CN114703404A - Aluminum foil material for low-density pinhole positive current collector of new energy lithium battery and preparation method of aluminum foil material - Google Patents

Aluminum foil material for low-density pinhole positive current collector of new energy lithium battery and preparation method of aluminum foil material Download PDF

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CN114703404A
CN114703404A CN202210201104.3A CN202210201104A CN114703404A CN 114703404 A CN114703404 A CN 114703404A CN 202210201104 A CN202210201104 A CN 202210201104A CN 114703404 A CN114703404 A CN 114703404A
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rolling
aluminum foil
current collector
aluminum
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CN114703404B (en
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徐成志
任素贞
万宝伟
王毓玮
张彩龙
孙晓璇
玛日古丽·图尔荪
王芬
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Jiangsu Dingsheng New Energy Material Co Ltd
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • 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
    • 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

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  • Mechanical Engineering (AREA)
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  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metal Rolling (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention belongs to the field of aluminum material manufacturing, and relates to an aluminum foil material for a low-density pinhole positive current collector of a new energy lithium battery and a preparation method thereof, wherein the method comprises the following steps: preparing alloy components; fe element pretreatment technology; a smelting furnace is combined with a multi-step refining technology; an online multistage composite filtration technology; a heat treatment technique; cold rolling; and (5) foil rolling. Compared with the prior art, the aluminum foil material for the positive current collector is produced by a green short-flow method, and has the characteristics of excellent mechanical property, low-density pinholes and the like through the optimization of alloying treatment, an element pretreatment technology, a composite refining technology, an online filtering technology and a processing technology. In the aspect of environmental protection, the process technology of the invention belongs to a green manufacturing technology, and compared with the traditional hot rolling technology, the process technology reduces the energy consumption and the carbon emission by more than 30 percent, and has wide application market.

Description

Aluminum foil material for low-density pinhole positive current collector of new energy lithium battery and preparation method of aluminum foil material
Technical Field
The invention belongs to the field of aluminum material manufacturing, and relates to an aluminum foil material for a low-density pinhole positive current collector of a new energy lithium battery and a preparation method thereof.
Background
With the understanding of people on the environmental protection concept, the new energy lithium battery automobile has the low-carbon and environmental-protection travel advantages and becomes the first choice of people. In recent years, the occupancy of new energy lithium battery automobiles is increased year by year, and the market demand is expanded along with the positive electrode current collector aluminum foil material of the lithium battery as a key material of the new energy lithium battery. The continuous driving mileage is continuously enlarged, the energy density of the lithium battery is higher and higher, so that the requirement on the surface density of the aluminum foil material of the positive current collector of the lithium battery is higher and higher, the thickness of the aluminum foil material of the positive current collector of the lithium battery is expected to be further reduced from 15 mu m to below 8-10 mu m, and the reduction degree reaches 33% -46%; according to the prior art, the number of the thinned pinholes can reach 50 per square meter, but the requirement of a downstream customer on the pinholes of the thinned aluminum foil material of the positive current collector of the lithium battery is not contrary to the requirement of a high-density pinhole. With the thinning of the thickness of the aluminum foil material of the current collector of the positive electrode of the lithium battery, the occurrence of pinholes is a necessary phenomenon, but how to control the aluminum foil material of the current collector of the positive electrode of the lithium battery to have no high-density pinholes needs to optimize the preparation process of the aluminum foil material of the current collector of the positive electrode of the lithium battery. In the prior art, CN 110423920A mainly aims at the 6.5 mu m soft packing foil product to improve the process and meet the requirement of packing tightness of the soft packing foil product in the service process; CN 111519050A improves the processing process of the electronic label foil 15 μm product, solves the problems of rolling dark lines, texture stripes, easy tape breakage and the like in the aluminum foil production process; CN 112921213A solves the problems that the number of pinholes per square meter of an aluminum foil for packaging 5-7 μm milk is less than 300, the aperture of the pinholes is less than 0.1mm, and the leakage of glue is avoided when downstream milk packaging customers are placed for gluing and compounding. The three prior arts do not relate to the control of the low-density pinholes in the thickness interval of 8-10 μm of the aluminum foil material of the current collector of the lithium battery and the service characteristics of the lithium battery, and meanwhile, the three prior arts adopt the traditional hot rolling technology, have the defects of high energy consumption, high pollution and the like, and do not accord with the development direction of the double-carbon policy advocated by the state. Therefore, a special technology for a lithium battery anode current collector aluminum foil material capable of meeting the low-density pinholes with the thickness interval of 8-10 μm and the service characteristics of a lithium battery is needed to meet the development requirements of new energy lithium batteries in the future.
Disclosure of Invention
In order to overcome the defects, the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery and the preparation method thereof are produced by a green short-flow casting and rolling method, and the microalloying optimization proportion, the online aluminum melt quality treatment and filtration technology and the heat treatment process optimization in the cold rolling process are adopted, so that the aluminum foil material for the positive current collector of the lithium battery can meet the service characteristics of low-density pinholes and lithium batteries in the thickness range of 8-10 mu m, and meanwhile, the aluminum foil material for the positive current collector of the lithium battery has excellent mechanical properties, is convenient for rolling a difficult-to-break strip after the positive material is coated subsequently, has the Vickers hardness of 50-60Hv, the tensile strength of 260-280MPa, the elongation of more than or equal to 3.0 percent and the number of pinholes of less than or equal to 10/square meter. The excellent mechanical property can promote the follow-up processing property of the positive current collector aluminum foil material of the lithium battery, and meanwhile, the thickness is greatly reduced, so that the energy density of the new energy lithium battery can be improved, and the cruising ability of the new energy automobile is improved. The invention adopts the casting-rolling-cold rolling process flow to replace the conventional hot rolling-cold rolling process flow, has the advantages of short flow and low production cost, and has good application prospect.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
an aluminum foil material for a low-density pinhole positive current collector of a new energy lithium battery is prepared from the following raw materials in percentage by mass: 0.4 to 0.55 percent of Fe, 0.05 to 0.1 percent of Si, 0.01 to 0.02 percent of Ti, 0.35 to 0.45 percent of Mn and the balance of aluminum; (Fe content-Si content): the Mn content is 1: 1.
The invention also provides a preparation method of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery, which is characterized by comprising the following steps of: proportioning the raw materials according to claim 1, and adding Fe element pretreated by dilute nitric acid and cleaned and dried at the bottom of a smelting furnace; after 2/3 molten aluminum is leveled, adding Si element and Mn element into a smelting furnace, synchronously adding a covering agent, and introducing mixed gas of nitrogen and argon to carry out powder blowing refining; introducing molten aluminum into a filter box, carrying out three-stage filtration, and then carrying out cast rolling through a casting and rolling machine to obtain a cast-rolling coil blank; and (4) rolling the cast-rolled coil blank for 2 passes and then carrying out heat treatment. Welding the outer ring, tightening the steel strip on the surface of the steel strip, and carrying out homogenization annealing in a high-temperature annealing furnace to obtain a semi-finished product of the aluminum coil; and cold rolling and foil rolling the obtained semi-finished product to the thickness of the finished product.
Further, the pretreatment step of the Fe element comprises the following steps: dissolving Fe element in 0.1-0.15% dilute nitric acid solution for 20-30min, washing in deionized water for 1-2h, drying in a drying box to remove water, introducing 99.5-99.7% nitrogen gas into the drying box, keeping the temperature of furnace gas at 100 ℃ and 110 ℃, and preserving the heat for 3-5 h.
Further, the refining step is as follows: adding a refining agent according to the proportion of 1.5-2.0kg/t of molten aluminum, simultaneously introducing mixed gas of nitrogen and argon to carry out powder blowing refining, wherein the refining is controlled according to 30min, and the refining is divided into 3 stages; in the first stage, 0-10min, a refining route in a smelting furnace walks according to a W-shaped route; in the second stage, 10-20min, the refining route in the smelting furnace walks according to the 'Z-shaped' route; in the third stage, 20-30min, the refining route in the smelting furnace walks according to a 'loop-shaped' route; after the operation is finished, introducing nitrogen into the smelting furnace, keeping the positive pressure in the furnace, and standing for 1 h. And when the scum can not be seen on the surface of the aluminum liquid visually, performing a converter turning procedure.
Further, in the three-stage filtration, the mesh number of the first-stage filter plates is 30PPi, the temperature in the heat preservation box is controlled to be 720-725 ℃, and argon is introduced into the filter box; the mesh number of the second-stage filter plate is 50PPi, the temperature in the heat preservation box is controlled at 714-719 ℃, and mixed gas of nitrogen and argon is introduced into the filter box; the number of the third stage filter plates is 70PPi, the temperature in the heat preservation box is controlled to be 705 plus 710 ℃, and nitrogen is introduced into the filter box.
Further, the homogenizing annealing process comprises: keeping the temperature for 10 hours at the temperature of 380 ℃ of furnace gas. And then heating to the target heating temperature of 430-.
Furthermore, the convexity of the working roll of the cold rolling mill is controlled to be 0.02-0.04mm, the roughness Ra value is 0.2-0.3 mu m, the online plate type is controlled to be 7-10I during rolling, the oil temperature is controlled to be 38-43 ℃, the flow of an oil nozzle is controlled to be 48-55 percent, and the acid value of an oil product is controlled to be 0.1-0.25 mgKOH/g. Wherein the ash content of the rolling oil is controlled to be 5-8 g/L.
Furthermore, in the foil rolling process, the rolling oil additive is controlled to be 5-15%, the online plate type is controlled to be 3-5I, and the temperature of the rolling oil is controlled to be 40-50 ℃.
Further, carrying out metallographic analysis on the homogenized coiled material, wherein the size of second-phase particles is controlled to be 1-5 mu m, and the second-phase particles are uniformly distributed; wherein the particles with the size of 1-3 μm account for more than 80%.
Further, the volume ratio of argon to nitrogen in the mixed gas of nitrogen and argon is 1: 1.
A preparation method of an aluminum foil material for a low-density pinhole positive current collector of a new energy lithium battery comprises the following steps:
(1) preparing alloy components: according to (Fe content-Si content, i.e. mass of iron minus mass of silicon): 1:1 (mass percent), 0.4-0.55% of Fe, 0.05-0.1% of Si, 0.01-0.02% of Ti, 0.35-0.45% of Mn and the balance of aluminum, wherein the sum of the weight percentages of Fe, Si, Ti, Mn and Al is 100%. And (4) carrying out alloy element proportioning.
(2) Fe element pretreatment technology: proportioning the alloys in the step (1) according to a proportion, adding a pretreated Fe element at the bottom of a smelting furnace, wherein the pretreatment process comprises the steps of dissolving the Fe element in a 0.1-0.15% dilute nitric acid solution for 20-30min, then transferring the solution into deionized water for cleaning for 1-2h, putting the solution into a drying box for removing moisture, introducing 99.5-99.7% nitrogen protection gas into the drying box, keeping the temperature of furnace gas at 100 ℃ and 110 ℃, and preserving the heat for 3-5 h.
(3) Smelting furnace composite multi-step refining technology: when the molten aluminum 2/3 is leveled, Si element and Mn element are added into the smelting furnace, and covering agent of 2-3kg/t molten aluminum is synchronously added to prevent the molten aluminum from further oxidizing and slagging. And (3) refining 2-4 hours after the covering agent is added, adding the refining agent according to the proportion of 1.5-2.0kg/t of aluminum water, introducing mixed gas of nitrogen and argon (volume ratio, argon: nitrogen is 1:1) at the same time, blowing powder for refining, controlling the refining for 30min, and totally dividing into 3 stages. In the first stage, 0-10min, a refining route in a smelting furnace walks according to a W-shaped route; in the second stage, 10-20min, the refining route in the smelting furnace walks according to the 'Z-shaped' route; in the third stage, 20-30min, the refining route in the smelting furnace walks according to a 'loop-shaped' route; after the operation is finished, introducing nitrogen into the smelting furnace, keeping the positive pressure in the furnace, and standing for 1 hour. And when the scum can not be seen on the surface of the aluminum liquid visually, performing a converter turning procedure.
(4) The online multistage composite filtering technology comprises the following steps: introducing the aluminum water treated in the step (3) into a filter box, wherein the filter box adopts a three-stage filtering process, the number of first-stage filter plates is 30PPi, the temperature in a heat preservation box is controlled to be 720-; the number of the second stage filter plates is 50PPi, the temperature in the heat preservation box is controlled at 714-719 ℃, and a mixed gas of nitrogen and argon is introduced into the filter box (volume ratio, argon: nitrogen is 1: 1); the mesh number of the third-stage filter plate is 70PPi, the temperature in the heat preservation box is controlled at 705-710 ℃, and nitrogen is introduced into the filter box; then the molten aluminum is passed through a casting and rolling machine to obtain a cast and rolled coil blank with the thickness of 6.8 mm.
(5) The heat treatment technology comprises the following steps: and (4) rolling the cast-rolled coil obtained in the step (4) for 2 passes, and then carrying out heat treatment. And (3) welding an outer ring, tightening a steel strip on the surface of the steel strip, carrying out homogenization annealing in a high-temperature annealing furnace, and keeping the temperature for 10 hours at the furnace gas temperature of 380 ℃. Then heating to a target heating temperature of 430-; and carrying out metallographic analysis on the homogenized coiled material, wherein the size of second phase particles is controlled to be 1-5 mu m, and the second phase particles are uniformly distributed. Wherein the particles with the size of 1-3 μm account for more than 80%. After the standard is reached, the next process is carried out, the probability of generating pinholes is reduced as the size of the second phase is smaller, and otherwise, the size of the second phase is large, and the large-density pinholes are generated.
(6) Cold rolling: and (3) rolling the semi-finished product obtained in the step (5) to 0.15-0.25mm, wherein the convexity of a working roll of a cold rolling machine is controlled to be 0.02-0.04mm, the roughness Ra value is 0.2-0.3 mu m, the online plate shape is controlled to be 7-10I during rolling, the oil temperature is controlled to be 38-43 ℃, the flow of an oil nozzle is controlled to be 48-55 percent, and the acid value of an oil product is controlled to be 0.1-0.25 mgKOH/g. Wherein the ash content of the rolling oil is controlled to be 5-8 g/L.
(7) Foil rolling: transferring the material obtained in the step (6) to a foil rolling mill, and rolling the material to a finished product with the diameter of 8-10 mu m by 3-5 rollers, wherein the rolling oil additive is controlled to be 5-15% (weight percentage), the online plate type is controlled to be 3-5I, and the rolling oil temperature is controlled to be 40-50 ℃. And after the finished product is off-line, carrying out off-line pinhole inspection in a darkroom.
The finished product of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery, which is obtained by the invention, has the Vickers hardness of 50-60Hv, the tensile strength of 260-280MPa, the elongation of more than or equal to 3.0 percent and the number of pinholes of less than or equal to 10 per square meter.
Advantageous effects
Compared with the traditional aluminum foil material for the positive current collector produced by hot rolling and cold rolling, the production process of the aluminum foil material for the positive current collector has the advantages of short flow, low energy consumption and the like. Hair brushThe conventional hot rolling process of the Ming flow part produces products of the same type, the period is reduced from 30 days to 15 days, the period is shortened by more than 15 days, and the production period is shortened by more than 30 percent; in the aspects of energy consumption and carbon emission, hot rolling face milling and hot rolling procedures are omitted, and the energy consumption is reduced by more than 30%. The technical innovation aspect has the following advantages that (a) the special pretreatment process technology of the raw material Fe element is utilized to eliminate Fe2O3And Fe3O4And the like, which affect the pinholes; (b) meanwhile, the method is matched with the technical modes of eliminating foreign matters in the molten aluminum by online three-stage filtration, introducing mixed inert shielding gas to prevent molten aluminum from slagging and the like; (c) the smelting furnace is utilized to carry out comprehensive refining on the aluminum melt by utilizing a composite multi-step refining technology, the purity of the aluminum melt is ensured, and after the refining is finished, inert protective gas is introduced into the furnace to prevent the aluminum liquid from being oxidized doubly; and (d) the homogenization treatment process and the cold foil rolling process are optimized, so that the particles of the material tend to be dispersed and distributed, the particle size is fine and uniform, and the particle size of the second phase is controlled to be 1-5 mu m and is distributed uniformly. Wherein the particles with the size of 1-3 mu m account for more than 80 percent, thereby further reducing the probability of generating pinholes; (e) meanwhile, properly adding Mn element according to the following ratio (Fe content-Si content): the Mn content is 1:1, and when the Fe element which is easy to form a coarse alloy phase is in priority to the Si element, an alpha-Al-Fe-Si ternary phase is formed; the rest of Fe element and MnAl6Form a dispersed and distributed replacement solid solution (Mn, Fe) Al6Alloy phase, thereby providing precise control over the size of the second phase particles in the material. Therefore, the aluminum foil material for the positive current collector has the characteristics of excellent mechanical property, low-density pinholes and the like, the Vickers hardness is 50-60Hv, the tensile strength is 260-280MPa, and the elongation is more than or equal to 3.0%. Compared with the pinhole density of 50 per square meter for producing the aluminum foil material for the positive current collector in the prior art, the pinhole number density of the aluminum foil material for the positive current collector is less than or equal to 10 per square meter, and compared with the pinhole density, the pinhole density is greatly reduced by more than 80 percent. In the aspect of environmental protection, the process technology of the invention belongs to a green manufacturing technology, and compared with the traditional hot rolling technology, the process technology reduces the energy consumption and the carbon emission by more than 30 percent, and has wide application market.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
An aluminum foil material for a low-density pinhole positive current collector of a new energy lithium battery comprises the following steps,
example 1:
(1) preparing alloy components: according to the weight percentage, the Fe content (the weight percentage is below) is 0.4 percent, the Si content is 0.05 percent, the Ti content is 0.01 percent, the Mn content is 0.35 percent, and the balance is aluminum, wherein the sum of the weight percentages of Fe, Si, Ti, Mn and Al is 100 percent. And (4) proportioning alloy elements.
(2) Fe element pretreatment technology: proportioning the alloys in the step (1) according to a proportion, adding a pretreated Fe element at the bottom of a smelting furnace, wherein the pretreatment process comprises the steps of dissolving the Fe element in 0.1% dilute nitric acid solution for 30min, washing in deionized water for 1h, removing water in a drying box, introducing 99.5% nitrogen protection gas into the drying box, keeping the temperature of furnace gas at 100 ℃ for 5 h.
(3) Smelting furnace composite multi-step refining technology: when the molten aluminum 2/3 is leveled, Si element and Mn element are added into the smelting furnace, and covering agent of 2kg/t molten aluminum is synchronously added to prevent the molten aluminum from further oxidizing and slagging. And 2 hours, carrying out a refining process, adding a refining agent according to the proportion of 1.5kg/t of aluminum water, introducing a mixed gas of nitrogen and argon (volume ratio, argon: nitrogen is 1:1) at the same time, blowing powder for refining, and controlling the refining according to 30min and dividing into 3 stages in total. In the first stage, 0-10min, the refining route in the smelting furnace is carried out according to a W-shaped route; in the second stage, 10-20min, the refining route in the smelting furnace walks according to the 'Z-shaped' route; in the third stage, 20-30min, the refining route in the smelting furnace walks according to a 'loop-shaped' route; after the operation is finished, introducing nitrogen into the smelting furnace, keeping the positive pressure in the furnace, and standing for 1 h. And when the scum can not be seen on the surface of the aluminum liquid visually, performing a converter turning procedure.
(4) The online multistage composite filtration technology comprises the following steps: introducing the aluminum water treated in the step (3) into a filter box, wherein the filter box adopts a three-stage filtering process, the number of first-stage filter plates is 30PPi, the temperature in a heat preservation box is controlled at 720 ℃, and argon is introduced into the filter box; the number of the second stage filter plates is 50PPi, the temperature in the heat preservation box is controlled at 714 ℃, and a mixed gas of nitrogen and argon is introduced into the filter box (volume ratio, argon: nitrogen is 1: 1); the number of the third stage filter plates is 70PPi, the temperature in the heat preservation box is controlled at 705 ℃, and nitrogen is introduced into the filter box; then the molten aluminum is passed through a casting and rolling machine to obtain a cast and rolled coil blank with the thickness of 6.8 mm.
(5) The heat treatment technology comprises the following steps: and (4) rolling the cast-rolled coil obtained in the step (4) for 2 passes, and then carrying out heat treatment. And welding the outer ring, tightening the steel strip on the surface of the steel strip, carrying out homogenization annealing in a high-temperature annealing furnace, and keeping the temperature for 10 hours at the furnace gas temperature of 380 ℃. Heating to a target heating temperature of 430 ℃ at a speed of 3 ℃/min, preserving heat for 5 hours after the target heating temperature is reached, cooling furnace gas at a speed of 5 ℃/min, immediately discharging the furnace gas when the temperature of the furnace gas reaches 280 ℃, and then air-cooling to obtain a semi-finished product of the aluminum coil; and carrying out metallographic analysis on the homogenized coiled material, wherein the size of the second phase particles is controlled to be 1-5 mu m, and the second phase particles are uniformly distributed. Wherein particles of 1-3 μm size account for 85%.
(6) Cold rolling: and (3) rolling the semi-finished product obtained in the step (5) to 0.15mm, wherein the convexity of a working roll of a cold rolling mill is controlled to be 0.02mm, the roughness Ra value is 0.2 mu m, the online plate type is controlled to be 7I during rolling, the oil temperature is controlled to be 38 ℃, the flow of an oil nozzle is controlled to be 48 percent, and the acid value of an oil product is controlled to be 0.1 mgKOH/g. Wherein the ash content of the rolling oil is controlled at 5 g/L.
(7) Foil rolling: transferring the material obtained in the step (6) to a foil rolling mill, and rolling the material to a finished product with the diameter of 8 mu m by 3-5 rollers, wherein the rolling oil additive is controlled at 5% (weight percentage), the online plate type is controlled at 3I, and the rolling oil temperature is controlled at 40 ℃. And after the finished product is off-line, carrying out off-line pinhole inspection in a darkroom.
The finished product of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery has the Vickers hardness of 50Hv, the tensile strength of 260MPa, the elongation of 3.2 percent and the number of pinholes of 6 per square meter.
Example 2:
(1) preparing alloy components: according to the weight percentage of Fe content (the weight percentage is below) 0.55%, Si content 0.1%, Ti content 0.02%, Mn content 0.45% and the balance of aluminum, wherein the sum of the weight percentage of Fe, Si, Ti, Mn and Al is 100%. And (4) carrying out alloy element proportioning.
(2) Fe element pretreatment technology: proportioning the alloys in the step (1) according to a proportion, adding a pretreated Fe element at the bottom of a smelting furnace, wherein the pretreatment process comprises the steps of dissolving the Fe element in 0.15% dilute nitric acid solution for 20min, washing in deionized water for 2h, removing water in a drying box, introducing 99.7% nitrogen protection gas into the drying box, keeping the temperature of furnace gas at 110 ℃ for 5 h.
(3) Smelting furnace composite multi-step refining technology: when the molten aluminum 2/3 is leveled, Si element and Mn element are added into the smelting furnace, and 3kg/t of aluminum water covering agent is synchronously added to prevent the aluminum liquid from further oxidizing and slagging. And 4 hours of refining, adding a refining agent according to the proportion of 2.0kg/t of aluminum water, introducing a mixed gas of nitrogen and argon (volume ratio, argon: nitrogen is 1:1) at the same time, blowing powder for refining, and controlling the refining for 30min and totally dividing into 3 stages. In the first stage, 0-10min, the refining route in the smelting furnace is carried out according to a W-shaped route; in the second stage, 10-20min, the refining route in the smelting furnace runs according to the 'Z-shaped' route; in the third stage, 20-30min, the refining route in the smelting furnace walks according to a 'loop-shaped' route; after the operation is finished, introducing nitrogen into the smelting furnace, keeping the positive pressure in the furnace, and standing for 1 h. And when the scum can not be seen on the surface of the aluminum liquid visually, performing a converter turning procedure.
(4) The online multistage composite filtration technology comprises the following steps: introducing the aluminum water treated in the step (3) into a filter box, wherein the filter box adopts a three-stage filtering process, the number of first-stage filter plates is 30PPi, the temperature in a heat preservation box is controlled at 725 ℃, and argon is introduced into the filter box; the mesh number of the second stage filter plate is 50PPi, the temperature in the heat preservation box is controlled at 719 ℃, and a mixed gas of nitrogen and argon is introduced into the filter box (volume ratio, argon: nitrogen is 1: 1); the number of the third stage filter plates is 70PPi, the temperature in the heat preservation box is controlled at 710 ℃, and nitrogen is introduced into the filter box; the molten aluminum then passed through a cast-rolling mill to obtain cast-rolled coil stock of 6.8mm thickness.
(5) The heat treatment technology comprises the following steps: and (4) rolling the cast-rolled coil obtained in the step (4) for 2 passes, and then carrying out heat treatment. And welding the outer ring, tightening the steel strip on the surface of the steel strip, carrying out homogenization annealing in a high-temperature annealing furnace, and keeping the temperature for 10 hours at the furnace gas temperature of 380 ℃. Heating to a target heating temperature of 480 ℃ at the speed of 5 ℃/min, preserving heat for 3h after the target heating temperature is reached, cooling furnace gas at the speed of 8 ℃/min, immediately discharging the furnace gas when the furnace gas reaches 280 ℃, and then air-cooling to obtain a semi-finished product of the aluminum coil; and carrying out metallographic analysis on the homogenized coiled material, wherein the size of the second phase particles is controlled to be 1-5 mu m, and the second phase particles are uniformly distributed. Wherein the particles with the size of 1-3 μm account for 88%.
(6) Cold rolling: and (3) rolling the semi-finished product obtained in the step (5) to 0.25mm, wherein the convexity of a working roll of a cold rolling mill is controlled to be 0.04mm, the roughness Ra value is 0.3 mu m, the online plate type is controlled to be 10I during rolling, the oil temperature is controlled to be 43 ℃, the flow of an oil nozzle is controlled to be 55 percent, and the acid value of an oil product is controlled to be 0.25 mgKOH/g. Wherein the ash content of the rolling oil is controlled at 8 g/L.
(7) Foil rolling: transferring the material obtained in the step (6) to a foil rolling mill, and rolling the material to a finished product with the diameter of 10 mu m by 3-5 rollers, wherein the additive of the rolling oil is controlled at 15% (weight percentage), the online plate type is controlled at 5I, and the temperature of the rolling oil is controlled at 50 ℃. And after the finished product is off-line, carrying out off-line pinhole inspection in a darkroom.
The finished product of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery, which is obtained by the invention, has the Vickers hardness of 60Hv, the tensile strength of 280Mpa, the elongation of 3.8 percent and the number of pinholes of 3 per square meter.
Comparative example 1
Preparing alloy components: according to the weight percentage of Fe content (the weight percentage is below) 0.35%, Si content 0.15%, Ti content 0.05%, Mn content 0.15% and the balance of aluminum, wherein the sum of the weight percentage of Fe, Si, Ti, Mn and Al is 100%. And (4) carrying out alloy element proportioning. The remaining production steps are carried out according to the example 1, and the finished product of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery, which has the Vickers hardness of 45Hv, the tensile strength of 220Mpa, the elongation of 2.3 percent and the number of pinholes of 45 per square meter, is obtained.
Compared with the embodiment 1, in the embodiment, because the proportion of Fe, Si and Mn elements is unreasonable, a large amount of Fe elements have no corresponding alloy element proportion, so that the embodiment has large Fe-Al phases distributed in a needle shape in the subsequent production process, the pinholes of the product are increased, and the number of the pinholes is 45 per square meter; the mechanical property is reduced, the tensile strength is 220Mpa, and the elongation is 2.3 percent.
Comparative example 2
1) Preparing alloy components: according to the weight percentage, the Fe content (the weight percentage is below) is 0.4 percent, the Si content is 0.05 percent, the Ti content is 0.01 percent, the Mn content is 0.35 percent, and the balance is aluminum, wherein the sum of the weight percentage of Fe, Si, Ti, Mn and Al is 100 percent. And (4) carrying out alloy element proportioning.
(2) Smelting furnace composite multi-step refining technology: and (2) proportioning the alloys in the step (1) according to a proportion, adding Si and Mn elements into a smelting furnace after 2/3 molten aluminum is leveled, and synchronously adding 2kg/t of a covering agent of the molten aluminum to prevent the molten aluminum from being further oxidized and slagging. And 2 hours, carrying out a refining process, adding a refining agent according to the proportion of 1.5kg/t of aluminum water, introducing a mixed gas of nitrogen and argon (volume ratio, argon: nitrogen is 1:1) at the same time, blowing powder for refining, and controlling the refining according to 30min and dividing into 3 stages in total. In the first stage, 0-10min, a refining route in a smelting furnace walks according to a W-shaped route; in the second stage, 10-20min, the refining route in the smelting furnace runs according to the 'Z-shaped' route; in the third stage, 20-30min, the refining route in the smelting furnace walks according to a 'loop-shaped' route; after the operation is finished, introducing nitrogen into the smelting furnace, keeping the positive pressure in the furnace, and standing for 1 h. And when the scum can not be seen on the surface of the aluminum liquid visually, performing a converter turning procedure.
(3) The online multistage composite filtration technology comprises the following steps: introducing the aluminum water treated in the step (2) into a filter box, wherein the filter box adopts a three-stage filtering process, the number of first-stage filter plates is 30PPi, the temperature in a heat preservation box is controlled at 720 ℃, and argon is introduced into the filter box; the number of the second stage filter plates is 50PPi, the temperature in the heat preservation box is controlled at 714 ℃, and a mixed gas of nitrogen and argon is introduced into the filter box (volume ratio, argon: nitrogen is 1: 1); the number of the third stage filter plates is 70PPi, the temperature in the heat preservation box is controlled at 705 ℃, and nitrogen is introduced into the filter box; the molten aluminum then passed through a cast-rolling mill to obtain cast-rolled coil stock of 6.8mm thickness.
(4) The heat treatment technology comprises the following steps: and (4) rolling the cast-rolled coil obtained in the step (3) for 2 passes, and then carrying out heat treatment. And welding the outer ring, tightening the steel strip on the surface of the steel strip, carrying out homogenization annealing in a high-temperature annealing furnace, and keeping the temperature for 10 hours at the furnace gas temperature of 380 ℃. Heating to a target heating temperature of 430 ℃ according to 3 ℃/min, keeping the temperature for 5h after the target heating temperature is reached, then cooling the furnace gas according to 5 ℃/min, immediately discharging the furnace gas when the furnace gas temperature reaches 280 ℃, and then air-cooling to obtain a semi-finished product of the aluminum coil; and carrying out metallographic analysis on the homogenized coiled material, wherein the size of the second phase particles is controlled to be 1-5 mu m, and the second phase particles are uniformly distributed. Wherein particles of 1-3 μm size account for 85%.
(5) Cold rolling: and (3) rolling the semi-finished product obtained in the step (4) to 0.15mm, wherein the convexity of a working roll of a cold rolling mill is controlled to be 0.02mm, the roughness Ra value is 0.2 mu m, the online plate type is controlled to be 7I during rolling, the oil temperature is controlled to be 38 ℃, the flow of an oil nozzle is controlled to be 48 percent, and the acid value of an oil product is controlled to be 0.1 mgKOH/g. Wherein the ash content of the rolling oil is controlled at 5 g/L.
(6) Foil rolling: transferring the material obtained in the step (5) to a foil rolling mill, and rolling the material to a finished product with the diameter of 8 mu m by 3-5 rollers, wherein the rolling oil additive is controlled at 5% (weight percentage), the online plate type is controlled at 3I, and the rolling oil temperature is controlled at 40 ℃. And after the finished product is off-line, carrying out off-line pinhole inspection in a darkroom.
The finished product of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery, which is obtained by the invention, has the Vickers hardness of 50Hv, the tensile strength of 260MPa, the elongation of 3.2 percent and the number of pinholes of 35 per square meter.
Compared with the example 1, in the example, because of the lack of the Fe element treatment process, the oxide of the Fe element is an important reason causing the exceeding of the pinhole of the aluminum foil, the oxide of the Fe generally exists in the aluminum foil in the form of inclusion, and the oxide of the Fe falls out of the aluminum foil along with the reduction of the thickness of the aluminum foil, so that the elongation percentage of the surface of a finished product is 3.2 percent, the number of the pinholes is 35 per square meter, the formed pinholes exceed the standard, and the mechanical property is reduced.
Comparative example 3
(1) Preparing alloy components: according to the weight percentage of Fe content (the weight percentage is below) 0.4%, Si content 0.05%, Ti content 0.01%, Mn content 0.35%, and the rest is aluminum, wherein the sum of the weight percentage of Fe, Si, Ti, Mn and Al is 100%. And (4) carrying out alloy element proportioning.
(2) Fe element pretreatment technology: proportioning the alloys in the step (1) according to a proportion, adding a pretreated Fe element at the bottom of a smelting furnace, wherein the pretreatment process comprises the steps of dissolving the Fe element in 0.1% dilute nitric acid solution for 30min, washing in deionized water for 1h, removing water in a drying box, introducing 99.5% nitrogen protection gas into the drying box, keeping the temperature of furnace gas at 100 ℃ for 5 h.
(3) The online multistage composite filtration technology comprises the following steps: introducing the aluminum water treated in the step (2) into a filter box, wherein the filter box adopts a three-stage filtering process, the number of first-stage filter plates is 30PPi, the temperature in a heat preservation box is controlled at 720 ℃, and argon is introduced into the filter box; the number of the second stage filter plates is 50PPi, the temperature in the heat preservation box is controlled at 714 ℃, and a mixed gas of nitrogen and argon is introduced into the filter box (volume ratio, argon: nitrogen is 1: 1); the number of the third stage filter plates is 70PPi, the temperature in the heat preservation box is controlled at 705 ℃, and nitrogen is introduced into the filter box; the molten aluminum then passed through a cast-rolling mill to obtain cast-rolled coil stock of 6.8mm thickness.
(4) The heat treatment technology comprises the following steps: and (4) rolling the cast-rolled coil obtained in the step (3) for 2 passes, and then carrying out heat treatment. And welding the outer ring, tightening the steel strip on the surface of the steel strip, carrying out homogenization annealing in a high-temperature annealing furnace, and keeping the temperature for 10 hours at the furnace gas temperature of 380 ℃. Heating to a target heating temperature of 430 ℃ according to 3 ℃/min, keeping the temperature for 5h after the target heating temperature is reached, then cooling the furnace gas according to 5 ℃/min, immediately discharging the furnace gas when the furnace gas temperature reaches 280 ℃, and then air-cooling to obtain a semi-finished product of the aluminum coil; and carrying out metallographic analysis on the homogenized coiled material, wherein the size of the second phase particles is controlled to be 1-5 mu m, and the second phase particles are uniformly distributed. Wherein particles of 1-3 μm size account for 85%.
(5) Cold rolling: and (3) rolling the semi-finished product obtained in the step (4) to 0.15mm, wherein the convexity of a working roll of a cold rolling mill is controlled to be 0.02mm, the roughness Ra value is 0.2 mu m, the online plate type is controlled to be 7I during rolling, the oil temperature is controlled to be 38 ℃, the flow of an oil nozzle is controlled to be 48 percent, and the acid value of an oil product is controlled to be 0.1 mgKOH/g. Wherein the ash content of the rolling oil is controlled at 5 g/L.
(6) Foil rolling: transferring the material obtained in the step (5) to a foil rolling mill, and rolling the material to a finished product with the diameter of 8 mu m by 3-5 rollers, wherein the rolling oil additive is controlled to be 5 percent (weight percentage), the online plate type is controlled to be 3I, and the rolling oil temperature is controlled to be 40 ℃. And after the finished product is off-line, carrying out off-line pinhole inspection in a darkroom.
The finished product of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery has the Vickers hardness of 50Hv, the tensile strength of 260MPa, the elongation of 3.2 percent and the number of pinholes of 55 per square meter.
Compared with the embodiment 1, the composite refining process is absent in the embodiment, on one hand, the aluminum alloy is easy to react with water in air and materials in the smelting process, and the phenomenon that the hydrogen content of the aluminum melt exceeds the standard is generated; on the other hand, the aluminum melt is contacted with air in the smelting process, and the slagging phenomenon occurs. Both the two phenomena need refining process to process, and if no refining process is carried out, the phenomena that the number of pinholes is 55 per square meter and the pinholes exceed standards in the example can be caused.
Comparative example 4
(1) Preparing alloy components: according to the weight percentage, the Fe content (the weight percentage is below) is 0.4 percent, the Si content is 0.05 percent, the Ti content is 0.01 percent, the Mn content is 0.35 percent, and the balance is aluminum, wherein the sum of the weight percentages of Fe, Si, Ti, Mn and Al is 100 percent. And (4) carrying out alloy element proportioning.
(2) Fe element pretreatment technology: proportioning the alloys in the step (1) according to a proportion, adding a pretreated Fe element at the bottom of a smelting furnace, wherein the pretreatment process comprises the steps of dissolving the Fe element in 0.1% dilute nitric acid solution for 30min, washing in deionized water for 1h, removing water in a drying box, introducing 99.5% nitrogen protection gas into the drying box, keeping the temperature of furnace gas at 100 ℃ for 5 h.
(3) Smelting furnace composite multi-step refining technology: when the molten aluminum 2/3 is leveled, Si element and Mn element are added into the smelting furnace, and 2kg/t of aluminum water covering agent is synchronously added to prevent the aluminum liquid from further oxidizing and slagging. And 2 hours, carrying out a refining process, adding a refining agent according to the proportion of 1.5kg/t of aluminum water, introducing a mixed gas of nitrogen and argon (volume ratio, argon: nitrogen is 1:1) at the same time, blowing powder for refining, and controlling the refining according to 30min and dividing into 3 stages in total. In the first stage, 0-10min, the refining route in the smelting furnace is carried out according to a W-shaped route; in the second stage, 10-20min, the refining route in the smelting furnace walks according to the 'Z-shaped' route; in the third stage, 20-30min, the refining route in the smelting furnace walks according to a 'loop-shaped' route; after the operation is finished, introducing nitrogen into the smelting furnace, keeping the positive pressure in the furnace, and standing for 1 h. And when the scum can not be seen on the surface of the aluminum liquid visually, performing a converter turning procedure. Then the molten aluminum passes through a casting and rolling machine to obtain a casting and rolling coil blank with the thickness of 6.8 mm.
(4) The heat treatment technology comprises the following steps: and (4) rolling the cast-rolled coil obtained in the step (3) for 2 passes, and then carrying out heat treatment. And welding the outer ring, tightening the steel strip on the surface of the steel strip, carrying out homogenization annealing in a high-temperature annealing furnace, and keeping the temperature for 10 hours at the furnace gas temperature of 380 ℃. Heating to a target heating temperature of 430 ℃ according to 3 ℃/min, keeping the temperature for 5h after the target heating temperature is reached, then cooling the furnace gas according to 5 ℃/min, immediately discharging the furnace gas when the furnace gas temperature reaches 280 ℃, and then air-cooling to obtain a semi-finished product of the aluminum coil; and carrying out metallographic analysis on the homogenized coiled material, wherein the size of the second phase particles is controlled to be 1-5 mu m, and the second phase particles are uniformly distributed. Wherein particles of 1-3 μm size account for 85%.
(5) Cold rolling: and (3) rolling the semi-finished product obtained in the step (4) to 0.15mm, wherein the convexity of a working roll of a cold rolling mill is controlled to be 0.02mm, the roughness Ra value is 0.2 mu m, the online plate type is controlled to be 7I during rolling, the oil temperature is controlled to be 38 ℃, the flow of an oil nozzle is controlled to be 48 percent, and the acid value of an oil product is controlled to be 0.1 mgKOH/g. Wherein the ash content of the rolling oil is controlled at 5 g/L.
(6) Foil rolling: transferring the material obtained in the step (5) to a foil rolling mill, and rolling the material to a finished product with the diameter of 8 mu m by 3-5 rollers, wherein the rolling oil additive is controlled to be 5 percent (weight percentage), the online plate type is controlled to be 3I, and the rolling oil temperature is controlled to be 40 ℃. And after the finished product is off-line, carrying out off-line pinhole inspection in a darkroom.
The finished product of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery has the Vickers hardness of 50Hv, the tensile strength of 260MPa, the elongation of 3.2 percent and the number of pinholes of 30 per square meter.
Compared with the embodiment 1, the online multistage composite filtration technology process is absent in the embodiment, on one hand, in the smelting process of the aluminum alloy, the non-metal oxide in the hearth and the launder can be mixed into the aluminum melt, and due to overlarge density and size, the foreign matter can not be cleaned out by the conventional refining and degassing process and can be continuously mixed into the aluminum melt, the online filtration process is required for treatment, and if the filtration process is not adopted, the phenomena that the number of pinholes is 30 per square meter and the number of the pinholes exceeds the standard can be caused.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery is characterized by being prepared from the following raw materials in percentage by mass: 0.4 to 0.55 percent of Fe, 0.05 to 0.1 percent of Si, 0.01 to 0.02 percent of Ti, 0.35 to 0.45 percent of Mn and the balance of aluminum; (Fe content-Si content): the Mn content is 1: 1.
2. The preparation method of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein the method comprises the following steps: proportioning the raw materials according to claim 1, and adding Fe element pretreated by dilute nitric acid and cleaned and dried at the bottom of a smelting furnace; after 2/3 molten aluminum is leveled, adding Si element and Mn element into a smelting furnace, synchronously adding a covering agent, and introducing mixed gas of nitrogen and argon to carry out powder blowing refining; introducing molten aluminum into a filter box, carrying out three-stage filtration, and then carrying out cast rolling through a casting and rolling machine to obtain a cast-rolling coil blank; and (4) rolling the cast-rolled coil blank for 2 passes and then carrying out heat treatment. Welding the outer ring, tightening the steel strip on the surface of the steel strip, and carrying out homogenization annealing in a high-temperature annealing furnace to obtain a semi-finished product of the aluminum coil; and cold rolling and foil rolling the obtained semi-finished product to the thickness of the finished product.
3. The preparation method of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein the pretreatment step of Fe element is as follows: dissolving Fe element in 0.1-0.15% dilute nitric acid solution for 20-30min, washing in deionized water for 1-2h, removing water in a drying box, introducing 99.5-99.7% nitrogen gas into the drying box, keeping the temperature of furnace gas at 100-.
4. The preparation method of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein the refining step is as follows: adding a refining agent according to the proportion of 1.5-2.0kg/t of aluminum water, and simultaneously introducing mixed gas of nitrogen and argon to carry out powder blowing refining, wherein the refining is controlled according to 30min, and the refining is divided into 3 stages; in the first stage, 0-10min, a refining route in a smelting furnace walks according to a W-shaped route; in the second stage, 10-20min, the refining route in the smelting furnace walks according to the 'Z-shaped' route; in the third stage, 20-30min, the refining route in the smelting furnace walks according to a 'loop-shaped' route; after the operation is finished, introducing nitrogen into the smelting furnace, keeping the positive pressure in the furnace, and standing for 1 h. And when the scum can not be seen on the surface of the aluminum liquid visually, performing a converter turning procedure.
5. The preparation method of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein in the three-stage filtration, the number of the first stage filter plates is 30PPi, the temperature in the heat preservation box is controlled at 720-725 ℃, and argon is introduced into the filter box; the number of the second stage filter plates is 50PPi, the temperature in the heat preservation box is controlled at 714-; the number of the third stage filter plates is 70PPi, the temperature in the heat preservation box is controlled to be 705 plus 710 ℃, and nitrogen is introduced into the filter box.
6. The preparation method of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein the homogenization annealing process comprises the following steps: keeping the temperature for 10 hours at the furnace gas temperature of 380 ℃; and then heating to the target heating temperature of 430-.
7. The preparation method of the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein the convexity of the working roll of the cold rolling mill is controlled to be 0.02-0.04mm, the roughness Ra value is 0.2-0.3 μm, the online plate type during rolling is controlled to be 7-10I, the oil temperature is controlled to be 38-43 ℃, the oil nozzle flow is controlled to be 48-55%, and the acid value of the oil product is controlled to be 0.1-0.25 mgKOH/g. Wherein the ash content of the rolling oil is controlled to be 5-8 g/L.
8. The method for preparing the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein in the foil rolling process, the rolling oil additive is controlled to be 5-15%, the online plate type is controlled to be 3-5I, and the rolling oil temperature is controlled to be 40-50 ℃.
9. The method for preparing the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein metallographic analysis is performed on the homogenized coiled material, wherein the size of the second phase particles is controlled to be 1-5 μm and the second phase particles are uniformly distributed; wherein the particles with the size of 1-3 μm account for more than 80%.
10. The method for preparing the aluminum foil material for the low-density pinhole positive current collector of the new energy lithium battery as claimed in claim 1, wherein the volume ratio of argon to nitrogen in the mixed gas of nitrogen and argon is 1: 1.
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CN111349825A (en) * 2020-04-26 2020-06-30 江苏鼎胜新能源材料股份有限公司 Preparation method for producing high-toughness battery aluminum foil by using short-process casting and rolling blank
CN111607722A (en) * 2020-07-09 2020-09-01 包头常铝北方铝业有限责任公司 Aluminum foil for air conditioner and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116043070A (en) * 2023-01-09 2023-05-02 江苏鼎胜新能源材料股份有限公司 Preparation method of aluminum foil material for battery with low-density second-phase particles

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