Recovery processing equipment for waste lithium battery and electrode material recovery method

Abstract

The invention relates to the technical field of lithium battery recovery, and provides a waste lithium battery recovery processing device and an electrode material recovery method, a battery tray, a conveying mechanism, a transfer device, a track annular mechanism, a discharge device, a cutting device, a separation device, a blanking fixing mechanism, a blanking manipulator and a storage mechanism are arranged above a workbench; the battery tray comprises a tray body, and a fixing block is arranged on the tray body; the conveying mechanism is used for conveying the battery tray to the transfer device; a plurality of sliding block devices are arranged on the track annular mechanism, and the transferring device is used for sucking the battery trays and conveying the battery trays to the corresponding sliding block devices on the track annular mechanism; the discharging device, the cutting device, the separating device and the discharging fixing mechanism are sequentially and correspondingly matched with the track annular mechanism, the discharging fixing mechanism is correspondingly matched with the discharging mechanical arm, and the discharging mechanical arm is used for loading the processed waste lithium batteries into the storage mechanism. According to the invention, the waste lithium battery can be well recycled.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium battery recycling, and in particular to a recycling and processing device for waste lithium batteries and an electrode material recycling method. Background Art

[0002] With the popularity of portable electronic devices and electric vehicles, the use of lithium batteries has increased dramatically, accompanied by a large number of retired waste lithium batteries. Lithium batteries contain valuable materials that can be recycled and reused after the battery life ends.

[0003] When recycling waste batteries, the batteries will first be discharged, cut and separated. Through battery discharge treatment, the residual electric energy in the waste power lithium battery can be effectively removed to avoid fire and explosion of the battery in the subsequent process; battery cutting mainly refers to the destruction of the battery shell structure by mechanical means to expose the internal components of the battery, which facilitates the subsequent separation and sorting of materials. The traditional discharge, cutting and separation of waste lithium batteries is carried out manually by staff, which is very inconvenient and time-consuming.

[0004] On the other hand, with the rapid development of the new energy vehicle industry, the demand for lithium-ion batteries and the amount of scrapped batteries are increasing year by year. From a structural point of view, the positive and negative electrode materials of batteries include rare metal resources such as cobalt, lithium, nickel, and manganese. With the rapid growth of rare metal prices, the recycling and reuse of metal materials in lithium batteries is imminent.

[0005] At present, there is no relatively complete pretreatment equipment to disassemble and process waste lithium batteries. A waste lithium battery recycling equipment is needed to solve the problem of waste lithium battery pretreatment and ensure the continuity and efficiency of waste lithium battery recycling and processing. Summary of the invention

[0006] The present invention provides a recycling device for waste lithium batteries and an electrode material recycling method, which can better carry out the recycling of waste lithium batteries.

[0007] A recycling and processing device for waste lithium batteries according to the present invention comprises a workbench, on which a battery tray, a conveying mechanism, a transfer device, a track ring mechanism, a discharge device, a cutting device, a separation device, a material fixing mechanism, a material unloading manipulator, and a storage mechanism are arranged;

[0008] The battery tray comprises a tray body, on which a fixing block is provided, and the fixing block is used to fix the waste lithium battery to be processed on the tray body;

[0009] The conveying mechanism is used to convey the battery tray to the transfer device;

[0010] A plurality of slider devices are provided on the track ring mechanism, and the transfer device is used to absorb the battery tray and send it to the corresponding slider device on the track ring mechanism, and the slider device is used to fix the battery tray and transfer it;

[0011] The discharge device, cutting device, separation device and unloading fixing mechanism are matched with the track ring mechanism in sequence, and the unloading fixing mechanism and the unloading manipulator are matched with each other. The unloading manipulator is used to load the processed waste lithium batteries into the storage mechanism.

[0012] Preferably, the transfer device includes a fixed frame installed on the workbench, a sliding beam is installed above the fixed frame, a battery cell loading and mounting frame that can slide horizontally is provided on the lithium battery sliding beam, a battery cell loading and mounting frame is provided with a battery loading and placing seat that can slide up and down, and a vacuum suction cup manipulator is installed on the battery loading and placing seat, and the vacuum suction cup manipulator is used to suck the battery tray.

[0013] Preferably, the battery cell loading and mounting frame is provided with a sensor for monitoring movement, a vacuum filter and a pressure gauge, and the bottom surface of the sliding beam is provided with an induction steel sheet for positioning.

[0014] Preferably, a transmission assembly and a motor are sequentially provided at one end of the sliding beam.

[0015] Preferably, the track ring mechanism comprises a track base, the track base is driven by a main drive wheel and an auxiliary drive wheel, the main drive wheel is connected to a drive motor drive shaft, and the plurality of slider devices are evenly mounted on the track base.

[0016] Preferably, the slider device includes a slider body, a positioning rod is provided on one side of the slider body, the positioning rod is connected to a connecting block, and the connecting block can adjust the position of the positioning rod; a guide wheel is provided at the bottom of the slider body, and the guide wheel slides with the outer side of the track base; an arc-shaped groove is provided on the other side of the slider body.

[0017] Preferably, a controller, a power module and an ultrasonic positioning sensor module are provided in the slider body, the controller is used to control the positioning rod, the ultrasonic positioning sensor module is used to maintain the spacing, and the power module is used to supply power.

[0018] Preferably, the material unloading fixing mechanism includes two fixing seats, the fingertips of the two fixing seats are connected to a limiting rod, a plurality of fixing blocks are provided on the limiting rod, and a limiting clamp is provided on the fixing block, and the limiting clamp cooperates with the arc-shaped clamping groove; a rotating shaft is provided at the center of the limiting rod, and the rotating shaft is connected to a transfer rod, which can drive the rotating shaft to rotate under the drive of a cylinder.

[0019] The present invention provides a method for recycling electrode materials of waste lithium batteries, which adopts the above-mentioned recycling and processing equipment for waste lithium batteries and comprises the following steps:

[0020] 1. After the waste lithium batteries to be processed are processed by the discharge device, cutting device, separation device, material fixing mechanism and material unloading manipulator, the internal materials of the battery core are obtained;

[0021] 2. Remove the binder on the electrode by air calcination to obtain the positive electrode material powder of waste lithium battery;

[0022] 3. The cathode material powder of waste lithium battery is mixed with alcohol substances to react in a subcritical water system, and more than 99% of Li enters the leachate containing Li+, while the transition metal substances remain in the leaching residue;

[0023] 4. Directly leaching transition metal substances with sulfuric acid to obtain precipitation, and then drying and sorting to obtain corresponding metal powder;

[0024] 5. Li + The leachate Li + Recovered by carbonization precipitation, the specific reaction is as follows:

[0025] 2Li + +Na 2 CO 3 =Li 2 CO 3 ↓+2Na +

[0026] 6. The obtained lithium carbonate precipitate is sorted and dried in a vacuum or inert gas environment, and the alcohol-containing leaching solution is recycled for Li + Extraction preparation;

[0027] 7. Calcine the obtained lithium carbonate and transition metal in an oxygen-rich environment to obtain raw materials for recycled lithium batteries.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] 1) In the present invention, the whole process of discharging, cutting and separating of lithium battery recycling pretreatment is automated through the conveying mechanism, the transfer device, the track ring mechanism and the unloading manipulator, which greatly improves the work efficiency.

[0030] 2) The present invention processes waste lithium batteries according to a set order, realizes automated cutting and separation operations of lithium batteries, and the processing technology has a high degree of automation, greatly improves work efficiency, and has good market application value.

[0031] 3) The organic solvent used in the present invention can be evaporated, recycled and reused, and the recycling efficiency is high. In addition, the critical fluid has a high extraction capacity and mass transfer capacity, which can simultaneously achieve the degradation of organic pollutants in electronic waste and the leaching and recovery of rare metals. Compared with the extraction method in the normal pressure environment, the supercritical environment method for recycling waste lithium battery positive electrode materials can shorten the leaching time and reduce the solvent consumption. It is a highly selective, green, efficient and low-cost lithium battery recycling technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 A schematic diagram of the three-dimensional structure of a recycling and processing device for waste lithium batteries in an embodiment;

[0033] Figure 2 A schematic diagram of the structure of a battery tray in an embodiment;

[0034] Figure 3 It is a structural schematic diagram of the transfer device in the embodiment;

[0035] Figure 4 It is a structural schematic diagram of the track ring mechanism in the embodiment;

[0036] Figure 5 It is a structural schematic diagram of the slider device in the embodiment;

[0037] Figure 6 It is a structural schematic diagram of the material fixing mechanism in the embodiment;

[0038] Figure 7 The present invention is a flow chart of a method for recycling electrode materials of waste lithium batteries in an embodiment. DETAILED DESCRIPTION

[0039] In order to further understand the content of the present invention, the present invention is described in detail in conjunction with the accompanying drawings and embodiments. It should be understood that the embodiments are only for explaining the present invention and are not intended to limit it.

[0040] Example

[0041] like Figure 1 As shown, this embodiment provides a recycling and processing device for waste lithium batteries, which includes a workbench 1, and a battery tray 2, a conveying mechanism 3, a transfer device 4, a track ring mechanism 5, a discharge device 6, a cutting device 7, a separation device 8, a material fixing mechanism 10, a material unloading manipulator 12, and a storage mechanism 11 are arranged above the workbench 1;

[0042] like Figure 2 As shown, the battery tray 2 includes a tray body 21, on which a fixing block 22 is provided, and the fixing block 22 is used to fix the waste lithium battery 23 to be processed on the tray body 21;

[0043] The conveying mechanism 3 is used to convey the battery tray 2 to the transfer device 4;

[0044] A plurality of slider devices 9 are provided on the track ring mechanism 5, and the transfer device 4 is used to absorb the battery tray 2 and send it to the corresponding slider device 9 on the track ring mechanism 5, and the slider device 9 is used to fix the battery tray 2 and transfer it;

[0045] The discharge device 6, the cutting device 7, the separation device 8 and the unloading fixing mechanism 10 are matched with the track ring mechanism 5 in sequence. The unloading fixing mechanism 10 and the unloading robot 12 are matched with each other. The unloading robot 12 is used to load the processed waste lithium batteries 23 into the storage mechanism 11.

[0046] The battery tray 2 is initially stored in the storage box, and the battery tray 2 is pushed onto the conveying mechanism 3 by the sliding pushing device.

[0047] like Figure 3 As shown, the transfer device 4 includes a fixed frame 41 installed on the workbench 1, a sliding beam 42 is installed above the fixed frame 41, a battery cell loading and mounting frame 43 that can slide horizontally is provided on the lithium battery sliding beam 42, a battery cell loading and mounting frame 43 is provided with a battery loading and placing seat 44 that can slide up and down, and a vacuum suction cup manipulator 45 is installed on the battery loading and placing seat 44, and the vacuum suction cup manipulator 45 is used to suck the battery tray 2.

[0048] The cell loading and mounting frame 43 is provided with a sensor 46 for monitoring movement, a vacuum filter 48 and a pressure gauge 49, and the bottom surface of the sliding beam 42 is provided with an induction steel sheet 47 for positioning.

[0049] A transmission assembly 411 and a motor 410 are sequentially disposed at one end of the sliding beam 42 .

[0050] like Figure 4 As shown, the track ring mechanism 5 includes a track base 51 , which is driven by a main driving wheel 52 and an auxiliary driving wheel 54 , the main driving wheel 52 is connected to a driving motor transmission shaft 53 , and the multiple slider devices 9 are evenly installed on the track base 51 .

[0051] like Figure 5 As shown, the slider device 9 includes a slider body, a positioning rod 91 is provided on one side of the slider body, the positioning rod 91 is connected to a connecting block 92, and the connecting block 92 can adjust the position of the positioning rod 91; a guide wheel 93 is provided at the bottom of the slider body, and the guide wheel 93 slides with the outer side of the track base 51; an arc-shaped groove 97 is provided on the other side of the slider body.

[0052] A controller 94 , a power module 95 and an ultrasonic positioning sensor module 96 are disposed in the slider body. The controller 94 is used to control the positioning rod 91 , the ultrasonic positioning sensor module 96 is used to maintain the spacing, and the power module 95 is used to supply power.

[0053] like Figure 6 As shown, the material unloading fixing mechanism 10 includes two fixing seats 101, and the two fixing seats 101 are connected to a limiting rod 105 at their fingertips. A plurality of fixing blocks 102 are provided on the limiting rod 105, and a limiting clamp 106 is provided on the fixing block 102. The limiting clamp 106 cooperates with the arc-shaped clamping groove 97; a rotating shaft 104 is provided at the center of the limiting rod 105, and the rotating shaft 104 is connected to a transfer rod 107, and the transfer rod 107 can drive the rotating shaft 104 to rotate under the drive of a cylinder 103.

[0054] The working principle of this embodiment is: first, the waste lithium battery 23 to be processed is placed in the battery tray 2 and fixed, then sent to the end loading point through the conveying mechanism 3, and the battery tray 2 is transferred to the slider device 9 on the track ring mechanism 5 through the transfer device 4. Under the cooperation between the track base 51 and the slider device 9, the waste lithium battery 23 and the battery tray 2 are driven to move toward the discharge device 6. When reaching the designated processing position, the controller 94 controls the positioning rod 91 to retract and engage with the positioning groove on the discharge device 6, so that the slider device 9 stops moving. After this step is processed, the controller 94 controls the positioning rod 91 to retract again and disengage from the positioning groove, so that the slider device 9 and the waste lithium battery 23 continue the next step along the track. The slider device 9 is equipped with an ultrasonic displacement sensor 96, which can detect and maintain the distance between the slider devices 9. The next step is cutting. The cutting device 7 can cut the shell of the waste lithium battery 23. After the battery shell is cut, the slider device 9 continues to move along the track to the separation device 8. The manipulator of the separation device 8 will accurately peel off the battery shell according to the positioning to complete the removal of the battery shell. Finally, the slider device 9 continues to move to the position of the blanking fixing mechanism 10, and the slider device 9 is fixed by the cooperation of the limit clamp 106 and the arc-shaped card slot 97, and the processed waste lithium battery 23 is loaded into the storage mechanism 11 through the blanking manipulator 12, completing the recycling pretreatment of the waste lithium battery 23.

[0055] like Figure 7 As shown, this embodiment provides a method for recycling electrode materials of waste lithium batteries, which adopts the above-mentioned recycling and processing equipment for waste lithium batteries and includes the following steps:

[0056] 1. After the waste lithium battery 23 to be processed is processed by the discharge device 6, the cutting device 7, the separation device 8, the material fixing mechanism 10, and the material unloading manipulator 12, the internal material of the battery cell is obtained;

[0057] 2. Remove the binder on the electrode by air calcination to obtain the positive electrode material powder of waste lithium battery;

[0058] 3. The powder of the cathode material of the waste lithium battery is mixed with alcohol substances to react in a subcritical water system, and more than 99% of the Li enters the Li-containing + in the leachate, while the transition metal species remain in the leaching residue;

[0059] 4. Directly leaching transition metal substances with sulfuric acid to obtain precipitation, and then drying and sorting to obtain corresponding metal powder;

[0060] 5. Li + The Li+ in the leachate is recovered by carbonization precipitation. The specific reaction is as follows:

[0061] 2Li + +Na 2 CO 3 =Li 2 CO 3 ↓+2Na +

[0062] 6. The obtained lithium carbonate precipitate is sorted and dried in a vacuum or inert gas environment, and the alcohol-containing leaching solution is recycled for Li + Extraction preparation;

[0063] 7. Calcine the obtained lithium carbonate and transition metal in an oxygen-rich environment to obtain raw materials for recycled lithium batteries.

[0064] The calcination temperature in the step 2 is 500°C.

[0065] The alcohol substance in step 3 is selected from common methanol, ethanol, ethylene glycol and propanol. A comparative analysis shows that ethylene glycol has the highest lithium ion extraction rate at a concentration of 50%, so ethylene glycol is preferably used as the alcohol substance.

[0066] In the step 3, the subcritical water environment is 200° C., so that both water and ethylene glycol are in a subcritical state.

[0067] In the step 3, LC-MS analysis of the solution after the subcritical reaction shows that ethylene glycol coexists with the generated organic compounds in the solution. The characteristics of these organic compounds are that their long carbon chain ends have hydroxyl or aldehyde groups, so that the solution of the subcritical reaction maintains the reducing property.

[0068] The concentration of sulfuric acid in step 4 is 2 mol / L, and the acid leaching temperature is 60° C. The leaching rates of transition metals (Ni, Co, Mn) are 80.3%, 84.1% and 92.8% respectively.

[0069] (Comparative Example 1) The process was carried out in pure water, and the remaining steps were the same as above. The lithium leaching efficiency was 13.5% and the pH value was 11.2.

[0070] (Comparative Example 2) The reaction was carried out in pure ethylene glycol, and the remaining steps were the same as above. The lithium leaching efficiency was significantly improved to 99.5%, and the pH value was 8.2.

[0071] (Comparative Example 3) The process was carried out in 50% ethylene glycol solution. The remaining steps were the same as above. The lithium leaching efficiency was slightly lower than that in Comparative Example 2, which was 99.1%, but the pH value was increased to 12.4.

[0072] By comparing the pH values ​​of Comparative Example 3 with those of Comparative Example 2, we can infer the presence of LiOH in the leachate, because the pH value increased from 8.2 to 12.6. The pH value comparison between Comparative Example 3 and Comparative Example 1 further shows that there are other substances in the leachate besides LiOH, because the pH value only increased from 11.4 to 12.6, while OH - and Li + The molar ratio of H is 1:1. The lithium leaching efficiency is significantly improved, but the increase in pH is small, which can be calculated by the pH calculation formula pH = -lg [H + ]=14+lg[OH - ] to explain.

[0073] In this embodiment, the entire process of discharging, cutting and separating of lithium battery recycling pretreatment is automated through the conveying mechanism 3, the transfer device 4, the track ring mechanism 5 and the unloading robot 12, which greatly improves the work efficiency.

[0074] This embodiment processes the waste lithium batteries 23 according to a set order to achieve automated cutting and separation of the lithium batteries. The processing technology has a high degree of automation, greatly improves work efficiency, and has good market application value.

[0075] The organic solvent used in this embodiment can be evaporated, recycled and reused, and the recycling efficiency is high. In addition, the critical fluid has a high extraction capacity and mass transfer capacity, and can simultaneously achieve the degradation of organic pollutants in electronic waste and the leaching and recovery of rare metals. Compared with the extraction method in the normal pressure environment, the supercritical environment method for recycling waste lithium battery positive electrode materials can shorten the leaching time and reduce the solvent consumption. It is a highly selective, green, efficient and low-cost lithium battery recycling technology.

[0076] The present invention and its embodiments are described schematically above, and the description is not restrictive. The drawings show only one embodiment of the present invention, and the actual structure is not limited thereto. Therefore, if a person skilled in the art is inspired by it and designs a structural method and an embodiment similar to the technical solution without creativity without departing from the purpose of the invention, they shall all fall within the protection scope of the present invention.

Claims

1. A recycling and processing device for waste lithium batteries, characterized in that: The invention comprises a workbench (1), wherein a battery tray (2), a conveying mechanism (3), a transfer device (4), a track ring mechanism (5), a discharge device (6), a cutting device (7), a separation device (8), a material unloading fixing mechanism (10), a material unloading manipulator (12), and a storage mechanism (11) are arranged above the workbench (1); The battery tray (2) comprises a tray body (21), and a fixing block (22) is provided on the tray body (21). The fixing block (22) is used to fix the waste lithium battery (23) to be processed on the tray body (21); The conveying mechanism (3) is used to convey the battery tray (2) to the transfer device (4); A plurality of slider devices (9) are provided on the track ring mechanism (5); the transfer device (4) is used to absorb the battery tray (2) and transfer it to the corresponding slider device (9) on the track ring mechanism (5); the slider device (9) is used to fix the battery tray (2) and transfer it; The discharge device (6), the cutting device (7), the separation device (8) and the material unloading fixing mechanism (10) are matched with the track ring mechanism (5) in sequence, and the material unloading fixing mechanism (10) and the material unloading manipulator (12) are matched with each other. The material unloading manipulator (12) is used to load the processed waste lithium batteries (23) into the storage mechanism (11).

2. The recycling equipment for waste lithium batteries according to claim 1, characterized in that: The transfer device (4) comprises a fixed frame (41) mounted on the workbench (1), a sliding beam (42) is mounted above the fixed frame (41), a battery cell loading mounting frame (43) capable of horizontal sliding is mounted on the lithium battery sliding beam (42), a battery cell loading and placing seat (44) capable of upward and downward sliding is mounted on the battery cell loading and placing seat (43), a vacuum suction cup manipulator (45) is mounted on the battery loading and placing seat (44), and the vacuum suction cup manipulator (45) is used to suck the battery tray (2).

3. The recycling equipment for waste lithium batteries according to claim 2 is characterized in that: The battery core loading and mounting frame (43) is provided with a sensor (46) for monitoring movement, a vacuum filter (48) and a pressure gauge (49), and the bottom surface of the sliding beam (42) is provided with an induction steel sheet (47) for positioning.

4. The recycling equipment for waste lithium batteries according to claim 3 is characterized in that: A transmission assembly (411) and a motor (410) are sequentially arranged at one end of the sliding crossbeam (42).

5. The recycling equipment for waste lithium batteries according to claim 4 is characterized in that: The track ring mechanism (5) comprises a track base (51), the track base (51) is driven by a main drive wheel (52) and a secondary drive wheel (54), the main drive wheel (52) is connected to a drive motor drive shaft (53), and the plurality of slider devices (9) are evenly mounted on the track base (51).

6. The recycling equipment for waste lithium batteries according to claim 5 is characterized in that: The slider device (9) comprises a slider body, a positioning rod (91) is provided on one side of the slider body, the positioning rod (91) is connected to a connecting block (92), and the connecting block (92) can adjust the position of the positioning rod (91); a guide wheel (93) is provided at the bottom of the slider body, and the guide wheel (93) is slidably matched with the outer side of the track base (51); and an arc-shaped slot (97) is provided on the other side of the slider body.

7. The recycling equipment for waste lithium batteries according to claim 6 is characterized in that: A controller (94), a power module (95) and an ultrasonic positioning sensor module (96) are arranged in the slider body. The controller (94) is used to control the positioning rod (91), the ultrasonic positioning sensor module (96) is used to maintain the spacing, and the power module (95) is used to supply power.

8. The recycling and processing equipment for waste lithium batteries according to claim 7 is characterized in that: The material blanking fixing mechanism (10) comprises two fixing seats (101), the fingertips of the two fixing seats (101) are connected to a limiting rod (105), a plurality of fixing blocks (102) are arranged on the limiting rod (105), the fixing blocks (102) are provided with a limiting clamping head (106), and the limiting clamping head (106) cooperates with the arc-shaped clamping groove (97); a rotating shaft (104) is arranged at the center of the limiting rod (105), and the rotating shaft (104) is connected to a transfer rod (107), and the transfer rod (107) can drive the rotating shaft (104) to rotate under the drive of a cylinder (103).

9. A method for recycling electrode materials from waste lithium batteries, characterized in that: The method adopts a recycling and processing device for waste lithium batteries as described in any one of claims 1 to 8, and comprises the following steps:

1. After the waste lithium battery (23) to be processed is processed by the discharge device (6), the cutting device (7), the separation device (8), the material fixing mechanism (10), and the material unloading manipulator (12), the internal material of the battery cell is obtained; 2. Remove the binder on the electrode by air calcination to obtain the positive electrode material powder of waste lithium battery; 3. The powder of the cathode material of the waste lithium battery is mixed with alcohol substances to react in a subcritical water system, and more than 99% of the Li enters the Li-containing + in the leachate, while the transition metal species remain in the leaching residue; 4. Directly leaching transition metal substances with sulfuric acid to obtain precipitation, and then drying and sorting to obtain corresponding metal powder; 5. Li + The Li+ in the leachate is recovered by carbonization precipitation. The specific reaction is as follows: <h2 style=";text-align:left;direction:ltr">2Li<h2 style=";text-align:left;direction:ltr"> + <h2 style=";text-align:left;direction:ltr"> +Na2CO3=Li2CO3↓+2Na<h2 style=";text-align:left;direction:ltr"> + 6. The obtained lithium carbonate precipitate is sorted and dried in a vacuum or inert gas environment, and the alcohol-containing leaching solution is recycled for Li + Extraction preparation; 7. Calcine the obtained lithium carbonate and transition metal in an oxygen-rich environment to obtain raw materials for recycled lithium batteries.

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