CN110846542B - Aluminum alloy for battery case of new energy automobile and production process of aluminum alloy - Google Patents

Aluminum alloy for battery case of new energy automobile and production process of aluminum alloy Download PDF

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CN110846542B
CN110846542B CN201911266257.0A CN201911266257A CN110846542B CN 110846542 B CN110846542 B CN 110846542B CN 201911266257 A CN201911266257 A CN 201911266257A CN 110846542 B CN110846542 B CN 110846542B
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aluminum alloy
battery case
new energy
refining
energy automobile
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CN110846542A (en
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崔立新
赵晓光
焦培勇
韩连涛
张伟
许庆斌
成凯
李明壮
王志伟
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Shandong Innovation Precision Technology Co Ltd
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Shandong Innovation Metal Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/10Alloys based on aluminium with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/053Changing 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 zinc as the next major constituent

Abstract

The invention relates to the field of metallurgy, in particular to an aluminum alloy for a battery case of a new energy automobile and a production process thereof. The aluminum alloy product comprises the following elements in percentage by mass: zn: 3.4-5.1; mg: 2.3-2.7; cu: 1.7-1.9; fe: 0.3-0.8; mn: 0.1-0.4; si: 0.1-0.3; cr: 0.15-0.26; ti: 0.12-0.15; the balance being Al and unavoidable impurities. The preparation process comprises multiple procedures of refining, filtering, casting, calendaring, homogenizing treatment, artificial aging, hot static pressure treatment and the like. The aluminum alloy plate produced by the process has the characteristics of high tensile strength and yield strength, high hardness and excellent fatigue resistance; the method is very suitable for manufacturing the battery case of the new energy automobile.

Description

Aluminum alloy for battery case of new energy automobile and production process of aluminum alloy
Technical Field
The invention relates to the field of metallurgy, in particular to an aluminum alloy for a battery case of a new energy automobile and a production process thereof.
Background
The new energy automobile is an automobile which adopts unconventional automobile fuel as a power source, integrates advanced technologies in the aspects of power control and driving of the automobile, and is advanced in technical principle, new in technology and new in structure. The new energy automobile in the current market is mainly an electric automobile, and the electric automobile takes electric power as a power source and utilizes a motor to drive the automobile to rotate. In order to improve safety and cruising performance, the conventional electric automobile mainly adopts a lithium battery pack as a power storage assembly.
One of the most important factors affecting the endurance of the electric vehicle is the vehicle body mass, and the lower the vehicle body mass, the longer the driving range supported by the battery on the basis of the same capacity. Therefore, a large amount of aluminum alloy is used as a structural material of a vehicle body in the existing new energy electric vehicle; the aluminum alloy has the characteristics of high mechanical strength and relatively low density. The battery pack used by the electric automobile is externally provided with a metal protection layer for protecting the internal battery cell, so that the battery cell is prevented from generating faults such as short circuit, combustion or explosion due to external force factors. The conventional battery case is mainly prepared by using a 6xxx aluminum alloy material. The aluminum alloy material has good formability, weldability and high mechanical strength, and can be strengthened by heat treatment. However, the hardness and fatigue resistance of the material are relatively insufficient. When the battery is used as a battery case material, a sharp object is easy to pierce, so that the internal battery core structure is damaged, liquid leakage or short circuit and the like occur, and even the automobile can be ignited and burnt. The not enough life that then can influence battery pack of fatigue resistance can, and electric automobile's battery combination car itself should be a long-life durable vehicle, if the battery case along with life's increase, mechanical strength changes, produces micro defect in the structure, then can show the guard action that reduces internal electric core to influence electric automobile's security.
Therefore, on the basis of ensuring the mechanical strength and the processing performance of the aluminum alloy material, the hardness and the fatigue resistance of the material are improved; becomes the most important means for improving the safety and service life of the battery shell and the battery assembly. However, the aluminum alloy materials of various 6xxx series provided by the current market can not meet the performance requirements at the same time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a production process of an aluminum alloy for a battery case of a new energy automobile, and the aluminum alloy plate produced by the process has the characteristics of high tensile strength and yield strength, high hardness and excellent fatigue resistance.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the aluminum alloy for the battery case of the new energy automobile comprises the following elements in percentage by mass: zn: 3.4-5.1; mg: 2.3-2.7; cu: 1.7-1.9; fe: 0.3-0.8; mn: 0.1-0.4; si: 0.1-0.3; cr: 0.15-0.26; ti: 0.12-0.15; the balance being Al and unavoidable impurities.
Preferably, the aluminum alloy product comprises the following elements in percentage by mass: zn: 3.8-4.3; mg: 2.5-2.6; cu: 1.73-1.82; fe: 0.65-0.70; mn: 0.27-0.35; si: 0.23-0.24; cr: 0.18-0.20; ti: 0.14-0.15; the balance being Al and unavoidable impurities.
Further preferably, the element composition of the aluminum alloy also comprises Zr element which is not higher than 0.4% and Re element which is not lower than 0.15%, wherein the Re element comprises La, Pr and Nd.
More preferably, the mass ratio of La, Pr and Nd in the Re element is 4:2: 3.
The production process of the aluminum alloy for the battery case of the new energy automobile comprises the following steps:
(1) calculating the mass of each raw material according to the element formula, adding electrolytic aluminum liquid into the smelting furnace, controlling the temperature of the aluminum liquid to be 725-745 ℃, and continuously adding simple substance metal and intermediate alloy into the aluminum liquid;
(2) adding a refining agent into the aluminum liquid according to the dosage of 0.32-0.35kg/t, spraying powder and refining for 18-20min, wherein the refining temperature is 746-750 ℃; refining, slagging off, and sampling and analyzing the components of the molten alloy;
(3) calculating and supplementing simple substance metal and/or intermediate alloy according to the analysis result; stirring at 745-750 deg.C for 4-5min, adding refining agent with the same amount as the above step, and refining for 12-14 min;
(4) keeping the refined aluminum alloy melt at the temperature of 730-; finally, casting the melt to obtain a bar;
(5) homogenizing the cast rod, extruding to obtain a round bar, cutting the round bar, and rolling to obtain a plate;
(6) heating the aluminum alloy plate to 530 ℃ and 535 ℃, and carrying out quenching treatment after heat preservation for 1-1.5 h; carrying out artificial aging treatment after quenching, wherein the heating temperature in the artificial aging process is 180-;
(7) after the artificial aging treatment, the plate is sent into hot isostatic pressing treatment equipment, and is subjected to hot hydrostatic pressing treatment for 2-2.3 hours at the pressure of 95-110MPa and the temperature of 415-420 ℃ to obtain the required aluminum alloy plate.
Preferably, the refining agent is FF102 refining agent.
Preferably, the filtering process in the step (4) adopts a double-stage filter plate for plate-type filtering, and the size of the maximum inclusion in the filtered aluminum liquid is not more than 15 μm.
Preferably, the furnace temperature of the homogenization treatment in the step (5) is 560-.
Preferably, the pressure medium in the hot isostatic pressing equipment is selected from nitrogen or argon.
The invention has the following beneficial effects:
on the basis of the formula of the 6xxx series aluminum alloy material, the aluminum alloy material provided by the invention adjusts the proportion of a plurality of elements, so that the strength and the hardness of the alloy are obviously provided, and the corrosion resistance of the alloy is not reduced, thereby obviously improving the weather resistance and the service life of the aluminum alloy.
In the aluminum alloy, the added rare earth element and the added zirconium element can refine grains, control the recrystallization texture, reduce the secondary crystal spacing, reduce gas and impurities in the alloy and enable the impurity phase to tend to be spheroidized when the aluminum alloy is cast; therefore, the metallographic structure of the aluminum alloy is more uniform, the generation of structural defects is reduced, and the fatigue resistance of the alloy is obviously improved. Meanwhile, the surface tension of the melt can be reduced, the fluidity is increased, the casting into ingots is facilitated, and the process performance is obviously influenced.
In the production process, the cast aluminum alloy material is homogenized and rolled to obtain the plate, and the plate is sequentially subjected to quenching, artificial aging and hot isostatic pressing, so that the finally obtained plate has a more uniform and compact microstructure, the hardness and the wear resistance of the plate are obviously enhanced, and the high temperature resistance of the plate is improved. And various performance requirements of the battery case of the new energy automobile are met.
Detailed Description
The following examples are provided to more clearly illustrate the technical solutions of the present invention, and should not be construed as limiting the scope of the present invention.
Example 1
The aluminum alloy for the battery case of the new energy automobile comprises the following elements in percentage by mass: zn: 3.4; mg: 2.3; cu: 1.7; fe: 0.3; mn: 0.1; si: 0.1; cr: 0.15; ti: 0.12; the balance being Al and unavoidable impurities.
The element composition of the aluminum alloy also comprises 0.4 percent of Zr element and 0.15 percent of Re element, and the Re element comprises La, Pr and Nd.
The mass ratio of La, Pr and Nd in the Re element is 4:2: 3.
The production process of the aluminum alloy for the battery case of the new energy automobile comprises the following steps:
(1) calculating the mass of each raw material according to the element formula, adding electrolytic aluminum liquid into the smelting furnace, controlling the temperature of the aluminum liquid to be 725 ℃, and continuously adding simple substance metal and intermediate alloy into the aluminum liquid;
(2) adding a refining agent into the molten aluminum according to the using amount of 0.32kg/t, spraying powder and refining for 18min, wherein the refining temperature is 746 ℃; refining, slagging off, and sampling and analyzing the components of the molten alloy;
(3) calculating and supplementing simple substance metal and/or intermediate alloy according to the analysis result; stirring at 745 deg.C for 4min, adding refining agent with the same amount as above, and refining for 12 min;
(4) keeping the refined aluminum alloy melt at 730 ℃ and standing for 40min, filtering the aluminum liquid, degassing on line, and supplementing an aluminum-titanium-boron line for grain refinement; finally, casting the melt to obtain a bar;
(5) homogenizing the cast rod, extruding to obtain a round bar, cutting the round bar, and rolling to obtain a plate;
(6) heating the aluminum alloy plate to 530 ℃, preserving heat for 1h, and then quenching; carrying out artificial aging treatment after quenching, wherein the heating temperature in the artificial aging process is 180 ℃, and the heat preservation time is 7 h;
(7) and after the artificial aging treatment, the plate is sent into hot isostatic pressing equipment, and is subjected to hot hydrostatic pressing treatment for 2 hours at the pressure of 95MPa and the temperature of 415 ℃ to obtain the required aluminum alloy plate.
Wherein the refining agent is FF102 refining agent.
And (4) performing plate filtration by using a double-stage filter plate in the filtration process in the step (4), wherein the size of the maximum impurities in the filtered aluminum liquid is not more than 15 mu m.
And (5) carrying out homogenization treatment at the furnace temperature of 560 ℃, keeping the temperature for 5h, and cooling in a spraying manner.
And (4) selecting nitrogen as the pressure medium in the hot isostatic pressing treatment equipment in the step (7).
Example 2
The aluminum alloy for the battery case of the new energy automobile comprises the following elements in percentage by mass: zn: 5.1; mg: 2.7; cu: 1.9; fe: 0.8; mn: 0.4; si: 0.3; cr: 0.26; ti: 0.15; the balance being Al and unavoidable impurities.
The element composition of the aluminum alloy also comprises 0.3 percent of Zr element and 0.16 percent of Re element, and the Re element comprises La, Pr and Nd.
The mass ratio of La, Pr and Nd in the Re element is 4:2: 3.
The production process of the aluminum alloy for the battery case of the new energy automobile comprises the following steps:
(1) calculating the mass of each raw material according to the element formula, adding electrolytic aluminum liquid into the smelting furnace, controlling the temperature of the aluminum liquid to be 745 ℃, and continuously adding simple substance metal and intermediate alloy into the aluminum liquid;
(2) adding a refining agent into the molten aluminum according to the using amount of 0.35kg/t, spraying powder and refining for 20min, wherein the refining temperature is 750 ℃; refining, slagging off, and sampling and analyzing the components of the molten alloy;
(3) calculating and supplementing simple substance metal and/or intermediate alloy according to the analysis result; stirring at 750 deg.C for 5min, adding refining agent with the same amount as the above step, and refining for 14 min;
(4) keeping the refined aluminum alloy melt at 740 ℃ and standing for 50min, filtering the aluminum liquid, degassing on line, and supplementing an aluminum-titanium-boron line for grain refinement; finally, casting the melt to obtain a bar;
(5) homogenizing the cast rod, extruding to obtain a round bar, cutting the round bar, and rolling to obtain a plate;
(6) heating the aluminum alloy plate to 535 ℃, and carrying out quenching treatment after heat preservation for 1.5 h; carrying out artificial aging treatment after quenching, wherein the heating temperature in the artificial aging process is 195 ℃, and the heat preservation time is 8 h;
(7) and after the artificial aging treatment, the plate is sent into hot isostatic pressing equipment, and is subjected to hot hydrostatic pressing treatment for 2.3 hours at the pressure of 110MPa and the temperature of 420 ℃ to obtain the required aluminum alloy plate.
Wherein the refining agent is FF102 refining agent.
And (4) performing plate filtration by using a double-stage filter plate in the filtration process in the step (4), wherein the size of the maximum impurities in the filtered aluminum liquid is not more than 15 mu m.
And (5) carrying out homogenization treatment at 575 ℃ for 6h, and cooling in a spraying manner.
And (4) selecting argon as the pressure medium in the hot isostatic pressing treatment equipment in the step (7).
Example 3
The aluminum alloy for the battery case of the new energy automobile comprises the following elements in percentage by mass: zn: 3.9; mg: 2.5; cu: 1.8; fe: 0.6; mn: 0.3; si: 0.2; cr: 0.21; ti: 0.14; the balance being Al and unavoidable impurities.
The element composition of the aluminum alloy also comprises 0.35 percent of Zr element and 0.18 percent of Re element, and the Re element comprises La, Pr and Nd.
The mass ratio of La, Pr and Nd in the Re element is 4:2: 3.
The production process of the aluminum alloy for the battery case of the new energy automobile comprises the following steps:
(1) calculating the mass of each raw material according to the element formula, adding electrolytic aluminum liquid into the smelting furnace, controlling the temperature of the aluminum liquid to be 735 ℃, and continuously adding simple substance metal and intermediate alloy into the aluminum liquid;
(2) adding refining agent into the molten aluminum according to the dosage of 0.34kg/t, spraying powder and refining for 19min, wherein the refining temperature is 748 ℃; refining, slagging off, and sampling and analyzing the components of the molten alloy;
(3) calculating and supplementing simple substance metal and/or intermediate alloy according to the analysis result; stirring at 747 deg.C for 4.5min, adding refining agent with the same amount as above, and refining for 13 min;
(4) supplementing the refined aluminum alloy melt, keeping the temperature of 735 ℃ and standing for 45min, filtering the aluminum liquid, degassing on line, and supplementing an aluminum-titanium-boron line for grain refinement; finally, casting the melt to obtain a bar;
(5) homogenizing the cast rod, extruding to obtain a round bar, cutting the round bar, and rolling to obtain a plate;
(6) heating the aluminum alloy plate to 533 ℃, and carrying out quenching treatment after heat preservation for 1.3 h; carrying out artificial aging treatment after quenching, wherein the heating temperature in the artificial aging process is 190 ℃, and the heat preservation time is 7.5 h;
(7) and after the artificial aging treatment, the plate is sent into hot isostatic pressing equipment, and is subjected to hot hydrostatic pressing treatment for 2.2 hours at the pressure of 100MPa and the temperature of 417 ℃ to obtain the required aluminum alloy plate.
Wherein the refining agent is FF102 refining agent.
And (4) performing plate filtration by using a double-stage filter plate in the filtration process in the step (4), wherein the size of the maximum impurities in the filtered aluminum liquid is not more than 15 mu m.
And (5) carrying out homogenizing treatment at the furnace temperature of 570 ℃, keeping the temperature for 5.5h, and cooling in a spraying manner.
And (4) selecting argon as the pressure medium in the hot isostatic pressing treatment equipment in the step (7).
Performance testing
1. According to the test method in GB/T3880-:
table 1: performance test results of the aluminum alloy materials of the embodiment and the comparison group
Figure BDA0002312927660000091
The experimental results are analyzed to find that the yield strength and the tensile strength of the aluminum alloy material provided by the embodiment are close to those of the sample of the control group, and are slightly stronger than those of the product of the control group; on the basis of a hardness test result, the product provided by the embodiment is obviously better than a control group, and the hardness of the aluminum alloy material is improved by 11.71%.
2. The microstructure and fatigue fracture morphology of the aluminum alloy provided in this example were analyzed by Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM). The result shows that the fatigue damage resistance of the aluminum alloy is very excellent, the fatigue limit of a smooth sample (Kt is 1) under the conditions of room-temperature rotating bending and high-temperature axial loading respectively reaches 178.4 MPa and 345.7MPa, and the fatigue limit of a notch sample (Kt is 2.2) under the conditions of room-temperature rotating bending loading is 85.9 MPa. Is obviously stronger than the prior 6xxx series aluminum alloy of each grade.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. The utility model provides an aluminum alloy for new energy automobile battery case which characterized in that: according to the mass percentage, the aluminum alloy product comprises the following elements: zn: 3.9; mg: 2.5; cu: 1.8; fe: 0.6; mn: 0.3; si: 0.2; cr: 0.21; ti: 0.14;
the element composition of the aluminum alloy also comprises 0.35 percent of Zr element and 0.18 percent of RE element, wherein the RE element comprises La, Pr and Nd;
the mass ratio of La, Pr and Nd in the RE element is 4:2: 3; the balance of Al and inevitable impurities;
the preparation process of the aluminum alloy comprises the following steps:
(1) calculating the mass of each raw material according to the element formula, adding electrolytic aluminum liquid into the smelting furnace, controlling the temperature of the aluminum liquid to be 725-745 ℃, and continuously adding simple substance metal and intermediate alloy into the aluminum liquid;
(2) adding a refining agent into the aluminum liquid according to the dosage of 0.32-0.35kg/t, spraying powder and refining for 18-20min, wherein the refining temperature is 746-750 ℃; refining, slagging off, and sampling and analyzing the components of the molten alloy;
(3) calculating and supplementing simple substance metal and/or intermediate alloy according to the analysis result; stirring at 745-750 deg.C for 4-5min, adding refining agent with the same amount as the above step, and refining for 12-14 min;
(4) keeping the refined aluminum alloy melt at the temperature of 730-; finally, casting the melt to obtain a bar;
(5) homogenizing the cast rod, extruding to obtain a round bar, cutting the round bar, and rolling to obtain a plate;
(6) heating the aluminum alloy plate to 530 ℃ and 535 ℃, and carrying out quenching treatment after heat preservation for 1-1.5 h; carrying out artificial aging treatment after quenching, wherein the heating temperature in the artificial aging process is 180-;
(7) after the artificial aging treatment, the plate is sent into hot isostatic pressing treatment equipment, and is subjected to hot hydrostatic pressing treatment for 2-2.3 hours at the pressure of 95-110MPa and the temperature of 415-420 ℃ to obtain the required aluminum alloy plate.
2. The production process of the aluminum alloy for the battery case of the new energy automobile according to claim 1, characterized in that: and (4) performing plate-type filtration by using a double-stage filter plate in the filtration process in the step (4), wherein the size of the maximum inclusion in the filtered aluminum liquid is not more than 15 mu m.
3. The production process of the aluminum alloy for the battery case of the new energy automobile according to claim 1, characterized in that: the furnace temperature of the homogenization treatment in the step (5) is 560-.
4. The production process of the aluminum alloy for the battery case of the new energy automobile according to claim 1, characterized in that: and the pressure medium in the hot isostatic pressing treatment equipment is nitrogen or argon.
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Denomination of invention: An aluminum alloy for battery shell of new energy vehicle and its production process

Effective date of registration: 20211220

Granted publication date: 20201229

Pledgee: Agricultural Bank of China Limited Zouping sub branch

Pledgor: SHANDONG CHUANGXIN PRECISION TECHNOLOGY Co.,Ltd.

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Date of cancellation: 20221231

Granted publication date: 20201229

Pledgee: Agricultural Bank of China Limited Zouping sub branch

Pledgor: SHANDONG CHUANGXIN PRECISION TECHNOLOGY Co.,Ltd.

Registration number: Y2021980015347