CN103397227A - Aluminum alloy foil for lithium ion battery positive electrode current collector and preparation method thereof - Google Patents
Aluminum alloy foil for lithium ion battery positive electrode current collector and preparation method thereof Download PDFInfo
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Abstract
The invention provides an aluminum alloy foil for a lithium ion battery positive electrode current collector and a preparation method thereof. The aluminum alloy foil comprises the following components: 0.8-2.0% of Fe, less than or equal to 0.4% of Mn, less than or equal to 0.3% of Si, less than or equal to 0.25% of Mg, less than or equal to 0.02% of Ti, less than or equal to 0.004% of B, and the balance of Al as well as unavoidable impurity elements. The process comprises the following steps of: firstly casting cast ingots, carrying out surface milling and homogenizing heat treatment on the cast ingots, hot rolling, cold rolling, intermediate annealing, and finally rolling into a finished aluminum alloy foil, wherein the temperature in the homogenizing heat treatment is 580-640 DEG C, and the temperature preservation time is 2-15 hours; the total rolling reduction quantity of hot rolling is not less than 85%; the intermediate annealing is carried out when a hot rolled plate is cold rolled to 0.6-2.0mm; before the intermediate annealing, the total cold rolling deformation rate of the plate material is not less than 70%; the total rolling deformation rate from the intermediate annealing to the completion of the finished product aluminum alloy foil is not less than 97%; the intensity and the elongation rate of the aluminum alloy foil are improved, and the specific resistance is lowered.
Description
Technical field
The present invention relates to a kind of lithium ion cell positive collector with alloy foil and preparation method thereof, belong to the non-ferrous metal technical field.
Background technology
Lithium ion battery has that operating voltage is high, energy density is large, memory-less effect, have extended cycle life and the advantage such as pollution-free, becomes main force's power supply of each electronic product.Fashionable along with global plug-in hybrid-power automobile and pure electric automobile, lithium ion battery starts more and more to be applied to the electromobile field.
Alloy foil mainly plays conduction and supports positive electrode material in lithium ion battery, not directly contribution of capacity to lithium ion battery, so, reduce alloy foil thickness by the intensity that improves alloy foil, can increase the glue spread of collector alloy foil surfactant, reach the purpose that increases the battery specific energy.
At present, most of lithium ion batteries mainly adopt the 1XXX aluminium alloy with low-resistivity as collector alloy foil material, thickness is in 20 μ m left and right, and because its strength ratio is lower, aluminum foil thickness, after being thinned to 15 μ m left and right, the broken belt accident occurs easily when positive electrode material is coated with., from the foreign patent of consulting, by the alloying raising alloy foil intensity of alloy foil, come the thickness of attenuate alloy foil to become a kind of development trend.
The patent No. is the JPA2010236055 Japanese Patent,, by adding in aluminium more than the elements such as Mn, Mg have brought up to 200MPa with the tensile strength of alloy foil, prevents from, in the active substance coating process, broken belt occurs.
The patent No. is the JP2008150651 Japanese Patent, by interpolation Mn, Cu, Mg element, makes the tensile strength of alloy foil bring up to 280～380MPa, the problem that when while having solved coating, active substance is easily peeled off with rolling, the crimp radius smaller part breaks.
Above-mentioned patent has solved the problem of alloy foil undercapacity, but by alloying, improves intensity, can cause the rising of alloy foil resistivity, increases the internal resistance of lithium ion battery, reduces effective output energy of lithium ion battery.
Summary of the invention
The objective of the invention is to overcome the problem of the alloy foil resistivity deficiency that prior art produces, provide a kind of lithium ion cell positive collector with alloy foil and preparation method thereof.
Purpose of the present invention is achieved through the following technical solutions:
Lithium ion cell positive collector alloy foil, the quality percentage composition of its composition is: Fe0.8～2.0%, Mn≤0.4%, Si≤0.3%, Mg≤0.25%, Ti≤0.02%, B≤0.004%, all the other are Al and the impurity element that is difficult to avoid.
Further, above-mentioned lithium ion cell positive collector alloy foil, the thickness of described alloy foil are 5～30 μ m, tensile strength 〉=200MPa, unit elongation 〉=2%, resistivity≤3.5 μ Ω ﹒ cm.
Lithium ion cell positive collector of the present invention, with the preparation method of alloy foil, at first goes out ingot casting according to the composition proportion founding, and ingot casting is milled face, homogenizing thermal treatment, hot rolling, cold rolling, and process annealing, last paper tinsel is rolled to the finished product alloy foil; Wherein, the heat treated temperature of homogenizing is 580～640 ℃, and soaking time is 2～15 hours; The total draught of hot rolling is not less than 85%; Hot-rolled sheet is cold rolled to 0.6～2.0mm and carries out process annealing, and before process annealing, the cold rolling total deformation rate of plate is not less than 70%; Batch annealing or continuous annealing are adopted in process annealing; Process annealing is not less than 97% to the rolling total deformation rate between the finished product alloy foil.
Further, above-mentioned lithium ion cell positive collector is with the preparation method of alloy foil, and the temperature range of described batch annealing is 270 ℃～350 ℃, and temperature rise rate is 20 ℃/h～100 ℃/h, and soaking time is 1～10h, then air cooling.
Further, the above-mentioned lithium ion cell positive collector preparation method of alloy foil, the temperature range of described continuous annealing is 380 ℃～480 ℃, and temperature rise rate is not less than 10 ℃/s, and soaking time is not less than 10s, then water-cooled.
The substantive distinguishing features that technical solution of the present invention is outstanding and significant progressive being mainly reflected in:
The present invention, by controlling the preparation technology of alloying constituent and alloy foil, improves intensity and the unit elongation of alloy foil, has reduced simultaneously the resistivity of alloy foil.
Embodiment
Lithium ion cell positive collector alloy foil, its composition: Fe0.8～2.0%, Mn≤0.4%, Si≤0.3%, Mg≤0.25%, Ti≤0.02%, B≤0.004%, all the other are Al and the impurity element that is difficult to avoid.
Fe is the main strengthening element in alloy, and the scope of Fe content is 0.8～2.0%, Fe content lower than 0.8% the time, the intensity that can not obtain to require, and Fe content forms a large amount of Al-Fe compounds while surpassing 2.0%, causes the alloy foil solidity to corrosion to descend.
The Mn element is the strengthening element in alloy, Mn≤0.4%, if Mn element addition surpasses 0.4%, the resistivity of alloy foil will obviously raise, and not meet the demands.
Si is the impurity element in alloy, and Si≤0.3%, Si content higher than 0.3% the time, easily form thick compound in material, make alloy foil produce pin hole.
Mg is the strengthening element in alloy, Mg≤0.25%, and when Mg content surpassed 0.25%, the ductility of material was not enough, the making difficulty of alloy foil.
Ti is the grain refining element, can add with aluminium titanium master alloy form, also can add with the Al-Ti-B intermediate alloy form.Need to control the Ti addition below 0.02%, the addition of B is below 0.004%, otherwise easily forms thick compound, makes alloy foil form pin hole.
The thickness range of alloy foil is 5～30 μ m, and thickness is less than 5 μ m, and the Alloy Foil preparation is difficult; Thickness is greater than 30 μ m, and the specific storage of lithium ion battery is not enough.
Tensile strength 〉=the 200MPa of alloy foil, unit elongation 〉=2%, the not enough 200MPa of tensile strength, unit elongation less than 2%, broken belt easily occurs in alloy foil when the coating positive active material.
The resistivity of alloy foil≤3.5 μ Ω ﹒ cm, resistivity is greater than 3.5 μ Ω ﹒ cm, and the internal resistance of battery is excessive, and output efficiency is low.
The lithium ion cell positive collector, with the preparation method of alloy foil, carries out melting and casting by the composition requirement to aluminium alloy, then mills face, homogenizing thermal treatment, hot rolling, cold rolling, and process annealing, last paper tinsel is rolled to the finished product alloy foil.Wherein, the heat treated temperature of homogenizing is 580～640 ℃, and soaking time is 2～15 hours; The total draught of hot rolling is not less than 85%; Hot-rolled sheet is cold rolled to 0.6～2.0mm carries out process annealing, before process annealing, the cold rolling total deformation rate of plate is not less than 70%; Process annealing can be used batch annealing or continuous annealing, and the temperature range of batch annealing is 270 ℃～350 ℃, and temperature rise rate is 20 ℃/h～100 ℃/h, and soaking time is 1～10h, then air cooling; The temperature range of continuous annealing is 380 ℃～480 ℃, and temperature rise rate is not less than 10 ℃/s, and soaking time is not less than 10s, then water-cooled; Process annealing is not less than 97% to the rolling total deformation rate between the finished product alloy foil.
Melting and casting: at first with the technical pure aluminium ingot 710～770 ℃ of fusings, add aluminium manganese master alloy, ferro-aluminum master alloy, aluminium silicon master alloy, pure magnesium ingot etc., cast after melting purification, degasification, add in chute in castingprocesses and contain the Ti grain-refining agent, control composition content, Fe0.8～2.0%, Mn≤0.4%, Si≤0.3%, Mg≤0.25%, Ti≤0.02%, B≤0.004%;
Homogenizing thermal treatment: temperature is 580～640 ℃, and the hold-time is 2～15 hours, and temperature surpasses 640 ℃ can cause the alloy burning,, lower than 580 ℃, can not realize the purpose of homogenizing.
Hot rolling: the hot rolling total reduction is not less than 85%, is beneficial to the fragmentation of intermetallic compound, guarantees the carrying out of following process and obtains superior product performance.
Cold roller and deformed rate before process annealing: the cold rolling total deformation rate before process annealing is not less than 70%.Before process annealing, cold roller and deformed rate is less than 70%, and the grain fineness number that reaches the finished product alloy foil after process annealing is large, the unit elongation that can not obtain to require.
Process annealing thickness: the process annealing thickness range is 0.6～2.0mm, and the process annealing thickness range all can cause finished product alloy foil unit elongation less than 2% less than 0.6mm or greater than 2mm.
The process annealing system: the process annealing mode can be batch annealing or continuous annealing.
270 ℃～350 ℃ of the temperature ranges of batch annealing, 20 ℃/h of temperature rise rate～100 ℃/h, soaking time 1～10h, then air cooling.The batch annealing temperature is less than 270 ℃, and recrystallize does not occur material.Annealing temperature surpasses 350 ℃, and Mn element back dissolving again, in matrix, increases the resistivity of material.Annealing time was less than 1 hour, and recrystallize does not occur material; Annealing time surpasses 10 hours, coarse grains, and the intensity of alloy foil, unit elongation can not reach requirement.Temperature rise rate is less than 20 ℃/h, and production cost increases; Temperature rise rate is greater than 100 ℃/h, and the inside and outside non-uniform temperature of aluminium volume, cause the aluminium foil performance inhomogeneous.
The temperature range of continuous annealing is 380 ℃～480 ℃, and temperature rise rate is not less than 10 ℃/s, and soaking time is not less than 10s, then water-cooled; The continuous annealing temperature is less than 380 ℃, and recrystallize can not occur material, and the unit elongation of finished product alloy foil can not reach requirement; The continuous annealing temperature is greater than 480 ℃, and production cost increases and material property is not obviously improved.The continuous annealing soaking time is less than 10s, and recrystallize does not occur sheet material, and the unit elongation of finished product aluminium foil can not reach requirement.
Cold roller and deformed rate after process annealing: the cold roller and deformed rate after process annealing is not less than 97%.Cold rolling reduction after process annealing is less than 97%, and the unit elongation of alloy foil can't reach 2%.
The embodiment I
Table 1 is for to prepare the embodiment of the alloy foil that meets the demands by alloying constituent of the present invention, and the performance of using the alloy foil of the alloy manufacturing outside alloying constituent of the present invention.The technique of utilizing alloying constituent in embodiment to prepare alloy foil is: melting, casting also ingot casting are milled face and homogenizing is processed.The homogenizing treatment temp is 620 ℃, and temperature rise rate is 50 ℃/hour, insulation 8h, air cooling after insulation finishes.Ingot casting after homogenizing is processed carries out hot rolling, and the hot rolling cogging temperature is 440 ℃, and the hot rolling deformation amount is 88%, and the thickness of the hot-rolled sheet that obtains is 6mm.Carry out cold rolling and the process annealing processing to hot-rolled sheet, then carry out the rolling of alloy foil, finished product alloy foil thickness is 15 μ m.Process annealing thickness is 1.2mm.Batch annealing is adopted in process annealing, and annealing temperature is 300 ℃, and temperature rise rate is 30 ℃/h, and soaking time is 2 hours, and is cooling in air after insulation.In test-results, intensity does not meet that 200MPa is above, unit elongation does not meet 2% or more, resistivity do not meet that 3.50 μ Ω ﹒ cm are following to be required, and the picture underscore represents below its numerical value.
The impact of table 1 composition alloy performance
In embodiment as shown in table 1, sequence number 1-5 meets scope of the present invention, and tensile strength, unit elongation and resistivity meet requirement of the present invention.On the other hand, in comparative example, sequence number 6-8 is because of discontented foot composition range of the present invention, so cause following result:
Comparative example 6 is too high because of the Mn constituent content, causes the resistance alloys rate to be discontented with the unabridged version scope of invention.
Comparative example 7 is too high because of the Si constituent content, and obtained Foil pinhole is too much, and the aluminium foil mechanical property can't accurately obtain.
Comparative example 8 is because of the Mg too high levels, extends rate variance, and the alloy foil rollability reduces, alloy foil that can not rolling 5～30 μ m.
Comparative example 9 is too low because of Fe content, causes alloy strength can not meet requirement of the present invention.
The embodiment II
Alloy B in his-and-hers watches 1 is carried out the preparation of alloy foil by different technique, wherein homogenizing annealing process is 620 ℃, and 8 hours, temperature rise rate was 50 ℃/h.The temperature rise rate of box-type furnace process annealing is 35 ℃/h, and the continuous annealing temperature rise rate is 100 ℃/s.The impact of table 2 expression preparation technology alloy performance.More than tensile strength does not meet 200MPa, unit elongation does not meet more than 2%, and resistivity does not meet following the creating conditions of requiring of 3.50 μ Ω ﹒ cm, uses the underscore mark below its numerical value.
The manufacturing process of table 2 embodiment and comparative example and performance
In embodiment as shown in table 2, the preparation technology of sequence number 10-13 meets scope of the present invention, and the unit elongation of gained alloy foil, tensile strength and resistivity meet requirement of the present invention.In comparative example, sequence number 14-17 is because of discontented foot processing range of the present invention, so cause following result:
Comparative example 14 is because of the deformation rate after process annealing less than 97%, and the not enough 0.6mm of process annealing thickness, cause alloy unit elongation, the requirement of the present invention of the discontented foot of intensity.
Comparative example 15, less than 70%, causes the Alloy Foil unit elongation can not meet requirement of the present invention because of deformation rate before process annealing.
Comparative example 16, lower than 270 ℃, causes the Alloy Foil unit elongation can not meet requirement of the present invention because of the process annealing temperature.
Comparative example 17, higher than 350 ℃, causes Alloy Foil resistivity can not meet requirement of the present invention because of the process annealing temperature.
In sum, the present invention, by rational technique, carries out the preparation of alloy foil to the alloy in composition range, and the lithium ion battery plus plate current-collecting body aluminium foil of high strength, high-elongation, low-resistivity can be provided.
What need to understand is: the above is only the preferred embodiment of the present invention; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. lithium ion cell positive collector alloy foil, it is characterized in that the quality percentage composition of its composition is: Fe 0.8 ~ 2.0%, Mn≤0.4%, Si≤0.3%, Mg≤0.25%, Ti≤0.02%, B≤0.004%, all the other are Al and the impurity element that is difficult to avoid.
2. lithium ion cell positive collector alloy foil according to claim 1, it is characterized in that: the thickness of described alloy foil is 5 ~ 30 μ m, tensile strength 〉=200MPa, unit elongation 〉=2%, resistivity≤3.5 μ Ω ﹒ cm.
3. lithium ion cell positive collector claimed in claim 1 is with the preparation method of alloy foil, it is characterized in that: at first according to the composition proportion founding, go out ingot casting, ingot casting is milled face, homogenizing thermal treatment, hot rolling, cold rolling, process annealing, last paper tinsel is rolled to the finished product alloy foil; Wherein, the heat treated temperature of homogenizing is 580 ~ 640 ℃, and soaking time is 2 ~ 15 hours; The total draught of hot rolling is not less than 85%; Hot-rolled sheet is cold rolled to 0.6 ~ 2.0mm and carries out process annealing, and before process annealing, the cold rolling total deformation rate of plate is not less than 70%; Batch annealing or continuous annealing are adopted in process annealing; Process annealing is not less than 97% to the rolling total deformation rate between the finished product alloy foil.
4. lithium ion cell positive collector according to claim 3 is with the preparation method of alloy foil, it is characterized in that: the temperature range of described batch annealing is 270 ℃ ~ 350 ℃, temperature rise rate is 20 ℃/h ~ 100 ℃/h, and soaking time is 1 ~ 10h, then air cooling.
5. lithium ion cell positive collector according to claim 3 is with the preparation method of alloy foil, and it is characterized in that: the temperature range of described continuous annealing is 380 ℃ ~ 480 ℃, and temperature rise rate is not less than 10 ℃/s, and soaking time is not less than 10s, then water-cooled.
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| CN104388766A (en) * | 2014-11-27 | 2015-03-04 | 广西南南铝箔有限责任公司 | Production method of aluminum foil for lithium-ion battery |
| CN105063429A (en) * | 2015-07-15 | 2015-11-18 | 浙江中金铝业有限公司 | Method for preparing aluminum foil for lithium battery |
| CN105951006A (en) * | 2016-05-05 | 2016-09-21 | 广东金兰新材料有限公司 | Aluminum foil suitable for lithium ion battery and preparation method thereof |
| JP2018066051A (en) * | 2016-10-21 | 2018-04-26 | 三菱アルミニウム株式会社 | Aluminum alloy foil for battery collector and method for producing the same |
| CN108220696A (en) * | 2018-01-09 | 2018-06-29 | 山西沃特海默新材料科技股份有限公司 | A kind of preparation method of lithium ion battery aluminium foil, micropore aluminium foil and micropore aluminium foil |
| CN112553507A (en) * | 2019-09-10 | 2021-03-26 | 山东南山铝业股份有限公司 | Aluminum foil for high-mechanical-property lithium ion battery anode current collector and processing method |
| CN114901844A (en) * | 2019-12-25 | 2022-08-12 | Ma铝株式会社 | Aluminum alloy foil |
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| CN112553507A (en) * | 2019-09-10 | 2021-03-26 | 山东南山铝业股份有限公司 | Aluminum foil for high-mechanical-property lithium ion battery anode current collector and processing method |
| CN114901844A (en) * | 2019-12-25 | 2022-08-12 | Ma铝株式会社 | Aluminum alloy foil |
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Application publication date: 20131120 |