CN117276554A - Composite current collector, composite pole piece, manufacturing method of composite pole piece and lithium battery - Google Patents
Composite current collector, composite pole piece, manufacturing method of composite pole piece and lithium battery Download PDFInfo
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- CN117276554A CN117276554A CN202311315718.5A CN202311315718A CN117276554A CN 117276554 A CN117276554 A CN 117276554A CN 202311315718 A CN202311315718 A CN 202311315718A CN 117276554 A CN117276554 A CN 117276554A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
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- 238000000034 method Methods 0.000 claims abstract description 17
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- 238000007756 gravure coating Methods 0.000 claims description 16
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 14
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 10
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- 229910052721 tungsten Inorganic materials 0.000 claims description 3
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- 239000006183 anode active material Substances 0.000 claims description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
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- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 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
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- 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)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present disclosure provides a composite current collector, a composite pole piece, 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; the second metal material layer is arranged on one side of the substrate layer away from the first metal material layer; at least part of the substrate layer is of a porous structure, metal particles are filled in the porous structure, and the metal particles are configured to enable the first metal material layer and the second metal material layer to be conducted. The composite current collector realizes conduction between two metal layers through the metal particles filled in the porous structure, has simple preparation process and fewer procedures, is convenient to directly weld with external metal lugs, and further reduces the production cost and the overall weight of the battery.
Description
Cross Reference to Related Applications
The present disclosure claims chinese patent application No. submitted in china at 2022, 12 and 23.
202211667749.2, 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, a composite pole piece, a manufacturing method of the composite pole piece 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 complex structure of the composite current collector causes difficult welding of the electrode lugs, thereby influencing the overall performance of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a composite current collector, a composite pole piece, a manufacturing method thereof and a lithium battery, which can solve the technical problem of low performance 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
the second metal material layer is arranged on one side of the substrate layer away from the first metal material layer;
at least part of the substrate layer is of a porous structure, metal particles are filled in the porous structure, and the metal particles are configured to enable the first metal material layer and the second metal material layer to be conducted.
In some embodiments, the porous structure is located at an edge of the substrate layer.
In some embodiments, the substrate layer is made of a composite material of one or more of polyethylene terephthalate, o-phenylphenol, 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, poly (vinylidene fluoride-co-chlorotrifluoroethylene), silicone, vinylon, polypropylene, polyethylene, polystyrene, polyether nitrile, polyurethane, polyphenylene oxide, polyester, polysulfone, and derivatives thereof.
In some embodiments, the substrate layer has a thickness of 4-8 μm.
In some embodiments, the diameter of the metal particles is approximately equal to the thickness of the substrate layer.
In some embodiments, the first metal material layer has a thickness of 0.3-2 μm and/or the second metal material layer has a thickness of 0.3-2 μm.
In some embodiments, the metal layer and/or the metal particles are 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 of the present invention, in some embodiments,
a first active material layer is arranged on one side, far away from the substrate layer, of the first metal material layer; and
a second active material layer is arranged on one side of the second metal material layer away from the substrate layer;
the second active material layer has the same polarity as the first active material layer.
In some embodiments, the orthographic projections of at least one of the first active material layer and the second active material layer at the first metal material layer or the second metal material layer do not overlap.
In some embodiments, the second active material layer is the same as the first active material layer as either the negative electrode active material or the positive electrode active material.
In some embodiments, the metal particles are applied to the porous structure of the substrate layer by at least one of gravure coating or extrusion coating.
In some embodiments, the first metal material layer and/or the second metal material layer is formed using one or more selected from evaporation, deposition, and sputtering.
The embodiment of the disclosure also provides a composite pole piece, which comprises:
a composite current collector according to any one of the preceding claims;
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.
The embodiment of the disclosure also provides a lithium battery, which comprises the composite pole piece.
The embodiment of the disclosure also provides a manufacturing method of the composite current collector, which comprises the following steps:
providing a substrate layer, wherein at least part of the substrate layer is of a porous structure;
coating metal particles at the porous structure of the substrate layer, so that the metal particles fill the porous structure;
forming a first metal material layer on one side of the substrate layer; and
and forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein the first metal material layer and the second metal material layer are conducted through the metal particles.
In some embodiments, coating metal particles at the porous structure of the substrate layer comprises:
metal particles are coated at the porous structure of the substrate layer by at least one of gravure coating or extrusion coating.
In some embodiments, coating metal particles at the porous structure of the substrate layer comprises:
the metal particles are coated at the porous structure at the edge position of the substrate layer by at least one of gravure coating or extrusion coating.
In some embodiments, a first metal material layer is formed on one side of the substrate layer; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer, including:
forming a first metal material layer on one side of the substrate layer by at least one of evaporation, deposition and sputtering; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer by at least one of evaporation, deposition and sputtering.
The embodiment of the disclosure also provides a manufacturing method of the composite current collector, which comprises the following steps:
providing a substrate layer, wherein at least part of the substrate layer is of a porous structure;
forming a first metal material layer on one side of the substrate layer;
coating metal particles on the porous structure on the other side of the substrate layer, so that the metal particles fill the porous structure; and
and forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein the first metal material layer and the second metal material layer are conducted through the metal particles.
In some embodiments, coating metal particles at the porous structure on the other side of the substrate layer comprises:
the metal particles are coated at the porous structure of the other side of the substrate layer by at least one of gravure coating or extrusion coating.
In some embodiments, coating metal particles at the porous structure of the substrate layer comprises:
the metal particles are coated at the porous structure at the edge position of the substrate layer by at least one of gravure coating or extrusion coating.
In some embodiments, a first metal material layer is formed on one side of the substrate layer; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer, including:
forming a first metal material layer on one side of the substrate layer by at least one of evaporation, deposition and sputtering; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer by at least one of evaporation, deposition and sputtering.
The embodiment of the disclosure also provides a manufacturing method of the composite pole piece, which comprises the following steps:
a method of manufacturing a composite current collector as claimed in any one of the preceding claims;
coating a first active material layer on one side of the first metal material layer away from the substrate layer; and
a second active material layer is coated on one side of the second metal material layer far away from the substrate layer,
wherein at least one of the first active material layer and the second active material layer does not overlap in orthographic projection of the first metal material layer or the second metal material layer.
In some embodiments, further comprising:
and arranging a tab in a region of the first metal material layer and/or the second metal material layer, which is not coated with the first active material layer and/or the second active material layer.
Compared with the related art, the embodiment of the disclosure has the following technical effects:
the composite current collector realizes conduction between two metal layers through the metal particles filled in the porous structure, has simple preparation process and fewer procedures, is convenient to directly weld with external metal lugs, and further reduces the production cost and the overall weight of the battery.
According to the preparation method of the composite current collector, the conduction point is prevented from being additionally built between two metal layers, and the conduction between the metal layers is realized by directly filling metal particles in the porous structure, so that the internal resistance is reduced, and the overall size and weight of the composite current collector are reduced; in addition, metal particles can be filled in the porous structure through a gravure coating or extrusion coating process, so that the process is simple, the operation is quick, the spraying plating of a subsequent metal layer is not influenced, and the production efficiency is greatly improved.
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 method of manufacturing a composite current collector according to further embodiments of the present disclosure;
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 order to improve the energy density and the safety of the battery, a composite current collector obtained by compositing a high polymer film and a metal coating is provided. In the related art, a polymer film is adopted in the middle of the composite current collector, and an insulating layer formed by the polymer film can not conduct metal plating layers on two sides, so that the traditional welding mode is not applicable any more. If the lugs of the multilayer composite current collector are directly welded, the welding cannot be successful due to the effect of the insulating layer; or the composite current collector lugs and the metal lugs which are alternately stacked together are welded, and the welding cannot be successfully performed. Therefore, the insulating structure of the composite current collector makes the tab welding mode of the lithium battery complex in steps, low in processing efficiency and unfavorable for reducing the overall weight and cost of the 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; the second metal material layer is arranged on one side of the substrate layer away from the first metal material layer; at least part of the substrate layer is of a porous structure, metal particles are filled in the porous structure, and the metal particles are configured to enable the first metal material layer and the second metal material layer to be conducted.
The composite current collector realizes conduction between two metal layers through the metal particles filled in the porous structure, has simple preparation process and less working procedures, can realize direct welding with the metal lugs of the lithium battery through single-layer lug welding, and further reduces the production cost and the overall weight of the 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 30, 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 arranged on one side of the substrate layer 30, for example on the lower side as shown in fig. 1. The second metal material layer 20 is arranged on a side of the substrate layer 30 remote from the first metal material layer 10, for example on the upper side as shown in fig. 1. Wherein at least part of the substrate layer 30 is a porous structure, and metal particles 40 are filled in the porous structure, and the metal particles 40 are configured to make the first metal material layer 10 and the second metal material layer 20 conductive.
The substrate layer 30 is a high polymer substrate layer with a porous structure, and the porous structure may be uniformly distributed on the entire surface of the substrate layer 30, or may be distributed in one or more local areas of the substrate layer 30, for example, in a side edge position of the substrate layer 30, or in a plurality of discrete local areas.
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 base material layer 30 may be, for example, a composite material of one or more selected from polyethylene terephthalate, o-phenylphenol, 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, poly (vinylidene 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.
The porous structure of the substrate layer 30 is filled with metal particles 40, the metal particles 40 are coated on the porous structure of the substrate layer by at least one of gravure coating or extrusion coating, and the metal particles 40 are filled in the porous structure to make the first metal material layer 10 and the second metal material layer 20 conductive.
In some embodiments, the metal particles 40 may be filled in the porous structure of one or more partial regions as described above, for example, as shown in fig. 1, where the metal particles 40 are filled in one side edge position of the substrate layer 30, and of course, the metal particles 40 may also be filled in one or more discrete partial regions of the substrate layer 30, where the partial regions may be located in an edge position or an intermediate position of the substrate layer 30, so long as the filled metal particles 40 can conduct the first metal material layer 10 and the second metal material layer 20.
In some embodiments, the substrate layer has a thickness of 4-8 μm, for example 5-7 μm. The base material layer 30 needs to be thinned as much as possible while ensuring its insulating properties and structural stability. The diameter of the metal particles is approximately equal to the thickness of the substrate layer and is also 4-8 μm, so that the metal particles can keep the same thickness as the substrate layer on the premise of keeping the first metal material layer 10 and the second metal material layer 20 conductive after filling the porous structure, and the flatness of the first metal material layer 10 and the second metal material layer 20 is ensured after receiving the first metal material layer 10 and the second metal material layer 20.
In some embodiments, the composite current collector 100 may form the first metal material layer 10 and the second metal material layer 20 on both sides of the high polymer substrate layer using a film forming process, respectively, and thus the composite current collector may have a very thin thickness. The metal layer and/or the metal particles are 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 metal particles are selected from copper, aluminum to enhance electrical conductivity between the first metal material layer 10 and the second metal material layer 20.
In some embodiments, the first and second metal material layers 10 and 20 may be the same and different materials, for example, the first and second metal material layers 10 and 20 may be copper or aluminum to enhance the conductivity of the composite current collector 100. 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. In some embodiments, the first metal material layer 10 and/or the second metal material layer 20 may form a single film layer using Cu. The Al resource is abundant, the price is lower than that of Cu, and the film layer has certain ductility, thereby being beneficial to the winding of the composite current collector in the process of manufacturing the lithium battery. Al is relatively stable in air, basically does not react in dry air, has high oxidation potential, is not easy to oxidize under high potential, has good conductivity, and can be used for forming a single film layer by adopting Al as the first metal material layer 10 and/or the second metal material layer 20.
In some embodiments, the first metal material layer has a thickness of 0.3-2 μm and/or the second metal material layer has a thickness of 0.3-2 μm.
In some embodiments, as shown in fig. 1, at least one of the first metal material layer 10 and 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.
Experiments show that the sheet resistance of the composite current collector is 33mΩ/≡, and the conductivity of the first metal material layer and the second metal material layer is good.
The straight pull force of the composite current collector is 27N/15mm and is greater than that of the traditional current collector by 25N/15mm, which indicates that the welding of the composite current collector is superior to the welding straight pull force of the traditional current collector after successful welding.
The welding residual rate of the composite current collector and the electrode lug on one side of the electrode lug is 90% after the welding, which shows that the welding effect is good. 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 200, the composite pole piece 200 including the composite current collector 100 of the previous embodiments, the first active material layer 50, and the second active material layer 60.
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.
In some embodiments, as shown in fig. 2, a first active material layer 50 is disposed on a side of the first metal material layer 10 away from the substrate layer 30; and a second active material layer 60 is disposed on a side of the second metal material layer 20 away from the base material layer 30; the second active material layer 60 has the same polarity as the first active material layer 50. For example, the second active material layer 60 is the same as the first active material layer 50 as the negative electrode active material or the positive electrode active material. Both sides of the composite current collector 100 may be coated with a positive electrode active material or a negative electrode active material, respectively, to form the composite electrode sheet 200, and thus the thickness of the formed composite electrode sheet 200 may be made very thin.
The first active material layer 50 is disposed on a side of the first metal material layer 10 remote 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 remote 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 first metal material layer 10 remote from the base material layer 30. Coating processes include, for example, spraying, printing, roll coating, spin coating, and the like.
The second active material layer 60 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 second metal material layer 20 remote from the base material layer 30 with a negative electrode active material slurry. Coating processes include, for example, spraying, printing, roll coating, spin coating, and the like.
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 reducing the weight of the lithium battery.
In some embodiments, when the composite pole piece 200 is a negative polarity composite pole piece, the second active material layer 60 and the first active material layer 50 are both negative active materials, and when the composite pole piece 200 is a positive polarity composite pole piece, the second active material layer 60 and the first active material layer 50 are both positive active materials. 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.
In some embodiments, as shown in fig. 2, the orthographic projections of at least one of the first active material layer 50 and the second active material layer 60 on the first metal material layer 10 or the second metal material layer 20 do not overlap. For example, the second active material layer 60 is partially coated on the first metal material layer 10, and does not completely overlap with the orthographic projection of the first metal material layer 10 or the second metal material layer 20, so as to expose a portion of the first metal material layer 10 for welding the tab 70. It can be appreciated that the composite pole piece 200 can make the first metal material layer 10 or the second metal material layer 20 be conducted with the positive electrode or the negative electrode of the lithium battery through the pole lug 70 only by arranging the single pole lug 70 at the exposed position, so as to improve the welding effect at the pole lug, reduce the resistance at the pole lug and improve the conductivity of the lithium battery. The composite pole piece 200 of the application directly welds the lugs of the multi-layer composite current collector, or welds the lugs of the multi-layer composite current collector and the metal lugs which are alternately stacked together, so that the number of layers of the metal lugs used in the welding of the composite current collector is greatly reduced, and the weight of the battery is further reduced.
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 that of 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 conductive performance and lighter weight.
Experiments show that the sheet resistance of the composite current collector is 32mΩ/≡, and the conductivity of the first metal material layer and the second metal material layer is good.
The straight pull force of the composite current collector is 30N/15mm and is greater than that of the traditional current collector by 25N/15mm, which indicates that the welding of the composite current collector is superior to the welding straight pull force of the traditional current collector after successful welding.
The welding residual rate of the composite current collector and the electrode lug on one side of the electrode lug is 100%, which shows that the welding effect is good.
The internal resistance (2000 mAh) of the cell formed by the composite current collector is 14mΩ -15 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 having a non-conductive base material, and is equivalent to the internal resistance of the traditional metal cell, and good conductivity can still be satisfied. 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: providing a substrate layer, wherein at least part of the substrate layer is of a porous structure.
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.
S20: and coating metal particles at the porous structure of the substrate layer, so that the metal particles fill the porous structure.
In some embodiments, the metal particles are coated at the porous structure of the substrate layer by at least one of gravure coating or extrusion coating.
In some embodiments, the metal particles are coated by at least one of gravure coating or extrusion coating at the porous structure at the edge locations of the substrate layer.
For example, the metal particles are selected to be copper, 5 μm in diameter, to increase conductivity and maintain the same thickness of the substrate layer.
S30: and forming a first metal material layer on one side of the substrate layer.
In some embodiments, the first metal material layer is formed by at least one of evaporation, deposition, and sputtering on a side of the substrate layer. 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.
For example, the first metal material layer is copper with a thickness of 1 μm to increase conductivity and make the composite current collector as thin and slim as possible.
S40: and forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein the first metal material layer and the second metal material layer are conducted through the metal particles.
In some embodiments, the second metal material layer is formed by at least one of evaporation, deposition, and sputtering on a side of the substrate layer remote from the first metal material layer. 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.
For example, the second metal material layer is aluminum with a thickness of 1 μm to increase conductivity and make the composite current collector as thin and light as possible.
Experiments prove that the thickness of the composite current collector is 6.5-7 um, compared with the traditional current collector, the composite current collector is very thin, and the sheet resistance of the composite current collector is 32mΩ/≡, which indicates that the conductivity of the first metal material layer and the second metal material layer is good.
The straight pull force of the composite current collector is 27N/15mm and is greater than that of the traditional current collector by 25N/15mm, which indicates that the welding of the composite current collector is superior to the welding straight pull force of the traditional current collector after successful welding.
The welding residual rate of the composite current collector and the electrode lug on one side of the electrode lug is 100%, which shows that the welding effect is good.
The internal resistance (2000 mAh) of the cell formed by the composite current collector is 14mΩ -15 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 having a non-conductive base material, and is equivalent to the internal resistance of the traditional metal cell, and good conductivity can still be satisfied.
The weight of the composite current collector cell (5500 mAh) is about 85g, and the weight of the traditional current collector cell (5500 mAh) is about 98g, so that the weight of the composite current collector cell is lighter than that of the traditional current collector cell.
Some embodiments of the present disclosure further provide a method for manufacturing a composite current collector, and fig. 4 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. 4, the manufacturing method of the composite current collector includes the steps of:
s100: providing a substrate layer, wherein at least part of the substrate layer is of a porous structure.
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.
S200: and forming a first metal material layer on one side of the substrate layer.
In some embodiments, the first metal material layer is formed by at least one of evaporation, deposition, and sputtering on a side of the substrate layer.
S300: and coating metal particles at the porous structure at the other side of the substrate layer, so that the metal particles fill the porous structure.
In some embodiments, the metal particles are coated by at least one of gravure coating or extrusion coating at the porous structure on the other side of the substrate layer.
In some embodiments, the metal particles are coated by at least one of gravure coating or extrusion coating at the porous structure at the edge location of the other side of the substrate layer.
S400: and forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein the first metal material layer and the second metal material layer are conducted through the metal particles.
In some embodiments, the second metal material layer is formed by at least one of evaporation, deposition, and sputtering on a side of the substrate layer remote from the first metal material layer.
Some embodiments of the present disclosure further provide a method for manufacturing a composite pole piece, and fig. 5 is a method for manufacturing a composite pole piece according to some embodiments of the present disclosure. As shown in fig. 5, the manufacturing method of the composite pole piece comprises the following steps:
s1000: a composite current collector was manufactured.
The method of manufacturing the composite current collector is as described above and will not be described herein.
S2000: and coating a first active material layer on one side of the first metal material layer away from the substrate layer.
For example, a negative electrode active material slurry is formed by coating the side of the first metal material layer 10 remote from the base material layer 30, and specifically, a negative electrode active material slurry is formed on the side of the first metal material layer 10 remote from the base material layer 30, for example, by a coating process. Coating processes include, for example, spraying, printing, roll coating, spin coating, and the like.
S3000: and a second active material layer is coated on one side of the second metal material layer far away from the substrate layer, wherein the orthographic projection of at least one of the first active material layer and the second active material layer on the first metal material layer or the second metal material layer is not overlapped.
For example, the anode active material slurry is coated on the side of the second metal material layer 20 away from the base material layer 30, and a space is partially reserved in the first metal material layer or the second metal material layer during the coating process. Coating processes include, for example, spraying, printing, roll coating, spin coating, and the like.
In some embodiments, the method of manufacturing a composite pole piece further comprises:
s4000: and arranging a tab in a region of the first metal material layer and/or the second metal material layer, which is not coated with the first active material layer and/or the second active material layer.
And arranging a tab in a welding mode at a region of the first metal material layer and/or the second metal material layer, which is not coated with the first active material layer and/or the second active material layer, so as to form a conductive electrode.
Experimental tests prove that the sheet resistance of the composite current collector is 30mΩ/≡, and the conductivity of the first metal material layer and the second metal material layer is good.
The straight pull force of the composite current collector is 35N/15mm and is greater than that of the traditional current collector by 25N/15mm, which indicates that the welding of the composite current collector is superior to the welding straight pull force of the traditional current collector after successful welding.
The welding residual rate of the composite current collector and the electrode lug on one side of the electrode lug is 100%, which shows that the welding effect is good.
The internal resistance (2000 mAh) of the cell formed by the composite current collector is 13.8mΩ -14 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 is equivalent to the internal resistance of the traditional metal cell, and good conductivity can still be satisfied.
The weight of the composite current collector cell (5500 mAh) is about 84g, and the weight of the traditional current collector cell (5500 mAh) is about 98g, so that the weight of the composite current collector cell is lighter than that of the traditional current collector cell.
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
the second metal material layer is arranged on one side of the substrate layer away from the first metal material layer;
at least part of the substrate layer is of a porous structure, metal particles are filled in the porous structure, and the metal particles are configured to enable the first metal material layer and the second metal material layer to be conducted.
2. The composite current collector of claim 1 wherein said porous structure is located at an edge of said substrate layer;
optionally, the material of the substrate layer is one or more of polyethylene terephthalate, o-phenylphenol, 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, poly (vinylidene fluoride-co-chlorotrifluoroethylene), organosilicon, vinylon, polypropylene, polyethylene, polystyrene, polyether nitrile, polyurethane, polyphenyl ether, polyester, polysulfone and derivatives thereof;
optionally, the thickness of the substrate layer is 4-8 μm;
the diameter of the metal particles is approximately equal to the thickness of the substrate layer;
optionally, the thickness of the first metal material layer is 0.3-2 μm, and/or the thickness of the second metal material layer is 0.3-2 μm;
optionally, the metal layer and/or the metal particles are 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.
3. The composite current collector of claim 1 wherein,
a first active material layer is arranged on one side, far away from the substrate layer, of the first metal material layer; and
a second active material layer is arranged on one side of the second metal material layer away from the substrate layer;
the second active material layer has the same polarity as the first active material layer.
Optionally, orthographic projections of at least one of the first active material layer and the second active material layer on the first metal material layer or the second metal material layer do not overlap;
alternatively, the second active material layer and the first active material layer are the same as the anode active material or the cathode active material.
4. The composite current collector of claim 1, wherein said metal particles are applied to the porous structure of said substrate layer by at least one of gravure coating or extrusion coating.
5. The composite current collector of claim 1, wherein said first metal material layer and/or said second metal material layer is formed using one or more selected from the group consisting of evaporation, deposition and sputtering.
6. A composite pole piece, characterized in that the composite pole piece comprises:
a composite current collector according to any one of claims 1 to 5;
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.
7. A lithium battery comprising the composite pole piece of claim 6.
8. A method of manufacturing a composite current collector, the method comprising:
providing a substrate layer, wherein at least part of the substrate layer is of a porous structure;
coating metal particles at the porous structure of the substrate layer, so that the metal particles fill the porous structure;
forming a first metal material layer on one side of the substrate layer; and
forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein the first metal material layer and the second metal material layer are conducted through the metal particles;
optionally, coating metal particles at the porous structure of the substrate layer, comprising:
coating metal particles at the porous structure of the substrate layer by at least one of gravure coating or extrusion coating;
optionally, coating metal particles at the porous structure of the substrate layer, comprising:
coating metal particles at the porous structure at the edge position of the substrate layer by at least one of gravure coating or extrusion coating;
optionally, forming a first metal material layer on one side of the substrate layer; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer, including:
forming a first metal material layer on one side of the substrate layer by at least one of evaporation, deposition and sputtering; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer by at least one of evaporation, deposition and sputtering.
9. A method of manufacturing a composite current collector, the method comprising:
providing a substrate layer, wherein at least part of the substrate layer is of a porous structure;
forming a first metal material layer on one side of the substrate layer;
coating metal particles on the porous structure on the other side of the substrate layer, so that the metal particles fill the porous structure; and
forming a second metal material layer on one side of the substrate layer far away from the first metal material layer, wherein the first metal material layer and the second metal material layer are conducted through the metal particles;
optionally, coating metal particles at the porous structure on the other side of the substrate layer, comprising:
coating metal particles at the porous structure of the other side of the substrate layer by at least one of gravure coating or extrusion coating;
optionally, coating metal particles at the porous structure of the substrate layer, comprising:
coating metal particles at the porous structure at the edge position of the substrate layer by at least one of gravure coating or extrusion coating;
optionally, forming a first metal material layer on one side of the substrate layer; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer, including:
forming a first metal material layer on one side of the substrate layer by at least one of evaporation, deposition and sputtering; and forming a second metal material layer on a side of the substrate layer away from the first metal material layer by at least one of evaporation, 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 8 to 9;
coating a first active material layer on one side of the first metal material layer away from the substrate layer; and
a second active material layer is coated on one side of the second metal material layer far away from the substrate layer,
wherein orthographic projections of at least one of the first active material layer and the second active material layer on the first metal material layer or the second metal material layer are not overlapped;
optionally, the method further comprises:
and arranging a tab in a region of the first metal material layer and/or the second metal material layer, which is not coated with the first active material layer and/or the second active material layer.
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