CN110004329A - A kind of high-strength high conductivity Al-Fe-La-xCu alloy foil - Google Patents
A kind of high-strength high conductivity Al-Fe-La-xCu alloy foil Download PDFInfo
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- CN110004329A CN110004329A CN201910280259.9A CN201910280259A CN110004329A CN 110004329 A CN110004329 A CN 110004329A CN 201910280259 A CN201910280259 A CN 201910280259A CN 110004329 A CN110004329 A CN 110004329A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
-
- 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
-
- 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
- C22F1/057—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 of alloys with copper as the next major constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of high-strength high conductivity Al-Fe-La-xCu alloy foil, and at being grouped as including Fe:0.06~0.3wt%, La:0.06~0.2wt%, Cu:0~0.3wt%, remaining includes aluminium.Alloy foil of the invention maintains high-intensitive and high conductivity, and the alloy foil tensile strength of cold rolling state is 203~235MPa, and conductivity is 56~59%IACS；Alloy foil tensile strength after 160 DEG C of heat treatment in 5 hours is 180~219MPa, and conductivity is 56~58.7%IACS.
Description
Technical field
The present invention relates to a kind of high-strength high conductivity Al-Fe-La-xCu alloy foils.
Background technique
With the worsening of the non-renewable energy resources such as petroleum, natural gas rapidly depleted with ecological environment, sustainable
Before the new clean energy resource of economy and society sustainable development occurs, the mankind can only be above and below the service efficiency that energy is continuously improved
Time, therefore, storage and release to energy will propose increasingly higher demands.Lithium ion battery is high with its energy density, fills
Discharging efficiency height, good cycling stability, operating temperature range is wide, operating voltage is high, self discharge is small, memory-less effect, safety collar
The features such as guarantor, becomes 21 century ideal energy storage device.
Plus plate current-collecting body alloy foil mainly plays electric action in lithium ion battery and support anode coating is lived
The effect of property substance, does not help the capacity of lithium ion battery directly.So two main property of collector alloy foil
Can index be tensile strength and conductivity, the alloy foil of tensile strength and conductivity good combination property is only lithium ion battery and needs
The positive current collector material wanted.In order to mitigate lithium ion battery weight and increase lithium ion battery specific energy, need compared with
More positive active materials are coated on thin collector foil, even if to require alloy foil still to have in lower thickness higher for this
Intensity, it is also desirable to alloy foil has good electric conductivity.
Currently, the positive current collector material for most of lithium ion batteries is mainly that (such as 1060 aluminium close 1XXX aluminium alloy
Gold, 1070 aluminium alloys etc.) and 8XXX aluminium alloy (such as 8021 aluminium alloys, 8079 aluminium alloys).In the aluminium using the two series
When alloy does current collector material, since its intensity is relatively low (>=150MPa), to prevent collector alloy foil in coating anode
It is broken during active material, needs the aluminium foil that comparison is thick, will increase battery weight in this way, decrease positive electrode active material
The coated weight of matter is unfavorable for increasing the capacity of lithium ion battery, and conductivity height is the basic guarantor that lithium ion battery is well run
Card, so market is highly desirable to find collector aluminium alloy that is a kind of new while having good tensile strength and conductivity.
It is dry due to needing to carry out the active material of coating 100~200 DEG C of drying process in cell fabrication processes
Processing can make the strength reduction of collector aluminium foil, be easy to produce winding gauffer, active material and alloy foil table in winding
The adaptation in face declines, and is easy to produce rupture in the subsequent processing, and is unfavorable for collector and collects active material generation
Electric current, the output of biggish current versus can not be formed.
The Al-Fe-Si-Cu-Mn-Mg-Zn-Ti-Zr aluminium alloy reported in patent CN 102245788A is a variety of by adding
The anode current collector of lithium ion battery aluminium foil that alloying element obtains, cold rolling state tensile strength are 204MPa~268MPa, but
It is that conductivity is lower (47.89~55.61%IACS), and does not report the influence of Heat Treatment on Al foil intensity and conductivity.Patent
In CN 102569817A Al-Mn aluminium alloy by add Mn element obtain cold rolling state alloy foil conductivity it is good (>=
57.86%IASC), tensile strength is 191.1MPa~205.6MPa, although it is big to have reached tensile strength in GB/T 33143
In the requirement for being equal to 150MPa, but the patent does not report the influence of Heat Treatment on Al foil intensity, can not judge after heat treatment whether
Still meet tensile strength >=150MPa requirement in GB/T 33143.Patent CN 105658826A passes through addition Fe, Si, Cu, Ti
Tensile strength is the anode current collector of lithium ion battery aluminium foil of 242MPa~335MPa after waiting elements to obtain cold rolling, through 150 DEG C 3
Its tensile strength is greater than 230MPa after hour heat treatment, but conductivity is not high (50.7~55.7%IASC), can not still keep away
Exempt to influence positive active material performance because conductivity is low.
Summary of the invention
The present invention provides at a kind of high-intensitive, high conductivity and heat to solve the problems, such as that above-mentioned comprehensive performance is insufficient
High-intensitive and high conductivity plus plate current-collecting body Al-Fe-La-xCu alloy foil is still kept after reason, it is common low strong to substitute
Degree, low conductivity plus plate current-collecting body alloy foil.Aluminium alloy foil for lithium ion battery positive current collector of the invention is protected simultaneously
High-intensitive and high conductivity is held, the alloy foil tensile strength of cold rolling state is 203~235MPa, and conductivity is 56~59%
IACS；Alloy foil tensile strength after 160 DEG C of heat treatment in 5 hours is 180~219MPa, and conductivity is 56~58.7%
IACS。
The purpose of the present invention is be achieved through the following technical solutions:
A kind of high-strength high conductivity Al-Fe-La-xCu alloy foil, at being grouped as including Fe:0.06~0.3wt%, La:
0.06~0.2wt%, Cu:0~0.3wt%, remaining includes aluminium.
It is 0.05~0.25wt% that the preferred weight at the copper in being grouped as, which matches,.
The tensile strength of the alloy foil is 180~219MPa, and conductivity is 56~58.7%IACS.
A kind of manufacturing method of alloy foil comprising the steps of:
1) intermediate alloy Al-75wt%Fe, Al-20wt%La, Al-50wt%Cu, founding are added during alloy melting
Aluminium alloy cast ingot out；
2) to the homogenize process for casting 590 ± 10 DEG C of holdings 8 hours of resulting aluminium alloy cast ingot work；
3) hot rolling, cold rolling and intermediate annealing are implemented to the aluminum alloy blank after homogenize process, obtain with a thickness of 0.04~
The alloy foil of 0.09mm.
The ingredient comparison of high-strength high conductivity aluminium alloy and comparative example aluminium alloy of the invention is shown in Table 1.
The aluminium alloy of the present invention of table 1 and comparative example al alloy component (wt%)
The present invention is by three Aluminium alloy foil for lithium ion battery positive current collector patents (patent CN102245788A, patent
CN102569817A and patent CN105658826A) and an anode current collector of lithium ion battery Aluminium Alloys in Common Use 8079Al conduct
Comparative example.Comparative example 1 is patent CN102245788A, gives a kind of aluminum alloy foil for current collector and its manufacturing method.Comparison
Example 2 is patent CN102569817A, gives a kind of aluminium alloy foil for current collector of anode of lithium ion battery and preparation method thereof.It is right
Ratio 3 is patent CN105658826A, gives a kind of electrode collector alloy foil and its manufacturing method.Comparative example 4 is
8079Al alloy.
From table 1 it follows that aluminium alloy of the present invention has reduced Fe element compared with the al alloy component of comparative example 1
Dosage, and silicon addition, Mg, Mn, Ti, Zn and Zr are free of, but increase the dosage of Cu, and be added to rare-earth elements La.Fe
Element all has an impact to the intensity and conductivity of aluminium alloy, and adding the very few intensity that can be enabled aluminum alloy to cannot improve, but electric
Conductance is relatively high；The intensity that adding can excessively enable aluminum alloy to greatly improves but conductivity can also decline to a great extent.In order to guarantee
Alloy foil has high conductivity and high intensity simultaneously, and the present invention is added to less Fe element.While in order to make up Fe content
The relatively fewer defect that intensity can be made inadequate, the present invention utilize the strengthening effect of Cu element, increase the content of Cu element.La member
It is known as and is conducive to refinement crystal grain, prevent the generation of large scale precipitated phase.The al alloy component design of comparative example 2 is very simple, only adds
Mn element is added, Mn can alleviate local deformation, while improve tensile strength and elongation percentage.With the al alloy component of comparative example 3
It compares, Fe content of the present invention is less, and is free of Ti element.In addition the addition meeting refining alloy crystal grain of La element, promotes aluminium alloy
Al3Fe Second Phase Precipitation and nodularization can also generate AlFeLa cenotype, further reinforced alloys.With the aluminium alloy of comparative example 4 at
Split-phase ratio, design of alloy of the present invention are simpler.
Alloy foil prepared in accordance with the present invention is that one kind has the high-strength high conductivity of rolling state and still has after being heat-treated
There is the Al-Fe-La-xCu alloy foil of high-strength high conductivity, can be used for anode current collector of lithium ion battery.
Specific embodiment
Detailed description of the preferred embodiments below.
Hereinafter, by embodiment, the present invention is described in detail, but the present invention is not limited to these embodiments.
A kind of high-strength high conductivity Al-Fe-La-xCu alloy foil, it is characterised in that: at be grouped as including Fe:0.06~
0.3wt%, La:0.06~0.2wt%, Cu:0~0.3wt%, remaining includes aluminium.
It is 0.05~0.25wt% that the preferred weight at the copper in being grouped as, which matches,.
The tensile strength of the alloy foil is 180~219MPa, and conductivity is 56~58.7%IACS.
A kind of manufacturing method of alloy foil described in claim 1-3 comprising the steps of:
1) intermediate alloy Al-75wt%Fe, Al-20wt%La, Al-50wt%Cu, founding are added during alloy melting
Aluminium alloy cast ingot out；
2) to the homogenize process for casting 590 ± 10 DEG C of holdings 8 hours of resulting aluminium alloy cast ingot work；
3) hot rolling, cold rolling and intermediate annealing are implemented to the aluminum alloy blank after homogenize process, obtain with a thickness of 0.04~
The alloy foil of 0.09mm.
The alloy cast ingot with a thickness of 40mm is made in the aluminium alloy that ingredient shown in table 2 is prepared using vacuum induction melting method.So
Afterwards, 590 ± 10 DEG C of homogenize process for being kept for 8 hours, facing later, milling face are carried out to the ingot casting.At 500 ± 10 DEG C
At a temperature of implement to be hot-rolled down to 3mm thickness, hot rolled plate cold rolling (intermediate 300 DEG C of stress relief annealings) is obtained with a thickness of 0.04~
The alloy foil of 0.09mm.
2 al alloy component of table
Then the heat treatment in 5 hours of 160 DEG C of constant temperature is carried out, to obtained each aluminium alloy foil material, tensile strength is measured, prolongs
Rate, conductivity are stretched, and is evaluated.Test result is shown in Table 3.
The performance test process carried out to the aluminum alloy sample of heterogeneity in above-described embodiment and comparative example is as follows:
(1) tensile tests at room: being made standard tensile specimen according to national standard GB/T 228-2002, omnipotent in Zwick Z20
It is stretched on tensile testing machine, measures tensile strength and elongation percentage；In addition, the back tender in simulation lithium ion battery manufacture craft
Sequence cuts along rolling direction to the alloy foil after 160 DEG C of heat treatments in constant temperature 5 hours, measures tension by above-mentioned same mode
Intensity and elongation percentage.Using alloy foil as when anode current collector of lithium ion battery material, the preferred of cold rolling state alloy foil resists
Tensile strength is 200MPa or more, and the preferred tensile strength of alloy foil is 180MPa or more after heat treatment.
(2) conductivity is tested: using the conductivity of 2.069 conductance instrument of SIGMATEST test aluminum alloy specimen.
Using alloy foil as when anode current collector of lithium ion battery material, preferably conductivity is 55%IACS or more.
3 alloy foil the performance test results of table
It can be confirmed by the result of table 3, the alloy foil in Examples 1 to 6 all meets cold rolling state tensile strength and is greater than
Tensile strength after 200MPa, heat treatment is greater than 180MPa and conductivity is greater than the preferred requirement of 55%IACS.Preferred component aluminium
Alloy Foil No. 3 and No. 5 maintain high-intensitive and high conductivity, the tension of most preferably ingredient alloy foil 3 cold rolling states
Intensity is 235.67MPa, conductivity 56.64%IACS, and tensile strength is after 160 DEG C of heat treatment in 5 hours
219.33MPa conductivity 56.12%IACS.Alloy foil has very high tensile strength and conductivity after cold rolling, 160
After heat treatment in DEG C of constant temperature 5 hours, the tensile strength of most of alloy foils slightly declines, and conductivity is almost unchanged.
Compared to the alloy foil in 3 comparative examples, the alloy foil intensity in the embodiment of the present invention is greatly improved, highest
Promoted 71.4%, this is because in comparative example the Fe constituent content of alloy foil it is too low and be not added with Cu member usually make up intensity lack
It loses.
Compared with the alloy foil in 4 comparative examples, the alloy foil either cold rolling state in the embodiment of the present invention 3 is still
Heat treatment state all has high-intensitive and high conductivity simultaneously, also indicates that alloy foil of the invention has good comprehensive performance.
The present invention is designed by using reasonable ingredient so that the alloy foil in above-described embodiment has obtained good foil
Material performance.The addition of appropriate Fe element is so that intensity of aluminum alloy improves, and a small amount of Cu element also has the effect for improving alloy strength
Fruit.The addition of La element can improve the microstructure of alloy, and promote aluminium alloy Al with refining alloy crystal grain3The second phase of Fe
Precipitation and nodularization, can also generate AlFeLa cenotype, play the role of strengthening aluminum metal substrate, but the crystal grain refinement of excess La is imitated
Fruit weakens, and metal strengthening effect also weakens.
Based on embodiment, the present invention is described above, but the present invention is not limited only to embodiment, all to be gone out by the present invention
The variation of hair, these variations also belong to the scope of protection of the invention.
Claims (4)
1. a kind of high-strength high conductivity Al-Fe-La-xCu alloy foil, it is characterised in that: at be grouped as including Fe:0.06~
0.3wt%, La:0.06~0.2wt%, Cu:0~0.3wt%, remaining includes aluminium.
2. alloy foil according to claim 1, which is characterized in that the preferred weight at the copper in being grouped as matches
For 0.05~0.25wt%.
3. alloy foil as claimed in claim 2, which is characterized in that the tensile strength of the alloy foil is 180~219MPa,
Conductivity is 56~58.7%IACS.
4. a kind of manufacturing method of alloy foil described in claim 1-3, which is characterized in that comprise the steps of:
1) intermediate alloy Al-75wt%Fe, Al-20wt%La, Al-50wt%Cu are added during alloy melting, founding goes out aluminium
Alloy cast ingot；
2) to the homogenize process for casting 590 ± 10 DEG C of holdings 8 hours of resulting aluminium alloy cast ingot work；
3) hot rolling, cold rolling and intermediate annealing are implemented to the aluminum alloy blank after homogenize process, obtain with a thickness of 0.04~
The alloy foil of 0.09mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910280259.9A CN110004329A (en) | 2019-04-09 | 2019-04-09 | A kind of high-strength high conductivity Al-Fe-La-xCu alloy foil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910280259.9A CN110004329A (en) | 2019-04-09 | 2019-04-09 | A kind of high-strength high conductivity Al-Fe-La-xCu alloy foil |
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| CN110004329A true CN110004329A (en) | 2019-07-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139378A (en) * | 2020-01-19 | 2020-05-12 | 上海华峰铝业股份有限公司 | Aluminum foil for high-strength high-conductivity current collector and preparation method thereof |
| CN111224108A (en) * | 2020-01-19 | 2020-06-02 | 上海华峰铝业股份有限公司 | Positive current collector of low-resistivity lithium ion battery |
| CN112899505A (en) * | 2021-01-13 | 2021-06-04 | 上海华峰铝业股份有限公司 | High-strength aluminum alloy foil for positive current collector and preparation method thereof |
| CN114703405A (en) * | 2022-04-12 | 2022-07-05 | 江苏中基复合材料有限公司 | High-strength high-conductivity Al-Fe-La-Cu aluminum alloy foil and preparation method thereof |
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| JP5182784B2 (en) * | 2007-03-13 | 2013-04-17 | 住友軽金属工業株式会社 | Aluminum alloy foil for electrolytic capacitor electrode |
| CN103733398A (en) * | 2011-07-29 | 2014-04-16 | 株式会社Uacj | Collector, electrode structure, non-aqueous electrolyte battery, and electricity storage component |
| CN103748717A (en) * | 2011-07-29 | 2014-04-23 | 株式会社Uacj | Aluminum alloy foil for electrode collector and production method therefor |
| CN108823437A (en) * | 2018-06-29 | 2018-11-16 | 华峰日轻铝业股份有限公司 | A kind of high intensity collector alloy foil and its manufacturing method |
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2019
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Patent Citations (4)
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| JP5182784B2 (en) * | 2007-03-13 | 2013-04-17 | 住友軽金属工業株式会社 | Aluminum alloy foil for electrolytic capacitor electrode |
| CN103733398A (en) * | 2011-07-29 | 2014-04-16 | 株式会社Uacj | Collector, electrode structure, non-aqueous electrolyte battery, and electricity storage component |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111139378A (en) * | 2020-01-19 | 2020-05-12 | 上海华峰铝业股份有限公司 | Aluminum foil for high-strength high-conductivity current collector and preparation method thereof |
| CN111224108A (en) * | 2020-01-19 | 2020-06-02 | 上海华峰铝业股份有限公司 | Positive current collector of low-resistivity lithium ion battery |
| CN112899505A (en) * | 2021-01-13 | 2021-06-04 | 上海华峰铝业股份有限公司 | High-strength aluminum alloy foil for positive current collector and preparation method thereof |
| CN114703405A (en) * | 2022-04-12 | 2022-07-05 | 江苏中基复合材料有限公司 | High-strength high-conductivity Al-Fe-La-Cu aluminum alloy foil and preparation method thereof |
| CN114703405B (en) * | 2022-04-12 | 2023-01-31 | 江苏中基复合材料有限公司 | High-strength high-conductivity Al-Fe-La-Cu aluminum alloy foil and preparation method thereof |
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