Device and method for recovering metal ions from waste lithium-ion batteries

Abstract

The present invention discloses a device for recovering metal ions from waste lithium-ion batteries. The device comprises a discharge storage tank, a crushing tank, a screening tank, a drying box, an organic matter removal tank, an alkaline solution tank, and an adsorption and desorption tank. A conveyor belt is provided between the bottom outlet of the discharge storage tank and the top inlet of the crushing tank. A conveyor belt is provided between the bottom outlet of the crushing tank and the top inlet of the screening tank. A metal shell recovery outlet and an electrode material outlet are provided at the bottom of the screening tank. The electrode material outlet is connected to the drying box. A conveyor belt is provided between the bottom outlet of the drying box and the top inlet of the organic matter removal tank. A conveyor belt is provided between the bottom outlet of the organic matter removal tank and the top inlet of the alkaline solution tank. The liquid outlet of the alkaline solution tank is connected to the bottom of the adsorption and desorption tank. From the discharge of raw materials to the final lithium ion recovery, the present invention can effectively recover metal ions and realize the resource utilization of waste batteries.

Description

Technical Field

[0001] The present invention belongs to the field of battery recycling, and in particular relates to a device and method for recycling metal ions in lithium-ion batteries. Background Art

[0002] Over the past two decades, the market for lithium-ion batteries (LIBs) has grown significantly, with their widespread application in consumer electronics, electric vehicles, and energy storage. However, at the end of their useful life, a large number of retired LIBs are generated, containing a large amount of valuable metal elements and hazardous substances. Improper disposal can lead to resource waste, environmental pollution, and safety issues. Therefore, the recovery and recycling of retired LIBs has become a research hotspot and has attracted global attention.

[0003] Existing lithium-ion battery electrode materials generally use lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, and ternary materials. Retired ternary lithium-ion batteries are rich in valuable metal elements such as lithium, nickel, and cobalt. Co accounts for 5% to 20%, Ni 5% to 12%, Mn 7% to 10%, and Li 2% to 5%. The potential resource is enormous and has high economic value for recycling.

[0004] In the prior art, there are few disclosures on the recovery devices for metals in waste lithium-ion batteries, and the structures are relatively complex. The present invention provides a complete set of recovery devices, from the discharge of raw materials to the final lithium ion recovery, which can effectively recover metal ions and realize the resource utilization of waste batteries. Summary of the Invention

[0005] The present invention overcomes the defects of the prior art and provides a device and method for recovering metal ions from waste lithium-ion batteries.

[0006] The technical solutions of the present invention are as follows.

[0007] A device for recovering metal ions from waste lithium-ion batteries comprises a discharge storage tank, a crushing tank, a screening tank, a drying box, an organic matter removal tank, an alkali liquid tank, a pH adjustment tank, and an adsorption and desorption tank; a conveyor belt is provided between the bottom outlet of the discharge storage tank and the top inlet of the crushing tank; a conveyor belt is provided between the bottom outlet of the crushing tank and the top inlet of the screening tank; a metal shell recovery outlet and an electrode material outlet are provided at the bottom of the screening tank; the electrode material outlet is connected to the drying box, a conveyor belt is provided between the bottom outlet of the drying box and the top inlet of the organic matter removal tank, a conveyor belt is provided between the bottom outlet of the organic matter removal tank and the top inlet of the alkali liquid tank, the liquid outlet of the alkali liquid tank is connected to the pH adjustment tank, and the bottom outlet of the pH adjustment tank is connected to the bottom of the adsorption and desorption tank.

[0008] Furthermore, the screening trough consists of a screening trough body, a vibrating conveyor belt, a fan, and a collecting trough; a fan is provided on one side of the screening trough body, and more than one vibrating conveyor belt is provided in the screening trough body, and a Z-shaped structure is formed between the vibrating conveyor belts; a collecting trough for collecting electrode powder is provided at the bottom of the side opposite to the fan inside the screening trough body, and the outlet of the collecting trough is the electrode material outlet, and a metal shell outlet is provided below the vibrating conveyor belt. The screening trough mainly utilizes the different densities of the battery shell material and the motor material, and adopts fan airflow for screening, and the screened motor material enters the electrode powder collection trough, and other substances enter the metal shell outlet through the vibrating conveyor belt.

[0009] Furthermore, the adsorption and desorption tank has a liquid outlet and a liquid inlet at the top and bottom respectively.

[0010] Furthermore, the adsorption and desorption tank is provided with a placement rack, an adsorbent placement container, a spoiler, a placement rack and an adsorbent placement container from bottom to top; the adsorbent placement container is placed on the placement rack; the adsorbent placement container is a columnar structure made of a mesh material and is filled with lithium adsorbent.

[0011] Furthermore, an ultrasonic column is provided on the placement rack, and an adsorbent placement container channel is correspondingly provided on the adsorbent placement container. When the adsorbent placement container is placed on the placement rack, the adsorbent placement container channel is just inserted into the ultrasonic column.

[0012] Furthermore, the bottoms of the discharge storage tank, crushing tank, organic matter removal tank and alkali liquid tank are all provided with liquid outflow outlets, and valves are provided on the liquid outflow outlet pipes.

[0013] A method for recovering metal ions from waste lithium-ion batteries using the device comprises the following steps:

[0014] (1) Place the discarded batteries in an electrical storage tank, add a saturated KCl solution to the electrical storage tank 1, and perform a discharge operation; then, after the liquid is discharged, open the bottom outlet so that the discharged batteries enter the crushing tank through a conveyor belt; the discharge operation time is 12 to 24 hours;

[0015] (2) In the crushing tank, after the crushing equipment crushes the battery and discharges the liquid, the bottom outlet is opened, so that the crushed battery enters the screening tank through the conveyor belt for screening, wherein the metal shell is screened out through the metal shell outlet for recycling; the electrode powder is screened out through the electrode material outlet and then enters the drying box for drying operation, wherein the drying box performs low-temperature drying and removal of the electrolyte;

[0016] (3) The dried electrode material enters the organic matter removal tank through a conveyor belt, and the organic matter removal tank is a pyrolysis device; after the electrode material is pyrolyzed in the organic matter removal tank to remove organic matter, the bottom outlet is opened, allowing the electrode material to enter the alkali solution tank through the conveyor belt;

[0017] (4) The alkali liquid tank 7 is filled with sodium hydroxide solution. After soaking for 12 to 20 hours, the soaking liquid enters the pH adjustment tank, and an acidic solution is added to form a suspension until the pH is 6 to 7. The suspension enters the adsorption and desorption tank 8 to recover the metal. After recovery, pure water is used to desorb the inside of the adsorption and desorption tank 8; the ultrasonic power in the adsorption and desorption tank 8 is 20 to 90 kHz; the metal ions are lithium ions.

[0018] In the above method, in step (2), the drying temperature is 200-300°C.

[0019] In the above method, in step (3), the pyrolysis is: heating the electrode material at 300-500°C for 3-6 hours.

[0020] In the above method, in step (4), the metal recovery is the recovery of lithium ions.

[0021] Compared with the prior art, the advantages of the present invention are:

[0022] The present invention starts with the recycling of waste lithium-ion batteries and provides a complete metal ion recovery device. The device can realize the whole process from discharge to metal ion recovery, reduces the number of manual operations, and has a simple structure and is easy to implement. In addition, the present invention can efficiently recover lithium ions. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a flow chart of a method for recovering metal ions from waste lithium-ion batteries of the present invention;

[0024] Figure 2 This is a schematic diagram of a device for recovering metal ions from waste lithium-ion batteries according to the present invention;

[0025] Figure 3 Schematic diagram of the internal structure of the screening tank;

[0026] Figure 4 Schematic diagram of the external structure of the screening tank;

[0027] Figure 5 This is a schematic diagram of the interior of the screening tank from a top-down perspective;

[0028] Figure 6 Schematic diagram of the internal structure of the adsorption and desorption tank;

[0029] Figure 7 a cross-sectional view of a container for placing adsorbent;

[0030] Figure 8 Schematic diagram of the structure of the ultrasonic column;

[0031] Figure 9 It is a structural diagram of the placement rack and ultrasonic column;

[0032] Figure 10 A schematic diagram of the container for placing the adsorbent from an upward angle;

[0033] Figure 11 is a cross-sectional view of the spoiler;

[0034] Figure 12 A top view of the spoiler.

[0035] The components in the figure are as follows: discharge storage tank 1, crushing tank 2, conveyor belt 3, screening tank 4, vibrating conveyor belt 4.1, fan 4.2, collection tank 4.3, drying box 5, organic matter removal tank 6, alkali liquid tank 7, adsorption and desorption tank 8, adsorbent storage container 8.1, adsorbent storage container channel 8.2, ultrasonic column 8.3, storage rack 8.4, spoiler 8.5, liquid outflow outlet 9, pH adjustment tank 10. DETAILED DESCRIPTION

[0036] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0037] Example 1

[0038] like Figure 2As shown, a device for recovering metal ions from waste lithium-ion batteries includes a discharge storage tank 1, a crushing tank 2, a screening tank 4, a drying box 5, an organic matter removal tank 6, an alkali liquid tank 7, a pH adjustment tank 10 and an adsorption and desorption tank 8; a conveyor belt 3 is provided between the bottom outlet of the discharge storage tank 1 and the top inlet of the crushing tank 2; a conveyor belt 3 is provided between the bottom outlet of the crushing tank 2 and the top inlet of the screening tank 4; a metal shell recovery outlet and an electrode material outlet are provided at the bottom of the screening tank 4; the electrode material outlet is connected to the drying box 5, a conveyor belt 3 is provided between the bottom outlet of the drying box 5 and the top inlet of the organic matter removal tank 6, a conveyor belt 3 is provided between the bottom outlet of the organic matter removal tank 6 and the top inlet of the alkali liquid tank 7, the liquid outlet of the alkali liquid tank 7 is connected to the pH adjustment tank 10, and the bottom outlet of the pH adjustment tank 10 is connected to the bottom of the adsorption and desorption tank 8. The bottoms of the discharge storage tank 1 , the crushing tank 2 , the organic matter removal tank 6 and the alkali liquid tank 7 are all provided with liquid outflow outlets 9 , and valves are provided on the pipelines of the liquid outflow outlets 9 .

[0039] In this embodiment, the liquid inlet at the bottom of the adsorption and desorption tank 8 is connected to the pH adjustment tank 10 and the external desorption liquid, such as Figure 2 As shown, valve A and valve B respectively control the entry of two liquids.

[0040] like Figures 3 to 5 As shown, in this embodiment, the screening trough 4 consists of a screening trough body, a vibrating conveyor belt 4.1, a fan 4.2, and a collecting trough 4.3; a fan 4.2 is provided on one side of the screening trough body, and more than one vibrating conveyor belt 4.1 is provided in the screening trough body, and a Z-shaped structure is formed between the vibrating conveyor belts 4.1; a collecting trough 4.3 for collecting electrode powder is provided at the bottom of the side opposite to the fan 4.2 inside the screening trough body. In this embodiment, one end of the collecting trough 4.3 is tilted downward, and the outlet of the collecting trough 4.3 is the electrode material outlet, and a metal shell outlet is provided below the vibrating conveyor belt 4.1.

[0041] like Figure 6 As shown, in this embodiment, the adsorption and desorption tank 8 has a liquid outlet and a liquid inlet at the top and bottom respectively. The adsorption and desorption tank 8 is provided with a placement rack 8.4, an adsorbent placement container 8.1, a spoiler 8.5, a placement rack 8.4 and an adsorbent placement container 8.1 from bottom to top; the adsorbent placement container 8.1 is placed on the placement rack 8.4; the adsorbent placement container 8.1 is a columnar structure made of a mesh material, and is filled with a lithium adsorbent. The mesh material allows the external solution to enter the adsorbent placement container to contact and adsorb lithium ions. Figure 8 and Figure 9As shown, an ultrasonic column 8.3 is provided on the placement rack 8.4, and an adsorbent placement container channel 8.2 is correspondingly provided on the adsorbent placement container 8.1. When the adsorbent placement container 8.1 is placed on the placement rack 8.4, the adsorbent placement container channel 8.2 is just inserted into the ultrasonic column 8.3.

[0042] The spoiler 8.5 in this embodiment is as follows Figure 11 and Figure 12 As shown, a plurality of strip-shaped spoiler columns are provided in the spoiler plate body, and the passing liquid forms turbulence in the spoiler columns.

[0043] Example 2

[0044] The preparation method of the adsorbent in the adsorbent placement container in the above-mentioned Example 1 is as follows:

[0045] (1) 5 kg of coal fly ash, 20 kg of kaolin, 7 kg of attapulgite and 8 kg of starch were mixed, the materials were mixed with 25 kg of water, ground, centrifuged, the precipitate was taken, extruded into a spherical state, and then calcined at 5 ° C for 3 h to obtain the treated filler carrier;

[0046] (2) First, take 100g of boric acid and 100g of sodium hexametaphosphate, add them to 100L of water to prepare a mixed solution of boric acid and sodium hexametaphosphate; take 1500g of AlCl3 and 700g of NaAlO2 and dissolve them in the mixed solution of boric acid and sodium hexametaphosphate (50L each), add 15kg of filler carrier to the mixed solution of AlCl3, let it stand for 5h, and then place the solution in a water bath with the water bath temperature controlled at 55℃; add the NaAlO2 mixed solution and 50L of LiCl solution (15g / L), and then slowly add ammonia solution to control the pH value at 4~5;

[0047] (3) Centrifuge at 150 rpm for 20 min and dry the precipitate;

[0048] (4) Elution was performed in deionized water for 5 h to obtain the adsorbent.

[0049] Example 3

[0050] This embodiment uses the device in Example 1 and the adsorbent in Example 2.

[0051] (1) Place the discarded batteries in a battery storage tank 1, add a saturated KCl solution to the battery storage tank 1, and soak the batteries in the saturated KCl solution for 12 hours; then, after draining the liquid, open the bottom outlet to allow the discharged batteries to enter the crushing tank 2 through the conveyor belt 3;

[0052] (2) In the crushing tank 2, after the crushing equipment crushes the battery and discharges the liquid, the bottom outlet is opened, so that the crushed battery enters the screening tank 4 through the conveyor belt 3 for screening, wherein the metal shell is screened out through the metal shell outlet for recycling; the electrode powder is screened out through the electrode material outlet and then enters the drying box 5 for drying at 200°C. The drying box 5 performs low-temperature drying and removal of the electrolyte;

[0053] (3) The dried electrode material passes through the conveyor belt 3 and enters the organic matter removal tank 6, which is a pyrolysis device. The electrode material is heated at 500°C for 3 hours in the organic matter removal tank 6 to remove organic matter, and then the bottom outlet is opened to allow the electrode material to pass through the conveyor belt 3 and enter the alkali solution tank 7.

[0054] (4) The alkali liquid tank 7 is filled with sodium hydroxide solution. After soaking for 12 hours, it enters the pH adjustment tank 10, and hydrochloric acid solution is added to form a suspension with a pH of 6-7. At this time, valve A is opened and valve B is closed. The suspension enters the adsorption desorption tank 8 to recover lithium ions. The ultrasonic power in the adsorption desorption tank 8 is 20kHz. After recovery, valve A is closed and valve B is opened to use pure water to desorb the inside of the adsorption desorption tank 8. The recovered desorption liquid is collected to achieve lithium ion recovery.

[0055] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the invention. Obviously, the embodiments described are only some embodiments of the present invention, rather than all embodiments. Based on these embodiments, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in this field can still combine, add, delete or make other adjustments to the features in the various embodiments of the present invention according to the circumstances without conflict, without making creative work, so as to obtain different other technical solutions that do not deviate from the concept of the present invention in essence, and these technical solutions also fall within the scope of protection of the present invention.

Claims

1. A device for recovering metal ions from waste lithium-ion batteries, characterized in that: The invention comprises a discharge storage tank (1), a crushing tank (2), a screening tank (4), a drying box (5), an organic matter removal tank (6), an alkali liquid tank (7), a pH adjustment tank (10) and an adsorption desorption tank (8); a conveyor belt (3) is provided between the bottom outlet of the discharge storage tank (1) and the top inlet of the crushing tank (2); a conveyor belt (3) is provided between the bottom outlet of the crushing tank (2) and the top inlet of the screening tank (4); a metal shell recovery outlet and an electrode material outlet are provided at the bottom of the screening tank (4); the electrode material outlet is connected to the drying box (5); a conveyor belt (3) is provided between the bottom outlet of the drying box (5) and the top inlet of the organic matter removal tank (6); a conveyor belt (3) is provided between the bottom outlet of the organic matter removal tank (6) and the top inlet of the alkali liquid tank (7); the liquid outlet of the alkali liquid tank (7) is connected to the pH adjustment tank (10); and the bottom outlet of the pH adjustment tank (10) is connected to the bottom of the adsorption desorption tank (8); The adsorption and desorption tank (8) is provided with a first placement rack, a first adsorbent placement container, a spoiler (8.5), a second placement rack, and a second adsorbent placement container from bottom to top; the first adsorbent placement container and the second adsorbent placement container are placed on the first placement rack and the second placement rack, respectively; the first adsorbent placement container and the second adsorbent placement container are cylindrical structures made of mesh material and are filled with lithium adsorbent; The first placement rack and the second placement rack are provided with ultrasonic columns (8.3), and the first adsorbent placement container and the second adsorbent placement container are correspondingly provided with adsorbent placement container channels (8.2). When the first adsorbent placement container and the second adsorbent placement container are placed on the first placement rack and the second placement rack, the adsorbent placement container channels (8.2) are just inserted into the ultrasonic columns (8.3).

2. The device for recovering metal ions from waste lithium-ion batteries according to claim 1, wherein: The screening trough (4) consists of a screening trough body, a vibrating conveyor belt (4.1), a fan (4.2), and a collecting trough (4.3); a fan (4.2) is provided on one side of the screening trough body, and one or more vibrating conveyor belts (4.1) are provided in the screening trough body, with a Z-shaped structure formed between the vibrating conveyor belts (4.1); a collecting trough (4.3) for collecting electrode powder is provided at the bottom of the side opposite to the fan (4.2) inside the screening trough body, the outlet of the collecting trough (4.3) is an electrode material outlet, and a metal shell outlet is provided below the vibrating conveyor belt (4.1).

3. The device for recovering metal ions from waste lithium-ion batteries according to claim 1, wherein: The adsorption and desorption tank (8) has a liquid outlet and a liquid inlet at the top and bottom, respectively.

4. The device for recovering metal ions from waste lithium-ion batteries according to claim 1, wherein: The bottoms of the discharge storage tank (1), the crushing tank (2), the organic matter removal tank (6) and the alkali liquid tank (7) are all provided with liquid outflow outlets (9), and valves are provided on the pipelines of the liquid outflow outlets (9).

5. A method for recovering metal ions from waste lithium-ion batteries using the device according to any one of claims 1 to 4, characterized in that: The steps include: (1) placing the discarded batteries in a discharge storage tank (1), adding a saturated KCl solution to the discharge storage tank (1) and performing a discharge operation; then, after the liquid is discharged, opening the bottom outlet, allowing the discharged batteries to enter the crushing tank (2) through a conveyor belt (3); the discharge operation time is 12 to 24 hours; (2) In the crushing tank (2), after the crushing equipment crushes the battery and discharges the liquid, the bottom outlet is opened, so that the crushed battery enters the screening tank (4) through the conveyor belt (3) for screening, wherein the metal shell is screened out through the metal shell outlet for recycling; the electrode powder is screened out through the electrode material outlet and then enters the drying box (5) for drying operation, wherein the drying box (5) is used to dry and remove the electrolyte at low temperature; (3) The dried electrode material passes through the conveyor belt (3) and enters the organic matter removal tank (6), which is a pyrolysis device; after the electrode material is heated in the organic matter removal tank (6) to remove organic matter, the bottom outlet is opened, allowing the electrode material to pass through the conveyor belt (3) and enter the alkali solution tank (7); (4) The alkali liquid tank (7) is filled with sodium hydroxide solution. After soaking for 12 to 20 hours, the soaking liquid enters the pH adjustment tank, and an acidic solution is added to form a suspension until the pH is 6 to 7. The suspension enters the adsorption desorption tank (8) to recover the metal. After recovery, pure water is used to desorb the inside of the adsorption desorption tank (8); the ultrasonic power in the adsorption desorption tank (8) is 20 to 90 kHz; the metal ions are lithium ions.

6. The method according to claim 5, characterized in that In step (2), the drying temperature is 200-300°C.

7. The method according to claim 5, characterized in that In step (3), the pyrolysis is as follows: the electrode material is heated at 300-500°C for 3-6 hours.

8. The method according to claim 5, characterized in that In step (4), the recovered metal is the recovery of lithium ions.

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