CN114420891B - High-voltage lithium ion battery current collector, preparation method and application - Google Patents
High-voltage lithium ion battery current collector, preparation method and application Download PDFInfo
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- CN114420891B CN114420891B CN202111417518.1A CN202111417518A CN114420891B CN 114420891 B CN114420891 B CN 114420891B CN 202111417518 A CN202111417518 A CN 202111417518A CN 114420891 B CN114420891 B CN 114420891B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000013329 compounding Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000011241 protective layer Substances 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 229910021389 graphene Inorganic materials 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- -1 graphite alkyne Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 8
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 claims description 8
- 238000004528 spin coating Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- 238000010345 tape casting Methods 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- 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 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 5
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000020 Nitrocellulose Substances 0.000 claims description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940116333 ethyl lactate Drugs 0.000 claims description 4
- 229920001220 nitrocellulos Polymers 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229940116411 terpineol Drugs 0.000 claims description 4
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 239000010405 anode material Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910015734 LixMnyOz Inorganic materials 0.000 description 3
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization 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
- H01M4/661—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
- 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
-
- 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
- H01M4/665—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a high-voltage lithium ion battery current collector, a preparation method and application thereof, wherein carbon-based materials are dispersed into a dispersing agent-alcohol solution and are ultrasonically mixed to obtain a carbon-based material mixed solution; adding a slurry solvent into the carbon substrate mixed solution, and heating to evaporate the solvent to obtain carbon-based slurry; and compounding the carbon-based slurry on the positive current collector, and thermally annealing to obtain the high-voltage lithium ion battery current collector with the protective layer attached to the positive current collector. And wrapping a layer of carbon-based material on the surface of the positive current collector, and achieving the problem that the current collector is corroded through electrochemical stability of carbon, so that stable operation of the high-voltage lithium ion battery is finally achieved.
Description
Technical Field
The invention relates to a lithium ion battery anode material in the technical field of electrochemistry, in particular to a method for preparing a high-voltage lithium ion battery current collector, the current collector and application thereof.
Background
Since 1901, lithium ion batteries have been applied to industrialized production, researchers are rapidly updating and improving anodes, cathodes and electrolytes, but research on current collectors is not greatly progressed, and particularly current collectors which are completely matched with high-voltage lithium ion batteries do not appear with the appearance of high-voltage lithium ion battery anodes. Therefore, high voltage tolerant current collectors remain challenging. At high voltage, aluminum is used as a positive current collector, is easily corroded into pits, and even gradually strips active substances to lose the effect of the current collector. So even if aluminum is used as the positive electrode current collector, the surface modification is particularly important. Lithium metal is very active, resulting in particularly important stability of the current collector at high voltages, so finding a suitable material is also critical to solving the current collector problem.
Disclosure of Invention
The invention aims to provide a method for preparing a high-voltage lithium ion battery current collector, which comprises the steps of preparing a carbon substrate mixed solution by dispersing a carbon substrate into a dispersing agent-alcohol solution, and preparing the carbon substrate mixed solution into carbon-based slurry; and compounding the carbon-based slurry onto the positive current collector, wrapping a layer of carbon-based material on the surface of the positive current collector, and achieving the problem that the current collector is corroded through electrochemical stabilization of carbon, so that the stable operation of the high-voltage lithium ion battery is finally achieved.
The aim of the invention is achieved by the following technical scheme.
In one aspect of the invention, a method for preparing a high-voltage lithium ion battery current collector is provided, comprising the following steps:
s1: according to the mass ratio of 1: (100-500) dispersing the carbon-based material into a dispersant-alcohol solution, and carrying out ultrasonic mixing to obtain a carbon-based material mixed solution;
s2: according to the mass ratio of 1: (10-70) adding a slurry solvent into the carbon substrate mixed solution, and heating to evaporate the solvent to obtain carbon-based slurry;
s3: and compounding the carbon-based slurry on the positive current collector, and thermally annealing to obtain the high-voltage lithium ion battery current collector with the protective layer attached to the positive current collector.
Preferably, the carbon-based material is one or more of graphene, graphite alkyne, carbon nanotube and conductive carbon black.
Preferably, the dispersant-alcohol solution is a mixture of dispersant and alcohol according to a mass ratio of 1: (10-70) and mixing.
Preferably, the alcohol in the dispersant-alcohol solution is a combination of one or more of methanol, ethanol, ethylene glycol, and isopropanol.
Preferably, the dispersing agent is one or more of methylcellulose, ethylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and nitrocellulose.
Preferably, the ultrasonic time of the carbon-based material and the dispersant-ethanol solution is 10-30min.
Preferably, the slurry solvent is one or more of cyclohexanone, terpineol, ethanol, ethylene glycol, isopropanol, ethyl lactate, octyl acetate and diethylene glycol dimethyl ether.
Preferably, the heating temperature is 60-150 ℃ and the time is 0.5-1h.
Preferably, the positive electrode current collector comprises a single-sided light metal, a double-sided light metal or a rough or carbon material; the metal is one of aluminum foil, stainless steel foil, nickel foil or copper foil; the carbon material is one of carbon cloth or carbon paper.
Preferably, the carbon-based material protective layer is compounded by means of ink slurry knife coating, spin coating or spray coating; the thickness of the positive current collector is 1-20 mu m by adopting blade coating compounding, the thickness of the positive current collector is 50nm-1 mu m by adopting spin coating compounding, and the thickness of the positive current collector is 20-800nm by adopting spray coating compounding.
Preferably, the thermal annealing temperature is 300-500 ℃ and the time is 0.5-2h.
In another aspect, the invention provides a high-voltage lithium ion battery current collector prepared by the method.
In still another aspect of the invention, the high-voltage lithium ion battery current collector prepared by the method is applied to a high-voltage lithium ion battery anode material. Wherein the positive electrode active material is LiNi 0.5 Mn 1.5 O 4 、LiCoO 2 、LiFePO 4 Li-rich (LixMnyOz) or Li 3 V 2 PO 4 One or more of the following.
The invention has the beneficial effects that:
based on the fact that most of the electrolyte contains fluorine at present, hydrofluoric acid is obtained after decomposition, and the hydrofluoric acid can greatly corrode the current collector.
How to prepare a carbon-based material which is uniformly dispersed and uniformly wrap the carbon-based material on the surface of the positive current collector is a difficulty in solving the problem of corrosion resistance of the positive current collector.
The invention is based on the problem of easy agglomeration of carbon-based materials, and the surfaces of each piece and particle of carbon materials are coated by selecting a proper dispersing agent, so as to achieve the separation effect between layers and particles, thereby obtaining the uniformly dispersed carbon material dispersion liquid.
The invention is based on the current collector protected by carbon materials in the current market, but the carbon materials are unevenly dispersed or curled, powder removed or too thick, so that the carbon materials are evenly adhered on the current collector, which is a technical difficulty.
The invention provides the compounding of the carbon-based material and the current collector, which has higher compounding quality, high adhesion and simple process flow; the carbon material is not affected by hydrofluoric acid, and meanwhile, the hydrofluoric acid is effectively prevented from entering the aluminum surface.
The invention can efficiently realize the corrosion resistance of the current collector under the condition of only changing the surface state of the current collector, has simple preparation process and is suitable for large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate and do not limit the invention, and together with the description serve to explain the principle of the invention:
fig. 1 is a preparation method of a graphene composite aluminum foil of example 1;
fig. 2 is a graphene composite aluminum foil prepared in example 1;
FIG. 3 is a plot of the rate performance of example 1;
fig. 4 (a) - (c) are the rate capability of the high-voltage lithium ion battery current collector protected by different carbon materials after loading different positive electrodes.
Detailed Description
The present invention will now be described in detail with reference to the drawings and the specific embodiments thereof, wherein the exemplary embodiments and descriptions of the present invention are provided for illustration of the invention and are not intended to be limiting.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a high-voltage lithium ion battery current collector, which includes the following steps:
s1: according to the mass ratio of 1: (100-500) dispersing the carbon-based material into a dispersant-alcohol solution, and mixing the solution with ultrasonic waves for 10-30min to obtain a carbon-based material mixed solution.
Wherein the carbon-based material is one or more of graphene, graphite alkyne, carbon nano tube or conductive carbon black. The dispersing agent is one or more of methylcellulose, ethylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate or nitrocellulose.
The dispersant-alcohol solution is prepared from dispersant and alcohol according to a mass ratio of 1: (10-70) mixing to prepare the material, wherein the dispersing agent is one or a combination of more of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and cellulose nitrate; the alcohol is one or more of methanol, ethanol, ethylene glycol and isopropanol.
S2: according to the mass ratio of 1: (10-70) adding a slurry solvent into the carbon substrate mixed solution, heating at 60-150 ℃ for 0.5-1h, and evaporating the solvent to obtain the carbon-based slurry.
Wherein the slurry solvent is one or a combination of a plurality of cyclohexanone, terpineol, ethanol, glycol, isopropanol, ethyl lactate, octyl acetate and diethylene glycol dimethyl ether.
S3: compounding the carbon-based slurry onto the positive electrode current collector, and compounding the carbon-based material protective layer by means of ink slurry knife coating and spin coating; thermally annealing at 300-500 ℃ for 0.5-2h, and compositing the carbon-based material protective layer by means of ink slurry knife coating, spin coating or spray coating; the thickness of the positive current collector is 1-20 mu m by adopting blade coating compounding, the thickness of the positive current collector is 50nm-1 mu m by adopting spin coating compounding, and the thickness of the positive current collector is 20-800nm by adopting spray coating compounding.
The positive electrode current collector comprises a single-sided light metal and a double-sided light metal; the metal is aluminum foil, stainless steel foil, nickel foil or copper foil; the carbon material is carbon cloth or carbon paper.
The prepared high-voltage lithium ion battery current collector can be applied to a high-voltage lithium ion battery positive electrode material, wherein the positive electrode active material is LiNi 0.5 Mn 1.5 O 4 、LiCoO 2 、LiFePO 4 Li-rich (LixMnyOz) or Li 3 V 2 PO 4 One or more of the following.
The invention is further illustrated by the following examples.
Example 1
S1: according to the mass ratio of 1:200, dispersing carbon-based material graphene into a dispersant-alcohol solution, mixing and carrying out ultrasonic treatment for 10min to obtain graphene mixed solution.
Wherein, the mass ratio of the dispersant-alcohol solution is 1:50 dispersant methylcellulose and ethanol.
S2: according to the mass ratio of 1: and 50, adding a slurry solvent cyclohexanone into the graphene mixed solution, heating at 100 ℃ for 0.5h, and evaporating the solvent to obtain graphene slurry.
S3: the graphene slurry was compounded on an aluminum foil 200mm long and 100mm wide for the positive current collector, as shown in fig. 2. The graphene protective layer is compounded by means of ink paste knife coating, and thermal annealing is carried out for 1h at 300 ℃ to obtain the high-voltage lithium ion battery current collector with the thickness of 1 mu m and attached with the graphene protective layer on the positive current collector, wherein the high-voltage lithium ion battery current collector is shown in figure 2.
The rate performance of the half battery is shown in fig. 3, and it can be seen from fig. 3 that the aluminum current collector with graphene protection has excellent rate performance after being loaded with the positive electrode material compared with the aluminum current collector without graphene protection.
The prepared high-voltage lithium ion battery current collector is arranged on the anode material LiNi of the high-voltage lithium ion battery 0.5 Mn 1.5 O 4 And (5) applying the method.
Example 2
S1: according to the mass ratio of 1:300 dispersing the carbon-based material carbon nano tube into a dispersing agent-alcohol solution, mixing and carrying out ultrasonic treatment for 20min to obtain a carbon nano tube mixed solution.
Wherein, the mass ratio of the dispersant-alcohol solution is 1:70 dispersant ethylcellulose and ethylene glycol.
S2: according to the mass ratio of 1:30 adding slurry solvent terpineol into the carbon nano tube mixed solution, heating for 1h at 120 ℃, and evaporating the solvent to obtain the carbon nano tube slurry.
S3: and compounding the carbon nano tube slurry on a stainless steel foil of the positive electrode current collector, compounding the carbon nano tube protective layer by spraying the ink slurry, and thermally annealing for 2 hours at 350 ℃ to obtain the high-voltage lithium ion battery current collector with the thickness of 500nm and the carbon nano tube protective layer attached to the positive electrode current collector.
The prepared high-voltage lithium ion battery current collector is prepared in the high-voltage lithium ion battery anode material LiCoO 2 、LiFePO 4 And (5) applying the method.
Example 3
S1: according to the mass ratio of 1:100, dispersing carbon-based material graphene and graphite alkyne into a dispersant-alcohol solution, and mixing and carrying out ultrasonic treatment for 30min to obtain graphene and graphite alkyne mixed solution.
Wherein, the mass ratio of the dispersant-alcohol solution is 1: the 40 dispersant hydroxymethyl cellulose is prepared by mixing with isopropanol.
S2: according to the mass ratio of 1:70, adding slurry solvents ethyl lactate and octyl acetate into graphene and graphite alkyne mixed solution, heating at 80 ℃ for 1h, and evaporating the solvent to obtain carbon-based slurry.
S3: and compounding graphene and graphite alkyne slurry on the nickel foil of the positive electrode current collector, compounding the graphene and graphite alkyne protective layer in a mode of ink slurry knife coating, and thermally annealing at 400 ℃ for 1h to obtain the high-voltage lithium ion battery current collector with the thickness of 20 mu m and attached with the graphene and graphite alkyne protective layer on the positive electrode current collector.
The prepared high-voltage lithium ion battery current collector is applied to a high-voltage lithium ion battery anode material Li-rich (LixMnyOz).
Example 4
S1: according to the mass ratio of 1:500 dispersing the carbon-based conductive carbon black into a dispersant-alcohol solution, and mixing and ultrasonic treatment for 15min to obtain a conductive carbon black mixed solution.
Wherein, the mass ratio of the dispersant-alcohol solution is 1:10 dispersant hydroxyethyl cellulose, cellulose acetate and methanol and ethanol.
S2: according to the mass ratio of 1: and 10, adding a sizing agent solvent of ethylene glycol and isopropanol into the conductive carbon black mixed solution, heating at 60 ℃ for 1h, and evaporating the solvent to obtain the conductive carbon black sizing agent.
S3: and compounding the conductive carbon black slurry on a copper foil of the positive electrode current collector, compounding a carbon-based material protective layer by means of spin coating of the ink slurry, and thermally annealing at 500 ℃ for 0.5h to obtain the high-voltage lithium ion battery current collector with the thickness of 800nm and the conductive carbon black protective layer attached to the positive electrode current collector.
The prepared high-voltage lithium ion battery current collector is prepared in the high-voltage lithium ion battery anode material Li 3 V 2 PO 4 And (5) applying the method.
Compared with an unprotected aluminum current collector, the high-voltage lithium ion battery current collector prepared by the embodiment of the invention has greatly improved multiplying power performance, and under the current of more than 2C, the graphene-protected aluminum current collector prevents the corrosion behavior of hydrofluoric acid which is a decomposition product of electrolyte; the existence of the graphene protective layer increases the binding force, so that the electrode material and the current collector are tightly linked; the rate performance is related to conductivity, and the current collector can still better contribute to capacity and be tightly connected under a large current.
As can be seen from fig. 4 (a) -4 (c), the carbon material-protected high-voltage lithium ion battery current collector prepared by the method of the present invention has excellent rate capability. Depending on the corrosion protection of the carbon material and the adhesion of the carbon material to the current collector and the excellent electrical conductivity.
Claims (5)
1. The preparation method of the high-voltage lithium ion battery current collector is characterized by comprising the following steps of:
s1: according to the mass ratio of 1: (100-500) dispersing a carbon-based material into a dispersant-alcohol solution, and carrying out ultrasonic mixing to obtain a carbon-based material mixed solution;
s2: according to the mass ratio of 1: (10-70) adding a slurry solvent into the carbon substrate mixed solution, and heating to evaporate the solvent to obtain carbon-based slurry; heating at 60-150deg.C for 0.5-1 hr;
s3: compounding the carbon-based slurry on a positive current collector, and thermally annealing to obtain a high-voltage lithium ion battery current collector with a protective layer attached to the positive current collector;
the carbon-based material is one or more of graphene, graphite alkyne, carbon nano tube and conductive carbon black;
the dispersing agent-alcohol solution is prepared from dispersing agent and alcohol according to a mass ratio of 1: (10-70) mixing and preparing;
the alcohol in the dispersant-alcohol solution is one or a combination of more of methanol, ethanol, ethylene glycol and isopropanol;
the dispersing agent is one or a combination of more of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and nitrocellulose;
the ultrasonic time of the carbon-based material and the dispersant-ethanol solution is 10-30min;
the slurry solvent is one or a combination of more of cyclohexanone, terpineol, ethanol, glycol, isopropanol, ethyl lactate, octyl acetate and diethylene glycol dimethyl ether;
the thermal annealing temperature is 300-500 ℃ and the time is 0.5-2h.
2. The method for preparing a high-voltage lithium ion battery current collector according to claim 1, wherein the positive electrode current collector comprises a single-sided light metal, a double-sided light metal or a carbon material; the metal is one of aluminum foil, stainless steel foil, nickel foil or copper foil; the carbon material is carbon cloth or carbon paper.
3. The method for preparing the high-voltage lithium ion battery current collector according to claim 1, wherein the carbon-based material protection layer is compounded by means of ink paste knife coating, spin coating or spray coating; the thickness of the positive current collector is 1-20 mu m by adopting blade coating compounding, the thickness of the positive current collector is 50nm-1 mu m by adopting spin coating compounding, and the thickness of the positive current collector is 20-800nm by adopting spray coating compounding.
4. A high voltage lithium ion battery current collector prepared by the method of any one of claims 1-3.
5. The use of a high voltage lithium ion battery current collector as defined in claim 4 in a positive electrode of a high voltage lithium ion battery, wherein the positive electrode active material is LiNi 0.5 Mn 1.5 O 4 、LiCoO 2 、LiFePO 4 Or Li (lithium) 3 V 2 PO 4 One or more of the following.
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