CN114669622B - Preparation method of battery aluminum foil and battery aluminum foil - Google Patents
Preparation method of battery aluminum foil and battery aluminum foil Download PDFInfo
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- CN114669622B CN114669622B CN202210294612.0A CN202210294612A CN114669622B CN 114669622 B CN114669622 B CN 114669622B CN 202210294612 A CN202210294612 A CN 202210294612A CN 114669622 B CN114669622 B CN 114669622B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/58—Roll-force control; Roll-gap control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B45/004—Heating the product
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
- B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
- B21B45/0269—Cleaning
- B21B45/0275—Cleaning devices
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- 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
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/003—Aluminium alloys
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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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a battery aluminum foil and the battery aluminum foil, wherein the preparation method of the battery aluminum foil sequentially comprises the following steps: the raw material formula is prepared by adopting a semi-continuous casting method to obtain an ingot; milling a cold interlayer and a segregation phase of the cast ingot; heating the milled cast ingot by adopting a heating furnace; performing hot continuous rolling on the ingot after the heating treatment to obtain a hot rolled blank; cold rolling the hot rolled blank to obtain an aluminum foil blank; foil rolling is carried out on the aluminum foil blank to obtain the aluminum foil of the battery. The thickness of the battery aluminum foil prepared by the method is kept between 0.01 and 0.015mm, the tensile strength reaches 220 to 235Mpa, the elongation reaches 4.8 to 6.0 percent, the surface quality is more excellent without color difference defects, and the surface wetting tension value can reach 35 multiplied by 10 ‑3 N/m, can keep 15 seconds without breaking into small liquid drops, has less than 0.006 pinholes per square meter and has less plate-shaped collapse less than 0.5mm, thereby meeting the requirements of the power battery of the new energy vehicle on the aluminum foil of the battery.
Description
[ field of technology ]
The invention relates to the technical field of aluminum processing, in particular to a preparation method of a battery aluminum foil and the battery aluminum foil.
[ background Art ]
Development of new energy automobiles is an important measure for coping with climate change and promoting green development, and at present, the new energy automobiles are more energy-saving and pollution-free compared with the traditional gasoline-driven automobiles. Especially, the pure electric automobile driven by the power battery is better and more appreciated by users.
The electric power source of the electric automobile is basically a lithium ion power battery, the power battery is a mobile energy source composed of an anode, a cathode and electrolyte, and the anode of the power battery needs to be used for a battery aluminum foil.
The existing battery aluminum foil has the defects of more pinholes, low strength, poor surface quality and poor plate shape, and cannot meet the requirement of a power battery on the battery aluminum foil.
Therefore, it is necessary to provide a method for manufacturing a battery aluminum foil and a battery aluminum foil to solve the above problems.
[ invention ]
The embodiment of the invention aims to provide a preparation method of a battery aluminum foil and the battery aluminum foil, which are used for solving the problems that the existing battery aluminum foil has more pinholes, low strength, poor surface quality and poor plate shape, so that the requirement of a power battery on the battery aluminum foil cannot be met.
In a first aspect, an embodiment of the present invention provides a method for preparing an aluminum foil for a battery, including the following steps:
s1, preparing a raw material formula by adopting a semi-continuous casting method to obtain an ingot;
the raw material formula comprises the following components in percentage by mass: si=0.02-0.06%, fe=0.10-0.16%, cu=0.02-0.029%, mg < 0.005%, mn < 0.005%, zn < 0.01%, ti=0.008-0.014%, al > 99.70%, wherein, the element Si adopts AlSi20 intermediate alloy, the element Fe adopts aluminum iron agent 80FeAl, the element Cu adopts AlCu20 intermediate alloy, the element Ti adopts online grain refiner-added aluminum titanium boron wire;
s2, milling a cold interlayer and a segregation phase of the cast ingot;
s3, heating the milled cast ingot by adopting a heating furnace, wherein the heating comprises homogenizing heating and heat preservation heating;
s4, performing hot continuous rolling on the ingot after the heating treatment to obtain a hot rolled blank with the thickness of 6.0-8.5mm, wherein the finishing temperature of the hot continuous rolling is 320-330 ℃, the hot continuous rolling comprises hot rough rolling and hot finish rolling, the hot rough rolling comprises 21 passes, and the brush rolls are respectively put into 15 th, 17 th, 19 th and 21 st passes, and the hot finish rolling is put into the brush rolls in the whole process;
s5, cold rolling the hot rolled blank to obtain an aluminum foil blank with the thickness of 0.15-0.25mm, wherein the thickness of the intermediate blank is 4.0-6.0mm when the cold rolling is carried out to an intermediate pass, the intermediate blank is cleaned after the cold rolling is carried out to the intermediate pass, and after the cleaning, the intermediate blank is subjected to complete recrystallization annealing, and then the rolling of the rest passes is carried out;
and S6, foil rolling is carried out on the aluminum foil blank to obtain the battery aluminum foil with the thickness of 0.01-0.015 mm.
Preferably, in the step S1, the semi-continuous casting method sequentially includes steps of batching, smelting, refining, slag skimming, converter, refining, slag skimming, standing, degassing, filtering and casting, and sawing the dummy ingot head part and the gate part after the ingot is obtained.
Preferably, the joint of the cast movable launder and the fixed launder is connected by adopting aluminum silicate cotton material, the content of slag balls with the grain diameter of more than 0.2mm in the aluminum silicate cotton is less than 3%, the heat conductivity coefficient of the aluminum silicate cotton is 0.1-0.12W/m Kelvin, and the aluminum silicate cotton is made of Al 2 O 3 And SiO 2 Composition of, wherein the Al 2 O 3 And the SiO 2 The mass fraction of (2) is more than 99.5%.
Preferably, in step S2, the milling is performed by using a face milling machine, and a cutterhead of the face milling machine is spray-lubricated by using D100 rolling base oil.
Preferably, in step S3, before the milled ingot enters the heating furnace, cleaning a hearth of the heating furnace by using a dust collector, and wiping an upper surface and a lower surface of the ingot by using a cleaning agent, wherein the number of times of wiping is three, the cleaning agent is applied to the ingot by using scouring pad for the first time and the second time for wet wiping, and the cleaning agent is applied to the ingot by using dry scouring pad for the third time.
Preferably, in step S4, before hot continuous rolling is performed on the ingot after the heating treatment, a flushing device is used to flush the upper surface and the lower surface of the ingot, the hot rough rolling and the brush roller for hot finish rolling are cleaned by an off-line device, two end surfaces of the hot rolled blank are welded by argon arc welding 4 points, wherein the off-line device is an ultrasonic cleaning device, the cleaning medium is kerosene, the time is 30-40min, each end surface of the hot rolled blank is welded with two points, an inner ring is welded at the 2-3 th layer, and an outer ring is welded at the 2-3 rd layer.
Preferably, in the step S5, the filter aid in the cold-rolled rolling oil plate type filtering system is a combination of femafiltin, clay and diatomite, 5t of rolling oil, 5kg of femafiltin, 5-8kg of clay and 60kg of diatomite are added into a stirring oil tank in a precoating stage in the cold-rolled filtering process to form a filter cake with the thickness of 7-9mm, and 5kg of femafiltin, 5-8kg of clay and 20kg of diatomite are added in a filtering stage in the filtering process.
Preferably, in the step S5, the cold rolling is performed by using rolling oil, and during the cold rolling, the surface of the strip at the uncoiling position of the line of the cleaning machine is sprayed by using D40 solvent oil and then is washed by using water, wherein the bromine valence of the rolling oil is less than 10mgBr/100g, the rolling oil comprises base oil and additives, and the aniline point of the base oil is 80-90 ℃.
Preferably, in the step S6, a flocculant of a hydrocarbon anion functional group is added into the rolling oil of the foil rolling, the rolling force of the intermediate pass of the foil rolling is 2800-3000KN, the rolling force of the final pass is 2200-2400KN, and the outlet coiling tensile stress of each pass is 35MPa.
In a second aspect, an embodiment of the invention provides a battery aluminum foil, which is manufactured by the manufacturing method of the battery aluminum foil and is applied to a power battery of an energy vehicle.
Compared with the prior art, the preparation method of the battery aluminum foil of the invention prepares the battery aluminum foil by limiting the raw material formulation and sequentially adopting the processes of semi-continuous casting method, milling, heating treatment, hot continuous rolling, cold rolling and foil rolling, can keep the thickness of the battery aluminum foil at 0.01-0.015mm, has the tensile strength of 220-235 Mpa, the elongation of 4.8-6.0%, has better surface quality without color difference defect, and has the surface wetting tension value of 35 multiplied by 10 -3 N/m, can keep 15 seconds without breaking into small liquid drops, has less than 0.006 pinholes per square meter and has less plate-shaped collapse less than 0.5mm, thereby meeting the requirements of the power battery of the new energy vehicle on the aluminum foil of the battery.
[ description of the drawings ]
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly introduced below, it being obvious that the drawings in the description below are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art, wherein:
fig. 1 is a schematic flow chart of a method for preparing a battery aluminum foil according to an embodiment of the present invention;
fig. 2 is a table diagram of rolling parameters of foil rolling provided by an embodiment of the invention;
fig. 3 is a graph showing the plate shape collapse amount of the aluminum foil of the battery detected by the off-line plate shape meter according to the embodiment of the invention.
[ detailed description ] of the invention
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, the embodiment of the invention provides a preparation method of a battery aluminum foil, which comprises the following steps:
step S1, preparing a raw material formula by adopting a semi-continuous casting method to obtain an ingot.
Specifically, the raw material formula comprises the following components in percentage by mass: si=0.02-0.06%, fe=0.10-0.16%, cu=0.02-0.029%, mg < 0.005%, mn < 0.005%, zn < 0.01%, ti=0.008-0.014%, al > 99.70%, wherein, the element Si adopts AlSi20 intermediate alloy, the element Fe adopts aluminum iron agent 80FeAl, the element Cu adopts AlCu20 intermediate alloy, the element Ti adopts on-line adding grain refiner AlTiboron wire, and the rest elements are not prepared otherwise.
Specifically, the element Al is more than 99.70%, the prepared aluminum foil is easy to react with oxygen in the air, a compact oxide film is generated on the surface of the aluminum foil to prevent further reaction of aluminum, and the thin oxide film has a certain protection effect on aluminum in electrolyte and can prevent oxidation of a current collector. The surface oxide film of the aluminum foil is not dense and can be subjected to pitting corrosion, and when the aluminum content in the aluminum foil is lower, the oxide film is not dense and is more prone to pitting corrosion, so that the service life of the battery is influenced. The purer the aluminum alloy material is, the surface density is correspondingly reduced, the lower the weight of the power battery is, the higher the conductivity is, the smaller the heating value of the battery is, and the requirements of the power battery of the new energy automobile can be met better.
The traditional Fe agent is fluxing agent except element Fe, so that non-metallic compound slag inclusion is easy to generate, the purity of a melt is influenced, and more pinhole phenomena are easy to occur in the produced battery aluminum foil; feAl is easy to exist in the aluminum-iron intermediate alloy 3 The coarse second phase can cause the performance of the produced battery aluminum foil to be deteriorated, and the battery aluminum foil is difficult to break even in subsequent rolling with a large processing rate, so that the pinhole phenomenon is increased dramatically. The aluminum-type iron agent adopted in the embodiment is composed of the element Fe and the element Al, so that the problems can be avoided, namely the number of pinholes is reduced.
Specifically, after the ingot is obtained, sawing is carried out on the dummy ingot head part and the pouring gate part so as to saw the defective part of the ingot completely.
Specifically, the semi-continuous casting method sequentially comprises the steps of batching, smelting, refining, slag skimming, converter refining, slag skimming, standing, degassing, filtering and casting, wherein the joint of the movable launder and the fixed launder for casting is connected by adopting an aluminum silicate cotton material, and after the connection, the aluminum silicate cotton material is firmly prevented from leaking aluminum water.
Specifically, the content of slag balls with the grain diameter of more than 0.2mm in the aluminum silicate cotton is less than 3 percent, the heat conductivity coefficient of the aluminum silicate cotton is 0.1-0.12W/m Kelvin, and the aluminum silicate cotton is made of Al 2 O 3 And SiO 2 Composition of, wherein the Al 2 O 3 And the SiO 2 The unit of the thermal conductivity is also expressed as W/(m.k) by mass fraction of more than 99.5%.
The compact aluminum silicate cotton can ensure that aluminum silicate fibers and slag balls cannot fall into aluminum water to cause slag inclusion, and can avoid the phenomenon that the aluminum foil of the obtained battery has more pinholes; the low heat conductivity coefficient leads the aluminum water temperature of the launder to be reduced less, and the ingot tissue is compact.
And S2, milling the cold interlayer and the segregation phase of the cast ingot.
Specifically, during milling, not only the cold interlayer and the segregation phase of the cast ingot can be performed, but also other parts can be performed according to actual requirements, and certainly, the milling is ensured to be clean.
Specifically, milling is performed by adopting a face milling machine, and a cutterhead of the face milling machine is spray-lubricated by adopting D100 rolling base oil. Therefore, the milled cast ingot can keep smooth in surface, and the defects that the milling mark, aluminum sticking and the like affect the appearance of more pinholes on the aluminum foil of the battery are avoided.
The D100 rolling base oil is easy to volatilize, the surface of the cast ingot can be kept dry to the greatest extent, a thicker oil film is attached to the surface of the cast ingot by the traditional milling cutter oil, so that foreign matters such as aluminum ash, aluminum scraps and dust are accumulated, the risk of pinholes in a battery aluminum foil is greatly increased, and meanwhile, the D100 rolling base oil is higher in cost performance and easier to obtain in the traditional milling cutter oil.
And step S3, heating the milled cast ingot by adopting a heating furnace.
Wherein the heating treatment comprises homogenizing heating and heat preservation heating.
Specifically, before the milled cast ingot enters the heating furnace, a dust collector is adopted to clean a hearth of the heating furnace, so that the furnace is free of foreign matters such as dust and the like, and a clean hearth is maintained.
Specifically, before the milled cast ingot enters the heating furnace, cleaning agents are adopted to wipe the upper surface and the lower surface of the cast ingot, wherein the cleaning times are three times, the cleaning agents are smeared on the scouring pad for the first time and the second time, the cleaning agents are used for cleaning the third time by adopting a dry scouring pad, and the cleaning agents have the properties of being volatile and not causing adverse reactions on the surface of the cast ingot. Therefore, the surface of the cast ingot can be ensured to be clean and free of foreign matters, and the phenomenon that more pinholes are formed in the aluminum foil of the battery is avoided.
And S4, performing hot continuous rolling on the ingot after the heating treatment to obtain a hot rolled blank with the thickness of 6.0-8.5 mm.
Specifically, the finishing temperature of the hot continuous rolling is 320-330 ℃, the hot continuous rolling comprises hot rough rolling and hot finish rolling, the hot rough rolling comprises 21 passes, the 15 th pass, the 17 th pass, the 19 th pass and the 21 st pass are all put into a brush roller, and the hot finish rolling is put into the brush roller in the whole process. In this way, the quality of the roll surfaces of the rolls in the rolling process can be ensured to be uniform and good.
Specifically, before hot continuous rolling is performed on the ingot after the heating treatment, a flushing device is used for flushing the upper surface and the lower surface of the ingot, and ionic water is used for flushing. Therefore, the surface of the cast ingot is clean and free of foreign matters, and the phenomenon that more pinholes are formed in the aluminum foil of the battery is avoided.
Specifically, the brush rolls of the hot rough rolling and the hot finish rolling are cleaned by an off-line device, wherein the off-line device is an ultrasonic cleaning device, and the cleaning medium is kerosene for 30-40min. Therefore, the brush of the brush roller after cleaning has no non-metallic foreign matters such as aluminum powder, and the like, so that the phenomenon that the aluminum foil of the battery is pressed in due to pollution to the roller is avoided.
Specifically, argon arc welding 4 points are adopted on two end faces of the hot rolled blank, wherein two points are welded on each end face of the hot rolled blank, an inner ring is welded at the 2 nd layer to the 3 rd layer, and an outer ring is welded at the 2 nd layer to the 3 rd layer. Therefore, the defects of sticking, interlayer scratch and the like caused by the temperature reduction shrinkage of the hot rolled blank can be prevented, so that the surface quality of the aluminum foil of the battery is improved, and the problem of more pinholes is avoided.
And S5, cold rolling the hot rolled blank to obtain an aluminum foil blank with the thickness of 0.15-0.25 mm.
Specifically, when the intermediate billet is cold rolled to an intermediate pass, the thickness of the intermediate billet is 4.0-6.0mm, after the intermediate billet is cold rolled to the intermediate pass, the intermediate billet is cleaned, and after the intermediate billet is cleaned, the intermediate billet is subjected to complete recrystallization annealing, and then the intermediate billet is subjected to rolling of the remaining pass.
The intermediate billet is a hot-rolled billet when the hot-rolled billet is subjected to the cold rolling to an intermediate pass.
Specifically, the filter aid in the cold rolling oil plate type filtering system adopts a combination of the femafiltin, the clay and the diatomite, 5t of rolling oil, 5kg of femafiltin, 5-8kg of clay and 60kg of diatomite are added into a stirring oil tank in a precoating stage in the cold rolling filtering process to form a filter cake with the thickness of 7-9mm, and 5kg of femafiltin, 5-8kg of clay and 20kg of diatomite are added in a filtering stage in the filtering process. Compared with the traditional filtering process adopting pure clay and diatomite, the method can reduce the use amount of the diatomite by 85-90%.
The larger the filter aid usage amount is, the larger the risk of battery aluminum foil pinholes is caused in the rolling oil, and according to the filtering process of the embodiment, the light transmittance of the rolling oil can be ensured to reach more than 95%, and aluminum powder, iron powder and SiO which fall off from a roller can not appear 2 And the alien substances are pressed into the aluminum foil blank so as to avoid the defect that more pinholes are formed in the aluminum foil of the battery. Meanwhile, clean rolling oil for cold rolling can create preconditions for qualification of the surface wetting tension value of the battery aluminum foil.
Specifically, the cold rolling is performed by adopting rolling oil, wherein the bromine number of the rolling oil is less than 10mgBr/100g, the unsaturated hydrocarbon ratio is low, the rolling oil comprises base oil and an additive, and the aniline point of the base oil is 80-90 ℃. Thus, the rolling oil has good wettability to the roller and the surface of the aluminum foil blank, and meanwhile, the oil film for rolling lubrication is uniform, and the surface of the aluminum foil blank is uniform.
Specifically, D40 solvent oil is sprayed on the surface of the strip at the uncoiling position of the cleaning machine line in the cold rolling process, and then water is used for flushing, wherein the D40 solvent oil is environment-friendly. Therefore, the D40 solvent oil can be used as a nonpolar substance, the surface of the aluminum oxide material is not corroded, the compatibility with oil such as rolling lubricating oil, mechanical oil and the like is good, residues of various substances such as S, P, cl and other polar elements are removed more easily, the phenomenon that the surface is deteriorated, more pinholes are caused by aluminum powder sintering oxidation residues is avoided, and the surface of the aluminum foil of the battery is more excellent.
And S6, foil rolling is carried out on the aluminum foil blank to obtain the battery aluminum foil with the thickness of 0.01-0.015 mm.
In particular, the foil rollingA flocculant of hydrocarbon anionic functional groups is added to the rolling oil. So that substances such as aluminum powder and colloid in the rolling oil which influence the surface wetting tension of the aluminum foil can be removed, and the surface wetting tension value of the aluminum foil reaches 35 multiplied by 10 -3 N/m, and keeping the surface wetting tension value to meet the requirement on the premise of not passing through a traditional corona roller without breaking into small liquid drops for 15 seconds.
Specifically, the rolling force of the middle pass of foil rolling is 2800-3000KN, the rolling force of the final pass is 2200-2400KN, and the outlet coiling tensile stress of each pass is 35MPa. By controlling the rolling force parameters of each pass, the actual roll gap shape in rolling can be kept constant.
In addition, as shown in fig. 2, according to actual requirements, rolling parameters of each pass in the foil rolling process can be adaptively adjusted.
Specifically, the embodiment adopts the air pressure difference method plate-shaped roller to automatically detect the plate shape, and the constant outlet coiling tensile stress is beneficial to the plate-shaped roller to better optimize the plate shape feedback mechanism and adjust. The outlet coiling tensile stress is too large and too small, or the coiling tensile stress of each pass is too large, larger errors exist in the feedback of the plate-shaped roller, the actual roller gap is changed due to the feedback of the back bending roller, the rolling oil injection and other technological parameter changes, the adjustment of the plate shape is not facilitated, and therefore the plate shape of the aluminum foil of the final battery is poor.
The air pressure difference method is that the plate-shaped roller mainly comprises a plurality of roller rings and a hollow shaft, when compressed air is introduced into the hollow shaft, an air cushion is formed, the roller rings suspend, when the aluminum foil plate shape is bad, the pressure on each roller ring is uneven, and after the aluminum foil plate shape is converted into an electric signal, the electric signal is fed back to adjust the plate shape.
Therefore, the obtained aluminum foil plate shape of the battery can be excellent by controlling rolling process parameters such as rolling force, outlet coiling tensile stress and the like, meanwhile, as shown in fig. 3, the off-line plate shape meter is adopted to automatically detect the plate shape collapse amount of the aluminum foil of the battery, wherein the collapse amount is smaller than 0.5mm, the abscissa is the width of the aluminum foil, and the ordinate is the collapse amount of the plate shape detection, and the unit is mm. The plate shape collapse amount of the battery aluminum foil is defined as the strain of the battery aluminum foilForce of 0.6Kg/mm 2 And (3) the cell aluminum foil is uneven along the width direction of the foil, wherein the lowest point of the curve represents a zero point value.
The rolling oil in the different steps can be the same rolling oil or different rolling oils according to actual requirements.
The battery aluminum foil is prepared by limiting the raw material formulation and sequentially adopting the processes of semi-continuous casting method, milling, heating treatment, hot continuous rolling, cold rolling and foil rolling, the thickness of the battery aluminum foil can be kept between 0.01 and 0.015mm, the tensile strength reaches 220 to 235Mpa, the elongation reaches 4.8 to 6.0 percent, the surface quality is better without color difference defects, and the surface wetting tension value can reach 35 multiplied by 10 -3 N/m, can be kept for 15 seconds without breaking into small liquid drops, and has less than 0.006 pinholes per square meter and less than 0.5mm plate-shaped collapse.
The battery aluminum foil used for the power battery needs to meet the following conditions: the thickness is kept between 0.01 and 0.015mm, the tensile strength is more than 200Mpa, the elongation is more than 3 percent, the surface quality is excellent, the color difference is avoided, and the surface wetting tension value is more than 32 multiplied by 10 -3 N/m, can keep 10 seconds can not appear breaking into the phenomenon of droplet, and pinhole number is less than 3/square meter, and the volume of collapsing is less than 8mm under the plate-shaped, and the technical effect that this embodiment reached can all satisfy the condition of the battery aluminium foil that power battery used, therefore, it can also satisfy the demand of power battery to battery aluminium foil.
The invention also provides another embodiment, and provides a battery aluminum foil which is manufactured by the manufacturing method of the battery aluminum foil in the embodiment, and the battery aluminum foil in the embodiment is applied to a power battery of a new energy vehicle.
Because the battery aluminum foil in the embodiment is made by the method for manufacturing the battery aluminum foil in the above embodiment, the battery aluminum foil in the embodiment can also achieve the technical effects achieved by the method for manufacturing the battery aluminum foil in the above embodiment, and the details are not repeated here.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The preparation method of the battery aluminum foil is characterized by comprising the following steps of:
s1, preparing a raw material formula by adopting a semi-continuous casting method to obtain an ingot;
the raw material formula comprises the following components in percentage by mass: si=0.02-0.06%, fe=0.10-0.16%, cu=0.02-0.029%, mg < 0.005%, mn < 0.005%, zn < 0.01%, ti=0.008-0.014%, al > 99.70%, wherein, the element Si adopts AlSi20 intermediate alloy, the element Fe adopts aluminum iron agent 80FeAl, the element Cu adopts AlCu20 intermediate alloy, the element Ti adopts online grain refiner-added aluminum titanium boron wire;
s2, milling a cold interlayer and a segregation phase of the cast ingot;
s3, heating the milled cast ingot by adopting a heating furnace, wherein the heating comprises homogenizing heating and heat preservation heating;
s4, performing hot continuous rolling on the ingot after the heating treatment to obtain a hot rolled blank with the thickness of 6.0-8.5mm, wherein the finishing temperature of the hot continuous rolling is 320-330 ℃, the hot continuous rolling comprises hot rough rolling and hot finish rolling, the hot rough rolling comprises 21 passes, and the brush rolls are respectively put into 15 th, 17 th, 19 th and 21 st passes, and the hot finish rolling is put into the brush rolls in the whole process;
s5, cold rolling the hot rolled blank to obtain an aluminum foil blank with the thickness of 0.15-0.25mm, wherein the thickness of the intermediate blank is 4.0-6.0mm when the cold rolling is carried out to an intermediate pass, the intermediate blank is cleaned after the cold rolling is carried out to the intermediate pass, and after the cleaning, the intermediate blank is subjected to complete recrystallization annealing, and then the rolling of the rest passes is carried out;
and S6, foil rolling is carried out on the aluminum foil blank to obtain the battery aluminum foil with the thickness of 0.01-0.015 mm.
2. The method for preparing a battery aluminum foil according to claim 1, wherein in the step S1, the semi-continuous casting method sequentially comprises the steps of batching, smelting, refining, slagging-off, converter, refining, slagging-off, standing, degassing, filtering and casting, and sawing a dummy ingot head part and a sprue part after the ingot is obtained.
3. The method for preparing aluminum foil for battery as claimed in claim 2, wherein the joint of the cast movable launder and the fixed launder is made of aluminum silicate cotton material, wherein the content of slag balls with the grain diameter of more than 0.2mm in the aluminum silicate cotton is less than 3%, the heat conductivity of the aluminum silicate cotton is 0.1-0.12W/m Kelvin, and the aluminum silicate cotton is made of Al 2 O 3 And SiO 2 Composition of, wherein the Al 2 O 3 And the SiO 2 The mass fraction of (2) is more than 99.5%.
4. The method for preparing aluminum foil for battery according to claim 1, wherein in the step S2, the milling is performed by a face milling machine, and a cutterhead of the face milling machine is spray-lubricated by D100 rolling base oil.
5. The method for preparing aluminum foil for battery as claimed in claim 1, wherein in the step S3, before the milled cast ingot enters the heating furnace, a dust collector is used to clean a hearth of the heating furnace, a cleaning agent is used to wipe the upper surface and the lower surface of the cast ingot, wherein the number of times of wiping is three, a scouring pad is used for wetting the cleaning agent for the first time and the second time, and a dry scouring pad is used for wiping for the third time.
6. The method for manufacturing aluminum foil for battery according to claim 1, wherein in the step S4, before the ingot after the heat treatment is subjected to the hot continuous rolling, a flushing device is used to flush the upper surface and the lower surface of the ingot, the brush rolls for the hot rough rolling and the hot finish rolling are cleaned by an off-line device, the two end surfaces of the hot rolled blank are welded by argon arc welding to form 4 points, wherein the off-line device is an ultrasonic cleaning device, the cleaning medium is kerosene, the time is 30-40min, each end surface of the hot rolled blank is welded to form two points, an inner ring is welded to the 2-3 layers, and an outer ring is welded to the 2-3 layers.
7. The method for preparing aluminum foil for battery according to claim 1, wherein in the step S5, a filter aid in the cold-rolled rolling oil plate type filtering system is a combination of femtocells, clay and diatomite, wherein 5t of rolling oil, 5kg of femtocells, 5-8kg of clay and 60kg of diatomite are added into a stirring tank in a precoating stage in the cold-rolled filtering process, so as to form a filter cake with a thickness of 7-9mm, and 5kg of femtocells, 5-8kg of clay and 20kg of diatomite are added into a filtering stage in the filtering process.
8. The method for preparing aluminum foil for battery as claimed in claim 1, wherein in the step S5, the cold rolling is performed by using rolling oil, the surface of the strip at the uncoiling position of the line of the cleaning machine is sprayed with D40 solvent oil and then washed with water in the cold rolling process, wherein the bromine valence of the rolling oil is less than 10mgBr/100g, the rolling oil comprises base oil and additive, and the aniline point of the base oil is 80-90 ℃.
9. The method for preparing aluminum foil for battery according to claim 1, wherein in the step S6, a flocculant of hydrocarbon anion functional group is added into the rolling oil of the foil rolling, the rolling force of the middle pass of the foil rolling is 2800-3000KN, the rolling force of the last pass is 2200-2400KN, and the outlet coiling tensile stress of each pass is 35MPa.
10. A battery aluminum foil, characterized in that the battery aluminum foil is manufactured by the manufacturing method of the battery aluminum foil according to any one of claims 1 to 9, and the battery aluminum foil is applied to a power battery of an energy vehicle.
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