CN115537609A - Preparation method of aluminum foil for lithium ion battery and aluminum foil for lithium ion battery - Google Patents
Preparation method of aluminum foil for lithium ion battery and aluminum foil for lithium ion battery Download PDFInfo
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- CN115537609A CN115537609A CN202211283454.5A CN202211283454A CN115537609A CN 115537609 A CN115537609 A CN 115537609A CN 202211283454 A CN202211283454 A CN 202211283454A CN 115537609 A CN115537609 A CN 115537609A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 127
- 239000011888 foil Substances 0.000 title claims abstract description 115
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims abstract description 50
- 238000007670 refining Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000005097 cold rolling Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000005266 casting Methods 0.000 claims abstract description 11
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000013461 design Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 14
- 238000007872 degassing Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000003851 corona treatment Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000012856 weighed raw material Substances 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003446 memory effect Effects 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0268—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment between cold rolling steps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
- C22B9/023—By filtering
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/001—Aluminium or its alloys
-
- 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 preparation method of an aluminum foil for a lithium ion battery and the aluminum foil for the lithium ion battery, wherein the preparation method of the aluminum foil for the lithium ion battery sequentially comprises the following steps: weighing raw material formulas according to component design; firstly, putting the raw material formula into a smelting furnace for smelting to obtain aluminum liquid, and then refining the aluminum liquid in the furnace to obtain an aluminum melt; carrying out external on-line refining on the aluminum melt; continuously casting and rolling the aluminum melt after the external online refining to obtain a cast-rolled plate; cold rolling the cast-rolled plate to obtain a cold-rolled plate; carrying out foil rolling on the cold-rolled sheet to obtain a foil with the thickness of 0.01-0.015mm; and putting the foil into a splitting machine for splitting to obtain the aluminum foil for the lithium ion battery. The tensile strength of the aluminum foil for the lithium ion battery prepared by the method is larger than or equal to 195Mpa, the elongation is larger than or equal to 4.0 percent, and the requirement of the aluminum foil for the lithium ion battery can be met.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of aluminum foil production, in particular to a preparation method of an aluminum foil for a lithium ion battery and the aluminum foil for the lithium ion battery.
[ background of the invention ]
Lithium ion batteries have been widely used due to their advantages of high operating voltage, light weight, large specific energy, long cycle life, safety, no memory effect, no environmental pollution, etc., and are mainly used in the fields of digital batteries, new energy automobile power batteries and other energy storage batteries. With the continuous improvement of energy conservation, environmental protection and green economy, especially the rapid improvement of new energy automobiles, the lithium ion battery also plays an increasingly important role in the aspects of automobile power batteries and large energy storage batteries.
In a lithium ion battery, a current collector generally used for a positive electrode of the lithium ion battery is an aluminum foil, that is, an aluminum foil for the lithium ion battery. The characteristics of the lithium ion battery determine that the product of the aluminum foil for the lithium ion battery needs to have the indexes of high conductivity, high strength, high elongation, good surface quality, good plate shape and the like, and the requirements are far higher than those of other aluminum foil products. Most of the existing aluminum foils are made of 99.0-99.5% of industrial pure aluminum, and generally, the higher the purity, the lower the tensile strength and the higher the elongation. And the tensile strength can be improved by increasing the impurity content, but the elongation rate is reduced, and when the purity of the aluminum is too low, the brittleness of the material is increased, the rolling performance is poor, pinholes are easy to generate, and the aluminum alloy is not suitable for rolling thin products. The purity is too high to be beneficial to processing, the elongation is improved, but during rolling, particularly in the first pass of rolling after annealing, the phenomenon of stick adhesion is easy to generate seriously, the roll surface is whitened, the lubricating condition is deteriorated, the friction coefficient between a roll and a rolled piece is increased, and the generation of pinholes can be caused.
In addition, 1080 alloy is not included in the current national standard GB/T33143-2022 aluminum and aluminum alloy foil for lithium ion batteries, and the requirements on the 1070 alloy are as follows: the mechanical properties of the aluminum foil with the thickness of 0.010-0.015mm are respectively that the tensile strength is more than or equal to 185MPa and the elongation is more than or equal to 2.0 percent. However, as the power battery customers put forward higher and higher requirements on the tape breakage frequency of the aluminum foil during post-processing, the general requirements are that the tensile strength of the aluminum foil is more than or equal to 190Mpa, the elongation is more than 3.0%, and the aluminum foil still can maintain good mechanical properties in a high-speed stretching state, and if the aluminum foil for the lithium ion battery is produced according to the standard of the conventional aluminum foil, the actual requirements cannot be met.
Therefore, it is necessary to provide a method for preparing an aluminum foil for a lithium ion battery and an aluminum foil for a lithium ion battery to solve the above problems.
[ summary of the invention ]
The embodiment of the invention aims to provide a preparation method of an aluminum foil for a lithium ion battery and the aluminum foil for the lithium ion battery, and aims to solve the problem that the aluminum foil prepared by the existing method cannot meet the requirement of the aluminum foil for the lithium ion battery.
In a first aspect, an embodiment of the present invention provides a method for preparing an aluminum foil for a lithium ion battery, including the following steps:
s1, weighing a raw material formula according to component design;
the raw material formula comprises the following components in percentage by mass: less than or equal to 0.07 percent of Si, less than or equal to 0.14 percent of Fe, less than or equal to 0.015 percent of Cu, less than or equal to 0.01 percent of Mn, less than or equal to 0.01 percent of Mg, less than or equal to 0.01 percent of Ni, less than or equal to 0.02 percent of Zn, less than or equal to 0.03 percent of Ti, less than or equal to 0.10 percent of other impurity elements and the balance of Al;
s2, firstly putting the weighed raw material formula into a smelting furnace for smelting to obtain molten aluminum, and then refining the molten aluminum in the furnace to obtain an aluminum melt; the element Ti is configured in a mode of adding Al-Ti-B wires on line, and the elements Si, fe and Cu are added in a mode of controlling impurity elements;
s3, performing external online refining on the aluminum melt in a mode of online adding the Al-Ti-B wires, online degassing by a degassing tank and double filtering by a tubular filter tank and a ceramic filter sheet in sequence;
s4, continuously casting and rolling the aluminum melt subjected to the online refining outside the furnace in a casting and rolling machine injection mode through a runner to obtain a cast and rolled plate with the thickness of 6.5-7.5 mm;
step S5, cold rolling the cast rolling plate to obtain a cold rolling plate with the thickness of 0.25-0.35mm; in the cold rolling process, when the thickness of the cast-rolled plate reaches 0.40-0.55mm, semi-annealing treatment is carried out;
s6, carrying out foil rolling on the cold-rolled sheet to obtain a foil with the thickness of 0.01-0.015mm;
and S7, putting the foil into a splitting machine for splitting to obtain the aluminum foil for the lithium ion battery.
Preferably, in the Al-Ti-B wire added on line, the mass percent of element Ti is 4.5-5.5%, and the mass percent of element B is 0.8-1.2%.
Preferably, in the step S1, the element Al in the raw material formula is configured by adding aluminum liquid into an aluminum ingot, and the adding proportion of the aluminum ingot is greater than or equal to 50%.
Preferably, in the step S2, the temperature of refining in the furnace is 730-750 ℃, the time of refining in the furnace is 20-30min, and the frequency of refining in the furnace is 3.5-4.5 h/time; and after the refining in the furnace is finished, transferring the obtained aluminum melt into a heat preservation furnace for standing.
Preferably, in the step S3, the addition amount of the Al-Ti-B wire added in the online manner is 1.8-2.0kg/t.Al; the inert gas filled in the online degassing tank is argon, and the flow of the argon is 10-25L/min; the pipe-type filter box and the ceramic filter plate are both in a double filtering mode of 50+60 meshes; after the on-line refining outside the furnace is finished, the hydrogen content of the aluminum melt is less than or equal to 0.12mL/100gAl.
Preferably, in the step S4, the casting and rolling speed of the cold rolling is 800-1100mm/min, and the length of the rolling area is 55-70mm; the grain size of the cast-rolled plate is first grade, the difference between the same plate and the cast-rolled plate is less than or equal to 0.03mm, the difference between the longitudinal plates at the periphery is less than or equal to 0.12mm, the convexity is 0-0.03mm, and the edge cracking is less than 3mm.
Preferably, in the step S5, the cold rolling passes are 6.5-7.5mm → 3.5-4.5mm → 1.8-2.5mm → 1.2-1.5mm → 0.6-0.8mm → 0.4-0.55mm → 0.25-0.35mm in sequence; and the temperature of the semi-annealing treatment is 265 +/-5 ℃, the heat preservation time is 25-30h, and after the heat preservation time of the semi-annealing is finished, the side cooling is started to naturally cool the cast-rolled plate.
Preferably, in the step S6, the reduction passes of the foil rolling are sequentially 0.25-0.35mm → 0.115-0.175mm → 0.045-0.075mm → 0.025-0.035mm → 0.01-0.015mm; the roughness of the working roll in the finished product pass of foil rolling of the cold-rolled sheet is 0.14 mu m, and the convexity is 120 per mill mm.
Preferably, in the step S7, in the slitting process, the foil is detected by an online pinhole detector, and the surface of the foil is subjected to corona treatment.
In a second aspect, an embodiment of the present invention provides an aluminum foil for a lithium ion battery, where the aluminum foil for a lithium ion battery includes the following components by mass: less than or equal to 0.07 percent of Si, less than or equal to 0.14 percent of Fe, less than or equal to 0.015 percent of Cu, less than or equal to 0.01 percent of Mn, less than or equal to 0.01 percent of Mg, less than or equal to 0.01 percent of Ni, less than or equal to 0.02 percent of Zn, less than or equal to 0.03 percent of Ti, less than or equal to 0.10 percent of other impurity elements, and the balance of Al; the aluminum foil for the lithium ion battery is prepared by the preparation method of the aluminum foil for the lithium ion battery.
Compared with the prior art, the preparation method of the aluminum foil for the lithium ion battery and the prepared aluminum foil for the lithium ion battery are strictly limited by the range of each element and the adding mode, so that the purity of the prepared aluminum foil for the lithium ion battery can be ensured, the adverse factors such as slag inclusion or coarse hard compounds formed by impurity elements are reduced, and the tensile strength is improved; performing external online refining by adding Al-Ti-B wires online, degassing in an online degassing tank and double filtering in a tubular filter tank and a ceramic filter plate, providing nucleation particles for refined grains, removing more than 95% of impurities with the diameter of 3-8 mu m, improving the purity of aluminum melt, and reducing the defect rate of pinholes, air passages, slag inclusion and the like in a cast-rolled plate obtained after continuous casting and rolling; in the cold rolling process, when the thickness of the cast-rolled plate reaches 0.40-0.55mm, the semi-annealing treatment is carried out, so that the defects of partial rolling work hardening and internal stress can be eliminated, the cold-rolled plate recovers plasticity, and foil rolling is facilitated under the condition of ensuring higher tensile strength and certain elongation; in addition, the tensile strength of the prepared aluminum foil for the lithium ion battery is greater than or equal to 195MPa and the elongation is greater than or equal to 4.0 percent by combining the limitation of other process steps, so that the requirement of the aluminum foil for the lithium ion battery is met.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
fig. 1 is a schematic flow chart illustrating steps of a method for manufacturing an aluminum foil for a lithium ion battery according to an embodiment of the present invention.
[ detailed description ] embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing an aluminum foil for a lithium ion battery, which includes the following steps, as shown in fig. 1:
s1, weighing a raw material formula according to component design.
The raw material formula comprises the following components in percentage by mass: less than or equal to 0.07 percent of Si, less than or equal to 0.14 percent of Fe, less than or equal to 0.015 percent of Cu, less than or equal to 0.01 percent of Mn, less than or equal to 0.01 percent of Mg, less than or equal to 0.01 percent of Ni, less than or equal to 0.02 percent of Zn, less than or equal to 0.03 percent of Ti, less than or equal to 0.10 percent of other impurity elements and the balance of Al.
In the present embodiment, al is 1080 aluminum alloy: the aluminum alloy is an aluminum alloy variety with the corresponding alloy mark of 1080 according to the requirements of the national standard GB/T3190-2020, wherein the aluminum content is not less than 99.80%.
The elements Si, fe and Cu are added in an impurity element control mode, the highest content of the elements is strictly limited, the purity of the alloy is ensured, and the adverse effects of slag inclusion or coarse hard compounds and the like formed by the impurity elements are reduced. Wherein, the trace elements of Fe and Cu mainly exist in a solid solution state, which contributes to the improvement of the strength of the aluminum alloy.
The element Ti is configured in a mode of adding Al-Ti-B wires on line, and in the embodiment, the mass percent of the element Ti of the Al-Ti-B wires is 4.5-5.5%, and the mass percent of the element B is 0.8-1.2%, so that nucleation particles can be effectively provided for refined grains.
The element Al in the raw material formula is configured by adding aluminum liquid and aluminum ingots, preferably, the adding proportion of the aluminum ingots is more than or equal to 50%, the solid-liquid ratio is set, the alloy elements are convenient to control, and meanwhile, the energy-saving effect is realized.
The raw material formula does not add any waste.
S2, putting the weighed raw material formula into a smelting furnace for smelting to obtain aluminum liquid, and refining the aluminum liquid in the furnace to obtain an aluminum melt.
Wherein the temperature of refining in the furnace is 730-750 ℃, the time of refining in the furnace is 20-30min, and the frequency of refining in the furnace is 3.5-4.5 h/time; and after the refining in the furnace is finished, transferring the obtained aluminum melt into a heat preservation furnace for standing.
Before the in-furnace refining of the smelting furnace, the remelting type solid refining agent is added in batches for multiple times after the molten aluminum obtained by smelting is stably kept stand for a period of time.
And S3, sequentially adding the Al-Ti-B wires into the aluminum melt on line, degassing by an on-line degassing box and performing online refining outside the furnace in a mode of double filtering by a tubular filtering box and a ceramic filtering sheet.
Wherein the addition amount of the Al-Ti-B wire added on line is 1.8-2.0kg/t.Al, and the Al-Ti-B wire is added in a launder, which can provide nucleation particles for refining grains; the inert gas filled in the online degassing tank is argon, and the flow of the argon is 10-25L/min; the tubular filter box and the ceramic filter sheet are both in a double filtering mode of 50+60 meshes, namely the tubular filter box is subjected to two-pass filtering, the mesh number of the two-pass filtering is respectively 50 meshes and 60 meshes, and the ceramic filter sheet is also subjected to two-pass filtering, and the mesh number of the two-pass filtering is respectively 50 meshes and 60 meshes.
When the on-line degassing box removes hydrogen, scum is carried into the surface of the aluminum melt, and the melt is subjected to double filtration, so that more than 95% of impurities with the size of 3-8 mu m can be removed, the purity of the aluminum melt is improved, and the defect rates of pinholes, air passages, slag inclusion, looseness and the like in a cast-rolled plate obtained after continuous casting and rolling are reduced.
And after the on-line refining outside the furnace is finished, the hydrogen content of the aluminum melt is less than or equal to 0.12mL/100gAl.
In the present embodiment, ti is mainly a compound TiB 2 、TiAl 3 In the form of nucleation particles to refine the grains.
And S4, continuously casting and rolling the aluminum melt after the online refining outside the furnace in a casting and rolling machine injection mode through a runner to obtain a cast and rolled plate with the thickness of 6.5-7.5 mm.
Wherein the casting and rolling speed of the cold rolling is 800-1100mm/min, and the length of the rolling area is 55-70mm.
The grain size of the obtained cast-rolled plate is one grade, the thickness difference (same plate difference) of the whole plate is less than or equal to 0.03mm, the thickness difference (one-circle longitudinal plate difference) of one-circle longitudinal plate is less than or equal to 0.12mm, the thickness difference (convexity) between the middle part and the two side parts of the same position of the plate is 0-0.03mm, and the split edge of the plate is less than 3mm.
And S5, cold rolling the cast rolling plate to obtain a cold rolling plate with the thickness of 0.25-0.35mm.
The cold rolling passes of the cast-rolled plate of the embodiment are six, and the cold rolling passes are respectively as follows: 6.5-7.5mm → 3.5-4.5mm → 1.8-2.5mm → 1.2-1.5mm → 0.6-0.8mm → 0.4-0.55mm → 0.25-0.35mm.
Wherein, in the cold rolling process, when the thickness of the cast-rolled plate reaches 0.40-0.55mm, semi-annealing treatment is carried out; and the temperature of the semi-annealing treatment is 265 +/-5 ℃, the heat preservation time is 25-30h, and after the heat preservation time of the semi-annealing treatment is finished, the side cooling is started so as to naturally cool the cast-rolled plate in the annealing furnace. The process can eliminate the residual stress generated by cold rolling deformation through the control of the semi-annealing treatment, retain part of rolling work hardening, and is more beneficial to foil rolling under the conditions of improving plasticity and ensuring higher strength.
The technological parameters of the cold rolling are shown in the following table I:
TABLE I, cold Rolling Process parameters
The quality control of the plate shape during cold rolling is as follows:
1) After the working roll is replaced each time, the preheating roller (working roll) is adhered to for more than 10 minutes, and before the pass of the finished product, 2-3 rolls of thick materials are produced; the hot convexity of the roller is improved, the roller shape is stabilized, and the online plate shape is not more than 15I in the finished product pass.
2) And selecting a proper plate shape (the casting and rolling plate) control curve according to the width of the product so as to ensure the quality of the plate shape.
3) When the roller is replaced and the maintenance is carried out regularly, the normal operation of the plate shape control system is ensured.
The surface quality during the cold rolling is controlled as follows:
1) Cleaning a material roll before feeding, cleaning a roller during roller changing, and cleaning a guide roller and a plate roller before production;
2) And (4) replacing the roller before the finished product is produced, detecting that the surface of the working roller has no serious knife mark, vibration line and the like, and determining whether the roller state meets the surface requirement of the product.
3) The first roll before finished products and the first roll after finished products are produced are checked to see whether the surface has defects such as roller mark, scratch, aluminum adhesion, surface stripe and the like, so that the surface defects in batches are avoided;
4) Ensure the rolling oil filtering system to be normal so as to ensure the quality of the rolling surface.
And S6, carrying out foil rolling on the cold-rolled sheet to obtain a foil with the thickness of 0.01-0.015mm.
Wherein the foil rolling process sequentially comprises rough rolling, intermediate rolling and finish rolling.
In the embodiment, the foil rolling passes of the cold-rolled sheet are four passes, and the rolling passes of the foil rolling are respectively 0.25-0.35mm → 0.115-0.175mm → 0.045-0.075mm → 0.025-0.035mm → 0.01-0.015mm.
The roughness of the working roll in the finished product pass of foil rolling of the cold-rolled sheet is 0.14 mu m, the roll surface convexity (convexity) of the working roll is 120 per mill mm, and the finished product pass is the last reduction pass.
The technological parameters of the foil rolling are shown in the following table II:
TABLE II, technological parameter table of foil rolling
And S7, putting the foil into a splitting machine for splitting to obtain the aluminum foil for the lithium ion battery.
In the slitting process, the foil is detected by an online pinhole detector, and the surface of the foil is subjected to corona treatment.
The foil is detected by an online pinhole detector, so that the quantity, size and distribution of pinholes can be monitored in real time, and the quality of the pinholes of the product is ensured to be good. And when the slitting equipment is used for slitting, the required width specification is obtained, and the corona treatment is carried out on the surface of the foil in the slitting process, so that the surface dyne value of the foil can be improved, the wettability of the surface of the prepared aluminum foil for the lithium ion battery is improved, and the subsequent spraying treatment is facilitated.
In addition, according to actual requirements, steps of packaging and warehousing can be sequentially added after the aluminum foil for the lithium ion battery is obtained.
The aluminum foil for lithium ion batteries: the aluminum foil is suitable for aluminum foil products for lithium ion battery current collectors, and is mainly applied to the fields of digital batteries, new energy automobile power batteries, large energy storage batteries and the like.
Compared with the prior art, the preparation method of the aluminum foil for the lithium ion battery and the prepared aluminum foil for the lithium ion battery are strictly limited by the range of each element and the adding mode, so that the purity of the prepared aluminum foil for the lithium ion battery can be ensured, the adverse factors such as slag inclusion or coarse hard compounds formed by impurity elements are reduced, and the tensile strength is improved; performing external online refining by adding Al-Ti-B wires online, degassing in an online degassing tank and double filtering in a tubular filter tank and a ceramic filter plate, providing nucleation particles for refined grains, removing more than 95% of impurities with the diameter of 3-8 mu m, improving the purity of aluminum melt, and reducing the defect rate of pinholes, air passages, slag inclusion and the like in a cast-rolled plate obtained after continuous casting and rolling; in the cold rolling process, when the thickness of the cast-rolled plate reaches 0.40-0.55mm, the semi-annealing treatment is carried out, so that the defects of partial rolling work hardening and internal stress can be eliminated, the cold-rolled plate recovers plasticity, and foil rolling is facilitated under the condition of ensuring higher tensile strength and certain elongation; in addition, by combining the limitation of other process steps, the tensile strength of the prepared aluminum foil for the lithium ion battery is greater than or equal to 195MPa, and the elongation is greater than or equal to 4.0%, so that the requirement of the aluminum foil for the lithium ion battery is met.
For further illustration, the invention provides five examples for verification, and the following description will be made by defining the mass percentages of the elements in the raw material formula by five specific examples in table three:
table three, five concrete examples show the mass percentage table of each element of the raw material formula
The mechanical property test of the 0.013 μm thick aluminum foil for lithium ion batteries prepared by the above preparation method according to the raw material formulation of the above examples one to five was performed, and the test results are shown in the following table four:
TABLE IV, mechanical property test result table
Through the description of the specific examples of the first to fifth examples, it can be seen that the tensile strength of the aluminum foil for lithium ion batteries, which is prepared by the preparation method of the aluminum foil for lithium ion batteries, is 0.013mm in thickness, is 195-205MPa, the elongation is 4.2-4.9%, and the elongation is not obviously reduced under the high-speed stretching condition of 300mm/min and is kept at the level of more than 4.0%; the alloy has high purity, high tensile strength and elongation, and few pinholes, so that the rolling and strip breaking times can be obviously reduced, and the scrap of 70EA pole pieces caused by strip breaking can be reduced by one ton of aluminum through actual production and use tracking. Therefore, the aluminum foil for the lithium ion battery, which is prepared by the preparation method of the aluminum foil for the lithium ion battery, can effectively solve the problems of high strength and low elongation or high elongation and low strength of the existing industrial pure aluminum.
The invention also provides another embodiment, which is an aluminum foil for the lithium ion battery, wherein the aluminum foil for the soft package lithium ion battery comprises the following components in percentage by mass: less than or equal to 0.07 percent of Si, less than or equal to 0.14 percent of Fe, less than or equal to 0.015 percent of Cu, less than or equal to 0.01 percent of Mn, less than or equal to 0.01 percent of Mg, less than or equal to 0.01 percent of Ni, less than or equal to 0.02 percent of Zn, less than or equal to 0.03 percent of Ti, less than or equal to 0.10 percent of other impurity elements and the balance of Al; the aluminum foil for the lithium ion battery is prepared by the preparation method of the aluminum foil for the lithium ion battery in the embodiment, and is applied to the lithium ion battery.
Since the aluminum foil for a lithium ion battery in this embodiment is prepared by the method for preparing an aluminum foil for a lithium ion battery in the above embodiment, the aluminum foil for a lithium ion battery in this embodiment can also achieve the technical effects achieved by the method for preparing an aluminum foil for a lithium ion battery in the above embodiment, and details are not described here.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of an aluminum foil for a lithium ion battery is characterized by comprising the following steps:
s1, weighing a raw material formula according to component design;
the raw material formula comprises the following components in percentage by mass: less than or equal to 0.07 percent of Si, less than or equal to 0.14 percent of Fe, less than or equal to 0.015 percent of Cu, less than or equal to 0.01 percent of Mn, less than or equal to 0.01 percent of Mg, less than or equal to 0.01 percent of Ni, less than or equal to 0.02 percent of Zn, less than or equal to 0.03 percent of Ti, less than or equal to 0.10 percent of other impurity elements and the balance of Al;
s2, firstly putting the weighed raw material formula into a smelting furnace for smelting to obtain molten aluminum, and then refining the molten aluminum in the furnace to obtain an aluminum melt; the element Ti is configured in a mode of adding Al-Ti-B wires on line, and the elements Si, fe and Cu are added in a mode of controlling impurity elements;
s3, performing external online refining on the aluminum melt in a mode of online adding the Al-Ti-B wires, online degassing by a degassing tank and double filtering by a tubular filter tank and a ceramic filter sheet in sequence;
s4, continuously casting and rolling the aluminum melt after the online refining outside the furnace in a casting and rolling machine injection mode through a runner to obtain a cast and rolled plate with the thickness of 6.5-7.5 mm;
step S5, cold rolling the cast rolling plate to obtain a cold rolling plate with the thickness of 0.25-0.35mm; in the cold rolling process, when the thickness of the cast-rolled plate reaches 0.40-0.55mm, semi-annealing treatment is carried out;
s6, carrying out foil rolling on the cold-rolled sheet to obtain a foil with the thickness of 0.01-0.015mm;
and S7, putting the foil into a splitting machine for splitting to obtain the aluminum foil for the lithium ion battery.
2. The method for preparing the aluminum foil for the lithium ion battery according to claim 1, wherein in the Al-Ti-B wire added on-line, the mass percent of element Ti is 4.5-5.5%, and the mass percent of element B is 0.8-1.2%.
3. The method for preparing the aluminum foil for the lithium ion battery according to claim 1, wherein in the step S1, the element Al in the raw material formula is configured by adding aluminum liquid into an aluminum ingot, and the adding proportion of the aluminum ingot is greater than or equal to 50%.
4. The method for preparing the aluminum foil for the lithium ion battery according to claim 1, wherein in the step S2, the temperature of in-furnace refining is 730 to 750 ℃, the time of in-furnace refining is 20 to 30min, and the frequency of in-furnace refining is 3.5 to 4.5 h/time; and after the refining in the furnace is finished, transferring the obtained aluminum melt into a heat preservation furnace for standing.
5. The method for preparing the aluminum foil for the lithium ion battery according to claim 1, wherein in the step S3, the addition amount of the Al-Ti-B wire added in-line is 1.8 to 2.0kg/t.al; the inert gas filled in the online degassing tank is argon, and the flow rate of the argon is 10-25L/min; the pipe-type filter box and the ceramic filter plate are both in a double filtering mode of 50+60 meshes; after the on-line refining outside the furnace is finished, the hydrogen content of the aluminum melt is less than or equal to 0.12mL/100gAl.
6. The method for preparing an aluminum foil for a lithium ion battery according to claim 1, wherein in the step S4, the casting and rolling speed of the cold rolling is 800 to 1100mm/min, and the length of the rolling zone is 55 to 70mm; the grain size of the cast-rolled plate is first grade, the difference between the same plate and the cast-rolled plate is less than or equal to 0.03mm, the difference between the longitudinal plates at the periphery is less than or equal to 0.12mm, the convexity is 0-0.03mm, and the edge cracking is less than 3mm.
7. The method of manufacturing an aluminum foil for lithium ion batteries according to claim 1, wherein in step S5, the cold rolling is performed with the reduction passes of 6.5 to 7.5mm → 3.5 to 4.5mm → 1.8 to 2.5mm → 1.2 to 1.5mm → 0.6 to 0.8mm → 0.4 to 0.55mm → 0.25 to 0.35mm in this order; and the temperature of the semi-annealing treatment is 265 +/-5 ℃, the heat preservation time is 25-30h, and after the heat preservation time of the semi-annealing treatment is finished, the side cooling is started to naturally cool the cast-rolled plate.
8. The method for preparing an aluminum foil for a lithium ion battery according to claim 1, wherein in the step S6, the reduction passes of the foil rolling are, in order, 0.25 to 0.35mm → 0.115 to 0.175mm → 0.045 to 0.075mm → 0.025 to 0.035mm → 0.01 to 0.015mm; the roughness of the working roll in the finished product pass of foil rolling of the cold-rolled sheet is 0.14 mu m, and the convexity is 120 per mill mm.
9. The method for preparing the aluminum foil for the lithium ion battery according to claim 1, wherein in the step S7, the foil is detected by an online pinhole detector during the slitting process, and the surface of the foil is subjected to corona treatment.
10. The aluminum foil for the lithium ion battery is characterized by comprising the following components in percentage by mass: less than or equal to 0.07 percent of Si, less than or equal to 0.14 percent of Fe, less than or equal to 0.015 percent of Cu, less than or equal to 0.01 percent of Mn, less than or equal to 0.01 percent of Mg, less than or equal to 0.01 percent of Ni, less than or equal to 0.02 percent of Zn, less than or equal to 0.03 percent of Ti, less than or equal to 0.10 percent of other impurity elements and the balance of Al; the aluminum foil for lithium ion batteries is produced by the method for producing an aluminum foil for lithium ion batteries according to any one of claims 1 to 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107099701A (en) * | 2017-04-26 | 2017-08-29 | 洛阳龙鼎铝业有限公司 | A kind of preparation method of lithium ion battery high intensity aluminium foil |
| WO2018201125A1 (en) * | 2017-04-28 | 2018-11-01 | Board Of Regents, The University Of Texas System | Multiphase metal foils as integrated metal anodes for non-aqueous batteries |
| CN111793759A (en) * | 2020-08-11 | 2020-10-20 | 华北铝业有限公司 | 1070 high-performance aluminum foil for lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099701A (en) * | 2017-04-26 | 2017-08-29 | 洛阳龙鼎铝业有限公司 | A kind of preparation method of lithium ion battery high intensity aluminium foil |
| WO2018201125A1 (en) * | 2017-04-28 | 2018-11-01 | Board Of Regents, The University Of Texas System | Multiphase metal foils as integrated metal anodes for non-aqueous batteries |
| CN111793759A (en) * | 2020-08-11 | 2020-10-20 | 华北铝业有限公司 | 1070 high-performance aluminum foil for lithium ion battery and preparation method thereof |
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