Battery waste recovery pretreatment process

Abstract

The invention relates to the field of waste storage battery recycling, in particular to a battery waste recycling pretreatment process which comprises the following steps: S1, directionally shearing battery waste to obtain a sheared material; s2, the sheared material is placed in vibration thermal desorption equipment, a furnace door is closed, a heating system and a vibration system are started, and vibration thermal desorption screening treatment is synchronously conducted on the sheared material under the protective atmosphere condition; and S3, a heating system and a vibration system of the vibration thermal desorption furnace are closed, oversize products and undersize products are collected, and pretreatment is completed. Through integration of directional shearing and vibration thermal desorption screening, the problems that traditional battery waste pretreatment operation is complex, the industrialization cost is high, wet treatment is difficult due to metal impurity entrainment, and the separation and recovery effect is poor are solved, and the economic benefits and the industrialization value of battery waste recovery and regeneration are remarkably improved.

Description

Technical Field

[0001] The present application relates to the field of waste battery regeneration, and in particular to a pretreatment process in the process of waste battery regeneration. Background Art

[0002] Waste metal-ion batteries contain toxic substances, as well as valuable and scarce metals such as lithium, cobalt, nickel, and manganese. They have strong resource attributes. If they are not treated or treated improperly, they will not only cause great harm to the environment, but also cause a huge waste of non-renewable resources. The green resource-based and efficient recycling and reuse of waste metal-ion batteries is a hot and difficult issue that needs to be urgently resolved in the new energy industry.

[0003] According to the process characteristics, the recycling process of waste metal ion batteries can be divided into two categories: pyrometallurgy and wet metallurgy. Among them, wet metal recycling has the advantages of high product purity and convenient reuse of recycled products. Therefore, it has become the mainstream process for recycling waste metal ion batteries. The whole process of wet metal recycling mainly includes discharge, disassembly, crushing, sorting, valuable metal leaching, separation and purification steps.

[0004] In engineering applications, discharge, disassembly, crushing and sorting are generally referred to as pretreatment. The effect of pretreatment directly determines the efficiency and difficulty of subsequent wet extraction. For example, when the current collector, shell and other materials containing aluminum, copper, iron and other substances fail to be effectively separated from the active material in the pretreatment stage and enter the subsequent wet leaching stage, no matter what reagent is used for leaching and recovery, aluminum, iron, copper and other metal impurities will inevitably enter the liquid phase, forming impurity elements that are difficult to separate and purify in the future. The separation process is not only complicated and lengthy, causing additional resource consumption, but also inevitably causes the loss of target metal entrainment in the impurity removal and purification stage, resulting in a low recovery rate of target metal. More importantly, it will inevitably enter the final product and become a harmful substance that affects the performance of the terminal battery product. Therefore, the sorting effect of the pretreatment stage directly affects the comprehensive economic and social benefits of the subsequent wet treatment of waste metal ion batteries and even the overall regeneration and recovery process.

[0005] As far as the crushing and sorting links are concerned, the current process generally includes the following steps: crushing, heat treatment, and then physical separation such as fine crushing, air separation, magnetic separation, flotation, and gravity separation, either alone or in combination, to obtain pole powder and metal substances such as copper, aluminum, and iron. For example, the pretreatment process disclosed in CN209348803U is: first, the waste lithium-ion batteries after complete discharge are sent to a coarse crusher to be cut into 5-10cm materials; then the coarsely crushed materials are sent to a crusher for crushing, and the batteries are opened to form battery fragments with a size of 15-20mm; most of the black powder, plastic diaphragms, and steel shells in the battery fragments are sorted out by a multi-stage sorting device; the materials after multi-stage sorting are sent to a pyrolysis furnace to sort out the binder, electrolyte, and incompletely sorted materials in the materials. The plastic diaphragm is subjected to a non-polluting pyrolysis treatment; the material is then cooled in a material cooling bin and sent to a second vibrating screen to sort out the black powder in the pyrolyzed material to obtain a copper-aluminum current collector with a small amount of black powder adhered thereto; the copper-aluminum current collector is sent to a fine crusher for fine crushing, and the copper and aluminum in the material are crushed into materials with a size of 1-3 mm, and the remaining black powder in the material is rubbed and dispersed, so as to further improve the recovery rate of the black powder, and make the sizes of copper and aluminum have a higher consistency, and copper and aluminum are sorted in subsequent sorting.

[0006] The above process eventually causes the pole powder and metal components such as copper, aluminum, and iron to be crushed into millimeter-level fine particles with very small differences in the actual ball surface area, and then broken up by friction. The processing process is long, the equipment is complex, the operation is difficult and the cost is high, and a variety of sorting equipment is required. In addition, most crushing equipment is repeated and disordered crushing (such as ball mills, rod mills, hammer crushers, single-axis and double-axis crushers, roller crushers, etc.). During the crushing process, highly ductile copper, aluminum, iron and other metal components are repeatedly squeezed and kneaded, and then wrapped with a large amount of black powder, making it difficult to separate and recover in subsequent sorting. Even for shear-type crushing equipment, the material is repeatedly sheared and crushed during the disordered shearing and crushing process in the crusher. It is difficult to avoid the compaction of the active layer and the infiltration of active substances into metal phases such as current collectors. In addition, the current crushing process eventually crushes metal phases such as copper foil, aluminum foil, and shells into millimeter-level fine powders, and black powder pole powder and copper, aluminum, iron and other metal powders are mixed with each other. Therefore, various reasons in the current crushing mode result in a low recovery rate of extreme powder and metal phase, and the content of metal impurities such as aluminum, copper, and iron in the black powder is high (usually higher than ≥4%), which greatly reduces the sorting efficiency and effect. It not only causes poor economic benefits in the pretreatment stage, but also greatly increases the difficulty and cost of extraction and purification in the subsequent wet process.

[0007] In addition, the current heat treatment equipment is usually an externally heated rotary kiln or a fixed anaerobic furnace, and pyrolysis and screening are carried out at different stages. During the operation of the externally heated rotary kiln, the lithium battery crushed materials are continuously turned and squeezed in the hot state in the furnace, and the shell, aluminum foil, copper foil, black powder, etc. collide, squeeze and rub against each other, inevitably The black powder that has been desorbed or loosened after pyrolysis is re-pressed onto the surface of the shell, aluminum foil, copper foil and other materials or embedded in the above-mentioned materials, while the anaerobic fixed furnace is mostly static thermal desorption. The above-mentioned pyrolysis methods all have uneven thermal desorption to varying degrees, some extreme powders are difficult to fall off the aluminum foil and copper foil, and the pyrolysis and screening processes are separated, resulting in low black powder desorption efficiency and poor desorption effect. Summary of the invention

[0008] The present invention provides a battery waste recycling and regeneration pretreatment process to solve at least one problem existing in the above-mentioned prior art.

[0009] The technical solution of the present invention is as follows: A battery waste recycling and regeneration pretreatment process comprises the following steps: S1, directional shearing of battery waste to obtain sheared material; S2, placing the sheared material in a vibration thermal desorption device, closing the furnace door, starting the heating system and the vibration system, and synchronously performing vibration thermal desorption and screening treatment on the sheared material under protective atmosphere conditions; S3: Turn off the heating system and vibration system of the vibration thermal stripping furnace, collect the screened material and the screened material, and complete the pretreatment.

[0010] Furthermore, the battery waste in S1 includes used batteries, battery cells, pole pieces, scraps or a combination of two or more of the above.

[0011] Furthermore, in S1, the battery waste is subjected to directional shearing in more than one direction, preferably directional shearing in the length direction and / or the width direction.

[0012] Furthermore, in S1, the vibration thermal desorption equipment includes a screening device, and the screening device is provided with a sieve plate or a sieve mesh, and the upper part of the sieve plate or the sieve mesh is a vibration thermal desorption zone, and the lower part is an aggregate zone.

[0013] Furthermore, in S1, the length of the sheared material is 0.1-0.9 times or 10-60 cm of any side of the sieve plate or mesh; the width of the sheared material is less than 10 cm, preferably less than 7 cm, and more preferably 2-5 cm.

[0014] Furthermore, in S1, the thickness of the sheared material is less than 3 cm, preferably less than 2 cm, and more preferably less than 1 cm.

[0015] Furthermore, in S1, the sheared material has a flat cross-section or at least one side has an uneven cross-section.

[0016] Furthermore, the uneven cross-section shapes include toothed cross-sections, arc-shaped cross-sections, and angular cross-sections.

[0017] Furthermore, the shear material is a mixture of a shear material with a smooth cut surface and a shear material with an uneven cut surface on at least one side.

[0018] Furthermore, in S1, the sheared material having at least one side with an uneven cut surface accounts for more than 20% of the total mass, preferably more than 30%, and more preferably more than 50%.

[0019] Furthermore, in S1, the sieve plate or mesh is a detachable sieve plate or mesh, and the aperture or side length of the through holes on the sieve plate or mesh is 0.5-0.95 times, preferably 0.7-0.9 times, and more preferably 0.8-0.9 times the width of the shear material.

[0020] Furthermore, in S2, the vibration thermal desorption temperature is 300-650°C, preferably 350-600°C, and more preferably 400-500°C.

[0021] Furthermore, in S2, the thermal desorption is variable temperature thermal desorption, and the variable temperature steps are 2-4 steps. Preferably, the temperature difference between each temperature step is above 50°C.

[0022] Furthermore, in S2, the vibration thermal desorption time is 30 min-300 min, preferably 45-240 min, and more preferably 60-180 min.

[0023] Furthermore, S2 further includes vibration drying, wherein the vibration drying is performed before the vibration thermal desorption, the drying temperature is 100-200° C., and the drying time is 15-60 min.

[0024] Furthermore, in S2, the vibration amplitude of the vibration thermal desorption and / or vibration drying is 1-30 cm, preferably 2-20 cm, and more preferably 3-10 cm.

[0025] Furthermore, in S2, the vibration frequency of the vibration thermal desorption and / or vibration drying is 10 Hz-1000 Hz, preferably 20-500 Hz, and more preferably 30-100 Hz.

[0026] Furthermore, in S2, the vibration thermal desorption and / or vibration drying is variable frequency and / or variable amplitude vibration.

[0027] Furthermore, in S2, during the vibration drying and / or vibration thermal desorption process, the inclination angle of the vibration thermal desorption device or the screening device is adjusted, and the inclination angle is ≤60°, preferably ≤45°, and more preferably ≤30°.

[0028] Furthermore, in S2, the protective atmosphere includes argon, nitrogen or a combination thereof.

[0029] Compared with the prior art, the beneficial effects of the present invention are: 1. The pretreatment process of battery waste is simple. After discharge, used batteries can be directly sheared without disassembly. The traditional discharge, disassembly, crushing, thermal desorption and sorting are simplified into discharge, shearing and thermal desorption separation processes, which eliminates the disassembly and sorting processes while effectively simplifying and optimizing the crushing and sorting processes, greatly improving the processing efficiency, reducing the investment in closed factories, equipment, power costs, etc., significantly reducing the processing costs, and avoiding the safety hazards that are difficult to overcome in the current disassembly process from the root.

[0030] 2. The pure dry treatment process is adopted to effectively avoid the use of wet desorbents such as acids and alkalis and organic solvent desorbents, eliminate the dissolution loss of lithium during wet pretreatment, the low efficiency caused by solid-liquid separation, the pollution of the operating environment by reagent volatilization and the health threat to operators, and at the same time avoid the defects of poor adaptability of organic reagent materials, high cost, difficulty and high cost of post-processing.

[0031] 3. The waste lithium batteries, disassembled battery cells, pole pieces and other battery waste are sheared in a certain direction in a regular and directional manner with a large shear size. While improving the shearing efficiency and reducing the shearing cost, it avoids the compaction and entrapment of black powder caused by traditional disordered and / or multiple crushing. The desorption and separation of black powder and pole pieces are good, and the entrapment and inter-embedding of metal impurities in the current collector and shell are effectively avoided, which effectively solves the separation and recycling problems faced by subsequent wet recycling from the root.

[0032] 4. Performing thermal desorption, vibration and screening simultaneously can not only effectively strengthen thermal desorption and optimize the desorption process, but also effectively avoid the difficulty of subsequent wet separation caused by the pulverization of metal materials, and realize the effective separation of materials such as pole pieces and shells from black powder in the hot state, thus achieving high-quality and efficient thermal desorption raw material separation pretreatment.

[0033] 5. By controlling the shear material shape, vibration thermal desorption and other parameters, the vibration thermal desorption effect is further optimized to improve the thermal desorption efficiency and separation and recovery effect of black powder. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by ordinary technicians in this field without creative work belong to the protection scope of the present application.

[0035] The screening space of the screening device used in the embodiment of the present invention is 0.6m*0.6m*0.9m (total height, of which the height of the thermal desorption zone is 0.6m).

[0036] Example 1 The discharged waste blade battery is directional sheared into 12cm*4.5cm*1.35cm sheared material, and the sheared material is placed in a vibration thermal desorption device, which includes a screening device, and a sieve plate with a 4.0cm*4.0cm sieve hole is provided in the screening device. The upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 5 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system and vibration system of the vibration thermal desorption device are started. The temperature is raised to 550℃ and treated at 550℃ for 45min, wherein the amplitude is 25mm and the vibration frequency is 90Hz. The sheared material in the screening device is synchronously subjected to vibration thermal desorption screening treatment. After the treatment is completed, the vibration thermal desorption furnace and the protective gas switch are turned off, and the sieve and the sieve are collected to complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate of this embodiment is 86.70%, and the black powder does not contain metal impurities such as aluminum, copper, and iron.

[0037] Example 2 The discharged waste batteries are directional sheared into 16cm*3cm*1.35cm sheared materials, and the sheared materials are placed in a vibration thermal desorption device, which includes a screening device, a sieve plate with an aperture of 2.5cm, the upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 4 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system and vibration system of the vibration thermal desorption device are started. The temperature is heated to 150°C, and after vibration drying for 30 minutes, the temperature is raised to 450°C and treated at 450°C for 60 minutes, and then raised to 600°C and treated at 600°C for 60 minutes, wherein the amplitude is 20mm, the vibration frequency is 50Hz, and the sheared materials in the screening device are synchronously subjected to vibration thermal desorption screening treatment. After the treatment is completed, the vibration thermal desorption furnace and the protective gas switch are turned off, the sieve-surface material and the sieve-underface material are collected, and the vibration thermal desorption screening process of the battery black powder is completed. The black powder recovery rate of this embodiment is 96.91%, and the black powder does not contain metal impurities such as aluminum, copper, and iron.

[0038] Example 3 The cells obtained by disassembling the discharged waste batteries are directional sheared into sheared materials of 20cm*3cm*10mm, and the sheared materials are placed in a vibration thermal desorption device, which includes a screening device, a sieve plate with an aperture of 2.5cm, the upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 5 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system and vibration system of the vibration thermal desorption device are started. The temperature is heated to 150°C, and the temperature is raised to 500°C after vibration drying for 30 minutes and vibrated at 500°C for 150 minutes, wherein the amplitude is 20mm and the vibration frequency is 60Hz. The sheared materials in the screening device are synchronously subjected to vibration thermal desorption screening treatment. After the treatment is completed, the vibration thermal desorption furnace and the protective gas switch are turned off, and the sieve-surface and sieve-underface materials are collected to complete the vibration thermal desorption screening process of battery black powder. The black powder recovery rate in this embodiment is 98.69%, and the black powder does not contain metal impurities such as aluminum and copper.

[0039] Example 4 The waste positive electrode sheet is directional sheared into 20cm*4.5cm*100μm sheared material, and the sheared material is placed in a vibration thermal desorption device, which includes a screening device, and a sieve plate with a 4.0cm*4.0cm sieve hole is provided in the screening device. The upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 4 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system and vibration system of the vibration thermal desorption device are started. The temperature is raised to 450℃ and vibrated at 450℃ for 120min, wherein the amplitude is 30mm and the vibration frequency is 40Hz. The sheared material in the screening device is synchronously subjected to vibration thermal desorption screening treatment. After the treatment is completed, the vibration thermal desorption furnace and the protective gas switch are turned off, and the sieve and the sieve are collected to complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate of this embodiment is 98.85%, and the black powder does not contain metal impurities such as aluminum.

[0040] Example 5 The waste positive electrode sheets are directionally sheared into 20cm*4.5cm*100μm shear materials, and the shear materials are placed in a vibration thermal desorption device, wherein 30wt% of the shear materials have serrated long sides with a sawtooth specification of 1cm (bottom)*1cm (height), and the rest are regular shear materials. A sieve plate with a 4.0cm*4.0cm sieve hole is provided in the screening device, the upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 4 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, the heating system and vibration system of the vibration thermal desorption equipment are started, the temperature is raised to 450℃ and vibrated at 450℃ for 90min, wherein the amplitude is 10mm and the frequency is 50Hz for the first 60min, and the amplitude is 30mm and the frequency is 40Hz for the next 30min. The shear materials in the screening device are synchronously subjected to vibration thermal desorption screening treatment. After the treatment is completed, the vibration thermal desorption furnace and the protective gas switch are turned off, and the sieve-over and sieve-under materials are collected to complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate of this embodiment is 99.33%, and the black powder does not contain metal impurities such as aluminum.

[0041] Example 6 The waste positive electrode sheet is directionally sheared into 20cm*4.5cm*100μm sheared materials, and the sheared materials are placed in a vibration thermal desorption device, which includes a screening device, a sieve plate with a 4.0cm*4.0cm sieve hole is arranged in the screening device, the upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone, and the loading amount is 1 / 4 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system and vibration system of the vibration thermal desorption device are started. The temperature is raised to 450°C and vibrated at 450°C for 75min, wherein the amplitude of the first 45min is 10mm and the vibration frequency is 50Hz, and the amplitude of the next 30min is 30mm and the vibration frequency is 40Hz, and the inclination angle of the side where the long side of the sheared material in the screening device is located is changed every 10 minutes during the vibration process, so that the plane where the sieve plate is located forms an angle of 30° with the horizontal plane, and the sheared material in the screening device is synchronously subjected to vibration thermal desorption screening treatment. After the treatment is completed, the vibration thermal desorption furnace and the protective gas switch are turned off, and the sieve-over and sieve-under materials are collected to complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate of this embodiment is 99.51%, and the black powder does not contain metal impurities such as aluminum.

[0042] Example 7 The waste positive electrode sheet was directional sheared into 20cm*4.5cm*100μm sheared material, and the sheared material was placed in a vibration thermal desorption device, the vibration thermal desorption device comprising a screening device, a sieve plate with a 4.0cm*4.0cm sieve hole was arranged in the screening device, the upper part of the sieve plate was a vibration thermal desorption zone, and the lower part was a gathering zone, and the loading amount was 1 / 4 of the volume of the thermal desorption zone. After the loading was completed, the furnace door was closed, nitrogen was introduced, the heating system and the vibration system of the vibration thermal desorption device were started, and the temperature was raised to 35 0℃ and vibrate at 350℃ for 30min, then heat to 450℃ and vibrate at 450℃ for 30min, then heat to 550℃ and vibrate at 550℃ for 30min, wherein the amplitude of the first 30min is 10mm and the frequency is 50Hz, the amplitude of the second 30min is 20mm and the frequency is 40Hz, and the amplitude of the last 30min is 30mm and the frequency is 30Hz, and the shear material in the screening device is simultaneously subjected to vibration thermal desorption screening treatment. After the treatment is completed, turn off the vibration thermal desorption furnace and the protective gas switch, collect the sieve and the sieve, and complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate of this embodiment is 99.11%, and the black powder does not contain metal impurities such as aluminum.

[0043] Example 8 The waste positive electrode sheets are directional sheared into 20cm*4.5cm*100μm sheared materials and collected in a screening device, wherein 30wt% of the sheared materials are long-side double-sided serrated, with a sawtooth specification of 1cm (bottom edge)*1cm (height), and the rest are regular sheared materials. The screening device is provided with a sieve plate with a 4.0cm*4.0cm sieve hole, the upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 4 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, the heating system and vibration system of the vibration thermal desorption equipment are started, the temperature is raised to 350℃ and vibrated at 350℃ Treat for 20 minutes, then heat to 450℃ and vibrate at 450℃ for 20 minutes, then heat to 550℃ and vibrate at 550℃ for 20 minutes, wherein the amplitude of the first 20 minutes is 10mm, the frequency is 50Hz, the amplitude of the second 20 minutes is 20mm, the frequency is 40Hz, and the amplitude of the last 20 minutes is 30mm, the frequency is 30Hz, and the inclination angle of the long side of the shear material in the screening device is changed every 10 minutes during the vibration process, so that the plane where the sieve plate is located forms an angle of 30° with the horizontal plane, and the shear material in the screening device is synchronously subjected to vibration thermal desorption screening. After the treatment is completed, turn off the vibration thermal desorption furnace and the protective gas switch, collect the sieve and the sieve, and complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate of this embodiment is 99.85%, and the black powder does not contain metal impurities such as aluminum.

[0044] Comparative Example 1 The cells obtained by disassembling the discharged waste batteries are directional sheared into sheared materials of 20cm*3cm*10mm, and the sheared materials are placed in a vibration thermal desorption device, which includes a screening device, a sieve plate with an aperture of 2.5cm, the upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 5 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system of the vibration thermal desorption device is started. The temperature is raised to 150°C, and the temperature is raised to 500°C after drying for 30 minutes and treated at 500°C for 75 minutes. The sheared materials in the screening device are subjected to thermal desorption treatment. After the thermal desorption is completed, the heating system and the nitrogen switch are turned off, and the vibration system is turned on after cooling to room temperature, wherein the amplitude is 20mm, the vibration frequency is 60Hz, and the vibration time is 75min. After the treatment is completed, the vibration system is turned off, and the sieve-surface and sieve-underface materials are collected to complete the vibration thermal desorption screening process of battery black powder. The black powder recovery rate in this embodiment is 93.16%, and the black powder does not contain metal impurities such as aluminum and copper.

[0045] Comparative Example 2 The battery cells obtained after discharge and disassembly are repeatedly crushed by a double-roll crusher until all of them pass through a 20mm*20mm sieve hole and then placed in a screening device. The screening device is provided with a sieve plate with a 50-mesh sieve hole. The upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 5 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system and vibration system of the vibration thermal desorption equipment are started. The temperature is raised to 150°C, and the temperature is raised to 500°C after vibration drying for 30 minutes and treated at 500°C for 150 minutes, wherein the amplitude is 20mm and the vibration frequency is 60Hz. After the treatment is completed, the vibration system of the vibration thermal desorption furnace is closed, and the sieve and the sieve are collected to complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate in this embodiment is 85.22%, and the aluminum impurity content in the black powder is 4.61%, and the copper content is 4.17%.

[0046] Comparative Example 3 The batteries obtained after discharge are repeatedly crushed by a double-roll crusher until all of them pass through a 20mm*20mm sieve hole and then placed in a screening device. The screening device is provided with a sieve plate with a 50-mesh sieve hole. The upper part of the sieve plate is a vibration thermal desorption zone, and the lower part is an aggregate zone. The loading amount is 1 / 5 of the volume of the thermal desorption zone. After the loading is completed, the furnace door is closed, nitrogen is introduced, and the heating system of the vibration thermal desorption equipment is started. The temperature is heated to 150°C, dried for 30 minutes, and then heated to 450°C and treated at 450°C for 30 minutes, and then heated to 600°C and kept at 600°C for 30 minutes. The sheared material in the screening device is subjected to thermal desorption treatment. After the thermal desorption is completed, the heating system and the nitrogen switch are turned off, and the vibration system is turned on after cooling to room temperature, wherein the amplitude is 20mm, the vibration frequency is 50Hz, and the vibration time is 60min. After the treatment is completed, the vibration system is turned off, and the sieve-surface and sieve-underface materials are collected to complete the vibration thermal desorption screening process of the battery black powder. The black powder recovery rate in this embodiment is 81.63%, the aluminum impurity content in the black powder is 5.17%, and the copper content is 4.29%.

[0047] It can be seen from the above embodiments and comparative examples that the waste battery recycling pretreatment process of the present invention can effectively separate and recycle battery powder, simplify the pretreatment process, and fundamentally solve the wet recovery problem caused by impurities entrained in battery powder.

[0048] The above embodiments are only used to illustrate the technical method of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical method of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical method of the present invention.

Claims

1. A battery waste recycling pretreatment process, characterized in that: The process comprises the following steps: S1, directional shearing of battery waste to obtain sheared material; S2, placing the sheared material in a vibration thermal desorption device, starting a heating system and a vibration system, and synchronously performing vibration thermal desorption and screening treatment on the sheared material under protective atmosphere conditions; S3: Turn off the heating system and vibration system of the vibration thermal stripping furnace, collect the screened material and the screened material, and complete the pretreatment.

2. The pretreatment process according to claim 1, characterized in that: The battery waste in S1 includes used batteries, battery cells, pole pieces, scraps or a combination of two or more thereof; and / or, in S2, the protective atmosphere includes argon, nitrogen or a combination thereof.

3. The pretreatment process according to claim 1, characterized in that: In the above S1, the battery waste is subjected to directional shearing in one or more directions, preferably directional shearing in the length direction and / or the width direction.

4. The pretreatment process according to claim 1 or 3, characterized in that: The vibration thermal desorption equipment includes a screening device, which is provided with a sieve plate or a sieve mesh, the upper part of the sieve plate or the sieve mesh is a vibration thermal desorption zone, and the lower part is an aggregate zone; in S1, the length of the sheared material is 0.1-0.9 times or 10-60cm of any side of the sieve plate or the sieve mesh; and / or the width of the sheared material is less than 10cm, preferably less than 7cm, more preferably 2-5cm; and / or the thickness of the sheared material is less than 3cm, preferably less than 2cm, more preferably less than 1cm.

5. The pretreatment process according to claim 4, characterized in that: The sieve plate or mesh is a detachable sieve plate or mesh, and the aperture or side length of the through holes on the sieve plate or mesh is 0.5-0.95 times, preferably 0.7-0.9 times, and more preferably 0.8-0.9 times the width of the shear material.

6. The pretreatment process according to claim 1 or 3, characterized in that: In S1, the sheared material has a flat cross-section or at least one side has an uneven cross-section.

7. The pretreatment process according to claim 6, characterized in that: The uneven cross-section shapes include serrated cross-sections, arc-shaped cross-sections, and angular cross-sections; and / or the sheared material is a mixture of a flat cross-section sheared material and a sheared material with an uneven cross-section on at least one side; preferably, the sheared material with an uneven cross-section on at least one side accounts for more than 20% of the total mass, preferably more than 30%, and more preferably more than 50%.

8. The pretreatment process according to claim 1 or 3, characterized in that: In S2, the vibration thermal desorption temperature is 300-650°C, preferably 350-600°C, and more preferably 400-500°C; and / or, the thermal desorption is variable temperature thermal desorption, the variable temperature steps are 2-4 steps, and preferably the temperature difference between each step is above 50°C; and / or, the vibration thermal desorption time is 30min-300min, preferably 45-240min, and more preferably 60-180min; and / or, it also includes vibration drying, and the vibration drying is carried out before the vibration thermal desorption, the drying temperature is 100-200°C, and the drying time is 15-60min.

9. The pretreatment process according to claim 1 or 3, characterized in that: In S2, the vibration amplitude of the vibration thermal desorption and / or vibration drying is 1-30cm, preferably 2-20cm, more preferably 3-10cm; and / or, the vibration frequency of the vibration thermal desorption and / or vibration drying is 10Hz-1000Hz, preferably 20-500Hz, more preferably 30-100Hz; and / or, the vibration thermal desorption and / or vibration drying is variable frequency and / or variable amplitude vibration.

10. The pretreatment process according to claim 4, characterized in that: In S2, during the vibration drying and / or vibration thermal desorption process, the inclination angle of the vibration thermal desorption device or the screening device is adjusted, and the inclination angle is ≤60°, preferably ≤45°, and more preferably ≤30°.