A method for recycling waste nickel-cobalt-manganese lithium batteries

Abstract

This scheme provides a method for recycling waste nickel-cobalt-manganese-lithium batteries. In this scheme, in a closed device, the electrolyte in the waste battery is separated and collected by low-temperature heating. The battery diaphragm will not decompose under low-temperature heating conditions, which is conducive to the subsequent recycling of the diaphragm, and at the same time avoids the generation of a large amount of toxic and harmful gases such as chloride and dioxin by high-temperature heating. This scheme uses nitric acid to selectively leach nickel, cobalt, manganese, and lithium in the positive electrode material of the battery, and does not leach metal copper, metal iron, and metal aluminum. Copper, iron, and aluminum are effectively separated at one time. The concentrations of copper, aluminum, and iron in the leachate are all less than 0.1g / L, and the leaching rates of metal nickel, cobalt, manganese, and lithium are all greater than 99.2%. It can efficiently recover nickel, cobalt, manganese, and lithium, and the nitric acid used can also be recycled. This method does not introduce cationic impurities during the recovery process, has a short process flow, consumes less auxiliary materials, and has low energy consumption. The obtained nickel, cobalt, manganese, and lithium metal solutions are of high purity, and the recovery rates of nickel, cobalt, manganese, and lithium are all greater than 99.0%.

Description

Technical Field

[0001] The invention relates to the field of lithium battery recycling, and in particular to a method for recycling waste nickel-cobalt-manganese lithium batteries. Background Art

[0002] Nickel-cobalt-manganese lithium batteries are widely used in the field of new energy vehicles due to their high energy density, good thermal stability and good cycle performance. With the rapid development of the new energy industry, a large number of nickel-cobalt-manganese lithium batteries will face the problem of scrapping in the future. Untreated battery positive and negative electrode materials and chemical substances such as polyolefin separators will cause serious pollution to the ecological environment. Therefore, the development of an efficient nickel-cobalt-manganese lithium battery recycling method is beneficial to environmental protection and can avoid waste of resources.

[0003] Nickel-cobalt-manganese lithium batteries mainly include positive electrode, negative electrode, electrolyte and diaphragm. At present, the recycling process of nickel-cobalt-manganese lithium batteries usually requires dismantling and crushing the nickel-cobalt-manganese lithium batteries first, and then obtaining valuable metals such as lithium, cobalt, nickel and manganese through chemical solvent leaching, extraction and precipitation. The existing process mainly separates the battery fluid and diaphragm by high-temperature heating during the disassembly process. During the heating process, a large amount of flue gas containing harmful components such as chlorides and dioxins is generated, causing secondary pollution to the environment.

[0004] In addition, after crushing and screening, the existing battery recycling process still has high copper, iron and aluminum contents in the positive electrode battery powder. In the subsequent lithium recovery process, a step-by-step removal method is generally adopted to remove aluminum, iron and copper. The process is long, inefficient, and will produce a large amount of waste slag, affecting the recovery rate of valuable metals. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention provides a method for recycling waste nickel-cobalt-manganese lithium batteries, comprising the following steps:

[0006] Step 1: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials;

[0007] Step 2: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 100-250°C;

[0008] Step 3: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%;

[0009] Step 4: adding the battery powder obtained after the physical separation to a nitric acid solution with a concentration of 10%-60%, reacting for 2-15 hours at a reaction temperature of 30-80° C., and filtering to obtain a nickel nitrate, cobalt manganese lithium leaching solution and solid waste residue;

[0010] Step 5: adding 60%-98% concentrated sulfuric acid to the nickel-cobalt-manganese-lithium nitrate leaching solution, heating to 45° C.-95° C., reacting for 3-9 hours, to obtain a nickel-cobalt-manganese-lithium sulfate solution;

[0011] Step 6: adding water and an impurity remover to the nickel cobalt manganese lithium sulfate solution, adjusting the pH value of the nickel cobalt manganese lithium sulfate solution to 3.5-5.0, and filtering to obtain the impurity-removed nickel cobalt manganese lithium sulfate solution;

[0012] Step 7: adding an ion regulator to the nickel, cobalt and manganese lithium sulfate solution after impurities are removed, so that the molar ratio of nickel, cobalt and manganese in the nickel, cobalt and manganese lithium sulfate solution after impurities are one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding sodium hydroxide solution, filtering, washing and drying to obtain nickel, cobalt and manganese ternary composite hydroxide, filtering the obtained lithium solution, precipitating with sodium carbonate, filtering, washing and drying to obtain lithium carbonate.

[0013] Preferably, step 3 further comprises the following steps:

[0014] The solid material is crushed for a second time, and the diameter of the material after the second crushing is less than 1.5 cm;

[0015] The secondary crushed materials are screened, and then separated by magnetic separation and gravity separation to obtain copper, iron, aluminum, diaphragm and battery powder.

[0016] Preferably, step 4 also includes: spraying and absorbing the nitrogen oxides generated during the reaction with water to form an acidic substance which is recycled to step 4, and step 5 also includes: spraying and absorbing the nitrogen oxides generated during the reaction with water to form an acidic substance which is recycled to step 4.

[0017] Preferably, the heating temperature in step 2 is 150-200°C.

[0018] Preferably, the concentration of the nitric acid solution in step 4 is 30-50%, the reaction time is 6-10 hours, and the reaction temperature is 40-60°C.

[0019] Preferably, in step 4, the concentrations of copper, aluminum and iron in the nickel-cobalt-manganese-lithium nitrate leaching solution are all less than 0.1 g / L.

[0020] Preferably, the impurity remover is one or more of nickel hydroxide, nickel carbonate, cobalt hydroxide, cobalt carbonate, manganese hydroxide, manganese carbonate, lithium hydroxide, lithium carbonate, nickel sulfide, cobalt sulfide, manganese sulfide and lithium sulfide, and the ion regulator is one or more of nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, manganese sulfate and manganese chloride.

[0021] Preferably, in step 6, the pH value of the nickel cobalt manganese lithium sulfate solution is adjusted to 4.0-4.5.

[0022] Preferably, the ion concentration range of the nickel cobalt manganese lithium sulfate solution after impurities removal in step 6 satisfies: 60g / L≤Ni+Co+Mn+Li≤160g / L, and the ion mass ratio satisfies: (Ni+Co+Mn+Li) / (Cu+Fe+Al+Ca+Mg)≥3300.

[0023] In view of the deficiencies in the prior art, the present invention also provides a method for recycling waste nickel-cobalt-manganese lithium batteries, comprising the following steps:

[0024] Step 1: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials;

[0025] Step 2: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 100-250°C;

[0026] Step 3: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%;

[0027] Step 4: adding the battery powder obtained after the physical separation to a nitric acid solution with a concentration of 10%-60%, reacting for 2-15 hours at a reaction temperature of 30-80° C., and filtering to obtain a nickel nitrate, cobalt manganese lithium leaching solution and solid waste residue;

[0028] Step 5: adding water and an impurity remover to the nickel-cobalt-manganese-lithium nitrate leachate, adjusting the pH value of the nickel-cobalt-manganese-lithium nitrate leachate to 3.5-5.0, and filtering to obtain the impurity-removed nickel-cobalt-manganese-lithium nitrate leachate;

[0029] Step 6: adding an ion regulator to the impurity-removed lithium nickel cobalt manganese nitrate leachate so that the molar ratio of nickel, cobalt and manganese in the impurity-removed lithium nickel cobalt manganese nitrate leachate is one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding sodium hydroxide solution, filtering, washing and drying to obtain a nickel cobalt manganese ternary composite hydroxide, filtering the obtained lithium solution, precipitating with sodium carbonate, filtering, washing and drying to obtain lithium carbonate.

[0030] The beneficial effects of this application are as follows:

[0031] 1. This solution uses low-temperature heating in a closed device to separate and collect the electrolyte in waste batteries. The battery diaphragm will not decompose under low-temperature heating conditions, which is conducive to the subsequent recycling of the diaphragm. At the same time, it avoids the generation of large amounts of toxic and harmful gases such as chlorides and dioxins caused by high-temperature heating.

[0032] 2. This scheme uses nitric acid to selectively leach nickel, cobalt, manganese and lithium in the positive electrode material of the battery, without leaching metallic copper, metallic iron and metallic aluminum, and effectively separates copper, iron and aluminum at one time. The concentrations of copper, aluminum and iron in the leachate are all less than 0.1g / L, and the leaching rates of metallic nickel, cobalt, manganese and lithium are all greater than 99.2%. Nickel, cobalt, manganese and lithium can be efficiently recovered, and the nitric acid used can also be recycled.

[0033] 3. No cationic impurity elements are introduced during the recovery process, the process flow is short, the auxiliary material energy consumption is low, the obtained nickel, cobalt, manganese and lithium metal solutions are of high purity, and the recovery rates of nickel, cobalt, manganese and lithium are all greater than 99.0%. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art are briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0035] Figure 1 A flowchart of a method for recycling waste nickel-cobalt-manganese lithium batteries provided by an embodiment of the present invention;

[0036] Figure 2 A flow chart of another method for recycling waste nickel-cobalt-manganese lithium batteries provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0037] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the protection scope of the present invention.

[0038] In view of the existing shortcomings, this scheme provides a method for recycling waste nickel-cobalt-manganese lithium batteries. Figure 1 , which is a flow chart of a method for recycling waste nickel-cobalt-manganese lithium batteries provided by an embodiment of the present invention. The specific steps of the method are as follows:

[0039] S100: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials;

[0040] S200: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure, and obtaining a solid material, wherein the reaction temperature is 100-250° C.;

[0041] S300: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the battery powder contains 0.2%-6.0% copper, 0.2%-6.0% aluminum and 0.2%-6.0% iron;

[0042] S400: adding a nitric acid solution with a concentration of 10%-60% to the battery powder obtained after the physical separation, reacting for 2-15 hours at a reaction temperature of 30-80° C., filtering to obtain a nickel-cobalt-manganese-lithium nitrate leaching solution and solid waste residue, wherein the concentrations of copper, aluminum and iron in the nickel-cobalt-manganese-lithium nitrate leaching solution are all less than 0.1 g / L;

[0043] S500: adding 60%-98% concentrated sulfuric acid to the nickel-cobalt-manganese-lithium nitrate leaching solution, heating to 45° C.-95° C., reacting for 3-9 hours, to obtain a nickel-cobalt-manganese-lithium sulfate solution;

[0044] S600: adding water and an impurity remover to the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 3.5-5.0, and filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution after impurities removal;

[0045] S700: adding an ion regulator to the nickel, cobalt, manganese lithium sulfate solution after impurities are removed, so that the molar ratio of nickel, cobalt and manganese in the nickel, cobalt, manganese lithium sulfate solution after impurities are removed is one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding sodium hydroxide solution, filtering, washing and drying to obtain nickel, cobalt and manganese ternary composite hydroxide, filtering the obtained lithium solution, precipitating with sodium carbonate, filtering, washing and drying to obtain lithium carbonate.

[0046] Example 1

[0047] Step 1: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials;

[0048] Step 2: The crushed material is placed in a closed environment for heating reaction, and the condensed electrolyte is collected by negative pressure to obtain a solid material. The reaction temperature is 150° C. The collected electrolyte can be purified and reused as the electrolyte of the battery;

[0049] Step 3: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%;

[0050] Step 4: adding the battery powder obtained after the physical separation into a 30% nitric acid solution, reacting for 6 hours at a reaction temperature of 40° C., and filtering to obtain a nickel nitrate, cobalt manganese lithium leaching solution and solid waste residue;

[0051] Step 5: adding 98% concentrated sulfuric acid to the nickel-cobalt-manganese-lithium nitrate leaching solution, heating to 95° C., and reacting for 9 hours to obtain a nickel-cobalt-manganese-lithium sulfate solution;

[0052] Step 6: adding water and nickel hydroxide, nickel carbonate, cobalt hydroxide, manganese sulfide and lithium sulfide to the nickel cobalt manganese lithium sulfate solution, adjusting the pH value of the nickel cobalt manganese lithium sulfate solution to 3.5, filtering to obtain the nickel cobalt manganese lithium sulfate solution after impurities are removed, wherein the ion concentration range of the nickel cobalt manganese lithium sulfate solution after impurities are satisfied: 60g / L≤Ni+Co+Mn+Li≤160g / L, and the ion mass ratio is satisfied: (Ni+Co+Mn+Li) / (Cu+Fe+Al+Ca+Mg)≥3300;

[0053] Step 7: Add nickel sulfate, nickel chloride and cobalt sulfate to the impurity-removed nickel cobalt manganese lithium sulfate solution, so that the molar ratio of nickel, cobalt and manganese in the impurity-removed nickel cobalt manganese lithium sulfate solution is 1:1:1, then add sodium hydroxide solution, filter, wash and dry to obtain nickel cobalt manganese ternary composite hydroxide, filter the obtained lithium solution, precipitate with sodium carbonate, filter, wash and dry to obtain lithium carbonate. Among them, nickel cobalt manganese ternary composite hydroxide can meet the national standard of nickel cobalt manganese ternary composite hydroxide GB / T26300-2020, and lithium carbonate can meet the industry standard of battery-grade lithium carbonate YST 582-2013.

[0054] Example 2

[0055] Step 1: First, the used nickel-cobalt-manganese lithium batteries are discharged and then crushed to obtain crushed materials;

[0056] Step 2: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 200° C.;

[0057] Step 3: performing secondary crushing on the solid material, wherein the diameter of the material after secondary crushing is less than 1.5 cm; screening the material after secondary crushing, and then performing magnetic separation and gravity separation to obtain copper, iron, aluminum, diaphragm and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%;

[0058] Step 4: adding the battery powder obtained after the sorting to a 50% nitric acid solution, reacting for 10 hours at a reaction temperature of 60° C., filtering to obtain a nickel-cobalt-manganese-lithium nitrate leaching solution and solid waste residue, and the nitrogen oxides generated during the reaction can be absorbed by spraying with water to form an acidic substance that is recycled to step 4;

[0059] Step 5: adding 60% concentrated sulfuric acid to the nickel-cobalt-manganese-lithium nitrate leaching solution, heating to 65° C., reacting for 5 hours to obtain a nickel-cobalt-manganese-lithium sulfate solution, spraying and absorbing nitrogen oxides generated during the reaction with water to form acidic substances that can be recycled;

[0060] Step 6: adding water and cobalt carbonate, manganese hydroxide, manganese carbonate, lithium hydroxide, lithium carbonate, nickel sulfide and cobalt sulfide to the nickel cobalt manganese lithium sulfate solution, adjusting the pH value of the nickel cobalt manganese lithium sulfate solution to 4.5, and filtering to obtain the nickel cobalt manganese lithium sulfate solution after impurities are removed;

[0061] Step 7: Add cobalt sulfate, cobalt chloride, manganese sulfate and manganese chloride to the impurity-removed nickel cobalt manganese lithium sulfate solution, so that the molar ratio of nickel, cobalt and manganese in the impurity-removed nickel cobalt manganese lithium sulfate solution is 5:2:3, then add sodium hydroxide solution, and then filter, wash and dry to obtain nickel cobalt manganese three-element composite hydroxide, and filter the obtained lithium solution through sodium carbonate precipitation, filtration, washing and drying to obtain lithium carbonate. Among them, the nickel cobalt manganese three-element composite hydroxide can meet the national standard of nickel cobalt manganese three-element composite hydroxide GB / T26300-2020, and the lithium carbonate can meet the industry standard of battery-grade lithium carbonate YST 582-2013.

[0062] Example 3

[0063] Step 1: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials;

[0064] Step 2: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 250° C.;

[0065] Step 3: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%;

[0066] Step 4: adding the battery powder obtained after the physical separation into a 10% nitric acid solution, reacting for 15 hours at a reaction temperature of 80° C., and filtering to obtain a nickel nitrate, cobalt manganese lithium leaching solution and solid waste residue;

[0067] Step 5: adding 80% concentrated sulfuric acid to the nickel-cobalt-manganese-lithium nitrate leaching solution, heating to 75° C., and reacting for 3 hours to obtain a nickel-cobalt-manganese-lithium sulfate solution;

[0068] Step 6: adding water, nickel hydroxide, nickel carbonate, cobalt hydroxide, cobalt carbonate, manganese hydroxide, manganese carbonate, lithium hydroxide, lithium carbonate, nickel sulfide, cobalt sulfide, manganese sulfide and lithium sulfide to the nickel cobalt manganese lithium sulfate solution, adjusting the pH value of the nickel cobalt manganese lithium sulfate solution to 5.0, and filtering to obtain the nickel cobalt manganese lithium sulfate solution after impurities are removed;

[0069] Step 7: Add manganese chloride to the impurity-removed nickel-cobalt-manganese lithium sulfate solution, so that the molar ratio of nickel, cobalt and manganese in the impurity-removed nickel-cobalt-manganese lithium sulfate solution is 6:2:2, then add sodium hydroxide solution, filter, wash and dry to obtain nickel-cobalt-manganese ternary composite hydroxide, filter the obtained lithium solution, precipitate with sodium carbonate, filter, wash and dry to obtain lithium carbonate. Among them, the nickel-cobalt-manganese ternary composite hydroxide can meet the national standard of GB / T26300-2020 nickel-cobalt-manganese ternary composite hydroxide, and the lithium carbonate can meet the industry standard of YST 582-2013 battery-grade lithium carbonate.

[0070] Example 4

[0071] Step 1: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials;

[0072] Step 2: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 100° C.;

[0073] Step 3: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%;

[0074] Step 4: adding the battery powder obtained after the physical separation into a 20% nitric acid solution, reacting for 2 hours at a reaction temperature of 30° C., and filtering to obtain a nickel nitrate, cobalt manganese lithium leaching solution and solid waste residue;

[0075] Step 5: adding 90% concentrated sulfuric acid to the nickel cobalt manganese lithium nitrate leaching solution, heating to 55° C., and reacting for 3 hours to obtain a nickel cobalt manganese lithium sulfate solution;

[0076] Step 6: adding water and cobalt sulfide to the nickel cobalt manganese lithium sulfate solution, adjusting the pH value of the nickel cobalt manganese lithium sulfate solution to 4.0, and filtering to obtain the nickel cobalt manganese lithium sulfate solution after impurities are removed;

[0077] Step 7: Add nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, manganese sulfate and manganese chloride to the impurity-removed nickel cobalt manganese lithium sulfate solution, so that the molar ratio of nickel, cobalt and manganese in the impurity-removed nickel cobalt manganese lithium sulfate solution is 8:1:1, then add sodium hydroxide solution, filter, wash and dry to obtain nickel cobalt manganese three-element composite hydroxide, filter the obtained lithium solution, precipitate with sodium carbonate, filter, wash and dry to obtain lithium carbonate. Among them, nickel cobalt manganese three-element composite hydroxide can meet the national standard of nickel cobalt manganese three-element composite hydroxide GB / T26300-2020, and lithium carbonate can meet the industry standard of battery-grade lithium carbonate YST 582-2013.

[0078] In view of the existing deficiencies, this scheme also provides a method for recycling waste nickel-cobalt-manganese-lithium batteries. Figure 2 , which is a flow chart of another method for recycling waste nickel-cobalt-manganese lithium batteries provided by an embodiment of the present invention. The specific steps of the method are as follows:

[0079] S10: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials;

[0080] S20: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 100-250° C.;

[0081] S30: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%;

[0082] S40: adding the battery powder obtained after the physical separation into a nitric acid solution with a concentration of 10%-60%, reacting for 2-15 hours at a reaction temperature of 30-80° C., and filtering to obtain a nickel nitrate, cobalt manganese lithium leaching solution and solid waste residue;

[0083] S50: adding water and an impurity remover to the nickel-cobalt-manganese-lithium nitrate leaching solution, adjusting the pH value of the nickel-cobalt-manganese-lithium nitrate leaching solution to 3.5-5.0, and filtering to obtain the nickel-cobalt-manganese-lithium nitrate leaching solution after impurities removal;

[0084] S60: adding an ion regulator to the impurity-removed nickel-cobalt-manganese lithium nitrate leachate so that the molar ratio of nickel, cobalt and manganese in the impurity-removed nickel-cobalt-manganese lithium nitrate leachate is one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding sodium hydroxide solution, filtering, washing and drying to obtain nickel-cobalt-manganese ternary composite hydroxide, filtering the obtained lithium solution, precipitating with sodium carbonate, filtering, washing and drying to obtain lithium carbonate.

[0085] Preferably, step 3 further comprises the following steps:

[0086] The solid material is crushed for a second time, and the diameter of the material after the second crushing is less than 1.5 cm;

[0087] The secondary crushed materials are screened, and then separated by magnetic separation and gravity separation to obtain copper, iron, aluminum, diaphragm and battery powder.

[0088] Preferably, step 4 further comprises: spraying and absorbing the nitrogen oxides generated during the reaction with water to form acidic substances for recycling.

[0089] Preferably, the heating temperature in step 2 is 150-200°C.

[0090] Preferably, the concentration of the nitric acid solution in step 4 is 30-50%, the reaction time is 6-10 hours, and the reaction temperature is 40-60°C.

[0091] Preferably, in step 4, the concentrations of copper, aluminum and iron in the nickel-cobalt-manganese-lithium nitrate leaching solution are all less than 0.1 g / L.

[0092] Preferably, the impurity remover is one or more of nickel hydroxide, nickel carbonate, cobalt hydroxide, cobalt carbonate, manganese hydroxide, manganese carbonate, lithium hydroxide, lithium carbonate, nickel sulfide, cobalt sulfide, manganese sulfide and lithium sulfide, and the ion regulator is one or more of nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, manganese sulfate and manganese chloride.

[0093] In this embodiment, the nickel-cobalt-manganese sulfate system commonly used in modern industry is abandoned, the step of removing nitrate ions is reduced, the process is shortened, and energy consumption can be greatly reduced.

[0094] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work should fall within the protection scope of the present invention.

Claims

1. A method for recycling waste nickel-cobalt-manganese lithium batteries, characterized in that: The steps include: Step 1: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials; Step 2: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 100-250°C; Step 3: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%; Step 4: adding the battery powder obtained after the physical separation to a nitric acid solution with a concentration of 10%-60%, reacting for 2-15 hours at a reaction temperature of 30-80° C., and filtering to obtain a nickel-cobalt-manganese-lithium nitrate leaching solution and solid waste residue; the concentrations of copper, aluminum and iron in the nickel-cobalt-manganese-lithium nitrate leaching solution are all less than 0.1 g / L; Step 5: adding 60%-98% concentrated sulfuric acid to the nickel cobalt manganese lithium nitrate leachate, heating to 45°C-95°C, reacting for 3-9 hours, to obtain a nickel cobalt manganese lithium sulfate solution; Step 5 also includes: spraying and absorbing the nitrogen oxides generated during the reaction with water to form an acidic substance that is recycled to step 4; Step 6: adding water and an impurity remover to the nickel-cobalt-manganese-lithium sulfate solution, adjusting the pH value of the nickel-cobalt-manganese-lithium sulfate solution to 3.5-5.0, and filtering to obtain the nickel-cobalt-manganese-lithium sulfate solution after impurities are removed; the impurity remover is one or more of nickel hydroxide, nickel carbonate, cobalt hydroxide, cobalt carbonate, manganese hydroxide, manganese carbonate, lithium hydroxide, lithium carbonate, nickel sulfide, cobalt sulfide, manganese sulfide and lithium sulfide, and the ion concentration range of the nickel-cobalt-manganese-lithium sulfate solution after impurities are removed meets: 60g / L≤Ni+Co+Mn+Li≤160g / L, and the ion mass ratio meets: (Ni+Co+Mn+Li) / (Cu+Fe+Al+Ca+Mg)≥3300; Step 7: adding an ion regulator to the nickel, cobalt and manganese lithium sulfate solution after impurities are removed, so that the molar ratio of nickel, cobalt and manganese in the nickel, cobalt and manganese lithium sulfate solution after impurities are one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding sodium hydroxide solution, filtering, washing and drying to obtain nickel, cobalt and manganese ternary composite hydroxide, filtering the obtained lithium solution, precipitating with sodium carbonate, filtering, washing and drying to obtain lithium carbonate; wherein the nickel, cobalt and manganese ternary composite hydroxide meets the national standard of nickel, cobalt and manganese ternary composite hydroxide GB / T26300-2020, the lithium carbonate meets the industry standard of battery-grade lithium carbonate YST 582-2013, and the recovery rates of nickel, cobalt, manganese and lithium are all greater than 99.0%.

2. The method according to claim 1, characterized in that The step 3 also includes the following steps: The solid material is crushed for a second time, and the diameter of the material after the second crushing is less than 1.5 cm; The secondary crushed material is sieved, and then subjected to magnetic separation and gravity separation to obtain copper, iron, aluminum, diaphragm and battery powder, wherein the battery powder has a copper content of 6.0%, an aluminum content of 6.0%, and an iron content of 6.0%.

3. The method according to claim 1, characterized in that The step 4 also includes: spraying and absorbing the nitrogen oxides generated in the reaction process with water to form acidic substances that are recycled to step 4.

4. The method according to claim 1, characterized in that: The heating temperature in step 2 is 150-200°C.

5. The method according to claim 1, characterized in that: The concentration of the nitric acid solution in step 4 is 30-50%, the reaction time is 6-10 hours, and the reaction temperature is 40-60°C.

6. The method according to claim 1, characterized in that The ion regulator is one or more of nickel sulfate, nickel chloride, cobalt sulfate, cobalt chloride, manganese sulfate and manganese chloride.

7. The method according to claim 1, characterized in that In step 6, the pH value of the nickel cobalt manganese lithium sulfate solution is adjusted to 4.0-4.

5.

8. A method for recycling waste nickel-cobalt-manganese lithium batteries, characterized in that: The steps include: Step 1: crushing the pretreated waste nickel-cobalt-manganese lithium batteries to obtain crushed materials; Step 2: placing the crushed material in a closed environment for heating reaction, collecting the condensed electrolyte by negative pressure to obtain a solid material, and the reaction temperature is 100-250°C; Step 3: physically separating the solid material to obtain copper, iron, aluminum, a separator and battery powder, wherein the copper content of the battery powder is 0.2%-6.0%, the aluminum content is 0.2%-6.0%, and the iron content is 0.2%-6.0%; Step 4: adding the battery powder obtained after the physical separation to a nitric acid solution with a concentration of 10%-60%, reacting for 2-15 hours at a reaction temperature of 30-80° C., and filtering to obtain a nickel nitrate, cobalt manganese lithium leaching solution and solid waste residue; Step 5: adding water and an impurity remover to the nickel-cobalt-manganese-lithium nitrate leachate, adjusting the pH value of the nickel-cobalt-manganese-lithium nitrate leachate to 3.5-5.0, and filtering to obtain the impurity-removed nickel-cobalt-manganese-lithium nitrate leachate; Step 6: adding an ion regulator to the impurity-removed lithium nickel cobalt manganese nitrate leachate so that the molar ratio of nickel, cobalt and manganese in the impurity-removed lithium nickel cobalt manganese nitrate leachate is one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1, then adding sodium hydroxide solution, filtering, washing and drying to obtain a nickel cobalt manganese ternary composite hydroxide, filtering the obtained lithium solution, precipitating with sodium carbonate, filtering, washing and drying to obtain lithium carbonate.

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