CN109402458B - 3003 alloy double-sided dark aluminum foil for high-strength lithium battery and manufacturing method thereof - Google Patents
3003 alloy double-sided dark aluminum foil for high-strength lithium battery and manufacturing method thereof Download PDFInfo
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- CN109402458B CN109402458B CN201811512009.5A CN201811512009A CN109402458B CN 109402458 B CN109402458 B CN 109402458B CN 201811512009 A CN201811512009 A CN 201811512009A CN 109402458 B CN109402458 B CN 109402458B
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- 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
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- 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
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- 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
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- 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
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
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- 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 3003 alloy double-sided dark aluminum foil for a high-strength lithium battery and a manufacturing method thereof, wherein the 3003 alloy double-sided dark aluminum foil comprises the following components: fe. Si, Cu, Ti, Mn, Mg, Zn and Al. The invention controls the element proportion of 3003 alloy, and prepares double-sided dark aluminum foil through smelting and cast-rolling process, cold rolling process and foil rolling process, and the N layers of aluminum foils are overlapped together for rolling, so that more than 3 aluminum foil products can be obtained, and the mechanical property index of the high-conductivity aluminum foil for the lithium battery is improved, the tensile strength of the finished product of the material is up to 258.64-270.21MPa, the elongation can reach 3.8-5.1%, the plate shape is obviously improved, the production efficiency is improved by more than 50%, the surface is free of oil, and the surface wetting tension is more than or equal to 33 dynes.
Description
Technical Field
The invention belongs to the technical field of battery foil preparation, and particularly relates to a 3003 alloy double-sided dark aluminum foil for a high-strength lithium battery and a manufacturing method thereof.
Background
In recent years, the new energy automobile industry in China develops rapidly, and lithium batteries are the key for the development of new energy automobiles. With the development of battery technology, especially the new energy automobile field, higher requirements are put forward on lithium batteries, and the battery industry also puts forward new requirements on aluminum foils for batteries. The aluminum foil has the advantages of high dimensional accuracy, clean and uniform surface, no scratch and other defects, balanced plate shape, extremely thin thickness, high tensile strength and high elongation. With the trend of thinning aluminum foils for lithium batteries, tensile strength, elongation and surface quality needs to be improved. The tensile strength and the elongation rate of the aluminum foil for the conventional lithium battery can not meet the requirement of thinning while the aluminum content is 99 percent, so that more products adopt a mode of adding alloy elements to improve the mechanical property of the aluminum foil at present. However, the aluminum foil product for batteries has high requirements for tensile strength and elongation due to the particularity of performance requirements.
For example, the chinese patent application document "an aluminum foil for lithium battery" (publication No. CN105018799A) discloses an aluminum foil for lithium battery, which comprises the following components by mass percent: fe: 0.38-0.45%; si: 0.1-0.15; cu: 0.03-0.06%; ti: 0.015-0.02%; mn: less than or equal to 0.03 percent; mg: less than or equal to 0.03 percent; zn: less than or equal to 0.03 percent; the balance being Al and unavoidable impurities. Can be prepared by the following steps: smelting and cast rolling process: heating and smelting an aluminum foil raw material for a lithium battery into an aluminum alloy melt; refining, slagging off, grain refining, degassing, deslagging and filtering treatment are sequentially carried out; continuously casting and rolling the filtered aluminum alloy melt into a blank; the cold rolling process comprises the following steps: firstly cold rolling a blank, and then carrying out primary annealing treatment, rough rolling and secondary annealing treatment; foil pressing treatment: and (4) finish rolling the annealed aluminum foil, and finally slitting to obtain the finished aluminum foil for the lithium battery. However, the aluminum foil for the battery produced by the process has the following problems: (1) the tensile strength and the elongation are insufficient, and the surface wetting tension is not high; (2) the bright surface is provided with oil, so that the coating uniformity and the conductivity of the lithium battery substrate are influenced; (3) in the case of the plate type, the plate type of 2-sheet pack rolling is not good enough; (4) only 2 aluminum foils can be produced in one-time production, so that the production efficiency is low, and the yield is not improved.
Disclosure of Invention
The invention aims to provide a 3003 alloy double-sided dark aluminum foil for a high-strength lithium battery and a manufacturing method thereof, and aims to solve the practical technical problems that the aluminum foil for the battery produced by the existing production process is low in tensile strength and elongation, poor in plate shape and low in production efficiency, and the uniformity and the conductivity of a coating of a lithium battery substrate are directly influenced due to the fact that oil is carried on the surface of the aluminum foil.
In order to solve the technical problems, the invention adopts the following technical scheme:
a3003 alloy double-sided dark aluminum foil for a high-strength lithium battery comprises the following components in percentage by mass: fe: 0.4-0.5%, Si: less than or equal to 0.10 percent, Cu: 0.05-0.09%, Ti: 0.01-0.025%, Mn: 1.0-1.1%, Mg: less than or equal to 0.005 percent, Zn: less than or equal to 0.005 percent and the balance of Al.
Further, the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery comprises the following components in percentage by mass: fe: 0.46%, Si: 0.08%, Cu: 0.079%, Ti: 0.023%, Mn: 1.04%, Mg: 0.003%, Zn: 0.004%, and the balance of Al.
Furthermore, the thickness of the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery is 0.01-0.025mm, the tensile strength is 258.64-270.21MPa, and the elongation is 3.8-5.1%.
The invention also provides a manufacturing method of the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery, which comprises the following steps:
(1) smelting, casting and rolling process
a. Firstly, putting the waste into a smelting furnace, and then putting an aluminum ingot and molten aluminum, wherein the weight of the aluminum ingot accounts for 10-20% of the total weight;
parameters are as follows: solid-liquid ratio 3: 7;
b. smelting in a smelting furnace, adding alloy after smelting, introducing nitrogen and a refining agent for refining after standing, slagging off after refining, adjusting and standing components, and checking that the components are qualified;
parameters are as follows: the smelting time is 4-6 hours, the smelting temperature is 730-760 ℃, the standing time after smelting is 25-40 minutes, and the refining time is 15-20 minutes;
c. b, sending the molten aluminum prepared in the step b into a heat preservation furnace for turning down, starting a powder injection refiner after the turning down is finished to add a refining agent into the molten aluminum in the standing furnace for secondary refining and rechecking components, slagging off after each refining, refining once every certain time, wherein the refining time is 15-20 minutes, slagging off after standing for 5-10 minutes, and refining once every 1.5-2 hours;
parameters are as follows: refining the molten aluminum in the standing furnace for 15-20 minutes each time, slagging off after standing for 5-10 minutes, refining once every 1.5-2 hours, and refining at the temperature of 740-;
d. degassing the aluminum liquid by adopting argon, adjusting the rotating speed of a graphite rotor, ensuring that the hydrogen content of the aluminum liquid is less than or equal to 0.12ml/100gAl, and adding Ti wires for grain refinement;
parameters are as follows: the rotation speed of the graphite rotor is 400-;
e. d, sending the aluminum liquid prepared in the step d into a front box which is arranged in front of a casting and rolling machine and bears the aluminum liquid, after entering a casting nozzle, casting and rolling the aluminum liquid by a casting and rolling roller with built-in circulating water, and then coiling the aluminum liquid into a cold-rolled blank by a coiling device;
parameters are as follows: the grinding requirement of the casting roller is controlled to be 0.25-0.30mm in middle and high, the middle and high symmetry degree is 0.005-0.015mm, the roughness is 0.8-1.0um, and the cylindricity of the roller reaches 0.005-0.015 mm; the temperature of the front box is controlled to be between 700 and 715 ℃, the liquid level height of the front box is between 10 and 20mm, the length of a rolling area is between 55 and 60mm, the casting and rolling speed is controlled to be between 800 and 900mm/min, and the pressure of cooling water is controlled to be between 0.3 and 0.4 MPa;
(2) cold rolling process
a. Roll grinding parameters and rolling oil indexes;
parameters are as follows: the roughness of the cogging roll is 0.7um and 0mm in the middle and high, the roughness of the foil billet pass roll is 0.45um and 0mm in the middle and high, and the viscosity of the rolling oil is 2.1-2.8mm2S, acid value less than or equal to 0.15mgKOH/g, flash point>The rolling oil content is 8-8.5% at 100 ℃, and the oil product transmittance is more than or equal to 95%;
b. performing cold rolling on the cold-rolled coil by using a cold rolling mill, rolling the cold-rolled coil to a thickness of 4.0-4.2mm, and rolling the cold-rolled coil to 0.24mm in total for 6 passes to obtain an aluminum foil blank; the rolling process comprises the following steps: the method comprises the following steps of first cold rolling, uniform annealing, second cold rolling, recoiling and trimming, third cold rolling, recoiling and trimming and foil rolling, wherein the first cold rolling is performed from 7.0mm in thickness to 4.0mm in thickness; in the second cold rolling, the thickness is reduced from 4.0mm to 2.1mm, and then the thickness is reduced to 1.2 mm; in the third cold rolling, the thickness is reduced to 0.68mm from 1.2mm, then the thickness is reduced to 0.4mm, and finally the thickness is reduced to 0.24 mm;
c. adopting a uniform annealing process, and pressing again after the uniform annealing process, wherein the rolling reduction thickness is uniformly reduced to 0.24 Mm;
parameters are as follows: the uniform annealing process comprises the following steps: heating to 550 ℃ within 0 hour, preserving heat for 18-20 hours, cooling to 520 ℃ within 0.5-1 hour, preserving heat for 6-7 hours, and finally directly discharging from the furnace for air cooling;
d. the rewinding and edge cutting adopt 1.2mm and 0.24mm for twice edge cutting, and the total edge cutting amount is 60-70 mm;
parameters are as follows: the blade clearance is 0.1-0.12mm, the shearing speed is 300-;
(3) foil rolling process:
a. foil rolling is carried out on the aluminum foil by using a rough roller and a finish roller, rolling oil is added in the foil rolling process, the rolling frequency is more than 4 times, the thickness of each rolling accounts for 30-45% of the total thickness before the rolling, the pass of a finished product is controlled to be 35-38%, and the viscosity of the rough rolling oil is 1.8-2.5mm2S, acid value less than or equal to 0.1mgKOH/g, flash point>The rolling oil content is 5-5.5% at 85 ℃, and the oil product transmittance is more than or equal to 97%; the viscosity of the finish rolling oil is 1.7-2.3mm2S, acid value less than or equal to 0.03mgKOH/g, flash point>The rolling oil content is less than 5 percent at 80 ℃, and the oil product transmittance is more than or equal to 97 percent;
b. rolling, namely, converting N pieces of rolled coils into finished products of finish rolling, firstly doubling two sheets together into 2 sheets, rolling the third sheet and the closed 2 sheets again to obtain 3 sheets, and rolling N pieces by analogy;
parameters are as follows: the speed is 600-650m/nim, and the coiling tensile stress is 30-35N/mm2The pressure of the flattening roller is 3-5kg/c of square meter;
c. in the finished product pass, the N pieces of aluminum foil combined by the rolling machine are rolled in a finishing mill, and the aluminum foil which is not contacted with the roller is a double-sided hidden aluminum foil product;
d. and (4) slitting, namely slitting and rewinding the aluminum foil after finish rolling, pouring out the double-sided dark aluminum foil, and then dividing the aluminum foil into finished aluminum foils for lithium batteries with different specification requirements by using a horizontal slitting machine.
Further, in the smelting and cast-rolling process, the waste is first-grade waste, and the first-grade waste refers to plates, coiled materials, coiled scrap edges, cast-rolled coil head tails and standing furnace emptying block materials with the thickness of more than or equal to 1.0 mm.
Further, in the step b of the smelting and casting-rolling process, the refining agent consists of the following components in percentage by weight: 40-70% of potassium chloride, 15-30% of sodium aluminum fluoride, 1-10% of hexafluorobenzene, 5-15% of calcium sulfide and 5-20% of sodium sulfate.
Further, the refining agent is used in an amount of 1kg/T aluminum.
Further, in the step c of the smelting and casting-rolling process, the refining agent consists of the following components in percentage by weight: 40-70% of potassium chloride, 15-30% of sodium aluminum fluoride, 1-10% of hexafluorobenzene, 5-15% of calcium sulfide and 5-20% of sodium sulfate.
Further, the refining agent is used in an amount of 2kg/T aluminum.
Further, the purity of the argon in the smelting and casting-rolling process step d is 99.995%.
The invention has the following beneficial effects:
(1) the invention controls the element proportion of 3003 alloy, and prepares double-sided dark aluminum foil through smelting and cast-rolling process, cold rolling process and foil rolling process, and the N layers of aluminum foils are overlapped together for rolling, so that more than 3 aluminum foil products can be obtained, and the mechanical property index of the high-conductivity aluminum foil for the lithium battery is improved, the tensile strength of the finished product of the material is as high as 258.64-270.21MPa, the elongation rate can reach 3.8-5.1%, the plate type is obviously improved, the production efficiency is improved by more than 50%, no oil is carried on the surface, the surface wetting tension is more than or equal to 33 dyne values, and the practical technical problems that the aluminum foil for the battery produced by the existing production process is low in tensile strength and elongation rate, poor in plate type and low in production efficiency, and the uniformity, the conductivity and the like of the coating of the lithium battery substrate are directly.
(2) The 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery produced by the invention has the thickness tolerance within +/-3 percent, the width tolerance within +/-1 mm, the dyne value is more than or equal to 33, the dark aluminum foil is effectively controlled, no lotus leaf edge exists, the service performance and the surface quality of a finished product are high, and the aluminum foil can be suitable for most batteries.
(3) According to the invention, the double-sided dark aluminum foil is prepared by adjusting the components of the aluminum alloy, adding Cu, Mn, Mg and Ti, adjusting the appropriate dosage and changing the synergistic effect among the elements through a smelting and casting-rolling process, a cold rolling process and a foil rolling process, so that the performance of the aluminum foil is effectively improved, and the requirement for preparing the battery aluminum foil can be met.
Drawings
FIG. 1 is a schematic diagram of the double-sided blind aluminum foil finished product of the present invention which is rolled by 3-sheet rolling and then rolled.
Illustrated in the figure are: 1 is a roller; 2, double-sided dark aluminum foil; 3 is a single-sided smooth aluminum foil; a is a bright surface which is in contact with the roller; and B is a dark surface (a matte surface) which is not contacted with the roller, namely the double-sided dark aluminum foil.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In an embodiment, the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery comprises the following components in percentage by mass: fe: 0.4-0.5%, Si: less than or equal to 0.10 percent, Cu: 0.05-0.09%, Ti: 0.01-0.025%, Mn: 1.0-1.1%, Mg: less than or equal to 0.005 percent, Zn: less than or equal to 0.005 percent and the balance of Al.
The manufacturing method of the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery comprises the following steps:
(1) smelting, casting and rolling process
a. Firstly, putting the waste into a smelting furnace, and then putting an aluminum ingot and molten aluminum, wherein the weight of the aluminum ingot accounts for 10-20% of the total weight, the waste is primary waste, and the primary waste refers to plates, coiled materials, coiled waste edge materials, cast-rolled coil head tails and standing furnace emptying block materials with the thickness of more than or equal to 1.0 mm;
parameters are as follows: solid-liquid ratio 3: 7;
b. smelting in a smelting furnace, adding alloy after smelting, introducing nitrogen and a refining agent for refining after standing, slagging off after refining, adjusting and standing components, and checking that the components are qualified;
parameters are as follows: the smelting time is 4-6 hours, the smelting temperature is 730-760 ℃, the standing time after smelting is 25-40 minutes, the refining time is 15-20 minutes, and the refining agent comprises the following components in percentage by weight: 40-70% of potassium chloride, 15-30% of sodium aluminum fluoride, 1-10% of hexafluorobenzene, 5-15% of calcium sulfide and 5-20% of sodium sulfate; the amount of the refining agent is 1kg/T aluminum.
c. B, sending the molten aluminum prepared in the step b into a heat preservation furnace for turning down, starting a powder injection refiner after the turning down is finished to add a refining agent into the molten aluminum in the standing furnace for secondary refining and rechecking components, slagging off after each refining, refining once every certain time, wherein the refining time is 15-20 minutes, slagging off after standing for 5-10 minutes, and refining once every 1.5-2 hours;
parameters are as follows: refining the molten aluminum in the standing furnace for 15-20 minutes each time, slagging off after standing for 5-10 minutes, refining once every 1.5-2 hours at the refining temperature of 740-: 40-70% of potassium chloride, 15-30% of sodium aluminum fluoride, 1-10% of hexafluorobenzene, 5-15% of calcium sulfide and 5-20% of sodium sulfate; the amount of the refining agent is 2kg/T aluminum.
d. Degassing the aluminum liquid by adopting argon with the purity of 99.995 percent, adjusting the rotating speed of a graphite rotor, ensuring that the hydrogen content of the aluminum liquid is less than or equal to 0.12ml/100gAl, and adding Ti wires for grain refinement;
parameters are as follows: the rotation speed of the graphite rotor is 400-500r/min, and the speed of the added Ti wire is 200-230 mm/min.
e. D, sending the aluminum liquid prepared in the step d into a front box which is arranged in front of a casting and rolling machine and bears the aluminum liquid, after entering a casting nozzle, casting and rolling the aluminum liquid by a casting and rolling roller with built-in circulating water, and then coiling the aluminum liquid into a cold-rolled blank by a coiling device;
parameters are as follows: the grinding requirement of the casting roller is controlled to be 0.25-0.30mm in middle and high, the middle and high symmetry degree is 0.005-0.015mm, the roughness is 0.8-1.0um, and the cylindricity of the roller reaches 0.005-0.015 mm; the temperature of the front box is controlled to be between 700 and 715 ℃, the liquid level height of the front box is between 10 and 20mm, the length of a rolling area is between 55 and 60mm, the casting and rolling speed is controlled to be between 800 and 900mm/min, and the pressure of cooling water is controlled to be between 0.3 and 0.4 MPa.
(2) Cold rolling process
a. Roll grinding parameters and rolling oil indexes;
parameters are as follows: the roughness of the cogging roll is 0.7um and 0mm in the middle and high, the roughness of the foil billet pass roll is 0.45um and 0mm in the middle and high, and the viscosity of the rolling oil is 2.1-2.8mm2S, acid value less than or equal to 0.15mgKOH/g, flash point>The rolling oil content is 8-8.5% at 100 ℃, and the oil product transmittance is more than or equal to 95%.
b. And (3) carrying out reduction cold rolling on the cold rolled coil by using a cold rolling mill, rolling the cold rolled coil to a thickness of 4.0-4.2mm, and rolling the cold rolled coil to 0.24mm in 6 passes to obtain the aluminum foil blank. The rolling process comprises the following steps: the method comprises the following steps of first cold rolling, uniform annealing, second cold rolling, recoiling and trimming, third cold rolling, recoiling and trimming and foil rolling, wherein the first cold rolling is performed from 7.0mm in thickness to 4.0mm in thickness; in the second cold rolling, the thickness is reduced from 4.0mm to 2.1mm, and then the thickness is reduced to 1.2 mm; in the third cold rolling, the thickness is reduced from 1.2mm to 0.68mm, then the thickness is reduced to 0.4mm, and finally the thickness is reduced to 0.24 mm.
The rolling parameters are shown in the following table:
c. adopting a uniform annealing process, and pressing again after the uniform annealing process, wherein the rolling reduction thickness is uniformly reduced to 0.24 Mm;
parameters are as follows: the uniform annealing process comprises the following steps: heating to 550 ℃ within 0 hour, preserving heat for 18-20 hours, cooling to 520 ℃ within 0.5-1 hour, preserving heat for 6-7 hours, and finally directly discharging from the furnace for air cooling.
d. The edge cutting of the recoiling adopts two times of edge cutting of 1.2mm and 0.24mm, and the total edge cutting amount is 60-70 mm.
Parameters are as follows: the blade clearance is 0.1-0.12mm, the shearing speed is 300-;
(3) foil rolling process:
a. foil rolling is carried out on the aluminum foil by using a rough roller and a finish roller, rolling oil is added in the foil rolling process, the rolling frequency is more than 4 times, the thickness of each rolling accounts for 30-45% of the total thickness before the rolling, and the pass of a finished product is controlled to be 35-38%. The viscosity of the rough rolling oil is 1.8-2.5mm2S, acid value less than or equal to 0.1mgKOH/g, flash point>The rolling oil content is 5-5.5% at 85 ℃, and the oil product transmittance is more than or equal to 97%; the viscosity of the finish rolling oil is 1.7-2.3mm2S, acid value less than or equal to 0.03mgKOH/g, flash point>The rolling oil content is less than 5 percent at the temperature of 80 ℃, and the oil product transmittance is more than or equal to 97 percent.
The rolling parameters are shown in the following table: take 0.012mm as an example
b. And (4) rolling, namely rolling the finished product to the thickness by adopting N pieces of rolled coils. Firstly, doubling the two sheets together into 2 sheets, then combining the third sheet with the combined 2 sheets to obtain 3 sheets, and repeating the steps to combine N sheets.
Parameters are as follows: speed 600-Stress of 30-35N/mm2The pressure of the flattening roller is 3-5kg/c of square meter;
c. and in the finished product pass, the N pieces of aluminum foil combined by the rolling machine are subjected to overlapping rolling in a finishing mill, and the aluminum foil which is not contacted with the roller is a double-sided hidden aluminum foil product (shown in figure 1). The traditional process has the advantages that the finished product pass is limited to 2-sheet rolling, the production efficiency is low, the invention can be used for rolling finished products of 3 sheets, 4 sheets and N sheets, and the yield is obviously improved;
d. and (4) slitting, namely slitting and rewinding the aluminum foil after finish rolling, pouring out the double-sided dark aluminum foil, and then dividing the aluminum foil into finished aluminum foils for lithium batteries with different specification requirements by using a horizontal slitting machine.
Example 1
A3003 alloy double-sided dark aluminum foil for a high-strength lithium battery comprises the following components in percentage by mass: fe: 0.41%, Si: 0.10%, Cu: 0.08%, Ti: 0.01%, Mn: 1.02%, Mg: 0.005%, Zn: 0.005% and the balance of Al.
The manufacturing method of the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery comprises the following steps:
(1) smelting, casting and rolling process
a. Firstly, putting the waste into a smelting furnace, and then putting an aluminum ingot and molten aluminum, wherein the weight of the aluminum ingot accounts for 12% of the total weight, the waste is primary waste, and the primary waste refers to plates, coiled materials, coiled waste edge materials, cast-rolled coil head tailings and emptying block materials in a standing furnace, wherein the thickness of the primary waste is more than or equal to 1.0 mm;
parameters are as follows: solid-liquid ratio 3: 7;
b. smelting in a smelting furnace, adding alloy after smelting, introducing nitrogen and a refining agent for refining after standing, slagging off after refining, adjusting and standing components, and checking that the components are qualified;
parameters are as follows: the smelting time is 6 hours, the smelting temperature is 730 ℃, the standing time after smelting is 25 minutes, the refining time is 15 minutes, and the refining agent comprises the following components in percentage by weight: 40% of potassium chloride, 30% of sodium aluminum fluoride, 4% of hexafluorobenzene, 6% of calcium sulfide and 20% of sodium sulfate; the amount of the refining agent is 1kg/T aluminum.
c. B, sending the molten aluminum prepared in the step b into a heat preservation furnace for turning down, starting a powder injection refiner after the turning down is finished to add a refining agent into the molten aluminum in the standing furnace for secondary refining and rechecking components, slagging off after each refining is finished, refining once every certain time, wherein the refining time is 15 minutes, slagging off after standing for 5 minutes, and refining once every 1.5 hours;
parameters are as follows: refining the molten aluminum in the standing furnace for 15 minutes each time, slagging off after standing for 5 minutes, refining once every 1.5 hours, wherein the refining temperature is 740 ℃, and the refining agent consists of the following components in percentage by weight: 45% of potassium chloride, 25% of sodium aluminum fluoride, 10% of hexafluorobenzene, 12% of calcium sulfide and 8% of sodium sulfate; the amount of the refining agent is 2kg/T aluminum.
d. Degassing the aluminum liquid by adopting argon with the purity of 99.995%, adjusting the rotating speed of a graphite rotor, ensuring that the hydrogen content of the aluminum liquid is 0.12ml/100gAl, and adding Ti wires for grain refinement;
parameters are as follows: the rotation speed of the graphite rotor is 400r/min, and the speed of the added Ti wires is 200 mm/min.
e. D, sending the aluminum liquid prepared in the step d into a front box which is arranged in front of a casting and rolling machine and bears the aluminum liquid, after entering a casting nozzle, casting and rolling the aluminum liquid by a casting and rolling roller with built-in circulating water, and then coiling the aluminum liquid into a cold-rolled blank by a coiling device;
parameters are as follows: the middle height of the grinding requirement of the casting roller is controlled to be 0.25mm, the middle-high symmetry degree is 0.005mm, the roughness is 0.8um, and the cylindricity of the roller reaches 0.005 mm; the temperature of the front box is controlled at 700 ℃, the liquid level height of the front box is 10mm, the length of a rolling area is set to be 55mm, the casting and rolling speed is controlled at 800mm/min, and the pressure of cooling water is controlled to be 0.3 MPa.
(2) Cold rolling process
a. Roll grinding parameters and rolling oil indexes;
parameters are as follows: the roughness of the cogging roll is 0.7um and 0mm in the middle and high, the roughness of the foil billet pass roll is 0.45um and 0mm in the middle and high, and the viscosity of the rolling oil is 2.2mm2The acid value is 0.15mgKOH/g, the flash point is 112 ℃, the rolling oil content is 8 percent, and the oil transmittance is 95 percent.
b. And (3) carrying out reduction cold rolling on the cold rolled coil by using a cold rolling mill, rolling the cold rolled coil to a thickness of 4.0-4.2mm, and rolling the cold rolled coil to 0.24mm in 6 passes to obtain the aluminum foil blank. The rolling process comprises the following steps: the method comprises the following steps of first cold rolling, uniform annealing, second cold rolling, recoiling and trimming, third cold rolling, recoiling and trimming and foil rolling, wherein the first cold rolling is performed from 7.0mm in thickness to 4.0mm in thickness; in the second cold rolling, the thickness is reduced from 4.0mm to 2.1mm, and then the thickness is reduced to 1.2 mm; in the third cold rolling, the thickness is reduced from 1.2mm to 0.68mm, then the thickness is reduced to 0.4mm, and finally the thickness is reduced to 0.24 mm.
The rolling parameters are shown in the following table:
c. adopting a uniform annealing process, and pressing again after the uniform annealing process, wherein the rolling reduction thickness is uniformly reduced to 0.24 Mm;
parameters are as follows: the uniform annealing process comprises the following steps: heating to 550 ℃ within 0 hour, preserving heat for 18 hours, cooling to 520 ℃ within 0.5 hour, preserving heat for 6 hours, and finally directly discharging from the furnace for air cooling.
d. The edge cutting of the recoiling adopts two times of edge cutting of 1.2mm and 0.24mm, and the total edge cutting amount is 60 mm.
Parameters are as follows: the blade clearance is 0.1mm, the shearing speed is 300m/min, and the uncoiling tension is 30 kn;
(3) foil rolling process:
a. foil rolling is carried out on the aluminum foil by using a rough roller and a finish roller, rolling oil is added in the foil rolling process, the rolling frequency is more than 4 times, the thickness of each rolling accounts for 32% of the total thickness before the rolling, and the pass of a finished product is controlled at 35%. The viscosity of the rough rolling oil is 1.8mm2(s), the acid value is 0.1mgKOH/g, the flash point is 86 ℃, the rolling oil content is 5 percent, and the oil product transmittance is 97 percent; the viscosity of the finish rolling oil is 1.8mm2The acid value is 0.03mgKOH/g, the flash point is 82 ℃, the rolling oil content is 4.8 percent, and the oil product transmittance is 97 percent.
The rolling parameters are shown in the following table: take 0.012mm as an example
b. And (4) rolling, namely rolling the finished product to the thickness by adopting N pieces of rolled coils. First, the two sheets are doubled together into 2 sheets, and the third sheet is rolled with the doubled 2 sheets to obtain 3 sheets.
Parameters are as follows: speed 620m/nim, coiling tensile stress 32N/mm2The pressure of the flattening roll is 3kg/c square meter;
c. and in the finished product pass, 3 pieces of aluminum foil combined by the rolling machine are subjected to overlapping rolling in a finishing mill, and the aluminum foil which is not contacted with the roller is a double-sided hidden aluminum foil product (shown in figure 1). The traditional process has the advantages that the finished product passes are only limited to 2-sheet rolling, the production efficiency is low, the invention can be used for 3-sheet rolling finished products, and the yield is obviously improved;
d. and (4) slitting, namely slitting and rewinding the aluminum foil after finish rolling, pouring out the double-sided dark aluminum foil, and then dividing the aluminum foil into finished aluminum foils for lithium batteries with different specification requirements by using a horizontal slitting machine.
Example 2
A3003 alloy double-sided dark aluminum foil for a high-strength lithium battery comprises the following components in percentage by mass: fe: 0.46%, Si: 0.08%, Cu: 0.079%, Ti: 0.023%, Mn: 1.04%, Mg: 0.003%, Zn: 0.004%, and the balance of Al.
The manufacturing method of the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery comprises the following steps:
(1) smelting, casting and rolling process
a. Firstly, putting the waste into a smelting furnace, and then putting an aluminum ingot and molten aluminum, wherein the weight of the aluminum ingot accounts for 16% of the total weight, the waste is first-grade waste, and the first-grade waste refers to plates, coiled materials, coiled waste edge materials, cast-rolled coil head tailings and emptying block materials in a standing furnace, and the thickness of the first-grade waste is not less than 1.0 mm;
parameters are as follows: solid-liquid ratio 3: 7;
b. smelting in a smelting furnace, adding alloy after smelting, introducing nitrogen and a refining agent for refining after standing, slagging off after refining, adjusting and standing components, and checking that the components are qualified;
parameters are as follows: the smelting time is 5 hours, the smelting temperature is 750 ℃, the standing time after smelting is 32 minutes, the refining time is 18 minutes, and the refining agent comprises the following components in percentage by weight: 60% of potassium chloride, 18% of sodium aluminum fluoride, 5% of hexafluorobenzene, 12% of calcium sulfide and 5% of sodium sulfate; the amount of the refining agent is 1kg/T aluminum.
c. B, sending the molten aluminum prepared in the step b into a heat preservation furnace for turning down, starting a powder injection refiner after the turning down is finished to add a refining agent into the molten aluminum in the standing furnace for secondary refining and rechecking components, slagging off after each refining is finished, refining once every certain time, wherein the refining time is 18 minutes, slagging off after standing for 7 minutes, and refining once every 1.6 hours;
parameters are as follows: the refining time of the molten aluminum in the standing furnace is 18 minutes each time, slag is removed after the standing furnace is kept for 7 minutes, the molten aluminum is refined once every 1.6 hours, the refining temperature is 750 ℃, and the refining agent consists of the following components in percentage by weight: 48% of potassium chloride, 23% of sodium aluminum fluoride, 7% of hexafluorobenzene, 12% of calcium sulfide and 10% of sodium sulfate; the amount of the refining agent is 2kg/T aluminum.
d. Degassing the aluminum liquid by adopting argon with the purity of 99.995%, adjusting the rotating speed of a graphite rotor, ensuring that the hydrogen content of the aluminum liquid is 0.1ml/100gAl, and adding Ti wires for grain refinement;
parameters are as follows: the rotation speed of the graphite rotor is 450r/min, and the speed of the added Ti wires is 220 mm/min.
e. D, sending the aluminum liquid prepared in the step d into a front box which is arranged in front of a casting and rolling machine and bears the aluminum liquid, after entering a casting nozzle, casting and rolling the aluminum liquid by a casting and rolling roller with built-in circulating water, and then coiling the aluminum liquid into a cold-rolled blank by a coiling device;
parameters are as follows: the grinding requirement of the casting roller is that the middle height is controlled to be 0.26mm, the middle-high symmetry is 0.01mm, the roughness is 0.9um, and the cylindricity of the roller reaches 0.012 mm; the temperature of the front box is controlled at 710 ℃, the liquid level height of the front box is 16mm, the length of a rolling area is set to be 58mm, the casting and rolling speed is controlled at 850mm/min, and the pressure of cooling water is controlled to be 0.35 MPa.
(2) Cold rolling process
a. Roll grinding parameters and rolling oil indexes;
parameters are as follows: the roughness of the cogging roll is 0.7um and 0mm in the middle and high, the roughness of the foil billet pass roll is 0.45um and 0mm in the middle and high, and the viscosity of the rolling oil is 2.5mm2And/s, the acid value is 0.13mgKOH/g, the flash point is 110 ℃, the rolling oil content is 8.3 percent, and the oil product transmittance is 95.4 percent.
b. And (3) carrying out reduction cold rolling on the cold rolled coil by using a cold rolling mill, rolling the cold rolled coil to a thickness of 4.0-4.2mm, and rolling the cold rolled coil to 0.24mm in 6 passes to obtain the aluminum foil blank. The rolling process comprises the following steps: the method comprises the following steps of first cold rolling, uniform annealing, second cold rolling, recoiling and trimming, third cold rolling, recoiling and trimming and foil rolling, wherein the first cold rolling is performed from 7.0mm in thickness to 4.0mm in thickness; in the second cold rolling, the thickness is reduced from 4.0mm to 2.1mm, and then the thickness is reduced to 1.2 mm; in the third cold rolling, the thickness is reduced from 1.2mm to 0.68mm, then the thickness is reduced to 0.4mm, and finally the thickness is reduced to 0.24 mm.
The rolling parameters are shown in the following table:
c. adopting a uniform annealing process, and pressing again after the uniform annealing process, wherein the rolling reduction thickness is uniformly reduced to 0.24 Mm;
parameters are as follows: the uniform annealing process comprises the following steps: heating to 550 ℃ within 0 hour, preserving heat for 19 hours, cooling to 520 ℃ within 0.8 hour, preserving heat for 6.5 hours, and finally directly discharging from the furnace for air cooling.
d. The edge cutting of the recoiling adopts two times of edge cutting of 1.2mm and 0.24mm, and the total edge cutting amount is 65 mm.
Parameters are as follows: the blade clearance is 0.1mm, the shearing speed is 320m/min, and the uncoiling tension is 33 kn;
(3) foil rolling process:
a. foil rolling is carried out on the aluminum foil by using a rough roller and a finish roller, rolling oil is added in the foil rolling process, the rolling frequency is more than 4 times, the thickness of each rolling accounts for 42% of the total thickness before the rolling, and the pass of a finished product is controlled at 36%. The viscosity of the rough rolling oil is 2.2mm2(s), the acid value is 0.08mgKOH/g, the flash point is 90 ℃, the rolling oil content is 5.3 percent, and the oil product transmittance is 97.2 percent; the viscosity of the finish rolling oil is 2.1mm2The acid value is 0.03mgKOH/g, the flash point is 82 ℃, the rolling oil content is 4.5 percent, and the oil product transmittance is 97.4 percent.
The rolling parameters are shown in the following table: take 0.012mm as an example
b. And (4) rolling, namely rolling the finished product to the thickness by adopting N pieces of rolled coils. Firstly, doubling the two sheets together into 2 sheets, then combining the third sheet with the combined 2 sheets to obtain 3 sheets, and repeating the above steps to combine 4 sheets.
Parameters are as follows: speed 630m/nim, coiling tensile stress 32N/mm2The pressure of the flattening roll is 4kg/c square meter;
c. and 4, in the finished product pass, overlapping and rolling the 4 pieces of aluminum foil combined by the rolling machine in a finishing mill, wherein the aluminum foil which is not contacted with the roller is a double-sided hidden aluminum foil product. The traditional process has the advantages that the finished product passes are only limited to 2-sheet rolling, the production efficiency is low, 4-sheet rolled finished products can be obtained, and the yield is obviously improved;
d. and (4) slitting, namely slitting and rewinding the aluminum foil after finish rolling, pouring out the double-sided dark aluminum foil, and then dividing the aluminum foil into finished aluminum foils for lithium batteries with different specification requirements by using a horizontal slitting machine.
Example 3
A3003 alloy double-sided dark aluminum foil for a high-strength lithium battery comprises the following components in percentage by mass: fe: 0.5%, Si: 0.07%, Cu: 0.09%, Ti: 0.022%, Mn: 1.02%, Mg: 0.002%, Zn: 0.004%, and the balance of Al.
The manufacturing method of the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery comprises the following steps:
(1) smelting, casting and rolling process
a. Firstly, feeding the waste into a smelting furnace, and then feeding an aluminum ingot and molten aluminum, wherein the weight of the aluminum ingot accounts for 20% of the total weight, the waste is primary waste, and the primary waste refers to plates, coiled materials, coiled waste edge materials, cast-rolled coil head tailings and emptying block materials in a standing furnace, wherein the thickness of the primary waste is more than or equal to 1.0 mm;
parameters are as follows: solid-liquid ratio 3: 7;
b. smelting in a smelting furnace, adding alloy after smelting, introducing nitrogen and a refining agent for refining after standing, slagging off after refining, adjusting and standing components, and checking that the components are qualified;
parameters are as follows: the smelting time is 6 hours, the smelting temperature is 730 ℃, the standing time after smelting is 40 minutes, the refining time is 20 minutes, and the refining agent comprises the following components in percentage by weight: 40% of potassium chloride, 28% of sodium aluminum fluoride, 9% of hexafluorobenzene, 15% of calcium sulfide and 8% of sodium sulfate; the amount of the refining agent is 1kg/T aluminum.
c. B, sending the molten aluminum prepared in the step b into a heat preservation furnace for turning down, starting a powder injection refiner after the turning down is finished to add a refining agent into the molten aluminum in the standing furnace for secondary refining and rechecking components, slagging off after each refining is finished, refining once every certain time, wherein the refining time is 20 minutes, slagging off after standing for 10 minutes, and refining once every 2 hours;
parameters are as follows: the refining time of the molten aluminum in the standing furnace is 20 minutes each time, slag is removed after the standing furnace is kept for 10 minutes, the molten aluminum is refined once every 2 hours, the refining temperature is 760 ℃, and the refining agent consists of the following components in percentage by weight: 45% of potassium chloride, 25% of sodium aluminum fluoride, 10% of hexafluorobenzene, 10% of calcium sulfide and 10% of sodium sulfate; the amount of the refining agent is 2kg/T aluminum.
d. Degassing the aluminum liquid by adopting argon with the purity of 99.995%, adjusting the rotating speed of a graphite rotor, ensuring that the hydrogen content of the aluminum liquid is 0.12ml/100gAl, and adding Ti wires for grain refinement;
parameters are as follows: the rotation speed of the graphite rotor is 500r/min, and the speed of the added Ti wires is 230 mm/min.
e. D, sending the aluminum liquid prepared in the step d into a front box which is arranged in front of a casting and rolling machine and bears the aluminum liquid, after entering a casting nozzle, casting and rolling the aluminum liquid by a casting and rolling roller with built-in circulating water, and then coiling the aluminum liquid into a cold-rolled blank by a coiling device;
parameters are as follows: the middle height of the grinding requirement of the casting roller is controlled to be 0.30mm, the middle-high symmetry degree is 0.015mm, the roughness is 1.0um, and the cylindricity of the roller reaches 0.015 mm; the temperature of the front box is controlled at 715 ℃, the liquid level height of the front box is 20mm, the length of a rolling area is set to be 60mm, the casting and rolling speed is controlled at 900mm/min, and the pressure of cooling water is controlled to be 0.4 MPa.
(2) Cold rolling process
a. Roll grinding parameters and rolling oil indexes;
parameters are as follows: the roughness of the cogging roll is 0.7um and 0mm in the middle and high, the roughness of the foil billet pass roll is 0.45um and 0mm in the middle and high, and the viscosity of the rolling oil is 2.8mm2And/s, the acid value is 0.14mgKOH/g, the flash point is 112 ℃, the rolling oil content is 8.5 percent, and the oil transmittance is 95 percent.
b. And (3) carrying out reduction cold rolling on the cold rolled coil by using a cold rolling mill, rolling the cold rolled coil to a thickness of 4.0-4.2mm, and rolling the cold rolled coil to 0.24mm in 6 passes to obtain the aluminum foil blank. The rolling process comprises the following steps: the method comprises the following steps of first cold rolling, uniform annealing, second cold rolling, recoiling and trimming, third cold rolling, recoiling and trimming and foil rolling, wherein the first cold rolling is performed from 7.0mm in thickness to 4.0mm in thickness; in the second cold rolling, the thickness is reduced from 4.0mm to 2.1mm, and then the thickness is reduced to 1.2 mm; in the third cold rolling, the thickness is reduced from 1.2mm to 0.68mm, then the thickness is reduced to 0.4mm, and finally the thickness is reduced to 0.24 mm.
The rolling parameters are shown in the following table:
c. adopting a uniform annealing process, and pressing again after the uniform annealing process, wherein the rolling reduction thickness is uniformly reduced to 0.24 Mm;
parameters are as follows: the uniform annealing process comprises the following steps: heating to 550 ℃ within 0 hour, preserving heat for 20 hours, cooling to 520 ℃ within 1 hour, preserving heat for 7 hours, and finally directly discharging from the furnace for air cooling.
d. The edge cutting of the recoiling adopts two times of edge cutting of 1.2mm and 0.24mm, and the total edge cutting amount is 70 mm.
Parameters are as follows: the blade clearance is 0.12mm, the shearing speed is 350m/min, and the uncoiling tension is 35 kn;
(3) foil rolling process:
a. foil rolling is carried out on the aluminum foil by using a rough roller and a finish roller, rolling oil is added in the foil rolling process, the rolling frequency is more than 4 times, the thickness of each rolling accounts for 45% of the total thickness before the rolling, and the pass of a finished product is controlled at 38%. The viscosity of the rough rolling oil is 2.5mm2(s), the acid value is 0.1mgKOH/g, the flash point is 88 ℃, the rolling oil content is 5.2 percent, and the oil product transmittance is 97 percent; the viscosity of the finish rolling oil is 2.2mm2The acid value is 0.03mgKOH/g, the flash point is 82 ℃, the rolling oil content is 4.3 percent, and the oil product transmittance is 97.5 percent.
The rolling parameters are shown in the following table: take 0.012mm as an example
b. And (4) rolling, namely rolling the finished product to the thickness by adopting N pieces of rolled coils. Firstly, doubling the two sheets together into 2 sheets, then combining the third sheet with the combined 2 sheets to obtain 3 sheets, and repeating the above steps to combine 5 sheets.
Parameters are as follows: speed 650m/nim, tensile coiling stress 35N/mm2The pressure of the flattening roll is 5kg/c square meter;
c. and (4) in the finished product pass, overlapping and rolling 5 pieces of aluminum foil combined by the rolling machine in a finishing mill, wherein the aluminum foil which is not contacted with the roller is a double-sided hidden aluminum foil product. The traditional process has the advantages that the finished product passes are only limited to 2-sheet rolling, the production efficiency is low, 5-sheet rolled finished products can be obtained, and the yield is obviously improved;
d. and (4) slitting, namely slitting and rewinding the aluminum foil after finish rolling, pouring out the double-sided dark aluminum foil, and then dividing the aluminum foil into finished aluminum foils for lithium batteries with different specification requirements by using a horizontal slitting machine.
Comparative example
The battery foils were prepared by the process of examples 1-5 using the chinese patent application "an aluminum foil for lithium batteries" (publication No. CN 105018799A).
The aluminum foils obtained in examples 1 to 3 and comparative example were subjected to tensile strength and elongation property tests, and end surface quality, foil surface oiliness, foil surface quality, dark surface bright spots, plate type, number of sheets of aluminum foil produced at one time were measured, and the results are shown in the following table.
From the above table, it can be seen that: (1) as can be seen from the data of examples 1-3 and comparative examples, the aluminum foils prepared in examples 1-3 were substantially equivalent in the quality of the end face, the quality of the foil face, and the bright spots of the dark face; in contrast, the tensile strength of the aluminum foil prepared in examples 1 to 3 was at least 43.69% higher than that of the comparative example; in the case of plate types, although the plate types prepared in examples 1-3 and comparative example are slightly loose with two ribs, the plate types prepared in examples 1-3 by adopting the rolling process with more than 3 sheets are obviously better than the plate types prepared by two rolling processes in comparative example; on the basis of one-time production of the number of the aluminum foils, the process of the examples 1 to 3 can produce more than 3 aluminum foils at one time, while the comparative example can produce only 2 aluminum foils, so that the aluminum foils prepared by the examples 1 to 3 are not only better in quality, but also more in production quantity, and the production efficiency is improved by more than 50%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A3003 alloy double-sided dark aluminum foil for a high-strength lithium battery is characterized by comprising the following components in percentage by mass: fe: 0.4-0.5%, Si: less than or equal to 0.10 percent, Cu: 0.05-0.09%, Ti: 0.01-0.025%, Mn: 1.0-1.1%, Mg: less than or equal to 0.005 percent, Zn: less than or equal to 0.005 percent and the balance of Al;
the manufacturing method of the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery comprises the following steps:
(1) smelting, casting and rolling process
a. Firstly, putting the waste into a smelting furnace, and then putting an aluminum ingot and molten aluminum, wherein the weight of the aluminum ingot accounts for 10-20% of the total weight;
parameters are as follows: solid-liquid ratio 3: 7;
b. smelting in a smelting furnace, adding alloy after smelting, introducing nitrogen and a refining agent for refining after standing, slagging off after refining, adjusting and standing components, and checking that the components are qualified;
parameters are as follows: the smelting time is 4-6 hours, the smelting temperature is 730-760 ℃, the standing time after smelting is 25-40 minutes, and the refining time is 15-20 minutes;
c. b, sending the molten aluminum prepared in the step b into a heat preservation furnace for turning down, starting a powder injection refiner after the turning down is finished to add a refining agent into the molten aluminum in the standing furnace for secondary refining and rechecking components, slagging off after each refining, refining once every certain time, wherein the refining time is 15-20 minutes, slagging off after standing for 5-10 minutes, and refining once every 1.5-2 hours;
parameters are as follows: refining the molten aluminum in the standing furnace for 15-20 minutes each time, slagging off after standing for 5-10 minutes, refining once every 1.5-2 hours, and refining at the temperature of 740-;
d. degassing the aluminum liquid by adopting argon, adjusting the rotating speed of a graphite rotor, ensuring that the hydrogen content of the aluminum liquid is less than or equal to 0.12ml/100gAl, and adding Ti wires for grain refinement;
parameters are as follows: the rotation speed of the graphite rotor is 400-;
e. d, sending the aluminum liquid prepared in the step d into a front box which is arranged in front of a casting and rolling machine and bears the aluminum liquid, after entering a casting nozzle, casting and rolling the aluminum liquid by a casting and rolling roller with built-in circulating water, and then coiling the aluminum liquid into a cold-rolled blank by a coiling device;
parameters are as follows: the grinding requirement of the casting roller is controlled to be 0.25-0.30mm in middle and high, the middle and high symmetry degree is 0.005-0.015mm, the roughness is 0.8-1.0um, and the cylindricity of the roller reaches 0.005-0.015 mm; the temperature of the front box is controlled to be between 700 and 715 ℃, the liquid level height of the front box is between 10 and 20mm, the length of a rolling area is between 55 and 60mm, the casting and rolling speed is controlled to be between 800 and 900mm/min, and the pressure of cooling water is controlled to be between 0.3 and 0.4 MPa;
(2) cold rolling process
a. Roll grinding parameters and rolling oil indexes;
parameters are as follows: the roughness of a cogging roll is 0.7um and 0mm high, the roughness of a foil billet pass roll is 0.45um and 0mm high, the viscosity of rolling oil is 2.1-2.8 mm/s, the acid value is less than or equal to 0.15mgKOH/g, the flash point is greater than 100 ℃, the content of the rolling oil is 8-8.5 percent, and the oil product transmittance is greater than or equal to 95 percent;
b. performing cold rolling on the cold-rolled coil by using a cold rolling mill, rolling the cold-rolled coil to a thickness of 4.0-4.2mm, and rolling the cold-rolled coil to 0.24mm in total for 6 passes to obtain an aluminum foil blank; the rolling process comprises the following steps: the method comprises the following steps of first cold rolling, uniform annealing, second cold rolling, recoiling and trimming, third cold rolling, recoiling and trimming and foil rolling, wherein the first cold rolling is performed from 7.0mm in thickness to 4.0mm in thickness; in the second cold rolling, the thickness is reduced from 4.0mm to 2.1mm, and then the thickness is reduced to 1.2 mm; in the third cold rolling, the thickness is reduced to 0.68mm from 1.2mm, then the thickness is reduced to 0.4mm, and finally the thickness is reduced to 0.24 mm;
c. adopting a uniform annealing process, and pressing again after the uniform annealing process, wherein the rolling reduction thickness is uniformly and gradually reduced to 0.24
Mm；
Parameters are as follows: the uniform annealing process comprises the following steps: heating to 550 ℃ within 0 hour, preserving heat for 18-20 hours, cooling to 520 ℃ within 0.5-1 hour, preserving heat for 6-7 hours, and finally directly discharging from the furnace for air cooling;
d. the rewinding and edge cutting adopt 1.2mm and 0.24mm for twice edge cutting, and the total edge cutting amount is 60-70 mm;
parameters are as follows: the blade clearance is 0.1-0.12mm, the shearing speed is 300-;
(3) foil rolling process:
a. foil rolling is carried out on the aluminum foil by using a rough roller and a finish roller, rolling oil is added in the foil rolling process, the rolling frequency is more than 4 times, the thickness of each rolling accounts for 30-45% of the total thickness before the rolling, the pass of a finished product is controlled to be 35-38%, the viscosity of the rough rolling oil is 1.8-2.5 mm/s, the acid value is less than or equal to 0.1mgKOH/g, the flash point is more than 85 ℃, the content of the rolling oil is 5-5.5%, and the transmittance of the oil is more than or equal to 97%; the viscosity of finish rolling oil is 1.7-2.3 mm/s, the acid value is less than or equal to 0.03mgKOH/g, the flash point is greater than 80 ℃, the content of the rolling oil is less than 5 percent, and the transmittance of the oil product is greater than or equal to 97 percent;
b. rolling, namely, converting N pieces of rolled coils into finished products of finish rolling, firstly doubling two sheets together into 2 sheets, rolling the third sheet and the closed 2 sheets again to obtain 3 sheets, and rolling N pieces by analogy;
parameters are as follows: the speed of 600 plus one square meter is 650m/nim, the coiling tensile stress is 30-35N/mm, and the flattening roller pressure is 3-5 kg/c;
c. in the finished product pass, the N pieces of aluminum foil combined by the rolling machine are rolled in a finishing mill, and the aluminum foil which is not contacted with the roller is a double-sided hidden aluminum foil product;
d. and (4) slitting, namely slitting and rewinding the aluminum foil after finish rolling, pouring out the double-sided dark aluminum foil, and then dividing the aluminum foil into finished aluminum foils for lithium batteries with different specification requirements by using a horizontal slitting machine.
2. The 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery as claimed in claim 1, which comprises the following components in percentage by mass: fe: 0.46%, Si: 0.08%, Cu: 0.079%, Ti: 0.023%, Mn: 1.04%, Mg: 0.003%, Zn: 0.004%, and the balance of Al.
3. The 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery as claimed in claim 1, wherein the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery has a thickness of 0.01-0.025mm, a tensile strength of 258.64-270.21MPa, and an elongation of 3.8-5.1%.
4. A method for manufacturing a 3003 alloy double-sided dark aluminum foil for a high-strength lithium battery according to any one of claims 1 to 3, comprising the steps of:
(1) smelting, casting and rolling process
a. Firstly, putting the waste into a smelting furnace, and then putting an aluminum ingot and molten aluminum, wherein the weight of the aluminum ingot accounts for 10-20% of the total weight;
parameters are as follows: solid-liquid ratio 3: 7;
b. smelting in a smelting furnace, adding alloy after smelting, introducing nitrogen and a refining agent for refining after standing, slagging off after refining, adjusting and standing components, and checking that the components are qualified;
parameters are as follows: the smelting time is 4-6 hours, the smelting temperature is 730-760 ℃, the standing time after smelting is 25-40 minutes, and the refining time is 15-20 minutes;
c. b, sending the molten aluminum prepared in the step b into a heat preservation furnace for turning down, starting a powder injection refiner after the turning down is finished to add a refining agent into the molten aluminum in the standing furnace for secondary refining and rechecking components, slagging off after each refining, refining once every certain time, wherein the refining time is 15-20 minutes, slagging off after standing for 5-10 minutes, and refining once every 1.5-2 hours;
parameters are as follows: refining the molten aluminum in the standing furnace for 15-20 minutes each time, slagging off after standing for 5-10 minutes, refining once every 1.5-2 hours, and refining at the temperature of 740-;
d. degassing the aluminum liquid by adopting argon, adjusting the rotating speed of a graphite rotor, ensuring that the hydrogen content of the aluminum liquid is less than or equal to 0.12ml/100gAl, and adding Ti wires for grain refinement;
parameters are as follows: the rotation speed of the graphite rotor is 400-;
e. d, sending the aluminum liquid prepared in the step d into a front box which is arranged in front of a casting and rolling machine and bears the aluminum liquid, after entering a casting nozzle, casting and rolling the aluminum liquid by a casting and rolling roller with built-in circulating water, and then coiling the aluminum liquid into a cold-rolled blank by a coiling device;
parameters are as follows: the grinding requirement of the casting roller is controlled to be 0.25-0.30mm in middle and high, the middle and high symmetry degree is 0.005-0.015mm, the roughness is 0.8-1.0um, and the cylindricity of the roller reaches 0.005-0.015 mm; the temperature of the front box is controlled to be between 700 and 715 ℃, the liquid level height of the front box is between 10 and 20mm, the length of a rolling area is between 55 and 60mm, the casting and rolling speed is controlled to be between 800 and 900mm/min, and the pressure of cooling water is controlled to be between 0.3 and 0.4 MPa;
(2) cold rolling process
a. Roll grinding parameters and rolling oil indexes;
parameters are as follows: the roughness of a cogging roll is 0.7um and 0mm high, the roughness of a foil billet pass roll is 0.45um and 0mm high, the viscosity of rolling oil is 2.1-2.8 mm/s, the acid value is less than or equal to 0.15mgKOH/g, the flash point is greater than 100 ℃, the content of the rolling oil is 8-8.5 percent, and the oil product transmittance is greater than or equal to 95 percent;
b. performing cold rolling on the cold-rolled coil by using a cold rolling mill, rolling the cold-rolled coil to a thickness of 4.0-4.2mm, and rolling the cold-rolled coil to 0.24mm in total for 6 passes to obtain an aluminum foil blank; the rolling process comprises the following steps: the method comprises the following steps of first cold rolling, uniform annealing, second cold rolling, recoiling and trimming, third cold rolling, recoiling and trimming and foil rolling, wherein the first cold rolling is performed from 7.0mm in thickness to 4.0mm in thickness; in the second cold rolling, the thickness is reduced from 4.0mm to 2.1mm, and then the thickness is reduced to 1.2 mm; in the third cold rolling, the thickness is reduced to 0.68mm from 1.2mm, then the thickness is reduced to 0.4mm, and finally the thickness is reduced to 0.24 mm;
c. adopting a uniform annealing process, and pressing again after the uniform annealing process, wherein the rolling reduction thickness is uniformly and gradually reduced to 0.24
Mm；
Parameters are as follows: the uniform annealing process comprises the following steps: heating to 550 ℃ within 0 hour, preserving heat for 18-20 hours, cooling to 520 ℃ within 0.5-1 hour, preserving heat for 6-7 hours, and finally directly discharging from the furnace for air cooling;
d. the rewinding and edge cutting adopt 1.2mm and 0.24mm for twice edge cutting, and the total edge cutting amount is 60-70 mm;
parameters are as follows: the blade clearance is 0.1-0.12mm, the shearing speed is 300-;
(3) foil rolling process:
a. foil rolling is carried out on the aluminum foil by using a rough roller and a finish roller, rolling oil is added in the foil rolling process, the rolling frequency is more than 4 times, the thickness of each rolling accounts for 30-45% of the total thickness before the rolling, the pass of a finished product is controlled to be 35-38%, the viscosity of the rough rolling oil is 1.8-2.5 mm/s, the acid value is less than or equal to 0.1mgKOH/g, the flash point is more than 85 ℃, the content of the rolling oil is 5-5.5%, and the transmittance of the oil is more than or equal to 97%; the viscosity of finish rolling oil is 1.7-2.3 mm/s, the acid value is less than or equal to 0.03mgKOH/g, the flash point is greater than 80 ℃, the content of the rolling oil is less than 5 percent, and the transmittance of the oil product is greater than or equal to 97 percent;
b. rolling, namely, converting N pieces of rolled coils into finished products of finish rolling, firstly doubling two sheets together into 2 sheets, rolling the third sheet and the closed 2 sheets again to obtain 3 sheets, and rolling N pieces by analogy;
parameters are as follows: the speed of 600 plus one square meter is 650m/nim, the coiling tensile stress is 30-35N/mm, and the flattening roller pressure is 3-5 kg/c;
c. in the finished product pass, the N pieces of aluminum foil combined by the rolling machine are rolled in a finishing mill, and the aluminum foil which is not contacted with the roller is a double-sided hidden aluminum foil product;
d. and (4) slitting, namely slitting and rewinding the aluminum foil after finish rolling, pouring out the double-sided dark aluminum foil, and then dividing the aluminum foil into finished aluminum foils for lithium batteries with different specification requirements by using a horizontal slitting machine.
5. The method for manufacturing the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery as claimed in claim 4, wherein the scrap material in the smelting and cast-rolling processes is a primary scrap material, and the primary scrap material is a plate material, a coiled scrap edge material, a cast-rolled coil end material and a standing furnace emptying block material with the thickness of more than or equal to 1.0 mm.
6. The method for manufacturing the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery as recited in claim 4, wherein the refining agent in the step b of the melting and casting-rolling process comprises the following components in percentage by weight: 40-70% of potassium chloride, 15-30% of sodium aluminum fluoride, 1-10% of hexafluorobenzene, 5-15% of calcium sulfide and 5-20% of sodium sulfate.
7. The method for manufacturing the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery as recited in claim 6, wherein the amount of the refining agent is 1kg/T aluminum.
8. The method for manufacturing the 3003 alloy double-sided dark aluminum foil for the high-strength lithium battery as recited in claim 4, wherein the refining agent in the step c of the melting and casting-rolling process comprises the following components in percentage by weight: 40-70% of potassium chloride, 15-30% of sodium aluminum fluoride, 1-10% of hexafluorobenzene, 5-15% of calcium sulfide and 5-20% of sodium sulfate.
9. The method for manufacturing a 3003 alloy double-sided dark aluminum foil for a high-strength lithium battery as claimed in claim 8, wherein the amount of the refining agent is 2kg/T aluminum.
10. The method for manufacturing a 3003 alloy double-sided dark aluminum foil for a high-strength lithium battery as claimed in claim 4, wherein the purity of the argon gas in the smelting and casting-rolling process step d is 99.995%.
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| CN111254320B (en) * | 2020-03-05 | 2022-03-15 | 江苏鼎胜新能源材料股份有限公司 | High-strength material for flexible connection of new energy power battery and manufacturing method thereof |
| CN112662916A (en) * | 2020-12-30 | 2021-04-16 | 郑州金辉新能源电子材料有限公司 | Aluminum foil for power battery and preparation process thereof |
| CN114405999B (en) * | 2021-12-16 | 2022-11-25 | 安徽中基电池箔科技有限公司 | Production process of 1060 alloy battery aluminum foil with high elongation |
| CN115247239B (en) * | 2021-12-30 | 2023-05-26 | 兰州理工大学 | Aluminum alloy strip for power battery shell and production method thereof |
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| CN115233045B (en) * | 2022-08-05 | 2023-10-13 | 厦门厦顺铝箔有限公司 | Production process of aluminum foil for high-manganese ultrahigh-strength battery |
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