CN114292982B - Control method for steel shot defects for battery case of new energy automobile - Google Patents
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Abstract
The invention discloses a method for controlling steel shot defects for a new energy automobile battery shell, which is characterized in that the steel shot defects for the new energy automobile battery shell are reduced by controlling the key parameter combinations such as the tapping temperature of a converter, the oxygen content, the RH decarburization ending oxygen content, the RH scrap adding time, the RH aluminum adding times, the RH aluminum grain-alloy adding time interval, the net circulation time after RH alloying, the cleaning depth of a continuous casting blank and the like, especially considering ladle slag as a main secondary oxidation source, the ladle slag is reduced by adopting the means of reducing the slag quantity of the converter by leaving steel in the converter, adding a large amount of carbon powder into the ladle in a reasonable time in the tapping process to modify the ladle top slag, the ladle by leaving steel in the ladle and the like.
Description
Technical Field
The invention belongs to the technical field of ferrous metallurgy, and particularly relates to a method for controlling steel shot defects for a battery case of a new energy automobile.
Background
The new energy automobile is an automobile which adopts unconventional automobile fuel as a power source and integrates the advanced technology in the aspects of power control and driving of the automobile, and has new technology, new structure and advanced technical principle. When the automobile runs, the electric energy output by the storage battery drives the motor to run through the controller, and the torque output by the motor drives the wheels to advance or retreat through the transmission system. The new energy automobile battery pack is formed by stacking a plurality of batteries in series.
In order to avoid safety accidents such as fire, explosion and the like caused by leakage and corrosion of electrolyte generated by nickel plating leakage and plating, no sand hole defect and smooth surface are required for the punched battery steel shell. On the other hand, the thickness specification of the finished battery case is as low as 0.3mm and 0.5mm, which requires that the battery case steel has good punching properties. At present, a low-carbon aluminum killed steel component system is mostly adopted in the metallurgical industry, trace titanium elements are added to improve anisotropy, and controllable adjustment of performance within a certain range is realized by adjusting the content of elements such as carbon and the like, so that different stamping requirements of users are met. The metallurgical industry generally adopts a converter-RH-continuous casting process path to produce the steel for the battery case of the new energy automobile, and the main problem is that the battery case steel is easy to generate sand hole defects after the stamping of clients is finished, so that batch battery case products are scrapped. How to control the sand hole defect is a common problem in steel mills.
Disclosure of Invention
The invention aims to provide a control method for the steel shot defects for the battery case of the new energy automobile, which can obviously reduce the steel shot defects for the battery case of the new energy automobile.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a control method of steel shot hole defect for new energy automobile battery case adopts the process of converter smelting-RH vacuum treatment-continuous casting to produce, specifically comprising the following steps:
(1) In the converter smelting step, the end point temperature of the converter is controlled to be 1675-1690 ℃ so as to ensure that the RH process does not need temperature compensation, and the end point oxygen content of the converter is less than or equal to 600ppm; adding metallurgical lime and carbon powder into a ladle in the tapping process of the converter to modify ladle slag, and leaving part of molten steel in the converter after tapping;
(2) In the RH vacuum treatment step, the target range of the oxygen content after decarburization is 100-350ppm, if the temperature of the RH incoming molten steel is high, the cooling of the scrap steel needs to be finished 5min before the decarburization is finished; during RH treatment, aluminum particles are added for deoxidization and alloying only once when decarburization is finished, and aluminum is not added for the second time to adjust the Als content of molten steel; adding alloy to adjust Mn and Ti to target range after aluminum particles are added for more than or equal to 3min, and recycling time after the alloy is added for more than or equal to 8min;
(3) In the continuous casting step, constant-pull-speed casting is controlled; leaving part of molten steel in the ladle; and performing four-side flame cleaning on the continuous casting blank.
In the step (1), the addition amount of metallurgical lime is 1.0-5.0kg/t steel; the addition amount of carbon powder is 0.5-1kg/t steel; the carbon powder is added between 1/10 and 1/2 of the tapping time.
In the metallurgical lime, caO is more than or equal to 85 percent, siO 2 Less than or equal to 3.50 percent, and the activity degree is more than or equal to 230ml; the metallurgical lime with the granularity of 8-50 mm accounts for more than or equal to 80 percent.
The carbon powder comprises the following components: c (C) Fixing device More than or equal to 92 percent, and the carbon powder with the granularity of 1-4 mm accounts for more than or equal to 90 percent.
In the step (1), 2-10 tons of molten steel is remained in the converter after tapping.
In the step (1), the steel is produced under the condition that the use times of the steel tapping hole are less than or equal to 60 times, the use times of the steel tapping hole are generally about 120 times, the inner diameter of the steel tapping hole is increased along with the increase of the use times of the steel tapping hole, and the slag coiling and the slag discharging are easy to increase in the steel tapping process.
In the step (2), if the RH incoming molten steel temperature is high, the cooling of the scrap steel needs to be finished 5 minutes before the decarburization is finished, and if the RH incoming molten steel temperature is more than or equal to 1625 ℃, the RH incoming molten steel temperature is regarded as high.
In the step (2), the dip tube is produced under the condition that the use times of the RH dip tube is less than or equal to 50 times, and the dip tube is not subjected to gunning before and during production, so that the gunning material is prevented from being dissolved in molten steel in the treatment process, and the cleanliness of the molten steel is prevented from being deteriorated. The RH dip pipe is generally used for about 120 furnaces, and the dip pipe is deteriorated in the later stage of the pipe age, and from the viewpoint of safety, the dip pipe is required to be subjected to gunning maintenance after the treatment of each furnace is finished, so that the steel grade is produced in the earlier stage of the pipe age.
In the step (2), if the oxygen content of decarburization is more than 350ppm, the cycle time after the alloy is added is prolonged to be more than or equal to 10min.
In the step (3), the pulling speed control range is 1.0-1.7m/min; the molten steel remained in the ladle is more than or equal to 15 tons.
In the step (3), the scarfing depth is more than or equal to 4mm.
In the step (3), the ladle long nozzle is forbidden to be burned and washed by oxygen, namely if the ladle long nozzle is directly replaced by the oxygen if the ladle long nozzle is burned and washed by oxygen, the nozzle refractory material can absorb oxygen, and secondary oxidization of molten steel is caused.
In the step (1), when the end point oxygen of the converter is more than 600ppm, the converter steel is improved, and the converter steel is not used for the battery case steel; and/or, when the RH aluminum particle adding frequency in the step (2) is more than or equal to 2 times, the furnace steel is improved and judged, and the furnace steel is not used for the battery case steel.
In the step (3), when the continuous casting has fluctuation of the pulling speed and/or fluctuation of the liquid level of the continuous casting crystallizer is > +/-3 mm, the corresponding continuous casting blank is improved, and the continuous casting blank is not used for the battery case steel.
The steel for the battery case of the new energy automobile comprises the following chemical components in percentage by weight: 0.0030 to 0.0060 percent of C, less than or equal to 0.030 percent of Si, 0.20 to 0.60 percent of Mn, less than or equal to 0.025 percent of P, less than or equal to 0.015 percent of S, 0.020 to 0.080 percent of Als and 0.030 to 0.090 percent of Ti.
According to the method for controlling the steel shot defects for the battery case of the new energy automobile, the steel shot defects for the battery case of the new energy automobile are reduced by controlling key parameter combinations such as the tapping temperature of the converter, the oxygen content, the RH decarburization ending oxygen content, the RH scrap adding time, the RH aluminum adding times, the RH aluminum grain-alloy adding time interval, the RH net circulation time after adding alloy, the cleaning depth of continuous casting billets and the like, particularly considering the steel ladle slag as a main secondary oxidation source, reducing the slag quantity of the converter by adopting the converter steel-retaining, adding a large amount of carbon powder into the steel ladle in a reasonable time in the tapping process, modifying the top slag of the steel ladle, controlling the steel ladle steel-retaining and the like.
In the industrial mass production process of the steel mill, the invention creatively establishes that 'converter endpoint oxygen is more than 600ppm, RH aluminum grain adding times are more than or equal to 2 times, continuous casting has drawing speed fluctuation, continuous casting crystallizer liquid level fluctuation > +/-3 mm' is a new energy battery case steel abnormal production event, degradation and improvement treatment is needed when the event occurs, if the degradation and improvement treatment is not needed to be continuously used as battery case steel, the adverse effect that the product sand hole defect rate corresponding to the corresponding continuous casting blank is obviously increased can occur.
The combination of the technical measures is that the inventor of the invention firstly proposes in the metallurgical industry through careful thinking and long-term research, solves the technical problem that the battery shell product has high sand hole defect rate which puzzles the steel mill for many years, and has remarkable economic benefit.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for controlling the steel shot defects of the battery case of the new energy automobile, by adopting the method, the steel shot defects of the battery case of the new energy automobile are reduced by 63.3%, the batch and stable production of the steel for the battery case of the new energy automobile is realized, and the method has remarkable economic benefit.
Drawings
FIG. 1 is a process flow and main technical measures diagram of the production of a steel casting blank for a battery case of a new energy automobile;
FIG. 2 is a macroscopic morphology of steel shot defects for battery cases;
FIG. 3 is an SEM test result of steel shot defects for battery cases;
fig. 4 is a graph showing the number of inclusions and the size of steel castings for battery cases in examples and comparative examples.
Detailed Description
In order to further explain the concept of the invention, the invention is further described by taking steel for smelting a new energy battery case in a converter with nominal capacity of 300 tons as an example.
Example 1: furnace number: a, molten steel amount: 300.6 ton
The chemical composition of the new energy automobile battery case steel is shown in table 1.
The steel process flow for the battery case of the new energy automobile is as follows: converter-RH vacuum treatment-slab continuous casting.
(1) Producing steel for the battery case of the new energy automobile by using a converter seat with the steel tapping hole using times of 15 times, wherein the steel tapping time is 6.5 minutes;
(2) The end point oxygen of the converter is controlled to 425ppm at 1685 ℃;
(3) 620kg of metallurgical lime and 152kg of carbon powder are added in the tapping process to modify ladle slag: wherein, metallurgical lime CaO:92%, siO 2 :1.2%, activity 246ml; the metallurgical lime with the granularity of 8-50 mm accounts for 89 percent; carbon powder C Fixing device 94.5 percent, and the carbon powder with the granularity of 1-4 mm accounts for 91 percent; carbon powder is added when tapping for 68 seconds;
(4) Lifting the converter when 7 tons of molten steel exist in the converter in the later stage of tapping of the converter, and stopping tapping;
(5) The RH furnace seat production of the RH dip pipe with the use times of 36 times is selected, and the dip pipe is not gunned before and during the production of the steel for the battery shell;
(6) The temperature of the RH incoming molten steel of the furnace steel is 1634 ℃, and 1.2 tons of scrap steel is added 7min before decarburization is finished for cooling; the oxygen content after RH decarburization is 302ppm, 331kg of aluminum particles are added at one time to deoxidize and alloy the molten steel;
(7) Adding alloy after aluminum particles are added for 5min to adjust Mn and Ti elements to target ranges, and circulating for 8.6min to break the blank after the alloy is added;
(8) During casting, due to equipment failure of a continuous casting billet cutting machine, the pulling speed is reduced from 1.5m/min to 0.9m/min, the corresponding 2 nd casting billet in the pulling speed reducing period is changed into non-battery shell steel, and even if the following steps (10) - (12) are carried out on the 2 nd casting billet, the sand hole defect rate of the corresponding battery shell product of the 2 nd casting billet can be up to 1.6 per mill, so that the casting billet produced under the condition can be applied to the non-battery shell steel product which does not pay attention to the sand hole defect;
(9) During casting, when a 4 th continuous casting blank is cast, the liquid level of a crystallizer is shifted, the instantaneous liquid level fluctuation is 3.2mm, the corresponding 4 th casting blank is changed into non-battery shell steel, and even if the following steps (10) - (12) are carried out on the 4 th casting blank, the sand hole defect rate of the 4 th casting blank corresponding to a battery shell product is still up to 1.45 per mill, so that the casting blank produced under the condition can be applied to the non-battery shell steel product which does not pay attention to the sand hole defect;
(10) Closing the ladle slide plate when the molten steel amount of the ladle is remained for 16 tons;
(11) Performing four-side flame cleaning on the continuous casting blank, wherein the cleaning depth is 4.2mm;
(12) During the continuous casting ladle changing period, the inner side of the ladle long nozzle is found to have residual steel, the long nozzle is changed, and oxygen is not adopted to burn and wash the ladle long nozzle.
Example 2: furnace number: b, molten steel amount: 312.4 tons
(1) Producing steel for the battery case of the new energy automobile by using a converter seat with the tapping hole using times of 33 times, wherein the tapping time is 5.7 minutes;
(2) The end point temperature of the converter is 1682 ℃, and the end point oxygen is 592ppm;
(3) 325kg of metallurgical lime and 174kg of carbon powder are added in the tapping process to modify ladle slag: wherein, metallurgical lime CaO:94%, siO 2 :1.1%, activity 237ml; the metallurgical lime with the granularity of 8-50 mm accounts for 91 percent; carbon powder C Fixing device 95.2 percent, and the carbon powder with the granularity of 1-4 mm accounts for 93 percent; carbon powder is added when tapping for 50 seconds;
(4) Lifting the converter when molten steel is 8 tons in the converter in the later stage of steel tapping of the converter, and stopping steel tapping;
(5) The RH furnace seat production of the RH dip pipe with the use times of 43 times is selected, and the dip pipe is not gunned before and during the production of the steel for the battery shell;
(6) The temperature of the molten steel of the furnace steel RH in-station is 1627 ℃, and 0.7 ton of scrap steel is added and cooled 6min before decarburization is finished; the RH decarburization finishing oxygen content is 367ppm, 364kg of aluminum particles are added at one time to deoxidize and alloy the molten steel;
(7) Adding alloy after aluminum particles are added for 6min to adjust Mn and Ti elements to a target range, and circulating for 12min to break the blank after the alloy is added;
(8) During casting, the pulling speed of continuous casting is stabilized at 1.6m/min, and no fluctuation exists;
(9) Closing the ladle slide plate when the molten steel amount of the ladle is 17 tons;
(10) Performing four-side flame cleaning on the continuous casting blank, wherein the cleaning depth is 4.1mm;
(11) During the continuous casting ladle changing period, the ladle long nozzle has no residual steel, and oxygen is not adopted to burn and wash the ladle long nozzle, so that the ladle long nozzle can be continuously used.
Example 3: furnace number: c, molten steel amount: 298.7 ton
(1) Producing steel for the battery case of the new energy automobile by using a converter seat with the steel tapping hole using times of 45 times, wherein the steel tapping time is 4.8 minutes;
(2) The end point temperature of the converter is 1687 ℃, and the end point oxygen is controlled to 548ppm;
(3) 1025kg of metallurgical lime and 168kg of carbon powder are added in the tapping process to modify ladle slag: wherein, metallurgical lime CaO:87%, siO 2 :1.4%, activity 241ml; the metallurgical lime with the granularity of 8-50 mm accounts for 95 percent; carbon powder C Fixing device 94.6 percent, and the carbon powder with the granularity of 1-4 mm accounts for 92 percent; carbon powder is added when tapping for 32 seconds;
(4) Lifting the converter when the molten steel is 9 tons in the converter in the later stage of steel tapping of the converter, and stopping steel tapping;
(5) The RH furnace seat production of the RH dip pipe with the use times of 22 times is selected, and the dip pipe is not gunned before and during the production of the steel for the battery shell;
(6) The temperature of the molten steel of the furnace steel RH in-station is 1617 ℃, and no scrap steel is needed to be added for cooling; the oxygen content after RH decarburization is 349ppm, 347kg of aluminum particles are added at one time to deoxidize and alloy the molten steel; adding alloy to adjust Mn and Ti elements to target range after 5min after aluminum particles are added, stripping and dropping large residual steel blocks from a vacuum tank body into a steel ladle after the alloy is added, sampling molten steel Als content of 0.017 percent, and adding 112kg aluminum particles to adjust molten steel Als to ensure that molten steel Als reaches the standard. Because aluminum grains are added to the furnace steel RH twice, the furnace steel RH is changed into non-battery shell steel, and after the furnace steel RH is changed into non-battery shell steel, even if the steps (7) - (10) in the embodiment 2 are repeated, the sand hole defect rate of the finally obtained casting blank still reaches up to 2.20 per mill, and the casting blank produced under the condition can be applied to a non-battery shell steel product which does not pay attention to the sand hole defect.
Comparative example: and (3) producing new energy battery case steel by a conventional process: furnace number: d, molten steel amount: 311.4 ton
(1) Randomly selecting converter seat conditions for producing the steel for the battery case, wherein the service life of a tapping hole is 89 times, and the tapping time is 4.1 minutes;
(2) The converter endpoint temperature is 1689 ℃, and the endpoint oxygen is controlled to 619ppm;
(3) 578kg of metallurgical lime is added in the tapping process to adjust the components of ladle slag;
(4) Manually seeing that the converter is lifted when slag flows to a ladle from the later stage of tapping of the converter, and stopping tapping;
(5) Randomly selecting RH furnace seat production, and carrying out gunning on the dip pipe before and during the production of the steel for the battery shell, wherein the service life of the dip pipe is 102 times;
(6) The temperature of the RH incoming molten steel of the furnace steel is 1633 ℃, 1.1 ton of scrap steel is added 3min before decarburization is finished, and the temperature is reduced; the oxygen content after RH decarburization is 368ppm, 349kg of aluminum particles are added to deoxidize and alloy the molten steel;
(7) And adding alloy to adjust Mn and Ti elements to target ranges after 3min after aluminum particles are added, and adding 28kg of aluminum particles to adjust Als content of molten steel during the period. Circulating for 4min after adding the alloy to break the air;
(8) During casting, the drawing speed is reduced from 1.6m/min to 1.0m/min due to the failure of the ladle turret, and the corresponding 4 th casting blank during the drawing speed is continuously used as battery shell steel;
(9) Closing the ladle slide plate when the ladle molten steel amount is remained at 0 ton;
(10) And performing four-side flame cleaning on the continuous casting blank, wherein the cleaning depth is 2.8mm.
(11) During the continuous casting ladle changing period, the residual steel is found at the inner side of the ladle long nozzle, and oxygen is adopted to burn and wash the ladle long nozzle, and the ladle long nozzle is continuously used after the burning and washing.
The main indexes of the examples and the comparative examples are shown in Table 2:
table 2 comparison of the main index of examples and comparative examples
Table 2:
the number and size of inclusions in the examples are compared with those in the comparative examples, as shown in FIG. 4.
As can be seen from table 2 and fig. 4,
(1) The RH station entering ladle top slag TFe of the embodiment is 6.83%, which is reduced by 45.8% compared with 12.6% of the comparative example; the total oxygen of the continuous casting blank of the example is 12.3ppm on average, which is reduced by 23.1% compared with the comparative example of 16 ppm; the average sand hole defect rate of the embodiment is 0.55 per mill, which is reduced by 63.3 percent compared with the comparative example 1.5 per mill;
(2) Example inclusions have a number density of 28.2 inclusions/mm on average 2 Comparative example 45.6 pieces/mm 2 The reduction is 38.3 percent; the area ratio of the inclusions in the example was 90.3ppm on average, which was 38.0% lower than that in the comparative example 145.5 ppm.
The foregoing detailed description of a method for controlling steel shot defects for a battery case of a new energy vehicle with reference to the embodiments is illustrative and not restrictive, and several embodiments can be listed according to the defined scope, so that variations and modifications are possible without departing from the general inventive concept.
Claims (9)
1. The control method of the steel shot hole defect for the battery case of the new energy automobile is characterized by adopting a converter smelting-RH vacuum treatment-continuous casting process for production, and specifically comprises the following steps:
(1) In the converter smelting step, the end point temperature of the converter is controlled to be 1675-1690 ℃, and the end point oxygen content of the converter is less than or equal to 600ppm; adding metallurgical lime and carbon powder into a ladle in the tapping process of the converter to modify ladle slag, and leaving part of molten steel in the converter after tapping;
(2) In the RH vacuum treatment step, the target range of the oxygen content after decarburization is 100-350ppm, if the temperature of the RH incoming molten steel is high, the cooling of the scrap steel needs to be finished 5min before the decarburization is finished; during RH treatment, aluminum particles are added for deoxidization and alloying only once when decarburization is finished, and aluminum is not added for the second time to adjust the Als content of molten steel; adding alloy to adjust Mn and Ti to target range after aluminum particles are added for more than or equal to 3min, and recycling time after the alloy is added for more than or equal to 8min;
(3) In the continuous casting step, constant-pull-speed casting is controlled; molten steel is reserved in the ladle to be more than or equal to 15 tons; performing four-side flame cleaning on the continuous casting blank, wherein the flame cleaning depth is more than or equal to 4mm;
the weight percentage of C in the steel for the battery case of the new energy automobile is 0.0030-0.0060 percent, and the weight percentage of Ti is 0.030-0.090 percent.
2. The method for controlling steel shot defects for a battery case of a new energy automobile according to claim 1, wherein in the step (1), the addition amount of metallurgical lime is 1.0-5.0kg/t steel; the addition amount of carbon powder is 0.5-1kg/t steel; the carbon powder is added between 1/10 and 1/2 of the tapping time.
3. The method for controlling steel shot defects for a battery case of a new energy automobile according to claim 1, wherein in the step (1), 2-10 tons of molten steel is left in the converter after tapping.
4. The method for controlling steel shot defects for a battery case of a new energy automobile according to claim 1, wherein in the step (1), the production is performed under the condition that the number of times of use of the tap hole is less than or equal to 60 times.
5. The method for controlling steel shot defects for a battery case of a new energy automobile according to claim 1, wherein in the step (2), the dip tube is produced under the condition that the use time of the RH dip tube is less than or equal to 50 times, and the dip tube is not subjected to gunning before and during the production.
6. The method for controlling steel shot defects for a battery case of a new energy automobile according to claim 1, wherein in the step (3), the pulling speed is controlled within a range of 1.0-1.7m/min.
7. The method for controlling steel shot defects for a battery case of a new energy automobile according to claim 1, wherein in the step (1), when the endpoint oxygen of the converter is more than 600ppm, the furnace steel is modified so as not to be used for the battery case steel; and/or, when the RH aluminum particle adding frequency in the step (2) is more than or equal to 2 times, the furnace steel is improved and judged, and the furnace steel is not used for the battery case steel.
8. The method for controlling the steel shot hole defect for the battery case of the new energy automobile according to claim 1, wherein in the step (3), when the drawing speed fluctuation occurs in continuous casting and/or the liquid level fluctuation of the continuous casting crystallizer is > +/-3 mm, the corresponding continuous casting blank is modified and judged, and the method is not used for the battery case steel.
9. The method for controlling steel shot defects for a battery case of a new energy automobile according to claim 1, wherein the steel for the battery case of the new energy automobile comprises the following chemical components in percentage by weight: 0.0030-0.0060% of C, less than or equal to 0.030% of Si, 0.20-0.60% of Mn, less than or equal to 0.025% of P, less than or equal to 0.015% of S, 0.020-0.080% of Als and 0.030-0.090% of Ti.
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