layer far away from the substrate layer. Specifically, a second active material slurry, such as a positive electrode active material slurry, is applied to a side of the second metal material layer away from the base material layer to form a second active material layer, such as a positive electrode active material layer. Coating processes include, for example, spraying, printing, roll coating, spin coating, and the like.
Experiments show that the sheet resistance of the first metal material layer 10 is 33mΩ/≡, which indicates that the conductivity of the first metal material layer 10 formed by the first metal material layer 11 and the second metal material layer 12 is good.
The straight tensile force of the composite current collector 100 is 27N/15mm and is greater than that of the traditional current collector 25N/15mm, which indicates that the composite current collector 100 has stronger tensile force.
The welding residual rate of the composite current collector 100 and the tab on one side of the tab is 100% after welding, which indicates that the welding effect is good.
The internal resistance (2000 mAh) of the cell formed by the composite current collector 100 is 15mΩ -15.5 mΩ, and the internal resistance (2000 mAh) of the cell of the traditional current collector is 13mΩ, which indicates that the composite current collector still has smaller internal resistance of the cell under the condition of non-conductive base material, and the internal resistance is only 15 percent (less than 30 percent) greater than the internal resistance of the traditional metal cell, and the composite current collector still can meet good conductive performance.
The composite current collector cell weight (5500 mAh) is about 79g, and the conventional current collector cell weight (5500 mAh) is about 98g, so the composite current collector cell weight is lighter than the conventional current collector cell weight.
And (3) testing electrical properties: the ternary system circulation of the composite current collector cell has the discharge capacity retention rate of 75% after 1700 times of circulation, has no obvious reduction, is approximately equal to the ternary system circulation performance of the traditional current collector cell, and can meet the electrical performance requirement.
Finally, it should be noted that: in the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The above embodiments are merely for illustrating the technical solution of the present disclosure, and are not limiting thereof; although the present disclosure has been described in detail with reference to the foregoing embodiments, it should 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 corresponding technical solutions of the embodiments of the present disclosure.
Claims (10)
1. A composite current collector for a lithium battery, the composite current collector comprising:
a substrate layer;
the first metal material layer is arranged on one side of the substrate layer, and one side of the first metal material layer, which is far away from the substrate layer, is configured to be coated with a first active material; and
the second metal material layer is arranged on one side, far away from the first metal material layer, of the substrate layer, and one side, far away from the substrate layer, of the second metal material layer is configured to be coated with a second active material, and the polarity of the second active material is opposite to that of the first active material.
2. The composite current collector of claim 1 wherein the first layer of metallic material comprises:
a first sub-metal material layer disposed on the one side of the base material layer; and
and the second sub-metal material layer is arranged on one side of the first sub-metal material layer away from the base material layer, and one side of the second sub-metal material layer away from the first sub-metal material layer is configured to be coated with the first active material.
3. The composite current collector of claim 2 wherein the orthographic projection of the first sub-metallic material layer onto the substrate layer coincides with the orthographic projection of the second sub-metallic material layer onto the substrate layer.
4. A composite current collector according to any one of claims 1 to 3, wherein the substrate layer is made of one or more selected from polyethylene terephthalate, o-phenylphenol, cast polypropylene, polyimide polyvinylchloride, polybutylene terephthalate, polyethylene naphthalate, polyetheretherketone, polyamide, polyethylene glycol, polyamideimide, polycarbonate, cyclic polyolefin, polyphenylene sulfide, polyvinyl acetate, polytetrafluoroethylene, polymethylene naphthalene, polyvinylidene fluoride, polyethylene naphthalate, polypropylene carbonate, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-co-trifluorochloroethylene, silicone, vinylon, polypropylene, polyethylene, polystyrene, polyethernitrile, polyurethane, polyphenylene oxide, polyester and polysulfone and derivatives thereof;
optionally, the thickness of the substrate layer is 4-8 μm;
optionally, the material of any one of the first metal material layer and the second metal material layer is selected from one or more of Ni, ti, cu, ag, au, pt, fe, co, cr, W, mo, al, mg, K, na, ca, sr, ba, si, ge, sb, pb, in and Zn;
optionally, the material of the first sub-metal material layer includes Al, and the material of the second sub-metal material layer includes Cu;
optionally, the thickness of the first sub-metal material layer is 0.2-2 μm, and the thickness of the second sub-metal material layer is 0.1-2 μm;
optionally, the material of the second metal material layer comprises Al, and the thickness of the second metal material layer is 0.3-4 μm;
optionally, at least one of the first sub-metal material layer and the second sub-metal material is formed using one or more selected from evaporation, deposition, and sputtering;
optionally, the second metal material layer is formed by one or more selected from evaporation, deposition and sputtering;
optionally, the first active material includes a negative active material, and the second active material includes a positive active material.
5. A composite pole piece, characterized in that the composite pole piece comprises:
the composite current collector of any one of claims 1 to 4;
the first active material layer is arranged on one side of the metal material layer away from the substrate layer; and
the second active material layer is arranged on one side of the two metal material layers away from the base material layer.
6. A lithium battery comprising the composite pole piece of claim 5.
7. A method of manufacturing a composite current collector, the method comprising:
providing a substrate layer;
forming a first metal material layer on the substrate layer, wherein one side of the first metal material layer, which is far away from the substrate layer, is configured to be coated with a first active material; and
and forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein one side of the second metal material layer far away from the substrate layer is configured to be coated with a second active material, and the polarity of the second active material is opposite to that of the first active material.
8. The manufacturing method according to claim 7, wherein forming a first metal material layer on the base material layer includes:
forming a first sub-metal material layer on one side of the substrate layer; and
forming a second sub-metal material layer on a side of the first sub-metal material layer away from the substrate layer, the side of the second sub-metal material layer away from the first sub-metal material layer being configured to coat the first active material;
optionally, the orthographic projection of the first sub-metal material layer on the substrate layer coincides with the orthographic projection of the second sub-metal material layer on the substrate layer;
optionally, forming the first sub-metal material layer on one side of the substrate layer includes:
forming an Al first sub-metal material layer on one side of the substrate layer by adopting one or more selected from vapor deposition, deposition and sputtering;
optionally, forming a second sub-metal material layer on a side of the first sub-metal material layer away from the substrate layer includes:
and forming a Cu second sub-metal material layer on one side of the first sub-metal material layer far away from the substrate layer by adopting one or more selected from vapor deposition, deposition and sputtering.
9. The manufacturing method according to any one of claims 7 to 8, wherein forming a second metal material layer on a side of the base material layer remote from the first metal material layer comprises:
and forming an Al second metal material layer on one side of the substrate layer far away from the first metal material layer by adopting one or more selected from vapor deposition, deposition and sputtering.
10. A method of manufacturing a composite pole piece, comprising:
a method of manufacturing a composite current collector as claimed in any one of claims 7 to 9;
coating a first active material on one side of the first metal material layer away from the substrate layer; and
and coating a second active material on one side of the second metal material layer far away from the substrate layer.
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| CN202211667775 | 2022-12-23 | ||
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