CN115710651B - Preparation method of lithium battery aluminum foil and lithium battery aluminum foil - Google Patents
Preparation method of lithium battery aluminum foil and lithium battery aluminum foil Download PDFInfo
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- CN115710651B CN115710651B CN202211277788.1A CN202211277788A CN115710651B CN 115710651 B CN115710651 B CN 115710651B CN 202211277788 A CN202211277788 A CN 202211277788A CN 115710651 B CN115710651 B CN 115710651B
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 147
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000011888 foil Substances 0.000 title claims abstract description 134
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005096 rolling process Methods 0.000 claims abstract description 58
- 238000007670 refining Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005266 casting Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000005097 cold rolling Methods 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003851 corona treatment Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000010731 rolling oil Substances 0.000 claims description 3
- 238000009966 trimming Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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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
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- Metal Rolling (AREA)
Abstract
The invention discloses a preparation method of a lithium battery aluminum foil and the lithium battery aluminum foil, wherein the preparation method comprises the following steps: s1, preparing an aluminum melt from a raw material formula by adopting smelting and furnace refining methods; s2, refining the aluminum melt on line; step S3, casting and rolling the aluminum melt to obtain a cast-rolled blank with the thickness of 6.5-7.5 mm; s4, cold rolling the cast-rolled blank to obtain a foil-rolled blank; s5, foil rolling is carried out on the foil rolled blank; and S6, slitting the foil rolled aluminum foil to obtain the lithium battery aluminum foil. The thickness of the aluminum foil of the lithium battery prepared by the preparation method is 0.010mm, the tensile strength is more than or equal to 190MPa, the elongation is more than or equal to 4.0%, the alloy is high in purity, the rolling process is reasonable, the average thickness difference is controlled within +/-3%, the number of pinholes of a finished product is less than 0.3 per square meter, the risk of breakage times of a client-side roller is reduced, and the conductivity and the capacity of the lithium battery are improved.
Description
[ Field of technology ]
The invention relates to the technical field of aluminum processing, in particular to a preparation method of an aluminum foil of a lithium battery and the aluminum foil of the lithium battery.
[ Background Art ]
The weight reduction of the automobile is to reduce the servicing weight of the automobile as much as possible on the premise of ensuring the strength and the safety performance of the automobile, thereby improving the dynamic property of the automobile, reducing the fuel consumption and reducing the exhaust pollution. The lithium ion battery has the characteristics of high working voltage, light weight, large specific energy, long cycle life, safety, no memory effect, no pollution to the environment and the like.
In recent years, with the mature application of lithium ion batteries in new energy power automobiles, large-scale energy storage and the Internet of things, the explosive development of the lithium battery industry is promoted. The aluminum foil of the battery is used as a positive current collector of the lithium battery, is not only a carrier of active substances, but also a conductor for collecting current, is required to have high strength and conductivity, and is an important component of the lithium battery.
The higher the purity of the aluminum foil, the better the conductivity; the thinner the aluminum foil thickness, the greater the energy density. The impurity element content of the aluminum melt is reduced, the purity of the aluminum foil finished product can be improved, but the phenomenon of sticking rollers is correspondingly increased in the rolling process when the purity is too high, and the rolling difficulty of the aluminum foil is increased. The purity is too low, the tensile strength is low, the number of pinholes is large and is difficult to control, and the breakage during rolling is easy to cause. At present, the precedent for producing the aluminum foil for the 10 mu m double-sided light lithium ion power battery by using the aluminum alloy with the aluminum content of more than 99.60% is not available at home.
Therefore, it is necessary to provide a method for preparing an aluminum foil for a lithium battery and an aluminum foil for a lithium battery to solve the above-mentioned drawbacks.
[ Invention ]
The embodiment of the invention aims to provide a preparation method of a lithium battery aluminum foil and the lithium battery aluminum foil, which are used for solving the problems that the surface quality, the comprehensive mechanical property and the stamping forming property of the existing aluminum alloy plate are poor, meanwhile, the strength is low, the internal residual internal stress is large after hot pressing, and the requirement of serving as a battery pack side plate cannot be met.
In a first aspect, an embodiment of the present invention provides a method for preparing an aluminum foil for a lithium battery, the method comprising the steps of:
S1, preparing an aluminum melt from a raw material formula by adopting smelting and furnace refining methods;
The raw material formula comprises the following components in percentage by mass: less than or equal to 0.05 percent of Si, less than or equal to 0.15 percent of Fe, less than or equal to 0.05 percent of Cu, less than or equal to 0.03 percent of Mn, less than or equal to 0.03 percent of Mg, less than or equal to 0.03 percent of Ni, less than or equal to 0.03 percent of Zn, 0.02 to 0.03 percent of Ti, more than or equal to 99.60 percent of Al, and less than or equal to 0.03 percent of other single impurities;
s2, refining the aluminum melt on line; the method comprises the steps of adding Al-Ti5-B1 filaments on line, continuously filling pure argon with the concentration of more than or equal to 99.999% on line for degassing, and carrying out on-line refining on the furnace in a double filtering mode to obtain refined aluminum melt;
Step S3, casting and rolling the aluminum melt to obtain a cast-rolled blank with the thickness of 6.5-7.5 mm; the temperature of the front box of the casting and rolling is 690-710 ℃, and the speed of the casting and rolling is 900-1000mm/min;
S4, cold rolling the cast-rolled blank to obtain a foil-rolled blank; rolling the cast-rolled blank to a foil-rolled blank with the thickness of 0.25-0.30mm in 6 passes, wherein when the cold rolling reduction is 90% -95%, low-temperature annealing is carried out, and the foil-rolled blank is rolled by the last pass after the low-temperature annealing;
S5, foil rolling is carried out on the foil rolled blank; the foil rolling passes are respectively (0.25-0.30) mm, (0.12-0.15) mm, (0.050-0.060) mm, (0.020-0.025) mm, (0.012-0.014) mm and 0.010mm, and foil rolled aluminum foil is obtained;
and S6, slitting the foil rolled aluminum foil to obtain the lithium battery aluminum foil.
Preferably, in the step S1, the prepared aluminum liquid and the pure aluminum ingot are filled into a melting furnace according to the components of the raw material formula, and the ratio of the aluminum liquid to the pure aluminum ingot is less than or equal to 30%, so as to realize batching, wherein the elements of Si, fe and Cu are controlled in the form of impurity elements, and the element of Ti is added in the form of an Al-Ti-B intermediate alloy wire outside the furnace.
Preferably, in the step S1, in the smelting, a mode of spraying a refining agent into the furnace and filling pure argon is adopted to remove gas and slag so as to realize the furnace refining, the furnace refining temperature is 735-755 ℃, the refining agent is a powder refining agent, the spraying amount of the powder refining agent is 1+/-0.2 Kg/t.al, the furnace refining time is 20-30 minutes, the furnace refining frequency is 3.5-4.5 h/time, and slag skimming is carried out after each furnace refining.
Preferably, in the step S2, the addition amount of Al-Ti5-B1 wires is 2+/-0.3 kg/t, the flow rate of pure argon is 15-25L/min, and double filtration is realized by adopting a tubular filtration and plate filtration system, wherein the filtration meshes are respectively 50 meshes and 60 meshes, and the online hydrogen content is less than or equal to 0.10mL/100gAl.
Preferably, in the step S3, the fluctuation range of molten aluminum of the front box is controlled to be +/-1 mm, the length of a casting and rolling area is 55-65mm, the grain size of the upper surface and the lower surface of a casting and rolling plate is first-grade, the same plate difference is less than or equal to 0.03mm, the longitudinal plate difference in a circle is less than or equal to 0.10mm, and the convexity is 0-0.02mm.
Preferably, in the step S4, the low-temperature annealing is performed after the fifth pass is rolled to 0.40-0.45mm, the annealing temperature is 260+/-5 ℃, and the heat preservation time is 20-25 hours.
Preferably, in the step S5, the hardness of the working roll is 90-95HSD, the roughness is 0.12 μm, the convexity is 0.09mm, the dimensional deviation is +/-1%, the thickness of the rolled foil is monitored in real time through an online thickness detection system, and the thickness deviation is automatically corrected and controlled, so that the thickness of the aluminum foil is controlled within a range of +/-3%.
Preferably, in step S6, the aluminum foil of the lithium battery is placed into the splitting machine, the cutting is performed by using a disc cutter, the defects of aluminum powder, burrs and seal marks are controlled during the splitting, the on-line pinhole detection is performed on the aluminum foil of the lithium battery during the splitting process, the number, the size and the distribution position of pinholes are monitored in real time, and the part which does not meet the requirements is removed.
Preferably, the preparation method further comprises step S7:
rewinding the cut lithium battery aluminum foil, and carrying out corona treatment on the surface of the lithium battery aluminum foil twice in the rewinding process, wherein the corona power is 12-18KW, and the speed is 100-150m/min.
In a second aspect, an embodiment of the present invention provides an aluminum foil for a lithium battery, where the aluminum foil for a lithium battery is composed of the following components in percentage by mass: less than or equal to 0.05 percent of Si, less than or equal to 0.15 percent of Fe, less than or equal to 0.05 percent of Cu, less than or equal to 0.03 percent of Mn, less than or equal to 0.03 percent of Mg, less than or equal to 0.03 percent of Ni, less than or equal to 0.03 percent of Zn, 0.02 to 0.03 percent of Ti, more than or equal to 99.60 percent of Al, and less than or equal to 0.03 percent of other single impurities; the lithium battery aluminum foil is prepared by the preparation method of the lithium battery aluminum foil.
Compared with the prior art, the preparation method of the lithium battery aluminum foil comprises the steps of limiting a raw material formula, sequentially adopting smelting, online refining, cast rolling, cold rolling, foil rolling, slitting and rewinding to prepare the lithium battery aluminum foil, wherein in the cold rolling stage, rough rolling is carried out to a preset thickness, and then low-temperature annealing treatment is carried out; the foil rolling stage adopts low-reduction rate and large convexity rolling; the tensile strength of the aluminum foil of the lithium battery is more than or equal to 190MPa, the elongation is more than or equal to 4.0%, the thickness of the finished product is 10 mu m, the thickness difference is concentrated to +/-3%, the pinhole surface density is less than 0.3 per square meter, and no large pinholes of more than 0.5mm are formed; the 10 mu m double-sided light high-extension aluminum foil for the lithium battery is produced by foil rolling, so that the conductivity and the capacity of the battery are improved, and the requirement of the battery as a lithium battery is completely met.
[ 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 step flow diagram of a preparation method of an aluminum foil for a lithium battery according to an embodiment of the present 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 lithium battery aluminum foil, which is used for producing three batches of aluminum foil finished products with the thickness of 0.010mm and the width of 600-800mm by taking a lithium ion positive current collector aluminum foil for a new energy automobile as an example. The preparation method comprises the following steps:
and S1, preparing an aluminum melt by adopting a smelting and furnace refining method for the raw material formula.
Wherein the raw material formula comprises the following components in percentage by mass: less than or equal to 0.05 percent of Si, less than or equal to 0.15 percent of Fe, less than or equal to 0.05 percent of Cu, less than or equal to 0.03 percent of Mn, less than or equal to 0.03 percent of Mg, less than or equal to 0.03 percent of Ni, less than or equal to 0.03 percent of Zn, 0.02 to 0.03 percent of Ti, more than or equal to 99.60 percent of Al, and less than or equal to 0.03 percent of other single impurities.
In the embodiment, the prepared aluminum liquid and the pure aluminum ingot are sequentially filled into a melting furnace according to the components of the raw material formula, and an aluminum melt is prepared by a smelting and furnace refining method, wherein the aluminum liquid and the pure aluminum ingot are controlled according to a ratio of 7:3 so as to realize batching, si, fe and Cu elements are controlled in the form of impurity elements, ti elements are added in the form of Al-Ti-B intermediate alloy wires outside the furnace and are controlled as alloy elements, and the melt in the melting furnace is degassed and deslagged in the form of spraying a refining agent and filling high-purity argon.
In the embodiment, the refining agent is sprayed into the furnace and pure argon is filled into the furnace for degassing and deslagging to realize the refining in the furnace, the refining temperature in the furnace is 735-755 ℃, the refining agent is powder refining agent, the spraying amount of the refining agent is 1+/-0.2 Kg/t.Al, the refining time in the furnace is 20-30 minutes, the refining frequency in the furnace is 3.5-4.5 h/time, and slag skimming is carried out after each refining in the furnace.
The smelting method comprises two steps of batching and refining in a furnace.
The batching includes loading the batched aluminum liquid and pure aluminum ingot into a melting furnace in sequence, wherein the ratio of the aluminum liquid to the pure aluminum ingot is less than or equal to 30 percent.
Furnace refining is controlled by controlling Si, fe and Cu in the form of impurity elements; ti element is added in an external furnace in the form of an Al-Ti-B intermediate alloy wire and is used as alloy element for controlling, so as to play a role in refining grains. Degassing and deslagging the melt by adopting a mode of spraying a refining agent and filling high-purity argon, wherein the refining temperature in a furnace is 735-755 ℃, and spraying a powder refining agent of 1+/-0.2 Kg/t.Al, the refining time is 20-30 minutes, and the refining frequency is 3.5-4.5 h/time. The refining temperature, time and frequency are moderate, and the obtained aluminum foil cast-rolled blank has better tensile strength and elongation rate effects.
S2, refining the aluminum melt on line; the refined aluminum melt is obtained by online adding Al-Ti5-B1 wires, online continuously filling pure argon with the concentration of more than or equal to 99.999 percent for degassing, and online refining in a furnace in a double filtering mode.
In the embodiment, the addition amount of the Al-Ti5-B1 wires is 2+/-0.3 kg/t, the flow rate of pure argon is 15-25L/min, the double filtration is realized by adopting a tubular filtration system and a plate filtration system, the filtration meshes are respectively 50 meshes and 60 meshes, and the online hydrogen content is less than or equal to 0.10mL/100gAl.
Specifically, the Al-Ti5-B1 wire is sequentially added in the diversion trench, high-purity argon is filled in, and double filtration is carried out, so that the external refining is carried out, and the addition amount of the Al-Ti5-B1 wire is 2+/-0.3 kg/t, thereby playing a role in refining grains. Argon flow is 15-25L/min, and the three-well tubular filtration and plate filtration system double filtration modes are adopted to carry out external online refining, wherein the filtration mesh number is 50 and 60, and the online hydrogen content is less than or equal to 0.10mL/100gAl. Good filtering effect and convenient impurity removal and degassing. The plate type filtering system can be a ceramic filter plate, and has good filtering effect.
The online refining is to sequentially add Al-Ti5-B1 wires on line in a diversion trench for modification treatment, continuously fill high-purity argon with purity more than 99.999% on line for degassing, and conduct online refining outside the furnace in a double-filtering mode of a tubular filter box and a ceramic filter plate.
Step S3, casting and rolling the aluminum melt to obtain a cast-rolled blank with the thickness of 6.5-7.5 mm; the temperature of the front box of the casting and rolling is 690-710 ℃, and the speed of the casting and rolling is 900-1000mm/min. The high temperature casting and rolling can improve the mechanical property and the forming property of the aluminum foil, and the high temperature section can spheroidize primary phase particles generated in the casting process so as to further improve the forming property of the aluminum foil.
In this embodiment, in the step S3, the fluctuation range of the molten aluminum in the front box is controlled to be ±1mm, the length of the casting and rolling area is 55-65mm, the grain size of the upper surface and the lower surface of the casting and rolling plate is one-stage, the same plate difference is less than or equal to 0.03mm, the longitudinal plate difference in one circle is less than or equal to 0.10mm, and the convexity is 0-0.02mm.
Specifically, the temperature 690-710 ℃ is set in the front box, the fluctuation range of molten aluminum in the front box is controlled to be +/-1 mm, the length of a casting rolling area is 55-65mm, the casting rolling speed is 900-1000mm/min, the thickness of casting rolling blanks is 6.5-7.5mm, the grain size of the upper surface and the lower surface of a casting rolling plate is one-stage, the same plate difference is less than or equal to 0.03mm, the longitudinal plate difference in one week is less than or equal to 0.10mm, and the convexity is 0-0.02mm.
S4, cold rolling the cast-rolled blank to obtain a foil-rolled blank; and rolling the cast-rolled blank to a foil-rolled blank with the thickness of 0.25-0.30mm in 6 passes, wherein the foil-rolled blank is formed by performing low-temperature annealing until the cold rolling reduction ratio is 90% -95% and performing last pass rolling after the low-temperature annealing.
In this embodiment, in the step S4, the low-temperature annealing is performed in the fifth pass until the thickness reaches 0.40-0.45mm, the annealing temperature is 260±5 ℃, and the heat preservation time is 20-25 hours.
Specifically, the cast-rolled coiled tape is rolled to be 0.25-0.30mm thick through 6 passes until the cold rolling reduction is 90% -95% (0.40-0.45 mm thick), wherein the low-temperature annealing is carried out in the fifth pass to be 0.40-0.45mm thick, the annealing temperature is 260+/-5 ℃, the heat preservation time is 20-25 hours, and the final rolling is carried out after the annealing to obtain the foil rolling blank.
S5, foil rolling is carried out on the foil rolled blank; the foil rolling passes are respectively as follows:
foil rolling is carried out on the foil rolled blank; the foil rolling passes are respectively (0.25-0.30) mm, (0.12-0.15) mm, (0.050-0.060) mm, (0.020-0.025) mm, (0.012-0.014) mm and 0.010mm, and the foil rolled aluminum foil is obtained.
In this embodiment, in the step S5, the hardness of the working roll is 90-95HSD, the coarse superelevation is 0.12 μm, the convexity is 0.09mm, the dimensional deviation is ±1%, the thickness of the rolled foil is monitored in real time by an online thickness detection system, and the thickness deviation is automatically corrected and controlled, so that the thickness of the aluminum foil is controlled within the range of ±3%.
In this embodiment, in step S5, during 5 passes of rolling of the finished product, the thickness of the rolled foil is monitored in real time by an online thickness detection system, and the thickness deviation is automatically corrected and controlled, so that the thickness of the aluminum foil is controlled within a range of ±3%. In this step, the foil rolling process parameters are shown in table 1, and the rolling oil parameters of each pass are shown in table 2:
table 1 technological parameters of foil rolling of aluminum foil
Specifically, the reduction passes of foil rolling are respectively:
(0.25-0.30) mm- (0.12-0.15) mm- (0.050-0.060) mm- (0.020-0.025) mm- (0.012-0.014) -0.010mm. The rolling of the finished product pass 5 adopts a low reduction rate process less than 30 percent, the rolling speed of the finished product pass is 600-700m/min, the hardness of a working roll is 90-95HSD, the coarse superdegree is 0.12 mu m, the convexity is 0.09mm, and the dimensional deviation is +/-1 percent.
Table 2 rolling oil parameters for foil rolling:
and S6, slitting the foil rolled aluminum foil to obtain the lithium battery aluminum foil.
In this embodiment, in the step S6, the foil rolled strip is placed into a splitting machine, a disc cutter of the splitting machine is used for trimming, the defects of edges such as aluminum powder, burrs and marks are strictly controlled during splitting, online pinhole detection is performed on the aluminum foil during splitting, the number, the size and the distribution position of pinholes are monitored in real time, and the aluminum foil which does not meet the requirements is removed; and (7) putting the aluminum foil meeting the requirements into the step (S7). The ultra-thin double-sided light aluminum foil is obtained, the pinhole density of the aluminum foil is low, the high tensile strength and the high elongation are maintained, and the conductivity and the battery capacity of the aluminum foil for the lithium ion power battery are improved.
And S7, rewinding the aluminum foil of the lithium battery after the slitting treatment, and carrying out corona treatment on the surface of the aluminum foil of the lithium battery twice in the rewinding process, wherein the corona power is 12-18KW, and the speed is 100-150m/min.
Specifically, the surface of the aluminum foil is subjected to corona treatment twice in the rewinding process, so that the dyne value of the surface of the aluminum foil is improved, the wettability of the surface of the aluminum foil is improved, and the subsequent spraying treatment is facilitated. The corona power is 12-18KW, and the speed is 100-150m/min.
And finally, packaging the finished aluminum foil. Is used for protecting the finished aluminum foil.
Specifically, the aluminum foil of the lithium battery is prepared through the steps S1-S7, the thickness of the aluminum foil is 0.010mm, the tensile strength is more than or equal to 190MPa, and the elongation is more than or equal to 4.0%. The alloy of the aluminum foil of the lithium battery has high purity, the rolling process is reasonable, the average thickness difference is controlled within +/-3%, the number of pinholes of a finished product is less than 0.3 per square meter, the risk of breakage times of a client-side roller can be reduced, and the conductivity and the capacity of the lithium battery are improved.
The invention provides three examples for verification according to the preparation scheme:
the mass percentages of the components of the raw material formulas of the first to third embodiments are shown in Table 3:
Table 3 mass percentages of the components of the raw material formulation of each example
| Chemical element | Si | Fe | Cu | Mg | Mn | Zn | Ti | Ni | Al |
| Standard requirements | ≤0.05 | ≤0.15 | ≤0.05 | ≤0.03 | ≤0.03 | ≤0.03 | 0.02-0.032 | ≤0.03 | ≥99.7 |
| Example 1 | 0.04 | 0.13 | 0.01 | 0.02 | 0.01 | 0.01 | 0.03 | 0.02 | 99.78 |
| Example two | 0.03 | 0.14 | 0.04 | 0.01 | 0.02 | 0.03 | 0.02 | 0.01 | 99.74 |
| Example III | 0.05 | 0.13 | 0.03 | 0.03 | 0.03 | 0.01 | 0.03 | 0.01 | 99.71 |
Examples one to three performance parameters of lithium battery aluminum foils obtained by the preparation method of the present invention are shown in table 4:
table 4 performance of lithium battery aluminum foil of each example
| Sequence number | Tensile Strength/Mpa | Elongation/% | Average thickness deviation/% | Pinhole count/square meter |
| Example 1 | 203.34 | 4.69 | 2.5 | 0.13 |
| Example two | 207.53 | 4.55 | 2.4 | 0.10 |
| Example III | 204.19 | 4.81 | 2.7 | 0.12 |
As can be seen from tables 3 and 4 above:
In the first example, the aluminum foil prepared by the steps S1 to S7 was found to have a tensile strength of 203.34MPa, an elongation of 4.69%, an average thickness deviation of 2.4% and a pinhole count of 0.13 pinholes/m 2, and the raw materials were prepared from 0.04% Si, 0.13% Fe, 0.01% Cu, 0.02% Mg, 0.01% Mn, 0.01% Zn, 0.03% Ti, 0.02% Ni, 99.78% Al, and the balance of other single impurities.
In the second example, the aluminum foil prepared by the steps S1 to S7 was found to have a tensile strength of 207.53MPa, an elongation of 4.55%, an average thickness deviation of 2.5% and a pinhole count of 0.10 pinholes/m 2, and the raw materials were prepared from 0.03% Si, 0.14% Fe, 0.04% Cu, 0.01% Mg, 0.02% Mn, 0.03% Zn, 0.02% Ti, 0.01% Ni, 99.74% Al, and the balance of other single impurities.
In the third example, the aluminum foil prepared by the steps S1 to S7 was found to have a tensile strength of 204.19MPa, an elongation of 4.81%, an average thickness deviation of 2.7% and a pinhole count of 0.12 pinholes/m 2, and the aluminum foil was prepared from the raw materials of 0.05% Si, 0.13% Fe, 0.03% Cu, 0.03% Mg, 0.03% Mn, 0.01% Zn, 0.03% Ti, 0.01% Ni, 99.77% Al, and the balance of other single impurities.
In the first to third examples, the aluminum foil with the thickness of 0.010mm produced by the preparation method of the steps S1 to S7 has the tensile strength of more than or equal to 190MPa and the elongation of more than or equal to 4.0%. The alloy of the invention has high purity, reasonable rolling process, average thickness difference controlled within +/-3 percent, and less than 0.3 per square meter pinholes, thereby reducing the risk of rolling and taping times at the client side and improving the conductivity and capacity of the lithium battery.
The embodiment of the invention also provides an aluminum foil for the lithium battery, which is used for the lithium battery and comprises the following components in percentage by mass: less than or equal to 0.05 percent of Si, less than or equal to 0.15 percent of Fe, less than or equal to 0.05 percent of Cu, less than or equal to 0.03 percent of Mn, less than or equal to 0.03 percent of Mg, less than or equal to 0.03 percent of Ni, less than or equal to 0.03 percent of Zn, 0.02 to 0.03 percent of Ti, more than or equal to 99.60 percent of Al, and less than or equal to 0.03 percent of other single impurities; the lithium battery aluminum foil is prepared by the preparation method of the lithium battery aluminum foil.
Because the lithium battery aluminum foil in the embodiment is made by the method for preparing the lithium battery aluminum foil in the above embodiment, the lithium battery aluminum foil in the embodiment can also achieve the technical effects achieved by the method for preparing the lithium 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 (8)
1. The preparation method of the lithium battery aluminum foil is characterized by comprising the following steps of:
S1, preparing an aluminum melt from a raw material formula by adopting smelting and furnace refining methods;
The raw material formula comprises the following components in percentage by mass: less than or equal to 0.05 percent of Si, less than or equal to 0.15 percent of Fe, less than or equal to 0.05 percent of Cu, less than or equal to 0.03 percent of Mn, less than or equal to 0.03 percent of Mg, less than or equal to 0.03 percent of Ni, less than or equal to 0.03 percent of Zn, 0.02 to 0.03 percent of Ti, more than or equal to 99.60 percent of Al, and less than or equal to 0.03 percent of other single impurities;
In the step S1, during smelting, a refining agent is sprayed into a furnace and pure argon is filled into the furnace for degassing and deslagging to realize the refining in the furnace, the refining temperature in the furnace is 735-755 ℃, the refining agent is a powder refining agent, the spraying amount of the powder refining agent is 1+/-0.2 Kg/t.Al, the refining time in the furnace is 20-30 minutes, the refining frequency in the furnace is 3.5-4.5 h/time, and slag skimming is carried out after each refining in the furnace;
S2, refining the aluminum melt on line; the method comprises the steps of adding Al-5Ti-1B wires online, continuously filling pure argon with the concentration of more than or equal to 99.999% online for degassing, and carrying out on-line refining in a furnace in a double filtering mode to obtain refined aluminum melt;
Step S3, casting and rolling the aluminum melt to obtain a cast-rolled blank with the thickness of 6.5-7.5 mm; the temperature of the front box of the casting and rolling is 690-710 ℃, and the speed of the casting and rolling is 900-1000mm/min;
S4, cold rolling the cast-rolled blank to obtain a foil-rolled blank; rolling the cast-rolled blank to a foil-rolled blank with the thickness of 0.25-0.30mm in 6 passes, wherein when the cold rolling reduction is 90% -95%, low-temperature annealing is carried out, and the foil-rolled blank is rolled by the last pass after the low-temperature annealing;
S5, foil rolling is carried out on the foil rolled blank; the foil rolling passes are respectively (0.25-0.30) mm, (0.12-0.15) mm, (0.050-0.060) mm, (0.020-0.025) mm, (0.012-0.014) mm and 0.010mm, and foil rolled aluminum foil is obtained; wherein the rolling speeds of the foil rolling passes are respectively 800-1000m/min, 1000-1200m/min and 600-650m/min; the alcohol content of the rolling oil in the foil rolling pass is respectively 4.0-4.5%, 3.0-4.0%, 0.7-1.4% and 1.0-2.0%;
S6, slitting the foil rolled aluminum foil to obtain the lithium battery aluminum foil;
And S7, rewinding the aluminum foil of the lithium battery after the slitting treatment, and carrying out corona treatment on the surface of the aluminum foil of the lithium battery twice in the rewinding process, wherein the corona power is 12-18KW, and the speed is 100-150m/min.
2. The method for preparing aluminum foil for lithium battery according to claim 1, wherein in the step S1, the prepared aluminum liquid and pure aluminum ingot are filled into a melting furnace according to the components of the raw material formula, and the ratio of the aluminum liquid to the pure aluminum ingot is less than or equal to 30%, so as to realize batching, wherein Si, fe and Cu elements are controlled in the form of impurity elements, and Ti elements are added in the form of Al-Ti-B intermediate alloy wire outside the furnace.
3. The method for preparing the aluminum foil for the lithium battery according to claim 1, wherein in the step S2, the addition amount of Al-5Ti-1B wires is 2+/-0.3 kg/t, the flow rate of pure argon is 15-25L/min, double filtration is realized by adopting a tubular filtration and plate filtration system, the filtration meshes are respectively 50 meshes and 60 meshes, and the online hydrogen content is less than or equal to 0.10mL/100gAl.
4. The method for preparing aluminum foil for lithium battery according to claim 1, wherein in the step S3, the fluctuation range of aluminum water in the front box is controlled to be +/-1 mm, the length of the casting area is 55-65mm, the grain size of the upper surface and the lower surface of the casting plate is one level, the same plate difference is less than or equal to 0.03mm, the longitudinal plate difference in one week is less than or equal to 0.10mm, and the convexity is 0-0.02mm.
5. The method for preparing aluminum foil for lithium battery according to claim 1, wherein in the step S4, the low-temperature annealing is performed after the fifth pass rolling to 0.40-0.45mm, the annealing temperature is 260+ -5 ℃, and the heat preservation time is 20-25 hours.
6. The method for preparing aluminum foil for lithium battery according to claim 1, wherein in the step S5, the hardness of the working roll is 90-95HSD, the roughness is 0.12 μm, the convexity is 0.09mm, the size deviation is +/-1%, the thickness deviation is monitored in real time by an online thickness detection system, and the automatic correction control is carried out to control the thickness deviation to ensure that the thickness of the aluminum foil is within +/-3%.
7. The method for preparing aluminum foil for lithium battery as claimed in claim 1, wherein in the step S6, the aluminum foil for lithium battery is put into a slitter, a disc cutter is used for trimming, aluminum powder, burrs and imprint edge defects are controlled during slitting, online pinhole detection is carried out on the aluminum foil for lithium battery during slitting, the number, size and distribution position of pinholes are monitored in real time, and unsatisfactory parts are removed.
8. The lithium battery aluminum foil is used for a lithium battery and is characterized by comprising the following components in percentage by mass: less than or equal to 0.05 percent of Si, less than or equal to 0.15 percent of Fe, less than or equal to 0.05 percent of Cu, less than or equal to 0.03 percent of Mn, less than or equal to 0.03 percent of Mg, less than or equal to 0.03 percent of Ni, less than or equal to 0.03 percent of Zn, 0.02 to 0.03 percent of Ti, more than or equal to 99.60 percent of Al, and less than or equal to 0.03 percent of other single impurities; the lithium battery aluminum foil is prepared by the preparation method of the lithium battery aluminum foil according to any one of claims 1 to 7.
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