CN116504988A - Composite current collector, preparation method thereof and lithium ion battery - Google Patents
Composite current collector, preparation method thereof and lithium ion battery Download PDFInfo
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- CN116504988A CN116504988A CN202211665008.0A CN202211665008A CN116504988A CN 116504988 A CN116504988 A CN 116504988A CN 202211665008 A CN202211665008 A CN 202211665008A CN 116504988 A CN116504988 A CN 116504988A
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 291
- 239000011241 protective layer Substances 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 230000037452 priming Effects 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 12
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002174 Styrene-butadiene Substances 0.000 claims description 7
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 7
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 239000004816 latex Substances 0.000 claims description 7
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- 239000011115 styrene butadiene Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 4
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
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- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
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- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000003851 corona treatment Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
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- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229910001120 nichrome Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
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- 229920002635 polyurethane Polymers 0.000 claims description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 239000005543 nano-size silicon particle Substances 0.000 claims 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 8
- 239000012964 benzotriazole Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a composite current collector, a preparation method thereof and a lithium ion battery. The composite current collector comprises a polymer layer, and a conductive layer I and a conductive layer II which are arranged on two sides of the polymer layer, wherein the polymer layer comprises a base material, and a modified layer I and a modified layer II which are arranged on two sides of the base material. The method comprises the following steps: (1) Preparing a modified layer I on the upper surface of the base material, and preparing a modified layer II on the lower surface of the base material to obtain a polymer layer; (2) And preparing a conductive layer I on the modified layer I, and preparing a conductive layer II on the modified layer II to obtain the composite current collector. The invention can prepare the composite current collector which meets the production requirement of the battery, reduces the thickness of the electrode assembly, improves the energy density of the battery, and reduces the risk of falling or stripping of the conductive layer from the polymer film layer, thereby prolonging the service life of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a composite current collector, a preparation method thereof and a lithium ion battery.
Background
Current collectors are one of the important components of lithium ion batteries and function to carry active materials, collect and conduct electrons. The ideal lithium ion battery current collector should satisfy: (1) high electrical conductivity; (2) good chemical and electrochemical stability; (3) high mechanical strength; (4) good compatibility and binding force with electrode active materials; (5) low cost and easy availability; (6) light weight. The traditional current collector generally takes aluminum foil as a positive current collector and copper foil as a negative current collector. However, the thickness of the copper foil and the aluminum foil is difficult to be reduced due to the limitation of the preparation technology, the requirements of people on the current collector of the lithium ion battery are not met, and the potential safety hazard is large.
Compared with the traditional metal foil, the lithium ion battery adopting the composite current collector has the advantages of high safety, high energy density and long service life. However, the adhesion between the conductive layer of the composite current collector and the polymer substrate is too low.
Therefore, it is desirable to develop a current collector that improves the adhesion of the polymer layer to the conductive layer.
Disclosure of Invention
The invention aims to solve the problem of low adhesion between a polymer layer and a conductive layer in a composite current collector in the prior art, and provides a composite current collector, a preparation method thereof and a lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides a composite current collector, wherein the composite current collector comprises a polymer layer and a conductive layer I and a conductive layer II provided on both sides of the polymer layer, wherein the polymer layer comprises a substrate and a modified layer I and a modified layer II provided on both sides of the substrate.
The second aspect of the invention provides a preparation method of the composite current collector, wherein the method comprises the following steps:
(1) Preparing a modified layer I on the upper surface of the base material, and preparing a modified layer II on the lower surface of the base material to obtain a polymer layer;
(2) Preparing a conductive layer I on the modified layer I, and preparing a conductive layer II on the modified layer II to obtain a composite current collector;
optionally, the step (2) includes the steps of:
(a) Preparing a priming layer I on the modified layer I, and preparing a priming layer II on the modified layer II;
(b) Preparing a conductive layer body layer I on the priming layer I, and preparing a conductive layer body layer II on the priming layer II;
(c) And preparing a protective layer I on the conductive layer body layer I, and preparing a protective layer II on the conductive layer body layer II to obtain the composite current collector.
A third aspect of the present invention provides a lithium ion battery comprising the aforementioned composite current collector.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
aiming at the problem of insufficient bonding force between a polymer layer and a conductive layer in the conventional composite current collector for the lithium ion battery, the bonding force between the polymer layer and the conductive layer is improved by modifying a base material, so that the composite current collector which meets the production requirement of the battery is prepared, the thickness of an electrode assembly is reduced, the energy density of the battery is improved, and the risk that the conductive layer is separated or stripped from the polymer film layer is reduced, thereby prolonging the service life of the battery.
Drawings
FIG. 1 is a schematic view of a first construction of a composite current collector according to the present invention;
fig. 2 is a schematic view of a second structure of the composite current collector according to the present invention.
Description of the reference numerals
1 a substrate; 2 modifying the layer I;3 modifying layer II;4, priming layer I;5, priming layer II;6 conductive layer body layer I;7 a conductive layer body layer II;8, a protective layer I; and 9, protecting the layer II.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a composite current collector, as shown in fig. 1, which comprises a polymer layer, and a conductive layer I and a conductive layer II arranged on two sides of the polymer layer, wherein the polymer layer comprises a base material 1, and a modified layer I2 and a modified layer II 3 arranged on two sides of the base material.
According to the invention, the modified layers are arranged on the two sides of the polymer layer, so that the cohesive force between the polymer layer and the conductive layer is improved, the composite current collector which meets the production requirement of the battery is prepared, the thickness of the electrode assembly is reduced, the energy density of the battery is improved, and the risk that the conductive layer is separated or stripped from the polymer film layer is reduced, so that the service life of the battery is prolonged.
In some embodiments of the invention, the thickness of the polymer layer is 1.2-30 μm, for example 1.2 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 23 μm, 25 μm, 30 μm, and any value in the range of any two values mentioned above, preferably 2.4-14 μm.
In some preferred embodiments of the invention, the thickness of the substrate 1 is in the range of 1-20 μm, for example 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, and any value in the range of any two values mentioned above, preferably 2-12 μm.
In some preferred embodiments of the invention, the thickness of the modified layer I2 and the modified layer II 3 are each independently of the other from 0.1 to 5. Mu.m, for example from 0.1. Mu.m, 0.5. Mu.m, 1. Mu.m, 2. Mu.m, 3. Mu.m, 4. Mu.m, 5. Mu.m, and any value in the range of any two values mentioned above, preferably from 0.2 to 1. Mu.m.
In some preferred embodiments of the invention, the thickness of the conductive layer I and the conductive layer II are each independently 0.06-13 μm, e.g. 0.06 μm, 0.5 μm, 1 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 10 μm, 13 μm, and any value in the range of any two values mentioned above, preferably 0.12-2.6 μm.
In some preferred embodiments of the invention, the composite current collector has a thickness of 1.22-51 μm, e.g. 1.22 μm, 10 μm, 20 μm, 30 μm, 40 μm, 51 μm, and any value in the range of any two values mentioned above, preferably 2.44-18.2 μm.
In some preferred embodiments of the invention, the adhesion between the polymer layer and the conductive layer I and between the polymer layer and the conductive layer II is each independently 0.5-20N/15mm, e.g. 0.5N/15mm, 1N/15mm, 2N/15mm, 3N/15mm, 4N/15mm, 5N/15mm, 6N/15mm, 7N/15mm, 8N/15mm, 9N/15mm, 10N/15mm, 11N/15mm, 12N/15mm, 13N/15mm, 14N/15mm, 15N/15mm, 16N/15mm, 17N/15mm, 18N/15mm, 19N/15mm, 20N/15mm, and any value in the range of any two values mentioned above, preferably 0.5-15N/15mm.
In the invention, the adhesion force between the polymer layer and the conductive layer I and between the polymer layer and the conductive layer II is tested by a universal tensile machine, and the specific testing method is shown in national standard GB/T2792-2014 (test method of adhesive tape peel strength).
In some embodiments of the present invention, as shown in fig. 2, the conductive layer I includes a primer layer I4, a conductive layer body layer I6, and a protective layer I8 in this order, and the conductive layer II includes a primer layer II 5, a conductive layer body layer II 7, and a protective layer II 9 in this order; wherein the modified layer I2 is adjacent to the priming layer I4, and the modified layer II 3 is adjacent to the priming layer II 5.
In some preferred embodiments of the present invention, the structure of the composite current collector includes a protective layer I, a conductive layer body layer I, a primer layer I, a modified layer I, a substrate, a modified layer II, a primer layer II, a conductive layer body layer II, and a protective layer II from top to bottom.
In some preferred embodiments of the invention, the thickness of the primer layer I4 and the primer layer II 5 are each independently from 0.005 to 3 μm, for example from 0.005 μm, 0.05 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, and any value in the range of any two values mentioned above, preferably from 0.01 to 0.1 μm.
In some preferred embodiments of the invention, the thickness of the conductive layer bulk layer I6 and the conductive layer bulk layer II 7 are each independently from 0.05 to 5 μm, for example 0.05 μm, 0.5 μm, 1 μm, 3 μm, 4 μm, 5 μm, and any value in the range of any two values mentioned above, preferably 0.1 to 1.5 μm.
In some preferred embodiments of the invention, the thickness of the protective layer I8 and the protective layer II 9 is each independently 0.005-5 μm, for example 0.005 μm, 0.05 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, and any value in the range of any two values mentioned above, preferably 0.01-1 μm.
In some embodiments of the invention, the substrate is selected from at least one of Polyethylene (PE), biaxially oriented polypropylene (BOPP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), poly-p-phenylene terephthalamide (PPTA), polyimide (PI), polycarbonate (PC), polyetheretherketone (PEEK), polyoxymethylene (POM), poly-p-phenylene sulfide (PPS), poly-p-phenylene oxide (PPO), polyvinylchloride (PVC), polyamide (PA), and Polytetrafluoroethylene (PTFE).
The biaxially oriented polypropylene film (BOPP) is prepared by co-extruding polypropylene particles to form a sheet and then stretching in the longitudinal and transverse directions (bidirectionally). Biaxially oriented polypropylene films known in the art may be used in the present invention.
In some preferred embodiments of the present invention, the materials of the modified layer I2 and the modified layer II 3 are each independently selected from at least one of ethylcellulose, methylenesuccinic acid, styrene, nano-silica, nano-alumina, carboxymethyl cellulose, guanidinoacetic acid, isocyanate, polyurethane, nano-silica sol, chitosan, graphene oxide, polycaprolactone, and styrene-butadiene latex.
In the invention, the material is selected as the material of the modified layer, so that the bonding force between the polymer layer and the conductive layer is further improved, and the risk of falling or stripping of the conductive layer from the polymer film layer is reduced, thereby prolonging the service life of the battery. The material of the modified layer is methylene succinic acid, which can activate the surface of the base material and increase the wetting tension and the reactivity of the surface of the base material, thereby improving the adhesion between the polymer layer and the conductive layer.
In some preferred embodiments of the present invention, the primer layer I4 and the primer layer II 5 are each independently a metal film layer or a non-metal film layer.
In some preferred embodiments of the present invention, the material of the metal film layer is nickel or nichrome. The material of the metal film layer can also be chromium, nickel-copper alloy and the like.
In some preferred embodiments of the present invention, the non-metallic film layer is an aluminum oxide, such as Al 2 O 3 。
In some preferred embodiments of the present invention, the conductive layer body layer I6 and the conductive layer body layer II 7 are aluminum, and the protective layer I8 and the protective layer II 9 are each independently a metal film layer or a conductive polymer film layer.
In some preferred embodiments of the present invention, the material of the metal film layer is nickel.
In some preferred embodiments of the present invention, the material of the conductive polymer film layer is doped polypyrrole or doped polyaniline.
In the present invention, the doped polyaniline may be doped with protonic acid, or the doped polypyrrole may be prepared by chemical doping (e.g., sulfonic acid group doping) or electrochemical doping. The use of doped polypyrrole or doped polyaniline as the conductive polymer film layer can provide excellent conductivity.
In some preferred embodiments of the present invention, the conductive layer body layer I6 and the conductive layer body layer II 7 are copper, and the protective layer I8 and the protective layer II 9 are each independently a metal film layer or a passivation layer.
In some preferred embodiments of the present invention, the material of the metal film layer is nickel.
In some preferred embodiments of the present invention, the material of the passivation layer is modified benzotriazole (modified BTA).
In a preferred embodiment, the modified benzotriazole is benzotriazoleMixtures of oxazole (BTA) and 2-Mercaptobenzothiazole (MBT). When preparing passivation layer, after conducting layer body layer is treated by BTA, a layer of complex (Cu) formed by BTA and monovalent copper ion can be formed on copper surface 2 BTA) protective film can prevent further corrosion of copper. The hydrogen atom on the mercapto group of the 2-Mercaptobenzothiazole (MBT) molecule can be dissociated in water, and the chemical adsorption between the sulfur atom and copper forms a very firm complex (Cu-MBT) protective film to inhibit the corrosion of copper. When the passivation layer is prepared, the 2-Mercaptobenzothiazole (MBT) can enhance the corrosion inhibition effect of the Benzotriazole (BTA) and reduce the influence of the independent use of the Benzotriazole (BTA) on the environment.
In some preferred embodiments of the invention, the tensile strength of the composite current collector is equal to or greater than 150MPa, preferably 150-400MPa. The thermal shrinkage rate of the material of the polymer layer is less than or equal to 3 percent after the material is treated for 30 minutes at 150 ℃.
In the present invention, the tensile strength is measured by HG/T2580-2008 (measurement of tensile strength and elongation at break of rubber or plastic coated fabrics), and the thermal shrinkage after 30min of treatment at 150℃is measured by ASTM D-1204 (test method for linear dimensional change of non-rigid thermoplastic sheet or film at high temperature) specified by society for testing and materials.
The composite current collector provided by the invention has strong bonding force between the polymer layer and the conductive layer, can reduce the risk of falling off or stripping of the conductive layer from the polymer film layer, can reduce the thickness of an electrode assembly and improve the energy density of the battery and prolong the service life of the battery when being applied to a lithium ion battery.
The second aspect of the invention provides a preparation method of the composite current collector, wherein the method comprises the following steps:
(1) Preparing a modified layer I on the upper surface of the base material, and preparing a modified layer II on the lower surface of the base material to obtain a polymer layer;
(2) And preparing a conductive layer I on the modified layer I, and preparing a conductive layer II on the modified layer II to obtain the composite current collector.
According to the invention, the modified layers are arranged on the two sides of the polymer layer, so that the cohesive force between the polymer layer and the conductive layer is improved, the composite current collector which meets the production requirement of the battery is prepared, the thickness of the electrode assembly is reduced, the energy density of the battery is improved, and the risk that the conductive layer is separated or stripped from the polymer film layer is reduced, so that the service life of the battery is prolonged.
In some embodiments of the invention, the step (2) comprises the steps of:
(a) Preparing a priming layer I on the modified layer I, and preparing a priming layer II on the modified layer II;
(b) Preparing a conductive layer body layer I on the priming layer I, and preparing a conductive layer body layer II on the priming layer II;
(c) And preparing a protective layer I on the conductive layer body layer I, and preparing a protective layer II on the conductive layer body layer II to obtain the composite current collector.
In some embodiments of the present invention, in step (1), after the substrate is subjected to surface treatment, the modifying solution is coated on the upper and lower surfaces of the substrate, and the modified layer is formed after drying, so as to finally obtain the polymer layer.
In the invention, the substrate is modified after being subjected to surface treatment, so that the activity of the surface of the substrate can be improved, and a better modification effect can be obtained.
In some preferred embodiments of the invention, the surface treatment is a corona treatment, which can increase the roughness and reactivity of the substrate surface.
In some preferred embodiments of the invention, the method of preparing the modifying solution is: and blending the itaconic acid and the styrene-butadiene latex in the presence of a solvent to obtain a modified solution.
In some preferred embodiments of the invention, the solvent is water or ethanol.
In some preferred embodiments of the present invention, the mass fraction of the itaconic acid in the modifying solution is 0.5 to 15%, preferably 1 to 10%.
In some preferred embodiments of the present invention, the mass fraction of the styrene-butadiene latex in the modified solution is 0.3 to 10%, preferably 0.5 to 5%.
In some preferred embodiments of the present invention, the itaconic acid and styrene butadiene rubber are blended by ultrasonic bonding with mechanical agitation.
In some preferred embodiments of the invention, the blending is performed under sealed conditions.
In some preferred embodiments of the invention, the blending is performed under a protective atmosphere, preferably a nitrogen atmosphere.
In some preferred embodiments of the invention, the blending temperature is 20-150 ℃, preferably 50-120 ℃.
In some preferred embodiments of the invention, the blending time is from 0.5 to 15 hours, preferably from 1 to 10 hours.
In the invention, better modification effect can be obtained by adopting the modification mode, namely, the bonding force between the polymer layer and the conductive layer is stronger.
In some embodiments of the present invention, in the step (a), when the primer layer I and the primer layer II are metal film layers, the sputtering method is used to prepare the primer layer I and the primer layer II.
In some preferred embodiments of the present invention, the operating conditions of the sputtering method include: vacuum degree higher than 10 - 3 Pa; the main roll temperature is-25 ℃ to 35 ℃, such as-25 ℃, -15 ℃, -5 ℃, 0 ℃, 10 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, or any value in between the foregoing; the main roller running speed is below 20m/min, such as 2m/min, 5m/min, 10m/min, 15m/min, 20m/min, or any value between the foregoing values; the sputtering power is 20kW or less, for example 3kW, 5kW, 15kW, 20kW, or any value in between the foregoing values.
In some preferred embodiments of the present invention, in step (a), when the primer layer I and the primer layer II are nonmetallic film layers, an in-situ reaction method is used to prepare the primer layer I and the primer layer II.
In some preferred embodiments of the present invention, in step (b), the conductive layer bulk layer I and the conductive layer bulk layer II are prepared using an evaporation method.
In some preferred embodiments of the invention, the evaporation method is vapor-blocking or electron gun evaporation.
In the present invention, the evaporation-blocking means a resistance heating evaporation method.
In some preferred embodiments of the present invention, in the step (c), when the protective layer I and the protective layer II are metal film layers, the sputtering method is used to prepare the protective layer I and the protective layer II.
In some preferred embodiments of the present invention, the operating conditions of the sputtering method include: vacuum degree higher than 10 - 3 Pa; the main roll temperature is-25 ℃ to 35 ℃, such as-25 ℃, -15 ℃, -5 ℃, 0 ℃, 10 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, or any value in between the foregoing; the main roller running speed is below 20m/min, such as 2m/min, 5m/min, 10m/min, 15m/min, 20m/min, or any value between the foregoing values; the sputtering power is 20kW or less, for example 3kW, 5kW, 15kW, 20kW, or any value in between the foregoing values.
In some preferred embodiments of the present invention, in step (c), when the protective layer I and the protective layer II are conductive polymer film layers or passivation layers, the protective layer I and the protective layer II are prepared by a coating method.
In some preferred embodiments of the invention, the coating process is performed using a micro gravure coater with a coating accuracy of less than 3 μm, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, or any value in between.
The preparation method of the composite current collector is simple and easy to operate, no waste liquid is generated in the preparation process, the production cost is low, and the product performance is good.
A third aspect of the present invention provides a lithium ion battery comprising the aforementioned composite current collector.
Compared with the traditional copper foil current collector or aluminum foil current collector, the lithium ion battery prepared by using the composite current collector can have smaller thickness of an electrode assembly and higher energy density of the battery, and the service life of the battery can be further prolonged.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The composite current collector is characterized by comprising a polymer layer, and a conductive layer I and a conductive layer II which are arranged on two sides of the polymer layer, wherein the polymer layer comprises a base material, and a modified layer I and a modified layer II which are arranged on two sides of the base material.
2. A composite current collector according to claim 1, wherein the polymer layer has a thickness of 1.2-30 μm, preferably 2.4-14 μm;
preferably, the thickness of the substrate is 1-20 μm, preferably 2-12 μm;
preferably, the thickness of the modified layer I and the modified layer II is each independently 0.1-5 μm, preferably 0.2-1 μm;
preferably, the thickness of the conductive layer I and the conductive layer II is each independently 0.06-13 μm, preferably 0.12-2.6 μm;
preferably, the thickness of the composite current collector is 1.22-51 μm, preferably 2.44-18.2 μm;
preferably, the adhesion between the polymer layer and the conductive layer I and between the polymer layer and the conductive layer II is each independently 0.5-20N/15mm, preferably 0.5-15N/15mm.
3. The composite current collector according to claim 1 or 2, wherein the conductive layer I comprises a primer layer I, a conductive layer body layer I and a protective layer I in this order, and the conductive layer II comprises a primer layer II, a conductive layer body layer II and a protective layer II in this order;
wherein the modified layer I is adjacent to the base layer I, and the modified layer II is adjacent to the base layer II;
preferably, the thickness of the primer layer I and the primer layer II is each independently 0.005-3 μm, preferably 0.01-0.1 μm;
preferably, the thickness of the conductive layer body layer I and the conductive layer body layer II are each independently 0.05-5 μm, preferably 0.1-1.5 μm;
preferably, the thickness of the protective layer I and the protective layer II is each independently 0.005 to 5. Mu.m, preferably 0.01 to 1. Mu.m.
4. A composite current collector according to any one of claims 1-3, wherein the substrate is selected from at least one of polyethylene, biaxially oriented polypropylene, polyethylene terephthalate, polyethylene naphthalate, poly-paraphenylene terephthalamide, polyimide, polycarbonate, polyetheretherketone, polyoxymethylene, poly-paraphenylene sulfide, poly-paraphenylene ether, polyvinylchloride, polyamide, and polytetrafluoroethylene;
preferably, the materials of the modified layer I and the modified layer II are each independently selected from at least one of ethylcellulose, itaconic acid, styrene, nano silicon dioxide, nano aluminum oxide, carboxymethyl cellulose, guanidinoacetic acid, isocyanate, polyurethane, nano silica sol, chitosan, graphene oxide, polycaprolactone and styrene-butadiene latex.
5. The composite current collector according to claim 3 or 4, wherein the primer layer I and primer layer II are each independently a metallic film layer or a non-metallic film layer;
preferably, the material of the metal film layer is nickel or nichrome;
preferably, the nonmetallic film layer is aluminum oxide;
preferably, the conductive layer body layer I and the conductive layer body layer II are aluminum, and the protective layer I and the protective layer II are each independently a metal film layer or a conductive polymer film layer; preferably, the material of the metal film layer is nickel; preferably, the material of the conductive polymer film layer is doped polypyrrole or doped polyaniline;
preferably, the conductive layer body layer I and the conductive layer body layer II are copper, and the protective layer I and the protective layer II are each independently a metal film layer or a passivation layer; preferably, the material of the metal film layer is nickel; preferably, the material of the passivation layer is modified benzotriazole.
6. A method of preparing a composite current collector, the method comprising the steps of:
(1) Preparing a modified layer I on the upper surface of the base material, and preparing a modified layer II on the lower surface of the base material to obtain a polymer layer;
(2) Preparing a conductive layer I on the modified layer I, and preparing a conductive layer II on the modified layer II to obtain a composite current collector;
optionally, the step (2) includes the steps of:
(a) Preparing a priming layer I on the modified layer I, and preparing a priming layer II on the modified layer II;
(b) Preparing a conductive layer body layer I on the priming layer I, and preparing a conductive layer body layer II on the priming layer II;
(c) And preparing a protective layer I on the conductive layer body layer I, and preparing a protective layer II on the conductive layer body layer II to obtain the composite current collector.
7. The method according to claim 6, wherein in the step (1), after the substrate is subjected to surface treatment, the modifying solution is coated on the upper and lower surfaces of the substrate, and the polymer layer with a structure of modified layer I-substrate-modified layer II is obtained after drying;
preferably, the surface treatment is corona treatment;
preferably, the preparation method of the modified solution comprises the following steps: blending the itaconic acid and the styrene-butadiene latex in the presence of a solvent to obtain a modified solution;
preferably, the solvent is water or ethanol;
preferably, in the modified solution, the mass fraction of the itaconic acid is 0.5-15%, preferably 1-10%;
preferably, in the modified solution, the mass fraction of the styrene-butadiene latex is 0.3-10%, preferably 0.5-5%;
preferably, the itaconic acid and the styrene-butadiene latex are blended by ultrasonic combination with mechanical stirring;
preferably, the blending is performed under sealed conditions;
preferably, the blending is performed under a protective atmosphere, preferably a nitrogen atmosphere;
preferably, the blending temperature is 20-150 ℃, preferably 50-120 ℃;
preferably, the blending time is from 0.5 to 15 hours, preferably from 1 to 10 hours.
8. The method according to claim 6 or 7, wherein in the step (a), when the primer layer I and the primer layer II are metal film layers, a sputtering method is adopted to prepare the primer layer I and the primer layer II;
preferably, the operating conditions of the sputtering method include: vacuum degree higher than 10 -3 Pa; the temperature of the main roller is between minus 25 ℃ and 35 ℃; the running speed of the main roller is below 20 m/min; the sputtering power is below 20 kW;
preferably, in the step (a), when the primer layer I and the primer layer II are nonmetallic film layers, an in-situ reaction method is adopted to prepare the primer layer I and the primer layer II.
9. The method according to any one of claims 6 to 8, wherein in step (b), the conductive layer bulk layer I and the conductive layer bulk layer II are prepared by an evaporation method;
preferably, the evaporation method is evaporation-resistant or electron gun evaporation;
preferably, in the step (c), when the protective layer I and the protective layer II are metal film layers, a sputtering method is adopted to prepare the protective layer I and the protective layer II;
preferably, the operating conditions of the sputtering method include: vacuum degree higher than 10 -3 Pa; the temperature of the main roller is between minus 25 ℃ and 35 ℃; the running speed of the main roller is below 20 m/min; the sputtering power is below 20 kW;
preferably, in the step (c), when the protective layer I and the protective layer II are conductive polymer film layers or passivation layers, a coating method is adopted to prepare the protective layer I and the protective layer II;
preferably, the operating conditions of the coating process include: the coating accuracy is 3 μm or less.
10. A lithium ion battery comprising the composite current collector of any one of claims 1-5.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024131866A1 (en) * | 2022-12-23 | 2024-06-27 | 安迈特科技(北京)有限公司 | Negative electrode current collector and preparation method therefor, and lithium-ion battery |
| WO2024131980A1 (en) * | 2022-12-23 | 2024-06-27 | 安迈特科技(北京)有限公司 | Composite current collector, and preparation method therefor and use thereof in lithium-ion battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024131866A1 (en) * | 2022-12-23 | 2024-06-27 | 安迈特科技(北京)有限公司 | Negative electrode current collector and preparation method therefor, and lithium-ion battery |
| WO2024131980A1 (en) * | 2022-12-23 | 2024-06-27 | 安迈特科技(北京)有限公司 | Composite current collector, and preparation method therefor and use thereof in lithium-ion battery |
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