GB2624545A - Method for recovering battery powder by low-temperature pyrolysis desorption - Google Patents

Method for recovering battery powder by low-temperature pyrolysis desorption Download PDF

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GB2624545A
GB2624545A GB2318191.0A GB202318191A GB2624545A GB 2624545 A GB2624545 A GB 2624545A GB 202318191 A GB202318191 A GB 202318191A GB 2624545 A GB2624545 A GB 2624545A
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battery
pyrolysis
temperature
reaction
pressure
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GB202318191D0 (en
Inventor
Yu Haijun
Xie Yinghao
Li Aixia
Zhang Xuemei
Li Changdong
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Publication of GB202318191D0 publication Critical patent/GB202318191D0/en
Publication of GB2624545A publication Critical patent/GB2624545A/en
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0002—Preliminary treatment
    • C22B15/0004—Preliminary treatment without modification of the copper constituent
    • C22B15/0006—Preliminary treatment without modification of the copper constituent by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0038—Obtaining aluminium by other processes
    • C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)

Abstract

Disclosed is a method for recovering battery powder by low-temperature pyrolysis desorption, comprising: enabling reaction of a waste battery crushed material in a mixed atmosphere, under an air pressure of 3-8 MPa, and at a temperature of 120-150°C, the mixed atmosphere being mixed gas of CO2, NO, and O2; enabling reaction of the obtained reaction product under a negative pressure and at a temperature of 310-360°C; and then sorting to obtain copper-aluminum foil and battery powder. According to the present invention, a combined process of low-temperature high-pressure pyrolysis and medium-temperature negative-pressure pyrolysis is used, and the temperature of the whole process is controlled to be 400°C or below, such that the purpose of separating from a current collector can be achieved; chain scission of a polymer is achieved, and oxidation of copper and aluminum is avoided.

Description

METHOD FOR RECOVERING BATTERY POWDER BY LOW-TEMPERATURE PYROLYSIS DESORPTION
TECHNICAL FIELD
The present disclosure relates to the field of battery recovering, and in particular relates to a method for recovering battery powder by low-temperature pyrolysis desorption.
BACKGROUND
Lithium-ion battery has a complex structure and consists of a shell, a separator, a cathode, an anode and other components. In the process of recovering waste batteries, it is necessary to separate different components through a series of methods. Among them, the anode consists of graphite, a binding agent, a conductive agent and a current collector copper foil, and the cathode is made by coating active material powder, a binding agent and a conductive agent on a current collector aluminum foil, wherein the active material powder of cathode mainly includes LiCo02, LiNi02, LiMn02, LiFePO4, LiNixCo,Mni_.,02 and so on.
The pretreatment process of recovering waste lithium-ion batteries usually requires certain technical methods to desorb and separate the active material powder from the current collector.
At present, the separation of active materials from the current collector mainly has three aspects: (0 According to the characteristics of metal aluminum that it can be dissolved in alkaline solution, immersing the cathode winding core in alkaline solution can achieve the purpose of separating the cathode powder from the current collector. This method has the advantages of low energy consumption and strong operability. However, the current collector aluminum foil enters the solution in the form of ions, which requires further recovering. In addition, this process requires a large amount of alkaline solution. In order to prevent secondary contamination of the alkaline solution, neutralization treatment is required, which will require additional cost. In order to avoid the contamination of the powder by the introduced alkaline solution, during the filtration process, the desorbed active materials should be frilly washed or neutralized by acid. By dissolving the binding agent PVDF in an organic solvent, the current collector metal foil can be recovered in the form of solid, but the organic solvent is usually expensive and not suitable for large-scale industrial applications. (-7,-) Directly heating the battery to a specific temperature in the air can deactivate the binding agent to achieve the purpose of separating the current collector aluminum foil, and it is also the most reported pyrolysis pretreatment process for recovering lithium battery.
The pyrolysis pretreatment process is widely used in the existing industrial production, but there are also some major problems, such as: (-0 The temperature of conventional pyrolysis is above 500 °C, due to the complex types of materials, at this temperature, the combustion of the electrolyte and separator occurs, which easily causes a violent local reaction in the pyrolysis furnace, resulting in temperature out of control. When the aluminum metal in the battery is at the temperature above 600 °C, an aluminothermic reaction will occur, resulting in a sharp rise in instantaneous temperature, burning through the pyrolysis furnace, and bringing a great safety risk. C4. At this temperature, the metal copper and aluminum in the battery are lamely oxidized, resulting in high impurity content in the battery powder. During the subsequent acid leaching, the oxides are dissolved, resulting in a large amount of copper and aluminum slag, which brings great pressure to the subsequent purification.
SUMMARY
The present disclosure aims to solve at least one of the above-mentioned technical problems existing in the prior art. Therefore, the present disclosure provides a method for recovering battery powder by low-temperature pyrolysis desorption, which can achieve the purpose of separating the active material of the waste battery from the current collector at a relatively low temperature.
In one aspect, the present disclosure provides a method for recovering battery powder by low-temperature pyrolysis desorption, comprising the following steps.
Si: discharging, disassembling and pulverizing a waste battery to obtain a pulverized material; 52: subjecting the pulverized material to a reaction in a mixed atmosphere at a pressure of 3-SMIPa and a temperature of 120-150°C, wherein the mixed atmosphere is a mixed gas of CO2, NO, and 02 with a volume ratio of 100: (10-15):(0-2), and S3: subjecting a reaction material obtained in the step 52 to a reaction under negative pressure at a reaction temperature of 310-360°C, and then screening a resulting reacted material to obtain a copper-aluminum foil and the battery powder.
In some embodiments of the present disclosure, in the step Sl, a particle size of the pulverized material is 5 cm or less.
In some embodiments of the present disclosure, in the step Si, the waste battery is at least one selected from the group consisting of a ternary lithium ion battery, a lithium iron phosphate battery, a lithium cobaltate battery, a lithium manganate battery, or a lithium nickelate battery.
In some embodiments of the present disclosure, in the step S2, the reaction is performed for 3-5h In some embodiments of the present disclosure, in the step S2, the reaction is performed in a pyrolysis furnace, and a filling rate of the pulverized material in the pyrolysis furnace is controlled to be 5-15%.
In some embodiments of the present disclosure, in the step S3, a pressure of the negative pressure is from -0.01 to -0.08MPa.
In some embodiments of the present disclosure, in the step S3, the reaction is performed for 1-3.
In some embodiments of the present disclosure, after the reaction in the step S2 is completed, the pressure in the pyrolysis furnace is released to normal pressure at a rate of 0.1-0.5 MPa/min, and then a vacuum pump is started to pump the pyrolysis furnace to the negative pressure.
In some embodiments of the present disclosure, in the step S3, the reaction temperature is achieved by raised at a rate of 5-10°C/min.
In some embodiments of the present disclosure, in the copper-aluminum foil obtained in the step S3, a content of copper is not less than 45 wt %, and a content of aluminum is not less than 35 wt %.
In some embodiments of the present disclosure, in the battery powder obtained in the step S3, a content of aluminum is not higher than 0.5wt%.
In some embodiments of the present disclosure, in the step S3, the screening comprises: performing screening by using a double-layer screen, and an obtained material in an upper layer is the copper-aluminum foil, and an obtained material in a bottom layer is the battery powder.
According to a preferred embodiment of the present disclosure, the present disclosure has at least the following beneficial effects.
1. In the embodiments of the present disclosure, in view of the problem that the waste battery is prone to safety hazards and large-area oxidation of copper and aluminum at a relatively high pyrolysis temperature, a combined process of low-temperature high-pressure pyrolysis and medium-temperature negative-pressure pyrolysis is used, in which the temperature of the whole process is controlled at 400 °C or less, and the medium-temperature negative-pressure pyrolysis is carried out under oxygen-free conditions, so as to avoid the combustion of the electrolyte and separator in the pulverized material and the subsequent phenomenon of temperature out of control, thereby protecting the pyrolysis furnace, and reducing the oxidation degree of copper and aluminum.
2. Under the condition of high-pressure mixed gas, NO is used as a free radical with single electron, and it has high activity under a temperature of 100 °C or more, and can randomly attack carbon-carbon bond in organic polymers under the catalysis of trace oxygen, so that the polymer is scissioned to form small molecular compounds, in which way the thermal decomposition temperature of the polymer is reduced. Reference is made to the following reaction formula: NO+[-CH2-CF2-]-42,1-CH2-N=O+ R2-CF2-N=0.
The unique absorption characteristics of PVDF to carbon dioxide may cause a large volume expansion, leading to certain mechanical damage to PVDF, which is conducive to the further in-depth scission of carbon-carbon bonds by NO.
In the present disclosure, under the relatively low temperature, the scission of the polymer is realized, the oxidation of copper and aluminum is avoided, and the occurrence of aluminothermic reaction is further avoided.
3. During the negative-pressure pyrolysis, the organic polymer after scission can be decomposed and carbonized at a slightly high temperature without the need of heating to 500 °C or more, the electrolyte therein can easily reach the boiling point under negative pressure, and enter the waste gas processing system in a gaseous state. In addition, the copper and aluminum are not oxidized, and the aluminothermic reaction does not occur, achieving the purpose of separation and desorption of the battery powder from the copper and aluminum foil.
BRIEF DESCRIPTION OF DRAWINGS
The present disclosure will be further described below in conjunction with the drawings and embodiments, wherein: FIG. I is a process flow diagram of the present disclosure.
DETAILED DESCRIPTION
The concept of the present disclosure and the technical effects produced by the present disclosure will be clearly and completely described below with reference to the examples, so as to fully understand the purpose, characteristics and effects of the present disclosure. Obviously, the described examples are only a part of the examples of the present disclosure, rather than all the examples. Based on the examples of the present disclosure, other examples obtained by those skilled in the art without creative efforts are all within the protection scope of the present disclosure.
Example 1
Provided was a method for recovering battery powder by low-temperature pyrolysis desorption.
With reference to FIG. 1, the specific process was as follows: Step 1: A waste ternary lithium-ion battery was discharged, disassembled, and then pulverized into a pulverized material with a particle size of 5cm or less Step 2: The pulverized material was added into a pyrolysis furnace with a controlled filling rate of 5%. Then the pyrolysis furnace was introduced with a high-pressure mixed gas and then sealed, in which the air pressure was controlled to be 3MPa, and the temperature was controlled to be 120 °C, maintaining for 5h, wherein the high-pressure mixed gas was a mixed gas of CO2, NO and 02 with a volume ratio of 100:10:0.1.
Step 3: After the reaction was completed, the pressure in the furnace was released to normal pressure at a rate of 0.1MPa/min, and a vacuum pump was started to pump the furnace to negative pressure. The pressure in the pyrolysis furnace was controlled to be -0.011'vIPa, and the temperature was raised to 310 °C at a heating rate of 5°C/min, maintaining for 3h.
Step 4: After the pyrolysis reaction was completed, the materials in the pyrolysis furnace were screened with a double-layer screen to obtain the copper-aluminum foil after pyrolysis in the upper layer, and the battery powder desorbed during the pyrolysis process in the bottom layer.
Monitoring the conditions in the pyrolysis furnace: during the high-pressure pyrolysis, it was only observed that droplets seemingly appeared on the surface of the pulverized material, and the volume expanded slightly, while no other obvious changes were observed. During the negative-pressure pyrolysis, the temperature in the furnace remained constant, the powder material desorbed obviously and metallic luster appeared.
Example 2
Provided was a method for recovering battery powder by low-temperature pyrolysis desorption. The specific process was as follows: Step 1: A waste ternary lithium-ion battery was discharged, disassembled, and then pulverized into a pulverized material with a particle size of 5 cm or less Step 2: The pulverized material was added into a pyrolysis furnace with a controlled filling rate of 10%. Then the pyrolysis furnace was introduced with a high-pressure mixed gas and then sealed, in which the air pressure was controlled to be 5MPa, and the temperature was controlled to be 130 °C, maintaining for 4h, wherein the high-pressure mixed gas was a mixed gas of CO2, NO and 02 with a volume ratio of 100:13:1.
Step 3: After the reaction was completed, the pressure in the furnace was released to normal pressure at a rate of 0.3MPa/min, and a vacuum pump was started to pump the furnace to negative pressure. The pressure in the pyrolysis furnace was controlled to be -0.04MPa, and the temperature was raised to 340 °C at a heating rate of 8°C/min, maintaining for 2h.
Step 4: After the pyrolysis reaction was completed, the materials in the pyrolysis furnace were screened with a double-layer screen to obtain the battery material after pyrolysis in the upper layer, and the battery powder desorbed during the pyrolysis process in the bottom layer Monitoring the conditions in the pyrolysis furnace: during the high-pressure pyrolysis, it was only observed that droplets seemingly appeared on the surface of the pulverized material, and the volume expanded slightly, while no other obvious changes were observed. During the negative-pressure pyrolysis, the temperature in the furnace remained constant, the powder material desorbed obviously and metallic luster appeared.
Example 3
Provided was a method for recovering battery powder by low-temperature pyrolysis desorption. The specific process was as follows: Step 1: A waste ternary lithium-ion battery was discharged, disassembled, and then pulverized into a pulverized material with a particle size of 5cm or less.
Step 2: The pulverized material was added into a pyrolysis furnace with a controlled filling rate of 15%. Then the pyrolysis furnace was introduced with a high-pressure mixed gas and then sealed, in which the air pressure was controlled to be 8MPa, and the temperature was controlled to be 150 °C, maintaining for 3h, wherein the high-pressure mixed gas was a mixed gas of CO2, NO and 02 with a volume ratio of 100:15:2.
Step 3: After the reaction was completed, the pressure in the furnace was released to normal pressure at a rate of 0.5MPa/min, and a vacuum pump was started to pump the furnace to negative pressure. The pressure in the pyrolysis furnace was controlled to be -0.08MPa, and the temperature was raised to 360 °C at a heating rate of 10°C/min, maintaining for lh.
Step 4: After the pyrolysis reaction was completed, the materials in the pyrolysis furnace were screened with a double-layer screen to obtain the battery material after pyrolysis in the upper layer, and the battery powder desorbed during the pyrolysis process in the bottom layer Monitoring the conditions in the pyrolysis furnace: during the high-pressure pyrolysis, it was only observed that droplets seemingly appeared on the surface of the pulverized material, and the volume expanded slightly, while no other obvious changes were observed. During the negative-pressure pyrolysis, the temperature in the furnace remained constant, the powder material desorbed obviously and metallic luster appeared.
Comparative Example 1 Provided was a method for recovering battery powder by pyrolysis desorption. This method differed from Example 1 in that: the low-temperature and high-pressure pyrolysis was not performed in Comparative Example L The specific process was as follows: Step 1: A waste ternary lithium-ion battery was discharged, disassembled, and then pulverized into a pulverized material with a particle size of 5cm or less.
Step 2: The pulverized material was added into a pyrolysis furnace with a controlled filling rate of 5%.
Step 3: A vacuum pump was started to pump the furnace to negative pressure. The pressure in the pyrolysis furnace was controlled to be -0.01MPa, and the temperature was raised to 310 °C at a heating rate of 5°C/min, maintaining for 3h.
Step 4: After the pyrolysis reaction was completed, the materials in the pyrolysis furnace were screened with a double-layer screen to obtain the battery material after pyrolysis in the upper layer, and the battery powder desorbed during the pyrolysis process in the bottom layer.
Monitoring the conditions in the pyrolysis furnace: During the negative-pressure pyrolysis, the temperature in the furnace remained constant, molten droplets appeared on the surface of the pulverized material, which agglomerated after cooling, and no obvious metallic luster appeared.
Comparative Example 2 Provided was a method for recovering battery powder by pyrolysis desorption. This method differed from Example 2 in that: the low-temperature and high-pressure pyrolysis was not performed in Comparative Example 2. The specific process was as follows: Step 1: A waste ternary lithium-ion battery was discharged, disassembled, and then pulverized into a pulverized material with a particle size of 5cm or less.
Step 2: The pulverized material was added into a pyrolysis furnace with a controlled filling rate of 10%.
Step 3: A vacuum pump was started to pump the furnace to negative pressure. The pressure in the pyrolysis furnace was controlled to be -0.04MPa, and the temperature was raised to 340 °C at a heating rate of 8°C/min, maintaining for 2h.
Step 4: After the pyrolysis reaction was completed, the materials in the pyrolysis furnace were screened with a double-layer screen to obtain the battery material after pyrolysis in the upper layer, and the battery powder desorbed during the pyrolysis process in the bottom layer Monitoring the conditions in the pyrolysis furnace: During the negative-pressure pyrolysis, the temperature in the furnace remained constant, molten droplets appeared on the surface of the pulverized material, which agglomerated after cooling, and no obvious metallic luster appeared.
Comparative Example 3 Provided was a method for recovering battery powder by pyrolysis desorption. This method differed from Example 3 in that: the low-temperature and high-pressure pyrolysis was not performed in Comparative Example 3. The specific process was as follows: Step 1: A waste ternary lithium-ion battery was discharged, disassembled, and then pulverized into a pulverized material with a particle size of 5cm or less.
Step 2: The pulverized material was added into a pyrolysis furnace with a controlled filling rate of15%.
Step 3: A vacuum pump was started to pump the furnace to negative pressure. The pressure in the pyrolysis furnace was controlled to be -0.08MPa, and the temperature was raised to 360 °C at a heating rate of 10°C/min, maintaining for lh.
Step 4: After the pyrolysis reaction was completed, the materials in the pyrolysis furnace were screened with a double-layer screen to obtain the battery material after pyrolysis in the upper layer, and the battery powder desorbed during the pyrolysis process in the bottom layer Monitoring the conditions in the pyrolysis furnace: During the negative-pressure pyrolysis, the temperature in the furnace remained constant, molten droplets appeared on the surface of the pulverized material, which agglomerated after cooling, and no obvious metallic luster appeared.
Comparative Example 4 Provided was a method for recovering battery powder by pyrolysis desorption. This method differed from Example 2 in that: in Comparative Example 4, the low-temperature and high-pressure pyrolysis was not performed, and the pyrolysis temperature in step 3 was increased. The specific process was as follows: Step 1: A waste ternary lithium-ion battery was discharged, disassembled, and then pulverized into a pulverized material with a particle size of 5cm or less.
Step 2: The pulverized material was added into a pyrolysis furnace with a controlled filling rate of 10%.
Step 3: A vacuum pump was started to pump the furnace to negative pressure. The pressure in the pyrolysis furnace was controlled to be -0.04MPa, and the temperature was raised to 450 °C at a heating rate of 8°C/min, maintaining for lh.
Step 4: After the pyrolysis reaction was completed, the materials in the pyrolysis furnace were screened with a double-layer screen to obtain the battery material after pyrolysis in the upper layer, and the battery powder desorbed during the pyrolysis process in the bottom layer.
Monitoring the conditions in the pyrolysis furnace: During the negative-pressure pyrolysis, after the temperature in the furnace reached 450 °C, a flame appeared, the temperature was out of control and raised by itself, sparks splashed rapidly, and the material was in a reddish molten state and had no obvious metallic luster after cooling.
The battery powders and metal foils obtained in Examples 1-3 and Comparative Examples 1-4 were tested, and the results are shown in Table 1
Table 1
Content of aluminum in battery Content of copper in battery powder wt/% Content of aluminium Content of copper in metal Content of nickel in metal foil Content of cobalt in metal foil Content of manganese powder we% in metal foil we% wt/% wt/% in metal foil wt/% foil wt/% Example 1 0.36 0.21 37.1 49.1 0.11 0.26 0.12 Example 2 0.34 0.25 36.9 48.7 0.12 0.22 0.11 Example 3 0.33 0.22 36.7 47.6 0.11 0.21 0.10 Comparative Example 1 0.41 0.33 11.7 15.6 17.3 8.1 10.7 Comparative Example 2 0.40 0.34 13.2 16.7 14.6 7.4 9.1 Comparative 0.42 0.37 14.8 18.9 13.2 6.8 7.7
Example 3
Comparative Example 4 9.6 5.7 6.7 68.8 0.14 0.23 0.11 In Comparative Examples 1-3, a large amount of transition metal remained in the metal foil, indicating that the pyrolysis temperature is insufficient, for which the pyrolysis reaction is difficult to be performed completely. In Comparative Example 4, the aluminothermic reaction obviously occurs, all aluminum is basically oxidized into black powder, and no formed aluminum foil is obtained.
The examples of the present disclosure have been described in detail above in conjunction with the drawings, but the present disclosure is not limited to the above-mentioned examples. Within the scope of knowledge possessed by those of ordinary skill in the art, various changes can also be made without departing from the spirit of the present disclosure. Furthermore, the examples and features in the examples of the present disclosure may be combined with each other without conflict

Claims (10)

  1. CLAIMS1. A method for recovering battery powder by low-temperature pyrolysis desorption, comprising the following steps: Si: discharging, disassembling and pulverizing a waste battery to obtain a pulverized material; S2: subjecting the pulverized material to a reaction in a mixed atmosphere at a pressure of 3-8MPa and a temperature of 120-150°C, wherein the mixed atmosphere is a mixed gas of CO2, NO, and 02 with a volume ratio of 100: (10-15):(0-2); and 53: subjecting a reaction material obtained in the step 52 to a reaction under negative pressure at a reaction temperature of 310-360°C, and then screening a resulting reacted material to obtain a copper-aluminum foil and the battery powder.
  2. 2 The method according to claim 1, wherein in the step S 1, a particle size of the pulverized material is 5 cm or less.
  3. 3. The method according to claim 1, wherein in the step S 1, the waste battery is at least one selected from the group consisting of a ternary lithium ion battery, a lithium iron phosphate battery, a lithium cobaltate battery, a lithium manganate battery, or a lithium nickelate battery.
  4. 4. The method according to claim 1, wherein in the step S2, the reaction is performed for 3-5h.
  5. The method according to claim 1, wherein in the step S2, the reaction is performed in a pyrolysis furnace, and a filling rate of the pulverized material in the pyrolysis furnace is controlled to be 5-15%.
  6. 6. The method according to claim 1, wherein in the step S3, a pressure of the negative pressure is from -0.01 to -0.081\4Pa.
  7. 7. The method according to claim 1, wherein in the step S3, the reaction is performed for 1-3h.
  8. 8. The method according to claim 5, wherein after the reaction in the step S2 is completed, the pressure in the pyrolysis furnace is released to normal pressure at a rate of 0.1-0.5 MPa/min, and then a vacuum pump is started to pump the pyrolysis furnace to the negative pressure.
  9. 9. The method according to claim 1, wherein in the step S3, the reaction temperature is achieved by raised at a rate of 5-10°C/min
  10. 10. The method according to claim 1, wherein in the step S3, the screening comprises: performing screening by using a double-layer screen, and an obtained material in an upper layer is the copper-aluminum foil, and an obtained material in a bottom layer is the battery powder.
GB2318191.0A 2022-06-23 2022-09-20 Method for recovering battery powder by low-temperature pyrolysis desorption Pending GB2624545A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210716640.7A CN115172923A (en) 2022-06-23 2022-06-23 Method for recovering battery powder through low-temperature pyrolysis desorption
PCT/CN2022/119978 WO2023245889A1 (en) 2022-06-23 2022-09-20 Method for recovering battery powder by low-temperature pyrolysis desorption

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