A whole resource recycling process for waste lithium batteries

Abstract

The application discloses a kind of waste lithium battery full resource recovery process, belong to waste battery recovery process field, including the following steps: waste lithium phosphate black powder beating-up, then add acid, reaction, filtration, obtain first filtrate;First filtrate carries out reduction reaction, filtration, obtain second filtrate;Remove aluminium ion in second filtrate, filtration, obtain third filtrate;Remove titanium ion of third filtrate, filtration, obtain fourth filtrate;Adjust the iron phosphorus ratio of fourth filtrate, drop hydroperoxide and lye, after reaction filtration, obtain iron phosphate and fifth filtrate;Iron phosphate is carried out multistage beating-up, washing, then into flash column, again calcination, obtain qualified iron phosphate;Adjust the pH of fifth filtrate, filtration, after filtrate calcium removal, concentrate, obtain lithium salt solution;Lithium salt solution is dropped into phosphorus source solution, after reaction filtration, obtain lithium phosphate;Lithium phosphate is beaten-up, washing, aging, stir wash after into flash column, remove magnetism and obtain qualified lithium phosphate.The present application is widely used.

Description

Technical Field

[0001] This invention belongs to the field of waste lithium battery recycling technology, and relates to a full-resource recycling process for waste lithium batteries. Background Technology

[0002] In recent years, with the increasing number of retired electric vehicles, a large amount of waste lithium batteries have also been generated, posing a huge challenge to environmental protection.

[0003] The existing recycling process for waste lithium batteries mainly uses pH-adjusted precipitation to separate lithium phosphate, iron phosphate, and other impurity metals. Although the process is simple and can produce high-purity iron phosphate and lithium phosphate, it has high requirements for the raw materials of waste lithium batteries, especially the aluminum content. Otherwise, it will be difficult to separate aluminum impurities from the iron phosphate slag, which will easily lead to excessive impurities in the subsequently synthesized iron phosphate. Summary of the Invention

[0004] The purpose of this invention is to provide a process for the full-resource recycling of waste lithium batteries, which solves the above-mentioned problems existing in the current waste lithium battery resource recycling processes.

[0005] The technical solution adopted in this invention is as follows:

[0006] A process for the complete recycling of waste lithium batteries includes the following steps:

[0007] S1, Recycling Ferric Phosphate

[0008] S1.1. Pulverize the waste lithium iron phosphate black powder at a solid-liquid ratio of 1:4-6, then add acid solution to adjust the pH to 1-3, heat and react for 3-6 hours, filter to obtain the first filtrate;

[0009] S1.2 Add a reducing agent to the acidic first filtrate to carry out a reduction reaction, reducing the copper ions and ferric ions in the first filtrate, filter, and obtain the second filtrate;

[0010] S1.3 Add a precipitant to the second filtrate to remove aluminum ions, filter, and obtain the third filtrate;

[0011] S1.4 Adjust the pH of the third filtrate to 2-3, react to precipitate titanium ions, filter, and obtain the fourth filtrate;

[0012] S1.5 Add phosphoric acid to the fourth filtrate to adjust the iron-to-phosphorus ratio to 1:1.01-1.2. Then, hydrogen peroxide and alkaline solution are added dropwise simultaneously. The addition time of hydrogen peroxide and alkaline solution is 1-2 hours. The temperature is controlled at 40-60℃ during the addition process. After the addition is completed, the reaction continues. After the reaction is completed, filter to obtain the fifth filter residue and the fifth filtrate. The fifth filter residue is iron phosphate.

[0013] S1.6 After multi-stage pulping and washing of ferric phosphate, the washed ferric phosphate is passed into a flash evaporation tower to remove 95% of the total free water; then the ferric phosphate is calcined in a rotary kiln to obtain qualified ferric phosphate.

[0014] S2, Recycling Lithium Phosphate

[0015] S2.1 Adjust the pH of the fifth filtrate to 4-6, react at 30-55℃, then adjust the pH to 10-12, filter, pass the filtrate through resin to remove calcium, then pass it through a nanofiltration membrane and MVR for concentration to obtain a lithium salt solution with a lithium ion concentration of 12-18 g / L.

[0016] S2.2 Prepare a phosphorus source solution with a phosphorus concentration of 0.7-1.2 mol / L. First, add the phosphorus source solution to the synthesis vessel, and then add the lithium salt solution dropwise to the synthesis vessel. The dropwise addition time is 60-150 min, and the dropwise addition temperature is 40-70℃. After the dropwise addition is completed, continue the reaction for 30-90 min and then filter to obtain lithium phosphate.

[0017] S2.3. The synthesized lithium phosphate is pulped, washed, aged, and stirred before being passed into a flash evaporation tower to remove moisture and then demagnetized to obtain qualified lithium phosphate.

[0018] This application addresses the issue of high impurity content requirements in traditional recycling methods for waste lithium iron phosphate black powder. By first removing impurities in stages and then recovering iron phosphate and lithium phosphate, it can process waste lithium iron phosphate black powder with high aluminum and titanium content, thus solving the problem of gradually increasing aluminum, titanium and other impurities in waste lithium iron phosphate black powder on the current market.

[0019] Furthermore, the multi-stage pulping in step S1.6 includes the following specific steps:

[0020] First stage pulping: Pulping ferric phosphate at a solid-liquid ratio of 1:6-12, heating to 55-80℃, stirring and washing for 50-60 minutes, filtering, and then the ferric phosphate enters the second stage pulping;

[0021] Second stage pulping: The ferric phosphate obtained after the first stage pulping and filtration is pulped at a solid-liquid ratio of 1:3-7. Phosphoric acid of 4-10% of the mass of ferric phosphate is added, the temperature is raised to 85-90℃, and the reaction continues for 30-90 minutes until the ferric phosphate turns white. After filtration, the ferric phosphate enters the third stage pulping.

[0022] Third-stage pulping: The ferric phosphate obtained after the second-stage pulping and filtration is pulped at a ratio of 1:6-7, heated to 40-55℃, stirred and washed for 20-45 minutes, and then filtered to obtain multi-stage pulped ferric phosphate.

[0023] Further, the specific steps of pulping, washing, aging, and stirring the synthesized lithium phosphate in step S2.3 are as follows: The synthesized lithium phosphate is pulped at a solid-liquid ratio of 1:11-14, stirred and washed at 45-80℃ for 35-50 minutes, and then filtered. The stirred and washed lithium phosphate is pulped again at a solid-liquid ratio of 1:9-11, and phosphoric acid is added at a ratio of 4.12-7.5% of the mass of lithium phosphate. The temperature is raised to 92-100℃, aged for 45-85 minutes, and then filtered. Subsequently, the aged lithium phosphate is stirred and washed at a solid-liquid ratio of 1:10-15 for 20-35 minutes at a temperature of 40-50℃. After filtration, the lithium phosphate is passed into a flash evaporation tower.

[0024] Furthermore, based on the lithium ion content in the lithium salt solution, the phosphorus excess coefficient in the phosphorus source solution added in step S2.2 is 1.03-1.2.

[0025] Furthermore, the amount of hydrogen peroxide used in step S1.5 is 1.1-1.5 times the theoretical amount of ferrous ions in the fourth filtrate.

[0026] Furthermore, the reducing agent in step S1.2 is a two-component reducing agent, comprising component A and component B; component A is a composite of silica-based copper ion-imprinted polymer loaded with nano-zero valent iron; and component B is sustained-release ascorbic acid microspheres.

[0027] In step S1.2, the molar ratio of nano-zero valent iron in component A to copper ions in the first filtrate is 1.2:1;

[0028] In step S1.2, the molar ratio of ascorbic acid in component B to ferric ions in the first filtrate is 1.2:1.

[0029] In this application, if the copper ions in the first step are not completely reduced or the ferric ions are not reduced to ferrous ions, it will interfere with the removal of aluminum ions in the second step, causing competitive precipitation of aluminum ions and increasing the amount of precipitant used. The precipitation conditions and results are difficult to control. For waste lithium iron phosphate black powder, the concentration of copper ions is not very high. As the reduction reaction proceeds and ferric ions compete with the reducing agent, the removal rate of copper ions will decrease. Therefore, this application designs a two-component reducing agent for the recovery process of first removing impurities and then recovering iron phosphate and lithium phosphate. Component A can specifically and efficiently adsorb copper ions, achieving the enrichment of copper ions and separating copper ions and ferric ions in the solution. The enriched copper ions are reduced by iron, effectively improving the removal rate of copper ions. Ferric ions are reduced by ascorbic acid. To avoid the ineffective consumption of ascorbic acid, this application uses a slow-release type of ascorbic acid. In this application, both component A and component B are solid substances that will not disintegrate in the solution. After the reduction reaction is completed, component A and component B can be removed by the filtration process without introducing a large amount of other components into the solution, thus avoiding increasing the difficulty of subsequent solution processing.

[0030] Furthermore, the precipitant in S1.3 is at least one of oxalic acid, sodium fluoride, and sodium oxalate.

[0031] Furthermore, the reducing agent is prepared by the following method:

[0032] Preparation of component A:

[0033] A1. 100 parts by weight of silica gel were refluxed in 1M nitric acid solution at 80°C for 2 hours, washed, dried and dispersed in toluene, 15 parts by weight of 3-mercaptopropyltrimethoxysilane were added, and the mixture was refluxed at 110°C for 12 hours under nitrogen protection. After the reaction, the mixture was filtered, washed and dried to obtain mercapto-modified silica gel.

[0034] A2. Thiolized silica gel was added to a copper ion solution and adsorbed until saturated. Then, it was mixed with methacrylic acid monomer, BPO initiator, and ethylene glycol dimethacrylate crosslinking agent, and polymerized at 60-70℃. After the reaction, EDTA was used as an eluent, and the mixture was dried to obtain a silica gel-based copper ion imprinted polymer. The amount of methacrylic acid monomer was 5% of the mass of the thiolated silica gel, the amount of BPO initiator was 0.3% of the mass of the thiolated silica gel, and the amount of ethylene glycol dimethacrylate crosslinking agent was 15% of the mass of the thiolated silica gel.

[0035] A3. Dissolve 50 parts by weight of FeSO4·7H2O in 400 parts by weight of deionized water, stir evenly, add silica-based copper ion imprinted polymer, stir at 40°C for 4 hours, and then slowly add a reducing solution containing 18 parts by weight of sodium borohydride under nitrogen protection. React for 1 hour, filter, wash, and dry to obtain component A.

[0036] Preparation of component B:

[0037] B1. Dissolve 4 parts by weight of sodium alginate and 20 parts by weight of ascorbic acid in 100 parts by weight of deionized water, stir evenly to obtain a mixture, then add 2 parts by weight of calcium carbonate powder to the mixture, stir evenly to form a suspension.

[0038] B2. Gradually add the suspension dropwise to the calcium chloride solution. After the addition is complete, stir the reaction for 30 minutes, filter, wash, and dry to obtain component B.

[0039] Furthermore, in S1.6, the inlet air temperature of the flash tower is controlled within 500℃, the outlet temperature is controlled between 100-150℃, and the mixing temperature is 120-160℃.

[0040] In step S2.3, the inlet air temperature of the flash tower is controlled within 350℃, the outlet temperature is controlled between 110-145℃, and the mixing temperature is between 120-150℃.

[0041] Further, the alkaline solution in S1.5 is at least one of a sodium carbonate solution with a mass fraction of 10-30%, a sodium hydroxide solution with a mass fraction of 10-20%, and ammonia water.

[0042] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0043] 1. The present invention provides a process for the full resource recycling of waste lithium batteries. This process first removes impurities in stages and then recycles iron phosphate and lithium phosphate, replacing the existing process that only separates iron phosphate, lithium phosphate and impurity metal ions through pH precipitation. It can process waste lithium iron phosphate black powder with high content of aluminum, titanium and other materials. In the process of recycling iron and lithium, multiple metal ions are removed in a distributed manner. The removed metals can be recycled and reused, thus realizing the full resource recycling of waste lithium batteries.

[0044] 2. In order to improve the impurity removal rate, the present invention designs a reducing agent suitable for this application, which efficiently reduces copper ions and ferric ions in the first step, which not only improves the removal rate of copper ions, but also facilitates the subsequent removal of aluminum ions, etc. The reducing agent has a solid two-component core component, which is easy to remove after use under efficient reduction conditions and will not introduce a large number of other impurity components.

[0045] 3. This invention has low requirements for the quality of raw materials from waste lithium iron phosphate batteries and is suitable for the treatment of waste lithium iron phosphate batteries with a wide range of impurity contents. Attached Figure Description

[0046] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort, wherein:

[0047] Figure 1 This is a photograph of the ferric phosphate of the present invention;

[0048] Figure 2 This is a physical image of the lithium phosphate of this invention;

[0049] Figure 3 This is an electron micrograph of reducing agent component A of the present invention.

[0050] Figure 4 This is an electron microscope image of reducing agent component B of the present invention. Detailed Implementation

[0051] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments. The components of the embodiments of the invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0052] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0053] It should be noted that relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0054] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0055] This invention provides a process for the complete recycling of waste lithium batteries, which first recycles iron phosphate and then lithium phosphate, including the following steps:

[0056] S1, Recycling Ferric Phosphate

[0057] S1.1. Pulverize the waste lithium iron phosphate black powder at a solid-liquid ratio of 1:4-6, then add acid solution to adjust the pH to 1-3, heat and react for 3-6 hours, filter to obtain the first filtrate;

[0058] S1.2 Add a reducing agent to the acidic first filtrate to carry out a reduction reaction, reducing the copper ions and ferric ions in the first filtrate, filter, and obtain the second filtrate;

[0059] S1.3 Add a precipitant to the second filtrate to remove aluminum ions, filter, and obtain the third filtrate;

[0060] S1.4 Adjust the pH of the third filtrate to 2-3, react to precipitate titanium ions, filter, and obtain the fourth filtrate;

[0061] S1.5 Add phosphoric acid to the fourth filtrate to adjust the iron-to-phosphorus ratio to 1:1.01-1.2. Then, add hydrogen peroxide and alkaline solution dropwise simultaneously. The dropwise addition time of hydrogen peroxide and alkaline solution is 1-2 hours. The temperature during the dropwise addition process is controlled at 40-60℃. After the dropwise addition is completed, the subsequent reaction is carried out. After the reaction is completed, filter to obtain the fifth filter residue and the fifth filtrate. The fifth filter residue is iron phosphate.

[0062] S1.6 After multi-stage pulping and washing of ferric phosphate, the washed ferric phosphate is passed into a flash evaporation tower to remove 95% of the total free water; then the ferric phosphate is calcined in a rotary kiln to obtain qualified ferric phosphate.

[0063] S2, Recycling Lithium Phosphate

[0064] S2.1 Adjust the pH of the fifth filtrate to 4-6, react at 30-55℃, then adjust the pH to 10-12, filter, pass the filtrate through resin to remove calcium, then pass it through a nanofiltration membrane and MVR for concentration to obtain a lithium salt solution with a lithium ion concentration of 12-18 g / L.

[0065] S2.2 Prepare a phosphorus source solution with a phosphorus concentration of 0.7-1.2 mol / L. First, add the phosphorus source solution to the synthesis vessel, and then add the lithium salt solution dropwise to the synthesis vessel. The dropwise addition time is 60-150 min, and the dropwise addition temperature is 40-70℃. After the dropwise addition is completed, continue the reaction for 30-90 min and then filter to obtain lithium phosphate.

[0066] S2.3. The synthesized lithium phosphate is pulped, washed, aged, and stirred before being passed into a flash evaporation tower to remove moisture and then demagnetized to obtain qualified lithium phosphate.

[0067] The multi-stage pulping in step S1.6 includes the following specific steps:

[0068] First stage pulping: Pulping ferric phosphate at a solid-liquid ratio of 1:6-12, heating to 55-80℃, stirring and washing for 50-60 minutes, filtering, and then the ferric phosphate enters the second stage pulping;

[0069] Second stage pulping: The ferric phosphate obtained after the first stage pulping and filtration is pulped at a solid-liquid ratio of 1:3-7. Phosphoric acid of 4-10% of the mass of ferric phosphate is added, the temperature is raised to 85-90℃, and the reaction continues for 30-90 minutes until the ferric phosphate turns white. After filtration, the ferric phosphate enters the third stage pulping.

[0070] Third-stage pulping: The ferric phosphate obtained after the second-stage pulping and filtration is pulped at a ratio of 1:6-7, heated to 40-55℃, stirred and washed for 20-45 minutes, and then filtered to obtain multi-stage pulped ferric phosphate.

[0071] The specific steps for pulping, washing, aging, and stirring the synthesized lithium phosphate in step S2.3 are as follows: The synthesized lithium phosphate is pulped at a solid-liquid ratio of 1:11-14, stirred and washed at 45-80℃ for 35-50 minutes, and then filtered. The washed lithium phosphate is pulped again at a solid-liquid ratio of 1:9-11, and phosphoric acid is added at a ratio of 4.12-7.5% of the lithium phosphate mass. The temperature is raised to 92-100℃, and the aging is carried out for 45-85 minutes, followed by filtration. Then, the aged lithium phosphate is stirred and washed at a solid-liquid ratio of 1:10-15 for 20-35 minutes at a temperature of 40-50℃. After filtration, the lithium phosphate is passed into a flash evaporation tower.

[0072] Based on the lithium ion content in the lithium salt solution, the phosphorus excess coefficient in the phosphorus source solution added in step S2.2 is 1.03-1.2.

[0073] The amount of hydrogen peroxide used in step S1.5 is 1.1-1.5 times the theoretical amount used to oxidize the ferrous ions in the fourth filtrate.

[0074] The reducing agent in step S1.2 is a two-component reducing agent, comprising component A and component B; component A is a composite of silica-based copper ion-imprinted polymer loaded with nano-zero valent iron; component B is sustained-release ascorbic acid microspheres.

[0075] In step S1.2, the molar ratio of nano-zero valent iron in component A to copper ions in the first filtrate is 1.2:1;

[0076] In step S1.2, the molar ratio of ascorbic acid in component B to ferric ions in the first filtrate is 1.2:1.

[0077] The precipitant in S1.3 is at least one of oxalic acid, sodium fluoride, and sodium oxalate.

[0078] The reducing agent is prepared by the following method:

[0079] Preparation of component A:

[0080] A1. 100 parts by weight of silica gel were refluxed in 1M nitric acid solution at 80°C for 2 hours, washed, dried and dispersed in toluene, 15 parts by weight of 3-mercaptopropyltrimethoxysilane were added, and the mixture was refluxed at 110°C for 12 hours under nitrogen protection. After the reaction, the mixture was filtered, washed and dried to obtain mercapto-modified silica gel.

[0081] A2. Thiolized silica gel was added to a copper ion solution and adsorbed until saturated. Then, it was mixed with methacrylic acid monomer, BPO initiator, and ethylene glycol dimethacrylate crosslinking agent, and polymerized at 60-70℃. After the reaction, EDTA was used as an eluent, and the mixture was dried to obtain a silica gel-based copper ion imprinted polymer. The amount of methacrylic acid monomer was 5% of the mass of the thiolated silica gel, the amount of BPO initiator was 0.3% of the mass of the thiolated silica gel, and the amount of ethylene glycol dimethacrylate crosslinking agent was 15% of the mass of the thiolated silica gel.

[0082] A3. Dissolve 50 parts by weight of FeSO4·7H2O in 400 parts by weight of deionized water, stir evenly, add silica-based copper ion imprinted polymer, stir at 40°C for 4 hours, and then slowly add a reducing solution containing 18 parts by weight of sodium borohydride under nitrogen protection. React for 1 hour, filter, wash, and dry to obtain component A.

[0083] Preparation of component B:

[0084] B1. Dissolve 4 parts by weight of sodium alginate and 20 parts by weight of ascorbic acid in 100 parts by weight of deionized water, stir evenly to obtain a mixture, then add 2 parts by weight of calcium carbonate powder to the mixture, stir evenly to form a suspension.

[0085] B2. Gradually add the suspension dropwise to the calcium chloride solution. After the addition is complete, stir the reaction for 30 minutes, filter, wash, and dry to obtain component B.

[0086] The inlet air temperature of the flash tower in S1.6 is controlled within 500℃, the outlet temperature is controlled between 100-150℃, and the mixing temperature is 120-160℃.

[0087] In step S2.3, the inlet air temperature of the flash tower is controlled within 350℃, the outlet temperature is controlled between 110-145℃, and the mixing temperature is between 120-150℃.

[0088] The alkaline solution in S1.5 is at least one of a sodium carbonate solution with a mass fraction of 10-30%, a sodium hydroxide solution with a mass fraction of 10-20%, and ammonia water.

[0089] Example 1

[0090] The microstructure of the reducing agent (component A) prepared above is shown in the figure below. Figure 3 As shown, the microstructure of component B is as follows: Figure 4 As shown in Table 1), the preferred embodiment of the present invention provides a full-resource recycling process for waste lithium batteries, wherein the parameters of waste lithium iron phosphate black powder (black powder 1) are shown in Table 1.

[0091] Table 1 Parameters of Black Powder 1

[0092] Fe(%) P(%) Li (%) Al (ppm) Ca (ppm) Cu (ppm) Ti (ppm) Black Fan 1 18.520 10.370 2.62 13454 234.02 21745 1247

[0093] The specific steps are as follows:

[0094] The black powder 1 was pulped at a solid-liquid ratio of 1:4, then sulfuric acid and sodium dithionite were added to adjust the pH to 1.6, and the temperature was controlled at 60℃. The reaction was then carried out for 3 hours, followed by filtration to obtain the first filtrate. A reducing agent (component A, microstructure shown in the diagram) was added to the first filtrate. Figure 3 As shown, the microstructure of component B is as follows: Figure 4As shown), the reaction was carried out at 30℃ for 1 hour. The molar ratio of nano-zero ferric iron in component A of the reducing agent to copper ions in the first filtrate was 1.2:1, and the molar ratio of ascorbic acid in component B of the reducing agent to ferric ions in the first filtrate was 1.2:1. The copper and ferric ions were reduced, and the mixture was filtered to obtain the second filtrate. Sodium oxalate was added to the second filtrate to remove aluminum ions. The reaction temperature was 50℃, and the reaction time was 4 hours. The mixture was filtered to obtain the third filtrate. Trisodium phosphate was then added to the third filtrate to adjust the pH to 2.4, and the reaction was carried out at 45℃ for 50 minutes. The mixture was filtered to obtain the fourth filtrate. Phosphoric acid was then added to the fourth filtrate to adjust the iron-phosphorus ratio to 1:1.04. Simultaneously, hydrogen peroxide and a 20% sodium carbonate solution were added dropwise. The amount of hydrogen peroxide used was 1.35 times the theoretical amount. The pH was adjusted to 2.5 using the 20% sodium carbonate solution, and the addition time was 1 hour. The temperature during the addition process was controlled at [temperature missing]. At 45℃, after the dropwise addition was completed, the reaction continued for 40 minutes, followed by filtration to obtain ferric phosphate (fifth filter residue) and the fifth filtrate. The synthesized ferric phosphate was then slurried at a solid-liquid ratio of 1:12, washed at 80℃ for 60 minutes, and filtered to obtain ferric phosphate. The ferric phosphate was then slurried again at a solid-liquid ratio of 1:3, and 4% (by weight) of phosphoric acid was added. The temperature was raised to 95℃ until the ferric phosphate turned white, and the reaction continued for 45 minutes before filtration to obtain ferric phosphate. The filtered ferric phosphate was then slurried again at a solid-liquid ratio of 1:6, stirred and washed at 40℃ for 20 minutes, filtered, and washed. The washed ferric phosphate was then passed into a flash evaporation tower with an inlet air temperature of 450℃, an outlet temperature of 140℃, and a mixing temperature of 145℃ to remove 95% of the total free water. Finally, it was calcined in a rotary kiln at 780℃ under a negative pressure of -330 Pa for 2 hours. The sulfur content in the ferric phosphate was 0.01%, and the specific surface area was 4.1 m². 2 / g, to obtain qualified ferric phosphate, such as Figure 1 As shown;

[0095] Ammonia was added to the fifth filtrate to adjust the pH to 5.5. After reacting at 30°C for 20 min, calcium oxide was added to adjust the pH to 12. After filtration, the filtrate was passed through a resin to remove calcium ions to 0.8 ppm. The solution was then concentrated using a nanofiltration membrane and MVR to obtain a lithium salt solution with a lithium ion concentration of 14.63 g / L. Subsequently, a phosphorus source solution with a phosphorus concentration of 1 mol / L was prepared. The phosphorus source solution was first added to the synthesis vessel, and then the lithium salt solution was added dropwise. The phosphorus excess coefficient in the added phosphorus source solution was 1.14. The lithium salt solution was added over a period of 90 min at a temperature of 45°C. After the addition was completed, the reaction was continued for 30 min, followed by filtration to obtain phosphoric acid. Lithium; the synthesized lithium phosphate was slurried at a solid-liquid ratio of 1:13, stirred and washed at 80℃ for 50 min, and then filtered to obtain lithium phosphate; the stirred lithium phosphate was slurried again at a solid-liquid ratio of 1:9, and phosphoric acid was added at a concentration of 4.12% of the lithium phosphate mass. The mixture was heated to 95℃ and aged for 45 min, then filtered to obtain lithium phosphate; the aged lithium phosphate was then stirred and washed again at a solid-liquid ratio of 1:15 for 20 min at a stirring temperature of 50℃; the washed lithium phosphate was then passed into a flash evaporation tower, with the inlet air temperature controlled at 345℃, the outlet temperature at 145℃, the mixing temperature at 150℃, and the product moisture content controlled at 0.1%; subsequently, demagnetization was performed to obtain qualified lithium phosphate, such as... Figure 2 As shown; the magnetic field strength of the cavity during demagnetization is 4500GS, and the number of magnetic particles is 51pcs / kg.

[0096] Example 2

[0097] The microstructure of the reducing agent (component A) prepared above is shown in the figure below. Figure 3 As shown, the microstructure of component B is as follows: Figure 4 As shown in Table 2), the preferred embodiment of the present invention provides a full-resource recycling process for waste lithium batteries, wherein the parameters of waste lithium iron phosphate black powder (black powder 2) are shown in Table 2.

[0098] Table 2 Parameters of Black Powder 2

[0099] Fe(%) P(%) Li (%) Al (ppm) Ca (ppm) Cu (ppm) Ti (ppm) Black Pink 2 19.157 11.32 2.54 8947 154 13564 768

[0100] The specific steps are as follows:

[0101] The black powder was pulped at a solid-liquid ratio of 1:5, then sulfuric acid was added to adjust the pH to 1.5, and the temperature was controlled at 70℃. The reaction was then carried out for 5 hours, followed by filtration to obtain the first filtrate. A reducing agent was added to the first filtrate. The molar ratio of nano-zero ferric iron in component A of the reducing agent to copper ions in the first filtrate was 1.2:1, and the molar ratio of ascorbic acid in component B of the reducing agent to ferric ions in the first filtrate was 1.2:1. The reaction was carried out at 30℃ for 2 hours to reduce the copper and ferric ions. The mixture was then filtered. The second filtrate was obtained. Sodium oxalate and sodium fluoride (mass ratio 1:1) were added to the second filtrate to remove aluminum ions. The reaction temperature was 65℃, and the reaction time was 3 hours. After filtration, the third filtrate was obtained. Disodium hydrogen phosphate was then added to the third filtrate to adjust the pH to 2.3, and the reaction was carried out at 65℃ for 45 minutes. After filtration, the fourth filtrate was obtained. Phosphoric acid was then added to the fourth filtrate to adjust the iron-to-phosphorus ratio to 1:1.06. Simultaneously, hydrogen peroxide and a 20% sodium hydroxide solution were added dropwise, with the amount of hydrogen peroxide used being 1.4 times the theoretical amount. 0 times, adjust the pH to 2.8 using 20% ​​sodium hydroxide solution, add over 1.5 hours, control the temperature at 55℃ during the addition process, continue the reaction for 50 minutes after the addition is complete, filter to obtain the fifth filtrate and ferric phosphate; then slurry the synthesized ferric phosphate with a solid-liquid ratio of 1:11, wash at 75℃ for 50 minutes, filter to obtain ferric phosphate; then slurry the ferric phosphate with a solid-liquid ratio of 1:4, add 5% phosphoric acid by weight of ferric phosphate, heat to 90℃ until the ferric phosphate turns white, and continue the reaction for 30 minutes. After filtration, ferric phosphate is obtained. The filtered ferric phosphate is then slurried with a solid-liquid ratio of 1:7 and washed at 55℃ for 30 minutes. It is then filtered again and washed. The washed ferric phosphate is passed into a flash evaporator with an inlet air temperature of 440℃, an outlet temperature of 135℃, and a mixing temperature of 139℃ to remove 92% of the total free water. Finally, it is calcined in a rotary kiln at 730℃ under a negative pressure of -320Pa for 3 hours. The resulting ferric phosphate has a sulfur content of 0.013% and a specific surface area of ​​5.24 m². 2 / g, yielding qualified ferric phosphate.

[0102] Sodium hydroxide was added to the fifth filtrate to adjust the pH to 5.2. After reacting at 40℃ for 30 min, calcium oxide was added to adjust the pH to 11. After filtration, the filtrate was passed through a resin to remove calcium ions to 0.65 ppm. The solution was then concentrated by passing it through a nanofiltration membrane and MVR to obtain a lithium salt solution with a lithium concentration of 15.81 g / L. Subsequently, a phosphorus source solution with a phosphorus concentration of 1.1 mol / L was prepared. The phosphorus source solution was first added to the synthesis vessel, and then the lithium salt solution was added dropwise to the synthesis vessel. The phosphorus excess coefficient in the added phosphorus source solution was 1.2 (1.2 times the theoretical amount). The lithium salt solution was added dropwise over 110 min at a temperature of 55℃. After the addition was completed, the reaction was continued for 40 min, and then filtered to obtain lithium phosphate. The synthesized phosphoric acid... Lithium was pulped at a solid-liquid ratio of 1:14, stirred and washed at 70℃ for 50 min, and then filtered to obtain lithium phosphate. The stirred lithium phosphate was then pulped at a solid-liquid ratio of 1:11, and phosphoric acid was added at a mass of 5.32% of the lithium phosphate. The mixture was heated to 92℃, aged for 50 min, and then filtered to obtain lithium phosphate. The aged lithium phosphate was then stirred and washed again at a solid-liquid ratio of 1:14 for 30 min at a temperature of 40℃. The washed lithium phosphate was then passed into a flash evaporation tower with an inlet air temperature controlled at 340℃, an outlet temperature of 143℃, a mixing temperature of 148℃, and a product moisture content controlled at 0.11%. Subsequently, the product was demagnetized to obtain qualified lithium phosphate. The magnetic field strength of the cavity during demagnetization was 4300 GS, and the magnetic particle size was 104 pcs / kg.

[0103] Example 3

[0104] The microstructure of the reducing agent (component A) prepared above is shown in the figure below. Figure 3 As shown, the microstructure of component B is as follows: Figure 4 As shown in Table 3), the preferred embodiment of the present invention provides a full-resource recycling process for waste lithium batteries, wherein the parameters of waste lithium iron phosphate black powder (black powder 3) are shown in Table 3.

[0105] Table 3 Parameters of Black Powder 3

[0106] Fe(%) P(%) Li (%) Al (ppm) Ca (ppm) Cu (ppm) Ti (ppm) Black Pink 3 16.130 10.140 2.37 10124 198 9104 554

[0107] The black powder was pulped at a solid-liquid ratio of 1:6, then sulfuric acid and sodium sulfite were added to adjust the pH to 2. The temperature was controlled at 65℃, and the reaction was allowed to proceed for 3.5 hours. The mixture was then filtered to obtain the first filtrate. A reducing agent was added to the first filtrate. The molar ratio of nano-zero ferric iron in component A of the reducing agent to copper ions in the first filtrate was 1.2:1, and the molar ratio of ascorbic acid in component B of the reducing agent to ferric ions in the first filtrate was 1.2:1. The mixture was reacted at 40℃ for 1.5 hours to reduce the copper ions and... Ferrous ions were removed by filtration to obtain a second filtrate. Oxalic acid and sodium fluoride (mass ratio 1:1) were added to the second filtrate to remove aluminum ions. The reaction temperature was 55℃, and the reaction time was 3.5 h. The filtrate was then filtered to obtain a third filtrate. Disodium hydrogen phosphate and sodium hydroxide were then added to the third filtrate to adjust the pH to 2.5. The reaction was carried out at 40℃ for 35 min, and the filtrate was filtered to obtain a fourth filtrate. Phosphoric acid was then added to the fourth filtrate to adjust the iron-to-phosphorus ratio to 1:1.08. Simultaneously, hydrogen peroxide and ammonia were added dropwise, with the amount of hydrogen peroxide being [amount missing]. Add 1.3 times the dosage, adjust the pH to 2.1 with ammonia solution, add over 2 hours, maintain the temperature at 50℃ during the addition, and continue the reaction for 50 minutes after the addition is complete. Filter to obtain ferric phosphate and the fifth filtrate. Then, slurry the synthesized ferric phosphate at a solid-liquid ratio of 1:6, wash at 55℃ for 60 minutes, and filter to obtain ferric phosphate. Slurry the ferric phosphate again at a solid-liquid ratio of 1:7, add 10% (by weight) phosphoric acid, heat to 85℃ until the ferric phosphate turns white, and continue the reaction for 90 minutes. The ferric phosphate was obtained by filtration; the filtered ferric phosphate was then slurryed with a solid-liquid ratio of 1:7, stirred and washed at 45℃ for 45 minutes, filtered, and washed. The washed ferric phosphate was then passed into a flash evaporation tower with an inlet air temperature of 430℃, an outlet temperature of 130℃, and a mixing temperature of 135℃ to remove 88% of the total free water. Finally, it was calcined in a rotary kiln at 650℃ under a negative pressure of -300Pa for 4 hours. The sulfur content in the ferric phosphate was 0.015%, and the specific surface area was 8.71 m². 2 / g, yielding qualified iron phosphate;

[0108] Sodium carbonate was added to the fifth filtrate to adjust the pH to 4.5. The reaction was carried out at 70℃ for 150 min, followed by another addition of sodium carbonate to adjust the pH to 10. After filtration, the filtrate was passed through a resin to remove calcium ions to 0.53 ppm. The solution was then concentrated using a nanofiltration membrane and MVR to obtain a lithium salt solution with a lithium concentration of 17.26 g / L. Subsequently, a phosphorus source solution with a phosphorus concentration of 1.2 mol / L was prepared. The phosphorus source solution was first added to the synthesis vessel, followed by the lithium salt solution added dropwise. The phosphorus excess coefficient in the added phosphorus source solution was 1.03. The addition time was 150 min, and the addition temperature was 60℃. After the addition was completed, the reaction was continued for 90 min, followed by filtration to obtain lithium phosphate. The synthesized lithium phosphate was reacted with a solid-liquid ratio of 1:1. 4. Pulping: After stirring and washing at 45℃ for 35 minutes, filter to obtain lithium phosphate. Pulp the washed lithium phosphate at a solid-liquid ratio of 1:10, add phosphoric acid (7.5% of the lithium phosphate mass), heat to 100℃, age for 85 minutes, and then filter to obtain lithium phosphate. Subsequently, wash the aged lithium phosphate again at a solid-liquid ratio of 1:10 for 35 minutes at a temperature of 45℃. Pass the washed lithium phosphate into a flash evaporation tower with an inlet air temperature controlled at 330℃, an outlet temperature of 125℃, a mixing temperature of 130℃, and a product moisture content controlled at 0.3%. Then, demagnetize to obtain qualified lithium phosphate. During demagnetization, the cavity magnetic field strength is 4200GS, and the magnetic particle size is 150pcs / kg.

[0109] Comparative Example 1

[0110] Based on Example 1, the difference from Example 1 is that a reducing agent was added to the first filtrate in this comparative example. The reducing agent used was iron powder, and the excess coefficient of the iron powder was 1.2 (1.2 times the theoretical amount); all other aspects were the same.

[0111] Comparative Example 2

[0112] Based on the black powder of Example 1 of this application, this comparative example provides a recovery method based on pH precipitation, including the following steps: placing black powder 1 in a container; adding phosphoric acid (molar ratio of phosphoric acid to lithium iron phosphate is 0.8) and hydrogen peroxide (molar ratio of hydrogen peroxide to lithium iron phosphate is 1.2) dropwise to the black powder, continuing to add deionized water to the required liquid-solid ratio (5:1), slurrying, reacting at 70°C for 60 min, filtering, washing the filter residue to obtain the first filter residue and lithium-rich solution; adding phosphoric acid to adjust the acid-to-material ratio (H3PO4 / Fe) of the lithium-rich solution. 3+ The molar ratio was 1:0.95. The pH of the solution was then adjusted to 2 with deionized water, resulting in a white suspension. After filtration, a secondary filter residue and filtrate were obtained. The secondary filter residue was dehydrated to obtain a yellowish-white iron phosphate product. The pH of the filtrate was adjusted to 8 (using sodium hydroxide to adjust the pH) and then filtered to remove the precipitate. The pH of the filtrate was further adjusted to 12 (using sodium hydroxide to adjust the pH). After filtration and drying, white lithium phosphate was obtained.

[0113] Comparative Example 3

[0114] Based on Example 1, only component A was added to the reducing agent in this comparative example, and component B was not added; all other aspects were the same.

[0115] Comparative Example 4

[0116] Based on Example 1, only component B was added to the reducing agent in this comparative example, and component A was not added; all other aspects were the same.

[0117] Comparative Example 5

[0118] Based on Example 1, the reducing agent component A in this comparative example does not include copper ion imprinted polymer, and nano-zero valent iron is directly loaded onto sulfhydryl silica gel; all other aspects are the same, and the preparation method of the reducing agent can be modified accordingly.

[0119] Comparative Example 6

[0120] Based on Example 1, in this comparative example, ascorbic acid in reducing agent component B is added directly as a reducing agent and is not prepared as a microsphere structure; all other aspects are the same.

[0121] Comparative Example 7

[0122] Based on Example 1, the difference between this comparative example and Example 1 is that: after obtaining ferric phosphate (fifth filter residue) and fifth filtrate in step S1.5, this comparative example does not perform the multi-stage pulping and washing process of ferric phosphate in step S1.6, but directly sends the ferric phosphate (fifth filter residue) obtained in step S1.5 into the flash evaporator for the next step of processing; the rest are the same.

[0123] Comparative Example 8

[0124] Based on Example 1, the difference between this comparative example and Example 1 is that the synthesized lithium phosphate in this comparative example is not subjected to pulping, washing, aging, or stirring. After obtaining lithium phosphate in step S2.2 (the first time lithium phosphate was obtained in the method of Example 1), it is directly fed into the flash evaporator for subsequent processing; the rest are the same.

[0125] Experimental Example 1

[0126] The components in the finished ferric phosphate products prepared in Examples 1-3 and Comparative Examples 1-7 were tested using existing technologies, and the results are shown in Table 4.

[0127] Table 4 Finished Ferric Phosphate

[0128] F (wt%) P (wt%) Fe / P Magnetic impurities (wt%) Cu (ppm) Ti (ppm) Al (ppm) Ca (ppm) BET (m² / g) D50 (μm) Example 1 36.01 20.78 0.96 0.046 4.9 263.19 49.46 0.5 4.1 3.815 Example 2 36.08 20.81 0.96 0.032 1.2 243.51 30.14 0.5 5.24 3.741 Example 3 36.10 20.84 0.96 0.031 1.6 213.32 35.12 0.6 8.71 3.201 Comparative Example 1 34.85 21.12 0.91 0.058 52.9 512.47 105.3 1.5 3.52 5.213 Comparative Example 2 33.15 21.45 0.86 0.153 98.7 805.61 198.24 1.82 2.03 10.245 Comparative Example 3 35.12 21.25 0.92 0.048 5.1 315.28 85.17 0.52 4.05 4.032 Comparative Example 4 35.58 21.08 0.93 0.041 78.9 248.95 62.33 1.1 4.48 3.782 Comparative Example 5 35.35 21.15 0.92 0.044 32.6 268.41 51.22 0.6 4.12 3.801 Comparative Example 6 35.20 21.2 0.91 0.052 9.8 272.15 62.18 1.3 3.85 4.186 Comparative Example 7 34.12 21.32 0.88 0.081 18.5 398.74 152.36 1.89 3.12 6.03

[0129] Experimental Example 2

[0130] The composition of the finished lithium phosphate products prepared in Examples 1-3 and Comparative Examples 2 and 8 was tested using existing technologies, and the results are shown in Table 5.

[0131] Table 5. Testing of Lithium Phosphate Finished Products

[0132] Lithium phosphate (wt%) Moisture content (wt%) Al (ppm) Ca (ppm) Cu (ppm) Fe (ppm) Na (ppm) Example 1 99.74% 0.1% 3.79 0.48 1.13 9.82 63.15 Example 2 99.80% 0.11% 5.41 0.41 0.62 13.13 50.81 Example 3 99.80% 0.3% 4.56 0.39 1.54 13.87 61.24 Comparative Example 2 97.52% 0.25% 105.34 25.14 45.82 88.95 152.36 Comparative Example 8 99.28% 0.1% 12.35 0.71 5.47 25.64 95.47

[0133] Based on the above test examples, the iron phosphate and lithium phosphate recycled in this application can both reach battery grade, are also applicable in black powder with high aluminum content, have low requirements for the impurity content in raw materials, and have a wide range of applications.

[0134] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, and improvements made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A process for the complete recycling of waste lithium batteries, characterized in that: Includes the following steps: S1, Recycling Ferric Phosphate S1.

1. Pulverize the waste lithium iron phosphate black powder at a solid-liquid ratio of 1:4-6, then add acid solution to adjust the pH to 1-3, heat and react for 3-6 hours, filter to obtain the first filtrate; S1.

2. A reducing agent is added to the acidic first filtrate to carry out a reduction reaction, reducing the copper ions and ferric ions in the first filtrate. The filtrate is then filtered to obtain a second filtrate. The reducing agent is a two-component reducing agent, comprising component A and component B. Component A is a composite of silica-based copper ion imprinted polymer loaded with nano-zero ferric iron. Component B is a sustained-release ascorbic acid microsphere. S1.3 Add a precipitant to the second filtrate to remove aluminum ions, filter, and obtain the third filtrate; S1.4 Adjust the pH of the third filtrate to 2-3, react to precipitate titanium ions, filter, and obtain the fourth filtrate; S1.5 Add phosphoric acid to the fourth filtrate to adjust the iron-to-phosphorus ratio to 1:1.01-1.

2. Then, add hydrogen peroxide and alkaline solution dropwise simultaneously. The dropwise addition time of hydrogen peroxide and alkaline solution is 1-2 hours. The temperature during the dropwise addition process is controlled at 40-60℃. After the dropwise addition is completed, the subsequent reaction is carried out. After the reaction is completed, filter to obtain the fifth filter residue and the fifth filtrate. The fifth filter residue is iron phosphate. S1.6 After multi-stage pulping and washing of ferric phosphate, the washed ferric phosphate is passed into a flash evaporation tower to remove 95% of the total free water; then the ferric phosphate is calcined in a rotary kiln to obtain qualified ferric phosphate. S2, Recycling Lithium Phosphate S2.1 Adjust the pH of the fifth filtrate to 4-6, react at 30-55℃, then adjust the pH to 10-12, filter, pass the filtrate through resin to remove calcium, then pass it through a nanofiltration membrane and MVR for concentration to obtain a lithium salt solution with a lithium ion concentration of 12-18 g / L. S2.2 Prepare a phosphorus source solution with a phosphorus concentration of 0.7-1.2 mol / L. First, add the phosphorus source solution to the synthesis vessel, and then add the lithium salt solution dropwise to the synthesis vessel. The dropwise addition time is 60-150 min, and the dropwise addition temperature is 40-70℃. After the dropwise addition is completed, continue the reaction for 30-90 min and then filter to obtain lithium phosphate. S2.

3. The synthesized lithium phosphate is pulped, washed, aged, and stirred before being passed into a flash evaporation tower to remove moisture and then demagnetized to obtain qualified lithium phosphate.

2. The process for full-resource recycling of waste lithium batteries according to claim 1, characterized in that: The multi-stage pulping in step S1.6 includes the following specific steps: First stage pulping: Pulping ferric phosphate at a solid-liquid ratio of 1:6-12, heating to 55-80℃, stirring and washing for 50-60 minutes, filtering, and then the ferric phosphate enters the second stage pulping; Second stage pulping: The ferric phosphate obtained after the first stage pulping and filtration is pulped at a solid-liquid ratio of 1:3-7. Phosphoric acid of 4-10% of the mass of ferric phosphate is added, the temperature is raised to 85-90℃, and the reaction continues for 30-90 minutes until the ferric phosphate turns white. After filtration, the ferric phosphate enters the third stage pulping. Third-stage pulping: The ferric phosphate obtained after the second-stage pulping and filtration is pulped at a ratio of 1:6-7, heated to 40-55℃, stirred and washed for 20-45 minutes, and then filtered to obtain multi-stage pulped ferric phosphate.

3. The process for full-resource recycling of waste lithium batteries according to claim 1, characterized in that: The specific steps for pulping, washing, aging, and stirring the synthesized lithium phosphate in step S2.3 are as follows: The synthesized lithium phosphate is pulped at a solid-liquid ratio of 1:11-14, stirred and washed at 45-80℃ for 35-50 minutes, and then filtered. The washed lithium phosphate is pulped again at a solid-liquid ratio of 1:9-11, and phosphoric acid is added at a ratio of 4.12-7.5% of the lithium phosphate mass. The temperature is raised to 92-100℃, and the aging is carried out for 45-85 minutes, followed by filtration. Then, the aged lithium phosphate is stirred and washed at a solid-liquid ratio of 1:10-15 for 20-35 minutes at a temperature of 40-50℃. After filtration, the lithium phosphate is passed into a flash evaporation tower.

4. The process for full-resource recycling of waste lithium batteries according to claim 1, characterized in that: Based on the lithium ion content in the lithium salt solution, the phosphorus excess coefficient in the phosphorus source solution added in step S2.2 is 1.03-1.

2.

5. The process for full-resource recycling of waste lithium batteries according to claim 1, characterized in that: The amount of hydrogen peroxide used in step S1.5 is 1.1-1.5 times the theoretical amount of ferrous ions in the fourth filtrate.

6. The process for full-resource recycling of waste lithium batteries according to claim 1, characterized in that: In step S1.2, the molar ratio of nano-zero ferric iron in component A to copper ions in the first filtrate is 1.2:1; in step S1.2, the molar ratio of ascorbic acid in component B to ferric ions in the first filtrate is 1.2:

1.

7. The process for full resource recycling of waste lithium batteries according to claim 1, characterized in that: The precipitant in S1.3 is at least one of oxalic acid, sodium fluoride, and sodium oxalate.

8. The process for full-resource recycling of waste lithium batteries according to claim 6, characterized in that: The reducing agent is prepared by the following method: Preparation of component A: A1. 100 parts by weight of silica gel were refluxed in 1M nitric acid solution at 80°C for 2 hours, washed, dried and dispersed in toluene, 15 parts by weight of 3-mercaptopropyltrimethoxysilane were added, and the mixture was refluxed at 110°C for 12 hours under nitrogen protection. After the reaction, the mixture was filtered, washed and dried to obtain mercapto-modified silica gel. A2. Thiolized silica gel was added to a copper ion solution and adsorbed until saturated. Then, it was mixed with methacrylic acid monomer, BPO initiator, and ethylene glycol dimethacrylate crosslinking agent, and polymerized at 60-70℃. After the reaction, EDTA was used as an eluent, and the mixture was dried to obtain a silica gel-based copper ion imprinted polymer. The amount of methacrylic acid monomer was 5% of the mass of the thiolated silica gel, the amount of BPO initiator was 0.3% of the mass of the thiolated silica gel, and the amount of ethylene glycol dimethacrylate crosslinking agent was 15% of the mass of the thiolated silica gel. A3. Dissolve 50 parts by weight of FeSO4·7H2O in 400 parts by weight of deionized water, stir evenly, add silica-based copper ion imprinted polymer, stir at 40°C for 4 hours, and then slowly add a reducing solution containing 18 parts by weight of sodium borohydride under nitrogen protection. React for 1 hour, filter, wash, and dry to obtain component A. Preparation of component B: B1. Dissolve 4 parts by weight of sodium alginate and 20 parts by weight of ascorbic acid in 100 parts by weight of deionized water, stir evenly to obtain a mixture, then add 2 parts by weight of calcium carbonate powder to the mixture, stir evenly to form a suspension. B2. Gradually add the suspension dropwise to the calcium chloride solution. After the addition is complete, stir the reaction for 30 minutes, filter, wash, and dry to obtain component B.

9. The process for full-resource recycling of waste lithium batteries according to claim 1, characterized in that: The inlet air temperature of the flash tower in S1.6 is controlled within 500℃, the outlet temperature is controlled between 100-150℃, and the mixing temperature is 120-160℃. In step S2.3, the inlet air temperature of the flash tower is controlled within 350℃, the outlet temperature is controlled between 110-145℃, and the mixing temperature is between 120-150℃.

10. The process for full-resource recycling of waste lithium batteries according to claim 1, characterized in that: The alkaline solution in S1.5 is at least one of a sodium carbonate solution with a mass fraction of 10-30%, a sodium hydroxide solution with a mass fraction of 10-20%, and ammonia water.

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