Lithium ion ceramic diaphragm aluminum oxide recovery device and method

Abstract

The invention discloses a lithium ion ceramic diaphragm aluminum oxide recovery device, which comprises a disassembly unit, an aluminum oxide recovery unit, a lithium ion battery, an aluminum oxide recovery unit and an aluminum oxide recovery unit, the pretreatment unit is used for cleaning the taken-out ceramic diaphragm; the acid leaching unit is used for removing pollutants on the surface of the ceramic diaphragm and filtering a solution subjected to acid leaching; the acid leaching unit is connected with the precipitation unit through a pipeline, and the precipitation unit generates aluminum oxide precipitate by adjusting the pH value of a filtering solution. According to the invention, the recovery efficiency and precision of aluminum oxide in the ceramic diaphragm are high, the purity and quality of the recovered aluminum oxide are ensured, and a guarantee is provided for reutilization of the aluminum oxide; the method using the device is easy to operate, aluminum oxide in the lithium ion ceramic diaphragm can be efficiently recycled, the resource utilization rate is increased, the requirement for native resources is reduced, and the production cost is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium ion battery manufacturing, and in particular to a lithium ion ceramic diaphragm aluminum oxide recovery device and method. Background Art

[0002] Lithium-ion battery is a secondary battery, i.e. a rechargeable battery, which mainly relies on the movement of lithium ions between the positive and negative electrodes to work. With the widespread application of lithium-ion batteries, the number of waste lithium-ion batteries continues to increase. As an important component of lithium-ion batteries, lithium-ion ceramic diaphragms contain a large amount of aluminum oxide. Effectively recycling aluminum oxide in lithium-ion ceramic diaphragms has important economic and environmental significance.

[0003] Commonly used recovery methods generally adopt electrolytic reduction and physical separation technology. However, these methods have limited recovery efficiency and purity of alumina, and the more complicated processes will also bring high costs. Summary of the invention

[0004] The purpose of the present invention is to solve the problems of the above-mentioned background technology and to propose a lithium ion ceramic diaphragm alumina recovery device and method.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A lithium-ion ceramic diaphragm alumina recovery device comprises: a disassembly unit, the disassembly unit is used to remove the ceramic diaphragm in the battery; a pretreatment unit, the pretreatment unit is used to clean the removed ceramic diaphragm; an acid leaching unit, the acid leaching unit is used to remove surface pollutants of the ceramic diaphragm and filter the solution after acid leaching; the acid leaching unit is connected to a precipitation unit through a pipeline, and the precipitation unit generates alumina precipitate by adjusting the pH of the filtered solution.

[0007] As a further solution of the present invention: the disassembling unit includes a cutting machine, the cutting machine is provided with a mechanical arm, a tool is provided at the end of the mechanical arm, and the mechanical arm is provided with a groove for accommodating the tool.

[0008] As a further solution of the present invention: a clamp is provided at the end of the robotic arm, and the robotic arm is provided with a groove for accommodating the clamp.

[0009] As a further solution of the present invention: the pretreatment unit includes a cleaning box, a conveyor belt is arranged at the top inlet of the cleaning box, a water outlet is opened at the bottom of the side of the cleaning box, and a support tray is detachably arranged in the cleaning box, and the support tray is a mesh sieve tray structure.

[0010] As a further solution of the present invention: the acid leaching unit includes an acid leaching reactor, a filter screen is detachably connected to the inside of the acid leaching reactor, and a stirring mechanism is arranged above the filter screen.

[0011] As a further solution of the present invention: the acid leaching reactor is connected to a first liquid inlet pipeline and a second liquid inlet pipeline, and the second liquid inlet pipeline is connected to the precipitation unit.

[0012] As a further solution of the present invention: the sedimentation unit is a bottle structure narrowed in the middle, and the sedimentation unit includes an upper cavity and a lower cavity, and a throat portion is arranged between the upper cavity and the lower cavity.

[0013] As a further solution of the present invention: an interface part is arranged above the upper cavity, and two interface parts are arranged, one interface part is connected to the second liquid inlet pipe, and the other interface part is connected to the third liquid inlet pipe.

[0014] A method for using a lithium ion ceramic diaphragm alumina recovery device, comprising:

[0015] S1, the disassembly unit disassembles the waste lithium-ion battery and removes the ceramic diaphragm in the battery;

[0016] S2, placing the disassembled ceramic diaphragm into a pretreatment unit, cleaning the surface stains of the ceramic diaphragm with deionized water, and drying the cleaned ceramic diaphragm at a preset temperature;

[0017] S3, placing the pretreated ceramic diaphragm into an acid leaching unit, introducing a certain amount of acid solution into the acid leaching unit, and leaching the ceramic diaphragm in the acid solution for a preset time;

[0018] S4, filtering the solution after acid leaching to remove insoluble impurities;

[0019] S5, transferring the filtered solution to a precipitation unit, introducing an alkaline solution into the precipitation unit, and generating an alumina precipitate after a neutralization precipitation reaction;

[0020] S6. Place the alumina precipitate in a drying unit and dry it at a preset temperature to obtain a recovered alumina product.

[0021] As a further solution of the present invention: in step S5, when the pH value of the solution reaches 8-9, the introduction of the alkaline solution is stopped.

[0022] Beneficial effects of the present invention:

[0023] (1) In the present invention, the recovery efficiency of aluminum oxide in the ceramic diaphragm is high and the precision is high, thus ensuring the purity and quality of the recovered aluminum oxide and providing guarantee for its reuse.

[0024] (2) In the present invention, the method using the device is not only simple to operate, but also can efficiently recover the aluminum oxide in the lithium ion ceramic diaphragm, improve resource utilization, reduce the demand for primary resources, and reduce production costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The present invention will be further described below in conjunction with the accompanying drawings.

[0026] Figure 1 It is a structural schematic diagram of a lithium ion ceramic diaphragm alumina recovery device of the present invention;

[0027] Figure 2 yes Figure 1 Schematic diagram of the structure of the disassembly unit in the cutting state

[0028] Figure 3 yes Figure 1 A schematic diagram of the structure of the disassembly unit in the clamping state;

[0029] Figure 4 yes Figure 1 Schematic diagram of the structure of the medium acid leaching unit;

[0030] Figure 5 yes Figure 1 Schematic diagram of the structure of the medium precipitation unit;

[0031] Figure 6 It is a flow chart of the lithium ion ceramic diaphragm aluminum oxide recovery method of the present invention.

[0032] In the figure: 1. disassembly unit; 11. cutting machine; 12. robotic arm; 13. fixture; 14. tool; 2. pretreatment unit; 21. cleaning box; 22. conveyor belt; 23. water outlet; 24. tray; 3. acid leaching unit; 31. acid leaching reactor; 32. stirring mechanism; 33. filter; 4. sedimentation unit; 41. upper cavity; 42. interface; 43. throat; 44. lower cavity; 5. drying unit; 6. first liquid inlet pipe; 7. second liquid inlet pipe; 8. third liquid inlet pipe. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] See also Figure 1 As shown, the present invention is a lithium ion ceramic diaphragm aluminum oxide recovery device, comprising: a disassembly unit 1, and the disassembly unit 1 is used to take out the ceramic diaphragm in the battery.

[0035] See also Figure 2-Figure 3 As shown, specifically, the disassembly unit 1 includes a cutting machine 11, and the cutting machine 11 is provided with a robotic arm 12. A tool 14 is rotatably connected to the end of the robotic arm 12, and a clamp 13 is also rotatably connected to the end of the robotic arm 12. The robotic arm 12 is provided with a groove for accommodating the tool 14 and the clamp 13, and the tool 14 and the clamp 13 can be removed from the robotic arm 12, and the disassembly methods include but are not limited to snap disassembly and bolt disassembly.

[0036] Among them, the clamp 13 can be a vacuum clamp, a pneumatic clamp, or a mechanical clamp. Preferably, tweezers among mechanical clamps are used. Tweezers have a low cost, are easy to replace frequently, have a good clamping effect, and are not easy to fall off.

[0037] See also Figure 1 As shown, a pre-treatment unit 2 is also included, and the pre-treatment unit 2 is used to clean the removed ceramic diaphragm.

[0038] Specifically, the pretreatment unit 2 includes a cleaning box 21, a conveyor belt 22 is arranged at the top entrance of the cleaning box 21, and the tweezers can place the clamped ceramic diaphragm on the conveyor belt 22, and the ceramic diaphragm is transported to the cleaning box 21 through the conveyor belt 22. The cleaning box 21 is connected to the external water source through a pipeline, and a water outlet 23 is provided at the bottom of the side of the cleaning box 21. A support tray 24 is detachably arranged in the cleaning box 21, and the support tray 24 is a mesh sieve plate structure. The ceramic diaphragm transported by the conveyor belt 22 is supported by the support tray 24.

[0039] In this embodiment, an external water source introduces deionized water into the cleaning box 21, and the deionized water rinses the surface of the ceramic diaphragm to remove surface stains. The deionized water after rinsing flows out from the water outlet 23. The ceramic diaphragm expression can be further cleaned by an uninterrupted non-circulating cleaning method.

[0040] See also Figure 1 , Figure 4 As shown, an acid leaching unit 3 is arranged on one side of the pretreatment unit 2, and the acid leaching unit 3 is used to remove surface pollutants of the ceramic diaphragm and filter the solution after the acid leaching.

[0041] Among them, the acid leaching unit 3 includes an acid leaching reactor 31, a filter screen 33 is detachably connected to the acid leaching reactor 31, and a stirring mechanism 32 is arranged above the filter screen 33. The stirring mechanism 32 can adopt a structure in which a motor drives a stirring paddle to rotate. It should be noted that the motor needs to be arranged outside the acid leaching reactor 31 to prevent the motor from being corroded and damaged by the acid solution. The form of the stirring paddle includes but is not limited to a stirring rod and a frame stirring paddle. The acid leaching reactor 31 is connected to a first liquid inlet pipe 6, and the acid solution in the external container enters the acid leaching reactor 31 through the first liquid inlet pipe 6.

[0042] The acid leaching reactor 31 is connected to a second liquid inlet pipe 7 , and the connection between the second liquid inlet pipe 7 and the acid leaching reactor 31 is arranged below the filter screen 33 , so as to discharge the solution passing through the filter screen 33 .

[0043] See also Figure 1 , Figure 5 As shown, the second liquid inlet pipe 7 is connected to the precipitation unit 4, and the precipitation unit 4 generates aluminum oxide precipitation by adjusting the pH of the filtered solution.

[0044] Furthermore, the sedimentation unit 4 is a bottle structure with a narrowed middle portion, and the sedimentation unit 4 includes an upper cavity 41 and a lower cavity 44, a throat portion 43 is arranged between the upper cavity 41 and the lower cavity 44, an interface portion 42 is arranged above the upper cavity 41, and two interface portions 42 are arranged, one interface portion 42 is connected to the second liquid inlet pipe 7, and the other interface portion 42 is connected to the third liquid inlet pipe 8, and the alkaline solution in the external container enters the sedimentation unit 4 through the third liquid inlet pipe 8 and a neutralization reaction occurs.

[0045] In this embodiment, the solution in the acid leaching reactor 31 is transported to the precipitation unit 4 through the second liquid inlet pipe 7, and then the alkaline solution is introduced into the precipitation unit 4 through the third liquid inlet pipe 8. At this time, the two solutions undergo an acid-base neutralization reaction to generate alumina precipitate.

[0046] It can be understood that the throat portion 43 can serve as a buffer flow channel to reduce the flow rate and distribution of the liquid, increase the contact and reaction time of the two solutions, ensure that the two solutions are effectively mixed in the precipitation unit 4, make the reaction process more uniform, and thus improve the reaction efficiency and reaction stability.

[0047] See also Figure 1 As shown, a drying unit 5 is arranged on one side of the precipitation unit 4, and the drying unit 5 can adopt a hot air drying furnace or a vacuum drying box. Preferably, the drying unit adopts a hot air drying furnace, which removes moisture attached to the surface of the aluminum oxide precipitation by heating air.

[0048] See also Figure 6 As shown, a method for a lithium ion ceramic diaphragm alumina recovery device comprises:

[0049] S1, disassembly unit 1 disassembles the waste lithium-ion battery and removes the ceramic diaphragm in the battery.

[0050] Specifically, the mechanical arm 12 on the cutting machine 11 is extended, and the mechanical arm 12 is connected to the tool 14 to cut the waste lithium-ion battery. After cutting, the tool 14 is recovered, and the tweezers are extended, and the tweezers sense the ceramic diaphragm to clamp it out.

[0051] S2. Place the disassembled ceramic diaphragm into the pretreatment unit 2, clean the surface stains of the ceramic diaphragm with deionized water, and dry the cleaned ceramic diaphragm at a preset temperature.

[0052] Specifically, the tweezers place the ceramic diaphragm on the conveyor belt 22, and the ceramic diaphragm cup conveyor belt 22 is transported to the tray 24 in the cleaning box 21. The external water source introduces deionized water into the cleaning box 21, and an uninterrupted non-circulating cleaning method is adopted. The deionized water rinses the surface of the ceramic diaphragm to remove the surface stains, and the rinsed deionized water flows out from the water outlet 23. The cleaned ceramic diaphragm is placed in the drying unit 5 for drying, and the drying condition is 80°C and dried for 2 hours.

[0053] S3, the pretreated ceramic diaphragm is placed in the acid leaching unit 3, and an acid solution is introduced into the acid leaching unit 3, wherein the acid solution is a 2 mol / L hydrochloric acid solution, and the mass volume ratio of the ceramic diaphragm to the hydrochloric acid solution is 1:5 (g / mL). After the hydrochloric acid solution is introduced, the stirring mechanism 32 stirs the solution, so that the ceramic diaphragm is acid-leached in the acid solution for 3 hours, thereby removing metal ions and improving surface properties.

[0054] S4. The solution after acid leaching is filtered through the filter screen 33 to remove insoluble impurities.

[0055] S5. The filtered solution is transferred to the precipitation unit 4, and an alkaline solution is introduced into the precipitation unit 4 until the pH value of the solution reaches 8-9, and an aluminum oxide precipitate is generated after the neutralization precipitation reaction.

[0056] Specifically, the second liquid inlet pipe 7 transports the solution in the acid leaching reactor 31 to the precipitation unit 4, and then the alkaline solution is introduced into the precipitation unit 4 through the third liquid inlet pipe 8. The alkaline solution is a 2 mol / L sodium hydroxide solution. After the two solutions enter the upper cavity 41, the flow rate is slowed down at the throat portion 43 and mixed in the lower cavity 44. At this time, the two solutions undergo an acid-base neutralization reaction, the reaction time is 1 hour, and aluminum oxide precipitation is generated after the reaction.

[0057] During the acid-base neutralization reaction, a stirring paddle may be provided in the lower cavity 44 to accelerate the mixing and reaction of the two solutions, or the mixing and reaction of the solutions may be accelerated by shaking the precipitation unit 4 .

[0058] It is understandable that when the precipitation unit 4 is shaken, the throat portion 43 also has a splash-proof function to prevent the droplets generated by the collision of the solution with the inner wall of the precipitation unit 4 from flowing back upward. Since the acid-base neutralization reaction is an exothermic process, the air with increased temperature in the precipitation unit 4 will rise upward, and the throat portion 43 can discharge the rising air smoothly.

[0059] S6. The aluminum oxide precipitate is taken out from the precipitation unit 4 and placed in the drying unit 5, and dried at a preset temperature to obtain a recovered aluminum oxide product.

[0060] The preset temperature is a range value, which is 100°C to 150°C. In this embodiment, the preset temperature is 120°C and the drying time is 4 hours. The drying time can be adjusted according to different drying temperatures.

[0061] After testing, the purity of the aluminum oxide product recovered in this embodiment reaches more than 95%, and the experimental data are as follows:

[0062] Take 10 g of each of the five batches of ceramic diaphragms cleaned in step S2 and record them as W. 总 The aluminum oxide product purified by the method after the cleaned ceramic diaphragm is processed by steps S3 to S5 is weighed and recorded as W Al2O3 , the formula for calculating the purity of alumina products is as follows:

[0063] Purity (%) = (W Al2O3 / W 总 )×100%

[0064] The results are shown in Table 1:

[0065] Table 1

[0066]

[0067]

[0068] The inventors have found that there are some disadvantages in the electrolytic reduction method and physical separation technology in the prior art. The electrolytic reduction method requires high voltage and special equipment during operation, with high energy consumption and high cost. At the same time, by-products are easily produced during the electrolysis process, which further increases the complexity of separation and purification, and the more complicated process will also bring high costs. Physical separation techniques such as screening and magnetic separation are usually used for preliminary separation, but for complex mixtures containing aluminum oxide and other substances, the accuracy is limited and it is difficult to achieve high-purity separation. In addition, physical separation is also difficult to handle nano-scale particles and impurities attached to the surface, which has a great impact on the purity of the recovered aluminum oxide.

[0069] In the present application, the method using the device is not only simple to operate, but also can efficiently recover alumina in lithium-ion ceramic diaphragms, improve resource utilization, reduce the demand for primary resources, and reduce production costs.

[0070] From the perspective of environmental protection, the present application extracts aluminum oxide from waste lithium-ion batteries, which can avoid environmental pollution caused by waste diaphragms and prevent aluminum oxide from causing potential harm to soil and water sources. Compared with physical separation technology, the present invention has high recovery efficiency and high precision for aluminum oxide in ceramic diaphragms, ensuring the purity and quality of the recovered aluminum oxide and providing guarantee for its reuse.

[0071] The method is easy to operate and can be combined with existing battery production processes to easily realize industrial production.

[0072] It should be noted that in step S3, magnetic separation technology can be used, that is, for a system containing magnetic impurities, the magnetic impurities can be separated by an external magnetic field, thereby indirectly separating aluminum oxide from other impurities. However, the premise of this technology is that other substances in the system are not magnetic or have weak magnetism and cannot interfere with the separation of aluminum oxide.

[0073] Magnetic separation technology can quickly and effectively remove magnetic impurities in the system. For the case of a large amount of magnetic substances, this method can effectively improve the separation efficiency and reduce the burden of subsequent processing steps. Targeted removal of magnetic impurities can also improve the purity of the final recovered alumina, making it more in line with the requirements of recycling and reuse.

[0074] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made according to the scope of application of the present invention should still fall within the scope of the claims of the present invention.

Claims

1. A lithium ion ceramic diaphragm alumina recovery device, characterized in that: include: A disassembly unit (1), wherein the disassembly unit (1) is used to remove a ceramic diaphragm from a battery; A pretreatment unit (2), the pretreatment unit (2) being used for cleaning the removed ceramic diaphragm; An acid leaching unit (3), wherein the acid leaching unit (3) is used to remove surface contaminants of the ceramic diaphragm and filter the solution after the acid leaching; The acid leaching unit (3) is connected to the precipitation unit (4) through a pipeline, and the precipitation unit (4) generates aluminum oxide precipitation by adjusting the pH of the filtered solution.

2. A lithium ion ceramic diaphragm alumina recovery device according to claim 1, characterized in that: The disassembly unit (1) comprises a cutting machine (11), the cutting machine (11) being provided with a mechanical arm (12), a knife (14) being provided at the end of the mechanical arm (12), and a groove for accommodating the knife (14) being provided in the mechanical arm (12).

3. A lithium ion ceramic diaphragm alumina recovery device according to claim 2, characterized in that: A clamp (13) is provided at the end of the mechanical arm (12), and the mechanical arm (12) is provided with a groove for accommodating the clamp (13).

4. A lithium ion ceramic diaphragm alumina recovery device according to claim 1, characterized in that: The pretreatment unit (2) comprises a cleaning box (21), a conveyor belt (22) is arranged at the top inlet of the cleaning box (21), a water outlet (23) is arranged at the bottom of the side of the cleaning box (21), and a receiving tray (24) is detachably arranged in the cleaning box (21), and the receiving tray (24) is a mesh sieve tray structure.

5. A lithium ion ceramic diaphragm alumina recovery device according to claim 1, characterized in that: The acid leaching unit (3) comprises an acid leaching reactor (31), a filter screen (33) is detachably connected to the inside of the acid leaching reactor (31), and a stirring mechanism (32) is arranged above the filter screen (33).

6. A lithium ion ceramic diaphragm alumina recovery device according to claim 5, characterized in that: The acid leaching reactor (31) is connected to a first liquid inlet pipeline (6) and a second liquid inlet pipeline (7), and the second liquid inlet pipeline (7) is connected to the precipitation unit (4).

7. A lithium ion ceramic diaphragm alumina recovery device according to claim 6, characterized in that: The sedimentation unit (4) is a bottle structure with a narrowed middle portion. The sedimentation unit (4) comprises an upper cavity (41) and a lower cavity (44). A throat portion (43) is provided between the upper cavity (41) and the lower cavity (44).

8. A lithium ion ceramic diaphragm alumina recovery device according to claim 7, characterized in that: An interface portion (42) is provided above the upper cavity (41), and two interface portions (42) are provided, one interface portion (42) is connected to the second liquid inlet pipe (7), and the other interface portion (42) is connected to the third liquid inlet pipe (8).

9. A method for using the lithium ion ceramic diaphragm alumina recovery device according to any one of claims 1 to 8, characterized in that: include: S1, a disassembly unit (1) disassembles the waste lithium-ion battery and removes the ceramic diaphragm in the battery; S2, placing the disassembled ceramic diaphragm into the pretreatment unit (2), cleaning the surface stains of the ceramic diaphragm with deionized water, and drying the cleaned ceramic diaphragm at a preset temperature; S3, placing the pretreated ceramic diaphragm into an acid leaching unit (3), introducing a certain amount of acid solution into the acid leaching unit (3), and leaching the ceramic diaphragm in the acid solution for a preset time; S4, filtering the solution after acid leaching to remove insoluble impurities; S5, transferring the filtered solution to a precipitation unit (4), introducing an alkaline solution into the precipitation unit (4), neutralizing the precipitation reaction to generate an aluminum oxide precipitate; S6. Place the aluminum oxide precipitate in a drying unit (5) and dry it at a preset temperature to obtain a recovered aluminum oxide product.

10. The method according to claim 9, characterized in that In step S5, when the pH value of the solution reaches 8-9, the introduction of the alkaline solution is stopped.

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