Method for separating and recovering valuable metals from ternary lithium batteries

Abstract

The present application relates to lithium battery material recycling technical field, specifically relates to a kind of method for separating and recycling valuable metal of ternary lithium battery.The method will waste ternary lithium battery be discharged after stripping the metal shell of battery, battery crushing is carried out under inert atmosphere environment, the fragment after crushing is calcined under inert atmosphere, iron class substance is separated and recovered by magnetic separation after cooling fragment, copper, aluminium class substance is separated and recovered by electrostatic separator, nickel, cobalt, manganese, lithium element is dissolved by adding acid solution, saturated sodium carbonate solution is added to control the pH value of solution, stirring is started to heat reaction, the coprecipitate of nickel, cobalt, manganese is precipitated, and is recovered by filtration;Saturated sodium carbonate solution is added to the filtrate, white precipitate is lithium carbonate, and lithium element is recovered.The method realizes the effective recovery and reuse of valuable metal components in the positive electrode material of waste ternary lithium ion battery, and has important significance.

Description

Technical Field

[0001] This invention relates to the field of lithium battery material recycling technology, and in particular to a method for separating and recycling valuable metals from ternary lithium batteries. Background Technology

[0002] Ternary lithium batteries are lithium-ion rechargeable batteries that use nickel, cobalt, and manganese transition metal oxides as cathode materials. They combine the excellent cycle performance of lithium cobalt oxide, the high specific capacity of lithium nickel oxide, and the high safety and low cost of lithium manganese oxide. They utilize molecular-level mixing, doping, coating, and surface modification methods to synthesize composite lithium-intercalated oxides with synergistic effects of multiple elements such as nickel, cobalt, and manganese. They are currently a widely researched and applied type of lithium-ion rechargeable battery. From a materials perspective, the "ternary" in ternary lithium batteries refers to polymers containing three metal elements—nickel, cobalt, and manganese or aluminum—which serve as the cathode in ternary lithium batteries. All three are indispensable; each element plays a crucial role, and the characteristics of each element also constrain battery performance. These metal elements are the focus of recycling when using spent ternary lithium batteries.

[0003] A lithium battery discharge method during the lithium battery recycling and dismantling process (patent publication number: CN112331947A) includes: generating plasma using a plasma discharge method to form a discharge conduction channel, and conducting the positive and negative electrodes of the lithium battery through the discharge conduction channel to achieve lithium battery discharge; this method can fully and safely release the energy stored in the lithium battery, meeting the requirements of green industrialized mass production. It not only has many advantages such as advanced technology, high level of intelligence, low pollution, and low energy consumption, but also conforms to the current trend of lithium battery development and meets the overall intelligent development needs of society.

[0004] The high-efficiency separation and recycling process for lithium batteries (patent publication number: CN111653845B) includes: Step 1, classifying the collected waste lithium batteries by shape; Step 2, removing the lithium battery casing using a lithium battery casing separation device; Step 3, collecting casing fragments and battery cores that fall from the lithium battery casing separation device using a collector; Step 4, filtering the casing fragments and battery cores using a vibrating screen device to complete the separation and recycling of the casing material and battery cores. This invention first classifies the collected waste lithium batteries by shape, separating cylindrical lithium batteries and performing specialized separation on them to improve separation and recycling efficiency. Secondly, the lithium battery casing separation device vertically and obliquely cuts the lithium battery casing, forming sheet-like structures that facilitate the separation of the lithium battery casing and battery cores, reducing the difficulty of subsequent recycling and improving separation and recycling efficiency.

[0005] Effective recycling and reuse of valuable metal components in spent ternary lithium-ion battery cathode materials can promote the stable development of electrochemical energy storage and new energy vehicle industries, and realize energy recycling, which is of great significance.

[0006] Based on this, the present invention proposes a method for separating and recovering valuable metals from ternary lithium batteries. Summary of the Invention

[0007] In order to overcome the shortcomings of the prior art, this invention provides a method for separating and recycling valuable metals from ternary lithium batteries, thereby realizing the recycling of metal resources such as lithium, cobalt, nickel, and manganese.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] A method for separating and recovering valuable metals from ternary lithium batteries, characterized by comprising the following steps:

[0010] Step 1: According to the mass fraction, after discharging the waste ternary lithium batteries, peel off the metal casing of the batteries, crush the batteries in an inert atmosphere, and calcine the crushed fragments in an inert atmosphere for 1-2 hours, and then cool them naturally.

[0011] Step 2: After cooling, the fragments are separated by magnetic separation to recover iron-containing materials, and by electrostatic separation to recover copper-containing materials. 100-200 parts of the residual powder are weighed and added to 300-600 parts of acid solution to dissolve. After stirring evenly, 30-75 parts of reducing agent and 20-45 parts of amine oxime ligand are added. The mixture is heated to react and dissolve nickel, cobalt, manganese and lithium elements.

[0012] Step 3: Add ammonia to the solution obtained in Step 2 to control the pH value of the solution to 10-11, turn on the stirrer, heat the reaction for 90-200 minutes, and precipitate nickel, cobalt and manganese co-precipitate, which is then filtered and recovered.

[0013] Step 4: Add 500-900 parts of saturated sodium carbonate solution to the filtrate obtained after filtration in Step 3, stir and react at room temperature for 30-60 minutes to obtain a white precipitate of lithium carbonate, and recover the lithium element.

[0014] In the above scheme, in step one, the waste ternary lithium battery is discharged to below 0.5V.

[0015] In the above scheme, the inert atmosphere in step one is selected from at least one of nitrogen, helium or argon.

[0016] In the above scheme, the calcination temperature in step one is 450-650℃.

[0017] In the above scheme, the acid solution in step two is selected from one or more mixtures of hydrochloric acid solution, sulfuric acid solution, and acetic acid solution, and the concentration of the acid solution is 10-30%.

[0018] In the above scheme, the reducing agent in step two is selected from at least one of sodium sulfite, sodium nitrite, and ferrous sulfate.

[0019] In the above scheme, the reaction temperature in step two is controlled at 50-80℃, and the reaction time is 1-3h.

[0020] In the above scheme, the preparation method of the ametoxime ligand in step two is as follows:

[0021] According to the mass fractions, add 16-32 parts of 1,4-dimercaptooximebenzene, 0.4-3.5 parts of (4-pentenyl)triphenylphosphine bromide, and 22-45 parts of sodium dimercaptosuccinate to a stirred tank. Then add 200-300 parts of N-methylpyrrolidone and 2-5 parts of diethylamine to the stirred tank, purge with nitrogen, and react at 60-70°C for 30-60 minutes. Then remove N-methylpyrrolidone by distillation to obtain the megamicroxime ligand.

[0022] In the above scheme, the concentration of ammonia water in step three is 1-5 mol / L.

[0023] In the above scheme, the reaction temperature in step three is 40-60℃.

[0024] The beneficial effects achieved by the present invention using the above technical solution are as follows: This solution:

[0025] Ligands containing phenylphosphine bromide and a metallo-oxime groups can improve the reduction and recovery of nickel, cobalt, and manganese. These ligands may form complexes with metal ions through coordination interactions, thereby promoting the reduction and recovery of metal elements. The specific reaction mechanism involves the coordination of the phosphine bromide and metallo-oxime groups in the ligand with the metal ions to form stable complexes. These complexes act as catalysts during the reduction process, lowering the reduction energy of the metal ions and improving the reduction and recovery efficiency. Furthermore, the structure and functional groups of the ligands may also affect the selective reduction and recovery of metal ions. The technical effects of this ligand-derived technology include increased metal element recovery rate, improved recovery selectivity, reduced reduction energy, and reduced side reactions. Overall, this ligand improves the recovery efficiency by catalyzing the reduction and recovery process of metal elements through coordination interactions. Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with embodiments. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0028] Example 1

[0029] A method for separating and recovering valuable metals from ternary lithium batteries, characterized by comprising the following steps:

[0030] Step 1: After discharging the waste ternary lithium battery, peel off the metal casing of the battery, crush the battery in an inert atmosphere, calcine the crushed fragments in an inert atmosphere for 1 hour, and then cool them naturally.

[0031] Step 2: After cooling, the fragments are separated and iron-containing materials are recovered by magnetic separation, and copper and aluminum-containing materials are separated and recovered by electrostatic separator. 100g of residual powder is weighed and added to 300g of acid solution to dissolve. After stirring evenly, 30g of reducing agent and 20g of amine oxime ligand are added. The mixture is heated to react and dissolve nickel, cobalt, manganese and lithium elements.

[0032] Step 3: Add ammonia to the solution obtained in Step 2 to control the pH value of the solution to 10, turn on the stir, heat and react for 90 minutes to precipitate nickel, cobalt and manganese co-precipitate, and filter and recover;

[0033] Step 4: Add 500g of saturated sodium carbonate solution to the filtrate obtained after filtration in Step 3, stir and react at room temperature for 30 minutes to obtain a white precipitate of lithium carbonate, and recover the lithium element.

[0034] In step one, the waste ternary lithium battery is discharged to below 0.5V.

[0035] In step one, the inert atmosphere is selected from nitrogen.

[0036] The calcination temperature in step one is 450℃.

[0037] In step two, the acid solution is selected from hydrochloric acid solution, and the acid concentration is 10%.

[0038] In step two, the reducing agent is selected from sodium sulfite.

[0039] In step two, the reaction temperature is controlled at 50°C and the reaction time is 1 hour.

[0040] The preparation method of the amine oxime ligand in step two is as follows:

[0041] 16g of 1,4-dimercaptooximebenzene, 0.4g of (4-pentenyl)triphenylphosphine bromide, and 22g of sodium dimercaptosuccinate were added to a stirred tank. Then, 200g of N-methylpyrrolidone and 2g of diethylamine were added to the stirred tank, nitrogen gas was introduced, and the reaction was carried out at 60°C for 30 minutes. The N-methylpyrrolidone was then removed by distillation to obtain the megamioxime ligand.

[0042] The concentration of ammonia in step three is 1 mol / L.

[0043] The reaction temperature in step three is 40°C.

[0044] The metal content in the residual powder after battery disassembly and calcination was measured by ICP, and the metal content in the recycled materials was analyzed and calculated to obtain the following results: the yields of nickel, cobalt, manganese and lithium in this example are 89.4%, 99.5%, 93.2% and 98.9%, respectively.

[0045] Example 2

[0046] A method for separating and recovering valuable metals from ternary lithium batteries, characterized by comprising the following steps:

[0047] Step 1: After discharging the waste ternary lithium battery, peel off the metal casing of the battery, crush the battery in an inert atmosphere, calcine the crushed fragments in an inert atmosphere for 1 hour, and then cool them naturally.

[0048] Step 2: After cooling, the fragments are separated and iron-containing materials are recovered by magnetic separation, and copper and aluminum-containing materials are separated and recovered by electrostatic separator. 150g of residual powder is weighed and added to 400g of acid solution to dissolve. After stirring evenly, 45g of reducing agent and 28g of amine oxime ligand are added. The mixture is heated to react and dissolve nickel, cobalt, manganese and lithium elements.

[0049] Step 3: Add ammonia to the solution obtained in Step 2 to control the pH value of the solution to 10, turn on the stir, heat the reaction for 135 minutes, and precipitate nickel, cobalt and manganese co-precipitate, which is then filtered and recovered.

[0050] Step 4: Add 650g of saturated sodium carbonate solution to the filtrate obtained after filtration in Step 3, stir and react at room temperature for 40 minutes to obtain a white precipitate of lithium carbonate, and recover the lithium element.

[0051] In step one, the waste ternary lithium battery is discharged to below 0.5V.

[0052] In step one, the inert atmosphere is selected from helium.

[0053] The calcination temperature in step one is 550℃.

[0054] In step two, the acid solution is selected from sulfuric acid solution, and the concentration of the acid solution is 20%.

[0055] In step two, the reducing agent is selected from sodium nitrite.

[0056] In step two, the reaction temperature is controlled at 65℃ and the reaction time is 2 hours.

[0057] The preparation method of the amine oxime ligand in step two is as follows:

[0058] 24g of 1,4-dimercaptooximebenzene, 1.8g of (4-pentenyl)triphenylphosphine bromide, and 30g of sodium dimercaptosuccinate were added to a stirred tank. Then, 250g of N-methylpyrrolidone and 3.5g of diethylamine were added to the stirred tank, nitrogen gas was introduced, and the reaction was carried out at 65°C for 40 minutes. The N-methylpyrrolidone was then removed by distillation to obtain the megamioxime ligand.

[0059] The concentration of ammonia in step three is 2.5 mol / L.

[0060] The reaction temperature in step three is 50°C.

[0061] The metal content in the residual powder after battery disassembly and calcination was measured by ICP, and the metal content in the recycled materials was analyzed and calculated to obtain the following results: the yields of nickel, cobalt, manganese and lithium in this example are 91.2%, 99.7%, 94.8% and 99.3%, respectively.

[0062] Example 3

[0063] A method for separating and recovering valuable metals from ternary lithium batteries, characterized by comprising the following steps:

[0064] Step 1: After discharging the waste ternary lithium batteries, peel off the metal casing of the batteries, crush the batteries in an inert atmosphere, and calcine the crushed fragments in an inert atmosphere for 2 hours, followed by natural cooling.

[0065] Step 2: After cooling, the fragments are separated and iron-containing materials are recovered by magnetic separation, and copper and aluminum-containing materials are separated and recovered by electrostatic separator. 150g of residual powder is weighed and added to 500g of acid solution to dissolve. After stirring evenly, 60g of reducing agent and 35g of amine oxime ligand are added. The mixture is heated to react and dissolve nickel, cobalt, manganese and lithium elements.

[0066] Step 3: Add ammonia to the solution obtained in Step 2 to control the pH value of the solution to 11, turn on the stir, heat the reaction for 180 minutes, and precipitate nickel, cobalt and manganese co-precipitate, which is then filtered and recovered.

[0067] Step 4: Add 800g of saturated sodium carbonate solution to the filtrate obtained after filtration in Step 3, stir and react at room temperature for 50 minutes to obtain a white precipitate of lithium carbonate, and recover the lithium element.

[0068] In step one, the waste ternary lithium battery is discharged to below 0.5V.

[0069] In step one, the inert atmosphere is selected from argon.

[0070] The calcination temperature in step one is 600℃.

[0071] In step two, the acid solution is selected from acetic acid solution, and the concentration of the acid solution is 20%.

[0072] In step two, the reducing agent is selected from ferrous sulfate.

[0073] In step two, the reaction temperature is controlled at 70℃ and the reaction time is 2 hours.

[0074] The preparation method of the amine oxime ligand in step two is as follows:

[0075] 28g of 1,4-dimercaptooximebenzene, 2.6g of (4-pentenyl)triphenylphosphine bromide, and 40g of sodium dimercaptosuccinate were added to a stirred tank. Then, 250g of N-methylpyrrolidone and 4g of diethylamine were added to the stirred tank, nitrogen gas was introduced, and the reaction was carried out at 65°C for 50 minutes. The N-methylpyrrolidone was then removed by distillation to obtain the megamicroxime ligand.

[0076] The concentration of ammonia in step three is 4 mol / L.

[0077] The reaction temperature in step three is 50°C.

[0078] The metal content in the residual powder after battery disassembly and calcination was measured by ICP, and the metal content in the recycled materials was analyzed and calculated to obtain the following results: the yields of nickel, cobalt, manganese and lithium in this example are 91.4%, 99.7%, 95.1% and 99.4%, respectively.

[0079] Example 4

[0080] A method for separating and recovering valuable metals from ternary lithium batteries, characterized by comprising the following steps:

[0081] Step 1: After discharging the waste ternary lithium batteries, peel off the metal casing of the batteries, crush the batteries in an inert atmosphere, and calcine the crushed fragments in an inert atmosphere for 2 hours, followed by natural cooling.

[0082] Step 2: After cooling, the fragments are separated and iron-containing materials are recovered by magnetic separation, and copper and aluminum-containing materials are separated and recovered by electrostatic separator. 200g of residual powder is weighed and added to 600g of acid solution to dissolve. After stirring evenly, 75g of reducing agent and 45g of amine oxime ligand are added. The mixture is heated to react and dissolve nickel, cobalt, manganese and lithium elements.

[0083] Step 3: Add ammonia to the solution obtained in Step 2 to control the pH value of the solution to 11, turn on the stir, heat the reaction for 200 minutes, and precipitate nickel, cobalt and manganese co-precipitate, which is then filtered and recovered.

[0084] Step 4: Add 900g of saturated sodium carbonate solution to the filtrate obtained after filtration in Step 3, stir and react at room temperature for 60 minutes to obtain a white precipitate of lithium carbonate, and recover the lithium element.

[0085] In step one, the waste ternary lithium battery is discharged to below 0.5V.

[0086] In step one, the inert atmosphere is selected from nitrogen.

[0087] The calcination temperature in step one is 650℃.

[0088] In step two, the acid solution is selected from acetic acid solution, and the acid concentration is 30%.

[0089] In step two, the reducing agent is selected from sodium sulfite.

[0090] In step two, the reaction temperature is controlled at 80℃ and the reaction time is 3 hours.

[0091] The preparation method of the amine oxime ligand in step two is as follows:

[0092] 32g of 1,4-dimercaptooximebenzene, 3.5g of (4-pentenyl)triphenylphosphine bromide, and 45g of sodium dimercaptosuccinate were added to a stirred tank. Then, 300g of N-methylpyrrolidone and 5g of diethylamine were added to the stirred tank, nitrogen gas was introduced, and the reaction was carried out at 70°C for 60 minutes. The N-methylpyrrolidone was then removed by distillation to obtain the megamicromime ligand.

[0093] The concentration of ammonia in step three is 5 mol / L.

[0094] The reaction temperature in step three is 60°C.

[0095] The metal content in the residual powder after battery disassembly and calcination was measured by ICP, and the metal content in the recycled materials was analyzed and calculated to obtain the following results: the yields of nickel, cobalt, manganese and lithium in this example are 91.6%, 99.8%, 95.5% and 99.6%, respectively.

[0096] Comparative Example 1

[0097] In this example, no amylopyridine oxime ligand is added in step two; the remaining steps are the same as in Example 1.

[0098] The metal contents in the residual powder after battery disassembly and calcination were measured by ICP, and the metal contents in the recycled materials were analyzed and calculated to obtain the following results: the yields of nickel, cobalt, manganese and lithium in this example are 82.3%, 97.7%, 88.5% and 98.4%, respectively.

[0099] Comparative Example 2

[0100] In this example, 1,4-di-di-mercaptooximebenzene is not added during the preparation of the mesamidooxime ligand; the remaining steps are the same as in Example 1.

[0101] The metal content in the residual powder after battery disassembly and calcination was measured by ICP, and the metal content in the recycled materials was analyzed and calculated to obtain the following results: the yields of nickel, cobalt, manganese and lithium in this example are 84.4%, 98.1%, 89.5% and 98.5%, respectively.

[0102] The present invention has been described above through specific embodiments and examples. However, these descriptions are merely illustrative and should not be construed as limiting the scope of protection of the present invention. Without departing from the spirit and scope of the present invention, those skilled in the art can make various improvements, modifications, or equivalent substitutions to the technical solutions and implementation methods of the present invention, and all such modifications and substitutions should fall within the scope of protection of the present invention.

Claims

1. A method for separating and recovering valuable metals from ternary lithium batteries, characterized in that, Includes the following steps: Step 1: According to the mass fraction, after discharging the waste ternary lithium batteries, peel off the metal casing of the batteries, crush the batteries in an inert atmosphere, and calcine the crushed fragments in an inert atmosphere for 1-2 hours, and then cool them naturally. Step 2: After cooling, the fragments are separated by magnetic separation to recover iron-containing materials, and by electrostatic separation to recover copper-containing materials. 100-200 parts of the residual powder are weighed and added to 300-600 parts of acid solution to dissolve. After stirring evenly, 30-75 parts of reducing agent and 20-45 parts of amine oxime ligand are added. The mixture is heated to react and dissolve nickel, cobalt, manganese and lithium elements. Step 3: Add ammonia to the solution obtained in Step 2 to control the pH value of the solution to 10-11, turn on the stirrer, heat the reaction for 90-200 minutes, and precipitate nickel, cobalt and manganese co-precipitate, which is then filtered and recovered. Step 4: Add 500-900 parts of saturated sodium carbonate solution to the filtrate obtained after filtration in Step 3, stir and react at room temperature for 30-60 minutes to obtain a white precipitate of lithium carbonate, and recover the lithium element; The preparation method of the amine oxime ligand in step two is as follows: According to the mass fractions, add 16-32 parts of 1,4-dimercaptooximebenzene, 0.4-3.5 parts of (4-pentenyl)triphenylphosphine bromide, and 22-45 parts of sodium dimercaptosuccinate to a stirred tank. Then add 200-300 parts of N-methylpyrrolidone and 2-5 parts of diethylamine to the stirred tank, purge with nitrogen, and react at 60-70°C for 30-60 minutes. Then remove N-methylpyrrolidone by distillation to obtain the megamicroxime ligand.

2. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, In step one, the waste ternary lithium battery is discharged to below 0.5V.

3. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, In step one, the inert atmosphere is selected from at least one of nitrogen, helium, or argon.

4. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, The calcination temperature in step one is 450-650℃.

5. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, In step two, the acid solution is selected from one or more mixtures of hydrochloric acid solution, sulfuric acid solution, and acetic acid solution, and the concentration of the acid solution is 10-30%.

6. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, In step two, the reducing agent is selected from at least one of sodium sulfite, sodium nitrite, and ferrous sulfate.

7. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, In step two, the reaction temperature is controlled at 50-80℃ and the reaction time is 1-3 hours.

8. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, The concentration of ammonia in step three is 1-5 mol / L.

9. The method for separating and recovering valuable metals from ternary lithium batteries according to claim 1, characterized in that, The reaction temperature in step three is 40-60℃.