CN110205524A - A kind of high extension power battery aluminium foil and preparation method thereof - Google Patents
A kind of high extension power battery aluminium foil and preparation method thereof Download PDFInfo
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- CN110205524A CN110205524A CN201910558953.2A CN201910558953A CN110205524A CN 110205524 A CN110205524 A CN 110205524A CN 201910558953 A CN201910558953 A CN 201910558953A CN 110205524 A CN110205524 A CN 110205524A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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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- 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 invention discloses a kind of high extension power battery aluminium foils and preparation method thereof, the aluminium foil alloy material proportion are as follows: 0.2-0.4%Si, 1.2-1.3%Fe, 0.2-0.3%Cu, 0.05-0.1%Zr, 0.05-0.1%Ti, 0.02-0.05%B, remaining is Al and the inevitable impurity less than 0.15%；The percentage is mass percent, the preparation method is followed successively by melting, primary rotten, casting, secondary metamorphic, homogenizing annealing, cold rolling and finished products, preparation process of the present invention is simple compared to common process, and lumber recovery and energy-saving can be improved simultaneously, aluminium foil tensile strength >=230MPa prepared by the present invention, elongation percentage >=6.0% substantially increases aluminium foil applied to the service performance of power battery and the yield rate of lithium ion battery.
Description
Technical field
The present invention relates to a kind of high extension power battery aluminium foils and preparation method thereof, belong to aluminium foil technical field.
Background technique
New-energy automobile has become the hot spot of world development, and wherein new-energy automobile the main direction of development is using power
The hybrid electric vehicle and pure electric vehicle of lithium ion battery.In recent years, power lithium-ion battery industry is by countries in the world government
Pay much attention to and supports energetically.Compared with conventional batteries, power lithium-ion battery is high with energy density, operating voltage is high, again
Measure that light, small in size, self discharge is small, memory-less effect, have extended cycle life, charge the advantages such as quickly, simultaneously because without lead, cadmium etc.
Heavy metal, referred to as New Green Energy product-derived.With the raising that the development of the new energy vehicles and energy conservation and environmental protection require, power
The market space of lithium ion battery is by further expansion.
It is 48.5GWh that the whole world in 2016, which is applied to electric automobile power battery scale, is consumer electronics, power, energy storage three
The maximum plate of increment in macroplate.It will be more than 340GWh that GGII, which expects global electric automobile lithium battery demand in 2022,
Scale is 7 times in 2016.
Chinese automobile dynamic lithium battery yield is 30.8GWh within 2016, increases by 82.2% on a year-on-year basis.As the following lithium battery is raw
The popularization degree raising etc. of skill upgrading, cost decline, new-energy automobile and auxiliary facility is produced, 3 years futures new-energy automobile moves
Power battery requirements will keep sustainable growth, and GGII expects Chinese automobile dynamic lithium battery yield in 2022 and is up to 215GWh,
Increase nearly 6 times within year-on-year 2016.
Currently, in power battery aluminium foil, the manufacturers such as domestic merchants' Aluminum, northeast light-alloy and external aluminium sheet supply
Quotient is using melting --- hot rolling --- cold-rolling process process, and production is got up with high energy consumption, and process is more, and low wait of lumber recovery lacks
Point.And casting and roll process production dynamic lithium battery aluminium sheet at home and abroad rarely has people to be related to, program processing technology difficulty is big, produces work
Skill is stringent.
Power function material is used as the current-collector of lithium ion battery with aluminium foil, and tensile strength allows for obtaining preferable
The electrode for being coated with graphite isoreactivity substance when elongation percentage is low, is carried out roll calendering etc. and flattened by control if tensile strength is excessively high
In process, power function material aluminium foil adapts to active material surface characteristic without enough deformations, and power function material is used
Contact performance between aluminium foil and active material is deteriorated；On the contrary, if electrode when tensile strength is lower coated with active material exists
It carries out roll calendering etc. to flatten in process, so that electrode size stability and planarization is deteriorated, and is also easy to produce fracture etc. and ask
Topic.There must also be enough elongation percentage simultaneously, if elongation percentage is low, the electrode for being coated with active material is carrying out roll calendering etc.
When flattening process, power function material aluminium foil itself will generate internal stress, and divide, and directly affect battery capacity, follow
The performances such as ring service life.Under normal conditions, lithium ion battery industry is the anode of negative collector electrode, aluminum foil thickness using battery aluminium foil
It is differed at 10 to 50 microns.Common lithium battery pure aluminum foil has the alloy designations H18 states such as 1060,1050,8011, according to current electricity
Pond foil market situation is using 1235 alloys as main alloying material.And lithium battery manufacturing enterprise is used as high-end power function material aluminium
Foil is mainly produced from external import hot rolling base production power function material with aluminium foil, and China is in high-end power function material
Essentially consist in that intensity is partially soft, elongation percentage is low, compactness is insufficient, surface roughness is uneven, surface matter compared with foreign countries with aluminium foil
Measure cleannes not enough and other issues, at present.Existing power battery aluminium foil tensile strength is generally in 190Mpa, elongation percentage 4%, and
Tensile strength is corresponding with extension, and intensity is high, then extends just low.
Summary of the invention
Based on the deficiencies of the prior art, the present invention is intended to provide it is a kind of it is high extend power battery aluminium foil manufacture material and
Preparation method further improves power battery aluminium foil while keeping or raising aluminium alloy high-strength, compactness are good
High-elongation.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of high extension power battery aluminium foil, the aluminium foil alloy material proportion are as follows: 0.2-0.4%Si, 1.2-1.3%
Fe, 0.2-0.3%Cu, 0.05-0.1%Zr, 0.05-0.1%Ti, 0.02-0.05%B, remaining is for Al and less than 0.15%
Inevitable impurity；The percentage is mass percent.
A kind of high preparation method for extending power battery aluminium foil, characterized in that the following steps are included:
1) melting is matched according to alloy material, and aluminium ingot raw material is added, and aluminium silicon intermediate alloy, aluminium is added after raw material melting
Iron intermediate alloy, copper-aluminium master alloy carry out composition adjusting；Raw material imports standing furnace after melting, is become in standing furnace
Matter processing；Smelting temperature reaches 680-700 DEG C and leads furnace in the process, and Metamorphism treatment, Metamorphism treatment are carried out in standing furnace after leading furnace
It is the addition aluminum-zirconium alloy into standing furnace, controls the total amount of aluminum-zirconium alloy in rotten, contains the zirconium weight before casting in molten aluminum
Amount is in 0.05-0.1%；
2) casting: the molten aluminum handled well is subjected to casting, secondary metamorphic is carried out in degasification tank, secondary metamorphic is in degasification
In case plus aluminium titanium boron wire, the total amount of Al-Ti-B alloy in rotten is controlled, makes the titanium weight content before casting in molten aluminum in 0.05-
0.1%, boron weight content is in 0.02-0.05%；
3) homogenizing annealing: the casting produced volume is first subjected to Homogenization Treatments, annealing process are as follows: furnace gas temperature
450-500 DEG C of heating, when metal temperature reaches 420-460 DEG C, heat preservation 5-6 hours of 420-460 DEG C of converter gas temperature is cold after annealing
But room temperature is arrived.
4) cold rolling: the good aluminium volume of Homogenization Treatments is subjected to cold rolling calendering, then trimming is cold-rolled to finished product thickness, cold rolling
It is cooling using ROLLING OIL in the process.
5) finished products: the aluminium volume of finished product thickness is subjected to stress relief annealing, to reach the mechanical property of requirement.
Further, zirconium weight content is 9%-11% in aluminum-zirconium alloy described in step (1), remaining is aluminium.
Further, titanium weight content is 4.5-5.5% in aluminium titanium boron wire described in step (2), and boron weight content is
0.9-1.2%, remaining is aluminium.
Further, in step (4) ROLLING OIL viscosity: 1.7-2.1 (40 DEG C of mm2/ s), saponification number: 4.0-
6.0mgKOH/g, hydroxyl value: 0.05-0.1mgKOH/g, acid value: 0.1-0.3mgKOH/g.
Further, finished product annealing process in step (5) are as follows: 120-180 DEG C of furnace gas temperature heating, holding 4-8 hours, so
330-380 DEG C of furnace gas temperature heating afterwards is kept for 6-10 hours, and then 150-200 DEG C of furnace gas temperature, is kept for 3-5 hours.
Reaction mechanism:
Main adding elements are described as follows in the present invention:
Si:0.2-0.4% (hereinafter, the content of each ingredient indicates weight %) Si is the essential element for refining crystal grain, simultaneously
Casting Rolled Sheet face crack tendence can be reduced, in order to obtain said effect, preferably adds 0.2% or more Si, but Si content
When higher than 0.4%, low-alloyed plasticity can be dropped, is easily broken off, therefore Si content is preferably limited to 0.2-0.4%；
Fe:1.2-1.3%, the Fe maximum solubility in aluminium are 0.052%, when iron-content is greater than 0.052% in aluminium,
Its tissue generated is α (Al) and α (Al)+FeCl3Eutectic prevents alloy structure from being roughened, preferably adds to obtain the effect
Add 1.2% or more Fe, but the tissue then generated when Fe is more than 1.3% is primary crystal FeAl3And α (Al)+FeCl3Eutectic, just
Brilliant FeAl3In needle-shaped or fine strip shape, hard crisp and indissoluble reduces alloy plasticity, therefore Fe content is preferably limited to 1.2-1.3%；
Cu:0.2-0.3%, the addition of copper can reduce transgranular and intergranular potential difference, so that improving alloy resists stress corruption
Erosion effect, while spot corrosion can be made to become homogeneous corrosion, it reduces material surface roughness and preferably adds to obtain the effect
Add 0.2% or more Cu, but when copper content is higher than 0.3%, form hardening constituent with other elements, and change stress corrosion and
Toughness.Therefore Cu content is preferably limited to 0.2-0.3%；
Zr:0.05-0.1%, Zr energy thinning microstructure, change the second phase crystal form, form the ZrAl3 of small and dispersed more
Dephasing hinders recrystallization and crystal grain to grow up, and in order to obtain the effect, preferably adds 0.05% or more Zr, but works as Zr content
Crystallization particle is provided higher than 0.1%, Zr, it is hard to tolerate, the defects of forming informal voucher, is deposited in molten aluminum.Therefore Zr content is preferably limited to
0.05-0.1%.
Ti:0.05-0.1%, titanium mainly play a part of to refine crystal grain as important processing additive.In order to obtain
Effect is stated, preferably adds 0.05% or more, when Ti content is higher than 0.1%, coarse Al can be formed in Casting Rolled Sheet3Ti is mentioned
The brittleness of high plate.Therefore, the Ti content is preferably limited to 0.05-0.1%.
B:0.02-0.05%, B are added in a manner of TiB2 particle, and the crystal grain of as cast condition is refined, and improve recrystallization temperature
Degree preferably adds 0.02% or more B, but when B content is higher than 0.05%, is easy to produce gas to obtain the effect
Road, the defects of being mingled with.Therefore, the B content is preferably limited to 0.02-0.05%.
The high power battery aluminium foil that extends produced by the invention uses Metamorphism treatment twice, interacts, mentions between alloy
The high plastic deformation of material, elongation percentage is improved while ensure that high intensity, improves the paintability of material, is solved
Because performance is bad, the problem of caused electrode size stability and planarization are deteriorated.The compactness of material is good simultaneously, coating
Uniformity and good conductivity.
Compared with prior art, the present invention has the advantages that protrusion:
(1) present invention is produced using casting and roll process, eliminates ingot casting, hot rolling cogging, assembly weldering in conventional production process
It connects, the complex techniques processes such as method hot rolling, while improving lumber recovery, it is energy-saving.
(2) power battery aluminium foil is extended using the high of 5-10 μm of production that the method for the present invention may be implemented to stablize batch.
Aluminium foil tensile strength >=230MPa produced by the invention, elongation percentage >=6.0%, significantly larger than other condition of equivalent thickness battery aluminium foils
Can, to substantially increase the service performance of aluminium foil and the yield rate of lithium ion battery.The surface density of the produced aluminium foil of the present invention
>=45.36g/m, it is thick it is poor≤1.5%, and coating performance is more excellent.
Specific embodiment
The invention will be further described below.Following embodiment is only used for clearly illustrating technical side of the invention
Case, and not intended to limit the protection scope of the present invention.
Embodiment 1:
Height extend power battery with aluminium foil melting by weight percentage: Si:0.2%, Fe:1.22%, Cu:0.23%, Zr:
0.06%, Ti:0.05%, B:0.03%, remaining is the proportion of impurity element and aluminium as basic composition, preparation raw material.
It is specific the preparation method is as follows:
1) melting is matched by alloy composition, wherein waste material is embedded in furnace bottom, herein, can be used for clear away waste, then by aluminium
Ingot is added, and aluminium silicon intermediate alloy, ferro-aluminum intermediate alloy, copper-aluminium master alloy are added after raw material melting and carries out composition adjusting；Raw material
Standing furnace is imported after melting, and Metamorphism treatment is carried out in standing furnace；Smelting temperature reaches 690 DEG C and leads furnace in the process, leads furnace
Metamorphism treatment is carried out in standing furnace afterwards, Metamorphism treatment is the addition aluminum-zirconium alloy into standing furnace, zirconium in the aluminum-zirconium alloy
Weight content 9.35%, remaining is aluminium；The total amount of aluminum-zirconium alloy during control is rotten contains the zirconium weight before casting in molten aluminum
Amount is 0.06%；
2) casting: the molten aluminum handled well is subjected to casting, secondary metamorphic is carried out in degasification tank, secondary metamorphic is in degasification
Add aluminium titanium boron wire in case, titanium 4.52% in the aluminium titanium boron wire, boron 1.13%, remaining is aluminium；Al-Ti-B alloy during control is rotten
Total amount, make the titanium weight content before casting in molten aluminum 0.05%, boron weight content is 0.03%；
3) homogenizing annealing: the casting volume produced first carries out Homogenization Treatments, annealing process are as follows: furnace gas temperature 470
DEG C heating, when metal temperature reaches 430 DEG C, 430 DEG C of converter gas temperature keep the temperature 6 hours, room temperature is cooled to after annealing.
4) cold rolling: the good aluminium volume of Homogenization Treatments is subjected to cold rolling calendering, then trimming is cold-rolled to finished product thickness, cold rolling
It is cooling using ROLLING OIL in the process, the viscosity of ROLLING OIL: 1.89 (40 DEG C of mm2/ s), saponification number: 5.2mgKOH/g, hydroxyl value:
0.08mgKOH/g, acid value: 0.2mgKOH/g.
5) finished products: finished product thickness aluminium volume carry out stress relief annealing, reach suitable mechanical property (tensile strength,
Elongation percentage), annealing process are as follows: 150 DEG C of furnace gas temperature heatings are kept for 6 hours, then 360 DEG C of furnace gas temperature heatings, and holding 8 is small
When, then 180 DEG C of furnace gas temperature, are kept for 4 hours.
The extension power battery aluminium foil produced according to above-mentioned steps, tensile strength 237MPa, elongation percentage 7.3%.
Embodiment 2:
Height extend power battery with aluminium foil melting by weight percentage: Si:0.36%, Fe:1.28%, Cu:0.23%,
Zr:0.08%, Ti:0.07%, B:0.04%, remaining is the proportion of impurity element and aluminium as basic composition, preparation raw material.
It is specific the preparation method is as follows:
1) melting is matched by alloy composition, wherein waste material is embedded in furnace bottom, then aluminium ingot is added, and is added after raw material melting
Enter aluminium silicon intermediate alloy, ferro-aluminum intermediate alloy, copper-aluminium master alloy and carries out composition adjusting；Raw material imports standing after melting
Furnace carries out Metamorphism treatment in standing furnace；Smelting temperature reaches 700 DEG C and leads furnace in the process, is become in standing furnace after leading furnace
Matter processing, Metamorphism treatment are the addition aluminum-zirconium alloys into standing furnace, the weight content 9.35% of zirconium in the aluminum-zirconium alloy,
Remaining is aluminium；The total amount of aluminum-zirconium alloy during control is rotten makes the zirconium weight content before casting in molten aluminum 0.09%；
2) casting: the molten aluminum handled well is subjected to casting, secondary metamorphic is carried out in degasification tank, secondary metamorphic is in degasification
Add aluminium titanium boron wire in case, titanium 4.52% in the aluminium titanium boron wire, boron 1.13%, remaining is aluminium；Al-Ti-B alloy during control is rotten
Total amount, make the titanium weight content before casting in molten aluminum 0.1%, boron weight content is 0.05%；
3) homogenizing annealing: the casting volume produced first carries out Homogenization Treatments, annealing process are as follows: furnace gas temperature 490
DEG C heating, when metal temperature reaches 430 DEG C, 430 DEG C of converter gas temperature keep the temperature 6 hours, room temperature is cooled to after annealing.
4) cold rolling: the good aluminium volume of Homogenization Treatments is subjected to cold rolling calendering, then trimming is cold-rolled to finished product thickness, cold rolling
It is cooling using ROLLING OIL in the process.The viscosity of ROLLING OIL: 1.9 (40 DEG C of mm2/ s), saponification number: 5.5mgKOH/g, hydroxyl value:
0.08mgKOH/g, acid value: 0.2mgKOH/g.
5) finished products: finished product thickness aluminium volume carry out stress relief annealing, reach suitable mechanical property (tensile strength,
Elongation percentage), annealing process are as follows: 150 DEG C of furnace gas temperature heatings are kept for 6 hours, then 360 DEG C of furnace gas temperature heatings, and holding 8 is small
When, then 180 DEG C of furnace gas temperature, are kept for 4 hours.
The extension power battery aluminium foil produced according to above-mentioned steps, tensile strength 248MPa, elongation percentage 6.9%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (6)
1. a kind of high extension power battery aluminium foil, characterized in that the aluminium foil alloy material proportion are as follows: 0.2-0.4%Si,
1.2-1.3%Fe, 0.2-0.3%Cu, 0.05-0.1%Zr, 0.05-0.1%Ti, 0.02-0.05%B, remaining is Al and is less than
0.15% inevitable impurity；The percentage is mass percent.
2. a kind of high preparation method for extending power battery aluminium foil according to claim 1, characterized in that including following
Step:
1) melting is matched according to alloy material, and aluminium ingot raw material is added, and aluminium silicon intermediate alloy is added after raw material melting, in ferro-aluminum
Between alloy, copper-aluminium master alloy carry out composition adjusting；Raw material imports standing furnace after melting, and rotten place is carried out in standing furnace
Reason；Smelting temperature reaches 680-700 DEG C and leads furnace in the process, leads and carries out Metamorphism treatment after furnace in standing furnace, Metamorphism treatment be to
Aluminum-zirconium alloy is added in standing furnace, controls the total amount of aluminum-zirconium alloy in rotten, and the zirconium weight content before casting in molten aluminum is made to exist
0.05-0.1%；
2) casting: the molten aluminum handled well is subjected to casting, secondary metamorphic is carried out in degasification tank, secondary metamorphic is in degasification tank
Add aluminium titanium boron wire, control the total amount of Al-Ti-B alloy in rotten, makes titanium weight content before casting in molten aluminum in 0.05-0.1%,
Boron weight content is in 0.02-0.05%；
3) homogenizing annealing: the casting produced volume is first subjected to Homogenization Treatments, annealing process are as follows: furnace gas temperature 450-
500 DEG C of heatings, when metal temperature reaches 420-460 DEG C, heat preservation 5-6 hours of 420-460 DEG C of converter gas temperature is cooled to after annealing
Room temperature.
4) cold rolling: the good aluminium volume of Homogenization Treatments is subjected to cold rolling calendering, then trimming is cold-rolled to finished product thickness, cold-rolled process
It is middle cooling using ROLLING OIL.
5) finished products: the aluminium volume of finished product thickness is subjected to stress relief annealing, to reach the mechanical property of requirement.
3. a kind of high preparation method for extending power battery aluminium foil according to claim 2, characterized in that step (1)
Described in aluminum-zirconium alloy zirconium weight content be 9%-11%, remaining is aluminium.
4. a kind of high preparation method for extending power battery aluminium foil according to claim 2, characterized in that step (2)
Described in aluminium titanium boron wire titanium weight content be 4.5-5.5%, boron weight content is 0.9-1.2%, remaining is aluminium.
5. a kind of high preparation method for extending power battery aluminium foil according to claim 2, characterized in that step (4)
The viscosity of middle ROLLING OIL: 1.7-2.1 (40 DEG C of mm2/ s), saponification number: 4.0-6.0mgKOH/g, hydroxyl value: 0.05-0.1mgKOH/g,
Acid value: 0.1-0.3mgKOH/g.
6. a kind of high preparation method for extending power battery aluminium foil according to claim 2, characterized in that step (5)
Middle finished product annealing process are as follows: 120-180 DEG C of furnace gas temperature heating is kept for 4-8 hours, then 330-380 DEG C of furnace gas temperature heating,
It is kept for 6-10 hours, then 150-200 DEG C of furnace gas temperature, is kept for 3-5 hours.
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| CN111822504A (en) * | 2020-07-02 | 2020-10-27 | 江苏鼎胜新能源材料股份有限公司 | Method for manufacturing medicinal aluminum foil |
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| CN113611816A (en) * | 2021-08-05 | 2021-11-05 | 山西中科华孚电池研究总院有限公司 | Heat treatment method of battery aluminum foil, battery aluminum foil obtained by heat treatment method and lithium ion battery |
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