Resource recycling treatment method for retired batteries

Abstract

The invention relates to a resource recycling treatment method of a decommissioned battery, and relates to the technical field of safety disposal and resource recycling of decommissioned power batteries, and the method comprises the following steps: sequentially confirming the battery type and the abnormal type of the decommissioned battery, detecting the initial parameter of the decommissioned battery, and setting the puncture parameter of a pneumatic nail gun according to the confirmed type; when the type of the decommissioned battery is confirmed to be a burned battery or a soft package battery, the decommissioned battery is preprocessed through an abnormal battery preprocessing module, then the decommissioned battery is placed in a discharging groove, steel nails are punctured into the decommissioned battery through a pneumatic nail gun according to set pneumatic nail gun puncturing parameters, continuous short-circuit discharging is achieved, the voltage of the decommissioned battery after discharging is reduced to 0.5 V or below, and the decommissioned battery is discharged. A discharge battery is obtained; and then carrying out underwater crushing, dehydration, scattering, sorting, drying and screening on the discharge battery. The resource recycling treatment method for the retired batteries is a treatment method which is full-flow-coverage, safe, efficient and high in recycling degree.

Description

Technical Field

[0001] This application relates to the field of safe disposal and resource recycling technology of retired power batteries, and more specifically, to a method for the resource recycling and processing of retired batteries. Background Technology

[0002] With the explosive growth of the new energy vehicle industry, my country is experiencing a rapid wave of retired power batteries. It is estimated that by 2025, the total amount of retired power batteries will exceed 1 million tons, of which abnormal batteries (including water-damaged batteries, batteries burned at high temperatures, and damaged pouch batteries) caused by accidents, aging, or improper storage will account for as much as 15%-20%, with an annual generation of 150,000-200,000 tons. These batteries suffer from internal structural damage, electrolyte leakage, and abnormal internal resistance. They not only carry high levels of residual charge but are also highly susceptible to short circuits during disposal, triggering a chain reaction of exothermic reactions that produce large amounts of flammable and explosive gases such as CO and H2. Traditional disposal methods pose extremely high risks of combustion, explosion, and environmental pollution, making safe disposal a pressing need.

[0003] Currently, the industry's commonly used retired battery processing technologies primarily target normal batteries, exhibiting significant shortcomings or even complete absence in the processing of abnormal batteries. Current solutions lack safety designs that adequately cover the risks associated with abnormal batteries, and the processing systems lack specific adaptations for abnormal batteries. Neither safety nor recycling designs meet the needs of abnormal batteries. Current solutions not only suffer from safety issues but also from problems with resource recycling efficiency and equipment compatibility.

[0004] Therefore, there are gaps in aspects such as "safety control parameters, dedicated pretreatment, and multi-resource closed-loop recycling" for abnormal batteries, which cannot solve the problems of high safety risks, low resource recovery rates, and low equipment compatibility in the handling of abnormal batteries.

[0005] Therefore, this application is hereby submitted. Summary of the Invention

[0006] The purpose of this application is to provide a method for the resource recycling and processing of retired batteries. This method can cover multiple types of abnormal batteries, is safe and controllable throughout the process, has a high resource recovery rate, and good environmental compatibility. It aims to completely solve the problems of safety risks, resource waste, and secondary pollution in the processing of abnormal batteries.

[0007] To achieve the above objectives, the present invention provides the following technical solution: In a first aspect, this application provides a method for the resource recycling and processing of retired batteries, comprising: S1. Raw material characteristic detection: The battery type and abnormality type of the retired battery are confirmed in sequence, and the initial parameters of the retired battery are detected at the same time. The puncture parameters of the pneumatic nail gun are set according to the confirmed type. The battery type includes ternary lithium battery or lithium iron phosphate battery, and the abnormality type includes water immersion, fire, soft pack or broken material. S2. Underwater needle discharge: The decommissioned battery after confirmation of its type is then placed in the discharge tank and steel nails are inserted into the decommissioned battery using the pneumatic nail gun according to the set puncture parameters to achieve continuous short-circuit discharge. After discharge, the voltage of the decommissioned battery drops below 0.5V to obtain a discharged battery. When the decommissioned battery after confirmation of its type is a fire-damaged battery or a soft-pack battery, it is first pre-treated by the abnormal battery pre-treatment module before being placed in the discharge tank. S3. Underwater crushing: The discharge battery is directly conveyed to the twin-shaft crusher via a plate chain conveyor. The crushing is completed in an underwater environment where the liquid level is 5-10 cm higher than the material and the oxygen content is <0.1%. The crushed material is retrieved by a mechanical screen to obtain the crushed battery. S4. Dehydration and dispersion: The broken battery is dehydrated and dispersed to obtain bulk material; S5. Sorting: The bulk material is sorted to obtain aluminum shell and non-aluminum shell material; S6. Drying and screening: The sorted aluminum-free material is dried and then screened to obtain a mixture of battery powder and electrode membrane.

[0008] In an optional embodiment, the initial parameters include initial voltage, remaining charge, internal resistance, and water content, wherein the initial voltage of the ternary lithium battery is 3.5-3.7V and the remaining charge is ≤25% SOC; the initial voltage of the lithium iron phosphate battery is ≤3.6V and the remaining charge is ≤90% SOC. And / or, based on the confirmed type, set the pneumatic nail gun puncture parameters including: When the battery type is an NCM811 ternary lithium battery and the abnormality type is water immersion or fire damage, the needle penetration parameter is: needle penetration cross-section ratio 1.025 × 10⁻⁶. -4 -1.035×10 -4 mm 2 / mm 3 Needle insertion depth 45-55mm; When the battery type is an NCM622 ternary lithium battery and the abnormality type is water immersion or soft pack, the needle penetration parameter is: needle penetration cross-section ratio 1.045 × 10⁻⁶. -4 -1.055×10 -4 mm 2 / mm 3 Needle insertion depth 45-55mm; When the battery type is lithium iron phosphate battery and the anomaly type is fire, soft-pack, or broken material, the needle penetration parameter is: needle penetration cross-section ratio 2.06 × 10⁻⁶. -4 -3.7×10 -4 mm 2 / mm 3 Needle insertion depth 50-220mm; And / or, the working air pressure of the pneumatic nail gun is 0.6-0.8MPa, the diameter of the steel nail is 2-4mm, the water temperature during underwater needle piercing discharge is ≤60℃, the water depth is 45-55cm, the needle piercing time is 0.8-1.2min, and the underwater protection time is 55-70min.

[0009] In an optional implementation, the abnormal battery pretreatment module includes a fire-damaged battery pretreatment mechanism, a pouch battery pretreatment mechanism, and a safety monitoring mechanism. Preferably, the pretreatment mechanism for the burned battery includes an internal resistance sensor located at the entrance of the discharge tank, used to detect the internal resistance of the cell of the retired battery in real time and adjust the puncture depth accordingly, and a hot air pre-blowing device for removing carbon black from the surface of the retired battery; when the internal resistance sensor detects that the internal resistance of the retired battery is 50-80mΩ, the puncture depth is increased to 78mm, and when it is >80mΩ, it is increased to 90mm; the hot air pre-blowing device removes the carbon black from the surface of the retired battery by pre-blowing with hot air at 40-50℃ for 30s; Preferably, the soft-pack battery pretreatment mechanism includes a softening unit disposed at the inlet of the discharge tank for softening the aluminum-plastic film, a negative pressure adsorption mechanism for peeling off the aluminum-plastic film, and an anti-winding blade; the temperature of the softening unit is 40-50℃, the softening time is 15-25s, and the negative pressure value of the negative pressure adsorption mechanism is -0.05MPa; Preferably, the safety monitoring mechanism includes a temperature sensor and a hydrogen concentration detector installed in the discharge tank. When the water temperature in the discharge tank exceeds 60°C or the hydrogen concentration exceeds 1%, the system automatically replenishes water and starts nitrogen purging until the indicators return to the safe range.

[0010] In an optional embodiment, the twin-shaft crusher has a rotational speed of 100-150 rpm, a cutter head spacing of 4-6 mm, an operating power of 25-35 KW, a crushed material particle size of ≤50 mm, and a mechanical grid aperture of 8-12 mm. And / or, the top of the twin-shaft crusher is provided with an annular nitrogen gas distribution ring, which is divided into a feeding gas distribution zone, a crushing gas distribution zone, and a discharging gas distribution zone. The pressure in the feeding gas distribution zone is 0.028-0.032 MPa, the pressure in the crushing gas distribution zone is 0.018-0.022 MPa, and the pressure in the discharging gas distribution zone is 0.008-0.012 MPa. The oxygen content in the crushing gas distribution zone is <0.05%. And / or, the flow velocity of the water in the twin-shaft crusher is 0.3-0.5 m / s; And / or, the bottom of the twin-shaft crusher is also provided with a black powder deposition tank; And / or, a temperature sensor, a current sensor, and a first high-pressure water gun are also installed inside the top of the twin-shaft crusher. The temperature sensor is connected to the annular nitrogen gas distribution ring and the control mechanism and water flow control valve of the twin-shaft crusher. The current sensor is connected to the first high-pressure water gun. When the temperature sensor detects a local temperature > 80°C, the nitrogen pressure is increased to 0.05MPa, the water flow rate is increased to 0.8m / s, and the twin-shaft crusher is shut down for 20-40s. When the current sensor detects a current fluctuation of > ±10% in the twin-shaft crusher, the speed is automatically reduced by 10rpm and the first high-pressure water gun is started for flushing.

[0011] In an optional embodiment, the sorting is performed using an eddy current separator, which is equipped with an adjustable baffle, the adjustable height of which is 0-10mm. And / or, the eddy current separator is equipped with an automatically rotating vibrating screen, and a second high-pressure water gun for rinsing the vibrating screen is provided above the vibrating screen; Preferably, the aperture of the vibrating screen is 13-17mm, the vibrating screen is rotated once every 20-40 minutes, and each rotation lasts for 8-12 seconds. During the interval, the second high-pressure water gun washes the vibrating screen, and the pressure of the second high-pressure water gun is 0.2-0.4MPa.

[0012] In an optional embodiment, the drying process includes placing the aluminum-free material in a paddle dryer and heating it with saturated steam at 120°C. The paddle dryer has an operating power of 70-75 kW, and nitrogen gas is also introduced into the paddle dryer at a flow rate of 40-60 m³ / h. 3 / h, the oxygen content is controlled in real time by an oxygen analyzer to be <5%, the drying time is 20-40min, and the output moisture content is ≤5%.

[0013] In an optional embodiment, the resource recycling method for retired batteries further includes S7, exhaust gas treatment: the exhaust gas generated in steps S2-S5 is subjected to first exhaust gas treatment, and the exhaust gas generated in step S6 is subjected to second exhaust gas treatment. The first waste gas treatment includes condensing the waste gas generated in steps S2-S5 at 4-6°C, followed by catalytic oxidation of carbon monoxide at 280-320°C using Pt / Al2O3 as a catalyst, then performing a two-stage alkaline scrubbing with 5%-10% NaOH to remove fluorides, and finally activated carbon adsorption. The treatment volume of the first waste gas treatment is 3500-4500 m³ / h. 3 / h; The second waste gas treatment includes two-stage condensation of the waste gas generated in step S6. The temperature of the first condensation is 4-6℃, and the temperature of the second condensation is -12~-8℃. After condensation, the waste gas is sprayed with NaOH at a concentration of 8%-12% to remove fluorides, and then adsorbed by activated carbon.

[0014] In an optional embodiment, the resource recycling method for the retired batteries further includes S8, wastewater treatment: sequentially subjecting the wastewater to lithium fluoride co-precipitation, oil separation, and recycling, wherein the lithium fluoride co-precipitation includes adding Na2CO3 solution to the wastewater to make Li... + and F - A LiF·NaF double salt precipitate is formed, followed by stepwise analysis with 2 mol / L HCl. First, NaF is dissolved at 45-55℃ to generate NaCl for recycling. Then, LiF is dissolved at 75-85℃ for lithium precipitation, with a fluorine recovery rate >90%. The oil separation involves adding 19.5%-20.5% sodium sulfate solution to the solution after the fluorine-lithium co-precipitation, stirring at 200-300 rpm for 20-40 minutes, followed by oil separation to remove the oil phase from the electrolyte. The recycling process involves recycling the wastewater after oil separation 4-6 times to the underwater crushing in step S3. After the recycling is completed, the recycled wastewater is dried to recover lithium carbonate.

[0015] In an optional embodiment, the electrolyte after oil separation is recovered by three-stage distillation, wherein DMC is recovered at 40-60℃, EMC at 70-90℃, and EC at 110-130℃, with a purity of >99.5%. The tail gas is adsorbed by modified activated carbon and then desorbed by hot air and circulated, with an organic carbon recovery rate of >95%.

[0016] In an optional embodiment, the resource recycling and processing method for retired batteries further includes constructing a full-process parameter self-learning system. This system collects more than 10,000 sets of abnormal battery processing data, uses a neural network algorithm to construct and input initial parameters, and then outputs operating parameters. The parameters are automatically updated every 100 tons of batteries processed. The initial parameters include at least one of battery type, abnormality type, and equipment status, and the operating parameters include puncture depth, nitrogen pressure, and drying temperature.

[0017] The beneficial effects of this application include: The resource-based recycling method for retired batteries provided in this application is the first to develop a quantitative discharge parameter table for different battery systems (high-nickel / low-nickel / LFP / lithium cobalt oxide / lithium manganese oxide / sodium-ion batteries) and different abnormality types (water-immersed / fire-damaged / soft-pack batteries), clearly defining critical safety thresholds and filling a technological gap in the industry. Before underwater needle-puncture discharge, specialized pretreatment is performed on abnormal batteries, innovatively adapting internal resistance to puncture depth and pre-peeling aluminum-plastic film for fire-damaged, soft-pack, and water-immersed batteries, filling another industry gap. The underwater needle-puncture discharge and underwater crushing are seamlessly connected via a plate chain conveyor, completely eliminating the risk of oxygen exposure during the transfer process, reducing the needle-puncture explosion rate of ternary lithium batteries from the industry average of 15% to 0%, and stably controlling the hydrogen concentration at ≤1% (below the lower explosion limit). Therefore, the resource-based recycling method for retired batteries provided in this application is a comprehensive, safe, efficient, and highly resource-based treatment method.

[0018] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 A process flow diagram of the resource recycling and treatment method for retired batteries provided in this application; Figure 2 A schematic diagram of the structure of the resource recycling device for retired batteries involved in the resource recycling method for retired batteries provided in this application; Figure 3 A schematic diagram of the needle discharge principle of the needle discharge device provided in this application.

[0021] Icons: 100 - Recycling and processing equipment for retired batteries; 110 - Needle discharge equipment; 120 - Plate chain conveyor; 130 - Twin-shaft crusher; 140 - Mechanical bar screen; 150 - Dehydration equipment; 160 - Single-shaft disperser; 170 - Eddy current separator; 180 - Paddle dryer; 190 - Circular vibrating screen. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. The components of the embodiments of this application described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0023] In the description of this application, it should be noted that the terms "inner" and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product is in use. They are used only for the convenience of describing this application and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application. Furthermore, the terms "first," "second," etc., are used only to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0024] In the description of this application, it should also be noted that, unless otherwise expressly specified and limited, the terms "setup" and "connection" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this application based on the specific circumstances.

[0025] Please see Figure 1 and Figure 2 This application provides a method for the resource recycling and processing of retired batteries, which is carried out using a retired battery resource recycling and processing device 100. The retired battery resource recycling and processing device 100 includes a needle discharge device 110, a plate chain conveyor 120, a twin-shaft crusher 130, a dewatering device 150, a single-shaft disperser 160, an eddy current separator 170, a paddle dryer 180, and a circular vibrating screen 190 connected in sequence. A mechanical bar is arranged below the twin-shaft crusher 130 to retrieve the crushed material inside the twin-shaft crusher 130. The structure of the above device will be described in the subsequent method description. Parts not described indicate conventional structures and are not limited in this application.

[0026] The method for resource recycling of retired batteries provided by this invention includes the following steps: S1. Raw material characteristic detection: Confirm the battery type and abnormality type of the retired battery in sequence, and at the same time check the initial parameters of the retired battery. Set the puncture parameters of the pneumatic nail gun according to the confirmed type. Currently, the industry's commonly used retired battery processing technologies primarily target normal batteries, leaving significant shortcomings and even gaps in the treatment of abnormal batteries. Existing technologies lack systematic parameter guidance for handling abnormal batteries: for ternary lithium batteries, different nickel contents (such as NCM811 and NCM622) lead to significant differences in the needle penetration explosion threshold, but existing literature only vaguely mentions "high charge makes them prone to explosion," lacking precise quantitative parameters. Actual tests show that when the charge of an NCM811 battery exceeds 20%, the needle penetration explosion rate surges to 18.7%; while for lithium iron phosphate batteries prone to fire (internal resistance > 50mΩ), reliable discharge parameter specifications are lacking, and indiscriminate handling can easily lead to aluminum casing cracking or electrolyte leakage.

[0027] Therefore, before performing underwater nailing discharge on retired batteries, this application first confirms the battery type and abnormality type of the retired batteries. The battery type includes ternary lithium batteries or lithium iron phosphate batteries, and the abnormality type includes water immersion, fire damage, soft pack, or broken material. The initial parameters include initial voltage, remaining capacity, internal resistance, and water content. By confirming the battery type, abnormality type, and initial parameters of the retired batteries, and setting specific pneumatic nail gun puncture parameters according to the confirmed type, the safety of puncture is effectively guaranteed.

[0028] When the battery type is NCM811 ternary lithium battery and the abnormality type is water immersion or fire, the needle penetration parameter is: needle penetration cross-section ratio 1.025 × 10 -4 -1.035×10 -4 mm 2 / mm 3 Needle insertion depth 45-55mm; When the battery type is NCM622 ternary lithium battery and the abnormality type is water immersion or soft pack, the needle penetration parameter is: needle penetration cross-section ratio 1.045 × 10 -4 -1.055×10 -4 mm 2 / mm 3 Needle insertion depth 45-55mm; When the battery type is lithium iron phosphate battery and the anomaly type is fire, soft pack, or broken material, the needle penetration parameter is: needle penetration cross-section ratio 2.06 × 10⁻⁶. -4 -3.7×10 -4 mm 2 / mm 3 The needle insertion depth is 50-220mm.

[0029] By setting the above parameters, it can be seen that this application has developed a "needle penetration cross-section ratio - needle penetration depth" correlation table and a quantitative discharge parameter table for different battery systems and different abnormality types, and clarified the critical safety threshold (e.g., ternary lithium cross-section ratio 1.03 × 10⁻⁶). -4 This fills a technological gap in the industry and avoids the blind approach of "general multi-directional needle puncture" described in existing technologies.

[0030] S2. Underwater Needle Puncture Discharge: After confirming the type of the retired battery, place it in the discharge tank of the needle puncture discharge device 110 and, according to the set pneumatic nail gun puncture parameters, use a pneumatic nail gun to puncture the retired battery with steel nails to achieve continuous short-circuit discharge. After discharge, the voltage of the retired battery drops below 0.5V, resulting in a discharged battery. The specific operation is as follows: The confirmed type of retired battery is manually placed in the discharge tank of the needle puncture discharge device 110. The clamping mechanism inside the needle puncture discharge device 110 clamps the battery, lowers the battery into the water, and moves it to the puncture position. The pneumatic nail gun punctures the retired battery with steel nails to achieve continuous short-circuit discharge for about 1 minute. After puncture, the battery continues to remain in the water for 55-70 minutes to avoid violent short-circuit discharge that could cause combustion or even explosion. After the water holding time ends, the battery is moved to the unloading position, the clamping mechanism is released, and the battery is pushed out and conveyed by a plate chain conveyor.

[0031] Meanwhile, before puncture, when feeding the decommissioned batteries of the above-mentioned types, an abnormal battery pretreatment module is set up in the discharge tank. The abnormal battery pretreatment module includes a fire battery pretreatment mechanism, a soft-pack battery pretreatment mechanism, and a safety monitoring mechanism.

[0032] The pretreatment mechanism for fire-damaged batteries includes an internal resistance sensor located at the entrance of the discharge tank, which is used to detect the internal resistance of the retired battery cells in real time and adjust the puncture depth accordingly, and a hot air pre-blowing device for removing carbon black from the surface of the retired battery. When the internal resistance sensor detects that the internal resistance of the retired battery is 50-80mΩ, the puncture depth is increased to 78mm, and when it is >80mΩ, it is increased to 90mm. The hot air pre-blowing device removes carbon black from the surface of the retired battery by pre-blowing with hot air at 40-50℃ for 30s.

[0033] The pretreatment mechanism for soft-pack batteries includes a softening unit located at the inlet of the discharge tank for softening the aluminum-plastic film, a negative pressure adsorption mechanism for peeling off the aluminum-plastic film, and an anti-winding blade; the temperature of the softening unit is 40-50℃, the softening time is 15-25s, and the negative pressure value of the negative pressure adsorption mechanism is -0.05MPa.

[0034] The safety monitoring system includes a temperature sensor and a hydrogen concentration detector installed in the discharge tank. When the water temperature in the discharge tank exceeds 60°C or the hydrogen concentration exceeds 1%, the system automatically replenishes water and starts nitrogen purging until the indicators return to the safe range.

[0035] Please see Figure 3 In underwater needle discharge, this application uses an industrial-grade pneumatic nail gun with a working air pressure of 0.6-0.8 MPa, a nail diameter of 2-4 mm, a water temperature ≤60℃, a water depth of 45-55 cm, a needle penetration time of 1 minute, and an underwater protection time of 55-70 minutes. The pneumatic nail gun in this application continuously penetrates the battery casing to form a stable short-circuit circuit, ensuring the nail penetrates the battery casing and contacts the electrode, thus creating a continuous short circuit. This directly reduces the abnormal battery voltage to below 0.5V without requiring additional discharge steps, resulting in a 200% improvement in efficiency compared to the previous method. Please refer to the schematic diagram of the underwater needle discharge process. Figure 3 When the steel needle pierces the battery, it provides a path for a short circuit inside the battery, causing the current to rise rapidly and the voltage to drop rapidly, allowing the battery to complete the discharge process in a short time.

[0036] S3. Underwater Crushing: The discharged battery is directly conveyed to the twin-shaft crusher 130 via a plate chain conveyor. Crushing is completed in an underwater environment where the liquid level is 5-10 cm higher than the material and the oxygen content is <0.1%. The water flow velocity in the twin-shaft crusher 130 is 0.3-0.5 m / s. After crushing, the material is retrieved by a mechanical screen 140 to obtain the crushed battery.

[0037] While current technologies include underwater needle discharge solutions, they still employ a "sealed transfer via a stuffing box" method. After discharge, the battery is exposed to air for over 30 minutes. Actual measurements show that during this process, the hydrogen concentration can rise sharply from 0.8% to 5.2%, far exceeding the lower explosive limit of 4.0%, posing a serious safety hazard. This application, however, combines underwater needle discharge with underwater crushing and directly utilizes a plate chain conveyor for transport, completely eliminating the risk of oxygen exposure during transfer. This reduces the needle discharge explosion rate of ternary lithium batteries from the industry average of 15% to 0%, while maintaining a stable hydrogen concentration of ≤1% (below the lower explosive limit). The plate chain conveyor is made of high-temperature resistant rubber (80℃), and its conveying speed is matched to the speed of the twin-shaft crusher (130), for example, 0.5 m / s.

[0038] When the twin-shaft crusher 130 is used for crushing, the crusher operates at a speed of 100-150 rpm, with a cutter head spacing of 4-6 mm and an operating power of 25-35 KW. The crushed material has a particle size of ≤50 mm, and the mechanical screen 140 has an aperture of 8-12 mm. The twin-shaft crusher 130 can effectively crush the discharged batteries, and the mechanical screen 140 is used for retrieval, ensuring rapid retrieval and transportation to the next process, thus maintaining process continuity. A black powder sedimentation tank is also installed at the bottom of the twin-shaft crusher 130. Smaller particles fall into the black powder sedimentation tank through the gaps in the mechanical screen 140. Collecting this black powder further improves resource utilization.

[0039] In this application, the top of the twin-shaft crusher 130 is provided with an annular nitrogen gas distribution ring. The annular nitrogen gas distribution ring is divided into a feeding gas distribution zone, a crushing gas distribution zone, and a discharging gas distribution zone. The pressure in the feeding gas distribution zone is 0.028-0.032 MPa, the pressure in the crushing gas distribution zone is 0.018-0.022 MPa, and the pressure in the discharging gas distribution zone is 0.008-0.012 MPa. The oxygen content in the crushing gas distribution zone is <0.05%. By utilizing the annular nitrogen gas distribution ring, the pressure in different zones can be adjusted to achieve a nitrogen gradient distribution and ensure the safety of the entire crushing process.

[0040] In this application, a temperature sensor, a current sensor, and a first high-pressure water gun are also installed inside the top of the twin-shaft crusher 130. The temperature sensor is an infrared temperature sensor with a response time of 0.1s. The temperature sensor is connected to the annular nitrogen gas distribution ring, the control mechanism of the twin-shaft crusher 130, and the water flow control valve. When the temperature sensor detects a local temperature >80℃, the nitrogen pressure is increased to 0.05MPa, the water flow rate is increased to 0.8m / s, and the twin-shaft crusher 130 is shut down for 20-40s, reducing the accident rate to 0.01%. When the current sensor detects a current fluctuation of >±10% in the twin-shaft crusher 130, the speed is automatically reduced by 10rpm and the first high-pressure water gun is activated for flushing. The pressure of the first high-pressure water gun is 0.2-0.4MPa.

[0041] S4. Dehydration and Dispersion: The crushed battery is placed in the dehydration equipment 150 for dehydration, and then sent to the single-shaft disperser 160 for dispersion to obtain bulk material.

[0042] S5. Sorting: Bulk materials are sorted by eddy current separator 170 to separate aluminum shell and non-aluminum shell materials.

[0043] The eddy current separator 170 is equipped with adjustable baffles, with an adjustable height of 0-10mm. Combined with an infrared material level sensor, the material layer thickness control accuracy is improved to ±0.5mm. Experiments show that when the material layer thickness is 5mm, the aluminum shell separation purity reaches 95.3%, and the impurities (copper foil / black powder) are only 3.2% (the industry average impurity rate is 20%).

[0044] Furthermore, the eddy current separator 170 is equipped with an automatically rotating vibrating screen, and a second high-pressure water gun for rinsing the vibrating screen is installed above the screen. The screen has an aperture of 13-17mm, and rotates every 20-40 minutes, with each rotation lasting 8-12 seconds. During this time, the second high-pressure water gun rinses the screen at a pressure of 0.2-0.4MPa. This application achieves self-cleaning of the eddy current separator 170 through the combination of the automatically rotating vibrating screen and the high-pressure water gun. The separated aluminum shells enter an aluminum shell collection trough, which is tilted at a 30° angle to ensure rapid sliding of the separated aluminum shells, preventing accumulation and secondary mixing.

[0045] S6. Drying and screening: The separated aluminum-free material is dried and then screened through a 190° circular vibrating screen to obtain a mixture of battery powder and electrode membrane.

[0046] Paddle drying involves placing the aluminum-free material into a paddle dryer 180 and heating it with 120℃ saturated steam. The paddle dryer 180 has an operating power of 70-75 KW. Nitrogen gas is also introduced into the paddle dryer 180 at a flow rate of 40-60 m³ / h. 3 The drying process involves controlling the oxygen content to be <5% in real time using an oxygen analyzer, with a drying time of 20-40 minutes and an output moisture content ≤5%. By controlling the oxygen content during the drying process, the combustion of organic solvents (such as EC / DMC) in the electrolyte upon contact with oxygen can be effectively prevented. Furthermore, the output moisture content in this application can be detected by a humidity sensor installed at the discharge port. When the moisture content exceeds 5%, the residence time of the aluminum-free material in the paddle dryer 180° can be appropriately extended, thereby effectively controlling the moisture content and ensuring that the black powder does not clump during subsequent storage.

[0047] S7. Waste gas treatment: The waste gas generated in steps S2-S5 is subjected to first waste gas treatment, and the waste gas generated in step S6 is subjected to second waste gas treatment. The first waste gas treatment process includes condensing the waste gas generated in steps S2-S5 at 4-6℃, followed by catalytic oxidation of carbon monoxide at 280-320℃ using Pt / Al2O3 as a catalyst. The waste gas is then subjected to a two-stage alkaline scrubbing process with 5%-10% NaOH to remove fluorides, with the pH controlled at approximately 10-11 during the scrubbing process. Following this, the waste gas undergoes activated carbon adsorption. The treatment volume for the first waste gas treatment is 3500-4500 m³ / h. 3 / h; The second waste gas treatment includes two-stage condensation of the waste gas generated in step S6. The temperature of the first condensation is 4-6℃, and the temperature of the second condensation is -12~-8℃. After condensation, the waste gas is sprayed with NaOH at a concentration of 8%-12% to remove fluorides, and then adsorbed by activated carbon.

[0048] This application differentiates the treatment of waste gas generated at different stages by using different processes, resulting in superior treatment effects.

[0049] S8. Wastewater Treatment: The wastewater is sequentially treated with lithium fluoride co-precipitation, oil separation, and recycling. Lithium fluoride co-precipitation includes adding Na₂CO₃ solution to the wastewater to allow the Li₂CO₃ to precipitate. + and F - A LiF·NaF double salt precipitate is formed, followed by stepwise analysis with 2 mol / L HCl. First, NaF is dissolved at 45-55℃ to generate NaCl for recycling. Then, LiF is dissolved at 75-85℃ for lithium precipitation, with a fluorine recovery rate >90%. Oil separation involves adding 19.5%-20.5% sodium sulfate solution to the solution after fluorine-lithium co-precipitation, stirring at 200-300 rpm for 20-40 minutes, followed by oil separation to remove the oil phase from the electrolyte. Recycling involves recycling the wastewater after oil separation 4-6 times to the crushing water. After recycling, the recycled wastewater is dried to recover lithium carbonate.

[0050] Battery breakage wastewater is not a single liquid, but a typical "oil-water-solid" three-phase mixture system, with core components including: "Aqueous phase": This phase contains dissolved electrolytes from the electrolyte solution (such as LiPF6, which decomposes into Li upon contact with water). + F - The "solid phase" consists of: "plasma" and a small amount of water-soluble impurities; "oil phase": organic solvents in the electrolyte (such as dimethyl carbonate, ethyl carbonate, etc., which are difficult to dissolve in water and will exist in the water as floating oil or emulsified oil); "solid phase": a small amount of solid impurities such as battery casing fragments and electrode powder mixed in during the crushing process.

[0051] In this application, the wastewater is first subjected to lithium fluoride co-precipitation (before oil separation, Na2CO3 is added to remove Li). + F - To avoid interference from the oil phase in ion recovery, the process involves oil separation (adding sodium sulfate to demulsify and separate 92% of the organic solvent (oil phase)), followed by recycling (wastewater is recycled 5 times after oil separation, reducing COD by 70%). The entire process is designed sequentially to recover key ions (Li, F), remove organic impurities (oil phase), and ultimately achieve wastewater recycling, thus solving the problem that traditional processes cannot handle three-phase mixed systems.

[0052] The circulating wastewater is fed into a drum dryer and dried at 120℃. After drying, lithium-containing black powder (lithium content 0.8-1.2g / L) is obtained. Through acid leaching (2mol / L HCl) and precipitation (Na2CO3) processes, the lithium recovery rate reaches 82.3%, and the purity of the recovered lithium carbonate is >99.5%, which can be directly used for the reprocessing of battery materials.

[0053] The electrolyte (containing EC / DMC / EMC) after oil separation is recovered through three-stage distillation. Specifically, DMC is recovered at 40-60℃, EMC at 70-90℃, and EC at 110-130℃, with a purity of >99.5%. The tail gas is adsorbed by modified activated carbon and then desorbed by hot air and recycled, with an organic carbon recovery rate of >95%.

[0054] This application achieves a closed-loop synergistic recovery of "fluorine-lithium-carbon" through specific wastewater treatment, increasing the fluorine resource recovery rate to 90% and the electrolyte organic carbon recovery rate to >95%, forming a complete chain of technological barriers.

[0055] Cleaning wastewater (such as equipment flushing water) is treated in a sedimentation tank (2-hour retention time) and then filtered through a precision filter (1μm pore size) before being fed into the underwater crushing system. The water resource recycling rate reaches 72%, and the fresh water consumption per ton of treated water is reduced from 0.8m³. 3 Reduced to 0.24m 3 To address the current problem of water waste caused by technology.

[0056] Regarding resource recycling, the mainstream processes in the industry generally achieve a lithium recovery rate of only 25%-30% in wastewater, and do not involve targeted lithium recovery modules. They only treat wastewater through simple neutralization and precipitation, resulting in a loss of approximately 0.5-0.8 kg of lithium resources per ton of wastewater, causing significant resource waste. Furthermore, waste gas treatment is not considered, and fluorides generated from LiPF6 decomposition are not removed, leading to significant environmental compliance pressures. In terms of equipment compatibility, existing technical solutions have strong limitations and are unable to meet the processing needs of various types of abnormal batteries. They can only process square aluminum-cased batteries and cannot be adapted to pouch batteries (where aluminum-plastic film is easily wrapped around the equipment), failing to meet the processing needs of large-scale, mixed-state abnormal batteries. The waste gas and wastewater treatment processes provided in this application significantly improve upon these problems. They innovate wastewater lithium extraction processes, increasing the lithium recovery rate from 30% to >80%; optimize the water resource recycling system, achieving a wastewater recycling rate of >70%, reducing fresh water consumption; and improve multi-stage waste gas treatment, ensuring that VOCs, fluorides, and other indicators are superior to national standards.

[0057] S9. A full-process parameter self-learning system is constructed. By collecting more than 10,000 sets of abnormal battery processing data, a neural network algorithm is used to construct and input initial parameters, and then output operating parameters. The parameters are automatically updated every 100 tons of batteries processed. The initial parameters include at least one of battery type, abnormality type, and equipment status, and the operating parameters include puncture depth, nitrogen pressure, and drying temperature. This application achieves full-process adaptive optimization through an artificial intelligence-driven parameter self-learning system.

[0058] The full-process parameter self-learning system provided in this application is a dedicated model customized and optimized for abnormal battery handling scenarios.

[0059] Basic framework: Based on the deep neural network (DNN) commonly used in industrial scenarios, it integrates the temporal feature capture capability of recurrent neural network (LSTM) (to adapt to dynamic changes in data such as temperature and hydrogen concentration during processing).

[0060] I. Algorithm Types and Architectures A fusion model of convolutional neural network and long short-term memory network (CNN-LSTM) is adopted, combining the capabilities of "spatial feature extraction + temporal dependency learning" to adapt to the multi-dimensional and temporal parameter requirements of the retired battery processing process: The CNN module is used to extract spatial features from multi-dimensional data such as battery physical and chemical properties. It sets up three convolutional layers (with kernel sizes of 3×3, 5×5, and 7×7, and channel numbers of 32, 64, and 128 respectively), combined with max pooling layers (with a pooling kernel of 2×2) and dropout layers (with a dropout rate of 0.25) to achieve feature dimensionality reduction and overfitting suppression.

[0061] LSTM module: Used to learn the temporal dependencies of process parameters (such as the temporal correlation of parameters in the "crushing-dissolving-separation" process). It sets up 2 layers of LSTM units (with 256 and 128 hidden layer nodes respectively) and introduces an attention mechanism to weight key temporal features, thereby strengthening the learning of parameters in the core process stages.

[0062] Output layer: The fully connected layer outputs the operating parameters of each process in the decommissioned battery processing (such as crushing speed, acid dissolution temperature, stirring rate, and reagent dosage).

[0063] II. Data Acquisition and Preprocessing 1. Data Dimensions: Collect full-process processing data for at least 10,000 sets of abnormal batteries (overcharge, over-discharge, bulging, abnormal internal resistance, etc.), including: Basic battery information: model, nominal capacity, number of cycles; Physical characteristics: size, weight, casing material; Chemical composition: positive and negative electrode active materials (such as NCM, LFP), electrolyte composition, and metal impurity content; Process parameters: crushing force, screening size, drying temperature, acid concentration, reaction temperature, stirring rate, and reaction time; Product indicators: metal recovery rate, purity, wastewater / waste gas treatment effect, etc.

[0064] 2. Preprocessing method: The numerical data is normalized by mean-variance, and the categorical features (such as battery model and material) are one-hot encoded to ensure that the data format is uniform and meets the model input requirements.

[0065] III. Model Training and Optimization 1. Loss function and optimizer: Mean squared error (MSE) is chosen as the loss function, and Adam is used as the optimizer (initial learning rate 0.001, decaying by 0.1 every 50 iterations) to balance training efficiency and convergence accuracy.

[0066] 2. Training strategy: Batch size is set to 128, and the number of iterations is 300; an early stopping mechanism is introduced (training stops when the validation set loss does not decrease for 20 consecutive iterations) to avoid overfitting.

[0067] 3. Model update mechanism: After processing 100 tons of batteries, the actual process parameters and product indicators of that batch are collected, labeled as new training samples and incorporated into the dataset. The model is then retrained to update the parameters, achieving a closed-loop self-learning mechanism of "data-model-process".

[0068] IV. Parameter Output and Application Initial parameter input: The model uses historical best process parameters or domain expert experience values ​​as initial inputs. Based on the trained weights, the model outputs suggested operating parameters for each process (such as the rotation speed of the crushing process, the temperature and acid concentration of the acid dissolution process, etc.).

[0069] Parameter-guided production: The output operating parameters are directly used for equipment control in the decommissioned battery processing line (such as parameter adjustment of crushers and reactors), realizing intelligent control of the process.

[0070] The full-process parameter self-learning system has the following effects: (1) Multi-dimensional heterogeneous data fusion module: Breaking the limitation of "single parameter input", it encodes heterogeneous data such as "battery attributes (such as NCM811 nickel content), equipment parameters (such as needle penetration depth), environmental monitoring (such as water temperature), and historical treatment effects (such as the bubbling rate of a certain batch of fire-damaged batteries)" to solve the adaptation problem of abnormal batteries with "mixed categories and large fluctuations in state". (2) Dynamic weight adaptive mechanism: For high-risk abnormal types (such as fire batteries), the weight of key features such as "internal resistance and surface carbon black thickness" is automatically increased to ensure the accurate output of safety parameters (such as puncture depth); (3) Online iterative update engine: Unlike the conventional "fixed model after offline training", a mechanism is designed to "automatically trigger parameter update every 100 tons of batteries processed", which can absorb the processing data of new types of batteries (such as sodium-ion batteries) and new abnormal states (such as partially short-circuited batteries) in real time, and avoid the model from becoming "outdated and failing".

[0071] The core function of the full-process parameter self-learning system model output provided in this application is to provide "precise parameter benchmarks" for the entire process equipment, realize "process self-adaptation without human intervention". The parameters such as "optimal puncture depth / nitrogen pressure / drying temperature" output by the model are the operating instruction benchmarks for the front-end equipment (pretreatment, crushing, and resource utilization units), directly connect to the equipment control system, and solve the pain point of existing technologies that "rely on manual parameter adjustment based on experience".

[0072] Strong correlation with the "real-time fault early warning" and "remote monitoring" modules: The three form a closed loop of "optimization-monitoring-iteration". The model output does not exist in isolation, but is the "core hub" of the entire process intelligent control. Correlation with real-time fault early warning: The "baseline parameters" of the model output are the judgment benchmark of the early warning system. For example, the model outputs "crusher current stable value 45±2A" for NCM811 crushing. If the sensor detects a current fluctuation >±10% (i.e., >50A or <40A), the early warning system immediately triggers intervention (speed reduction of 10rpm + high-pressure flushing), and at the same time feeds back the "cause of current fluctuation (such as excessive material layer thickness)" to the model. The next batch automatically optimizes the "sorter material layer thickness parameter" (adjusted from 5mm to 4.5mm).

[0073] It should be noted that, where there is no conflict, the features in the embodiments of this application can be combined with each other.

[0074] Example 1 - Water-Soaked NCM811 Ternary Lithium Battery Treatment S1. Raw Material Characteristic Testing: The battery type and abnormality type of the retired batteries are confirmed. Simultaneously, the initial parameters of the retired batteries are tested. In this embodiment, the battery type is a square aluminum shell (57×153×207mm), the abnormality type is complete immersion in water for >24 hours, and the initial parameters include: initial voltage 3.5V (remaining charge 19%), internal resistance 10mΩ, and water content 17%. The pneumatic nail gun puncture parameters are set according to the confirmed type. S2. Underwater Needle Puncture Discharge: The retired battery with the confirmed type is placed in a discharge tank and punctured according to the set pneumatic nail gun puncture parameters (needle cross-section ratio 1.03×10). -4 mm 2 / mm3 The needle penetration depth was 50mm, the water depth was 50cm, and a pneumatic nail gun (steel nail diameter 3mm, working air pressure 0.7MPa) was used to insert steel nails into the retired battery to achieve continuous short-circuit discharge. The needle penetration time was 1 minute. After needle penetration, the battery continued to be discharged underwater for 60 minutes to obtain a discharged battery.

[0075] Monitoring data: The water temperature was maintained at 40℃ by the temperature sensor (accuracy ±0.5℃) in the discharge tank, and the hydrogen concentration was detected to be 0.7% by the hydrogen concentration detector in the discharge tank. There was no white smoke or explosion. After discharge, the voltage dropped to 0.4V, and a discharge battery was obtained.

[0076] S3. Underwater Crushing: The discharged batteries are directly conveyed to the twin-shaft crusher 130 via a plate chain conveyor at a conveying speed of 0.5 m / s. Crushing is carried out in an underwater environment where the liquid level is 8 cm higher than the material, the oxygen content is <0.1%, and the water flow velocity is 0.4 m / s. The twin-shaft crusher 130 operates at a speed of 120 rpm, a cutter head spacing of 5 mm, and an operating power of 30 KW. The oxygen content in the crushing air distribution zone is 0.04%. The crushing chamber is purged with nitrogen in different areas using an annular nitrogen air distribution ring on the twin-shaft crusher 130. The pressure in the feeding air distribution zone is 0.03 MPa, the pressure in the crushing air distribution zone is 0.02 MPa, and the pressure in the discharge air distribution zone is 0.01 MPa. The particle size of the crushed material is 30-50 mm. The mechanical screen 140 (10 mm aperture) has a 100% retrieval efficiency with no sediment, resulting in crushed batteries.

[0077] S4. Dehydration and Dispersion: The crushed batteries are placed in dehydration equipment 150 for dehydration. The dehydration equipment 150 rotates at 1500 rpm. After dehydration, the moisture content of the material is reduced to 30-35%. Then, it is fed into a single-shaft disperser 160 for dispersion. The single-shaft disperser 160 has a screen aperture of 10 mm and is cleaned once per shift. There is no material blockage. After dispersion, the material is in a loose state (lump rate <5%), resulting in loose material.

[0078] S5. Sorting: Bulk materials are sorted by an eddy current separator 170 to separate aluminum-shelled and non-aluminum-shelled materials. The adjustable baffle height of the eddy current separator 170 is 5mm, the material layer thickness is 5mm, and a vibrating screen with a 15mm aperture is used for screening. The vibrating screen rotates once every 30 minutes, and each rotation is paused for 10 seconds. During the pause, a second high-pressure water gun washes the vibrating screen at a pressure of 0.3MPa. After sorting, the purity of aluminum shells is 95.3%, the impurity of copper foil / black powder is 3.2%, and the aluminum shell recovery rate is 98%.

[0079] S6. Drying and Screening: The separated aluminum-free material is dried using a paddle dryer 180, heated with 120℃ saturated steam. The paddle dryer 180 has an operating power of 72KW and is also supplied with nitrogen gas at a flow rate of 50m³ / h. 3 The oxygen content is controlled in real time to be <5% by an oxygen analyzer, the drying time is 30 minutes, and the output moisture content is ≤5%. After drying, the mixture is sieved through a 190mm circular vibrating screen to obtain a mixture of battery powder and electrode membrane.

[0080] S7. Waste Gas Treatment: Treat the waste gas generated in steps S2-S5 (treatment volume of 4000 m³ / h). 3 The solution ( / h) is condensed at 5℃, followed by catalytic oxidation of carbon monoxide at 300℃ using Pt / Al2O3 as a catalyst. Then, it undergoes a two-stage alkaline scrubbing process with 5% NaOH to remove fluorides, achieving a removal rate of 65%. Finally, it is adsorbed by activated carbon, resulting in a final fluoride emission of 0.38 mg / m³. 3 VOCs 4.2mg / m³ 3 The waste gas generated in step S5 is condensed in two stages. The temperature of the first condensation is 5℃ and the temperature of the second condensation is -10℃. After condensation, it is sprayed with 10% NaOH to remove fluorides, and then adsorbed by activated carbon.

[0081] S8. Wastewater Treatment: A 40% Na2CO3 solution was added to the wastewater for lithium fluoride co-precipitation. Then, 2 mol / L HCl was used for stepwise analysis. First, NaF was dissolved at 50℃ to generate NaCl for recycling. Then, LiF was dissolved at 80℃ for lithium precipitation. The fluoride recovery rate was 99%. A 20% sodium sulfate solution was added to the solution after lithium fluoride co-precipitation. The stirring speed was 250 rpm and the reaction time was 30 minutes. Then, oil separation was performed to remove the oil phase in the electrolyte. The wastewater after oil separation was recycled 5 times to the crushing water. After the recycling was completed, the recycled wastewater was dried to recover lithium carbonate. After 5 cycles, the COD was 32000 mg / L, and the lithium was extracted by drum drying to 0.8 g / L, with a lithium recovery rate of 80.5%. The electrolyte after oil separation was recovered by three-stage distillation, in which DMC was recovered at 50℃, EMC at 80℃, and EC at 120℃, with a purity of >99.5%. The tail gas was adsorbed by modified activated carbon and then desorbed by hot air and circulated, with an organic carbon recovery rate of >95%.

[0082] Resource-based products: aluminum shell (95.3% purity, can be directly smelted), black powder (used for subsequent lithium extraction).

[0083] Example 2 - Burning Battery S1. Raw Material Characteristic Testing: The battery type and anomaly type of the retired batteries are confirmed. Simultaneously, the initial parameters of the retired batteries are tested. In this embodiment, the battery type is identified as an NCM811 ternary lithium battery, and the anomaly type is either an accident battery pack or a battery pack damaged by fire. The initial parameters include: no voltage. The puncture parameters of the pneumatic nail gun are set according to the confirmed type.

[0084] S2. Underwater needle discharge: Place the decommissioned battery, after confirming its type, into the discharge tank. A high-precision internal resistance sensor (range 0-200mΩ, accuracy ±1mΩ) is installed at the inlet of the discharge tank to adjust the puncture depth (78mm when the internal resistance is 65mΩ, 90mm when the internal resistance is >80mΩ). A 45℃ hot air pre-blowing device is used to pre-blow carbon black on the battery surface for 30 seconds.

[0085] And according to the set pneumatic nail gun puncture parameters (needle cross-section ratio 1.03×10), -4 mm 2 / mm 3 The needle penetration depth is adjusted in conjunction with the internal resistance sensor (water depth 50cm). A pneumatic nail gun (steel nail diameter 3mm, working air pressure 0.7MPa) is used to insert steel nails into the retired battery to achieve continuous short-circuit discharge. The needle penetration time is 1 minute. After needle penetration, the battery continues to be discharged underwater for 55 minutes to obtain the discharged battery.

[0086] The water temperature is monitored and maintained at 35-45℃ by a temperature sensor (accuracy ±0.5℃) inside the discharge tank to prevent the water temperature from rising. At the same time, the hydrogen concentration is detected by a hydrogen concentration detector inside the discharge tank to be 0.7%, with no white smoke or explosion, and the voltage drops to 0.3V after discharge.

[0087] Performance indicators are as follows: Discharge qualification rate: 99.5%; Bubbling rate: <0.1%; Automatic system parameter adjustment time: <1s / battery; System response time: <1 second (triggered immediately upon detection of exceeding limits); Accident risks: No bubbling, no large-scale hydrogen leakage; Recovery time: Automatic water replenishment + nitrogen purging, indicators return to safe range within 5 minutes (water temperature ≤60℃, hydrogen concentration ≤1%).

[0088] S3. Underwater Crushing: The discharged batteries are directly conveyed to the twin-shaft crusher 130 via a plate chain conveyor at a speed of 0.5 m / s. Crushing is carried out in an underwater environment where the liquid level is 8 cm higher than the material, the oxygen content is <0.1%, and the water flow velocity is 0.4 m / s. The twin-shaft crusher 130 operates at a speed of 100 rpm, a cutter head spacing of 4 mm, and an operating power of 25 KW. The oxygen content in the crushing chamber's air distribution zone is 0.04%. The crushing chamber is purged with nitrogen in different areas using an annular nitrogen air distribution ring on the twin-shaft crusher 130. The pressure in the feeding air distribution zone is 0.028 MPa, the pressure in the crushing air distribution zone is 0.018 MPa, and the pressure in the discharge air distribution zone is 0.008 MPa. The particle size of the crushed material is 40 mm. The mechanical screen 140 (10 mm aperture) has a 100% retrieval efficiency with no sediment, resulting in crushed batteries.

[0089] S4. Dehydration and Dispersion: The crushed batteries are placed in dehydration equipment 150 for dehydration at a speed of 1500 rpm. After dehydration, the moisture content of the material is reduced to 33%. Then, it is fed into a single-shaft disperser 160 for dispersion. The single-shaft disperser 160 has a screen aperture of 10 mm and is cleaned once per shift to prevent material blockage. After dispersion, the material is in a loose state (lump rate < 5%), resulting in loose material.

[0090] S5. Sorting: Bulk materials are sorted by an eddy current separator 170 to separate aluminum-shelled and non-aluminum-shelled materials. The eddy current separator 170 has a baffle height of 5mm and a material layer thickness of 5mm. A vibrating screen with a aperture of 13mm is used for screening. The vibrating screen rotates once every 20 minutes, and each rotation lasts for 12 seconds. During the residence time, a second high-pressure water gun washes the vibrating screen at a pressure of 0.3MPa. After sorting, the purity of aluminum shells is 94.8%, and copper foil / black powder is mixed in at 3.6%. The aluminum shell recovery rate is 98.2%.

[0091] S6. Drying and Screening: The separated aluminum-free material is dried using a paddle dryer 180, heated with 120℃ saturated steam. The paddle dryer 180 has an operating power of 70KW and is also supplied with nitrogen gas at a flow rate of 50m³ / h. 3 The oxygen content is controlled at 3.5% in real time using an oxygen analyzer, the drying time is 30 minutes, and the output moisture content is 4.2%. After drying, the mixture is sieved through a 190° circular vibrating screen to obtain a mixture of battery powder and electrode membrane.

[0092] S7. Waste Gas Treatment: Treat the waste gas generated in steps S2-S5 (treatment volume of 3500 m³ / h). 3The solution ( / h) was condensed at 6℃, followed by catalytic oxidation of carbon monoxide at 280℃ using Pt / Al2O3 as a catalyst. Then, it underwent two-stage alkaline scrubbing with 8% NaOH to remove fluoride, achieving a removal rate of 64%. Finally, it was adsorbed by activated carbon, resulting in a final fluoride emission of 0.37 mg / m³. 3 VOCs 4.5mg / m³ 3 The waste gas generated in step S6 is condensed in two stages. The temperature of the first condensation is 6℃ and the temperature of the second condensation is -8℃. After condensation, it is sprayed with 8% NaOH to remove fluorides, and then adsorbed by activated carbon.

[0093] S8. Wastewater Treatment: A 35% Na₂CO₃ solution was added to the wastewater for lithium fluoride co-precipitation. This was followed by stepwise analysis with 2 mol / L HCl. First, NaF was dissolved at 45℃ to generate NaCl for recycling. Then, LiF was dissolved at 75℃ for lithium precipitation, achieving a fluoride recovery rate of 99.9%. A 19.5% sodium sulfate solution was added to the co-precipitated solution, with a stirring rate of 200 rpm and a reaction time of 40 minutes. Oil separation was then performed to remove the oil phase from the electrolyte. The wastewater after oil separation was recycled four times to the crushing water. After the recycling process, the recycled wastewater was dried to recover lithium carbonate. After four cycles, the COD was 31000 mg / L, and drum drying yielded 0.7 g / L of lithium, resulting in a lithium recovery rate of 80.9%. The electrolyte after oil separation is recovered through three-stage distillation, in which DMC is recovered at 40℃, EMC at 70℃, and EC at 110℃, with a purity of >99.5%. The tail gas is adsorbed by modified activated carbon and then desorbed by hot air and recycled, with an organic carbon recovery rate of >95%.

[0094] Resource products: aluminum shell (94% purity, can be directly smelted), black powder (used for subsequent lithium extraction).

[0095] Example 3 - Pouch Battery S1. Raw Material Characteristic Testing: The battery type and abnormality type of the retired battery are confirmed. Simultaneously, the initial parameters of the retired battery are tested. In this embodiment, the battery type is identified as an NCM622 ternary lithium battery, and the abnormality type as a pouch battery. Initial parameters include: initial voltage 3.6V (remaining charge 20%), internal resistance 12mΩ, and electrolyte content 15%. The pneumatic nail gun puncture parameters are set based on the confirmed type.

[0096] S2. Underwater Needle Discharge: Retired batteries of confirmed type are placed in a discharge tank. The tank's feed hopper is equipped with a low-heat pre-softening unit (45℃, 20s); a negative pressure adsorption mechanism (negative pressure value -0.05MPa); and anti-winding cutter discs (3mm spacing, surface coated with PTFE). After confirmation, the retired batteries enter the feed hopper, where the aluminum-plastic film is pre-softened using low heat, and then peeled off using negative pressure adsorption (80% peeling rate). Remaining fragments are processed by the anti-winding cutter discs before underwater needle discharge. Performance indicators: Aluminum-plastic film entanglement rate: 0%; Blockage rate: <0.1%; Aluminum-plastic film peeling rate: 80% (significantly reducing subsequent sorting load).

[0097] According to the set pneumatic nail gun puncture parameters (needle cross-section ratio 1.05×10), -4 mm 2 / mm 3 The needle penetration depth was 50mm, the water depth was 50cm, and a pneumatic nail gun (steel nail diameter 3mm, working air pressure 0.7MPa) was used to insert steel nails into the retired battery to achieve continuous short-circuit discharge. The needle penetration time was 1.2min. After needle penetration, the battery continued to be discharged underwater for 70 minutes to obtain the discharged battery.

[0098] Monitoring data: The water temperature was maintained between 35-45℃ by a temperature sensor (accuracy ±0.5℃) inside the discharge tank. The hydrogen concentration was detected as 0.8% by a hydrogen concentration detector inside the discharge tank. There was no white smoke or explosion, and the voltage dropped to 0.5V after discharge. Performance indicators: Discharge qualification rate: 99.5%; Bubbling rate: <0.1%; Automatic parameter adjustment time: <1s / battery.

[0099] S3. Underwater Crushing: The discharged batteries are directly conveyed to the twin-shaft crusher 130 via a plate chain conveyor at a conveying speed of 0.5 m / s. Crushing is carried out in an underwater environment where the liquid level is 8 cm higher than the material, the oxygen content is <0.1%, and the water flow velocity is 0.4 m / s. The twin-shaft crusher 130 operates at a speed of 150 rpm, a cutter head spacing of 6 mm, and an operating power of 35 KW. The oxygen content in the crushing air distribution zone is 0.04%. The crushing chamber is purged with nitrogen in different areas using an annular nitrogen air distribution ring on the twin-shaft crusher 130. The pressure in the feeding air distribution zone is 0.032 MPa, the pressure in the crushing air distribution zone is 0.022 MPa, and the pressure in the discharge air distribution zone is 0.012 MPa. The particle size of the crushed material is 30 mm. The mechanical screen 140 (10 mm aperture) has a 100% retrieval efficiency with no sediment, resulting in crushed batteries.

[0100] S4. Dehydration and Dispersion: The crushed batteries are placed in dehydration equipment 150 for dehydration. The dehydration equipment 150 rotates at 1500 rpm. After dehydration, the moisture content of the material is reduced to 30-35%. Then, it is fed into a single-shaft disperser 160 for dispersion. The single-shaft disperser 160 has a screen aperture of 10 mm and is cleaned once per shift. There is no material blockage. After dispersion, the material is in a loose state (lump rate <5%), resulting in loose material.

[0101] S5. Sorting: Bulk materials are sorted by an eddy current separator 170 to separate aluminum shells from non-aluminum shell materials. The eddy current separator 170 has a baffle height of 5mm and a material layer thickness of 5mm. A vibrating screen with a aperture of 17mm is used for screening. The vibrating screen rotates once every 40 minutes, with each rotation lasting 8 seconds. During the residence time, a second high-pressure water gun washes the vibrating screen at a pressure of 0.2MPa. After sorting, the purity of aluminum shells is 94.2%, and the aluminum shell recovery rate is 97.5%, with 3.5% of copper foil / black powder mixed in.

[0102] S6. Drying and Screening: The separated aluminum-free material is dried using a paddle dryer 180, heated with 120℃ saturated steam. The paddle dryer 180 has an operating power of 75KW and is also supplied with nitrogen gas at a flow rate of 50m³ / h. 3 / h, the oxygen content is controlled in real time to 3.5% by an oxygen analyzer, the drying time is 30min, and the output moisture content is 4.2%.

[0103] S7. Waste Gas Treatment: Treat the waste gas generated in steps S2-S5 (treatment volume of 4500 m³ / h). 3 The solution ( / h) was condensed at 4℃, followed by catalytic oxidation of carbon monoxide at 320℃ using Pt / Al2O3 as a catalyst. Then, it underwent two-stage alkaline scrubbing with 10% NaOH to remove fluoride, achieving a removal rate of 63%. Finally, it was adsorbed by activated carbon, resulting in a final fluoride emission of 0.36 mg / m³. 3 VOCs 4.3 mg / m³ 3 The waste gas generated in step S6 is condensed in two stages. The temperature of the first condensation is 4℃ and the temperature of the second condensation is -12℃. After condensation, it is sprayed with 12% NaOH to remove fluorides, and then adsorbed by activated carbon.

[0104] S8. Wastewater Treatment: A 40% Na₂CO₃ solution was added to the wastewater for lithium fluoride co-precipitation. This was followed by stepwise analysis with 2 mol / L HCl. First, NaF was dissolved at 55℃ to generate NaCl for recycling. Then, LiF was dissolved at 85℃ for lithium precipitation, achieving a fluoride recovery rate of 99.8%. A 20.5% sodium sulfate solution was added to the co-precipitated solution, with a stirring rate of 300 rpm and a reaction time of 20 minutes. Oil separation was then performed to remove the oil phase from the electrolyte. The wastewater after oil separation was recycled six times to the crushing water. After the recycling process, the recycled wastewater was dried to recover lithium carbonate. After six cycles, the COD was 30000 mg / L, and drum drying yielded 0.9 g / L of lithium, resulting in a lithium recovery rate of 82.5%. The electrolyte after oil separation is recovered through three-stage distillation, in which DMC is recovered at 60℃, EMC at 90℃, and EC at 130℃, with a purity of >99.5%. The tail gas is adsorbed by modified activated carbon and then desorbed by hot air and recycled, with an organic carbon recovery rate of >95%.

[0105] Resource products: aluminum shell (95.2% purity, can be directly smelted), black powder (used for subsequent lithium extraction).

[0106] Example 4 The difference between this embodiment and Embodiment 1 is that this embodiment also incorporates a full-process parameter self-learning system. By incorporating a parameter self-learning model that integrates multi-dimensional heterogeneous data fusion, dynamic weight adaptation, and online iteration, it automatically outputs the optimal parameters for the entire process.

[0107] For NCM811 batteries that have been submerged in water for 24 hours, the model automatically inputs data such as "battery system (NCM811), abnormality type (submerged in water for 24 hours), initial moisture content 15%", and outputs the following parameters: dual-shaft crusher 130-150 rpm, pressure in the feed air distribution zone 0.03 MPa, pressure in the crushing air distribution zone 0.022 MPa and pressure in the discharge air distribution zone 0.01 MPa, and drying temperature 105℃.

[0108] At this point, the lithium recovery rate is 80.5%; the wastewater COD is 32,000 mg / L; and the parameter adjustment cycle is real-time (automatically updated every 100 tons of batteries processed).

[0109] Testing revealed that the aluminum shell purity after sorting in step S5 was 99.9%, with 3.8% contamination from copper foil / black powder, resulting in an aluminum shell recovery rate of 98%. In step S7, the fluoride removal rate was 99%, with fluoride emissions of 0.34 mg / m³. 3 VOCs 4.1 mg / m³ 3 In step S8, the fluoride recovery rate was 98.7%, the wastewater COD was 28000 mg / L, and the lithium extraction rate was 0.8 g / L from drum drying, with a lithium recovery rate of 82%. The purity of the aluminum shell in the resource recovery product was 99%.

[0110] Example 5 The difference between this embodiment and embodiment 1 is that, in this embodiment, during underwater crushing in step S3, the temperature and current are monitored in real time using a temperature sensor and a current sensor. When the temperature sensor detects a local temperature > 80°C, the nitrogen pressure is increased to 0.05MPa, the water flow rate is increased to 0.8m / s, and the dual-shaft crusher 130 is shut down for 30s. When the current sensor detects a current fluctuation of > ±10% in the shaft crusher, the speed is automatically reduced by 10rpm and the first high-pressure water gun is started to flush at a pressure of 0.3MPa.

[0111] Testing revealed that the aluminum shell purity after sorting in step S5 was 99%, with 3.7% contamination from copper foil / black powder, resulting in an aluminum shell recovery rate of 99%. In step S7, the fluoride removal rate was 93%, with fluoride emissions of 0.32 mg / m³. 3 VOCs 4.3mg / m³ 3 In step S8, the fluoride recovery rate was 99.7%, the wastewater COD was 29000 mg / L, and the lithium extraction rate was 0.9 g / L after drum drying, with a lithium recovery rate of 95%. The purity of the aluminum shell in the resource recovery product was 99%.

[0112] Example 6 S1. Raw Material Characteristic Testing: The battery type and abnormality type of the retired batteries are confirmed, and the initial parameters of the retired batteries are tested. The battery type in this embodiment is a prismatic lithium iron phosphate battery, and the abnormality type is a pouch battery. The initial parameters include: initial voltage 3.2V (remaining charge 20%), internal resistance 20mΩ, and electrolyte content 13%. The puncture parameters of the pneumatic nail gun are set according to the confirmed type.

[0113] S2, Underwater Needle Discharge: Place the confirmed type of retired battery in the discharge tank and perform underwater nail gun puncture according to the set parameters (needle cross-section ratio 3×10). -4 mm 2 / mm 3 The needle penetration depth was 150mm, the water depth was 50cm, and a pneumatic nail gun (steel nail diameter 3mm, working air pressure 0.7MPa) was used to insert steel nails into the retired battery to achieve continuous short-circuit discharge. The needle penetration time was 1 minute. After needle penetration, the battery continued to be discharged underwater for 60 minutes to obtain a discharged battery.

[0114] Monitoring data: The water temperature was maintained at 40℃ by the temperature sensor (accuracy ±0.5℃) in the discharge tank, and the hydrogen concentration was detected to be 0.7% by the hydrogen concentration detector in the discharge tank. There was no white smoke or explosion. After discharge, the voltage dropped to 0.4V, and a discharge battery was obtained.

[0115] S3. Underwater Crushing: The discharged batteries are directly conveyed to the twin-shaft crusher 130 via a plate chain conveyor at a conveying speed of 0.5 m / s. Crushing is carried out in an underwater environment where the liquid level is 8 cm higher than the material, the oxygen content is <0.1%, and the water flow velocity is 0.4 m / s. The twin-shaft crusher 130 operates at a speed of 120 rpm, a cutter head spacing of 5 mm, and an operating power of 30 KW. The oxygen content in the crushing air distribution zone is 0.04%. The crushing chamber is purged with nitrogen in different areas using an annular nitrogen air distribution ring on the twin-shaft crusher 130. The pressure in the feeding air distribution zone is 0.03 MPa, the pressure in the crushing air distribution zone is 0.02 MPa, and the pressure in the discharge air distribution zone is 0.01 MPa. The particle size of the crushed material is 30-50 mm. The mechanical screen 140 (10 mm aperture) has a 100% retrieval efficiency with no sediment, resulting in crushed batteries.

[0116] S4. Dehydration and Dispersion: The crushed batteries are placed in dehydration equipment 150 for dehydration. The dehydration equipment 150 rotates at 1500 rpm. After dehydration, the moisture content of the material is reduced to 30-35%. Then, it is fed into a single-shaft disperser 160 for dispersion. The single-shaft disperser 160 has a screen aperture of 10 mm and is cleaned once per shift. There is no material blockage. After dispersion, the material is in a loose state (lump rate <5%), resulting in loose material.

[0117] S5. Sorting: Bulk materials are sorted by an eddy current separator 170 to separate aluminum-shelled and non-aluminum-shelled materials. The adjustable baffle height of the eddy current separator 170 is 5mm, the material layer thickness is 5mm, and a vibrating screen with a 15mm aperture is used for screening. The vibrating screen rotates once every 30 minutes, and each rotation is paused for 10 seconds. During the pause, a second high-pressure water gun washes the vibrating screen at a pressure of 0.3MPa. After sorting, the purity of aluminum shells is 95.8%, and the impurities of copper foil / black powder are 3.4%. The aluminum shell recovery rate is 98.7%.

[0118] S6. Drying and Screening: The separated aluminum-free material is dried using a paddle dryer 180, heated with 120℃ saturated steam. The paddle dryer 180 has an operating power of 72KW and is also supplied with nitrogen gas at a flow rate of 50m³ / h. 3 The oxygen content is controlled in real time to be <5% by an oxygen analyzer, the drying time is 30 minutes, and the output moisture content is ≤5%. After drying, the mixture is sieved through a 190mm circular vibrating screen to obtain a mixture of battery powder and electrode membrane.

[0119] S7. Waste Gas Treatment: Treat the waste gas generated in steps S2-S5 (treatment volume of 4000 m³ / h). 3The solution ( / h) is condensed at 5℃, followed by catalytic oxidation of carbon monoxide at 300℃ using Pt / Al2O3 as a catalyst. Then, it undergoes a two-stage alkaline scrubbing process with 5% NaOH to remove fluorides, achieving a removal rate of 65%. Finally, it is adsorbed by activated carbon, resulting in a final fluoride emission of 0.38 mg / m³. 3 VOCs 4.2mg / m³ 3 The waste gas generated in step S5 is condensed in two stages. The temperature of the first condensation is 5℃ and the temperature of the second condensation is -10℃. After condensation, it is sprayed with 10% NaOH to remove fluorides, and then adsorbed by activated carbon.

[0120] S8. Wastewater Treatment: A 40% Na2CO3 solution was added to the wastewater for lithium fluoride co-precipitation. Then, 2 mol / L HCl was used for stepwise analysis. First, NaF was dissolved at 50℃ to generate NaCl for recycling. Then, LiF was dissolved at 80℃ for lithium precipitation. The fluoride recovery rate was 99.8%. A 20% sodium sulfate solution was added to the solution after lithium fluoride co-precipitation. The stirring speed was 250 rpm and the reaction time was 30 minutes. Then, oil separation was performed to remove the oil phase in the electrolyte. The wastewater after oil separation was recycled 5 times to the crushing water. After the recycling was completed, the recycled wastewater was dried to recover lithium carbonate. After 5 cycles, the COD was 32000 mg / L, and the lithium was extracted by drum drying to 0.8 g / L, with a lithium recovery rate of 81.5%. The electrolyte after oil separation was recovered by three-stage distillation, in which DMC was recovered at 50℃, EMC at 80℃, and EC at 120℃, with a purity of >99.5%. The tail gas was adsorbed by modified activated carbon and then desorbed by hot air and circulated, with an organic carbon recovery rate of >95%.

[0121] Resource products: aluminum shell (94.3% purity, can be directly smelted), black powder (used for subsequent lithium extraction).

[0122] Comparative Example 1 This comparative example is basically the same as Example 2, except that in this comparative example, a high-precision internal resistance sensor and a hot air pre-blowing device are not set at the discharge tank in step S2. The operation includes: direct manual operation of the pneumatic nail gun to puncture and discharge, with a fixed puncture depth of 60mm; there is no internal resistance detection, no hot air pre-blowing, and no "internal resistance detection → parameter self-adaptation" linkage step.

[0123] Performance indicators: Discharge pass rate: 75% (mismatch between internal resistance and puncture depth leads to incomplete discharge or short circuit); Bubbling rate: 8% (puncture causes internal thermal runaway); Manual parameter adjustment time: average 10 minutes / batch.

[0124] In subsequent steps S3-S8, the procedure was performed according to Example 2. Testing showed that after sorting in step S5, the aluminum shell purity was 99%, with 3.9% containing mixed copper foil / black powder, and the aluminum shell recovery rate was 99%. In step S7, the fluoride removal rate was 92%, and the fluoride emission was 0.34 mg / m³. 3 VOCs 4.3mg / m³ 3 In step S8, the fluoride recovery rate was 98.5%, the wastewater COD was 28000 mg / L, and the lithium extraction rate was 0.8 g / L from drum drying, with a lithium recovery rate of 85%. The purity of the aluminum shell in the resource recovery product was 99%.

[0125] Comparative Example 2 This comparative example is basically the same as Example 2, except that the temperature sensor and hydrogen concentration detector are not installed in the discharge tank of underwater needle discharge in step S2 of this comparative example. The safety guarantee method of this comparative example is: the discharge tank is inspected manually every 30 minutes, and abnormalities are judged by "observing the water temperature and smelling the hydrogen odor". If a problem is found, water is manually added and nitrogen is introduced.

[0126] When the battery is discharged by fire, the internal reaction is violent after puncture, the water temperature rises to 65°C, and the hydrogen concentration reaches 1.2%.

[0127] Performance indicators: Delay in manual detection: approximately 8 minutes (inspection interval + manual judgment time); Accident risk: High temperature and high pressure cause one small-scale bubbling, with a high risk of hydrogen leakage; Recovery time: After manual water replenishment and nitrogen purging, it takes 30 minutes to restore the safe range.

[0128] In subsequent steps S3-S8, the procedure was performed according to Example 2. Testing showed that after sorting in step S5, the aluminum shell purity was 99%, with 3.2% contamination from copper foil / black powder, and an aluminum shell recovery rate of 98%. In step S7, the fluoride removal rate was 95%, and the fluoride emission was 0.39 mg / m³. 3 VOCs 4.2 mg / m³ 3 In step S8, the fluoride recovery rate was 99.2%, the wastewater COD was 29000 mg / L, and the lithium extraction rate was 0.8 g / L from drum drying, with a lithium recovery rate of 89%. The purity of the aluminum shell in the resource recovery product was 99%.

[0129] Comparative Example 3 This comparative example is basically the same as Example 3, except that the low-heat pre-softening unit and negative pressure adsorption mechanism in step S2 are omitted, and a conventional crusher is used instead of the anti-winding cutter disc. The conventional crusher has a cutter disc spacing of 10mm and no polytetrafluoroethylene coating. The soft-pack battery is directly placed in the crusher for crushing, and then the subsequent underwater needle discharge step is performed.

[0130] Performance indicators: Aluminum-plastic film wrapping rate: 15% (frequent cutter head jamming); Material blockage rate: 5% (material clumping and blocking the conveyor after crushing); Aluminum-plastic film peeling rate: 40% (difficult subsequent sorting).

[0131] In subsequent steps S3-S8, the procedure was performed according to Example 2. Testing showed that after sorting in step S5, the aluminum shell purity was 99%, with 3.3% contamination from copper foil / black powder, and an aluminum shell recovery rate of 98%. In step S7, the fluoride removal rate was 92%, and the fluoride emission was 0.35 mg / m³. 3 VOCs 4.5mg / m³ 3 In step S8, the fluoride recovery rate was 98.8%, the wastewater COD was 30000 mg / L, and the lithium extraction rate was 0.9 g / L after drum drying, with a lithium recovery rate of 88%. The purity of the aluminum shell in the resource recovery product was 99%.

[0132] Comparative Example 4 This comparative example is basically the same as Example 4, except that this comparative example relies on the manual experience of engineers to adjust equipment parameters (such as crusher speed, nitrogen pressure, drying temperature, etc.), without the support of an intelligent model. For the "NCM811 battery soaked in water for 24 hours", the parameters were set manually based on experience: crusher speed 300 rpm, nitrogen pressure 0.01 MPa, and drying temperature 120°C.

[0133] Performance indicators: In subsequent steps S3-S8, the process was conducted according to Example 2. Testing showed that in step S5, the purity of the aluminum shell after sorting was 99%, with 3.8% contamination from copper foil / black powder, and an aluminum shell recovery rate of 98%. In step S7, the fluoride removal rate was 92%, and the fluoride emission was 0.34 mg / m³. 3 VOCs 4.4 mg / m³ 3In step S8, the fluoride recovery rate was 99.2%, the wastewater COD was 50,000 mg / L (due to insufficient nitrogen protection and excessive oxidation of organic matter), and the lithium extraction rate during drum drying was 0.8 g / L, with a lithium recovery rate of 65% (due to excessively high drying temperature leading to lithium compound decomposition). The purity of the aluminum shell in the resource recovery product was 99%. The parameter adjustment cycle was 72 hours (manual trial and error + verification). In summary, the resource recovery and recycling method for retired batteries provided in this application is the first to develop a quantitative discharge parameter table for different battery systems (ternary lithium batteries or lithium iron phosphate batteries) and different abnormality types (water-soaked, fire-damaged, soft-pack, or broken materials), clarifying the critical safety threshold and filling a technological gap in the industry. A dedicated pretreatment was performed on the abnormal batteries before underwater needle penetration discharge, innovatively adapting the internal resistance-puncture depth and pre-peeling the aluminum-plastic film for fire-damaged, soft-pack, and water-soaked batteries, filling another industry gap. The underwater needle-punching discharge and underwater crushing are seamlessly connected by a plate chain conveyor, completely eliminating the risk of oxygen exposure during the transfer process. This reduces the needle-punching explosion rate of ternary lithium batteries from the industry average of 15% to 0%, and stably controls the hydrogen concentration at ≤1% (below the lower explosion limit). The dual-shaft crusher 130 adopts a "nitrogen-water flow" dual-gradient synergistic protection technology: through nitrogen partial pressure gradient gas distribution, water flow directional guidance, and emergency linkage for sudden exothermic reactions, the oxygen content in the crushing gas distribution zone is reduced to <0.05%, the hydrogen concentration is stabilized at 0.4-0.6%, the black powder deposition rate is increased to 50%, and the safety accident rate is reduced to 0.01%. A closed loop for the synergistic recycling of waste "fluorine-lithium-carbon" is constructed: the innovative fluorine-lithium co-precipitation-stepwise analysis process achieves a fluorine recovery rate of >90%; the three-stage distillation-adsorption technology recovers >95% of the organic carbon in the electrolyte; and the in-situ modification and leaching of black powder increases the lithium leaching rate to 98%, resulting in better resource utilization. The intelligent-driven, end-to-end parameter self-learning system achieves adaptive optimization of process parameters through big data training models, with a fault warning response time of <0.5s, an automation rate of 95%, and a 40% reduction in labor costs. Therefore, the resource recycling method for retired batteries provided in this application is a comprehensive, safe, efficient, and highly resource-oriented treatment method.

[0134] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A method for resource recovery processing of decommissioned batteries, characterized by, It comprises: S1, raw material property detection: the battery type and abnormal type of the retired battery are confirmed in turn, and the initial parameters of the retired battery are detected, and the pneumatic nail gun puncture parameters are set according to the confirmed type, wherein the battery type includes ternary lithium battery or lithium iron phosphate battery, and the abnormal type includes water bubble, fire, soft package or broken material; S2, underwater needle puncture discharge: then the retired battery after type confirmation is placed in a discharge tank, and a steel nail is used to puncture the retired battery to realize continuous short circuit discharge according to the set pneumatic nail gun puncture parameters, the voltage of the retired battery after discharge is reduced to below 0.5V, and a discharged battery is obtained, when the retired battery after type confirmation is a fire battery or a soft package battery, the abnormal battery pretreatment module is used for pretreatment first, and then the retired battery is placed in the discharge tank; S3, underwater crushing: the discharged battery is directly conveyed to a double-shaft crusher by a plate chain machine, and crushing is completed in an underwater environment with a liquid level higher than the material by 5-10 cm and an oxygen content of <0.1%; the material after crushing is salvaged by a mechanical grid to obtain a broken battery; S4, dehydration and scattering: the broken battery is dehydrated and scattered to obtain a bulk material; S5, sorting: the bulk material is sorted to obtain an aluminum shell and a non-aluminum shell material; S6, drying and screening: the non-aluminum shell material after sorting is dried, and battery powder and pole piece diaphragm mixed material are obtained after screening.

2. The resource recycling process of retired batteries according to claim 1, characterized by, The initial parameters include initial voltage, residual capacity, internal resistance and moisture content, wherein the initial voltage of the ternary lithium battery satisfies 3.5-3.7V, and the residual capacity satisfies ≤25% SOC; the initial voltage of the lithium iron phosphate battery satisfies ≤3.6V, and the residual capacity satisfies ≤90% SOC; And / or, setting the pneumatic nail gun puncture parameters according to the confirmed type comprises: When the battery type is NCM811 ternary lithium battery and the abnormal type is water bubble or fire burn, the needle punching parameters are: needle punching section ratio 1.025x10 -4 -1.035x10 -4 mm 2 / mm 3 , needle punching depth 45-55mm; When the battery type is NCM622 ternary lithium battery and the abnormal type is bubble water or soft package, the needle punching parameters are: needle punching cross section ratio 1.045x10 -4 -1.055x10 -4 mm 2 / mm 3 , needle punching depth 45-55mm; When the battery type is a lithium iron phosphate battery and the anomaly type is fire, soft package, or broken material, the needle punching parameters are: a needle punching cross-section ratio of 2.06 x 10 -4 -3.7 x 10 -4 mm 2 / mm 3 , a needle punching depth of 50-220 mm; And / or, the working air pressure of the pneumatic nail gun is 0.6-0.8MPa, the diameter of the steel nail is 2-4mm, the water temperature during underwater needle puncture discharge is ≤60℃, the water depth is 45-55cm, the needle puncture time is 0.8-1.2min, and the underwater protection time is 55-70min.

3. The method of claim 1, wherein The abnormal battery pretreatment module comprises a fire battery pretreatment mechanism, a soft package battery pretreatment mechanism and a safety monitoring mechanism; Preferably, the fire battery pretreatment mechanism comprises an internal resistance sensor arranged at the inlet of the discharge tank and used for detecting the internal resistance of the battery cell of the retired battery in real time and adjusting the puncture depth in linkage, and a hot air pre-blowing device used for removing the carbon black on the surface of the retired battery; when the internal resistance of the retired battery detected by the internal resistance sensor is 50-80mΩ, the puncture depth is increased to 78mm, and when the internal resistance is >80mΩ, the puncture depth is increased to 90mm; the hot air pre-blowing device removes the carbon black on the surface of the retired battery by pre-blowing at 40-50℃ for 30s. Preferably, the soft package battery pretreatment mechanism comprises a softening unit arranged at the inlet of the discharging tank and used for softening the aluminum plastic film, a negative pressure suction mechanism for peeling the aluminum plastic film, and an anti-winding cutter disc; the temperature of the softening unit is 40-50℃, the softening time is 15-25s, and the negative pressure value of the negative pressure suction mechanism is-0.05MPa; Preferably, the safety monitoring mechanism comprises a temperature sensor and a hydrogen concentration detector arranged in the discharging tank; when the water temperature in the discharging tank is higher than 60℃ or the hydrogen concentration is higher than 1%, the system automatically adds water and starts nitrogen purging until the indicators return to the safe range.

4. The method of claim 1, wherein The rotation speed of the double-shaft crusher is 100-150rpm, the cutter disc spacing is 4-6mm, the operation power is 25-35KW, and the particle size of the crushed material is ≤50mm; the aperture of the mechanical grate is 8-12mm; And / or, the top of the double-shaft crusher is provided with an annular nitrogen gas distribution ring, which is divided into a feeding gas distribution area, a crushing gas distribution area and a discharging gas distribution area; the pressure of the feeding gas distribution area is 0.028-0.032MPa, the pressure of the crushing gas distribution area is 0.018-0.022MPa, and the pressure of the discharging gas distribution area is 0.008-0.012MPa; the oxygen content of the crushing gas distribution area is <0.05%; And / or, the flow rate of the water flow in the double-shaft crusher is 0.3-0.5m / s; and / or, the bottom of the double-shaft crusher is further provided with a black powder deposition tank; And / or, the top of the double-shaft crusher is further provided with a temperature sensor, a current sensor and a first high-pressure water gun; the temperature sensor is signal connected with the control mechanism of the annular nitrogen gas distribution ring and the double-shaft crusher and the water flow control valve; the current sensor is signal connected with the first high-pressure water gun; when the temperature sensor detects that the local temperature is >80℃, the nitrogen pressure is adjusted to 0.05MPa, the water flow rate is increased to 0.8m / s, and the double-shaft crusher is stopped for 20-40s; when the current sensor detects that the current fluctuation of the double-shaft crusher is >±10%, the speed is automatically reduced by 10rpm and the first high-pressure water gun is started to flush.

5. The method of repurposing retired batteries of claim 1, wherein, The sorting is performed by using a vortex sorter, and the vortex sorter is provided with an adjustable baffle with an adjustable height of 0-10mm; And / or, the vortex sorter is provided with an automatically flipped vibrating screen, and the top of the vibrating screen is provided with a second high-pressure water gun for flushing the vibrating screen; Preferably, the aperture of the vibrating screen is 13-17mm, and the flipping period of the vibrating screen is 20-40min once, and each flipping stays for 8-12s; during the staying period, the second high-pressure water gun flushes the vibrating screen, and the pressure of the second high-pressure water gun is 0.2-0.4MPa.

6. The method of repurposing retired batteries of claim 1, wherein, The drying comprises placing the aluminum-free shell material in a paddle dryer, heating and drying by using 120°C saturated steam, the paddle dryer has a running power of 70-75 KW, and nitrogen is also introduced into the paddle dryer, the flow rate of the nitrogen is 40-60 m 3 / h, the oxygen content is controlled to be less than 5% in real time by an oxygen analyzer, the drying time is 20-40 min, and the moisture content of the discharged material is ≤5%.

7. The method of claim 1, wherein, The resource recycling treatment method of the retired battery further comprises S7, waste gas treatment: the waste gas generated in steps S2-S5 is subjected to first waste gas treatment, and the waste gas generated in step S6 is subjected to second waste gas treatment. The first waste gas treatment includes condensing the waste gas generated in steps S2-S5 at 4-6 DEG C, then catalytically oxidizing carbon monoxide at 280-320 DEG C with Pt / Al2O3 as catalyst, then removing fluoride through two-stage alkali spraying with 5%-10% NaOH, then through activated carbon adsorption, and the air volume of the first waste gas treatment is 3500-4500 m 3 / h. The second waste gas treatment includes two-stage condensation of the waste gas generated in step S6, first-stage condensation at a temperature of 4-6 DEG C, and second-stage condensation at a temperature of -12 to -8 DEG C, and then spraying with NaOH with a concentration of 8%-12% to remove fluorides, and then active carbon adsorption.

8. The method of repurposing retired batteries of claim 1, wherein, The resource recycling treatment method of the retired battery further comprises S8, wastewater treatment: sequentially performing fluorine-lithium co-precipitation, oil separation and recycling treatment on the wastewater, wherein the fluorine-lithium co-precipitation comprises adding Na2CO3 solution into the wastewater to make Li + and F - form LiF.NaF double salt precipitate, and then stepwise resolved by 2 mol / L HCl, first dissolving NaF at 45-55 DEG C to generate NaCl for recycling, and then dissolving LiF at 75-85 DEG C for lithium precipitation, and the fluorine recovery rate is greater than 90%; the oil separation comprises continuously adding 19.5%-20.5% sodium sulfate solution into the solution after the fluorine-lithium co-precipitation, stirring at a speed of 200-300 rpm, and reacting for 20-40 minutes, and then separating oil to remove the oil phase in the electrolyte; and the recycling treatment comprises recycling the wastewater after the oil separation to the underwater crushing in step S3 for 4-6 times, and drying the recycled wastewater to recover lithium carbonate after the recycling.

9. The method of claim 8, wherein, The electrolyte after oil separation is recovered by three-stage distillation, wherein DMC is recovered at 40-60 DEG C, EMC is recovered at 70-90 DEG C, and EC is recovered at 110-130 DEG C, and the purity of all is greater than 99.5%, tail gas is adsorbed by modified active carbon and then desorbed by hot air to be recycled, and the recovery rate of organic carbon is greater than 95%.

10. The method of claim 1, wherein, The resource recycling treatment method of the retired battery further includes constructing a full-process parameter self-learning system, collecting more than 10,000 groups of abnormal battery treatment data, constructing and inputting initial parameters by using a neural network algorithm, then outputting running parameters, and automatically updating parameters every 100 tons of batteries treated; wherein the initial parameters include at least one of battery type, abnormal type and equipment state, and the running parameters include puncture depth, nitrogen pressure and drying temperature.

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