CN114420891A - 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
- Publication number
- CN114420891A CN114420891A CN202111417518.1A CN202111417518A CN114420891A CN 114420891 A CN114420891 A CN 114420891A CN 202111417518 A CN202111417518 A CN 202111417518A CN 114420891 A CN114420891 A CN 114420891A
- Authority
- CN
- China
- Prior art keywords
- current collector
- carbon
- lithium ion
- ion battery
- voltage lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000013329 compounding Methods 0.000 claims abstract description 20
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 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 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 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
- 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
- -1 graphdiyne Chemical compound 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
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 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
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000005507 spraying 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
- 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
- 229910011304 Li3V2 Inorganic materials 0.000 claims description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 4
- 229910015734 LixMnyOz 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
- 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 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
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 229960004592 isopropanol Drugs 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 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
- 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Images
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, wherein a carbon-based material is dispersed into a dispersant-alcohol solution and subjected to ultrasonic mixing 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 carrying out thermal annealing to obtain the high-voltage lithium ion battery current collector with the protective layer attached to the positive current collector. The surface of the positive current collector is coated with a layer of carbon-based material, so that the problem that the current collector is corroded is solved through the electrochemical stability of carbon, and finally the stable operation of the high-voltage lithium ion battery is 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 put into practical use, and have been put into industrial production, researchers are rapidly updating and improving anodes, cathodes, and electrolytes, but there is no great progress in the research on current collectors, and particularly with the appearance of high-voltage lithium ion battery anodes, current collectors that are completely matched with high-voltage lithium ion batteries do not appear. Therefore, high voltage resistant current collectors still face challenges. At high voltage, aluminum, which is used as the positive current collector, is easily corroded into pits, and even gradually peels off active substances, and loses the effect of the current collector. The modification of the surface is particularly important even if aluminum is used as the positive electrode current collector. The lithium metal has very high activity, so that the stability of the current collector under high voltage is particularly important, and therefore, the search for a suitable material is also the key for solving the problem of the current collector.
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 dispersing a carbon-based material into a dispersing agent-alcohol solution to prepare a carbon-based material mixed solution, and preparing a carbon-based slurry from the carbon-based material mixed solution; the carbon-based slurry is compounded on the positive current collector, the surface of the positive current collector is coated with a layer of carbon-based material, the problem that the current collector is corroded is solved through the electrochemical stability of carbon, and finally the stable operation of the high-voltage lithium ion battery is achieved.
The purpose of the invention is realized by the following technical scheme.
In one aspect of the present invention, a method for preparing a current collector of a high voltage lithium ion battery is provided, which comprises the following steps:
s1: according to the mass ratio of 1: (100-500) dispersing the carbon-based material into a dispersing agent-alcohol solution, and performing 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 carrying out thermal 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, graphdiyne, carbon nanotube and conductive carbon black.
Preferably, the dispersant-alcohol solution is prepared by mixing a dispersant and an alcohol according to a mass ratio of 1: (10-70) mixing and preparing.
Preferably, the alcohol in the dispersant-alcohol solution is one or more of methanol, ethanol, ethylene glycol and isopropanol.
Preferably, the dispersant is one or more of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and cellulose nitrate in combination.
Preferably, the carbon-based material and the dispersant-ethanol solution are subjected to ultrasonic treatment for 10-30 min.
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 0.5-1 h.
Preferably, the positive current collector comprises a single-sided smooth metal, a double-sided smooth 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 in a blade coating, spin coating or spraying mode of ink slurry; the thickness of the positive current collector obtained by blade coating and compounding is 1-20 mu m, the thickness of the positive current collector obtained by spin coating and compounding is 50nm-1 mu m, and the thickness of the positive current collector obtained by spray coating and compounding is 20-800 nm.
Preferably, the thermal annealing temperature is 300-500 ℃, and the time is 0.5-2 h.
In another aspect of the invention, the high-voltage lithium ion battery current collector prepared by the method is provided.
On the other hand, the high-voltage lithium ion battery current collector prepared by the method is applied to the high-voltage lithium ion battery anode material. Wherein the positive electrode active material is LiNi0.5Mn1.5O4、LiCoO2、LiFePO4Li-rich (LixMnyOz) or Li3V2PO4One or more of (a).
The invention has the beneficial effects that:
according to the invention, based on the fact that almost all 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 uniformly dispersed carbon-based material and uniformly wrap the carbon-based material on the surface of the positive current collector is a difficult point for solving the problem of corrosion resistance of the positive current collector.
According to the invention, based on the problem that the carbon-based material is easy to agglomerate, the surface of each sheet and particle carbon material is coated by selecting a proper dispersant, so that the effect of separation between sheets and particles is achieved, and the uniformly dispersed carbon material dispersion liquid is obtained.
The carbon material-protected current collector is based on the current collector in the current market, but the carbon material is not uniformly dispersed, or has the phenomena of curling, powder shedding or over-thick thickness, so that the carbon material is uniformly adhered to the current collector, which is a technical difficulty.
The invention provides the composition of the carbon-based material and the current collector, the composite quality is higher, the adhesive force is high, and the process flow is simple; the carbon material is not influenced by hydrofluoric acid, and simultaneously, the hydrofluoric acid is effectively prevented from entering the surface of the aluminum.
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 embodiment(s) of the invention and together with the description serve to explain the principles 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 graph of rate performance for example 1;
fig. 4(a) - (c) show the rate performance of the current collectors of the high-voltage lithium ion batteries protected by different carbon materials loaded with different anodes.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a current collector of a high-voltage lithium ion battery, including the following steps:
s1: according to the mass ratio of 1: (100-500) dispersing the carbon-based material into a dispersing agent-alcohol solution, and carrying out ultrasonic mixing for 10-30min to obtain a carbon-based material mixed solution.
The carbon-based material is one or more of graphene, graphite alkyne, carbon nano tube or conductive carbon black. The dispersant is one or more of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate or cellulose nitrate.
The dispersant-alcohol solution is prepared by mixing a dispersant and alcohol according to a mass ratio of 1: (10-70) mixing the components, wherein the dispersing agent is one or 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 substrate slurry.
Wherein the slurry solvent is one or more of cyclohexanone, terpineol, ethanol, glycol, isopropanol, ethyl lactate, octyl acetate and diethylene glycol dimethyl ether.
S3: compounding carbon-based slurry on the anode current collector, and compounding the carbon-based material protective layer in a manner of blade coating and spin coating of the ink slurry; performing thermal annealing at the temperature of 300-; the thickness of the positive current collector obtained by blade coating and compounding is 1-20 mu m, the thickness of the positive current collector obtained by spin coating and compounding is 50nm-1 mu m, and the thickness of the positive current collector obtained by spray coating and compounding is 20-800 nm.
The positive 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 LiNi0.5Mn1.5O4、LiCoO2、LiFePO4Li-rich (LixMnyOz) or Li3V2PO4One or more of (a).
The following different examples are given to further illustrate the invention.
Example 1
S1: according to the mass ratio of 1: and 200, dispersing the carbon-based material graphene into a dispersing agent-alcohol solution, and carrying out mixing and ultrasonic treatment for 10min to obtain a graphene mixed solution.
Wherein the dispersant-alcoholic solution is prepared from the following raw materials in a mass ratio of 1: 50 dispersant methylcellulose and ethanol.
S2: according to the mass ratio of 1: 50 adding a slurry solvent cyclohexanone into the graphene mixed solution, heating for 0.5h at 100 ℃, and evaporating the solvent to obtain the graphene slurry.
S3: the graphene slurry was compounded onto an aluminum foil having a length of 200mm and a width of 100mm of the positive current collector, as shown in fig. 2. The graphene protective layer is compounded in a blade coating mode through ink slurry, and is thermally annealed for 1h at 300 ℃, so that the current collector of the high-voltage lithium ion battery with the thickness of 1 mu m and the graphene protective layer attached to the positive current collector is obtained as shown in figure 2.
The half-cell test is performed, the rate performance of the half-cell test is shown in fig. 3, and it can be seen from fig. 3 that compared with the aluminum current collector without graphene protection, the aluminum current collector with graphene protection has excellent rate performance after being loaded with the positive electrode material.
The prepared high-voltage lithium ion battery current collector is applied to the positive electrode material LiNi of the high-voltage lithium ion battery0.5Mn1.5O4The application is as follows.
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, and carrying out mixing and ultrasonic treatment for 20min to obtain a carbon nano tube mixed solution.
Wherein the dispersant-alcoholic solution is prepared from the following raw materials in a mass ratio of 1: 70 dispersant ethyl cellulose and glycol.
S2: according to the mass ratio of 1: 30 adding a 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 nanotube slurry on the stainless steel foil of the positive current collector, compounding the carbon nanotube protective layer in an ink slurry spraying manner, and thermally annealing at 350 ℃ for 2h to obtain the high-voltage lithium ion battery current collector with the thickness of 500nm and the carbon nanotube protective layer attached to the positive current collector.
The prepared high-voltage lithium ion battery current collector is applied to a high-voltage lithium ion battery anode material LiCoO2、LiFePO4The application is as follows.
Example 3
S1: according to the mass ratio of 1: 100, dispersing the carbon-based materials graphene and the graphite alkyne into a dispersing agent-alcohol solution, and carrying out mixing ultrasonic treatment for 30min to obtain a graphene and graphite alkyne mixed solution.
Wherein the dispersant-alcoholic solution is prepared from the following raw materials in a mass ratio of 1: 40 dispersant hydroxymethyl cellulose and isopropanol.
S2: according to the mass ratio of 1: 70 adding slurry solvents of ethyl lactate and octyl acetate into the mixed solution of graphene and graphite alkyne, heating for 1h at 80 ℃, and evaporating the solvent to obtain the carbon-based slurry.
S3: compounding graphene and graphite alkyne slurry on a positive current collector nickel foil, compounding the graphene and the graphite alkyne protective layer in a blade coating mode through ink slurry, and carrying out thermal annealing at 400 ℃ for 1h to obtain the high-voltage lithium ion battery current collector with the thickness of 20 mu m and the graphene and graphite alkyne protective layer attached on the positive 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 material conductive carbon black into a dispersing agent-alcohol solution, and carrying out mixing and ultrasonic treatment for 15min to obtain a conductive carbon black mixed solution.
Wherein the dispersant-alcoholic solution is prepared from the following raw materials in a mass ratio of 1: 10 dispersant hydroxyethyl cellulose, cellulose acetate, methanol and ethanol.
S2: according to the mass ratio of 1: 10 adding slurry solvents of ethylene glycol and isopropanol into the conductive carbon black mixed solution, heating for 1h at 60 ℃, and evaporating the solvent to obtain the conductive carbon black slurry.
S3: and compounding the conductive carbon black slurry on the copper foil of the positive current collector, compounding the carbon-based material protective layer in a mode 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 current collector.
Prepared high-voltage lithium ion battery current collector in high-voltage lithium ion battery anode material Li3V2PO4The application is as follows.
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 rate performance, and the aluminum current collector protected by the graphene prevents the corrosion behavior of a decomposition product hydrofluoric acid of electrolyte under the current of more than 2C; the existence of the graphene protective layer increases the adhesive force, so that the electrode material and the current collector are tightly linked; the rate capability is related to the conductivity, and the capacity can be better contributed under large current, and the current collector is tightly connected.
As can be seen from fig. 4(a) -4(c), the high voltage lithium ion battery current collector protected by the carbon material 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 (10)
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 the carbon-based material into a dispersing agent-alcohol solution, and performing 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 carrying out thermal annealing to obtain the high-voltage lithium ion battery current collector with the protective layer attached to the positive current collector.
2. The method for preparing the current collector of the high-voltage lithium ion battery according to claim 1, wherein the carbon-based material is one or more of graphene, graphdiyne, carbon nanotubes and conductive carbon black.
3. The preparation method of the current collector of the high-voltage lithium ion battery according to claim 1, comprising the following steps: the dispersing agent-alcohol solution is characterized in that the dispersing agent-alcohol solution is prepared by mixing a dispersing agent and alcohol according to a mass ratio of 1: (10-70) mixing to prepare;
the alcohol in the dispersant-alcohol solution is one or a combination of methanol, ethanol, ethylene glycol and isopropanol;
the dispersant is one or more of methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate and cellulose nitrate;
the ultrasonic time of the carbon-based material and the dispersant-ethanol solution is 10-30 min.
4. The method for preparing the current collector of the high-voltage lithium ion battery according to claim 1, wherein the slurry solvent is one or more of cyclohexanone, terpineol, ethanol, ethylene glycol, isopropanol, ethyl lactate, octyl acetate and diethylene glycol dimethyl ether.
5. The method for preparing the current collector of the high-voltage lithium ion battery according to claim 1, wherein the heating temperature is 60-150 ℃ and the heating time is 0.5-1 h.
6. The method for preparing the current collector of the high-voltage lithium ion battery according to claim 1, wherein the positive current collector comprises a single-sided smooth metal, a double-sided smooth 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.
7. The method for preparing the current collector of the high-voltage lithium ion battery as claimed in claim 1, wherein the carbon-based material protective layer is compounded by blade coating, spin coating or spray coating of ink slurry; the thickness of the positive current collector obtained by blade coating and compounding is 1-20 mu m, the thickness of the positive current collector obtained by spin coating and compounding is 50nm-1 mu m, and the thickness of the positive current collector obtained by spray coating and compounding is 20-800 nm.
8. The method as claimed in claim 7, wherein the thermal annealing temperature is 300-500 ℃ and the time is 0.5-2 h.
9. A high voltage lithium ion battery current collector prepared according to the method of any one of claims 1 to 8.
10. The application of the high-voltage lithium ion battery current collector on the high-voltage lithium ion battery positive electrode material according to claim 9, wherein the positive electrode active material is LiNi0.5Mn1.5O4、LiCoO2、LiFePO4Li-rich (LixMnyOz) or Li3V2PO4One or more of (a).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111417518.1A CN114420891B (en) | 2021-11-25 | 2021-11-25 | High-voltage lithium ion battery current collector, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111417518.1A CN114420891B (en) | 2021-11-25 | 2021-11-25 | High-voltage lithium ion battery current collector, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114420891A true CN114420891A (en) | 2022-04-29 |
| CN114420891B CN114420891B (en) | 2023-12-19 |
Family
ID=81265928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111417518.1A Active CN114420891B (en) | 2021-11-25 | 2021-11-25 | High-voltage lithium ion battery current collector, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114420891B (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050022370A1 (en) * | 2003-07-30 | 2005-02-03 | Hei Long Jiang Zhong Qiang Power-Tech Co., Ltd. | High-capacity polymeric Li-ion cell and its production method |
| CN102569816A (en) * | 2012-02-14 | 2012-07-11 | 中南大学 | Positive electrode of lithium sulfur battery and preparation method thereof |
| US20120315550A1 (en) * | 2009-12-11 | 2012-12-13 | Ningbo Institute Of Materials Technology And Engineering, Chinese Academy Of Sciences | Graphene-modified lithium iron phosphate positive electrode active material, preparation of the same and lithium-ion secondary cell |
| CN102832392A (en) * | 2012-06-27 | 2012-12-19 | 长沙业翔能源科技有限公司 | Current collector carbon coated aluminum foil and its preparation method |
| KR20130013524A (en) * | 2011-07-28 | 2013-02-06 | 삼성에스디아이 주식회사 | Positive electrode for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN104600320A (en) * | 2013-10-30 | 2015-05-06 | 上海悦达墨特瑞新材料科技有限公司 | Functional copper foil based on graphene and preparation method thereof |
| JP2016143462A (en) * | 2015-01-30 | 2016-08-08 | 日立化成株式会社 | Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| US20180102533A1 (en) * | 2016-10-09 | 2018-04-12 | Optimum Battery Co., Ltd. | Negative electrode for lithium ion battery and method for preparing the same |
| CN108039449A (en) * | 2017-12-07 | 2018-05-15 | 福建荣华科技有限公司 | The preparation method and lithium ion battery of lithium ion battery |
| CN108428855A (en) * | 2018-01-29 | 2018-08-21 | 深圳市沃特玛电池有限公司 | A kind of preparation method and lithium ion battery of utter misery foil |
| CN108550787A (en) * | 2018-04-26 | 2018-09-18 | 北京石墨烯研究院 | Lithium ion cell positive and lithium ion battery comprising it |
| CN109888295A (en) * | 2019-02-28 | 2019-06-14 | 合肥国轩高科动力能源有限公司 | A kind of affluxion body in lithium ion batteries coating paste, collector and preparation method thereof |
| CN109950549A (en) * | 2019-04-16 | 2019-06-28 | 中国科学院过程工程研究所 | A kind of lithium ion battery collector and preparation method thereof |
| CN112751075A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能***有限公司 | Lithium ion battery and preparation method thereof |
-
2021
- 2021-11-25 CN CN202111417518.1A patent/CN114420891B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050022370A1 (en) * | 2003-07-30 | 2005-02-03 | Hei Long Jiang Zhong Qiang Power-Tech Co., Ltd. | High-capacity polymeric Li-ion cell and its production method |
| US20120315550A1 (en) * | 2009-12-11 | 2012-12-13 | Ningbo Institute Of Materials Technology And Engineering, Chinese Academy Of Sciences | Graphene-modified lithium iron phosphate positive electrode active material, preparation of the same and lithium-ion secondary cell |
| KR20130013524A (en) * | 2011-07-28 | 2013-02-06 | 삼성에스디아이 주식회사 | Positive electrode for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN102569816A (en) * | 2012-02-14 | 2012-07-11 | 中南大学 | Positive electrode of lithium sulfur battery and preparation method thereof |
| CN102832392A (en) * | 2012-06-27 | 2012-12-19 | 长沙业翔能源科技有限公司 | Current collector carbon coated aluminum foil and its preparation method |
| CN104600320A (en) * | 2013-10-30 | 2015-05-06 | 上海悦达墨特瑞新材料科技有限公司 | Functional copper foil based on graphene and preparation method thereof |
| JP2016143462A (en) * | 2015-01-30 | 2016-08-08 | 日立化成株式会社 | Negative electrode active material for lithium ion secondary battery and lithium ion secondary battery |
| US20180102533A1 (en) * | 2016-10-09 | 2018-04-12 | Optimum Battery Co., Ltd. | Negative electrode for lithium ion battery and method for preparing the same |
| CN108039449A (en) * | 2017-12-07 | 2018-05-15 | 福建荣华科技有限公司 | The preparation method and lithium ion battery of lithium ion battery |
| CN108428855A (en) * | 2018-01-29 | 2018-08-21 | 深圳市沃特玛电池有限公司 | A kind of preparation method and lithium ion battery of utter misery foil |
| CN108550787A (en) * | 2018-04-26 | 2018-09-18 | 北京石墨烯研究院 | Lithium ion cell positive and lithium ion battery comprising it |
| CN109888295A (en) * | 2019-02-28 | 2019-06-14 | 合肥国轩高科动力能源有限公司 | A kind of affluxion body in lithium ion batteries coating paste, collector and preparation method thereof |
| CN109950549A (en) * | 2019-04-16 | 2019-06-28 | 中国科学院过程工程研究所 | A kind of lithium ion battery collector and preparation method thereof |
| CN112751075A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能***有限公司 | Lithium ion battery and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| TAI YUE等: ""High-precision voltage measurement IP core for battery management SoC of electric vehicles"", 《 2014 12TH IEEE INTERNATIONAL CONFERENCE ON SOLID-STATE AND INTEGRATED CIRCUIT TECHNOLOGY (ICSICT)》, pages 3 * |
| WANG, ST等: ""Overcoming the High-Voltage Limitations of Li-Ion Batteries Using a Titanium Nitride Current Collector"", 《ACS APPLIED ENERGY MATERIALS》, vol. 2, no. 2, pages 974 - 978 * |
| 庄林;: "石墨烯增增强锂离离子电池池铝箔集流流体的抗抗腐蚀性性", no. 06 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114420891B (en) | 2023-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103715394B (en) | A kind of lithium ion cell positive and preparation method thereof | |
| CN111092210B (en) | Ternary positive electrode composite material and preparation method and application thereof | |
| CN109950546B (en) | Copper foil manufacturing process and negative current collector | |
| CN108199002A (en) | A kind of high specific energy negative electrode of lithium ion battery and preparation method thereof | |
| CN109461865A (en) | A kind of preparation method of coating polyetherimide diaphragm and the application in lithium-sulfur cell | |
| CN112635712A (en) | Negative plate and lithium ion battery | |
| CN103137942B (en) | The preparation method of a kind of ferric phosphate lithium cell collector and positive plate | |
| CN113644239A (en) | Silica composite material and preparation method thereof | |
| CN111430665A (en) | Positive plate and preparation method and application thereof | |
| CN110808356A (en) | Preparation method of lithium ion battery pole piece and lithium ion battery pole piece | |
| CN104752682A (en) | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery | |
| CN109411762A (en) | A kind of utter misery aluminium foil and preparation method thereof | |
| CN104900883A (en) | Preparation method of electroconductive agent for electrode | |
| CN113285050A (en) | Li-M-X-based solid lithium battery anode and preparation method thereof | |
| KR101919048B1 (en) | Manufacturing method of anode for lithium secondary battery | |
| CN114420891A (en) | High-voltage lithium ion battery current collector, preparation method and application | |
| CN110391422A (en) | A kind of lithium battery pole piece structure and its preparation process containing ceramic coating | |
| CN115528205A (en) | Double-step type pole piece and lithium ion battery | |
| EP4340073A1 (en) | Composite binder, negative electrode slurry, silicon negative electrode plate, and lithium-ion battery | |
| CN114520335B (en) | Carbon-based flexible integrated electrode of lithium ion battery and preparation method thereof | |
| CN102054979B (en) | A kind of battery electrode, its preparation method and battery | |
| Wang et al. | The preparation and electrochemical performance analysis of different porous silicon composites | |
| CN112382763A (en) | Organic matter/silicon composite material, battery cathode obtained from organic matter/silicon composite material and preparation method of battery cathode | |
| CN112864387A (en) | Negative electrode slurry and preparation method and application thereof | |
| CN108963185A (en) | A kind of high security fast charging type lithium ion battery anode active material, cathode and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |