CN107245607B - A kind of collector aluminium foil and its manufacturing method - Google Patents
A kind of collector aluminium foil and its manufacturing method Download PDFInfo
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- CN107245607B CN107245607B CN201710402331.1A CN201710402331A CN107245607B CN 107245607 B CN107245607 B CN 107245607B CN 201710402331 A CN201710402331 A CN 201710402331A CN 107245607 B CN107245607 B CN 107245607B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/40—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling foils which present special problems, e.g. because of thinness
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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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Abstract
The present invention relates to a kind of collector aluminium foil and its manufacturing methods.The ingredient of the collector aluminium foil includes Al, Si, Fe, Cu, Mg, its content are as follows: 99.90wt%≤Al < 100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤0.04wt%, 0.002wt%≤Cu≤0.005wt%, 0.005wt%≤Mg≤0.02wt%.The manufacturing method of the collector aluminium foil includes: to prepare alloy material first, it is set to meet following component requirements: 99.90wt%≤Al < 100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤0.04wt%, 0.002wt%≤Cu≤0.005wt%, 0.005wt%≤Mg≤0.02wt%, then by the alloy material founding at ingot casting, milling face, homogenizing annealing, hot rolling, cold rolling are carried out to the ingot casting, last foil rolls to obtain aluminium foil.
Description
Technical field
The present invention relates to the collectors of energy storage device, more particularly to a kind of collector aluminium foil and its manufacturing method.
Background technique
Energy storage device is the key that solve energy crisis and environmental pollution, it can not only effectively utilize the existing energy, and
And new energy can be developed and used.Wherein, lithium ion battery, supercapacitor, lithium-ion capacitor be current application and research compared with
For three mature big new type of energy storage device.Aluminium foil is energy storage device as the electrode current collecting body of above-mentioned three kinds main energy storage devices
Important component part, the effect for primarily serving collected current, carrying electrode active material.However, the afflux of the prior art
Corrosion resistance, tensile strength, elongation percentage and the conductivity of body need to be improved.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of collection with good tensile strength, elongation percentage and conductivity
Fluid aluminium foil and its manufacturing method.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of collector aluminium foil, the ingredient of the collector aluminium foil include Al, Si, Fe, Cu, Mg, content are as follows:
99.90wt%≤Al < 100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤0.04wt%, 0.002%
≤ Cu≤0.005wt%, 0.005wt%≤Mg≤0.02wt%.
Compared with the existing technology, collector aluminium foil of the invention belongs to high-purity aluminum foil, and the content of Al reaches 99.90wt%
More than, and by addition Si, Fe, Cu, Mg element, than other fine aluminiums or alloy aluminum have better corrosion resistance, conductivity,
Tensile strength and elongation percentage.
Wherein, Si element is the element that intensity can be improved after adding, and content is 0.01~0.03wt%.Si content is insufficient
It when 0.01wt%, does not almost work to intensity raising, and if needing the control of Si content using height in 0.01wt% or less
The production of fine aluminium ingot, cost increase considerably；When Si content is more than 0.03wt%, the conductivity of product will be reduced.
Fe element is also the element that intensity can be improved after adding, and content is 0.01~0.04wt%.Fe content is insufficient
When 0.01wt%, the intensity of demand cannot be obtained；When Fe content is more than 0.04wt%, the conductivity of product will be difficult to reach to want
It asks.
Cu element is also the element that intensity can be improved after adding, and content is 0.002~0.005wt%.Cu content is insufficient
When 0.002%wt, then it is difficult to realize improve the effect of intensity；Cu content is more than 0.005wt%, the elongation percentage and electric conductivity of product
It will all be affected.
Mg element is also the element that intensity can be improved after adding, and content is 0.005~0.02wt%.It is in aluminium alloy
Hardening constituent Mg can be formed with Si and Cu2Si and Al2When CuMg, Mg content are less than 0.005wt%, then need raw using high-purity aluminium ingot
It produces, cost increases considerably；When Mg content is more than 0.02wt%, the conductivity of product will be difficult to reach requirement.
In addition, be difficult to avoid that in aluminium foil ingredient there are some impurity elements.Collector aluminium foil is due in energy storage device
In constantly be in charging and discharging state, such as Fe and Cu can with Al formed primary battery, cause the erosion of Al, therefore collector aluminium
Corrosion resistance of the foil in active material or electrolyte can also significantly affect energy storage device lithium ion battery, supercapacitor, lithium from
The service life of sub-capacitor.Due to Al in air be easy self-protection, surface formed oxidation film can prevent Al into
One step oxidation, so that Al be protected not to be etched；And the presence of impurity element can destroy the continuity that aluminium foil surface forms oxidation film,
Making the corrosion stability of aluminium foil reduces, and impurity content is higher, and corrosion stability is lower.Therefore, the present invention is by adjusting in aluminium foil
Al, Si, Fe, Cu, Mg constituent content can be by impurity element improving tensile strength, elongation percentage and on the basis of conductivity
Content is maintained at an extremely low level, so that impurity element be avoided to destroy the continuity of aluminium foil surface oxidation film, improves aluminium foil
Corrosion resistance.
Further, the content of the collector aluminium foil are as follows: 99.92wt%≤Al < 100wt%, 0.01wt%≤Si≤
0.02wt%, 0.02wt%≤Fe≤0.03wt%, 0.002%≤Cu≤0.004wt%, 0.01wt%≤Mg≤
0.015wt%.
Further, the Fe content of the collector aluminium foil is higher than Si content.Fe content is higher than Si content and is conducive to reduce
Crystallization range in strip casting process reduces the crackle tendency of Casting Rolled Sheet.
The present invention also provides a kind of manufacturing methods of collector aluminium foil, first preparation alloy material, keep its satisfaction as follows
Component requirements: 99.90wt%≤Al < 100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤
Then 0.04wt%, 0.002%≤Cu≤0.005wt%, 0.005wt%≤Mg≤0.02wt% melt the alloy material
Ingot casting is cast, milling face, homogenizing annealing, hot rolling, cold rolling are carried out to the ingot casting, last foil rolls to obtain aluminium foil.
Compared with the existing technology, the present invention makes the collector aluminium by the control to collector with aluminium foil manufacturing process
The tensile strength of foil reaches 180MPa, and elongation percentage reaches 2.0% or more, to ensure to occur in subsequent electrode production process
Fracture.
Further, the alloy material first passes through melting and obtains melt, and melt forms ingot casting using casting；Fusion process
Including fusing, standing, refining, slagging-off and degasification, the hydrogen content of deaerated rear melt is controlled in 0.12ml/100gAl or less.It will
The hydrogen content of melt is controlled in reduced levels, it is possible to reduce the stomata and crackle of ingot casting improve surface property and the processing of ingot casting
Performance.
Further, the hydrogen content of deaerated rear melt is controlled in 0.10ml/100gAl or less.
Further, the temperature of homogenizing annealing be 520~610 DEG C, soaking time be 3~40h, the heating-up time be 10~
19h.If homogenizing annealing temperature is lower than 520 DEG C or time of homogenized annealing is less than 3h, it cannot achieve the purpose that homogenization, it is difficult to
Eliminate chemical component and structural inhomogeneities；If homogenizing annealing temperature is higher than 610 DEG C or time of homogenized annealing is higher than
It is broken to be unfavorable for subsequent rolling for 40h, inside ingot tissue crystal boundary straightened, and energy consumption is high, higher cost.
Further, the start rolling temperature of hot rolling is 500~560 DEG C, and finishing temperature is 240~340 DEG C, and passage is 20~35
Secondary, coils of hot rolled is with a thickness of 4~8mm.Since solid solubility of the Fe in aluminium is very low, if start rolling temperature is less than 500 DEG C, it will significantly
The precipitation for increasing Fe causes to be difficult to ensure the solid solution capacity for improving intensity；If start rolling temperature is higher than 560 DEG C, hot rolling speed
Slowly, production efficiency declines；If finishing temperature is higher than 340 DEG C, in hot rolled coil cold-rolled process, Fe is with compound form amount of precipitation
Increase, will lead to the decline of collector intensity；If finishing temperature is lower than 240 DEG C, speed is slow during hot rolling, production efficiency
Decline.
Further, the start rolling temperature of hot rolling is 510~550 DEG C, and finishing temperature is 270~330 DEG C, and passage is 21~25
Secondary, coils of hot rolled is with a thickness of 5~7mm.
Further, the size of the ingot casting is wide 1020~1100mm, 450~550mm of thickness, long 4000~6000mm.
In order to better understand and implement, the following detailed description of the present invention.
Specific embodiment
Collector aluminium foil of the invention, ingredient include Al, Si, Fe, Cu, Mg, content are as follows: 99.90wt%≤Al
< 100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤0.04wt%, Cu≤0.005wt%,
0.005wt%≤Mg≤0.02wt%.
Preferably, content are as follows: 99.92wt%≤Al < 100wt%, 0.01wt%≤Si≤0.02wt%,
0.02wt%≤Fe≤0.03wt%, Cu≤0.004wt%, 0.01wt%≤Mg≤0.015wt%.
The manufacturing method of collector aluminium foil of the invention includes the following steps: to prepare alloy material first, makes its satisfaction
Following component requirements: 99.90wt%≤Al < 100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤
0.04wt%, Cu≤0.005wt%, 0.005wt%≤Mg≤0.02wt%, then by the alloy material founding at ingot casting,
Milling face, homogenizing annealing, hot rolling, cold rolling are carried out to the ingot casting, last foil rolls to obtain aluminium foil.
Specifically, the process of the manufacturing method can be it is following several:
I, founding-milling face-homogenizing annealing-hot rolling-cold rolling-foil rolls；
II, founding-homogenizing annealing-milling face-hot rolling-cold rolling-foil rolls；
III, founding-milling face-homogenizing annealing-hot rolling-preannealing-cold rolling-intermediate annealing-foil rolls；
IV, founding-homogenizing annealing-milling face-hot rolling-preannealing-cold rolling-intermediate annealing-foil rolls.
Preannealing or intermediate annealing can be carried out in the fabrication process, but since preannealing and intermediate annealing can reduce aluminium
The work-hardening capacity of foil causes the tensile strength of aluminium foil to be declined, therefore preferably without preannealing and intermediate annealing.
Founding: prepare in industrial aluminium ingot, magnesium ingot, ferro-aluminum intermediate alloy, aluminium silicon intermediate alloy, aluminum bronze intermediate alloy and aluminium manganese
Between the alloy materials such as alloy, matched and weighed, reach following component requirements: 99.90wt%≤Al <
100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤0.04wt%, Cu≤0.005wt%, 0.005wt%
≤ Mg≤0.02wt%；The alloy material obtains melt through fusing, standing, refining, slagging-off and degasification, deaerated rear melt
Hydrogen content is controlled in 0.12ml/100gAl or less, it is preferred that the hydrogen content of melt is controlled in 0.10ml/100gAl after deaerated
Below；Melt is ingot casting using casting fast cooling shaping, and cast ingot dimension is preferred are as follows: wide 1020~1100mm, thickness 450~
550mm, long 4000~6000mm.
Homogenizing annealing: ingot casting is subjected to homogenizing annealing processing, soaking time 3 in 520~610 DEG C of temperature ranges
~40h, heating-up time are 10~19h.
Milling face: ingot casting must mill face before carrying out hot rolling, mill big face and be mingled with and surface scale, to prevent material volume rear
The major qualities defect such as hole is caused in continuous production process.
Hot rolling: carrying out hot rolling open rolling in 500~560 DEG C of temperature ranges, and hot rolling finishing temperature is 240~340 DEG C, hot rolling
Passage is 20~35 times, and the coils of hot rolled with a thickness of 4~8mm is made；Preferably, hot rolling start rolling temperature is 510~550 DEG C, heat
Rolling finishing temperature is 270~330 DEG C, and for coils of hot rolled with a thickness of 5~7mm, hot rolling pass is 21~25 times.
It further illustrates combined with specific embodiments below.
Embodiment
The collector aluminium foil of the embodiment of the present invention, chemical component and content are as shown in table 1.
The chemical component and content of 1 aluminium foil of table
The manufacturing method of the collector aluminium foil of the embodiment of the present invention, includes the following steps:
Examples 1 to 6 and 8~10 and comparative example a, b according to the above process I manufacture aluminium foil: first, in accordance with aluminium foil in table 1
Chemical component and content be ready to industrial aluminium ingot, magnesium ingot, ferro-aluminum intermediate alloy, aluminium silicon intermediate alloy, aluminum bronze intermediate alloy and
The alloy materials such as aluminium manganese intermediate alloy, alloy material is put into smelting furnace and is melted, by refining, slagging-off, stirring, analysis
With enter standing furnace after adjusting component, obtain melt after standing, refining, slagging-off, degasification, it is deaerated after melt hydrogen content
Control in 0.10ml/100gAl hereinafter, melt using casting fast cooling shaping be ingot casting, after sawing end to end, cast ingot dimension
For 1070 × 515 × 5200mm；Then milling face is carried out to ingot casting, mills big face and is mingled with and surface scale；Then to behind milling face
Ingot casting carry out homogenizing annealing, hot rolling, homogenizing annealing parameter and hot-rolled process parameter are as shown in table 2；Thereafter it is carried out continuously
Cold rolling and foil roll, and obtain thick 22 μm of the aluminium foil of foil.
2 homogenizing annealing of table and hot-rolled process parameter
Embodiment 7 III manufactures aluminium foil according to the above process: being ready to first, in accordance with the chemical component and content of aluminium foil in table 1
The alloy materials such as industrial aluminium ingot, magnesium ingot, ferro-aluminum intermediate alloy, aluminium silicon intermediate alloy, aluminum bronze intermediate alloy and aluminium manganese intermediate alloy,
Alloy material is put into smelting furnace and is melted, standing furnace is entered after refining, slagging-off, stirring, analysis and adjusting component,
Obtain melt after standing, refining, slagging-off, degasification, it is deaerated after melt hydrogen content control 0.10ml/100gAl with
Under, melt is ingot casting using casting fast cooling shaping, and after sawing end to end, cast ingot dimension is 1070 × 515 × 5200mm；So
Milling face is carried out to ingot casting afterwards, big face is milled and is mingled with and surface scale；Then homogenizing annealing, heat are carried out to the ingot casting behind milling face
It rolls, homogenizing annealing parameter and hot-rolled process parameter are as shown in table 2；Hot rolled coil is after cold rolling, among the progress of 0.52mm thickness
Annealing, intermediate anneal temperature are 320 DEG C, time 10h；It finally carries out foil to roll, obtains thick 22 μm of the aluminium foil of foil.
The process of 3003 alloy of comparative example manufacture aluminium foil are as follows: prepare first, in accordance with the chemical component and content of aluminium foil in table 1
The alloy materials such as good industry aluminium ingot, magnesium ingot, ferro-aluminum intermediate alloy, aluminium silicon intermediate alloy, aluminum bronze intermediate alloy and aluminium manganese intermediate alloy
Material, alloy material is put into smelting furnace and is melted, and is entered after refining, slagging-off, stirring, analysis and adjusting component and is stood
Furnace, obtains melt after standing, refining, slagging-off, degasification, and the hydrogen content of deaerated rear melt is controlled in 0.10ml/100gAl
Below；Melt obtains the casting volume of 7mm thickness after casting；Casting is rolled up after cold rolling, carries out intermediate annealing in 0.3mm thickness,
Intermediate anneal temperature is 365 DEG C, time 2h；It finally carries out foil to roll, obtains thick 22 μm of the aluminium foil of foil.
Test performance compares
To each aluminium foil obtained, tensile strength, elongation percentage and conductivity are measured, the results are shown in Table 3.
Tensile strength and elongation percentage: the aluminium alloy cut along rolling direction is measured using universal testing machine CMT6104
The tensile strength of foil, determination condition are as follows: sample dimensions being set as 10mm × 140mm, distance is set as 50mm between fixture, draws
It stretches speed and is set as 10mm/min.
Conductivity: electric specific impedance is measured using four probe method, relative electric conductivity is converted into and acquires.
As can be seen from Table 3, tensile strength >=180MPa of aluminium foil made from Examples 1 to 10, elongation percentage >=2.0%,
Conductivity > 60%IACS.Wherein, embodiment 7 has carried out intermediate annealing, although conductivity is higher, tensile strength and extension
Rate is compared with other embodiments, lower.
For comparative example a since Cu content is low, tensile strength is insufficient.
For comparative example b since Mg content is low, tensile strength is insufficient.
For 3003 alloy of comparative example since impurity element is excessive, conductivity is lower.
3 test performance of table compares
Compared with the existing technology, the present invention improves the tension of aluminium foil by control aluminium foil alloying component and preparation process
Intensity, elongation percentage and conductivity.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (5)
1. a kind of manufacturing method of collector aluminium foil, it is characterised in that: preparation alloy material first makes it meet following ingredient
It is required that: 99.90wt%≤Al < 100wt%, 0.01wt%≤Si≤0.03wt%, 0.01wt%≤Fe≤0.03wt%,
0.002wt%≤Cu≤0.005wt%, 0.005wt%≤Mg≤0.02wt%, then by the alloy material founding Cheng Zhu
Ingot carries out milling face, homogenizing annealing, hot rolling, cold rolling to the ingot casting, and last foil rolls to obtain aluminium foil；The homogenizing annealing
Temperature is 520~610 DEG C, and soaking time is 3~40h, and the heating-up time is 10~19h；The start rolling temperature of the hot rolling be 500~
560 DEG C, finishing temperature is 240~340 DEG C, and passage is 20~35 times, and coils of hot rolled is with a thickness of 4~8mm.
2. the manufacturing method according to claim 1, it is characterised in that: the alloy material first passes through melting and obtains melt,
Melt forms ingot casting using casting, and fusion process includes fusing, standing, refining, slagging-off and degasification, the hydrogen of deaerated rear melt
Content is controlled in 0.12ml/100gAl or less.
3. manufacturing method according to claim 2, it is characterised in that: the hydrogen content control of melt exists after deaerated
0.10ml/100gAl or less.
4. the manufacturing method according to claim 1, it is characterised in that: the start rolling temperature of hot rolling is 510~550 DEG C, finish to gauge
Temperature is 270~330 DEG C, and passage is 21~25 times, and coils of hot rolled is with a thickness of 5~7mm.
5. manufacturing method described in any claim according to claim 1~4, it is characterised in that: the ruler of the ingot casting
Very little is wide 1020~1100mm, 450~550mm of thickness, long 4000~6000mm.
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| CN110060871B (en) * | 2019-04-04 | 2021-07-09 | 乳源东阳光优艾希杰精箔有限公司 | Preparation method of 1XXX series cathode foil for aluminum electrolytic capacitor |
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| JPH05255790A (en) * | 1992-03-09 | 1993-10-05 | Nippon Foil Mfg Co Ltd | Aluminum alloy foil for electrode of electrolytic capacitor and its manufacture |
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